POLY(THIOPHENE-CO-BENZOTHIOPHENE-CO-DIBENZOTHIOPHENE) COPOLYMERS AND PROCESS FOR PREPARATION THEREOF

Abstract

A copolymer, poly(thiophene-co-benzothiophene-co-dibenzothiophene), and method of preparation thereof. The copolymer, poly(thiophene-co-benzothiophene-co-dibenzothiophene), having a formula (I):

##STR00001##

wherein x=H or R, y=H or R, z=H or R, and n=500-58000, wherein R is selected from alkyl or alicyclic chain substituents, and Ar is an aromatic ring.

Claims

1. A copolymer, poly(thiophene-co-benzothiophene-co-dibenzothiophene), having a formula (I) ##STR00004## wherein x=H or R, y=H or R, z=H or R, and n=500-58000, wherein R is selected from alkyl or alicyclic chain substituents, and Ar is an aromatic ring.

2. The copolymer as claimed in claim 1, wherein the copolymer exhibits absorbance in a region from 200-600 nm and fluorescence in a region from 400-700 nm.

3. The copolymer as claimed in claim 1, wherein the copolymer is soluble in an organic solvent, and is functionally active.

4. The copolymer as claimed in claim 3, wherein the organic solvent is selected from the group consisting of toluene, DCM, CHCl.sub.3, THF, DMF, dioxane, tetrachloroethylene, DMSO, and methanol.

5. The copolymer as claimed in claim 1, wherein the copolymer comprises one or more sulfur-containing heterocyclic compound, wherein the sulfur-containing heterocyclic compound is selected from the group consisting of polythiophene, an alkylated or alicyclic derivative of polythiophene, an alkylated or alicyclic derivative of polybenzothiophene and an alkylated or alicyclic derivative of polydibenzothiophenes.

6. The copolymer as claimed in claim 1, wherein the copolymer has a molecular weight (Mn) in a range from 500 to 58000.

7. The copolymer as claimed in claim 1, wherein sulfur content of the copolymer is in a range of 0.03% to 0.25%.

8. A process for preparing a copolymer, the process comprising: i. charging petroleum crude oil or petroleum refinery fraction in a two-necked round bottom flask; ii. adding FeCl.sub.3 powder as a catalyst through a funnel to form a mixture; iii. stirring the mixture at 70° C. for 12 hours; iv. adding hexane to the mixture; and v. separating the copolymer by centrifugation of the mixture; vi. drying the copolymer under vacuum at room temperature, wherein the copolymer has a formula (I) ##STR00005## wherein x=H or R, y=H or R, z=H or R, and n=500-58000; wherein R is selected from alkyl or alicyclic chain substituents, and Ar is an aromatic ring.

9. The process as claimed in claim 8, wherein yield of the copolymer ranges from 1.75 to 25.2%.

10. The process as claimed in claim 8, wherein the crude oil is petroleum crude oil or petroleum refinery fraction.

11. The process as claimed in claim 10, wherein the petroleum crude oil is selected from the group consisting of crude oil of API Gravity 40, crude oil of API Gravity 26, crude oil of API Gravity 18 and crude oil of API Gravity 15.

12. The process as claimed in claim 10, wherein the petroleum refinery fraction is selected from the group consisting of naphtha, gasoline, kerosene, diesel, LCO, VGO, HRO, foots oil, fuel oil, and VisTar streams and mixture thereof.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0024] The disclosure has other advantages and features which will be more readily apparent from the following detailed description of the disclosure and the appended claims, when taken in conjunction with the accompanying drawings, in which:

[0025] FIG. 1: .sup.1H NMR spectra of the gasoline and the P6 obtained after polymerization of the gasoline fraction

[0026] FIG. 2: .sup.1H NMR spectra of LCO and P9 obtained after polymerization of the LCO fraction

[0027] FIG. 3 FT-IR spectra of all polymers

[0028] FIG. 4 GPC chromatogram of all polymers and separated fractions

[0029] FIG. 5: Absorption spectra of petroleum polymers (P1 and P2) obtained from crude oils of API-26, and 40, Absorption spectra of petroleum fractions and polymers (P9, P10, and P14) obtained from the LCO, VGO, and VisTar fractions

[0030] FIG. 6: Fluorescence spectra of the polymers at different wavelengths

[0031] FIG. 7: Cyclic voltammograms of all polymers

[0032] FIG. 8: TGA and DTA curves of P6 and P8

DETAILED DESCRIPTION

[0033] While the disclosure has been disclosed with reference to certain embodiments, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted without departing from the scope of the disclosure. In addition, many modifications may be made to adapt to a particular situation or material to the teachings of the disclosure without departing from its scope.

[0034] Throughout the specification and claims, the following terms take the meanings explicitly associated herein unless the context clearly dictates otherwise. The meaning of “a”, “an”, and “the” include plural references. The meaning of “in” includes “in” and “on.” Referring to the drawings, like numbers indicate like parts throughout the views. Additionally, a reference to the singular includes a reference to the plural unless otherwise stated or inconsistent with the disclosure herein. The present disclosure emphasizes to provide a new family of conducting copolymers, namely poly (thiophene-co-benzothiophene-co-dibenzothiophene), with or without alkyl/alicyclic substituted derivatives, referred to hereafter in this document as Copoly-SCHAC, from petroleum crude oil of different sweetness and refinery fractions such as naphtha, gasoline, kerosene, diesel, LCO, VGO, HRO, foot oil, fuel oil, and VisTar streams.

[0035] The present disclosure also emphasizes to provide new conducting polymers that exhibit, high visible light absorbance, excellent fluorescent properties in the visible light region (400-800 nm), and good processability in organic solvents.

[0036] The present disclosure additionally emphasizes to provide a process for preparation of Copoly-SCHAC polymers and offer a broader range of solvent processability, and versatility of application.

[0037] In line with the above emphasizes, the present disclosure relates to a new class of poly(thiophene-co-benzothiophene-co-dibenzothiophene) based aromatic copolymers and process for preparation thereof.

[0038] The present disclosure includes a poly(thiophene-co-benzothiophene-co-dibenzothiophene) comprising repeating units of the formula (I):

##STR00003##

wherein R— represents alkyl/alicyclic chain substituents, and Ar— represents one or more aromatic rings.

[0039] In another embodiment, the present disclosure provides a new type/class of conjugated copolymers of thiophene, benzothiophene, dibenzothiophene, and higher analogs of sulfur monomers functionalized with alkyl/alicyclic side-chain substituents of formula (I).

[0040] The present disclosure also provides a functionally active copolymer poly(thiophene-co-benzothiophene-co-dibenzothiophene) obtained from petroleum crude oil and refinery fractions such as naphtha, gasoline, kerosene, diesel, LCO, VGO, HRO, foots oil, fuel oil, and VisTar streams.

[0041] The functionally active copoly-SCHACs are structurally characterized by various analytical techniques such as NMR, FT-IR, molecular weight measurements by GPC, UV, fluorescence spectral analysis, and cyclic voltammetry. The Figures from 1-12 illustrate the characterizations by analytical techniques of all the polymers. The synthesis of the Copoly-SCHACs from various petroleum crude oil and refinery fractions are described in examples 1 to 14. The synthesized polymers are structurally characterized with the help of NMR and FT-IR analytical techniques. The FT-IR spectra of synthesizing polymers presented in FIG. 3 show the vibration stretching frequency of the C—S bond at 710 nm.sup.−1. The molecular weight, the yield of polymers, sulfur content analysis, are listed in Table-1. The petroleum crude oil and refinery fractions have weaker absorption and emission beyond 300 nm, whereas the synthesized polymers have excellent absorption beyond 400 (FIG. 5) and emission in the range of 400-700 nm (FIG. 6). The visible light absorption and excellent emission properties of the polymers (P1-P14) reveal the materials' potentiality as functionally active materials (FIG. 7).

[0042] The thermal stability of P6 and P8 polymers are analyzed and given in FIG. 8. Thermogravimetric analysis (TGA) shows the stability of polymers up to 150° C. is <10 wt % degradation. In the temperature region from 150° C. to 350° C., the polymer degrades to 50 wt % by weight percentage. The thermal stability of poly(3-hexyl thiophenes) (P3HT), poly(benzothiophenes) (PBT), and poly(dibenzothiophenes) (PDBT) are excellent (<10 wt %) up to 350° C. The polymers presented in this disclosure are a combination of thiophene, benzothiophene, dibenzothiophene, and other aromatic units randomly distributed in the polymeric chain along with alkyl substituents at various positions on these aromatic rings. The presence of relatively labile alkyl units appear to be the primary contributor to decreased thermal stability of these new materials as compared with commercial available homopolymers P3HT, PBT, and PDBT. However, for ambient temperature operations going up to approximately 150° C., the various functional capabilities of the copoly-SCHAC family offer specific distinct advantages over existing commercial polymers in electronic and optical properties as well as in compounding or blending with other polymeric materials.

[0043] The absorption and emission spectra of the copoly-SCHAC polymers are compared with pure P3HT, PBT, and PDBT; it is found that pure P3HT, PBT, and PDBT have broader absorption up to 500 nm and emission extended beyond 750 nm, but the polymers presented in this disclosure have absorption up to 450 nm and emission spectra extended up to 650 nm. The absorption and emission behavior of P1-P14 are different due to the source of crude used and the effect of non-conjugated segments attached to the polymer, enabling a broad family of novel materials from which tailored options can be selected to service specific application requirements.

EXAMPLES

[0044] The following examples, which include preferred embodiments, will serve to illustrate the practice of this disclosure, it being understood that the particulars shown are by way of example and for purpose of illustrative discussion of preferred embodiments of the disclosure.

Example 1: Poly(Thiophene-Co-Benzothiophene-Co-Dibenzothiophene) (P1) from Crude Oil of API Gravity 40

[0045] 20 g of crude oil (API-40) was taken in a two-necked round bottom flask, and 1 g of FeCl.sub.3 powder as catalyst was added through a funnel. The mixture was stirred at 60° C. for 12 hours. The resultant polymer was separated by centrifugation and dried under a vacuum at room temperature. This polymer was designated as P1. The yield and molecular weight of the polymer P1 are given in Table-1, and proton NMR, FT-IR, GPC, UV and fluorescence, and CV are shown in FIGS. 1-8.

TABLE-US-00001 TABLE 1 Summary of petroleum crude oils, reaction parameters, polymer yields, molecular weight, and sulfur content analysis Quantity Dosages Poly- Name of feed of Reaction Temper- mer Sulfur of sample Catalyst on time ature Yields GPC Content S. NO. Sample (g) (g) (h) (° C.) (g) Mn Mw PDI (%) 1. P2 20 0.01 12 70 2.1 4567 6542 1.43 0.047 2. P4 20 1 12 70 7.56 58060  120526   2.075 0.216 3. P5 20 1 12 70 1.49 Not detectable 0.033 4. P6 20 1 12 70 0.35  988 1049 1.06 0.056 5. P8 20 1 12 70 0.45 1204 1391 1.15 0.096 6. P9 20 1 12 70 1.4 Not detectable 0.033

Example 2: Poly(Thiophene-Co-Benzothiophene-Co-Dibenzothiophene) (P2) from Crude Oil of API Gravity 26

[0046] 20 g of the crude oil (API-26) was taken in a two-necked round bottom flask, and 1 g of FeCl.sub.3 powder as catalyst was added through a funnel. The mixture was stirred at 70° C. for 12 hours. After 12 hours, hexane was added to the reaction mixture, and the resultant product polymer was separated by centrifugation and dried under vacuum at room temperature. This polymer was designated as P2. The yield and molecular weight of the polymer P2 are given in Table-1, and proton NMR, FT-IR, GPC, UV and fluorescence, and CV are shown in FIGS. 1-8.

Example 3: Poly(Thiophene-Co-Benzothiophene-Co-Dibenzothiophene) (P3) from Crude Oil of API Gravity 18

[0047] 20 g of the crude oil (API-18) was taken in a two-necked round bottom flask, and 1 g of FeCl.sub.3 powder as catalyst was added through a funnel. The mixture was stirred at 70° C. for 12 hours. After 12 hours, hexane was added to this reaction mixture, and the resultant product polymer (P3) was separated by centrifugation and dried under vacuum at room temperature. The yield and molecular weight of the polymer P3 are given in Table-1, and proton NMR, FT-IR, GPC, UV and fluorescence, and CV are shown in FIGS. 1-8.

Example 4: Poly(Thiophene-Co-Benzothiophene-Co-Dibenzothiophene) (P4) Using Crude Oil of API Gravity 15

[0048] 20 g of the crude oil (API-15) was taken in a two-neck round bottom flask, and 1 g of FeCl.sub.3 powder as catalyst was added through a funnel. The mixture was stirred at 70° C. for 12 hours. After 12 hours, hexane was added to this reaction mixture, and the resultant polymer was separated by centrifugation and dried under vacuum at room temperature. This polymer was designated as P4. The yield and molecular weight of the polymer P4 are given in Table-1, and proton NMR, FT-IR, GPC, UV, fluorescence, and CV are shown in FIGS. 1-8.

Example 5: Poly(Thiophene-Co-Benzothiophene-Co-Dibenzothiophene) (P5) Using a Petroleum Naphtha Fraction

[0049] 20 g of the naphtha fraction (boiling range of 30-90° C.) was taken in a two-necked round bottom flask. The flask was filled with a nitrogen atmosphere, and 1 g of FeCl.sub.3 powder as catalyst was added through a funnel. The mixture was stirred at 25° C. for 12 hours. The contents were cooled, and the product polymer (P5) was separated by centrifugation and dried under vacuum at room temperature. The yield and molecular weight of the polymer P5 are given in Table-1, and proton NMR, FT-IR, GPC, UV and fluorescence, and CV are shown in FIGS. 1-8.

Example 6: Poly(Thiophene-Co-Benzothiophene-Co-Dibenzothiophene) (P6) Using a Petroleum Gasoline Fraction

[0050] 20 g of the gasoline fraction (boiling range of 80-90° C.) was taken in the two-necked round bottom flask. The flask was filled with nitrogen atmosphere, and 1 g of the FeCl.sub.3 powder as catalyst was added through a funnel. The mixture was stirred at 25° C. for 12 hours. The contents were cooled, and the product polymer (P6) was separated by centrifugation and dried under vacuum at room temperature. This polymer was designated as P6. The yield and molecular weight of the polymer P6 are given in Table-1, and proton NMR, FT-IR, GPC, UV and fluorescence, and CV are shown in FIGS. 1-8.

Example 7: Poly(Thiophene-Co-Benzothiophene-Co-Dibenzothiophene) (P7) Using a Petroleum Kerosene Fraction

[0051] 20 g of a kerosene fraction (boiling range of 200-300° C.) was taken in a two-necked round bottom flask. The flask atmosphere was made inert using nitrogen flushing, to which 1 g of FeCl.sub.3 powder as catalyst was added through a funnel. The mixture was stirred at 25° C. for 12 hours. The contents were cooled, and the product polymer (P7) was separated by centrifugation and dried under vacuum at room temperature. The yield and molecular weight of the polymer P7 are given in Table-1, and proton NMR, FT-IR, GPC, UV and fluorescence, and CV are shown in FIGS. 1-8.

Example 8: Poly(Thiophene-Co-Benzothiophene-Co-Dibenzothiophene) (P8) Using a Petroleum Diesel Fraction

[0052] 20 g of a diesel fraction (boiling range of 150-380° C.) was taken in a two-necked round bottom flask. The flask atmosphere was made inert by nitrogen flushing, to which 1 g of FeCl.sub.3 powder as catalyst was added through a funnel. The mixture was stirred at 25° C. for 12 hours. The contents were cooled, and the product polymer (P8) was separated by centrifugation and dried under vacuum at room temperature. The yield and molecular weight of the polymer P8 are given in Table-1, and proton NMR, FT-IR, GPC, UV and fluorescence, and CV are shown in FIGS. 1-8.

Example 9: Poly(Thiophene-Co-Benzothiophene-Co-Dibenzothiophene) (P9) Using a LCO Fraction

[0053] 20 g of the LCO fraction was taken in a two-neck round bottom flask. The flask atmosphere was made inert by nitrogen. To this, 1 g of FeCl.sub.3 powder as catalyst was added through a funnel. The mixture was stirred at 25° C. for 12 hours. The contents were cooled, and the product polymer (P9) was separated by centrifugation and dried under vacuum at room temperature. The yield and molecular weight of the polymer P9 are given in Table-1, and proton NMR, FT-IR, GPC, UV and fluorescence, and CV are shown in was given in FIGS. 1-8.

Example 10: Poly(Thiophene-Co-Benzothiophene-Co-Dibenzothiophene) (P10) Using a VGO Fraction

[0054] 20 g of the VGO fraction was taken in a two-necked round bottom flask. The flask atmosphere was made inert by nitrogen flushing. To this, 1 g of FeCl.sub.3 powder as catalyst was added through the funnel. The resulting mixture was stirred at 70° C. for 12 hours. The contents were cooled, and the product polymer (P10) was separated by centrifugation and dried under vacuum at room temperature. The yield and molecular weight of the polymer P10 are given in Table-1, and proton NMR, FT-IR, GPC, UV and fluorescence, and CV are shown in FIGS. 1-8.

Example 11: Poly(Thiophene-Co-Benzothiophene-Co-Dibenzothiophene) (P11) Using a HRO Fraction

[0055] 20 g of the HRO fraction was taken in a two-necked round bottom flask. The flask was made inert by nitrogen flushing. To this 1 g of FeCl.sub.3 powder as catalyst was added through the funnel. The mixture was stirred at 100° C. for 12 hours. The contents were cooled, and the product polymer (P11) was separated by centrifugation and dried under vacuum at room temperature. The yield and molecular weight of the polymer P11 are given in Table-1, and proton NMR, FT-IR, GPC, UV and fluorescence, and CV are shown in FIGS. 1-8.

Example 12: Poly(Thiophene-Co-Benzothiophene-Co-Dibenzothiophene) (P12) Using a Petroleum Foots Oil Fraction

[0056] 20 g of the foots oil fraction was taken in a two-necked round bottom flask. The flask was made inert by nitrogen flushing. To this, 1 g of FeCl.sub.3 powder as catalyst was added through the funnel. The resulting mixture was stirred at 70° C. for 12 hours. The contents were cooled, and the product polymer (P12) was separated by centrifugation. The resultant polymer was dried under a vacuum at room temperature. This polymer was designated as P12. The yield and molecular weight of the polymer P12 are given in Table-1, and proton NMR, FT-IR, GPC, UV and fluorescence, and CV are shown in FIGS. 1-8.

Example 13: Poly(Thiophene-Co-Benzothiophene-Co-Dibenzothiophene) (P13) Using a Petroleum Fuel Oil Fraction

[0057] 20 g of the fuel oil fraction was taken in a two-necked round bottom flask. The flask was made inert by nitrogen flushing to which, 1 g of FeCl.sub.3 powder as catalyst was added through a funnel. The mixture was stirred at 70° C. for 12 hours. The contents were cooled, and the product polymer (P13) was separated by centrifugation and dried under vacuum at room temperature. The yield and molecular weight of the polymer P13 are given in Table-1, and proton NMR, FT-IR, GPC, UV and fluorescence, and CV are shown in FIGS. 1-8.

Example 14: Poly(Thiophene-Co-Benzothiophene-Co-Dibenzothiophene) (P14) Using the Petroleum VisTar Fraction

[0058] 20 g of the VisTar fraction was taken in a two-necked round bottom flask. The flask was inert by nitrogen flushing to which, 1 g of FeCl.sub.3 powder as catalyst was added through a funnel. The mixture was stirred at 70° C. for 12 hours. The contents were cooled, and the product polymer (P14) was separated by centrifugation and dried under vacuum at room temperature. This polymer was designated as P14. The yield and molecular weight of the polymer P14 are given in Table-1, and proton NMR, FT-IR, GPC, UV and fluorescence, and CV are shown in FIGS. 1-8.

ADVANTAGES

[0059] The various advantage of the present disclosure is: [0060] 1) Desulfurization of petroleum crude oil and refinery fractions via polymerization of sulfur compounds provides an entirely new class of copolymers, namely, poly(thiophene-co-benzothiophene-co-dibenzothiophene) or Copoly-SCHAC. [0061] 2) Copoly-SCHAC polymers having excellent conducting or semiconducting characteristics, high visible light absorbance, and broad fluorescence emission properties. [0062] 3) Copoly-SCHAC polymers are easy to synthesize and offer a broader range of solvent process ability, and versatility of applications in oil sector.