Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C15/00—Cyclic hydrocarbons containing only six-membered aromatic rings as cyclic parts
  • C07C15/12—Polycyclic non-condensed hydrocarbons
  • C07C15/14—Polycyclic non-condensed hydrocarbons all phenyl groups being directly linked
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
  • H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
  • H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
  • H01B3/20—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances liquids, e.g. oils
  • H01B3/22—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances liquids, e.g. oils hydrocarbons
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
  • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
  • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
  • B41M5/124—Duplicating or marking methods; Sheet materials for use therein using pressure to make a masked colour visible, e.g. to make a coloured support visible, to create an opaque or transparent pattern, or to form colour by uniting colour-forming components
  • B41M5/165—Duplicating or marking methods; Sheet materials for use therein using pressure to make a masked colour visible, e.g. to make a coloured support visible, to create an opaque or transparent pattern, or to form colour by uniting colour-forming components characterised by the use of microcapsules; Special solvents for incorporating the ingredients
  • B41M5/1655—Solvents
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
  • C07C2/54—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition of unsaturated hydrocarbons to saturated hydrocarbons or to hydrocarbons containing a six-membered aromatic ring with no unsaturation outside the aromatic ring
  • C07C2/64—Addition to a carbon atom of a six-membered aromatic ring
  • C07C2/66—Catalytic processes
  • C07C2/68—Catalytic processes with halides
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C2527/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
  • C07C2527/06—Halogens; Compounds thereof
  • C07C2527/125—Compounds comprising a halogen and scandium, yttrium, aluminium, gallium, indium or thallium
  • C07C2527/126—Aluminium chloride

Definitions

• alkylbiphenyl compounds are useful as dielectric materials.
• U.S. 2,172,391 which discloses the alkylation of diphenyl, suggests that ethylated diphenyl may be so used.
• This reference also points out, however, that alkylation of diphenyl with hydrocarbon of molecular weight above ethylene or propylene gives more viscous products which form wax-like crystals on standing.
• U.S. 2,837,724 discloses the preparation of t-butyl diphenyl and other tertiary alkyl diphenyls for use as a dielectric liquid for transformers.
• 4-t-butyl diphenyl is a solid at room temperature (M.P.
• the alkyldiphenyls to be used with the polychlorobenzenrs can he employed in the pure state or as mixtures of isomers and/or of products with different degrees of alkvlation obtained i n the course of their preparation.
• alkylbiphenyl s to be used with the polychlorobenzer.es are the various butyl isomers including 3-sec-butylbi ⁇ henyl, 4-sec-butylbiphenyl, and 4 ,4 ' -di -sec-butylbiphenyl, but the thrust of the disclosure: is the need to use a mixture of the polychlorobenzenes and alkylated bi- or terphenyl.
• 4,054,937 also discloses the use as a capacitor fluid a mixture of mono- and di-alkylated biphenyl where the aklyl group is C 2 to C 4 and where the fluid comprises 80 to 99% by weight of the mono-alkylated biphenyl and 1 to about 20% of the dialkylated biphenyl.
• the preferred species are normal alkyl and isopropyl. Alkyl groups above butyl are said to have higher pour points and may not be acceptable.
• alkylated biphenyls are useful as a dye solvent for carbonless paper (see, for example U.S. 4,085,949).
• U.S. 3,627,581 discloses isopropylbiphenyl and U.S. 3,732,141 shows mono-isopropylbiphenyl for this purpose.
• a mixture of phenylnaphthyl methanes and C 1 to C 6 alkyl biphenyls is disclosed as a dye solvent in U.S. 3,846,331.
• a particular mixture of a specific butylated diphenyl can readily be obtained without the contaminating t-butyl isomer and that the mixture has properties making it of particular value as a dielectric liquid and as a carbonless paper solvent.
• Such material is a water-white liquid with a pleasant odor consisting essentially of about 82% to 88% (preferably 85%) by weight of mono-sec-butylbiphenyl and about 12% to about 18% (preferably 15%) by weight of di-sec-butyl biphenyl.
• This mixture is readily obtained by alkylation of diphenyl with a highly pure 1-butene or 2-butene or their admixture at a mole ratio of butene to biphenyl of from about 0.5 to about 0.9 (i.e. a biphenyl to butene ratio of 2:1 to 1.1:1) at a temperature of at least about 250°F up to about 475 °F in the presence of an aluminum chloride catalyst, and vacuum distilling off the alkylation product at a temperature between about 370°F and about 440°F at 30 mm Hg of pressure.
• 1-butene or 2-butene or their admixture in any proportion may be used as the olefin for alkylation since they both give the same product.
• the butene used must be of high purity because other olefins, even other C 4 -olefins, drastically alter the properties of the alkylate product. Accordingly, the olefin used must have a purity of at least about 98% of 1- and/or 2-butene.
• the catalyst used is aluminum chloride. However, it is preferred to use this catalyst as a complex made from A1C1 3 , toluene, and methyl chloride by adding the A1C1, (500 parts by weight) to the dry toluene (100 gallons) and then adding the methyl chloride (9 gallons) with, agitation.
• the catalyst complex is a clear, yellow, low viscosity liquid which must be protected from moisture before use.
• the amount of catalyst used is not critical, but the catalyst complex is preferably used at 0.5 to about 1%, most preferably at a level of 45 gallons of complex per 2500 gallons of biphenyl which corresponds to 0.8 wt. % of solid A1C1 3 based on biphenyl.
• the complex composition is approximately 25-30 wt. % A1C1 3 , 50-60% toluene and 5-10 HC1, the latter derived from the added CH 3 C1.
• the butene to biphenyl ratio of between about 0.5 and 0.9 is another important parameter in order to obtain the desired product. In order to obtain a product with the preferred amount of 15% di-sec-butyl biphenyl and with a minimum of tri-sec-butyl product, the ratio should be at about 0.75.
• a butene to biphenyl mol ratio of 0.5 can be used to obtain the desired product but less total product will result per batch.
• a 0.9 mol ratio can also be used but in such case, less of the sec butyl biphenyl can be used in the final product. Commercial practice dictates that a mol ratio of 0.75 is about optimum.
• Figure 1 illustrates the relationship between mole ratio of reactants and the amounts of the various sec-butylbiphenyl isomers obtained. It is of interest to note that at the mole ratio used in the process, the amount of tri-sec-butylbiphenyl isomer is very low and no tetra-isoraer is present at all.
• the rate of addition of the butene to the biphenyl is not critical, but the presence of large amounts of unreacted butene in the reaction mass should be avoided in order to prevent the formation of butene polymers.
• the preferred procedure is to pump the catalyst complex into the molten biphenyl with agitation at about 160°F.
• the butene or butenes are then added at a rate which allows a maximum temperature of about 250°F to be held in the reactor.
• the mono- and di-sec-butyl biphenyl isomers, once formed, are very stable to further heating under conditions which might be expected to produce undesirable by-products.
• Alkylation in plant equipment is usually completed over a period of from about 3 to about 6 hours.
• the agitation is stopped and the entire reactor contents (catalyst plus hydrocarbon) are pumped to a hydrolyzer where they are contacted with 20 volume % of 20° Be.NaOH solution at 275-300°F for at least 1 hour, preferably
• the principal components of the alkylate at this point are unreacted biphenyl (b.p. 493°F) , mono sec-butyl biphenyl (b.p. 576-598°F) , di sec-butyl biphenyl (b.p. 598-691°F) , and higher boiling tri-alkylated biphenyls (bottoms) .
• the desired product containing from about 82% to about 88% mono and from about 14% to about 18% di sec-butyl biphenyl, is obtained from a vacuum distillation, typically at 30 mm Hg by taking cuts, preferably from cuts 2 through 16, (b.p. 370-440°F) using a 40 plate Heli-Grid column or its equivalent at 20:1 reflux ratio as shown in Figure 2 where the ordinate temperature values have been converted to the corrresponding values at 760 mm Hg. In general, cuts over a range from about 370° to about 440°F at 30 mm Hg are useful.
• the product is a water-white, liquid with the physical properties as listed in Table I.
• the product is essentially free of odor, but any odor that can be detected is pleasant.
• This low odor characteristic is a particularly desirable property when the product is used as a dye solvent for carbonless paper products and makes the liquid product of the invention superior to a mixture of 85% mono-isopropylbiphenyl and 15% diisopropyldiphenyl which has been used heretofore for such purpose.
• An unexpected and highly desirable property of the liquid product of the invention is its viscosity, which is an important parameter for electrical oils and for dye solvents for carbonless paper products.
• the lower molecular weight homologue i.e. the isopropyl biphenyl
• the lower molecular weight homologue has a suitable viscosity for these use applications, but any significant increase in viscosity would be detrimental.
• the products of this invention are higher homologues and have a higher molecular weight they would be expected to have a significantly higher viscosity and this is, in fact, the case with the t-butyl compounds which, as pointed out above are viscous liquids or solids.
• the viscosity of the liquid products of this invention are not significantly above that for the lower homologue and this is shown in the following Table II:
• the colorless product had a Saybolt viscosity (SUS C 100°F) of 49.1, was essentially free of odor and when evaluated as a carbonless paper solvent for the .dye was found to be quite satsifactory for commercial use.
• the product had the electrical properties shown in Table III and was also commercially acceptable as the dielectric oil in an electrical capacitor wherein the paper spacer was impregnated with the product.
• the liquid composition of the invention is also advantageous in that it has very favorable biological properties; e.g. ready biodegradability and low toxicity as shown by the tests summarized in Table IV.
• test material is not considered to be toxic.
• Inhalation rats: No mortality. Within two hours of exposure rats were eating and drinking; all animals gained weight. No abnormalities of internal organs .

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• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Physics & Mathematics (AREA)
• Spectroscopy & Molecular Physics (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
• Paper (AREA)

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• 1980
  • 1980-04-28 US US06/144,490 patent/US4287074A/en not_active Expired - Lifetime
• 1981
  • 1981-03-27 CA CA000373998A patent/CA1145925A/fr not_active Expired
  • 1981-04-06 IT IT20942/81A patent/IT1194139B/it active
  • 1981-04-15 NL NL8120164A patent/NL8120164A/nl unknown
  • 1981-04-15 WO PCT/US1981/000499 patent/WO1982000103A1/fr not_active Application Discontinuation
  • 1981-04-15 JP JP56501720A patent/JPS57501033A/ja active Pending
  • 1981-04-15 DE DE813148642A patent/DE3148642A1/de not_active Withdrawn
  • 1981-04-15 EP EP19810901244 patent/EP0056372A4/fr not_active Withdrawn
  • 1981-04-15 GB GB8130825A patent/GB2087586B/en not_active Expired
  • 1981-04-27 BE BE0/204614A patent/BE888578A/fr not_active IP Right Cessation
  • 1981-04-28 KR KR1019810001469A patent/KR830002101B1/ko not_active IP Right Cessation
  • 1981-04-28 ES ES502301A patent/ES502301A0/es active Granted
  • 1981-10-29 SE SE8105749A patent/SE8105749L/xx not_active Application Discontinuation
  • 1981-11-13 FI FI813604A patent/FI813604L/fi not_active Application Discontinuation

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