N-alil morfelin kükürt dioksit kopolimeri sentezi
Başlık çevirisi mevcut değil.
- Tez No: 75299
- Danışmanlar: YRD. DOÇ. DR. A. BAHATTİN SOYDAN
- Tez Türü: Yüksek Lisans
- Konular: Kimya, Chemistry
- Anahtar Kelimeler: Belirtilmemiş.
- Yıl: 1998
- Dil: Türkçe
- Üniversite: İstanbul Teknik Üniversitesi
- Enstitü: Fen Bilimleri Enstitüsü
- Ana Bilim Dalı: Kimya Mühendisliği Ana Bilim Dalı
- Bilim Dalı: Belirtilmemiş.
- Sayfa Sayısı: 66
Özet
Alil monomerleri radikal başlatıcılar ile oligomer verme eğilimindedirler. Çünkü, polimerizasyon esnasında yan reaksiyon ile alilik karbon üzerinde kararlı radikal oluşur ve bu radikal sonlandırıcı etkisi gösterir.Fakat, alil monomerleri kükürt dioksid ve vinil monomerleri ile kopolimerler verir. Böylelikle N-alil morfolin ile kükürt dioksid kopolimeri hazırlandı ve başlangıç monomeri N-alil morpholinin alil klorür ile kondensasyonundan sentez edildi. Oluşan kopolimerin yapısı genel spektroskobik teknikleri ve elementel analiz ile açıklandı.Elektron verme eğiliminden dolayı, N-alil morfolin kükürt dioksid (elektron alan) ile bir kopolimer oluşturduğu görüldü.
Özet (Çeviri)
Allyl monomers tend to give oligomers with radical initiators. Because, during the polymerization a side reaction yielding stable radical on allylic carbon is competitive with the propagation and this radical exhibites terminating effect. However allyl monomers can give copolymers with sulphur dioxide and vinyl monomers. The aim of the project is to prepare copolymer of N-allyl morpholine with sulphur dioxide. Synthesis of N-allyl morpholine has been performed by Hofmann alkylation reaction of morpholine with allyl chloride. Structure of the monomer has been elucidated by conventional specrroscopic methods and elemantary microanlysis. Its homopolimerization gives only a viscous liquid with low yields, in the precence of radical initators. But in appropriate conditions it can be copolymerized with SO2 and styrene monomers. An alternating copolymer is obtained in DMSO solvent under atmospheric pressure at 60°C in reasonable yields. Its copolymerization with styrene in dioxane at 80°C gives corresponding copolymer. Structure of the polymers have been assigned by H-NMR and FT-IR spectroscopy. Polymerization of allyl monomers by radical initiation results in formation of only low molecular-weight homopolymers, due to degradative chain transfer. Only some of suitable allyl monomers can give high molecular weight polymers by coordination catalysts(44). Whereas these monomers may undergo copolymerizations with various vinyl monomers including sulfur dioxide(45). Diallyl monomers in which both allyl groups are attached to the same atom undergo cyclopolymerizations to give five membered repeating units in the main chain(46). Recent developments on the subject indicate that by new procedures high molecular-weight homopolymers of the diallyl monomers are attainable. Recently it has been reported that these monomers can also form alternating copolymers with S02(47). With the exception of vinyl monomers conjugated with polar groups, almost all the vinyl monomers tend to form alternating copolymers with sulfur dioxide(48). In the most of the earlier reports, to attain high molecular weights, SO2 copolymerizations have been suggeted to run in pressure vessells. However recent developments represent that these polymerizations can be achieved under atmospheric pressure, using DMSO solvent which strongly absorbs S02(49). In this study we have described synthesis of N-allyl morpholine and its copolymer with sulfur dioxide, using the same methodology. Also itscopolymerizability with styrene has been studied. Having ionizable tertiary amine functions, these copolymers may be of interest for some applications such as polyelectrolyte etc. Morever there are only few reports, in the literature, dealing with the polymers carrying tertiary amine functions. One of which is poly(N-alkyl ethylene imine)(50) and the other one is poly(2-dimethylamino ethyl methacrylate)(51). In laboratory all the chemicals used were analytical grade commercial products; 3-chloro propene(allyl chloride)(E.Merck), Morpholine(Fluca). They were used without further purification. Viscosity measurments were carried out in DMF solutions at 30°C±0.2, using Ubbelohde viscometer. XH-NMR spectra were taken by a Bruker Model 200 MHz (with DMSOa-e or CDC13 solvents). FT-IR spectra were recorded at Mattson 1000 FT-IR Spectrophotometer with KBr disc. In the synthesis of N-allyl morpholine the following results were recorded. In elementary micro analysis: %found (Calc.forC7Hi3NO); C:65.9% (66.1), H:10.8%(10.2), N:10.8%(11.0). The density d20°c =0.77 g/mL. ^-NMR spectra and FT-IR spectra are given in Fig. 1 and Fig.2b respectively. L_^\JWV 6.0 5.0 4.0 3.0 2.0 1.0 0.0 PPM Fig.l *H-NMR Spectra of N-allyl morfoline in CDCl3(with TMS as internal standart). XI^ o^ 4000 3000 2000 1000 Fig.2 FT-IR Spectra of a)Morpholine, b)N-allyl morpholine 400 XllIn copolimerization with sulfur dioxide the following results were recorded. In elementary micro analysis :% found(Calc.for C7H13NO3S, by neglecting end groups); C:42.1%(44.0), H:6.8%(7.5), N:7.3%(6.8). XH-NMR spectra in (DMSOd^) and FT- IR spectra of the polymer are shown in Fig.4 and Fig.3.a respectively. Inherent viscosity of the polymer in DMF (0.2 g/lOOmL) was found to be 0.30 dL.g“1 (at 30°C±0.2). The polimer is soluble in H20, ethanol, DMSO, DMF and insoluble in acetone and toluene. 9-0 B.O 7.0 6.0: 5-0 4-0 PPM 3.0 2-0 1.0 0.0 Fig.4 'H-NMR Spectra of N-allyl morpholine-S02 copolymer xiii4000 3000 2000 1000 400 Fig. 3 : FT-IR Spectra of a)Copolymer with SO2, b)Copolymer with styrene XIVIn the copolymerization with styrene the following results were obtained. Viscosity of the polymer in DMF(0. lg/lOmL) ^=0. 12 dL.g*1 at 30°C±0.2. 'H-NMR spectra (in CDC13) and FT-IR spectra of the copolymer are shown in Fig.5 and Fig.3.b respectively. The polymer is soluble in DMF, DMSO, and acidified water, sightly soluble in toluene and insoluble in acetone and ethyl acetate. v. 3 Fig.5 : !H-NMR Spectra of N-allyl morpholine-styrene copolymer XVClassical Hoffman alkylation of morpholine with allyl chloride gives rise to N- allyl morpholine in high yields (Scheme 1). t ^ KOH t V O NH+ a-CH^-CHKIl, > O N- CH,-CH=CH, N / CH3OH \ / 2 2 (Scheme 1) 'H-NMR spectra of the product in fig. 1 clearly establishe the structure expected. As it can be seen from the spectra, the product is highly pure. Probable impurities arrising from quaternization products have been eliminated during the final distillation. Later on, we have observed that quaternization of the N-allyl morpholine with allyl chloride practically does not occur by direct interaction of the two. In the NMR spectra = CH proton shows multiplet signals centered at 5.85 ppm. Whereas, = CH2 protons of the vinyl group give another multiplet at 5.2 ppm. CH2 protons between nitrogen atom and vinyl group represent a sharp doublet at 3.0 ppm. The signals of CH2 protons adjacent to nitrojen in the morpholine group are observed 2.4 ppm as an unsymmetrical triplet. The other ring protons of the morpholine ring show another triplet at 3.7 ppm. The integral ratios are also consistent with each other. Comparision of the IR spectra of morpholine with those of N-allyl morpholine obtained confirms the transformation expected (see fig.l.a and l.b). N-H streching vibrations of morpholine observed at 3320 cm”1 disappear almost completely in the spectra of the allyl compound. New bands associated with C = C streching vibrations and olephinic C - H strecing vibrations are observed as sharp peaks at 1655 cm“1 and 3060 cm”1 respectively. Attempts for homopolymerization of N-allyl morpholine in different solvents with common peroxide initators were always unsuccesful, as in the case for well- known allyl monomers. Most probably here the tertiary amino group act as trapping agent for peroxy radicals. Because tertiary amine-peroxide is well known redox couple and generates alkyl amine radicals. And the alkyl amine radicals are known to initiate radical polimerizations. Also the allyl amine does not polymeriza in ordinary conditions. But for the first time Harrada and Hasegawa in 1984, succeded to polimerize allyl amine in phosphoric acid to yield a polymer with molecular weights as high as 45.000 (8). Presumably the phosphoric acid prevents oxidation of amino groups by blocking the nucleophilicity of the nitrogen atom involving. But we have not studied on homopolymerization of N-allyl morpholine, any further. We fell it worths studying in detail. What we interest was especially its copolymerizability with sulphur dioxide. Because tertiary amines are known to form charge transfer compounds with S02 in aprotic solvents (52). However in the presence of water S02 bounded to the amine as sulphite anion. In both forms S02 is released as the temperature rises. XVIFor this reason we attempted to copolimerize the allyl monomer with SO2 in water and methanol under atmospheric pressure at different temperatures. But only very small amounts (1-3 %) of a waxy residue was obtained by this procedure. f cm + SOz N. K2S2Q8 DMSO - f CH2- CH- S-X V 1 Un cm I I- O + Styrene -J-GJ2- CH-^ - f- cm- en Diojane (BzjCy J&L (Scheme 2) The copolymer was obtained by the Asrof Ali's method (52) using S02 preabsorbed by DMSO. ^-NMR spectra of the copolymer in fig.3 is a good evidence of polymer formation. The multiplet peaks of the monomer (in fig.l) associated with olephinic protons disappear in the spectra of the copolymer. New peaks observed in 2.4-4 ppm range indicate protons of saturated carbon-carbon bonds. The protons of morpholine rings in the copolymer shift slightly to down fields and appear at 2.5 and 3.8 ppm due to deshielding effect of the sulfone group in the main chain. Copolymerization of N-allyl morpholine with styrene in the precence of acetic acid gives a white copolymers which is soluble in concentrated hydrochloric acid. In the NMR spectra of this product (fig.4) the broad signals lying 6.3-7.4 ppm range arrise from the phenyl protons of the styrene component. From the integral ratios of aromatic and aliphatic protons percentage of the N-allyl morpholine moiety in the copolymer can be deduced as 1 1.0 %. As a consequence, N-allyl morpholine can be copolymerize with sulphur dioxide and styrene. Having tertiary amine function, N-allyl morpholine may be of interest for preparing copolymers which would be useful as speciality membranes for gas separations etc. xvii
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