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Doctoral Thesis
DOI
https://doi.org/10.11606/T.46.2016.tde-27092016-103414
Document
Author
Full name
Susana Shimizu
E-mail
Institute/School/College
Knowledge Area
Date of Defense
Published
São Paulo, 2004
Supervisor
Committee
EL Seoud, Omar A. (President)
Baptista, Mauricio da Silva
Gehlen, Marcelo Henrique
Itri, Rosangela
Petri, Denise Freitas Siqueira
Title in Portuguese
Novos tensoativos catiônicos: efeitos da estrutura do grupo hidrofílico sobre adsorção e agregação em soluções aquosas
Keywords in Portuguese
Físico-química orgânica
Química coloidal
Soluções aquosas (Propriedades físico-químicas)
Abstract in Portuguese
Foram sintetizadas duas séries de tensoativos catiônicos de estruturas gerais RCONH(CH2)2-N+(CH3)3 Cl- e RCONH(CH2)2-N+(CH3)2-CH2-C6H5 Cl-, sendo RCO uma cadeia acílica contendo 10, 12, 14 e 16 átomos de carbono. Estes tensoativos foram sintetizados pela reação do ácido carboxílico puro com N,N-dimetiletilenodiamina resultando na amidoamina correspondente. A quaternização desta última foi feita pela reação com cloreto de benzila ou com iodeto de metila. Os iodetos foram convertidos nos correspondentes cloretos por troca-iônica. A localização média da interface micelar e a conformação do grupo hidrofílico na micela foram investigadas por IV e RMN. A adsorção na interface solução-ar e a micelização foram estudadas por diversas técnicas: calorimetria, condutância, FEM (força eletromotriz), IV de FT, RMN e tensão superficial. Os resultados foram comparados com os de tensoativos catiônicos comuns, como R'N+(CH3)3R" Cl-, sendo R' = grupo alquílico contendo de 10 a 16 carbonos e R" = um grupo metila ou benzila. A adsorção e a micelização dos tensoativos contendo o "espaçador" (CONH-CH2-CH2) são mais favoráveis. Os valores de ΔGºads e ΔGºmic mais negativos para estes tensoativos, refletem principalmente a transferência mais favorável do grupo polar da solução aquosa para a interface solução/ar e/ou para a micela. Isto ocorre devido à formação de ligações de H, diretas e/ou via água, entre os grupos amida dos monômeros de tensoativo na interface e micela. As diferenças nos valores de ΔGºcabeça+CH3 dos tensoativos com e sem o grupo amida na adsorção (ΔΔGº ads cabeça+CH3 = -17.2 kJ mol-1) e micelização (ΔΔGº ads cabeça+CH3 = -5 a -7 kJ mol-1) estão de acordo com a energia de ligações de H fracas. Os resultados de IV de FT e RMN de 1H comprovaram a formação destas ligações de H e indicaram que a carbonila está presente na interface e o grupo benzila está voltado para o interior da micela.
Title in English
New cationic surfactants: effects of structure of the hydrophilic group on adsorption and aggregation in aqueous solutions
Keywords in English
Aqueous solutions (Physicochemical properties)
Colloidal chemistry
Organic physical chemistry
Abstract in English
Two series of cationic surfactants have been synthesized: benzyl-(2acylaminoetil) dimethylammonium chlorides, RCONH(CH2)2-N+(CH3)3 Cl-, and (2-acylaminoethyl)dimethylammonium chlorides, RCONH(CH2)2-N+(CH3)2-CH2-C6H5 Cl-, where RCO refers to an acyl group with 10, 12, 14 and 16 carbon atoms. These surfactants were obtained by reacting chromatographically pure carboxylic acids with N,N-dimethylethylenediamine to give an intermediate amidoamine. The latter was quaternized with benzyl chloride or methyl iodide. Surfactants with iodide counter-ion were transformed into the corresponding chlorides by ion exchange on a macro-porous resin. The average position of micellar interface and conformation of the headgroup were studied by FTIR and NMR. A multi-technique approach has been employed in order to study the effects of the presence of the "spacer" group (-CONH- CH2-CH2) on the adsorption and aggregation of these surfactants. The techniques employed were: calorimetry, conductance and EMF measurements, FTIR, NMR, surface tension, and Iight scattering. Surfactants with the spacer group (CONH-CH2-CH2) have more favorable Gibbs free energies of adsorption and/or micellization due to the more favorable transfer of the head-group from bulk phase to the interface and/or the micelle. This is attributed to the formation of direct, and/or water-mediated H-bonding between the surfactant amide groups. Differences in values of ΔGºHead-group+CH3 of surfactants with and without spacer group (ΔΔGº ads Head-group+CH3 = -17.2 kJ mol-1 and ΔΔGº ads Head-group+CH3 = -5 a -7 kJ mol-1 for adsorption and/or micellization, respectively) are in agreement with weak hydrogen bonding. Additional evidence for H-bond formation and for the (average) conformation of the benzyl head-group in the micelle was provided by FTIR and NMR data. The former showed that the amide group is highly hydrated, whereas the latter showed shielding/deshielding of the methylene groups of the surfactant hydrophobic tail, in agreement with a conformation in which the benzyl group is "bent" toward the micellar interior.
 
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Publishing Date
2016-09-27
 
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