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* GB785934 (A) Description: GB785934 (A) ? 1957-11-06 Fertilizer materials Description of GB785934 (A) Translate this text into Tooltip [75][(1)__Select language] Translate this text into The EPO does not accept any responsibility for the accuracy of data and information originating from other authorities than the EPO; in particular, the EPO does not guarantee that they are complete, up-to-date or fit for specific purposes. We, Fiso Ns Limi TED, a British Company, of Harvest House, Felixstowe, Suffolk, England, do hereby declare the invention, for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly des- cribed in and by the following statement:- The present invention relates to an improved method for the prevention of caking of granulated fertilizers. It is known that fertilizer materials in granular form containing superphosphates are liable to caking on storage either in bulk or in packages, and various methods have been tried to overcome
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* GB785934 (A)

Description: GB785934 (A) ? 1957-11-06

Fertilizer materials

Description of GB785934 (A) Translate this text into Tooltip

[75][(1)__Select language] Translate this text into

The EPO does not accept any responsibility for the accuracy of data and information originating from other authorities than the EPO; in particular, the EPO does not guarantee that they are complete, up-to-date or fit for specific purposes.

We, Fiso Ns Limi TED, a British Company, of Harvest House, Felixstowe, Suffolk, England, do hereby declare the invention, for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly des- cribed in and by the following statement:- The present invention relates to an improved method for the prevention of caking of granulated fertilizers. It is known that fertilizer materials in granular form containing superphosphates are liable to caking on storage either in bulk or in packages, and various methods have been tried to overcome this disadvantage including inter alia treatment of fertilizer material with various surface active agents. It has now been found that by spraying the fertilizer material with a dilute aqueous solution of an alkali metal lauryl sulphate far superior results are obtained in the prevention of caking than with other surface active agents. Accordingly the present invention provides a process for the treatment of phosphorus-containing fertilizer materials which comprises spraying the fertilizer material in granular form with a dilute aqueous solution of an alkali metal lauryl sulphate The alkali metal lauryl sulphate is preferably sodium lauryl sulphate. The proportion of alkali metal lauryl sulphate employed may vary over

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a wide range, but suitably it is used in amount corresponding to 1-3 pounds per ton The aqueous alkali metal lauryl sulphate solution suitably contains 3-10 % of alkali metal lauryl sulphate depending on the temperature at which it is used, the limit of room temperature solubility being about 7 %. The treatment of the granulated fertilizer may be carried out before or after cooling lPrice 3 S 6 d l 735,934 and before or after sieving as is desired One feature which will determine the desired method of spraying will be the final moisture 45 content of the product Thus for example the granulated fertilizer in a hot condition may be sprayed with aqueous sodium lauryl sulphate at or about the same temperature so that the final moisture content will be 50 that desired, or alternatively the cold granulated fertilizer may be sprayed with the solution and thereafter dried, if desired, to the required moisture content. The spraying of the granulated fertilizer 55 is suitably effected by means of fine sprays or jets of standard construction which spray into relatively small amounts of the fertilizer -as for example while it is carried on a conveyor belt or while the granulated 60 fertilizer is falling in a stream from a conveyor or like source. The granular fertilizer material treated according to the present invention may be one containing superphosphates, such as 653 triple superphosphates According to a preferred embodiment of the invention the fertilizer treated is one containing superphosphates, ammonium sulphate and potassium chloride, for example containing 9 % 70 nitrogen, 9 % total phosphorus pentoxide and % potassium oxide. The following example is given to illustrate the process of the present invention. Granular fertilizer material containing 75 superphosphates, ammonium sulphate and potassium chloride at a temperature of -60 C was sprayed with a 7 5 % aqueous solution of sodium lauryl sulphate also at a temperature of 50 W-60 ' C in 80 amount corresponding to 0 15 % sodium lauryl sulphate on the weight of the fertilizer material The resulting product when cooled had a moisture content of about 2 % The PATENT SPECIFIATION Inventor:-TH Oi ILAS PRIDE DEE. Date of filing Complete Specification: June 20, 1955. Application Date: June 19, 1954 No 18075154. Complete Speci Jication Published: Nov 6, 1957. Index at Acceptance -glasses 94 ( 1), C 23; and 111, B 3 (C 1: 03: 04: F 2). International Classification:-B 65 b CO 5 b, c, d. COMPLETE SPECIFICATION. Fertilizer Materials. 785,934 granular material so treated showed no signs of caking on

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storage.

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* GB785935 (A)

Description: GB785935 (A) ? 1957-11-06

Improvements in or relating to the production of webs or mats of bondedstaple lengths of grouped filaments

Description of GB785935 (A)

A high quality text as facsimile in your desired language may be available amongst the following family members:

CH329667 (A) DE1054672 (B) CH329667 (A) DE1054672 (B) less Translate this text into Tooltip

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The EPO does not accept any responsibility for the accuracy of data and information originating from other authorities than the EPO; in particular, the EPO does not guarantee that they are complete, up-to-date or fit for specific purposes.

PATENT SPECHICA Tff N Ta Inventor: -STANLEY PALMER. Dafe oj filing Complete Specijfcatiorn: Sept 28, 1955. App l)ication Date: Oct 7, 1954 No 28921 /54. Comaplete Spec-:fcation Published: Nov 6 19 7,. Index at Acceptance:-Classes 56, r 59; 120 ( 1), Bl D; 120 ( 2), D 2 G

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3 (B:X); ( 3), F( 21: X); and 140, A( 20: 2 G: 5 G 6: 12), G. International Classification:-CO 3 b DO 1 b DO 2 d DO 4 j. COMPLETE SPECIFICATION. Improvements in or relating to the Production of Webs or Miats of Bonded Staple Lengths, of Grouped Filaments. WC, VERSIL Li MITED, of Rayner Mills, Liversedge, Yorkshire, a British Company, do hereby declare the invention, for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement:- This invention relates to the production of webs or mats of bonded staple lengths of grouped filaments formed by grouping together a number of continuous monofilaments of extrudable material, such as glass or thermoplastic, bonding the grouped filaments together by the application of a binder, attenuating the grouped filaments and cutting them into short lengths which are distributed in random arrangement onto a moving conveyor surface for forming a web or mat in which the distributed lengths of grouped filaments may be bonded together by an appropriate binding agent applied thereto. Such webs or mats are particularly suitable for use in resin-impregnated sheets and laminates intended for the manufacture of moulded articles, such as vehicle bodies, boat hulls and the like, the random arrangement of the short lengths of grouped filaments providing a reinforcement resistant to bending stresses in any direction. The invention is particularly concerned with improvements in apparatus for the production of such webs or mats of the kind broadly comprising means for forming a number of continuous monofilaments, means for grouping and bonding together the monofilaments, means for attenuating the grouped filaments, and means for cutting the grouped filaments into short lengths which r pa, 71 are distributed onto a moving conveyor surface for forming the web or mat. The present invention has for its object to provide improved, simple and effective apparatus for the purpose, which is of particular application to the production of webs or mats from continuously extruded glass filaments. According to the present invention, apparatus of the kind referred to for producing a web or mat consisting of short lengths of grouped and bonded monofilaments distributed in random arrangement to form a layer in which the short lengths are bonded together, comprises a first continuously operating ejector air-traction device arranged to receive and attenuate the grouped and bonded monofilaments, a second intermittently operating air-traction device adapted to feed the grouped filaments emerging from the first air-traction device to an oscillating cutter device, acting to cut the grouped filaments into

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short lengths, and a third continuously operating air-traction device arranged to tension the grouped filaments during the cutting operation and to discharge the cut lengths in random arrangement onto a continuously moving conveyor surface for forming the web or mat The means for grouping the filaments may comprise a drum adapted to receive a plurality of mono filaments from an extrusion die plate or nozzles and having a V groove for grouping the filaments. The third ejector air-traction device may be adapted to be oscillated laterally to distribute the staple lengths over the width of said conveyor surface. The part of the conveyor surface adapted to receive the cut lengths may be arranged I 59935 to travel upwardly on an inclined path over a suction box serving to retain the cut lengths on the conveyor surface while a suitable bonding medium is applied. The first air-traction device may be provided with a blade so disposed at the inlet end as to remove any bead that may be fprmed in the event of breakage of an extruded monofilament. The apparatus may comprise two or more units arranged in parallel to distribute cut lengths of grouped and bonded filaments onto a common carrier or conveyor surface either in parallel or in overlapping bands or in successively applied layers. The conveyor surface may be a paper or like base which, when the distributed cut lengths of grouped filaments are bonded together, forms part of the web or mat. The invention is hereinafter described, by way of example, with reference to the accompanying diagrammatic drawings, in which: Fig 1 is a diagrammatic side elevation illustrating one embodiment of apparatus according to the invention; Fig 2 is a detail side elevation of the cutter device shown in Fig 1; Fig 3 is an end elevation corresponding to Fig 2; and Fig 4 is a plan view of the hopper and drum shown in Fig 1. In carrying the invention into effect according to one embodiment, and in particular application of the invention to the production of a web or mat from bonded staple lengths of grouped and bonded glass monofilaments, monofilaments 1 are extruded downwardly from a die plate 2 of a furnace 3 and are guided by means of a hopper 4 on to the periphery of a rotatable element 5, such as a drum or disc having a V groove 6 whereby the filaments 1 are grouped together The hopper 4 may have an arcuate extension 7 extending round part of the periphery of the rotatable element 5 within the V groove 6 A suitable adhesive, such as a monomer of a low pressure resin, is sprayed on to the filaments 1 from a nozzle 8, or otherwise applied to the filaments at any point before or during their contact with the rotatable element 5, so that the filaments forming the group are caused to adhere together.

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The grouped and bonded filaments 9 are led off from the drum horizontally and pass through a first ejector air traction device of conventional form which, in withdrawing the grouped filaments 9 from the rotatable element 5, exerts traction thereon and thereby attenuates the filaments 1 The air traction device 10 is continuously operated by a blast of air supplied by a blower 11 driven by a motor 12 and conducted through a pipe 13 and a branch pipe 14. A second ejector air traction device 15 receives air from the pipe 13 through a branch pipe 16 under the control of a valve 17 operated by means such as an eccentric 18 on a shaft 19 driven from a motor 20 70 so that the feed action of the device 15 is intermittently interrupted A cutter device 21 is driven from the shaft 19 so as to operate to cut the grouped filaments 9 when the feed action of the ejector air traction device 75 is interrupted During non-feeding periods of the device 15 the grouped filaments 9 fed continuously forward by the device 10 may form a loop at an intermediate position, as indicated at 22 so A third ejector air traction device 23 is arranged at the outlet side of the cutter device 21 to receive the staple lengths 24 as they are cut off from the grouped filaments 9, the device 23 being continuously sit operated by a blast of air from the pipe 13 through the branch pipe 25 so as to tension the grouped filaments during the cutting operation and to discharge the staple lengths 24 on to a carrier or conveyor sur go face 26 travelling upwardly on an inclined path and at a relatively slow speed over a suction box 27 which serves to retain the staple lengths 24 on the surface 26 while they are treated with a suitable bonding Do medium to form a web or mat on the surface 26. In order to distribute the staple lengths over the width of the conveyor surface 26, and in random overlapping arrangement so 100 as to build up a suitable thickness of web or mat, the ejector air traction device 23 may be mounted to Pivot about a vertical axis adjacent its inlet end and oscillated laterally by any suitable means, e g a crank and 105 connecting rod arrangement driven through suitable reduction gearing from the motor 20. The cutter device 21 comprises a blade 28 carried by a slide 29 operated through a 110 connecting rod 30 from a crank 31 or an eccentric (not shown) on the shaft 19, the blade 28 acting upwardly against a block 32 to sever the grouped filaments 9 to form the staple lengths 24 115 In the event of breakage of a filament 1 between the rotatable element 5 and the furnace 3, the temperature at a point 33 below the die plate 2 is sufficient to melt off the issuing portion of the broken filament 120 to form a bead of glass which eventually gravitates drawing a filament behind it and passes into the guide hopper 4 whereby it is grouped and bonded to the unbroken filaments

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and drawn forward by the first 12 _ 5 ejector air traction device 10 A serrated blade 34 is arranged at the inlet end of the traction device 10 so as to remove, by impact, the bead 35 of glass and a portion of the filament behind it and thus avoid inter 130 785,935 ment onto a continuously moving conveyor 55 surface for forming the web or mat.

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* GB785936 (A)

Description: GB785936 (A) ? 1957-11-06

Improvements in or relating to incorporation of solid materials in oil

Description of GB785936 (A)

A high quality text as facsimile in your desired language may be available amongst the following family members:

DE1064181 (B) FR1121942 (A) US3117085 (A) DE1064181 (B) FR1121942 (A) US3117085 (A) less Translate this text into Tooltip

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The EPO does not accept any responsibility for the accuracy of data and information originating from other authorities than the EPO; in particular, the EPO does not guarantee that they are complete, up-to-date or fit for specific purposes.

785,936 No 37167/54. Application made in United States of America on Dec 24, 1953.

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Complete Specification Published: Nov 6, 1957. Index at Acceptance:-Classes 59, A 7 (D: F: G: K: M), A( 42: 48); and 91, F(l: 2: 3). International Classification:-C 5 l On. COMPLETE SPECIFICATION Improvements in or relating to Incorporation of Solid Materials in Oil. We, TEXACO DEVELOPMENT CORPORAto Nl, a corporation organised under the laws of the State of Delaware, United States of America, of 135, East 42nd Street, New York, 17, State of New York, United States of America, do hereby delare the invention, for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the folloi-ing statement:- This invention relates to the incorporatcedn of a solid material in a lubricating oil such as the compounding of a solid grease comlponent with a lubricating oil in the ueanufacture of grease. In the past greases have been manufactured which contained particles of solid materials such as silica or carbon, but 2 O ditculty was encountered because the -rinding of such solid materials to the necessary fineness was an expensive and time consuming procedure, and furthermore could not be fitted satisfactorily into a confinuous grease manufacturing process Also, netting of some extremely fine solid particles with oil was hard to accomplish. According to the invention, there is proided a method of preparing a suspension dt' a solid material in a lubricating oil, which comprises mixing relatively coarse particles of said solid material with a vaporizable liquid, passing the resulting mixre into a heating zone to vaporize said m,luid and form a dispersion of said solid particles in vapors flowing at a high veloc-y, subjecting said high-velocity dispersion so conditions of turbulence sufficient to red 2 uce said solid particles to fine particles of a greatly reduced size, and compounding sa d fine particles with said lubricating oil. The process of the present invention, V.hen applied to the manufacture of a crease, may comprise mixing the solid ease component with a liquid to form a fluid composition such as a slurry or gel, passing the fluid composition into the initial portion of a long tubular zone, heating the fluid composition in the tubular zone and vaporizing liquid therefrom thereby form 50 ing a dispersion of particles of solid material in vapor, passing this dispersion through the latter portion of the tubular zone at high velocity in turbulent flow such that the solid particles impinge against one another 55 and the tube walls and are converted to fine particles of a size suitable for grease manufacture, and at least partially forming the grease by

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compounding the fine particles with liquid lubricating oil When the solid 60 particles are such that they do not act as a gelling agent in the lubricating oil, soap should be included in the mixture to complete the formation of the grease The described procedure is particularly advantage 65 ous because a large quantitv of solid material can be suspended continuously in a relatively small quantity of liquid, continuous size reduction thus being economically and easily integrated into a continuous grease 70 ' manufacturing process. For illustrating the invention two forms of the process outlined generally above will be described In the first form, solid particles are mixed as a slurry in lubricating oil 75 which is then vaporized in the tubular zone to effect the grinding The lubricating oil vapors then are condensed to form a thickened dispersion of solid particles in the lubricating oil, which dispersion may be with 80 drawn If desired, a soap may be incorporated for example by injecting it into the flowing dispersion of solid particles in the oil vapors before the condensing step. In the second form the solid particles are 85 mixed with water or other liquid to form a fluid composition such as a gel or slurry, and after passage through a heated tubular fluid energy grinder according to the invention the vapors are separated from the 90 PATENT SPECIFICATION 1.'1 q 4 Date of Application and filing Complete Specification: Dec 23, 1954. 785,936 ground solid particles which thereafter are compounded with lubricating oil, with or without the addition of a soap to form a completed grease. The principles of the invention will be described more in detail below with reference to the accompanying drawings, wherein: Figs 1 and 2 are schematic flow diagrams showing arrangements of apparatus for manufacturing a grease by the first and second forms of the process of the invention, respectively The symbol " V " in these diagrams signifies a valve. Referring to Fig 1, relatively coarse particles of a solid unhydrated or hydrated grease component from a supply conduit 10 are mixed with a lubricating oil from conduit 12 in a slurry mixer 11 with or without the addition of conventional additives such as corrosion inhibitors, oxidation inhibitors, and viscosity index improvers (e g high mol wt polymerized olefins through conduit 34) A continuous stream of slurry is then passed at a velocity of 112 to 10 feet per second by a pump through a conduit 13 and into the initial portion of a great length of steel tubing which may be arranged in any desired manner in a heater 17, as in the shape of one or more coils Heater 17 may be fired in any desired way, for example with oil, gas, or coal While only one heater

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17 is shown, it is evident that a series of heaters can be employed, each housing a coil of tubing Tubing 15 can be of any suitable size, for example 1/2 to 1 inch tubing 200800 feet long. In tubing 15 the oil is heated to a temperature at Itast above the lower limit of its boiling range, advantageously above the upper limit also, and vaporizes to form a flowing dispersion of particles of solid material in oil vapors The actual temperature depends upon the particular oil used and the pressure employed, but for substantially complete vaporization in general should be about 100-300 'F above the top of the oil's boiling range, but below about 8000 F to avoil decomposition Operation at relatively low temperatures is achieved by maintaining a vacuum in the system, thus assuring that decomposition will not occur, such operation being especially advantageous when using special lubricating oils such as alcohols and esters having low decomposition temperatures. Another way to avoid high temperatures is to bleed steam or nitrogen into the svstern at any selected point, advantageously before the slurry enters the heater 17, to reduce the partial pressure of the lubricating oil. The dispersion of solids in vapors flows at a high velocity, advantageously in ordinary circumstances in excess of 100 feet per second (fps) and in a highly turbulent manner through the latter portion of the tubing and a conduit 19 During its passage through tubing 15 and conduit 19 the solid 70 particles are greatly reduced in size by forcible impingement against one another and the walls of the tubing Some materials may tend to erode coil 15 if they flow at high velocity therein To prevent such er 75 osion the velocity in coil 15 is kept low, say below 100 fps, and most of the size reduction is accomplished by passing the dispersion at high velocity through a tubular nozzle 21 in the conduit 19 Nozzle 21 may ( have any suitable shape to increase velocity and reduce pressure, such as that of a convergent or convergent-divergent orifice having a throat which, for example, may have a diameter of 118 to 3/16 inch Size 85 reduction also may be accomplished by passing the dispersion at high velocity through a pair of opposed nozzles so that streams impinge against one another at an angle of 180 ' or less Such nozzles can beg 9 fed from a pair of heater coils, or the effluent from one heater coil can be split and fed to both nozzles. The vaporous dispersion then enters a cooler 23 wherein a cooling medium such 95 as water is circulated in heat exchange relationship therewith, for example by flowing over a series of tubes carrying the dispersion In the cooler the temperature of the vaporous dispersion is reduced only 100 sufficiently to condense the oil vapours while any uncondensible gas or water which may be present is maintained in the

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vapor state. From cooler 23 the liquefied dispersion flows through a conduit 25 into a collecting 105 hopper 27, wherein it is agitated continuously by a motor-driven stirrer 29 to assure separation of any steam bubbles therefrom. the steam passing off by way of a conduit 31 at the top of the hopper The liquid pro 110 duct is withdrawn from the bottom of hopper 27 through a valve-controlled outlet 33. Instead of removing steam in hopper 27, or in addition thereto, there may be employed a centrifugal separator between it and the 15 cooler 23, through which air is blown from the bottom to assist in getting rid of steam. The product in hopper 27 will be a grease when the solid particles are of a material that has a gelling action on the lubri 120 cating oil However, when the solid particles are of a material which has little or no gelling action on thelubricating oil a nuantity of soap should be introduced into the dispersion to supplement the solid par 125 tides in their thickening or gelling action. Soap mav be iniected at anv place in the svstem between the mixer l and the outlet 33 We have shown by wav of illustration the introduction of soap from a supplv con 130 785,936 duit 35 into the discharge tube 19, alternatively through a va'lve-coiitrolled condu 5 it 37 upstream of nozzle 21 or a valve-contro Iled conduit 39 downstream of the nozzle. When the soap is injected upstream of the nozzle it is intimately and thoroughly mixed with the vaporous dispersion as it passes through nozzle 21 at high velocity. A less thorough, but still effective, mixing -an be expected when the soap enters cond Juit 19 downstream of the nozzle, or when no nozzle is used It is apparent that soap also may be added in the hopper 27 where it is thoroughly mixed with the oil dispersion by the stirrer 29. The following specific examples illus-rate how the form of the invention described in connection with Fig I can be ap2 plied to prepare specific grease compositions. EXAMPLE I A slurry is made up consisting 82 %' by weight of a mineral oil having a viscosity of 41 SUS (Saybolt Universal Seconds) at 1000 F and a boiling range of 534-700 'F, together with 18 % by weight of graphite fragments averaging about 1/8 inch in diaineter 2200 lbs /hr of this slurry are pumped into 1/2 " heater tubing 15, 600 eet long, wherein it is heated to a temperaAure of 750 'F and vaporizes, the resulting dispersion reaching a velocity in excess of 500 feet per second Nozzle 21 is omitted.

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Thereafter the dispersion enters the cooler 23, and the resulting dispersion of ultra fine carbon particles in oil is discharged into the hiopper 27 as a very fluid hot grease which is withdrawn through outlet 33. EXAMPLE 11 A slurry consisting 18 % of graphite fragments and 820,% of mineral oil is passed through the system of Fig 1 as described in Example I A hot sodium stearate soap at temperature of 250 'F is introduced through conduit 37 in a steady stream flowing in such volume as to provide a mixture containing about 15 % of soap The resulto ing grease leaving the outlet 33 has a thicker consistency than that described in Exam7 le I and sets to form a relatively thick and v'iscous grease when cooled. EXAMPLE III A slurry composed about 40 % by weight -if silica gel particles (containing 60 % water bv weight) 2 4 mesh in size (U S Standard) and about 60 % of a naphthene base 6 o ubricating oil having a viscosity of about SITS at 1000 F and a boiling range of t 19-878 'F is made up in the slurry mixer 11 800 lbs/hr of this slurry are pumped troumh the conduit 13 and a 1/2 " heater i 5 t Slbe 400 feet lone where it is heated to 800 'F and the water of the silica gel and most of the oii content ox the slurry are vaporized The resulting dispersion attains a velocity in excess of 1000 feet per second in passing through nozzle 21 The 70 oil is then condensed in cooler 23 by cooling the vapors to a temperature of 400 'F. while the water vapor from the silica gel remains in the vaporous condition The resulting liquid grease containing ultra fine 75 particles of silica is then passed into the receiver 27 wherein the grease is agitated to cause entrapped water vapor to separate and pass out through conduit 31. EXAMPLE IV The same mixture of silica gel and lubricating oil is made up and passed through the system of Fig 1 as described in Example Ill The gelling action of the ultra fine sili 85 ca however, is supplemented by bleeding in hot liquid sodium stearate soap at a temperature of 350 'F through conduit 37 in a volume to provide 5 1, of soap by weight in the final mixture 90 Referring to Fig 2 of the drawings, the second embodiment of the invention involves mixing a solid grease component from supply conduit 42 with a liquid from conduit 44 in a mixer 41 to form a slurry, 95 conventional additives as hereinbefore described also being introduced through conduit 82 if desired Preferably the slurry employs as the liquid component water or another easily vaporizable liquid other than 100 the oil of the final grease The slurry is then pumped through a conduit 43 into a long heating tube 45

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which may be coiled or otherwise arranged within a gas or oil fired heater 47 The water or other slurry liquid 105 is vaporized by heating it to a temperature well above its boiling point, and a dispersion of solid particles in the resulting vapor is formed which flows continuously at high velocity in turbulent flow through the lat 10 ter portion of tubing 45. The resulting dispersion then passes by a conduit 49 through a nozzle 51 of the type described in connection with Fig 1, and then into a separator 53 wherein the vapor 115 is separated from the solid particles, the vapor passing off at the top through a conduit 55 and the dry solid particles passing continuously out the bottom through an outlet 57 Nozzle 31 is not essential and 120 may be omitted if desired Separator 53 may have any desired conventional construction such as that of a cyclone separator wherein the vapor is separated from the solid particles by centrifugal action, with or without 125 the addition of air blowing up through the separator from the bottom to dry the solid. After the solid particles leave separator 53 a grease is compounded by mixing a lubricating oil with the particles and, where 130 785,936 necessary, by also adding soap to effect gelation Lubricating oil is supplied by a conduit 59 to a heater 61 and thence by a conduit 63 into the outlet conduit 57 for mixture with the solid particles The resulting suspension flows by conduit 65 into a mixer 67 of any suitable conventional construction, such as one having a motordriven spiral mixing screw 69. When the solid particles are of a material such as silica which has a gelling action on lubricating oil it frequently is not necessary to add soap However, when a soap is necessary to effect gelation or to supplement the action of the solid particles it is supplied by a conduit 71 to heater 61 and thence by a conduit 73 into the mixer 67 w-herein it is intimately blended with the oil and solid particles. The economy of operation is improved bky using steam from the top of the separator 53 as the heating medium for the heater 61 Process steam also is passed from heater 61 through a jacket 75 surrounding mixer 67 for heating the grease during compounding This process steam may be su E olemented by the addition of auxiliary ste;> a from conduits 77 and 79. aome solids such as silica can only be wet Ji h great difficulty by the oil employed for makin a arease This difficulty can be alleviated by incorporatihi a small quantity of oil, such as 1 to 5 ' in the liquid cornv-ilnlt of the slurry in 'ixe, 4 anorzin Lie oil with the slurty liquid, ard tnen controllingi the temperature in separator 53 by suitable cooling fluid so tnat only the oil condenses uniformly on the - -ividual fine sold particles Another va; o introduce t"e oil

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into line 49 either befoce or af er t. nozzle 51 and allo v io condense on e surfac-s of the particles in separator 53 The resulting oil "F particles are h blended with lubr cat in oil to form tile Crease Other suitable materials for improving oil wettabilitv a-e alkali and alkar-ne earth metal petroleum sulfonates such sodium and potassium petroleum sulfonates, these materials also acting as dispersingc agents to improve the suspension o' solid particles in slurry liquid. Wettability of the solid particles can also be improved by mixing in the slurry feed L a small quantity, say up to 2-', by weight, of iron or lead salts such as the chloride or nitrate and subsequently bleeding in hydroceo sulfide through a condulit $ 1 or into the separator 53 to form the sulode Which condilions the particles for oil v ettability. The following examnles,Cill illustrate ho-wtz the method describ N connection ith Fia 2 is carried out to produce sneciz geyase compositions. EXAMPTL E Fraaments of graphite abount 1/8 inch in diameter are mixed with water in the mixer 4 i to form a slurry containing 50 ( by Weight of graphite which is then passed at the rate of 700 lbs/hr through the heated tubing 45 for disintegrating the graphite 70 A velocity in excess ot 1700 feet per second is attained by passage through 45 In the separator 53 the steam is separated and passes off through conduit 55 leaving dry hot finely divided carbon particles in the 75 bottom of the separator A stream of a paraffinic lubricating oil havng a viscosity of about 300 SUS at 210 AF is then passed through the heater 61 wherein it is heated to a temperature of 220 F and enters them 8 a conduit 65 for mixture with the carbon particles leaving separator 53 The proportions are such as to produce a final grease containing 25 'A bvweight of carbon and 7 Cf' bv, eht of mineral oil The resulting 85 crude mixture of carbon and oil is delivered to rni xer 67 while a stream of hot aluminum stearate soap at 350 WF is simultaneously supplied from conduit 73 in sufficient volume tor O/Id 5 ' ba eight of soap in the finali 90 creae After mixing thoroughly in the noi Or 67 at a tem 73 rature of 35 ( 0)F the fin-reise is d'schareed through outleb -A HI 3 v LL 95 2 69 parts of silica gel particles 2-4 mesha Iu ime orouhl i:: r 7 K 2: parts of water byr t'P l, a,jor lvr'"on{ of the siia: oms 'a hii _ 1 the water 100 B resulting fuid is passed at a rate of Al Of 9 pourids pr hour through the 1/2 inch t 7 'buiai keatine coils 'S he ein the water hecea to Cale 3 4, to form a fllp<S Oa oig ' aq Ly in excess 105 t -/' g af, ? Ken no b A'ter passing int 5st 3 ihe team is r;'5 v-e thrciumcd 155 and I -de 1 spherical S ii artriees ce t 12 rough outlet 57, havN nreducell sii ze -o b e en 005 and 10 7 m'croa

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dian'e Lr H mineral oil of t t 3 ' SU,,Scolt at li F-F is hz p>ilied throughi condu -t ( i' volume such as prcvide a final crease consisting 85" 'etal oil aand 15 of silica by weight 115 T Airs inid-ure is then passeds into the mixer Ad ezhere an intimate dispers on is accomplished at a temperature of 250 F, after v X-Cla liquid Crease is discharged through -t 1e A 84 120 E Xv AMPLE V Li Finely-divided silica prepared as desCeib ed in Example Vi is mixed with mineral 1 ci of 3001) S US viscosity at l SYRF from conduit 63 in proportions to provide about 125 by weight of silica and 80 , by weight of lubricating oil in the final product This mixture is then passed into mixer 67 which simultaneously is supplied with a sodium stearate soap from conduit 73 in volume to 130 785,936 provide 5 %c,/ by weight of soap in the final grease After intimate mixing at a temperature of 300 TF the resulting liquid grease is discharged through outlet 84. The principles of the invention have been illustrated above in connection with specific grease components It is apparent, however, that they also apply wvhen other components in other proportions are employed. For example, solid particles of many other gelling agents may be used, such as alumina, magnesia; calcium or magnesium hydroxides; ferrous or ferric oxides and hydroxides; vanadium oxide, silicates of magnesium, calcium, and aluminium; calcium sulfate, calcium carbonate, calcium phosphate, clay, and various forms of carbon such as carbon blacks Such gelling agents may be employed in amounts between 1 and 25 % of the final grease by weight, the amount in any specific case depending upon the characteristics of the particular gelling agent employed, the grease consistency desired, and the quantity of soap used in conjunction therewith. Extremely fine sub-division of the particles is necessary, and it is advantageous that they be fine enough so that one gram has a surface area of 200 to 750 square meters as determined by absorption of a mono-layer of nitrogen. All solid materials do not necessarily have a gelling action on lubricating oil. Substances which do not, however, often are used in conjunction with gelling agents to impart specific properties to the grease. Among such additives are asbestos, mica, and talc, all of which may be incorporated in a grease by following the present invention Others are antimony sulfide, metal powders such as aluminium, lead, zinc, and copper; borax, barium sulfate, tricresyl phosphate, and sodium metaphosphate. Such additives may be introduced into the initial mixture through conduits 34 and 82 or at any other selected point Alternatively, two

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separate grinding systems maybe used for two solids, both preferably discharging to a common point where mixture occurs. The oil phase of a grease also can be varied widely, as is well known in the art. In general the oil phase can be composed of lubricating oil fractions of petroleum, which are a mixture of naphthenic, aliphatic, and aromatic hydrocarbons When a natural mineral base lubricating oil is employed it may have a viscosity between 35 SUS at 100 l F and 1,000 SUS at 210 'F depending upon the characteristics of the desired final grease product Synthetic lubricating oils, such as the water soluble monoalkyl ethers of oxy-ethylene-oxy-1,2,-propylene copolymers, may also be employed. One such synthetic lubricating oil sold by Carbide and Carbon Chemicals Corporation under the name "Ucon" fluid (the word "Ucon " is a registered Trade Mark) has viscosihes between 100 and 660 g JUS at Id F. The types of soap used in greases are well known in the art and may be employed in the method of the present invention to produce a grease of the desired final character 75. istics Metal soaps of aliphatic fatty acids and hydroxy fatty acids having more than 11 carbon atoms are generally employed, for example, salts of oleic, palmitic, myristic, arachidic, stearic, hydroxy stearic, and 8 C behenic acids Other soaps are those of sulfonic, resin and naphthenic acids Typical metal radicals in soaps are aluminium, lead and lithium, for example as aluminium stearate, lead 12-hydroxy stearate, or 11th 85 ium 12-hydroxy stearate Other metallic radicals include one or more of copper, cobalt, nickel, cadmium, mercury, strontium, zinc, sodium, and iron. A soap may also be formed in situ by in 91 corporating a soap-forming base such as aluminium hydroxide in the original slurry or gel in mixer 11 or 41, and then later adding a soap-forming organic acid such as stearic acid to the mix after the latter has left the 95 heating coils. While the invention has been specifically described in connection with grease manufacture, it will be apparent that it can be utilized for the incorporation of solid mnat i O o erials into lubricating oils for other purposes. Our prior Specification Serial No. 683,318 describes and claims a process for reducing the particle size of a solid material 105 which comprises admixing said solid in granular form with a vaporizable liquid in an amount sufficient to form a fluid mixture of said solid in said liquid, passing said mixture as a confined stream in turbulent flow 11 o into a heating zone, vaporizing substantially all of said liquid from said mixture in

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said heating zone thereby forming a dispersion of solid particles in the resulting vapor flowing as a confined stream in highly turbulent 115 flow, and maintaining said stream of dispersion in highly turbulent flow over an elongated path, characterised by the fact that the dispersion of solid particles and vapor within said zone attains a velocity of at 120 least 60 feet per second and at least sufficient to shatter said solid particles by collision.

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* GB785937 (A)

Description: GB785937 (A) ? 1957-11-06

Biguanides

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The EPO does not accept any responsibility for the accuracy of data and information originating from other authorities than the EPO; in particular, the EPO does not guarantee that they are complete, up-to-date or fit for specific purposes.

COMPLETE SPECIFICATION Biguanides. We, IMPERIAL CHEMICAL INDUSTRIES LIMITED, of Imperial Chemical House, Millbank, London, S.W.1, a British Company, do hereby declare the invention, for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement:

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This invention relates to new biguanides and more particularly it relates to new bisbiguanides which possess antimicrobial activity and to processes for the manufacture of the said new bis-biguanides. According to our invention we provide the new bis-biguanides which are of the formula: <img class="EMIRef" id="026473770-00010001" /> wherein A stands for a phenyl radical, which may optionally be substituted by alkyl, alkoxy or nitro groups or by halogen, wherein X stands for an alkylene radical of not more than 3 carbon atoms, wherein R stands for hydrogen or for an alkyl radical or an arallryl radical, wherein n is an integer from 2 to 12 inclusive and wherein the polymethylene chain (CH2)n may optionally be interrupted by oxygen atoms and/or by aromatic nuclei, and the salts thereof. According to a further feature of the invention we provide a process for the manufacture of the said new bis-biguanides and the salts thereof which comprises heating a bis-dicyandiamide of the formula: <img class="EMIRef" id="026473770-00010002" /> wherein n has the meaning stated above with an amine of the formula: A-X-NH-R wherein A, X and R have the meaning stated above, or the salts thereof. A suitable salt of the one or more amines may be for example the hydrochloride. The reaction may be carried out in the presence of -an inert diluent or solvent for example water, 8-ethoxyethanol or o-dichlorobenzene and there may also be optionally present a suitable copper compound for example copper sulphate. It is preferred to carry out the said process by heating a mixture of the bisdicyandiamide and a suitable salt of the amine for example the amine hydrochloride within the temperature range of from about 110 C. to about 160"C. According to yet a further feature of the invention we provide another process for the manufacture of the said new bis-biguanides and the salts thereof which comprises heating a diamine of the formula: NH2YCH2)nNH, wherein n has the meaning stated above, or a salt thereof, with a dicyandiamide of the formula : - <img class="EMIRef" id="026473770-00010003" /> wherein A, X and R have the meaning stated above. A suitable salt of the diamine may be for example the hydrochloride. It is preferred to carry out the said process by heating a mixture of the dicyandiamide and a suitable salt of the diamine for example the diamine hydrochloride within the temperature range of from about 110 C. to about 160"C. The higher salts of the said new bisbiguanides for example the bis-biguanide tetrahydrochlorides may be converted into lower salts for example the bis-biguanide dihydrochloride by interaction with a

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suitable ion exchange resin in the presence of an inert diluent or solvent for example water. Moreover certain salts of the new bis-biguanides may be obtained by interaction of the corresponding dihydrochloride, or a mixture of the corresponding tetrahydrochloride and the requisite amount of alkali for example sodium hydroxide, with a suitable alkali metal salt for example sodium acetate in the presence of an inert diluent or solvent for example ethanol. The less soluble alkali metal salt for example sodium chloride is removed by filtration and the desired bis-biguanide salt for example the bis-biguanide acetate may be recovered from the inert diluent or solvent by any means known to the art. As stated above, the new substances are useful as antimicrobial agents. We have found for example that they possess ~ very high bactericidal and bacteriostatic activity when tested in vitro against grame negative organisms for example Salmonella dublin, Bacterium coli and Pseudomonas pyocyanea and against gram positive organisms for example Streptococcus agalactiae (Streptococcus pyogenes Integer), Staphylococcus aureus and Clostridium welchii. Because of their high degree of bactericidal and bacteriostatic activity the new substances are useful for many purposes, for example in medical and surgical practice for sterilisation of instruments or of body tissues, as additions to wood pulp to obviate the decay consequent on the growth of fungi and bacteria, as additives to rubber latex likewise for preservative purposes, for the control of slime in paper mills and they are useful also as mothproofing agents for textiles. The new bis-biguanides may be conveniently used in the form of the salts thereof and particularly those salts derived from the common inorganic acids for example the hydrochlorides or from the common organic acids for example the acetates. The said salts are soluble in aqueous solvents for example water. The said new bis-biguanides are not discoloured when subjected to the action of bleaching agents for example aqueous chlorine or aqueous sodium hypochlorite. The invention is illustrated but not limited by the following Examples in which the parts are by weight: EXAMPLE 1 A mixture of 5 parts of hexamethylenebis dicyandiamide and 5.74 parts of benzylamine hydrochloride is heated at 140-150 C. for 29 hours. It is then dissolved in 40 parts of methanol at 60 C. and the solution is cooled and there is added to it a solution of hydrogen chloride in ether until the reaction mixture is strongly acid to Congo Red. More ether is

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added, if necessary, until precipitation is complete. It is then filtered and the residual solid is dried. 1: 6 - Di - (N' : N,1-benzyldiguanidoNr: N.l)-hexane tetrahydrochloride is obtained as a crystalline solid of m.p. 234--236"C. EXAMPLE 2 A mixture of 2.5 parts of hexamethylene bisdicyandiamide and 3.15 parts of P-pheayl- ethylamine hydrochloride is heated in an oil bath, the temperature of which is 150 160 C., during 1-3- hours. The reaction product is then dissolved in ethanol, clarified with carbon and filtered and the filtrate is diluted with ether. There is thus obtained 1: 6 - di (N1 : Nllss - phenylethyldiguanido - N.: N51) hexane dihydrochloride as a colourless crystal line solid, m.p. 194-19SC. EXAMPLE 3 A mixture of 3.15 parts of N-methylbenzyl amine hydrochloride and 2.5 parts of hexa methylenebisdicyandiamide is heated in an oil bath, the temperature of which is 150 160 C., during 15- hours. The reaction product is then dissolved in ethanol, clarified with carbon and filtered and the filtrate is diluted with ether. The mixture so obtained is filtered and the solid residue is then dissolved in cold ethanol, clarified with carbon and filtered and the filtrate is diluted with ether. There is thus obtained 1: 6-di - (Nl: Nll - benzyl - Nl: Nll- methyldiguanido - Ns: Nsl) - hexane dihydro chloride as a colourless crystalline solid, m.p. 169-172 C. EXAMPLE 4 A mixture of 1.25 parts of hexamethylene bisdicyandiamide and 2.13 parts of 3 : 4-di- chlorobenzylaminehydrochloride is heated in an oil bath, the temperature of which is 150 160 C., during 3 hours. The reaction product is then dissolved in ethanol, clarified with carbon and filtered and the filtrate is diluted with ether. There is thus obtained 1: 6-di (Ni: N11 - 3:4 - dichlorobenzyldiguanido N5 : N11)-hexane dihydrochloride as a colourless crystalline solid,

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m.p. 230--236"C. When~the 2.13 parts of 3 : 4-dichlorobenzyl amine hydrochloride used as starting material are replaced by 1.78 parts of o-chlorobenzyl amine hydrochloride and the period -of heating is 40 minutes instead of 3 hours, there is obtained, in a similar manner, 1: 6-di(Nl: Nll-o-chlorobenzyldiguanido - N5: N11).. hexane dihydrochloride as a colourless crystalline solid, m.p. 197--200"C., after crystallisa .tion from water. EXAMPLE 5 A mixture of 1.25 parts of hexamethylenebisdicyandiamide and 2.13 parts of 2: 6-dichlorobenzylamine hydrochloride is heated in an oil bath, the temperature of which is 150- 160 C., during 30 minutes. The product is then dissolved in 48 parts of hot ethanol, clarified with charcoal and filtered and the filtrate is cooled and diluted with ether. The supernatant liquid is decanted from a sticky residue, further ether is added to the residue and the mixture so obtained is filtered. The solid residue is dissolved in methanol and the solution is diluted with ether to give 1: 6-di(N1: N11 - 2: 6 - dichlorobenzyldiguanidoN, : N51)-hexane dihydrochloride as a colourless crystalline solid, m.p. 234-237 C. EXAMPLE 6 A mixture of 1.25 parts of hexamethylenebisdicyandiamide and 1.88 parts of ,8-p- methoxyphenylethylamine hydrochloride is heated in an oil bath, the temperature of which is 150--160"C., during 3 hours. The reaction product is dissolved in hot ethanol, clarified with carbon and filtered and the filtrate is diluted with ether. The supernatant liquid is decanted from an oily residue, more ether is added to the residue and the mixture so obtained is filtered. The solid residue is then dissolved in cold ethanol, clarified with carbon and filtered. The filtrate is diluted with ether and there is thus obtained 1: 6-di- [N1: N11-P- (p-methoxyphenyl)ethyldiguanido - N,: N,1J- hexane dihydrochloride as a colourless crystalline solid, m.p. 197-200'C. EXAMPLE 7 A mixture of 1.25 parts of hexamethylenebisdicyandiamide and 1.72 parts of a-methyl- ,B-phenylethylamine hydrochloride is heated in an oil bath, the temperature of which is 150- 160 C., during 2-t hours. The reaction product is dissolved in hot ethanol, clarified with carbon and filtered and the filtrate is diluted with ether and the mixture so obtained filtered. The solid residue is dissolved in cold ethanol, the solution is filtered and the filtrate is diluted with ether. The mixture is then filtered and the solid residue is crystallised from water, with clarification by the addition of carbon and there is thus obtained 1: 6-di-(N1: N11 - - methyl - - phenylethyldiguanidoN,: N,1) - hexane

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dihydrochloride as a colourless crystalline solid, m.p. 230232 C. EXAMPLE 8. A mixture of 2.5 parts of hexamethylenebisdicyandiamide and 3.77 parts of p-nitrobenzylamine hydrochloride is heated in an oil bath, the temperature of which is 150--160" C., during 3 hours. The reaction product is dissolved in hot methanol, clarified with carbon and filtered and the filtrate is diluted with ether. The supernatant liquid is decanted from an oily residue, more ether is added to the residue and the mixture so obtained is filtered. The solid residue is dissolved in cold p-eth- oxyethanol, clarified with carbon and filtered and the filtrate is diluted with ether. The supernatant liquid is decanted from an oily residue, more ether is added to the residue and the mixture so obtained is filtered. The solid residue is dried at 63" C. at a pressure of 0.5 mm. of mercury and there is thus obtained 1: 6 - di - (N1 : Nll ~ p - nitrobenzyl- diguanido - N, : N,1)-hexane dihydrochloride as a crystalline solid, m.p. 150--154" C. EXAMPLE 9. A mixture of 1.33 parts of di-n-propyletherco: wi - bisdicyandiamide and 1.44 parts of benzylamine hydrochloride is heated in an oil bath, the temperature of which is 145150 C., during 1 hour. The reaction product is crystallised from water, with clarification by the addition of carbon, and there is thus obtained #:#1-di-(N1:N11-benzyldiguanido-N, N.1) - di - n - propylether dihydrochloride as a colourless crystalline solid, m.p. 198-199". EXAMPLE 10. A mixture of 2.38 parts of di - n - propylether - co: wi - bisdicyandiamide and 3.18 parts of p - chlorobenzylamine hydrochloride is heated in an oil bath, the temperature of which is 150--160" C., during 3 hours. The reaction product is dissolved in water and treated with aqueous ammoniacal copper sulphate solution. The aqueous supernatant liquid is decanted from a tarry residue, aqueous dioxan is added to the residue and the mixture so obtained is filtered. The solid residue is dissolved in dilute aqueous hydrochloric acid and the solution is treated with hydrogen sulphide. The mixture so obtained is filtered and the filtrate is then evaporated to a small volume and diluted with an equal volume of concentrated aqueous hydrochloric acid. There is thus obtained w:wl - di - (Nl: N11 - p - chlorobenzyldiguanido - N, : N,1)-di- n - propyl ether tetrahydrochloride as a colourless crystalline solid, m.p. 223225 C. EXAMPLE 11. A mixture of 2.3 parts of hexamethylenebisdicyandiamide and 3.56 parts of m-chlorobenzylamine hydrochloride is heated in an oil bath, the

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temperature of which is 150--160" C., during 3 hours. The reaction product is dissolved in hot water, clarified with carbon and filtered. The cooled filtrate is diluted with concentrated aqueous hydrochloric acid and there is thus obtained 1: 6-di-(N, : N11 - m chlorobenzyldiguanido - N,: N,1) - hexane tetrahydrochloride as a colourless crystalline solid, m.p. 218221 C. When the 3.56 parts of m-chlorobenzylamine hydrochloride used as starting material are replaced by 4.26 parts of 2:4 - dichlorobenzylamine hydrochloride there is obtained in a similar manner, 1:6 - di - (N1:Ni1. - 2:4 dichlorobenzyldiguanido - N, : N,1) - hexane tetrahydrochloride as a colourless crystalline solid, m.p. 204207 C, EXAMPLE 12. A mixture of 1.25 parts of hexamethylene bisdicyandiamide and 1.58 parts of p-methyl benzylamine hydrochloride is heated in an oil bath, the temperature of which is 150160 C., during 3 hours. The reaction product is dissolved in ethanol, clarified with carbon and filtered and the filtrate is diluted with ether. The mixture so obtained is filtered and the solid residue is then crystallised twice from water with clarification by the addition of car bon. There is thus obtained 1: 6 - di - (N,: N11 - p - methylbenryldiguanido - N1: N11)- hexane dihydrochloride as a colourless crystal line solid, m.p. 211216 C. EXAMPLE 13. A mixture of 1.25 parts of hexamethylene bisdicyandiamide and 2.34 parts of dibenzyl amine hydrochloride is heated in an oil bath, the temperature of which is 150-160' C., during 3 hours. The reaction product is dis solved in ethanol, clarified with carbon and filtered and the filtrate is diluted witch ether. The supernatant mother liquid is decanted from an oily residue and more ether is added to the residue. The mixture so obtained is fil tered and the solid residue is dissolved in the minimum of water and the solution is salted with sodium chloride. The mixture is cooled to 0-5' C. and filtered and the solid residue is washed with ice-cold aqueous sodium chlor ide solution and then dried under vacuum.

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There is thus obtained 1:6 - di - (N1: N11 dibenzyldiguanido - N, : N,1)-hexane dihydro chloride dihydrate as a colourless crystalline solid. EXAMPLE 14. A mixture of 0.46 part of hexamethylene bisdicyandiamide and 0.9 part of 2:4: 5 trichlorobenzylamine hydrochloride is heated in an oil bath, the temperature of which is 150160 C., during 3 hours. The reaction product is dissolved in hot water and the solu tion is added to a hot solution of aqueous ammoniacal cupric chloride. The mixture is cooled and filtered and the solid residue is washed with water and then dissolved in warm dilute aqueous hydrochloric acid. The solution so obtained is treated with hydrogen sulphide and then filtered after addition of carbon.- The filtrate is evaporated to dryness in vacua and there is thus obtained 1:6 - di - (N,: N11-2: 4:5 - trichlorobenzyldiguanido - N:Nl) - -hexane tetrahydrochloride as a colourless crys talline solid, m.p. 207210 C. EXAMPLE 15. A mixture of 1.25 parts of hexamethylene -bisdicyandiamide and 2.06 parts of a - (p - chlorobenzyl) - ethylamine hydrochloride is heated in an oil bath, the temperature of which is 150160 C., during 2,' hours. The reaction product is dissolved in hot ethanol, clarified with carbon and filtered and the filtrate is cooled and diluted with ether. The mixture is filtered and the solid residue is dis solved in hot ethanol, clarified with carbon and filtered. The filtrate is then cooled and diluted with ether and there is thus obtained 1:6 - di - [N1:N11 - ? - (p - chlorobenzyl) ethyldiguanido - N5:N51] - hexane dihydro chloride as a colourless crystalline solid, m.p. 202204 C. EXAMPLE 16. A mixture of 0.7 part of m - xylene w1 - bisdicyandiamide and 0.93 part of p chlorobenzylamine hydrochloride is heated in

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an oil bath, the temperature of which is 150 160 C., during 1 hour. The reaction product is crystallised from water, with clarification by the addition of carbon, and there is thus obtained w: w1 - di- (N,:Nll - p - chloro benzyldiguanido - N,: N,') - m - xylene di hydrochloride as a colourless crystalline solid, m.p. 200203 C. EXAMPLE 17. A mixture of 2.09 parts of p - chlorobenzyl dicyandiamide and 1.23 parts of decamethyl enediamine dihydrochloride is heated in an oil bath, the temperature of which is 150160 C., during 3 hours. The reaction product is crystallised from hot water, with clarification by the addition of carbon, and there is thus obtained 1:10 - di - (N1:N11 - p - chloro - benzyldiguanido - N1: N,1) - decane dihydro chloride as a colourless crystalline solid, m.p. 18018Z C. When the 1.23 parts of decamethylene diamine dihydrochloride used as starting material are replaced by 0.95 part of hexa methylenediamine dihydrochloride, there is obtained, in a similar manner, 1: 6-di-(N,: N11 ~ p - chloro - benzyldiguanido - Ns: N,1)- hexane dihydrochloride as a colourless crystal line solid, m.p. 194-197 C. When the 1.23 parts of decamethylene di amine dihydrochloride used as starting mater ial are replaced by 1.38 parts of dodeca methylenediamine dihydrochloride and the time of reaction is 22' hours instead of 3 hours, there is obtained, in a similar manner, 1:12 - di - (N,: Nll-p-chlorobenzyldiguanido- N5:N51) - dodecane dihydrochloride as a colourless crystalline solid, m.p. 198201 C. EXAMPLE 18. A mixture of 3.48 parts of benzyldicyandi- amide and a hydrochloride, obtained by evaporation of 1.72 parts of decamethylene diamine in methanol and an excess of hydro gen chloride in methanol is heated on a steam -bath during 2-t- hours. The reaction product is - dissolved in dilute aqueous hydrochloric

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acid and the solution is treated with aqueous ammoniacal cupric chloride solution. The supernatant liquid is then decanted from an oily residue and the residue is washed first with dilute aqueous sodium hydroxide solution and then twice with hot water by stirring and decantation. The oily residue is extracted with dilute aqueous hydrochloric acid and the extract is then treated with hydrogen sulphide. The mixture so obtained is filtered and the filtrate is evaporated to dryness in vacuo. There is thus obtained 1: lO-di-(Nl: Nl benzyldiguanido - N5: N51) - decane tetra hydrochloride as a colourless crystalline solid, m.p. 149155 C. EXAMPLE 19. A mixture of 1.74 parts of benzyldicyandiamide and 1.38 parts of dodecamethylenediamine dihydrochloride is heated in an oil bath, the temperature of which is 150160 C., during 3 hours. The reaction product is dissolved in hot water, clarified with carbon and filtered and the filtrate is then cooled and diluted with concentrated aqueous hydrochloric acid. There is thus obtained 1: 12-di(N1: N11 - benzyldiguanido - N5:N51)-dode- cane tetrahydrochloride as a colourless crystalline solid, m.p. 219222 C. EXAMPLE 20. A mixture of 1.95 parts of ethylenebis dicyandiamide, 4.5 parts of benzylamine, and 25 parts by volume of a 20% w/v aqueous solution of hydrated copper sulphate is stirred and heated under reflux in 10 parts of ethoxyethanol for 4-t- hours. The reaction mixture is cooled and filtered, the solid residue is washed first with 50% aqueous u -ethoxyeth- anol and then with water. It is then stirred with dilute aqueous ammonia solution and filtered. The solid residue so obtained is suspended in boiling water and dilute aqueous hydrochloric acid is added and the mixture is then filtered hot. The filtrate is cooled and the mixture so obtained is filtered. Hydrogen sulphide is passed through a filtrate at a temperature of 6070 C. and the mixture is filtered. The filtrate is adjusted to pH 7-8 by the addition of dilute aqueous ammonia and is then evaporated to dryness under reduced pressure. The solid residue is stirred with methanol and filtered. The filtrate is evaporated to dryness and the solid residue is crystallised from a small amount of water to give 1:6 - di - (N,:N11 - benzyldiguanido - N5: Nrl) - ethane dihydrochloride as a colourless crystalline solid, m.p. 238239 C. EXAMPLE 21.

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A mixture of 35.6 parts of o-chlorobenzylamine hydrochloride, 25 parts of hexamethylenebisdicyandiamide and 15 parts of water is stirred and heated in an oil bath, the temperature of which is 145-150' C. for 17 hours. The reaction mixture is diluted with 250 parts of water and the solution so obtained is brought to the boiling point, clarified by the addition of charcoal and filtered. The filtrate is cooled and there is thus obtained 1:6-di(N1: N11 - o- chlorobenzyldiguanido - N5: N,1) - hexane dihydrochloride as a colourless crystalline solid, m.p. 197200 C. EXAMPLE 22. A mixture of 34.6 parts of p-chlorobenzylamine hydrochloride, 24.2 parts of hexamethylenebisdicyandiamide and 14.5 parts of water are stirred and heated under reflux in an oil bath, the temperature of which is 145150 C., during 19Q hours. The reaction mixture is then diluted with 150 parts of water, stirred during 10 minutes and then filtered. The filtrate is made strongly acid to Congo Red, by the addition of concentrated aqueous hydrochloric acid, cooled during several hours and then filtered. The solid residue is washed with dilute aqueous hydrochloric acid and dried and there is thus obtained 1: 6 - di - (N, : N11 - p - chioro- benzyldiguanido - N, : N51) - hexane tetra hydrochloride as a colourless crystalline solid, m.p. 244247 C. What we claim is : - 1. New bisbiguanides which are of the formula:- <img class="EMIRef" id="026473770-00050001" /> wherein A stands for a phenyl radical, which may optionally be substituted by alkyl, alkoxy or nitro groups or by halogen, wherein X stands for an alkylene radical of not more than 3 carbon atoms, wherein R stands for hydrogen or for an alkyl radical or an aralkyl radical, and wherein n is an integer from 2 to 12 inclusive and wherein the polymethylene chain (CH2)n may optionally be interrupted by oxygen atoms and/or by aromatic nuclei, and the salts thereof.

* Sitemap * Accessibility * Legal notice * Terms of use * Last updated: 08.04.2015 * Worldwide Database * 5.8.23.4; 93p

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* GB785938 (A)

Description: GB785938 (A) ? 1957-11-06

Improvements in the production of polyvinyl compounds

Description of GB785938 (A) Translate this text into Tooltip

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The EPO does not accept any responsibility for the accuracy of data and information originating from other authorities than the EPO; in particular, the EPO does not guarantee that they are complete, up-to-date or fit for specific purposes.

PATENT SPECIFICATION Date of filincj Complete Specification: Feb 3, 1956. Application Date: Feb 16, 1955 No 4591155. Complete Specification Published: Nov 6, 1957. Index at Accepta Pne:-Class 2 ( 6), P 7 (D 2 Al: Fl, F 7 Pl(C: El: E 2: ESE 6), P 7 P 2 (Al: A 5: C), P 8 (D 2 B 2: F 1), F 8 P 1 ( 0: El: E 2: E 3: E 6), PSP 2 (A 1 5: 0). International Classilication:-C 08 f. COMPLETE SPECIFICATION. Improvements in the Production of Polyvinyl Compounds. I, HAROLD NEWBY, of British nationality, of 47 Lincoln's Inn Fields, London, W C 2, do hereby declare this invention (which has been communicated to me from abroad by Chemische Werke Huls Aktiengesellschaft, a German Company, of ( 21 A) Marl, Kreis Recklinghausen, Germany), for which I pray that a patent may be granted to me, and the method by which it is to be performed, to be particularly described in and by the following statement: It is already known to prepare polyvinyl compounds by polymerisation of vinyl compounds, such as styrene, substituted styrenes, vinyl esters, vinyl chloride, vinylidene chloride, acrylic acid esters or acrylonitrile, or their mixtures, in aqueous suspensions of pulverulent inorganic compounds insoluble in the monomeric compounds while effecting mechanical movement and with the aid of actvators Barium sulphate, kaolin, phosphates of calcium, barium, magnesium and

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zinc, talc, magnesium carbonate, aluminium hydroxide, kieselguhr, apatite and other minerals may for example be used as insoluble inorganic compounds In this way globular polymers are obtained because the drops of the monomeric vinyl compounds formed by the strong mechanical motion (stirring or shaking) are prevented by the pulverulent inorganic compounds from flowing together or agglomerating during the polymerisation It has also already been proposed to carry out the suspension polymerisation of vinyl compounds in the presence of high molecular weight organic compounds which are colloidally soluble in water, as for example gelatin, polyvinyl alcohol, polyacrylic acid or polyvinyl pyrrolidone The polymers obtained by suspension polymerisation are distinguished from those obtained by emulsion polymerisation by the fact that when suitable suspension agents are used they are clear and colourless and behave considerable more favourably in electrical respects. My foreign correspondents have now found that popyvinyl compounds can be prepared in a specially advantageous manner by polymerising monomeric vinyl compounds in aqueous suspensions of pulverulent inorganic substances which are insoluble in the monomeric vinyl compounds while stirring and with the aid of activators which are soluble in the monomeric vinyl compounds, by working in the presence of small amounts of silicone oils. The term silicone oil is intended to include those organopolysiloxanes and organohydroxypolsiloxanes which have a linear or slightly branched structure and correspond to the formula M Dx M, in which M represents a monofunctional chain member, e g. (CH,)3,Si-, which is connected with the chain by one oxygen atom, D represents a difunctional chain member, such as -Si(CH,)2-, which is connected with the chain by two oxygen atoms and x represents an integer of 50 to 500, as for example alkyl-silicones, in particular methyl-silicones with viscosities of 20 to 2000 centistokes at 20 C, trifunctional chain members, so called T members, such as -Si CH 3, only being present in a subordinate degree (cf E G Rochow, Einffirung, in die Chemie der Silikone, 1952, page 95 et secq) The silicone oils are used in amounts of 0 0001 to 0 1 % by weight with reference to the weight of the monomeric vinyl compound The Dulverulent inorganic substances which are insoluble in the monomeric vinyl compounds and which have a 7859938 grain size between about 0 1 and 1 micron, are used in amounts of from 0 05 to 1 5 % by weight with reference to the weight of the monomeric vinyl compound By varying the amount of the added silicone oil and the added pulverulent inorganic substance it is possible to vary the grain size of the resultant polymer within wide limits. The activators used are soil-soluble compounds which effect the

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polymerisation by decomposition of radicals, as for example benzoyl peroxides, cumene hydroperoxide, lauroyl peroxide, di-tertiary-butyl peroxide and other organic peroxides Nitrogenous activators of the type of azo-di-isobutyronitrile are also suitable In many cases it may be advantageous to use more than one activator in the polymerisation, especially those of which the decomposition temperature lies in different ranges, so that as the polymerisation temperature rises the second or subsequent activator comes into action. The polymerisation temperature is determined by the decomposition temperature of the polymerisation accelerator and lies in the range of 500 to 1300 C The ratio of the organic phase to the aqueous phase can be varied within relatively wide limits, the preferred ratio is approximately 15:1 to 1:1 5, 0 but ratios of 3:1 to 1:3 are possible The p H value of the polymerisation mixture usually lies between 5 and 9. The following Examples will further illustrate this invention but the invention is not restricted to these Examples. EXAMPLE 1. 8 kilograms of styrene to which have been added 16 grams of benzoyl peroxide are added while stirring to a suspension of 64 grams of barium sulphate in 16 litres of water Polymerisation is carried out with vigorous stirring at 85 ' C and is ended after 10 hours The grain size of the resultant Polymer lies between 0 1 and 1 5 millimetres without any sharply defined maximum. If the procedure of the foregoing paragraph is followed with an addition of 500 milligrams of a silicone oil obtainable in commerce under the trade name "Siliconentschaumer Bayer 100 ", the maximum of the grain size lies between 0 5 and 0 6 millimetre and amounts to 75 % of the polymer The remainder is distributed over a 5 larger and smaller grains. EXAMPLE 2. 16 kilograms of styrene activated with 32 grams of benzoyl peroxide are added to an aqueous suspension of 30 grams of tricalcium phosphate in 16 kilograms of water and polymerised for 10 hours at 85 ' C. while stirring vigorously A very inhomogeneous polymer is obtained with a grain size between 0 25 and 1 5 millimetres and a weakly defined maximum at 0 5 millimetre. If the procedure of the foregoing paragraph is followed with an addition of 0 5 gram of the silicone oil used in Example 1, a very homogeneous polymer is obtained with a maximum of the grain size between 0.5 and 0 75 millimetre amounting to more than 85 % of the polymer obtained. If the procedure of the second paragraph of this Example is followed but substituting 8 kilograms of methyl methacrylate for the styrene,

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there is obtained, after washing with hydrochloric acid and removal of the tricalcium phosphate followed by filtration and washing, polymethyl methacrylate with a grain distribution of O 8 to 0 4 millimetre. Coarser and finer grains of polymer are present only to a subordinate extent. EXAMPLE 3. 300 grams of styrene in which are 85 dissolved 9 milligrams of silicone oil, 0 5 gram of benzoyl peroxide and 0 15 gram of di-tertiary butyl peroxide are polymerised with 450 grams of water in which 0 6 gram of tricalcium phosphate is suspended while 90 stirring vigorously in a 2 litre flask provided with a reflux condenser and stirrer The whole is first kept at 855 C for 8 hours, then the temperature is raised to 95 > C. in the course of 2 hours and then for a 95 further 6 hours to 115 ' C, the flask being suspended in an oil bath A granular polymer is obtained having a very narrow grain distribution range with a maximum at 0.5 millimetre 100

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