* GB785313 (A)

Description: GB785313 (A) ? 1957-10-23

Glazing bar assemblies

Description of GB785313 (A)

PATENT SPECIFICATION 7859313 Inventors:-JACK FOX-WILLIAMS and HAROLD GRAHAM MUSGRAVE. Date of filinq Complete Specification: Dec 21, 195 5. a Application Date: Dec 23, 1954 No 37296/54. Complete Specification Pyihligsled: Oct 23, 1957. Index at Acceptance:-Class 20 ( 3), E( 2: 3 10). International Classification:-E 04 f. COMPLETE SPECIFICATION. Glazing Bar Assemblies. We, WILLIAMS & WILLIAMS LIMITED, a Company registered under the Laws of Great Britain, of Reliance Works, Chester, do hereby declare this 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 glazing bar assemblies of the kind comprising a girder member having a web, projecting laterally from which is a part constituting an abutment arranged to support the edge portion of a sheet of glass or other sheet material (hereinafter for convenience assumed to be glass) above which the web extends, the girder member having also formed thereon a rib or shoulder constituting the upper side of a groove or channel lying between the abutment and the web with the mouth of the groove facing the web, and a resilient cover strip having a laterally extending upper portion formed so that its outer edge part engages the upper face of a piece of glass resting upon the abutment and a downwardly projecting portion which is formed to extend between the glass and the web with its upper part or a part intermediate in its width engaging the web while its lower edge portion is formed so that when such downwardly extending portion is pressed downwardly to force the laterally extending portion resiliently into close contact with the upper face of the glass, such

3.5 lower edge part slides over the edge of the rib or shoulder and springs resiliently into the groove under the rib or shoulder and is retained therein by the reaction between the cover strip and the glass on the one hand and the cover strip and the web on the other. For convenience it has been assumed above that the girder member is horizontal or inclined It is to be understood, however, that the invention is also' applicable to assemblies in which the girder member is vertical, that is to say the glass lies in a vertical plane. While such a glazing bar assembly has considerable practical advantages in that it provides for the glass being held in firm engagement with the abutment, allows for such differences in the thickness of the glass as are normally encountered in practice, allows for a satisfactory degree of tolerance in the disposition of the glazing bars between which the glass extends and in the width of the glass, and enables assembly of the cover strips to be effected without special tools or the provision of loose parts, it has been found that, whereas the parts of the cover assembly can be assembled readily in many instances, occasions occur, as for example when the parts of the assembly have been stored or left in the open for some time and have acquired a relatively thick coating of oxide or like corrosion. when the force required to assemble the cover strips tends to be excessive and assembly therefore becomes difficult. Usually the parts are of aluminium alloy which automatically acquires a hard coating of oxide when exposed to the atmosphere. which coating may increase in depth due to lengthy exposure and which if it is fractured, tends to break up into small hard crystalline particles The difficulty of assembly in the case of aluminium alloy parts is therefore attributed to the fact that the pressure in between the cover strip and the web and/or the edge of the rib or shoulder when assembly is attempted causes such small hard crystalline particles to F Pm 4,5 _ 1 785,313 break away from the oxide coating and to dig into the surfaces of the girder member and cover strip, thus in effect tending to key them together and prevent their sliding over one another in the manner required during assembly. It is an object of the present invention to provide an improved glazing bar assembly of the kind referred to in which the assembly t) of the cover strips in position will be facilitated and the ease of this assembly will tend to be unaffected by the coating of oxide or corrosion of the parts as may be met with in practice due to their being stored or 1.5 exposed for a substantial period before being stored or exposed for a substantial period before assembly. In a glazing bar assembly of the kind referred to according to the present inven't O tion the face of the web and/or the part of the cover strip which bears against such face during assembly is formed

with one or more projections so as to provide a limited area of contact between the cover strip and the ' web during the insertion of the cover strip, this maintaining adjacent parts of the cover strip and of the web at least mainly out of contact during such assembly. In one arrangement a shallow longitudinal 3 It rib, of possibly only a few thousandths of an inch height and width, may be formed at the appropriate position on the face of the web where it will be engaged by the cover strip during assembly of the latter and thus :; provide a limited area of contact between the cover strip and the web and maintain the cover strip mainly out of engagement with the said face of the web during insertion of the cover strip Moreover in such a case the cover strip may itself be formed with a slight bend providing a concave recess in the face which lies adjacent to the web, at a position such that the rib will lie in the concave recess thus formed when the cover strip is fully inserted into position. In an alternative and preferred arrangement, according to the present invention the face of the downwardly extending part of the cover strip which bears against the web and/or such face of the web is formed with a series of longitudinally displaced projec. tions of limited area providing small contact areas between the cover strip and the web during the insertion of the cover strip and maintaining the parts of the cover strip between them, during such insertion at least, mainly out of contact with the web. In one convenient arrangement the lon'itudinally displaced projections are in the if) form of "pips" formed, for example, with the formation of corresponding depressions in the face of the cover strip remote from the web In a typical example a single row only of such "pips" might be provided, these being spaced from one another by about 4 inches, but it is to be understood that the spacing is in no way critical and that two or more rows of projections or "pips" might be provided while the spacing of the "pips" in any case can vary widely 70 The disposition of the "pips" or other projections in relation to the width of the part of the cover strip or of the web on which they are formed may either be such that when the cover strip is fully inserted 75 into position the "pips" lie out of contact with the opposed surface which they engaged during assembly or such that the "pips" or projections maintain contact with such opposed surface, the former disposition being,,o however, in most cases preferable since the cover strip when fully inserted can then make a continuous line of contact with the web, thus tending to exclude air andl or moisture and to provide an arrangement 8. which, apart from the increased ease of assembly, is comparable in every way when assembled, with known glazing bar assemblies of the kind referred to.

According to a further feature of the in P 0) vention the part of the lower edge portion of the cover strip which engages the edge of the rib or shoulder during assembly of the cover strip or such edge portion of the rib or shoulder may be formed so that such 95 engagement takes place only over separate longitudinally displaced areas of such lower edge portion, since this also may facilitate assembly while not detracting from the effectiveness of the arrangement when I'A) assembly is complete For example, in such an arrangement the areas of the lower edge portion of the cover strip which do not engage the edge of the rib or shoulder during assembly of the cover strip may be pre 105 vented from such engagement merely by being bent inwards towards the part of the cover strip which engages the web, in relation to the edge portions which engage the edae of the rib Thus the edge portion of 110 the cover strip which engages the edge of the rib during assembly may be of a generally sinuous form or have definite sections bent inwards so as to lie approximately parallel to and nearer the web than 11. the sections which alternate therewith. The invention mav be performed in various different ways but two specific embodiments will now be described by way of example with reference to the accom 12 t panying drawings in which:Figure 1 is a cross section through one complete glazing bar assembly with glazing material and cover strip in position; Figures 2 and 3 are perspective views of 125 the cover strip shown in Figure 1: and Figure 4 is a cross sectional view corresp-onding to Figure I of a modified form of glazing bar assembly according to the invention accommodate the rib 13 when the cover strip is in its fully inserted position as shown.

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* GB785314 (A)

Description: GB785314 (A) ? 1957-10-23

Improvements in and relating to the polymerisation of olefines

Description of GB785314 (A)

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

BE543941 (A) FR1142456 (A) NL107439 (C) BE543941 (A) FR1142456 (A) NL107439 (C) 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.

AMENDED SPECIFICATION Reprinted as amended in accordance with the Decision of the Superintending Examiner acting for the Comptroller General, dated the twenty-second day of June, 1967, under Section 14, of the Patents Act, 1949. PATENT SPECIFICATION 785,314 Inventors: MERVYN FREDERICK VINCENT, HUGH WILMA BOULTON REED and PETER SMITH Date of filing Complete Specification (under Section 3 ( 3) of the Patents Act, 1949): Dec 9, 1955. Application Date: Dec24, 1954 No 37361/54. Application Date: April IS, 1955 No 10883/55. Application Date: July 15, 1955. Application Date: Aug 11, 1955. Application Date: Aug 11, 1955. Application Date: Sept 2, 1955. Complete Specification Published: Oct 23, 1957. No 20512/55. No 23204/55. No 23207/55. No 25239/55. Index at acceptance:-Classes 1 ( 1), A 3 B 1; and 2 ( 6), P 7 A, P 7 C( 6 A:14 B:20 B:20 C), P 7 D 1 (A: B:X), P 7 (D 2 A 1:FX), P 7 P 1 (A:B:C:D:X), P 7 P( 3:4 C:5:6 A:6 G:6 X), P 7 T 1 (C:X).

International Classification:-B Olj CO 8 f. COMPLETE SPECIFICATION Improvements in and relating to the Polymerisation of Olefines We, IMPERIAL CHEMICAL INDUSTRIES LIMITED, Imperial Chemical House, Millbank, London, S 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 the polymerisation of olefines. It is an object of the invention to provide a process whereby olefines are polymerised smoothly and rapidly to polymers, those of higher molecular weight being eminently suitable for working up into, for example, filaments, foils, sheets and tubes having very desirable properties, and those of lower molecular weight being eminently suitable as chemical intermediates. The invention is applicable to the polymerisation of ethylene and alpha-olefines. Examples of alpha-olefines are propylene, butene-1, isobutylene and styrene. According to the invention there is provided a process for the polymerisation of olefines in which the olefine is brought into contact with a reaction medium comprising a material formed by reacting a transition metal halide, as hereinafter defined, with at least one organo-compound wherein the I Prrcr organo-compound is an alkali metal alkyl, alkenyl, alkynyl, aryl or aralkyl, or ethyl aluminium sesquichloride. The alkali metal alkyl may be, for example lithium butyl or sodium amyl Mixtures of 35 the organo-compounds may be employed. The transition metal halide is defined as a halide of a transition metal of Group IV to VI inclusive of the Periodic System Mixtures of the above defined transition metal 40 halides may be used and these mixtures may be used with mixtures of the organo-compounds We prefer to use a chloride such as for example, molybdenum pentachloride and tungsten hexachloride Particularly suitable 45 halides are titanium tetrachloride and vanadium tetrachloride. The organo-compound and the transition metal halide should be brought together in a molecular ratio within the range 20:1 50 to 1: 20 Suitable ratios are 15: 1, 10: 1, 8: 1, 6: 1 and less It is particularly convenient to use molecular ratios within the range 4: 1 to 1:4 in order to economise in the use of valuable transition metal halide Lower ratios 55 than 1: 4 may be used for example 1: 6, 1:8, 1:10 and 1:12. However, the choice of a particular molecular ratio depends on the properties, particularly the physical properties, required in the 60

Pr<polymer While the effect of other factors e.g pressure, temperature, composition of the organo and transition metal compounds, must be taken into account, in general increase in the molar ratio organo-compound to transition metal halide leads to an increase in the molecular weight of the polymer or to an increase in the proportion of relatively high melting polymer in the polymerisation product. The polyethylenes produced by the process of the invention are insoluble in ether and highly crystalline The solid polymers produced according to the process of the invention from other olefines may contain substantial amounts of material substantially insoluble in ether and giving the regular X-ray diffraction pattern of a crystalline material These materials insoluble in ether have higher melting points, higher densities and lower solubilities in organic solvents than the corresponding materials soluble in ether They can also be extruded and fabricated into filaments, sheets and tubes. The reaction medium preferably also comprises a solvent The solvent may be an olefine in the liquid state under the conditions of the polymerisation process, provided that no substantial amount of undesired product is formed from the olefine Except when the solvent is such an olefine, the solvent should be inert under the reaction conditions. Suitable inert solvents are paraffinic, aromatic and alicyclic hydrocarbons. The olefine may be brought into contact with the reaction medium in a variety of ways If the olefine is a gas, it may for example, be passed across the surface of the medium or bubbled through the medium If the olefine is a liquid under the conditions of operating the process it may be mixed with the medium. Mixtures of olefines may be polymerised. The olefines may be pure or in admixture with substances e g other hydrocarbons or hydrogen, which are inert under the conditions of the polymerisation reaction. The pressure at which the polymerisation is carried out may be atmospheric, below atmospheric or above atmospheric pressure, up to for example, 100 atmospheres Temperatures within a wide range may be used. The particular combination of temperature and pressure selected depends largely on whether it is desired to operate the process with the olefine in the gaseous or liquid phase. If the olefine is to be polymerised in the liquid phase the temperature selected must be below the critical temperature and sufficient pressure applied to maintain the olefine in the liquid state. When the polymerisation process is carried out with the olefine in the

vapour phase, temperatures as high as 3000 C may be used However, it is preferred to use temperatures below 1000 C Very suitable temperatures are within the range 20 to 800 C, especially within the range 400 to 600 C Temperatures down to about -800 C, however, may be employed. Water and oxygen should not be present in the apparatus in which the polymerisation is effected in more than relatively small amounts since they decompose organo-compounds Air is suitably displaced from the apparatus by an inert atmosphere of for example, nitrogen. The process of the invention may usefully be conducted in the presence of a polymer soluble anti-oxidant in order to obtain polymers stabilised against oxidation during their further processing A very suitable antioxidant is bis( 2 hydroxy 3 alpha methylcyclohexyl 5 methyl phenyl) methane. EXAMPLE 1 The apparatus used consisted of a 1-litre flask fitted with a stirrer, reflux condenser and gas inlet tube Water was excluded from the apparatus and the air displaced by an atmosphere of nitrogen. The reaction medium used comprised 0 02 M titanium tetrachloride and 0 04 M lithium butyl, in 200 mls of petroleum ether (b pt. 40-600 C) as solvent Ethylene was passed at a rate of 40 litres/hr through a gas meter and drying tower and then into the flask so that it contacted the surface of the reaction medium The exit gases from the flask were led from the top of the reflux condenser through a drying tower and a gas meter. The maximum temperature attained was 40 GC and after an hour the experiment was terminated and the gas in the flask was displaced by nitrogen, the flask cooled to room temperature and ethanol added until the deposit of polymer became light coloured The deposit of polyethylene was then filtered, washed with ethanol and dried 25 5 gms of polymer were obtained. EXAMPLE 2 110 A reaction medium was prepared by mixing 9 4 grams sodium amyl, 9 6 grams vanadium, tetrachloride and 200 grams pentane, in a reaction vessel from which oxygen was excluded byrmeans of nitrogen Moisture was 115 excluded from the reactants and apparatus. The stirred reaction medium was mairtained at a temperature of about 300 C and ethylene passed into the reaction vessel so that it contacted the surface of the reaction 120 medium A solid deposit immediately began to form. After 2-4 hours the supply of ethylene was stopped and 40 grams ethanol added to the reaction mixture The solid was polymer 125 filtered from the mixture, washed with ethanol and then with water until the filtrate was colourless 17 grams of white polyethylene

785,314 the same solvent 21 9 litres of ethylene were absorbed representing a conversion to polymer of 55 %. EXAMPLE 6 A 300 c c high-pressure autoclave fitted with a stirrer was surrounded with a cooling medium so that the temperature of the contents of the autoclave was maintained at 00 C. To the autoclave were added 0 35 g. (-0 00184 moles) of titanium tetrachloride and the vessel was then evacuated and pressured with ethylene to 40 atmospheres This pressure is the vapour pressure of ethylene at 00 G and consequently liquid ethylene was formed in the vessel From an auxiliary pressure vessel 9 4 c c of a 0 78 molar solution of lithium butyl (= 0 00735 moles) in petroleum ether of b p 600 to 800 C were added, and the mixture stirred for one hour, keeping pressure and temperature as near 40 atmospheres and O C respectively as possible On releasing the pressure and filtering the contents of the vessel, washing with methanol and hydrochloric acid and drying, 14 g of a white solid polymer of ethylene were obtained having a density of 0 947 g/c c, a grade number of O 003, a yield stress of 345 kg/cm 2, a break stress of 345 kg/cm 2, and showing an extension at break of 150 %. Grade number (melt index) was determined according to A S T M Specification D 1238- 52 T. EXAMPLE 7 The apparatus used consisted of a 1-litre flask fitted with a gas-inlet tube, a dropping funnel, a condenser and a stirrer Water was excluded from the apparatus and the air displaced by an atmosphere of nitrogen. Titanium tetrachloride dissolved in 25 to ml of solvent was added to 150 ml of solvent in the flask, the solution vigorously stirred and ethyl aluminium sesquichloride dissolved in 25 to 50 ml of solvent then added The solvent was petroleum ether (boiling point 60 to 800 C) Stirring was continued and dried propylene containing approximately % propane passed into the flask at 30 litres per hour so that it contacted the surface of the solution The reaction was stopped by adding sufficient methanol to the reaction mixture to decompose any residual catalyst. The results obtained are given in the following table. having a melt viscosity at 1970 C of 1.83 X 108 poises were obtained. EXAMPLE 3 The experiment described in Example 4 was repeated using the same reaction conditions The reaction medium was prepared by mixing 9 4 grams sodium amyl, 5 5 grams molybdenum pentachloride and 200 grams pentane Ethylene was passed over the medium for 2 w hours.

grams of ethanol were then added to the reaction mixture and the solid polymer separated by filtration, washed successively with pentane, ethanol, dilute bromine water, dilute caustic soda solution and water The solid polymer was then dried at 450 C for 8 hours 3 grams of polyethylene having a melt viscosity at 1970 C of 3 38 X 101 poises were obtained. EXAMPLE 4 The following experiment illustrates the polymerisation of ethylene at low temperatures using a similar apparatus and technique to that described in Example 1. 9 6 ml of a 0 78 molar solution of lithium n-butyl in petroleum ether (b p 600 to 800 C) and 265 ml of the same petroleum ether were placed under an atmosphere of nitrogen in a 500 ml flask, the flask cooled in a solid CO 2-ethanol bath to -700 C and 0 35 g. of titanium tetrachloride dissolved in 25 ml. petroleum ether added to the contents of the flask A pale cream precipitate was formed. While vigorously stirring the contents of the flask and maintaining the temperature at -700 C ethylene was passed into the flask for 1-j hour 6 1 g of a pale cream fluffy polyethylene were isolated The polyethylene was 65 % crystalline as detremined by infrared absorption; it softened at 1290 C and had a density of 0 945 g /ml at 200 C. EXAMPLE 5 The following experiment was carried out using a similar apparatus and technique to that described in Example 1 In the experiment ethylene was polymerised by passing it at 40 litres/hr for 1 hour into the 1-litre flask so that it contacted a reaction medium formed by reacting 1 g ethyl aluminium sesquichloride ((C 2 Hj),A 2 Gl,) dissolved in 50 ml petroleum ether ( 600 to 801 C) with 1 g. titanium tetrachloride mixed with 50 ml of 785,314 4 785,314 TABLE The polymer was a mobile liquid.

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* GB785315 (A)

Description: GB785315 (A) ? 1957-10-23

Improvements in methods and apparatus for intermittently progressing stripmaterial

Description of GB785315 (A)

PATENT SPECIFICATION 785, Date of filing Complete Specification: Jan 2, 1956. Application Date: Dec 28, 1954 No 37401/54. I / Complete Specification Published: Oct 23, 1957. Index at Acceptance:-Classes 83 ( 4), 02 C 3 A; and 100 ( 1), C 8 D 2 A. International Classification:-B 23 d. COMPLETE SPECIFICATION. Improvements in Methods and Apparatus for Intermittently Progressing Strip Material. We, WILLIAM RHODES LIMITED, of Carnton Cross Mills, Leeds 2, a British Company, and JOSEPH CEMM, a British Subject, of Rhodosteel Works, Leeds 12, 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 improvements in methods and apparatus for intermittently progressing strip material and is particularly concerned with methods and apparatus for intermittently progressing strip material such for example as metals in the form of metal strip or metal wire into dies which are subsequently acted on under pressure in a press for forming the strip material into pre-determined shapes according to the dies. One known method of intermittently feeding strip material is to pass the material between two or more rollers which may be provided with serrations or flutes for preventing slip between the rollers and the material The rollers are rotated a predetermined amount so as to progress the strip material therebetween For feeding strip material into dies within a press this method is not entirely satisfactory since it is necessary to feed precisely the same length of strip each time into the die and it is, therefore, necessary to provide geared synchronising mechanism for rotating the rollers the same number of turns or portion of a turn each time Due to wear of gear wheels,

chains and other like driving means it often occurs that a different length of strip material is fed into the dies Furthermore there is a moment of inertia to overcome to rotate the wheels and also it is necessary to provide positive braking action to prevent over-feeding of the material when the lPrice 3 s 6 d l wheels are operated at comparatively high speeds. It is one object of the present invention to to provide an improved method of intermittently progressing strip material into a die. It is another object of the invention to provide improved apparatus for intermittently progressing strip. With the above and other objects in view the present invention provides in a press or similar machine of the type having a base plate and a top plate movable towards and away from the base plate, means for intermittently progressing strip material comprising a forked reciprocatable member through which the strip material passes actuated by the movement of relative separation and advancement of the top and bottom plates of the press, means for securing strip material relative to the reciprocatable member for advancement of the strip material in one direction only and means for securing the strip material against movement in the other direction. The strip is conveniently secured to the reciprocatable member by gripping means associated with the member, which secures the strip thereto for advancement in one direction but releases the advanced strip for movement of the member along the strip in the opposite direction The means for securing the advanced strip against movement in the opposite direction preferably comprises a fixed support having similar gripping means associated therewith, which permits advancement of the strip but prevents it from moving in the opposite direction The gripping means associated with the reciprocatable member and the fixed support conveniently comprises a pivoted member having a strip engaging portion, the i 315 785,315 member being so pivoted that relative movement of the strip to the pivoted member is possible in only one direction The pivoted member preferably has an adjustable gripping blade and may be spring biased into engagement with the strip The pivot is conveniently off-set from the vertical plane of the blade Conveniently the reciprocatable member and the fixed support are 1 f forked to accommodate the gripping members and to allow the strip material to pass therethrough The reciprocatable member is preferably mounted to slide in or on guide means parallel to the direction in which the strip is to be progressed. Conveniently the reciprocatable memnber co-operates with one arm of a bell crank lever pivoted relative to the bottom plate, the other arm of the lever co-operating with an adjustable projection on the ton plate causing the bell crank to pivot and move the reciprocatable

member. An adjustable stop or the like nmay be provided for limiting movement of the reciprocatable member and spring means may be provided for biasing the reciprocatable member against the stop. In order that the invention may be more readily understood reference will now be 3 " given to the drawings accompanying the Provisional Specification in which - Figure 1 is a side elevation of apparatus according to the present invention. Figure 2 is a section on the line A-A 3-5 looking in the direction of the arrows. A top plate I and a base plate 2 of a subpress are provided with attachments in the form of apparatus according to the present invention comprising a slotted member 3 which is provided with a slot 5 and an adjustable bolt 4 located therein A bell crank 6 is pivoted about a pin 7 mounted on a pillar 27 secured to the base plate 2 The bell crank 6 is provided with an open-ended slot 8 at the lower end thereof A reciprocatable member 13 is provided with flanges for co-operation with a track formed in the base plate 2 The member 13 is provided with a pin 9 extending from one side thereof, which pin is encircled by the slot 8. The member 13 is forked at its upper end and a gripping member 26 Is located between the forks and mounted about an off-set pivot pin 17 A pin 16 secured to the gripping a member 26 is arranged to move in a slot 15 formed in one of the forks of the movable member 13 and a coil spring 14 biases the arioping member such that the pin 16 is at the tower end of said slot 15 A blade 19 is 6, " secured within a slot formed in the gripping member 26 by an adjustable screw 18 The reciprocatable member 13 is spring biased by a coil spring 10 secured to a pin on the member and anchored to a pillar 11 secured Il to the base plate 2 An adjustable screw 12 acts as a stop to determine the distance of the member 13 from said pillar 11 A strip securing attachment comprises a fixed support 22 secured to the base plate and having a gripping member 20 pivotally mounted 70 relative thereto, said member having a blade secured therein by a screw 23, the member is spring biased by a coil spring 21. In operation strip material 24 may be progressed intermittently towards dies or the 7,5 like located between the top and base plates of a press in the following manner: As the top plate 1 rises the pin 4 abuts the bell crank 6 pivoting said crank about the pin 7 and forcing the reciprocatable mem 8 O ber 13 forwards by means of the pin 9, encircled by the slot 8 The member 13 slides in a horizontal plane in the track formed in the bottom plate 2, and the blade 19 firmly secures the strip 24 relative to the

member, 85 thus progressing the strip material The strip material in moving between the support 22 and the blade on the gripping member 20, pivots said member 20 about its pivot pin but as soon as the force progressing the 90 strip is released the member 20 returns under the influence of the coil spring 21 and prevents movement of the strip in the reverse direction The coil spring 10 returns the member 13 to its position of abutting the 95 adjustable screw 12, the gripping member 26 pivots about the pin 17 so as to permit the blade 19 to ride over the strip material. The len gthi of strip material progressed each time may be adjusted by (a) the position of 10 ' the adjustable bolt 4 within the slot 5 thus determining how far the top plate 1 is to mnove before it contacts the bell crank and (b) by adjustment of the adjustable screw 12 which determines the extent to which the 105 member 13 may be returned after progressing the strip material. It will be appreciated that the present invention provides a method and apparatus for positively progressing intermittently strip 110 material without the employmnent of rotating devices such for example as fluted wheels. Furthermore the invention provides a method and apparatus which ensures accuracy in the length of strip material which 11 l is progressed each time and the apparatus is such that it may be mounted immedkitely adjacent to dies located in a press so that there is substantially less chance of the strip m Paterial being de-formed or otherwise avoid 120 in beine fed into the dies This is particularly important when the stria material is of thin section or of soft material. The invention -rav be easily adjusted for variation of different lengths of material 125 wlh ch it is desired to -;,proarers and furthermore the invention his the advantage of heine ramid -nd pesitive in action, an advantage not possessed bv rotating feed devices which have an inertia to overcome vhen I i 755,3 is starting and momentum to brake when stopping.

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* GB785316 (A)

Description: GB785316 (A) ? 1957-10-23

Rubber antioxidant mixtures and their application

Description of GB785316 (A)

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

BE544058 (A) DE1090850 (B) FR1139514 (A) NL94557 (C) US2923753 (A) BE544057 (A) DE1157384 (B) FR1149680 (A) NL94556 (C) BE544058 (A) DE1090850 (B) FR1139514 (A) NL94557 (C) US2923753 (A) BE544057 (A) DE1157384 (B) FR1149680 (A) NL94556 (C) 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 Inventors: BORIS NICHOLAS LEYLAND and RONALD LEE STAFFORD 785,316 Date of filing Complete Specification: Dec 12, 1955. Application Date: Dec 31, 1954. No 37774154. Complete Specification Published: Oct 23, 1957. Index at acceptance:-Class 70, E 14. International Classification:-CO 8 c. COMPLETE SPECIFICATION Rubber Antioxidant Mixtures and their Application We, IMPERIAL CHEMICAL INDUSTRIES LIMITED, of Imperial Chemical House, Millbank, London, S W 1, a British Company, do hereby declare the invention, for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement:-

This invention relates to rubber antioxidant mixtures and their application to natural rubber in order to protect the rubber against deterioration by oxidation both before and after vulcanisation, especially in the presence of copper or manganese. According to the present invention we provide a process for protecting natural rubber against deterioration by oxidation, especially in the presence of copper or manganese, which comprises incorporating into the rubber, at any suitable stage before curing, at least one mercaptoarylimidazole and at least one N: N 1disubstituted diaryl, alkylaryl or cycloalkylaryl p-phenylene diamine. The mercaptoarylimidazole may be used as such or in the form of its metal salt, for example its zinc, magnesium or calcium salt. The preferred mercaptoarylimidazole is 2mercaptobenzimidazole but others may be used, for example 2: 21-dibenzimidazyl disulphide. We are aware that it has already been proposed to use mixtures of antioxidants generally, and in particular, phenyl-a-naphthylamine and phenyl-13-naphthylamine, with mercaptoarylimidazoles in order to enhance the antioxidant effect However it has not hitherto been observed that any special effect with respect to oxidation in the presence of copper or manganese is obtained and it has not been proposed to use mixtures of the N: N'disubstituted p-phenylene diamines of our invention with mercaptoarylimidazoles We have discovered that such mixtures have an unexpected, outstanding effect on the oxidation of natural rubber in the presence of copper lPrice 3 s 6 d l or manganese and our present invention is based upon this discovery. Suitable N: N-disubstituted p-phenylene diamines include N: N -di -/3 naphthyl pphenylene diamine, N: N'-di-a-naphthyl-pphenylenediamine, N: N'-diphenyl-p-phenylenediamine N cyclohexyl N' phenyl pphenylene diamine, N-sec butyl-Nl-,3-naphthyl-p-phenylene diamine and N: NI-dicyclohexyl-p-phenylene diamine. The proportion of mercaptoarylimidazole to be used in the process of this invention may be from about 50 % to about 200 % of the weight of the N: N'-disubstituted p-phenylene diamine; preferably the proportion is about % The amount of the combined agents used in the rubber is conveniently from 0 5 % to 4 0 % of the weight of the rubber hydrocarbon. The efficacy of the process of this invention may be even further enhanced by the further incorporation into the rubber of a coppersequestering agent, for example ethylene diamine tetracetic acid or a metal salt thereof, a disalicylal alkylene diamine, 8-hydroxyquinoline or p-aminophenol Suitable proportions of the agents are from 3 % to 10 % of the total weight of the mercaptoarylimidazole, the N:N'-disubstituted p-phenylene diamine and the copper-sequestering

agent employed. The agents may be added to the rubber mix singly or in combination In the latter case it is convenient to use the agents as a preformed mixture and such preformed mixtures of mercaptoarylimidazole, N: N' disubstituted diaryl, alkylaryl or cycloalkylaryl p-phenylene diamine and, optionally, a copper-sequestering agent form a further feature of this invention. The invention is illustrated but not limited by the following Examples in which parts and percentages are by weight. EXAMPLE 1. Vulcanisable rubber compounds were made -up by the conventional method according to the following formulae Pkee 25 p so MIX Pale crepe rubber Zinc oxide Blanc fixe Stearic acid Sulphur Diphenylguanidine Copper stearate N: NI-di-,/-naphthyl-pphenylenediamine N-cyclohexyl-NW-phenyl-pphenylenediamine 2-mercaptobenzimidazole The mixes were vulcanised for 150 minutes at 141 C The antioxidant effect was measured by observing the time in hours to absorb a given amount of oxygen The sheet was enclosed in a glass cell maintained at 900 MIX Time in hours to attain 0 O-uptake of 0 5 % 1.0 % A 1 3 0.5 0.2 B 1 3 0.5 0.2 C 1 3 0.5 0.2 D 1 3 0.5 0.2 2 1 2 1 1 1 C and containing oxygen The amount of oxygen absorbed was calculated from the rise 20 of mercury in a single manometer tube attached to the glass cell. A B C D 25.5 34 2 34 2 56 3 47.2 66 8 66 7 101 3 Similar compounds as given above, vulcanised and tested in the same way but containing phenyl-c-naphthylamine and phenyl-,3-naphMIX Pale crepe rubber Zinc oxide Blanc fixe Stearic acid Sulphur Diphenylguanidine Copper stearate Phenyl-7-naphthylamine Phenyl-13-naphthylamine 2-mercaptobenzimidazole MIX Time in hours to attain 0,-uptake of 0 5 % thylamine as antioxidants were also made for comparison. a 1 3 0.5 0.2 b 1 3 0.5 0.2 a b c 10 1 3 0.5 0.2 d 1 3 0.5 0.2 1 c d Z 2.3 25 6 24 5 29 5 40.7 47 5 44 0 54 5 785,316 1.0 % 785,316 EXAMPLE 2. The following compounds were prepared in the conventional manner. MIX Pale crepe rubber Zinc oxide Blanc fixe Stearic acid Titanium dioxide Sulphur Zinc diethyldithiocarbamate N: N 1-di-ft-naphthyl-pphenylenediamine 2-mercaptobenzimidazole 8-hydroxyquinoline p-aminophenol Copper stearate These mixes were vulcanised for 12 minutes at 125 C. The antioxidant effect was measured by determining the tensile strengths of ringshaped test pieces which had been aged for varying periods in an oxygen bomb under 300 p s i oxygen pressure at 70 C; curves MIX t-50 % period E 1 2.0 0.375 F 1 2.0 0.375 G 1 2.0 0.375 H 1 2.0 0.375 2 1 1 0 95 1 0 9 0 95 e_ O 1 0 1 0.2 0 2 0 2 0 2 were drawn for each mix, of tensile strength against duration of ageing and from

the 25 curves was interpolated the time in days for the tensile strength to fall to 50 % of the unaged sample. The following results were obtained: E F G H 9.2 16 0 16 4 17 0 EXAMPLE 3. The following mixes were prepared in the conventional manner:MIX Pale crepe rubber Zinc oxide Blanc fixe Stearic acid Titanium dioxide Sulphur 2-mercaptobenzthiazole N: N 1-di-,G-naphthyl-pphenylenediamine 2-mercaptobenzimidazole disalicylal ethylene diamine Copper stearate These mixes were vulcanised for 30 minutes at 1410 C and the antioxidant effect was J 1 2.5 0.5 K 1 2.5 0.5 2 1 - 0 85 0 15 0.2 0 2 L 1 2.5 0.5 1 0.2 measured as in Example 2. The following results were obtained: MIX t-50 % period in days j K L 8.2 137 118 785,316 EXAMPLE 4. The following mixes were prepared in the conventional manner: MIX Pale crepe rubber Zinc oxide Blanc fixe Stearic acid Sulphur Diphenylguanidine Copper stearate N: If-di-13-naphthyl-pphenylenediamine N-cyclohexyl-N 1-phenyl-pphenylenediamine p-Aminophenol 2-mercaptobenzimidazole The mixes M and N were vulcanised for minutes at 141 C and tested by the bomb ageing method described in Example 2 The mixes P, Q and R were vulcanised for 150 MIX t-50 % period in days MIX time in hours to attain oxygen uptake of 1 0 % M 1 3.0 0.5 0.2 N 1 3.0 0.5 0.2 p 1 3.0 0.5 0.2 Q 1 3.0 0.5 0.2 R 1 3.0 0.5 0.2 2 1 _ 2 1 1 _ _ _ 0 1 1 1 0 9 minutes at 1410 C and tested by the oxygenabsorption method described in Example 1. The following results were obtained: M N 6.0 13 0 P Q R 67 101 96 EXAMPLE 5. The following mixes were prepared in the conventional manner: MIX Pale crepe rubber Copper stearate 2-mercaptobenzimidazole N: NW-di-/3-naphthyl-pphenylenediamine N-cyclohexyl-Nl-phenylp-phenylenediamine The above mixes were oxidised at 90 C. on stainless-steel gauze trays placed in the MIX Time in hours to obtain an oxygen uptake

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* GB785317 (A)

Description: GB785317 (A) ? 1957-10-23

Rubber antioxidant mixtures and their application

Description of GB785317 (A)

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BE544058 (A) DE1090850 (B) FR1139514 (A) NL94557 (C) US2923753 (A) BE544057 (A) DE1157384 (B) FR1149680 (A) NL94556 (C) BE544058 (A) DE1090850 (B) FR1139514 (A) NL94557 (C) US2923753 (A) BE544057 (A) DE1157384 (B) FR1149680 (A) NL94556 (C) less Translate this text into Tooltip

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PATENT SPECIFICATION Inventors: BORIS NICHOLAS LEYLAND and RONALD LEE STAFFORD 785,317 Date of filing Complete Specification: Dec 12, 1955. Application Date: Dec 31, 1954. No 37775/54. Complete Specification Published: Oct 23, 1957. Index at acceptance:-Class 70, E 14. International Classification:-CO 8 c. COMPLETE SPECIFICATION Rubber Antioxidant Mixtures' and their Application We, IMPERIAL CHEMICAL INDUSTRIES LIMITED, of Imperial Chemical House, Millbank, London, S W 1, a British Company, do hereby decare 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 rubber antioxidant mixtures and their application to, natural rubber in order to protect the rubber against deterioration by oxidation, both before and after vulcanisation, especially in the presence of copper or manganese. According to the present invention we provide a process for protecting natural rubber against deterioration by oxidation, especially in the presence of copper or manganese, which copprises: incorporating into the rubber, at any suitable stage before curing, at least one mercaptoarylimidazole and at least one phenol containing at least one tertiary alkyl or alkylcycloalkyl radical having from 4 to 8 carbon atoms. The mercaptoarylimidazole may be used as such or in the form of its metal salt, for example its zinc, calcium or magnesium salt. The preferred mercaptoarylimidazole is 2mercaptobenzimidazole but others may be used, for example 2: 21-dibenzimidazyl disulphide. We are aware that it has already been proposed to use mixtures of antioxidants generally with mrzrcaptoarylimidazolles in order to enhance the antioxidant effect However it has not hitherto been observed that any special effect with respect to oxidation in the presence of copper or manganese is obtained and it has not been proposed to use mixtures of the phenols of our invention with mercaptoarylimidazoles: We have discovered that such mixtures have an unexpected, outstanding effect on the oxidation of natural rubber in the presence of copper or manganese and our present 4 ic 3-4 d L invention is based upon this discovery 45 Phenols that can be used in the process of this invention include those described in Specifications 677,584, 719,101, 29722/51, 25975/52, 30638/52 and 11052/53; they may be, for example, bis( 2-hydroxy-3-tert 50 butyl 5 methylphenyl) methane, bisl 2hydroxy-3-(a-methylcyclohexyl) 5 methylphenyll -methane, bis( 2-hydroxy-y 3-tert -butyl5-ethylphenyl)-methane, 2: 2 ' dihydroxy 3tert octyl-3 -methyl-5: 51-dimethyldiphenyl 55 methane, 2: 21-dilhydroxy-3-teit -butyl-3 '-(amethylcyclohexyl) 5:51 dimethyldiphenylmethane, 2: 21-dihydroxy-3: 31-di-tert -butyl5: 51-dimethyldiphenyl-a: a-butane, 2: 6 dimethyl-4-tert -butylphenol, 2: 6-di-tert -butyl 60 4 methylphenol, 2,(a-metlhylcyclohexyl)-4: 6dimethylphenol or the metal salts thereof. The proportion of mercaptoarylimidazole to be used in the process of this invention may be from about 50 % to about 200 % of the weight 65 of the phenol; preferably the proportion is about 100 % The amount of the combined agents used in the rubber is conveniently from 0.5 % to 4 0 i% of the weight of the rubber hydrocarbon 70 The efficacy of the process of this, invention.

may be even further enhanced by the further incorporation into the rubber of a coppersequestering agent, for example ethylene diamine tetracetic acid or a metal salt thereof, a 75 disalicylal alkylenediamine, 8-hydroxyquinoline or p-aminophenol However the phenolic antioxidants described and their mixtures with the mercaptoarylimidazoles give compounds which do not stain on exposure to light and 80 when it is desired to retain this advantage the copper sequestering agents 8-hydroxyquinoline and p-aminophenol should not be used Suitable proportions of these agents are from 3 % ,' to 10 % of the total weight of the mercapto 85 arylimidazole, the substituted phenol and the copper-sequestering agent employed If it is desired to retain the advantage of a non-stainPly S 3 Cz -/-uv mu J Prlce Zp ing compound then the upper limit of 10 % should not be exceeded in the case of the disalicylal alkylenediamines. The agents may be added to the rubber mix singly or in combination In the latter case it is convenient to use the) agents as a preformed mixture and such pre-formed mixtures of mercaptoarylimidazole, a phenol containing at least one tertiary alkyl or alkylcycloalkyl radical having from 4 to 8 carbon atoms and, optionally, a copper-sequestering agent form a further feature of this invention. The invention is illustrated but not limited by the following Examples, in which parts and percentages are by weight. EXAMPLE 1. Vulcanisable rubber compounds were made the following formulw in up by the conventional methods according to by weight. which the parts are MIX Pale crepe rubber Zinc oxide Blanc fixe Stearic acid Sulphur Copper stearate Diphenyl guanidine bisl 2hydroxy 3 tert buryl 5 methylphenyll -methane bisl 2 hydroxy 3 (, -methylcyclohesyl)-5methylphenyll methane bis( 2-hydroxy-3-tert -butyl 5 ethyiphenyl)methane 2-mercaptobenzimidazole The mixes were vulcanised in sheets nct greater than O 8 mm thick for 150 minutes at 1410 C The antioxidant effect was measured by observing the time in hours to absorb a given amount of oxygen The sheet was MIX Time in hours to attain 02-uptake of 0 5 ' 1.0 % A 1 3 0.2 0.5 B 1 3 0.2 0.5 C D 100 10 75 1 1 3 3 0.2 0 2 0.5 0 5 E 1 3 0.2 0.5 F 1 3 0.2 0.5 2 1 2 1 2 1 _ 1 enclosed in a glass cell maintained at 90 ' C. and containing oxygen The amount of oxygen absorbed was calculated from the rise of mercury in a simple manometer tube attached to the glass cell. A B C D E F 31.8 36 6 26 6 30 7 18 25 52.0 64 7 44 0 52 5 32 46 5 EXAMPLE 2. Vulcanisable rubber compounds were made the following formule in which the parts are up by the convenional methods according to by weight. MIX Pale crepe rubber Zinc oxide Blanc fixe Stearic acid Sulphur

Copper stearate Diphenyl guanidine 2-( 7-methylcyclohexyl)-4: 6-dimethylptienol 2: 6-di-tert -butyl-4-methylphenol 2-mercaptobenzimidazole The mixes were vulcanised in sheets not greater than 0 8 mm thick for 150 minutes at MIX Time in hours to attain O -uptake of 0 5 O 1.0 1 G _ _ _ 100 _ _ _ 10 _ _ 75 H 1 K 1 1 1 1 _ _ _ 3 3 3 3 0 2 0 2 02 0 2 _ O 5 0 5 0 5 0 5 2 1 2 1 1 1 1410 C and the antioxdant effect was measured as in Example 1. G 17.5 30.2 H 21.0 38.6 J 12.5 24.0 K 22.2 40.0 785,317 785,317 EXAMPLE 3. The following ccmpounds were prepared in the conventional manner: MIX Pale crepe rubber Zinc oxide Blanc fixe Stearic acid Titanium dioxide Sulphur Zinc diethyldithiocarbamate Copper stearate bisl 2 hydroxy 3 (c-methylcyclohexyl)-5methylphenyll methane 2-mercaptobenzimidazole ethylene-bis(iminodiacetic acid) disalicylal ethylene diamine disodium salt of ethylene-bis(iminodiacetic acid) These mixes were vulcanised for 12 minutes at 125 C. The antioxidant effect was measured by determining the tensile strengths of ringshaped test pieces which had been aged for varying periods in an oxygen bomb under 300 MIX t-50 % period in days 1 2.0 0.375 0.2 M 1 2.0 0.375 0.2 N 1 2.0 0.375 0.2 0 1 2.0 0.375 0.2 2 1 1 1 1 0 9 0 9 0 1 0 1 p 1 2.0 0.375 0.2 0.95 0.95 _ _ _ 0 1 p.s i oxygen pressure at 700 C; curves were drawn for each mix, of tensile strength against duration of ageing and from the curves was interpolated the time in days for the tensile strength to, fall to, 50 % of the unaged sample. The following results were obtained: L M N O P 8.4 14 5 15 0 12 5 15 4 EXAMPLE 4. The following mixes were prepared in the conventional manner: MIX Q Pale crepe rubber 100 Zinc oxide 10 Blanc fixe 75 Stearic acid Titanium dioxide Sulphur 2-mercaptobenzthiazole bisl 2 hydroxy 3 (a,-methylcyclohexyl)-5methylphenyll methane 2-mercaptobenzimidaizole disalicylal ethylene diamine Copper stearate These mixes were vulcanised at 1410 C and the antioxidant effect was measured as in Example 3. 1 2.5 0.5 R 1 2.5 0.5 2 1 _ 0 9 _ 0 1 0.2 0 2 The following results were obtained: MIX Q R t-50 % period in days 11 6 15 5 785,317 EXAMPLE 5. The following mixes were prepared in the conventional manner: S T U V W X Y Z Pale crepe rubber Zinc oxide Blanc fixe Stearic acid Sulphur Diphenylguanidine Copper stearate bisl 2-hydroxy3 t> mjtfhylcyclohexyl)5-methylphenyllmethane 2:6-tert butyl-4methylphenol bis( 2-hydroxy3-tert butyl-5-methylphenyl)methane 2 ( 2-irl thyicyclohexyl)-4:6dimethylphenol 2-mercaptobenzimidazole 100 100 100 100 100 100 100 10 10 10 10 10 10 10 75 75 75 75 75 75 75 1 1 1 1 1 1

1 1 3.0 3 0 3 0 3 0 3 0 3 0 3 0 3 0 0.5 0 5 O 5 0 5 0 5 O 5 0 5 0 5 0.2 0 2 0 2 0 2 0 2 0 2 0 2 0 2 2 1 2 1 _ 2 2 1 _ 1 The mixes were vulcanised for 75 minutes at method described in Example 3. MIX 141 C and tested by the bomb ageing S T U V W X Y Z 2.5 8 5 1 0 5 2 4 5 13 5 1 5

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