U.S. patent number 3,666,683 [Application Number 04/832,881] was granted by the patent office on 1972-05-30 for scintillation counting composition containing oxdiazole.
Invention is credited to Rudolf Anliker, Erwin Maeder, Karl Schmid, Adolf Emil Siegrist.
United States Patent |
3,666,683 |
Maeder , et al. |
May 30, 1972 |
SCINTILLATION COUNTING COMPOSITION CONTAINING OXDIAZOLE
Abstract
The invention relates to a composition of matter for counting
atomic disintegrations of radioactive material which is accompanied
by emission of .beta.-rays which contains an oxdiazole compound of
the formula ##SPC1## Wherein A.sub.1 is a branched chain alkyl,
B.sub.1 is hydrogen, phenyl, lower alkyl, or lower alkoxy, and m is
1 or 2. The counts per minute emitted by the material dispersed in
the scintillation liquid are measured with a suitable instrument
such as a liquid scintillation spectrometer.
Inventors: |
Maeder; Erwin (Aesch/Bl,
CH), Anliker; Rudolf (Binningen, CH),
Schmid; Karl (Reinach/Bl, CH), Siegrist; Adolf
Emil (Basel, CH) |
Family
ID: |
25262844 |
Appl.
No.: |
04/832,881 |
Filed: |
June 9, 1969 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
Issue Date |
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577168 |
Sep 1966 |
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Current U.S.
Class: |
436/58;
252/301.17; 548/143; 250/483.1; 525/375; 548/145 |
Current CPC
Class: |
G01T
1/2042 (20130101) |
Current International
Class: |
G01T
1/00 (20060101); G01T 1/204 (20060101); C07d
085/54 (); G01t 001/204 () |
Field of
Search: |
;252/408,301.2
;260/93.6,307,309,144 ;250/83,83.6 ;356/98 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Goolkasian; John T.
Assistant Examiner: McCamish; M. E.
Parent Case Text
CROSS-REFERENCE TO RELATED APPLICATION
This application is a division of Ser. No. 577,168, filed Sept. 6,
1966, and now abandoned.
Claims
What is claimed is:
1. A composition of matter for scintillation counting containing a
solvent selected from the group consisting of benzene, or an
alkylbenzene that is liquid at room temperature and a
dioxane+naphthalene+water mixture and 0.01 to 5 percent by weight,
referred to the total amount of scintillation liquid, of an
oxdiazole derivative of the formula ##SPC15##
in which A.sub.1 represents an alkyl group containing three to
seven carbon atoms and at least one chain branching, and B.sub.1
represents a member selected from the group consisting of hydrogen
atom, a phenyl group, and an alkyl group which contains one to
seven carbon atoms and may be branched or a lower alkoxy group, and
m is a whole number from 1 to 2.
2. A composition of matter for scintillation counting according to
claim 1 containing a solvent toluene and 0.01 to 5 percent by
weight, referred to the weight of the whole liquid, of an oxdiazole
derivative of the formula ##SPC16##
in which B.sub.2 represents a member selected from the group
consisting of a tertiary butyl group and a phenyl group.
3. A composition of matter according to claim 1 containing as
oxdiazole derivative the compound of the formula ##SPC17##
4. A composition of matter according to claim 1 containing as
oxdiazole derivative the compound of the formula ##SPC18##
5. A composition of matter according to claim 1 containing as
oxdiazole derivative the compound of the formula ##SPC19##
6. A composition of matter according to claim 1 containing as
oxdiazole derivative the compound of the formula ##SPC20##
7. A composition of matter according to claim 1 containing as
oxdiazole derivative the compound of the formula ##SPC21##
8. A composition of matter for scintillation counting method
substantially consisting of a polymeric material which contains at
least one compound of the general formula ##SPC22##
in which A.sub.1 represents an alkyl group which contains three to
seven carbon atoms and at least one chain branching; B.sub.1
represents a member selected from the group consisting of a
hydrogen atom, a phenyl group, an alkyl group which contains one to
seven carbon atoms and a lower alkoxy group, and m stands for a
whole number from 1 to 2.
Description
The present invention relates to the use of selected oxdiazole
derivatives for scintillation counting methods in atomic
disintegrations.
While a number of oxdiazole derivatives have already been proposed
for use in scintillation counting, especially in liquid systems,
these compounds do not satisfy fully all the requirements they
should satisfy. This refers above all to a high energy transfer at
an extremely short extinction time combined with a low absorption
coefficient for self-quenching and with a high solubility in the
solvents or solvent systems preferably employed in liquid
scintillation counting methods. An adequate chemical stability
(stability towards the action of light and towards acids and
alkalies) is moreover a precondition for their suitability
anyway.
It has now been found that a small selection of certain oxdiazole
derivatives satisfy all of these requirements. According to this
invention there are thus used oxdiazole derivatives comprising the
structural element ##SPC2##
--in which A.sub.1 represents an alkyl group which contains three
to seven carbon atoms and at least one chain branching, and m and n
each is 1 or 2 (n meaning that A.sub.1 represents one or two
substituents)--as scintillator substances.
Primarily, there are used in this invention oxdiazole derivatives
of the formula ##SPC3##
In which A.sub.1 represents an alkyl group which contains three to
seven carbon atoms and at least one chain branching, and B.sub.1
represents a hydrogen atom, a phenyl group, an alkyl group having
one to seven carbon atoms, which may be branched, or a lower alkoxy
group, and m = 1 or 2--as scintillation substance for use in liquid
scintillation counting.
The scintillation liquids concerned are characterized in that they
contain as solvent benzene or an alkylbenzene which is liquid at
room temperature or a dioxane+naphthalene+water mixture and 0.01 to
5 percent by weight (referred to the total weight of the
scintillation liquid) of an oxdiazole derivative of the formula
(2).
Of special importance within the scope of this invention is the use
of oxdiazole derivatives of the formula ##SPC4##
--in which B.sub.2 represents a tertiary butyl group or a phenyl
group--in liquid scintillation counting methods. In this case the
scintillation liquids contain preferably toluene as solvent and
0.01 to 5 percent by weight (referred to the total weight of the
scintillation liquid) of an oxdiazole derivative of the formula
(3).
As examples from the above-mentioned types of oxdiazoles the
following compounds may be mentioned: ##SPC5##
From the foregoing it will be realized that the use of the said
scintillation substances is of special importance to liquid
scintillation counting methods in conjunction with certain solvent
systems. Thus, this invention further includes a method of counting
atomic disintegrations accompanied by the emission of .beta.-rays,
by means of the liquid scintillation method in predominantly
aromatic hydrocarbons as scintillator solvents, characterized in
that the scintillation liquid used is a solution of an oxidazole of
the formula ##SPC6##
(in which A.sub.1, B.sub.1 and m have the above meanings) in
benzene, or in an alkylbenzene liquid at room temperature, in a
mixture of methanol+toluene, methylcellosolve+naphthalene+toluene
or dioxane+naphthalene+water.
The specific oxdiazoles mentioned in connection with the liquid
scintillation counting method described above are even as such
scintillators that satisfy all above-mentioned requirements. In
addition, they may also be used as so-called primary solutes in the
narrower sense, that is to say as a primary substance activated to
emit light by an energy-rich radiation released by an atomic
disintegration; these primary substances are combined with the
usual secondary solutes, that is to say substances distinguished by
an emission of longer wavelength. Such suitable secondary solutes
are, for example, 1,4-di-[2-(5-phenyloxazolyl)]-benzene,
1,4-di-[2-(4-methyl-5-phenyloxazolyl)]-benzene and
1,4-di-(4'-isopropylstyryl)-benzenes. Furthermore, they may be
combined with neutron capture solutes, gamma conversion solutes,
further solvent additives, gels, suspending assistants or
solubilizers. The counting method used may, of course, be either an
internal or an external method.
Suitable solvents for the liquid scintillation counting method are
above all aromatic hydrocarbons that are liquid at room temperature
(provided no solvent combination is used) such, for example, as
benzene, toluene, a xylene, ethylbenzene, 1,3,5-triethylbenzene,
cumene, a cymene, phenylcyclohexane, also ethers such as anisole,
dioxane, 1,2-dimethoxyethane; non-aromatic hydrocarbons such as
cyclohexane, heptane and the like; or finally solvent mixtures such
as toluene+methanol and possibly water, toluene+ethanol,
naphthalene+dioxane, naphthalene+toluene and possibly water,
naphthalene+dioxane+water, methylcellosolve+naphthalene+toluene and
possibly water, naphthalene+tributylphosphate or other commercial
mixtures of aromatic hydrocarbons recommended for these
purposes.
The concentration of the oxdiazole derivatives to be used in the
present process may principally vary within wide limits which are
defined or restricted by practical considerations. For example in
the lower region it must be chosen so that an adequate transmission
to the photomultiplier is ensured, whereas the upper region is
delineated by the appearance of visible absorption of the
self-quenching. Though thus, for example, for the preparation of
stock solutions (which are suitably diluted for use) concentrations
of 10 percent or higher are quite acceptable, the working
concentrations most suitable for actual practice range
approximately from 0.1 to 3 percent, preferably from 0.4 to 2
percent (all percentages are by weight, referred to the total
weight of the solution).
Apart from toluene, preferred solvent systems are the systems
toluene+methanol (1:1) with the addition of about 2 percent of
water, methylcellosolve+toluene+naphthalene (40:60:8) with addition
of up to 4 percent of water, dioxane+toluene+naphthalene (40:60:8)
with up to 10 percent of water, or toluene+methanol+ethanolamine
(50:44:6). The composition of the solvent system depends above all
on the nature of the substrate or of the isotope to be counted. For
isotope counting there are, for example, most frequently used
C.sup.14, H.sup.3, S.sup.35, P.sup.32, Fe.sup.59, Fe.sup.55,
I.sup.125 and I.sup.131.
The technical advance residing in the oxdiazoles to be used in this
invention is especially the fact that they represent as such
scintillators that can be used by themselves (that is to say
without a secondary solute) which not only satisfy all other
requirements to a great extent but above all also display excellent
solubility properties such as the hitherto known highest grade
scintillators of the oxdiazole series did not possess. This is
especially true of the particularly good solubility in transparent
solvents having a high flash point.
In addition to the range of applicability described above the
oxdiazoles defined above may be used quite generally wherever the
task involved is the transformation of an energy-rich radiation
into measurable light.
An important sphere of application is, for example, their use for
so-called plastics scintillators. In this use the scintillator may
be homogeneously dispersed in the polymers concerned (polymerizate,
polycondensate or polyadduct) before proceeding to the final
shaping operation (casting, drawing, moulding, injection moulding
or the like), and the whole is then shaped. According to another
possibility the scintillator is added to the starting materials
used in the manufacture of the polymer, thus for example to the
monomers, before polymerization, whereupon the whole is polymerized
(examples: polystyrene, polyvinyltoluene). Further variants of the
use of the above-mentioned scintillators result readily from the
conventional operations practized in this technique.
The oxdiazoles to be used in the present process can be
manufactured by known methods, for example
a. by reacting 2 mols of a carboxylic acid ##SPC7##
or of an ester thereof with 1 mol of hydrazine in the presence of a
phosphoric acid whose water content is inferior to that of
orthophosphoric acid (especially polyphosphoric acid); this method
is particularly suitable for synthesizing symmetrical oxdiazoles,
that is to say those in which A.sub.1 = B.sub.1, or
b. by treating a diacylhydrazine of the formula ##SPC8##
(for m = 1 according to formula [2]) with a non-sulphonating
dehydrating agent or
c. by reacting an imidoether upon a suitable carboxylic acid
hydrazide at an elevated temperature in the presence of a
solvent.
Unless otherwise indicated, parts and percentages in the following
manufacturing instructions and examples are by weight.
A. 10.0 Parts of hydrazine hydrate are stirred dropwise at
50.degree. C into 400 parts of polyphosphoric acid (83% P.sub.2
O.sub.5), with the temperature rising to about 80.degree. C. Then
71.2 parts of para-tertiary butylbenzoic acid are added and while
excluding air the temperature is raised within 30 minutes to
125.degree. C. The batch is stirred for 8 hours at 125.degree. to
130.degree. C, whereupon a clear, colorless solution forms. After
cooling to about 50.degree. C, the whole is vigorously stirred into
1,000 parts of cold water, the precipitated reaction product is
suctioned off and washed with water until the washings run neutral
to congo red. After drying, there are obtained 66.7 parts (= 100
percent of theory) of 2,5-bis-[4'-para-tertiary
butylphenyl-(1')]-1,3,4-oxdiazole of the formula ##SPC9##
as an almost colorless powder which melts at 135.degree. to
136.degree.C. After recrystallization from ethanol+water (7:1) it
forms colorless flakes melting at 139.degree. to 141.degree.C.
B. 29.6 parts of the diacylhydrazine of the formula ##SPC10##
are brought to the boil in 150 parts by volume of freshly distilled
thionylchloride within 1 hour while being stirred, and the whole is
then refluxed for 2 hours, whereupon a clear, pale-yellow solution
forms. The excess thionylchloride is then distilled off, first
under atmospheric pressure and then under vacuum. The residue is
triturated with ice water, whereupon it solidifies; it is filtered
off, washed with water until the washings run neutral and dried, to
yield about 27.6 parts (= 99.3 percent of theory) of 2-[4'-tertiary
butylphenyl-(1')]-5-phenyl-1,3,4-oxdiazole of the formula (6) as a
colorless powder which on recrystallization from ethanol+water
(3:1) forms colorless flakes; it melts at 98.degree. on 99.degree.
C and displays in an ethanolic solution three absorption maxima at
288 m.mu. (.epsilon. = 30,400), 238 m.mu. (.epsilon. = 7,550) and
232 m.mu. (.epsilon.= 7,350). Solubility in 100 ml of ethanol at
20.degree.C: 4.00 grams.
The following 1,3,4-oxdiazole derivatives are accessible by the
method described above:
a. 2-[4'-tertiary
butylphenyl-(1')]-5-[4"-methylphenyl-(1")]-1,3,4-oxdiazole of the
formula ##SPC11##
in colorless, fine crystals from ethanol+water (7:2). Melting
point: 111.degree. to 112.degree.C. Solubility in 100 ml of ethanol
at 20.degree.C: 2.92 grams. Ultraviolet absorption in ethanol,
maxima at 291 m.mu. (.epsilon. = 31,000) and 242 m.mu. (.epsilon. =
8,650).
b. 2-[4'-tertiary
butylphenyl-(1')]-5-[4"-methoxyphenyl-(1")]-1,3,4-oxdiazole of the
formula ##SPC12##
Colorless, fine crystals from ethanol, melting at 162.5.degree. to
163.5.degree.C. Solubility in 100 ml of ethanol at 20.degree.C:
0.605 gram. Ultraviolet absorption in ethanol, .lambda..sub.max 298
m.mu. (.epsilon. = 32,000) and 249 m.mu. (.epsilon. = 6,100).
c. 2,5-bis-[4'-tertiary butylphenyl-(1')]-1,3,4-oxdiazole of the
formula (5) (see above).
C. A mixture of 212 g of diphenyl-4-carboxylic acid hydrazide and 2
liters of anhydrous ortho-dichlorobenzene is stirred at room
temperature, then 197 g of 4-tertiary butylbenzoylchloride and 81
ml of anhydrous pyridine are added; the thick paste is heated
within 1 hour to 100.degree. to 105.degree.C and stirred at this
temperature for 1 hour. Within a further hour the reaction mixture
is then heated to 140.degree. to 145.degree.C, whereupon an almost
complete solution is obtained. 90 ml of thionylchloride are then
dropped in within 45 minutes at 140.degree. to 145.degree.C,
whereupon a turbid solution forms which is stirred on for 15
minutes after the dropwise addition is complete.
The bulk of the solvent is then evaporated under vacuum and 1 liter
of ethanol is dropped in so that the reaction mixture is kept at
the reflux temperature, whereupon a crystalline precipitate soon
forms which is suctioned off at room temperature, and the filter
cake is washed with alcohol and dried, to yield 295 g of a greyish,
crystalline powder melting at 135.degree. to 136.degree.C.
Crystallization from n-propanol with the aid of active carbon
furnishes 240 g of the compound of the formula ##SPC13##
in the form of colorless prisms melting at 136.degree. to
137.degree.C. C.sub.22 H.sub.22 ON.sub.2 (mol. weight: 354.43)
calculated: C 81.32 H 6.26 N 7.90% found: 81.27 6.14 7.92%.
D. 5.2 Grams of oxalic acid dihydrazide and 10 ml of anhydrous
pyridine are added at 40.degree. to 50.degree.C to a solution of
14.5 g of 4-isopropylbenzoylchloride in 200 ml of anhydrous
ortho-dichlorobenzene. In the course of 2 hours the reaction
mixture is heated to 130.degree. to 135.degree.C, whereupon a
thinly liquid paste is obtained. Within 30 minutes at 130.degree.
to 135.degree.C 20 ml of thionylchloride are dropped in, whereupon
a clear solution forms which is stirred for another 15 minutes at
this temperature and then allowed to cool.
The excess thionylchloride and the solvent are then almost
completely evaporated under vacuum. The residue is stirred with 100
ml of methanol, whereupon a light-brown, crystalline precipitate is
obtained which is suctioned off and washed with methanol.
Two recrystallizations from alcohol in the presence of bleaching
earth furnish 7 g of the bis-oxdiazolyl compound of the formula
##SPC14##
in the form of small colorless needles melting at 175.degree. to
176.degree.C. C.sub.22 H.sub.22 O.sub.2 N.sub.4 (mol. weight:
374.45)
calculated: C 70.57 H 5.92 N 14.96% found: 70.65 5.91 14.84%.
In the following examples all measurements were recorded in counter
tubes poor in potassium with the use of a liquid scintillation
spectrometer TRI-CARB model Ex-2, makers Messrs. Packard Inst.
Comp. Inc., Ill.
EXAMPLE 1
20 ml each of a solution of 5 g of the compound of the formula (9)
and of the formula (5) in 1 liter of toluene are introduced into a
counter tube and mixed with 1 ml of a solution of benzoic acid
marked with C.sup.14 having an activity of 0.01 microCurie. The
counter tube is inserted into the counter and the counts per minute
(= cpm) are counted. At a high-voltage of 900 Volts and a
calibration from 100 to 600 there are recorded 13,630 cpm for
compound (9) and 13,200 for compound (5).
EXAMPLE 2
20 ml each of a solution of 5 g of the compound of the formula (9)
and of the formula (5) in 1 liter of toluene are introduced into a
counter tube, and 0.1 ml of toluene marked with H.sup.3, having an
activity of 0.01 microCurie, is added. At a high-voltage of 1,100
Volts and a calibration from 100 to 600 there are recorded 6,600
cpm for the compound (9) and 5,930 cpm for the compound (5).
EXAMPLE 3
20 ml each of a solution of 10 g of the compound of the formula (9
) and of the formula (5) in 1 liter of toluene are mixed in a
counter tube with 1.0 ml of an ethanolic solution of
1-butyl-3-(para-tolylsulphonyl)-urea marked with S.sup.35. The
activity added is 0.01 microCurie. The counter tube is then
inserted in the counter and the counts per minute are counted. At a
high-voltage of 900 Volts and a calibration from 100 to 600 in the
measuring channel there are recorded 13,200 cpm for compound (9)
and 12,950 cpm for compound (5).
EXAMPLE 4
20 ml of a solution of 10 g of the compound of the formula (9) in a
mixture of 400 ml of methylcellosolve, 80 g of naphthalene and 600
ml of toluene are introduced in a small measuring cylinder, and 0.5
ml of water marked with H.sup.3, having an activity of 0.01
microCurie, is added. At a high-voltage of 1,200 Volts and a
calibration from 100 to 600, 2,200 counts per minute are
counted.
EXAMPLE 5
A mixture of 1 g of 2-[4'-tertiary
butylphenyl-(1')]-5-biphenylyl-1,3,4-oxdiazole of the formula (9)
and 100 g of vinyltoluene distilled twice under 11 mm Hg pressure
(mixture of the ortho, meta and para isomers) is introduced into a
Pyrex glass tube of 25 mm diameter which is fused at one end. The
tube is repeatedly evacuated to a pressure of 0.1 mm Hg and
scavenged with pure nitrogen. Finally, the tube is once more
evacuated to 0.1 mm Hg pressure and the tube is fused at the other
end. The tube is then heated within 2 hours in a furnace to
110.degree.C while ensuring by carefully revolving it that the
compound of the formula (9) is completely dissolved. To polymerize
the batch in the tube it is maintained for 24 hours at
110.degree.C, then heated for 24 hours at 130.degree.C and for 48
hours at 140.degree.C. The following cooling and detensioning phase
at 75.degree.C takes 81 hours. When the batch has cooled to room
temperature, the resulting transparent polymer core is recovered by
smashing the glass tube. To measure the relative count rate the
core is turned down to a diameter of 20 mm, sawn up into discs 10
mm thick, and these discs are polished. The measure of the light
output is the relative amplitude (RPH) of the counts produced by
the Cs.sup.137 conversion electrons. For counting a Philips 56 AVP
photomultiplier with a ratio
2,2-para-phenylene-bis-(5-phenyloxazole) : terphenyl of 1.30
(photomultiplier characteristic) is used. The counting standard
used is the commercial plastics scintillator NE 102 A (makers
Nuclear Enterprises Ltd.) whose RPH value is taken as equal to
1.00. The plastics scintillator according to this invention
displays an RPH value of 1.10. A plastics scintillator prepared in
identical manner from polyvinyl-toluene, which contains 2 percent
of the compound of the formula (9) and 0.1 percent of
2-[4'-biphenylyl-(1')]-6-phenyl-benzoxazole, gives the high RPH
value of 1.23.
* * * * *