Abstract : Synthesis And Imidization Of Disuccinamic Acid As Polyvinyl Alcohol-Composite Polymer Zakaria H. Aiube Fadhel S. Matty Hiba A. Ghani Al-zaidi Department of Chemistry/ College of Education for Pure Science (Ibn Al–Haitham) / University of Baghdad Received in : 26 February 2014, Accepted in : 18 March 2014 Abstract Two arylenedisuccinamic acids, namely 1,4-phenylene-disuccinamic acid and 4,4'- biphenyl-disuccinamic acid were prepared from the reaction of two moles of succinic anhydride with one mole of 1,4-phenylenediamine dihydrochloride and beinzidine respectively.Dehydration of arylenedisuccinamic acid in the pressence of polyvinyl alcohol (PVA) and catalytic amount of concentrated.H2SO4,gives N,N'-arylenedisuccinimides- PVAcomposite polymers. Dehydration of arylenedisuccinamic acid (without PVA) in the pressence of catalytic amount of conc. H2SO4 gives N,N'-arylenedisuccinimides. Arylenedisuccinamic acid and arylenedisuccinimides characterized by CHN-analysis,FT.IR and 1H,C13-NMR.Spectral analysis. Keywords: Succinic anhydride, 1,4-pheneylenediamin dihydrochloride,binzidine, acetic anhydride-sodium acetate, PVA. 211 | Cemistry @a@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@ÚÓ‘Ój�n€a@Î@Úœäñ€a@‚Ï‹»‹€@·rÓ:a@Âig@Ú‹©@Ü‹127@@ÖÜ»€a@I2@‚b«@H2014 Ibn Al-Haitham Jour. for Pure & Appl. Sci. Vol. 27 (2) 2014 Introduction Many imides have been prepared via a dehydration of amic acids. Several dehydrating agents can be used for dehydration of amic acids, like acetyl chloride- triethylamine[1,2,3,4],thionylchloride[5,6]aceticanhydride-sodiumacetate[7,8], phosphorous pentoxid[9] and phosphorous trichloride[10]. Many cyclicimide have biological activities including antibacterial[11], antifungal[12,13], analgesic[14,15]and antitumor[16], as well as, some of cyclic imide acts as plant growth stimulation[15] and corrosion inhibitors. Morover PVA is a known polymeric material having good chemical stability and hydrophilicity[17]polyvinyl alcohol is well known as water-soluble polymer and widely used as fiber, film, adhesive, gel and stabilizer of polymer and organic and in organic particles[18]. In addition, PVA extends the industrial application in optical, pharmaceutical, medical and membrane fields intense research on composite materials with enhanced mechanical[19] and thermal properties[20].To data, however, much of the research carried out has only focused on tensile strength, hardness which are essential quantities and can be very important in some applications[21].In this study PVA/amic and PVA/imide composite was prepared and its properties were investigated. Experimental Perparation of succinic anhydride A stirred mixture of (59g, 0.5mol) succinic acid and (94.5ml,1.02g,1mol) redistilled acetic anhydride, into round bottom flask provided with reflux condenser and calcium chloride drying tube , was refluxed until the solid succinic acid was dissolved and then for further an hour. Reaction mixture allowed to cool in refrigerator ,a crystalline succinic anhydride was formed, filtered then washed two times with (2x40ml) dry ether, yield (45g, 90%). m.p. 118-120 °C [119-120], its FT.IR-spectrum which showed the appearance of symmetrical and asymmetrical stretching vibration of (C=O, anhydride) at (1782, 1863 cm-1) respectively[22]. Preparation of arylenedisuccinamic acids [M3,M2] I/1,4-phenylenedisuccinamic acid [M3] To a clear stirred solution of (1.0g, 0.0055mol) phenylendiamin dihydrochlorid in (12 ml) water, (0.54g, 0.0054mol) succinic anhydride was added. Reaction mixture was stirred for filtered an hour, a precipitated succinic acid was formed, filtered, washed with water, recrystallized from boiling water yield (12.0g, 80٪) m.p. above 300°C, CHN-analysis and spectral data (Table 1). II/4,4'-biphenyldisuccinamic acid [M2] To a clear solution of (0.46g, 0.0025 mol) benzidine in (20 ml) of acetone, (0.5g, 0.0050mol) of succinic anhydride was added. Reaction mixture was stirred under reflux for (2 hours), a solid was formed. Reaction mixture was cooled, filtered and the precipitate was washed with water, to give 4,4׳- biphenyl-disuccinamic acid yield (0.8g, 83.3%); m.p. above 300 °C; CHN- analysis and spectral data (Table 1). Preperation of disuccinimide- PVA composide polymer A clear solution of (0.1g, 0.32mmol) of arylendisuccinamic acid(M3,M2) in (10 ml) of DMSO was added to a clear solution of (0.35g) PVA dissolved in (10 ml) of DMSO and (4 drops) of concentrated sulphuric acid were added. Reaction mixture was heated at 80 °C for (2 hours), cooled to room temperature, divided into two equal parts: A-Acetone was added to the first part of reaction mixture, until a coagulated precipitate was formed, acetone solution was decanted and a precipitate was washed with (5 ml) 5% sodium 212 | Cemistry @a@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@ÚÓ‘Ój�n€a@Î@Úœäñ€a@‚Ï‹»‹€@·rÓ:a@Âig@Ú‹©@Ü‹127@@ÖÜ»€a@I2@‚b«@H2014 Ibn Al-Haitham Jour. for Pure & Appl. Sci. Vol. 27 (2) 2014 carbonate solution, then with acetone. Dissolved in (2 ml) of DMSO and poured into glass mold rectangular shape with dimension 15x5 cm2 and 0.5 cm height made and used for casting a polymer, leaved for few days, at room temperature to dryness, a thin film was Formed, dried at 80 °C for 6 hours. FT.IR-spectrum of the film showed ʋ C=O symmetrical and asymmetrical stretching absorption of PVA-imide at (1778-1780,1707-1710 cm-1). B- Second part of mixture was poured into glass mold rectangular shape with dimension 15x5 cm2 and 0.5 cm height made and used for casting a polymer, and was left for few days, at room temperature to dryness, a thin film was obtained, dried at 80 °C for 6 hours. FT.IR- spectrum of the film showed ʋ C=O symmetrical & asymmetrical stretching absorption of PVA-imide at (1778-1780,1707-1710 cm-1). Imidization of arylenedisuccinamic acids(M3,M2) with catalytic amount of conc H2SO4 (without PVA) To a clear solution of (0.0015mol) arylenedisuccinamic acids (M3,M2) in (20 ml) DMSO at 80 °C, a (4 drops) of concentration sulphuric acid was added. Then reaction mixture was stirred at 80 °C for 2 hours, it was cooled to room temperature and added to ice-cooled water, solid was formed, filtered and washed with 5%-sodium bicarbonate solution, then with water. Recrystallized form DMF to give N,N'-arylenedisuccinimide physical properties, CHN- analysis and spectral analysis are given in the table(2). Results and discussion It is known that, PVA can be modified by esterification reaction with many dicarboxylic acids like[23,24]In this work, we prepared some arylenedisuccinamic acid, like 1,4- phenlenedisuccinamic acid (M3) and 4,4'-biphyldisuccinamic acid (M2) via reaction of (2 moles) of succinic anhydride with one mole of phenylenediamin and benzidine respectively. C C O O O + NH2 Ar2 NH2 H2 C H2 C CHO2C O H N Ar H N C O H2 C H2 C CO2H Treatment of areylendisuccinamic acid (M3, M2) with PVA in the presence of a catalytic amount of concentrated sulphuric acid (as a normal esterification condition), leads to format arylendisuccinimides (M5,M4) as a composite-PVA Polymers, rather than arylenedisuccinamte-PVApolymer, which are characterized by their (C=O, imide) symmetrical & asymmetrical vibration bands of arylenedisuccinimides(M5,M4)-PVA composite polymers filmes at (1778,1705cm-1) and (1778,1710cm-1). 213 | Cemistry @a@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@ÚÓ‘Ój�n€a@Î@Úœäñ€a@‚Ï‹»‹€@·rÓ:a@Âig@Ú‹©@Ü‹127@@ÖÜ»€a@I2@‚b«@H2014 Ibn Al-Haitham Jour. for Pure & Appl. Sci. Vol. 27 (2) 2014 O OH OH OH C O CO O OH OH OH H+/-H2O Esterif ication process Cross-linke polymer C CO2H O N H Ar N H C O CO2H C C O O N Ar N C C O O + PVA H+/-H2O Imidization process PVAcomposite polymer Fig. (1).Shows esterification and Imidization process. Treatment of areylendisuccinamic acid (M3, M2) with catalytic amount of concentrated sulphuric acid (without PVA), also gives arylendisuccinimides (M5,M4) respectively, characterized by identity of arylenedisuccinimide CHN-analysis, FT.IR-spectral analysis shows symmetrical & asymmetrical stretching vibration of imide (C=O, imide) at (1778,1705cm-1) and (1780, 1708cm-1 ) rather than (C=O ester) stretching vibration, and C13- NMR(proton decoupled) shows there types of signals belong to CH2 at δ (28ppm), aromatic carbons at δ (126-127ppm), and C=O imide carbon and at δ (176ppm), besides C13-NMR spectral (DEPT) indicated & CH2 carbones at δ (27.88ppm). So, it is clear to conclude, that imidization prosses areylendisuccinamic acid (M3,M2) to give arylendisuccinimides (M5,M4) is much faster than esterification process of areylendisuccinamic acid with PVA, and conc. H2SO4 acts as a dehydrating agents. Finaly, we can conclude a suggested mechanism for dehydration of arylenedisuccinamic acid (M3,M2) to arylenedisuccinimides (M5,M4) as fallows. in presence a catalytic amount of concentrated sulphuric acid : 214 | Cemistry @a@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@ÚÓ‘Ój�n€a@Î@Úœäñ€a@‚Ï‹»‹€@·rÓ:a@Âig@Ú‹©@Ü‹127@@ÖÜ»€a@I2@‚b«@H2014 Ibn Al-Haitham Jour. for Pure & Appl. Sci. Vol. 27 (2) 2014 Fig.(2).Mechanism for dehydration. Glass transition temperatures(Tg)of the composite PVA-imide The glass transition temperature (Tg) of the Imid-polyvinyl alcohol composites was determined from DSC figure. The glass transition temperature which is a measure of segmental mobility depends on the rigidity of the composites polymers. Relatively higher Tg was found for the compositions with high aromatic contents[25]. In this work composite polymers (M4A, M4B and M4C) are biphenyl based composite imide, and (M5A, M5B and M5C) are Phenylene based composite imide. And (34.25°C) for PVA Table (3) presents the glass transition temperature (Tg) composites polymer (100.12°C, 131.25°C and 161.48°C) have higher than that composites polymer (34.30°C,35.87°C and 38.43°C). This result could be attributed to higher rigidity of biphenyl as composite and the table shows the (Tg) value increased with the increasing of the weight of additive. C N O C O OH H Ar N C O H C O HO 2H+ C N O C OH OH H Ar N C O H C OH HO C N O C H Ar N C O H C OH OH HO OH C N O C Ar N C O C OH O HO O H H H H C C O N Ar N C C O H2O O OH2 OH H C C O N Ar N C C O O O - 2H2O - 2H+ Ar = 1,4phenylene, 4,4'-biphenyl 215 | Cemistry @a@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@ÚÓ‘Ój�n€a@Î@Úœäñ€a@‚Ï‹»‹€@·rÓ:a@Âig@Ú‹©@Ü‹127@@ÖÜ»€a@I2@‚b«@H2014 Ibn Al-Haitham Jour. for Pure & Appl. Sci. Vol. 27 (2) 2014 Brinell hardness test Hardness meanes the measurement of the material resistance to a localized deformation and the ductile absorbs more quantity of energy, also as the concentration of the fillers is increased. The ability of the filler to form chain structure in the polymeric medium becomes increasingly important[26,27].Hardness results table (4,5)showed that brinell hardness values [HBr(N/mm2)] of PVA/amic and PVA/imide composite were higher than that of neat PVA. And also composite PVA have good resistance to indention and that could be due to the existence of filler particles which leads to transfer some of the applied stress to the filler particles. Ultimate tensile strength Ultimate strength is the maximum stress that material can with stand while being stretched or bulled before failing or breaking[28]. Mechanical tests show that compared with pure PVA, the tensile strength of the composite are greatly improve table (6,7) the ultimate tensile strength enhancement is attributable to the extremely high strength and the degree rein formant which is depudent on the dispersion state controlled by hydrogen bond. References 1-Roderick.W.R. (1957) 1H and 13C NMR spectra for a series of arylmaleamic acids, arylmaleimides, arylsuccinamic acids and arylsuccinimides,J. Am, MAGNETIC RESONANCE IN CHEMISTRY, Chem.. Soc., 79, 1710,37,(682-686). 2-Cotter. J.; Sauers. C. and Whelane. J. ( )1961 maleamic acids cyclodehydration with anhydrides DFT studyin the gas phase and solution,Revue roumaine de chimie,56,2,(89-95). 3-Pyridi. T.M. and Fraih. M. (1982) J. Macromol. Sci. Chem., A(18),159. 4-Alasli.N.A. ( )2000 Ph.D. Thesis, Chem. Dept. College of Sci. Univ. of Baghdad. 5-Pyridi.T.M. and Harwood.H.J. (1972) maleamic acids cyclodehydration with anhydrides DFT studyin the gas phase and solution,Revue roumaine de chimie,56,2,(89-95). 6-Warren.W. and Briggs.R. (1931) Ber., 26, 64B(1931), C.A.25, 2418. 7-Searle.N.E.(1973) N-phenylmaleimide[Maleimide,N-phenyl-],Organic syntheses,Coll.vol.,5,944. 8-Cava.M.; Deana. A.; Mauth.K. and Mitchell.M. (1961) N-phenylmaleimide[Maleimide,N- phenyl-],Organic syntheses,Coll.vol.,41,93. 9-Barakat.M.Z.; Shehat. S.K. and Elsadr. M.M. (1957) J. Chem. Soc., 23, 4133. 10-Kulev.L.; Gireva.R. and Stepova.G. (1963) Obshch. Kim, 32, 2812 (1931), C.A. 58, 8961. 11-Correa.R. and Filho.V.C. (1997) Pharm. Sci., 3, 67. 12-Brian. G.E. and Tawney. P.O.(1961) U.S. Pat., 2, 989, 436 (1961), C.A., 55, 23915. 13-Filho.V.C. and Correa. R. (1998) Farmaco, 53, 55. 14-Andricopulo.A.D. and Muller.L.A. (2000) Farmaco, 55, 319. 15-Brunner.G.; Georg.H. and Marcus.B. ( ) 1988 Eur. Pat. Appl. Ep. 260/288 16 March. 16-Andricopulo.A.D. and Yunes.R.A. (1968) Quimica Nova, 21, 5, (573). 17- Immelman.E.; Sanderson.R.D.; Jacols.E.E. and Vanreemen.A.J. (1993) J .Appl. polymer sci,50 1013. 18- Finched.C.A. (1992) polyvinyl alcohol – Development, John wiley and son.Chichester. 19-Daltons.A.B.;Collins.S.(2003) Nature,423,703. 20-Biercuk.M.J.; Ltaguno.M.C. ( )2002 etal,App. Phys. Lett.80 2767. 21-Chen.W.; Tao.x.; Xue.P. and Cheng.X. (2005) ''Applied Surface Science'' , 252, 1404- 1409. 22-VOGEL(1972) voglel a test book of practical organic chemistry fourth Edition 23-Vacshosaz.J.and Koopaic. N. (2002) Iranian Polymer Journal 17(11), No. 2 (123-131). 216 | Cemistry @a@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@ÚÓ‘Ój�n€a@Î@Úœäñ€a@‚Ï‹»‹€@·rÓ:a@Âig@Ú‹©@Ü‹127@@ÖÜ»€a@I2@‚b«@H2014 Ibn Al-Haitham Jour. for Pure & Appl. Sci. Vol. 27 (2) 2014 24-Al-Mousawy.Z.A.; Badri, D.H. and Aiube, Z.H.(2012) ''J. Food Industries & Nutr. Sci''., 2(1): 57-64. 25-Gere.J.M.(2004) Mechanice of materials, 6 th. Ed. , Belment, CA; Brooksl col. Thomas learning .xx,940P. 26-Foro.C.L.and Cicals.G.L. (2000) The Energy Absorbing properties of composite material, Engineering Materials , M.K. 27-Harper.C.A. (2000) ''Modern plastics Hand book '' ,Companies, Inc.,Newyork. 28-Pavlina.E.J. ( )2008 Vorral of material Engineering and performance , 17:6 December. Table(1): Physical parameters. Compounde CHN-analysis cale./found C,H,N FT.IR ʋ (cm-1) NH,OH,CH,C=OamideI, CONHamidII, C=Ocarboxyl 1H-NMR δ(ppm) M3 54.55/55.42;5.19/5.5;9.09/9.66 3290,3147; 3055; 2926; 1654;1552; 1697 2CH2 (3.35,4H) Aromatic H(7.5-7.6,4H) NH amide (9.85,1H) COOH(12,1H) M2 62.5/60.97;5.20/5.54;7.29/7.36 3302,3180;7107,3041;3041,2931; 1654; 1521; 1697 2CH2 (3.37,4H) AromaticH (7.3-7.6,4H) NH amid (9,1H) COOH(12,1H) Table(2): Physical parameters. Compound m.p(°C) Yiled. FT.IR(C=O)(cm-1) C13.NMR(ppm) M5 above300 °C 71٪ 1778,1708 CH2 (28) Arom. (126-127) C=O (176) M4 above300 °C 69٪ 1778,1705 CH2 (28) Arom. (126-127) C=O (176) Table(3): Thermal behavior of synthesized polymers. Samples Tg (°C) M6 34.25 M4A 100.12 M4B 131.25 M4C 161.25 M5A 34.30 M5B 35.87 M5C 38.43 217 | Cemistry @a@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@ÚÓ‘Ój�n€a@Î@Úœäñ€a@‚Ï‹»‹€@·rÓ:a@Âig@Ú‹©@Ü‹127@@ÖÜ»€a@I2@‚b«@H2014 Ibn Al-Haitham Jour. for Pure & Appl. Sci. Vol. 27 (2) 2014 Table(4): Brinell hardness for (composite PVA-amic compounds). Samples HBr (N/mm2) M6 60 M6 & M7 63 M6 & M8 65 M6 & M9 66 M6 & M10 74 M6 & M11 75 M6 & M12 77 Table(5): Brinell hardness for (composite PVA-imide compounds). Samples HBr (N/mm2) M6 60 M6 & M5A 60.5 M6 & M5B 62 M6 & M5C 66 M6 & M4A 67 M6 & M4B 69 M6 & M4C 73 Table(6): Ultimate tensile strength for (composite PVA-amic compounds). Samples Ultimate tensile strength (KJ/m2) M6 10 M6 & M7 13 M6 & M8 15 M6 & M9 17 M6 & M10 17 M6 & M11 22 M6 & M12 27 Table(7): Ultimate tensile strength for (composite PVA -imide compounds). Samples Ultimate tensile strength (KJ/m2) M6 10 M6 & M5A 12 M6 & M5B 15 M6 & M5C 16 M6 & M4A 18 M6 & M4B 20 M6 & M4C 27 M1=Succinicanhydride,M6=PVA,M7=CompositeM6(0.15g)&(0.05g)M3,M8=CompositeM6 (0.15g)&(0.1g)M3,M9=CompositeM6(0.15g)&(0.15g)M3,M10=CompositeM6(0.15g)&(0.05g) M2,M11=CompositeM6(0.15g)&(0.1g)M2,M12=CompositeM6(0.15g)&(0.15g)M2,M4C=Comp ositeM6(0.15g)&(0.15g)M4,M4B=CompositeM6(0.15g)&(0.1g)M4,M4A=CompositeM6(0.15g) &(0.05g)M4,M5A=CompositeM6(0.15g)&(0.05g)M5,M5B=CompositeM6(0.15g)&(0.1g)M5,M 5C=CompositeM6(0.15g)&(0.15g)M5. 218 | Cemistry @a@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@ÚÓ‘Ój�n€a@Î@Úœäñ€a@‚Ï‹»‹€@·rÓ:a@Âig@Ú‹©@Ü‹127@@ÖÜ»€a@I2@‚b«@H2014 Ibn Al-Haitham Jour. for Pure & Appl. Sci. Vol. 27 (2) 2014 طة بولي فینایل اسبو مركبات احماض ثنائي السكسینامیكلوتحلق تكوین كبولیمرات مركبة -الكحول ھادي ایوب زكریا فاضل سلیم متي ھبھ احمد غني جامعة بغداد / ابن الھیثم -كلیة التربیة للعلوم الصرفة/ قسم الكیمیاء 2014آذار 18، قبل البحث في : 2014كانون الثاني 26استلم البحث في : الخالصة ب��اي فین��ل ثن��ائي -4,4و M3) السكس��ینامیك(فنیل��ین ثن��ائي -1,4حض��رت احم��اض اریل��ین ثن��ائي السكس��ینامیك مث��ل فنیل�ین ثن�ائي االمی�د ثن�ائي الھیدروكلوری�د -1,4) من تفاعل مولین من انھدرید الخلی�ك م�ع م�ول واح�د م�ن M2السكسینامیك( .والبن��������������������������������������������������������������������������������������زدین عل��������������������������������������������������������������������������������������ى الت��������������������������������������������������������������������������������������والي طة ح�امض الكبریتی�ك المرك�ز وبوج�ود اس�المحف�رة بو M2) (M3,جزیئة ماء من احماض اریلین ثنائي السكس�ینامیك تسحب وعن��د س��حب .كب��ولي م��رات مركب��ة M5,M4(-PVAاریل��ین ثن��ائي السكس�نماید(-N,N)اعط��ي PVAب�ولي فینای��ل الكح��ول ( اریل�����ین ثن������ائي -N,N'اعط�����ي ایض������ا مركب�����ات PVAوج�����ود نفس�����ھا وم������ن دون الظ�����روف جزیئ�����ة الم�����اء تح������ت C13,1H-NMR .و FT.IRواطیاف CHN شخصت ھذه المركبات بواسطة التحالیل .)M5,M4السكسینماید( ، انھدرید الخالت ، خالت فنیلین داي امین داي ھایدروكلوراید -4و1، انھدرید السكسینیك :الكلمات المفتاحیة .الصودیوم ، بولي فینایل الكحول 219 | Cemistry @a@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@ÚÓ‘Ój�n€a@Î@Úœäñ€a@‚Ï‹»‹€@·rÓ:a@Âig@Ú‹©@Ü‹127@@ÖÜ»€a@I2@‚b«@H2014 Ibn Al-Haitham Jour. for Pure & Appl. Sci. Vol. 27 (2) 2014