US3600445A - Organic scintillators - Google Patents

Organic scintillators Download PDF

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US3600445A
US3600445A US566489A US3600445DA US3600445A US 3600445 A US3600445 A US 3600445A US 566489 A US566489 A US 566489A US 3600445D A US3600445D A US 3600445DA US 3600445 A US3600445 A US 3600445A
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bis
compounds
rings
binaphthyl
substituents
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Hermann O Wirth
Werner Kern
Gunter Herrmann
Fritz U Herrmann
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Merck KGaA
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C43/00—Ethers; Compounds having groups, groups or groups
    • C07C43/02—Ethers
    • C07C43/20—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring
    • C07C43/205—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring the aromatic ring being a non-condensed ring
    • C07C43/2055—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring the aromatic ring being a non-condensed ring containing more than one ether bond
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C15/00—Cyclic hydrocarbons containing only six-membered aromatic rings as cyclic parts
    • C07C15/20—Polycyclic condensed hydrocarbons
    • C07C15/24—Polycyclic condensed hydrocarbons containing two rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C15/00—Cyclic hydrocarbons containing only six-membered aromatic rings as cyclic parts
    • C07C15/40—Cyclic hydrocarbons containing only six-membered aromatic rings as cyclic parts substituted by unsaturated carbon radicals
    • C07C15/50—Cyclic hydrocarbons containing only six-membered aromatic rings as cyclic parts substituted by unsaturated carbon radicals polycyclic non-condensed
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C43/00—Ethers; Compounds having groups, groups or groups
    • C07C43/02—Ethers
    • C07C43/20—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring
    • C07C43/202—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring the aromatic ring being a naphthalene
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S585/00—Chemistry of hydrocarbon compounds
    • Y10S585/929—Special chemical considerations
    • Y10S585/93—Process including synthesis of nonhydrocarbon intermediate
    • Y10S585/931—Metal-, Si-, B-, or P-containing, e.g. Grignard
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S585/00—Chemistry of hydrocarbon compounds
    • Y10S585/929—Special chemical considerations
    • Y10S585/93—Process including synthesis of nonhydrocarbon intermediate
    • Y10S585/935—Halogen-containing

Definitions

  • This invention relates to oligoaryl compounds and, in particular, to the use of such compounds in scintillation counters.
  • Liquid and plastic scintillators are of increasing economic importance as radiation detectors. They are used primarily for the detection and the examination of radioactive substances, for the detection of elementary particles and quanta, and for the determination of their nature, energy, and lifetime.
  • the mode of action depends upon the fluorescence phenomenon. Passing through the activated state, a quantity of photons is formed in proportion to the quantity of primary radiation. These photons can then be registered photo-electrically, for example, by a photomultiplier tube. This method of counting is now of considerable technological significance, particularly in the examination of weak emitters of B-rays, such as C and H
  • the device employed is known in the art as a scintillation counter.
  • a compound to be used as a scintillator must possess a high light output and be readily soluble in certain solvents, such as preferably alkyl aromatics or vinyl polymers thereof. A substance which does not dissolve is unusable for this purpose, no matter how high its light output.
  • the scintillators normally used heretofore are paraterphenyl, 2,5-diphenyloxazol (PPO), and 2,5-bis[5'- tert.-butyl-benzoxazolyl-(2)]-thiophen (BBOT).
  • PPO paraterphenyl
  • BBOT 2,5-bis[5'- tert.-butyl-benzoxazolyl-(2)]-thiophen
  • Methylor methoxy-substituted oligophenylenes have also been suggested for this use, but their solubility is not satisfactory.
  • Their synthesis is, for example, described in Makromolekulare Chemie, vol. XXIX, p. 164.
  • An object of this invention is to provide organic scintillators having improved properties.
  • Another object of this invention is to provide novel chemical compounds and their methods of manufacture.
  • a further object is to provide improved articles of commerce, such as paints, lacquers, and detergent compositions, based on the organic scintillators of this invention.
  • organic scintillators which not only are very readily soluble but also have a good, and sometimes an extraordinarily high, light output and which, in addition, are characterized by a remarkable chemical stability towards radiation.
  • organic scintillators are oligoaryl compounds of Formula I, as follows:
  • n is an integer from 0-16;
  • A, B, and C represent conjugated phenyl or naphthyl radicals, of which at least one is substituted by at'least one R;
  • R is straight or branched and represents saturated or unsaturated alkyl or alkoxy radicals with 142. carbon atoms which, if desired, can be interrupted with oxygen atoms and/or can be substituted with R or R can represent R and R is a phenyl, biphenyl, naphthyl, or cycloaliphatic ring with 512 carbon atoms substituted, if desired, with lower alkyl or alkoxy groups;
  • n shall not represent zero if A and B are phenyl rings
  • R is an aromatic radical, it shall not be arranged in the para-position of the rings A and/or B,
  • the para-quinquiphenyls of Formula V are also important wherein the radicals R can also be the same or different and have the above-mentioned significance.
  • binaphthyl compounds of Formula IV are highly useful, as follows:
  • R and R have the above-mentioned significance. Still further, the para-quinquiphenyls of Formula VII are also of considerable interest, wherein the substituents R are the same or different and have the above-mentioned significance.
  • the compounds of the said Formulae I-XIII can be even further substituted by additional R radicals.
  • additional R radicals one or more substitutions in the following positions are preferred (nomenclature, see Makromolekulare Chemie [Macromolecular Chemistry], vol. 29, 1959, p. 167):
  • oligoaryls to be used as scintillators according to this invention are thus ring assemblies of aromatic com pounds which are composed of several phenyl and/or naphthyl rings directly connected with each other. It is of fundamental importance in this connection that the aromatic rings are disposed in conjugation to each other.
  • the phenyl rings must thus be bound, through the 1,4- position, whereas it is possible for the naphthyl rings to be connected through the preferred 1,4- and the 2,6- positions.
  • the connection of the naphthyl rings through the 1,2-position, which is also possible, is less favorable owing to steric hindrance of resonace.
  • n preferably represents 0-4. If phenyl and naphthyl rings alternate with one another, then n is preferably 0-8. In oligophenylenes, n can preferably represent any integer from 1 to 16, inclusive.
  • the aromatic rings must be substituted.
  • the higher oligoaryls, without such substitutions, are so slightly soluble that they cannot be used as scintillators, although they are quite satisfactory with respect to obtainable light output. It is, therefore, advantageous for the solubility of the oligoaryls to 'be not less than 10 g./l. toluene at 20 C.
  • the solubility of the oligoaryls to 'be not less than 10 g./l. toluene at 20 C.
  • the oligoaryl compounds with a higher degree of condensation, i.e., more than 4 rings generally more (at least 3) or longer R groups are required to achieve the necessary solubility, it being preferred, in this connection, to employ at least 3 R groups or at least one R group containing at least 6 carbon atoms.
  • R substituents give the oligoaryls an increased solubility. They also simultaneously counteract the concentration extinction of the fluorescence, which amounts to an additional gain in light output.
  • the optical properties of these compounds remain on the whole uninfluenced by the constitution of the R radical. It is therefore relatively unimportant, particularly in the case of longer-chain R substituents, which individual substituents are present in the chain.
  • extinguishing groups such as N SH, S, NH NH, N COOH, or OH should be avoided, if possible. Otherwise, only gradual changes in the solubility appear through the various substitutions, particularly in longer chains.
  • substituents are those in the para-positions and/or in the ortho-positions thereto of rings A and/or B.
  • substituents in the ortho-positions to a diaryl bond in the rings A, B, and/or C
  • Areas of interference of particular intensity which influence the conjugation of the system unfavorably are, for example, two substituents at two adjacent aryl rings which flank one and the same biaryl bond.
  • a quaterphenyl for example, contains an area of interference (e.g. substituents in the ortho-position to a biaryl bond between two adjacent rings), compensation must be achieved by the substitution of the rings A and/or B with an auxochrome in the para-position(s). If both parapositions are substituted by auxochromic groups (e.g. longer-chain, preferably branched alkoxy groups), then further substituents in the ortho-position can still be permissi'ble. These substituents should, however, preferably not be too bulky, i.e., for example, should not possess any secondary or tertiary carbon atom bound directly to a ring. Furthermore, substituents on adjacent rings which jointly flank the biaryl bond situated between them should generally not be too bulky.
  • auxochromic groups e.g. longer-chain, preferably branched alkoxy groups
  • the light output is generally particularly good if an undisturbed conjugated system of at least three aryl rings or a quaternary system impeded by only one area of interference is present.
  • These systems in and of themselves can, of course, occur at one or more various positions of a larger oligoaryl system, and then are not required to be disposed in conjugated form to one another.
  • the areas of interference have an ever lessening influence, decreasing with the number of rings in the scintillator.
  • R substituents there are not more than 16 R substituents in the oligoaryl compounds according to the present invention.
  • the number of R substituents is between 2 and 6.
  • the R substituent can be a straight or branched, saturated or unsaturated alkyl or alkoxy group with 1-42 carbon atoms which, if desired, can be interrupted by oxygen atoms and/or substituted by R Furthermore, R can also represent R but this substituent cannot then be arranged in the para-position of rings A and/or B if it is an aromatic radical.
  • R is a phenyl, biphenylyl, naphthyl, or cycloaliphatic ring with -12 carbon atoms substituted, if desired, by lower alkyl or alkoxy groups.
  • alkyls such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert.-butyl, n-amyl, or isoamyl
  • other suitable groups are also the higher homologs, such as hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, as well as their isomers and homologs with up to 42 carbon atoms, or the corresponding alkoxy groups.
  • Branched radicals such as, for example, 2-ethylhexyl, 2- butyloctyl, 2-hexyldecyl, 4-methylamy1, 4-methyl-2-prob pyl-l-pentyl, 2,2,4-trimethyl-l-pentyl, -phenylpropyl, 2,2- dimethylpentyl, 2,2-dimethylbutyl, 2,2-dimethy1hexyl, 2,2- dimethylpropyl, a-tolylbutyl, B-cyclohexylbutyl, hexahydrofarnesyl, tetrahydrogeranyl, or dihydrophytyl are particularly favorable.
  • the alkyl and alkoxy radicals can also be unsaturated, i.e., contain one or more, preferably 1-2 double bonds. If several double bonds are present in the R substituents, it is advisable to have them non-cumulative. It is advantageous, moreover, if one or two of these isolated double bonds stand in conjugated disposition to the oligoaryl system. Such a double bond functions as an auxochromic group.
  • the alkyl or alkoxy radicals can be interrupted with oxygen atoms at random positions. These oxaalkyl or oxaalkoxy radicals can also contain up to 42 chain atoms. The following are mentioned only as examples: 3-mothoxybutyl, 4-ethoxypentyl, 3-oxaamyl, 3,6,9-trioxaundecyl, 3,6-dioxaoctyl, 3,6,12,15 -tetraoxaheptadecylene- )-y If more than two oxygen atoms are contained in the R substituents, a particularly favorable arrangement is to have the oxygen atoms each between two carbon atoms (-O-C-COC-CO).
  • Such compounds can be prepared particularly well from ethylene oxide.
  • the maximum number of oxygen atoms be not more than about one-half the number of carbon atoms in the chain.
  • the terminal hydroxy group which inay form primarily is preferably etherified, i.e. methylated.
  • cycloaliphatic rings containing 5-12 carbon atoms are preferred radicals, e.g., cyclopentyl, cyclohexyl, bicyclohexyl, and decahydronaphthyl.
  • suitable aromatic radicals are, for example, phenyl, biphenylyl, and naphthyl. All of these rings can, in turn, be substituted by lower alkyl or alkoxy groups, preferably by methoxy, ethoxy, propoxy, butoxy, or amyloxy, or methyl, ethyl, propyl, butyl, or amyl.
  • oligoaryl compounds of the present invention which are to be substituted as defined above are, for example, the following:
  • the new compounds according to the present invention are prepared by processes known per se.
  • a useful method of synthesis is, for example, the organometallic carbonyl reaction (Makromoelekulare Chemie, vol. 29, p. 164, 1959), in which the organometallic compounds of the oligoaryls are reacted with cyclic or oligocyclic monoor diketones. This reaction is followed by a dehydrogenation and aromatization.
  • the new compounds can be more easily prepared by the biaryl condensation reaction according to Ullmann (Makromolekulare Chemie, vol. 63, p. 30, 1963).
  • aromatic iodo compounds are joined by eliminating the halogen by means of copper powder.
  • catalytic amounts of mercury By the addition of catalytic amounts of mercury, an increase in the yield can be achieved.
  • the iodoaryls necessary for this reaction are particularly easily produced by direct iodization using iodine/iodic acid (see Liebigs Annalen, vol. 643, p. 84, 1960). This method also includes the possibility of using the lower homologs as starting materials in the synthesis of the higher homologs.
  • the R substituents can be present in the starting products or can be introduced following the formation of the oligoaryl system. In the case of the polynuclear compounds, it is to be recommended for reasons of solubility that the desired R substituents be introduced before the aryl condensation reaction.
  • R represents an alkoxy radical.
  • R represents an alkoxy radical.
  • the reaction of oligoaryls containing carbonyl or carboxyl groups with organometallic compounds permits the introduction of such substituents in which R repre sents an alkyl radical or R
  • the carbinols formed first in this reaction can, for example, be converted to saturated alkanes by treatment with hydrogen iodide and red phosphorus.
  • the C-C bound radicals can also be introduced through the known nuclear alkylation reaction with Lewis acids (e.g., AlCl BF ZnCl wherein the corresponding olefins, halogenides, or alcohols can be used.
  • Lewis acids e.g., AlCl BF ZnCl wherein the corresponding olefins, halogenides, or alcohols can be used.
  • Those compounds according to the present invention which contain oxaalkyl groups possess not only the essential solubility in homopolar solvents but also a certain solubility in water. This property is of great advantage, for example, in the examination of aqueous specimens (for instance water containing tritium).
  • a whole series of compounds according to this invention also possess an extremely high solubility, which allows highly concentrated or over-saturated solutions to be prepared from them-a great advantage with respect to measuring problems.
  • the compounds are even oils which are miscible to an unlimited degree with homopolar solvents (non-polar solvents). They are described in more detail, for example, in US. patent specification 3,148,194.
  • the particularly short decay period of the new compounds is very favorable for many measurements, particularly for particle discrimination.
  • the decay periods of the fluorescence are reduced as the degree of condensation is increased.
  • the light output increases along with the degree of condensation (increasing values for n).
  • the relative yields of fluorescence of the new compounds on UV stimulation were determined with the aid of a spectrophotometer.
  • the compounds according to the present invention can be used in many ways as a result of their scintillator properties.
  • scintillation counters When used in scintillation counters, they are employed in combination with a transducer for converting light energy into electrical energy, and preferably with a photomultiplier tube.
  • a transducer for converting light energy into electrical energy and preferably with a photomultiplier tube.
  • Such use entails a process comprising exposing the scintillator substance to a source of 04-, [3- or also 'y-rays, to produce photons, and then converting such photons into electrical energy.
  • General properties of such scintillators and their use as counting media are, for example, largely described in U .S. patent specification 3,148,194. The details as given in this specification also apply to the compounds of the present invention.
  • EXAMPLE 1 2.46 g. of l -hydroxy-p-terphenyl (Journal Chemical Society [1939], p. 1283) are dissolved in the least pos sible hot alcohol and then combined with an alcoholic solution of 1.2 g. of potassium hydroxide. Following the addition of 4.9 g. of benzenesulfonic acid-2-butyloctylester, it is heated at reflux for 5 hours. The alcohol is largely distilled off and the residue subsequently worked up with water/ether. Purification is carried out by dissolution in benzene and chromatography over a column loaded with a mixture of calcium chloride, calcium oxide, and aluminum oxide. The resultant 1 -[2-butyloctyloxy- (1)]-p-terphenyl is a viscous oil which is miscible with all homopolar solvents in every proportion.
  • EXAMPLE 3 (a) 11.2 g. potassium hydroxide are dissolved in as little ethanol as possible. This solution is combined with the hot solution of 30 g. 4-iodo-4-hydroxybiphenyl (Journal American Chemical Society, vol. 66 [1944], p. 491) in ml. ethanol. Following the addition of 36.3 g. benzene-sulfonic acid 2 butyloctylester, the mixture is boiled at reflux for 5 hours; subsequently, the alcohol is largely distilled off. Working up is carried out with water/ methylene chloride. The 4-iodo-4'- [2-butyloctyloxy-(1)]- biphenyl is obtained in the crystalline form from ether/ methanol; M.P. 67 C.
  • EXAMPLE 4 26 g. 3-(tert.-butyl)-iodobenzene (Journal Chemical Society [1928], p. 2338), 4.1 g. 4,4-diiodobiphenyl, 27 g. copper powder, and 5 drops of mercury are heated, as in Example 3(b), for 3 hours at 200 C. and 2 hours each at 230 C. and 250 C.
  • the reaction mixture is extracted with petroleum ether. Following removal of the solvent, the 1 ,4 -bis-(tert.-butyl)-p-quaterphenyl results in the crystalline form on the addition of methanol. Purification is carried out by chromatographing over aluminum oxide charged with hydrochloric acid and then recrystallizing twice from petroleum ether. M.P. 196 0., 8:52 g./l.
  • EXAMPLE 5 (a) The Grignard solution consisting of 83 g. n-bromopentane and 13 g. magnesium chips in ether is reacted with the ethereal solution of 93 g. m-iodobenzaldehyde. The (3-iodophenyl) n pentylcarbinol thus formed is worked up in the usual way. Boiling point 123- 125 C.
  • EXAMPLE 6 (a) The Grignard solution consisting of 193 g. 2,2,4- trimethyl-bromopentane-( 1) and 25 g. magnesium chips in ether is reacted with the ethereal solution of 135 g. 4-iodobiphenyl-carboxylic acid-(4)-methylester (Makromolekulare Chemie, vol. 68 [1963], p. 92). The (4'- iodo)-biphenyl-'(4) bis [2,2,4-trimethylamyl-(1)]-carbinol thus formed is dehydrated with oxalic acid in dioxane (Makromolekulare Chemie, vol. 42 [1961], p.
  • EXAMPLE 7 (a) 11.5 g. p-terphenyl are reacted with 5 g. iodine and 2 g. iodic acid in a mixture of 120 ml. glacial acetic acid and 8 ml. sulfuric acid with stirring at C.
  • the l -iodo-p-terphenyl is purified of the accompanying diiodo derivative and starting product by fractional crystallization from xylene, M.P. 245 C.
  • EXAMPLE 8 23.2 g. l-iodoethylbenzene (Journalbonde Chemie, vol. 81 [1910], p. 559), 4.8 g. 1 ,3 -diiodo-p-terpheny1, 27 g. copper powder, and 5 drops of mercury are heated for 3 hours at 200 C. and 2 hours each at 230 C. and 250 C. The reaction product is extracted with benzene and then treated with methanol in order to remove the biphenyl derivative formed as a by-product. The 1 ,5 -diethyl-p-quinquiphenyl is isolated by distillation.
  • Identification is carried out by spectroscopy.
  • EXAMPLE 10 A well stirred mixture of 44.2 g. 3-(9-heptadecyl)-i0dobenzene, 20.3 g. 4,4-diiodobiphenyl, g. biphenyl, 38 g. copper powder, and 5 drops of mercury is heated for 3 hours at 200 C. and for 2 hours each at first 230 C. and then 250 C. The reaction mixture is extracted with benzene. The 3,3'-bis- (9'-heptadecyl)-biphenyl formed as a by-product is separated by distillation along with the biphenyl used assolvent. The remaining residue is separated by preparative layer chromatography.
  • the resultant 1 ,4 bis-(9-heptadecyl)-p-quaterphenyl has a waxy consistency with no precise melting point and is extremely readily soluble in homopolar solvents. 0f the higher homologs, the 1 ,6 -bis-(9-heptadecyl)-p-sexiphenyl, the l ,8 -bis-(9- heptadecyl -p-octiphenyl, the 1 ,10 -bis-(9-heptadecy1) -pdeciphenyl, and finally the 1 ,12 -bis-(9-heptadecyl)-pduodeciphenyl can be obtained and spectroscopically identified.
  • EXAMPLE 11 A hot solution of 2.86 g. 4,4-dihydroxy-1,1-binaphthyl (Chemische Industrie 10 [1887], 98) in ethanol is purified with a highly concentrated solution of 2.3 g. potassium hydroxide in ethanol. Following the addition of 8.1 g. benzenesulfonic acid-n-octylester, the mixture is refluxed for 5 hours; then the alcohol is largely distilled off. The precipitation of the alkylether is completed by the addition of water.
  • EXAMPLE 12 (a) 112 g. 1-hydroxy-4-bromonaphthalene are dissolved in as little alcohol as possible and then combined with an alcoholic solution of 60 g. potassium hydroxide. Following the addition of 445 g. benzenesulfonic acid-(2- tetradecyD-octadecyl-(1)-ester, the mixture is refluxed for 5 hours. The alcohol is largely distilled oif, then worked up with water/ether. The resultant 1-[2-(tetradecyl)-octadecycloxy-(1)]-4-bromonaphthalene is purified by molecular distillation. The compound has a waxy consistency.

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Cited By (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4143077A (en) * 1976-09-08 1979-03-06 Institut Francais Du Petrole Diaryloxy-meta-terphenyl derivatives, their manufacture and uses
US4217239A (en) * 1978-02-22 1980-08-12 Ciba-Geigy Corporation Composition for scintillation counting
US4359641A (en) * 1981-06-01 1982-11-16 The United States Of America As Represented By The United States Department Of Energy Liquid scintillators for optical fiber applications
US4361765A (en) * 1981-06-01 1982-11-30 The United States Of America As Represented By The United States Department Of Energy Ternary liquid scintillator for optical fiber applications
EP0084194A1 (de) * 1982-01-14 1983-07-27 MERCK PATENT GmbH Flüssigkristallmischungen
EP0130045A1 (en) * 1983-06-22 1985-01-02 Eli Lilly And Company Terphenyl derivatives
US4578213A (en) * 1984-04-27 1986-03-25 Sangamo Weston, Inc. High temperature plastic scintillator
US4594465A (en) * 1983-07-22 1986-06-10 The Secretary Of State For Defence In Her Britannic Majesty's Government Of The United Kingdom Of Great Britain And Northern Ireland Compounds containing a fluorobiphenylyl group
US4645618A (en) * 1982-02-25 1987-02-24 E. I. Du Pont De Nemours And Company Water soluble floors
US4657696A (en) * 1984-09-19 1987-04-14 Fisons Plc Scintillation counting medium and counting method
EP0388150A1 (en) * 1989-03-13 1990-09-19 Chisso Corporation Alkenyl ether derivatives and liquid crystal composition containing the same
EP0390322A3 (en) * 1989-02-28 1990-11-22 Mitsubishi Gas Chemical Company, Inc. Naphthalene compounds
US5037578A (en) * 1986-02-18 1991-08-06 Exciton Chemical Company O,O'-bridged oligophenylene laser dyes and dyestuff lasers and method of lasing therewith
US5041238A (en) * 1986-02-18 1991-08-20 Exciton Chemical Company o,o'-Bridged oligophenylene laser dyes, dyestuff lasers and methods of lasing therewith
US5110500A (en) * 1988-09-02 1992-05-05 University Of Florida Polysiloxane scintillator composition
US5447656A (en) * 1992-07-09 1995-09-05 Hoechst Aktiengesellschaft Meta-substituted aromatic compounds having six-membered rings, for use in liquid-crystal mixtures
US20040056186A1 (en) * 2002-09-19 2004-03-25 Schlumberger Technology Corporation High temperature scintillator
US20040206933A1 (en) * 2001-09-14 2004-10-21 Goodby John W Liquid crystal compounds with branched or cyclic end groups
WO2015015904A1 (ja) * 2013-08-01 2015-02-05 Jnc株式会社 液晶組成物および液晶表示素子
CN119798102A (zh) * 2025-03-14 2025-04-11 厦门大学 一种纯有机高分辨率玻璃闪烁体的制备方法和应用

Cited By (27)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4143077A (en) * 1976-09-08 1979-03-06 Institut Francais Du Petrole Diaryloxy-meta-terphenyl derivatives, their manufacture and uses
US4217239A (en) * 1978-02-22 1980-08-12 Ciba-Geigy Corporation Composition for scintillation counting
US4359641A (en) * 1981-06-01 1982-11-16 The United States Of America As Represented By The United States Department Of Energy Liquid scintillators for optical fiber applications
US4361765A (en) * 1981-06-01 1982-11-30 The United States Of America As Represented By The United States Department Of Energy Ternary liquid scintillator for optical fiber applications
EP0084194A1 (de) * 1982-01-14 1983-07-27 MERCK PATENT GmbH Flüssigkristallmischungen
US4645618A (en) * 1982-02-25 1987-02-24 E. I. Du Pont De Nemours And Company Water soluble floors
EP0130045A1 (en) * 1983-06-22 1985-01-02 Eli Lilly And Company Terphenyl derivatives
US4594465A (en) * 1983-07-22 1986-06-10 The Secretary Of State For Defence In Her Britannic Majesty's Government Of The United Kingdom Of Great Britain And Northern Ireland Compounds containing a fluorobiphenylyl group
US4578213A (en) * 1984-04-27 1986-03-25 Sangamo Weston, Inc. High temperature plastic scintillator
US4657696A (en) * 1984-09-19 1987-04-14 Fisons Plc Scintillation counting medium and counting method
US5037578A (en) * 1986-02-18 1991-08-06 Exciton Chemical Company O,O'-bridged oligophenylene laser dyes and dyestuff lasers and method of lasing therewith
US5041238A (en) * 1986-02-18 1991-08-20 Exciton Chemical Company o,o'-Bridged oligophenylene laser dyes, dyestuff lasers and methods of lasing therewith
US5110500A (en) * 1988-09-02 1992-05-05 University Of Florida Polysiloxane scintillator composition
US5146025A (en) * 1989-02-28 1992-09-08 Mitsubishi Gas Chemical Company, Inc. Naphthalene compounds
US5151549A (en) * 1989-02-28 1992-09-29 Mitsubishi Gas Chemical Company, Inc. Naphthalene compounds
EP0558157A1 (en) * 1989-02-28 1993-09-01 Mitsubishi Gas Chemical Company, Inc. Naphthalene compounds
EP0390322A3 (en) * 1989-02-28 1990-11-22 Mitsubishi Gas Chemical Company, Inc. Naphthalene compounds
EP0388150A1 (en) * 1989-03-13 1990-09-19 Chisso Corporation Alkenyl ether derivatives and liquid crystal composition containing the same
US5447656A (en) * 1992-07-09 1995-09-05 Hoechst Aktiengesellschaft Meta-substituted aromatic compounds having six-membered rings, for use in liquid-crystal mixtures
US7462427B2 (en) 2001-09-14 2008-12-09 Qinetiq Limited Liquid crystal compounds with branched or cyclic end groups
US20040206933A1 (en) * 2001-09-14 2004-10-21 Goodby John W Liquid crystal compounds with branched or cyclic end groups
US20040056186A1 (en) * 2002-09-19 2004-03-25 Schlumberger Technology Corporation High temperature scintillator
US6884994B2 (en) 2002-09-19 2005-04-26 Schlumberger Technology Corporation High temperature scintillator
WO2015015904A1 (ja) * 2013-08-01 2015-02-05 Jnc株式会社 液晶組成物および液晶表示素子
JPWO2015015904A1 (ja) * 2013-08-01 2017-03-02 Jnc株式会社 液晶組成物および液晶表示素子
US9714383B2 (en) 2013-08-01 2017-07-25 Jnc Corporation Liquid crystal composition and liquid crystal display device
CN119798102A (zh) * 2025-03-14 2025-04-11 厦门大学 一种纯有机高分辨率玻璃闪烁体的制备方法和应用

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CH529357A (de) 1972-10-15

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