Mannich kondenzasyonla katyonik polimer elde edilmesi
Cationic polymers by mannich condensation
- Tez No: 39840
- Danışmanlar: DOÇ.DR. OYA ATICI (GALİOĞLU)
- Tez Türü: Yüksek Lisans
- Konular: Kimya, Chemistry
- Anahtar Kelimeler: Belirtilmemiş.
- Yıl: 1994
- Dil: Türkçe
- Üniversite: İstanbul Teknik Üniversitesi
- Enstitü: Fen Bilimleri Enstitüsü
- Ana Bilim Dalı: Belirtilmemiş.
- Bilim Dalı: Belirtilmemiş.
- Sayfa Sayısı: 47
Özet
ÖZET Mannich Reaksiyon amonyak, primer amin veya sekonder aminler ile formaldehit ve en az bir aktif hidrojen atomu içeren bileşiklerin kondenzasyonundan meydana gelir. Reaksiyonun temel özelliği aktif hidrojen atomunun bir amino metil veya substitüe amino metil grup ile yer değiştirmesidir. Bu çalışmada aktif hidrojen içeren bileşik olarak poliakrilonitril (PAN), poliakrilonitrilcovinilasetat (PANcoVAc), metil selüloz (MC400) ve karboksi metil selüloz (CMC), amin bileşiği olarak dimetilamin (DMA), aktif hidrojen içermeyen bileşik olarak ise formaldehit kullanılmıştır. Reaksiyonlar su, ksilen veya dimetilformamid (DMF)ı çözücülerinde, 33, 55, veya 75 °C sıcaklıkta, pH=10.5 değerinde yapılmıştır. -C=0 içeren PANcoVAc ve CMC, -C=0 içermeyen PAN ve MC400'e göre daha yüksek verimle modifıye olmuştur. Yüksek sıcaklık, selülozlu deneylerde düşük verime neden olmuştur. Poliakrilonitrilli deneylerde spektral veriler DMFin formaldehit gibi davrandığını göstermiştir. DMA'lı reaksiyonlarda yumuşama noktalan yüksek, metal tutma özellikleri düşük, DMA yanında DMF de içeren reaksiyonlarda ise yumuşama noktalan düşük, metal tutma özellikleri yüksek çıkmıştır. Tüm ürünlerin Mannich kapasitelerinin yüksek olduğu alkali koşullarda 6 gün içinde kapasitenin düştüğü görülmüştür. IR ve NMR verilerinden tüm başlangıç polimerlerin Mannich modifıye olduğu polimerlerde -CH^NRj, -CH,OH, -CHiNR-/), ve. CH(OH)(NR2) gruplannın meydana geldiği söylenebilmiştir.
Özet (Çeviri)
The Mannich Reaction is carried out by using formaldehyde, ammonia, primary or secondary amine and a compound containing an active hydrogen atom. If the active hydrogen compound has two or three active hydrogen, the Mannich base may be condence with one or two additional molecules aldehyde, ammonia or amine. HCHO :NR, i 2 H Formaldehyde Seconder Amine 0“ CH, NR, i H OH ?^-> CH, - NR2 H :522_JcH2-NR2 < > CH, =NR, + 0H”O II -C-CH -C-C- -c =c- i CH2=NR- > -C-C-CH, -NR, I Polymers such as polyacrylamide, polymethacryiumide ex. may also be reacted with formaldehyde and amines. The modified polymers have completely different properties, such as solubility, swelling and may find further applications. In this study, polyacrylonitrile (PAN), polyacrylonitril-co-vinylacetate (PANcoVAc), methyl cellulose (MC400) and carboxymethylcellulose (CMC) were modified with Mannich reaction. All of them contain active hydrogen atom. Among these are the following type with the active hydrogen underlined. -CH-CN -OCOCH3 -OH -CH^COONa Polyacrylonitrile and Polyacrylonitrile-co- vinylacetate contain this group. Polyacrylonitrile- co-vinylacetate contain this group. Methyl cellulose and Carboxymethyl cellulose contain this group. Carboxymethyl cellulose contains this group. VIFirstly, we used Mannich reaction with polyacrylamide which has -CH- CONHj group to understand and see this reaction. The polyacrylamide (PAAm) solution obtained was heated at 90 °C for 30 min. with excess formaldehyde, the medium being kept basic with N^PC^ (or KOH). The resulting solution of amino methylated PAAm was heated with dimethylamine at 90 °C for 1 hour. The polymer solution thus prepared was poured into an excess of acetone to precipitate the polymer. The ER spectrum of this polymer was essentially identical with that of PAAm except for an absorbtion peak at about 1560 cm-1 which is assignable to the Amide II band HCHO -f CH2-CH-k (Base) >-f-CH2-CH-}-n m(CH^ >-f CH2-CH^- c=o c=o c=o NH2 NHCH,OH NHCH,N(CH3), PAAm Mannich Modified PAAm Products were converted to the hydrochloride salt with HC1. The initial capacity determination (AgN03 titration) gave a value of 3.7 mmol/g, calculated on free base. Stability measurement were also carried out under alkaline conditions (2 % NaOH / 10 % NaCl solutions). After 6 days the capacity had fallen 3.02 mmol/g. The reaction conditions and results are shown in the Table I. The Mannich reactions of acrylic and cellulosic starting materials were carried out in xylene, water and dimethylformamide (DMF) depend on the properties of the starting materials and final products. Water and (xylene-water mixture) we useful solvents for MC400 and CMC that are water soluble or have some degree of solubility in water. DMF was spesially used for increasing the solubility of PAN and PANcoVAc. In order to adjust the pH from 8 to 10.5, NajPC^ was used. The reactions containing DMF solvents, KOH was used instead of Na3P04. In these reactions, dimethylamine (DMA) was used as amine compound. Formaldehyde was the carbonyl compound which hasn't got any active hydrogen atoms. The ratio between DMA and formaldehyde was 1.2:1, 1:2, 1:3 and 1:4. The Mannich modifications of polyacrylonitrile-co-vinyl acetate and carboxymethyl cellulose gave better yields at similar conditions than that of polyacrylonitrile and methyl cellulose. The reaction temperature was usually kept at 55 °C. If the reaction temperature was increased, the yield of Mannich modified acrylonitrile polymers seemed not to change significantly. But the yield of cellulose reactions decreased with increasing reaction temperature so these reactions were done at 33 °C. vuTable I. The reaction condition and results with 7.5 g starting material. (1) % 43.75 DMA solution. (2) % 37 formaldehyde solution. (3) s : soluble i : insoluble. (4) PAAm s.p. : 238 °C, PANco VAc s.p. : 232 UC, PAN s.p. : 265 °C, MC400 s.p. : 240 °C“ CMC s.p. : 236 °C. (5) % 15 KOH solution. (6) The starting materials are 1.4 g. vuıThe yield of the Mannich modified acrylonitrile polymers were approximately equal to the original polymer both rising temperature and using water and xylene solvent. The higher yield (weight increase: from 0.13 g/g to 1.5 g/g) was obtained when DMF was used as a solvent under experimental conditions. According these (and the other results), we could say that DMF was reacted as similar as formaldehyde. Mannich modified final products had similar solubility properties to starting materials. The solubility of Mannich modified acrylonitrile polymers were soluble in DMF and DMSO and cellulose were soluble or swelling in the water. Softening point of both acrylonitrile and cellulose final product were higher than starting materials when dimethyl-amine were used, but they were reduced when DMF were used (Table I). All Mannich modified polymers could form complexes with copper (Table II). If DMA, DMF and formaldehyde were used in reaction, the formation of metal complex gave higher yield than the reaction using DMA and formaldehyde. Final products of cellulose were unsuitable for copper complexes. Table II. The capacity (t=0) and the stability (t=l day and/or 6 days) measurements of Mannich modified products. (1) Cu Chelating: PAAm: %30, PANcoVAc: % 80, PAN: % 49, MC400: %95, CMC: % 82. (2) % 15 KOH solution. (3) It cannot be determined by this method. IXThe capacities of the final products were bigger and the stabilities after the six days were smaller (Table II). The intrinsict viscosity of the using DMA was higher than the reaction using KOH and formaldehyde (respectively 0.9 and 0.7 dl/g at 25 °C in DMF). In the IR spectra of Mannich modified polymers, peaks at 1660, 1590, 1 100 and 660 cm-' are observed. 1H NMR spectra of the modified acrylonitrile final polymers in DMSOd6 show absorbtion peaks at 5 (ppm) 2.07-CH, - ?OCOCH3 and -N-CH3,2.73 OCOCH2-C-(NR2),,2.88-OCO-C-CH,NR,and-OCOCHCNR,,3.l2 NC-C-CKjNR,,3.15 -ÇH-CN, ”3.16 -CHX> and“-CH-(NR,),, 5.1 ' -CHOCOR, 7'95 -CONH- and/or -CONH,”. *H NMR spectra“ öf modified MC400 give peaks at 8 (ppm) 1.6 -N-CH3, 2.4 -2.7 -CO-C-CH:NR,, 0 2.99-3.1 OCH3, 3.3-3.5 -CO-C-CH,0-, 4-4.9 -CH-O-, -CH,0- and R-OH, 4.95 ROCHjMl,, 5 RO-ÇH-OR, 8.9 0=C-H. From all of these”data we can say that Mannich reaction forms between DMA, formaldehyde and polyacrylonitrile, polyacrylonitrile-co-vinylacetate, methyl cellulose and carboxy methyl cellulose. DMF also reacts with formaldehyde both Mannich and aldol condensation. From DMA -CH2N(CH3), and/or -CH.OH, from DMF -CH-N(CH3), and/or -CH-N(CH3), N(CH3)2“ ÖH particles can be formed after reactions. 0 O NH(CH3)2 + HCH [ and/or HCN(CH3), ] - _ DMA Formaldehyde DMF H2C=N(CH3)2([ and/or (CH3),NCH=N(CH3),] ?. ”- --SL P-CH Base, P-C: 1 1 P -C-CI^ -N(CH3)2 [ and/or P -C-CH-N(CH3): ] ' N(CH3)2
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