5606 5610.output

* GB786014 (A)

Description: GB786014 (A) ? 1957-11-06

Improvements in or relating to polymerization of normally gaseous mono-olefins

Description of GB786014 (A)

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DE1214001 (B) FR1142344 (A) NL101985 (C) US2912419 (A) NL101554 (C) DE1214001 (B) FR1142344 (A) NL101985 (C) US2912419 (A) NL101554 (C) less Translate this text into Tooltip

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PATENT SPECIFICATION 786 PO 14 -: Date of Application and filing Complete Specification March 7, 1956. l "i Appliati o m ae No7196/56. Application made in United States of America on March 8, 1955. Application made in United States of America on April 28, 1955. Complete Specification Published Nov 6, 1957. Index at Acceptance:-Classes 1 ( 1), A 3 81; and 2 ( 6), P 2 A, P 2 Dl(A: B), P 2 (FX: K 7), P 2 P 1 (B: C: E 3: X), P 2 P( 3: 5), P 2 P 6 (A: B: D: X), P 2 T 2 ( 13 D: E), P 7 A, P 7 DI(A: 13: X), P 7 D 2 A( 1: 21 B: 4), P 7 FX, P 7 K( 2: 7: 10), P 7 P 1 (B: C: E 3: X), P 7 P( 3:

5), P 7 P 6 (A: B: D: X), P 7 T 2 (E: D: E), P 10 A, P 1 OD 4 (A: X), PIO(FX: K 7), PIOPI(B: C E 3: X), P 1 OP( 3: 5), P 1 OP 6 (A: B: D: X), PA O T 2 (B: D: E). International Classification: -201 j CO 8 f. COMPLETE SPECIFICATION Improvernents in or relating to Polymnerization of Normally Gaseous Mono-Olefins We, STANDARD OIL COMPANY, a corporation organised under the laws of the State of Indiana, United States of America, of 910, South Michigan Avenue, City of Chicago, State of Illinois, United States of America, do hereby declare the invention, for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement: - This invention relates to a process for the preparation of high polymers, being normally solid materials, from charging stocks comprising essentially normally gaseous mono-olefins in the presence of novel catalysts comprising essentially an oxide of a metal of Group 5 a and/or a supported oxide of a metal of Group 6 a of the Periodic Table and certain compounds of aluminum. One object of our invention is to provide novel combinations of catalyst for the conversion of normally gaseous mono-olefins to high molecular weight normally solid polymers. Another object is to provide a low temperature, low pressure process for the conversion of ethylene-containing gases to high molecular weight, resinous materials characterized by high density and crystallinity Still another object is to provide a novel catalytic process for the conversion of propylene-containing gases to normally solid polymers, especially relatively crystalline modifications of solid polypropylenes Yet another object is to provide processes for the co-polymerization of ethylene and/or propylene-containing mixtures with various co-monomers to produce resinous products. The present invention provides a polymerization process for the production of a normally solid polymer which comprises contacting a charging stock comprising a monoolefinic hydrocarbon having 2 to 4 carbon lPrice 3 s 6 d l 1 a' / 12) 6,4 atoms, inclusive, per molecule with a catalyst comprising an oxide of a metal of Group 5 a and/or a supported oxide of a metal of Group 6 a of the Periodic Table and with a co-catalyst having the formula AIR,, in which R is selected from the class consisting of hydrogen and mono-valent hydrocarbon radicals. The present invention further provides a process for the polymerization of ethylene which comprises contacting ethylene with a catalyst comprising an oxide of a metal of Group 5 a and/or a supported oxide of a metal of Group 6 a of the Periodic Table and with a co-catalyst having the Formula AIR,, in which R is selected from the

class consisting of hydrogen and monovalent hydrocarbon radicals, effecting said contacting at a suitable polymerization temperature between 50 C and 2300 C, and recovering a resinous material having a melt viscosity of at least 1 X 10 poises. It is also within the purview of this invention to provide a process for the production of a normally solid polymer, which comprises contacting in a reactor, ( 1) a charging stock comprising a mono-olefinic hydrocarbon having 2 to 4 carbon atoms, inclusive, per molecule and ( 2) a compound having the formula AIR,, wherein R is selected from the group consisting of hydrogen and mono-valent hydrocarbon radicals, said compound being present in solution in an inert liquid solvent, with ( 3) a film comprising an oxide of a metal of Group a or 6 a of the Periodic Table extended upon the inner surface of said reactor; maintaining polymerization reaction conditions in said reactor; recovering a normally solid polymer thus produced. Briefly, the process of this invention comprises the conversion of a normally gaseous mono-olefin to high molecular weight, normally solid polymers by contact with a catalyst A/ R_ i 2. MCQ 11 a:_ u;n U 786,014 comprising an oxide of a metal of Group 5 a and/or a supported oxide of a metal of Group 6 a of the Periodic Table, and, as co-catalyst, an aluminium compound conforming to the general formula AIR,, wherein R is selected from the group consisting of hydrogen and monovalent hydrocarbon radicals The polymerization or co-polymerization process can be effected at suitable temperatures within the range of 50 to 2300 C and pressures ranging upwardly from atmospheric to any desired maximum pressure, for example, 15000, 30000 pounds per square inch gauge ( 1055, 2110 kg /cm ') or even higher pressures, suitably pressures between 200 and 5000 p s i g. ( 15 and 350 kg /cm 2) or 500 to 1000 p s i g. ( 35 to 70 kg /cm 2). The proportion of Group 5 a or 6 a metal oxide catalyst (including any catalyst support) 2 C with respect to the olefin charging stock may vary from 0 001 to 20 weight per cent, being not usually a critical feature of our process. The proportion of AIR, compound, based on the olefinic charging stock, can be varied within the range of 0 001 to 20 weight per cent, the precise proportion selected for use being dependent upon the desired rate of polymerization, (which increases with increasing concentration of AIR, in the reaction mixture), the concentration of contaminants in the olefinic feed stock which tend tor react with or destroy the ALR,, the particular olefin charging stock, temperature and other reaction variables. It is desirable to supply to the reaction zone an inert liquid medium

which serves both as a transport medium for solid products and as a solvent for the olefin feed stock and AIR. co-catalyst Suitable liquid reaction media for polymerization include various hydrocarbons, e g, liquid paraffins such as N 7-hentane or octanes, or aromatic hydrocarbons such as benzene, toluene or xylenes The polynmerization can be effected in the absence of a liquid reaction medium or solvent and solid catalyst containing accumulated solid polvmers can be treated from time to time, within or outside the conversion zone, to effect removal of polymers therefrom and if necessary, reactivation or regeneration of the catalyst for further use. In what follows, the invention will be described in greater detail and illustrated by working examples. The charging stock to the present polymerization process comprises essentially a normally gaseous mono-olefinic hydrocarbon, mixtures of such hydrocarbons, and mixtures comprising said hydrocarbons and co-monomers. The normally gaseous mono-olefins comprise ethylene, propylene and the butylenes such as 7-butene Co-monomers comprise polymerizable materials such as t-butvl-ethylene, conjugated diolefinic hydrocarbons such as butadiene and isoprene, styrene, Ar-alkyl styrenes; various vinyl compounds such as tetrafluoroethvlene, and trifluoromonochloro-ethylene. When co-monomers are employed with the principal charging stock, their proportion may range between 1 and 25 % by weight, based on the weight of the principal charging stock, such as ethylene 70 The oxide catalyst ingredients employed in the present invention are derivatives of metals of Group 5 a or Group 6 a (transition series members) of the Periodic Table, viz V, Cb, Ta, Cr, Mo, W and U or mixtures thereof 75 The Group 5 a oxides are preferably extended upon suitable supports and may be pentoxides, but are preferably at least partially pre-reduced to subpentavalent metal oxides before use and preferably before contact with the AIR, co 80 catalyst The Group 5 a catalyst or catalysts employed in the present invention can comprise VD,, V 0- V-0:1, VO Cb 0-, Cb O, Cb O; Ta 05, and Tab O We prefer to employ as Group 5 a catalysts, the oxides of vanadium 85 The Group 6 a oxides are extended upon suitable supports and are, preferably, at least partially pre-reduced to sub-hexavalent metal oxides before use and preferably before contact with the AIR: co-catalyst Mixed oxides 90 of Group 5 a or 6 a metals can also be employed in the present process Thus, in addition to the Group 5 a or 6 a metal oxide, the catalysts may comprise oxides of copper, tin, zinc, nickel, cobalt, titanium and zirconium Mixed metal 95 oxide catalysts can readily be made by calcining the desired metal salts of oxy acids of Group 5 a or 6 a

metals, wherein the Group a or 6 a metal appears in the anion, for example, salts of metavanadic acid or molyb 100 dic acid Thus, calcination of cobalt metavanadate yields catalysts containing cobalt oxide and an oxide of vanadium. The Group 6 a metal oxide can be extended upon suitable supports (having surface areas, 105 for example, between 1 and 1500 square meters per gram), for example, activated carbon; the difficultly reducible metal oxides such as alumina, magnesia, titania, zirconia and silica or their composites, e g, synthetic alu 110 minosilicates, and clays The catalytic activity of Group 5 a metal oxide catalysts is maximized by maximum exposure of surface to the reaction mixture and to this end are also extended upon similar suitable high area sup 115 ports (for example, between 100 and 500 square meters per gram) In some instances it may be desired to employ a relatively low surface area support for the Group 5 a or 6 a metal oxide, of which supports a variety are known 120 in the art, e g tabular alumina, various fused silicates, silicon carbide, diatomaceous earths, various metals, preferably treated to produce a relatively thin surface coating of the corresponding metal oxide thereon, such as iron or 125 steel containing a slight iron oxide coating or aluminium carrying a surface coating of aluminium oxide such as anodyzed aluminium. We may also employ relatively high surface area, relatively non-porous supports or carriers I 3 786,014 from the Group 5 a or 6 a metal oxide such as kaolin, zirconium oxide, iron oxide pigments and carbon black. The relative proportion of support to the catalytic metal oxide is not critical and may be varied throughout a relatively wide range such that each component is present in amounts of at least approximately 1 weight per cent It is preferable to employ a major proportion of the support The usual metal oxide: support ratios are in the range of 1: 20 to 1:1, or approximately 1:10 We may employ metal oxide catalysts composed of a supporting material containing about 1 to 80 %, preferably about 5 to 35 %, or approximately 10 %, of vanadia or molybdena or other Group 5 a or 6 a catalytic metal oxide supported thereon. The catalyst support may also comprise or consist essentially of suitable metal fluorides, particularly the fluorides of alkali metals, alkaline earth metals, Al, Ga or In High melting fluorides which are only slightly soluble, at most, in water are preferred A particularly desirable type of catalyst support comprises or consists essentially of A 1 F, The Group 5 a or 6 a metal oxide can be co-precipitated with or impregnated on a gelatinous slurry of hydrated A 1 E, and the composite catalyst can then be calcined prior to use. The Group 5 a or 6 a metal oxide can be incorporated in the catalyst support in any known manner, for example, by impregnation,

coprecipitation, co-gelling and/or absorption techniques which are well known in the catalyst art It may be desired to confine the metal oxide almost completely to a surface film on the support, rather than to achieve deep impregnation of the support with the metal oxide, in order to minimize mechanical disintegration of the catalyst by solid polymer. A brief review of the art of preparing supported vanadium oxide catalysts is presented in " Catalysis " edited by Paul H Emmett (published by Reinhold Publishing Corp, N Y ( 1954)-Vol 1, pages 328-9) Similar preparative methods can be employed to produce catalysts comprising oxides of columbium, tantalum, chromium, molybdenum, tungsten and uranium, or catalysts comprising oxides, of more than one Group Sa metal or oxides of more than one Group 6 a metal. In order to maximize the catalyst activity and reduce the requirements of the AMR, cocatalysts, it is preferable to effect partial reduction of catalysts comprising Group 5 a metal pentoxide or hexavalent Group 6 a metal oxides before use in the polymerization process The partial reduction and conditioning treatment of the solid metal oxide catalysts is preferably effected with hydrogen although other reducing agents such as carbon monoxide, mixtures of hydrogen and carbon monoxide (water gas, synthesis gas, etc), sulphur dioxide, hydrogen sulphide and dehydrogenatable hydrocarbons may be employed Hydrogen can be employed as a reducing agent at temperatures between about 350 C and about 8500 C, although it is more often employed at temperatures within the range of 4500 C to 6500 C 70 The hydrogen partial pressure in the reduction or conditioning operation can be varied from subatmospheric pressures, for example even 0.1 p s i ( 0 007 kg /cm ') (absolute), to relatively high pressures up to 3000 p s i g ( 210 75 kg./cm '), or even more The simplest reducing operation may be effected with hydrogen at about atmospheric pressure. Reducing gases such as carbon monoxide and sulphur dioxide may be used under sub 80 stantially the same conditions as hydrogen. Dehydrogenatable hydrocarbons, are usually employed at temperatures of at least 4500 C, and not above 8500 C Examples of dehydrogenatable hydrocarbons are acetylene, methane 85 and other normally gaseous paraffin hydrocarbons, normally liquid saturated hydrocarbons, aromatic hydrocarbons such as benzene, toluene and xylenes, normally solid polymethylenes and polyethylenes or paraffin waxes 90 The proportion of Group 5 a or 6 a metal oxide catalyst (including any support), based on the weight of the mono-olefinic charging stock, can range upwardly from 0 001 weight per cent to 20 weight per cent or even miore 95 In a polymerization operation carried out with a fixed bed of catalyst, the catalyst concentration relative to olefin can be

very much higher. The efficiency of the supported Group 5 a or 6 a metal oxide catalysts is extremely high in 100 the presence of AIR, co-catalysts, so that said metal oxide catalysts can be employed in very small proportions, based on the weight of charging stock, for example, between 0 01 and weight per cent, while maintaining high 105 conversion efficiency Moreover, in view of the high efficiency of the catalyst combinations employed in the present process, it is possible to operate in a practical manner with relatively low surface area Group 5 a metal oxide cata 110 lysts, for example fused vanadia catalysts or vanadia-silica glazes, supported in a very desirable manner, for example, upon the walls of the reactor. The AIR, compounds which can be used in 115 practicing our invention include compounds conforming to the general formula:A,-R, R 3, wherein R,, R and R, may be the same or different monovalent radicals selected from the 120 class consisting of hydrogen and monovalent hydrocarbon radicals Examples of suitable R groups include aryl radicals, aliphatic radicals or derivatives thereof such as: Alkyl, cycloalkyl-alkyl, cycloalkenylalkyl, 125 aryl-alkyl, cycloalkyl, alkylcycloalkyl, aryl786,014 cycloalkyl, cycloalkyl alkenyl, alkyl-aryl or cycloalkyl-aryl radicals. Specific examples of R groups for substitution in the above formula include:Methyl, ethyl, n-propyl, isopropyl, isobutyl, n-amyl, isoamyl, hexyl, n-octyl and Pz-dodecyl, 2-butenyl and 2-methyl-2-butenyl; Cyclopentyl-methyl, cyclohexyl-ethyl, cyclopentyl-ethyl, methy Lcyclopentylbdlhyl and 4cyclohexenylethyl; 2-phenylethyl, 2-phenylpropyl, R-naphthylethyl and methylnaphthylethyl, cyclopentyl, cyclohexyl and 2,2,1,bicycloheptyl; Methylcyclopentyl, dimethylcyclopentyl, ethylcyclopentyl, methylcyclohexyl, dimethylcyclo-hexyl, ethylcyclohexyl, isopropylcyclohexyl and 5-cyclopentadienyl; Phenylcyclopeniyl, phenylcyclohexyl and the corresponding naphthyl derivatives of 2 (, cycloalkyl groups; Phenyl, tolyl, xylyl, ethylphenyl, xenyl, naphthyl, methylnaphthyl, dimethylnaphthyl, ethylnaphthyl and cyclohexylphenyl and other AIR compounds of the type disclosed and suggested in British Specification No 713,081. The proportion of AIR, co-catalyst, based on the weight of the olefinic charging stock, can range from 0 001 to 20 weight per cent or even more, although it is usually employed in proportions between 0 001 and 10 weight per cent, e g, usually 0 01 to 5 weight per cent. The olefinic charging stock can be polymerized in the gas phase, but it is highly desirable to eect polymerization in the presence of a substantially inert liquid reaction medium which functions as a partial solvent for the monomer, which may function as a solvent for

the AIR, co-catalysts and which also functions as a liquid transport medium to remove normally solid polymerization products as a dispersion in said medium from the polymerization reactor, thus permitting efficient and continuous polymerization operations. Particularly suitable liquid reaction media are various classes of hydrocarbons or their mixtures which are liquid and substantially inert under the polymerization conditions of the present process Certain classes of aliphatic hydrocarbons can be employed as a liquid hydrocarbon reaction medium in the present process Thus, various saturated hydrocarbons (alkanes and cycloalkanes) which are liquid under the polymerization reaction conditions and which do not crack substantially under the reaction conditions, may be employed Either pure alkanes or cycloalkanes or commercially available mixtures, freed of catalyst poisons, may be employed For example, we may employ straight run naphthas or kerosenes containing alkanes and cyloalkanes Specifically, we may employ liquid or liquified alkanes such as -r-pentane, n-hexane, 2,3-dimethylbutane, noctane, iso-octane ( 2,2,4-trimethylpentane), ndecane, 7 i-dodecane, cyclohexane, methylcyclohexane, dimethylcyclopentane, ethylcyclohexane, decahydronaphtlivlene methyldecahydronaphthalene and dimethyldecahydronaphthalene. Members of the aromatic hydrocarbon series, particularly the mononuclear aromatic 70 hydrocarbons, viz, benzene, toluene, xylenes, mesitylene and xylene p-cymene mixtures can also be employed Tetrahydronaphithalene can also be employed In addition, we may employ such aromatic hydrocarbons as ethylbenzene, 75 isopropylbenzene, sec-butylbenzene, t-butylbenzene, ethyltoluene, ethylxylenes, henimellitene, pseudocumene, prehnitene, isodurene, diethylbenzenes and isoamylbenzene Suitable aroniatic hydrocarbon fractions can be 80 obtained by the selective extraction of aromatic naphthas, from hydroforming operations as distillates or bottoms, and from cycle stock fractions of cracking operations. We may also employ certain alkyl naphtha 85 lenes which are liquid under the polymerization reaction conditions, for example, 1methylnaphthalene, 2-isopropylnaphthalene and l-n-amylnaphthalene, or commercially produced fractions containing these hydrocar 90 bons. We may also employ a liquid hydrocarbon reaction medium comprising liquid olefins, e g. r-hexenes, cyclohexene, octenes and hexadecenes 95 The liquid hydrocarbon reaction medium should be freed of poisons before use in the present invention by acid treatment, e g with anhydrous p-tcluenesulphonic acid, sulphuric acid, or by equivalent treatments, for example 100 with aluminium halides, or other FriedelCrafts catalysts, maleic anhydride, calcium, calcium hydride, sodium or other

alkali metals, alkali metal hydrides, lithium aluminium hydride, hydrogen and hydrogenation 105 catalysts (hydrofining), filtration through a column of copper grains or 8th group metal, or by combinations of such treatment. Temperature control during the course of the polymerization process can be readily 110 accomplished owing to the presence in the reaction zone of a large liquid mass having relatively high heat capacity The liquid hydrocarbon reaction medium can be cooled by heat exchange inside or outside the reaction zone 115 It is desirable to minimize or avoid the introduction of water, oxygen carbon dioxide, acetylene or sulphur compounds into contact with the catalyst or co-catalyst Any known means may be employed to purify the olefinic 120 charging stocks of these material prior to their introduction into the polymerization reactor. The contact time or space velocity employed in the polymerization process will be selected with reference to the other process 125 variables, catalysts, the specific type of product desired and the extent of olefin conversion desired in any given run or pass over the catalyst In general, this variable is readily adjustable to obtain the desired results In 139 786,014 operations in which the olefin charging stock is caused to flow continuously into and out of contact with the solid catalyst, suitable liquid hourly space velocities are usually between about 0 1 and about 10 volumes, preferably 0.5 to 5 or about 2 volumes of olefin solution in a liquid reaction medium The amount of olefin in such solutions may be in the range of about 2 to 50 % by weight, preferably 2 to 15 weight per cent or, for example, 5 to 10 weight per cent. The following specific examples are introduced as illustrations of ouir invention and should not be interpreted as an undue limitation thereof The ethylene employed in the polymerization reactions was a commercial product containing onygen in the range of about 15 to 50 ppm (parts per million) The benzene employed in some of the examples was a commercial product of analytical grade, free of thiophene and dried before use by contact with sodium hydride The aluminium trimethyl promoter was prepared by the reaction of aluminium with methyl iodide (J A C S. 68, 2204 ( 1946)) and was vacuum fractionated at a reflux ratio of 100 to 1 before use (boiling range 65-7 C under 84 mm of Hg). The aluminium triethyl was prepared by the reaction of diethyl mercury with aluminium. Prior to use in polymerization the Group 6 a catalysts were calcined at temperatures within the range of about 430 to 5700 C, at atmospheric pressure, for periods within the range of about 12 to about 20 hours.

EXAMPLE 1. The Group 5 a metal oxide catalyst was 17 weight per cent VO, supported upon an activated alumina carrier It was prepared as follows: 100 ml (milliliters) of distilled water was brought to boiling and then 33 2 g. (grams) of oxalic acid and 15 6 g of V 2 O, were added The VQ, was added over the course of about one hour, yielding a soluble green aqueous complex The solution was filtered hot and then poured over 76 5 g of 1inch ( 0 32 centimeter) pills of activated (gamma-) alumina The mixture was evaporated to dryness with stirring and then calcined at about 5100 C and atmospheric pressure for 12 hours. A steel rocker bomb of about 300 ml capacity was charged with 20 g of the metal oxidealumina catalyst The reactor was also charged with 105 g of benzene and 49 g of ethylene. The aluminium trimethylco-catalyst ( 2 0 g) was introduced into the reactor in a sealed glass vial, which was broken beneath the surface of the benzene solvent Polymerization was effected at temperatures which were varied during the operation from 250 C to 104 C and ethylene pressures varying from 300 to 1000 pounds per square inch (p s i) ( 21 to 70 kg /cm 2) The total contact period was 4 hours Although there was no apparent diminution in catalytic activity at the end of 4 '5 hours, it became necessary to shut down the reactor because it was plugged with a solid polymer of ethylene and it became difficult to supply ethylene even at 1000 p s i ( 70 kg / cm.") Accordingly, ethylene supply was dis 70 continued, the reactor was allowed to cool to room temperature and gases were vented therefrom to atmospheric pressure The reactor was found to be packed with a tough, white, solid polymer of ethylene, 34 g, having a melt 75 viscosity of 1 4 x 101 poises (method of Dienes and Klemm, J Appl Phys 17, 458-71 ( 1946)) and density ( 25/24 C) of 0 9756. Analysis of the reaction mixture showed that none of the ethylene had been converted to 80 normally gaseous or normally liquid products. In this example ethylene was added initially and then intermittently through the course of the operation to maintain a pressure between 21 and 70 kg/cm' 85 Vanadia catalysts alone under the above operating conditions or, in fact, over a broad range of operating conditions, do not effect the conversion of ethylene to a normally solid polymer Aluminium trimethyl alone is like 90 wise ineffective for the conversion of ethylene to a normally solid polymer under the above operating conditions The combination of catalysts produces striking and unexpected results, viz high conversion rates and solid 95 polymers Furthermore the solid polymers have an almost unbranched structure, high crystallinity and high molecular weight. That the polymerization process of the present invention is due to the

specific interaction 100 of the specified catalyst components with the olefinic feed stocks will be apparent from the following comparative run in which aluminium, trimethyl was used with activated alumina in an attempt to polymerize ethylene 105 A 500 c c Magne-dash reactor (agitated bomb-type reactor) was charged with 10 g of activated alumina, which had been calcined in a muffle furnace at 5100 C and atmospheric pressure for 12 hours The reactor was then 110 charged with 40 g of benzene and a vial of aluminium trimethyl was broken beneath the surface of the benzene to supply 27 g of the co-catalyst The reactor was then closed and charged with 60 g of ethylene The contents 115 of the reactor were heated over the range of 20 to 1150 C under ethylene pressures varying between 500 and 900 p s i ( 35 and 63 kg / cm.') over a period of 3 hours No ethylene pressure drop was noted under any of the 120 experimental conditions It was found that none of the ethylene had been polymerized in this operation. EXAMPLE 2. The metal oxide catalyst was 17 weight per cent Va, supported on activated alumina prepared and activated by the method described in Example 1 The reactor was charged with O 05 g of the finely powdered metal oxide 786,014 catalyst and 102 g of benzene Aluminium trimethyl was introduced into the reactor by the method of Example 1 in the amount of 1.5 g The reactor was then closed, pressured with ethylene and the temperature ol the contents brought to 104 C under 1000 psi ( 70 kg./cm 2) ethylene pressure The total quantity of ethylene charged was 50 g The total contacting period was 20 hours The products worked up as in Example 1 to yield 10 g of a solid polymer of ethylene having a melt viscosity of 4 1 X 101 It will be noted that substantial ethylene conversion was achieved to form a very high molecular weight polymer through the use of only 0 017 weight per cent. of V 20 s, based on the total weight of ethylene charged Ethylene was not converted to gaseous or liquid polymers These data indicate the enormous efliciency of the particular catalyst -co-catalyst system herein employed. EXAMPLE 3. The rocking autoclave was charged with 9 g. of powdered commercial V 2,0, used without any supporting material The V,05 had been calcined at 600 C and atmospheric pressure for 12 hours before use The reactor charge also comprised 102 g of benzene, 2 9 g of aluminium trimethyl and 46 g of ethylene. The reactor contents were heated to 1150 C. under 1000 p s i ( 70 kg /cm') of ethylene for a total contacting period of 3 hours The reaction products were worked up as in Example 1. The reaction yielded 38 g of a solid polymer ofethylene No gaseous or

liquid products were produced. EXAMPLE 4. A catalyst was prepared by coating V 205 on metallic aluminium containing a surface coating of aluminium oxide Commercial aluminium turnings ( 99 99 % aluminium) were calcined at 535 to 540 C for one hour to provide a suitable surface coating of A 120} on aluminium metal A solution was prepared by adding 1 1 g of oxalic acid to 60 c c of boiling distilled water and thereafter adding 0.4 g of V O, The resultant solution was poured over 322 g of the surface-oxidized aluminium turnings and the mixture was stirred and evaporated to dryness The resultant product was calcined at 535-540 C. for 12 hours The reactor was charged with the resultant catalyst, 102 benzene, 2 1 g of aluminium trimethyl and 52 g of ethylene. The reactor contents were heated, while being rocked, to 1380 C under maximum ethylene pressure of 1000 p s i ( 70 kg /cm ') for a total contact period of 5 hours The products were worked up as in Example 1 to yield 34 g of a solid polymer of ethylene having a high molecular weight and density Analysis indicated that none of the ethylene had been converted to gaseous or liquid products. When essentially the same procedure of polymerization was used but the aluminium turnings were not pre-oxidized to produce a protective aluminium oxide coating, it was found that the yeild of solid ethylene polymer was only 1 1 g from a charge of 42 g (conditions: 113 C, ethylene pressure of 1100 p.s i ( 77 kg /cm 2), 4 hours, using 40 g of V 205-Ai catalyst and 2 5 g of aluminium trimethyl co-catalyst). From the foregoing data it will be appreciated that the V 2 Q 0-Al 2 G,-AI and aluminium trimethyl catalyst is characterized by outstanding polymerization efficiency It will be noted that the concentration of V,20,, based on ethylene, was only 0 77 weight per cent. EXAMPLE 5. This example is similar tc Example 1 but the amount of metal oxide catalyst was reduced and the benzene solvent was replaced by nheptane The autoclave was charged with 10 g. of 17 weight per cent V,0,-alumina prepared by the method of Example 1 and calcined before use in a muffle furnace at 5700 C and atmospheric pressure for 12 hours In addition, the reactor was charged with 79 g of 7 i-heptane, 2 7 g of aluminium trimethyl and 53 g of ethylene in all The reactor contents were heated with shaking to 1160 C under maximum ethylene pressure of 1000 p s i ( 70 kg./cm -) for a total contact period of 3 hours. The reaction mixture was worked up as in Example 1 The reaction was found to yield 41 g of a tough, solid polymer of ethylene and no liquid or gaseous products. EXAMPLE 6.

This example is similar to Example 5 but is characterized by the use of a substantially 100 lower proportion of the aluminium trimethyl co-catalyst The reactor was charged with 10 g of the same vanadia-alumina catalyst as was used in Example 5, which was calcined in a muffle furnace at 570 C and atmospheric 105 pressure for 14 hours The reactor was charged also with 77 g of n-heptane, 0 45 g of aluminium trimethyl and 44 g of ethylene The reactor contents were heated while rocking from room temperature to 107 C from an 110 initial ethylene partial pressure of 300 p s i. ( 21 kg /cm -) to a maximum ethylene partial pressure of 1000 p s i ( 70 kg /cm ') The total period of contacting ethylene with the catalysts was 3 5 hours Upon working up the 115 reaction products as before, it was found that the reaction product was 8 g of a white, tough solid polymer from ethylene No gaseous or liquid products were formed This example indicates the successful use of relatively small 120 proportions of both catalyst and co-catalyst. EXAMPLE 7. The steel rocking bomb was charged with 21 g of a vanadia-alumina catalyst having the same composition as the catalyst of Example 1, which was calcined before use in a muffle 786,014 furnace at atmospheric pressure and 6000 C. for 16 hours The reactor was also charged with 1 61 g of aluminium trimethyl, 63 g of n-heptane and 68 g of propylene The reactor contents were heated with shaking to 990 C. at pressures ranging from 60 p s i ( 4 2 kg / cm.2) to a maximum of 400 p s i ( 28 kg /cm ') for a total contacting period of 20 hours The reaction products were worked up as before to yield 1 2 g of liquid product and 6 O g of a solid polymer from propylene having a specific gravity ( 24/24 C) of 0 9507 and melt viscosity of 1 6 X 1010 The solid product was not sufficiently soluble in boiling xylenes to permit determination of its specific viscosity by the Staudinger method. EXAMPLE 8. The rocking bomb reactor was charged with g of catalyst having the same composition as the catalyst of Example 1, which was calcined before use in a muffle furnace at atmospheric pressure at 5700 C for 20 hours The reactor was also charged with 1 21 g of aluminium trimethyl, 24 g of ethylene, 61 g of propylene and 58 g of n-heptane The contents of the reactor were heated with agitation to 990 C at pressures varying from 60 p s i ( 42 kg / cm.2) to a maximum of 800 p s i ( 56 kg /cm '), over a total contacting period of 20 hours The reaction products were worked up as before and it was found that no liquid products were produced The reaction yielded 27 g of solid products having a specific gravity ( 24/24 ' C) of 0 9476 and melt

viscosity of 2 3 X 107 The solid product was not sufficiently soluble in boiling xylenes to permit determination of its specific viscosity by the Staudinger method. EXAMPLE 9. The process of Example 1 is repeated but 2 g of aluminium triphenyl are substituted for aluminium trimethyl The reaction products are worked up as before to yield a white, tough, solid polymer from ethylene. EXAMPLE 10. The process of Example 1 is repeated but the metal oxide catalyst is 10 weight per cent. of Cbh O, supported upon activated alumina. The products are worked up as before to yield a tough, solid, white polymer of ethylene. EXAMPLE 11. The process of Example 1 is repeated but weight per cent of Ta O, supported upon activated alumina is substituted in equal parts by weight for the vanadia-alumina catalyst of Example 1 The reaction mixture is worked up as in Example 1 to separate and recover normally solid polyethylene. EXAMPLE 12. The 300 c c steel autoclave was charged with 19 g of calcined 8 5 weight per cent. Mo O,-activated alumina catalyst, 105 g of benzene and 3 4 g of triethyl aluminium, which was charged under the surface of the benzene A total of 77 g of ethylene was charged to the autoclave The contents of the autoclave were agitated and heated in one hour from room temperature to 1210 C, then maintained at 1210 C for 3 hours The initial pressure at room temperature was 600 p s i ( 42 kg./cm Y) and the maximum pressure was 1000 p.s i ( 70 kg /cm 2) The reaction products were analyzed and it was found that 67 g of ethylene had been converted to an extremely high molecular weight polymer which was essentially insoluble in boiling xylenes It was further found that none of the ethylene had been converted to normally gaseous or normally liquid products. When the molybdena catalyst was used without a support, markedly inferior polymerization was obtained as will be observed from the following data The autoclave was charged with 13 g of calcined Mo O,, 93 g of n-heptane, 0 65 g of trimethyl aluminium and 32 g of ethylene The contents of the reactor were agitated and brought from room temperature to 240 ' _ over a period of 3 hours and then held at 240 ' G for 2 hours The initial pressure was 300 p s i ( 21 kg /cm Y) and rose to a maximum of 1100 p s i ( 77 kg / cm.2) The products were worked up and it was found that 18 g of liquid polymers had been

formed but only 0 4 g ( 1 q 25 weight per cent based on ethylene charged) of a normally solid polymer A very similar yield of solid polymer ( 0 5 g) was obtained when xylenes solvent was substituted for n-heptane, the other reaction conditions being similar. When triethyl aluminium alone was used as the catalyst, ethylene was not converted to a solid polymer as will appear from the following data The reactor was charged with 105 g of benzene, in which 2 6 g of triethyl aluminium were dissolved Then 50 g of ethylene were introduced into the reactor and the contents were agitated while heating from room temperature to 1710 C The initial pressure was 600 p s i ( 42 kg /cm -) and the maximum was 2000 p s i ( 140 kg /cm ') The reaction period was 4 hours The contents of the reactor were analyzed and it found that 4 g of liquid products had been produced but no gaseous or solid polymerization products were produced. Under similar operating condition it was found that ethylene was likewise not converted to solid polymerization products by treatment in the presence of trimethyl aluminium. EXAMPLE 13. The autoclave was charged with 20 g of 20 weight per cent Cr O,-activated alumina cata 120 lyst, 105 g of benzene and 3 2 g of triethyl aluminium The reactor was then pressured with 72 g of ethylene and the contents were heated with agitation from room temperature 786,014 to 1210 C for 3 hours The initial pressure was 600 p s i ( 42 kg /cm 2) and the maximum was 1000 p s i ( 70 k}g /cm 2) The reaction products were woried up and it was found that 61 g of a tough, solid, extremely high molecular weight polyethylene was produced which was essentially insoluble in boiling xylenes. None of the ethylene was converted to gaseous or liquid products. Relatively inferior results were obtained in ethylene polymerization with unsupported Cr 2,O catalyst as will be seen from the following data The autoclave was charged with 10 g of calcined C P (chemically pure) Cr 20,, 81 g of n-heptane, 0 63 g of aluminium trimethyl and 34 g of ethylene The contents of the reactor were heated with agitation to 104 C over a reaction period of 3 hours The initial pressure was 400 p s i ( 28 kg /cm -) and the maximum was 1000 p s i ( 70 kg / cm.2) The ethylene was converted to 12 g of a solid polymer. EXAMPLE 14. This example relates to the polymerization of propylene to an extremely high molecular weight solid polymer The reactor was a 300 c.c steel rocking bomb It was charged with 44 g 20-35 U S mesh cobalt molybdatealumina mixture The composition of the mixture was calculated as 3 weight per cent Co O, 9 weight per cent Mo O, and the remainder activated alumina, before the reducing treatment The catalyst was calcined at 4550 C.

under a pressure of 1 mm of mercury for 1 5 hours to give mixed metal oxides and then reduced, in the reactor, in a stream of hydrogen at 4550 C, 600 p s i ( 42 kg /cm ') for 1 hour The reactor was then charged with 87 g. of benzene, 3 g of triethyl aluminium and 77 g of propylene The reactor contents were agitated and heated to 104 C for 24 hours, the maximum pressure being 440 p si ( 31 kg./cm 2) The reaction yielded 10 g of liquid polymers of propylene and 15 g of a solid polymer of propylene having a specific viscosityx 10 of 16,400. EXAMPLE 15. The process of Example 12 was repeated, but the trieihyl aluminium was replaced by its molar equivalent of triphenyl aluminium The polyethylene product was worked up as in Example 12. The high molecular weight, extremely high density polymers of this invention have high tensile and impact strengths and minimal capacity to absorb odours, flavours and various solvents They open a new field of uses of polyethylene, polypropylenes, etc in many attractive applications, such as in carboys or other packaging means, and in plastic pipe. The polymers produced by the process of this invention can be subjected to such aftertreatment as may be desired to fit them for particular uses or to impart desired properties. Thus, the polymers can be extruded, mechani 65 cally milled, filmed or cast, or converted to sponges or latices Antioxidants, stabilizers, fillers, extenders, plasticizers, pigments, insecticides and fungicides, can be incorporated in the polyethylenes The polyethylenes may be 70 employed as coating materials, gas barriers, and binders to even a wider extent than polyethylenes made by prior processes. The polymers produced by the process of the present invention, especially the polymers 75 having high specific viscosities, can be blended with the lower molecular weight polyethylenes to impart stiffness or flexibility or other desired properties thereto The solid resinous products produced by the process of the present inven 80 tion can, likewise, be blended in any desired proportions with hydrocarbon oils, waxes, such as paraffin or petroleum waxes, with ester waxes, with high molecular weight polybutylenes, and with other organic materials Small 85 proportions between about O 01 and about 1 per cent of the various polymers produced by the process of the present invention can be dissolved or dispersed in hydrocarbon lubricating oils to increase V I (Viscosity Index) 90 and to decrease oil consumption when the compounded oils are employed in motors The polymerization products having molecular weights of 50,000 or more, provided by the present invention, can be employed in small 95 proportions to substantially increase the viscosity of fluent liquid

hydrocarbon oils and as gelling agents for such oils. The polymers produced by the present process can be subjected to chemical modifying 100 treatments, such as halogenation, halogenation followed by dehalogenation, sulphohalogenation by treatment with sulphuryl chloride or mixtures of chlorine and sulphur dioxide, sulphonation, and other reactions to which hydro 105 carbons may be subjected The polymers of this invention can also be irradiated by high energy X-rays (about 0 5 to 2 5 MEV or more) or by radioactive materials to effect cross-linking, and increases in softening temperature 110

* Sitemap * Accessibility * Legal notice * Terms of use * Last updated: 08.04.2015 * Worldwide Database * 5.8.23.4; 93p

* GB786015 (A)

Description: GB786015 (A) ? 1957-11-06

Improvements in or relating to cushion supports for the metatarsal arch ofthe foot and to foot aids incorporating such supports



US2835379 (A) US2835379 (A) less Translate this text into Tooltip


The EPO does not accept any responsibility for the accuracy of data and information originating from other authorities than the EPO; in

particular, the EPO does not guarantee that they are complete, up-to-date or fit for specific purposes.

PATENT SPECIFICATION 786 t 015 go ' Date of Application and filing Complete Specification: March 7, 1956. O% ' No 7226156. Application made in United States of America on March 7, 1955. Complete Specification Published: Nov 6, 1957. Index at acceptance:-Class 81 ( 2), F. International Classification:-A 61 b. COM Pi LETE 'Sl PE'CIFIGATI'ON Improvements in or relating to Cushion Supports' for the Metatarsal Arch of the Foot and to Foot Aids Incorporating such Supports We, THE SCHOLL MFG Co LIMITED, formerly The Scholl Manufacturing Company Limited, a British Company, of 190 i St John Street, London, E 'C l, England, do hereby declare the invention, for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and 'by the following statement: This invention relates to improvements in a tnetatarsal cushion support and to a foot aid package incorporating such a support, and more particularly to a simple form of foot correction device easily applicable to the human foot by a user of the device to provide cushioning support for the metatarsal arch of the human foot. Many and various types of devices have been developed in, the past for the purpose of lending corrective aid to the metatarsal arch of the human foot In some instances these devices were built directly into the article of footwear and became an integral part thereof. In other instances, the devices were built in an insertable and removable insole for an article of footwear, and still other instances the devices were made in the form of bandages, to circumscribe the foot, in the manner of adhesively attachable pads or supports for attachment directly to the foot, and in the form of adhesive devices for attachment to the insole of the article of footwear rather than upon the foot itself Many of these forms of metatarsal arch supporting means heretofore known required the attention of a skilled practitioner or operator to acquire the proper size of device and to locate the device properly That was particularly true if the device were mounted into an article of footwear already in wear by the user In most cases in the past, difficulty was experienced in selecting the proper size of lift for the metatarsal arch, 'and once a support was selected and the user provided with it, lPtice 3 s 6 d l thereafter there was no selectivity on the part of the user, even though the size may not have been accurate to start with Certainly there was no

selectivity or permissible variation of the metatarsal lift portion of the device during the course of treatment and as the foot responded to the treatment If due to response of the foot to treatment a smaller size lift was desirable, it was necessary for the user to purchase a completely new device, and, in some cases have expert attention for the mounting of the new device. With the foregoing in mind, an object of the present invention is to provide a foot corrective appliance especially adaptable to aid an afflicted metatarsal arch, and a device so constructed that the user may readily apply the device to the foot and vary the lift provided thereby, and the device is somewhat self-adjustable, in that it will tend to assume the proper location beneath the metatarsal arch, while no adhesive is necessary. Also a feature of the invention resides in the provision of a simple form of metatarsal arch supporting device which may be removed and, replaced at will, and which may be laundered whenever deemed necessary According to the present invention a cushion support for the metatarsal foot arch of the foot comprises a sheet of cushioning material, a toe loop extending from said sheet for engagement over an intermediate toe, and a metatarsal lift pad secured to the upper face of said sheet. Further a cushion support according to the invention includes a holder, a cushion support as defined above, mounted; on the holder and having a removable lift pad associated therewith and a plurality, of differently sized metatarsal arch supporting pads of cushioning material also mounted on the holder for selective removable affixation to the support. In order that the invention may be more clearly understood one construction in accordso ance therewith will now be described by way of example with reference to the accompanying drawing, in which: Figure 1 is a perspective view of a package shown in semi-open condition to disclose a foot corrective appliance and, a plurality of metatarsal lift elements for use with that appliance; Figure 2 is a transverse sectional view through the body of the appliance equipped with one of the metatarsal lift elements; and Figure 3 ' is a longitudinal vertical sectional view through the appliance equipped with a metatarsal lift element, In all the Figures the same numerals are employed to designate similar parts Referring to the drawing the package may be a container or holder of substantially any structural character, and in the drawing it is shown in the form of a mounting card 1 which may be encased in a suitable envelope 2 preferably having a transparent window 3 therein Mounted upon the card 1 is a foot corrective device including a body part 4 and a toe loop portion 5 The body part is equipped with a metatarsal lift element 6 of one size,

and the card carries a plurality of other metatarsal lift elements 7, 8 and 9 being shown in the drawing As will later appear herein, the lift 6 attached to the body 4 of the device may be removed when desired, and any of the elements 7, 8 and 9 mounted on the device in lieu thereof, so that the user has a rather complete selection of proper sizes of lifts for his particular foot. With reference now more particularly to Figures 2 and 3, it will be seen that the device equipped, with one of the lift elements, the lift element 16 being shown by way of example, is substantially an integral unitary structure with the element attached thereto. Preferably the body 4 comprises a sheet of cushioning material, and the toe 'loop extension 5 is preferably integral with that body part The under surface of the body and toe loop may be covered with a thin layer of fabric as indicated at 10 if so desired A preferred material for the body part is foam latex of the variety having inter-communicating cells therein so as to provide some ventilation due to the pulsations caused by successive applications and releases of foot pressure on the device A sheet of foam latex may be vulcanized' to a sheet of fabric 10, and then the device together with the toe loop portion may readily be stamped out of that laminated sheet. As shown in' both Figures 2 and 3, the body portion of the device is preferably of at least slightly concavo-convex shape with the concave side uppermost. Each of the lift elements'6, 7, 18 or 9 is also of cushioning material, and preferably of the same character of foam latex as the body 4 The undersurface of each lift element is preferably provided with a relatively thin layer of adhesive 11 of the pressure sensitive variety and, of a character that will not too firmly adhere to a foam latex surface under pressure so that it can be readily removed therefrom when desired The adhesive surface 70 will, however, adhere sufficiently to unite the lift to the body 4 against accidental or unintentional removal. As seen best in Figures 2 and 3 the lift 6, preferably tapers in all directions away from 75 a thicker central portion, and while the underside of the lift may be flat, if so desired, the upper side presents a convex surface Both faces of the lift may be convex if so desired, but in any event when the lift is attached to 80 the concave face of the body 4, the lift definitely does present a convex upper surface. Thus, when the device is in use, there is a convex upper surface against the plantar face of the metatarsal arch which is in keeping 85 with the structure of the metatarsal arch, and yet the body portion of the device is sufficiently concave so as to receive two or more of the

metatarsal heads in a manner to provide a soft yielding cushion support for the metatar 90 sal arch. In use, the package and the device is extremely simple and effective The user may place one of the lifts 6, 7, 8 or 9 upon the body portion 4 of the device, and try them 95 until the proper size of lift is found In applying the device to the foot it is a simple ex pedient to pass the toe loop 5 over one of the intermediate toes of the foot, and in most cases it will 'be passed over the second or third 100 toe so that the body of the device as well as the lift extends rearwardly under the metatarsal arch of the foot That is all that is necessary for the application of the device, and when the hose of the user is drawn on over i OS the foot, the device is properly positioned. When the foot is placed in an article of footwear, and the user stands or walks, the device will quickly position itself in the proper location, At any time during use, the device may 110 be removed, laundered if desired, and easily replaced Or if desired, the particular lift then on the device may be removed and another lift substituted therefor as the foot progresses in its response to treatment No special 115 skill is required at any time for the proper use of the device, it is simple in construction, economical, and highly durable.


* GB786016 (A)

Description: GB786016 (A) ? 1957-11-06

Weather resistant light-color composition containing butyl rubber



FR1148100 (A) US2889307 (A) FR1148100 (A) US2889307 (A) less Translate this text into Tooltip



PATENT SPECIFICATION 786,016 Date of Application and filing Complete Specification: March 15, 1956. | s Apia No 8118156. Application made in United States of America on March 18, 1955. Application made in United States of America on Dec 29, 1955. Complete Specification Published: Nov 6, 1957. Index at acceptance:-Classes 2 ( 6), P 2 A, P 2 C( 2: 8 B: 8 C: 10: 12 X: 17: 18: 20 A: 20 B), P 2 D( 1 A: 1 B: XX: 2 X), P 2 ( 1 ( 7: T 2 A), P 7 A, P 7 C( 2: 8 B: 8 C: 10: 12 X: 17: 18: 20 A: 20 B), P 7 (D 11 B: KI 2: T 2 A); and 144 ( 2), C 3 (B 9: J). International Classification:-B 62 g CO 8 d. COMPLETE SPECIFICATION Weather Resistant Light-Col'or Composition containing Butyl Rubber 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 synthetic rubbery compositions, and relates particularly to white or coloured butyl rubber compositions of improved weathering and discoloring resistance. The expression " butyl rubber " used in the present specification and claims means the well-known copolymer of a C,-C 8 isoolefin (particularly isobutylene) and a minor proportion of a Co-C,4 conjugated diolefin (particularly isoprene) The diolefin content of such copolymers may be from 05 % to 30 % by weight Particularly useful butyl rubber compositions are those derived from 90 % to 99 % by weight of isobutylene and 10 % to 1 % by weight of butadiene-1,3,

dimethyl butadiene, dimethallyl, myrcene, piperylene, allo-ocimene, and particularly isoprene. When butyl rubber is compounded with carbon black and cured, the product exhibits exceptionally good weathering resistance. However, butyl rubber white vulcanizates have heretofore weathered badly, becoming tacky and discolored This has been a serious deterrent to the use of butyl rubber white sidewall tires The automotive industry, as well as other industries, is also desirous of making white and pastel coloured parts from butyl rubber that will look attractive and in harmony with various painted parts and upholstery Also, in the insulated wire industry, it would be desirable to make white and pastel shades of butyl rubber insulation material Furthermore, white and pastel colored butyl rubber vulcanizates Is may be used in household equipment. According to the present invention, applicant has discovered that when butyl rubber is combined with certain proportions of magnesium oxide and/or calcium oxide, plus titanium dioxide and zinc oxide, light color vulcanizates may be obtained which resist weathering, discoloration, do not craze, and do not crack When calcium oxide is employed, the surface powdering phenomenon renders the vulcanizates self-cleaning. The present invention consists of improved synthetic rubbery compositions, comprising a butyl rubber, from 10 % to 150 % of magnesium oxide or calcium oxide, or mixtures thereof, from 10 % to 150 % of titanium dioxide, and from 3 % to 50 % of zinc oxide, all percentages being by weight based on the butyl rubber. Preferred ranges of the metal oxides in the compositions of the present invention are as follows: -magnesium and/or calcium oxide, from 20 % to 100 %: titanium oxide, from % to 100 %; zinc oxide, 5 % to 30 %, all percentages being by weight based on the butyl rubber. The compositions of the present invention may be prepared by the process which comprises heating in the presence of vulcanizing amounts of sulfur (preferably 5 to 5 parts of sulfur) about 100 parts of a butyl rubber and the metal oxides hereinbefore mentioned, and particularly in the presence of 0 5 to 2 parts by weight (preferably 75 to 125 parts by weight) of known non-staining accelerators such as tetra alkyl thiuram suffide, preferably tetra butyl thiuram disulfide or tetra methyl thiuram disulfide Other less preferred nonstaining accelerators include zinc polyalkyl dithiocarbamates containing preferably two CQ-C, alkyl groups including such compounds as zinc dimethyldithiocarbamate Also, 0 to 10 parts (and preferably 0 5 to 5 parts) by weight of stearic acid may be present as a mold release agent and 0 to 5 parts (and advantageously 0 1 to 0 5 parts) of ultramarine blue per 100 parts of the compolymer may likewise be

present whereby to produce a white synthetic rubber which is resistant to weathering and discoloring and is suitable for producing the white sidewalls of premium grade automobile tires, the surfaces of which may be optionally dusted with an anti-tack agent such as talc, mica and certain comminuted clays, as hereinafter described. An application of the compositions of the present invention is illustrated by the accompanying drawing which shows a cross-sectional view in perspective of a pneumatic tubeless tire employing therein the butyl rubber of the present invention wherein the tire is depicted as being molded on a conventional tubelesstype of tire wheel-rim Also, although the following description of the drawing is confined to a tubeless-tire, obviously the butyl rubber composition of the present invention may be likewise employed in conventional inner-tube containing tires. Z 5 The pneumatic tubeless tire comprises a hollow toroidal type member which is substantially "U"-shaped in cross-section by virtue of an open portion which extends around the inner periphery of the member In other words, the member is of a tubular type structure which has a cross-section in the form of an open-bellied body with spaced terminal portions to define a member generally resembling a horseshoe, wherein the open portion of the horseshoe-shaped member faces toward the interior circumference of said member The terminal portions constitute the bead portions 11-11 of the tire, inside of which are a plurality of bead wires adhesively embedded and molded in a rubber The outer surface of the bead portion is advantageously formed into an air sealing means such as a plurality of ribs to aid in adhesion to rim 12 when the tire is inflated The remaining outer surface of the tire also includes tread area 13 and sidewalls 14 The remaining construction of the tire may vary according to conventional fabrication but in general the tire is a multi-layered type of structure with an outer layer as abovementioned The layer next adjacent the outer layer generally comprises a carcass 15 which includes a rubber such as butyl rubber which has incorporated therein a fabric composed of a plurality of cotton, rayon, or nylon cords. The tire also includes an inner lining 16, advantageously made from butyl rubber which must be substantially impermeable to air The butyl rubber used in the inner lining preferably comprises a rubbery copolymer of 2099 weight percent of a C 4-C 7 isoolefin such as isobutylene and 1-80 weight percent of a C 4-C,, multi-olefin such as isoprene which has been at least partially vulcanized at least at 240-350 'F with from 0 2-10 0 weight percent sulfur based on the weight of the copolymer The above multi-layers, at least three in number, are conventionally bonded or otherwise adhered together; for example, by vulcanization to form a tire of a unitary structure.

The butyl rubber of the present composition 70 is employed as the sidewall for the rubber tire and is either white or pastel colored and likewise conventionally bonded or otherwise adhered (especially by vulcanization) to the tire to form a unitary structure In one em 75 bodiment, the tubeless tire comprises a casing of an outer layer including a tread, sidewall, and outer bead portions, wherein the sidewall comprises a rubbery copolymer of a major proportion of an isoolefin and a minor 80 proportion of a multi-olefin and magnesium oxide, titanium dioxide and zinc oxide in amounts according to the present invention. The tire also may advantageously comprise an intermediate layer or carcass of natural or 85 synthetic rubbers or mixtures of natural and/ or synthetic rubbers The tire also contains an inner layer of butyl rubber which has been at least partially vulcanized by heating for 3minutes or more at 240-350 '1 F with 0 2 90 -10 0 weight percent sulfur on a basis of the weight of the butyl rubber In conventional fabrication, the sidewall, as well as the various other components of the tire, are adhesively formed into the unitary structure by vulcaniza 95 tion. One particularly advantageous butyl rubber which may be used in the compositions of the present invention is produced from 0 5 to 5 parts by weight of isoprene and 99 5 to 95 100 parts by weight of isobutylene and the mixture of these reactants is cooled to a temperature within the range of -40 C to 1600 C. and then polymerized by the addition thereto of a catalyst solution of an aluminum halide 105 The resulting copolymer preferably has a Staudinger molecular weight between 25,000 and 100,000 When so prepared, the material is rubbery in nature, has the property of being curable with sulfur especially in the presence 110 of organic sulfides, particularly of the tetra alkyl thiuram sulfide type, as abovementioned. In another embodiment, pastel colored butyl rubber compositions as distinguished from white compositions may be prepared wherein 115 the cure is effected in the presence of such materials as p-dinitrosobenzene or p-quinone dioxime and their various homologs and derivatives Furthermore, for pastel colored butyl rubbers, the cure may be in the presence 120 of such compositions as ( 1) sulfur and a zinc dialkyl polythiocarbamate; ( 2) sulfur, lead oxide, and p-quinone dioxime; ( 3) sulfur, benzothiazyl disulfide and p quinone dioxime, ( 4) p-quinone dioxime dibenzoate, 125 lead oxide and sulfur, and ( 5) sodium and tellurium containing compositions. However, to produce a white butyl rubber, the above compositions are less desirable than the preferred sulfur tetra alkyl 130 786,016 specific embodiments.

Five different butyl rubbers were prepared as follows: BUTYL No 1 A copolymer of isobutylene and isoprene 70 was prepared as above-outlined, by mixing 99 parts by weight of isobutylene of 98 % purity with 1 part by weight of isoprene of 96 % purity This material was diluted with approximately 250 parts by weight of liquid 75 methyl chloride, and cooled to a temperature in the neighborhood of about 164 C To this cold mixture there was then added approximately 50 parts by weight of liquid methyl chloride containing dissolved therein 80 approximately 0 15 part by weight of aluminium chloride The aluminium chloride solution was added in the form of a fine jet under pressure to the body of the rapidly stirred, cold olefinic mixture The polymeriza 85 tion reaction began immediately and proceeded rapidly to the stage approximately 65 % conversion of the olefini G material into the polymer; this amount of catalyst being insufficient to convert the whole of the olefinic material 90 into polymer The polymer recovery had an iodine number of about 2 3. BUTYL No 2 A copolymer of isobutylene and isoprene was prepared by the same general process of 95 preparing Butyl No 1 but at a temperature of C and employing 1 5 % concentration of the catalyst whereby the whole of the olefinic materials was converted into polymer. BUTYL No 3 100 A copolymer of isobutylene and isoprene was prepared by the same general process for preparing Butyl No 2, but from a mixture of 97 5 parts of isobutylene, and 2 5 parts of isoprene, and finished by the procedure shown 105 for Butyl No 1, except that continuous polymerization was used, the temperature was CG and the concentration of the catalyst was 5 % A conversion of 100 % of the olefinic materials into polymer was obtained 110 BUTYL No 4 A copolymer of isobutylene and isoprene was prepared by the same general process for preparing Butyl No 2 but at 100 'C from a mixture of 90 parts of isobutylene and 10 115 parts of isoprene and employing a catalyst concentration of about 7 5 % A conversion of % of the olefinic materials into polymer was obtained. thiuram disulfide containing curing composition In a preferred embodiment to produce pastel colored butyl rubbers, the vulcanization is accomplished by sulfur in the presence of a tetra alkyl thiuram sulfide and also in the presence of at least 15 weight percent magnesium oxide as well as titanium dioxide and zinc oxide and the desired color is then obtained by adding an additional pigment or pigments to the composition as desired. Suitable pigments when employed in minor quantities for pastel butyl rubbers but which are generally unsatisfactory for white butyl rubber compositions are as follows: lead oxide, lead carbonate, barytes, lead sulphate, cadmium lead, calcium carbonate, ferric hydroxide, lead iron oxide, chrome-yellow lead chromate, Prussian blue and phthalocyanine.

Inorganic pigments are generally preferred and are employed either alone or in combination with organic pigments according to the color desired For pastel colored rubbers as distinguished from white rubbers, the white colored representatives of the above pigments or their equivalents may in some cases replace at least a portion of the titanium dioxide. Vulcanization of the foregoing types of compositions according to the present invention is advantageously for 5 minutes to 2 hours (e g 10 to 60 minutes) at 2500 or 275 to 350 'F or for about 1 to 10 minutes at 3500 to 4000 or 450 'F The higher the vulcanization temperature, the shorter may be the vulcanizing time and vice versa The optimum vulcanization conditions appear to be for 5 to 60 minutes at 3000 to 360 'F, preferably at 3200 to 340 'F Insofar as the degree of fineness of the sulfur is concerned, the sulfur may pass through a 50 mesh to about a 500 mesh screen However, a fineness of about 200 to 350 mesh or finer appears to be preferable for the self-cleaning white rubbery compositions of the invention. The copolymer of the invention which has been cured, has an improved elastic limit, tensile strength, abrasion resistance and flexure resistance Also, the mixture before curing may be compounded with various fillers, pigments, plasticizers, and anti-oxidants. For example, generally small amounts of conventional non-staining anti-oxidants or even a slightly colored anti-oxidant such as phenyl beta naphthylamine may be employed The non-staining anti-oxidants which are particularly efficacious for white butyl rubber, comprises 0 1-0 75 %, and preferably about 0.25 %, of either alkylated aromatic hydrocarbons or alkylated heterocyclics including substituted bisphenols such as bis( 2-hydroxy-3tert butyl-5-methyl) methane, or amido-substituted p-amino phenols such as lauroyl pamino-phenol or C,-G 9 alkylated diphenylamines such as heptylated diphenylamine. The present invention will be best understood from a description of the following BUTYL No 5 A copolymer of isobutylene and butadiene was prepared by the same general process for preparing Butyl No 2, but at a polymerization temperature of -78 C and a 5 % catalyst concentration was employed and 97 5 parts of isobutylene were employed to 2 5 parts of butadiene. The use of the above five butyl rubbers in accordance with the present invention is illustrated in the following examples: 786,016 Portions of the copolymers of Butyl Nos 2, 3, 4 and 5 were vulcanized in the presence of (a) titanium dioxide, (b) zinc oxide, (c) titanium dioxide and zinc oxide, and (d) titanium dioxide, zinc oxide, and magnesium oxide, as hereinafter indicated The use of tetramethyl thiuram disulfide was also advantageously employed as the

particular accelerator to accelerate the vulcanization Stearic acid was optionally but preferably employed as a mold release agent and ultramarine blue was optionally but preferably employed to obtain a whiter product The vulcanization was for 40 to 60 minutes at 295 F to 4 to 8 minutes at 350 C; the higher the vulcanizing temperature, the shorter the permissible vulcanizing time and vice versa The optimum vulcanization conditions appeared to be within the range of 8 to 25 minutes at 325 'F to 335 F. EXAMPLE 1 Run 1: 100 parts of the copolymer designated as Butyl No 2 was admixed with 100 parts of titanium dioxide and 10 parts zinc oxide; (all ratios being parts by weight) The above composition was vulcanized with 2 parts by weight of sulfur and 1 25 parts by weight of tetramethyl thiuram disulfide for 23 minutes at 330 'F and was aged in straight and in looped form according to A S T M. Standard Method D 518-44 The composition became tacky and badly discolored in about 4 weeks. Run 2: The above run was repeated, but with addition of 50 parts magnesium oxide, and after 14 months, the composition was not cracked, crazed, or discolored and its surface was dry. EXAMPLE 2 Run 1: The copolymer designated as Butyl No 4 was composited with 100 parts by weight of titanium dioxide and 10 parts by weight of zinc oxide, per 100 parts of copolymer The composition was vulcanized with 3 parts by weight of sulfur and 1 5 parts by weight of tetramethyl thiuram disulfide for 23 minutes at 330 'F The composition became tacky and badly discolored in S weeks when aged in straight and in looped form according to A S T M Standard Method D 518-44. Run 2: The above run was repeated but with the addition of 50 parts by weight of magnesium oxide per 100 parts of the copolymer After 14 months, the composition was not cracked, crazed, or discolored and its surface was dry. EXAMPLE 3 Run 1: The copolymer designated as Butyl No 5 was composited with 100 parts of titanium dioxide and 10 parts by weight of zinc oxide per 100 parts of the copolymer 60 The copolymer was then vulcanized for 23 minutes at 330 'F with 2 parts by weight of sulfur and 1 25 parts by weight of tetramethyl thiuram disuffide The above vulcanizate was aged in straight and in looped form according 65 to A S T M Standard Method D 51 S-44 and the composition became tacky and badly discolored after about 8 weeks. Run 2: The above run was repeated but with the addition of 50 parts by weight of 70 magnesium oxide per 100 parts of the copolymer After 14 months, the vulcanizate was not cracked, crazed, or discolored, and

the surface was dry. EXAMPLE 4 The copolymer designated as Butyl No 3 was composited with various amounts of titanium dioxide, zinc oxide and magnesium oxide per 100 parts by weight of copolymer. These compositions were then vulcanized for 23 minutes at 330 'F in the presence of 2 parts by weight of sulfur and 1 25 parts by weight of tetramethyl thiuram disulfide The above vulcanizate was then aged in straight and in looped form according to A S T M. Standard Method D 518-44 The results are now tabulated in Table I: TABLE I Parts by Weight DiscolorRun Ti O 2 Zn O Mg O Time Tacky ation 1 100 Cracking Crazing _ 10 3 100 10 8 weeks Yes 8 weeks Yes Bad Slight Slight Bad Slight Slight 50 14 months No None None None 50 6 months No Poor Very Slight 7 50 4 100 100 Slight 786,016 cracking or crazing The omission of the zinc oxide gave essentially no vulcanization and the omission of the titanium dioxide gave a composition of poorer discoloration and poorer original whiteness. EXAMPLES 5-17 Additional runs were conducted with the copolymer designated as Butyl No 3 at essentially the polymerization and vulcanization conditions given -in Example 4, except -where otherwise stated The results are tabulated in Table II: The above runs in Table I of Example 4 demonstrate that the use of titanium dioxide alone, zinc oxide alone, or a combination of titanium dioxide, and zinc oxide do not improve the discoloration, cracking and crazing, whereas applicant's three-component composition including about 50 parts by weight of magnesium oxide, in addition to the 100 parts by weight of titanium dioxide and 10 parts by weight of zinc oxide per 100 parts of the copolymer produces a vastly improved composition with substantially no discoloration, TABLE II Parts by Weight Per 100 Parts of Copolymer Time Example Ti O 2 Zn O Mg O (months) Tacky Discoloration Cracking Crazing (a) (b) 74 50 18 5 14 No None None None 6 (a) (c) 150 5 50.0 14 No Very Very Slight Slight 7 (a) (c) 150 10 50 14 No None None 8 (a) (d) 20 25 100 14 No, 9 (a) (e) 10 15 25 14 No 25 15 14 No 10 5 14 No Poor Very Vexy Slight Slight 10 25 14 No None None None 15 15 10 No, 15 5 10 No Poor 15 2 10 Slight Bad 15 10 Bad,, Very Very Slight Slight Slight,, , Slight 10 Essentially no vulcanization (a) The tensile strength, % of elongation, tensile modulus and Shore hardness were all satisfactory. (b) 3 parts by wt of sulfur, 1 part by wt of tetramethyl thiuram disulfide, vulcanized for min at 2950 C. (c) 3 parts by wt of < 325 mesh sulfur, 5 part by wt of tetra-methyl thiuram disulfide, vulcanized for 4 min at 3500 F.

(d) 0 1 part by wt of ultramarine blue, 1 5 parts by wt of sulfur, 5 part by wt of tetraethyl thiuram disulfide, 25 part of phenyl beta naphthylamine, vulcanized for min at 330 F. (e) 4 parts by wt of < 250 mesh sulfur, 2 parts by wt of tetra-methyl thiuram disulfide, parts by wt stearic acid as a mold release agent, 25 part of phenyl beta naphthylamine, vulcanized for 23 min at 3300 F. (f> 05 parts by wt of ultramarine blue, 1 75 parts by wt of sulfur, 2 parts by wt of tetra butyl thiuram disulfide, vulcanized for 28 min at 3350 F. (g) 1 part by wt stearic acid, 20 part by wt of ultra-marine blue, 10 parts by wt of m Inc oxide, 2 parts by wt of sulfur, and 1 25 parts by wt of tetra methyl thiuram disulfide, vulcanized at 330 F for-23 minutes. (a) (f) 11 (a) (g) 12 (a) (g) 13 (a) (g) 14 (a) (g) (a) (g) 16 (a) (g) 17 (g) 786,016 From the data in Table II of Examples 517, it is noted that an overall range of parts by weight of magnesium oxide per 100 parts of the copolymer is 15 parts by weight (Example 10) to 100 parts by weight (Example 8), since in Example II where the amount of magnesium oxide was reduced to 5 parts by weight there was noticeable cracking and crazing and the discoloration was poor Exam 'e 12, which was run under the identical conditions as Example 11 but contained 25 parts by weight of magnesium oxide, rather than 5 parts by weight of magnesium oxide, gave no discoloration, cracking or crazing As for the amount of titanium dioxide, the range given in the table includes 10 parts by weight (Example 9) to 150 parts by weight (Example 7), since within this range, providing that the amounts of the magnesium oxide and zinc oxide are properly regulated, there is no discoloration, cracking or crazing. As regards the parts by weight of zinc oxide, a comparison of Examples 6 and 7 indicate that the composition " slightly " discolors and cracks when only employing 5 parts by weight of zinc oxide (Example 6), whereas -when employing 10 parts by weight of zinc oxide (Example 7), the discoloration as well as the cracking and crazing is substantially nonexistent The composition of Example 5 which employs 50 parts by weight of zinc oxide is also suitable in that there is no discoloration, cracking or crazing of the ultimate composition Accordingly, although the preferred range for the zinc oxide is broadly 5 to 50 parts by weight, considering that larger amounts of magnesium oxide may advantageously be employed in the composition, and the total pigment loading should not be too high for utility, a narrower but advantageous range for the zinc oxide is from 10 to 30 parts by weight and especially from 15 to 25 parts by weight. Examples 13 to 16 show that whereas the use of at least 15 parts by weight of magnesium oxide (as in Example 13) improves discoloration,

cracking and crazing, that each of these characteristics are not satisfactory when only 5 parts by weight of magnesium oxide are employed (Example 14), and the results become progressively poorer as the amount of magnesium oxide is decreased (as in Examples and 16). EXAMPLES 18-20 Although the above Examples, as indicated, revealed a fairly wide overall operating range for the amounts of added titanium oxide, magnesium oxide, and zinc oxide; in order to determine the most preferred ratios and proportions of these ingredients, the following three experiments were run and results analyzed in detail as to their tensile strength, elongation, tensile modulus, and Shore hardness. In each example, 100 parts by weight of the copolymer designated as Butyl No 3 was admixed with the amounts by weight of titanium dioxide, magnesium oxide and zinc oxide as hereinafter indicated, with 1 part by weight stearic acid, and with the belowindicated amounts by weight of ultramarine blue The resulting compositions were vulcanized for 23 minutes at 330 '1 F in the presence of 2 parts by weight of sulfur, and 1 25 parts by weight of tetra methyl thiuram disulfide. However, the surface of the freshly cured white rubbery copolymer of Example 20 was dusted with an excess of talc and then wiped clean in order to preclude any tackiness The above vulcanizates were then aged in straight and in looped form according to A S T M. Standard Method D 518-44 After 14 months, the specimens were not cracked, crazed or discolored, and the surfaces thereof were dry and not tacky The results were all satisfactory and are now tabulated: TABLE III Parts by Weight per 100 Parts of Copolymer UltraMarine Ex Ti O Zn O Mg O Blue Tens. Mod. Tens Str % @ 300 % psi Elong Elong. 18 75 10 25 0 20 1345 585 390 55 19 100 10 50 0 25 1560 695 450 69 50 10 100 0 15 1350 680 490 74 Comparing the above preferred ranges embodied in the last three examples, the composition of Example 18 is the softest and most flexible of the three Its original whiteness and its resistance to discoloration and tackiness upon aging are very good The composition of Example 19 is not quite as flexible as that of Example 18, but it is flexible 95 enough for normal applications and it is always sufficiently flexible for use in tire sideShore Hardness 786,016 786,016 walls Its original whiteness and its resistance to discoloration and tackiness upon aging are slightly better than in the case of Example 18. The composition of Example 20 is somewhat similar to that of Example 19, and the original whiteness, resistance to discoloration and tackiness upon aging are likewise slightly better than for the composition of Example 18.

However, it tended to be very slightly sticky during its " processing," and although the resulting product was very satisfactory in that the vulcanizate was somewhat stiffer (which is desirable for some applications), the composition is not quite as advantageous as the composition disclosed in Example 19 Accordingly, the composition of Example 19 is preferred. Thus, the approximate range of parts by weight of the various constituents in applicant's composition per 100 parts by weight of copolymer are most preferably as follows: to 100 parts by weight of titanium dioxide, about 50 to 100 parts by weight of magnesium oxide, 1 to 3 % of stearic acid if present, 0 10 to 0 30 part by weight of ultramarine blue, if present, 10 to 20 parts by weight of zinc oxide, 2 to 3 parts by weight of sulfur as the vulcanizing agent, and 75 to 1.5 parts by weight of a tetra alkyl thiuram mono or poly sulfide as a vulcanizing accelerator. Furthermore, the amount of stearic acid if employed, may be controlled as desired for the particular processing equipment as a mold release agent, and although metal stearates such as zinc stearate are operative, stearic acid is preferred A blue pigment also may be incorporated to obtain a better shade of white. Although ultramarine blue has been found satisfactory in these experiments, other conventional blue pigments which are compatible with butyl type rubbers are also operative but not as preferred as ultramarine blue The concentration of the bluing agent may be adjusted, depending upon the ratio of the magnesium oxide to the titanium oxide and the amountof total titanium oxide present For example, since magnesium oxide does not have the hiding power of titanium dioxide, a change in the proportion of magnesium oxide to titanium dioxide would require a change in the amount of the bluing agent, if a bluing agent is employed. Insofar as the degree of fineness of the sulfur is concerned, the sulfur may pass through a 50 mesh to about 500 mesh screen. However, a fineness of 200 to 325 mesh or finer appears to be preferred for white compositions. EXAMPLE 21 A commercial grade of GR-I-18 rubber containing about 15-1 8 mol % isoprene with the balance being isobutylene was compounded as follows: Parts by Weight GR-I-18 (Non-Staining)-' Titanium Dioxide Magnesium Oxide Stearic Acid Zinc Oxide Sulfur Tetra Methyl Thiuram Disulfide 1.0 2.0 1.25 (GR-I-18 made in accordance with the process for producing Butyl No 3, supra, wherein the non-staining qualities were imparted by adding 0 25 parts by weight of lauroyl p-amino phenol thereto Another suitable material in place of the lauroyl p-amino phenol is 2,21-methylene bis( 4-methyl, 6tertiary butyl phenol)).

The above composition was then cured for minutes at 320 F and after 20 months of outdoor aging in straight and in looped form according to A S T M Standard Method D 518-44, the composition was not cracked, crazed, or discolored, its surface was dry, and its physical characteristics are now tabulated: Tensile Strength (psi) Elongation (E) in % Modulus (psi) at 300 % E at 500 % E at 600 % E 2225 700 250 525 1100 EXAMPLE 22 A commercial grade of G 1 R-I-17 rubber containing about 2 5 mol % isoprene with the balance being isobutylene was compounded as follows: Parts by Weight GR-I-17 (Non-Staining) 100 Titanium Dioxide 75 Calcium Oxide 25 Stearic Acid 1 0 Zinc Oxide 10 Sulfur 2 0 Tetra Methyl Thiuram Disulfide 1 25 (G 1 R-I-17 made non-staining by adding 0.25 parts by weight of lauroyl p-aminophenol thereto Another suitable material in place of the lauroyl p-amino phenol is 2,21methylene bis( 4 methyl, 6 tertiary butyl phenol)). The above composition was then cured for 23 minutes at 330 F and after 19 months of outdoor aging in straight and in looped form according to A S T M Standard Method 115 D 518-44, the composition was not cracked, only very slightly crazed, and not discolored. Its surface exhibited surface powdering which is very desirable to facilitate self-cleaning Its physical characteristics are now tabulated: Tensile Strength (psi) Elongation (%) Modulus (psi) at 300 % E at 500 % E Hardness, Shore 1550 680 250 535 EXAMPLE 23 The same copolymer (GR-I-17) as in Example 22 was composited with various amounts of titanium dioxide, calcium oxide, and zinc oxide per 100 parts by weight of copolymer These compositions were then vulcanized for 23 minutes at 330 'F in the presence of 2 parts by weight of sulfur and 1.25 parts by weight of tetramethyl thiuram disulfide The above vulcanizates were then aged in straight and in looped form according to A S T M Standard Method D 518-44. The results are now tabulated in Table IV. TABLE IV Parts by Weight DiscolorRun Ti O 2 Zn O Ca O Time Tacky ation Cracking Crazing 1 100 8 weeks yes Bad Slight Slight 2 10 8 weeks yes Bad Slight Slight 3 100 10 8 weeks yes Bad Slight Slight 4 100 10 25 19 months No None None None The above runs in Table IV of Example 23 demonstrate that the use of titanium dioxide alone, zinc oxide alone, or a combination of titanium dioxide, and zinc oxide do not improve discoloration, cracking and crazing, or produce desirable surface powdering However, the three-component composition of the invention including preferably 20 to 75 parts by weight of calcium oxide, in addition to the parts by weight of titanium dioxide and parts by weight of zinc oxide per 100 parts of the rubbery copolymer produced a

vastly improved composition with substantially no discoloration, cracking or crazing and with the self-cleaning characteristic of surface powdering The omission of the zinc oxide in formulation of the invention gave essentially no vulcanization and the omission of the titanium dioxide gave a composition of poor discoloration and poorer original whiteness.


* GB786017 (A)

Description: GB786017 (A) ? 1957-11-06

Improvements in or relating to grinding mills


PATENT SPECIFICATION 7869017 f a k e Date of Application and filing Complete Specification: April 10, 1956. No 10909/56. Application made in France on April 20, 1955. Complete Specification Published: Nov6, 1957. Index at acceptance:-Class 59, A 5 (A: C: D: E: H). International Classification:-BO 2 c. COMPLETE SIIECIFIOCATION Improvements; in or relating to Grinding Mills We, GEORGE WILFRID 'EDWARDS, a British Subject, and ROGER S Evi N, a French citizen, both of ( 63 Rue d'Avron, Paris (X Xe), France, 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 grinding mills of the kind including a rotatable grinding disc.

On operation of grinding mills having cooperating grinding discs at least one of which is rotatable at high speed, the substance being treated between such discs becomes heated. In certain cases it is necessary to limit this often harmful heating and to maintain the temperature as low as possible. When the grinding discs iare made of a heatconducting material, if is possible to effect cooling by circulation of water or any other cooling liquid; when however the grinding discs are made of non-conductive material, or if the cololing surfaces are inadequate, the temperature cannot be lowered sufficiently and in such a case intense evaporation often occurs at the outlet from the grinding discs where the hot material is ground or homogenised. It is the chief object of the present invention to provide means whereby the material treated during the grinding operation may be cooled and loss of solvent by evaporation minimised. According to one aspect the invention resides in a method of reducing the temperature of a product produced in a grinding mill incorporating cooperating grinding discs at least one of which is rotated at high speed such method being characterised in that a volatile medium which is present in or added to 40,the substance to be treated in the mill and is evaporated in the grinding zone as a result of the grinding operation is commingled with cooling air or vapour which is caused to pass over the product issuing from the grinding discs said volatile medium being subsequently separated as condensate from, said cooling air or vapour and being returned to the feed side of the mill or collected at some other point. In accordance with a further aspect of the invention a grinding mill comprising cooperat 50 ing grinding discs at least one of which is rotatable at high speed and means whereby the treated product issuing from such discs may be subjected to a flow of air or gaseous medium is characterised in that the air or 55 gaseous medium is circulated in a closed circuit which incorporates cooling means whereby volatile constituents which are evaporated from the product under treatment in the grinding zone m'ay be condensed, there 60 being means whereby condensate thus obtained may be withdrawn from the circuit. In order that the said invention may be clearly understood and readily carried into effect the same will be hereinafter more fully 65 described with reference to the accompanying drawing which shows a section through the grinding mill. The grinding mill illustrated is of ithe type equipped with, a high-speed grinding disc 70 and referring now to the drawing, 1 denotes a bearing which is capable of axial sliding movement within' a casing 2. In order to adjust the gap between the grinding discs the bearing is

adapted to be 75 moved axially with respect to the casing, this movement being imparted by means of la hand wheel 3 carrying two differential screwthreads 'one of which screws into the casing and the other on to the 'body of said bearing 80 Screwed to and centred on a shaft 4 which is carried by 'the bearing 1, is a grinding disc support hub 5 the latter carrying a plate 6 in which la grinding disc 7 ' is supported. The grinding disc 7 which is rotatable as 85 well as axially movable is mounted on a sleeve 8 ' and is located thereon by means of a nut 9 which carries vanes or wings 91. Thus the unit consisting of the grinding disc 7, sleeve f 8 and vane-carrying nut 9 is 90 centred directly on the shaft 4 and bears against the plate '6 The said unit is locked in position by means of a nut 10. 11 denotes a stationary grinding disc which is carried by and centred in a cover 12 fixed to the front of the easing 2. The product which is to be ground or homogenised is fed into a hopper 13 fixed to the cover 12. On operation of the mill the product will be entrained by the vanes on the nut 9 and will be sucked through the hopper and forced into the gap between the grinding discs 7 and 11, the width of said gap being adjustable by means of the hand wheel 3. When it passes betweein the grinding discs the product is spread out and is subjected to an intensiveshearing effect. Upon issuing from the grinding discs, the product is projected into a collecting chamber in the casing 2 and is finally evacuated through the channel 14 As the product passes between the grinding discs, part of the work done will be transformed into heat Moreover, as the product is ground evaporation will occur at the outlet from the grinding discs, especially when the substance being treated contains volatile products. The casing 2 of the apparatus is formed behind the collecting chamber with a secondary chamber 15 which is separated from the said collecting chamber by a partition 16. Mounted on that face of the plate 6 opposite the partition 16 are vanes or blades 17 which when the grinding disc 7 is rotating serve to produce an air flow which is drawn from the secondary chamber 15 and is expelled into the collecting chamber, to be finally evacuated through the channel 14. A collecting vessel or container 18 is fitted to the channel 14 and such vessel which may or may not be cooled, comprises at its lower or outlet end a trap 19 in such manner that liquid can be discharged from said outlet without air or vapours escaping from the collecting vessel at the same point.

Connected to the upper part of the collecting vessel is a pipe 23 leading to a cooler 20 which in turn is connected by another pipe 24 to the secondary chamber 15 of the grinding mill Thus there is a circulation of air or vapour in a closed circuit, which comprises: The secondary chamber 15 The collecting chamber The collecting vessel 18 The cooler 20 and Return to the secondary chamber 15 It will be apparent that the vapours liberated by the product will follow this circuit, and that they can be condensed when they pass through the cooler 20. Provided in the lower part of the cooler is a collector 21 incorporating a trap 22 adapted to discharge the condensed liquid This condensed liquid can be collected outside the apparatus, or re-admitted to the feed hopper 13 This quantity of volatile liquid will be evaporated again as it passes out of the grinding discs and, following the same circuit, will be condensed again in the cooler, then reintroduced into the product being fed into the mill, and so forth. At the time it is evaporated, the volatile liquid will take from the ambient medium i e 70 from the product being treated, heat corresponding to its heat of evaporation, and thus there will be a corresponding lowering of temperature. The heat taken from the product by the 75 volatile liquid will thus be conveyed to the cooler and transmitted to the cooling water at the time the vapours are condensed. It will therefore be seen that in the case of the aforesaid arrangement, the heat can be 80 taken from the product being treated in the grinding mill, and dissipated by water or any other cooling substance, through the intermediary of a volatile liquid already contained in the product or intentionally incorporated 85 in the product. By way of example, and without limiting the use of this method, the case of grinding paint may be quoted. A certain quantity of solvent compatible 90 with the paint and having a boiling point equal to or less than the maximum permissible temperature, may be deliberately added to the paint. It will be apparent from the foregoing ithat 95 the arrangement according to the invention as described hereinbefore affords the double advantage of extracting heat from the product being treated and of minimising the escape of solvents or of noxious vapours to the outside, 100 by providing a closed ventilation circuit within the apparatus.

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* GB786018 (A)

Description: GB786018 (A) ? 1957-11-06

Preparation of hydroabietyl alkylene diamine compounds

Description of GB786018 (A) Translate this text into Tooltip



COMPLETE SPECIFICATION Preparation of Hydroabietyl Alkylerle Diamine Compounds We, ABBOTT LABORATORIES, a corporation organized and existing under the laws of the State of Illinois, United States of America, of 14th Street and Sheridan Road, North Chicago, County of Lake, State of Illinois, United States of America, do hereby declare the invention, for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement: This invention relates generally to the preparation of hydroabietyl lower alkylene diamine compounds and more particularly to an improved method of treating a mixture of hydroabietylamines to obtain therefrom relatively pure dehydroabietyl lower alkylene diamine compounds. The hydroabietylamine, dehydroabietylamine, is a unique primary amine having a tricyclic ring structure which is obtained as part of a

mixture of amines prepared by the hydrogenation of rosin acid nitriles and has the following formula: <img class="EMIRef" id="026445174-00010001" /> Dehydroabietylamine is available commercially under the trade name "Rosin Amine D" which consists of at least about 40% and preferably of about 60% dehydroabietylamine and with the balance of the mixture consisting primarily of dihydroabietylamine, tetrahydroabietylamines and closely related isomeric amines. Dihydroabietylamine and tetrahydroabietylamine differ from dehydroabietylamine only by two and four hydrogen atoms respectively and possess many of the physical properties of dehydroabietylamine. It has previously been found that the dehydroabietyl lower alkylene diamines are particularly useful compounds in the synthesis of certain useful pharmaceutical compounds. Thus, for example, these dehydroabietyl lower alkylene diamines can be employed as intermediates for the preparation of N,N' - his - (dehydroabietyl)- alkylenediamine dibeiizylpenicillin salts by direct interaction of the amine, N,N1his - (dehydroabietyl) - ethylene - diamine, with dibenzylpenicillin acid or a water soluble dibenzyl-penicillin salt which form very sparingly water soluble salt products having marked therapeutic value. Such sparingly water-soluble salts and their preparation are described and claimed in our prior Specification No. 753,739. Heretofore, the hydroabietyl lower alkylene diamines have been prepared by treating two moles of the hydroabietylamine with one mole of an alkylene dihalide, such as ethylene dibromide, by dissolving the hydroabietylamine in a suitable reaction solvent, such as benzene, and refluxing the mixture. The dihalide reaction product is formed only very slowly and requires refluxing for periods of about 16 hours. Moreover, the desired amine product is difficult to isolate in a relatively pure form from the reaction solvent. It is therefore an object of the present invention to provide an improved and more economical method of obtaining hydoabietyl (e.g. dehydroabietyl) lower alkylene (e.g. ethylene) diamine compounds in a relatively pure form. It is also an object of this invention to provide an improved method of treating a hydroabietylamine mixture containing substantial amounts of dehydroabietylamine, dihydroabietylamine, and tetrahydroabietylamine in order to obtain directly therefrom a hydroabietyl lower alkylene diamine compound in relatively pure form. It has been found that a hydroabietyl lower alkylene diamine and particularly the dehydroabietyl lower alkylene diamines, such as dehydroabietylethylenediamine, can be prepared in a much more economical manner than heretofore by directly reacting the

dehydroabietylamine or a mixture containing dehydroabietylamine, dihydroabietylamine and tetrahydroabietylamine with a lower alkylene dihalide in the absence of a solvent by heating a mixture of the foregoing reactants to a temperature of about 70 C. whereupon the reaction proceeds exothermically and is completed in a matter of a few minutes in contrast with the many hours refluxing required heretofore. The dehydroabietyl lower alkylene diamine dihalide thus formed is readily recovered in crystalline form by slurrying the reaction mixture with an organic solvent, such as acetone, which serves as a dispersing agent to facilitate filtration or centrifuging. More specifically, it has been discovered that by directly reacting one molar equivalent of a dehydroabietylamine or a mixture containing a substantial proportion of dehydroabietylamine, such as Rosin Amine D, with one equivalent of a lower alkylene dihalide, such as ethylene dibromide or ethylene dichloride, without a solvent for the reactants or reaction products, the desired reaction unexpectedly proceeds at a very rapid rate and is completed in a much shorter period of time than when a solvent is present in which the reactants or reaction products are soluble. The hydroabietyl lower alkylene diamine dihalide formed is readily recovered as a crystalline solid simply by dispersing the reaction mixture with preferably between about two and four parts by weight of a polar solvent of the amphiprotic type of which acetone, ethyl alcohol, butyl acetate, and methyl isobutyl ketone are examples and which have a limited solubility for the hydroabietyl lower alkylene diamine dihalide product and thereafter recovering the product by filtering or centrifuging in the usual manner. According to the present invention, therefore, there is provided a method of preparing a hydroabietyl lower alkylene diamine compound which comprises admixing at least one hydroabietylamine and a lower alkylene dihalide; heating the reaction mixture to a temperature at which the reaction proceeds exothermically rapidly to completion; thereafter intimately contacting the reaction mixture containing a hydroabietyl lower alkylene diamine compound with an amphiprotic polar solvent; and separating a crystalline hydroabietyl lower alkylene diamine compound from the reaction mixture. The lower alkylene dihalides which can be employed in the present invention are those having from 2 to 8 carbon atoms per molecule and the expression "lower alkylene" wherever used in the present Specification and claims should be construed accordingly. Such lower alkylene dihalides include ethylene dichloride, ethylene dibromide, isopropylene dichloride and isopropylene dibromide. In the following specific examples are shown several specific embodiments of the present invention but it should be understood that the invention is not to be limited to the specific reactions disclosed

nor to the precise proportions or conditions set forth in the several specific examples, since the examples are given only for the purpose of illustrating the principle of the present invention. EXAMPLE I Rosin Amine D, 28.5 grams, is covered with ethylene dibromide, 18.7 grams, and heated on a steam bath. In 20 minutes the internal temperature rises to 115 C. and the solution thickens. The reaction mixture is then dissolved in four volumes of acetone and the crystalline dehydroabietylethylenediamine hydrobromide product readily separates. Upon filtration and drying, the white crystalline product consisting of relatively pure dehydroabietylethylenediamine dihydrobromide exhibits an equivalent weight of 391 (Theory 379). The said diamine product when dissolved in ethyl alcohol and examined under ultraviolet light exhibits ultraviolet absorption maxima at 268+1 and 276+1 millimicrons and a minimum at 273 t- 1 millimicrons which are characteristics of the said dehydroabietyl product and distinguishes from products containing primarily the dihydroabietyl or the tetrahydroabietyl amine groups. EXAMPLE II Rosin Amine D, 230 pounds, and ethylene dibromide, 150 pounds, are mixed by stirring in a stainless steel still. Heat is then applied until the temperature rises to 70 C. Heating is discontinued and 200 gallons of acetone is pumped in as rapidly as possible. The solution is then heated to reflux and stirred to break up clumps of crystals of dehydroabietylethylene diamine and to solubilize the other hydroabietyl diamines present. The reaction mixture is then cooled to 20 C. and centrifuged. The product is washed with 100 gallons of acetone and dried. The dehydroabietylethylenediamine dihydrobromide product has an equivalent weight of 394 (Theory 379). The said diamine product when dissolved in ethyl alcohol and examined under ultraviolet light exhibits ultraviolet absorption maxima at 268+1 and 276+1 millimicrons and a minimum at 273 + 1 millimicrons which are characteristics of the said dehydroabietyl product and distinguishes from products containing primarily the dihydroabietyl or the tetrahydroabietyl amine groups. EXAMPLE III Rosin Amine D, 227 grams, containing 45:/, dehydroabietylamine is covered with ethylene dichloride, 80 grams, and stirred and refluxed. The internal temperature rises to 115 C. and in approximately 70 minutes the solution becomes mushy. One liter of acetone is added to the reaction mixture. Upon filtration and drying, the white crystalline relatively pure dehydroabietylethylenediamine dihydrochloride product has an equivalent weight of 355 (Theory 335) and contains 80% dehydroabietylethylenediamine dihydrochloride. The

said diamine product when dissolved in ethyl alcohol and examined under ultraviolet light exhibits ultraviolet absorption maxima at 268 + 1 and 276 + 1 millimicrons and a minimum at 273 + 1 millimicrons which is characteristic of the said dehydroabietyl product. When the above diamine dihydrochloride product is treated with sodium hydroxide, a heavy oil is formed which on analysis is identified as being substantially the dehydroabietylethylenediamine base. EXAMPLE IV Rosin Amine D, 227 pounds, and ethylene dichloride, 80 pounds, are placed into a stainless steel still, stirred for 0.5 hours and heated for 1.25 hours. The temperature rises to 115 C. and the solution becomes mushy. To the reaction mixture is rapidly added 100 gallons of acetone and the crystalline precipitate is cooled to 20 C. The relatively pure dehydroabietylethylenediamine dihydrochloride product is then washed with the balance of the acetone and dried in an air dryer at 45" C. The monohydrated dihydrochloride salt of N,N1-bis- (dehydroabietyl)-ethylenediamine upon recrystallization from ethyl alcohol has a melting point with decomposition at 292295 C. An ethyl alcohol solution of the said product exhibits ultraviolet absorption maxima at 268 + 1 and 276+ 1 millimicrons and a minimum at 273 + 1 millimicrons. EXAMPLE V The dihydrochloride salt of the dehydroabietylethylenediamine base, 115 grams, as prepared in Example IV is extracted with a solvent mixture of about 4 liters of chloroform and 4 liters of water which is adjusted to about pH 10 and a second extraction is performed using a solution of about 2 liters of chloroform and the mixture readjusted to about pH 10 with 6N NaOH if necessary. The chloroform layer containing the mixed free base is separated from the aqueous layer containing NaCI and is washed with about 1/10 its volume of water to remove any NaCl in the wet chloroform solution. The chloroform solution containing a mixture of the free bases having a volume of about 6 liters is dried with anhydrous Na2SO4 and then filtered to obtain a clear solution containing about 1 kilogram of the mixed free bases. Approximately 230 grams of crude procaine penicillin G are extracted with a solution containing about 4 liters of ethyl acetate and 4 liters of water which has been adjusted to between pH 2 and 3 with 6N sulfuric acid at a temperature of about 5" C. The procaine penicillin G is thereafter again extracted with about 2 liters of ethyl acetate and the mixture is again adjusted to a pH of 2 to 3 with 6N sulfuric acid if necessary. The ethyl acetate solution containing penicillin G acid is then washed with about 1/10 its volume of water to remove any trace of sulfuric acid and water soluble procaine sulfate contained in

the ethyl acetate solution. The acetate solution having a volume of about 6 liters is dried with anhydrous Na,SO4 and then filtered to obtain a clear solution of approximately 300,000 units of penicillin per ml. The aqueous phase containing procaine sulfate can be treated to recover procaine therefrom. The chloroform solution of the free bases prepared in the above manner is then slowly added to the ethyl acetate solution of the penicillin G acid prepared in the above manner. A clear solution forms which rapidly becomes turbid as the bases react with the penicillin acid and crystallization commences. The reaction mixture is allowed to stand overnight in a cool room having a temperature of about 5" C. after thoroughly agitating the mixture. Thereafter the crystalline N, Nl-bis-(dehydroabietyl)-ethylenediamine - dibenzylpenicillin is filtered to separate therefrom the cooled mother liquor which contains quantities of the unprecipitated N,N1- bis -(dihydroabietyl)ethylenediamine - dibenzylpenicillin salt and N, Nl-bis- (tetrahydroabietyl)-ethylenediaminedibenzylpenicillin salt and other impurities. The precipitate is washed thoroughly with about 4 liters of a mixture of chloroform and ethyl acetate (1:1) which is divided into three separate portions. After the final washing the crystals are substantially colorless. The crystalline penicillin salt is thoroughly dried under vacuum at a temperature of about 35 C. The N,N1-bis- (dehydroabietyl)-ethylenediaminedibenzylpenicillin salt is obtained having purity as determined by solubility analysis in excess of 91% and melts with decomposition at 167-169 C. on a Kofler hot stage. The equivalent weights of the above disclosed dihydrohalide compounds of the present invention are determined by dissolving approximately 300 mg. of the hydrochloride in 50 cc. of glacial acetic acid and adding thereto 10 cc. of a 6% solution of mercuric acetate in glacial acetic acid. Thereafter the solution is titrated potentiometrically with 0.1 N perchloric acid in glacial acetic acid using silverglass electrodes and the equivalent weight calculated by dividing the weight of the sample in mg. by the product of the cubic centimeters of 0.1 N perchloric acid used and the normality. The polar solvents of the amphiprotic type are the most useful and suitable for recovering the dehydroabietylethylenediamine salts from the said dehydroabietyl alkylene diamine dihalides because they are inert toward the said dihalide products and have only limited solubility for the said dihalide product. In addition, the amphiprotic polar solvents cause the said dehydroabietyl alkylene diamine compound to crystallize in a form which greatly facilitates its recovery from the reaction mix ture by filtration or centrifuging. These amphiprotic

polar solvents are illustrated by the solvent acetone and include the solvents methyl isobutyl ketone, methyl acetate, butyl acetate, butyl alcohol, ethyl alcohol and isopropyl alcohol. What we claim is : - 1. A method of preparing a hydroabietyl lower alkylene diamine compound comprising admixing at least one hydroabietylamine and a lower alkylene dihalide; heating the reaction mixture to a temperature at which the reaction proceeds exothermically rapidly to completion; thereafter intimately contacting the reaction mixture containing a hydroabietyl lower alkylene diamine compound with an amphiprotic polar solvent; and separating a crystalline hydroabietyl lower alkylene diamine compound from the reaction mixture.


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