Modifiye keton/aldehit reçineleri
Modified keton/aldehyde resins
Yazar: NİLGÜN KIZILCAN
Danışman: PROF.DR. AHMET AKAR
İstanbul Teknik Üniversitesi / Fen Bilimleri Enstitüsü
Derece: Doktora, 1995
Konu: Kimya = Chemistry
Dizin: Aldehitler = Aldehydes ; Bazik ortam = Basic condition ; Karbonil bileşikler = Carbonyl compounds ; Keton = Ketone ; Modifikasyon = Modification ; Reçine = Resin

Özet:
ÖZET Bu çalışmada, bazik ortamda elde edilen siklohekzanon- formaldehit veya asetofenon- formaldehit reçineleri, üretimleri esnasında içerisine formaldehit ile veya ketonlarla reaksiyon verebilen çeşitli fonksiyonel gruplara sahip bileşikler katılarak modifiye edilmişlerdir. Ayrıca siklohekzanon- formaldehit, asetofenon- formaldehit ve onların bisfenollerle in situ modifiye reçineleri içerdikleri karboksil ve hidroksil grupları üzerinden modifiye edilmişlerdir. Asetofenon- formaldehit reçinesi bazik ortamda üretimi esnasında bisfenol-CB, bisfenol-CD, bisfenol-ACP ile in situ modifikasyonu yapılmıştır. Siklohekzanon formaldehit reçinesi ise fenol, bisfenol-C6, bisfenol-CD, bisfenol-ACP, salisilik asit, sitrik asit, asetaldehit, benzaldehit ve glioksal ile modifiye edilmiştir. Asetofenon- formaldehit reçinesi üretildikten sonra hidroksil grupları üzerinden asetik anhidrit, benzoilklorür, f talik anhidrit, maleik anhidrit, dodesilsüksinik anhidrit, oksi dif talik anhidrit, bi fenil dianhidrit ile modifiye edilmiştir. Siklohekzanon- formaldehit reçinesi de hidroksil grupları üzerinden f talik anhidrit, akrilonitril, dibutil ftalat, tetrahidrof talik anhidrit ve toluen di izosiyanat ile modifiye edilmiştir. Bisfenollerle in situ modifiye asetofenon- formaldehit ve siklohekzanon- formaldehit reçineler ininde hidroksil grupları üzerinden reaksiyonları gerçekleştirilmiştir. Siklohekzanon-bisfenol-C6- formaldehit, siklohekzanon- bisf enol-ACP -formaldehit, asetof enon- bis fenol -C6- formaldehit, asetof enon-bis fenol -CD- formaldehit reçinelerinin asetik anhidritle asetilleme, siklohekzanon- bi s fenol -A- formaldehit, siklohekzanon-bisfenol-C6- f ormaldehit, asetof enon- bis fenol -C6- formaldehit reçinelerinin benzoil klorür ile benzoilleme reaksiyonları yapılmıştır. Asetofenon- formaldehit, siklohekzanon-bisfenol-A- f ormaldehit, asetof enon-bisf enol-C6- formaldehit reçinelerimi; içerdikleri karboksil grupları üzerinden oksimi, semikarbazonu, asetofenon- formaldehit ve siklohekzanon-bisfenol-A-formaldehit reçinelerinin ise fenil hidrazonu elde edilmiştir. Elde edilen siklohekzanon- formaldehit, asetofenonformaldehit ve bunların in situ modifiye ve diğer üzerinden modifikasyon ürünlerinin çözünürlükleri, erime noktaları, *H NMR spektrumlar ı, FTIR spektrumları ile karakterizasyonu yapılmıştır. Vli

Abstract:
MODIFIED KETON/ALDEHYDE RESINS SUMMARY Ketone resins are prepared by reacting ketones containing a-hydrogen with reactive aldehydes such as formaldehyde. The most used ketonic resins are thermo plastic cyclohexanone- formaldehyde and acetophenone- formal dehyde resins. They are low molecular weight compounds, and are used in the coating industry as additives to modify the properties of high molecular weight film formers, e.g., acetophenone- formaldehyde resin improves brightness and light fastness of the paper lacquers. In this study, cyclohexanone- formaldehyde and aceto phenone- formaldehyde resins are modified during their preparation with a number of substances which react with formaldehyde or ketone under basic condition. Preparation of in situ modified cyclohexanone- formaldehyde resin with compounds such as phenol, 1, l-di(4-hydroxyl phenyl )cyclo- hexan, 1, 1 ' -di(4-hydroxyl phenyl jdodecane, 1-phenyl-l, 1 * - di(4-hydroxyphenyl )etane, salicylic acid, citric acid, glyoxal, benzaldehyde, acetaldehyde was studied. Aceto phenone- formaldehyde resin was in situ modified with compounds such as 1. 1 ' -di(4-hydroxyl phenyl) dodecane, 1- phenyl-1. 1 ' -di( 4-hydroxypheny )etan, 2, 4-dichloroaceto- phenone and 4-bromo acetophenone. The overall structure of cyclohexanone- formaldehyde (CF-resin) and acetophenone- formaldehyde resin (AF-resin) can be represented as follows : HOCHj CH.OH CF -OH HOCHj C-O -CH- CH2-)-OH AF In situ-modified CF-resin and AF-resin contain modifier compounds irregularly attached to the base resin, probably via methylene groups. As an example, the struc ture of in situ bisphenol-ACP and phenol modified CF-resin can be represented as CBacpF and CFF respectively. İn situ modified ketonic resin was examined with TLC, and the modified resins were found to have a condensation- type structure. There was no segregation. Furthermore, acetophenone- formaldehyde, cyclohexanone- formaldehyde and VillHO-GH HOCH CBjaF CFF CF AF Resins and in sitii modified resin OH.modified A-O-. Res in -O-A C=0.modified Resin -C=G COOBu A= - C- CH3 O II - c HOOC C-oH.En23 COOH ' - C- CH-CH2-COOH CH3 NH- C- Ç COOH O o II G= N-OH, N-NH- C-NH2 N~NH-<Ö) IXcarbonyl functional groups by reacting with a number of different reagents. Ketonic resins were modified via their carbonyl groups by reaction with semicarbazid, hydroxyl amine and phenyl hydrazine. The modification of ketonic resins via their hydroxyl groups were achieved by reaction with anhydride, toluene- 2,4- isocyanate, acrylonitrile and dibutyl phthalate. Anhydrides were acetic anhydride, phatalic anhydride, maleic anhydride, dodecenylsuccinic annydride, 3, 4, 3 ',4' biphenyl tetra carboxylic dianhydride(BPDA), 4,4'-oxydi- phtalic anhydride ( ODPA ). AF-resin modified with ODPA and BPDA can be represented as follows. 10* - 0- -CH - CH - -CH - O-C COOH HCO COOH COOH AF-ODPA r i ' C- O- CH4-CH- CH+O- C, OI V n IQ COOH J\ H O COOH COOH AF-BPDA Melting point and solubility of the ketonic resins were also determined as shown in Table 1. FTIR and NMR spectrum of the resins were used to prove the extend of modification.CD H X) 3 H O CO c a) H X) H O CO ?P x: O) ?H H CO ?P O x: CO x: CD H X) 3 H 0 CO ?P O x: CO x: CD H XJ 3 H O CQ ?P x: CQ CD H X) 3 H O CQ CO XX2.