Claims:WE CLAIM:
1. A process for preparing 1,8-diaminonaphthalene having purity greater than 98%, said process comprising the following steps:
(i) reducing crude dinitronaphthalene with a reducing agent, to obtain a product mixture comprising 1,8-diaminonaphthalene and 1,5-Diaminonaphthalene, wherein said crude dinitronaphthalene contains 1,5-dinitronaphthalene and 1,8-dinitronaphthalene in a weight ratio in the range of 1:3 to 1:6;
(ii) cooling the product mixture to a temperature in the range of 10 °C to 25 °C, to allow partial precipitation of 1,5-Diaminonaphthalene, to obtain a slurry;
(iii) filtering said slurry to obtain a first filtrate comprising crude 1,8-diaminonaphthalene and a solid residue comprising 1,5-Diaminonaphthalene;
(iv) reacting the first filtrate with hydrochloric acid to obtain hydrochloride salt of 1,8-diaminonaphthalene;
(v) mixing the hydrochloride salt, with water and an alkali at a temperature in the range of 70 °C to 80 °C, to obtain a biphasic mixture comprising a non-aqueous phase containing 1,8-Diaminonaphthalene and an aqueous phase comprising unused alkali; and
(vi) separating said non-aqueous phase at a temperature in the range of 70 °C to 80 °C, and further cooling to a temperature in the range of 20 °C to 30 °C, to obtain a precipitate of 1,8-Diaminonaphthalene having purity greater than 98%.
2. The process as claimed in claim 1, wherein said crude dinitronaphthalene contains 1,5-dinitronaphthalene and 1,8-dinitronaphthalene in a weight ratio of 1:4.
3. The process as claimed in claim 1, wherein said reducing agent is iron and hydrochloric acid, wherein step (i) of reduction is carried out at a temperature in the range of 55 °C to 70 °C, to obtain a resultant mixture.
4. The process as claimed in claims 1 or 3, wherein the resultant mixture is treated with a base, followed by the separation of said iron by hot filtration at a temperature in the range of 70 °C to 90 °C, to obtain the product mixture.
5. The process as claimed in claim 4, wherein the base is at least one selected from the group consisting of sodium bicarbonate, sodium hydroxide, sodium carbonate, potassium bicarbonate, potassium carbonate, and potassium hydroxide.
6. The process as claimed in claim 1, wherein step (iv) of obtaining the hydrochloride salt of 1,8-Diaminonaphthalene comprises the following steps:
(a) mixing the first filtrate with hydrochloric acid to obtain a mixture comprising solid phase and liquid phase;
(b) separating the solid phase from the mixture to obtain a wet cake comprising hydrochloride salt of 1,8-Diaminonaphthalene and hydrochloride salt of 1,5-Diaminonaphthalene;
(c) mixing the wet cake with concentrated hydrochloric acid and water, at a temperature in the range of 70 °C to 80 °C, for a time period in the range of 10 minutes to 90 minutes, to obtain a hot mixture, wherein amount of concentrated hydrochloric acid is in the range of 30 wt.% to 35 wt.% with respect to the wet cake; and
(d) filtering the hot mixture at a temperature in the range of 70 °C to 80 °C, to obtain a solid product containing the hydrochloride salt of 1,8-Diaminonaphthalene and second filtrate comprising the hydrochloride salt of 1,5-Diaminonaphthalene.
7. The process as claimed in claim 1, wherein in step (iv), the crude 1,8-Diaminonaphthalene is optionally separated from the first filtrate, prior to the reaction with hydrochloric acid.
8. The process as claimed in claim 1, wherein step (v) of mixing is carried out at a pH range of 8 to 11, wherein the alkali used is at least one selected from the group consisting of sodium bicarbonate, sodium hydroxide, sodium carbonate, potassium bicarbonate, potassium carbonate, and potassium hydroxide.
9. The process as claimed in claim 1, wherein the precipitate obtained in step (vi) is dried at a temperature in the range of 40 °C to 50 °C.
10. The process as claimed in claim 1, wherein the purity of 1,8-diaminonaphthalene is in the range of 98.5% to 99.5%.
Dated this 14th day of August, 2019

MOHAN DEWAN
of R.K. DEWAN & COMPANY
IN/PA-25
APPLICANT’S PATENT ATTORNEY

TO,
THE CONTROLLER OF PATENTS
THE PATENT OFFICE, AT MUMBAI
, Description:

FIELD
The present disclosure relates to a process for preparing and purifying 1,8-Diaminonaphthalene.
DEFINITION
As used in the present disclosure, the following terms are generally intended to have the meaning as set forth below, except to the extent that the context in which they are used indicate otherwise.
Crude dinitronaphthalene refers to dinitronaphthalene containing 1,5-dinitronaphthalene and 1,8-dinitronaphthalene in a weight ratio in the range of 1:3 to 1:6.
Crude 1,8-diaminonaphthalene refers to 1,8-diaminonaphthalene compound comprising at least 2 wt.% of 1,5-diaminonaphthalene as an impurity.
BACKGROUND
The background information herein below relates to the present disclosure but is not necessarily prior art.
Diaminonaphthalene derivatives are important intermediate compounds available as various positional isomers having the amino groups at varying positions such as 1,8-Diaminonaphthalene (1,8-DAN) and 1,5-Diaminonaphthalene (1,5-DAN) isomers. 1,8-DAN is used as an intermediate for organic synthesis of dyes, mainly in the production of solvent dyes. 1,8-DAN is also widely used as a raw material for the manufacture of cosmetics.
The currently used methods for the preparation of 1,8-Diaminonaphthalene are tedious, have poor reproducibility and lower yields. The conventional processes require hydrogen gas, which needs to be handled with precautionary measures. Further, the catalysts used in the conventional processes are expensive.
The conventional methods also produce a significant amount of 1,5-Diaminonaphthalene isomer along with the desired 1,8-Diaminonaphthalene isomer, that is difficult to separate by conventional methods, thus resulting in relatively lower purity of 1,8-Diaminonaphthalene. The conventional purification methods to obtain 1,8-Diaminonaphthalene, such as distillation, tend to degrade the 1,8-DAN isomer, thus affecting the yield of the desired product.
There is, therefore, felt a need to provide a simple and economical process for preparing and purifying 1,8-Diaminonaphthalene that obviates the above mentioned drawbacks.
OBJECTS
Some of the objects of the present disclosure, which at least one embodiment herein satisfies, are as follows.
It is an object of the present disclosure to ameliorate one or more problems of the prior art or to at least provide a useful alternative.
Another object of the present disclosure is to provide a simple and economical process for preparing 1,8-Diaminonaphthalene in relatively high yield.
Still another object of the present disclosure is to provide a process for purifying 1,8-Diaminonaphthalene.
Other objects and advantages of the present disclosure will be more apparent from the following description, which is not intended to limit the scope of the present disclosure.
SUMMARY
The present disclosure provides a process for preparing 1,8-diaminonaphthalene (1,8-DAN) having purity greater than 98%. The process comprises a step of reducing crude dinitronaphthalene with a reducing agent, to obtain a product mixture comprising 1,8-Diaminonaphthalene and 1,5-Diaminonaphthalene, wherein the crude dinitronaphthalene contains 1,5-dinitronaphthalene and 1,8-dinitronaphthalene in a weight ratio in the range of 1:3 to 1:6. The product mixture is cooled to a temperature in the range of 10 °C to 25 °C, to allow partial precipitation of 1,5-Diaminonaphthalene, to obtain a slurry. The slurry is filtered to obtain a first filtrate comprising crude 1,8-Diaminonaphthalene and a solid residue comprising 1,5-Diaminonaphthalene. The first filtrate is reacted with hydrochloric acid to obtain hydrochloride salt of 1,8-Diaminonaphthalene. The hydrochloride salt of 1,8-Diaminonaphthalene is mixed with water and an alkali at a temperature in the range of 70 °C to 80 °C, to obtain a biphasic mixture comprising a non-aqueous phase containing 1,8-Diaminonaphthalene and an aqueous phase comprising unused alkali. The non-aqueous phase is separated at a temperature in the range of 70 °C to 80 °C, and further cooled to a temperature in the range of 20 °C to 30 °C to obtain a precipitate of 1,8-Diaminonaphthalene having purity greater than 98%.
The step of obtaining the hydrochloride salt of 1,8-DAN comprises mixing the first filtrate with hydrochloric acid to obtain a mixture comprising solid phase and liquid phase. The solid phase is separated from the mixture to obtain a wet cake comprising hydrochloride salt of 1,8-Diaminonaphthalene and hydrochloride salt of 1,5-Diaminonaphthalene. The wet cake is mixed with aqueous hydrochloric acid at a temperature in the range of 70 °C to 80 °C, for a time period in the range of 10 minutes to 90 minutes, to obtain a hot mixture. The hot mixture is filtered at a temperature in the range of 70 °C to 80 °C, to obtain a solid product containing the hydrochloride salt of 1,8-Diaminonaphthalene and second filtrate comprising the hydrochloride salt of 1,5-Diaminonaphthalene.
DETAILED DESCRIPTION
Embodiments are provided so as to thoroughly and fully convey the scope of the present disclosure to the person skilled in the art. Numerous details, are set forth, relating to specific components, and methods, to provide a complete understanding of embodiments of the present disclosure. It will be apparent to the person skilled in the art that the details provided in the embodiments should not be construed to limit the scope of the present disclosure. In some embodiments, well-known processes, well-known apparatus structures, and well-known techniques are not described in detail.
The terminology used, in the present disclosure, is only for the purpose of explaining a particular embodiment and such terminology shall not be considered to limit the scope of the present disclosure. As used in the present disclosure, the forms "a,” "an," and "the" may be intended to include the plural forms as well, unless the context clearly suggests otherwise. The terms "comprises," "comprising," “including,” and “having,” are open ended transitional phrases and therefore specify the presence of stated features, integers, steps, operations, elements, modules, units and/or components, but do not forbid the presence or addition of one or more other features, integers, steps, operations, elements, components, and/or groups thereof. The particular order of steps disclosed in the method and process of the present disclosure is not to be construed as necessarily requiring their performance as described or illustrated. It is also to be understood that additional or alternative steps may be employed.
The terms first, second, third, etc., should not be construed to limit the scope of the present disclosure as the aforementioned terms may be only used to distinguish one element, component, region, layer or section from another component, region, layer or section. Terms such as first, second, third etc., when used herein do not imply a specific sequence or order unless clearly suggested by the present disclosure.
1,8-Diaminonaphthalene (1,8-DAN) and 1,5-Diaminonaphthalene (1,5-DAN) are isomers which are diamine derivatives of naphthalene having the chemical formula C10H6(NH2)2.

1,8-Diaminonaphthalene 1,5-Diaminonaphthalene
1,8-Diaminonaphthalene is a colorless solid which is commonly used as a precursor for commercial pigments. The currently used methods for the preparation of 1,8-Diaminonaphthalene are tedious, have poor reproducibility and relatively lower yields. The conventional processes require costly catalysts and hydrogen gas, which needs to be handled with precautionary measures.
The conventional methods also produce a significant amount of 1,5-Diaminonaphthalene along with the desired 1,8-Diaminonaphthalene isomer, that is difficult to separate, thus resulting in relatively lower purity of 1,8-Diaminonaphthalene. The conventional separation methods, such as distillation, tend to degrade 1,8-DAN, thus affecting the yield of the desired product.
The present disclosure provides a process for preparing 1,8-Diaminonaphthalene. The process is simple and economical that provides 1,8-DAN in comparatively high yield and purity.
In an aspect, the present disclosure provides a process for preparing 1,8-diaminonaphthalene (1,8-DAN) having purity greater than 98%.
In the first step, crude dinitronaphthalene is reduced with a reducing agent, to obtain a product mixture comprising 1,8-Diaminonaphthalene and 1,5-Diaminonaphthalene.
The crude dinitronaphthalene contains 1,5-dinitronaphthalene and 1,8-dinitronaphthalene in a weight ratio in the range of 1:3 to 1:6. In an exemplary embodiment, the crude dinitronaphthalene contains 1,5-dinitronaphthalene and 1,8-dinitronaphthalene in a weight ratio of 1:4.
In an embodiment, the reducing agent is iron and hydrochloric acid, wherein the reduction is carried out at a temperature in the range of 55 °C to 70 °C, to obtain a resultant mixture. In an embodiment, the reduction is carried out at 65 °C.
The molar ratio of the crude dinitronaphthalene and iron is in the range of 1:4 to 1:10. In an exemplary embodiment, the molar ratio of the crude dinitronaphthalene and iron is 1:6.
The molar ratio of the crude dinitronaphthalene and hydrochloric acid is in the range of 1:0.1 to 1:2. In an exemplary embodiment, the molar ratio of the crude dinitronaphthalene and hydrochloric acid is 1:0.2.
The hydrochloric acid has a concentration in the range of 30% to 35%.
In an embodiment, crude dinitronaphthalene is reduced using iron and hydrochloric acid, to obtain a resultant mixture. The resultant mixture is treated with a base followed by separation of the iron by hot filtration at a temperature in the range of 70 °C to 90 °C, to obtain the product mixture.
The base is at least one selected from the group consisting of sodium bicarbonate, sodium hydroxide, sodium carbonate, potassium bicarbonate, potassium carbonate, and potassium hydroxide. In an embodiment, the base is sodium carbonate.
In an exemplary embodiment, iron powder is added to water, followed by the addition of 30% concentrated hydrochloric acid. The resultant mixture is heated to 65 °C, while simultaneously adding crude dinitronaphthalene, containing 1,5-dinitronaphthalene and 1,8-dinitronaphthalene in a weight ratio of 1:4, to obtain a reaction mixture. The reaction mixture is stirred at 65 °C, followed by the addition of sodium carbonate and the resultant mass is allowed to settle, to obtain an upper aqueous layer and a residual layer. The upper aqueous layer is removed by decantantion, and toluene is added to the residual layer, followed by the removal of remaining water by steam distillation. The iron in the residual layer is separated by hot filtration at 80 °C, to obtain the product mixture.
In the next step, the product mixture is cooled to a temperature in the range of 10 °C to 25 °C, to allow partial precipitation of 1,5-Diaminonaphthalene, to obtain a slurry. The slurry is filtered to obtain a solid residue comprising 1,5-Diaminonaphthalene and a first filtrate comprising crude 1,8-Diaminonaphthalene.
The cooling of the product mixture enables partial removal of 1,5-Diaminonaphthalene, due to the relatively higher insolubility of 1,5-Diaminonaphthalene as compared to 1,8-Diaminonaphthalene at the temperature range of 10 °C to 25 °C.
The process of the present disclosure not only provides effective removal of impurities from the product mixture, but also enables to recover 1,5-Diaminonaphthalene.
In an exemplary embodiment, the product mixture is cooled to 15 °C.
In the next step, the first filtrate is reacted with hydrochloric acid to obtain hydrochloride salt of 1,8-Diaminonaphthalene.
In an embodiment, the step of obtaining the hydrochloride salt of 1,8-Diaminonaphthalene comprises mixing the first filtrate with hydrochloric acid to obtain a mixture comprising solid phase and liquid phase. The solid phase is separated from the mixture to obtain a wet cake comprising hydrochloride salt of 1,8-Diaminonaphthalene and hydrochloride salt of 1,5-Diaminonaphthalene. The wet cake is mixed with concentrated hydrochloric acid and water, at a temperature in the range of 70 °C to 80 °C, for a time period in the range of 10 minutes to 90 minutes, to obtain a hot mixture. The hot mixture is filtered at a temperature in the range of 70 °C to 80 °C, to obtain a solid product containing the hydrochloride salt of 1,8-Diaminonaphthalene and a second filtrate comprising the hydrochloride salt of 1,5-Diaminonaphthalene.
The hydrochloric acid, added to the wet cake, has a concentration in the range of 30% to 35%.
The amount of concentrated hydrochloric acid added to the wet cake is in the range of 30 wt.% to 35 wt.% with respect to the wet cake. In an exemplary embodiment, the amount of hydrochloric acid is 32 wt.% with respect to the wet cake.
1,5-Diaminonaphthalene is partially removed in the step of cooling of the filtrate. However, the remaining amount of 1,5-Diaminonaphthalene remains in the filtrate which forms the corresponding hydrochloride salt (of 1,5-DAN) in the wet cake (along with HCl salt of 1,8-DAN). Upon mixing the wet cake with hydrochloric acid, at the temperature range of 70 °C to 80 °C, the hydrochloride salt of 1,5-Diaminonaphthalene gets solubilized and is separated from the hydrochloride salt of 1,8-Diaminonaphthalene during hot filtration. The removal of 1,5-DAN by the formation of hydrochloride salt provides an improved technique than conventional methods such as distillation, thus resulting in comparatively higher yields. The degradation of the product observed during distillation is thus avoided in the process of the present disclosure.
In an embodiment, the crude 1,8-Diaminonaphthalene is optionally separated from the first filtrate, prior to the reaction with hydrochloric acid. Crude 1,8-diaminonaphthalene refers to 1,8-diaminonaphthalene compound comprising at least 2 wt.% of 1,5-diaminonaphthalene as an impurity. In an exemplary embodiment, crude 1,8-Diaminonaphthalene comprising 5 wt.% of 1,5-Diaminonaphthalene is purified by reaction with hydrochloric acid.
The amount of hydrochloric acid added to the crude 1,8-Diaminonaphthalene is in the range of 40 wt.% to 45 wt.%. In an exemplary embodiment, the amount of hydrochloric acid is 43 wt.%.
In the next step, the hydrochloride salt of 1,8-Diaminonaphthalene is mixed with water and an alkali at a temperature in the range of 70 °C to 80 °C, to obtain a biphasic mixture comprising a non-aqueous phase containing 1,8-Diaminonaphthalene and an aqueous phase comprising unused alkali. The non-aqueous phase is separated at temperature in the range of 70 °C to 80 °C, and further cooled to a temperature in the range of 20 °C to 30 °C, to obtain precipitate of 1,8-Diaminonaphthalene having purity greater than 98%.
The mixing of HCl salt of 1,8-DAN with the alkali is carried out at a pH range of 8 to 11.
In an exemplary embodiment, the alkali is added at 75 °C, till a pH of 10 is attained.
The alkali is at least one selected from the group consisting of sodium bicarbonate, sodium hydroxide, sodium carbonate, potassium bicarbonate, potassium carbonate, and potassium hydroxide.
The alkali has a concentration in the range of 45 wt.% to 55 wt.%.
In an embodiment, the alkali is aqueous sodium hydroxide solution having concentration of 50 wt.%.
In an embodiment, prior to the separation of the non-aqueous phase, the biphasic mixture is stirred at a temperature in the range of 70 °C to 80 °C, for a time period in the range of 10 minutes to 90 minutes. In an exemplary embodiment, the biphasic mixture is stirred at 75 °C for 60 minutes.
The precipitate of 1,8-DAN is dried at a temperature in the range of 40 °C to 50 °C. In an exemplary embodiment, the precipitate is dried at 45 °C.
The purity of 1,8-diaminonaphthalene is in the range of 98.5 % to 99.5%. In an embodiment the purity of 1,8-diaminonaphthalene is 99 %.
The process of the present disclosure is simple and economical that employs HCl purification method to obtain 1,8-Diaminonaphthalene in relatively high yields having relatively high purity, without using conventional distillation methods thus preventing degradation of the product.
The foregoing description of the embodiments has been provided for purposes of illustration and not intended to limit the scope of the present disclosure. Individual components of a particular embodiment are generally not limited to that particular embodiment, but, are interchangeable. Such variations are not to be regarded as a departure from the present disclosure, and all such modifications are considered to be within the scope of the present disclosure.
The present disclosure is further described in light of the following laboratory scale experiments which are set forth for illustration purpose only and not to be construed for limiting the scope of the disclosure. These laboratory scale experiments can be scaled up to industrial/commercial scale and the results obtained can be extrapolated to industrial/commercial scale.
Experimental Details
Experiment 1
Step 1 – Reduction of crude dinitronaphthalene and partial removal of 1,5-Diaminonaphthalene
Water (1 litre) was charged in the reaction vessel followed by addition of 310gm of iron powder and 20.5 mL of conc. HCl (30% concentration), to obtain a mixture. The mixture was heated at 65 °C, while simultaneously adding 200g of crude Dinitronaphthalene, containing 1,5-dinitronaphthalene and 1,8-dinitronaphthalene in a ratio of 1:4, to obtain a reaction mixture. The temperature of the reaction mixture was maintained at 65 °C till the completion of the reaction which was monitored by Thin Layer Chromatography (TLC), to obtain a resultant mixture comprising 1,8-diaminonaphthalene and 1,5-Diaminonaphthalene. 10g of sodium carbonate was added to the resultant mixture and the mass was allowed to settle to obtain an upper aqueous layer and a residual layer. The upper aqueous layer was then decanted and to the remaining residual layer, 740 mL toluene was added to obtain a mixture. The residual water was removed from the mixture by steam distillation and cooled to 80 °C followed by hot filtration to remove iron to obtain a product mixture. The product mixture was cooled to 15 °C to allow partial precipitation of 1,5-Diaminonaphthalene to obtain a slurry which was filtered to recover 20g of 1,5-Diaminonaphthalene and a first filtrate comprising crude 1,8-Diaminonaphthalene.
Step 2– Preparation of hydrochloride salt of diaminonaphthalene (wet cake)
The first filtrate (782 g) was mixed with concentrated HCl (149.2 g) to obtain a mixture comprising solid phase and liquid phase. The solid phase was separated from the mixture by filtration to obtain 200g of wet cake (comprising hydrochloride salt of 1,8-Diaminonaphthalene and hydrochloride salt of 1,5-Diaminonaphthalene).
Step 3 – Purification of wet cake to obtain 1,8-Diaminonaphthalene
30% concentrated hydrochloric acid (64 g) was added to water (125 mL) to obtain aqueous hydrochloric acid solution. The wet cake (200 g), as obtained in step 2, was mixed with the aq. HCl, at 75 °C, for 60 minutes to obtain a hot mixture. The hot mixture was filtered at 75 °C, to obtain a solid product containing the hydrochloride salt of 1,8-Diaminonaphthalene. The hydrochloride was mixed with 50% aq. sodium hydroxide solution, at 75 °C to obtain a biphasic mixture comprising a non-aqueous phase containing 1,8-Diaminonaphthalene and an aqueous phase comprising unused alkali. The non-aqueous phase was separated at 75 °C, and further cooled to 25 °C, to obtain precipitate of 1,8-Diaminonaphthalene (87 g) with a yield of 60% and purity of 99%, which was dried at 45 °C.
Experiment 2
Purification of crude 1,8-Diaminonaphthalene
30% concentrated hydrochloric acid (85 g) was added to water (125 mL) to obtain aqueous hydrochloric acid solution. 200 g of crude 1,8-diaminonaphthalene containing 5 wt.% of 1,5-Diaminonaphthalene, obtained commercially, was mixed with the aq. HCl, at 75 °C, for 60 minutes to obtain a hot mixture. The hot mixture was filtered at 75 °C, to obtain a solid product containing the hydrochloride salt of 1,8-Diaminonaphthalene. The hydrochloride salt was mixed with 50% aq. sodium hydroxide solution, at 75 °C to obtain a biphasic mixture comprising a non-aqueous phase containing 1,8-Diaminonaphthalene and an aqueous phase comprising unused alkali. The non-aqueous phase was separated at 75 °C, and further cooled to 25 °C, to obtain precipitate of 1,8-Diaminonaphthalene (160 g) with a recovery of 80%, and purity of 99%, which was dried at 45 °C.
TECHNICAL ADVANCEMENTS
The present disclosure described herein above has several technical advantages including but not limited to realization of a process for preparing 1,8-Diaminonaphthalene that:
? is simple and economical;
? avoids conventional methods of purification such as distillation, thereby avoiding degradation and improving yield;
? enables effective removal of 1,5-diaminonaphthalene from a mixture of 1,5- and 1,8-isomers; and
? uses HCl purification that provides 1,8-Diaminonaphthalene having relatively high purity.
Throughout this specification the word “comprise”, or variations such as “comprises” or “comprising”, will be understood to imply the inclusion of a stated element, integer or step, or group of elements, integers or steps, but not the exclusion of any other element, integer or step, or group of elements, integers or steps.
The use of the expression “at least” or “at least one” suggests the use of one or more elements or ingredients or quantities, as the use may be in the embodiment of the disclosure to achieve one or more of the desired objects or results.
Any discussion of documents, acts, materials, devices, articles or the like that has been included in this specification is solely for the purpose of providing a context for the disclosure. It is not to be taken as an admission that any or all of these matters form a part of the prior art base or were common general knowledge in the field relevant to the disclosure as it existed anywhere before the priority date of this application.
The numerical values mentioned for the various physical parameters, dimensions or quantities are only approximations and it is envisaged that the values higher/lower than the numerical values assigned to the parameters, dimensions or quantities fall within the scope of the disclosure, unless there is a statement in the specification specific to the contrary.
While considerable emphasis has been placed herein on the components and component parts of the preferred embodiments, it will be appreciated that many embodiments can be made and that many changes can be made in the preferred embodiments without departing from the principles of the disclosure. These and other changes in the preferred embodiment as well as other embodiments of the disclosure will be apparent to those skilled in the art from the disclosure herein, whereby it is to be distinctly understood that the foregoing descriptive matter is to be interpreted merely as illustrative of the disclosure and not as a limitation.