Claims:(1) A process for preparing polybutadiene rubber grafted maleic anhydride (PBR-g-MAH) graft copolymers comprising reacting maleic anhydride (MAH) onto polybutadiene rubber (PBR) cement in presence of free radical initiators and a solvent.
(2) The process as claimed in claim 1, wherein PBR cement comprises polybutadiene rubber, heptane, toluene, butadiene and butane and residual additives.
(3) The process as claimed in claim 1, wherein PBR cement comprises polybutadiene rubber at a concentration range of about 15 to 22 wt. %, heptane is at a concentration range of about 38 to 40 wt.%, toluene is at a concentration range of about 39 to 40 wt.%, butadiene is at a concentration range of about 2 to 3 wt.% and butane is at a concentration range of about 1 to 2 wt. % and residual additives is at a concentration range of about 0.04 to 0.08 wt. %.
(4) The process as claimed in claim 1, wherein the residual additives are selected from a group comprising Phosphate of polyoxyethylene alkyl phenyl ether (PPA) & Metal hydroxide of Ni, Co, Nd or combinations thereof.
(5) A process for preparing polybutadiene rubber grafted maleic anhydride (PBR-g-MAH) graft copolymers said process comprising step of
a. dissolving PBR cement in a solvent to obtain PBR cement solution; and
b. adding free radical initiators and malic anhydride to the PBR cement solution followed by heating to obtain the polybutadiene rubber grafted maleic anhydride (PBR-g-MAH) graft copolymer mixture.
(6) The process as claimed in claim 1 and claim 5, wherein the process further comprise isolation and purification; wherein said isolation is carried out by acts selected from a group comprising addition of solvent, precipitating, quenching, filtration, extraction, drying and combination of thereof;
(7) The process as claimed in claim 1 and claim 5, wherein the process further comprises the step of precipitating PBR-g-MAH graft copolymer in first organic solvent followed by washing with second organic solvent from the mixture obtained from claim 5 to remove unreacted maleic anhydride.
(8) The process as claimed in claim 7, wherein the said first organic solvent is selected from a group comprising methanol, ethanol, propanol, isopropanol and combinations thereof; and the second organic solvent is selected from a group comprising acetone, acetonitrile, ethyl acetate and combinations thereof.
(9) The process as claimed in claim 1 or claim 5, wherein said process is carried out at a temperature ranging from about 25 °C to about 100°C, and for a time period ranging from about 5 minutes to about 90 minutes.
(10) The process as claimed in claim 1 or claim 5, wherein free radical initiator is selected from a group comprising benzoyl peroxide (BPO), dicumyl peroxide (DCP) or their combination.
(11) The process as claimed in claim 1 or claim 5, wherein the benzoyl peroxide is employed at a concentration of about 4.13 to 16.52 mmol and dicumyl peroxide is employed at a concentration of about 0.0074 to 0.074 mmol.
(12) The process as claimed in claim 1 or claim 5, wherein the maleic anhydride is employed at a concentration ranging from about 0.015 mol – 0.31 mol.
(13) The process as claimed in claim 1, wherein the solvent is a hydrocarbon solvent.
(14) The process as claimed in claim 1, wherein the hydrocarbon solvent is selected from a group comprising heptane, toluene, cyclohexane and benzene or combinations thereof.
(15) The process as claimed in claim 1, wherein the hydrocarbon solvent is at a concentration ranging from about 5% weight / volume to 12 % weight / volume

Dated this 13th day of February 2020
Signature:
Name: Durgesh Mukharya
To: Of K&S Partners, Bangalore
The Controller of Patents Agent for the Applicant
The Patent Office, at Mumbai IN/PA-1541
, Description:TECHNICAL FIELD
[001]. The instant disclosure is in the field of chemical sciences, more particularly to synthetic chemistry and material science. The present disclosure generally relates to a process for preparing polybutadiene rubber grafted maleic anhydride (PBR-g-MAH) graft copolymers comprising reacting maleic anhydride (MAH) onto polybutadiene rubber (PBR) cement in presence of free radical initiators and a solvent.

BACKGROUND OF THE DISCLOSURE
[002]. Development of new elastomers with improved properties and performance for application in the area of tyre and automobile industry is critically important. Polybutadiene rubber (PBR) possesses higher concentration of the unsaturated double bonds which offers a unique opportunity for converting the conventional PBR to functionalized elastomers by using various functionalization techniques. Chemical modification of diene elastomers has emerged as an active field of research for increasing the physico-chemical and mechanical properties of these polymers. Incorporation of modified elastomers into different formulations will be useful in preparation of next-generation smart materials such as self-healing elastomers etc.
[003]. Therefore, there is a need to develop a new elastomer with improved properties and performance for application. The present disclosure tried to address said need to provide polybutadiene rubber grafted maleic anhydride (PBR-g-MAH) graft copolymers.

SUMMARY OF THE DISCLOSURE
[004]. The present disclosure relates to a process for preparing polybutadiene rubber grafted maleic anhydride (PBR-g-MAH) graft copolymers comprising reacting maleic anhydride (MAH) onto polybutadiene rubber (PBR) cement in presence of free radical initiators and a solvent.
[005]. The present disclosure relates to a process for preparing polybutadiene rubber grafted maleic anhydride (PBR-g-MAH) graft copolymers said process comprising step of
a. dissolving PBR cement in a solvent to obtain PBR cement solution; and
b. adding free radical initiators and malic anhydride to the PBR cement solution followed by heating to obtain the polybutadiene rubber grafted maleic anhydride (PBR-g-MAH) graft copolymer mixture.
[006]. In an embodiment of the present disclosure, the above said processes further comprise isolation and purification; wherein said isolation is carried out by acts selected from a group comprising addition of solvent, precipitating, quenching, filtration, extraction, drying and combination of thereof;
[007]. In another embodiment of the present disclosure, the above said processes further comprises the step of precipitating PBR-g-MAH graft copolymer initially in first organic solvent followed by washing with second organic solvent from the mixture obtained from claim 5 to remove unreacted maleic anhydride.
[008]. In yet another embodiment of the present disclosure, the said first organic solvent is selected from a group comprising methanol, ethanol, propanol, isopropanol and combinations thereof; and the second organic solvent is selected from a group comprising acetone, acetonitrile, ethyl acetate and combinations thereof.
[009]. In still another embodiment of the present disclosure, the process is carried out at a temperature ranging from about 25 °C to about 100°C, and for a time period ranging from about 5 minutes to about 90 minutes.

STATMENT OF THE DISCLOSURE
[0010]. The present disclosure generally relates to a process for preparing polybutadiene rubber grafted maleic anhydride (PBR-g-MAH) graft copolymers comprising reacting maleic anhydride (MAH) onto polybutadiene rubber (PBR) cement in presence of free radical initiators and a solvent.
[0011]. The present disclosure relates to a process for preparing polybutadiene rubber grafted maleic anhydride (PBR-g-MAH) graft copolymers said process comprising step of
c. dissolving PBR cement in a solvent to obtain PBR cement solution; and
d. adding free radical initiators and malic anhydride to the PBR cement solution followed by heating to obtain the polybutadiene rubber grafted maleic anhydride (PBR-g-MAH) graft copolymer mixture.

DESCRIPTION OF THE DISCLOSURE
[0012]. The foregoing has broadly outlined the features and technical advantages of the present disclosure in order that the detailed description of the disclosure that follows may be better understood. Additional features and advantages of the disclosure will be described hereinafter which form the subject of the description of the disclosure. It should also be realized by those skilled in the art that such equivalent methods do not depart from the scope of the disclosure. Further, for the purposes of the following detailed description, it is to be understood that the invention may assume various alternative variations and step sequences, except where expressly specified to the contrary. Moreover, other than in any operating examples, or where otherwise indicated, all numbers expressing, for example, quantities of ingredients used in the specification are to be understood as being modified in all instances by the term "about". It is noted that, unless otherwise stated, all percentages given in this specification and appended claims refer to percentages by weight of the total composition.
[0013]. Thus, before describing the present invention in detail, it is to be understood that this invention is not limited to particularly exemplified systems or process parameters that may of course, vary. It is also to be understood that the terminology used herein is for the purpose of describing particular embodiments of the invention only and is not intended to limit the scope of the invention in any manner.
[0014]. While the disclosure is susceptible to various modifications and alternative forms, specific embodiment thereof has been shown by way of examples and will be described in detail below. It should be understood, however, that it is not intended to limit the disclosure to the particular forms disclosed, but on the contrary, the disclosure is to cover all modifications, equivalents, and alternative falling within the spirit and the scope of the disclosure. Thus, the use of examples anywhere in this specification including examples of any terms discussed herein is illustrative only, and in no way limits the scope and meaning of the invention or of any exemplified term. Likewise, the invention is not limited to various embodiments given in this specification.
[0015]. Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains. In the case of conflict, the present document, including definitions will control.
[0016]. It must be noted that, as used in this specification and the appended claims, the singular forms "a," "an" and "the" include plural referents unless the content clearly dictates otherwise. Thus, for example, reference to a "solvent" may include two or more such solvents.
[0017]. The terms "preferred" and "preferably" refer to embodiments of the invention that may afford certain benefits, under certain circumstances. However, other embodiments may also be preferred, under the same or other circumstances. Furthermore, the recitation of one or more preferred embodiments does not imply that other embodiments are not useful, and is not intended to exclude other embodiments from the scope of the invention.
[0018]. As used herein, the terms "comprising" "including," "having," "containing," "involving," and the like are to be understood to be open-ended, i.e., to mean including but not limited to. Further, the terms “comprises”, “comprising”, or any other variations thereof, are intended to cover a non-exclusive inclusion, such that a method that comprises a list of acts does not include only those acts but may include other acts not expressly listed or inherent to such method. In other words, one or more acts in a method proceeded by “comprises… a” does not, without more constraints, preclude the existence of other acts or additional acts in the method.
[0019]. With respect to the use of substantially any plural and/or singular terms herein, those having skill in the art can translate from the plural to the singular and/or from the singular to the plural as is appropriate to the context and/or application. The various singular/plural permutations may be expressly set forth herein for sake of clarity.
[0020]. Any discussion of documents, acts, materials, devices, articles and 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.
[0021]. A detailed description for the purpose of illustrating representative embodiments of the present invention is given below, but these embodiments should not be construed as limiting the present invention.
[0022]. Unless otherwise indicated, all numbers expressing feature sizes, amounts, and physical properties used in the specification and claims are to be understood as being modified in all instances by the term "about." Accordingly, unless indicated to the contrary, the numerical parameters set forth in the foregoing specification and attached claims are approximations that can vary depending upon the desired properties sought to be obtained by those skilled in the art utilizing the teachings disclosed herein. The use of numerical ranges by endpoints includes all numbers within that range (e.g. 1 to 5 includes 1, 1.5, 2, 2.80, 3, 3.75, 4, and 5) and any range within that range.
[0023]. The present disclosure provides a process for preparing polybutadiene rubber grafted maleic anhydride (PBR-g-MAH) graft copolymers comprising reacting maleic anhydride (MAH) onto polybutadiene rubber (PBR) cement in presence of free radical initiators and a solvent.
[0024]. In an embodiment of the present disclosure, the PBR cement comprises polybutadiene rubber, heptane, toluene, butadiene and butane and other residual additives.
[0025]. In another embodiment of the present disclosure, the PBR cement comprises polybutadiene rubber at a concentration range of about 15 to 22 wt.%, heptane is at a concentration range of about 38 to 40 wt.%, toluene is at a concentration range of about 39 to 40 wt.%, butadiene is at a concentration range of about 2 to 3 wt.% and butane is at a concentration range of about 1 to 2 wt. % and other residual additives is at a concentration range of about 0.04 to 0.08 wt. %.
[0026]. In yet another embodiment of the present disclosure, the residual additives are selected from a group comprising Phosphate of polyoxyethylene alkyl phenyl ether (PPA) & Metal hydroxide of Ni, Co, Nd or combinations thereof.
[0027]. The present disclosure provides a process for preparing polybutadiene rubber grafted maleic anhydride (PBR-g-MAH) graft copolymers said process comprising step of
a. dissolving PBR cement in a solvent to obtain PBR cement solution; and
b. adding free radical initiators and maleic anhydride to the PBR cement solution followed by heating to obtain the polybutadiene rubber grafted maleic anhydride (PBR-g-MAH) graft copolymer mixture.
[0028]. In an embodiment of the present disclosure, the above said processes further comprise isolation and purification; wherein said isolation is carried out by acts selected from a group comprising addition of solvent, precipitating, quenching, filtration, extraction, drying and combination of thereof;
[0029]. In another embodiment of the present disclosure, the above said processes further comprises the step of precipitating PBR-g-MAH graft copolymer initially in first organic solvent followed by washing with second organic solvent from the mixture obtained from claim 5 to remove unreacted maleic anhydride.
[0030]. In yet another embodiment of the present disclosure, the said first organic solvent is selected from a group comprising methanol, ethanol, propanol, isopropanol and combinations thereof; and the second organic solvent is selected from a group comprising acetone, acetonitrile, ethyl acetate and combinations thereof.
[0031]. In still another embodiment of the present disclosure, the above said processes are carried out at a temperature ranging from about 25°C to about 100°C, and for a time period ranging from about 5 minutes to about 90 minutes.
[0032]. In still another embodiment of the present disclosure, the free radical initiator is selected from a group comprising benzoyl peroxide (BPO), dicumyl peroxide (DCP) or their combination.
[0033]. In still another embodiment of the present disclosure, the benzoyl peroxide is employed at a concentration of about 4.13 to 16.52 mmol and dicumyl peroxide is employed at a concentration of about 0.0074 to 0.074 mmol.
[0034]. In still another embodiment of the present disclosure, the maleic anhydride is employed at a concentration of ranging from about 0.015 mol to 0.31 mol.
[0035]. In still another embodiment of the present disclosure, the above said processes are carried out in presence of solvent, wherein the solvent is a hydrocarbon solvent.
[0036]. In still another embodiment of the present disclosure, the hydrocarbon solvent is selected from a group comprising heptane, toluene, cyclohexane and benzene or combinations thereof.
[0037]. In still another embodiment of the present disclosure, the hydrocarbon solvent is at a concentration ranging from about 5% weight/volume to 12 % weight/volume.
[0038]. PBR-g-MAH copolymers produced were characterized by IR showed 0.9-1.2 wt. % incorporation of MAH.
[0039]. The above said processes of grafting of MAH onto PBR using directly PBR cement does not require the step of dissolving the raw PBR in solvents while doing solution graft polymerization. This process can be implemented in any PBR plants to produce new grade of PBR graft copolymer.
[0040]. Additional embodiments and features of the present disclosure will be apparent to one of ordinary skill in art based upon description provided herein. The embodiments herein provide various features and advantageous details thereof in the description. Descriptions of well-known/conventional methods/steps and techniques are omitted so as to not unnecessarily obscure the embodiments herein. Further, the disclosure herein provides for examples illustrating the above described embodiments, and in order to illustrate the embodiments of the present disclosure certain aspects have been employed. The examples used herein for such illustration are intended merely to facilitate an understanding of ways in which the embodiments herein may be practiced and to further enable those of skill in the art to practice the embodiments herein. Accordingly, the following examples should not be construed as limiting the scope of the embodiments herein.

EXAMPLES
[0041]. Example 1: Graft Copolymerization of PBR cement with MAH
[0042]. The graft copolymerization of MAH onto PBR cement was carried out in toluene as solvent. PBR cement consists of PBR polymer (18 wt. %), Heptane (39 wt. %), Toluene (40 wt. %), Butadiene (2.4 wt. %), other residual additives (0.06 wt. %) & butane (1.5 wt. %). The graft copolymerization reaction was carried out in 250 ml of 3 neck round bottom flask with overhead stirrer under the nitrogen. In a typical reaction 11.27 gm (0.037 mol) of PBR cement was dissolved in 100 ml of toluene and 16.52 mmol of benzoyl peroxide (BPO) initiator was added at room temperature. The reaction mixture was heated and MAH was added and the reaction was carried out at 65oC for 5 to 90 minutes at 300 RPM. The reaction mixture cooled down to the room temperature under gentle nitrogen gas flow. The reaction mixture poured in to the 100 ml of methanol contained in beaker to precipitate the PBR-g-MAH copolymer and then washed with acetone to remove unreacted MAH. The washed PBR-g-MAH graft copolymer was dried under vacuum at 45oC for 3 hours.

The effect of variation of MAH concentration parameter (0.015 – 0.31 mol), Benzoyl peroxide parameter (4.13 to 16.52 mmol), Dicumyl Peroxide parameter (0.0074 to 0.074 mmol), reaction temperature parameter (25, 55 & 65 oC) & time duration parameter (5, 60 & 90 minutes) on the extent of grafting were studied. All the results are given in Table 1 showed a grafting percentage of 0.9 to 1.2.

All the results are given in Table 1 showed a grafting percentage of 0.9 to 1.2.

Table 1: Graft Copolymerization of MAH onto PBR cement: Effect of reaction parameters
Sr. No PBR (mol) BPO (mmol) DCP ( mmol) MAH (mol) Grafting (%)
1 0.037 4.13 0 0.03 0
2 0.037 8.26 0 0.03 1.1
3 0.037 16.52 0 0.03 1.2
4 0.037 16.52 0 0.015 1.1
5 0.037 16.52 0 0.030 1.1
6 0.037 16.52 0 0.045 1.1
7 0.037 16.52 0 0.31 1.1
8 0.037 0 0.0074 0.03 1
9 0.037 0 0.0148 0.03 0.9
10 0.037 0 0.074 0.03 1.1
11a 0.037 16.52 0 0.31 0
12b 0.037 16.52 0 0.31 0.5
13c 0.037 16.52 0 0.31 0
14d 0.037 16.52 0 0.31 0.4

Reaction conditions:
• From serial Number 1 to 10 experiments conducted at 65 °C & 90 minutes time
• 11a experiment conducted at 25 °C for 90 minutes
• 12a experiment conducted at 55 °C for 90 minutes
• 13c experiment conducted at 65 °C for 5 minutes
• 14d experiment conducted at 65 °C for 60 minutes

The FTIR analysis of PBR-MAH showed absorption at 1719 cm-1 due to the stretching of ->C=O group of MAH indicating the incorporation of MAH onto PBR chain. The broad peak observed at 3448 cm-1 due to the ring opening reaction of the MAH with water & formation of the carboxylic acid.

Differential scanning calorimetric (DSC) analysis was carried out for virgin PBR cement & PBR-g-MAH showed a glass transition temperature (Tg) -105 °C & -104 °C for PBR cement& PBR-g-MAH. The melting temperature (Tm) was observed at -9 °C & crystallization temperature (Tc) at -35 °C for the well order high 1,4-cis crystalline unit. Similar values of Tg and Tm were observed for PBR-g-MAH graft copolymer.

The thermo gravimetric analysis (TGA) was also done for virgin PBR cement & PBR-g-MAH showed a single step decomposition at 300°C which underwent to almost complete decomposition at 499 °C.

All these results clearly indicated the incorporation of MAH functional monomer onto PBR back bone without effecting inherent PBR characteristics during solution graft co-polymerization.

[0043]. Comparative Example 1: Temperature study
[0044]. The effect of the reaction temperature (25, 55 & 65 ?) studied on the MAH grafting with PBR cement (Table 1 Sr. 7, 11a, 12b). The graft copolymerization of MAH onto PBR cement was carried out in toluene as a solvent. PBR cement consists of PBR polymer (18 wt. %), Heptane (39 wt. %), Toluene (40 wt. %), Butadiene (2.4 wt. %), other residual additives (0.06 wt. %) & butane (1.5 wt. %). The graft copolymerization reaction was carried out in 250 ml of 3 neck round bottom flask with overhead stirrer under the nitrogen. In a typical reaction 11.27 gm (0.037 mol) of PBR cement was dissolved in 100 ml of toluene and 16.52 mmol of benzoyl peroxide (BPO iinitiator was added at room temperature. The reaction mixture was heated and MAH were added and the reaction was carried out at 65? for 5 to 90 minutes at 300 RPM. In a similar way the reactions were carried out at 25, 55 ? . All the reaction mixtures cooled down to the room temperature under gentle nitrogen gas flow. The reaction mixture poured in to the 100 ml of methanol present in a beaker to precipitate the PBR-g.MAH graft copolymer and then washed with acetone to remove unreacted MAH. The washed PBR-g-MAH was dried under vacuum at 45oC for 3 hours.

[0045]. Comparative Example 2: Time duration study
[0046]. The effect of the reaction time (5 minutes, 60 minutes and 90 minutes) studied on the MAH grafting with PBR cement (table 1, Sr. No 13c, 14d). The graft copolymerization of MAH onto PBR cement was carried out in toluene as solvent. PBR cement consists of PBR polymer (18 wt. %), Heptane (39 wt. %), Toluene (40 wt. %), Butadiene (2.4 wt. %), other residual additives (0.06 wt. %) & butane (1.5 wt. %). The graft copolymerization reaction was carried out in 250 ml of 3 neck round bottom flask with overhead stirrer under the nitrogen. In a typical reaction 11.27 gm (0.037 mol) of PBR cement was dissolved in 100 ml of toluene and 16.52 mmol of initiators (benzoyl peroxide (BPO) was added at room temperature. The reaction mixture was heated and MAH were added and the reaction was carried out at 65oC for 5 minutes at 300 RPM. The reaction mixture was cooled down to the room temperature under gentle nitrogen gas flow and poured in to the 100 ml of methanol contained in a beaker to precipitate the PBR-g-MAH copolymer and then washed with acetone to remove unreacted MAH. The washed PBR-g-MAH was dried under vacuum at 45oC for 3 hours. The extent of grafting of MAH increased with increasing reaction time from 10 to 90 minutes.

[0047]. Comparative Example 3: Effect of Initiators concentration
[0048]. The effect of the free radical initiators concentration of BPO (Table No 1, Sr, No 1, 2 & 3) & DCP (Table No 1, Sr. No. 8, 9 & 10) were also studied on the MAH grafting with PBR cement. sample using BPO the graft copolymerization of MAH onto PBR cement was carried out in toluene as solvent. PBR cement consists of PBR polymer (18 wt. %), Heptane (39 wt. %), Toluene (40 wt. %), Butadiene (2.4 wt. %), other residual additives (0.06 wt. %) & butane (1.5 wt. %). The graft copolymerization reaction was carried out in 250 ml of 3 neck round bottom flask with overhead stirrer under the nitrogen. In a typical reaction 11.27 gm (0.037 mol) of PBR cement was dissolved in 100 ml of toluene and 16.52 mmol BPO initiator was added at room temperature. The reaction mixture was heated and MAH were added and the reaction was carried out at 65oC for 5 to 90 minutes at 300 RPM. The DCP concentration at 0.0148 mmol and 0.074 mmol was also studied under identical conditions. The reaction mixture cooled down to the room temperature under gentle nitrogen gas flow and the reaction mixture poured in to the 100 ml of methanol contained in a beaker to precipitate PBR-g-MAH copolymer and then washed with acetone to remove unreacted MAH. The washed PBR-g-MAH was dried under vacuum at 45oC for 3 hours.

[0049]. Comparative Example 4: Effect of concentration of MAH study
[0050]. The effect of the MAH concentration (0.015 – 0.45 mol) studied on the MAH grafting with PBR cement. The graft copolymerization of MAH onto PBR cement was carried out in toluene as solvent. PBR cement consists of PBR polymer (18 wt. %), Heptane (39 wt. %), Toluene (40 wt. %), Butadiene (2.4 wt. %), other residual additives (0.06 wt. %) & butane (1.5 wt. %). The graft copolymerization reaction was carried out in 250 ml of 3 neck round bottom flask with overhead stirrer under the nitrogen. In a typical reaction 11.27 gm (0.037 mol) of PBR cement was dissolved in 100 ml of toluene and 16.52 mmol of initiators (benzoyl peroxide (BPO) was added at room temperature. The reaction mixture was heated and 0.045 mole MAH were added and the reaction was carried out at 65oC for 5 minutes at 300 RPM. The reaction mixture cooled down to the room temperature under gentle nitrogen gas flow. The reaction mixture poured in to the 100 ml of methanol to precipitate. The grafted rubber and then it is washed with acetone to remove unreacted MAH. The washed PBR-g-MAH was dried under vacuum at 45oC for 3 hours. The extended of grafting of MAH increases with increasing reaction time from 5 to 90 minutes.

[0051]. The foregoing description of the specific embodiments fully reveals the general nature of the embodiments herein that others can, by applying current knowledge, readily modify and/or adapt for various applications such specific embodiments without departing from the generic concept, and, therefore, such adaptations and modifications should and are intended to be comprehended within the meaning and range of equivalents of the disclosed embodiments. It is to be understood that the phraseology or terminology employed herein is for the purpose of description and not of limitation. Therefore, while the embodiments in this disclosure have been described in terms of preferred embodiments, those skilled in the art will recognize that the embodiments herein can be practiced with modification within the spirit and scope of the embodiments as described herein.

[0052]. While considerable emphasis has been placed herein on the particular features of this disclosure, it will be appreciated that various modifications 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 modifications in the nature of the disclosure or the preferred embodiments 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.