Poli (stiren) esaslı reçineler üzerinde sekonder amin sentezi ve aldehit ayrılması
Başlık çevirisi mevcut değil.
- Tez No: 55541
- Danışmanlar: PROF.DR. NİYAZİ BIÇAK
- Tez Türü: Doktora
- Konular: Kimya, Chemistry
- Anahtar Kelimeler: Belirtilmemiş.
- Yıl: 1996
- Dil: Türkçe
- Üniversite: İstanbul Teknik Üniversitesi
- Enstitü: Fen Bilimleri Enstitüsü
- Ana Bilim Dalı: Belirtilmemiş.
- Bilim Dalı: Belirtilmemiş.
- Sayfa Sayısı: 48
Özet
ÖZET Bu tez çalışması polimerik reçinelerin organik sentezlerde ve ayırmada kullanımıyla ilgili iki ayn kısımdan oluşmaktadır. Birinci kısımda çapraz bağlı poli(stiren) sülfonik asit esterleri elde edilmiş bunlann alkilleme reaktifi olarak kullanılabileceği gösterilmiş ve bu yolla sekonder aminlerin hazırlanmasına uygulanabileceği kanıtlanmıştır. Bu kanıtlama N-propil benzil amin ve N-allil anilin sentezi ile gösterilmiştir. Tezin ikinci kısmında klorosülfonlanmış poli(stiren) reçineye oligoetileniminlerin kararlı sülfamid bağlanyla bağlandığı oligoetilenimin fonksiyonlu yeni reçineler elde edilmiştir. Bu yeni reçinelerin aldehitlerin bir karışımdan aynlmasında kullanılabilecekleri ortaya konmuştur. Reçineleri amin sayısına bağlı olarak aldehit bağlama özellikleri incelenmiş ve bağlanan aldehitlerin geri kazanılma şartlan araştırılmıştır. Sonuçlar bu yeni reçinelerin aromatik aldehitlerin hidrokarbon karışımlarından aynlmasında basan ile kullanılabileceklerini göstermiştir. Başlangıç maddeleri gözönüne alındığında bu yeni reçinelerin endüstriyel boyutlarda kullanılmalarına bir engel bulunmadığı ortaya konmuştur.
Özet (Çeviri)
SUMMARY SYNTHESIS OF SECONDARY AMINES AND SEPERATION OF ALDEHYDES ON POLY(STYRENE) RESIN SUPPORTS This thesis is consisting of two parts. The first part deals with the use of polystyrene sulfonic acid esters for the preparation of unsymetrical secondary amines. The second part is related to the use of oligoethyleneimine contain polymeric resins in aldehyde seperation. Poly(Styrene) Sulfonic Acid Esters as Alkylating Agents:Preparation of Unsymmetrical Secondary Amines One of the route to prepare aliphatic secondary amines is the reaction of alkyl halides with calcium cyanamide followed by hydrolysis of the nitrile group. However, this procedure gives only symetrical dialkyl amines. Also in some cases Michael addition of primary amines to activated double bonds can give secondary amines. Alkylation of primary amines with dialkyl carbonates or dialkyl sulphates are well established general methods to prepare secondary amines. For the synthesis of the unsymetrical secondary amines, Hofmann alkylation of primary amines with alkyl halides, seems to be the most prefered method. However, the mixtures of secondary and tertiary amines are obtained, and the isolation of the products are difficult. Seperation of these amines require additional techniques such as distillation or Hinsberg derivatization. Also reduction of N-alkyl amides by LiAIH4 in ether or THF give unsymetrical secondary amines. Although the method is quite applicable, the reaction takes place in very long time of periods, i.e. 2, 3 days. Additionaly some serious explosions have been reported to occur during reduction with LiAIH4. In the Hinsberg derivatization method, amine mixtures are interacted with benzene sulfonyl chloride or p-toluene sulfonyl chloride ( tosyl chloride, Ts-CI ) in aprotic solvents, to give corresponding sulfonamides. Unlike secondary amines, primary amines form water soluble tosylates. Sulfonamides bearing hydrogen atom on sulfamide nitrogen are soluble in concentrated aqua alkaline solutions. These salts can react with alkyl halides to form sulfonamide derivative of secondary amine. Hydrolysis of the alkylated sulfonamide has been reported to give corresponding secondary amine. However, sulfonamides are known to be quite stable towards acid and alkaline hydrolysis. Although highly concentrated H2S04 ( 60% ) has been suggested for their hydrolysis, this approach was unsuccesfull in our hands. In the present study we have focussed on the possibility of the use of polymeric sulfonate esters for the preparation of secondary amines, starting from chlorosulfonated polystyrene resin. Chlorosulfonic acids readily form sulfonate esters with alcohols. These esters are usefull alkylating agents for amines, phenols and some groups possesing replaceable hydrogen atoms. For instance, dimethylsulphate is well known methylating agent, although it needs very strict precautions in use. In the literature there are few reports on preparation of N-alkyl amines, through alkyl visulfonates or tosylates. However, all the sulfate or sulfonate esters are known as extremely dangerous compounds and great care must be exercised in their handling. As far as we know no reports have been observed in the literature on the use of polymeric sulfonate esters as alkylating agents. Chlorosulfonated polystyrene resin has been demonstrated to be useful as alcohol protecting agent, in which the alcohol component can readily release upon treating with water. This approach has been used to slow release of perfume alcohols.Moreover polymeric trimethylsilyl sulfonate derived from Nafion-H has been demonstrated to be highly reactive silylating agent. In this study we have prepared polystyrene sulfonic acid esters and investigated their ability in alkylation of primary amines to obtain unsymetrical secondary amines which are difficult to prepare by other methods. For this purpose chlorosulfonated polystyrene-co-DVB ( 10% ) was transformed into sulfonate ester by alcohols. The resulting polymeric sulfonate esters were interacted with selected primary amines to obtain unsymetrical secondary amines. In this communication chlorosulfonated polystyrene resin has been demonstrated to be used in preparation of unsymmetrical secondary amines by four step reaction sequence as outlined in scheme 1. These steps involve; chlorosulfonation of the polystyrene resin, sulfonate ester formation by an alcohol vuCIS03H 0=Ş=0 1.HT 2. soa2 R1-OH R I NH (62-76%)“ NaOH o=s=o I OR2-NH^-R Schemie 1. Synthesis of secondary amines starting from polymeric sulphonate esters. vui( benzyl or allyl alcohol ), condensation with a primary amine ( propyl amine or aniline ) and liberation of the secondary amine. The degree of chlorosulfonation( DCS ) was determined by measurement of the chlorine content from alkaline hydrolysis of a sample of resin. DSC was found to be 63.65% mol in the sample obtained. In the second step the chlorosulfonation product was reacted with either excess of benzyl alcohol or allyl alcohol with pyridine as a base. It is important to note that, both chlorosulfonation and sulfonate ester forming steps are extremely exothermic reactions. When heating additional crosslinking resulted from further condensation of the chlorosulfonyl groups as in the case for chlorosulfonation of low molecular compounds. When chlorosulfonation is carried out at room temperature or at elevated temperatures the chlorine content is always lower than those of the products prepared at low temperature. For this reason step 1 and step 2 must be performed under effective cooling conditions. In step 2 exothermic conditions may cause formation of alkene or ether through dehydration and chlorosulfone groups turn to be sulfonic acid groups.lt has been found that ice-cooled solutions are satisfactory to avoid such side reactions and any discoloration does not occur. Probably the most important result of the study is that tertiary amines do not form as by product. This might be because of a kind of site isolation effect in polymers. Otherwise once a secondary amine formes, it may re-react with the other sulfonate ester groups to give tertiary amines. This might be because of the trapping of the secondary amine in salt form by sulfonate groups. This effect may a result from a large number of factors: steric effect of bulky group bounded to amino group, porosity of the support, solvent effect etc. A fully investigation of these effects are beyond the scope of this work. The secondary amines obtained by this method have been identified as benzyl propyl amine and N-allyl aniline on comparision with their original spectra. Although excess of amines were used to neutralize sulfonic acid groups, the secondary amine itself can bind ionicaly to sulfonic acid groups. For this reason alkaline treatment is essential to liberate the secondary amine formed in this step.This study reveals that the use of polymer supported chlorosulfonic acids can be applied as a general method for the preparation of unsymetrical secondary amines in reasonable yields, however, in order to obtain pure products, low molecular weight primary amines are the most suitable primary amine components due to easy of their removal from the mixtures. The regeneration of the resinous substract is straightforward and can easily be carried out by interaction of thionyl chloride as described previously. Consequently, polymeric sulfonate ester presented here can be used as alkylating agent and has advantage over conventional low molecular weight sulfate or sulfonate esters in preparation of unsymetrical secondary amines. On the other hand sulfonic esters of low molecular weight are difficult to handle due to skin irritation and carciogenic effects. Polymeric support makes it possible in handling. Recirculation of the polymeric support and purity of the resulting amine are additional advantages of the polymer bounded sulfonate esters. IXAldehyde Seperation by Polymer Supported Oligoethyleneimine Reversible aldehyde binding ability of N,N'-dialkylated or arilated 1,2-diamino ethanes have encourged us to investigate the of polymer supported oligoethylene imines in aldehyde seperation. Attachment of oligoethylene imines to the polymeric support was achived by treatment excess of oligoethylene imines, with chlorosulfonated styrene-divinylbenzene (%10) crosslinked resin, as outlined in Scheme 2. S z=0 Resin I z=1 Resin II z=2 Resin II CISQjH (2) HzN-C-CHz-CHz-NH-y-CHz-CH^NHz Ç jV-S-NH-C-CH^CHz-NH-^CHz-aVNl-b O In this reaction ethylenediamine, diethylenetriamine and triethylene tetramine are bonded to the polymer through sulfamide bonds. By this way one, two and three free amine groups are fixed onto polymer. Since the reaction of amines with chlorosulfone groups is fast and excess of amines is used, the sulfamidation reactions are assumed to proceed quantitatively. The resulting oligoethyleneimine modified spherical resin beads are interacted with alcohol solutions of benzaldehde, salicylaldeyhde and acetaldeyde seperately to test their aldehyde binding abilities. Aldehyde Binding Capasities of the Resin Samples To estimate the maximum capasity for aldehydes of the samples each (1g.) was contacted with 50 ml of 1.182 M aldehyde solutions, which were 7.5-8.7 times excess of the therotical capasities. Capasities were measured indirectly by monitoring of the residual aldehyde content of test solutions. Representative data ( Table 1 ) indicate that for benzaldeyde and acetaldehyde the maximum loading capasites of each resin are high and almost identical to the theoritical capasities. This reveals that sulfamidation is almost quantitative and all amine functions are being used in aldehyde sorption. It is important to note that, in Resin I two moles of amino group are being used for one mole of aldehyde sorbtion. In resin II and resin III, three and two moles of amino groups of each are bounded to one mole of aldehyde respectively. This result can be ascribed to the fact that sulfamide group does not take part in aldehyde binding. If this assumption is true in resin II two amine amine groups must be consumed for one mole of aldehyde. Whereas in Resin III one mole a half mole of amine function is being used for one mole of aldehyde. This implies that aldehyde binding occurs through five membered ring (diazole) formation and primary amine end groups can bind aldehyde through both ring formation or Schiff base formation. But ring formation will favour if the neighboared secondary amino group is available.Consequently in Resin I aldehyde is bonded through Schiff base formation and one mole of primary amine is consumed per aldehyde molecule. In Resin II one aldehyde molecule is bonded through five membered ring with two amino groups. Whereas in Resin III two secondary amines are used to form five membered ring with one aldehyde molecule and the remaining primary amino groups forms Schiff Base with the second aldehyde molecule. Totaly two moles of aldehyde are bounded in the Resin III for each function. This mechanism of aldehyde sorbtion is clearly established by the loading data represented in Tablel. Table 1. The Maximum Loading Capacities of Aldehydes of Resins Sorption capasities of the resins are apperently lower for salicylaldehyde probably because of its high steric effect arrising from phenolic OH group. On the other hand in case for acetaldehyde sorption the solution becomes colored during the experiment due to base cathalysed aldol condensation which is common for aldehydes carrying a-hydrogen. This is an important limitation for the resins in the sorption of many aliphatic aldehydes. Indeed the colored solution gives off characteristic odour of crotonaldehyde.which is the first condensation product of acetaldehyde. CH3-CHO + CH3-CHO OH CH3-CH=CH-CHO (3) Hence, by these resins aliphatic aldehydes having a-hydrogen can not be seperated without transformation. Aldehyde Sorbtion Kinetics of the Resins Aldehyde sorbtion kinetics of the resins were made by contacting diluted aldehyde solutions ( 6.04.10”2 M ). The amounts of sorbed aldehydes versus time plots in ( Fig. 1) represent that the rate of benzaldehyde sorption is very close for the resin II and resin III. Fast aldehyde binding ability of the resin III must be because of the spacer chain effect. Obviously the length of ethylene imine is longer than is the other two chain in resin III and this causes to fast aldehyde binding ability. Comparision of the kinetics of aldehyde binding to the resin III ( Fig.B2) indicate that the reaction rates is faster for acetaldehyde. This is in accordance with its molecular weight which provide fast diffusion capability, interestingly, all the aldehyde sorbtions studied obey second order reaction kinetics. This fact has been established clearly by plotting 1 / p vs time ( where p xiThis fact has been established clearly by plotting 1 / p vs time ( where p represents unreacted fraction of aldehyde). Rate constants for different aldehydes and resin are shown inTable 2. Table 2. Rate Constants For Different Aldehydes and Resin Sorption rate of acetaldehyde (107.6.10*2 mol“1.dk”1) is about five times faster than that of benzaldehyde. Aldehyde Desorption Kinetics of the Loaded Resins To investigate desorption kinetics, the loaded samples were subjected to hydrolysis in different acid concentrations. The amounts of stripped aldehydes were measured by monitoring aldehyde concentrations of acid solutions. All experiments show that aldehyde concentrations of the acidified solutions increase in time. Benzaldehyde desorption kinetics of the loaded resins (Fig.B3) represent that desorption rate of benzaldehyde is faster for the resin I. This can be ascribed to the rapid hydrolysis of the Schiff Bases. Hydrolysis of dizole rings must be somewhat difficult due to greater stability of five membered rings. Indeed aldehyde releasing facility of resins is in order resin I > resin II. Because in resin II aldehyde is bonded through five membered rings. Wheares in resin III aldehyde is bonded to the resin by the formation of both five membered ring and Schiff Base. Comparasion of the striping rates of the aldehydes from the resin III indicate that ( Fig.B4) acetaldehyde and benzaldehyde are released with almost equal rates. Whereas salicylaldehyde is stripped slowly. On the other hand aldehyde desorption is faster in higher acid concentrations as expected. Fig.B5 represent that benzaldehyde is desorbed rapidly from the resin III with 1M HCI solution. Desorption experiments indicate that percentage aldehyde desorptions do not go completion in methanol-water solutions, even in one hour. However, it has been observed that when the loaded samples are subjected to hydrolysis with 5 M aqua HCI solutions all the aldehyde contents of the resins are eluted in about 30 min. interfering Entities Although we have not been able to carry out quantitative competitive extraction experiments a qualitative test with acetone indicate that acetone also bounds to the resins. However, in the case splitting of acetone amine products on the polymer. Also alkyl halogenides are important interfering entities that a simple Hoffmann alkylation reaction they create tertiary and quaternary amino groups on polymer. Hence, aliphatic ketones and alkyl halogenides can be regards as interfering compounds in the aldehyde sorption. The method works well in presence of aliphatic and aromatic hydrocarbons, alcohols, phenols and water. xiiRegeneration of the Resins During aldehyde stripping with acid solution amino groups of the resin turn into salt form.These can easily freed by treatment with an aqua alkaline solutions. To avoid sodium salt formation through sulfamide groups diluted (0.1M) NaOH solutions are suitable for alkaline washing and followed by washing with boiling water. By this way the resins can be recycled without loosing aldehyde binding abilities. On conclusion, aldehydes can be seperated selectively from the mixtures by polymer supported oligoethyleneimines. Aldehyde sorption capasites and rates of the resins increase with increasing number of amino groups. However, aldehydes with a-hyrogen undergo aldol condensation during interaction with these resins. These resins are not suitable to use in sorbtion of alphatic aldehydes. This is important limitation that aliphatic aldehydes can not be seperated without formation of aldol condensation products. However, if the recovery of the aldehydes are not important, the resins can be used for the removal of trace amounts of aliphatic aldehydes. Since this resins prepared from commercially available materials with acceptiable costs and easy of their regeneration, these can be used for large scale applications. Xlll
Benzer Tezler
- Preparation of cross-linked poly (styrene) based resin amidated by staudinger reaction, modification with iminopropylene glycole and removal of the boron from aqueous solutions
Staudinger reaksiyonu ile aminlenmiş çapraz bağlı poli (stiren) esaslı reçinenin hazırlanması iminopropilen glikol ile modifikasyonu ve borun sulu çözeltilerden giderilmesinde kullanılması
ALEYNA BUĞÇE MASACI
Yüksek Lisans
İngilizce
2018
Polimer Bilim ve Teknolojisiİstanbul Teknik ÜniversitesiPolimer Bilim ve Teknolojisi Ana Bilim Dalı
PROF. DR. BAHİRE FİLİZ ŞENKAL
- Preparation of new polymeric sorbents for removal of organic wastes
Organik atıkların giderilmesi için yeni polimerik sorbentlerin hazırlanması
FATİH BİLDİK
Doktora
İngilizce
2016
Kimyaİstanbul Teknik ÜniversitesiKimya Ana Bilim Dalı
PROF. DR. BAHİRE FİLİZ ŞENKAL
- Synthesis of tris(hydroxymethyl)aminomethane modified polystyrene based polymeric sorbent and removal of boron from aqueous solutions
Tris(hidroksimetil)aminometan ile modifiye edilmiş polistiren esaslı polimerik sorbentin hazırlanması ve sulu ortamdaki borun giderilmesinde kullanılması
ARZU ERSOY
Yüksek Lisans
İngilizce
2017
Polimer Bilim ve Teknolojisiİstanbul Teknik ÜniversitesiPolimer Bilim ve Teknolojisi Ana Bilim Dalı
PROF. DR. BAHİRE FİLİZ ŞENKAL
- Synthesis of tris acetamide modified sulfonamide based resin for removing mercury salts from aqueous solutions
Tris asetamid modifiye çapraz bağlı sülfonamid esaslı reçinenin sentezi ve cıva tuzlarının sulu ortamlardan uzaklaştırılmasında kullanılması
İREM ÇOKGEZ
Yüksek Lisans
İngilizce
2015
Kimyaİstanbul Teknik ÜniversitesiKimya Ana Bilim Dalı
PROF. DR. BAHİRE FİLİZ ŞENKAL
