* GB784623 (A)

Description: GB784623 (A) ? 1957-10-09

Glyoxalidine corrosion inhibitors

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PATENT SPECIFICATION Inventor: AARON STERLIN 784,623 i,.o: Date of Application and filing Complete Specification: Sept 12, 1955. No 25981/55. A Complete Specification Published: Oct 9, 1957. Index at acceptance:-Classes 2 ( 3), B 4 (A 1: M), C 2 (A 3: AS: R 15: RIG), C 3 A 13 A 3 (A 4: BA: C); and 591, G 1 Al. International Classification:-CO 7 c, d C 10 g. COMPLETE SPECIFICATION Glyoxalidirne Corrosion Inhibitors We, NATIONAL ALUMINATE CORPORATION, a corporation organized and existing under the laws of the State of Delaware, United States of America, of 6216 West 66th Place, Chicago, State of Illinois, 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 new chemical compounds and their use in hydrocarbon liquids, more particularly gasoline, diesel fuel oil, and furnace oils, and to a method of inhibiting corrosion of ferrous metals caused by the presence of water in such liquids. Various attempts have been made to inhibit corrosion of ferrous metals in contact with hydrocarbon liquids such as gasoline and other

hydrocarbon fuels where the tendency to cause such corrosion has been due to the presence of small amounts of water In many cases, even though a particular chemical is effective in inhibiting corrosion the amount required may be so large as to cause other adverse or harmful effects For example, in gasoline the presence of a corrosion inhibitor may cause gum formation. One of the objects of the present invention is to provide a hydrocarbon liquid which is inhibited against corrosion by the presence of a very small amount of an inhibiting agent which does not otherwise adversely affect the properties of said hydrocarbon liquid. A further object of the invention is to provide new chemical compounds which are effective for this purpose. A still further object of the invention is to provide a new and improved method of treating ferrous metals to prevent corrosion caused by water Other objects will appear hereinafter. In accomplishing these objects in accordance with this invention, new compounds have been prepared which can be described broadly as salts of a glyoxalidine and an organic alilPrice 3 s 6 d l phatic dicarboxylic acid containing at least 10 carbon atoms, preferably 10 to 36 carbon atoms wherein the glyoxalidine nucleus the carbon atom in the 2-position is linked to a higher aliphatic hydrocarbon group containing at least 8 carbon atoms, the carbon atom in the 4-position is linked to hydrogen or a lower aliphatic group containing not more than 6 carbon atoms, the carbon atom in the 5-position is linked to hydrogen or a lower aliphatic group containing not more than 6 carbon atoms, there being at least one hydrogen atom on each of the carb on atoms in the 4and 5-positions, and the nitrogen atom in the 1-position is linked to hydrogen or a lower aliphatic group containing not more than 6 carbon atoms. These compounds can also be characterized as monoglyoxalidine salts of said organic aliphatic dicarboxylic acids or diglyoxalidine salts of such acids, depending upon whether one or two mols of the glyoxalidine is reacted with the organic aliphatic dicarboxylic acid. If only one mol of the glyoxalidine is reacted with the resultant compound is a monoamine salt containing a free carboxylic acid group. If two mols of the glyoxalidine are reacted the resultant compound is a diamine salt The glyoxalidines employed as starting materials are made by well known procedures by reacting a fatty acid with an aliphatic polyamine with the elimination of water. The glyoxalidines with which the present invention is particularly concerned are those in which the glyoxalidine portion of the molecule is derived by reacting together one of the acids from the group consisting of lauric acid, myristic acid, palmitic acid, oleic acid and stearic acid, with an aliphatic polyamine from the group

consisting of aminoethylethanolamine, diethylenetriamine and triethylenetetramine When the glyoxalidine is derived from aminoethylethanolamine the resultant product contains a hydroxyethyl group in the 1-position When the glyoxalidine is derived from diethylenetriamine the resultant product contains an aminoethyl group in the 1-position, and when the glyoxalidine is derived from triethylenetetramine the resultant product contains a ( 2-aminoethyl) aminoethyl group in the 1-position. The number of carbon atoms in the aliphatic hydrocarbon group in the 2-position is always one less than that in the aliphatic carboxylic acid from which the glyoxalidine is derived Thus, if the glyoxalidine is made from lauric acid the hydrocarbon group in the 2-position will contain 11 carbon atoms. If the glyoxalidine is made from oleic acid the hydrocarbon group in the 2-position will be a heptadecenyl group containing 17 carbon atoms The hydrocarbon group in the 2-position preferably contains 13 to 17 carbon atoms for the purpose of the present invention. Specific examples of glyoxalidines that can be reacted with sebacic acid, dilinoleic acid and other long chain organic aliphatic dicarboxylic acids in preparing salts suitable for the purpose of the invention are: -( 2hydroxyethyl)-2-undecyl glyoxalidine, 1-( 2hydroxyethyl)-2-tridecyl glyoxalicline, 1-( 2hydroxyethyl) 2 pentadecyl glyoxalidine, 1-( 2 hydroxyethyl) 2 heptadecyl glyoxalidine, 1-( 2 hydroxyethyl) 2 heptadecenyl glyoxalidine ( 1 ( 2 aminoethyl) 2 undecyl glyoxalidine, 1 ( 2 aminoethyl) 2 tridecyl glyoxalidine, 1 ( 2 aminoethyl) 2pentadecyl glyoxalidine, 1 ( 2 aminoethyl)2-heptadecyl glyoxalidine, 1-( 2-aminoethyl)2-heptadecenyl glyoxalidine, 1 l( 2-aminoethyl)-aminoethyll 2 undecyl glyoxalidine, 1 l( 2-aminoethyl) aminoethyll-2-tridecyl glyoxalidine, 1 l( 2 aminoethyl) aminoethyll-2-pentadecyl glyoxalidine, 1-l( 2-aminoethyl)-aminoethyll-2-heptadecyl glyoxalidine, 1-l( 2-anrincethyl) amincethyi-2-1 eptadecnyl glyoxalidine, 4-methyl-2-undecyl glyoxalidine, 4-methyl-2-tridecyl glyoxalidine, 4-methyl-2pentadecy I glyoxalidine, 4 methyl-2-heptadecyl glyoxalidine, 4 methyl-2-heptadecenyl glyoxalidine. The organic aliphatic dicarboxylic acid salts are prepared by mixing a glyoxalidine of the type described and an organic aliphatic dicarboxylic acid of the type described in mol ratios of 1:1 in case it is desired to prepare the monoamine salt, or 2: 1 in case it is desired to prepare the diamine salt, and warming the reaction mixture at temperatures sufficient to melt the dicarboxylic acid if it is a solid for 5 to 15 minutes with or without a catalyst until homogeneous materials are obtained. In the practice of the invention it has been found that especially

good results in inhibiting corrosion in gasoline containing water have been obtained by employing as the corrosion inhibiting agent the reaction products of sebacic acid and 1-( 2-hydroxy ethyl)-2-heptadecenyl glyoxalidine Especially good results have been obtained with the reaction product derived by reacting two mols of said glyoxalidine with one mol of sebacic acid. In order to evaluate the invention tests were made in hydrocarbon fuels to which water had been added. The organic aliphatic dicarboxylic acid salt of the glyoxalidine of the type previously described was prepared for use as a 10 ' by weight concentrate in a suitable solvent. The test specimens were hot rolled mild steel rods x 24 " of which a 2 length was polished with 3/0 emery cloth The particle size of the particles on the cloth corresponding to 3/0 is 120 mesh U S sieve. The test medium, for example, gasoline, was placed in a 25 x 150 mm screw cap tube. To 40 ml of the test medium were added first the inhibitor solution previously described and after mild agitation 10 %' by volume of distilled water which had been equilibrated with air The capped tube was then mechanically agitated at room temperature ( 75 F) for six hours by end over end tumbling. The test solution was then transferred to a numbered 25 x 150 mm test tube and the 5 water and hydrocarbon phases were permitted to separate The test specimen was inserted in the tube so that a part was exposed to the lower phase (water) without contacting any part of the container The tube was not dis S turbed for the 72-hour test duration. Other tests were set up as described above with selected materials in which 1 ' water instead of I O % was used. After completion of the test the specimen 11 was removed, rinsed with acetone and air dried It was then evaluated on the extent of visible corrosion Each test was made in duplicate If both specimens were not visibly corroded the material was classed as effective 11 and if both appeared to be corroded the material was called ineffective Wherever one of the pairs was uncorroded and the other corroded the test was repeated If, after retesting, either specimen vwas corroded the 1 material was judged to be ineffective at the tested concentration This criterion is identical with that used in ASTM D-665-49 T. The following examples illustrate some of the results obtained when compositions falling 1 within the scope of the invention were evaluated in the manner just described. EXAMPLE I The sabacic acid salt derived by reacting two mols of 1-( 2-hydroxyethyl)-2-hepta 1 decenyl glyoxalidine with one mol of sebacic acid at a temperature of about 133 C for about 5 to 15 minutes when

tested under the foregoing conditions in Standard Red Crown gasoline to which 10 % distilled water had 1. been added was effective in inhibiting corrosion of the test specimens at concentrations of part of said amine salt per million parts of gasoline in a series of six tests. 784,623 water system when tested according to the static corrosion test previously described at a concentration of 25 parts per million. The solvent which is used to dissolve the active effective ingredient is subject to some variation depending upon the solubility characteristics of the particular compound employed. In some cases, even though the corrosion inhibiting compound is insoluble in a particular solvent it will dissolve in a combination of solvents For instance, the compound tested in Example I is soluble in 100 % denatured ethyl alcohol, soluble in Indocene 90 (a petroleum fraction high in aromatic compounds and naphthenes) soluble in 99 % isopropanol, insoluble in virgin gas oil and soluble in xylene. This product dissolves satisfactorily in a mixture of xylene and naphtha As an illustration, where the corrosion inhibiting ingredient is to be added to gasoline a suitable concentrate has the following composition: Standard Red Crown gasoline has the following specification: Initial boiling point End point API Octane number % Sulphur Gum glass dish 94 F. 396 F. 60.6 83.7 0.10 1.6 m g. In a series of three tests at a concentration of 25 parts per million the said glyoxalidine sebacic acid salt completely inhibited corrosion under the test conditions described. In a series of six tests at a concentration of parts per million in said gasoline under the same test conditions there was slight to moderate corrosion of the test specimens. EXAMPLE II When the same corrosion inhibiting composition as in Example I was tested under agitated conditions according to ASTM method D-665 49 T using a temperature of F and strips of SAE-1018 steel instead of SAE-1020 or SAE-1025 steel the aforesaid diglyoxalidine sebacic acid salt was effective in preventing corrosion at a concentration of 0 31 parts per million in the gasoline. EXAMPLE III Under the same test conditions as in Example II at a concentration of 0 16 parts per million in the gasoline slight corrosion of the test specimens was obtained At a concentration of 0 08 parts per million heavy corrosion was obtained Thus, the effective minimum amount in inhibiting corrosion in gasoline with said composition under agitated

conditions is around 0 3 parts per million and under static conditions around 5 to 10 parts per million. EXAMPLE IV Results similar to those in Example I were obtained with the reaction product derived by reacting one mol of 1-( 2-hydroxy ethyl)-2heptadecenyl glyoxalidine with one mol of sebacic acid at a temperature of about 133 C. for about 5 to 15 minutes. EXAMPLE V The monoamine salt of a dimner acid was prepared by heating together at a temperature up to 100 F equimolecular proportions of 1( 2-hydroxy ethyl)-2-heptadecenyl glyoxalidine and a dimer acid containing about 85 % by weight of dilinoleic acid This product was effective in inhibiting corrosion in a gasolinewater system under the test conditions previously described at a concentration of 25 parts per million. EXAMPLE VI The reaction product was prepared by reacting together two mols of 1-( 2-hydroxy ethyl)-2-heptadecenyl glyoxalidine and one mol of a dimer acid containing about 85 % by weight dilinoleic acid This product was effective in inhibiting corrosion in a gasolineIngredients Weight Per cent Sebacic acid salt of Example I Xylene Naphtha (flash point 80 to 105 F) 12 Similarly other compositions can be pre 90 pared using suitable solvents. It will be understood that the effective corrosion inhibiting ingredient can be added directly to the hydrocarbon liquid provided it is soluble therein However, the amounts re 95 quired are so small that it is preferable to prepare a solution of the active ingredient containing about 5 to about 15 % thereof, the remainder being a suitable solvent which dissolves the corrosion inhibiting ingredient and 100 is miscible with the medium to, which the solution is to be added. It will be understood that some variations can be made in the preparation of the corrosion inhibiting chemicals and in the procedures 105 employed in using such chemicals As examples of other long chain aliphatic dicarboxylic acids which can be reacted with any of the glyoxalidines previously described there may be mentioned the acids known in the 110 trade as VR fatty acid and VR-1 acid VR fatty acid is an organic carboxy acid material which is a vegetable residue resulting from the distillation of soap stock This material contains ester bodies and has the following 115 characteristics: Acid value Saponification value Iodine value Color (Bartlett) Viscosity (Zahn G, at 75 13 C.) 15 seconds VR-1 acid is a mixture of polybasic acids with an average molecular weight of about 784,623 1000

It has an average of slightly less than two carboxylic acid groups per molecule It is a by-product acid from the manufacture of sebacic acid by the distillation of castor oil in the presence of sodium hydroxide, and is a dark amber, rather viscous liquid A typical sample of VR-1 acid has the following analysis: Acid number Iodine number Saponification number Unsaponifiable matter Moisture content 36 172 3.7 %, 3 5 % 0.86 % One of the important advantages of the present invention is that the addition of the compositions herein described to gasoline in the quantities which are effective in inhibiting corrosion has no adverse effects such as gum formation In actual tests using a corrosion inhibition composition consisting of 12 % by weight of the product obtained by reacting two mols of 1-( 2-hydroxy ethyl)-2-heptadecenyl glyoxalidine with one mole of sebacic acid, % by weight xylene and 53 % by weight of naphtha, there was a decrease in gum formation in the gasoline from 2 8 mg per ml to 1 0 mg per 100 ml at a concentration of 10 parts of the corrosion inhibiting chemical ( 84 parts of the solvent solution of said chemical) per million parts by weight of gasoline. The term "glyoxalidine" refers to a compound having the following structural formula. wherein R is an aliphatic hydrocarbon radical; R', Y and Z are either hydrogen or an aliphatic group, it being understood that for the purpose of the present invention R, R', Y and Z are further restricted in the manner previously described It should also be noted that in the preferred compounds of the present invention R is composed of carbon and hydrogen atoms, Y and Z are either hydrogen or groups consisting of carbon and hydrogen, and RI is either hydrogen, a group consisting of carbon and hydrogen, a group consisting of carbon, hydrogen and nitrogen, or a group consisting of carbon, hydrogen and oxygen In other words, in the preferred compounds with respect to RI the atoms in the group are 5 selected from the group consisting of hydrogen, carbon, nitrogen and oxygen.

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* GB784624 (A)

Description: GB784624 (A) ? 1957-10-09

Improvements in or relating to radio-active polymerization of styrene withunsaturated esters

Description of GB784624 (A)

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PATENT SPECIFICATION 784,624 Date of Application and filing Complete Specification: Sept 13, 1955. : | No 26153/55. J,/ Application made in United States of America on Oct I, 1954. Complete Specification Published: Oct 9, 1957. Index at acceptance:- Classes 1 ( 1), C; 2 ( 6), P 4 A, P 4 D 3 (A: Bi: B 3), P 4 K 7, P 4 P( 2 A 3: 2 B: 3: 5: 6 X), P 7 A, P 7 D 2 A( 1: 2 B: 4), P 7 K( 4: 8: 9), P 7 P( 2 A 3: 2 B: 3: 5: 6 X), P 8 A, P 8 D 2 (A: B 2), P 8 K 7, P 8 P( 2 A 3: 2 B: 3: 5: 6 X), P 9 A, P 9 D 1 B( 1: 2: 3), P 9 K 7, P 9 P( 2 A 3: 2 B: 3 ' 5: 6 X); and 91, F 1, G 1 A 1, P 3. International Classification:-CO 8 f Cl Og, m. COMPLETE SPECIFICATION Improvements in or relating to Radio-Active Polymerization of Styrene with Unsaturated Esters We, ESSO RESEARCH AND ENGINEERING COMPANY, a Corporation duly organised and existing under the laws of the State of Delaware, United States of America, of Elizabeth, New Jersey, 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 for the preparation of copolymers of styrene or alkylated styrene and, unsaturated esters by the use oi radio-active radiation Particularly the invention relates to oil-soluble copolymers useful as viscosity index improvers and pour point depressors obtained by such processes, and to oil compositions containing such copolymers. Copolymers of styrene and its homologues with other polymerizable materials, specifically esters of unsaturated materials, are knlmown in the art It has been known for some time that peroxide-catalyzed polymerization: of styrene alone, or with other polymerizable materials, has to be run at relatively high temperatures for relatively long periods of time in order to obtain copolymers of sufficiently high molecular weights to be useful as additive materials. It has now been found that copolymerization of styrene and its homologues with other polymerizable materials such as unsaturated esters, may be carried out at low temperatures and desirably high molecular weight copolymers are obtained in relatively short periods of time by exposing the monomers to the effect of radiation emitted by sources of high energy radioactivity. Types of radiation suitable for the purposes of invention include high energy electromagnetic radiation, such as gamma rays and WP, I X-rays and high velocity electrons, such as beta rays, as well as alpha particles. These types of radiation may be supplied by 45 naturally occurring radioactive materials, such as radium and its compounds, which emit alpha, beta and gamma rays Fission by-products of processes generating atomic power and/or fissionable materials, which emit high 50 energy gamma rays, afford a highly desirable and most abundant source of radioactivity suitable for the purposes of the invention These by-products include elements with atomic numbers ranging from 30 (Zinc) to 63 (Euro 55 pium) and, their compounds They are formed in the course of converting uranium, thorium and other fissionable material in an atomic reactor. Materials made radio-active by exposure to 60 neutron radiation, such as, radioactive Cobalt (Co 60), Europium 152 or Europium 154 which emit gamma rays, may likewise be used Suitable sources of high velocity electrons are the beams of electron accelerators, such as the Van 65 de Graaf generator or the Betatron In general, however, high intensity gamma radiation and its well-known sources, such as nuclear fission by-products and materials made radioactive by neutron

radiation are preferred for the pur 70 poses of the invention mainly because of the relatively high penetrating power of the gamma rays and the availability and ease of application of these sources of gamma radiation. The gamma radiation arising from an 75 atomic reactor which is producing power and/or fissionable material made also be employed in the concept of this invention The monomers may be circulated outside the neutron shield surrounding the reactor or they 80 may be circulated through the reactor itself. A reactor producing 1 kg of Plutonium per day would produce also 13 mev of gamma radiation per fission, 13 mev of gamma radiation can produce 550,000 ion pairs each of which can initiate the formation of a polymer molecule Thus, the unit used as a gamma ray source for copolymerization would also be simultaneously producing power and/or fissionable material. The present invention therefore comprises a process for producing copolymers of styrene or an alkylated styrene and an unsaturated ester, which comprises exposing a mixture of styrene or alkylated styrene and an unsaturated ester to radioactive radiation of intensity at least 10,000 Roentgens/hour for a time sufficient to increase the average molecular weight of the mixture. It has been found that unsaturated esters of the type here involved may be copolymerized with styrene or its homologues to form valuable viscosity index improvers and pour point depressants by exposure to, radiation of the type specified above Radiation time and intensity largely depend on the degree of copolymerization, i e, the molecular weight, desired for the end product Within the broad operable ranges of a few seconds to several hours, say 0.5 to 48 hours radiation time and 10,000 to 2,000,000 Roentgen per hour (R/hr) radiation intensity, copolymer molecular weights of any desired magnitude may be produced Conversion is the higher the longer the radiation time and the higher the radiation intensity, resulting in higher viscosities of the reaction product In general, the molecular weight of the copolymer varies directly with the concentra. tion of the reactants in the reaction mixture. Conditions suitable for the production of most lubricating oil additives coming withinr the scope of this invention include temperatures of O to 150 F, radiation times of 1 to 24 hours, preferably 2 to 10 hours, and radiation intensifies of 100,000 to 5,000,000 R/hr preferably 200,000 to 500,000 R/hr. The process of the invention has the following advantages: 1 High temperatures are not required to initiate the copolymerization reaction This means that the copolymerization may be carried out at ambient temperature without providing heat for the process With

peroxide initiated copolymerization, the reaction mixture must be heated to a temperature range in which the peroxide will decompose In using benzoyl peroxide, one of the more common methods for initiating commercial copolymerization reactions, it is necessary to heat the reactants to a fairly high temperature for polymerization to occur. 2 The reaction is easily controlled With peroxide copolymerization catalysts, the rate at which the chain initiators are produced depends not only upon the concentration of the peroxide and the temperature, but also upon little understood secondary chemical changes in the peroxide decomposition products The rate at which chain initiating gamma rays are produced by the radio-active source is constant Therefore, at a given temperature the copolymerization will be quite even and not, subject to sudden acceleration or deceleration as is the case with peroxide cata 70 lysts Also, with conventional peroxide catalysis it is necessary to heat the reaction mixture to, initiate the copolymerization process after which rapid cooling may be required so that the polymerization does not get out of 75 control Difficult control problems of this type are avoided in accordance with the invention. As a result, the products ordinarily will have a more uniform molecular weight range which will result in quality advantages, e g, better 80 shear stability. 3 There is no catalyst contamination in the products copolymerized by gamma irradiation. Since the radioactive material need not come in direct contact with the reactants, and since 85 the gamma rays themselves are merely particles of light, the problem of removing initiating materials from the resulting polymer does not exist The absence of catalyst contamination in the final product usually results 90 in greater thermal stability of the copolymer. It should be pointed out that gamma ray irradiation does not make a substance radioactive. 4 Radiation initiation is readily adaptable 95 for continuous copolymerization processes. Since irradiation from an irradiation source is regular and not affected by temperature or other outside phenomena, the catalytic effect is controlled in radiation initiated copolymer 100 izations solely by the time of residence of the reactant within the inadiation zone For all practical purposes, the initiator is not consumed as is the case with chemical initiators. In addition, a radiation source, such as a 105 gamma source, produces no products which must be removed from the reaction zone. These features permit the design of a plant which can manufacture polymer on a 24 hour per day basis by merely pumping monomers 110

through the radiation given out by a suitable source. As was stated above, the improved products of this invention are prepared by copolymerizing styrene or alkylated styrene with an un 115 saturated ester. The styrene or alkylated styrene used as one monomer may be used in amounts ranging from 10 0 vol % to 80 0 vol %, based on the total volume of the mixture and may be 120 selected from the group consisting of styrene and the various alkylated styrenes containing alkyl or alkylaryl substituent Ordinarily substituent groups containing from 5 to 18 carbon atoms are operable with methyl, ethyl and 125 alpha-methyl substituted styrene being preferred. The unsaturated ester monomer copolymerized with the styrene compound may be used in amounts from about 90 0 % to, 20 O vol % 130 784,624 A preferred embodiment of the present invention consists of exposing to radio-active radiation a mixture of 10,% to 80 % by volume of styrene or alkylated styrene and 90 % to 55 % by volume of an ester defined by the above formula, said radio-active radiation being of an intensity of from 100,000 to 5,000,000 Roentgens/hour, for a period of time of from half-hour to 48 hours, at a tern 60 perature of from O O F to 150 F, whereby an oil-soluble copclymer is formed. In some cases, it is desirable to dilute the monomer mixture during the reaction with a suitable solvent which is substantially inert to 65 gamma irradiation, such as; a saturated hydrocarbon, carbon tetrachloride or dioxane In this manner, cross-linking of the polymer to form oil-in-soluble gels is inhibited and the product is obtained in a readily usable form 70 The copolymers prepared in accordance with the invention may be used as lubricating oil additives in concentrations of O 001-10 wt. %, preferably O 01-5 0 wt 1 % When pour depressing is the primary objective, concentra 75 tions of 0 01-0 5 wt % are normally sufficient Larger concentrations of 05-5 0 wt. % are usually required for appreciable improvements in the viscosity index of the oils. The oil base stocks in which the copolymers 80 of the invention may be used may be paraflinic oils which normally require poor depressors as well as naphthenic or mixed base lubricating oils requiring viscosity index improvement, or oil blends requiring both pour depressing and 85 viscosity index improving additives These oils are preferably of lubricating oil grade having viscosities of 35 to 150 SUS at 210 F The polymers and copolymers may also be added to greases, paraffin wax or waxy compositions, 90 lighter hydrocarbon oils, such as Diesel fuel base stcks requiring pour depressing or other light oils including domestic heating oil base stocks, mineral seal oil, kerosene, etc. Oil compositions containing the copolymers 95 of the invention may be

further improved by the addition of conventional modifying agents, such as dyes, anti-oxidants, tackiness agents, etc, or of other types of pour depressors, such as wax-naphthalene condensation products, 100 wax-phenol condensation products as well as other viscosity index improvers, such as polybutenes, polyvinyl ethers, etc. Conventional means of irradiating materials with radioactive radiation may be employed 105 to,carry out the process of the invention For example, batches of the reaction mixtures may be inserted in or reactant streams passed through pipes made of or containing the radioactive material and shielded from the outside 110 to protect the operator In accordance with another procedure, the radioactive materials are stored in the bottom of a concrete or metallined pit which is filled with water to a level sufficient to absorb the radiation being 115 emitted The radioactive materials may be and may be any ester represented by the following formula: A >C=C< B D E wherein A, B, C and D are defined as follows: 1) A and D are carboxylic acid ester groups -C-OR, and B and E are hydrogen, i e, fumaric acid esters, maleic acid esters. 2) A and D are carboxylic acid ester groups, as above, and either B or E is a methyl group, the other being hydrogen, i e, cirraconic acid esters, mesaconic acid esters. 3) A and B are hydrogen, D is a carboxylic acid ester group, as above, and E is a methylene carboxylic acid ester group, i e, itaconic acid esters. 4) A and D are carboxylic acid ester groups as above, E is a methylene carboxylic acid ester group and B is hydrogen, i e, aconitic acid esters. 5) A, B and D are hydrogen and E is the group -O-R i e, vinyl acetate, vin 3 yl butyrate, or vinyl iaurate. 6) A and B are hydrogen, D is hydrogen or methyl group and E is the ester group 0 O 1 I H Utlor -COOR, i e, isopropenyl acetate, acrylic acid esters, methacrylicacid esters. Of the cperable monomers covered by the above, the preferred embodiments are the esters of fumaric, maleic, acrylic and methacrylic acid containing from 3 to 20 carbon atoms in, the ester group, such as the esters of these acids and the following alcohols: propanol butanol hexanol heptanol 2-ethyl hexanol octanol decanol dodecanol tetradecanol (myristyl alcohol) hexadecanol (cetyl alcohol) octadecanol (stearyl alcohol) Particularly desirable are the acid esters of branched chain alcohols produced by the well known catalytic oxonation of C, to CQ 2 oleflns with CO and H 2,, and the commercial mixture of alcohols obtained by the hydrogenation of coconut oil, said mixture containing Ca and C, alcohols. 784,624 held in metal containers or under a thin layer of concrete to

prevent direct contact with the water The reactants may either be lowered in batches into, the pit or passed through pipes through the pit in al position in which they are adequately exposed to the radiation emitted by the radioactive materials The water acts as a shield protecting the operator above the pit against radiation No radiation passes through the ground around the pit Other suitable means for carrying out the process of the invention may appear to those skilled in the art. The invention will be further illustrated by the following specific examples. EXAMPLE 1. a) A mixture of 83 parts by volume of di"Lorol " (the term "Lorol " is a Registered Trade Mark) fumarate and 17 parts by volume of styrene was exposed to the radiation emitted by radioactive cobalt (COG ) The "Lorol" B fumarate had been prepared by esterifying fumaric acid with "Lorol" B alcohols, which 'is a commercial mixture of normal alcohols containing from 8 to 18 carbon atoms derived from coconut oil and having an average molecular weight of 207 The sample was placed in a sealed glass container contamined in an aluminum canister This aluminum canister was then introduced into, the center of a pipe of the radioactive cobalt. The samples were exposed to a radiation intensity of about 235,000 R/hr at about 70 F. for about 24 hours At the end of this period, the product was a tughl, resinous, slightly rubbery material, almost transparent and completely soluble in hydrocarbon solvents and mineral oils This product was dissolved in a highly refined white mineral oil having a viscosity of 42 SUS at 210 F to form a 20 % solution, and compared with a product prepared with benzoyl peroxide as a catalyst. This product was prepared as follows: b) A mixture of 83 parts by volume of diLorol" fumarate and 17 parts by volume of styrene in 25 parts of a highly refined white mineral oil was maintained at 175 F whilz the catalyst was added in small increments. A total of 1 wt % benz- yl peroxide (based upon the monomers) was added during the first 25 hours of the reaction, and the reaction was continued, maintaining a temperature of F for a total of 75 hours Even after this long reaction timne the polymer was rather low in molecular weight as shown by comparison in Table I. TABLE I Viscosity of Styrene-Fumarate Copolymer Concentrates Blends in Oil A Copolymer 1 a) Gamma Rays 70 24 20 3,770 1 b) Benzoyl 175 75 20 93 5 Peroxide (Blend Oil A) 0 42 1 TABLE II Styrene-Fumarate Copolymers as V I Improvers Blends in Oil B Conc SUS

at SUS at Copolymer Wt % 100 F 210 F V I. 1 a) 3 6 559 9 102 0 144 0 1 b) 3 6 222 6 51 2 127 6 (Blend Oil B) 0 0 174 0 45 7 113 0 Temp Time, Weight SUS at Catalyst F Hours % 210 F. 784,624 -4 784,624 TABLE III Styrene-Fumarate Copolymers as Pour Depressants ASTM Pour Point, F in Mid-Continent SAE-10 Lubricant (Oil C) at Weight % Indicated 0.00 0 01 0 03 0 05 0.10 1 a) + 10 + 5 -30 -< 35 < 35 1 b) + 10 0 -25 -< 35 < 35 The foregoing data show that the gamma ray copolymer is an effective viscosity index improver while the peroxide copolymer is not' nearly as effective Both are potent pour depressants. EXAMPLE 2. A mixture of 83 parts by volume of di"Lorol" fumarate 1 and 17 parts by volume of styrene were dissolved in 25 parts by volume of a highly refined mineral oil having a viscosity of 42 SUS at 2100 F This mixture was exposed to gamma irradiation (by the method described in Example 1) of about 225,000 R/hr intensity at 150 F for 5 hours. The product was an excellent viscosity index improver as shown in Table IV. EXAMPLES 3 TO 5. Preparative details and viscosity index improving properties for these copolymers are described in Table IV. TABLE IV Preparation and Properties of Styrene-Fumarate Copolymers Gamma Irradiation Conditions Exp Monomer No Composition 2 83 "Lorol" Fumarate/17 Styrene 3 80 "Lorol" Fumarate/20 Styrene 3.6 % Blends in Oil B Intensity Temp Time SUS SUS R/hr F Hours 100 F 210 F. 225,000 150 225,000 I 00 V.I. 266 7 57 5 137 8 8 321 2 65 O 1 i 9,5 4 62 5 "Lorol" Fumarate/16 7 Butyl Fumarate/ 20.8 Styrene 56 8 "Lorol" Fumarate/15 2 Butyl Fumarate/ 28.0 Styrene 210,000 70 24 273 9 59 O 140,3 210,000 70 24 291 0 62 7 143 1 EXAMPLE 6. A mixture of 77 3 parts by volume cf di"Lorol" fumarate and 22 7 parts by volume of styrene was stirred with a mixture of 140 parts by volume water, 10 parts heptane and 0.75 parts sodium stearate emulsifier The resultant emulsion was exposed to gamma irradiation at 210,000 R/hr intensity at 70 F for 8 hours The yield of copolymer was 54 %, based upon the monomer charged This product was an excellent pour depressant as shown in Table V. EXAMPLE 7. This copolymer was prepared similar to Example 6 except irradiation was for 24 hours. The yield of copolymer was 83 % and this product was; also, an excellent pour depressant as shown in Table V. Copolymer 784,624 Example

No. TABLE V Styrene-Fumarate Copolymers as Pour Depressants ASTM Pour Point, F in Mid-Continent SAE-10 Lubricant (Oil C) at Weight % Indicated 0.00 0.01 0.03 0.05 0.20 6 + 10 -20 -25 -< 35 -35 7 + 10 -10 -30 < 35 <-35 Blends in Mid-Continent SAE-20 Lubricant (Oil D) 6 + 15 -20 -20 -20 -30 7 + 15 5 -20 -20 -30 To illustrate the difference between the copolymeric materials prepared in accordance with this invention from those described in British Patent Specification 589,233, details of preparation and inspection of tvo examples of that patent are set out in Table VI below. TABLE VI Examples from Patent Specification 589,233 Reaction Conditions Reactants Catalyst Time Temp 3 6 % Blend Mol % Bz 2 02 Hrs F SUS/210 F ( 1) Wt ( 2) C 12 Maleate/ 2 48 275 54 5 5,300 Styrene C 8 Fumarate/ 1 72 230 60 0 8,500 Methyl Styrene ( 1) Viscosity SUS/210 F of 3 6 wt % copolymer in base oil of 45 9 SUS/210 F. (Oil B). ( 2) Molecular weights estimated from 3 6 % blends. For purposes of comparison and to illustrate a copolymer of equal molar proportions of "Lorol" fumarate and styrene were prepared using gamma ray irradiation and a copolymer of C 10 fumarate mixture and styrene was prepared using a peroxide catalyst The latter copolymer had the highest molecular weight of any of the laboratory preparations of styrene copolymers, but was less than -, the molecular weight of the copolymer prepared with gamma rays Data on these preparations are set out in Table VII below. 784,624 TABLE VII Comparison of Reaction Conditions and Products Reaction Conditions Reactants % Time Temp Cony 3 6 % Blend Molecular Bz 202 Hrs F % SUS/210 F E Weight 82.6 g "Lorol" Fumarate/ 17.4 g Styrene (gamma (equimolar) rays) 24 70 81 3 131 0 24,500 158 g C 10 Fumarate/ 42 g Styrene (equimolar) 1 35 170 74 3 59 0 8,000 See Table VI above. See Table VI above. The data of Tables VI and VII above show that it is a practical impossibility to obtain copolymeric materials in the molecular weight range from about 12,500 to about 30,000, the range most practical for viscosity index improvers, using peroxide catalyst technique. The high molecular weight copolymers prepared by gamma rays are thus of a different type structure and are substantially different from those obtained with a peroxide catalyst.

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* GB784625 (A)

Description: GB784625 (A) ? 1957-10-09

Non-magnetic thermally compensated spring

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PATENT SPECIFICATION 784,625 Date of Application and filing Complete Specification Oct 3, 1955. No 28088/55. Application made in Switzerland on Oct 2, 1954. a/ Complete Specification Published Oct9, 1957. Index at Acceptance: -Classes 83 ( 2), A 155; and 83 ( 4), V 2. International Classification: -B 23 p C 22 f. COMPLETE SPECIFICATION Non-Magnetic Thermally Compensated Spring We, INSTITUT DR ING REINEI Aiw STR AuMANN A G, a Corporation organised under the Laws of Switzerland, and FRITZ STRAUMANN, a Citizen of Switzerland, both of Waldenburg, Basle-Campagne, Switzerland, 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:Hitherto, thermo-elastic

anomaly, for instance, in thermally compensated vibrating springs could only be achieved in the case of ferro-magnetic material by using the AE-effect produced by magneto-striction Non-magnetic materials were not amenable although it would have been highly desirable to use them with a view to obtaining this compensatory effect. Experiments have revealed that by a process of ordering, i e by the creation of a superlattice that can be induced by suitable thermal treatment to occur in the mono-crystal of metallic materials that crystallise in the cubic system, the functional variation of Young's modulus in relation to temperature may be made to exhibit an anomaly characterised by a very low thermo-elastic coefficient within a certain temperature range The thermo-elastic coefficient (X 1) is defined by the relationship: 1 d E il= where E=Young's modulus It E dt has also been found that ordering induced in monocrystals of materials that crystallise in the cubic system is capable of producing thermoplastic anistropy By means of an appropriate heat treatment, by drawing and/or rolling the poly-crystalline material, in any desired sequence of operations, a texture can be created in the wire or ribbon so treated which, provided the mono-crystal of the metallic material that crystallises in the cubic system becomes thermo-elastically anisotropic as a result of ordering, causes the desired thermoelastic anomaly to be much more pronounced. The thermally compensated non-magnetic spring according to the present invention, lPrce 3 s 6 d l which is suitable for use in vibrating systems of four springs under static stress therefore consists of a non-magnetic metallic material having a cubic face or body-centred crystal lattice, the mono-crystals of which show pronounced anisotropy of the thermoplastic coefficient, and having a texture exhibiting minimum values of the thermo-elastic coefficient preferably in the direction in which the spring wire or ribbon was drawn or rolled. Springs according to the invention are obtained by subjecting, preferably in the form of a wire or ribbon, a non-magnetic metallic material having a cubic face or body-centred crystal lattice and which exhibits both an anomaly of the thermo-elastic coefficient and a thermo-elastic anisotropy, to a process of homogenization at a temperature not exceeding 1200 C, followed by quenching, drawing down, and/or flat rolling, the total reduction in section produced by cold forming amounting to values up to about 95 %. The production of springs of special texture suitable for watches, clocks, apparatus, and the like, has been described in the British Patent Specification No 733,510. Hence, springs produced according to the invention are thermo-elastically anisotropic.

In the course of experiments, the thermoelastic anomaly of the mono-crystal of a-brass was successfully reproduced in the crystallite aggregate, i e in commercially produced 6brass in the form of an isotropic polycrystalline rod, by the production of wires and ribbons exhibiting a drawing or rolling texture and therefore a considerable measure of orientation in the minimum values of the thermo-elastic coefficient in the direction of drawing or rolling It was also found that the texture induced by drawing or rolling sufficiently reduced the thermo-elastic coefficient to satisfy the requirements of compensation in vibrating systems for clocks and watches Furthermore, it was established that cold drawing of the materials that had been subjected to the above described heat treatment produced a pronounced drawing or rolling texture wherein the ( 110) direction, i e the direction 784,625 of the diagonal of the face, was mainly parallel with the longitudinal dimensions of the wires or ribbons Finally, it was found that re-crystallisation at approximately 500 C further improved the texture The procedure above described was therefore successful in bringing the ( 110) or ( 100) direction, i e the direction of the diagonal and the edge of the face, respectively, preferentially into parallelism with the longitudinal axis of the wire or ribbon besides imparting to the treated spring material a low thermo-elastic coefficient owing to the subsequent ordering, i e formation of a super-lattice. It will be understood that the example described for the treatment of fl-brass is in no way intended to limit the scope of the invention, as other non-magnetic materials can be used instead of the fl)-brass to similar effect, i e. materials that are thermo-elastically anisotropic and which can be rolled to produce a textile giving minimum values of the thermoelastic coefficient in the longitudinal axis of the wire or ribbon.

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* GB784626 (A)

Description: GB784626 (A) ? 1957-10-09

Improvements in the production of 1.2-diaminocyclohexanes

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COMPLETE SPECIFICATION Improvements in the Production of 1. 2-Diaminocyclohexanes We, BADISCHE ANILIN- & SODA-FABRIK AKTIENGELLSCHAFT, a Joint Stock Company organised under the laws of Germany, of Ludwigshafen on Rhein, Germany, 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 :- There has not hitherto been a method for the production of 1. 2-diaminocyclohexanes which is useful for industrial purposes. A sequence of rections starting from anthranilic acid (A. Einhom and collaborators, Ber. deutsch. Chem. Ges 27 (1894) 2469 and Liebigs Ann. Chem. 295, 209) gives only bad yields of unsubstituted 1. 2-diaminocyclohexane. ihe reduction of ortho-nitroaniline or of 1. 2-diamine- benzene also has not hitherto given satisfactory results. As an initial material already containing the cyclohexane ring, 1. 2-dinitrazyclohexane has recently acquired interest ; because it can be prepared very simply by nitration of cyclohexane. Attempts to reduce it to 1.2-diaminocyclohexane with the usual ohe ! mical reducing agents, such as iron and hydrochloric acid or stannous chloride, have however been unsuccessful. If an attempt is made to hydrogenate 1.2-dinitrocyclohexane catalytically in an autoclave, heterogeneous products are obtained which consist for the most part of high molecular weight substances of unknown constitution. We have now found that 1. 2-diaminecyclo- hexane or a l-substituted-amino-2-amino- cyclohexane is obtained in good yields by

continuously leading 1. 2-dinitrocyclohexane over a hydrogenation catalyst, in the liquid phase, at a temperature from 50~ to 200~ C and at pressures off from. 100 to 300 atmospheres, together with an excess amount of hydrogen and ammonia when 1. 2-diaminocyclohexane is to be obtained, and an excess amount ouf hydrogen and a primary or secondary amine when 1-substituted-amino-2-amino- cydohexane is to be obtained. Suitable hydrogenation catalysts are for example metallic cobalt and nickel which have been obtained by reduction of the correspondin, oxides, and also the so-called Raney catalysts or also those which contain nickel or cobalt precipitated on carriers such as aluminium oxide. Indifferent diluents, such as methanol, ethanol, tetrahydrofurane or dioxane, may be used. Suitable amines are for example mono-and di-methylamine, mono-and di-ethylamine, mono- and di-butylamines, dodecylamine, didodeclamine, cyclohexylamine, N-methyl- and N-ethyl-cyclohexylamine, and also pyrrolidine, piperidine, hexamethylene imine, morpholine, piperazine, aniline, N-methyl-and N-ethyl- aniline, benzylamine, phenylpropylamine, mono-and di-ethanolamine, ethylene diamine or alpha-aminopyridine. In this way there are obtained very simply and in almost quantitative yields products from which very pure 1.2-diaminocyclohexanes can be recovered by a single fractional distillation. The reaction may be reproduced as follows in the case of using dimethylamine: <img class="EMIRef" id="026415701-00010001" /> The amines formed can be recovered from the reaction : mixture very simply in pure form and in excellent yields by distillation. It is surprising that by the use of primary or secondary amines instead of ammonia, the 1. 2-diaminocyclohexanes substituted on only one of the two nitrogen atoms are formed. Such compound have hitherto been inaccessible or only accessible by troublesome methods. The 1. 2-diaminocyclohexanes are valuable intermediate products, especially for complexforming agents, dyestuffs, textile assistants, oil assistants, fungicides, insecticides and pharmaceutical products. The following Examples will further illus- trate this invention but the invention is not restricted to these Examples. The parts are parts by weight. EXAMPLE 1. A solution of 300 parts of 1. 2-dinitrocyclo- hexane in 2500 parts of liquid ammonia per tiour and hydrogen ; are pumped continuously through a hydrogenation chamber 1. 6 metres long and 4. 4 centimetres in internal width filled with pellets of reduced cobalt or nickel oxide. The chamber is heated to 70 to 110 C and the pressure is

adjusted to about 250 atmospheres. By distillation of the reaction product, pure 1. 2-diaminocyclohexane of boil- ing point 87 C at 22 torr is obtained in a yield of about 90% of the theoretical yield. The ammonia can be reused after separating the water formed. EXAMPLE 2. A mixture of 300 parts of 1. 2-dinitrocyclo- hexane, 800 parts of methanol and 1900 parts of liquid ammonia per hour is led with Xhyidiro- gen under a pressure of about 250 atmospheres at a temperature of 70 to 110 C through the apparatus described in Example 1. By fractional distillation of the reaction product, very pure 1. 2-diaminocyclohexane is obtained in a yield of about 85% of the theoretical yield. Dioxane or tetrahydrofurane may be used : instead of methanol with a similar result. EXAMPLE 3. Z50 parts of a distillation residue from the industrial production of nitrocyclohexane by nitration of cyclohexane with nitric acid, which ; contains considerable amounts of 1. 2-dinitrocyclohexane, are dissolved in 2500 parts of liquid ammonia. This solution is pumped within an hour together with hydrogen at about 250 atmospheres pressure through a chamber 1. 6 metres long and 4. 35 centimetres in internal width filled with pellets of reduced cobalt or nickel oxide and heated to 55 to 115 C. By fractional distillation of the hydrogenation mixture, obtained continuously, cyclohexylamine passes over as first runnings. The bulk consists of pure 1. 2-diaminocyclohexane of the boiling point 87 C at 22 torr. The last runnings consists of polyamino compound ox unknown constitution. EXAMPLE 4. A solution of 300 parts of 1. 2-dinitrocyclo- hexane in 2500 parts of liquid dimethylamine is pumped per hour together with hydrogen under a pressure of 250 atmospheres and at 80 to 140 C through a hydrogenation vessel 1. 60 metres long and 4. 35 centimetres in internal width which is charged with about 2100 cubic centimetres of reduced cobalt or nickel oxide pellets. By fractional distillation of the reaction mixture, the dimethylamine which has not been converted is first obtained and this can be used again after separation of the water and ammonia formed ; then at 75 C and 5 torr 1- (dimethyl-amino-) 2-aminocyclohexane is obtained as a water-white oil in a yield of 92% of the theoretical yield. Similar high yields of the pure compound are obtained by using less dimethylamine and if necessary using methanol or tetrahydrofurane as diluent. EXAMPLE 5.

A solution of 300 parts of 1. 2-nitrocyclo- hexane in 2500 parts of monomethylamine is pumped per hour through the vessel described in Example 4 under a pressure of 250 atmospheres of hydrogen at 60 to 125 C. The excess of monomerhylamine is separated by distillation under pressure. The l- (methyl- amino-) 2-aminocyclohexane obtained in 95-,'. of the theoretical yield is a water-white liquid which boils at 52 C at 5 torr. EXAMPLE 6. 2000 parts by volume of a solution of 300 parts of 1. 2-dinitrocyclohexane in 275 parts of methanol and 5000 parts of diethylamine are pumped per hour under 300 atmospheres hydrogen pressure at 80 to 140 C through the vessel described in Example 4. The 1- (diethylamino-) 2-aminocyclohexane obtained in a good yield boils at 106 to 116 C at 29 torr. EXAMPLE 7. A solution of 300 parts of 1. 2-dinitrocyclo- hexane in 3000 parts of hexamethylene itnine is pumped hourly through the vessel described in the foregoing Examples at 70 to 140 C under 250 atmospheres hydrogen pressure, and the groduct worked up as described above. The 1- (hexamethyleneimino-) 2-aminocyclohexane obtained in excellent yields boils at 114 C under 8 torr. By using 2500 parts of piperidine per hour instead of the hexamethylene imine, 1- (piper- idino-) 2-aminocyclohexane is obtained in a yield of 80% of the theoretical yield ; it boils at 115 to 119 C at 14 torr. EXAMPLE 8. A solutionE of 300 parts of 1. 2-dinitrocyclohexane in 3000 parts of pyrrolidine is pumped per hour through the vessel used in Example 4 under 250 atmospheres hydrogen pressure at 93 to 130 C. In this way 1-(pyrrolidino-) 2aminocyclohexane, which boils at 111 C at 9 torr, is obtained in a yield of about 85, % of the theoretical yield. By using the same amount of morpholine instead of pyrrolidine, l-morpholine2-amino- cyclohexane of the boiling point 130 to 135 C at 12 torr is obtained in a similarly good yield. EXAMPLE 9. 250 parts of a distillation residue from the industrial production of nitrocyclohexane by, nitration of cyclohexane with nitric acid and which contains considerable amounts of 1. 2dinitrocyclohexane are dissolve in 2500 parts of liquid dimethylamine. This solution is pumped within 1 hour together wMh hydrogen at about 300 atmospheres pressure through a vessel of a length of 1. 6 metres and an ! internal width of 4. 35 centimetres which is filled with pellets of Raney cobalt and which is heated to 80 to 140 C. By fractional distillation of the continuouslv obtained hydrogenadon mixture, excess

dimethylamine and cyclohexylamine pass over as first runnings. Then pure l-(dimethylamino-) 2-aminocycloZ hexane distils over at 75 C at 5 torr. A mix- ture of polyamino compound of unknown constitution is obtained as last runnings. EXAMPLE 10. 2000 parts by volume of a solution of 400 parts of 1. 2-dinitrocyclohexane in 9500 parts of aniline are pumped per hour through the pressure vessel used in Example 4 under a hydrogen pressure of 300 atmospheres at 70' to 115 G. By fractional distillation of the continuously obtained hydrogenation mixture, 1-(phenyl-amino-)2-aminocyclohexane, which boils at 140'to 143 C at 2 torr, is obtained in an excellent yield. The compound solidifies after a short time to a colourless crystal mass. The aniline recovered as first runnings can be used again. Polyamino compound of high boiling point and of unknown constitution are obtained as last runnings. EXAMPLE 1 2000 parts by volume of a solution of 400 parts of 1.2-dinitrocyclohexane in 7500 parts of 28% ethylene diamine are pumped per hour through the pressure vessel used in Example 4 under a hydrogen pressure of 300 atmospheres at 70~ to 120~C. By fractional distillation of the continuously obtained hydrogenation mixture, 1-(?-aminoethylamino-)2aminocyclohexane, which boils at 112~ to 115 C at 4 torr, is obtained as a colourless oil. The recovered ethylene diamine can be used again, Polyamino compo, unds of the shigh boiling point and of unknown composition are obtained as last runnings.

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* GB784627 (A)

Description: GB784627 (A) ? 1957-10-09

Device for casting films

Description of GB784627 (A)

COMPLETE SPBCIFICATI ON Device for Casting Films We, J. P. BEMBERG AI(TIENGESELLSCHAFT, of Wuppertal-Oberbarmen, Germany, a Body corporate organised under the laws of Germany, 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 device for casting films. Casting devices which are used for the manufacture of films by the "apron" casting method are so arranged that the discharge slot is situated at a distance above the coagulation bath, so that the screen of solution issuing from the casting slot drops freely into the bath. If the temperature of the bath is about the same as or higher than that of the solution being cast, the vapours ascending from the bath condense on the colder lips of the casting element and form droplets thereon; these droplets drip from the casting element and form holes or streaks when they meet the film. This disadvantage was formerly avoided by passing the casting solution through a preheater which brought it to a temperature a few degrees higher than the temperature of the coagulation liquid. Furthermore, devices have been developed in which there are cavities in the walls of the casting element, hot liquid or steam being passed through these cavities. These cavities through which a stream of hot medium flows are always so arranged that the casting solution receives most of the heat; however, the metal block of which the casting element is made is also heated, and the consumption of heating energy with these devices is considerable. It has now been found that the problem can be solved by a substantially simpler arrangement. Since it is sufficient, in order to avoid condensation of liquid on the casting element, for the external surfaces of the casting element to have the same or a higher temperature than the bath, it is not necessary to heat the entire metal block. The heating which is produced by arranging electric heating elements along both sides of the lips of the casting element is sufficient to prevent any formation of droplets of liquid. Accordingly the present invention provides a device for casting films in a coagulation bath, comprising a casting element which does not dip into the liquid in the bath and has a casting slot with an electric heating element arranged along each side. The consumption of energy

required is substantially lower than with the arrangement previously proposed. The heating elements used are preferably chrome nickel wires with a diameter of 0.5 mm. and a resistance of 12 ohms, which are disposed in an iron tube with an internal diameter of about 10 mm. and are insulated by steatite beads. A voltage of 6-60 volts alternating current is completely adequate for heating purposes, a voltage regulator preferably being used. Figure 1 of the accompanying diagrammatic drawings is an end view, and Figure 2 is a side view, of one embodiment of the invention. In these drawings a casting element 1 has casting lips 2 defining a casting slot 3, and on each side of the casting lips 2 there is a heating element 4 disposed in a tube 5. The voltage applied to the heating element is controlled by a voltage regulator 6. What we claim is 1. A device for casting films in a coagulation bath, comprising a casting element which does not dip into the liquid in the bath and has a casting slot with an electric heating element arranged along each side. 2. A device as claimed in claim 1, wherein the heating elements are chrome nickel wires through which electric current can flow. 3. A device for casting films in a coagulation bath, substantially as described with reference to the accompanying drawings.