A cellulose substance-containing lacquer emulsion prepared from

Nitrocellulose combi-lacquers, prepared by dissolving nitrocellulose (NC), an alkyl resin, plasticiser and possibly optional lacquer additives in organic solvents are known. These lacquers may be used to lacquer surfaces such as e.g. wood, metal, paper, leather, plastics, etc. The disadvantage of these is the high solvent content of 60to80%.
EP 0 076 443 describes the preparation, inter alia, of aqueous NC/alkyd resin emulsions in which the solvent is entirely or partly replaced by water. If surfaces, e.g. of wood, are lacquered with these aqueous emulsions and the chemical resistance determined in accordance with DIN 68 861, part 1, 1 B, then the resistances to water, ethanol and acetone are not sufficient.
Chemically cross-linking aqueous two-component polyurethane coating agents with free polyisocyanates as hardeners for the binder were described in EP 0 358 979. According to that document, polyhydroxyacrylates as binder components are capable of emulsifying certain polyisocyanates with free isocyanate groups, these also being called lacquer polyisocyanates. The aqueous two-component system produced in this way cures to give cross-linked films. The lacquer polyisocyanates are biuret, urethane, uretdione and/or isocyanate group-containing oligomeric derivatives of readily available monomeric or simple diisocyanates, in particular of hexamethylene dilsocyanate (HDI), isophorone diisocyanate (IPDI) and/or bis(isocyanatocyclohexyl)methane (HMDI). The lacquer polyisocyanates used in accordance with EP 0 3 358 979 have a viscosity at 23xc2x0 C. of up to 1000 mPaxc2x7s and have an average NCO functionality of 2.2 to 5.
DE-OS-A 4 226 243 describes an aqueous two-component coating agent based on polyisocyanates and self-emulsifying fatty acid modified polyesters and poly-urethanes. European patent application EP-A 0 496 205 also describes aqueous binder combinations based on polyisocyanates and self-emulsifying urethane, carboxyl and hydroxyl group-containing polyester resins. German patent DE 3 122 030 describes coating compositions consisting of polyisocyanate and water-dilutable alkyd, melamine and acrylic resins which also contain water-miscible solvent.
The disadvantage of these water-dilutable two-component binders described above is the low solids content which can be achieved, the short pot life and the long drying/curing times. Furthermore, wetting onto wood, the initial hardness and the sandability are unsatisfactory.
Now, the object of the invention comprises improving the resistance of aqueous NC lacquer resin emulsions so that good resistances in accordance with DIN 68 861, part 1, B 1, are achieved with these aqueous single-component systems.
The invention concerns an aqueous emulsion the process of its preparation entails adding a cellulose substance to the reaction products or to a mixture of a poly-isocyanate with a lacquer resin that contains at least one hydroxyl group. A single component lacquer emulsion is obtained by adding at least one plasticizer and water and optionally at least one emulsifier and organic solvent.
The lacquer emulsions comprise a product prepared from:
a) 5-50 wt. % of cellulose substance
b) 5-50 wt. % of one or more hydroxyl group-containing lacquer resins
c) 0.1-10 wt. % of polyisocyanates with more than one free isocyanate group
d) 0.5-30 wt. % of plasticiser
e) 0.0-20 wt. % of emulsifier
f) 0.0-45 wt. % of at least one organic solvent
g) 10-65 wt. % of water
wherein the sum of a) to g) is always 100 wt. %, characterised in that the ratio by weight of cellulose substance to OH group-containing lacquer resin is 1:5 to 5:1 and the ratio by equivalents of OH groups (from the lacquer resin) to NCO groups is 1:0.01-1.0.
Suitable cellulose substances are preferably cellulose esters, in particular nitrocelluloses of any level of viscosity or plasticised nitrocelluloses or mixtures of these. Nitrocellulose, for example in conventional industrial nitrocellulose grades, i.e. cellulose nitrates with a nitrogen content of 10.7 to 12.6 wt. %, is very particularly suitable.
Other cellulose substances which can be used are cellulose acetobutyrate and cellulose acetopropionate in varying stages of viscosity and substitution.
Conventional lacquer resins may be used as lacquer resins if these contain isocyanate-reactive groups such as e.g. xe2x80x94OH, xe2x80x94COOH, xe2x80x94NH2, xe2x80x94CONH2. Conventional lacquer resins are e.g. alkyd, maleic acid, phenol, formaldehyde, xylene-formaldehyde, ketone, sulfonamide, aldehyde, amine, epoxy, carbamate, coumarone/indene resins, esters of saccharose and vinyl or acrylate resins and copolymers of these.
It is advantageous if the hydroxyl group-containing lacquer resins have an OH value between 20 and 200 mg KOH/g.
Plasticisers which may be used are conventional plasticisers such as e.g. the esters of aliphatic monocarboxylic acids, preferably with 2 to 18 carbon atoms such as cetyl acetate, glycol diacetate, stearates, ricinoleic acetate, dicarboxylic acids such as e.g. dioctyl adipate, dimethylcycohexylmethyl adipate, dibutyl sebacate; aromatic dicarboxylic acids such as e.g. dibutyl phthalate, dioctyl phthalate, dicyclohexyl phthalate, aliphatic tricarboxylic acids, preferably with 8 carbon atoms, of aromatic dicarboxylic acids and of monohydric alcohols with 2 to 10 carbon atoms, of dihydric alcohols with 2 to 6 carbon atoms and trihydric alcohols with 3 carbon atoms or the esters of inorganic acids such as e.g. tributyl phosphate, triphenyl phosphate; esters of citric acid with alcohols with 1 to 5 carbon atoms which may also be reacted with monocarboxylic acids with 1 to 4 carbon atoms; and also sulfonamides, oils such as castor oil and linseed oil and the alkoxylation products of the compounds mentioned such as e.g. ethoxylated castor oil and soya oil, stearates and phosphates.
The emulsifiers used are optionally anionic emulsifiers, for example long-chain alkylaryl sulfonates such as dodecylbenzene sulfonate or butylnaphthaline sulfonate, alkyl sulfates such as lauryl or stearyl alcohol sulfates, sulfosuccinates such as dioctyl disodium succinate, or non-ionic emulsifiers such as octyl- or nonylphenol-oxyethylates.
The disodium salts of sulfosuccinic acid derivatives of ethoxylated nonylphenols may also be mentioned as anionic emulsifiers.
Conventional organic solvents may be used as solvents provided the cellulose substance and the lacquer resin are soluble therein.
The polyisocyanates are any organic polyisocyanates with aliphatically, cycloaliphatically, araliphatically and/or aromatically bonded, free isocyanate groups which are liquid at room temperature. Particularly preferably, the polyisocyanates are polyisocyanates or polyisocyanate mixtures with exclusively aliphatically and/or cycloaliphatically bonded isocyanate groups with an (average) NCO functionality of between 1.8 and 5.0.
If required, the polyisocyanates may be used mixed with small amounts of inert solvents in order to lower the viscosity to a value within the range mentioned.
Suitable products are, for example, xe2x80x9clacquer polyisocyanatesxe2x80x9d based on hexamethylene diisocyanate or on 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethyl-cyclohexane (IPDI) and/or bis-(isocyanatocyclohexyl)-methane, in particular those which are based exclusively on bexamethylene diisocyanate. xe2x80x9cLacquer polyisocyanatesxe2x80x9d based on these diisocyanates are understood to be the biuret, urethane, uretdione and/or isocyanate group-containing derivatives known per se of these diisocyanates.
Also suitable according to the invention, but less preferred, aromatic polyisocyanates are in particular xe2x80x9clacquer polyisocyanatesxe2x80x9d based on 2,4-diisocyanatotoluene or technical grade mixtures of this with 2,6-diisocyanatotoluene or based on 4,4-diisocyantodiphenylmethane or mixtures of this with its isomers and/or higher homologues. These types of aromatic lacquer polyisocyanates are, for example, urethane group-containing isocyanates such as are obtained by reacting Excess amounts of 2,4-diisocyanatotoluene with polyhydric alcohols such as trimethylolpropane. Further aromatic lacquer polyisocyanates are, for example, trimers of the monomeric diisocyanates mentioned by way of example, i.e. the corresponding isocyanato-isocyanurates.
Basically, the use of unmodified polyisocyanates of the type mentioned by way of example is obviously also possible.
The polyisocyanate component may generally consist of any mixture at all of the polyisocyanates mentioned by way of example.
Hydrophilised polyisocyanates of the basic products mentioned above, which can readily be emulsified in water, are also suitable.
The cellulose substance/lacquer resin emulsion is prepared in accordance with EP 0 076 443.
Reaction, e.g. of the OH group-containing alkyd resin, dissolved in e.g. butyl acetate, with a polyisocyanate, is performed at temperatures up to a max. of 80xc2x0 C., preferably up to 60xc2x0 C., wherein the OH: NCO ratio has to be adjusted so that the resin does not gel but is still effectively film-forming. The NCO groups do not have to react completely with the OH groups in the lacquer resin.
The cellulose substance, plasticiser, optionally emulsifiers, optionally organic solvents are added to the alkyd resin modified in this way and stirred until fibres of the cellulose substance can no longer be seen. The material then passes through a highly viscous state. An oil-in-water emulsion (single-component system) is produced by adding water. It is also possible to add further hydrophilic polyisocyanates to this emulsion in order then to obtain a xe2x80x9ctwo-component systemxe2x80x9d.
The invention also provides use of the coating agent according to the invention in lacquers for the surface treatment of wood, metal, plastics, paper, leather or glass.
Depending on the area of application (e.g. wood, metal, plastics, paper, leather, glass and film lacquering), other known organic solvents may also be added to the emulsion, wherein a solvent concentration of 30%, with respect to the final lacquer formulation, should not be exceeded.
The viscosity may be adjusted for use in the desired application either with water or by adding water-soluble thickeners based e.g. on polyurethanes, cellulose, guar, starch and the like.
Furthermore, substances which improve the processing or application properties such as e.g. lubricants, gloss-improving agents, anti-foam agents, sandability-improving agents, flow control agents, stabilisers, light stabilisers and colorants, pigments and conventional lacquer additives may also be added to the emulsion, preferably to the aqueous phase.
Aqueous coating agent emulsions prepared according to the invention have very good flow characteristics, high gloss and good resistance to water, ethanol and acetone in accordance with DIN 68 861, part 1, 1 B.

Aqueous coating agent and its use in lacquers

Abstract: a) 5-50 wt. % of cellulose substance

Abstract: d) 0.5-30 wt. % of plasticizer

Abstract: e) 0.0-20 wt. % of emulsifier

Abstract: g) 10-65 wt. % of water

Abstract: wherein the sum of a) to g) is always 100 wt. %, characterized in that the ratio by weight of OH groups (from the lacquer resin) to NCO groups is 1:0.01-1.0 is described.


In accordance with the present invention, there is provided a golf swing training device which is uniquely configured to maintain a desirable bent wrist condition through the entirety of the downswing (including golf ball impact) and follow-though or finish of the golf swing. The training device allows the wearer to start the golf swing with the right wrist in its natural, generally flattened condition at address. Once the backswing of the golf stroke is initiated, the training device allows the wearer to bend the right wrist back naturally, and at different amounts so as to represent the different amounts of right wrist bend a golfer may employ for shorter and longer strokes. Once the right wrist has achieved its full amount of bend at the time of the downswing, the training device effectively maintains such bend throughout the entirety of the downswing and follow-through or finish of, the golf swing.

1. Technical Field of the Invention
The present invention relates generally to the game of golf and, more particularly, to a golf swing training device which is uniquely configured to maintain a desirable bent wrist condition through the entirety of the downswing (including golf ball impact) and follow-though or finish of the golf swing.
2. Description of the Related Art
In the game of golf, in order to control the golf ball, one must control the instrument (i.e., the golf club). The golf club consists of three primary components, which are the club head, the club shaft, and the club face. One of the biggest, if not the biggest problem, golfers battle in trying to develop and maintain an effective golf swing is the unnecessary and tremendously destructive flattening of the right wrist (in the case of a right-handed golfer) prior to or during the impact of the club face on the golf ball and separation of the ball therefrom. The stifling effects of a flattening right wrist of a right handed golfer during the downswing includes the loss of control of all three of the aforementioned components of the golf club, thereby resulting in a loss of distance and direction of the golf ball. More particularly, club head lag and the circular orbit of the club head (power), club face alignment (direction), and the club shaft plane (direction) are all destroyed by the flattening right wrist.
In order to incorporate right wrist flattening for a right handed golfer into a golf stroke procedure with any kind of reliability, one would need to trigger the flattening of the right wrist at the same point, flatten it at the same rate, and flatten it by the same amount. This, however, gives rise to a virtually insurmountable timing challenge that golfers struggle with and thus prevents consistency in the golf swing. A far superior procedure would be to completely omit the act of right wrist flattening from the stroke pattern. Since, in a sense, the moment of impact of the club face against the golf ball is golf's moment of truth as a result of the data transfer from the golf club to the ball which occurs at this moment, the ability to keep the right wrist in its bent condition as achieved at the top of the backswing is one of the major factors separating successful golfers from poor golfers. Along these lines, since one of the primary principles of the game and of a successful and effective golf swing is to create and sustain a line of compression, the undesirable right wrist flattening and its associated lag loss will account for the exact opposite effect, i.e., compression leakage.
There is currently known in the prior art certain golf swing training products which are adapted to prevent a flattening right wrist in a right handed golfer. However, these currently known products possess certain deficiencies which detract from their overall utility. More particularly, such existing products are configured to impart to the wearer/user a fixed, exact amount of wrist bend at the start position of the golf swing (i.e., at address). However, the full amount of wrist bend in the right wrist is typically not achieved by a player until the top of the backswing has been reached. In this regard, for most players, the natural condition of the right wrist at the starting position or address is generally flat, with the right wrist achieving a fully bent condition at the top of the backswing, and optimally maintaining such bent condition through the completion of the downswing (including impact) and follow-through. Since currently known wrist condition training devices fix the right wrist with a prescribed amount of bend at the outset, the wearer/user is unable to assume a normal, generally flat right wrist condition at address, and is further unable to bend the right wrist back naturally during the golf stroke, and in particular the backswing.
The present invention addresses and overcomes the deficiencies highlighted above by providing a golf swing training device which is uniquely configured to allow varying levels or degrees of right wrist bend during the backswing of the golf stroke, and to preserve the amount of right wrist bend achieved at the top of the backswing through the entire downswing of the wearer/user (including the point of impact between the club face and the golf ball), as well as the follow-through/finish of the golf swing. These, as well as other features and advantages of the present invention, will be described in more detail below.

Golf swing wrist condition training device


An image forming apparatus prints an image on paper. A developing roller supplies toner to an electrostatic latent image on a photoconductive drum to form a toner image. A developing blade forms a thin layer of toner on the developing roller. A transfer unit transfers the toner image onto the paper. A fixing unit fixes the toner image on the paper into a permanent image. The developing roller rotates at a circumferential speed from 150 to 250 mm/sec. The developing blade applies a line pressure in the range of 34-68 gf/cm to the developing roller. The toner has a glass transition temperature Tg from 45 to 77□, a softening temperature from 58 to 98□, a flow-beginning temperature Ts from 78 to 138□, and a melting point Tm from 105 to 189□. Tg, Ts, Tfb and Tm are related such that Tm>Tfb>Ts.

1. Field of the Invention
The present invention relates to an image forming apparatus.
2. Description of the Related Art
Conventional image forming apparatuses such as electrophotographic printers, copying machines, facsimile machines, and multi-function printers (MFP) employ an electrophotography technology that involves charging, exposing, developing, and transferring. A charging roller charges the surface of a photoconductive drum. An exposing unit illuminates the charged surface for the photoconductive drum in accordance with print data to form an electrostatic latent image on the photoconductive drum. A developing unit develops the electrostatic latent image with toner into a toner image. A transfer roller transfers the toner image onto paper. A fixing unit fuses the toner image on the paper into a permanent image.
After transferring the toner image onto the paper, a cleaning unit removes residual toner from the photoconductive drum.
It is required of a fixing unit that images are fixed at high speed with minimum heat energy. For this purpose, toner having a low glass transition temperature Tg is used for low-temperature fixing.
A toner having a low glass transition temperature Tg tends to cause offset and filming.
Offset is a phenomenon in which when a heat roller applies heat and pressure to the toner on the paper and then the paper is separated from the heat roller, some of the melted toner adheres to the heat roller, and the residual melted toner on the heat roller is then transferred onto the paper. The melted toner adhering to the paper causes unwanted residual images that appear on the paper at intervals of a distance equal to the circumference of the heat roller.
Filming is adhesion of melted toner to the developing blade that occurs due to heat and pressure given to the toner when the toner is rubbed between the developing blade and the developing roller.


The speed of disintegration of tablets containing a water-softening agent, especially water-insoluble, water-softening agent intended as detergency builder for fabric washing is enhanced by incorporating granules containing acetate (sodium acetate and/or potassium acetate) along with at least one other ingredient. Such tablets are provided, as are, methods of making the granules.

This invention relates to compositions in the form of tablets, containing a water-softening agent, methods of making a granular material for use in these tablets, and methods of making these tablets. These tablets may be embodied as detergent compositions for use in fabric washing, or as water-softening tablets, which could be used in fabric washing jointly with a composition containing detergent active, or could possibly be used in other applications, e.g. in machine dishwashing as an anti-limescale product.
Detergent compositions in tablet form have been described in a number of documents including, for example, GB 911204 (Unilever), WO 90/02165 (Henkel) and EP-A-711827 (Unilever) and are sold now commercially. Tablets have several advantages over powdered products: they do not require measuring and are thus easier to handle and dispense into the washload, and they are more compact, hence facilitating more economical storage.
Detergent tablets are generally made by compressing or compacting a detergent powder, which includes detergent active and detergency builder. EP-A-522766 explains that difficulty has been found in providing tablets which have adequate strength when dry, yet disperse and dissolve quickly when added to wash water. The problem has proved especially difficult with compositions containing insoluble aluminosilicate as detergency builder but also arises with compositions which contain sodium tripolyphosphate or other water-soluble builder.
EP-A-711827 teaches that speed of disintegration of tablets can be improved by including the highly water-soluble salt, sodium citrate. Tablet compositions exemplified in that document include sodium citrate dihydrate and also polyethylene glycol as an organic polymeric binder. This document briefly mentions that sodium acetate can be included in a composition as a lubricant to aid tableting. No information is given concerning the form in which sodium acetate might be incorporated as a lubricant. The amount of lubricant is not stated, but it would be appropriate to include only a small amount.
Detergent tablet compositions comprising acetates are also known from EP 264 701.
Detergent compositions comprising acetate are also known from DD 247 840, GB 2 318 575, EP 881 282 and U.S. Pat. No. 4,587,031. The inter-calcinating of potassium acetate molecules in clay particles is known from U.S. Pat. No. 5,672,555.
EP-A-838519 discloses that sodium acetate trihydrate and potassium acetate can function alone, or together, or in combination with sodium citrate dihydrate as effective tablet disintegrants in water-softening tablets. When mixtures of salts are used, crystals of each salt are incorporated into the overall mixture.
Surprisingly, we have now found that the amount of acetate in a tablet can be reduced whilst maintaining tablet solubility, by providing the acetate granulated with other ingredients in the same granule. These granules can be included in the tablet in approximately the same amount as known acetate granules or powder and have greater effect on the tablet solubility than might be expected from their content of acetate alone.
Broadly, the present invention provides a tablet of a compacted particulate composition wherein the tablet or a region thereof contains a water-softening agent and either sodium acetate or potassium acetate or both (the acetate), wherein the acetate is present in granules which contain at least one other ingredient.
The amount of water-softening agent will generally be at least 15% by weight of the composition of the tablet or region thereof. Depending on the function for which the tablets are intended the amount may range up to 90% by weight. In significant forms of this invention there is at least 15%, by weight of the composition, of a water-insoluble water softening agent.
Generally, the content of acetate in these granules is at least 0.1 mole per 100 gram of granules.
Thus, if the acetate is present as sodium acetate trihydrate, the weight percentage of sodium acetate trihydrate in the granules will be at least 13.6% of their weight. If, however, the acetate is present as anhydrous sodium acetate the amount of sodium acetate in the granules will thus be at least 8.2% of their weight. It is also possible that the sodium acetate is present in a partially hydrated form.
If the acetate is present as potassium acetate, the amount of potassium acetate in the granules will be at least 9.8% of their weight.
The acetate may be present as a mixture of any of these forms.
The lower limit of the acetate content of the granules may be 0.15, 0.25 or even 0.3 mole per 100 gram of granules.
It is unlikely that the content of acetate in the granules will exceed 1 mole per 100 gram of granules. Indeed, that content cannot be achieved with fully hydrated sodium acetate. The content may not exceed 0.65 mole per 100 gram of granules which would correspond to 53% by weight of anhydrous sodium acetate, 88% of sodium acetate trihydrate, or 66% by weight of potassium acetate.
A water-softening tablet of the invention is likely to contain at least 10% by weight of these acetate-containing granules, possibly at least 13% or 15%. It is unlikely that it will contain more than 35% of the granules, and may contain only up to 22% or 30% of the granules.
Accordingly, one aspect the present invention provides a tablet of a compacted particulate composition wherein the tablet or a region thereof comprises from 15 to 90% by weight of a water-softening agent, sodium and/or potassium acetate and optionally other ingredients, characterised in that the tablet or region contains at least 10% by weight of granules which contain both said acetate and at least one other ingredient, the content of said acetate in these granules being at least 0.1 mole per 100 gram of granules and the other ingredients being at least 5% by weight of the granules. Thus the acetate is no more than 95% by weight of the granules.
The total content of the acetate in the tablet or region may be only 0.01 Mol/100 g, or it may be 0.02 Mol/100 g, or 0.05 Mol/100 g. It is likely that there will be no more than 0.425 Mol/100 g of the acetate in the tablet or region, and the upper limit may be 0.3 Mol/100 g, or as low as 0.2 Mol/100 g, 0.15 Mol/100 g or even 0.1 Mol/100 g.
It is preferred that more than half of all the acetate in the tablet or region is contained in the granules, and as much as 75%, 90% or even all of the acetate may be in the granules (hereinafter referred to as xe2x80x9cco-granulesxe2x80x9d).
It is also preferred that the acetate is sodium acetate.
By reducing the amount of acetate required in a tablet to achieve satisfactory dissolution times, the present invention allows the amounts of other ingredients in the tablets to be increased may enable improvements in performance of the tablets to be made.
It is further preferred that the other ingredients of the co-granule are present in an amount of at least 10, 15 or 20% by weight of the granules.
It is also preferred that when the acetate is sodium acetate, the amount of water (bound or unbound) present in the co-granules is such as to be in a molar ratio of 2.5:1 to 3.5:1 to the sodium acetate. A second aspect of the invention provides a method of making the acetate co-granules described above, including the steps of neutralising acetic acid with a solid basic compound and granulating the resulting mixture, wherein in that the amount of solids added to the acetic acid includes sufficient basic compound to neutralise the acetic acid, and further material which forms the co-granule with the acetate.
In one embodiment, at least some or all of the further material is the same as the basic compound, so that an excess of the basic compound, compared to the stoichiometric amount required for neutralisation, is added to the acetic acid.
This method may be used to make granules containing either sodium or potassium acetate or both. The nature of the acetate depends on the solid basic compound used.
If making sodium acetate, it is preferred that the acetic acid is used in solution rather than as its glacial form, in order that the resulting sodium acetate may be at least partially hydrated.
A third aspect of the invention provides an alternative method of making the sodium acetate co-granules described above, including the steps of heating a hydrated form of sodium acetate above its melting point, and granulating the resulting melt with at least one solid tablet ingredient.
The method of the second or third aspects may be extended by the addition of the resulting acetate-containing co-granules to further ingredients to form a particulate composition as described in the first aspect of this invention. This particulate composition may be a detergent composition, as described in more detail below.
It is strongly preferred that the acetate co-granules have a mean particle size of above 250 xcexcm, preferably above 300 xcexcm (0.3 mm), better above 500 xcexcm (0.5 mm) to facilitate flow and handling of the particulate composition prior to and during compaction. The particle size will probably have a mean value less than 2 mm, preferably less than 1 mm. Poor powder flow is disadvantageous, inter alia, in that it leads to irregular filling of dies and inconsistent tablet weight and strength.
Details of suitable materials, as well as further preferences, will now be described.
Sodium acetate is well-known in anhydrous and trihydrated forms.
The anhydrous form is a hygroscopic powder, which is very soluble in water (119 g/100 g at 20xc2x0 C.)xe2x80x94Mol wt 82 g.
The trihydrate is available as transparent crystals or granules (and has a solubility of 76 g/100 g at 20xc2x0 C.)xe2x80x94Mol. wt. 136 g. When heated, it melts at 58xc2x0 C.xe2x80x94the melting process is the sodium acetate dissolving in its own water of crystallisation, and thus producing a very concentrated solution. This xe2x80x98meltxe2x80x99 becomes anhydrous, due to evaporation of the water if heated to 120xc2x0 C.
Sodium acetate is also commercially available in a spray-dried form, which does not have an integral number of water molecules per acetate. Such a form is made by spray-drying a solution of sodium acetate. The sodium acetate solution which is spray-dried may be a heated concentrated solution of sodium acetate, which itself may be made by the direct neutralisation of acetic acid in caustic soda. The solution of sodium acetate obtained by the neutralisation of the acetic acid with caustic soda, can be readily concentrated by heating, for example by heating with steam. This form of sodium acetate melts in a similar fashion to the trihydrate form. Partially hydrated sodium acetate can also be obtained by neutralising acetic acid (either glacial or in solution) with a sodium salt.
The use of a spray-dried form of sodium acetate in water-softening tablets is described in our co-pending application GB 9822090.8.
Potassium acetate exists in a an anhydrous form as either crystals, powder or flakes. It is rapidly deliquescent, and thus difficult to handle. It is also highly soluble (253 g/100 g of water at 20xc2x0 C.) and has a molecular weight of 98 g. It melts at 292xc2x0 C.
The other material present in the co-granule with acetate may be any ingredient usually present in water-softening or detergent tablets, as described below, or a mixture of these, although it is preferred that it is not an organic detergent. It is further preferred that the other ingredients are selected from water-soluble and -insoluble inorganic compounds, and water-soluble organic salts having no more than 3 carbon atoms in the molecule.
One preference for this ingredient is that the remainder of the co-granule is solid basic materialxe2x80x94this is particularly relevant to the second aspect of the invention, where the solid basic material can be the same as that used to neutralise the acetic acid. Typically, this compound may be a water-softening agent or a detergency builder, such as sodium or potassium carbonate. Alternatively, the remaining co-granule material can be a combination of solid basic material with other ingredients of the tablet.
Suitable materials for the co-granule may be ingredients which are less soluble than the form of acetate present in the co-granules. Alternatively they may be materials known as water-soluble disintegrants (which include materials having a water solubility of greater than 50 g/100 g at 20xc2x0 C., form). On the other hand, the preferred materials may have a water solubility of less than 50 g/100 g at 20xc2x0 C.
A solubility of at least 50 grams per 100 grams of water at 20xc2x0 C. is an exceptionally high solubility: many materials which are classified so as water soluble are less soluble than this.
Some materials with a water solubility of at least 50 grams per 100 grams of water are listed below, with their solubilities expressed so as grams of solid to form a saturated solution in 100 grams of water at 20xc2x0 C.:
Materials with a water solubility of less than 50 grams per 100 grams of water (at 20xc2x0 C.) include:
A further water-soluble disintegrant is a special form of sodium tripolyphosphate, which has more than 50% of it in the anhydrous phase I form.
A process for the manufacture of particles containing such a high proportion of the phase I form of sodium tripolyphosphate by spray drying below 420xc2x0 C. is given in U.S. Pat. No. 4,536,377. Desirably, this sodium tripolyphosphate is partially hydrated. The extent of hydration should be at least 1% by weight of the sodium tripolyphosphate in the particles. It may lie in a range from 2.5 to 4%, or it may be higher, e.g. up to 8%.
It is particularly envisaged that this invention will be applied to tablets containing water-insoluble water softening agent, notably alkali-metal aluminosilicate. However, it could be applied in tablets containing a soluble water-softening agent such as a condensed phosphate. It could be applied in tablets containing both soluble and insoluble water softening agentsxe2x80x94as might be used in countries where a restricted quantity of phosphate detergency builder is permitted.
It is very well known that water-insoluble alkali metal aluminosilicates can function to soften water, removing calcium ions and to a lesser extent magnesium ions by ion exchange. Aluminosilicates have become strongly favoured as environmentally acceptable detergency builders.
Alkali metal (preferably sodium) aluminosilicates used in tablets of the present invention may be either crystalline, amorphous or a mixture of the two. Such aluminosilicates generally have a calcium ion exchange capacity of at least 50 mg CaO per gram of aluminosilicate, comply with a general formula:
0.8-1.5Na2O.Al2O3.0.8-6SiO2
and incorporate some water. Preferred sodium aluminosilicates within the above formula contain 1.5-3.5 SiO2 units. Both amorphous and crystalline aluminosilicates can be prepared by reaction between sodium silicate and sodium aluminate, as amply described in the literature.
Suitable crystalline sodium aluminosilicate ion-exchange detergency builders are described, for example, in GB 1429143 (Procter and Gamble). The preferred sodium aluminosilicates of this type are the well known commercially available zeolites A and X, and mixtures thereof. Also of interest is the novel zeolite P described and claimed in EP 384070 (Unilever).
Another category of water-insoluble material which can function as a water-softening agent and detergency builder is the layered sodium silicate builders disclosed in U.S. Pat. Nos. 4,464,839 and 4,820,439 and also referred to in EP-A-551375.
These materials are defined in U.S. Pat. No. 4,820,439 as being crystalline layered sodium silicate of the general formula
NaMSixO2x+1.YH2O
where
M denotes sodium or hydrogen,
x is from 1.9 to 4 and y is from 0 to 20.
Quoted literature references describing the preparation of such materials include Glastechn. Ber. 37, 194-200 (1964), Zeitschrift fxc3xcr Kristallogr. 129, 396-404 (1969), Bull. Soc. Franc. Min. Crist., 95, 371-382 (1972) and Amer. Mineral, 62, 763-771 (1977). These materials also function to remove calcium and magnesium ions from water.
It is customary to use a water-soluble builder (water-softening agent) jointly with aluminosilicate, to enhance water-softening efficacy. Such water-soluble co-builders are generally used in an amount which is not greater than the amount of aluminosilicate, often less than half the amount of aluminosilicate. Water-soluble builders may be organic or inorganic. Inorganic builders that may be present include alkali metal (generally sodium) carbonate; while organic builders include polycarboxylate polymers, such as polyacrylates, acrylic/maleic copolymers, and acrylic phosphonates, monomeric polycarboxylates such as citrates, gluconates, oxydisuccinates, glycerol mono- di- and trisuccinates, carboxymethyloxysuccinates, carboxymethyloxymalonates, dipicolinates and hydroxyethyliminodiacetates.
Especially preferred supplementary builders are polycarboxylate polymers, more especially polyacrylates and acrylic/maleic copolymers, and monomeric polycarboxylates, more especially citric acid and its salts.
If a tablet contains only soluble water-softening agent, this may well be sodium tripolyphosphate, which is widely used as a detergency builder in some countries.
When using aluminosilicate or other insoluble detergency builder/water-softening agent it is often a commercial or legislative requirement to avoid phosphates. Some tablet compositions of the invention do not contain more than 5 wt % of inorganic phosphate builders, and are desirably substantially free of phosphate builders. However, tableted compositions containing some phosphate builder are also within the broad scope of the invention. In particular, a tablet or region thereof may contain at least 15 wt % insoluble water softening agent, with phosphate or other water-soluble builder in addition.
Tablets of this invention may include an organic water-soluble polymer, applied as a coating to some of the constituent particles, and serving as a binder when the particles are compacted into tablets. This polymer may be a polycarboxylate included as a supplementary builder, as mentioned earlier.
It is preferred that such a binder material, if present, should melt at a temperature of at least 35xc2x0 C., better 40xc2x0 C. or above, which is above ambient temperatures in many temperate countries. For use in hotter countries it will be preferable that the melting temperature is somewhat above 40xc2x0 C., so as to be above the ambient temperature. For convenience the melting temperature of the binder material should be below 80xc2x0 C.
Preferred binder materials are synthetic organic polymers of appropriate melting temperature, especially polyethylene glycol. Polyethylene glycol of average molecular weight 1500 (PEG 1500) melts at 45xc2x0 C. and has proved suitable. Polyethylene glycol of higher molecular weight, notably 4000 or 6000, can also be used.
Other possibilities are polyvinyl pyrrolidone, and polyacrylates and water-soluble acrylate copolymers.
The binder may suitably be applied to the particles by spraying, e.g. as a solution or dispersion. If used, the binder is preferably used in an amount within the range from 0.1 to 10% by weight of the tablet composition, more preferably the amount is at least 1% or even at least 3% by weight of the tablets. Preferably the amount is not over 8% or even 6% by weight unless the binder serves some other additional function.
Tablets may include other ingredients which aid tableting. Tablet lubricants include calcium, magnesium and zinc soaps (especially stearates), talc, glyceryl behapate, sugar Myvatex(trademark) TL ex Eastman Kodak, polyethylene glycols, and colloidal silicas (for example, Alusil(trademark) ex Crosfield Chemicals Ltd).
As mentioned above, compositions of this invention may be embodied as detergent compositions for use in fabric washing, in which case the composition will generally contain from 15 to 60% by weight of detergency builder, notably water-insoluble aluminosilicate, together with 5 to 50% by weight of one or more detergent-active compounds. Such a composition may well contain from 0.5 to 15% by weight of a supplementary builder, notably polycarboxylate, and also other detergency ingredients.
Another possibility is that the invention may be embodied in tablets whose principal or sole function is that of removing water hardness. In such tablets the water-softening agents, especially water-insoluble aluminosilicate, may provide from 50 to 90% of the tablet composition. A water-soluble supplementary builder may well be included, for instance in an amount from 2% to 30 wt % of the composition.
Water-softening tablets embodying this invention may include some detergent active. Notably, water-softening tablets may include nonionic surfactant which can act as a lubricant during tablet manufacture and as a low foaming detergent during use. The amount may be small, e.g. from 0.2 or 0.5% by weight of the composition up to 3% or 5% by weight.
Tablets for use in fabric washing will usually contain from 2% or 5% up to 50 wt %, more preferably from 5% or 8% up to 40 wt % of detergent-active compounds. These will most usually be anionic and nonionic surfactants and mixtures of the two. Amphoteric (including zwitterionic) and less commonly cationic detergents can also be used.
Anionic detergent-active compounds may be present in an amount of from 0.5 to 40 wt %, preferably from 2% or 4% to 30% or 40 wt %.
Synthetic (i.e. non-soap) anionic surfactants are well known to those skilled in the art. The anionic surfactant may comprise, wholly or predominantly, linear alkyl benzene sulphonate of the formula;
where R is linear alkyl of 8 to 15 carbon atoms and M+ is a solubilising cation, especially sodium.
Primary alkyl sulphate having the formula; ROSO3xe2x88x92 M+ in which R is an alkyl or alkenyl chain of 8 to 18 carbon atoms especially 10 to 14 carbon atoms and M+ is a solubilising cation, is also commercially significant as an anionic surfactant and may be used in this invention.
Frequently, such linear alkyl benzene sulphonate or primary alkyl sulphate of the formula above, or a mixture thereof will be the desired non-soap anionic surfactant and may provide 75 to 100 wt % of any anionic non-soap surfactant in the composition.
Examples of other non-soap anionic surfactants include olefin sulphonates; alkane sulphonates; dialkyl sulphosuccinates; and fatty acid ester sulphonates.
One or more soaps of fatty acids may also be included in addition to non-soap anionic surfactant. Examples are sodium soaps derived from the fatty acids from coconut oil, beef tallow, sunflower or hardened rapeseed oil.
Nonionic surfactant compounds include in particular the reaction products of compounds having a hydrophobic group and a reactive hydrogen atom, for example, aliphatic alcohols, acids, amides or alkyl phenols with alkylene oxides, especially ethylene oxide.
Specific nonionic surfactant compounds are alkyl (C8-22) phenol-ethylene oxide condensates, the condensation products of linear or branched aliphatic C8-20 primary or secondary alcohols with ethylene oxide, and products made by condensation of ethylene oxide with the reaction products of propylene oxide and ethylene-diamine. Especially preferred are the primary and secondary alcohol ethoxylates, especially the C9-11 and C12-15 primary and secondary alcohols ethoxylated with an average of from 3 to 20 moles of ethylene oxide per mole of alcohol.
Amphoteric surfactants which may be used jointly with anionic or nonionic surfactants or both include amphopropionates of the formula:
where RCO is a acyl group of 8 to 18 carbon atoms, especially coconut acyl.
The category of amphoteric surfactants also includes amine oxides and also zwitterionic surfactants, notably betaines of the general formula
where R4 is an aliphatic hydrocarbon chain which contains 7 to 17 carbon atoms, R2 and R3 are independently hydrogen, alkyl of 1 to 4 carbon atoms or hydroxyalkyl of 1 to 4 carbon atoms such as CH2OH, Y is CH2 or of the form CONHCH2CH2CH2 (amidopropyl betaine); Z is either a COOxe2x88x92 (carboxybetaine), or of the form CHOHCH2SO3xe2x80x94(sulfobetaine or hydroxy sultaine).
Another example of amphoteric surfactant is amine oxide of the form
where R1 is C10 to C20 alkyl or alkenyl, R2, R3 and R4 are each hydrogen or C1 to C4 alkyl while n is from 1 to 5.
Synthetic (i.e. non-soap) anionic surfactants are well known to those skilled in the art. Examples include alkylbenzene sulphonates, particularly sodium linear alkylbenzene sulphonates having an alkyl chain length of C8-C15; olefin sulphonates; alkane sulphonates; dialkyl sulphosuccinates; and fatty acid ester sulphonates.
Primary alkyl sulphate having the formula ROSO3xe2x88x92 M+ in which R is an alkyl or alkenyl chain of 8 to 18 carbon atoms especially 10 to 14 carbon atoms and M+ is a solubilising cation, is commercially significant as an anionic detergent active. It is frequently the desired anionic detergent and may provide 75 to 100% of any anionic non-soap detergent in the composition.
In some forms of this invention the amount of non-soap anionic detergent lies in a range from 0.5 to 15 wt % of the tablet composition.
It may also be desirable to include one or more soaps of fatty acids. These are preferably sodium soaps derived from naturally occurring fatty acids, for example, the fatty acids from coconut oil, beef tallow, sunflower or hardened rapeseed oil.
Suitable nonionic detergent compounds which may be used include in particular the reaction products of compounds having a hydrophobic group and a reactive hydrogen atom, for example, aliphatic alcohols, acids, amides or alkyl phenols with alkylene oxides, especially ethylene oxide either alone or with propylene oxide.
Specific nonionic detergent compounds are alkyl (C8-22) phenol-ethylene oxide condensates, the condensation products of linear or branched aliphatic C8-20 primary or secondary alcohols with ethylene oxide, and products made by condensation of ethylene oxide with the reaction products of propylene oxide and ethylene-diamine. Other nonionic detergent compounds include alkylpolyglycosides, long-chain amine oxides, tertiary phosphine oxides, and dialkyl sulphoxides.
Especially preferred are the primary and secondary alcohol ethoxylates, especially the C9-11 and C12-15 primary and secondary alcohols ethoxylated with an average of from 5 to 20 moles of ethylene oxide per mole of alcohol.
In certain forms of this invention the amount of nonionic detergent lies in a range from 4 to 40%, better 4 or 5 to 30% by weight of the composition.
Many nonionic detergent-active compounds are liquids. These may be absorbed on a porous carrier. Preferred carriers include zeolite; zeolite granulated with other materials, for example Wessalith CS(trademark), Wessalith CD(trademark) or Vegabond GB(trademark); sodium perborate monohydrate; Burkeite (spray-dried sodium carbonate and sodium sulphate as disclosed in EP-A-221776 of Unilever); and layered sodium silicate as described in U.S. Pat. No. 4,664,839.
Tableted detergent compositions according to the invention may contain a bleach system. This preferably comprises one or more peroxy bleach compounds, for example, inorganic persalts or organic peroxyacids, which may be employed in conjunction with activators to improve bleaching action at low wash temperatures. If any peroxygen compound is present, the amount is likely to lie in a range from 10 to 25% by weight of the composition.
Preferred inorganic persalts are sodium perborate monohydrate and tetrahydrate, and sodium percarbonate, advantageously employed together with an activator. Bleach activators, also referred to as bleach precursors, have been widely disclosed in the art. Preferred examples include peracetic acid precursors, for example, tetraacetylethylene diamine (TAED), now in widespread commercial use in conjunction with sodium perborate and sodium percarbonate; and perbenzoic acid precursors. The quaternary ammonium and phosphonium bleach activators disclosed in U.S. Pat. Nos. 4,751,015 and 4,818,426 (Lever Brothers Company) are also of interest. Another type of bleach activator which may be used, but which is not a bleach precursor, is a transition metal catalyst as disclosed in EP-A-458397, EP-A-458398 and EP-A-549272. A bleach system may also include a bleach stabiliser (heavy metal sequestrant) such as ethylenediamine tetramethylene phosphonate and diethylenetriamine pentamethylene phosphonate.
As indicated above, if a bleach is present and is a water-soluble inorganic peroxygen bleach, the amount may well be from 10% to 25% by weight of the composition.
The detergent tablets of the invention may also contain one of the detergency enzymes well known in the art for their ability to degrade and aid in the removal of various soils and stains. Suitable enzymes include the various proteases, cellulases, lipases, amylases, and mixtures thereof, which are designed to remove a variety of soils and stains from fabrics. Examples of suitable proteases are Maxatase(trademark), as supplied by Gist-Brocades N.V., Delft, Holland, and Alcalase(trademark), and Savinase(trademark), as supplied by Novo Industri A/S, Copenhagen, Denmark. Detergency enzymes are commonly employed in the form of granules or marumes, optionally with a protective coating, in amount of from about 0.1% to about 3.0% by weight of the composition; and these granules or marumes present no problems with respect to compaction to form a tablet.
The detergent tablets of the invention may also contain a fluorescer (optical brightener), for example, Tinopal(trademark) DMS or Tinopal CBS available from Ciba-Geigy AG, Basel, Switzerland. Tinopal DMS is disodium 4,4xe2x80x2bis-(2-morpholino-4-anilino-s-triazin-6-ylamino)stilbene disulphonate; and Tinopal CBS is disodium 2,2xe2x80x2-bis-(phenylstyryl)disulphonate.
An antifoam material is advantageously included, especially if the detergent tablet is primarily intended for use in front-loading drum-type automatic washing machines. Suitable antifoam materials are usually in granular form, such as those described in EP 266863A (Unilever). Such antifoam granules typically comprise a mixture of silicone oil, petroleum jelly, hydrophobic silica and alkyl phosphate as antifoam active material, sorbed onto a porous absorbed water-soluble carbonate-based inorganic carrier material. Antifoam granules may be present in an amount up to 5% by weight of the composition.
It may also be desirable that a detergent tablet of the invention includes an amount of an alkali metal silicate, particularly sodium ortho-, meta- or preferably alkali metal silicates at levels, for example, of 0.1 to 10 wt %, may be advantageous in providing protection against the corrosion of metal parts in washing machines, besides providing some measure of building and giving processing benefits.
Further ingredients which can optionally be employed in the detergent tablet of the invention include anti-redeposition agents such as sodium carboxymethylcellulose, straight-chain polyvinyl pyrrolidone and the cellulose ethers such as methyl cellulose and ethyl hydroxyethyl cellulose, fabric-softening agents; heavy metal sequestrants such as EDTA; perfumes; and colorants or coloured speckles.
A tablet of this invention, or a discrete region of such a tablet, is a matrix of compacted particles.
Preferably the particulate composition has an average particle size in the range from 200 to 2000 xcexcm, more preferably from 250 to 1400 xcexcm. Fine particles, smaller than 180 xcexcm or 200 xcexcm may be eliminated by sieving before tableting, if desired, although we have observed that this is not always essential.
While the starting particulate composition may in principle have any bulk density, the present invention is especially relevant to tablets made by compacting powders of relatively high bulk density, because of their greater tendency to exhibit disintegration and dispersion problems. Such tablets have the advantage that, as compared with a tablet derived from a low bulk density powder, a given dose of composition can be presented as a smaller tablet.
Thus the starting particulate composition may suitably have a bulk density of at least 400 g/liter, preferably at least 500 g/liter, and advantageously at least 700 g/liter.
Granular detergent compositions of high bulk density prepared by granulation and densification in a high-speed mixer/granulator, as described and claimed in EP 340013A (Unilever), EP 352135A (Unilever), and EP 425277A (Unilever), or by the continuous granulation/densification processes described and claimed in EP 367339A (Unilever) and EP 390251A (Unilever), are inherently suitable for use in the present invention.
A tablet of the invention may be either homogeneous or heterogeneous. In the present specification, the term xe2x80x9chomogeneousxe2x80x9d is used to mean a tablet produced by compaction of a single particulate composition, but does not imply that all the particles of that composition will necessarily be of identical composition.
The term xe2x80x9cheterogeneousxe2x80x9d is used to mean a tablet consisting of a plurality of discrete regions, for example layers, inserts or coatings, each derived by compaction from a particulate composition and large enough to constitute from 10 to 90% of the weight of the whole tablet.
It is possible that the acetate co-granules will be contained within one or more but not all such discrete regions of a heterogeneous tablet, such as a layer or an insert. The presence of such a layer or insert could assist break up of the entire tablet when placed in water.
Tableting entails compaction of a particulate composition. A variety of tableting machinery is known, and can be used. Generally it will function by stamping a quantity of the particulate composition which is confined in a die. Tableting may be carried out at ambient temperature or at a temperature above ambient which may allow adequate strength to be achieved with less applied pressure during compaction. In order to carry out the tableting at a temperature which is above ambient, the particulate composition is preferably supplied to the tableting machinery at an elevated temperature. This will of course supply heat to the tableting machinery, but the machinery may be heated in some other way also.
If any heat is supplied, it is envisaged that this will be supplied conventionally, such as by passing the particulate composition through an oven, rather than by any application of microwave energy.

Method of making water-softening and detergent compositions

Unilever Home and Personal Care USA a division of Conopco, Inc.


The invention relates to additives for improving lubricating properties of fuel oils, comprising

The present invention relates to an additive which comprises a long-chain carboxylic acid and/or its derivatives and one or more hydroxyl-containing polymers, fuel oils which contain such additives and the use of such additives for improving the lubricity of middle distillates.
Mineral oils and mineral oil distillates which are used as fuel oils contain in general 0.5% by weight or more of sulfur, which results in the formation of sulfur dioxide on combustion. To reduce the resulting environmental pollution, the sulfur content of fuel oils is being increasingly reduced. The introduction of standard EN 590 relating to diesel fuels currently prescribes a maximum sulfur content of 350 ppm in Germany. In Scandinavia, fuel oils containing less than 50 ppm and in exceptional cases less than 10 ppm of sulfur are already in use. These fuel oils are produced as a rule by subjecting the fractions obtained from mineral oil by distillation to refinement involving hydrogenation. However, the desulfurization also results in the removal of other substances which impart a natural lubricating effect to the fuel oils. These substances include polyaromatic and polar compounds.
However, it has been found that the friction- and wear-reducing properties of fuel oils deteriorate with an increasing degree of desulfurization. Often, these properties are so poor that corrosion phenomena have to be expected after only a short time on the materials lubricated with fuel, for example the distributor injection pumps of diesel engines. The maximum value of 360xc2x0 C. for the 95% distillation point specified according to EN 590 since the year 2000 and the further reduction of the 95% distillation point to below 350xc2x0 C. and in some cases below 330xc2x0 C., now implemented in Scandinavia, have further intensified these problems.
The prior art therefore describes approaches which are intended to solve this problem (so-called lubricity additives).
EP-A-0 680 506 discloses the use of esters of monobasic or polybasic carboxylic acids with monohydric or polyhydric alcohols as lubricity additives for fuel oils.
EP-A-0 802 961 discloses fuel oils which contain at least one hydroxylamine for improving their lubricating effect.
WO-99/36 489 discloses the use of mixtures of monomeric and polymeric fatty acids for improving the lubricating effect of low-sulfur middle distillates.
EP-A-0 743 974 discloses the use of mixtures of lubricity additives (esters of polyhydric alcohols and carboxylic acids having 10 to 25 carbon atoms or dicarboxylic acids) and flow improvers of ethylene/unsaturated ester copolymers for the synergistic improvement of the lubricating effect of highly desulfurized oils.
EP-A-0 807 676 discloses a fuel oil additive which increases the lubricity of said fuel oil and which, in addition to a carboxamide, comprises a cold flow improver and an ashless dispersant.
The polymeric additives of the prior art, which simultaneously improve the cold flow properties and lubricity of low-sulfur fuel oils, often have the disadvantage that, owing to their high viscosity, they have to be used as a solution or dispersion in suitable solvents in order to improve their handling. However, the use of solvents results in increased metering rates and hence in the transport of larger amounts of substances.
It was thus the object of the present invention to provide additive compositions which improve the cold flow and lubricating properties of fuel oils and are also effective when used as additives in small amounts.
Surprisingly, it was found that oil-soluble amphiphiles are very suitable as solvents for copolymers containing hydroxyl groups. In addition, lower metering rates are required than would be expected from the activity of the components.
The invention relates to additives for improving lubricating properties of fuel oils, comprising
A) 10-95% by weight of at least one oil-soluble amphiphile of the formulae
xe2x80x83and/or 2
R1xe2x80x94Xxe2x80x94R2xe2x80x83xe2x80x83(2)
in which R1 is an alkyl, alkenyl, hydroxyalkyl or aromatic radical having 1 to 50 carbon atoms, X is NH, NR3, O or S, y is 1, 2, 3 or 4, R2 is hydrogen or an alkyl radical carrying hydroxyl groups and having 2 to 10 carbon atoms and R3 is an alkyl radical carrying nitrogen and/or hydroxyl groups and having 2 to 10 carbon atoms or a C1-C20-alkyl radical,
B) 5-90% by weight of at least one copolymer which contains
B1) from 5 to 80 mol % of structural units which are derived from olefinically unsaturated compounds which have at least one free hydroxyl group
B2) from 20 to 95 mol % of structural units which are derived from olefinically unsaturated compounds which carry a hydrocarbon radical having at least 6 carbon atoms, and, if required,
B3) from 0 to 40 mol % of further structural units selected from the group consisting of (meth)acrylic acid, (meth)acrylates, vinyl esters, vinyl ethers and alkenes, with the proviso that the structural units stated under c) differ from the structural units stated under a) and b),
and the copolymer has an average molar mass Mw of from 500 to 100,000 g/mol and an OH number of from 10 to 350 mg KOH/g.
The invention furthermore relates to fuel oils which contain said additives.
The invention furthermore relates to the use of the additives for improving the lubricating properties of fuel oils.
The invention furthermore relates to a process for improving the lubricity of fuel oils.
The oil-soluble amphiphile (component A) comprises preferably a radical R1 having 5 to 40, in particular 12 to 26, carbon atoms. Particularly preferably, R1 is linear or branched and, in the case of linear radicals, contains from 1 to 3 double bonds. The radical R preferably has 2 to 8, particularly 2 to 6 carbon atoms and may be interrupted by nitrogen and/or oxygen atoms. In a further preferred embodiment, the sum of the carbon atoms of R1 and R2 is at least 10, in particular at least 15 and not more than 35, in particular not more than 28, carbon atoms. In a further preferred embodiment, the component A carries from 2 to 5 hydroxyl groups, each carbon atom carrying not more than one hydroxyl group.
In a preferred embodiment of the invention, X in the formula 1 is oxygen. These compounds are in particular fatty acids and esters of carboxylic acids and dihydric or polyhydric alcohols. Preferred esters contain at least 10, in particular at least 12, carbon atoms. It is also preferred if the esters contain free hydroxyl groups, i.e. the esterification of the polyol with the carboxylic acid is not complete. Suitable polyols are, for example, ethylene glycol, diethylene glycol and higher alkoxylation products, glycerol, trimethylolpropane, pentaerythritol and sugar derivatives. Further polyols containing hetero atoms, such as triethanolamine, are also suitable. In a further preferred embodiment of the invention, the compounds which form the component A of the additive are fatty acids having 10 to 22 carbon atoms. These may be saturated or unsaturated.
Preferred components A are straight-chain saturated fatty acids having up to 18 carbon atoms, such as caprylic acid (octanoic acid), capric acid (decanoic acid), lauric acid (dodecanoic acid), myristic acid (tetradecanoic acid), palmitic acid (hexadecanoic acid), stearic acid (octadecanoic acid), and in particular unsaturated fatty acids, such as oleic acid (octadecenoic acid), linoleic acid, linolenic acid and mixtures thereof, such as, for example, rapeseed oil acid, soybean fatty acid, sunflower fatty acid, peanut fatty acid and tall oil fatty acid. Furthermore, dimeric and oligomeric fatty acids, as formed in the oligomerization of unsaturated fatty acids, may be present. Preferably, at least 50%, in particular more than 70%, especially more than 90%, of the fatty acids have at least one double bond.
Oil-soluble partial esters of these fatty acids with polyols, such as, for example, ethylene glycol, diethylene glycol and higher oligomers of alkylene oxides and glycerol, pentaerythritol, sorbitol, diethanolamine, triethanolamine and alkoxylated polyamines, are furthermore preferred. Glyceryl monooleate is particularly preferred. Esters which carry at least two free OH groups and an alkyl radical having at least 8 carbon atoms are especially preferred. The esters preferably have OH numbers of from 10 to 200 mg KOH/g, preferably from 20 to 150 mg KOH/g. If X is a nitrogen-containing radical, reaction products of ethanolamine, diethanolamine, hydroxypropylamine, dihydroxypropylamine, n-methylethanolamine, diglycolamine and 2-amino-2-methylpropanol are suitable. The reaction is preferably carried out by amidation, the resulting amides also carrying free OH groups. Fatty acid monoethanolamides, fatty acid diethanolamides and fatty acid N-methylethanolamides may be mentioned as examples. R3 is preferably methyl or ethyl.
In one embodiment, the multifunctional additive may contain, as component A, compounds of the formula 3
in which R1 has the abovementioned meaning, R41 is a radical of the formula 3a
xe2x80x94(R43xe2x80x94NR44)mxe2x80x94R45xe2x80x83xe2x80x83(3a)
and R42 is a radical of the formula 3b
xe2x80x94(R43xe2x80x94NR44 )nxe2x80x94R45xe2x80x83xe2x80x83(3b),
R43 is a C2- to C10-alkylene group, R44 is hydrogen, methyl, C2- to C20-alkyl, a radical of the formula 3c
or an alkoxy radical, and R45 is H or a radical of the formula 3c, and m and n, in each case independently of one another, are an integer from 0 to 20,
a) m and n preferably not simultaneously being zero and
b) the sum of m and n being at least 1 and not more than 20.
R43 is preferably a C2- to C8-radical, in particular a C2- to C4-radical. The polyamine from which the structural unit formed from R41, R42 and the nitrogen atom linking them is derived is preferably ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine or a higher homolog of aziridine, such as polyethyleneimine, and mixtures thereof. Some of the amino groups may be alkylated. Star amines and dendrimers are also suitable. These are understood as meaning polyamines having in general 2-10 nitrogen atoms which are linked to one another via xe2x80x94CH2xe2x80x94CH2xe2x80x94 groups and which are saturated by acyl or alkyl radicals in the outer position.
R44 is preferably nitrogen, an acyl radical or an alkoxy group of the formula xe2x80x94(OCH2CH2)nxe2x80x94, where n is an integer from 1 to 10, or a mixture thereof.
Other suitable amphiphiles are compounds of the formula 3d
in which
R46 may have the same meaning as R1,
R47 may have the same meaning as R1 or is H or xe2x80x94[CH2xe2x80x94CH2xe2x80x94Oxe2x80x94]pxe2x80x94H and
R48 may have the same meaning as R2 and
p is an integer from 1 to 10,
with the proviso that at least one of the radicals R46, R47 and R48 carries an OH group. xcex3-Hydroxybutyric acid tallow fatty amide may be mentioned as an example.
The amides are generally prepared by condensation of the polyamines with the carboxylic acids or their derivatives, such as esters or anhydrides. Preferably from 0.2 to 1.5 mol, in particular from 0.3 to 1.2 mol, especially 1 mol, of acid are used per base equivalent. The condensation is preferably carried out at temperatures of from 20 to 300xc2x0 C., in particular from 50 to 200xc2x0 C., with removal of the water of reaction by distillation. For this purpose, solvents, preferably aromatic solvents, such as benzene, toluene, xylene, trimethylbenzene and/or commercial solvent mixtures, such as, for example, Solvent Naphtha, (copyright)Shellsol AB, (copyright)Solvesso 150 or (copyright)Solvesso 200, may be added to the reaction mixture. The products according to the invention generally have a titratable base nitrogen content of 0.01-5% and an acid number of less than 20 mg KOH/g, preferably less than 10 mg KOH/g.
y preferably assumes the value 1 or 2. Examples of preferred groups of compounds having y=2 are derivatives of dimeric fatty acids and alkenylsuccinic anhydrides. The latter may carry linear as well as branched alkyl radicals, i.e. they may be derived from linear a-olefins and/or from oligomers of lower C3-C5-olefins, such as poly(propylene) or poly(isobutylene).
Preferred polyols have 2 to 8 carbon atoms. They preferably carry 2, 3, 4 or 5 hydroxyl groups, but no more than the carbon atoms they contain. The carbon chain of the polyols may be straight, branched, saturated or unsaturated and, if required, may contain hetero atoms. It is preferably saturated.
Preferred carboxylic acids from which the radical R1 is derived have 5 to 40, in particular 12 to 30, carbon atoms. Preferably, the carboxylic acid has one or two carboxyl groups. The carbon chain of the carboxylic acids may be straight, branched, saturated or unsaturated. Preferably, more than 50% of the carboxylic acids (mixtures) used contain at least one double bond. Examples of preferred carboxylic acids include caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, elaidic acid, linoleic acid, linolenic acid and behenic acid, as well as carboxylic acids having hetero atoms, such as ricinoleic acid. Furthermore, dimeric and trimeric fatty acids, as are obtainable, for example, by oligomerization of unsaturated fatty acids, and alkenylsuccinic acids may be used.
In a preferred embodiment, ethers and amines of the formula 2 are used as component A. These are partial ethers of polyols, such as, for example, glyceryl monooctadecyl ether or amines carrying hydroxyl groups, as obtainable, for example, by alkoxylation of amines of the formula R1NH2 or R1R3NH with alkylene oxides, preferably ethylene oxide and/or propylene oxide. Preferably, 1-10, in particular 1-5, mol of alkylene oxide are used per H atom of the nitrogen.
The copolymer which forms component B of the additive according to the invention contains free OH groups.
In a preferred embodiment of the invention, the copolymer has an OH number of from 10 to 300, in particular from 20 to 250, mg KOH/g. In a further preferred embodiment, the copolymer has an average molecular weight Mw of from 700 to 10,000 g/mol. In a further preferred embodiment, the proportion of structural units (B1) is from 10 to 70 mol %, in particular from 15 to 60 mol %.
The olefinically unsaturated compounds which are the comonomers (B1) are preferably vinyl esters, acrylates, mono- and diesters of ethylenically unsaturated carboxylic acids, methacrylates, alkyl vinyl ethers and/or alkenes, which carry hydroxyalkyl, hydroxyalkenyl, hydroxycycloalkyl or hydroxyaryl radicals. These radicals contain at least one hydroxyl group which may be in any desired position of the radical but is preferably at the chain end ((xcfx89-position) or in the para-position in the case of ring systems.
The vinyl esters are preferably those of the formula 4
xe2x80x83CH2xe2x95x90CHxe2x80x94OCOR4xe2x80x83xe2x80x83(4)
in which R4 is C1-C30-hydroxyalkyl, preferably C1-C16-hydroxyalkyl, especially C2-C12-hydroxyalkyl and the corresponding hydroxyoxalkyl radicals. Suitable vinyl esters include 2-hydroxyethyl vinyl esters, xcex1-hydroxypropyl vinyl esters, 3-hydroxypropyl vinyl esters and 4-hydroxybutyl vinyl esters.
The acrylates are preferably those of the formula 5
CH2xe2x95x90CR5xe2x80x94COOR6xe2x80x83xe2x80x83(5)
in which R5 is hydrogen or methyl and R is C1-C30-hydroxyalkyl, preferably C1-C16-hydroxyalkyl, especially C2-C12-hydroxyalkyl and the corresponding hydroxyoxalkyl radicals. Suitable acrylates include hydroxyethyl acrylate, hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, hydroxyisopropyl acrylate, 4-hydroxybutyl acrylate and glyceryl monoacrylate. The corresponding esters of methacrylic acid and esters of ethylenically unsaturated dicarboxylic acids, such as maleic acid, fumaric acid or itaconic acid, with diols are just as suitable.
The alkyl vinyl ethers are preferably compounds of the formula 6
CH2xe2x95x90CHxe2x80x94OR7xe2x80x83xe2x80x83(6)
in which R7 is C1-C30-hydroxyalkyl, preferably C1-C16-hydroxyalkyl, especially C2-C12-hydroxyalkyl and the corresponding hydroxyoxalkyl radicals. Suitable alkyl vinyl ethers include 2-hydroxyethyl vinyl ether, hydroxypropyl vinyl ether, hexanediol monovinyl ether, 4-hydroxybutyl vinyl ether, diethylene glycol monovinyl ether and cyclohexanedimethanol monovinyl ether.
The alkenes are preferably monounsaturated hydroxyhydrocarbons having 3 to 30 carbon atoms, in particular 4 to 16 carbon atoms and especially 5 to 12 carbon atoms. Suitable alkenes include dimethylvinylcarbinol (xe2x95x902-methyl-3-buten-2-ol), allyloxypropanediol, 2-butene-1,4-diol, 1-buten-3-ol, 3-buten-1-ol, 2-buten-1-ol, 1-penten-3-ol, 1-penten-4-ol, 2-methyl-3-buten-1-ol, 1-hexen-5-ol, 5-hexen-1-ol and 7-octene-1,2-diol.
Preferred comonomers (B2) are olefinically unsaturated compounds which carry hydrocarbon radicals having at least 6 carbon atoms (excluding the olefinic group required for the polymerization). These hydrocarbon radicals may be linear, branched, cyclic and/or aromatic. In addition to hydrocarbon groups, they may also carry minor amounts of further functional groups having hetero atoms, such as, for example nitro, halogen, cyano or amino groups, provided that they do not impair the oil solubility. These are preferably monomers from the following groups:
b1) Vinyl esters of carboxylic acids having at least 7 carbon atoms, such as, for example, octylvinyl esters, 2-ethylhexylvinyl esters, vinyl laurate, octadecylvinyl esters, vinyl neononanoate, vinyl neodecanoate and vinyl neoundecanoate.
b2) (Meth)acrylates with alcohols having at least 6 carbon atoms, such as, for example, octyl acrylate, 2-ethylhexyl acrylate, decyl acrylate, dodecyl acrylate, tetradecyl acrylate, hexadecyl acrylate, and the corresponding esters of methacrylic acid and esters of ethylenically unsaturated dicarboxylic acids, such as maleic acid, fumaric acid or itaconic acid
b3) Alkyl vinyl ethers which carry at least one C6-alkyl radical, such as, for example, octadecyl vinyl ether
b4) Olefins and vinylaromatics having chain lengths of at least 6 carbon atoms, such as, for example, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, industrial xcex1-olefin cuts, such as C20-C24-xcex1-olefin, C24-C28-xcex1-olefin, C30+-xcex1-olefin, styrene, xcex1-methylstyrene and p-methoxystyrene.
It is also possible to use both individual comonomers B2 and mixtures of different comonomers of the individual and/or different monomers b1) to b4). Particularly preferred comonomers B2 are the abovementioned olefinically unsaturated compounds of groups b1) to b4) having hydrocarbon radicals which comprise at least 8 carbon atoms. Preferably, at least 10 mol %, particularly preferably at least 25 mol %, in particular more than 50 mol %, of the monomers B2 carry linear hydrocarbon radicals. Preferably, the proportion of comonomers B2 in the polymers according to the invention is from 30 to 90 mol %, in particular from 40 to 80 mol %.
If required, up to 40 mol % of acrylic acid or methacrylic acid, acrylates, such as methyl acrylate, ethyl acrylate, butyl acrylate, and the corresponding methacrylates, vinyl esters, such as vinyl acetate, vinyl propionate, hexylvinyl esters, such as ethylene, propene, butene, isobutene, pentene, hexene, 4-methylpentene, diisobutylene and norbornene, may be present as further comonomers B3. Nitrogen-containing monomers may also be present, such as, for example,
a) aminoalkyl acrylates and methacrylates, such as, for example, aminoethyl acrylate, aminopropyl acrylate, amino-n-butyl acrylate, N-methylaminoethyl acrylate, N,N-dimethylaminoethyl acrylate, N,N-diethylaminoethyl acrylate, N,N-dimethylaminopropyl acrylate, N,N-diethylaminopropyl acrylate and the corresponding methacrylates,
b) alkylacrylamides and alkylmethacrylamides, such as, for example, ethylacrylamide, butylacrylamide, N-octylacrylamide, N-propyl-N-methoxyethylacrylamide, N-acryloylphthalimide, N-acryloylsuccinimide, N-methylolacrylamide and the corresponding methacrylamides,
c) vinylamides, such as, for example, N-vinyl-N-methylacetamide and N-vinylsuccinimide,
d) aminoalkyl vinyl ethers, such as, for example, aminopropyl vinyl ether, diethylaminoethyl vinyl ether and diethylaminopropyl vinyl ether,
e) allylamine, N-allyl-N-methylamine, N-allyl-N-ethylamine and diallylamine, and
f) a heterocycle carrying a vinyl group, such as, for example, N-vinylpyrrolidone, methylvinylimidazole, 2-vinylpyridine, 4-vinylpyridine, 2-methyl-5-vinylpyridine, vinylcarbazole, vinylimidazole, N-vinyl-2-piperidone and N-vinylcaprolactam.
In order to achieve easier handling and better solubility of the additives, preferably up to 20 mol %, in particular up to 10 mol %, of the comonomers B2 and, if required B3 contain branched alkyl chains. Oligomers and polymers of lower olefins such as, for example, poly(propylene), poly(butene) and poly(isobutylene), are also suitable, those oligomers having a high proportion of terminal double bonds ( greater than 50 mol %, preferably  greater than 70 mol %, in particular  greater than 75 mol %) being preferred.
The melt viscosities of the copolymers at 140xc2x0 C. are preferably below 10,000 mPas, in particular from 10 to 2000 mPas and especially from 15 to 1000 mPas. In the context of the invention, oil-soluble means that at least 10% by weight, preferably at least 1% by weight, in particular at least 0.1% by weight, of the additive is soluble in the middle distillate into which the additive is to be introduced and gives a clear solution.
The copolymers which form the component B of the additive according to the invention can be prepared by direct polymerization of compounds which contain the stated structural units. It is also possible to prepare them by a polymer-analogous reaction.
For this purpose, it is necessary to prepare a polymer having free acid groups. These originate from the copolymerization of an olefinically unsaturated carboxylic acid or such a derivative of carboxylic acid with further comonomers B1, and if required, B2 defined here. These carboxylic acids and carboxylic acid derivatives are preferably maleic acid, acrylic acid, methacrylic acid, fumaric acid or itaconic acid and derivatives thereof. The monomers B1 carrying hydroxyl groups are prepared therefrom in a polymer-analogous reaction.
Preferred derivatives of the carboxylic acids are their anhydrides. Maleic anhydride is particularly preferred. In the case of copolymers of maleic anhydride (MAA) with xcex1-olefins, alternating copolymers which contain from about 40 to 60 mol % of MAA and 6-40% of xcex1-olefin are preferred.
For the preparation of the copolymers according to the invention by means of polymer-analogous reaction, the polymeric acid groups are reacted with at least bifunctional reagents which carry at least one OH function. The bonding to the polymer may take place via hydroxyl groups as ester and/or via primary or secondary amino groups in the form of amides, imides and/or ammonium salts. In order to avoid crosslinking reactions, it is possible to employ, for example, an excess of bifunctional reagent and/or a high dilution. The esterification, amidation or imidation is carried out as a rule with removal of water of reaction (azeotropic distillation, expulsion with gas stream, such as N2). The residual acid number is brought to values of  less than 150, preferably  less than 20, in particular  less than 10 mg, KOH/g. Examples of suitable reagents are ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, trimethylolpropane, mixed alkoxylates of ethylene oxide, propylene oxide and/or butylene oxide comprising up to 50, in particular up to 10 units derived from ethylene oxide, propylene oxide and/or butylene oxide, glycerol, pentaerythritol, sorbitol, ethanolamine, diethanolamine, triethanolamine, butyldiethanolamine, methyl diisopropylamine, aminopropanediol and alkoxylated polyamines. The latter may be derived, for example, from ethylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine and their higher homologs, which are alkoxylated with from 0.5 to 50, in particular 10, mol of ethylene oxide, propylene oxide and/or butylene oxide per H atom bonded to a N atom. The reaction with the polymer can be effected both via an OH group to give the ester and via a primary or secondary amino group to give the amide or imide.
The reaction of the copolymers containing acid groups is carried out at from 30 to 250xc2x0 C. in the course of from 0.5 to 20 hours. The hydroxy-functional reagent is reacted with amounts of from about 1 to about 2 mol per mole of polymerized acid (derivative).
In order to establish a lower OH number for a given base polymer and hence to improve the oil solubility, up to 50 mol % of the hydroxy-functional reagent can be replaced by alkylamines and/or alcohols having up to 24 carbon atoms. Furthermore, the copolymers B can be obtained by oxalkylation of the copolymers containing acid groups. Copolymers suitable for this purpose are, for example, those of acrylic acid, methacrylic acid, itaconic acid, fumaric acid, maleic acid or maleic anhydride with the comonomers B2 and, if required, B3. These are oxalkylated at the acid groups with C1- to C10-alkylene oxides. Preferred alkylene oxides are ethylene oxide, propylene oxide and butylene oxide. The oxalkylation is preferably effected using from 0.5 to 10 mol, in particular from 1 to 5 mol and especially from 1 to 2 mol of alkylene oxide per mole of acid group.
The copolymerization of the comonomers is carried out by known batchwise or continuous polymerization methods (in this context, cf. for example Ullmanns
Encyclopxc3xa4die der Technischen Chemie [Ullmann""s Encyclopedia of Industrial Chemistry], 5th Edition, Vol. A21, pages 305 to 413). Polymerization in solution, in suspension and in the gas phase and precipitation and mass polymerization are suitable. Mass and solution polymerization are preferred. The reaction of the comonomers is initiated by free radical initiators (free radical chain initiators). This class of substances includes, for example, oxygen, hydroperoxides, peroxides and azo compounds, such as cumyl hydroperoxide, tert-butyl hydroperoxide, dilauroyl peroxide, dibenzoyl peroxide, bis(2-ethylhexyl) peroxodicarbonate, tert-butyl permaleate, tert-butyl perpivalate, tert-butyl perbenzoate, dicumyl peroxide, tert-butyl cumyl peroxide, di(tert-butyl) peroxide, 2,2xe2x80x2-azobis(2-methylpropanonitrile) and 2,2xe2x80x2-azobis(2-methylbutyronitrile). The initiators are used individually or as a mixture of two or more substances, in amounts of from 0.01 to 20% by weight, preferably from 0.05 to 10% by weight, based on the comonomer mixture.
The polymerization is effected as a rule at temperatures of 40-300xc2x0 C., preferably at 80-250xc2x0 C., it being expedient to employ superatmospheric pressure when monomers and/or solvents having boiling points below the polymerization temperature are used. The polymerization is expediently carried out in the absence of air, for example under nitrogen, since oxygen adversely affects the polymerization. In choosing the initiator or the initiator system, it is expedient to ensure that the half-life of the initiator or initiator system at the chosen polymerization temperature is less than 3 hours. Preferably, it is from 0.5 minutes to one hour. For a given composition of the comonomer mixture, the desired molecular weight of the copolymer is obtained by varying the reaction parameters of concentration and temperature. In order to obtain low molecular weight copolymers, it is furthermore possible to add moderators. Suitable molecular weight regulators are, for example, aldehydes, ketones, alcohols and organic sulfur compounds, such as mercaptoethanol, mercaptopropanol, mercaptoacetic acid, mercaptopropionic acid, tert-butyl mercaptan, n-butyl mercaptan, n-octyl mercaptan, tert-dodecyl mercaptan and n-dodecyl mercaptan. Depending on the desired viscosity, the moderators are used in amounts of up to 20% by weight, preferably from 0.05 to 10% by weight, based on the comonomer mixture.
Apparatuses suitable for the polymerization are, for example, conventional stirred kettles having, for example, an anchor stirrer, paddle stirrer, impeller stirrer or multistage impulse countercurrent agitator and, for the continuous preparation, stirred kettle cascades, stirred reactors or static mixers.
A preferred process for the preparation of the copolymers, in addition to solvent-free mass polymerization, is solution polymerization. It is carried out in solvents in which the monomers and the copolymers formed are soluble. All solvents which meet this requirement and which do not react with the monomers and with the copolymers formed are suitable for this purpose. For example, these are organic, preferably aromatic solvents, such as cumene, toluene, xylene, ethylbenzene or commercial solvent mixtures, such as (copyright)Solvent Naphtha, (copyright)Shellsol AB or (copyright)Solvesso 150, 200.
In the preparation, all monomers can be initially taken and can be polymerized by adding a free radical initiator and supplying heat.
Expediently, however, the solvent and, if required, a part of the monomers (for example about 5-20%) are initially taken and the remainder of the monomer mixture is metered in with the initiator and, if required, coinitiator and regulator.
The concentration of the monomers to be polymerized is from 20 to 95% by weight, preferably from 50 to 90% by weight. The solid copolymer can be isolated by precipitation with suitable nonsolvents, such as acetone or methanol, or by evaporating the solvent. However, it is expedient to choose for the polymerization a solvent in which the polymer can be used directly according to the invention.
The additives according to the invention are added to the mineral oils or mineral oil distillates preferably as a mixture, the oil-soluble amphiphile A serving as a solvent for the copolymer B. Preferred mixtures are flowable at temperatures below 40xc2x0 C., i.e. they have a viscosity of less than 10 Pas, in particular  less than 1 Pas, at this temperature. If the viscosity and/or natural setting point of the mixture are too high for processing, up to 50% by weight, in particular up to 20% by weight, based on the additive, of a solvent may be added. Solvents may be aliphatic and/or aromatic hydrocarbons. The advantages of the additive combination according to the invention can how ever also be utilized in the case of separate metering of the components A and B.
Mineral oils or mineral oil distillates improved in their lubricating and/or cold flow properties by means of the additives contain from 0.001 to 2, preferably from 0.005 to 0.5, % by weight of additive, based on the distillate. The additives according to the invention may furthermore be used in the form of mixtures which comprise additives of the claimed type but of different qualitative and/or quantitative composition. The mixing ratio (in parts by weight) of the additive components may be varied over a wide range and may be, for example, from 20:1 to 1:20, preferably from 10:1 to 1:10. In this way, the additives can be adapted specifically to individual requirements.
For the preparation of additive packets for solving specific problems, the additives according to the invention can also be used together with one or more oil-soluble coadditives which by themselves improve the cold flow properties and/or lubricating effect of crude oils, lubricating oils or fuel oils. Examples of such coadditives are vinyl acetate-containing copolymers or terpolymers of ethylene, polar compounds which disperse paraffins (paraffin dispersants), comb polymers, alkylphenol/aldehyde resins and oil-soluble amphiphiles.
Thus, mixtures of the additives with copolymers which contain from 10 to 40% by weight of vinyl acetate and from 60 to 90% by weight of ethylene have proven to be particularly useful. According to a further embodiment of the invention, the additives according to the invention are used as a mixture with ethylene/vinyl acetate/vinyl neononanoate terpolymers or ethylene/vinyl acetate/vinyl neodecanoate terpolymers for improving the flowability of mineral oils or mineral oil distillates. The terpolymers of vinyl neononanoates or of vinyl neodecanoates contain from 10 to 35% by weight of vinyl acetate and from 1 to 25% by weight of the respective neo compound in addition to ethylene. Further preferred copolymers contain, in addition to ethylene and from 10 to 35% by weight of vinyl esters, also from 0.5 to 20% by weight of olefin, such as diisobutylene, 4-methylpentene or norbornene. The mixing ratio of the additives according to the invention with the ethylene/vinyl acetate copolymers described above or the terpolymers of ethylene, vinyl acetate and the vinyl esters of neononanoic or neodecanoic acid is (in parts by weight) from 20:1 to 1:20, preferably from 10:1 to 1:10.
For use as flow improvers and/or lubricity additives, the additives according to the invention may furthermore be used as a mixture with paraffin dispersants. Paraffin dispersants reduce the size of the paraffin crystals and ensure that the paraffin particles do not settle out but remain dispersed in colloidal form with substantially reduced tendency to sedimentation. Furthermore, they enhance the lubricating effect of the additives according to the invention. Paraffin dispersants which have proven to be useful are oil-soluble polar compounds having ionic or polar groups, for example amine salts and/or amides, which are obtained by reacting aliphatic or aromatic amines, preferably long-chain aliphatic amines, with aliphatic or aromatic mono-, di-, tri- or tetracarboxylic acids or their anhydrides (cf. U.S. Pat. No. 4,211,534). Other paraffin dispersants are copolymers of maleic anhydride and xcex1,xcex2-unsaturated compounds, which, if required, may be reacted with primary monoalkylamines and/or aliphatic alcohols (cf. EP 0 154 177), the reaction products of alkenylspirobislactones with amines (cf. EP 0 413 279 B1) and, according to EP 0 606 055 A2, reaction products of terpolymers based on xcex1,xcex2-unsaturated dicarboxylic anhydrides, xcex1,xcex2-unsaturated compounds and polyoxyalkylene ethers of lower unsaturated alcohols. Alkylphenol aldehyde resins are also suitable as paraffin dispersants.
Thus, the copolymers according to the invention can be used as a mixture with alkylphenol formaldehyde resins. In a preferred embodiment of the invention, these alkylphenol formaldehyde resins are those of the formula 7
in which R6 is C4-C50-alkyl or C4-C50-alkenyl, R7 is ethoxy and/or propoxy, n is a number from 5 to 100 and p is a number from 0 to 50.
Finally, in a further embodiment of the invention, the additives according to the invention are used together with comb polymers. These are understood as meaning polymers in which hydrocarbon radicals having at least 8, in particular at least 10, carbon atoms are bonded to a polymer backbone. Preferably, these are homopolymers whose alkyl side chains contain at least 8 and in particular at least 10 carbon atoms. In the case of copolymers, at least 20%, preferably at least 30%, of the monomers have side chains (cf. Comb-like Polymersxe2x80x94Structures and Properties; N. A. Platxc3xa9 and V. P. Shibaev, J. Polym. Sci. Macromolecular Revs. 1974, 8, 117 et seq.). Examples of suitable comb polymers are fumarate/vinyl acetate copolymers (cf. EP 0 153 176 A1), copolymers of a C6- to C24-xcex1-olefin and an Nxe2x80x94C6- to C22-alkylmaleimide (cf. EP 0 320 766), and furthermore esterified olefin/maleic anhydride copolymers, polymers and copolymers of xcex1-olefins and esterified copolymers of styrene and maleic anhydride.
Comb polymers can be described, for example, by the formula 8
In this formula,
A is Rxe2x80x2, COORxe2x80x2, OCORxe2x80x2, Rxe2x80x3xe2x80x94COORxe2x80x2 or ORxe2x80x2;
D is H, CH3, A or R;
E is H or A;
G is H, Rxe2x80x3, Rxe2x80x3xe2x80x94COORxe2x80x2, an aryl radical or a heterocyclic radical;
M is H, COORxe2x80x3, OCORxe2x80x3, ORxe2x80x3 or COOH;
N is H, Rxe2x80x3, COORxe2x80x3, OCOR, COOH or an aryl radical;
Rxe2x80x2 is a hydrocarbon chain having 8-150 carbon atoms;
Rxe2x80x3 is a hydrocarbon chain having 1 to 10 carbon atoms;
m is a number from 0.4 to 1.0; and
n is a number from 0 to 0.6.
The mixing ratio (in parts by weight) of the additives according to the invention with paraffin dispersants, resins or comb polymers is in each case from 1:10 to 20:1, preferably from 1:1 to 10:1.
The additives according to the invention are in particular suitable for improving the lubricating properties of animal, vegetable or mineral oils. Moreover, they simultaneously improve the cold flow properties of the oils containing the additives. They are particularly suitable for use in middle distillates. Middle distillates are defined in particular as those mineral oils which are obtained by distillation of crude oil and boil within a range from 120 to 450xc2x0 C., for example kerosene, jet fuel, diesel and heating oil. Preferably, the additives according to the invention are used in those middle distillates which contain 0.05% by weight of sulfur or less, particularly preferably less than 350 ppm of sulfur, in particular less than 200 ppm of sulfur and in specific cases less than 50 ppm of sulfur. These are in general those middle distillates which are subjected to refining with hydrogenation and which therefore contain only small amounts of polyaromatic and polar compounds which impart a natural lubricating reaction to them. The additives according to the invention are furthermore preferably used in those middle distillates which have 95% distillation points below 370xc2x0 C., in particular 350xc2x0 C. and in specific cases below 330xc2x0 C. They can also be used as components in lubricating oils.
The additives can be used alone or together with other additives, for example with other pour point depressants or dewaxing assistants, with corrosion inhibitors, antioxidants, sludge inhibitors, dehazers and additives for reducing the cloud point.

Mixtures of carboxylic acids, their derivatives and hydroxyl-containing polymers and their use for improving the lubricating effect of oils

Abstract: A) 10-95% by weight of at least one oil-soluble amphiphile of the formulae 1

Abstract: xe2x80x83and/or 2

Abstract: B1) from 5 to 80 mol % of structural units which are derived from olefinically unsaturated compounds, and

Abstract: B2) from 20 to 95 mol % of structural units which are derived from olefinically unsaturated compounds,