5246 5250.output

* GB785653 (A)

Description: GB785653 (A) ? 1957-10-30

Improvements in or relating to yarn carriers for full-fashioned hosieryknitting machines

Description of GB785653 (A)

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DE1022739 (B) US2859602 (A) DE1022739 (B) US2859602 (A) less Translate this text into Tooltip

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PATENT SPECIFICATION 785,653 -i X ^ Date of application and filing Complete Specification: May 17, 1955. No 14188/55 Application made in Germany on May 18, 1954 Complete Specification Published: Oct 30, 1957. lndex at acceptance:-Class 74 ( 2), C( 1 C 1: 17). International Classification:-DD 4 b. COMPLETE SPECIFICATION Improvements in or relating to Yarn Carriers for Full-Fashioned Hosiery Knitting Machines I, EDGAR GEORG SCHOB, a German National, of 14, Bahnhofstrasse, Emmendingen/Baden, Germany, do hereby declare the invention, for which I pray that a patent may be granted to me, and the method by which it is to be performed, to be particularly described in and by the following statement:The present invention relates to filat-bed knitting machines and more particularly to the

thread carriers thereof from which the thread is fed to the knitting needles. Prior to this invention it has been usual to employ a thin thread-guiding member comprising a fine-gauge tube which is mounted on the lower end of a thread carrier or thread carrier finger and through which the thread passes to the needles over the sinkers. In actual practice these thin thread-guiding tubes, especially for fine-gauge machines, are very difficult to produce and require considerable lateral space since the walls thereof may not be made below a certain strength, as otherwise the thread might be cut by the edge of the thread opening This danger is considerable Owing to the small inner diameter of the tubes, they easily become clogged, and the removal of obstructions requires a considerable time as well as necessitating frequent replacement of the tube. It is an object of the present invention to provide an arrangement wherein the aforementioned disadvantages are eliminated. Another object of the present invention is to provide a thread carrier which is much more easily threaded than the prior known thread-guiding tube, through which it is very difficult to pass the thread, especially if resinous matter or lint has settled therein. A further object of the present invention is, therefore, to provide a thread guide which does not exert an uncontrollable binding or braking action upon the thread which occurs very frequently when using thin, and easily clogged thread-guiding tubes, resulting in uneven tension of the thread in the stocking. lPrice 3 s M l Another object of the present invention is to provide a thread guide which is resilient and will deflect toward the side if it should engage with a sinker With these and other SO objects in view, there is provided, according to the invention, a flat bed knitting machine having a reciprocating thread carrier for feeding the thread to the knitting needles which carrier comprises a thread guide in the SS form of a thread guiding needle which projects towards the knitting needles and has at its end closest to the knitting needles, which end is pointed, an eye through which the thread passes to the knitting needles, the 60 needle being thinner than the space between adjacent sinkers of the machine. With the free end of the thread guiding needle pointed as aforesaid it is practically impossible for it ever to damage a sinker u 6 Another material advantage of the threadguiding needle according to the present invention is that, owing to its smaller diameter as compared with a thread-guiding tube, it takes up a space less than the space between 70 two adjacent sinkers, whereas the latter because of its larger diameter, the tube will always overlap the two sinkers. It is another important feature of the invention that it permits the

use of two thread 75 guiding needles on a single thread carrier, for example, when the work requires, two threads to be used simultaneously. Still another advantage of the thread-guiding needle is that it can be made of a better 80 steel and can be more easily and more highly polished than the customary thread-guiding tube. Further objects, features, and advantages of the present invention will be apparent 85 from the following detailed description thereof, as well as from the accompanying drawings, in which: Fig 1 shows a prior known construction of thread carrier with a thread-carrying tube 90 mounted thereon, in its position relative to the sinkers. Fig 2 is a side view of thread carrier according to the invention with a cliread-guiding needle at its free end; Fig 3 is a front view of the thread-guiding needle of Fig 2; and Fig 4 is a front view of a thread carrier according to the invention mounted thereon with two needles. Referring to the drawings, Fig 1 shows a prior known construction of thread carrier with a thread-carrying tube 2 mounted on its lower end so as to be in a position intermediate two sinkers 3 above the upper edge of a presser 4. 1 S The relative thickness of the tube 2 to thesinkers 3 and presser bar 4 as shown in the drawing substantially corresponds to the conditions prevailing in actual practice It is evident from this drawing that the tube 2 will be subject to considerable stresses and difficulties if used in the knitting of fine gauge fabrics. Fig 2 shows a thread carrier finger 5 of a thread carrier of a flat bed knitting machine, which has a thread-guiding needle 6 mounted on its free end and projecting towards the knitting needles (not shown) The thread 7 runs through a lead eye 8 and then through an eye 9 on the thread carrier finger 5 to a thread eye 10 in the thread-guiding needle 6. A preferred embodiment of the threadguiding needle 6 is shown, for example, in Fig 3 The needle has a shaft 7 which is thickened so as to permit the needle to be more easily secured to the free end of the thread carrier finger 5 Its free end which projects towards the knitting needles of the machine is provided with a thread eye 10, and the needle terminates in a sharp point 11 As is illustrated in Fig 2, the end of the thread 71 preferably leads forwardly along the needle 6 and then passes through the needle eye 10 toward the rear. Fig 4 illustrates the application of the invention to a thread carrier 12 which is provided with two thread-guiding needles 13 and 14 which are bent relative to each other above the sinkers at a point 15 and 16, respectively, so that, when seen from the front, the lower ends thereof are disposed at a 50 right angle to the sinkers and may be so close to each other as to permit both needles to pass safely between

two adjacent sinkers 3. It is evident from a comparison of Figs 1 and 4 that a thread-guiding needle may be 55 made of considerably thinner diameter than a thread-guiding tube as previously used, thus even permitting two needles to be used within the same area where only one tube could be used, apart from its advantage over 60 such a tube of being more easily threaded and not liable to collect lint or resinous matter which easily clogged the passage and opening of a tube and exerted a binding or braking action upon the thread which might 65 affect the quality of the hosiery knitted on the machine.

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* GB785654 (A)

Description: GB785654 (A) ? 1957-10-30

Improvements in or relating to the manufacture of metal tubes or metalsheaths of electric cables


PATENT SPECIFICATION Inventor: JAMES RONALD PENROSE Date of filing Complete Specification: April 20, 1956. Application Date: June 9, 1955. No 16577/55. Complete Specification Published: Oct 30, 1957. Index at acceptance:-Class 83 ( 4), 12 (C: E: F: lG). International Classification:-B 21 c. COMPLETE SPECIFICATION Improvements in or relating to the Manufacture of Metal Tubes or Metal Sheaths of Electric Cables LIMITED, a British Company, of 343/5,

Euston Road, London, N 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: - The present invention relates to a method of and means for the manufacture of metal tubes, or of metal sheaths of electric cables wherein the sheath is of plain cylindrical form. In the manufacture of metal tubes, it is sometimes required to reduce the diameter of the tube over the whole or a portion of its length Also, in the manufacture of cables, an insulated cable core, which term is hereinafter to be understood as including two or more such cores, may be drawn into a sheath, and it is necessary that the sheath shall be of sufficient internal diameter to permit the core to be drawn in without damage, the sheath being subsequently reduced in diameter to bear on the core. According to another mode of cable manufacture, the sheath is formed around the core by bending a metal strip transversely and uniting the edges by welding along a longitudinal seam For various reasons, and in particular to permit of the introduction at the point of welding of a shoe between the sheath and the cable core, it is necessary that the sheath as initially formed shall be of a diameter greater than that ultimately required, it being then reduced to this last-mentioned diameter. Hitherto it has been the practice to effect reduction in diameter of tubes or cable sheaths (generally designated hereafter as tubes) by means of a number, for example four, of rollers carried by a frame whereon they are mounted so as to be capable of rotation about axes parallel to that of the tube, the frame being rotated around the tube, which is caused to travel axially through the space between the rollers, and the latter being so adjusted that by this action the desired reduction is effected. lPrice 3 s 6 d l v Li-,, -dfe, In following this procedure, however, difficulty has been found in securing reduction in diameter in a uniform manner For instance, in respect of stainless steel or like high-tensile metals, there is a tendency for cracks to develop in the tube, whereas, when dealing with softer metals, such as aluminium or mild steel, the tube is liable to become deformed out of the cylindrical shape, particularly if the wall is thin, for example, has a thickness of 1/32 " for an outside tube diameter of 1 ". The present invention has for its main object an improved method of and means for reducing the diameter of a metal tube while, at the same time, overcoming the above drawbacks. According to the invention a method of reducing the diameter of a metal tube consists in subjecting its external surface to the action

of a tool having an operative surface which is concave toward the tube and is formed by a generatrix parallel, or slightly inclined, to the axis of the tube, the nearest point on the said operative surface to the axis of the tube being at a less distance from such axis than the external radius of the tube as unreduced, moving the tube in the direction of its axis and simultaneously producing relative rotation between the tool and the tube Under these conditions, the surface of contact between the tool and the tube will trace out a helical path around the tube and, in order that the latter as reduced in diameter shall be free from corrugations and truly cylindrical, it is necessary that the length of the operative tool surface, measured in a direction parallel to the axis of the tube, shall be not less than the axial travel of the tube during a complete relative rotation between the tool and the tube. In order that the tube as unreduced may be led smoothly into contact with the above operative surface of the tool, that surface is so formed that the tube first encounters a flared portion whereby its diameter is somewhat 785,654 reduced, the reduction ultimately reached being determined by the position of the main portion of the operative concave surface relatively to the axis of the tube These two portions of the operative surface are conveniently formed by generatrices respectively inclined and parallel to the axis of the tube At the point at which the reduced tube emerges from the operative surface of the tool, the latter is slightly flared in order to ensure smoothness of action. The tool may be made in the shape of an arc of circular or other form in which case it is convenient that it shall be rotated around the tube, while the latter is caused to progress in its axial direction In such apparatus the contact between the tool and the tube is necessarily of a rubbing character and lubrication of the surfaces in contact would be required Apparatus of this nature would be suitable only for comparatively slight reduction of the tube and in cases in which it is of aluminium or other comparatively soft metal. In practice, the tool most suitably takes the form of an annular member surrounding the tube and having an aperture whereof the periphery is continuous and constitutes the operative surface, the axis of this annular member being displaced laterally from the axis of the tube; the sum of this displacement and of the external radius of the tube as unreduced is greater than the radius of the said aperture, also the sum of the said displacement and of the radius of the said aperture is greater than the external radius of the tube as unreduced, whereby the operative surface of the aperture engages the wall of the tube and, on progression of the tube in the direction of its axis through the aperture simultaneously with rotation of the axis of the

annular member around that of the tube, serves to effect the desired reduction in diameter by bending the wall of the tube along a path of helical form The action is thus distinguished from the normal drawing-dowvn process wherein a tube is drawn in the axial direction through a ring die, whereof the aperture of a diameter less than that of the tube, bears on the latter simultaneously around its entire circumference. In this instance also contact between the tool and the tube is of a rubbing nature and is therefore subject to the above limitations In order that the method may be applicable in cases in which substantial reduction of the tube diameter is required, or the tube is of comparatively hard metal, such as stainless steel, the tool in the form of an annular member may be mounted so as itself to be capable of rotation in its own plane, in addition to the above relative rotation between its axis and that of the tube From this it results that contact between the tool and the tube is of a rolling character whereby friction is substantially eliminated and it is found possible to deal with the onerous conditions above referred to. The invention will now be more fully described with reference to the accompanying diagrammatic drawings, in which: Figure 1 is an axial section through an 70 apparatus for performing reduction in diameter of a metal tube, and Figure 2 is an axial section through a similar apparatus for performing reduction in diameter of a cable sheath 75 Referring now to Figure 1, the tube-reducing machine comprises a reducing head, indicated by the general reference 1, mounted within a fixed frame 2 for bodily rotation about an axis X-X which is the axis of 80 progression of the tube to be reduced For this purpose the reducing head is carried by a sleeve 3 which is rotatable in a bearing 4 in the frame 2 and is driven by a gear wheel _ keyed to the said sleeve 85 The reducing head has a bush 6 of internal diameter such that the bush will fit over and support the unreduced portion of the metal tube 7, and a bush 8 of smaller internal diameter to support the reduced portion 7 a of 90 the tube, these bushes 6 and 8 being fitted respectively within rings 9 and 10 by means of bearings 11 and 12 concentric with the axis X-X. A further ring 13 is carried between and 95 rigidly secured to each of the rings 9 and 11 Internally of the ring 13 is a member 14, hereinafter called the tool holder, within which the tube-reducing tool 15 is supported by a bearing 16 The tool holder 14 is axially im 100 movable, but adjustable diametrically across the ring 13; for this purpose there is provided in the ring 13 an adjusting bolt 17 threaded in a tapped hole in the ring and having a flange 18 bearing on a forked plate 19, secured to the 105 tool holder 14 By this means the latter may be adjusted relatively to the ring 13 to obtain a required

eccentricity of the axis of the tool with respect to the axis X-X of the tube. For this purpose, there are threaded on the 110 bolt 17 a nut 20 and a micrometer head 21 adapted to co-operate with a scale marked on a bush 22 fixed to the ring 13 In use, the nut and head 21 are locked together to form means whereby the bolt 17 may be turned so 115 as to cause the tool 15 to bear lightly on the tube 7 as unreduced: the nut 20 and head 21 having then been unlocked, the latter is set to the zero marking on the scale on the bush 22 and the nut and head are again 120 locked together, whereupon the bolt 17 is turned to impart the desired eccentricity to the tool 15 as indicated on the above micrometer scale. The tool 15 is constituted by an annulus 125 whereof the inner periphery provides the operative surface; in this example this surface is cylindrical over the main portion of its length in the axial direction The axis of the tool 15 is so displaced laterally, by means of 130 785,654 between the tube and the operative surface will then be obtained by reason of the fact that arcuate sections of the operative surface of the aperture progressively act to bend the wall of the tube inwards to the decreased 70 diameter desired. Figure 2 illustrates a machine operating on similar principles to that in Figure 1 and showing the application of the method of the invention to the reduction of a cable sheath 75 In this diagram parts of the machine which have corresponding function to those shown in Figure 1 are, where possible, indicated by the same references. In this case, the tool 151 is an annulus 80 whose operative surface is again of cylindrical form flared at its ends The operation of the machine is similar to that of the machine depicted in Figure 1 However, since the cable core 27 is only slightly smaller than the 85 internal diameter of the unreduced sheath 28, the supporting plug 25 of Figure 1 must be replaced by a hollow plug 29, if such a member be required, though this is by no means always the case 90 Although, in the examples of apparatus illustrated, the plane of the tool 15 or 151 is at right angles to the tube axis, it might be inclined thereto In that case the main portion of the operative surface would be conical, with 95 an entry section for the tube suitably flared. Reduction in diameter may be effected in stages by arranging for two or more reducing tools to operate on the tube in tandem. While, in the above modes of carrying the 100 invention into effect, the tool has been described as rotating around the tube, the opposite relation might be adopted, namely that the tool should be stationary and the tube rotated about an axis parallel, but eccentric, 105 to its own axis. After the above reducing operation, the tube is of substantially the

same cross sectional area as before, so that increase in wall thickness results Also the working of the metal produces, 110 at least in the case of some metals, a hardening effect whereby the tensile strength is increased. Consequently it is possible, in employing an overhead cable whereof the sheath has been treated in accordance with the present inven 115 tion, to use longer spans whereby economy is effected. Further, treatment of a tube in accordance with the present invention is effective for reducing it to a precise diameter and producing 120 a truly circular outline; the latter feature is especially of advantage in cases of overhead lines employing a cable wherein the sheath constitutes the outermost covering, since any departure from the truly cylindrical form 125 is liable to give rise to increased vibration or swinging of the cable when exposed to a cross wind.


* GB785655 (A)

Description: GB785655 (A) ? 1957-10-30

Detergent compositions



BE540474 (A) CH342684 (A) BE540474 (A) CH342684 (A) less Translate this text into Tooltip



Ot O 5 N PATENT SPECIFICATION i i ttor: PETER TAMBURO VITALE and CHARLES EDWARD BUCK Date of Application and filing Complete Specification July 8, 1955. No 19902155. Complete Specification Published Oct 30, 1957. Index at Acceptance:-Ciass 91, D(E: F: G: H: L: N: P). International Classification: -Clld. COM 1 PLETE SPECIFICATION Detergent Compositions ERRATA SPECIFICATION No 755,655 Page 1, line 62, after ' phenol " delete " phenol " Page 5, line 49, delete, top'" THE PATENT OFFICE, 12th December, 1957. 7855655 LVL-a U Li V 1 C 1 Lvai UL lituiui Um Ju Lt S Um C Unt volume to indicate the presence and approximate concentration of the detergent composition that is being employed but which will no:i foam excessively so as to fill the machine with foam and escape or " spill-over " therefrom through the inlet port provided at the top of the machine for the addition of detergent and bleach Excessive foam generated by certain compositions may also act to cushion the mechanical tumbling and washing action of the clothes in the machine and serve to overload the driving mechanism thereof by acting as a spin retardant when the basket of the machine is spun at high velocities if a body of foam fills the void between the rotating basket and its surrounding stationary enclosure. In the case of household automatic dishwashers it is desirable to employ a substantialhv non-foaming detergent composition since the presence of foam in such a machine greatly retards the mechanical action of the fine water sprayn employed to aid in the removal of soil. particularly from the surfaces being washed. oy Lut: mgner anpnauc alconoi wnicn may D,. present as a minor proportion of the mixture, for example in proportion by weight to the detergent of about 1: 1 to 1: 100. Certain detergent compositions according to the invention may produce, when used in tumbler type automatic washing machines in normal concentrations, a solution of approximately 4 % of the detergent composition in either hard (e g about 300 ppm hardness) or soft (e g about 50 ppm hardness) water at about 1200 F foaming to a height

between -2 inch and 5 inches during washing of household linens of average soil load. The compositions of the present invention, which are excellent detergents, may be prepared in liquid, paste or powdered form They may also contain inorganic builder salts as well as other adjuvant materials. The water soluble non-ionic detergents employed in compositions of the present invention may in general be produced by the addition or introduction of hydrophilic ether groups into an organic hydrophobic compound PATENT SPECIFICATION Inventoas: PETER TAMBURO VITALE and CHARLES EDWARD BUCK 785,65,5 Date of Application and filing Complete Specification July 8, 1955. No 199021/55. Complete Specification Published Oct 30, 1957. Index at Acceptance:-Class 91, D 2 (E: F: G: H: L: N: P). International Classification: Clld. COMPLETE SPECIFICATION Detergent Compositions We, COLGATE-PALMOLIVE COMPANY, a corporation organised and existing under the Laws of Delaware, United States of America, of 105, Hudson Street, Jersey City, Nevz 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 invention relates to detergent compositions having controlled foaming characteristics. In recent years there has developed a substantial need for detergent compositions having controlled foaming properties, frequently in conjunction with a high degree of detersive power In the case of automatic tumbler type washing machines, since the housewife commonly associates foaming with washing, for aesethetic purposes it is desirable to provide washing compositions which will form a stable foam of minimum but sufficient volume to indicate the presence and approximate concentration of the detergent composition that is being employed but which will not foam excessively so as to fill the machine with foam and escape or " spill-over " therefrom through the inlet port provided at the top of the machine for the addition of detergent and bleach Excessive foam generated by certain compositions may also act to cushion the mechanical tumbling and washing action of the clothes in the machine and serve to overload the driving mechanism thereof by acting as a spin retardant when the basket of the machine is spun at high velocities if a body of foam fills the void between the rotating basket and its surrounding stationary enclosure. In the case of household automatic dishwashers it is desirable to

employ a substantially non-foaming detergent composition since the presence of foam in such a machine greatly retards the mechanical action of the fine water sprays employed to aid in the removal of soil, particularly from the surfaces being washed. " Spill over ", or escape of excess foam, is also encountered in the case of these machines. In accordance with the present invention, detergent compositions comprise a water soluble non-ionic detergent of the polyalkylene ether type and a higher aliphatic alcohol having 10, to 20 carbon atoms Where a composition exhibiting high detergency and being characterized by production of similar volumes of foam when used in either soft or hard water is desired, a high alkyl aryl sulphonate detergent preferably also is present. In one form of the invention the detergent composition comprises a water soluble polyethylene oxide detergent condensate of an alkyl phenol phenol or a higher aliphatic monohydric alcohol or mixtures thereof, a water soluble salt of a higher alkyl aryl sulphonate detergent, and a higher aliphatic alcohol In such compositions the foam generated by the mixture of the non-ionic detergent and the sulphonated detergent is controlled by the higher aliphatic alcohol which may b present as a minor proportion of the mixture, for example in proportion by weight to the detergent of about 1: 1 to 1:100. Certain detergent compositions according to the invention may produce, when used in tumbler type automatic washing machines in normal concentrations, a solution of approximately 4 % of the detergent composition in either hard (e g about 300 ppm hardness) or soft (e g about 50 ppm hardness) water at about 1200 F foaming to a height between -1 inch and 5 inches during washing of household linens of average soil load. The compositions of the present invention, which are excellent detergents, may be prepared in liquid, paste or powdered form They may also contain inorganic builder salts as well as other adjuvant materials. The water soluble non-ionic detergents employed in compositions of the present invention may in general be produced by the addition or introduction of hydrophilic ether groups into an organic hydrophobic compound 785,655 or group, usually of all aliphatic, alkyl aryl ot aromatic structure The degree or proportion of hydrophilic ether groups will vary with the specific hydrophobic group, but will be sufficient to confer the desired water-solubility and detersive properties These detergents are known in the art and the determination of a specific hydrophilic-hydrophobic relationship for each type is a matter within the ability of a man skilled in the detergent art Such detergents are generally the water-soluble non-ionic polyalkylene

ether compounds, such as are obtained by condensation of alkylene oxide with a hydrophobic organic group, the latter containing usually at least about 8 carbon atoms, and preferably 8 to 22 carbon atoms. It is preferred to use the polyoxyalkylene condensates derived from ethylene oxide although other lower alkylene oxides, such as propylene oxide, butylene oxide, and the like have generally similar properties and may be substituted therefore While the number of alkylene oxide groups is controlled so as to yield the desired water-solubility and detersive properties and is dependent upon the character of the hydrophobic group, the product in the types of detergents included in composition of the present invention will possess usually from about 5-30 alkylene oxide groups. Among the suitable non-ionic detergents are the polyalkylene oxide condensates of an alkyl phenol, such as the polyglycol ethers of alkyl phenols having an alkyl group of at least about 6 and usually about 8 to 20 carbon atoms and an ethylene oxide ratio (number of ethenoxy groups per mole of condensate) of about 7 5, 8 5, 11 5, 20 5, 30 and the like The alkyl substituent on the aromatic nucleus may he di-isobutylene, diamyl, polymerised propylene, iso-octyl, nonyl, dimerized C,-GQ olefin, and the like Among other condensates with phenols is the alkylated fl-naphthol condensed with 8 moles of ethylene oxide the alkyl group having 6 to 8 carbon atoms. Further suitable detergents are the polyoxyalkylene esters of organic acids, such as the higher fatty acids, rosin acids, tall oil, or acids from the oxidation of petroleum, and the like. The polyglycol esters will usually contain from about 8 to about 30 moles of ethylene oxide or its equivalent and about 8 to 22 carbon atoms in the acyl group Suitable products are refined tall oil condensed with 16 or 20 ethylene oxide groups, or similar polyglycol esters of lauric, stearic, oleic and like acids. Additional suitable non-ionic detergents are the polyalkylene oxide condensates with higher fatty acid amides, such as the higher fatty acid primary amides and higher fatty acid mono and di-ethanol-amides Suitable agents are coconut fatty acid amide condensed with about 10 to 30 moles of ethylene oxide. The fatty acyl group will similarly have about 8 to 22 carbon atoms, and usually about 10 to 18 carbon atoms in such products The corresponding suphonamides may also be used if desired. Other suitable polyether non-ionic detergents are the polyalkylene oxide ethers of higher aliphatic alcohols Suitable alcohols are 70 those having a hydrophobic character, and preferably 8 to 22 carbon atoms Examples thereof are iso-octyl, nonyl, decyl, dodecyl, tridecyl, tetradecyl, hexadecyl, octadecyl and oleyl alcohols which may be condensed with 75 an appropriate amount of ethylene oxide, such as at

least about 6, and preferably about 10moles A typical product is tridecyl alcohol, produced by the Oxo process, condensed with about 12, 15 or 20 moles of ethylene oxide 80 The corresponding higher alkyl mercaptans or thioalcohols condensed with ethylene oxide are also suitable for use in compositions of the present invention. The water soluble polyoxyethylene con 85 densates with polyoxypropylene polymers may likewise be employed in compositions of the present invention The polyoxyprepylene polymer, which is prepared by condensing propylene oxide with an organic 90 compound containing at least one reactive hydrogen, represents the hydrophobic portion of the molecule, exhibiting sufficient water insolubility per se at a molecular weight of at least about 900, such as about 900 to 2400, 95 and preferably about 1200 to 1800 The increasing addition or condensation of ethylene oxide on a given water insoluble polyoxypropylene polymer tends to increase its wat r solubility and raise the melting point l-o such that the products may be water soluble, and normally liquid, pasty or solid in physical form The quantity of ethylene oxide varies with the molecular weight of the hydrophobic unit but will usually be at least about 20 %; 105 and preferably at least about 40 % by weight of the product With an ethylene oxide content of about 40 up to 50 ', there are usually obtained normally liquid products, above 50 "' soft wax-like products, and from about 70 110 % normally solid products may be obtained which can be prepared in flake form if desired. These condensates may be designated by the foilowving structure:Yl(C 3 H,0) 1-Hl 115 where Y is the residue of an organic compound which contained x active hydrogen atoms. n is an integer, 120 x is an integer, the values of N and x being such that the molecular weight of the compound, exclusive of E, is at least 900, as determined by hydroxy number, F is a polyoxyethvlene chain and consti 125 tutes 20-90 %, by weight of the compound and H is hydrogen. It is Dreferred to use products of the type just described having a total molecular weight 130 785,655 within the range of about 2000 to 10000, and preferably about 4000 to 8000 A suitable material is a condensate having a typical average molecular weight of about 7500, the hydrophobic polypropylene glycol being condensed with sufficient ethylene oxide until a normally solid water-soluble product is obtained which has an ethylene oxide content of about 80-90 % and a melting point usually of about 51-54 C Another material is a liquid condensate having an ethylene oxide content of 40-50 % and a molecular weight of about 4500. The higher aliphatic alcohols employed in compositions of the present invention are those having at least 10 to about 18 to 20 carbon atoms per molecule These aliphatic alcohols may be saturated or unsaturated

in character It is preferred to use the saturated primary alcohols Examples of suitable alcohols falling within this preferred classification are decanol, dodecanol, tetradecanol, hexadecanol and octadecanol It is also within the contemplation of the present invention to employ unsaturated higher aliphatic alcohols (e.g oleyl alcohol), branched chain and secondary higher aliphatic alcohols, and higher aliphatic diols It is not necessary to use the pure substances themselves as the commercial mixtures of these substances are also operable and are preferred from the viewpoint of economy. Thus, commercial mixtures of fatty alcohols containing predominantly the alcohols of 10 -to 18 carbon atoms are included within the scope of this invention, even though such mixtures may contain minor amounts of fatty alcohols of different chain length. The aliphatic alcohols may be derived either from natural or synthetic sources Many naturally occurring wax esters are an important source of higher aliphatic alcohols. Certain animal oils, chiefly those of marine origin such as sperm oil, also contain a high proportion of recoverable alcohols occurring as esters The most plentiful and economic sources for their production however are from fatty acids or aldehydes by reduction, or from oxidized petroleum stocks by processes known in the art, e g the Oxo process. The amount of these added higher aliphatic alcohols to be employed depends upon the particular aliphatic alcohol and detergent involved, and upon the characteristics desired of the final product Thus by proper selection of these components and their proportions it is possible to prepare substantially non-foaming compositions or compositions having restricted foaming power of various degrees The specific amount of these higher aliphatic alcohols to be employed is generally minor in proportion to the weight of the detergent employed and sufficient to bring about a marked reduction in the foaming power of the detergent Generally the ratio of nonionic detergent to higher aliphatic alcohol is within the range of about 1:1 to 100:1 and preferably about 4:1 to 25:1 by weight. The water soluble higher alkyl aryl sulphonate salts optionally used in conjunction with the polyalkylene oxide detergent condensates, 70 e.g of alkyl phenols or higher aliphatic monohydric alcohols in compositions embraced by the present invention may be mononuclear or polynuclear in structure More particularly the aromatic nucleus may be derived from ben 75 zene, toluene, xylene, phenol, cresols, naphthalene, and the like The alkyl substituent on the aromatic nucleus may vary widely as long as the desired detergent power of the active ingredient is preserved While the number of 80 sulphonic acid groups present on the nucleus may vary it is usual to have one such

group present in order to preserve as much as possible a balance between the hydrophilic and hydrophobic portions of the molecule 85 More specific examples of suitable alkyl aromatic sulphonates detergents are water soluble salts of the higher alkyl aromatic sulphonates The higher alkyl substituent on the aromatic nucleus may be branched or straight 90 chain in structure including such groups as decyl, dodecyl, "keryl " pentadecyl, mixed long-chain alkyls derived from long-chain fatty materials, cracked paraffin wax olefins, polymers of lower mono-olefins, and the like Pre 95 ferred examples of this class are the higher alkyl mononuclear aryl sulphonate salts wherein the alkyl group has about 8 to about 20, and preferably about 12 to 15 carbon atoms More particularly, it is preferred to use 100 the higher alkyl benzene sulphonate salts wherein the higher alkyl group has about 12 to 15 carbon atoms For example, propylene may be polymerized to the tetramer or pentamer and condensed with benzene in the pre 105 sence of a Friedel-Crafts catalyst to yield essentially the dodecyl benzene derivative which is suitable for sulphonation and neutralization to the desired sulphonate salts. The foaming characteristics of such sul 110 phonate-containing compositions may be adjusted to a certain extent by varying the ratio of the non-ionic detergent to the sulphonate salt However, the aliphatic alcohol is the primary means for controlling the foaming 115 characteristics of the compositions, acting both to reduce and substantially to equalize the amount of foam produced by particular compositions when used in hard water on the one hand or in soft water on the other The par 120 ticular proportions of the three components may therefore vary considerably within the limits wherein the ratio of non-ionic condensate to alkyl aryl sulphonate detergent is from about 10:1 to about 1:2 by weight, and the 125 ratio of the non-ionic condensate of the higher aliphatic alcohol is from about 40: 1 to about 1: 1 by weight In general it is preferred that there be more non-ionic condensate present than alkyl aryl sulphonate detergent and that 130 there be more alkyl aryl sulphonate detergent prrsent than there is higher aliphatic alcohol. Other adjuvant materials may be employed also The detergent compositions of the present invention may include any of those substances employed by the art in admixture with detergent compositions generally, provided the use of any such materials does not substantially adversely affect the desired properties. These adjuvant builders additives or like materials may be inorganic or organic in structur and may be mixed with the essential ingredients in any suitable manner Such inorganic water soluble builder salts as the various alkali metal phosphates, particularly the molecularlydehydrated polyphosphate salts may be employed in a

suitable proportion Examples of phosphate builders are pentasodium tripolyphosphate, hexasodium hexametaphosphate, tetrasodium pyrophosphate, and the like Other water soluble inorganic builder salts which may be present include sodium silicate, sulphate, carbonate, and the like In the case of such built compositions it is preferred that the non-ionic detergent be about 2 to 90 %, and usually 5 to 15 %' of the total composition, that the higher aliphatic alcohol be about 0 1 to 15 % and usually 0 5 to 5 % of the total composition, and that the water soluble inorganic builder salts be about 10 to 98 % and usually about 40 to 95 %-, of the total composition by weight Preferably, alkyl sulphonate salt constitutes about 5 to 10 %By and usually 4 to 10 %l of the total composition, replacing an equal amount of the aforesaid inorganic builder salts Suitable organic materials such as sodium carboxymethylcellulose, optical bleaches or other suitable organic additives may also be employed as desired. The controlled foaming power possessed by the present combination of essential ingredients may be illustrated by pour foam tests. The pour foam test is designed for comparative study of the relative foaming power of liquids and is described by Ross and Miles in " Oil and Soap ", May 1941, pages 99 to 102. In such test, a portion of the solution to be tested is placed in a jacketed measuring cylinder The foam is formed by allowing a second portion of solution to stream in from a fixed height through a standard orifice, resulting in a particular foam height generated by each test solution. The data on foam height in Table I were obtained in a pour foam test conducted at 1100 F using distilled water as a solvent for compositions comprising ani ethylene oxide condensate of iso-octyl phenol having about 10 ethylene oxide groups per molecule of condensate and the indicated proportions of various higher aliphatic alcohols. TABLE I Pour Foam Data, Solutions of Detergent Composition Weight ratio non-ionic Foam Foam detergent height, height, to fatty mm 0 25 % mm 0 75 Fatty alcohol alcohol solution solution None Infinite 160 200 n-Docanol 4:1 35 32 n-Decanol 8:1 70 90 n-Decanol 25: 1 40 75 n-Dodecanol 4:1 30 30 n-Dodecanol 8:1 57 65 n-Dodecanol 25:1 40 58 n-Tetradecanol 4:1 30 25 n-Tetradecanol 8:1 41 38 n-Tetradecanol 25:1 42 95 iz-Hexadccanol 4:1 35 35 it-Hexadecanol 8: 1 35 25 n-Hexadecanol 25:1 55 175 Table II presents data on the foam depressing effect of n-hexadecanol on various nonionic detergents obtained using the pour foam test at 0 25 % concentration of each detergent solution in distilled water at 110 F. Where proportionate amounts of fatty alcohol are indicated, such

amounts indicate the ratio by weight of the non-ionic detergent to thfatty alcohol. 785,655 785,655 TABLE II Pour Foam Data Non-Ionic Detergents and Mixtures thereof with n-Hexadecanol Weight ratio Foam Non-ionic detergent: height, detergent hexadecanol mm. A Infinite 65 A 100:1 45 A 25:1 0 B Infinite 195 B 25:1 179 B 4:1 45 C Infinite 60 C 25:1 40 A=ethylene oxide condensate of polypropylene glycol containing about 80% ethylene oxide and having a molecular weight of about 7500. B=Tridecyl alcohol condensed with about 12 moles of ethylene oxide. C=Tall oil (mixed resin and fatty acids) condensed with about 16 moles of ethylene oxide. From the data in Tables I and II it will be observed that the higher fatty alcohols of the present invention exhibit a foam reducing effect on non-ionic detergents which is of considerable magnitude in most instances. EXAMPLE I A satisfactory composition for use in an automatic dishwasher comprises:% by Ingredients weight Non-ionic detergent 15 n-hexadecanol 7 Pentasodium tripolyphosphate 40 Soda ash 3 Sodium sulphate 35 Same as non-ionic detergent A, above. This composition is tested by placing a 0.25 % solution of it in soft water about 150 F in an empty automatic dishwashing machine, running the machine through its cycle which involves a wash and two rinses, and observing conditions inside the machine through a glass port in the door of the machine The machine is of the top-opening top type employing a water jet and a motordriven water jet deflector in which foam, if present in quantity, seriously impedes the washing and rinsing action but in which the presence of a certain amount of foam is desirable during the wash cycle to indicate to the user the presence of sufficient washing agent. The composition is satisfactory because it foams to a limited extent during the wash cycle and no foaming occurs on rinsing If this composition is modified by substantially reducing the proportion of n-hexadecanol and replacing it by sodium sulphate, too much foam produced for satisfactory operation in this machine. EXAMPLE II A satisfactory formulation which produces substantially the same suitable small but indicative amount of foam when used in tumbler type automatic washing machines in normal concentrations for proper cleansing action in either hard or soft water comprises: % by Ingredients weight Non-ionic detergent 10 00 Dodecyl benzene sulphonate sodium salt 4 00 n-hexadecanol 1 50 Pentasodium

tripolyphosphate 25 00 Soda ash 10 00 Aqueous sodium silicate ( 43 5 % solids, Na O: Si O 2 -1:2 35) 6 00 Carboxymethylcellulose 050 Fluorescent dye O 06 Sodium sulphate 42 94 The non-ionic detergent is a nonyl phenolethylene oxide condensate containing about 9 5 ethenoxy groups per molecule of condensate. Table III gives the average foam height in inches for five tests of this composition in soft water ( 50 parts per million hardness) and in hard water ( 300 parts per million hardness) at the indicated times in minutes after the composition is added to a tumbler type automatic washing machine: TABLE III AVERAGE FOAM HEIGHT IN INCHES Water Minutes after composition added 2 3 5 7 5 10 Soft 0 65 0 80 1 10 1 35 1 65 Hard 0 32 0 39 0 58 0 81 1 06 In the automatic washing machine used in this test the clothes are washed in a rotating perforated cylindrical basket-like tumbler about 24 inches in diameter The basket 105 rotates on a horizontal axis, and access is had to it by means of a water-tight door in the front of the machine, the door being located is 6 785,655 adjacent to the open end of the basket An 8 inch diameter glass observation port is centrally located in the door and in normal operation of the automatic machine the liquid level during the washing cycle is about at the base of the observation port A composition is considered to have desirable foaming characteristics for use in such a machine if under normal conditions for satisfactory cleansing foam is produced during the washing cycle to a level approximately 1 to 5 inches above the base of the port The height of the foam produced during the washing cycle is observed through the observation port at the indicated time intervals after the detergent composition is added In these runs the amount of the detergent composition employed constitutes 0.26 % by weight of the solution in the machine which initially is at 1200 F The total washing cycle of the machine is a period of about 10 minutes in length The clothes used comprise items such as sheets, pillow cases, bath towels, hand towels, dish towels, face cloths, and table cloths which are soiled by home usage. A composition of the same formulation except that the n-hexadecanol was replaced by sodium sulphate produced much more foam in soft water under the same test conditions. In order to determine the detersive efficiency of the two compositions tested, a Hunter Reflectometer is used to measure the whiteness of these clothes before the first soiling and after the last of six successive soilings and washing The clothese washed in soft water solutions of the composition containing n-hexadecanol are significantly whiter than those washed in soft water solution of the composition not containing it, and there is no significant difference in the whiteness of the clothes washed in the hard water solutions of

the two compositions. Included with each load of wash used for the six soilings and washings of household articles referred to above are cotton swatches which has been artificially uniformly soiled with a standard soil The whiteness of these swatches is determined as described above before and after each washing as a second measure of the detersive powers of the two compositions The data show that the fatty alcohol significantly improves the detergency of the composition in soft water but does not significantly affect the detergency thereof in hard water. Similar results are obtained with compositions formulated within the ranges shown below, provided the first three ingredients are properly balanced in accordance with the present disclosure:- Ingredients weight o by Water soluble polyalkylene oxide detergent condensate of an alkyl phenol or a higher aliphatic monohydric alcohol or a mixture thereof 5-20 Alkyl aryl sulphonate 2-10 Higher aliphatic alcohol 05-5 Molecularly dehydrated phosphate 10-70 Sodium carbonate 0-20 Sodium silicate 0-10 Carboxymethylcellulose 02 Fluorescent dye 0-0 1 with the balance Largely sodium sulphate. Such compositions are preferred for low foaming detergents having high washing power.


* GB785656 (A)

Description: GB785656 (A) ? 1957-10-30

Rubber reaction product and preparation and uses thereof



BE540014 (A) DE1137865 (B) FR1134478 (A) NL96261 (C) BE565930 (A) BE540014 (A) DE1137865 (B) FR1134478 (A) NL96261 (C) BE565930 (A) less Translate this text into Tooltip



COMPLETE SPECIFICATION Rubber Reaction Product and preparation and uses thereof We, Esso RESEARCH AND ENGINEERING COMPANY, a Corporation duly organised and existing under the laws of the State of Delaware, United States of America, of Elizabeth, New Jersey, United States of America, do hereby declare the invention, for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement: This invention relates to improved processes for treating rubber, rubber including butyl rubber. More particularly it relates to reaction of rubbers with a nitroso aromatic compound containing at least one functional substituent other than a nitroso group, preferably a substituent less reactive than nitroso. The invention also relates to processes for treating fibres with such vulcanized rubbers. Butyl rubber, which had been known commercially under the designation GR-I for many years, and now is available under the trade name Enjay butyl, is exemplified by a high molecular weight copolymer of, for instance, 97-99% of isobutylene and 13% isoprene, and is a vulcanizable low unsaturation synthetic rubber having an iodine number in the range of 0.5 to 50, generally about 1 to 20. Products of this type which are known as "'Butyl rubbers" may be made by copolymerization of an isoolefin, preferably of 4 to 6 carbon atoms, e.g. isobutylene, methyl-2butene-l, and the like, with a minor proportion of a conjugated multiolefin of 4 to 14 carbon atoms, preferably a diolefin of 4 to 6 carbon atoms, e.g. butadiene, isoprene, piperylene, 2-methylpentadiene, dimethylbutadiene, etc. This copolymerization is

carried out at a temperature substantially below 0 C., preferably below c - 50 C., e.g. about * - 80" C. as maintained by solidified carbon dioxide as refrigerant, or even better - 103 C. as maintained by liquefied ethylene as refrigerant. The catalyst should be a dissolved Friedel-Crafts catalyst such as A1CI, dissolved in methyl chloride or other halogen-substituted alkane which does not polymerize under conditions used. Other known Friedel-Crafts catalysts may be used such as BF3, Albs3, SnCl4, TiCl4, ZrCl4, etc., as well as various E;riedel-Crafts complexes containing solubilizing hydrocarbon or alkoxy groups, or ether or other promoting groups, as known in this art. The polymerization is preferably carried out in the presence of about 0.5 to 20.0, preferably about 1 to 5, volumes of inert diluent, such as methyl chloride, ethyl chloride, ethylene, etc. or a material which is not only a diluent for the reactants but also a solvent for the resulting polymer, e.g. butane, heptane, etc. The resulting butyl rubber, which should have a Staudinger molecular weight of at least about 20,000, and preferably in the range of 30,000 to 100,000 or higher, may be recovered by any of the known recovery processes such as the wet finishing technique involving discharging the polymerization reaction liquid into a hot aqueous flash tank, then filtering and drying the polymer, or by so-called dry finishing involving flashing off solvent and unreacted raw materials without contacting with water or aqueous solutions. Butyl rubber made by such process has been available commercially for a number lof years and has found great utility in the manufacture of certain products such as automobile inner tubes, and in some respects is substantially superior to natural rubber or any of the high unsaturation synthetic rubbers such as dienestyrene, diene-nitrile, polychloroprene, etc., because the low unsaturation of the butyl rubber makes the product, both before and after vulcanization, much more resistant to oxidation and attack by chemical agents than the above-mentioned rubbery materials which have a high unsaturation on the order of 300 to 400 iodine number. However, the butyl rubber, probably inherently due to its low unsaturation, has not thus heretofore shown as great a degree of reinforcement or interaction with commonly used fillers such as carbon black, silica, etc., as do the high unsaturation rubbers. According to the present invention, it has now been discovered that vulcanizable rubber, particularly butyl rubber can be tremendously improved in filler-reinforcement properties if it is first subjected to a process comprising reacting a vulcanizable rubber an aromatic compound which has the general formula ON Ar Mm Y in which Ar is a mono- or polynuclear aromatic hydrocarbon

nucleus M is an aliphatic divalent group, m is zero, or an integer, and Y may be any one or more of the following groups OR C:OR COOR X CN NO2 NR2 in which R is hydrogen or a monovalent hydrocarbon radical and X is halogen. Examples of such monovalent hydrocarbon radicals are alkyl, aryl, alkaryls and cycloalkyl. One of the preferred aromatic compounds is an hydroxy-substituted mononitroso aromatic compound. These reagents are preferably nitrosophenolic type compounds having the empirical formula HO-Ar-NO, in which Ar represents an aromatic ring, which may be a benzene or naphthalene ring, etc., or lower alkyl homologs thereof containing 1 or more methyl, ethyl, etc. groups. Specific examples of such materials include the preferred compound paranitrosophenol, as well as paranitroso derivatives of other phenolic compounds, e.g. cresol, xylenol, isopropyl phenol, ethyl phenol, etc. and 1,4nitrosonaphthol, or other compounds such as those coming under the following graphical empirical formula: <img class="EMIRef" id="026473786-00020001" /> where R, Rl and 2 may be E, alkyl or aryl. Also, o- and m- compounds may be used, e.g. o-nitroso cresol (nitrosated o-cresol), nitrosated o-hydroxy diphenyl, etc. Esters of any of these various compounds may be used, such as the benzoate ester of p-nitrosophenol. Mis- tures thereof may also be used. Other classes of modifiers or reactants may be used, preferably coming within the scope of the general formula ON Ar MmY in which Ar is a mono- or polynuclear aromatic hydrocarbon nucleus with or without inert substituents, M is an aliphatic divalent hydrocarbon group, either saturated as in the formula CnH2n or slightly unsaturated as in C, E2n~2n where n may be an integer of 1 to 5 or 10 or higher, m is 0 or an integer from 1 to 10, and Y may be any one or more of the following groups: OR C:OR COOR X CN NO2 NR2 in which R is hydrogen or a monovalent hydrocarbon radical, e.g. aikyl, aryl, aralkyl, alkaryl, cycloallcyl, and X is halogen. Any of

these above-listed groups may contain relatively inert hydrocarbon groups in intermediate position, between the first and last elements of these groups. Thus, in case the empirical formula is ON Ar OR, some specific examples include the nitrosophenol type compounds described hereinabove, and corresponding either derivatives thereof such as p-nitrosophenyl methyl ether, m-nitrosophenyl cyclohexyl ether. If such compounds contain an intermediate group Mm, several species include p-nitroso benzyl alcohol, nitrosobenzyl ethyl ether. If the empirical formula used is ON Ar COR, some examples included are m-nitrosobenzaldehyde, p-nitrosophenyl ethyl ketone, or aldehyde derivatives such as ON CGHt, CH2CHO, ON CH, (cH,) CH CHO, etc. If the empirical formula is ON Ar COOR, examples include p-nitrosobenzoic acid, and corresponding ethyl, methyl and other esters. The simpler formula ON Ar X includes species such as p-nitrosochlorbenzene, o,pnitrosodichlorbenzene, and corresponding bromine or other halogen derivatives. When Y is a nitrile or cyano (-CN) group, specific examples will include p-nitroso cyanobenzene, -toluene, -naphthalene, etc. Within the scope of the empirical formula ON Ar NO2 are examples such as p-nitrosonitrobenzene, m-nitrosonitrobenzene, nitrosonitrotoluene, nitrosonitronaphthalene, etc. The general formula ON Ar NR2 includes, when R is hydrogen, species such as p-nitrosoaniline, -toluidine, -xylidine, etc., and when R is an alkyl or other hydrocarbon group, examples such as p-nitroso dimethyl aniline, m-nitroso diethyl aniline, etc. Other related, substituted amine groups NHCOR, NHCW, CO OR, etc. Homologs of any of the above-mentioned classes and species of compounds may be used in which the aromatic nucleus may have one or more other substituents of a non-functional character such as methyl or other alkyl, aryl, aralkyl, etc. groups. Normally, it is preferred to use nitroso aromatic compounds containing only one other functional nuclear substituent, preferably less reactive than the nitroso group, but it may be desirable for specific purposes to use nitrosoaromatic compounds containing two or even more other functional groups of the various types listed hereinabove, as for instance, nitrosoresorcinol, nitrososalicylic acid, nitrosohydroxy anisole, etc. This reaction of the nitrosoaromatic compounds with butyl rubber may be carried out in several ways such as by adding the desired amount of

p aranitrosophenolor other equivalent reagent onto a batch of butyl rubber being mixed on a conventional rubber mixing mill, or in a Banbury or other suitable equipment. The actual mixing may be accomplished on a cold mill, but in order to obtain the desired reaction the temperature of the mixture is preferably maintained at 250-350" F. The period of time of heating may range from about 20 minutes to 1 minute, the higher the temperature the shorter being the time. Preferred temperature range is 260 to 310" F. The preferred time of heating is generally from 2 to 15 minutes at 310 F. and at lower temperatures the time would be approximately that derived by multiplication of the above limits by a factor of 1.5 to 2 for each 10" C. decrease in temperature. One particularly desirable method of accomplishing the reaction of the nitrosophenolic or equivalent compound with the butyl rubber is to continuously feed the desired proportion of phenolic compound into an extruder in which butyl rubber is being continuously fed into one end, mixed, and extruded at the other end, such extruder being maintained at the desired temperature for effecting the reaction with the nitrosophenolic compound. It is found that the resulting nitrosopolyfunctional aromatic-butyl rubber reaction product which has pendant functional polar, but non-crosslinking, groups attached to it, now is susceptible to great improvements in tensile strength, modulus characteristics, and stress-strain relationships, when cured, particularly when compounded with various plasticizers and/or conventional rubber fillers such as various types of carbon black including channel black, furnace black, thermal black, as well as other strictly inorganic fillers such as the various silicas, aluminas, etc. with which the modified butyl develops a new type of affinity or bonding. Improvements are reflected not only in the above physical measurements but also in the dynamic properties (loss factor and % relative damping), ozone resistance, electrical resistivity, solution and compatibility with other types of rubbers, resins, solvents, etc., adhesion to tire cord, cloth, metal, paper, etc., and other properties, etc. The attached polar groups also permit a new type of vulcanization or curing not dependent upon, but supplemental to, the ordinary curing with sulfur and accelerators, or dinitrosobenzene or quinone dioxime cure. Although the mechanism of the chemical reactions involved in the present invention is not known with certainty, it is believed that under the reaction conditions used, the polyfunctional modifier is attached to the butyl polymer chain without substantial loss of unsaturation.

Although it is believed that this invention is particularly applicable to butyl rubber due to its low unsaturation, the invention may also be applied, with various degrees of benefit, to higher unsaturation synthetic rubbers, such as a special type of high unsaturation isobutylenediolefin Friedel-Crafts copolymer having an iodine number in the range of 50 to 175, and even to natural rubber or synthetic rubbers having a high unsaturation in the range of 300 to 400 iodine number, such as those mentioned in the earlier part of the specification. In the case of GR-S (butadienestyrene rubbery copolymer) or other synthetic rubbers having some cross-linking, or having a tendency to cross-link, probably due to the presence of 20% or more of side vinyl groups, the amount of nitrosophenolic compound to be used should be kept low, e.g. 0.1 to 1.0%, preferably 0.2 to 0.7%, based on the amount of rubber. The details and advantages of the invention will be better understood from a consideration of the following experimental data. EXAMPLE 1. 1 gram of p-nitrosophenol was mixed on a cold mill with 30 grams of GR-I-25 isobutylene-isophene copolymer (8 minute Mooney of 40-50 at 212" F., and a mole % unsaturation of about 1.9 to 2.3, corresponding to an iodine number of about 13 to 15.5). The mill was then heated and the mixture milled for 10 minutes at 300-310" F. The mill was then cooled and the polymer compounded according to the following recipe: GR-I25 Reaction Product - - 100.00 Zinc Oxide - - - - - - 5.00 Stearic Acid - - - - - - 1.00 Sulfur - - - - - - - 2.00 Tellurac* - - - - - - 1.00 Kosmobile 66** - - - - - 50.00 *Tellurim Diethyldithiocarbamate **@@ @ @ medium Processing Channel Black Specimens were then molded and the following inspections obtained: Stress-Strain Data for 751/300" F. Cure % Elongation Stress, psi 0 0 100 490 200 1475 300 2680 320 2850 Yerzley Oscillograph Data for 451/307 F. Cure Dynamic Modulus Loss Factor(nf) % Relative Damping 8.175 x 107 dyne cm.1 1.565 x 1 poises 17.28 sec. - 1 The above properties are vastly superior to those exhibited by a

conventional Butyl mix. EXAMPLE 2. 2 grams of p-nitrosophenol were mixed on a cool mill with 100 grams of QR-I-17 (Mooney about 60 to 70, mole % unsaturation about 1.4 to 1.8, corresponding to an iodine number of about 9.5 to 12.5). About -3- of this was then milled hot for 10 minutes at 260- 280 F. This reaction product was then split into two parts which were compounded as follows: GR-T-17 Reaction Product - - 100.00 Zinc Oxide - - 5.00 Stearic Acid - - - - - - 0.50 Hi-Sil C (silica) - - - - - 40.00 Sulfur - - - - - - - 2.00 Tellurac - - - - - - - 1.00 B.J.F. (3 anilinomethyl-2(3)-benzo thiazolethione) - - - - - 1.00 The above compound gave the following inspections: Stress-Strain Data for 751/300" F. Cure % Elongation Stress, psi 0 0 100 220 200 665 300 1445 400 2280 500 3000 590 3585 Yerzley Oscillograph Data for 451/307' F. Cure Dynamic Modulus Loss Factor (nf) % Relative Damping 5.868x107 dyne cm.-z 1.063x106 poises 13.51 sec.-1 This compound showed that 92.3% of the polymer was bound to the pigment (run by cyclohexane extraction of specimen). The above data are of extreme interest and importance, especially in view of the fact that a normal Butyl mix with this pigment shows the usual properties attending mineral filled compounds, i.e., low modulus @ 300% elongation, high loss factor and relative damping, low tensile strength. Hence, here we have for the chemically modified Butyl the long sought after mineral pigment which gives properties equivalent to carbon black. This may be readily perceived by comparison of the above stress-strain data with those obtained with the carbon black compound described below. GR-I-17 Reaction Product - - 100.00 Zinc Oxide - - - - - - 5.00 Stearic Acid - - - - - - 0.50 Tellurac - - - - - - - 1.00

Sulfur - - - - - - - 2.00 Kosmobile 66 - - - - - - 50.00 Stress-Strain Data for 751/300 F. Cures % Elongation Stress, psi 0 O 100 250 200 655 300 1440 400 2310 500 3250 600 3875 This compound showed 78.5% bound polymer as compared to 8-12% found in unmodified butyl compounds. EXAMPLE 3. A GR-I-17-p-nitrosophenol reaction product was prepared as in Example 2 and compounded as follows: GR-I-17 Reaction Product - - - 100.00 Zinc Oxide - - - - - - 5.00 Stearic Acid - - - - - - 2.00 Sulfur - - - - - - - 2.00 Tellurac - - - - - - - 1.00 Alon C (alumina) - - - - - 90.00 When cured for 751/300" F. this compound gave the following inspections. Tensile Modulus @ 300,% Elongation 2570 540 730 This represents a distinct improvement over untreated butyl rubber mixed compounds containing this filler. EXAMPLE 4. EFFECT OF P-NITROSOPHENOL CONCENTRATION ON CHANNEL BLACK COMPOUNDS A series of six compositions were made up in which GR-I-17 was treated with various amounts ranging from 0 to 2 parts by weight per 100, of p-nitrosophenol, using a 33% concentrate of p-nitrosophenol in Whitetex clay. The compounding ingredients and results are shown below. Parts by Weight Treated GRI171 100 Carbon Black (MPC) 50 Stearic Acid 1 Zinc Oxide 5 Parts by Weight

Sulfur 2 Tetramethyl Thiuram disulfide 1 Benzothiazyl disulfide 1 Treated with amount shown below of a 33% p-nitrosophenol/67%. Whitelex clay mix ture, by mixing the GR-I-17 and nitro sophenol on cool mill, then hot milling 10 mm. at 310" F., followed by compounding with other materials listed above. The compositions vulcanized at 307" F. were tested, with the results shown below. These data indicate that compared to the untreated butyl rubber (GR-I-17), the product which had been reacted with various amounts of p-nitrosophenol, all showed a very large increase in modulus at 300% and greatly improved resilience, as indicated particularly by the lower loss factor. It is especially remarkable that these surprisingly beneficial results are obtained with even as little as 0.1 parts by weight of p-nitrosophenol (i.e. 0.3 parts of the 1 concentrate in clay). TABLE I Oscillograph Data for 651/307 15. Cure Loss Factor Dynamic Modulus Nitroso- Mod. phenol Cured at (poises sec. (dyne cm. Reagent* (min.) Tens. 300% Elong. = x 10-6) 2 x 10-7) 0 30 3125 775 690 60 3150 1050 630 3.8 8.4 120 3150 1275 580 0.3 30 3230 1150 640 60 3150 1300 600 2.8 7.8 120 3275 1550 550 0.75 30 3225 1350 580 60 2900 1700 490 2.8 7.9 120 3000 1800 480 1.5 30 3200 1450 560 60 3100 1600 530 2.4 7.3 120 3000 1650 510 3 30 3100 1150 640 60 3000 1375 560 2.5 7.6 120 3000 1500 540 6 30 2950 1100 610 60 3000 1300 570 2.9 7.8 120 2950 1450 540 *Parts by wt. of p-nitrosophenol/clay mixture used

for treating 100 parts of GR-I-17. EXAMPLE 5. EFFECT OF P-NITROSOPHENOL ON DC RESISTIVITY. In order to test the DC electrical resistivity, a compounding recipe similar to that used in Example 4 was used, except that the butyl rubber used was a GR-I-15 (Mooney about 41-49, mole % unsaturation about 1.519), (both untreated and reacted with p-nitrosophenol), and the amount of stearic acid used was only 0.5 instead of 1.0. In Example 5, the butyl rubber, stearic acid and p-nitrosophenol (were used) were mixed on a cool mill, and then hot milled 20 minutes at 265" F. Then the rest of the compounding ingredients were added and the compositions were cured for 60 minutes at 307 F., and the products were tested for physical properties and DC resistivity, with the following results: TABLE II Nitrosophenol Mod. at DC Resistivity (parts/100 GR-I-15) Tens. 300% Elong. (ohm/cm.3) 0 2650 1080 585 4.59 x 107 1 2650 1380 525 1.05 x 1011 1* 2600 1775 425 3.22 x 10 * Black added on cool mill, then mixture hot milled 51/265 F. The above data in Table II show that this invention results in a 10,000 fold improvement in resistivity compared to exactly similar butyl rubber composition containing butyl rubber which has not been reacted with pnitrosophenol. The data in the last line of Table II show the further improvement in modulus at 300% effected by the added hot milling of the carbon black and the treated butyl rubber (1775 modulus compared to 1380 without the added hot milling, and compared to 1030 for the untreated butyl rubber). EXAMPLE 6. EFFECT OF TYPE OF CARBON BLACK. The following set of 8 tests shows the results obtained when applying the present invention to butyl rubber compositions containing 4 different types of carbon black, in each case comparing the results of the treated butyl rubber with a control of untreated butyl rubber. The general compounding recipe used was, the same as shown in Example 4. The treated butyl rubber compositions contained 3 parts by weight of the same 33 O concentrate of p-nitrosophenol-Whitetex clay as were used in Example 4, this mixture being added to 100 parts of GR-I-17 on a cool mill and then hot milled for 10 minutes at 310 F. In all of the 8 tests, the GR-I (treated or untreated) was mixed with the carbon black

and stearic acid on a cool mill and then hot milled for 5 minutes at 310 F. Then the rest of the compounding ingredients were added on a cool mill and the finished composition was then vulcanized at 307 F. and tested, the results being as shown here below in Table III. TABLE III Untreated GR-I-17 Treated GR-I-17 Cured Mod. Mod. Min.@ 307 F Tens. 300% Elong. Tens. 300% Elong. Coarse Thermal Black 30 750 450 530 1200 825 450 60 615 490 410 1025 900 340 120 600 500 400 1025 900 340 Oscil. Data (651/307 F.) Loss Factor (poise sec.-l x 10-G) 0.97 0.75 Dynamic Modulus (dyne cm.-2 X 10-7) 10- 6.51 6.78 Semi-Reinforcing Furnace Black 30 1750 800 580 2150 1500 460 60 1500 1000 460 2050 1600 390 120 1400 1000 430 1950 1650 370 Loss Factor (poise sec. -1 X 10-0) 2.42 1.08 Dynamic Modulus (dyne cm.-2 X 10-7) 10.58 7.63 High Modulus Furnace Black 30 1800 1300 490 2300 1840 410 60 1850 1550 400 2225 1950 305 120 1850 1650 360 2125 2025 330 Loss Factor (poise sec.-l x 10-6) 5.57 2.18 Dynamic Modulus (dyne cm.-2 X 10-7) 21.4 11.6 High Abrasion Furnace Black 30 2350 1400 500 2825 2025 440 60 2475 1700 430 2650 2150 370 120 2500 1875 420 2725 2300 370 Loss Factor (poise sec.-l x 10-6) 5.22 2.80 Dynamic Modulus (dyne cm.-2 x 10-7) 20.2 12.7 The above data in Table III show that in the case of each of the four types of carbon black, the nitrosophenol-treated butyl rubber (GR-I-17) has obtained an improved tensile strength, a substantially better modulus at 300%, and a much improved resilience (lower loss factor) compared to similar compositions prepared with the same type of carbon black but with untreated butyl rubber. It will be noted in this example that the carbon black was admixed and hot milled with the pretreated or unpretreated butyl rubber before the addition of curatives and subsequent vulcanization. EXAMPLE 7.

OTHER NITROSO PHENOLIC COMPOUNDS. The following tests are given to show how the invention may be applied by reacting butyl rubber with nitrosophenolic compounds other than p-nitrosophenol. In addition to data on an untreated butyl rubber (GR-I-17), comparative data are given on 0.5, 1.0 and 2.0'' of nitrosated o-cresol, and on 0.5 and 1.0 of nitrosated o-hydroxy diphenyl, and on 0.5:i, of benzoate ester of p-nitrosophenol. The general compounding recipe used in these tests was the same as that in Example 4, in each case using 50 parts of medium processing channel black as the filler. The procedure used was to first mix the GR-I-17 on a cool mill, add the nitrosophenolic compound, until thoroughly mixed on the cool mill, then hot milling for 10 minutes at 310 F., then adding the carbon black and stearic acid on the cool mill, and hot milling for 5 minutes at 310 F., followed by final addition of the other compounding ingredients on the cool mill, and then vulcanizing and testing the compositions. The results are given in Table IV. TABLE IV Oscillograph Data on 651/307OF. Cure Amount of Loss Factor Dynamic Modulus Nitrosated . Mod. Phenolic Min. ( Poises Dyne Compound Cure Tens. 300% Elong. (sec.-l x 10-6) (cam. x 107-) Nitrosated o-cresol 0 30 3150 925 650 60 3250 1175 580 4.6 10 120 3250 1275 570 0.5 30 3450 1375 600 60 3225 1425 530 2.5 7.7 120 3425 1550 520 1 30 3350 1425 590 60 3050 1675 500 2.4 7.8 120 3200 1875 470 2 30 3350 1400 605 60 3000 1625 500 2.5 7.7 120 3150 1600 500 Nitrosated o-hydroxy diphenyl 0.5 30 3150 1175 590 60 3075 1475 520 2.2 6.8 120 2925 1425 530 1 30 3150 1300 580 60 2850 1350 500 2.3 7.2 120 2950 1500 500

Benzoate Ester of p-nitrosophenol 0.5 30 2900 1150 610 60 2800 1400 520 3.0 7.5 120 2775 1575 480 The data in Table IV show that all three of the nitrosophenolic compounds tested give a substantially increased 300!% modulus compared to that obtained with the untreated butyl rubber control, the results obtained with the nitrosated o-cresol being somewhat better than those obtained with the nitrosated o-hydroxy diphenyl and the benzoate ester of p-nitrosophenol. The data in Table IV also show a substantially improved resilience (lower loss factor) compared to the untreated butyl rubber ccm- position. In the resiliency property, the data obtained with the nitrosated o-hydroxy diphenyl were slightly superior to those obtained with the nitrosated o-cresol and with the benzoate ester of p-nitrosophenol. EXAMPLE 8. EFFECT OF NITROSATED O-CRESOL ON SILICA COMPOUNDED BUTYL RUBBER COMPOSITIONS The following series of tests is given to show the improvements obtained by reacting a butyl rubber (GR-I-17) with concentrations ranging from 0 to 2 parts per 100, of nitrosated o-cresol, and mixing the resulting product with a silica filler, specifically Hi-Sil C, in the following recipe: Parts by Weight GRI17 100 Nitrosated o-cresol (as shown below) 0-2 Hi-Sil C (silica) 40 Stearic Acid 2 Zinc Oxide 5 Sulfur 2 Tellurium diethyldithiocarbamate 1 B.J.F. (3 anilinomethyl-2(3) benzothiazolethione) 1 The procedure used was to mix the nitrosated cresol with the GR-I-17 on the cool mill and then hot mill the mixture for 10 minutes at 310 F., then add the Hi-Sil C and stearic acid on the cool mill, and hot mill for 5 minutes at 310 F., followed by addition of the remaining compounding ingredients on the cool mill, and finally curing at 3070 F., and testing the cured products, w'ith the results shown below in Table V. TABLE V Oscillograph Data

on 651/307OF. Cure Loss Factor Dynamic Modulus Amoun reacted together and compounded according to the following recipe: Parts by Weight Smoked Sheet (Hevea) 100 Stearic Acid 2 p-Nitrosophenol 0--4, as shown below Carbon Black (MPC) 50 Zinc Oxide 5 Sulfur 2.5 Mercaptobenzothiazole 1 Phenyl-beta-naphthylamine 1 The procedure used was to mix the smoked sheet rubber, the stearic acid and the pnitrosophenol (when used) on a cool mill and then hot mill the mixture for 10 minutes at 310" F. Then the carbon black was added and mixed on the mill at about 155 F. (to prevent breakdown of the rubber), and then milled for 5 minutes at 310 F., followed by addition of the remaining compounding ingredients on the mill at about 155 F. The compositions were then cured at 287 F. and tested for resiliency properties, with the results shown herebelow in Table VI. TABLE VI Oscillograph Data on 65l/287 F. Cure Loss Factor Dynamic Modulus Amount of p-Nitrosophenol (poises sec.-1 x 10-6) (dyne cm.-2 X 10-7) 0 2.23 7.1 1 1.90 4.7 2 1.52 4.8 4 1.27 5.7 The above data in Table VI show that the reaction of natural rubber with p-nitrosophenol effects a very substantial improvement in the resiliency (low loss factor). The loss factor of 2.23 for the untreated rubber is decreased successively to 1.90, 1.52, and 1.27 by concentrations of 1, 2 and 4 parts of p-nitrosophenol per 100 of rubber respectively. EXAMPLE 10. EFFECT OF p-NITROSOPHENOL ON GR-S COMPOUND. When GR-S (butadiene-styrene) synthetic rubber is substituted in place of the Hevea smoked sheet rubber in the recipe used in Example 9, the following results are obtained: The GR-S control, and the GR-S reacted with 1 part of p-nitrosophenol per 100 of GR-S, could both be mixed and compounded satisfactorily;

but the mixtures containing 2 and 4 parts per 100, of p-nitrosophenol, though handling satisfactorily on the cool mill for mixing, and also for the hot milling for 10 minutes at 310" F., they were too highly crosslinked for proper mixing when the 50 parts of carbon black was added. The untreated GR-S control and the reaction product of GR-S with 1 part per 100, of p-nitrosophenol, were cured for 50 minutes at 287" F. and tested, with the following results: TABLE VII Oscillograph Data on 651/287 F. Cure Loss Factor Dynamic Modulus Mod. Amount of @ Poises Dyne p-nitrosophenol Tens. 300% Elong. (sec.-1 x 10-6) (cm.-2 x 10-7) Untreated GR-S 0 2850 1400 480 6.0 10.4 Treated GR-S 1 1900 190 4.5 I2.2 The data in above Table VII show that the reaction of 1 part of p-nitrosophenol with 100 parts of GR-S synthetic rubber effects a substantial improvement in resilience of the products, as indicated by a reduction in the loss factor from 6.0 to 4.5. This example indicates that higher concentrations of p-nitrosophenol effect too much crossAinking of this type of synthetic rubber, perhaps due to the presence of a substantial amount of side vinyl groups resulting from the butadiene in this type of synthetic rubber. From these data, it would appear that lower concentrations such as 0.1 to 1% of p-nitrosophenol are satisfactory for reacting with R-S synthetic rubber. EXAMPLE 11. ENJAY BUTYL 325 TREATED WITH 0.32 TO 1.3 % MODIFIER. A sample of Enjay Butyl 325, which has an 8 minute Mooney of 41 to 49 and unsaturation of 1.9 to 2.3%, was reacted with four different amounts ranging from 0.32 to 1.3%, of p-nitrosophenol, at 212" F. for four minutes and then mixed with carbon black (15 parts Pbilblack-O and 35 parts Kosmobile-66 per 100 of Butyl polymer), and curing agents (zinc oxide 5, sulfur 2, and Tellurac 1), vulcanized 40 minutes at 307" F., and tested for physical and dynamic'properties, along with an unmodified control for comparison. The results obtained are shown in the following table: TABLE VIII 1 2 3 4 5 % p-nitrosophenol 0.0 0.32 0.65 0.97 1.3

Mooney Viscosity - LR - 45 47 46 46 47 41 @ 212 F. Polymer 100 Mixing: Cooling Water on Black Philblack0 15 (3A Banbury) incorporated after Kosmobile-66 35 4-5 minutes Total Mixing Time 10 minutes Discharge Temp. ( F.) 320 340 340 330 335 Mooney Viscosity - LR 41 , 212 F. Stacked cool 81 86 87 87 86 Stacked hot 81 92 103 100 88 Vulc. 401 @, 307" F. Modulus, 100%, psi 380 500 500 480 500 200%, psi 850 1380 1380 1400 1380 300%, psi 1380 2310 2300 2350 2300 Tensile, psi 2640 2540 2570 2620 2580 Elong. % 465 330 335 325 340 Dynamic Properties, 122" F. 11f X 10-6,poise x cps 3.85 2.06 2.13 2.15 1.99 K X 10-7,dynes/cm-2 8.66 7.70 7.96 8.04 7.65 The above data show that the reaction of the butyl rubber with p-nitrosophenol before compounding and curing, produced a tremendous increase in modulus in the cured compositions, e.g. gave a 200% modulus of 1380 to 1400 compared to 850 for the unmodified control, and a 300% modulus of 2300 to 2350 compared to 1380 for the unmodified control, and also giving a great reduction in internal viscosity from 3.85 for the control down to 1.99 to 2.15 for the modified butyl compositions. EXAMPLE 12. COMPOSITIONS LII(E EXAMPLE 11, BUT CONTAINING OIL PLASTICIZER. Another series of tests was made quite similar to those of Example 11 except that in each case some hydrocarbon oil plasticizer was used in the composition when compounded and cured. Also, for comparison, an additional control test was made in which unmodified butyl polymer was heat treated with 50 parts of Kosmobile-66 carbon black, by hot milling and then 12.5 parts of hydrocarbon oil plasticizer added, and then curing agents added and the composition cured and tested in the same way as the p-nitrosophenol modified butyl rubber. The results obtained are shown in the following table. TABLE IX Heat No Heat Treatment Treated 1 2 3 4 5 6 % Modifier (p-nitrosophenol) 0.0 0.32 0.65 0.97 1.3

Kosmobile-66 35 35 35 35 35 50 Philblack0 15 15 15 15 15 Coray-230* 20 20 20 20 20 Faxarn-lO** - - - - - 12.5 Vulc. 401 @/ 307 F. (a) Modulus, 100%, psi 100 125 120 100 130 200 200%, psi 240 450 450 475 465 520 300%, psi 580 1060 1050 1060 1045 1140 Tensile, psi 2460 2340 2200 2260 2265 2730 Elong., % 745 550 520 530 540 545 Dynamic Properties, 122 F. #f x 10-6, poise x cps 1.94 1.10 1.28 1.15 1.21 1.10 K X 10-, dynes/cm-2 4.70 4.21 4.51 4.51 4.62 5.21 * Naphthenic lubricating oil base stock having a viscosity of about 230 sec. Saybolt at 210 F. ** Paraffinic lubricating oil base stock having a viscosity of about 40 sec. Saybolt at 210 F. (a) Full compound for control: Zinc Oxide 5, Sulfur 2, Tuads 1, Altar 1, for compounds 1-5 acceleration is changed to 1 part of Tellurac. The above data show that p-nitrosophenolmodified butyl rubber (Samples 2-5) gave almost double the modulus values (200% and 300% moduli) of the unmodified control test 1, and gave much lower internal viscosity values of 1.10 to 1.28, compared to 1.94 for the unmodified control test 1. These data show that without heat treatment of the butyl rubber with carbon black, the modification of the butyl rubber with 0.32 to 1.3% p-nitrosophenol gives substantially as great improvement in modulus and internal viscosity as is obtained by heat treatment of an unmodified butyl rubber with carbon black, as shown in test 6 for comparison. EXAMPLES 13 AND 14. BUTYL RUBBER MODIFIED WITH m-NITRO S OBENzALDEHYDE. The butyl rubber of the type used in Example 2 was modified by mixing 42 parts by weight of butyl rubber with 0.95 parts by weight of m-nitrosobenzaldehyde and hot milling this mixture for 20 minutes at 250260" F. This modified butyl was then compounded and cured in duplicate samples except that one part of p-phenylene diamine was used to obtain some additional curing by crosslinking of the modified butyl polymer molecules. The samples were then cured at 287" F. for periods ranging from 10 to 60 minutes, and the cured samples were tested for physical properties, with the results shown in the following table: TABLE X. 1 2 Modified Butyl - - - - 100 100 Zinc Oxide - - - - - 5 5

Stearic Acid - - - - 1 1 Kosmobile-66 - - - - 50 50 Sulfur - - - - - - 2 2 Tellurac - - - - - - 1 1 p-Phenylene Diamine - 1 Tensile-Mod. e @ Tensile-Mod. @ Cure 300-Elong. 300-Elong. 101/287 F. - 1 & 40-1680-3'60 151/287 F. 1530- 670-590 2140-2140-300 301/287 F. 2530- -295 601/287 F. 2370-1530-490 These data show that in the case of test 1 (without the use of p-phenylene diamine), the butyl rubber which had been modified with m-nitrosobenzaldehyde gave a 300% modulus of 1530 (at 60 minutes cure) which is surprisingly high compared to the substantially corresponding figure of 1050 obtained with an unmodified butyl control in Example 4. The above tests also show that the additional use of p-phenylene diamine in the curing compound produces an even stronger and faster cure to a 300% modulus of 1680 after only a 10 minute cure and 2140 at 15 minutes cure. Thus the p-phenylene diamine is so reactive with the m-nitrosobenzaldehydemodified butyl rubber that it would not be necessary to use as much as 1 part of pphenylene diamine per 100 of modified butyl polymer. For instance, 0.1 to 05 part would be sufficient under the conditions of the above tests, to obtain a substantial acceleration of the curing and increase of the modulus, without substantial reduction in % elongation. Other tests show that p-nitrosodimethylaniline, p-nitrosochlorbenzene, and p-nitrosobenzoic acid all react with butyl rubber substantially like p-nitrosophenol does. An embodiment of this invention relates to a novel method for coating natural and synthetic fibrous articles with the modified butyl rubber described above, such as by the coating of an automobile tire cord first with an aqueous solution of a resinous phenolicaldehyde condensation product, preferably resorcinol-formaldehyde, and then coating it with a cement comprising a volatile solvent solution of butyl rubber which has been reacted with a small amount of a compound, of the nature described above, this cement preferably also containing a rubber pigment or filler such as carbon black, and the resulting dried, coated cord is found to have much greater adhesion to butyl rubber layers used in constructing tires for autos, airplanes, etc. In the construction of many rubber articles such as tires, belting, etc., a fabric made of a natural fiber such as cotton or a synthetic fiber such as rayon or nylon is included in the structure to provide rigidity and strength. The performance of these structures is dependent upon the bond present between the rubber and the fabric. In the construction of automobile tires, latex dips have been developed using natural rubber latex or

any of several high unsaturation synthetic rubber latices which provide satisfactory adhesion not only to cotton tire cord which had been conventionally used in the past, but also to the more recently developed rayon cord and nylon cord, which have greater strength and smoother cord surfaces. On the other hand, butyl rubber which is a low unsaturation rubbery copolymer of an isoolefin such as isobutylene with a minor amount of a diolefin such as isoprene, does not normally have good adhesion to such fibers, particularly the synthetic fibers such as rayon and nylon. The present invention solves this difficulty and provides a strong bond between butyl rubber and such fibers, by reason of the coating technique as will be now described. The fabric to be coated such as tire cord is first dipped in an aqueous solution of a phenolic-aldehyde resin, preferably resorcinol and formaldehyde. The proportions should be about 0.2 to 6 moles of formaldehyde per mole of resorcinol and the concentration should be about 1 to 10, preferably about 2 to 5 wt. % resin solids in the water. A small amount of catalyst, preferably an alkaline condensation catalyst such as sodium hydroxide or carbonate should also be added. This catalyst may be used in a concentration of about 0.1 to 5.0, preferably 0.5 to 2.0 parts by weight per 100 parts of resorcinol. The resin solution may be prepared in many desired manner, but preferably is made by dissolving the resorcinol in the water, then adding the formaldehyde (commonly available as a 3540 X aqueous solution) and finally adding the caustic catalyst, preferably as 0.5 to 1.0% solution in water. The resin is then partially formed by reacting it at about 70-75 C. for 2 hours or so, and cooled to room temperature. The tire cord, such as rayon or nylon cord, is then dipped into this aqueous solution preferably without distorting the original shape or twist of the cord, and then the resin-coated cord is dried by any desired manner, such as in a circulating air oven for 1 to 10 minutes at 200300Q F., e.g. 5 minutes at 250" F., or for a longer time at lower temperature, e.g. room temperature. The resulting resin-coated cord is then dipped into a modified butyl rubber cement made as follows: The modified butyl rubber is made by reacting a butyl rubber with a small amount such as 0.1 to 5.00/0, preferably 0.5 to 3.0% of a compound, as described hereinabove. The preferred procedure is to add the modifier, such as nitrosophenol, to the butyl rubber on a cool mill, then heating to the desired reaction temperature, such as at 275 F. for 15 minutes or so, then cooling to about 75 to 125 F. and adding the stearic acid and carbon black or other pigment or filler, then hot

milling at about 225 to 350" F. inversely for about 15 to 3 minutes, for instance at 280 F. for five minutes, to effect the desired bonding of the carbon black with the butyl rubber-nitroso reaction product. The mill is then preferably cooled to about 75 to 125" F. and the curing agents added, after which it is then ready, with or without further cooling, for preparation of the modified butyl rubber cement by dissolving it in a concentration of about 8 to 20% by weight in a suitable volatile solvent, preferably an aliphatic hydrocarbon solvent of about 6 to 10, preferably 7 to 8 carbon atoms, such as heptane. Benzene and toluene may also be used. This cement may conveniently be prepared by dissolving the modified butyl rubber composition on a mixed weight and volume basis, by using proportions corresponding to about 10 to 25, preferably 15 to 20 grams of the compounded modified butyl rubber in 155 cc. of heptane. If desired, a small amount, such as 1 to 20 volume %, preferably about 5 to 10 volume of an alcohol such as isopropyl alcohol or ethyl alcohol or other volatile viscosityreducer may be added to the cement, to facilitate application of a larger amount of solids in a single dip. The auto tire cord which has already been coated with the aqueous resin solution and dried, is now dipped or otherwise coated with the modified butyl rubber cement composition just described, and it is then dried and heated in an air oven at 200 to 300" F. for about 10 to 1 minutes, e.g. at 250 F. for about 5 minutes, or for a longer time at room temperature to evaporate the volatile solvent. The resulting treated cord, which has now been first coated with a resorcinol-formaldehyde resin, and then coated with the modified butyl rubber composition, is now ready for use in constructing tire carcasses for autos, trucks, airplanes, etc., as well as numerous other uses such as conveyor belts and other products built up of a plurality of laminations of cord and butyl rubber, etc., the invention being especially applicable to such products which at least have one layer which is butyl rubber. The invention may also be applied in uses involving merely a single layer of a textile fabric such as cotton cloth, silk, etc., which may be either coated on one side or both sides, with the resin and modified butyl rubber treatment described above and then bonded to a layer of butyl rubber by calendering or any other suitable method for use in making tents, tarpaulins, raincoats, etc., as well as laminated fabrics, for instance composed of two layers of textile fabric bonded together by a single layer of butyl rubber. The following additional examples illustrate the treatment of tire cord. The adhesions were measured by a technique essentially similar to the

"H" test described by Lyons, Conrad and Nelson.'''* (The tire cords used were rayon tire cord of 1650/2 ply construction and nylon cord of 840/2 ply construction). A test specimen is prepared with a -2 inch length of treated cord vulcanized into the center of a 19 x A x - inch rubber matrix. The rubber matrix is reinforced with light cotton duck on the tmo long sides from which the cord does not protrude. The force required to pull the A inch length of cord from the rubber block is measured by means of a Scott Tensile Tester at a 20 inches per minute jaw separation rate. The following list gives identifications of materials referred to by trade means. Butyl rubber: GR-I 17 60 to 70 Mooney (8 min. @ 212 F.) & 9.5 to 12.5 iodine no. (Wijs) GR-I 25 40 50 13 15.5 Fillers: Kosmobile 66 (MPC)-a medium processing channel black. Philblack 0 (HAF)-a high abrasion furnace black. Hi Sil C silica Thermax (MT) -Medium Thermal Black (A Registered Trade Mark) Vulcanizing Accelerators: Altax -Benzothiazyl disulfide. (A Registered Trade Mark) B.J.F. -3 anilinomethyl-2(3)-benzothiazolethione. Tellurac-Tellurium diethyldithiocarbamate. Tuads -Tetramethyl thiuram disulfide. (A Registered Trade Mark) Softener: Forum 40-a treated paraffinic petroleum base oil of about 110 sec. Saybolt viscosity at 100 F. Pour Point, + 30 F. Flash @ 365 F. Misc.: R.T. -Room Temperature The Butyl rubber matrix from which the cord lengths were dislodged was prepared in the following formulation. Parts Ingredient by Weight GR-I-17 100 Kosmobile 66 50 Stearic Acid 0.5 Zinc Oxide 5.0

Sulfur 2.0 Tellurac (Tellurium diethyl dithiocarbamate) 1.0 Petroleum Softener (Forum 40) 15.0 Unless otherwise specified the test specimens were cured for 25 minutes at a tem perature of 320 F. The p-nitrosophenol used in following experiments was prepared by reaction of the sodium salt (Eastmans) with hydrochloric acid. The solution was cooled in ice water and the nitrosophenol separated by filtration. The product was dried in vacuum oven at 55 C. This invention is further described by the following examples. EXAMPLE 15 EFFECT ON ADHESION OF COMPOUNDING INGREDIENTS rN BUTYL RUBBER. Using a cool mill 2% by weight (4.4 g.) of p-nitrosophenol were added to 220 g. of CR- I-25. The nitrosophenol was reacted with the Butyl rubber by milling for 15 minutes at 270 F., the mill cooled, and 1 pt. (2.2 g.) of stearic add added. Portions of this modified rubber, labeled 87A, were used to prepare the following cements. Cement No. 1 2 3 4 5 6 7 Indent. 87- 1 2 3 4 7 8 9 87A, pts. 103 103 103 103 103 103 103 Kosmobile 66, pts. (MPC) - 30 50 50 50 - Philblack 0, pts. (HAF) - - - - - 50 Hi Sil C, pts. - - - - - - 50 Thermax, pts. (MT) - - - - 50 - Fillers added cool mill-then milled for 5 minutes at 280 F. to simulate banbury mixing--the mill cooled and curatives added as indicated below. Zinc Oxide 5 5 - 5 5 5 5 Sulfur 2 2 - 2 2 2 2 Tellurac 1 1 - 1 1 1 1 B.J.F. (3-anilinomethyl-2(3)-benzothiazolethione)- 1 Cements prepared by dissolving the following weights of each compound in 155 cc. heptane + 8 cc. of isopropyl alcohol. Grams 11.1 14.1 15.3 16.1 21.1 16.1 16.2 % by wt. 9.0 11.1 12.0 12.5 15.8 12.5 12.6 An aqueous solution of a resorcinolformaldehyde resin was prepared by dissolving 5 g. of resorcinol in 117 cc. of water.

To this solution was added 3.68 g. of 37% formaldehyde and 10 cc. of 0.5% NaOH as catalyst. The resin was partially formed by reacting at 70-75 C. for 2 hours (labeled 8so). This solution was then cooled to room temperature. The cord was treated by rapidly pulling it through a guide which forced it beneath the surface of the resin solution contained in a beaker. The original length and twist of the cord was preserved. The cords were dried by placing in a circulating air oven for 5 minutes at 250 F. The cements were applied using the same equipment and employing an air wipe to assist removal of the excess cement from the cord immediately after it had passed through the cement. The cord was again placed in the air oven at 250 F. for 5 minutes to remove residual solvent and "H" test specimens prepared. Cement 1 2 3 4 5 6 7 Adhesion of Butyl to rayon treated with 86A Pounds @ R.T. 11.9 17.4 19.5 20-22(a) 17.3 17.8 16.8 @ 212 F. 7.6 12.9 12.5 13.4 13.5 12.1 12.3 Adhesion of Butyl to nylon treated with 86A Pounds @ R.T. 14.4 13.7 @ 212 F. 9.6 8.1 (a) Value obscured by cord failures. The Butyl compound may be varied as is well known in the art and good adhesion obtained to rayon and nylon treated with a resorcinol-formaldehyde resin solution. Curatives are not required, cement 3 versus 4,- but - appear to favorably affect the adhesion strength. EXAMPLE 16 EFFECT OF NITROSOPMENOL CONCENTRATION. GR-I-25 was modified with from 0.5 to 5.0 pts. of~p-nitrosophenol per 100 of rubber as described in Example 11. The following data table lists the concentrations used and the adhesion to butyl rubber obtained on rayon tire cord treated with 86A prior to cement dipping. Cement 8 9 10 11 Ident. 87- 10 1'1 12 14 GR-I-25, pts. 100 100 100 100 p-Nitrosophenol, pts. 0.5 1.0 3.0 5.0 Cool mill mixed-reacted by milling for 15 minutes at 280 F. Stearic Acid 1 1 1 1 Kosmobile 66 50 50 50 50 Cool Mill mixed-milled at 280 F. for 5 minutes. Zinc Oxide 5 5 5 5 Sulfur 2 2 2 2 Tellurac 1 1 1 1 Cements prepared by dissolving the indicated grams of compound in 155 cc. of heptane + 8 cc. of isopropyl alcohol. grams 15.9 16.0 16.2 16.4 % by Wt. 12.4 12.5 12.6 12.8 Following dipping in resin solution 86A (24 hrs. old) and

cement the rayon cords were dried for 5 minutes at 250 F. "H" ADHESION RESULTS TO BUTYL RUBBER Pounds at R.T. 17.2 17.9 17.2 19.5 @ 212 F. 12.5 12.0 12.9 12.4 The adhesion obtained is not critically affected by the concentration of nitrosophenol employed. EXAMPLE 17 INFLUENCE OF AQUEOUS RESIN COMPOSITION. Effective resorcinol resins can be made using low mol ratios of formaldehyde to resorcinol if prepared in an alkaline system. The following table lists adhesions obtained to Butyi rubber using cement 9 from Example 12. Resins prepared by dissolving the resorcinol in sufficient water to result in a 3.% by weight resin solution, formalin and catalyst added. Solutions were held at 70 C. for 2 hours cooled to room temperature and rayon tire cord treated and dried 5 min. @ 250 F. The resin dipped cords were then treated with cement 9 and again dried for 5 min. at 250 F. Resin solution 1 2 3 4 5 6 7 8 9 10 11 12 Indent. 137 89 G H B C D E L M F G I K Mol Ratios Formaldehyde 0.0 0.2 0.4 0.6 0.8 1.0 1.0 1.0 0.0 0.2 0.6 1.0 Resorcinol 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 Catalyst NaOH Oxalic Acid g./100 g. of 1 1 1 1 1 1 0.5 2 1 1 1 1 Resorcinol Adhesion of Butyl Rubber to Rayon Pounds @ R.T. 6.5 16.3 17.1 18.3 19.6 19.0 18.2 16.3 7.6 8.8 8.9 10.0 @ 212 F. 10.8 11.5 13.6 14.0 13.7 12.9 13.3 5.6 Resin solutions prepared using alkaline condensation catalyst is required for good adhesion. The high temperature adhesion is greater for resin solutions containing 0.6 to 1 or higher mol ratios of formaldehyde to resort cinol. Mol ratios greater than 1:1 can be successfully employed. This is demonstrated below. The modified Butyl cement was prepared in a manner and composition similar to cement No. 4 2 pts. of p-nitrosophenol) except that -GR-I-17 was substituted for GR-I-25. Resin Solution 13 14 15 16 17 Indent 137 H B C D H Mol Ratios

Formaldehyde 0.8 1.0 2.0 3.0 2.0 Resorcinol 1.0 1.0 1.0 1.0 1.0 Catalyst NaOH - 1 g. per 100 g. Resorcinol Resin Concentration, Wt. % in water 5.0 5.0 5.0 5.0 2.5 Solutions held at 70 C. for 2 hours prior to cooling for cord treating. Treated with above resin solutions and dried 5 min. at 212" F. Cement treated and dried for 5 minutes at 212 F. ADHESION OF BUTYL RUBBER TO RAYON TIRE CORD Pounds @ R.T. 17.5 19.9 18.2 16.3 19.0 @ 212 F. 13.6 12.5 13.1 12.8 10.3 For comparison an adhesion value EXAMPLE 20 NITROSOI-HENOL MODIFICATION REACTION. The reaction of the Butyl rubber with the p-nitrosophenol need not be carried out prior to compounding as illustrated in the previous examples. The following compound was prepared on a cool mill with the nitrosophenol added last. Ingredient Pts. by Weight GR-I-17 100 Kosmobile 66 60 Stearic Acid 0.5 Zinc Oxide 5.0 Sulfur 2.0 Tellurac 1.0 p-Nitrosophenol 3.0 Cement Formulation grams 16.4 (12.8% by wt.) Solvent: 155 cc. heptane + 8 cc. isopropyl alcohol. Rayon tire cord treated with a resin solution similar to solution No. 15, and dried for 5 min. @ 225 F., was treated with above cement and dried again for 5 min. at 225 F. Adhesion at R.T., pounds 16.2 EXAMPLE 21 USE OF SODIUM SALT OF p-NITROSOPHENOL. Three hundred grams of GR-I-25 were compounded with 2 parts of sodium salt of p-nitrosophenol on a cool mill and divided into 2 equal portions. These were reacted on a hot mill and compounded as shown below. Reaction Conditions: 10 min. @ 2402S0 F., 10 min. @ 300310' F. Compounding Ingredients added on a cool mill, pts. by weight. Kosmobile 66 50 50

Zinc Oxide 5.0 5.0 Stearic Acid 0.5 0.5 Sulfur 2.0 2.0 Tellurac 1.0 1.0 Cements prepared by dissolving 16 g. in 155 cc. heptane and s cc. of isopropyl alcohol. Rayon cord lengths dipped in aqueous resin solution 14, dried for 5 minutes at 250 F. and again for 5 minutes at 250 F. following cement treating. ADHESION OF RAYON TO BUTYL RUBBER, "H" TEST~BESULTS Pounds at R.T. 15.9 16.1 at 212 F. 11.5 13.3 Excellent adhesions can be obtained using either the p-nitrosophenol or its sodium salt in conjunction with a resorcinol-formaldehyde resin dip on the cord. EXAMPLE 22 A partially reacted resin solution was prepared by holding the following at 70 C. for 2 hours. Resorcinol 15 g. 37% Formaldehyde 11.0 g. 1% NaOH 15.0 g. Distilled Water 149.7 g. After heating, this masterbatch solution was diluted by addition of more distilled water to prepare dips containing frorn 0.5 to 10% solids, based on formaldehyde and resorcinol content. Rayon cord lengths were treated with the solutions and dried for 5 minutes at 250 F. Solution A B C D B F /O Resin Solids 10.0 7.5 5.0 2.5 1.0 0.5 These dried resin treated cord lengths were then treated with a cement similar to Example 11-cement 4 except that 2.5 pts. p-nitrosophenol was reacted with the GIR-I-25. Cement treated cords were dried for 5 minutes at 250 F, and "H" type adhesion samples prepared, ADHESION OF BUTYL RUBBER TO RAYON, POUNDS: Room Tern. 11.9 14.3 19A 20.4 18.8 18.1 212" F. 9.6 9.3 129 135 '13.0 11.4 Range 1 to 51% solids appears most attractive. Higher concentrations might be used advantageously when squeeze rolls or other mechanical devices are used to limit the amount of pickup of the resin solution. EXAMPLE 23 This example uses room temperature reaction conditions for 24 hours (rather than 70 C. for 2 hours) to prepare resin solutions. These samples contain 5% resin solids based

on formaldehyde and resorcinol and, for the 3/1 mol ratio resin, 4 concentrations of sodium hydroxide. Rayon cord was used in the main series, but nylon data are also avail able for the 3/1 resin dips. Catalyst concen trations were from 0.5 to 4.0 pts./100 of resorcinol. ROOM TEMPERATURE REACTED RESIN SOLUTIONS (5% RESIN SOLIDS) Resin Solution 1 2 3 4 5 6 7 8 9 Mol ratio: formaldehyde to resorcinol 1/1 2/1 3/1 3/1 3/1 3/1 4/1 5/1 6/1 Catalyst Concentration: grams of NaOH per 100 of resorcinol 1 1 0.5 1.0 2.0 4.0 1 1 1 Resin solutions allowed to age 24 hours prior to treating tire cord. After passing through solution, cords were dried for 5 min. at 250 F., then treated cement used im previous example GR-I-25 reacted with 2.5 pts p-nitrosophenol. Final drying was for 5 min. at 250 F. Adhesion to Rayon: Room Temp. 16.1 18.4 18.4 20.2 19.6 17.7(a) 19.4 17.9(a) 20.0(a) 212 F. 13.4 14.0 16.3 14.0 17.0(a) 17.0(a) 15.0 14.3 Adhesion to Nylon: Room Temp. 9.5 11.2 12.9 16.5 212 F. - 10.0 9.0 9.3 (a) Number of cord failures encountered in testing these samples. EXAMPLE 24 This example demonstrates the application of the modified Butyl to the resin surface on the cord by calendering and use of small Banbury (No. 00- 5 lb. capadity) for reaction and mixing of MPC carbon black with the modified GR-I-25. In the No. 00 Banbury 2,000 g. of GR-I -25 and 22.5 g. of stearic acid were charged. After 2 minutes of mixing 250 g. of GR-I25 into which was milled 135 g. of 33'% pnitrosophenol on clay was added. The reaction was conducted by mixing for 8 minutes without cooling water. The temperature of the mix at dump was 335 F. as measured with a needle pyrometer. In 1872 g. of this modified GR-I-25 in the No. 00 Banbury 875 g. of MPC black was added using a total Banbury time of 104 minutes. The temperature at dump as taken above with needle pyrometer was 395 F. A compound for calendering was prepared by adding softener and curatives on a cool mill. Black compound 157 pts. by weight Coray 230(a) 5 Zinc Oxide 5 Sulfur 2 Tellurac 1 (a) Acid treated aromatic petroleum softener

Saybolt vis. 100 F.-10,533 sec. at 210 F.-235 sec.; Flash Point 525 F., Pour Point-15 F. Rayon tire cord treated with aqueous resin solution similar to resin solution #8 in previous example 19 and dried for 5 minutes at 250 F., were covered with the above compound using 3 roll laboratory calender. "H" type adhesion samples were prepared and an average adhesion value of 16.1 pounds obtained between this calendered cord and Butyl rubber. EXAMPLE 25 Wetting agents may be included in the aqueous dip and in the case of nylon raising the pH of the dip prior to cord treatment is frequently advantageous. This is demonstrated below: Aqueous Dip 1 2 3 Mol Ratio Formaldehyde to Resorcinol 5/1 5/1 5/1 Resin Solids, 1% 5 5 5 NaOH(a), g/100 resorcinol 1 1 1 Aged 24 hours-Following agents added prior to treating nylon tire cord. NaOH'a), g/100 g. resorcinol - 3 -' Aerosol OT, cc. of 5% solution per g. of resorcinol 5 3 Cords dried 5 minutes at 250 F. Cement used: Example 18 (2.5 pts. nitrosophenol in GR-I-25) and cords again dried for 5 minutes at 250 F. ADHESION TO NYLON AT ROOM TEMPERATURE Pounds 13.3 13.3 8.4 (a) Added as 1% solution. EXAMFLE 26. ADHESION OF PLASTICIZED MODIFIED BUTYL TO RAYON TIRE CORD. The same type of butyl rubber used in Examples 11 and 12 was similarly modified with various amounts ranging from 0 to 1.3% of p-nitrosophenol, as in Examples 11 and 12, and then compounded with various amounts ranging from 0 to 20 parts of hydrocarbon oil plasticizer per 100 of butyl polymer, and then all samples were compounded with carbon black and curing agents according to the following recipe: Polymer 100 Kosmobile-66 50 Philblack-0 15 Zinc Oxide 5 Sulfur 2 Tellurac 1

These samples were then tested for adhesion, to rayon tire cords which had been pretreated with 5% solution of resorcinol formaldehyde resin (using a molar ratio of formaldehyde to resorcinol of 5:1 and using 2% of NaOH as catalyst based on resorcinol resin solids, and the solution allowed to age 24 hours at room temperature prior to use), and the dipped cords dried 5 minutes at 250 F. The results of the adhesion tests are shown in the iolowing table; TABLE XI 1 2 3 4 5 % Modifier (p-nitrosophenol) 0.0 0.32 0.65 0.97 1.3 Plasticizer Coray 230 H - adhesion 20"/min; R.T. 0 parts 10 17.5 19.1 18.7 19.3 6 ,, - 18.5 17.8 18.7 19.3 12 ,, - 18.9 20.6 19.1 18.3 20 ,, - 19.0 17.8 19.3 19.0 These data show that the control sample 1 of modified butyl rubber gave an adhesion of only 10, without any oil plasticizer, whereas the butyl rubber which had been modified with 0.32 to 1.3% of p-nitrosophenol gave adhesion values ranging from about 17 to 21, either without plasticizer or with from 6 to 20 parts of oil plasticizer. This is a remarkable improvement considering the relatively small amount of chemical reagents used to modify the butyl rubber. What we claim is: 1. A process for pretreating rubbers before compounding and vulcanisation comprising reacting together in the absence of sulphur and a vulcanisable rubber and an aromatic compound having the empirical formula ON Ar M,t, Y, in which Ar is a mono- or polynucleat aromatic hydrocarbon nucleus, M is an aliphatic divalent hydrocarbon group, m is zero of an integer, and Y may be any one or more of the following groups: OR C:OR COOR X N NO2 NR, in which R is hydrogen or a monovalent hydrocarbon radical, and X is halogen. 2. A process according to Claim 1 wherein the mono- or polynuclear aromatic hydrocarbon nucleus is a substituted nucleus. 3. A process according to Claim 1 or Claim 2 wherein m is an integer of from 1 to 10 and M is an aliphatic divalent hydrocarbon group, either saturated or slightly unsaturated. 4. The process according to any of claims 1 to 3 comprising reacting a vulcanisable rubber with about 0.1 to 5.0% by weight of the said

aromatic compound. 5. Process according to any of claims 1 to 4 wherein the reaction between the said vulcanisable rubber and the said aromatic compound is carried out by heating a mixture thereof to a temperature of from 250 to 350 F. 6. Process according to any of claims 1 to 5 wherein the said aromatic compound is pnitroso phenol. * 7. Process according to any of claims 1 to 4 wherein the said aromatic compound is a nitroso aromatic aldehyde. 8. Process according to claim 7 wherein the said nitroso aromatic aldehyde is m-nitroso benzaldehyde. 9. Process according to any of daims 1 to 8 in which the vulcanisable rubber is butyl rubber. 10. Process according to Claim 9 in which the butyl rubber has an iodine number 0.5 to 50. 11. Process according to any of claims 1 to 9 in which the vulcanisable rubber has an iodine number of from 50 to 175. 12. Processes according to any of claims 1 to 9 in which a filler is admixed with the vulcanisable rubber and the said aromatic compound, and the mixture milled during the reaction between the rubber and 'the aromatic~ compound. 13. Processes according to claim 10 in which the filler is carbon black and/or silica. 14. Improved vulcanised rubbers comprising a vulcanisable rubber pretreated according to any one of claims 1 to 13, and which has thereafter been vulcanised. 15. Improved vulcanised rubbers as claimed in claim 14, containing a minor proportion of an oil plasticizer. 16. Improved vulcanised rubbers substantially as hereinbefore described in examples 1 to 14.

* GB785657 (A)

Description: GB785657 (A) ? 1957-10-30

Catalyst for gas phase oxidation reactions and processes effected therewith

Description of GB785657 (A) Translate this text into Tooltip



PATENT SPECIFICATION 789 C Date of Application and filing Complete Specification Sept 13, 1955. No 26223/55. Application made in United States of America on Sept 17, 1954. Complete Specification Published Oct 30, 1957. Index at Acceptance:-Classes 1 ( 1), A 3 (A 1 X: C 7); and 1 ( 2), F 1 U 12. International Classification: -B O Aj C Oic. COMPLETE SPECIFICATION Catalyst for Gas Phase Oxidation Reactions and processes effected therevwith We, E I DU PONT DE NEMOURS AND COMPANY, a Corporation organized and existing under the Laws of the State of Delaware, United States of America, of Wilmington, State of Delaware, United States of America, do hereby declare the invention, for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement: - This invention relates to a catalyst for gas phase oxidation reactions, which is particularly suitable for use in the synthesis of hydrogen cyanide. Several methods are presently known for the preparation of hydrogen cyanide, the more widely accepted methods utilizing a mixture of a nitrogen-containing gas, such as ammonia, a hydrocarbon, and oxygen-containing gas Of the many varieties of reactants which may be included in a mixture of this type, a desirable combination of reactants is ammonia, natural gas, and air. Along with the variety of reactants which may be combined to form hydrogen cyanide, commercial processes have taken many different directions in the type of catalyst which is employed in this reaction Although the catalyst employed is generally some form of platinum or one of its alloys, the physical form of the catalyst has varied widely and the catalyst has been in the form of a wire gauze, metallic

particles, and metallic coatings on various inert substrates One of the preferred procedures has been to employ naturally occurring beryl (beryllium aluminium silicate) in a granular form and coated with platinum or a platinum alloy. When a mixture of ammonia, natural gas, and air is passed over a catalyst comprising beryl coated with an 80 % platinum/20 % rhodium alloy, the yield of hydrogen cyanide from ammonia, as observed over many days of continuous operation, may reach a peak shortly after the beginning of operation and thereafter fall off over a period of several days until it is no longer economical to continue with the catalyst in its spent condition. Accordingly, the reaction is normally stopped at some predetermined low level of yield and the spent catalyst is replaced with new catalyst or is reactivated so that when operations are renewed the yield of hydrogen cyanide will again be at a high level. It is an object of this invention to provide an improved catalyst for gas phase oxidation reactions and more particularly to provide a catalyst which is capable of producing a higher yield of hydrogen cyanide from ammonia and of sustaining that high yield over a longer period of time than has been realized by employing the catalysts hitherto used in this process. According to the present invention there is provided a combination catalyst which comprises a layer of one or more gauzes of platinum or a platinum alloy containing at least 50 % platinum superposed on a layer of granular refractory material coated with platinum or a platinum alloy containing at least 50 % platinum. The catalyst of this invention is not limited by the number of gauzes employed, the exact structure and size of the granular material, or the exact composition of the catalytic metal In normal practice, the granular material is preferably of a size which will pass through a 6 to 10 mesh/linear inch screen and is formed into a bed in the reactor about to about 1 ' thick and the overlayer comprises a single gauze The granular material is preferably naturally occurring beryl (beryllium aluminium silicate) although other inert refractory materials, such as silica, porcelain and alumina may also be employed. The catalytic metal used as a coating on the granular material and also employed in the gauzes may be platinum or a platinum alloy containing at least 50 % platinum; a preferred alloy is one containing 80 to 90 % platinum and 20 to 1007 rhodium. Gauze to be incorporated in the catalyst L 5,657 785,657 according to the invention is X acivated by placing it between previously activated gauze and already used refractory material, carrying out the reaction for a 3 limited period of time, preferably from 3 to 30 hours, and then removing the gauze.

The reactant mixture which is oreferred for the synthesis of hydrogen cyanide is a mixture of ammonia, natural gas, and air It is to be understood, however, that hydrogen cyanide may be produced from mixtures of nitric oxide and hydrocarbons; ammonia, methane and oxygen; and other mixtures of gases comprising nitrogen compounds, oxygen, and carbon compounds, including hydrocarbons and carbon oxides. Moreover the invention is not limited to the production of hydrogen cyanide and other gas phase oxidation reactions, such as the oxidation of ammonia to nitric oxide, may be carried out in the presence of the catalyst according to the present invention. This invention may be illustrated by the several examples which follow in which parts and percentages are by weight unless otherwise specified:EXAMPLE 1 A converter was charged with a catalyst containing about 7 % by weight of an 80 %, platinum/20 % rhodium alloy forming a coating on the surface of finely divided beryl ( 6 to mesh/linear inch) A mixture of ammonia, natural gas, and air in the approximate volume ratio of 1:2:10 was then passed in contact with this catalyst The reaction was initiated by contacting the catalyst with a small wire loop electrically heated to a temperature above about 900 C The yield of hydrogen cyanide from ammonia was about 64 to 65 % at the beginning of the run, passing through a peak of about 67 % and dropped back to about the initial yield of 65 % in the first 7 to 8 days of the run, continued at a yield of about 64 to 62 % over the next 20 days and then dropped to a yield of about 57 % at about 30 days total operating time at which point the reaction was stopped The catalyst at the end of this time was considered to be spent or deactivated and according to practice known prior to this invention the catalyst would be reactivated by the replacement of 15 to 20 % of the used catalyst bed with new catalyst material. EXAMPLE 2 The converter was charged with a catalyst bed made of 6 sheets of 90 %O platinum/10 % rhodium gauze separated by -" layers of 6 to mesh porcelain chips Reactant gases in the same ratio as described in Example 1 were then passed in contact with this catalyst The highest yield of hydrogen cyanide from ammonia obtained by this catalyst was 60 % and the general pattern of the change of this yield with respect to elapsed operation time was the same as that described in Example 1 except that it was at a lower level After about days of continuous operation, the yield had decreased to about 53 to 54 %' and the reaction was stopped at this time. EXAMPLE 3 The spent catalyst bed described in Example 1 which had been used for

about 30 days and produced a yield of about 57 ' of ammonia to hydrogen cyanide was placed in a converter and a single sheet of 90 % platinum/10 %f O rhodium gauze was laid on top of the catalyst bed The reactant gases in the same ratio as described in Example 1 were then passed down through this combination catalyst The initial yield of hydrogen cyanide from ammonia was about 68 % O and this yield decreased with the elapse of time at such a slow rate that even after more than 40 davs the yield was in excess of 60 %. EXAMPLE 4 A single sheet of 90 % platinum/ 10 % 85 rhodium gauze laid over the top of a new granular catalyst bed similar to that described in Example 1 except that the alloy coating is %' platinum/100,( rhodium was charged into a converter The amount of precious 90 metal in the gauze plus that in the coating on the granular material was approximatelv the same quantity as that employed in the granular catalyst of Example 1 or the gauze catalyst of Example 2 The same reactant 95 gages and the same ratios as described in Example 1 were then passed down through this catalyst The activity of the catalyst bed increased over the first 2 or 3 days of operation to a value of about 70 %' yield of hydrogen 10 ( cyanide from ammonia This high yield of about 70 % continued for several days and finally decreased gradually over a period of about 60 days to about 62 %. EXAMPLE 5 I O T In a run similar to that described in Example 4 the converter was shut down after the entire catalyst bed had become active as evidenced by a high yield of hydrogen cyanide from ammonia Several sheets of new gauze 11 were then placed under the sheet of active gauze which was already in the converter The process was started up again and operated until the entire bed was completely active, as evidenced by a uniform incandescence 115 throughout the entire combination catalyst body, this resumption of activity requiring somewhat less than 3 hours The converter was shut down a second time and the new sheets of gauze were removed for use at a later 12 C time. Without the treatment described in Example new gauzes may require 1 to 4 days to become sufficiently activated in the hydrogen cyanide synthesis to produce the high yields 125 785,657 which have been described in the preceding examples The treatment described in Example 5 permits such gauzes to become activated in a matter of hours and thus permits a converter to produce a high yield of hydrogen cyanide in a short time after the beginning of a new cycle of operation employing a new, already activated, gauze Essentially complete activation of the catalyst gauze occurs probably during the first half-hour of operation, although it is not feasible to shut down a converter before the end of about the first 3 hours The maximum length

of time that the unactivated gauze should remain in the converter depends upon its position in the catalyst bed If the unactivated gauze is placed adjacent to another gauze, they may become welded together after about 30 hours in operation, and furthermore, they may lose weight after the manner of the activated gauze and become physically weak and not able to be handled without breaking or disintegrating If the new gauze is separated from other gauzes by layers of refractory material or layers of the granular catalyst employed as part of the combination catalyst body, the new gauze may remain in place longer than about 30 hours without the danger of becoming welded to another gauze, but it may lose weight and become physically weak as described above. The preferred time during which the new gauze is left in the combination catalyst body is from 3 to 30 hours. It is not known what causes the increased activity and the corresponding higher yield of desired product by combining a catalytic gauze with a granular catalyst bed in this process, although a synergistic effect is observed It is known that catalyst metal whether it be in a gauze or as a coating on granular material gradually disappears after many hours of operation in this process Whether this disappearance is due to erosion, volatilization, or sublimation is not known It has been > 5 observed, however, that in the process of this invention the gauze on the upstream side of the catalyst bed gradually loses weight and the granular material making up the remainder of the catalyst bed gradually gains weight. Furthermore, the granular catalyst material in addition to gaining weight increases its surface area by approximately 100 % Although it might be expected that the gauze catalyst would disappear by volatilization or other means, it is totally unexpected that this metal will appear again in the downstream operation of the bed since the entire bed is at the same temperature according to pyrometric measurements and since the converter is operated substantially under adiabatic conditions. Whatever may be the reasons for the superiority of the catalyst of this invention, there is a synergistic effect obtained by forming a combination catalyst body of catalytic gauzes and granular refractory material coated with catalytic metal At least 68 %, and usually about 70 %, of the ammonia is converted to hydrogen cyanide by this process, and furthermore the useful life of the catalyst is at least about 60 days Example 1 shows the effect obtained by employing the coated granular catalyst alone (a yield of 65 % to 57 % over 30 days of life) Example 2 shows the effect of using gauze catalyst and uncoated granular material (a yield of 60 % to 53 % over 30 days of life) Example 4 illustrates the synergism obtained by employing the

combination catalyst body of this invention, granular catalyst plus an overlayer of a single sheet of gauze (a yield of 70 % to 62 % over at least days of life) This effect in Example 4 was obtained employing approximately the same amount of catalyst metal (platinum-rhodium alloy) and the same reactant gas supply as in Example 1 or Example 2 The effect of this synergism therefore is to produce a higher yield than either of the other two catalysts could reach, maintain this higher yield for a long period of time, and have a useful life which is approximately 100 % greater than that of either of the other two systems.
