İtakonik asit esterlerinin poli(dimetil siloksan) ile aba tipi blok kopolimerlerinin sentezi ve karakterizasyonu
Başlık çevirisi mevcut değil.
- Tez No: 56043
- Danışmanlar: DOÇ.DR. NURSELİ UYANIK
- Tez Türü: Yüksek Lisans
- Konular: Kimya, Chemistry
- Anahtar Kelimeler: Esterler, Kopolimerler, Polidimetilsiloksan, Esters, Copolymers, Polydimethylsiloxane
- Yıl: 1996
- Dil: Türkçe
- Üniversite: İstanbul Teknik Üniversitesi
- Enstitü: Fen Bilimleri Enstitüsü
- Ana Bilim Dalı: Belirtilmemiş.
- Bilim Dalı: Belirtilmemiş.
- Sayfa Sayısı: Belirtilmemiş.
Özet
ÖZET Bu çalışmada iki çeşit makro başlatıcı elde edilmiş ve bunlar kullanılmak su¬ retiyle 3 farklı monomerden 8 adet ABA tipi blok kopolimer sentezlenmiştir. sentez aşamalı yöntemle gerçekleştirilmiştir. Bu amaçla önce hidroksil son grupları bulu¬ nan Poli(dimetilsiloksan) içeren Tegomerler diizosiyanat kullanılarak diizosiyanatla kapatılmış üretanlar haline getirilmiştir. Burada kullanılan Tegomerlerden biri, üçlü blok kopolimerlik bir yapıdadır. Diğer Tegomer ise molekül ağırlığı korunmak su¬ retiyle kapatma reaksiyonuna tabi tutulmuştur. Bu tegomerler blok veya dikoroetan çözeltisinde 80°C de N2 atmosferinde kapatma reaksiyonuna sokulmuştur (Üretan I ve Üretan ü). İkinci aşama ise diizosiyanat kaplı prepolimerlerin bir hidroperoksit ile (t-bütil hidroperoksit) reaksiyonu aşamasıdır. Reaksiyon oda sıcaklığında, N2 atmosferinde, karanlıkta katalizör eşliğinde gerçekleştirilmiştir. Her iki aşamada el¬ de edilen ürünlerin analitik tayinleri ve spektoskopik incelemeleri bu ara ürünlerin saflaştırılıp kurutulmasından sonra yapılmıştır. Bu reaksiyonlar sonunda elde edilen ve zincir uçlarında peroksit bulunan makrobaşlatıcılar (Mil ve MI2) dimetil itakonat, disiklohekzil itakonat ve dibütil itakonatın polimerizasyonunda kullanılarak ABA tipi blok kopolimerler sentez edilmiştir. Sentez 80°C sıcaklıkta, vakumda. 100-200 saatte gerçekleştirilmiştir. Örneklerin UV spektroskopik yöntemle kopolimerdeki blok uzunlukları ağırlık yüz- desiyle belilenmiş ve kopolimeıierin ÎR spektrumlarından yapıların aydınlatılması¬ na çalşılmıştır. Viskometrik ve GPC yöntemleriyle molekül ağırlıkları tayin edil¬ miştir. Çözünürlük paremetreleri değişik çözücülerde ölçülen intrinsik, viskozite öl¬ çümlerinden belirlenmiştir. V
Özet (Çeviri)
SYNTHESIS AND CHARACTERİZATION OF ABA TYPE COPOLYMERS OF POLY (DIMENTHYL SILOXANE) AND POLY (ITACONATE)S SUMMARY The preparation of linear polyurethanes composed of soft polyester seg- ments and hard polyurethane sequences was reported 30 years ago. Various oligomers, copolymers, and interpenetrating networks have been prepared by using prepolymers of diols, diisocyanates, hydroperoxides, and azo-compounds containing functional gro- ups. The copolymer synthesis which was carried out in our laboratuaries is based on the chemical combination of low molecular weight soft polyethers with glassy proper- ties of vinyl polymer. in this work, block copolymers were prepared by using stepwise procedu- re. Dimethyl itaconate. dicyclohexyl itaconate and dibutyl itaconate were chosen for the vinyl part of the copolymer. The preparation procedure of the block copolymers with these stepwise method are given below. The polymeric peroxycarbamates were prepared in 2 stages. At the first stage, the dried hydroxyl-terminated prepolymers (H-Si 6440 and H-Si 2311) and the aliphatic diisocyanate (IPDI) vere reacted at 70°C bulk ör in dichloro ethane solution under a blanket of dry nitrogen, for 96 h. The resulting pro- ducts were decantated with acetonitrile in order to separate the excess of diisocyanate. The resulting product was dried in vacuum at room temperature. The isocyanate con- tent of the end-capped products were determined by end group titration of isocyanates and this experimental results were found to be in agreement with the theoritical values. in the second step, the diisocyanate-terminated urethane (urethane I and urethane II) was reacted with dried t-butyl hydroperoxide in methylene chloride. A few drops of T12 catalysts was added to the reaction mixture. The reaction was carri¬ ed out under a dry nitrogen blanket, at room temperature, in the dark, for 200 h. The molar ratio of t-butyl hydroperoxide to urethane was approximately three. The resul¬ ting peroxicarbamate were isolated by decantating (ör precipitating) in acetonitrile and dried in acetonitrile and dried in vacuum at room temperature. Their molecular we- ights were calculated from their peroxide contents. The preparation conditions of mac- roinitiatiors are shown in table l. Vİ*qo 582 Sr-P-, ~ â * g - c v<«~ı £.5oqo -udri = l l w oCJ l“8 ^f +^ o «8ON</~, £.=ooO £ 3d« A O OîXcom ^_Oürop C3OZcörf 'J~!ı, ı. 'S 'S1!_ 5 % s u'Z îl 25Î X3 *§^ 'g ^ § 11g 5 03*> ”O Cu « S <l>S.3 -«o t-H5 3tNOO CUu «-ri ia o“ S? X 2oo 0««n-. Z Q<^nS.52 -i E-^ 13 3 Ou u203 =3 l S«2 *|+1-HM 1ODOO”O S o O OC E-iırııy-,S vCrı ^*> ^2 <U OC s z'e C i- -<^ıE ^S-H-S |.2 SSS S 'Sû >-l* viiThe stuctural formulas of the macroinitiators are: CH3 I CH3-C-OO-C- N-(Ci0H18)-N-C-O-(R*)i/2 | H I III CH3 O H HO J 2 Macroinitiator in Ml 1 R* is « (CH2)s-C-0 -f-R- II O --18 CH3 I -Si-0 I CH: CH2 I -Si-R-|-0-C-(CH2)5-- II CH3L O J 18 y 30 in Ml 2 R'is CH3 - (CH2)m - Si-O- Si-(CH2) I I - CH3 J 30 CH3 CH3 5<m<10 Synthesis of Copolymers The prepared macroinitiators were used as initiators for the synthesis of copolymers of dimethyl itaconate (DMI), dicyclohexylitaconate (DCHI) and dibutyl itaconate (DBI). Weighted amounts of the macroinitiators were mixed in predetermined amounts of monomer solution in the pyrex tubes. The mixtures were then degassed on a vacuum line (1.33xl0~2N/m2). The solutions were distributed in pyrex tubes immer sed in thermostatically controlled baths and polymerization was carried out for 300 h. at 80°C. The block copolymers of PDMI were dissolved in acetone and precipitated in petroleum ether 40-60°C fraction whereas PDCHI block copolymers were dissolved in toluene and precipitated in methanol, PDBI bock copolymers were dissolved in aceto ne and precipitated in methanol. The copolymers were filtered and dried in vacuum at room temperature. vmResults and Discussion In this work, 3 ABA type poly (dimethyl siloxane-b-dimethyl itaconate), 4 poly (dimethyl siloxane-b-dicyclohexyl itaconate) andl poly (dimethyl siloxane-b-di- butyl itaconate) block copolymers were prepared by using the hydroyl terminated H-Si 6440 and H-Si 231 1 prepolymers. The copolymerization reactions were earned out by step-wise procedure. At the first step-NCO terminated polymeric urethanes were prepared and then at the second step the macroinitiators were synthesized. MI 1 macroinitiator were synthesi zed by using H-Si 6440 and MI2 macroinitiator by using H-Si 231 1. The preparation conditions of the macronitiators and the results of the analytical charaterization of these intermediates were shown in table 1. The polymerization was carried out at 80°C, 100-200h. in toluene solution at the vacuum. The preparation conditions of the 8 block copolymers by using two kinds of macroinitiators were given in table 2. The block weight percents of the samples were determined by using UV methods. UV analysis were based on the determination of the absorbances of pure ho- mopolymers, of macroinitiators, and of copolymers at the specific wavelength in chlo roform. Intermediates and the products were characterized by IR spectroscopy. IR spectra of the first stage capping reaction with diisocynate, the -OH absorption peaks (at 3520 cm-1 and 3590cm-1) disappeared and the peak at 2280 cm-1 appeared due to the steching vibration of -NCO. In the second reaction step, the disappearance of the - NCO peak indicates the formation of the macroinitiators. In the infrared spectra of the whole samples, peaks around 3440 cm-1 were observed in all runs. This absorption is due to the -NH streching in the -NH-CO- group of the macroinitiator. This absorpti on peak in the spectrum of copolymer indicates, the corporation of the macroinitiator into the copolymer, which provides evidence for block copolymer formation. Molecu lar weights of the copolymers were determined by viscometric and gel permeation chromotographic measurements. Intrinsic viscosities were measured at 25°C in touene solution. The follo wing relationship for homopolymers were used approximately for copolymeric samp les: [Ti]=1.3xl(H M°-623 (dl/g) for PDCHI [ri]=6.4xl0-4 M0-68 (dl/g) for PDBI The intrinsic viscosities of DMI contanining block copolymers were mea sured in acetone at 25°C and also in benzene at 30°C. The results are given in table II. The solubility parameters of the block copolymers were determined by measuring of intrinsic viscosities of their solutions in various solvents. The solubility parameter of copolymer is equal to the solvent solubility parameter at [tl]=[T|]max. The existence of two extremum point [t\] 8 dependence should be expected because chemi-, cally different blocks would influence the behavior of block copolymers in solutions. This is also a kind of a proof of the occurance of the block copolymer. IXm 5! 3^^Pr;«n xı Etl10lriö-' 7. -f,o)K-,mmr-~,.- -r-> O -4-* 7 _3 S | -ı °-,-:<-! ^ S X -5Olir-'ır>«ON., BM-H-'-.-'-Ss S -§c 3O2İ c“o.-C/î 7 _Uç 2 ”3rıoqNO pNO £.>+3 x Sllıoö<No\IAİr^ CNX MJ?“ar> M « M ^â ö s-S-s g£U rr--- 3o..'.>ocı/^ 3S^ Ç**B«u^O^^^o^cx3Oo!C;S03 O_~^>r>cnrı>^iNooor-r-(ii”3 C)~-JOppppopvc;Su ^^^1.«öööööödcuh ^J^S 2 osI <f Jİ, cDS «t ffl£P ^ ^u _>.5 ~§°İ“S 33553522535!^ ^ '§ §3 İQİBBHH§3e '.S s ^^s S-22^ -Ü,2~5 ö r:.2§. İ^”2^ S^MOrr,05U j ı ^= s s :-3 0 ıs ıı-ı.siil «l§s g £ _^£ § ^“.2 ~: *-?r!°.^^P°!^CG§ S.'S -'^tONp-ONC!Oİ-ı~\S Sco\oor-oo'*ooot--r-ı-'O ”T5C ı-»O Js g^.2QQ.tS.-c-.---.rırın^<+; | z SSSSSSSİgJ lss 5-sıtfı «= oouo V3M U'>'> l.y.a jl.-J5V! - ^-ınP~.-^irsNOr-ooSS Q.ÜJ3 r°GS CJı-(P-l ** X
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