* GB785383 (A)

Description: GB785383 (A) ? 1957-10-30

Process and apparatus for demetallizing a metal carbonyl-containing gas

Description of GB785383 (A)

COMPLETE SPECIFICATION Process and Apparatus for Demetallizing a Metal Carbonyl Contai: g Gas We, GULF RESEARCH & DEVELOPMENT COMPANY, a corporation organized under the laws of the State of delaware, with place of husiness at Gulf Building, 7th Avenue & Grant Street, Pittsburgh 30, Pennsylvania, United States of America, 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 a process and apparatus for removing metals from a synthesis gas comprising hydrogen and carbon monoxide and containing the metals as carbonyls. More particularly. this invention relates to a process and apparatus for removing catalytic metals and metals employed for making steel alloys from a synthesis gas containing the catalytic and alloying metals as carbonyls. During the hydroformplation of olefines, which is also known as the carbohylation or oxonation of olefins, a product stream is produced which contains a mixture of hydroformylation reaction products and unreacted olefines, carbon monoxide and hydrogen. The hydroformylation reaction products usually contain a large propor- tion of aldehydes and smaller proportions of alcohols, acetals, and other organic products. The product stream is discharged from the hydroformylation stage at a hydroformylation pressure which is usually 105 to 315 kilograms per square centimetre, and a hydroformylation temperature of 38 to 316 C. The hydroformylation product stream also contains, in addition to the products mentioned above, a catalytic metal carbony. The catalytic metal is originally introduced into the hydroformylation reaction

stage as the carbonyl. or is converted to the carbonyl in the reaction zone. Cobalt or iron is usually employed as the catalytic metal. The walls of the hydroformylation reactor and the transfer lines used in the hydroformylation stage are usually made of iron or iron alloys. During the hydroformylation stage some of the metal in the walls of the hydroformylation reactor and the transfer lines finds its way into the hydroformylation reaction product where it appears as a metal carbonyl. In this way iron carbonyl is produced when the walls of the reactor and the transfer lines are constructed of iron and carbonyls of alloying metals are also produced when the walls are constructed of metal alloys. The alloying metal carbonyls, in addition to iron carbonyl, nsually comprise those of nickel, chromium, and molybdenum. The hydroformylation reaction products, the unreacted olefins, carbon monoxide, and hydrogen and the metal carbonyls together comprise the hydroformylation stage products or the total reaction products from the hydroformylation stage. The hydroformylation stage products leaving the reaction zone are generally cooled from a reaction temperature, which may be about 177 C'., to a temperature of 380 to 490 C. and may subsequently be passed to an intermediate pressure separator operating at a pressure substantially below that in the reaction zone and wherein the liquid hydroformylation stage product is separated from unreacted synthesis gas. The liquid hydroformylation stage product is removed from the separator for further processing, while the synthesis gas recovered may be recycled to the fresh synthesis gas feed line where it joins fresh synthesis gas to be used in the hydroformylation reaction zone. Tlie metal carbonyls in the hydro foimylation stage products are volatile, and, consequently, the synthesis gas separated fom the liquid portion of the hydroformylation stage product and recycled to the synthesis gas feed line carries some metal carbonyls along with it bv reason of their volatility. Prior to introducing the synthesis gas into the hydroformylation reaction zone the synthesis gas is compressed to reaction pressure by passing it through a gas compression pump wherein the temperature is high enough to decompose the metal carbonyls and deposit metal on the rotors or pistons thereof, thus causing operating and maintenance difficulties because of the resulting unbalance. Even small amounts of metal are objectionable since, with large throughput of synthesis gas. the metal deposits gradually build up to cause the above-mentioned difficulty. According to this invention it has been found that a synthesis gas

substantially free of metal carbonyls or free metals may be obtained from the synthesis gas carry- ing metal carbonyls recovered from the hydroformylation stage product and recycled to the fresh synthesis gas feed line by a process which comprises separating a gaseous phase comprising synthesis gas and metal carbonyls from the hydrofonnylation stage product, continuously passing said gaseous phase and fresh synthesis gas at an elevated temperature to a demetalling chamber, adjusting the amount and temperature of said fresh synthesis gas so as to obtain a misture of fresh synthesis gas and recovered synthesis gas having a temperature above the decomposition temperature of the metal carbonyl present having the highest decomposition temperature, and removed ing the resulting substantially metal-free mixture comprising fresh synthesis gas recovered synthesis gas from the demetalling zone. When a cobalt compound is employed as the catalyst in the hydroformylation stage, cobalt carbonyl is the metal carbonyl with the lowest decomposition tam- perature present in the hydroformylation misture, and the hydroformylation product is cooled below 669 C. before reducing the pressure to the intermediate pressure of 21 to 31.5 kilograms per square centimetre gauge. When iron is employed at the catalyst in the hydroformylation stage, the hydroformylation product is cooled to a temperature below 149 C. before reducing the pressure. The synthesis gas mixture in the demetalling zone is heated above 66 C., and preferably 74 to 100 C., to decompose cobalt car bonyl, while it is heated above 149 C., and preferably 1710 to 2160 C., to decom- pose iron and other metal carbonyls. When cobalt is employed as the catalyst preferred results are obtained when the demetalling chamber is divided into two zones. one being a decobalting zone, the other being a zone where other metal carbonyls are decomposed. For such an embodiment fresh synthesis gas is added to synthesis gas containing cobalt carbonyls in an amount and at a temperature sufficient to botain a temperature above 66 C. and below 149 C. in the first, or decobalting, zone. The decobalted hydroformylation product is removed from the decobalting zone and passed to the second zone, and additional fresh synthesis gas@@ then added to the second demetalling zone to obtain a new mixture at a temperature above 149 C. and preferably 160 to 216 C. Iron and other metal carbonyls are thus decomposed in the second demetalling zone and a substantially metal-free mixture comprising fresh synthesis gas and recovered synthesis gas is removed from the demetalling zone. The process of this invention can best be understoad by reference to the attached drawing the single figure of which shows a diagrammatic representation of apparatus which can be employed for carrying out the

process of this invention Referring to the drawing, carbon dioxide is introduced by line 5, steam by line 6 and natural gas by line 7 to gas producer 8. Fresh synthesis gas is removed from gas producer S by line 9 at a- synthesis gas temperature such as 81ti C. Steam is passed into line 9 by line 10 to cool the fresh synthesis gas to a temperature of 427 C., and the resulting mixture of synthesis gas and steam is removed by line 11. A portion of the synthesis gas and steam mixture is passed by line 12 containing valve 13, line 14a and 15a containing valve 16a into the upper portion 17a of demetalling tower 18a. Tower 18b is operated in parallel or in place of tower 18a while tower lSa is being reconditioned. However to simplify the description, reference will be made only to tower 18a, it being understood that tower 18b is operated in a similar manner. Accordingly, similar reference numerals, but having different subscripts, have been employed to identify similar parts of the demetalling towers. Synthesis gas recovered from a hydrofoimylation stage in a manner which will be described hereinafter is introduced at a temperature of 43 C. into the upper portion 17a of demetalling tower 18a by line 19 and line 20a containing valve 21a. The mixture of fresh and recovered synthesis gas at a temperature of 66 to 149 C. is passed down through an inert pack ing material 22a, snch as pumice, supported on a foraminous plate 23a in the upper portion 17a of demetalling tower 18a. Cobalt carbonyl in the recovered synthesis gas is thereby decomposed and free cobalt is deposited upon the pumice contained in the upper portion of the demetalling tower. A substantially cobalt-free synthesis gas is removed from the bottom of the formainous plate 23a in the upper portion 17a of demetalling tower 18a and is passed into the bottom portion 24a thereof. A mixture of fresh synthesis gas and steam at a temperature of 427 C. is introduced by line 14a and line 14a1 containing valve 26a into gas demetalling tower 18a below foraminous plate 23a. This mixture of fresh synthesis gas, steam and the decobalted recovered synthesis gas is passed through an inert packing material 25a, such as pumice, supported on formainous plate 27a. As the resulting mixture at a temperature in the range of 171 to 216 C. is passed through the lower bed of pumice, iron and other metal carbonyls are decomposed and frce iron and other alloying metals are deposited upon the pumice. Manholes 28a and 28a1 are provided for removing the pumice from demetalling tower l8a as desired or at intervals during which demetalling tower 18b is on stream. A substantially metal-free mixture of fresh and recovered synthesis

gas removed from tower 18a by line 29a containing valve 30a and by line 31. The demetalling mixture of fresh and recovered synthesis gas is combined with a fresh mixture of synthesis gas and steam from line 11 and line 32 containing valve 32a and the resulting mixture is passed to cooler 33 where it is cooled to a temperature below 93 C. The cooled mixture of fresh and recovered synthesis gas is then passed by line 34 to separator 35. Water is removed from separator 35 by line 36 containing valve 37 and is discharged. The cooled demetalled mixture of fresh and recovered synthesis gas is removed by line 3g and is passed by line 41 through gas compressor 41a to line 42, where it is combined with other charge materials, and then to the hydroformylation stage in the manner which will hereinafter be described. If desired, a portion of the cooled demetalled mixture of fresh and recovered synthesis gas can be removed from the system by line 43 containing valve 44. The specific method of carrying out the hydroformylation reaction forms no part of the present invention and any suitable procedure may be used such as one involving the use of a fixed bed reactor. Thus a procedure may be employed wherein the synthesis gas, olefin and catalyst, intro duced in the form of a salt of the metal, are flowed through an elongated reaction zone under turbulent flow conditions while controlling the temperature by indirect heat exchange withu a liquid such as water. Rererring to the drawing, in a typical example, catalyst which may be, for example the cobalt salt of any suitable organic acid, such as a fatty acid, prefer ably one containing at least 6 carbon atoms, of a naphethenic acid, is passed by line 45 into line 42, and a suitable olefin. such as heptene, is passed by line 46 to line 42. The resulting mixture of fresh and recycled synthesis gas, catalyst and olefin is passed by line 42 into an elongated reaction zone which. in a preferred enbodiment, is in the form of a coil 47 in a body of water under pressure at its boiling point at that pressure in the hydro formylation reaction 48. For example, for a reaction temperature of 177 C. the water should be maintained at a pressure of 8.4 kilograms per square centimetre gauge. The water is introduced through

line 49 containing valve 50 and the pres sure is maintained by means of a pressure control valve 61 in line 52 which releases the steam generated by reason of the exothermic reaction occurring within coil 47. The elongated reaction zone or coil 47 is extremely long compared to its diem eter. Thus it may be a pipe 25 to 125 milli metres in internal diameter having an elongation factor (ratio of length to diameter) of at least 1440. Under the con ditions indicated, the synthesis gas, olefin and catalyst are flowed through the reaction zone under turbulent flow conditions and the desired hydroformylation reaction resulting in the production of aldehydes accomplished. During the initial stages, the cobalt salt is apparently converted to cobalt carbonyl and thereofore the hydro formylation product removed through line 53 contains aldehydes, some alcohols, unreacted olefins and synthesis gas and cobalt carbonyl. Also even in cases where iron is not employed as a catalyst, the product frequently contains a small amount of iron and/or other alloying metals which, as has been pointed out hereinabove, is picked up from the equip ment employed. The hydroformylation product at sub stantially the reaction temperature is then passed by line 53 to cooler 54 to reduce the temperature to 38 to 49 C. and then passed by line 55 into high pressure separator 66 from which excess synthesis gas is removed through line 57 contain ing pressure control valve 58. The hydro formylation product is passed from separator 56 through line 57 containing pres sure control valve 58. The hydroformylation product is passed from separator 56 through line 59 to a pressure reducing valve 60 wherein the pressure is reduced to an intermeditate pressure of 21 to 31.5 kilograms per square centimetre gauge. Liquid hydroformylation product is then passed by line 61 to intermediate pressure separator 62. Liquid hydroformylation product is removed from intermediate pressure separator 62 and is passed through line 63 for further processing. Unreacted synthesis gas comprising hydrogen and carbon monoxide anc

containing metal carbonyl is removed overhead from intermediate pressure separator 62 by line 64 containing pressure control valve 65 and is then recycled by line 66 and line 19 to either or both of the demetalling towers at a temperature of 430 C. for processing in the manner which has been described hereinabove. If desired, a portion of the- synthesis gas containing cobalt and alloying metal carbonyls, can be vented from the system by line 67. An example of the process of this invention will now be described. 362 standard cubic metres per hour of synthesis gas containing hydrogen and carbon monoxide in a mol ratio of 1 : 1 are removed from gas producer 8 by line 9 at a temperature of 760 C. 510 standard cubic metres per hour of superheated steam are passed by line 1-O into the synthesis gas and the resulting misture at a temperature of 427 C. is removed by line 11. 63.7 standard cubic metres per hour of the 427 C. gas mixture are passed by line 12 through valve 23 to demetalling tower 18a while the remaining gas is passed forward through line 3.2 where it joins the effluent from line 31. 14.9 standard cubic metres per hour of the hot gases passing through valve 13 are led by lines 14a and 15a into the upper portion 17a of demetalling tower 18a. 100 standard cubic metres per hour of the recovered synthesis gas at a temperature of 43 C. are passed by lines 19 and 20a into upper portion 17a of demetalling tower 18a. The recycled gas contains 0.384 kilogram of cobalt and 0.112 kilogram of iron per 1000 standard cubic metres of recycled gas. 14.9 standard cubic metres per hour of the hot gas mixture passing through valve 13 are mixed with the 100 standard cubic metres of recovered gas in the upper portion 17a of demetalling tower 18a to obtain a mixture having a temperature of 93 C. 48.85 standard cubic metres per hour of the 427 C. gas mixture passing through valve 13 a re passed by line 14a1 into lower portion 24a of demetalling tower 18a intermediate catalyst beds 22a and 25a and are there mixed with the effluent from top bed 22a to obtain a mixture temperature of 193 C. before entering the bottom bed where the iron and alloying metal, if any. are deposited. Synthesis gas so treated will contain about 0.0032 kilogram of cobalt and about 0.00096 kilogram of iron per 1000 standard cubic metres. The purified recovered gas, admixed with the mixture of fresh synthesis gas and steam used for heating them, is then passed into rllain stream 32 which is at 4270 C. and the resultant mixture is passed to cooler 33. It should be noted that the recovered gas onters the system at 43 C. and leaves cooler 33 at approximately the same temperature, and therefore the duty of cooler 33 is not increased over that normally required to cool the fresh synthesis gas alone. The steam is removed from the resultant misture of fresh and recovered

synthesis gas in separator 83 and the resulting substantially metal-free misture of fresh and recovered synthesis gas is passed by lines 41 and 42 into hydroformylation reactor 48. Nine and a half kilograms of cobalt catalyst and 590 kilograms of olefin per hour are also introduced into the hydroformylation reactor 48. After passing through the hydroformylation reactor 48. cooler 54, high-pressure separator 56, pressure reducting valve 60 and intermediate pressure separator 62 in the manner previously described, 100 standard cubic metres per hour of synthesis gas are then recycled to demetalling tower 18a. What we claim is: 1. A process wherein synthesis gas comprising carbon monoxide and hydrogen are reacted with an olefin in the presence of a cobalt or iron catalyst in a hydroformylation reaction zone at an elevated pressure and an elevated temperature to obtain a reaction product comprising an aldehyde, unreacted synthesis gas comprising carbon monoxide and hydrogen and at least one metal carbonyl, and in which the unreacted synthesis gas carrying at least one metal carbonyl is subsequently recovered from said reaction product and recycled to the hydroformylation reaction zone, characterized in that said recovered gas is demetalled during the recycling process by passing said recovered synthesis gas misture and heated fresh synthesis gas to a demetalling chamber, the amount and temperature of the heated fresh synthesis gas entering the demetalling chamber being adjusted to obtain a mixture of fresh synthesis gas and recovered synthesis gas having a temperature higher than the decomposition

* GB785384 (A)

Description: GB785384 (A) ? 1957-10-30

Improvements relating to vulcanizable vinyl containing organopolysiloxanes

Description of GB785384 (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.

COMPLETE SPECIFICATION Improvements relating to Vulcanizable Vinyl containing Organopolysiloxanes We, GENERAL ELECTRIC COMPANY, a Corporation of the State of New York, United States of America, having its office at Schenectady 5, State of New York, Vuited States of America, 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 vulcanizable vinyl-containing oraunopolysiloxanes having carbon black and sulphur incorporated therein, to the process of vulcanizing these vulcanizable materials, and to the resulting vulcanizates. In the past, attempts have been made to form carbon black filled organopolysilosane elastomers by various methods However, in general, only inferior pro ducts have been obtained since the general method of cross-linking organopolysiloxane gums has been with typical free radical polymerization agents such as the acyl perosides, e.g., benzoyl peroxide, or with azo compounds such as ?,?1-azodiiso- butyronitrile. In general, these free radical cross-linking agents have been found to be relatively ineffective in polymerizing organopolysiloxane systems containing carbon black, presumably because of some reaction which occurs between the cross-liiiking agent and the carbon black. We have now discovered that by forming a highly viscous organopolysiloxane liquid or gum within the scope of the formula (I) hereinafter given which contains silicon bonded vinyl radicals, we are able to incorporate carbon black, and sulphur as the curing agents, into the vinylcontaining organopolysiloxane, and to vulcanize the resulting mixture by heat. The resulting vulcanizates are characterized by their flexibility at temperatures below 50 C., by their outstanding thermal stability at temperatures as high as 150 C., by their high tensile strength and elongation, and by their conducting properties. The vulcanizates are also characterized by their low cost because of use of the relatively inexpensive carbon black filler instead of the more expensive silica areogel which is usually used in organopolysiloxahe elastomers. The vulcanizable mixture according to this invention comprises from 60

to 94.5 parts by weight of an organopolysiloxane convertible to the solid, elastic state and having the average structure formula: (1) (CH2=CH)2(R)bSiO4-(2a+b) where a has a value of from 0.0086 to 0.18, b has a value from 1.80 to 2.0014 and the sum of a + b is equal to from 1.98 to 2.01, from 5 to 40 parts by weight of carbon black and from 0.o to 5 parts by weight of finely divided sulphur. In the above formula R represents organic radicals, at least 50 mole per cent of which are methyl, with the remainder (if any) of the radicals being selected from alkyl radicals, e.g., ethyl, propyl, butyl, octyl, decyl and octadecyl; cycloalkyl radicals. e.g., cyclohexyl and cycloheptyl; aryl radicals, e.g., phenyl, diphenyl and naphthyl; alkaryl radicals, e.g., tolyl, xylyl and ethylphenyl; aralkyl radicals, e.g., beuzyl and phenylethyl; and halogenated aryl radicals e.g., chlorophenyl and dibromophenyl. The vinyl-containing organopolysiloxane liquids and gums of formula (1) which may be compounded with carbon black and sulphur and subsequently vulcanized, may be described as organopolysiloxanes containing an average of from 1.98 to 2.01 organic radicals bonded to silicon through silicon carbon linkages with the rmainder of the valencies of the silicon atoms being satisfied by siliconoxygen linkages. Of these silicon bonded organic radicals, from 0.0086 to 0.18 silicon bonded vinyl radicals are present per silicon atom. The liquids and gums within the scope of formula (1) may be formed in the well known manner by the rearrangement and condensation (polymerization) of lower molecular weight organopolysiloxanes in the presence of a suitable organopolysilosane polymerization catalyst. The relatively low molecular weight starting materials used for the realTangement and condensation may comprise any mixture of low molecular weight organopolysiloxanes in which the silicon bonded organic radicals are present in a ratio suitable to give the desired general structure of formula (1) upon rearrangement and condensation. The viscous liquids and gums within the scope of formula (1) may be prepared by copolymerizing a low molecular weight organopolysiloxane containing silicon bonded vinyl radicals with one or more low molecular weight organopolysiloxanes containing only saturated hydrocarbon radicals attached to silicon The low molecular weight organopolysiloxanes containing silicon bonded vinyl radicals and the method of forming compositions within the scope of formula (1) are well known, see, for example, Patents Nos. 620,693 and 618,451. The relatively low molecular weight organopolysiloxanes containing a silicon bonded vinyl radical may be prepared, for example, by hydrolazing a silane containing at least one silicon bonded vinyl radical and at least one silicon bonded hydrolyzable group.

Thus, methylvinylsiloxanes may be prepared by hydrolyzing methylvinyldichlorosilane or methylvinyldiethoxysilane with water or aqueous HCl. This hydrolysis results in an aqueous phase and an organopolysiloxane phase containing both linear and cyclic methylvinyl- siloxanes of varying chain lengths. After hydrolysis, the organopolysiloxane phase may be distilled to isolate compounds such as 1,3,5-trimethyl-1,3,5,trivinylcyclotrisiloxane, 1,3,5,7-tetramethyl-1,3, 5,7-tetravinylcyclotetrasiloxane, 1,3,5,7, 9-pentamethyl-1,3,5,7,9-pentavinylcyclopentasiloxane, 1,3,5,7,9,11-hexamethyl1,3,5,7,9,11- hexavinylcyclotetrasiloxane, as well as higher cyclic methylvinylsiloxanes and a number of linear methylvinylsiloxanes. Other organopolysiloxanes containing silicon bonded vinyl radicals may be prepared by hydrolyzug silanes such as divinyldichlorosilane, divinyldiethoxysilane, vinyltriethoxysilane and trivinylchlorosilane, and separating the organopolysiloxane phase from the aqueous phase. The low molecular weight organopolysiloxane containing only saturated hydrocarbon radicals bonded to silicon with which the vinyl-containing organopolysiloxane is copolymerized, may be one or more cyclic organopolysiloxanes having the formula : (2) (R1)2SiOn where n is an integer from 3 to 10 or more and each R1 is selected from: alkyl radicals, e.g., methyl, ethyl, propyl, butyl, octyl and decyl; cycloalkyl radicals, e.g., cyclohexyl and cycloheptyl; aryl radicals, e.g., phenyl diphenyl and xylyl; aralkyl radicals, e.g., benzyl and phenylethyl; and haloaryl radicals, e.g., chlorophenyl and dibromophenyl. Typical compounds within the scope of formula ( ) include, for example, octamethylcyclo- tetrasiloxane, tetramethyltetraethylcyclotetrasiloxane and octaphenylcyclotetrasiloxane. In addition to supplying the saturated organopolysiloxane to the copolymer by means of the cyclic compounds within the scope of the formula (2) the saturated organopolysiloxanes may be also added in the form of the hydrolyzate of difunctional silanes such as the hydrolyzate of dimethyldichlorosilane, diethyldichlorosilane and methylethyldiacetoxysilane. Where it is desired to produce a gum withuin the scope of formula (1) where the sum of a + b is less than or greater than 2.00, trifunctional or monofunctional silosane units may be added in sufficient amount to produce the desired functionality in the polymerized product. The trifunctional siloxane units may be added as monoalkyl siloxane units in the usual fashion as the partial hydrolyzate of trifunctional alkyl siloxanes such as methyltrichlorosilane, methyltriacetoxysilane and ethyltrichlorosilane. These partial hydrolyzates of the trifunctional compounds may be prepared by hydrolyzing the trifunctional compounds with hydrochloric

acid or the like and separating the silicone layer from the aqueous phase. The monofunctional siloxane units may be a dded as trialkyl siloxane units and are most conveniently employed as part of a trialkylsilyl chainstopped alkyl polysiloxane such as hexamethyldisiloxane, octadecamethyloctasiloxane or other linear or branch-chain trialkylsilyl chain-stopped organopolysilosane such as are described in Patent So. 586,187. In selecting the particular saturated organopolysiloxanes to be copolymerized with the vinyl-containing organopolysiloxane, eale must be taken to ensure that enough silicon bonded methyl radicals are present so that at least 50 mole per cent of the R radicals of formula (1) are methyl. A typical mixture of an organopoly siloxane containing silicon bonded vinyl radicals and an organopolysiloxane containing only saturated organic radicals which may be used to form compositions within the scope of formula (1) is a mixture of 1,3,5,7,-tetramethyl 1,3,5,7,tetravinylcyclotetrasiloxane with octamethylcyclotetrasiloxane. After mixing these two compounds they may be rearranged and condensed (polymerized) to a gum by effecting reaction with a suitable organopolysiloxane polymerization catalyst. The low molecular weight organopolysiloxane containing silicon bonded vinyl radicals and the organopolysiloxane containing only saturated organopolysiloxane radicals may be copolymerized with known organopolysiloxane polymerization catalysts. Thus, vinyl-containing organopolysilosane mixtures may be polymerized to gums readily using from about 0.001 to 0.5 per cent, by weight, of a caseium hydroxide or rubidium hydroxide at elevated temperatures of the order of from about 110 to 1.50' C. in times ranging from about 10 to 30 minutes. These same mixtures may be also polymerized to gums with the transient organopolysilosane polymerization catalysts in a matter of minutes at temperatures of from about 110 to 130" C. These transient organo polysiloxane polymerization catalysts include the quaternary phosphonium hydroxides and quaternary phosphonium alkoxides. Typical quaternary phosphonium hydroxide, transient catalysts are tetra-n-butyl phosphonium hydroxide and butyltricycloheyl phosphonium hydroxide. These transient organopolysitoxane polymerization catalysts also include the solid quaternary ammoniuln hydroxides. These quaternary ammonium hydroxide catalysts are tetramethyl ammonium hydroxide and benzyltrimethyl ammonium hydroxide. In general, polymerization of the low molecular weight vinyl-containing organopolysil oxane mixture within the scope of formula (1) is effected by heating to a temperature of about 110 to 150 C. and then adding the desired the organopolysiloxane polymerization catalyst. llow- ever, if desired the catalyst may be added prior to heating of

the mixture to cause polymerization to a gum to be effected when the mixture is later heated to tem- peratures of the order of 110 to 150 C. The higher molecular weight vinyl-containing organopolysiloxane gum prepared by polymerizing an organopolysiloxane mixture having the average composition within formula (1) referred to hereinafter for the sake of brevity as " vinyl-containing gum A vulcanizable product may be prepared from the vinyl-containing gum described above in the same manner as vulcanizable materials are formed from natural and synthetic hydrocarbon rubber gums. Thus, the vinyl-containing gum may be mixed with carbon black; and finely divided sulphur as well as with accelerators, if desired, on differential rubber milling rolls. When incorporating a vulcanization accelerator into the product it is desirable to employ from 0.1 to 2.0 parts, by weight, of accelerator. Any of the typical vulcanization acelerators may be employed effectively to speed up the rate of vulcanization of the products. Among the accelerators are included, for example, mercaptobenzothiazole, diphenylguanidine, triphenylguanidine, tetramethylthiuramdisulphide, zincdimethyldithiocarbamate, thiocarbanilide, hexamethylenetetramine and benzothiazodisulphide. The milling operation may be carried out by adding the vinyl-containing gum to the rubber milling rolls and then adding the other ingredients which go into the compounded rubber. After the ingredients of the rubber are thoroughly mixed, which may be after a few minutes or few hours of milling depending on the rate of milling and the amount of material being milled, the milled products is removed from the rolls. This milled material may then be stored until it is desired to prepare the finished product or may be immediately calendered on heated rolls to form sheet material, extruded into various elongated shapes, or moulded in heated presses to form a vulcanized product of the desired shape. where presses are employed for curing the compounded gum, temperatures of from about 100" to 17o C. are employed for cure times which vary from 5 minutes to an hour depending the cure temperature used. The following examples are illustrative of the practice of the present invention and are not intended for purposes of limitation. EXAMPLE 1 This example described the preparation of low molecular weight organopolysiloxanes containing silicon bonded vinyl radicals. A mixture of 1000 grams (6.2 moles) of redistilled methylvinyldiethoxysilane (boiling point 133 C. at 1.0 atmosphere, refractive index nD20 1.4001, density d420 0.8620) and 1000 ml. of 6 normal hydrochloric acid refluxed for 72 hours. The resulting lower

organopolysiloxane phase was washed four times with distilled water, then dried over anhydrous potassium carbonate and filtered. This resulted in a mixed methylvinylsiloxane oil containing both cyclic and linear methylvinylpolysiloxanes of varying chain lengths. This oil was distilled rapidly after the addition of 1 per cent, by weight, of p-tert-butyl catechol as a polymerization inhibitor. The distillation was carried out at 0.5 mm. using a 12" Vigreux column. The fraction boiling between 60 and 135 C. at 0.5 mm. was collected and after the addition of another one per cent, by weight, of p-tert-butyl catcehol the distillate wsa fractionated under re duced pressure in a " by 16" protruded-packed column. This fractionation yielded (1) a fraction boiling at 111 to 112 C. at 10 mm., (2) a fraction boiling at 115 to 143 C. at 11 mm., and (3) a fraction boiling at 143 to 172.5 C. at 11 mm. Fraction (1) corresponded to 1,3,5,7,tetramethyl 1,3,5,7,-tetravinylcyclotetrasiloxane. Analysis of this compound showed it to contain 41.9 per cent carbon, 7.2 per cent H, 32.5 per cent Si; to have a molecular weight of 346 by cryoscopic determination using a solution of 0.240 grams of the siloxane in 19.17 grams of cyclohexane, and a molar refractivity. MRD 90.83. Theoretical values are 41.8 per cent carbon, 7.02 per cent hydrogen, 32.6 per cent silicon, molecular weight 344.7, MRD 91.20. Distillation of this compound in a small Vigreux column at atmospheric pressure without polymerization or decomposition showed its boiling point to be 224 to 244.5 C. at 758 mm. Fraction (2) was washed with 25 ml. portions of 1 per cent sodium carbonate until the p-tert-butyl catechol was removed (as evidenced by a negative ferric chloride test on the aqueous solution). The oil was dried over anhydrous potassiunl carbonate and distilled under reduced pressure in a " x 16" protruded-packed column. Distillation yielded 1,3,5,7,9pentamethyl - 1,3,5,7,9-pentavinylcyclopentasiloxane at 145 to 146 C. at 13 mm. This compound was analyzed and found to contain 41.6 per cent C, 7.2 per cent H, and 32.8 per cent Si, with a molecular weight of 437 and MRD 113.58. This compares with the theoretical values of 41.8 per cent C, 7.02 per cent H, 32.6 per cent Si, with a molecular weight of 430.8 and MRD 114.00. This siloxane could be distilled without polymerization or decomposition at 260 to 262 C. under 750 mm. Fraction (3) was re distilled under reduced pressure in a " x 16" protrudedpacked column to give pure 1,3,5,7,9,11hexamethyl-1,3,5,7,9,11-hexavinylcyclohexasiloxane which boiled between 160.5 and 161 C. at 5 mm. Analysis of this compound showed it to contain 41.3 per cent C, 7.1 per cent H, 31.3 per cent Si, with a molecular weight of 536 and MRD 135.58. This compares with

the theoretical values of 41.8 per cent C, 7.02 per cent H, and 32.6 per cent Si, with a molecular weight of 517.0 and MRD 136.80. This compound was distilled at atmospheric pressure and found to have a boiling point of 296 to 297 C. at 750 mm. The boiling points, melting points, indices of refraction and densities of the three compounds isolated above are listed in Table I. TABLE I Siloxane B.p. C. mm. M.P. C. nD20 d420 (CH3) (CH2=CH)SiO4 111-12 10 -43.5#0.1 1.4342 0.9875 224-224.5 758 (CH3) (CH2=CH)SiO5 145-146 13 -140 to - 136 1.4373 0.9943 261-262 758 (CH3) (CH2=CH)SiO6 160.5-161 5 - 123 to -119 1.4400 1.0050 172-172.5 11 296-297 758 EXAMPLE 2 A vinyl-containing organopolysiloxane gum was prepared by adding 3 parts, by weight, of 1,3,5,7,9-pentamethyl-1,3,5,7, 9-pentavinylcyclopentasiloxane to 97 parts, by weight, of octamethyleyclotetrasiloxane and heating the mixture to 135 C. At this point 0.05 per cent, by weight, of caesium hydroxide was added and the mixture polymerized to a gum within about 15 minutes. This vinyl-containing gum had the av erage s tructural formula (CH2-CH)0.026(CH2)1#974SiO. In a similar fashion, gums containing 2.0 to 4.0 per cent, by weight. of 1,3,5,7,9-pentamethyl1,3,5,7,9-pentavinylcyclopentasiloxane in octamethylcyclotetrasiloxane were prepared using amounts of caesium hydroxide as a polymerization catalyst which varied from about 0.001 to 0.5 per cent and using polymerization temperatures from about 130 to 150 C. This resulted in vinyl- containing gums of the average s tructural formulas (CH2=CH)0.017(CH3)1.983SiO and (CH2-CH).035(CH3)1.965SiO. respectively. EXAMPLE 3 A gum containing diphenyl siloxane units may be prepared by the method of Example 2, for example, by adding 3 part, by weight, of 1,3,5,7-tetramethyl1,3,5,7-tetravinylcyclotetrasiloxane, 47 parts, by weight, of octamethylcyclotetrasiloxane, and 50 parts, by weight, of octa phenylcyclotetrasiloxane to a temperature of about 150 C. and adding about 0.05 per cent, by weight, of caesium hydroxide based on the total weight of the organopolysiloxanes present. In a matter of 10 to 20 minutes a stiff gum will be formed. EXAMPLE 4 A carbon-filled, sulphur vuleanized organopolysiloxane rubber was prepared by milling together 50 grams of the 3 weight per cent

vinyl-containing organopolysiloxane gum of Example 2, 25 grams of carbon black (Kosmos 60) 1.5 grams of sulphur, 0.63 grams of benzothizodisulpride (Altax), and 0.13 gram of diphenyl guanidine. (" Xosmos is a Registered Trade lMarl). These ingredients were milled on differential rubber milling rolls for about 30 minutes until a uniform product was obtained. This product was press cured for 30 minutes at 150 C. to yield a rubber which had a tensile strength of 800 p.s.i. and an elongation at break of (;00 per cent. This rubber exhibited extremely high tear resistance, as indi cated by the fact that a notched sample was extremely difficult to tear and upon stretching the rubber, it was observed that it got warm just at natural rubber does in s tretching. This rubber was flexible at - 70 C. EXAMPLE 5 Another carbon-filIed, sulphur vulcanized organopolysiloxane rubber may be prepared by adding 10 parts, by weight of 1,3,o,7,-pentametllyl-1,3,A,7,-penta vinylcyclopentasiloxane to 90 parts, by weight, of octamethylcyclotetrasiloxane and heating the mixture to about 150 C. At this time 0.05 per cent, by weight, of caesium hydroxide are added and after 15 minutes a high molecular weight gum is obtained. This gum will have the average structural formula (CH2-CH)0.087(CH3)1.931 SiO. One hundred grams of this gum may be mixed with 30 grams of carbon black (Kosmos 60), 2 grams of mercaptobenzothiazole, 1 gram of diphenyl guanidine, and 4 grams of sulphur. The mixture is then milled on differential rubber milling rolls for about 30 minutes until an intimate mixture is obtained. The milled product may then be press cured at 150 C. for 60 minutes to yield an organopolysiloxane rubber which has a high tensile strength and which is flexible at temperatures as low as - 70 C. EXAMPLE 6 A vinyl-contlaining gum was prepared by mixing 3 grams of 1,3,5,7,-tetramethyl - 1,3,5,7 - tetravinylcyclotetrasiloxane prepared by the method of Example 1 with 97 grams of octamethylcyclotetrasiloxane and about 02 grams of tetrabutylphosphonium hydroside. This mixture was heated to a temperature of about 110 C. and after about 15 minutes a high molecular weight gum was obtained. Fifty grams of this gum were mixed with 25 grams of carbon black (Kosmos 60), 0.8 gram of benzothiazosulphide and 1.5 grams of sulphur. The mixture was milled

on differential rubber milling rolls for about 20 minutes until an intimate mixture was obtained. This milled product was then press cured at 150 C. for 45 minutes to yield and organopolysiloxane rubber having a tensile strength of 960 p.s.i. and an elongation at rupture of about 400 per cent. Although the vinyl-containing organo polysiloxane gums of the present invention have been described in the preceding examples only in terms of gums having a ratio of organic radicals to silicon atoms of 2.0, it should be understood that gums having a ratio of organic radicals to silicon atoms of from 1.98 to 2.01 may be prepared by the method of Example 2 by adding monofunctional or trifunctional siloxane units to the low molecular weight mixture before polymerization. With regard to the phenyl-containing siloxane units in the present invention it should be understood that the phenyl radicals may contain nuclear substituents such as, for example, alkyl radicals, e.g., methyl ethyl, propyl, butyl and octal, aryl radicals, e.g., phenyl, tolyl and naphthyl, as well as halogen substituents such as, for example, fluorine, chlorine and bromine. Although the sulphur vulcanized rubbers of the present invention have been described as containing only sulphur and accelerating agents, it should be understood that these rubbers may be compounded in the same manner as hydrocarbon rubbers with various additives such as accelerator activators, antioxidants, softeners and inhibitors. The vulcanizable organopolysiloxane, carbon black:, and sulphur mixtures of the present invention are valuable as intermediates in the preparation of sulphur cured organopolysiloxane rubbers. The sulphur cured organopolysiloxane rubbers have utility as gaskets and the like in applications where resilience and thenna.l stability are necessary at extremes of temperature. The carbon-filled, sulphur cured organopolysiloxane rubbers are particularly valuable because of the conducting property imparted to the rubber by the carbon filler. These carbon-filled rubbers are useful in applications where both flexibility and conductivity are required. A typical application is in the manufacture of flexible heating elements where the same number is required to be both flexible and conducting. What we claim is: - 1. A vulcanizable mixture comprising (A) from 60 to 94.5 parts, by weight, of an organopolysiloxane convertible to the solid, elastic state and having the average structure formula: (1) (CH.2=CH)a(R)bSiO4-(2a+b) where each R is an alkyl, cycloalliyl, aryl, alkaryl, aralkyl, or halogenated aryl radical, at least j01 mole per cent of said radicals being methyl radicals, a has a value from 0.0086 to 0.18, b has a value from 1.80 to 2.0014, the sum of a+b being equal to from 1.98 to 2.01, (B) from 5 to 40 parts. bv weight,

of @ carbon black, and (C) from 0.5 to 5 parts, by weight, of sulphur. 2. A vulcanizable mixture as claimed in Claim 1, comprising from 0.1 to 2.0 parts by weight, of a rubber vulcanization accelerator. :3. A vulcanizable mixture as claimed in Claim 1 or in Claim 2 wherein R in the formula represents methyl only. 4. The product prepared by heating the mixture claimed in any of Claims 1 to 3 until vulcanization has been effected.

* GB785385 (A)

Description: GB785385 (A) ? 1957-10-30

Apparatus for measuring muscular forces involved in various movements

Description of GB785385 (A)

PATENT SPECIFICATION Date of Application and filing Complete Specification: Aug 10, 1955. 785,385 No 23026/55. K 1 1 1 Application made in France on June 29, 1955. < W >/ Complete Specification Published: Oct 30, 1957. Index at acceptance:-Class 81 ( 2), K. International Classification:-A 61 b. COMPLETE SPECIFICATION Apparatus for Measuring Muscular Forces Involved in Various Movements I, LUCIEN LAURU, of 87, Boulevard de Courcelles, Paris 8 e, France, of French Nationality, do hereby declare the invention, 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: - This invention relates to apparatus for measuring the muscular forces necessary for the accomplishment of various movements such as, for example, for determining those logical actions which e nable working to take place with the minimum of fatigue and in consequence with the best possible physiological efficiency. The object of the invention is to provide an apparatus by which there may be measured from the centre of gravity of the subject the sum of

the forces exerted to execute a movement. An upright motionless subject supports at the level of his centre of gravity a force which is his weight. When the subject becomes active and makes the slightest movement, simultaneously with the unbalancing forces, other forces are created The latter impart at the centre of gravity the sum of the forces developed by the physiological effort, unitarily transferred to the point of postural support -in this instance the ground. According to the invention the apparatus for obtaining this result comprises a base which supports two horizontal superposed platforms having coupling elements for fixing the platforms to one another in all horizontal directions whilst permitting a certain degree of relative movement in a vertical direction one of these platforms being supported by elements responsive to the extent of vertical reactions to which it is subjected. whilst the other platform is coupled laterally to the base by elements responsive to the extent of the horizontal reactions to which the two platforms together are subjected. lPrice 3/6 l By this arrangement it will be apparent that it is possible to observe and/or record all the reactions taking place either in a vertical or in a horizontal direction when a subject on the upper platform makes the 50 slightest movement. In a preferred embodiment, the upper platform rests on the intermediate platform by means of the said elements sensitive to the value of the vertical reactions whilst the 55 intermediate platform is supported by the base through cables the extremities of which are preferably carried in supports vertically adjustable in relation to the base. Another characteristic feature of the in 60 vention is that the elements coupling the two platforms are in the form of leaf springs lying in planes parallel to the said platforms and each having one end fixed fiat below the lower side of the upper platform and the 65 other end fixed flat on the upper face of the intermediate platform. Preferably the relative movement of the two plates is limited by a tie bar having a resilient abutment 70 Another characteristic feature of the invention is that the elements responsive to either vertical or horizontal reactions are constituted by piezo-electric pick-ups. In a particular embodiment the base and 75 the platforms together are associated with a platform or plate the upper surface of which is preferably level with the upper platform and has fixing grooves. In one mode of performance, the said 80 plate carries at least one column with at least one device such as, for example, a handle operable by the person on the upper platform, means, for example, additional piezo-electric pick-ups, being provided for measuring the

85 value of the forces acting on the said device. Another characteristic feature of the invention is that the said device is carried by a head which is movable vertically along the column and preferably balanced by a coun 90 785,385 terweight. The invention will be more readily understood from the following description with reference to the accompanying drawings showing by way of example one embodiment of the invention. In these drawings:Fig 1 is a front elevation of an apparatus for measuring muscular forces according to the invention; Fig 2 is a plan view of the apparatus; Fig 3 is a section on line Il I-III of Fig. 2 on an enlarged scale, the column being shown sectioned, Fig 4 also on an enlarged scale is a section on line IV-IV of Fig 2; Fig 5 also on an enlarged scale is a section on the line V-V of Fig 2; Fig 6 on the same scale as that of Fig 5 is a section on line VI-VI of Fig 2; and Fig 7 is a graph showing in a particular case the curves of variations of muscular forces obtained and recorded by this apparatus. Referring now to Figs 1 to 3 there is shown a plate composed of several elements namely a base 1, two lateral elements 2 and an intermediate element 3 bolted against the base 1 The central part of the base 1 has a large hollow portion of generally triangular shape intended to contain all the recording means and which is surrounded by a floor comprising two side elements 4-and 5 and a central element 6 The upper faces of the floor, of the part of the base 1 which surround this floor of intermediate element 3 and of the two side elements 2 are situated in the same horizontal plane and have classic T section grooves 8 in which the heads of bolts such as 9 can be received for fixing on the plate as thus constituted all the apparatus or machine parts required for any particular analysis of muscular effort. In the example there is shown on each of the side elements of plate 2 a hollow column 11 bolted on the corresponding element and having vertical T-grooves 12 on one of the straight faces and into which there can again be introduced the heads of bolts 13 for supporting a sole plate 14 This sole plate 14 is also formed with horizontal T section grooves 15 into which the heads of bolts 16 can be introduced for supporting a special head 17 having a handle 21 movable around a horizontal axis 22, upon which handle the subject is required to exert a muscular effort, which is measurable as hereinafter indicated. Other handles 23 to 27 controlling locking means function to secure the handle 21 or all other measuring means over which the subject could exercise control. This assemblage can moreover occupy all the positions permitted by the lock-ing means controlled by the handles 23 to 27. Of course the arrangement of the handle 21 could be different Moreover, several similar handles could be provided or the or each

handle could be replaced by other measuring means. In order to determine the value of the 70 forces which will be exerted on the various necessary devices for the measurements required these devices could be provided with any suitable and classic force measuring device such as, for example, a device having 75 two quartz pick-ups such as are indicated at 28, 29 in Figs 1 and 4 The head 17 can be fixed at any desired height along grooves 12 of the column 11 by means of the bolts 16. The assembly of the weight of the sole plate 80 14, the head 17 and all the mechanisms carried by them is balanced by a counter weight 31 mounted inside the column 11 and connected to one end of a cable 32 whose other end is anchored to the head 17 The cable 85 32 passes over a free running grooved pulley 33 mounted on an axle 34 which is fixed in a frame 35 fixed on the top of the column, for example, by bolts 36. The axial spacing of two bolts 9 fixing the 90 column on the plate and which are located in the same groove is equal to the axial spacing of two of these bolts placed in two different grooves In other words these bolts are located at the apexes of a square on 95 which one could place the column either in the position shown or in a position in which its base is turned by 900 in one direction or the other. Moreover, all the grooves 8 of the plate 100 are equidistant so that the column can be located in whatever position is desired of the said plate. In the arrangement shown the two columns 11 and their equipment are symmetrical in re 105 gard to the vertical median plane of symmetry of the whole of the apparatus passing through the line III-III of Fig 2. The triangular hollow portion of the base 1 is filled by two platforms also of gener 110 ally triangular shape, namely an intermediate platform 41 and an upper platform 42 transmitting muscular effort reaction. In the bottom face of the intermediate platform 41 which is suitably ribbed there 115 is fixed a plate 43 (see also Figs 5 and 6) which rests on a suspension bar 44 carried at each of its ends in a groove 39, by the loop of a cable 45 the two ends of which are expanded and welded into a ferrule 46 The 120 two lengths of the cable 45 are threaded into a hollow dowel 47 adjustable for height by screw threading into a sleeve 48 force fitted into corresponding vertical grooves in the base 1 An abutment 49 screwed on the 125 dowel 47 and bearing against the top end of the sleeve 48 enables the dowel 47 to be locked at the desired height in relation to the base 1 Indiarubber wedges 51 are inserted between the suspension bars 44 and 130 785,385 the base for absorbing shocks during transport of the apparatus. The intermediate platform 41 is then supported at the three summits of

the triangle which it forms by means of cables 45 which rigidly determine its position vertically but which allow it to move quite freely sideways to a greater or lesser extent for the lowest amplitudes which are required for measurement of the forces in the horizontal plane in the two perpendicular directions XX' and YY' There is provided two groups of responsive elements or piezo-electric pick-ups. A first group comprises two pick-ups 54 and 55 arranged in the vertical plane containing the centre of gravity of the platform 41 (on the axis XX') for measuring transverse stresses, for example A second group comprises a pick-up 56 arranged on the axis YY' perpendicular to the first in the plane of symmetry of the apparatus and two other pickups 57 disposed symmetrically with reference to the said plane These five pick-ups are mounted similarly between the edge of the platform 41 and of the uprights 58 of the base l (see Figs 1, 2 and 6) One end of each pick-up bears against a face plate 61 (Fig 6) and the other end bears against the end of an adjusting screw 62 mounted in an abutment sleeve 63 force fitted into the upright 58 of the base 1 A locking nut 64 enables the screw 62 to be fixed in any position of adjustment. The upper platform 42 rests on the intermediate platform 41 through the intermediary of three piezo-electric pick-ups 67 (Figs 3 and 6) located respectively at the three corners of the triangle The lateral placing of the upper platform 42 on the intermediate platform 41 is ensured by leaf springs 68 the two ends of which are respectively fixed with these two platforms These leaf springs offer hardly any resistance to the vertical displacements of the upper platform in relation to the intermediate platform more because here again the amplitude of these displacements is imperceptible and in fact rather represents a pressure variation than an actual displacement A bolt 50 passes through the centre of gravity of the tw Q plates and a washer 52 backed by a rubber disc 53 acts as a resilient buffer opposing separation of the two platforms. In order that the value of the reactions to which the different piezo-electric pick-ups are submitted may be measured the latter are coupled to observation and/or recording apparatus (not shown) of any suitable classic type according to known layouts comprising, for example, electrometer stages sensitive to the tensions in the quartz crystals of the piezo-electric pick-ups, measurement amplifiers, measurement tubes, high frequency oscillators, repeater tubes, relaxation oscillators and their ancillary equipment. The apparatus which has been described above functions as follows: The person whose movements are to be analysed by measurement of the forces developed in the course of these movements 70 places himself on the

upper platform 42 and is asked to exert an effort on, say, handle 21. The useful force applied to said handle is measured with the aid of pick-ups 28 and 29. The vertical pick-ups 67 afford a measure 75 of the muscular forces set up in the vertical component, pick-ups 54 and 55, on the one hand, and the pick-ups 56 and 57 on the other hand, indicating the magnitude of the horizontal components in the two perpen 80 dicular directions, i e, transverse XX' and frontal YY' The ratio of the useful effort to the muscular effort provides an efficiency coefficient which varies with the position of handle 21 relatively to 85 the platform Said handle can be orientated in all directions and may represent, for instance, a spanner used by an operator to tighten a bolt. In order to utilise the apparatus a prelim 90 inary calibration as a function of the amplifier used is necessary Then the assembly is set to zero when the subject is on the platform so as to allow for the weight of the subject The slightest movement which the 95 subject makes results in variations of pressure on the pick-up of the tri-rectangular components (vertical, longitudinal and transversal). In order to avoid misjudging the magni 100 tude of the forces measured it is necessary to conserve the quantities of electricity released by the quartz of the pick-ups and in consequence to eliminate even the slightest leakage -For this reason it is preferable to 105 use an electrometer for measuring the potential differences created An inertia-free electrometer is constituted by a thermionic valve electrometer whose grid cathode resistance is more than 10 5 ohms The anode current 110 variations of this valve can be observed and/ or recorded through the intermediary, for example, of a cathode ray oscillograph. With the apparatus of the invention all phases of a movement can be analysed in 115 detail and those actions which result in useless expenditure of energy can be deduced. There can thus be determined which are the most necessary and sufficient actions for the rational accomplishment of a given task 120 By way of example Fig 7 shows the reactions to which the apparatus platform is submitted when a subject supported on this plat. form bends down, remains a moment in a bent position and then stands up again 125 (positions a, b, c, d, e, f, g) The axes OX 1, OX 2 and OX 3 are situated below some-diagrams of the positions of the subject and at each corresponding point of these axes there is indicated respectively the vertical frontal 130 785,355 and transverse components to which the platform is submitted at each instant In other words the three axes OX 1, OX-, OX, are the time axes and along the ordinates the forces are inscribed in kilograms At rest (columns a and g) all the components are nil On the vertica component X 1 the zero

corresponds to the weight of the subject The longitudinal components X and transverse cornponents X,3 only vary a slight amount in the course of this movement, taken by way of example. The vertical component will now be considered separately. At the beginning of the bending movement (column b) the subject develops forces for drawing his body downwards this is the wave motion. To stop the bending (column c) the contrary muscles act as a brake to limit the movement; this second part of the curve is the braking wave. When he is bent (column d I) the subject exerts on the platform a pressure equal to his weight Then when he recovers himself the driving and subsequent braking effort which he develops successively gives rise to a positive reaction followed by a negative reaction on the platform, the subject then returning to the original position (column g) where the platform reassumes its initial state. This very simple analysis is only by way of example to facilitate understanding of the mode of functioning of the apparatus but it will be appreciated that the latter permits of the analysis of more complex movements by studying components in the three spatial directions. It should be clearly understood that the invention is not limited to the mode of apparatus particularly described and shown but is capable of numerous variations as will be apparent to those skilled in the art within the scope of the invention as expressed in the appended claims.

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* GB785386 (A)

Description: GB785386 (A) ? 1957-10-30

Guanamines

Description of GB785386 (A)

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BE540608 (A1) CH336078 (A) FR1135806 (A) US2744943 (A) BE540608 (A1) CH336078 (A) FR1135806 (A) US2744943 (A) less Translate this text into Tooltip

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PATENT SPECIFICATION 785,386 Date of Application and filing Complete Specification: Aug 16, 1955. No 23593/55. Application made in United States of America on Aug 18, 1954. Complete Specification Published: Oct 30,1957. Index at acceptance:-Classes 2 ( 3), C 2 837 (AI: A 2: A 3: J: N); and 2 ( 6), P 1 D( 1 B: 6: 7), P 8 D( 2 A: 2 82: 3 A: 3 B: 4: 5: 8), P 8 K( 4: 6: 8:11), P 8 P 1 (D: El: E 3: E 5), P 8 P( 2 X: 3: 6 A), P 8 T 2 (D: X), P 11 D( 2 A: 7:8), P 11 K( 4: 6: 8: 11), P 11 P 1 (D: El: E 3: E 5), Pll P( 2 X: 3: 6 A), Pll T 2 (D: X). International Classification:-CO 7 c, d CO 8 f. COMPLETE SPECIFICATION Guanamines We, Ro Hm & HAAS COMPANY, a corporationi organized under the laws of the State of Delaware, United States, of America, of 222 West Washington Square, Philadelphia 5, Pennsylvania, United States of America, do hereby declare the invention, for which we pray that a parent 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 guanammnes. In, accordance with this invention,, there are provided guanamines of tie formula where R is hydrogen or an alkyl (particularly CQ-C, 2 alkyl), alkenyl, aralkyl, or cycloalkyl group, and A is a C 1-C 8 divalent saturated aliphatic hydrocarbon group. The invention also provides polymers and copolymers of the new compounds represented by the above formula.

The monomeric compounds of the invention are useful in the fleldsi of pesticides, corrosion inhibitors, or chemical intermediates. They can be reacted at the unsaturated linkage with compounds having a reactive hydrogen and yielding a carbanion They can be reacted at the amino groups, as with formaldehyde They can be polymerized They can be copolymerized with, other polymerizable ethylenwic compounds, particularly with monovinylidene compounds The latter are of interest in providing coating materials The polymers, and copolymers react with form'aldehyde to' form methylol compounds and t Pr'r' ethers thereof which are of value in improving papers and in finishing textiles The above properties distinguish the new monomeric compounds of the invention from previously known guanamin Aes which lack the particular unsaturated nitrogen-containing ring substituent which characterises the present new compounds. The new monomeric compounds are prepared by condensing methaerylamidonitriles of the formula CI, G=C(CH)CON(R)ACN with dicyandiaride in the presence of a strong base as catalyst and in the presence of an alcohol as solvent As typical solvents there may be used methanol, ethanol, propanol, isopropyl alcohol or butanol, or methoxyethanol, etoxyethanod, or a mixture of alcohols The reaction is usually carried out at temperatures between 50 and 1250 C The reaction mixture may conveniently be heated under reflux. As catalyst, there may be used an alkali metal hydroxide, at sodium alcoholate, a potassium alcmholate, or a low molecular weight quaternary ammonium hydroxide, such as potassium hydroxide, sodiumi hydroxide, potassium butoxide, potassium ethoxidde sodium ethoxide, sodium methoxide, cholme, trimethylbenzylamonium hydroxide, dimiethyldibenzylammolnium hydroxide, trimethylbenzylammonium methoxide and trimethylbenzylammonium butoxide The usual amount of catalyst is from about 2 % to 20 % of the weight of the reacts. The product is obtained as a residue which can be often purified by recrystallization or by trituration, The starting methacrylamidonttriles are available, for example, through the method of Jacobson, wherein methacrylyl chloride is re' acted with an amminoitrile, RNHACN. A typical preparation is that of a-(methacrylamnido)isobutyronitrile To a solution of 209 parts of methaaylyl chloride in 418 parts of benzene, there is added a-amlinoisobutyros O ^ nitrile in an amount of 336 parts dissolved in 672 parts of benzene, the mixture being stirred and cooled to keep the temperature below 45 C The mixture is stirred for three hours The solid product is filtered off and is washed with dilute aqueous potassium carbonate solution and with water The washed product is recrystallized from 300 parts of hot water and dried The product melts at 102 1040 C Other illustrative preparations follow.

There are mixed 49 parts of 3-aminopropionitrile and 36 6 parts of methacrylyl chloride There is thus formed 41 9 parts of fl(methacrylamido)propionitrile, melting at 46 -48 C. A solution of 138 parts of N-cyclohexylaminoacetenitrile is dissolved in 138 parts of benzene and treated with 52 parts of mnthacrylyl chloride in an equal weight of benzene. There forms a solid amine hydrochloride, which is filtered off and washed with benzene. The benzene solutions are washed with dilute hydrochloric acid and water to remove amine, treated with charcoal, and evaporated to yield 93 parts of N-cyclohexylmethacrylamidoacetonitrile, melting at 740-760 C. In similar manner, 152 parts of N cyclohexyl-L 6-aminopropionitrile and 52 3 parts of methacrylyl chloride are reacted to give 104 parts of N cydohexyl B-(methacrylamsido)propionitrile melting at 43 144 C Likewise, N-methyl-5-(methacrylamido)isobutyronitrile is obtained as a colorless solid melting at 68 -7 L 1 C, while N-methyl-B 6-(methacrylamido)propionitrile is obtained as a colorless liquid boiling at 102 -104 G/0 2 mm. In the same way N-henzyl or N-allyl methacrylanrdepropionitriles or isobutyronitriles may be prepared. Typical anonitriles which are useful for forming the intermediate methacrylamidonitriles, as above, include N-methylamineacetonitrile, N butylamino;acetenitrile, Nbenzylaminoacetonitrile, N-cyclohexylaminoacetonitrile, c-aminopropionitrile, methylammnopropionitrile, a-ectylaminfoprepionitrile, a benzylamiinoprropionitrile, M cyclohexylaminopropionitrile, x-aminoisobutyronitrile, methylaminoisobutyronitrile, z-n-butylaminoisobutyronitrile, a benzylaminoisobutyronitrile, a-octylaninoisobutyronitrile, -dcdecylaminoisobutyronitrile, a -tyclchexylaminoisobutyronitrile, a-allylaminoisobutyronitrile, -methylct-amlnobutyronitrilet x-methyl-et-me-thylminohutyronitrile, c m thyl-xt-benzylaminobutyronitrile, a-methyl-t-octylaminoibutyronitrile, z methyl-a-allylaminobutyronirrile, ca-methyl-2cyclohexylaminobutyronitrile, methyl aminocapronitrile, a methyl-v-methylaminecapronitrile, a methyl a -benzylaminocapronitrile, a methyl c allylaminocapronitrile, E methyl-a-aminocaprylonitrile, a' methyl->'methylaminocaprylonitrile, l methyl-g -octylaminocaprylonitrile, i-methyl-7-b enzylamino6 caprylonitrile, /3 aminoisobutyronitrile, /3methylaminoisobutyronitrile, /-benzylaminoisobutyrenitrile, /3-allylanminoisobutyronitrile, /-dodecylaminoisobutyronitrile, /,-cyclohexylaminoisubutyrenitrile, / aminobutyronitrile, / methylarninobutyronitrile, p octylamino 70

propionitrile and /3-dodecylaminopropionitrile. These aminonitriles are reacted with methacrylyl chloride or bromide to form the methacrylamidonitriles which are then reacted with dicyandiamide 75 In the following illustrative examples, there are shown typical procedures for forming the guanamines of this invention Parts here, as above, are by weight. EXAMPLE 1 80 A mixture of 16 7 parts of 9 -(methacrylamido)isobutyronitrile, 8 4 parts of dicyandiamide, and 80 parts of iscpropyl alcohol is prepared and heated to 850 C Thereto is slowly added a solution, of 1 3 parts of 85 %,' 85 pure potassium hydroxide in 11 7 parts of isopropyl alcohol ever a 30-minute period. The reaction mixture is heated under reflux for 10 hours The reaction mixture is filtered. The filtrate is evaporated under reduced 90 pressure to give a dry resin-like material. This is recrystallized from hot water to give 10 6 parts of a colorless solid which is identified as a (methacrylamido)isobutyroguanarrine This produpt contains by 95 analysis 35 3 % of nitrogen (theory 35 6 %,') and melts at 160 -163 C This compound is a particularly desirable one because it has good solubility in organic solvents due to the isobutylene group 100 In the same way there is prepared from Nmethyl (methacrylamido)isobutyronitrile and dicyandiamide the corresponding N-methyl-,(methacrylamido)isobutyroguanamine As obtained this is a glassy solid which contains the 105 theoretical amount of nitrogen It, too, has good solvent solubility The same method applied to N-benzyl->-(methacrylamido)isobutyronitrile yields the corresponding Nbenzyl X (methacrylamido)isobutyroguan 110 amine, also as a glassy solid. EXAMPLE 2 There are mixed 97 2 parts of fl-(methacrylamidolpropionitrile, 55 6 parts of dicyandiamide, 87 parts of potassium hydroxide, 115 and 460 parts of isopropyl alcohol The mixture is heated at reflux temperature for 12 hours The reaction mixture is filtered and the filtrate is chilled Crude product separates and is taken cff, washed with methanol, and 120 dried The yield is 147 parts of /3-(methacrylamidc)propioguanamine, melting at 184 1850 C It contains by analysis 37 0 %O of nitrogen (theory 37 8 %). In the same way N-methyl-?-(methacryl 125 amido)propioguanamiine is formed It melts above 250 ' C As obtained, this product is found to contain 35 4 ' of nitrogen (theory 35.6 %). 785,386 785,386 3 EXAMPLE 3 There are mixed 82 4 parts of N-cyclohexylmethacrylamidoacetronitrile,

33 6 parts of dicyandiamide, and 350 parts, of isoipropyl alcohol Thereto is slowly added a solution of 5 3 parts of potassium hydroxide in 44 7 parts of isopropyl alcohol The mixture is heated under reflux for eight hours and worked up as above. There is obtained N-cyclohexylmethacrylamidoacetoguanamine in anl amount of 94 parts This is recrystallized from methanol to give a product melting at 273 -2740 C. and containing 29 O % of nitrogen by analysis (theory 29 0 %). In the same way N-cyclohexyl-/3-(methacrylamido)propionniitrile is reacted with dicyandiamide to' give N-cyclohexyl-P-(methaarylamidopropioiguanamine, melting at 220 2210 C and containing by analysis 27 5 % of nitrogen (theory 27 6 %). The monomeric guanamines of the invention are polymerizable under the action of free radical initiators, such as the azo' catalysts or organic peroxides There may be used for this purpose such compounds asi dimethyl or diethyl azosdiisobutyrate, azodiisobutyronitrile, or azoibis(a-m ethylbutyronitrile), or benzoyl peroxide or caproyl peroxide. The said guanamines may be polymerized to give homopolymers or polymerized together with different monovinylidene compounds; to' give copolymers Such polymeric products also yield valuable methylo{lated derivatives, i e derivatives obtainable by the reaction of the polymeric products with formaldehyde. As an example of a polymer preparation, five parts of x-(methacrylamido')iso'butyroguan Iamline and 25 parts of methyl alcohol are treated with benzoyl peroxide in increments tot a total of O 25 part while the solution is heated under reflux The solution becomes distinctly viscous and polymer forms hi a yield of over 95 % if the polymerization is carried on for about 24 hours with occasional addition of catalyst Somewhat better polymerization is effected with the azo' initiators. A mixture of five parts of fl-(N-methacrylN-ectylamido')propioguanamine, ten parts of dimethylfolrmram;ide, and 0 2 part of dimethyl azodiisobutyrate is heated at 750 C for 16 hours under nitrogen A viscous solution of polymer results. In the same way any of the monomeric guanamines of this invention can be treated with a free radical catalyst with formation of polymers Likewise, the guanamines enter into copolymiers with other polymerizable vinylidene compounds, particularly mronovinyliden E compounds For this purpose, there may be used esters of acrylic acid, methacrylic acid, such as the methyl, ethyl, butyl, octyl, dodecyl, octadecyl, benzyl, cyclohexyl, methoxyethyl, dimethylaminoethyl, dimethylaminopropyl, morphollinopropyll, or pipieridinopropyl esters,

acrylamide, methacrylamide, N-methylacrylamide, N-octylacrylamide, or other Nsubstituted acrylamlides or their methacrylamide counterparts, acrylonitrile, methacrylonitrile, vinyl acetate, vinyl propionate, vinyl 70 pyridine, vinylpyrrole or ureidoethyl vinyl ether. As regards the copolymers, in many cases but a small proportion of the guanamine is used to supply groups which are reactive, as 75 to formaldehyde, and which can, therefore, serve to' cross-link the copolymer Here 1 % to' perhaps 50 % of the guanamine is ample for this use Yet many useful copolymers can be made in which the guanamiine is the chief 80 comonomer. A solution is prepared from 95 parts of uninhibited methyl methacrylate, 11 8 parts of a (methacrylamido)isobutyrogu aamine, and 2.1 parts of benzoyl peroxide in 131 parts of 85 ethoxyethyl acetate This solution is slowly added to a reaction vessel equipped with stirrer and a tube for admitting a stream of nitrogen' and heated with aan oil bath at 1000 C Thei mixture is heated for 4 5 hours 90 During this, time, two additions of catalyst are made, each time 0 2 part of benzoyl peroxide in 15 parts, of ethoyethyl acetate being supplied The amount of copolymer formed was determined from the non-volatile content 95 The product is a 36 2 % solution of copolymer. The solution has a Gardner-Holdt viscosity of X+. Some of this copolymer was; treated with butyl hemiformal in butanol and applied as 100 a coating on metal plates, 4 % butyl acid phthalate being added to supply a catalyst. The solution was applied to a metal plate which was baked at 1500 C for 30 minutes. The film was hard, of good colon, and resistant 105 to solvents. In the same way, there may be copolymerized 12 parts of a (methacrylamiidoisobutyro guanamine, 25 parts methyl methacrylate and parts of ethyl acryate The copolymer is 110 formed in a 99 % yield with use of 2 5 % of benzoyl peroxide as catalyst over a 5 5 hour period The films from this copolymer are tough and may be insolubilized as above by thel action of formaldehyde 115 There are mixed, with stirring, 0 9 part of N methyl P (methacrylamidoi)propioguan. amine and 95 5 parts of ethoxyethyl acetate. The mixture is heated to 800 C while 47 5 parts of methyl methacrylate containing 1 5 120 part of azodiisobutyrnitrile is slowly added. Copolymerization is complete after about four hours The product is not homiogeneous, but there is nevertheless formed copolymer of the two' starting materials, 125 For many purposes the new guanaxmines may be converted to salts by reacting with a strong inorganic acid, such as hydrochloric, hydrobromic, sulfuric, or phosphoric Since there are two amino groups present in the 130 785,386 guanamines, salts may be

formed with one such group or with both The polymers and many copolyymers may likewise be converted to salt forms The salts are convenient for handling polymers in a water-soluble form. For example, a portion of 2 3 grams of (methacrylanido)isobutyroguanamine is taken up; in 20 mnl of water with partial solution Upon treatment with 20 ml of 0 5 N hydrochloric acid solution complete solution is obtained As this solution stands at low temperature, some hydrochloride of this; guanamine precipitates The salt is obtained quantitatively by evaporation under reduced pressure It is dried at 75 ' C at a pressure of 35 mm, to give a white solid which does not melt below 2600 C By analysis this dried salt contains 12 5 % of chlorine Theoretical chlorine for Cl O Hl TN,,OCL is 13 %. In the same way, a portion of 2 36 grams of N-m-thyl-13-(me 5thacrylamido)propioguanamine is slurried in water and treated with 20 ml of 0 5 N hydrochloric acid solution to give a clear solution When this solution is evaporated, a glassy solid is obtained From its chlorine analysis it contains some dihydrochloride. When about one part by weight of either of the above salts is taken up in three parts of where R is a hydrogen atom or an alkyl, alkenyl, aralkyl or cycloalkyl group, and A is a divalent saturated aliphatic hydrocarbon group containing from 1 to 8 carbon atoms. 2 A compound having the formula of

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* GB785387 (A)

Description: GB785387 (A) ? 1957-10-30

Therapeutic fat products and the manufacture thereof

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COMPLETE SPECIFICATION Therapeutic Fat Products and the manufacture thereof We, THE UPJOHN COMPANY, a corporation organized and existing under the laws of the State of Michigan, United States of America, of 3u1 Henrietta Street, Kalamazoo, State of Michigan, United States of America, 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 a therapeutic fat product, and more particularly relates to an improved therapeutic fat product suitable for both oral and intravenous use. The use of a therapeutic fat product to supplement the diet of those suffering from various illnesses is now well established in the medical field. One example of an oral form of such a product wherein a mixture of phosphatides and a polyethylene glycol mono ether is used as the suspension stabilizing agent may be found in U.S. Patent 2,646,354. Such products while enjoying considerable success have not been found satisfactory for intravenous use since the fat in such products is not readily cleared from the blood. A successful product in this field must contain fat which is rapidly cleared from the vascular system, give a low thermogenic response upon injection, and be physically stable over long periods of time. It is therefore an object of this invention to provide an improved therapeutic product suitable for both oral and intravenous use, which gives better fat clearance from the vascular system, is easier to emulsify, has greater physical stability and has negligible pyrogenic effect upon intravenous administration. It has now been found that by using a polyalkylene glycol as the emulsifying agent instead of those previously used such a desired therapeutic fat product is obtained. In a broad sense the composition of the present invention comprises a fixed, metabolizable oil (stably suspended in water with or without sugar through the use of polyalkylene glycol as an emulsifying agent. More particularly the

invention consists essentially of the discovery of the suitability of an ethylene oxidepolypropylene glycol condensation product as a stabilizing agent for a therapeutic fat product which is suitable for intravenous as well as oral use. The condensation product can also be characterized as a polyalkylene glycol in which the alkylene units consist of ethylene and propylene units, said propylene units being in non-terminal positions and connected to each other in a chain. The metabolizable, fixed oils suitable for the composition of the present invention include naturally occurring vegetable and animal oils as well as synthetic glyceride oils. Among those found to be most suitable are olive oil, peanut oil, coconut oil, sesame oil, cotton seed oil and corn oil. Olive oil and cotton seed oil are preferred for intravenous use, and a combination of peanut oil and coconut oil is preferred for oral use. The coconut oil is preferred solely for its flavor characteristics. The physical stability of emulsions of these oils is important. Particles of these oils should be less than about 2.5 microns in diameter and preponderantly about 0.5 micron in diameter. These particle sizes should be maintained under various conditions considered valid indicators of physical stability. Suitable sugars are the monosaccharides such as glucose and fructose and the disaccharides such as sucrose and maltose. The caloric value of the saccharides is about the same. In the oral product the quantity of sugar considered desirable is in part dependent upon its sweetness. Disaccharides, such as sucrose and maltose, being sweeter and having more flavor are preferably present in smaller quantities than the monosaccharides, such as glucose and fructose, in the oral product. The ethylene oxide-polypropylene glycol condensation products of the composition of the present invention are a well-defined group of chemical compounds. These products are represented by the following formula: HO(C2H4O)a(C3H6O)b(C2H4O)cH wherein a, b and c are positive integers which can be varied over a considerable range to provide an inherently flexible group of compounds which can be adjusted to many situatons. Thus the molecular weight of either the hydrophobic portion (propylene oxide portion) or of the hydrophilic portions (ethylene oxide portions) can be varied in small increments over a wide range. It is therefore possible to prepare a product to meet any requirements of molecular weight or of hydrophobic-hydrophlic balance. Within the limitations inherent in the preferred composition of the present invention, it is desirable to use a formula having a "base" molecular weight between about 1500 and about 1800 with between about eighty and about ninety percent ethylene oxide in the molecule. The "base" is the polypropylene glycol unit. Such a formaula can also be desigmated by

reference to the structural formula as one in which b equals between about 25 and about 32 and a+c equals between about 136 and about 368. Such a product is designated by the manu Facturer (Wyandottte Chemicals Corporation) and herein as Pluronic F 68. The "F" designates the flake form. The compounds are also available in liquid and paste form. In addition to the Pluronics it is preferred to use soybean phosphatides (lecithin) to improve the suspension and stabilization characteristics of the composition of the present invention. For the intravenous product the lecithin should be used in purified form to minimize the possibility of systemic reactions thereto. Other ingredients include an anti-oxidant to prevent oxidation of the oils during processing and rancidity during storage. Edible antioxidants of the class of phenols such as tertiary butyl anisoles are suitable. It is preferred to use a combination of tertiary butyl4-hydroxy anisole, propylgallate, and citric acid. The concentrations of the various ingredients which can be utilized in the present invention can be varied over a wide range. However the desirable overall characteristics tend to limit somewhat the permissible variations in the concentration of particular ingre- dents. One such characteristic is the caloric value of the fat and sugar in any particular combination. Other such characteristics are limitations associated with the route of intended administration, such as the oral route as opposed to the intravenous route. Another characteristic which tends to limit the amount of ingredients is the viscosity of the suspension. When the weight of the oil amounts to more than about 55 percent of the total weight/volume of the product, the viscosity of the suspension is so high that it is no longer free flowing and easily consumed. The viscosity can of course be higher for the oral product than for the parenteral product. Thus the upper limt for intravenous use would be about forty percent weight/volume. For the oral product the caloric value is so low when the weight of oil in the product is below about thirty percent weight/volume that the increased volume required becomes an increasrng handicap. The caloric value for an intravenous product need not be as high as an oral product. Thus the lower limit for the intravenous product is about ten percent weight/volume. The preferred concentration of oil is about forty percent weight/volume for oral use and fifteen percent weight/volume for intravenous use. From the standpomt of sweetness and caloric value (which set an upper and lower limit respectively) between about five and about 25 percent weight/ volume of the water used in the oral product of the present invention can be

a sugar. Between about five and about fifteen percent weight/volume is preferred for the disaccharides and between about ten to twenty percent weight/volme is preferred for the monosaccharides. For the intravenous product between about three percent and ten percent weight/volume of water is preferred. Once the concentrations of the oils and sugars have been fixed within the ranges specified above, the concentration of the preferred Pluronic can be varied from about 0.5 to about 1.5 percent weight/voThme for the oral product and from about 0.2 to about 0.5 percent weight/volume (0.3 percent preferred) for the intravenous product. The con centration of the soybean phosphatides for intravenous use can be varied between about one to about three percent weight/volume, and the concentration for oral use should be at least about two percent weight/volume, Thus, the amounts of Pluronic and phosphatides utilised in the composition of the present invention are important once the amounts of oil and sugar are determined. A therapeutic fat product suitable for oral use comprises 30 to about 55% w/v of an edible bland oil and about 5 to about 25% w/v of the water of a sugar together with about 0.5 to about 1.5% w/v of an ethylene oxide-polypropylene glycol condensation product and about 2% w/v of soybean phosphatides and water. Also a process for the preparation of a therapeutic fat product suitable for oral and intravenous use comprises the emulsification of a metabolizable, non-toxic fixed oil with or without a sugar in an aqueous vehicle con taining a minor proportion of an ethylene oxide-polypropylene glycol condensation product emulsifying agent The ethylene oxidepolypropylene glycol condensation product preferably has a base unit between about 1500 and about 1800 with between about 80 and about 90% ethylene oxide in the molecule. The addition of a minor proportion of a soybean phosphatide as an additional emulsifying agent is preferably used. Preferably the oral therapeutic fat product is prepared by using about 30 to about 44% of oil together with about 5 to about 25% w/v of the water of a sugar and about 0.5 to about 1.5% w/v of the ethylene oxidepolypropylene glycol condensation product and about 2% w/v of soybean phosphatides and water. Preferably the intravenous therapeutic fat product is prepared by using about 10 to about 40% w/v of oil

together with about 3 to about 10% w/v of water of a sugar and about 0.2 to about 0.5% w/v of the ethylene oxidepolypropylene glycol consensation product and about 1 to about 3% w/v of purified lecithin and water. The following examples are illustrative of the present invention but are not to be construed as limiting. The parts and percentages are on a weight/volume basis unless otherwise specified. EXAMPLE 1. ORAL PRODUCT. In order to make up a 100,000 cubic centimeter batch of an oral product, the following composition may be prepared 10 % Dextrose anhydrous 10,000 grams 1.5 % Pluronic F68 1,500 grams 2 % Soybean Lecithin (Glidden Lecithin Grade RG) 2,000 grams 0. 1 % Sodium benzoate 100 grams 0.05 % Disodium ethylene diamine tetra - acetate 50 grams 36 % Peanut oil U.S.P. crackerjack grade 36,000 grams 4 % Coconut oil 4,000 grams .008% Tertiary butyl-4-hydroxy anisole (Sustaine, Universal Oil Products) 8 grams Deionized water 47,500 cc. The water is heated to a temperature of 95 degrees centigrade. The following materials are dissolved in order in the water: dextrose, lecithin, Pluronic, sodium benzoate and disodium ethylene diamine tetra-acetate. The solution is stirred for twenty minutes. The butyl anisole is dissolved in the coconut and peanut oils. The oils are added to the solution, and the temperature is adjusted to seventy degrees centigrade. The whole is then homogenized by two passes through a Manton Gaulin homogenizer. The product is then filled, while still warm, into pint bottles. The product is assayed for fat content, dextrose content, stability (centrifuge test) and bacteria count EXAMPLE 2. INTRAVENOUS PRODUCT. 200,000 Cubic centimeters of an intravenous fat product may be prepared as follows 1.2% Soybean Lecithin (Glidden LecithinGradeRG, purified) 2, 400 grams 15 % Olive Oil U.S.P. 30,000 grams 4 % Dextrose anhydrous 8,000 grams 0.3% Pluronic F 68 600 grams Water for injection-sufficient to male up 200,000 cc. The lecithin is purified to minimize reactions to possible impurities by dissolving in petroleum ether, l filtering and precipitating with acetone. The day before manufacturing an excess of water is added to

two tanks and brought to an active boil for ten minutes. On the same day lecithin is added to the oil contained in a partially jacketed steam kettle; and, while stirring rapidly, the temperature is raised to sixty degrees centigrade in ten minutes. After the lecithin is dissolved, the temperature is reduced to 25 degrees centigrade. The oil and water are allowed to stand overnight The water is adjusted to approximately eighty liters in tank No. 1 and eighty liters in tank No. 2. The temperature is raised in tank No. 1 to ninety degrees centigrade. Dextrose followed by the pluronic is added. The mixture of oil and lecithin is added. Sufficient water is added to tank No. 1 to bring the level up to 120 liters. This is mixed thoroughly for five minutes by rapid stirring with a Lightning Mixer while cooling to seventy degrees centigrade, and homogenized at 4000 pounds per square inch, for twenty minutes at seventy degrees centigrade, recycling into tank No. 1. Water is added from tank No. 2 at seventy degrees centigrade. With pressure at 4000 pounds per square inch the contents of tank No. 1 are homogenized into tanlr No. 2. This cycle is repeated two more times, and the product is filled into 600 cubic centimeter centrifuge bottles after passing through a sintered glass filter. The product is then autoclaved at 121 degrees centigrade for twenty minutes and cooled as rapidly as possible. The product is assayed for pyrogens, sterility, fat content and dextrose content. The following is a summary of comparative test results on intravenous products utilising two different emulsifiers. After preparation by the procedure of Example 2 several lots of two main types of intravenous preparations were checked for pyrogen response and physical stability. The results of these tests can be found in Tables I and IL Pyrogens are run on each lot of emulsion according to the procedures of the United States Pharmacopeia. Briefly, three rabbits (1500 grams or more) are infused through an ear vein with ten cubic centimeters of fat product per kilogram of rabbit within fifteen minutes after obtaining the normal rectal temperature. Time for infusion is approximately three-four minutes. The normal rectal temperature is that obtained fifteen minutes after placing the rabbits in stocks. Rectal temperatures are obtained at three one hour intervals following the iniection and the highest is compared with the normal. According to the U.S.P. defin ition a positive reaction is a rise of 0.6 degree centigrade or more in one of the three rabbits used, or a sum total of 1.4 degrees centigrade rise in all three rabbits used. If positive for

three rabbits, five rabbits are employed; and a positive reaction is redefined as one in which two or more of the rabbits show a rise of 0.6 degree centigrade or more. The emulsions shown in Table I are not satisfactory. However, most of the Pluronic emulsions shown in Table II pass the U.S.P. definition of a negative reaction, and those that don't are so marginal that they would very likely pass on the repeat test TABLE I Summary of "Demal" (Polyglycerol Ester of Oleic Acid) Emulsions* <img class="EMIRef" id="026447536-00040001" /> Evaluation** Pyrogens Initial Shaken Lot Max. C. Temperature rise in 3 hrs. 1.6 3.2 1.6 3.2 number or or or or Initial Repeat more more more more 3 1.2, .8, .8 .3, .2, .0, 1.0, 0 1.5, .8, 1.0, .1, .7 4.0 0.1 33 0.5 4 .2, 1.2, .6 .6, .3, .0, .0, .0 4.0 0 5 .0, .5 .6, .1, .5 4.5 0.2 26.7 0.2 6 .3, .0, .0 - 3.7 0.1 31.9 0.9 7 .4, .4, .7 .4, .5, .3, .0, .0 3.2 0.2 27.4 1.6 8 .4, .2, .6 .5, .4, .4, .6, .3 5.0 0 35.0 1.2 9 .8, .9, .4 .8, .9, .4, .5, .6 5.0 0.2 33.4 0.5 10 1.2, .4, .6 .6, .2, .3 7.0 0.4 30.0 0.4 11 .6, .4, .2 .9, .6, .6 50 0.2 38.8 0.6 12 .9, .4, .8 .5, .0, .5 4.4 0.1 34.4 1.4 13 .5, .6, .4 .6, .3, .5 4.8 0.3 36.0 0.7 14 .0, 1.3, .4 .2, .0, .0 4.3 0.3 25.0 0.5 15 .9, .0, .5 .5, .7, .2 4.7 0.4 27.0 0.2 16 .6, .6, 1.0 .0, .6, 1.0 3.8 0.2 21.0 0.2 17 .3, .6, .9 - 5.5 0.4 35.0 2.6 Averages 4.6 0.2 33 0.8

* Formulae of all these preparations are "Demal" 1% Polyglycerol Ester of Oleic Acid (manufactured by Emulsol Corporation), 1% Purified Phosphatide and 15% olive oil. ** Evaluation explained below. TABLE II Summary of Pluronic Emulsions* <img class="EMIRef" id="026447536-00050001" /> Evaluation** Initial Shaken 72 Irs. at 4 C. Purified Pyrogen Lot Phos- Max. C, 1,6 |3.2 1.6 3.2 num-| Pluronic phatide Temp. Rise or or or or ber % % in 3 hrs. more more more more 3 0.5 1. 0. 4,. 4,. 0 20.5 0.2 26.7 0.2 4 0.5 1. 0. 0,. .5, .0 8.9 0.5 11.7 0.5 5 0.5 1.2 4,. .6, .4 5.5 0.1 10.6 0.7 6 0.2 1.2 2,. .6, .1 6.0 0.1 26.9 1.2 7 0.5 1. 0. .3, .4,0 5.0 0.1 16.0 0.3 8 0.3 1.0 .4, 0, .4 12.9 0.8 15.9 1.1 9 0.3 1.0 .0, .0, .2 14.4 0.6 16.0 1.4 10 0.3 1. .6,0,0 8.4 0 13.1 0.9 * All formulae contain 15% olive oil ** Evaluation explained below The portion of Tables I and II entitled "Evaluation" summarizes the data obtained to indicate the physical stability of the emulsions. This data was obtained by evaluating each lot of fat emulsion before and after it is shaken 72 hours at four degrees centigrade. A five milliliter sample is withdrawn from the center of the bottle of emulsion (inverted five times to mix well) and diluted to 25 cubic centimeters with five percent dextrose. This dilution is used to fill a Petroff-Hauser bacterial counting chamber. Using oil immersion, a count of the fat particles 1.6 microns or more in diameter and also 3.2 microns or more in diameter in ten areas l;i50 square millimeter in size is made. The average is recorded as the value for that particular sample. This value multiplied by 12.5 million yields the count per milliliter of emulsion. The sampling in this test is sufficient to give a valid indication of physical stability. Table III represent data on the pyrogen of Pluronic and Demal emulsions. This information not only verifies the superiority of the Pluronic over the Demal emulsions as indicated by the previous

experiments, but it also gives a more accurate comparison of the pyrogenic effect of the emulsifying agents used. The first two emulsions tested were different lots varying only as to the emulsifying agent. The average rise in temperature clearly indicates that the Pluronic emulsion is superior to the Demal emulsion. To verify this result one percent of each of the two emulsifying agents was added to the same lot of material. The average rise in temperature olearly indicates that the Demal caused a greater pyrogenic response than the Pluronic emulsifier. This was further verified by testing the pyrogenic effect: of a one percent concentration of Demal in five percent dextrose solution. The data conclusively indicate that the Pluronic emulsions are superior to the Demal emulsions from the standpoint of pyrogenic response. TABLE III Demal 14 vs. Pluronic F68 as Coemulsifier in 15% Olive Oil Emulsion with Respect to Temperature. Responses Obtained following I.V. Administration to Rabbits. <img class="EMIRef" id="026447536-00060001" /> .3% Pluronic Emulsion Pluronic Lot No.9 Emulsion 1% Demal .3% Pluronic + 1% Lot No.9 Emulsion Emulsion Pluronic + 1% 1% Lot No. 17 Lot No. 9 F-68 Demal Demal* Ave. Range Ave. Range Rabbit C. No. C, C. No. C. C.Rise C.Rise C.Rise No. Rise Run Rie rise Run Rise 58 0.94 4 0.44-1.34 0.46 5 0.23-0.72 0.56 1.72

59 0.66 4 0.33-1.00 0.23 1 0.23 0.67 2.51

60 0.77 9 0.50-1.11 0.41 5 0.23-0.56 0.16 1.11 61 1.78 9 0.94-2.28 0.92 5 0.39-1.44 0.56 2.05 1.05 62 1.05 9 0.67-1.61 0.36 5 0.16-0.50 0.22 1.45 0.22 63 1.86 9 1.05-2.33 1.21 5 0.61-1.62 0.77 1.45 0.67 64 0.49 9 0.06-0.83 0.29 5 0.17-0.39 0.44 1.16 0.78 65 0.70 9 0.39 0.27 5 0.11- 0.11 0.73

1.11 1.00 0.56 66 1.46 9 0.78-1.89 0.91 5 0.67-1.23 0.53 2.17 1.00 67 0.55 8 0.23-1.11 0.42 5 0.34-0.50 0.50 1.17 0.94 68 1.02 8 0.73-1.62 0.57 5 0.45-0.83 0.44 1.33 0.89 69 1.96 8 1.55-2.28 1.28 4 0.89-1.50 - - 70 1.11 8 0.78- 0.67 5 0.50- 0.55 1.23 0.73 1.72 0.83 overall average CC. Rise 1.19 0.61 0.46 1.50 0.82 * 1% Demal in 5% Dextrose solution, all other ingredients eliminated. Other reasons for preferring the Pluronic emulsion over the Demal emulsion are as follows: the Pluronic emulsion produces no deposition of intravascular fat in rats while Demal emulsions almost always produce such a deposition of fat in rats (tests run in heart, liver, kidney, spleen and lung); the Demal formulae indicate a higher reaction rate in clinical trials by several different investigators while clinical experience with Pluronic emulsions on the other hand has been good. Standard toxicity tests which have been run in rats have proven the Pluronic formula to be non-toxic at the levels tested and in the amounts utilized in the compositions of the present invention. Certain emulsifying agents have been used in the emulsifying systems of some commercially available oral therapeutic fat producrs. While apparently satisfactory in an oral product, they have proven unsatisfactory in products intended for intravenous use. One reason for this is the unsatisfactory thermogenic response obtained from injection of these materials. Table IV shows the reaction obtained in a test group of five rabbits from one percent solutions of polyoxyalkylene ether of partial stearic acid ester (Agent A) and polyoxyalkylene ether of partial oleic acid ester (Agent B) both with five percent dextrose. Each figure represents the average maximum rise ia degrees centigrade occurring during the four hours following infusion. TABLE IV. Agent A Agent B 0.89 2.16 0.84 1.11 1.27 2.33

0.55 1. 27 1.50 2.22 Average 1.01 Average 1.82 Thus Agents A and B would not be an improvement over the oleic acid ester emulsifying agent on the bases of pyrogenic response. It is important that the emulsified oil in an intravenous fat product be cleared from the blood at a rapid rate. This problem is dealt with by Waddell et al. Am. J. Physiol. 174; 3942 (July, 1953). It is there reported that the rate of clearance of triglyceride oils is influenced by the emulsifying agents used. The co emulsifier disclosed and claimed in U.S. Patent 2,646,354, i.e., polyethylene glycol ether, is shown to decrease the rate of disappearance of emulsion from the blood. This decrease is serious enough to be referred to as "a first order reaction. The product of the present invention has exhibited no adverse effects in this respect, either in animal or clinical use.

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