4221 4225.output

* GB784628 (A)

Description: GB784628 (A) ? 1957-10-09

Improvements in the production of conjugated-unsaturated aldehydo carboxylicacid esters

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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.

COMPLET SPECIFICATION Improvements in the Production of Conjugated-Unsaturated Aldehydo Carboxylic Acid Esters We ; BADISCHE ANILIN- & SODA-FABRIK AKTIENGESELLSCHAFT, a Joint Stock Com- pany organised under the aaws of Germany, of Ludwigshafen on Rhein, Germany, do hereby declare the invention, for which we pray that a payant 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 production of valable conjugated-unsaturated aldehydo carboxylic acid esters, especially of 4-methylhexadtene :- (2. 4)-al- (l)- oic acid-(6) and 2.6-dimethyloctatricne (2.4.6)-al-(1)-oic acid-(8) lower alkyl esters. We hav efound that conjugated-unsaturated aldehydo carboxylic acid esters are obtained by reacting, while excluding water, aldehydo carboxylic acid esters of the general formula <img class="EMIRef" id="026415699-00010001" /> in which m ! and n lare 0 or 1 or 2 and the sum of m and n is 1, 2 or 3, R represents hydrogen or a lower alkyl group and RI represents a lower alkyl group, or the lower dialkyl acetals of said aldehydo carboxylic acid esters, the terms lower alkyl meaning alkyls of from 1

to 4 carbon atoms, in the presence of acid condensing agents with a vinyl ether of the general formula R-CH = CH-OR1 in which R and R1 have the same meaning as above, R and RI of the said general formulas being individually or cojointly either the same or different radicals of the aforesaid kind, and heating the resultant alkoxy aldehyde carboxylic acid esters or their dialkyl acetals in the presence of at least 1 mol of water per 1 mol of alkoxy aldehydo carboxylic acid ester with an acid until no more.'alcohol is split off. In the heating and splitting off of the alcohol more than 1 mol of water per mol of alkcxy aldehydo carboxylic acid ester or its diallyl- acetal can also be present. Often it is even advantageous to use an excess of water, e. g. 10 mols. The water is preferably added in small portions during the heating, advantage- ously in the presence of benzene or toluene. Suitable initial aldehydo carboxylic acid esters are, for lexampls 2-or 4-methylbutene- (2)-al-(l)-oic acid-(4) methyl, ethyl or butyl esters or their dimethyl or diethyl acetals, 1. 1. 3-trimethoxy-or-triethoxy-4-merhyl- hexene-(4)-oic acid-(6) mlethyl or ethyl esters or 1. 1. 3-triethoxyhexene-(4)-oic acid- (6) ethyl ester. Suitable vinyl ethers are, for example, vinyl or propenyl methyl, ethyl ! or propyl ethers. As acid condensing agents, there may be used for example, hydrogen halides, such as hydrogen fluoride, chloride and bromide, boron trifluoride, benzene, sulphonic acid p-toluene sulphonic acid or zinc chloride. They can be used in an amount of from about 0. 05 to about 10%. with reference to ithe amount of reactants. The saint acid agents may be used in the last step of the process, ive. in the splitting off of alcool. In the case of using the diethyl acetal of 2-methylbutene- (2)-al- (l)-oic acid- (4) ethyl ester (I) and vinyl ethyl iether (II) as starting materials, the process may be formulated as follows : <img class="EMIRef" id="026415699-00020001" /> If the ester III and propenyl ethyl ether (V) are used as the starting materials, the process may be formulated as follows : t <img class="EMIRef" id="026415699-00020002" /> In this way for example the hitherto unknown 4-methyl-hexadiene-(2.4) - al - (1)-oic acid-(6) ethyl ester IV is obtained by way of the singly unsaturated monoethoxy diethylacetal carboxylic acid ester III and the 2. 6dimethyloctatriene-(2. 4. 6)-al- (l)-oic. add- (S)- ethyl ester VII by way of the singly unsaturated diethoxy diethylacetal carboxylic acid ester VI. The conjugated unsaturated aldehydo carboxylic acid esters obtainable by the present process starting from technically accessible materials

are valuable intermediates for the synthesis of vitamins and vitamin-like compounds. The following Examples will further illustrate the invention but the invention is not restricted to these Examples. The parts, are by weight. EXAMPLE 1. 100 parts of 2-methyl-butene- (2)-al- (l)- oic acid-(4) ethyl ester of the boiling point 79 to 81 C. at 11 torr (obtainable by oxidation of omega-hydroxy-beta-methyl-crotonic acid ethyl ester or by condensation of propion- aldehyde with glyoxylic acid ethyl ester) are acetalized by stirring with 110 parts of absolute alcohol, 3 parts of ammonium nitrate and 180 parts of orthoformic acid ethyl ester for 15 hours at room temperature and then for 10 minutes at 70'C. The 1. l-diethoxy-2-methylbutene- (2)-oic acid- (4) ethyl ester thus obatained in a yield of 206 parts boils at 88 to 91 C. at 0. 7 torr. To 205 parts of this acetal ester there are added 0. 25 part of boron fluoride etherate and then, at 40 to 45 C., 40 parts of vinyl ethyl ether while stirring. After neutralization with potassium carbonate, the whole is fractionally distilled; 90 parts of initial material first pass over and then 130 parts of 1.1.3triethexy-4-methylhexene-(4)-oic acid- (6) ethyl ester of the boiling point 110'to 113- C. at 0. 4 torr are obtained. 20 parts of this ester are heated with 600 parts of benzene, 5 parts of water and 0. 2 part of pttoluene sulphonic acid ssith continuous reflux of the benzene until a transition temperature of 80'C., the boiling point cf pure benzene, has been reached. The remaining benzene solution is washed with 2 ,. potassium carbonate solution and then with water, dried over sodium sulphate and the benzene evaporated. There are obtained 18 pars of 4-methyl-hexadiene-(2.4)-al-(1)-oic acid (6) ethyl ester melting at 57 C. (recrystallized from cyclohexane) which in methanol solution exhibits an absorption spectrum having a band with #max=272 millimicrons, e=27000. The corresponding n-butyl ester prepared in an analogous manner has the boiling point 88 to 91 C. under a pressure of 0. 001 torr. EXAMPLE 2. To 128 parts of 1. 1. 3-triethoxy-4-methylhexene- (4)-oic acid-(6) ; ethyl ester obtained, as described in the second paragraph of Example 1 there are added 0. 8 part of boron fluoride etherate and then, at 50 to 55 C., 35 parts of propenyl ethyl ether. Fractional distillation yields 91 parts of initial materiaL and 34 parts of 1. 1. 3. 5-tetraethoxy-2. 6-dimethyloctene (6)-oic acid- (8) : ethyl ester of the boiling point 160 to 165 C. at 0. 05 torr. 34 parts of this compound are heated with 600 parts of benzene, 5

parts of water and 0. 2 part of para-toluene sulphonic acid with continuous return of the benzene until a transition temperature of 80'C., the boiling point of pure benzene, has been reached. The remaining benzene solution is shaken with 2% potassium carbonate solution and then with water, dried over sodium sulphate and the solvent evaporated. The residue is distilled at a pressure of 0. 003 torr and a bath Item- perature of 120 C. The 2. 6-dimzethyl-actariene-2. 4. 6)-al-(1)oic acid-(8) ethyl ester thus obtained solidifies and upon recrystallization from cyclohexane gives yellowish needles m & lting at 78 C. When taken up in methanol its absorption spectrum shows the following bandes-.' 300 millimicrons (inflection), e=29000 ; 315 millimicrons, # = 48000 ; and 327 millimicrons, e = 40000. EXEMPLE 3. To a solution of 250 parts of 4-methylhexadiene-(2.4)-al-(1)-oic acid-(6) ethyl ester (obtained by the method described in Example 1) in 230 parts of orthformic acid ethyl ester there is added a warm solution of 1. 4 parts of ammonium nitrate in 140 parts of absolute ethanol. After boiling for 1 hour under reflux, the dark coloured solution is diluted with methylene chloride and washed with dilute sodium carbonate solution. After drying over sodium sulphate, th esolvent and excess ethyl orthofonn, ate are distilled off. In the subsequent fractional distillation in high vacuum, 300 parts of 1. 1-diethoxy-4-methyl-hexadiene (2. 4)-oic acid-(6) ethyl ester of the boiling point 97 to 98 C. at 0. 05 torr pass over. To this there are added 0. 4 part of boron trifluoride diemereate and, gradually at 50 to 55 C., 100 parts of propenyl ethyl ether. Care is faken by temporary cooling that the said temperature is not exceeded. When all has been added, the whole is stirred for 30 minutes, cooled and neutralized with dibutyamine. The 1. 1. 3-triethoxy-2. 6-dimethyl-octa- diene- (4. 6)-oic acid- (8) ethyl ester thus obtained boils at 126 to 128 C at. 0. 01 torr ; the yield is 330 parts. This triethoxy carboxylic acid ester is heated in toluene solution with small amounts of water with the addition of para-toluene sulphonic acid until a transition temperature of 111 C, the boiling point of pure toluene, has been reached and it is further treated as described in the second paragraph of Example 2. 180 parts of 2.6-dimethyl-octatriene-(2.4.6)-al-(1) - oic acid (8) ethyl ester of the melting point 78 C. are thus obtained. EXAMPLE 4. To 200 parts of 2-methyl-butene- (2)-al- (l)- oic acid-(4) lethyR ester thlere are added 0. 4 part of boron trifluoride dietherate and then, at 45 C, 60 pars of vinyl ethyl ether. The neutralized rection product is dissolved in 300 parts of toluene and treated with small

amounts of water and para-itoluene sulphonic acid and heated as described in the last paragraph of Example 1 until the boiling point of pure toluene has been reached. The solvent is distilled off and the residue fractionally distilled in vacuo, whereby there pass over 120 parts of unchanged initial material and 60 parts of 4-methyl-hexadiene-(2.4)-al-(1)-oic acid-(6) ethyl ester of the boiling point 87 to 89 C. at 0.07 torr, which immediately crystallizes and melts zat 57 C. after being once recrystallized from cyclohexane.

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* GB784629 (A)

Description: GB784629 (A) ? 1957-10-09

Improved oxo process

Description of GB784629 (A)

COMPLETE SPECIFICATION Improved Oxo Process WeSSO RESEARCH AND ENGINEERING COMPANY, a Corporation duly organised and existing underthelawis 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 :- The present anvention relates to the prepara- tion, of oxygenated organic compounds by the reaction of carbon monoxide and hydrogen with carbon compounds containing olefinic linkages in the presence of a carbonylation catalyst. More specifically the present invention relates to catalyst combinations particularly adapted to catalyze this reaction.

It is now well known in the art that oxygenated organic compounds may be synthe- sized from organic compounds containing olefinic linkages by a reaction with carbon monoxide and hydrogen in the presence of a catalyst containing metals of the iron group, particularly cobalt, in an essentiallythree-stage process. In the first stage, the olefinic material, catalyst and the proper proportions of CO and H2 are reacted to give a product consisting predominantly of aldehydes containing one more carbon atom than the reacted olefin. This oxygenated organic mixture, which contains dissolve in it salts and the carbonyls and molecular complexes of the metal catalyst, is treated in a second stage to cause removal of soluble metal compounds from the organic material in a catalyst removal zone. The catalyst-free material is then generally hydrogenated tothe corresponding alcohols, or may be oxidized to the corresponding acid. This carbonylation reaction provides a particularly attractive method for preparing valable primary alcohols which find large markets, particularly as intermediates for plasticizers, detergents and solvents. Amenable to the reaction are long and short chained olefinic compounds, depending upon the type of alcohol desired. Not only (devins, but most organic compounds possessing at least one nonaromatic carbon-carbon double bond may be reacted by this method. Thus, straight and branch-chained olefins and diolefins, such as propylene, butylene, pentene, hexene, heptene, butadiene, pentadiene, styrene, olefin pcly- mers, such as di-and tri-isobutylene and hexene and heptene dimers, polypropylene, olefinic fractions from the hydrocarbon synthesis process, thermal or catalytic cracking operations, and other sources of hydrocarbon fractions containing olefins may be used as starting material, depending upon the nature of the final product desired. The catalyst in the first stage of the prior art processes is usually added in the form of salts of the catalytically active metal with high molecular fatty acids, such as stearic, oleic, palmitic and naphthenic acids. Thus, suitable catalysts are, for example, cabalt oleate or naphthenate. These salts are soluble in the liquid olefin feed and may be supplied to the first stage as hydrocarbon solution or dissolved in the olefin feed. The synthesis gas mixture fed to the first stage may consist of any ratio of H2 to CO, but preferably these gases are present in about equal volumes. The conditions for reacting devis with H2 and CO vary somewhat in accordance with the nature of the olefin feed, but the reaction is generally conducted at pressures in the range of about 1500 to 4500 p.s.i.g., and at temperatures in the range of about 150 -450 F. The ratio of synthesis gas to olefin feed may vary widely ; in

general, about 2500 to 15, 000 cubic feet of HZ+CO per barrel of olefin feed are em- ployez'. At the end of the first stage, when the desired conversion of olefins to oxygenated compounds has been effected, the product and unreacted material are. generality withdrawn to a. catalyst removal zone where dissolved catalyst is removed from the mixture by thermal treatment in the presence of an inert gas, a vapor, hot water, or dilute acid. Thereafter, the aldehydic reaction product is generally hydro genated to the corresponding alcohol. It has been recognized that substantially all forms of cobalt catalyze this reaction, for the active catalytic agent is cobalt hydrocarbonyl in all probability, this compound is synthe- sized in situ from the cobalt compound or metal originally introduced. However, it has been preferred to employ the compounds of cobalt that are oil-soluble, such as high molecular weight salts of cobalt, i. e. cobalt oleate or naphthenate. These materials form a homo- geneous reaction mixture and have a high reactivity or reaction rate, substantially higher than cobalt metal or oxide, or aqueous solutions of cobalt salts, such as cobalt formate or acetate. However, the use of high molecular weight cobalt carboxylates has certain disadvantages. They are pensive to prepare, requiring a variety of processing steps, and also contaminate the final reaction product with the acid or ester corresponding to the carboxylate employed. Furthermore, though the reactivity and reaction rates are high, leading to high olefin conversions, the aldehyde and alcohol selectivity resulting from use of these catalysts is not always satisfactory, and may be somewhat low. An alternativesystem is the use of metallic cobalt or slurry of cobalt oxide. These catalytic agents, though they have no residues to contaminate the aldehyde or alcohol product, and though they give a better alcohol selectivity than the oil-soluble cobalt soap, have a very slaw reaction rate. This is a very serions ; defect in continuous operation, for low reaction rates mean low throughput rates. Still another alternative has been the use of aqueous solutions of water-soluble cobalt salts, such as cobalt acetate. Here also the reaction rates of the aqueous solution are considerably slower at a given temperature than those of oil-soluble cobalt salts. Furthermore, in order to add an amount of cobalt acetate equivalent to cobalt oleate to provide the desired cobalt concentration of about 0. 3 weight percent, about 5-6 volume % of water (based on olefin) must be added to the olefin feed. Such a system has been found not to function efficiently, and to give a more unfavourable feed rate for a given olefin conversion relationship than cobalt oleate catalyst at equivalent cobalt concentration. This is illustrated in the following example, where a heptene fraction from a propylene-butylene

polymerization unit was continuously carbonylated with 0. 3 wt. % of cobalt catalyst at 340-350 F. Liquid Con Feed Rate version Catalyst System V/V/Hr. Mol % Cobalt Oleate in Olefin 0. 6 80 Cobalt Oleate in Olefin 1. 2 74 Cobalt Acetate in Water 0. 6 72 Cobalt Acetate in Water 1. 2 54 Thus with the aqueous cobalt acetate catalyst it is necessary to decrease olefin feed rate by almost 5OoO to achieve a conversion level equivalent to cobalt oleate. The relative reaction rates of a number of types of cobalt-containing substances at a temperature of 340350 F. are listed below : Induction Reaction Period Rate Catalyst Min. kx 102 Cobalt oleate 30 7. 8 Cobalt acetate solution (4% water in olefin) 20 1. 4 Cobalt Carbonate, Solid 5 0. 5 Cobalt Oxalate, Solid 5 0. 5 Cobalt Formate, Basic, Solid 5 0. 5 Cobalt Sulfat 7HOO < 5 0. 7 oba. lt Oxiv 4-5 0. 5 Cobalt Metal 4-7 0. 5 These Sgures show the great diversity in reaction rates characterizing various cobalt catalyst systems. The low reaction rates of the cobalt salts such as the oxalate, and carbonate and of Ithe oxide and metal are a direct result of the low rate of conversion of these solids to active catalyst, i. e. cobalt hydrocarbonyl. The present invention comprises a process for reacting olennic compounds with a mixture of H2 and CO in the presence of a cobalt catalyst at elevated tein-oerotures and pressures in a reaction zone to produce an aldehyde product, wherein the catalyst consists of an oxide of cobalt promoted with an organic acid having from two to seven carbon atoms per molecule. It is found that such a catalyst provides a reaction rate of the same magnitude as the oil soluble cobalt salts, for example, cobalt oleate previously used but is much cheaper and not associated with the disadvantages resuIting from the use of oil soluble salts. The acid may be introduced into the reaction zone in any convenient manner, either with the Oxo catalyst as a slurry, or separately as, for example, admixed with the olefin feed or recycle stream. In a

preferred embodiment, cobalt oxide is employed as a slurry in an organic liquid preferably the olefin feed, and glacial acetic acid is admixed with the said slurry. The slurry may be injected into the Oxo reactor by any conventional method of adding a slurry to a system under pressure. Such methods include slurry pumps, injectors and surge systems. Alternatively the cobalt oxide may be slurried in an organic liquid or part of the olefin feed and supplied to the reaction zone and the remainder of the olefin feed and the acid fed to the reaction zone separately or together. According to another form the cobalt oxide may be in the reaction zone as a fixed bed and the necessary quantity of acid fed to the reaction zone continuously together with or separately from the olefin feed. One embodiment of a system suitable for carrying out the present invention is shown diagram- matiaally in Figure I of the accompanying drawings. Turning now to Figure I, solid cobalt oxide of suitable particlesizeisintroducedinto mixing chamber 2 through hopper 4. Sufficient olefin feed or Oxo product is added to the mixing chamber through line 3 to form the said cobalt oxide Snto a slurry containing from 2 to 10% solids. Glacial acetic acid is then added to the extent 1-6 mols of acid per mol of cobalt oxide, preferably 3-4. 5 mols acid per mol of oxide. By means of the circulation pump 6, the mixture of cobalt oxide slurry and acid is circulated through lines 8, 10 and 15 to bo ! th the top and bottom of ! the mixing chamber. By means of a suitable surge pump liquid olefin or Oxo product is-introduced through lines 14 and 16 into surge vessel 18. The system is so designed that except under positive action from the surge pump, the pressure in the surge vessel is sufficiently low to allow slurry te pass through the lower check valves 12. Under positive action from the surge pump, theslurry is forced through the upper check valves 20. The slurry of cobalt oxide disperse in the acetic acid and olefnn feed or other organic medium, such as recycle aldehyde product or even alcohol distillation bottoms, is thus continuously injecte into carbonylation reactor 24 through line 22. The slurry which consists of about 0. 1 to 3% by weight of cobalt oxide calculated as cobalt, may be injecte at the rate of about 5 to 200 pounds per barrel of olefin, at pressures preferably equal to or slightly higher than those prevailing in reactor 24. A gas mixture comprising H2 and CO in approximately equal volumes, though 0. 5-2 volumes lI2/CO may be used, is supplie through line 26 andHowsconcurrentlywith preheated liquid olefin feed admitted through line 28, and with the catalyst slurry. Reactor 24 is preferably operated at pressures of about 2500-3500 psig. and temperatures of

300-375 F, depending upon the olefin feed and other reaction conditions. Liquid feed rates of 0. 2 to 2. 0 V/V hour may be employed. Liquid oxygenated reaction products consisting mainly of aldehydes, containing cobalt carbonyl in solution, as well as unreacted synthesis gases, are withdrawn overhead through line 30 from high pressure reactor 24 and thereafter freed from dissolved and suspended cobalt. Thus, the cobalt contaminated aldehyde product may be freed of dissolved cobalt by heating it in the presence of water or dilute acid, in particular dilute acetic acid, and thereafter hydrogenatedto the corresponding alcohol. If desired, it may be highly advantageous to filter the Oxo reactor effluent prior to or subsequent to decobalting, or both. The process of the present invention may be further illustrated by the following specific example. EXAMPLE The experimental procedure consisted in charging the olefin and solid catalyst to a bomb at room temperature, bringing the bomb up ta 100 psig. with 1/1 synthesis gas and heating to the desired reaction temperature, quickly increasing the synthesis gas pressure to 3000 psig., withdrawing samples of the product as the reaction proceeded (400-500 psig. drop) and stopping the run when final pressure had decreased to 1000 psig. The final olefin conversion was of the order of 4555% in all cases. The product samples were inspected for soluble cobalt content and olefin conversion, and the latter values used to calculate the average reaction velocity constant "k." Feed #C7 Olefins#C12 Olefins# Feed charge (including catalyst) #1067 grams (1500 c.c.)# Catalyst (0.2% by wt. of Cobalt Cobalt Plus Cobaltous plus Cobalt Cobalt Plus cobalt on feed) Oleate Oxide Acetic Oxide Acetic Oleate Oxide Acetic Acid Acid Acid Grms. catalyst 21 2.99 2.99 2.7 2.7 21.0 2.99 2.99 Grms. acetic acid - - 2.30 - 2.3 - - 2.3 Temperature, F. 358 356 361 358 375 351 347 365 Pressure at Start, Psig. #3000# Pressure at End, Psig. #1000# 3000 1000 % Olein Conversion 47.5 48.5 47 58 43 52 ( 49.5 Reaction Constant, k # 102 9.0 0.5 6.9 0.7 6.7 6.0 * 1.3 Relative Catalyst Activity 1 0.05 0.76 0.08 0.75 1 - 0.22 to Cobalt Oleate Inspection of Products # % Soluble Cobalt 0.13 0.001 0.005 0.007 0.002 0.12 0.000 0.01 CO No. 183 173 183 153 58 65

OH No. 26 48 32 52 116 100 Saponification On. 9 7 21 17 22 12 Acid No. 0.3 1 3 3.4 4.2 2.1 * No reaction after 5 hours. These results show clearly that while e cobaltic and cobaltous oxide show low activity of 1/15-1/7 that of cobalt oleate catalyst, the addition of 0. 1% by weight based on olefine feed of acetic acid to the oxides results in a 10 fold increase in catalyst activity and shorter induction period. A similar order of catalyst activity is noted in both the oxonation of a C, and the more difficultly oxonat- able 1r2 olefin. The effect of the addition of acid to cobalt oxide catalyst is shown clearly in figure 2 of the accompanying drawings, showing the variations of the reaction velocity constant with the addition of various adds, at various, mol ratios. These data show that organic acids in general have some effect ; the most notable being shown by acetic acid. Formic acid, on the other hand, actually was found to inhibit the reaction. This is consonant with the general finding that the first members of homologous series have characteristics different from those of higher members. It is also. noted that the highest rate increase effect is attained, in the case of acetic acid, at about 3-4 mols of acid per mol cobalt oxide used. The commercial cobalt oxide employed in these experiments analyzed about 25 % CoO and 75 % of the double compound CoO'-CoOg. This material is substantially completely insoluble in glacial acetic acid and even with H2SO4 is digested with a great deal of difficulty. On a stoichiometric basis, 6 mols of acetic acid would be associated with one mol of the commercial oxide calculated as cobalt acetate. The results, however, show that maximum increases in rates are obtained at an acid/oxide ratio less than. this stoichiometric quantity. These considerations would indicate that cobalt acetate is probably not formed in the course of the reaction or, if formed, it is present in an activated state. Toi determine whether it is the extent of acidity or degree of ionization that is res- ponsible for the increase in reaction rate, further experiments were carried out at 325 F. and 3000 psig. employing 85% phosphoric acid. No enhancement in activity of the cobalt oxide was observed even iafter 3 hours. Formic acid also, as has been pointed out, gave no enhancement. This add also is 10 times stronger than acetic acid. Toluene sulfonic add, which is also sstronger than acetic acid, gave some increase, but not to the extent found with acetic acid. Not all forms of cobalt may be activated in the manner described, but apparently only oil-and water-insoluble forms, such as the cobalt oxides. Thus figure 3 of the accompanying drawings clearly shows that

cobalt metal is unresponsive to the acid treatment, while solid cobalt acetate actually decreased in neaction velocity. The process of the present invention may be modified-in many ways without departing


* GB784630 (A)

Description: GB784630 (A) ? 1957-10-09

Organosiloxane emulsions


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FR1171982 (A) NL94246 (C) US2755194 (A) FR1171982 (A) NL94246 (C) US2755194 (A) less Translate this text into Tooltip

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

PATENT SPECIFICATION 784,630 Date of Application and filing Complete Specification Jan 19, 1956. No 1860/56, Application made in United States of America on Feb 7,

1955. Complete Specification Published Oct 9, 1957. Index at Acceptance:-Class 2 ( 7), T 6 (D 2: Dll: F 1: F 2: HI: J 1). International Classification: -C 08 g. COMPLETE SPECIFICATION Organosiloxane Emulsions We, MIDLAND SILICONES LIMITED, a British Company, of 19, Upper Brook Street, London, W.1, 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 novel organosiloxane emulsions. Organosiloxane emulsions, especially oil-inwater type emulsions, have been employed for a wide variety of uses such as car and furniture polishes, release agents, medicinal preparations, and cosmetics The unique properties of organosiloxanes and the ease with which organosiloxane emulsions can be used have assured them of an expanding popularity in industry. One of the most important properties sought in an emulsion is stability An emulsion can be defined as a dispersion of fine liquid particles within another immiscible liquid Such dispersions have a tendency to "break" or "cream " A very unstable dispersion, such as benzene in water, will separate very rapidly and can hardly be called an emulsion The very best emulsions exhibit practically no "creaming" and are said to be stable. There are many factors involved in the stability of emulsions and among the important factors are the emulsifying agent or agents employed, the particle size of the dispersed liquid, the nature of the dispersed liquid and the continuous or dispersing liquid Many experiments have been carried out and much has been written concerning such factors with relation to organosiloxane-in-water emulsions. In fact, relatively satisfactory siloxane emulsions have been available heretofore but certain deficiencies are still present. Heretofore, the organosiloxane-in-water emulsions have been largely inconsistent in their behaviour One production batch would be very stable, whereas the next batch might prove to have quite unsatisfactory stability. Unfortunately, the emulsions often" break" or cream after they have been shipped to the ultilPrice 3 s 6 d l mate user (e g, a rubber fabricator for use in rubber moulds) The consumer usually fails to recognise that separation has occurred until 50 he finds that the supposed emulsion is not accomplishing the desired result (e g, the rubber sticks to the moulds rather than being freely released) Therefore, it is of primary economic importance to the consumer and the 55 producer of organosiloxane-in-water emulsions that a

consistently stable emulsion be found. Separation or creaming in an emulsion can be the result of many variables including repeated freezing and thawing of the emulsion, 60 protracted standing, and too large a particle size in the emulsion as produced. It is the primary object of this invention to prepare an organosiloxane-in-water emulsion exhibiting a consistently reproducible 65 degree of stability heretofore unavailable. Another object is to produce an emulsion having a uniformly fine particle size heretofore unobtainable A further object is to produce an emulsion which will not separate or cream 70 after repeated freezing and thawing A further object is to produce an organosiloxane-inwater emulsion which remains stable on storage for several months or years. In accordance with this invention an organo 75 siloxane-in-water emulsion consists essentially of (A) from 0 05 to 90 per cent by weight calculated on the total emulsion of an organic solvent-soluble organopolysiloxane having the average general formula RD Si O 4 _n wherein 80 each R is a monovalent hydrocarbon radical or a halogenated monovalent hydrocarbon radical and N has an average value of from 0 9 to 3 0, (B) from 3 to 45 per cent by weight calculated on the weight of (A) of the trimethylnonyl ether of a polyethylene glycol, (C) 0 1 to 1 5 per cent by weight calculated on the weight of (A) of a sodium salt of an alkylated aryl polyether sulphate, and (D) the balance of the emulsion being water. The organosiloxane lingredient (A) abovel can be any organosilicon compound having the average general formula Rn Si OQ_, wherein each R is a monovalent hydrocarbon radical or a halogenated monovalent hydrocarbon radical. Illustrative of the wide range of radicals R can represent are alkyl radicals such as methyl, ethyl, butyl and octadecyl; alkenyl radicals such as vinyl and allyl; aryl radicals such as phenyl, naphthyl and xenyl; alicyclic radicals such as cyclohexenyl, cyclopentenyl and cyclohexyl; alkaryl radicals such as tolyl and xylyl; and aralkyl radicals such as benzyl, and/or any halogenated monovalent hydrocarbon radical such as tetrafluoroethyl, perfluorovinyl, dichlorophenyl, and,7,-trifluorotolyl. The organosiloxanes which are operative herein range from resins having an average of 0 9 organic radicals per silicon atom to liquids having an average of 3 organic radicals per silicon atom It is apparent to those skilled in the art that the siloxane must be a liquid or must be soluble in an organic solvent in order to prepare an emulsion therefrom Any siloxane having 2 or 3 organic radicals per silicon atom can be characterised as a liquid although the viscosity

of such material can range from less than 10 cs at 25 C to more than 10,000,000 cs at 25 C The resinous siloxanes (i.e, degree of substitution= 0 9 to 2) can be in the liquid state or can be solid or gel-like and yet be operative herein so long as they can be dissolved in an organic solvent such as toluene, benzene, naphtha and other petroleum solvents Preferred are the organosiloxanes having 2 to 3 organic groups per silicon atom. There are two emulsifying agents employed herein The trimethylnonyl ether of a polyethylene glycol is employed in conjunction with a sodium salt of an alkyl aryl polyether sulphate It has been found that when these two agents are employed in the emulsions of this invention in the amounts specified, significantly better emulsions are obtained than could be prepared with either agent alone or in combination with any other agent The particle size of the dispersed organosiloxane is greatly reduced to 0 5 microns and smaller. As a result of this outstanding and unexpected reduction in particle size the dispersed particles are more uniform in size and are more uniformly distributed throughout the emulsion system This in turn results in increased heat stability, reduces the creaming to the point of eliminating it, and allows easy dilution of the emulsion to any desired useful concentration (e g, 0 05 per cent by weight of organosiloxane). From a practical, commercial standpoint, the emulsions of this invention are extremely welcome to the producer and the consumer The producer can be assured of uniform quality of product and good product control This reduces costly returns of unsatisfactory material and saves time and money heretofore spent in trying to obtain a commercially saleable product from the unsatisfactory batches 65 of emulsion. The consumer is now assured of a noncreaming emulsion exhibiting improved properties over those obtained with earlier commercial emulsions Because of the uniformity 70 of the new emulsion, any coating made with it will be more uniform in thickness and quality Further, special handling techniques heretofore employed have been largely eliminated with the emulsions of this invention 75 The emulsions of this invention can be prepared in any desired manner The preferred method is to add the trimethylnonyl ether of polyethylene glycol and the sodium salt of alkyl aryl polyether sulphate to the organo 80 siloxane, and intimately intermix them by milling or mixing by any desired means This mixture is then added to water with appropriate mixing techniques employed to secure a stable, uniform emulsion Alternatively, all of 85 the ingredients can be admixed in a single step by adding them together and mixing. The amount of organosiloxane employed should be at least 0 05 per cent

by weight based on the total weight of the emulsion 90 Although this invention is operative with less than 0 05 per cent of organosiloxane, it is impractical to reduce the organosiloxane below this amount and thus practically dilute out its effectiveness The upper limit on the propor 95 tion of organosiloxane to water lies at the inversion point of the emulsion, that is at the point where the organosiloxane-in-water emulsion inverts to become a water-in-organosiloxane emulsion This is generally at a point 100 of about 90 per cent by weight of organosiloxane. The emulsions of thisinvention are primarily useful as mould release agents such as are employed by rubber fabricators, and plastics 105 fabricators They are also useful in emulsions employed to render fabrics and/or leather water repellent Various uses of these materials will require the addition of rust inhibitors, anti-oxidants and other additives and this 110 invention is intended to include the addition of minor amounts of such additives. The following examples illustrate the invention All parts and percentages in the examples are by weight unless otherwise specified 115 EXAMPLE 1. parts of a liquid dimethylsiloxane having a viscosity of 350 cs at 25 C were added to 1.8 parts of trimethylnonyl ether of polyethylene glycol, having a molecular weight of about 120 609, and containing 9 to 11 ethylene oxide radicals per molecule (available commercially as Tertigol TMN) and 0 15 part of a sodium salt of alkyl aryl polyether sulphate (available commercially as Triton W-30 the word 125 "Triton" being a Registered Trade Mark). This mixture was manually mixed using a 784,630 784,630 stirring rod 5 parts of water were added to the mixture and the entire mix was sent through a colloid mill Thereafter 10 parts of water were added and the mix again was sent through the colloid mill Finally 47 5 parts of water were added with the mix again being sent through the colloid mill The colloid mill was set at medium for the first milling operation and was set progressively finer with each succeeding milling until on the final milling it was set at the extremely fine position The resulting emulsion had particles of 0 5 W or lower It was very stable and did not cream after months on the shelf Centrifuging for 30 minutes at an average force of 1200 times the force of gravity produced less than 2 per cent. separation and the gentle shaking quickly rehomogenised the emulsion The emulsion did not break or cream after extended heating and boiling nor did repeated freezing and thawing result in separation or creaming This emulsion was the equal of any heretofore known in all physical properties and was far superior in heat stability, shelf life, compatibility, ease of emulsifying and dilution, average particle

size, hard water stability and pumping stability. EXAMPLE 2. Employing the process of Example 1, an emulsion was prepared containing 35 parts of a phenylmethylsiloxane copolymer consisting of 50 mol per cent phenylmethylsiloxane, 28 mol per cent of monomethylsiloxane, 14 mol per cent of monophenylsiloxane, and 8 mol per cent of diphenylsiloxane dissolved in 35 parts of xylene, 2 8 parts of the trimethylnonyl ether of polyethylene glycol of Example 1, 0 2 part of the sodium salt of alkyl aryl polyether sulphate of Example 1 and 61 parts of water. This emulsion was equivalent to that which was obtained in Example 1. EXAMPLE 3. Equivalent results, were obtained when a vinylmethylsiloxane or a chlorophenylethylsiloxane was substituted for the dimethylsiloxane of Example 1.


* GB784631 (A)

Description: GB784631 (A) ? 1957-10-16

Improvements in or relating to road or like rollers


PATENT SPECIFICATION 72 A-,03 1 Date of filing Complete Specification: Jan 4, 1954. Application Date: Jan 5, 1953. No 245153. Complete Specification Published: Oct 16, 1957. Index at acceptance:-Class 144 ( 2), C 2 A. International Classification:-B 62 g.

COMPLIETE SPECIFICATION Improvements in or relating to Road or like Rollers We, EDDISON PLANT LIMITED, a British Company, of Syston Lane, Belton, Grantham, and ERNEST JOHN SPRIGGS, a British Subject, of the Company's address, 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 road, footpath and similar rollers and is concerned with the provision of rubber or other resilient treads for the roller wheels of such vehicles with the object of reducing the road shocks, vibration and consequent wear and tear throughout the machine which are experienced while such vehicles are travelling on the highway, and also increasing road adhesion and improving travelling speed. According to the invention a resilient tread for a roller wheel of a road or like roller comprises a plurality of pads of rubber or other resilient material arcuate in the direction of their length and linked together end to end to encircle the periphery of said roller wheel and a flexible tensionable element which also encircles said periphery and overlies said plurality of pads so that when tightened it secures said plurality of pads in position, portions of the pads projecting forwardly and rearwardly at the front and rear ends of each pad so that they are disposed respectively in front of and behind complementary portions of the adjacent pads as a result of which some portion of the surface of the complete annular tread formed by the linked pads is always in contact with the ground and thereby ensures a smooth rolling action. Preferably each of the pads comprises a substantially rectangular cushion of rubber or other resilient material bonded or otherwise secured to the convex surface of a substantially rectangular metal base plate curved from end to end to conform substantially to the curvature of the circumference of the roller wheel to which the pads are to be attached The flexible element may comprise, for example, a wire rope or cable which encircles a portion of the metal base 50 plates of the plurality of arcuate pads which is devoid of overlying rubber or other resilient cushion. Alternatively each of the pads may be composed wholly, or substantially wholly, of 5 s rubber or other resilient material-that is to say the cushion and base plate may be constructed in one piece in rubber or other resilient material-the flexible element in this case being in the form of a metal band 60 Preferably the said plurality of arcuate pads are linked together by means of pin and slot connections formed between the front and rear ends of adjacent pads Two wire ropes or cables, or two metal bands, are ad 65 vantageously

employed which encircle lateral side portions of the substantially rectangular metal or rubber or like base plates of the pads to which lateral side portions the resilient cushion of such pads does 7 Q not extend. A preferred embodiment of the invention will now be described, by way of example, with reference to the accompanying drawings in which: 75 Figure 1 is a plan view of one pad and a portion of an adjacent pad of the resilient tread, Figure 2 is a broken side elevation of the pads shown in Figure 1, 80 Figure 3 is a side elevation on a somewhat larger scale of a toggle device for connecting the opposite ends of one of the flexible elements and placing tension on the latter to retain the pads in position, the figure show 85 ing the lever and link of the toggle device straight, instead of being curved to conform to the periphery of the roller wheel as in actual practice, to render the pivotal arrangement of the toggle device more 90 readily understandable, and Figure 4 is a plan view of the toggle device 2 784,631 shown in Figure 3. Referring to Figures 1 and 2 of the drawings, a series of similar pads 10, each comprising a relatively thick cushion 1 of rubS her or other resilient material of suitable composition and bonded or otherwise secured to a relatively thin steel base plate 12, are linked together to form a continuous tread for each of the roller wheels, front and rear, of a road, footpath or similar roller. Each pad formed by the aforesaid resilient cushion 11 on its steel base plate 12 is a completely separate unit constituting one link of the tread and the number of links required to form the tread of a given roller wheel is governed by the circumference of the latter The surface of each steel base plate 12, which is of generally rectangular plan form, is curved from end to end, as shown in Figure 2, to conform to the curvature of the circumference of the roller wheel to which it is to be attached. The lateral side portions 13 of each substantially rectangular steel base plate 12 are left free of the overlying resilient cushion 11 and at one end each of such lateral side portions is provided with an upstanding headed pin 14 while at its other end it is formed with a longitudinally extending lug 15 which is 310 joggled outwardly, as shown at 515 a, relatively to the centre of curvature of the plate to permit the lug to overlie the adjacent base plate An elongated slot 16 of slightly greater width than the diameter of the pins 14 is formed centrally in each of the lugs and is enlarged at its outer end, as shown at 16 a, to allow the head of one of the pins of the next pad to pass through such enlarged portion In order to link the pads 10 together to form the complete annular tread the pins 14 are inserted into the enlarged portions 16 a of the slots 16 at the adjacent ends

of adjacent pads after which the pads are slid towards each other in a longitudinal direction to bring the head of each pin over the narrow portion of the slot. It will be appreciated that the movement of the pins 14 forwards or backwards along the elongated slots 16 permits lengthening or shortening of the complete tread, the maximum lengthening of the latter being equal to the length of the narrow portion of each slot minus the diameter of the pin, multiplied by the number of pads; the length of each pad and the number of pads in each tread are so determined that the maximum lengthening equals the length of one pad. Although substantially rectangular in plan form the central portion of each pad, i e the part of the base plate 12 having the overlying resilient cushion 11 secured thereto, is formed with complementary chevronshaped ends 17, 18 so that the rear end 18 of one pad has portions disposed behind portions of the front end 17 of the following pad in the line of travel whereby some portion of the surface of the comilete annular tread formed by the linked pads is always in contact with the ground, thus ensuring smooth rolling action 70 A pair of steel wire ropes or cables 19, shown in broken lines in Figures 1 and 2, encircle the lateral side portions 13 of all the pads 10 on each side of the complete annular tread and are tightened to strap the 75 pads to the periphery of the roller whee 121 in a manner to be described T' e ropes 19 lie on the outer surface of the side portions 13 of the base plates and are positioned between the pins 14 and the side walls of the 80 cushions 11. The wire ropes or cables 19 are of predetermined length and to one end of each rope a steel hook 20 is welded or otherwvise secured, a further and more elongated form 85 of hook 21 being welded to the opposite end of each rope as shown in Figures 4 and 5. In order to secure and tighten the wire ropes 19 in position a toggle device 22 is provided, comprising a lever 23 and link 24 pivotally 90 connected by a fulcrum pin 25 The lever 23 lies between the free ends of the parallel limbs of the link 24, the opposite ends of such limbs being connected by a pin 26 with which the hock 20 is engaged A transversely 91 arranged pin 27 at the inner end of the lever 23 is engaged with the hook 21 and when the free end of the lever is pressed towards the surface of the side portion 13 of the base plate above which the toggle 22 lies to bring 100 the lever and link 24 into longitudinal alignment the two hooks 20 and 21 and the ends of the rope 19 attached thereto are brought towards each other and are held in tension to clamp and secure the pads 10 in position 105 Each limb of the link 24 is provided with a series of equally spaced holes 28 with any opposite two of which the fulcrum pin 25 can be selectively engaged to shorten or lengthen the toggle device 22 and thus obtain

110 adjustment of the tension on the rope 19. The transverse pin 27 is arranged on the longitudinal centre line of the lever 23 and the holes formed in the latter to accept the fulcrum pin 25 are arranged below such 115 centre line so that when the lever is pressed downwardly to bring it into longitudinal alignment with the link 24 the fulcrum pin is nearer the surface of the base plate 12 than the transverse pin 27 and the toggle de 120 vice 22 automatically locks in position, the stem of the hook 21 being sufficiently thin to allow the fulcrum pin to fall into position A hole 29 is, however, provided on each side of the lever 23 through which a 125 locking pin (not shown) can be inserted, such pin also engaging with an opposite pair of the series of holes 28 in the limbs of the link 24 to finally secure the toggle device in its locked position The series of holes 28 in 130 784,631 each ok the pads comprises a substantially rectangular cushion and a base portion or 55 plate constructed wholly, or substantially wholly, of rubber or other resilient material, the cushion and 'base plate being constructed in one piece.


* GB784632 (A)

Description: GB784632 (A) ? 1957-10-16

Improvements relating to glass lids


PATENT SPECIFICATION Inventor: RALPH BROWN 78 d 4,132 Date of filing Complete Specification: Sept 16, 1954. Application Date: Sept 19, 1953. Complete Specification Published: Oct 16, 1957.

Index at acceptance:-Class 66, A( 213: 6 A: 7 A 2: 7 A 5 B). International Classification:-A 47 j. COMPLETE SPECIFICATION Improvements relating to Glass Lids We, THE B Ri W Is H HEAT RESISTING GLASS COMPANY LIMITED, a British Company, of Phoenix Works, Loxdale Street, Bilston, in the County of Stafford, 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: - The present invention relates to moulded glass lids for dishes, and has for its object to provide a new or improved construction which will permit of ready removal of the lid from its associated dish when so used or is alternatively will permit of its use when inverted as a dish on its own account. According to the present invention we provide a combination lid and dish of moulded glass having a top wall and side walls extending downwardly therefrom so as to form an inverted bowl or dish-like member, the top wall having at its upper surface a portion or portions constituting a base upon which the lid can stand in a stable manner when inverted and also having a lifting handle which is accommodated wholly in a recess in the top wall, the lower edges of the side walls lying substantially below the lowest part of the under surface of the top wall so as to render the lid suitable for use as a dish when inverted. In the foregoing statement and hereinafter the combination lid and dish will be defined and described (except where the context specifically otherwise requires) in its role as a lid and terms having reference to a predetermined orientation (e g under surface and upper-surface) are to be construed accordingly. In a preferred form, the combination lid and dish of moulded glass is formed as an inverted bowl or dish-like member having downwardly extending side walls united to the periphery of a top wall having in its upper surface a depression of which the lowest portion of the under-surface does n Qt lPrice 3 s 6 d) project substantially below a level half way down the inner-surfaces of the side walls, this depression containing a handle of undercut form integrally united with the bowl or 50 dish-like member, and having its upper extremity lying below those portions of the upper-surface of the lid which surround said depression and form a base upon which the lid can stand in a stable manner when in i S verted for use as a dish. For convenience in manufacture as well as to enhance the appearance it is preferred that the depression has a part-spherical form or other convenient concave form of curved 60 cross section. The volumetric capacity of the article as a dish may be selected to

lie in the range one half to four pints. From a more limited aspect a combina 65 tion lid and dish according to the present invention comprises a pressed glass body formed as an inverted bowl or dish-like member of approximately uniform wall thickness having downwardly divergent side 70 walls and a top wall including a depression of a depth not substantially greater than half that of the side walls as presented at the under surface of the lid and affording an under-surface which is free from pockets 75 grooves or like local cavities difficult of access for cleaning purposes and which merges with the inner-surfaces of the side walls, likewise free from such cavities, through a rounded corner of sufficient radius 80 to avoid retention or entrapping of particles of food stuff, the depression containing a handle of undercut form integrally united with the top wall and formed therewith in the same pressing operation, such handle 85 lying wholly beneath the rim of the depression. The handle may comprise a pair of rib like handle elements extending transversely of the recess or depression and undercut form 90 in cross section, such handle elements being united integrally with the base and/or sides No 25906/53. of the recess or depression. Each of these handle elements may have a web united integrally with the base of the depression and a thickened flange or bead I at the upper edge of such web and between adjacent ends of thle webs may be left a gap which is overhung by inwardly projecting end portions of the flanges or beads This latter feature enables the user to lift the lid by meeting the first finger and thumb of one hand through the gap and utilising the overhlanging portions of the flanges or beads to lift the lid, thereby avoiding any substantial contact with the webs of the handle elements which owing to their being integrally united with the base of the depression may attain a somnewhat higher working temperature than the flanges or beads. In our prior Patent No 696,520 there is claimed a moulded glass lid on which is formed a handle comprising upwardly projecting limbs joined integrally at their lower ends to the lid and having free upper end portions defining a gapped bridge spaced above the surface of the lid. The invention is illustrated in the acconmpanying drawings wherein:Figure 1 is a plan view of one construction of combination lid and dish in accordance with the invention. Figure 2 is a cross sectional view of the jcombination lid and dish shown in its role as a lid serving as a closure member for a vessel body as illustrated, and Figure 3 is a similar cross sectional view showing the combination lid and dish in its role as a dish. X nh combination lid and 'di's ray be rnoulded from any suitable ('-T If glass but l 40 gass of the known bore-silicate type is prefered,

such glass having a relati-;ey low co-Icient of thermal e xpanslson n'ai:tingm the arile to be suajntd, witilt _a'c to iheaing and cooling involved' in normal cc'king operations in an oven. The body of the article may be -orimed as a glass pressing preferably o aopro_'_mately uniform wall thic kness as illustra td and may be of any desired configuration as seen in plan, for example circular (as illustrated), but oval or rectangular shapes in tie latter case with rounded corners may be utiiised if desired. The marginal portions of the body may project downwardly and also diverge from each other to constitute side walls 10 and these side walls are united integrally with a top wall which, in the construction illustrated, is formed over substantially its whole area as a depression 11. It will be understood that this depression need not occupy the whole area of the top wall although this form is preferred in that it enables a sufficiently deep depression to be produced whilst maintaining the various radii involved in its junction with the side walls as well as lthe radius of curvature of the under-surface of the depression itself to be maintained at a high value, thereby avoiding the danger of retaining or entrap 70 ping particles of food stuffs when the article is m use as a dish. The depression may have a depth of about one-half the depth of the side walls although depths in the range one-third to 75 two-thirds the depths of the side walls may be utfiised, and preferably thile depression itself is in the form of a part-spherical or other suitably curved shell as shown The under-surface of the depression itself and O the inler surface of ti e side walls are smooth and free urom pockets, grooves or the like local cavities which would be difficult of access for leaning purpozes and the undersurface of the depression 11 merges smoothly 85 withl the inner surface of the side walls through rounded comrners 12 having a substantial radius as shown. The outer surfaces of the side walls may be formed with circumferentially extending 90 s Ihallow grooves intersecting with each other in apexes 13 merely to enhance the exterior appearance, and at the lower extremity of the side walls a rebate 14 may be formed for mating with the rim 15 of a vessel body 95 16,when the article is in use as a lid It will be apparent that the volumetric capacity of the vessel body differs from that of the lid in its role as a dish thereby affording the user a choice of volumetric capacities 100 Within the depression is contained a handle which may comprise a pair of handle elements 17 of rib like form extending diametrically of the depression. As best seen in Figure 3 all of these handle 10 j eiemenis may be formed with a web 18 which is united integrally with the upper surface

of e depression 11 and the upper edge of each web may have an integral flange or bead 19 which is thicker than the web so as to pro 110 duce an undercut cross section. Tiee inner end portions 20 of the flanges or beads 19 may be continued beyond the inner edges 21 of the webs so as to overhang ti P 7 gap 22 left between the inner edges of 115 the webs, these latter conveniently being of part circular form so that the gap 22 is in the form of a circular or approximately circular hole This form of handle construction has the advantages already pointed out 120 For the best advantage the circular portion of the gap 22 may have a diameter of about -s of an inch and the narrower part of the gap which lies between the portions 20 of the flanges or beads may be about 3 of an 125 inch. The upper extremities of the handle elements lie beneath the rim 23 of the depression so that when in use as a dish as seen in Figure 3 the article will stand in a stable 130 a 784,632 uniform wall thickness having downwardly divergent side walls and a top wall including a depression of a depth il Ot substantally 6 d greater than half hat Oif he side walls as presented at the unde'-surface of the lid and alfording an under- ur ce Wilicil is iree from poc e-s grooveb or ii e locai cavlies ciificult or access or cleaning purposes and which 6,5 merges with the inner-surfaces of the side walls, likewise free from such cavities, through a rounded corner of sufficient radius to avoid retention or entrapping of particles of food stuff, the depression containing a 70 handle of undercut form integrally united with the top wall and formed therewith in the same pressing operation, such handle lying wholly beneath the rim of the depression 75 6 A combination lid and dish according to any of the preceding claims formed as a pressing of borosilicate glass having a thermal coefficient of expansion low enough to permit the article to be subjected to the 80 heating and cooling involved in normal cooking operations in an oven. 7 A combination lid and dish according to any of the preceding claims wherein the handle comprises a pair of rib-like handle 85 elements extending transversely of the recess or depression and of undercut form in cross section, such handle elements being united integrally with the base and/or sides of the recess or depression 90 O A combinsation lid and dish according

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