Anhidrit grubu içeren polimerlerin modifikasyonu

Abstract

Çok fonksiyonlu monomerlerden olan maleik anhidrit, Etilen, stiren, vinil klûrür, vinil asetat gibi vinil mo - nomerleri ile kolayca kopolimer oluşturur. Anhidrit fonk siyonel grubu polimere hidroFilikiik,.yapışabilirlik,boya- nabirlik, ısıya dayanabilirlik ve hidroksil içeren bile şiklerle, amonyakla, amin bileşikleri ile reaksiyon aere- bilirlik sağlar. Bu çalışmada rnaleik anhidrit stiren (PoliSMAN) ve rnaleik anhidrit-estiren-divinilbenzen terpolimeri(Poli SMAIMDVB) ilaç, koku ve antioksidant özelliklere sahip salisilik asit, 2-fenil etanol, eugenol ve parasetamol gibi reaktiflerle modiflye edildi. Ayrıca reaktif bileşik lerin hidroliz yöntemi ile polimerden kontrollü salınması incelendi. Kopolimer ve terpolimer 80 C'de dibenzoil peroksit serbest radikal başlatıcı ile ve maksimum iki saatte orta lama % 95 verimle elde edildiler. PoliSMAIMDVB terpo- limerinin çeşitli çözücülerde çözünmemesi., aseton ve diok- san da şişmesi onun, biolojik kullanılabilir bir polimer olan, poliSMAN ile reaksiyonların nasıl yapılacağına karar verilmesine yardımcı oldu. PoliSMAIM ve PoliSMANDVB *nin hidroksil grubu içeren salisilik asit, 2-fenil etanol, eugenol ve parasetamol ile esterleştirme reaksiyonu, çözü cü olarak gl. asetik asit, aseton ve dioksan alınarak, der. H"BD, katalizörü ile 5D-9D C gibi değişik reaksiyon ısıla rında ve 2k-3h saat sürelerle gerçekleştirildi. Reaksiyon lar sonucunda oluşan polimerlerin İR spektrumundaki anhid rit grubuna ait 1B60-17B0 ve 1220 cnrf^'deki pikler azaldı, asit veya estere ait 172D ve 11B0 cm~ 'deki pikler oluş tu. NMR spektrumunda ise reaktiflere uygun pikler ortaya çıktı. Analitik yöntem ve İR spektrumu yardımı ile uza yan reaksiyon süresinde yükselen dönüşüm belirlendi. Sı caklık yükselmesi ve uzayan reaksiyon sürelerinde daha az verim ile modifiye polimer elde edildi. Aynı zamanda mo lekül ağırlıklarında, azalma göründü. Elde edilen modifi ye polimerlerin yumuşama noktası ve çeşitli çözücülerde çözünürlükleri değişti. Modifiye polimerlerin der. Hg2SO4 damlatılmış suda 24,4B, ve 72 saat gibi değişik sürelerde 50-90oC sıcaklıklarda hidroliz edildiğinde uzayan süre ve yükselen sıcaklıkta tamamen hidroliz olduğu belirlendi.

Maleic anhydride copolymers such as maleic anhydride/ ethylen, methyl vinyl ether, styrene and vinyl chloride are available commerically. An anhydride groups containing copolymers may be reacted with hydroxyl compounds and ammonia or amine to yield the esters, amide, ammonium or amine salts. The modified copolymers have completly different properties, such as solubility, swelling and may find further applications. In this study maleic anhydride-styrene and maleic anhydrite-styrene-divinyl benzen copolymers were modified with salicylic acid, 2-phenyl ethanol, eugenol and paraceta mol. The modified polymers maybe used as a controlled release system for salicylic acid, 2-phenyl ethanol, eugenol and paracetamol. Both maleicanhydride-styrene (PolySMAIM) and maleic anhydride styrene-divinyl benzen (PolySMANDVB) copolymers were prepared by.using dibezoylperoxide (DBPD) as free radical initiator at BDDC. The ratio Df styrene TTo~maleic anhydride was about 1 :1. Ch^-C H-ÇIİ-CH CK-CH *? CK-CH-CH-CH-CH-CH polySMAN PolySMANDVB VI The purified polySMAN ues soluble indioxane,acetone and insoluble in aromatic and chlorinated hydrocarbons, but polySMANDUE swelling in dioxane and acetone. The intirinsic viscosity of polySMAN was approximately D.2B o*l/g, in a 1% acetone solution at 25 C. The polySMAN and the polySMANDVB had softening temperature of 19D-2BDDC and 2BD-300DC respectively The infrared spectra of polymeric films cast from acetone dt dioxane solution indicated the absorbtioxis bands of anhydride carbonyl group at 186D,17BD cm", anhydride E-0 at 1 22D cm~ and aromati ring at 1 63D-7DD cm. stic The simplest esterification reaction of both poly- styrene-maleic anhydride and poly styrene-maleic anhyriride-divinylbenzen were readily occureri with salicylic acid, 2-phenyl ethanol, eugenol and paracetamol in gl. acetic asid, acetone or dioxane solution at 5D-9DDC'in various time such as 24,4B, 72,96 hours. ur, £00H n ^ H06 h{10 * HÇ-C-OH &0H T u (J Salicylic acid mod. poly., 5D°cfasetone H^-C-OH HC-^X""^ / O^^n 0 2-phenyl alcohol mod. poly. BD-9D°C gl. acetic arid or diDxsne HU- -C H( '"^> \ PolySMAN or PolySMANDUB D°C 5D°C or B0°C aseton, o op f u UC-Ç-OH I Oe dioxan CH^HrCl-L fC-C-( f 0 f*\NH(COCHJ ugenol «od.poly. S^Njwfcw H^-ckJ UÇ-C-OH ^ Q paracetamol mod. poly. vii The resulting modified polySMAN and polySMANDVB had a structure and properties different from the original polymers. Softening point and solubility of the modified polymers were shown in the following Table (reaction time : ^8 hr. ). 1)- Sa: Salicylic acid, F: 2-Phenyl ethanol, E: Eugenol, P: Paracetamol 2)- S: Soluble 5h: soluble hot Sl.h: Slightly soluble hot. SLü: Swelling SLü : Swelling hot SLül. : Slightlyswelling hot i: Insoluble The softening points of polymers were generally not sharp and were offen accompanied by decomposition. In anddition other data had also determined such as solution viscosities, average molecular weight, content of maleic anhytride. vm The composition of modified copolymer Lias estimated from the IR spectra. All the copolymers revealed similar characteristic peak's. The acid or ester ^C = 0 and anhydride /C = 0 of modified copolymers was appeared as turn peaks at 1720 and 1B6D or 1760 cm~ respectively. Degradation of modified copolymers in reaction medium was exhibited time from 2k tD 96 hours. H NMR spectrum of modified copolymers was also shown characteristic peaks. Modified polymer were shown that chemical release control, i.e, hydrolytic properties of various bands was an effective means of controlling release of functional compounds. 0 HC-C-O-f? HC-C-OH H H20 \ P, HÇ-C-0H -> I +R0H Modified polySMAN or PolySMANDVB PolySMA or PolySMA DUB ROH: 00H fHjCH^H salicylic 2-phenyl acid ethanol ;H2_ChtC^ NH(C0CH3) eugenol paracetamol IX H2SD4 Hydrolize reactions were occured, in various times such as 24,4B,72 hours at 50-90DC with cone. In high temperatures, polymer degradation were determined. Hydrolytic behaviour of modified polymers shown in the following table (reaction temperature: 90 C, reaction time: 4B hr.). 1 ) reaction temperature : 50 QC 2) reaction time : 72 hr. The modified polySMAN and polySMANDVB hydrolysis reaction time and the temperature were very important. Increasing modified. polySMAN hyrolysis temperature and time mas caused the expected increase in the yield of the reactant. Higher hydrolysis temperatures were caused thermal degradation. Longer hydrolysis heating time and temperature of the modified polySMANDVB mere decreased to yield of reactant. p.olymers had similar solubities. PolySMAN and polySMANDVB esters of antioxidant, parfüme and pharmaceutical alcohols were synthesized using salycylic acid, 2-phenyl ethanol, eugenol and parcetamDle in the presence of acidic solution.