PHTHALIMIDINE- CONTAINING CARDO BISPHENOLS BEARING PENDANT FURYL GROUP AND POLYMERS THEREFROM
20250154318 ยท 2025-05-15
Inventors
- Deepak Mannusing MAHER (Pune, IN)
- Aniket Anil Talanikar (Pune, IN)
- Samadhan Suresh NAGANE (Pune, IN)
- Prakash Purushottam Wadgaonkar (Pune, IN)
Cpc classification
C08G63/6858
CHEMISTRY; METALLURGY
International classification
Abstract
The present invention relates to phthalimidine-containing bisphenol monomers bearing pendant furyl group of Formula (I) and (co) polymers of Formula (II) obtained by polycondensation of varying mixtures of monomer of Formula (I) and bisphenol-A with aromatic diacid chlorides and the processes for the preparation thereof.
Claims
1-10. (canceled)
11. A phthalimidine-containing bisphenol monomer compound of Formula (I): ##STR00020## where: R.sub.1 and R.sub.2 are independently selected from the group consisting of H, substituted or unsubstituted straight or branched C.sub.1-C.sub.5 alkyl, and substituted or unsubstituted straight or branched C.sub.1-C.sub.5 alkoxy; and n is an integer from 1 to 8.
12. The phthalimidine-containing bisphenol monomer compound of claim 11, wherein R.sub.1 and R.sub.2 are independently selected from the group consisting of: H; unsubstituted straight or branched C.sub.1-C.sub.5 alkyl; straight or branched C.sub.1-C.sub.5 alkyl substituted with a straight or branched substituted or unsubstituted C.sub.1-C.sub.5 alkyl or a straight or branched substituted or unsubstituted C.sub.1-C.sub.5 alkoxy; unsubstituted straight or branched C.sub.1-C.sub.5 alkoxy; and straight or branched C.sub.1-C.sub.5 alkoxy substituted with a straight or branched substituted or unsubstituted C.sub.1-C.sub.5 alkyl or a straight or branched substituted or unsubstituted C.sub.1-C.sub.5 alkoxy.
13. A process for synthesizing the phthalimidine-containing bisphenol monomer compound of claim 11, the process comprising: refluxing phenolphthalein with 1-(furan-2-yl)-alkylamine at 140 C. to 160 C. for 40 hours to 60 hours to obtain the compound of Formula (I).
14. The process according to claim 13, further comprising: purifying the compound of Formula (I) by recrystallizing using 1:1 (v/v) mixture of ethanol and water.
15. A (co) polymer comprising monomers of the phthalimidine-containing bisphenol monomer compound according to claim 1, the (co) polymer having of Formula (II): ##STR00021## wherein, R.sub.1 and R.sub.2 are independently selected from the group consisting of H, substituted or unsubstituted straight or branched C.sub.1-C.sub.5 alkyl, and substituted or unsubstituted straight or branched C.sub.1-C.sub.5 alkoxy; n is an integer from 1 to 8; x is a number of moles of the phthalimidine-containing bisphenol monomer compound; y is a number of moles of bisphenol-A; and Ar is chosen from ##STR00022##
16. The (co) polymer of claim 15, wherein R.sub.1 and R.sub.2 are independently selected from the group consisting of: H; unsubstituted straight or branched C.sub.1-C.sub.5 alkyl; straight or branched C.sub.1-C.sub.5 alkyl substituted with a straight or branched substituted or unsubstituted C.sub.1-C.sub.5 alkyl or a straight or branched substituted or unsubstituted C.sub.1-C.sub.5 alkoxy; unsubstituted straight or branched C.sub.1-C.sub.5 alkoxy; and unsubstituted straight or branched C.sub.1-C.sub.5 alkoxy; and straight or branched C.sub.1-C.sub.5 alkoxy substituted with a straight or branched substituted or unsubstituted C.sub.1-C.sub.5 alkyl or a straight or branched substituted or unsubstituted C.sub.1-C.sub.5 alkoxy.
17. A process for synthesizing the (co) polymer of claim 15, the process comprising: (a) mixing the phthalimidine-containing bisphenol monomer compound, bisphenol-A, and a base under stirring at from 0 C. to 10 C. for 1 hour to obtain a reaction mixture; (b) adding, into the reaction mixture of (a), benzyltriethylammonium chloride and a solution of aromatic diacid chloride in a solvent and stirring the reaction mixture vigorously at 2000 rpm at 0 C. to 10 C. for 1 hour to obtain the compound of Formula (II).
18. The process according to claim 17, wherein: the base is chosen from sodium hydroxide, potassium hydroxide, or cesium hydroxide; and the solvent is chosen from dichloromethane or chloroform.
19. The process according to claim 17, wherein the aromatic diacid chloride is selected from isophthaloyl chloride, terephthaloyl chloride, 4,4-biphenyldicarbonyl chloride, 2,6-naphthalenedicarbonyl dichloride, or mixtures thereof.
20. A polymer comprising recurring units of the phthalimidine-containing bisphenol monomer compound according to claim 11, wherein the polymer is selected from aromatic polycarbonates, polyether sulfones, or polyetherketones.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
[0038]
[0039]
[0040]
[0041]
DETAILED DESCRIPTION OF THE INVENTION
[0042] Accordingly, to accomplish the objectives, the present invention provides phthalimidine-containing bisphenol monomers bearing pendant furyl group of Formula (I) as depicted below:
##STR00005##
[0043] wherein,
[0044] R.sub.1 and R.sub.2 are either same or different and selected from the group consisting of H, C.sub.1-C.sub.5 substituted or unsubstituted, straight or branched alkyl, alkoxy;
n=18.
[0045] In another embodiment, the present invention provides a process for the synthesis of phthalimidine-containing bisphenol monomers of Formula (I), wherein the process comprises the steps of: [0046] a) heating the reaction mixture of phenolphthalein (1) and 1-(furan-2-yl)-alkylamine (2) at a temperature in the range of 140-160 C. for a period in the range of 40-60 h; [0047] b) removing the excess 1-(furan-2-yl)-alkylamine (2) from the reaction mixture obtained at step a) under reduced pressure; [0048] c) dissolving the reaction mixture obtained at step b) in a solvent at 25-35 C. and washing the organic layer with water; [0049] d) concentrating the organic layer obtained at step c) under reduced pressure and dissolving the obtained crude product in aqueous sodium hydroxide solution; [0050] e) neutralizing the obtained basic solution with dilute HCl to obtain a solid; [0051] f) filtering the obtained solid at step e) and washing with cold water; [0052] g) recrystallizing the solid product obtained at step f) from 1:1 (v/v) mixture of ethanol and water to obtain the bisphenol monomer of Formula (I).
[0053] The synthesis of bisphenol monomers of Formula (I) is depicted below in
[0054] The solvent at step c) is selected from dichloromethane or ethyl acetate.
[0055] Yet another embodiment of the present invention provides (co) polymer of Formula (II) obtained by polycondensation of varying mixtures of monomers of Formula (I) and bisphenol-A with aromatic diacid chlorides. Formula (II) is as depicted below:
##STR00006##
[0056] wherein,
[0057] R.sub.1 and R.sub.2 are either same or different and selected from the group consisting of H, C.sub.1-C.sub.5 substituted or unsubstituted, straight or branched alkyl, alkoxy;
n=18;
[0058] x=moles of monomer of Formula (I), y=moles of bisphenol-A; and
##STR00007##
[0059] In yet another aspect, the present invention relates to a process for the synthesis of (co) polymer of Formula (II) using polycondensation of varying mixtures of monomer of Formula (I) and bisphenol-A with aromatic diacid chlorides, wherein the process comprises the steps of: [0060] a. mixing monomer of Formula (I), bisphenol-A and a base under stirring at a temperature in a range of 0-10 C. for 1 hour to obtain a reaction mixture; and [0061] b. benzyltriethylammonium chloride (BTEAC) and solution of aromatic diacid chloride in a solvent into the reaction mixture obtained at step a) and stirring the reaction mixture vigorously at 2000 rpm at 0-10 C. for 1 h to obtain the compound of Formula (II).
[0062] In another embodiment of the present invention, the base is selected from sodium hydroxide, potassium hydroxide, cesium hydroxide and so on.
[0063] In another embodiment of the present invention, the solvent is dichloromethane or chloroform.
[0064] In another embodiment of the present invention, the process further comprises step of purifying the compound of Formula (II) by recrystallizing using 1:1 (v/v) mixture of ethanol and water
[0065] Another embodiment of the present invention provides a process for the synthesis of (co) polymer of Formula (II) obtained by polycondensation of varying mixtures of monomer of Formula (I) and bisphenol-A with aromatic diacid chlorides, wherein the process comprises the steps of:
[0066] a) mixing monomer of Formula (I), bisphenol-A (3) and 1M NaOH and stirring the reaction mixture at a temperature in the range of 0-10 C. for 1 h; [0067] b) adding benzyltriethylammonium chloride (BTEAC) and solution of aromatic diacid chloride (4) in a solvent into the reaction mixture obtained at step a); [0068] c) stirring the reaction mixture obtained at step b) vigorously at 2000 rpm at 8-10 C. for 1 h; [0069] d) pouring the reaction mixture obtained at step c) into hot water to precipitate the solid; [0070] e) filtering and washing the solid obtained at step d) with water to remove inorganic impurities; [0071] f) dissolving the solid obtained at step e) in a solvent and pouring the obtained solution into a solvent mixture of methanol and water (1:1, v/v) to obtain the polymer of Formula (II).
[0072] The preparation of polymer of Formula (II) is depicted in
[0073] The solvent at step b) and step f) is selected from dichloromethane or chloroform. Aromatic diacid chloride is selected from isophthaloyl chloride (IPC), terephthaloyl chloride (TPC), mixture of IPC and TPC, 4,4-biphenyldicarbonyl chloride and 2,6-naphthalenedicarbonyl dichloride.
[0074] In an embodiment, the present invention relates to a polymer comprising the recurring units of compound of Formula (I).
[0075] In another embodiment of the present invention, the polymers are selected from aromatic polycarbonates, polyether sulfones, and polyetherketones.
[0076] In another embodiment of the present invention, the incorporation of phthalimidine moieties offers advantages such as improved thermal characteristics. Glass transition temperature (T.sub.g) values of (co) polyesters were in the range 202-242 C. and temperature for 10% weight loss (T.sub.10) in thermogravimetric analysis under nitrogen atmosphere were in the range 415-452 C. (Co) polyesters demonstrated improved solubility characteristics and were soluble in common organic solvents such as dichloromethane, chloroform and tetrahydrofuran. The solution processability of polymers to form films is advantageous in the formation of membrane materials for gas separation and in coatings.
[0077] In another embodiment of the present invention, the polymers possessing pendant furyl groups based on phthalimidine containing cardobisphenols provide interesting opportunities for post-polymerization modification and cross-linking reactions with the use of appropriately functionalized maleimide and bis-maleimide, respectively.
[0078] In another embodiment of the present invention, the thermo-reversible cross-linking via bis-maleimide allows the polymers to improve thermal and mechanical properties with an added advantage of recyclability unlike conventional thermosetting resins.
EXAMPLES
[0079] Following examples are given by way of illustration and therefore should not be construed to limit the scope of the invention.
Example1: Synthesis of 2-(furan-2-ylmethyl)-3, 3-bis (4-hydroxyphenyl) isoindolin-1-one
##STR00008##
[0080] Into a 250 mL two-necked round bottom flask equipped with a reflux condenser, an addition funnel and a magnetic stirring bar were charged phenolphthalein (1) (10.0 g, 31.4110.sup.3 mol), and 1-(furan-2-yl)-alkyl-amine (2) (36.61 g, 376.910.sup.3 mol). The reaction mixture was heated at 150 C. for 48 h. The excess 1-(furan-2-yl) methanamine was removed under reduced pressure. The reaction mixture was cooled to 30 C., dissolved in ethyl acetate (200 mL) and washed with water (2100 mL). The ethyl acetate layer was separated, dried over anhydrous sodium sulfate and filtered. Ethyl acetate was removed under reduced pressure and the obtained product was dissolved in aqueous sodium hydroxide solution, followed by neutralization with dilute hydrochloric acid. The obtained precipitate was separated out by filtration and washed with cold water. The product was purified by recrystallization from a mixture of ethanol and water (1:1, v/v). Yield: 4.9 g (35%). Melting Point: 284 C.
[0081] FT-IR (KBr, cm.sup.1): 3385 (OH), 1667 (CO), 1507 (CC)
[0082] .sup.1H NMR (DMSO-d.sub.6, ppm): 9.50 (br. s, 2H), 7.73 (d, 1H), 7.55 (t, 1H), 7.47 (d, 1H), 7.37-7.31 (m, 2H), 6.92 (d, 4H), 6.66 (d, 4H), 6.66 (d, 1H), 5.46 (d, 1H), 4.49 (s, 2H).
[0083] .sup.13C NMR (DMSO-d.sub.6, ppm): 167.4, 157.2, 152.0, 150.9, 141.5, 132.7, 130.6, 129.8, 129.4, 128.3, 124.0, 123.2, 115.4, 110.5, 107.1, 74.9, 74.9, 39.3.
Example2
Representative Procedure for Synthesis of Aromatic (Co) Polyesters Bearing Pendant Furyl Groups
[0084] Into an oven-dried 100 mL two-necked round bottom flask equipped with a high-speed mechanical stirrer and an addition funnel were placed BPF (0.750 g, 1.8810.sup.3), BPA (0.430 g, 1.8810.sup.3) and 1M NaOH (8.5 mL). The reaction mixture was stirred at 10 C. for 1 h. Afterwards, benzyltriethylammonium chloride (BTEAC) (57 mg) was added into the reaction mixture. The solution of isophthaloyl chloride (IPC) (0.7669 g, 3.77610.sup.3 mol) dissolved in dichloromethane (7 mL) was added in one lot into the reaction mixture and the mixture was stirred vigorously at 2000 rpm at 10 C. for 1 h. The reaction mixture was poured into hot water; the precipitated polymer was filtered, and washed several times with water to remove the inorganic impurities. Polyester was dissolved in dichloromethane (25 mL) and the solution was poured into a mixture of methanol and water (1:1, v/v) (1000 mL) to precipitate the polymer. The polyester was filtered, washed with methanol and dried at 50 C. under reduced pressure for 24 h.
[0085] Copolyesters given in the table-1 below were also synthesized by polycondensation of varying molar ratios of BPF and bisphenol-A with aromatic diacid chlorides such as terephthaloyl chloride or isophthaloyl chloride using the similar procedure.
TABLE-US-00001 TABLE 1 % Molar composition of copolyestersbearing pendant furyl groups calculated by .sup.1H NMR spectra Feed Observed Polyester BPF, BPF, code Copolyester mol % mol % FPE-2
[0086] Inherent viscosity values of (co) polyesters were found in the range 0.51-1.1 dL/g and GPC data showed Mn values in the range 25,400-48,900 g/mol. These data given in table 2 below specified the formation of reasonably high molecular weight (co) polyesters. As expected from a step growth polymerization mechanism, the dispersity values were close to 2.
TABLE-US-00002 TABLE 2 Results of synthesis of (co)polyesters bearing pendant furyl groups Molecular weight Polyester BPF BPA IPC .sub.inh (g mol.sup.1) .sup.b Dispersity code mol % mol % mol % dL/g.sup.a Mn Mw Mw/Mn FPE-1 100 00 100 0.81 31,700 68,700 2.1 FPE-2 50 50 100 0.51 25,400 52,400 2.0 FPE-3 40 60 100 0.89 37,600 79,400 2.1 FPE-4 30 70 100 1.00 42,500 80,000 1.9 FPE-5 20 80 100 1.10 48,900 94,400 1.9 FPE-6 10 90 100 0.74 27,100 53,100 1.9
Example3: Thermal Properties of (co) Polyesters Bearing Pendant Furyl Groups
[0087] Thermal behavior of (co) polyesters bearing pendant furyl groups was evaluated by thermogravimetric (TG) analysis at a heating rate of 10 C./min under nitrogen atmosphere. The Tg values of (co) polyesters were evaluated by DSC at a heating rate of 10 C./min under nitrogen atmosphere. The data obtained were given in the table below.
TABLE-US-00003 TABLE 3 Thermal properties of (co) polyesters bearing pendant furyl groups Char (Co)polyester Tg T.sub.10 Yield Code (Co)polyester ( C.).sup.a ( C.).sup.b (%).sup.c FPE-1
[0088] The single value of Tg of all the copolyesters support the formation of random copolymers was inferred from .sup.13C NMR spectroscopy studies. The homopolyester FPE-1 containing cardophthalimidine moieties exhibited Tg value of 242 C. It is to be noted that reported Tg value of polyester obtained by polycondensation of BPA with IPC is 180 C. As anticipated, Tg values decreased with increase in mol % incorporation of BPA in the series of (co) polyesters. The T.sub.10 values of (co) polyesters were in the range 415-452 C. which indicated their higher thermal stability.
ADVANTAGES OF THE INVENTION
[0089] A simple and convenient process for the synthesis of phthalimidine-containing bisphenol monomers bearing pendant furyl group linked via an alkylene spacer is developed [0090] Readily available and inexpensive chemicals are involved in the process [0091] These phthalimidine-containing cardobisphenols are potentially useful for the synthesis of a range of step growth polymers such as aromatic polycarbonates, polyesters, poly (arylene ether)s, cyanate esters, epoxy resins, etc. [0092] The polymers exhibit desirable combination of properties such as improved thermal properties accompanied by solubility in common organic solvents. These properties offer advantages in terms of solution processability and applications as high temperature thermoplastics.