Synthesis of new multifunctional olefin monomers and polymers by reactions of a- hydroxymethyl methyl vinyl ketone

Abstract

ÖZET Bu çalışmada a-HMMVK ve poli-a-HMMVK dan yeni monomer ve polimerlerin sentezlenmesi amaçlanmıştır. CH2OH ^CHaOH CH2 = c' +0^-0^ c=o c=o CH3 CH3 a-HMMVK Poll-a-HMMVK a-HMMVK metil vinil ketonun DABCO katalizörlüğünde formaldehit ile reaksiyonundan sentezlenmiştir. Ayrıca aseton ve formaldehitten sentezlenen 1,1,1,-trimetilolaseton un yüksek sıcaklıkta vakum altında pirolizi ile de a-HMMVK elde edilmiştir. a-HMMVK serbest radikal başlatıcısı AIBN ile ısıtılarak polimerleştirümiş poli-a-HMMVK elde edilmiştir. a-HMMVK DABCO ile de oda sıcaklığında ısıülmaksızm polimerleştirilmiştir. DSC analizi ile poli- a-HMMVK nun camsı geçiş sıcaklığı 2.7 °C olarak belirlenmiştir. a-HMMVK nun stiren, metil akrilat, metakrilonitril, n- butilmetakrilat ve vinil asetat ile yeni kopolimerleri elde edilmiştir.XIII a-HMMVK nun biseter türevinin çok iyi bir çarpraz bağlayıcı olduğu belirlenmiştir. Süren, metil metakrilat, akrilo nitril, n-butil metakrilat, metakrilo nitril, metil akrilat, vinyl asetat ve a-HMMVK nun biseter ile yeni çarpraz bağlı kopolimerleri elde edilmiştir. Poli-a-HMMVK nun fenilizosiyanat, ve toluen 2,4 dlisosiyanat ile DABCO katalizörümde ve katalizörsüz reaksiyonlarından fenilüretan, toluen-2,4-bisüretan ve toluen 2-izosiyanat-4 mono uretan, poli-a- HMMVK nun sodiumhipoklorit ile reaksiyonundan poli-a-hidroksi metil akrilik asit yeni polimerler olarak sentezlenmiştir. Diğer yeni bir polimer poli-a-HMMVK nun hidrazin ile reaksiyonundan elde edilmiştir. Ayrıca poli-a-HMMVK nun aldol kondensasyonu ile yeni bir merdiven tipi polimer sentezlenmeye çalışılmıştır. Sentezlenen monomer ve polimerlerin spektroskopik karakterizasyonu FT1R ve 1H-NMR spekralan ile yapılmıştır.a-HMMVK nun asetat esteri, biseter, bromür, klorür, trlmetll silll eter türevleri yeni multJfonksiyonlu olefin monomerler olarak, a-HMMVK nun asetil klorür, para-toluen sulfonik asit. fosfor tribromür, tiyonil klorür, trimetil silil klorür ile reaksiyonlarından sentezlenmiş ve bu türevlerin serbest radikal polimerizasyonu ile polimerleştirilmesinden yeni polimerler edilmiştir. O O II II CHo C CHo C CH2 = C O CH3 CH2 = C O N,c=o c=o i.0 CH3 CH3 asetat esteri türevi fenil üretan türevi H3Cx ^CHa /CH2C1 _ /CH2N /SiN CHo = C CH2 - C O CH ı2 - ^v * / ( / CHc /=ö yC=° CH3 klorür türevi trimetilsilil eter türevia-HMMVK nun asetat esteri, biseter, bromür, klorür, trlmetll silll eter türevleri yeni multJfonksiyonlu olefin monomerler olarak, a-HMMVK nun asetil klorür, para-toluen sulfonik asit. fosfor tribromür, tiyonil klorür, trimetil silil klorür ile reaksiyonlarından sentezlenmiş ve bu türevlerin serbest radikal polimerizasyonu ile polimerleştirilmesinden yeni polimerler edilmiştir. O O II II CHo C CHo C CH2 = C O CH3 CH2 = C O N,c=o c=o i.0 CH3 CH3 asetat esteri türevi fenil üretan türevi H3Cx ^CHa /CH2C1 _ /CH2N /SiN CHo = C CH2 - C O CH ı2 - ^v * / ( / CHc /=ö yC=° CH3 klorür türevi trimetilsilil eter türevi

The aim in this research is to synthesize new multifunctional monomers and polymers with novel physical and chemical properties by reactions of cc-HMMVK and poly-a-HMMVK. CH2OH ^CHzOH CH2 = C^ +CH2-C^ c=o ^0=0 CH3 CH3 a-HMMVK Poly-a-HMMVK a-HMMVK was synthesized through a new route by reaction of methyl vinyl ketone with formaldehyde by using DABCO as catalyst. It was also synthesized from acetone and formaldehyde via 1,1,1-trimethylol acetone following the procedure given in the literature with some modifications. a-HMMVK polymerized to give poly-a-HMMVK with a free radical initiator 2,2!-azobisisoburyronitrile by heating. It also polymerized with DABCO at room temperature. Tg of poly-a-HMMVK was determined as 2.7 °C by DSC analysis.Copolymerization of a-HMMVK with styrene, methylacrylate, methaciylonitrile, n-butylmethacrylate, and vinylacetate gave new copolymers. Acetate ester, bisether, bromide, chloride, trimethylsilyether derivatives of a-HMMVK were synthesized as new multifunctional monomers, except chloride, by reactions of a-HMMVK with acetyl chloride, p- toluene sulphonic acid, phosphorous tribromlde, thionyl chloride, and trimethylsilyl chloride respectively. They were polymerized to give their respective polymers as new multifunctional polymers by free radical addition polymerization. O II CHo C / z/ / / CH2 = C O CH3 >=o CH3 CH2 CH2 = C O 2 / c=o CH3 X,0 N I H the acetate ester derivative the phenyl urethane derivative CHoCl CH, = C / ( c=o CH, H3Cn ^CHa CHo Si CH2 = C^ O CH3 /C=o CH3 the chloride derivative the trimethylsilyl ether derivativeVIII the bisether derivative the bromide derivative a-HMMVK 2,4-dinitrophenyl hydrazone, a-ethoxymethyl methyl vinyl ketone 2,4-dinitrophenyl hydrazone, and a-HMMVK phenyl urethane were synthesized as new derivatives of a-HMMVK. They did not polymerize. CH3 H /CH2 O.CH2 N02 CHj, N02 CH2 = C^ H JL, CH2 = Cv H ' /C=N-N-iJ-N02 /C=N-N-^y-N02 CH3 CH3 the hydrazone derivative the ethyl ether, hydrazone derivative Surprisingly, 1,1-dichloromethyl acetone was obtained from a- HMMVK, and a-chloromethyl methyl vinyl ketone was synthesized by reaction of 1,1-dichloromethyl acetone with DMSO. Although a- chloromethyl methyl vinyl ketone and 1,1-dichloromethyl acetone are known compounds, they were first synthesized from a-HMMVK in this research.IX It was found that bisether of a-HMMVK was an excellent crosslinklng agent for various monomers. Coporymerization of biseter with styrene, methyl methacrylate, acrylonitrile, n-butyl methacrylate, methaciylo nitrile, methyl aciylate, vinylacetate and a-HMMVK gave new crosslinked polymers. Poly-a-HMMVK phenyl urethane, toluene-2,4-bisurethane, and toluene-2-isocyanate-4-monourethane were synthesized as new polymers by reactions of poly- a-HMMVK with phenyl isocyanate and tolylene diisocyanate with and without catalyst. Poly-a-HMMVK was reacted with hydrazine to give a new polymer. Poly-a-HMMVK was oxidized to poty-a- hydroxymethyl acrylic acid which is a new polymer by reaction of poly-a- HMMVK with sodium hypochlorite through haloform reaction. A new ladder type polymer was tried to be obtained under the influence of base by aldol condensation of methyl carbonyl groups of poly-a-HMMVK. The spectroscopic characterization of the monomers and polymers synthesized was carried out by using FTIR and 1H-NMR.