Alla Bedahnane, Abdelilah
Total activity: 151
Research group
POL - Polymers
Department
Department of Chemical Engineering
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abdel.allaupc.edu
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1 to 50 of 151 results
  • Complexes of polyglutamic acid and long-chain alkanoylcholines: Nanoparticle formation and drug release

     Tolentino Chivite, Ainhoa; Alla Bedahnane, Abdelilah; Martinez de Ilarduya Saez de Asteasu, Antxon; Muñoz Guerra, Sebastian
    International journal of biological macromolecules
    Date of publication: 2014-05-01
    Journal article

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    Ionic complexes of microbial poly(¿-glutamic acid) and alkanoylcholines are fully bio-based comb-like systems able to self-organize in an ordered amphiphilic structure made of hydrophobic and hydrophilic alternating layers. Incubation of complex films under physiological conditions for one month promoted dissociation of the complex and hydrolysis of the choline ester without almost degradation of polyglutamic acid. Complex decomposition rates were depending on alkanoyl chain length and on complex stoichiometry as well. Nanoparticles with 50¿100 nm diameter were successfully prepared from the stearoylcholine complex with a surfactant to polymer ratio of 0.75 and loaded with theophylline, carbamazepine or doxorubicin drugs. The releasing of the drugs from nanoparticles took place upon incubation at very different rates depending on the drug. Theophylline and carbamazepine were discharged in hours whereas doxorubicin was very slowly delivered along months. The observed differences were related to the different interaction mechanism operating between the drug and the complex

    Ionic complexes of microbial poly(¿-glutamic acid) and alkanoylcholines are fully bio-based comb-like systems able to self-organize in an ordered amphiphilic structure made of hydrophobic and hydrophilic alternating layers. Incubation of complex films under physiological conditions for one month promoted dissociation of the complex and hydrolysis of the choline ester without almost degradation of polyglutamic acid. Complex decomposition rates were depending on alkanoyl chain length and on complex stoichiometry as well. Nanoparticles with 50–100 nm diameter were successfully prepared from the stearoylcholine complex with a surfactant to polymer ratio of 0.75 and loaded with theophylline, carbamazepine or doxorubicin drugs. The releasing of the drugs from nanoparticles took place upon incubation at very different rates depending on the drug. Theophylline and carbamazepine were discharged in hours whereas doxorubicin was very slowly delivered along months. The observed differences were related to the different interaction mechanism operating between the drug and the complex

  • Thermal behavior of long-chain alkanoylcholine soaps

     Tolentino Chivite, Ainhoa; Alla Bedahnane, Abdelilah; Martinez de Ilarduya Saez de Asteasu, Antxon; Font-Bardía, Mercè; León Cabanillas, Salvador; Muñoz Guerra, Sebastian
    RSC Advances
    Date of publication: 2014-01-01
    Journal article

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    Long-chain alkanoylcholines prepared from fatty acids (nACh) are fully sustainable cationic surfactants that are known for their biological and medicinal properties. In the present work the thermal behavior of the homologous series of alkanoylcholine iodides with n = 12, 14, 16 and 18, has been examined within the 25-200 degrees C range of temperatures. Up to three thermotropic phases have been identified, and the thermal transitions implied in their interconversion have been characterized by DSC and simultaneous WAXS and SAXS analysis carried out in real-time. All three phases consist of a bilayered structure with alkanoyl chains confined in the space between the head group layers and interdigitated to a greater or lesser extent. Melting-crystallization of either the polymethylene segments or the choline iodide groups is involved in such transitions. Additionally, a crystal phase consisting also of a bilayered structure but excluding side chain interdigitation was observed upon crystallization from solution and its structure was elucidated by single-crystal X-ray diffraction direct methods. The close correlation existing between thermal properties, phase structure and n has been brought into evidence.

  • Bio-based poly(ethylene terephthalate) copolyesters made from cyclic monomers derived from tartaric acid

     Japu, Cristina; Martinez de Ilarduya Saez de Asteasu, Antxon; Alla Bedahnane, Abdelilah; Muñoz Guerra, Sebastian
    Polymer
    Date of publication: 2014-05-13
    Journal article

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    Two cyclic acetal compounds, 2,3-O-methylene L-threitol and dimethyl 2,3-O-methylene L-threarate, both coming from naturally-occurring tartaric acid, were used as comonomers to replace ethylene glycol and dimethyl terephthalate respectively, in the preparation of PET-based copolyesters by polycondensation in the melt. Synthesis results, structure and thermal properties of the two afforded copolyester series were evaluated and compared regarding composition and type of comonomer used in each case. All the copolyesters had a random microstructure and molecular weights in the 25,000¿35,000 g·mol-1 range. Their thermal properties varied logically with composition along each series but they significantly changed according to which acetal comonomer was used. PET copolyesters made from acetalized L-threitol displayed thermal stability and Tg comparable to PET, whereas these two properties were depressed in the copolyesters containing threarate units. Both types of copolyesters were able to crystallize for contents in tartaric acid derived units up to around 30% by adopting the crystal structure of PET. Crystallization rates and melting temperatures decreased with copolymerization in the two series but this effect was more noticeable in copolyesters made from threitol.

    Two cyclic acetal compounds, 2,3-O-methylene L-threitol and dimethyl 2,3-O-methylene L-threarate, both coming from naturally-occurring tartaric acid, were used as comonomers to replace ethylene glycol and dimethyl terephthalate respectively, in the preparation of PET-based copolyesters by polycondensation in the melt. Synthesis results, structure and thermal properties of the two afforded copolyester series were evaluated and compared regarding composition and type of comonomer used in each case. All the copolyesters had a random microstructure and molecular weights in the 25,000–35,000 g·mol-1 range. Their thermal properties varied logically with composition along each series but they significantly changed according to which acetal comonomer was used. PET copolyesters made from acetalized L-threitol displayed thermal stability and Tg comparable to PET, whereas these two properties were depressed in the copolyesters containing threarate units. Both types of copolyesters were able to crystallize for contents in tartaric acid derived units up to around 30% by adopting the crystal structure of PET. Crystallization rates and melting temperatures decreased with copolymerization in the two series but this effect was more noticeable in copolyesters made from threitol.

  • Bio-based PBT copolyesters derived from D-glucose: influence of composition on properties

     Japu, Cristina; Martinez de Ilarduya Saez de Asteasu, Antxon; Alla Bedahnane, Abdelilah; García Martín, Maria de Gracia; Galbis Pérez, Juan Antonio; Muñoz Guerra, Sebastian
    Polymer Chemistry
    Date of publication: 2014-05-07
    Journal article

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    Two series of bio-based PBT copolyesters were obtained by polycondensation in the melt of 2,4:3,5-di-O-methylene-D-glucitol (Glux-diol) or dimethyl 2,4:3,5-di-O-methylene-D-glucarate (Glux-diester) with 1,4-butanediol and dimethyl terephthalate. The glucose-based bicyclic compounds used as comonomers were synthesized from commercially available 1,5-D-gluconolactone. The prepared PBT copolyesters had weight-average molecular weights in the 30 000¿50 000 range; they had a random microstructure, and they were stable above 300 °C. The copolyesters containing less than 30% of sugar-based units were semicrystalline and were found to adopt the triclinic structure of PBT. These copolyesters with low contents in Glux were able to crystallize from the melt but at lower rates than PBT. The Tg value of PBT steadily increased with the incorporation of Glux units in the polyester chain with an increasing ratio of around 1.7 °C or around 1 °C per %Glux point, depending on which unit, the diol or the diacid, was replaced. The copolyesters hydrolyzed at higher rates than PBT, and those containing glucarate units displayed an appreciable susceptibility towards biodegradation.

  • Carbohydrate-based PBT copolyesters from a cyclic diol derived from naturally occurring tartaric acid: a comparative study regarding melt polycondensation and solid-state modification

     Lavilla Aguilar, Cristina; Gubbels, Erik; Alla Bedahnane, Abdelilah; Martinez de Ilarduya Saez de Asteasu, Antxon; Noordover, Bart A. J.; Koning, Cor E.; Muñoz Guerra, Sebastian
    Greenchemistry
    Date of publication: 2014-04-01
    Journal article

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    2,3-O-Methylene-L-threitol (Thx) is a cyclic carbohydrate-based diol prepared by acetalization and subsequent reduction of the naturally occurring tartaric acid. The structure of Thx consists of a 1,3-dioxolane ring with two attached primary hydroxyl groups. Two series of partially bio-based poly(butylene terephthalate) (PBT) copolyesters were prepared using Thx as a comonomer by melt polycondensation (MP) and solid-state modification (SSM). Fully random copolyesters were obtained after MP using mixtures of Thx and 1,4-butanediol in combination with dimethyl terephthalate. Copolyesters with a unique block-like chemical microstructure were prepared by the incorporation of Thx into the amorphous phase of PBT by SSM. The partial replacement of the 1,4-butanediol units by Thx resulted in satisfactory thermal stabilities and gave rise to an increase of the Tg values, this effect was comparable for copolyesters prepared by MP and SSM. The partially bio-based materials prepared by SSM displayed higher melting points and easier crystallization from the melt, due to the presence of long PBT sequences in the backbone of the copolyester. The incorporation of Thx in the copolyester backbone enhanced the hydrolytic degradation of the materials with respect to the degradation of pure PBT.

    2,3-O-Methylene-L-threitol (Thx) is a cyclic carbohydrate-based diol prepared by acetalization and subsequent reduction of the naturally occurring tartaric acid. The structure of Thx consists of a 1,3-dioxolane ring with two attached primary hydroxyl groups. Two series of partially bio-based poly(butylene terephthalate) (PBT) copolyesters were prepared using Thx as a comonomer by melt polycondensation (MP) and solid-state modification (SSM). Fully random copolyesters were obtained after MP using mixtures of Thx and 1,4-butanediol in combination with dimethyl terephthalate. Copolyesters with a unique block-like chemical microstructure were prepared by the incorporation of Thx into the amorphous phase of PBT by SSM. The partial replacement of the 1,4-butanediol units by Thx resulted in satisfactory thermal stabilities and gave rise to an increase of the Tg values, this effect was comparable for copolyesters prepared by MP and SSM. The partially bio-based materials prepared by SSM displayed higher melting points and easier crystallization from the melt, due to the presence of long PBT sequences in the backbone of the copolyester. The incorporation of Thx in the copolyester backbone enhanced the hydrolytic degradation of the materials with respect to the degradation of pure PBT.

  • Sulfonated poly(hexamethylene terephthalate) copolyesters: enhanced thermal and mechanical properties

     Bautista Betancur, Mayka Irina; Martinez de Ilarduya Saez de Asteasu, Antxon; Alla Bedahnane, Abdelilah; Muñoz Guerra, Sebastian
    Journal of applied polymer science
    Date of publication: 2013-09-15
    Journal article

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    A series of poly(hexamethylene terephthalate-co-hexamethylene 5-sodium sulfoisophthalate) copolyesters containing from 5 to 50 mol % of sulfonated units as well as the two parent homopolymers are prepared by melt polycondensation. The polyesters are obtained with high molecular weights, which decrease with the increased content of sulfonated units in the copolymer. Polyesters with 5 and 10 mol % of sulfonated units are semicrystalline whereas for contents equal or above 20 mol % they are unable to crystallize from the melt. Thermogravimetric analysis show that the thermal stability decreases with the content in sulfonated units. Isothermal crystallizations of semicrystalline copolyesters show that the insertion of the sulfonated units causes a reduction of crystallizability, most probably due to the occurrence of ionic aggregations. It is observed a synergistic effect on the mechanical properties for copolymers with contents of around 5 mol % where the elongation at break increases drastically. Moreover, the hydrolytic degradationof the copolymer is enhanced with the content in sulfonated units.

    A series of poly(hexamethylene terephthalate- co -hexamethylene 5-sodium sulfoisophthalate) copolyesters containing from 5 to 50 mol % of sulfonated units as well as the two parent homopolymers are prepared by melt polycondensation. The polyesters are obtained with high molecular weights, which decrease with the increased content of sulfonated units in the copolymer. Polyesters with 5 and 10 mol % of sulfonated units are semicrystalline whereas for contents equal or above 20 mol % they are unable to crystal- lize from the melt. Thermogravimetric analysis show that the thermal stability decreases with the content in sulfonated units. Isother- mal crystallizations of semicrystalline copolyesters show that the insertion of the sulfonated units causes a reduction of crystallizabil- ity, most probably due to the occurrence of ionic aggregations. It is observed a synergistic effect on the mechanical properties for copolymers with contents of around 5 mol % where the elongation at break increases drastically. Moreover, the hydrolytic degrada- tion of the copolymer is enhanced with the content in sulfonated units

  • Bio-based poly(hexamethylene terephthalate) copolyesters containing cyclic acetalized tartrate units

     Japu, Cristina; Martinez de Ilarduya Saez de Asteasu, Antxon; Alla Bedahnane, Abdelilah; Muñoz Guerra, Sebastian
    Polymer
    Date of publication: 2013-03-08
    Journal article

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    A cyclic acetal of dimethyl l-tartrate (dimethyl 2,3-di-O-methylene l-threarate, Thx) was used as comonomer of dimethyl terephthalate (DMT) in the polycondensation with 1,6-hexanediol (HD) in the melt. Random copolyesters PHTxThxy with contents in tartrate units up to 50% were obtained with satisfactory molecular weights (Mw between 20,000 and 50,000) and dispersities slightly above 2, and without apparent discoloration. The copolyesters started to decompose above 300 °C. The Tg of the copolyesters oscillated between +9 and -9 °C with values steadily decreasing with increasing contents in Thx units. All the copolyesters as well as the homopolyester entirely made of tartrate units were semicrystalline with Tm falling from ~145 °C for PHT to ~70 °C for PHThx with intermediate values decreasing as the content in Thx increased. Copolyesters containing up to 30% of tartrate units were able to crystallize from the melt at crystallization rates that were delayed by the presence of tartrate units. The PHT70Thx30 copolyester displayed significant hydrodegradability when incubated in aqueous buffer and also certain biodegradability when subjected to the action of porcine pancreas lipases.

    A cyclic acetal of dimethyl l-tartrate (dimethyl 2,3-di-O-methylene l-threarate, Thx) was used as comonomer of dimethyl terephthalate (DMT) in the polycondensation with 1,6-hexanediol (HD) in the melt. Random copolyesters PHTxThxy with contents in tartrate units up to 50% were obtained with satisfactory molecular weights (Mw between 20,000 and 50,000) and dispersities slightly above 2, and without apparent discoloration. The copolyesters started to decompose above 300 °C. The Tg of the copolyesters oscillated between +9 and −9 °C with values steadily decreasing with increasing contents in Thx units. All the copolyesters as well as the homopolyester entirely made of tartrate units were semicrystalline with Tm falling from ∼145 °C for PHT to ∼70 °C for PHThx with intermediate values decreasing as the content in Thx increased. Copolyesters containing up to 30% of tartrate units were able to crystallize from the melt at crystallization rates that were delayed by the presence of tartrate units. The PHT70Thx30 copolyester displayed significant hydrodegradability when incubated in aqueous buffer and also certain biodegradability when subjected to the action of porcine pancreas lipases.

  • Comblike Ionic Complexes of Poly(gamma-glutamic acid) and Alkanoylcholines Derived from Fatty Acids

     Tolentino Chivite, Ainhoa; León Cabanillas, Salvador; Alla Bedahnane, Abdelilah; Martinez de Ilarduya Saez de Asteasu, Antxon; Muñoz Guerra, Sebastian
    Macromolecules
    Date of publication: 2013-02-15
    Journal article

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    A series of ionic complexes with almost stoichio- metric composition have been “ synthesized ” from bacterial poly( γ - glutamic acid) and alkanoylcholines derived from fatty acids with 12, 14, 16, and 18 carbon atoms. The complexes were stable up to temperatures close to 200 ° C and were non-water-soluble but readily soluble in organic solvents. In the solid state they adopted the biphasic structure typical of comblike systems with the polypeptide chains arranged in sheets and periodically separated by a para ffi nic phase which was partially crystallized for C14, C16, and C18. The window width of the layered structure was estimated by SAXS to be within the 3.6 − 4.5 nm range, and WAXS showed that the alkyl tails were crystallized in a hexagonally packed lattice with a d 100 spacing of 0.41 nm. These complexes displayed reversible melting of the para ffi nic phase in the 40 − 65 ° C range at temperatures with values increasing with the length of the alkanoyl group. A slight expansion of the intersheet distance occurred at melting followed by contraction upon heating at higher temperatures but without signi fi cant alteration of the layered structure. The 13 C CP-MAS NMR analysis revealed the underlying polymethylene anti -to- gauche conformational conversion that takes place at the thermal transition. An energy-based simulation study of the crystallization process a ff orded a molecular picture of the complex and evidenced the favoring e ff ect of the choline structure on the packing of the alkyl side

  • High Tg bio-based aliphatic polyesters from bicyclic D-mannitol

     Lavilla Aguilar, Cristina; Alla Bedahnane, Abdelilah; Martinez de Ilarduya Saez de Asteasu, Antxon; Muñoz Guerra, Sebastian
    Biomacromolecules
    Date of publication: 2013-03-11
    Journal article

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    The carbohydrate-based diol 2,4:3,5-di-O-methylene-d-mannitol (Manx) has been used to obtain aliphatic polyesters. Manx is a symmetric bicyclic compound consisting of two fused 1,3-dioxane rings and bearing two primary hydroxyl groups. In terms of stiffness, it is comparable to the widely known isosorbide, but it affords the additional advantages of being much more reactive in polycondensation and capable of producing stereoregular polymers with fairly high molecular weights. A fully bio-based homopolyester (PManxS) has been synthesized by polycondensation in the melt from dimethyl succinate and Manx. The high thermal stability of PManxS, its relatively high glass transition temperature (Tg = 68 °C) and elastic modulus, and its enhanced sensitivity to the action of lipases point to PManxS as a polyester of exceptional interest for those applications where biodegradability and molecular stiffness are priority requirements. In addition, random copolyesters (PBxManxyS) covering a broad range of compositions have been obtained using mixtures of Manx and 1,4-butanediol in the reaction with dimethyl succinate. All PBxManxyS were semicrystalline and displayed Tg values from -29 to +51 °C steadily increasing with the content in Manx units. The stress¿strain behavior of these copolyesters largely depended on their content in Manx and they were enzymatically degraded faster than PBS.

    The carbohydrate-based diol 2,4:3,5-di- O -methylene- D -mannitol (Manx) has been used to obtain aliphatic polyesters. Manx is a symmetric bicyclic compound consisting of two fused 1,3-dioxane rings and bearing two primary hydroxyl groups. In terms of sti ff ness, it is comparable to the widely known isosorbide, but it a ff ords the additional advantages of being much more reactive in polycondensation and capable of producing stereoregular polymers with fairly high molecular weights. A fully bio-based homopolyester (PManxS) has been synthesized by polycondensation in the melt from dimethyl succinate and Manx. The high thermal stability of PManxS, its relatively high glass transition temperature ( T g =68 ° C) and elastic modulus, and its enhanced sensitivity to the action of lipases point to PManxS as a polyester of exceptional interest for those applications where biodegradability and molecular sti ff ness are priority requirements. In addition, random copolyesters (PB x Manx y S) covering a broad range of compositions have been obtained using mixtures of Manx and 1,4-butanediol in the reaction with dimethyl succinate. All PB x Manx y S were semicrystalline and displayed T g values from − 29 to +51 ° C steadily increasing with the content in Manx units. The stress − strain behavior of these copolyesters largely depended on their content in Manx and they were enzymatically degraded faster than PBS.

  • D-Glucose-derived PET copolyesters with enhanced Tg

     Japu, Cristina; Martinez de Ilarduya Saez de Asteasu, Antxon; Alla Bedahnane, Abdelilah; García Martín, Maria de Gracia; Galbis Pérez, Juan Antonio; Muñoz Guerra, Sebastian
    Polymer Chemistry
    Date of publication: 2013-06-21
    Journal article

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    2,4:3,5-Di-O-methylene-D-glucitol and dimethyl 2,4:3,5-di-O-methylene-D-glucarate have been copolymerized with ethylene glycol and dimethyl terephthalate by polycondensation in the bulk to produce PET copolyesters as well as their respective homopolyesters. The PET copolyesters with either the diol or the diacid counterpart partially replaced by Glux had molecular weights in the 20 000¿40 000 range and a random microstructure, and they were stable well above 300 C. The PET copolyesters containing more than 10¿15% of sugar-based units wereamorphous while those displaying crystallinity were observed to crystallize from the melt at much lower rates than PET. The glass transition temperature of PET dramatically increased with the incorporation of Glux, whichever unit, diol or diacid, was replaced, but the enhancing effect was stronger in the former case. the copolyesters exhibited a higher hydrolysis rate and an appreciable susceptibility towards biodegradation.

  • The structure of poly(gamma-glutamic acid)/nanoclay hybrids compatibilized by alkylammonium surfactants

     Tolentino Chivite, Ainhoa; León, Salvador; Alla Bedahnane, Abdelilah; Martinez de Ilarduya Saez de Asteasu, Antxon; Muñoz Guerra, Sebastian
    European polymer journal
    Date of publication: 2013-09-01
    Journal article

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    Stoichiometric ionic complexes of bacterial poly(c-glutamic acid) with the cationic N-octadecyland N-docosyl-N,N,N-trimethylammonium surfactants were mixed with alkylammonium modified bentonite (Cloisite 30B) to generate hybrid compounds covering a wide range of clay/polymer compositions. The structure of these compounds was examined by XRD and cryoTEM, which indicated extensive penetration of the biopolymer into the nanoclay galleries with widening or even destruction of the layered arrangement of the complex and the clay. Simultaneous SAXS/WAXS analysis in real time showed that hybrids with moderate inorganic contents displayed melting/crystallization upon heating/cooling within the 40¿70 C interval with concomitant expansion/contraction of the intersheet spacing. 13C CP-MAS NMR revealed that an anti-to-gauche conformational interconversionof the alkyl chains was involved in the melting/crystallization process. The results providedby energy-based dynamical simulations proved the feasibility of the polyacid and thenanoclay to be homogenized in the hybrid due to the compatibilizing effect of the surfactant.

    Stoichiometric ionic complexes of bacterial poly(γ-glutamic acid) with the cationic N-octadecyl and N-docosyl-N,N,N-trimethylammonium surfactants were mixed with alkylammonium modified bentonite (Cloisite 30B) to generate hybrid compounds covering a wide range of clay/polymer compositions. The structure of these compounds was examined by XRD and cryoTEM, which indicated extensive penetration of the biopolymer into the nanoclay galleries with widening or even destruction of the layered arrangement of the complex and the clay. Simultaneous SAXS/WAXS analysis in real time showed that hybrids with moderate inorganic contents displayed melting/crystallization upon heating/cooling within the 40–70 °C interval with concomitant expansion/contraction of the intersheet spacing. 13C CP-MAS NMR revealed that an anti-to-gauche conformational interconversion of the alkyl chains was involved in the melting/crystallization process. The results provided by energy-based dynamical simulations proved the feasibility of the polyacid and the nanoclay to be homogenized in the hybrid due to the compatibilizing effect of the surfactant.

  • Comb-like ionic complexes of hyaluronic acid with alkyltrimethylammonium surfactants

     Tolentino Chivite, Ainhoa; Alla Bedahnane, Abdelilah; Martinez de Ilarduya Saez de Asteasu, Antxon; Muñoz Guerra, Sebastian
    Carbohydrate polymers
    Date of publication: 2013-01-30
    Journal article

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    Stoichiometric complexes of hyaluronic acid with alkyltrimethylammonium surfactants bearing octadecyl, eicosyl and docosyl groups were prepared by ionic coupling in aqueous solution. The complexes were non soluble in water but soluble in organic solvents. In the solid state they self-assembled in a biphasic layered structure with the alkyl side chains forming a separate phase that melted in the 50–60 °C range. They were stable to heating up to above 200 °C.

  • PET copolyesters made from a D-mannitol-derived bicyclic diol

     Lavilla Aguilar, Cristina; Martinez de Ilarduya Saez de Asteasu, Antxon; Alla Bedahnane, Abdelilah; Muñoz Guerra, Sebastian
    Polymer Chemistry
    Date of publication: 2013-01-14
    Journal article

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  • Bio-based aliphatic polyesters from succinic acid and bicyclic D-mannitol

     Lavilla Aguilar, Cristina; Alla Bedahnane, Abdelilah; Martinez de Ilarduya Saez de Asteasu, Antxon; Muñoz Guerra, Sebastian
    International Symposium Frontiers in Polymer Science
    Presentation's date: 2013-05-21
    Presentation of work at congresses

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  • Bio-Based PET Copolyesters from a D-Mannitol-derived Bicyclic Diol

     Lavilla Aguilar, Cristina; Martinez de Ilarduya Saez de Asteasu, Antxon; Alla Bedahnane, Abdelilah; Muñoz Guerra, Sebastian
    Conferencia Internacional de Polímeros para Investigadores Noveles
    Presentation's date: 2013-11-04
    Presentation of work at congresses

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  • Sulfonated Poly(hexamethylene terephthalate) copolyesters

     Bautista Betancur, Mayka Irina; Martinez de Ilarduya Saez de Asteasu, Antxon; Alla Bedahnane, Abdelilah; Muñoz Guerra, Sebastian
    Conferencia Internacional de Polímeros para Investigadores Noveles
    Presentation's date: 2013-11-07
    Presentation of work at congresses

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  • Complexes of polyglutamic acid and choline surfactants for drug delivery

     Tolentino Chivite, Ainhoa; Alla Bedahnane, Abdelilah; Martinez de Ilarduya Saez de Asteasu, Antxon; León Cabanillas, Salvador; Muñoz Guerra, Sebastian
    European Polymer Congress
    Presentation's date: 2013-06-19
    Presentation of work at congresses

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  • Poly(ester-amide)s derived from PET with m-xylylene adipamide units

     Ascanio Nuñez, Yanireth; Martinez de Ilarduya Saez de Asteasu, Antxon; Alla Bedahnane, Abdelilah; Andrio Balado, Andreu; Compañ Morreno, Vicente; Muñoz Guerra, Sebastian
    International Symposium Frontiers in Polymer Science
    Presentation's date: 2013-05-21
    Presentation of work at congresses

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    In this work we have prepared poly(ester-amide)s (PETxMy) derived from poly(ethylene terephthalate) (PET) with the aim of improving its gas barrier properties, and then to expand its use for more demanding bottle field applications. The new PETxMy poly(ester-amide)s are obtained in the melt phase with incorporation of compound M in the first transesterification step. This compound was previously prepared by transesterification of dimethyl adipate with m-xylylenediamine (MXD6). The content of M units in the poly(ester-amide)s varied from 0 to 20 mol%. PETxMy were obtained with high yields, molecular weights (Mw) between 35,000-50,000 g mol-1 and dispersities between 2.3-3.3. All PETxMy were semicrystalline, although it was observed a reduction on both melting enthalpy and temperature (Tm) as well as in the glass transition temperature (Tg) with the increased content of M in the polyesteramide.

  • Bio-based high Tg PET copolyesters containing bicyclic acetalized glucose units

     Japu, Cristina; Martinez de Ilarduya Saez de Asteasu, Antxon; Alla Bedahnane, Abdelilah; García Martín, Maria de Gracia; Galbis Pérez, Juan Antonio; Muñoz Guerra, Sebastian
    International Symposium Frontiers in Polymer Science
    Presentation's date: 2013-05-22
    Presentation of work at congresses

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    Two series of copolyesters from ethylenglycol, dimethyl terephthalate and either 2,4:3,5-di-O-methylene-D-glucitol or dimethyl 2,4:3,5-di-O-methylene-D-glucarate, respectively, were prepared by melt-polycondensation with a wide range of compositions. The copolyesters had Mw in the 20,000-10,000 g¿mol-1 range with values decreasing with the content in sugar units, and had a random microstructure. Significant differences in properties were found between the two series. The incorporation of sugar residues in the PET chain caused a decrease in the thermal stability that was more notable in the case of the replacement of the terephthalic acid. In general the copolyesters displayed Tg increasing with the content in sugar units in the two series but the effect was stronger when the diol was the replaced unit.

  • Synthesis, structure and degradability of copolyesters derived from D-glucose

     García Martín, Maria de Gracia; Japu, Cristina; Martinez de Ilarduya Saez de Asteasu, Antxon; Alla Bedahnane, Abdelilah; Galbis Pérez, Juan Antonio; Muñoz Guerra, Sebastian
    European Symposium on Biopolymers
    Presentation's date: 2013-10-07
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    A series of aromatic copolyesters from ethylenglycol, dimethyl terephthalate and either 2,4:3,5-di-O-methylene-D-glucitol (PExGluxyT) or dimethyl 2,4:3,5-di-O-methylene-D-glucarate (PETxGluxy), respectively, were prepared by melt-polycondensation with a wide range of compositions. These non-stereoregular copolyesters had Mw in the 20,000-10,000 g¿mol-1 range with values decreasing with the content in sugar units, and had a random microstructure. The incorporation of sugar residues in the PET chain caused a decrease in the thermal stability that was more notable in the case of the replacement of the terephthalic acid. In general the copolyesters displayed Tg increasing with the content in sugar units but the effect was stronger when the diol was the replaced unit. Crystallinity was markedly depressed by copolymerization, and only copolyesters containing 15% of sugar units as maximum displayed melting but at temperatures much lower than PET. Several studies on the hydrodegradability and biodegradability of polyesters containing sugar units have revealed that their presence increase the hydrophilicity of the polymers and enhance the attack of water or enzyme to them. We now report on the effects that the incorporation of D-glucose units (diol or diester) exert on the hydrolytic and enzymatic degradation of PET, under different conditions. It was noticed that those copolyesters containing D-glucose diester units (PETxGluxy) were the most easily degradable under aggressive conditions of hydrodegradability (pH 2, 80 ºC). In addition to this, enzymatic degradation of both copolyesters, PExGluxyT and PETxGluxy, showed certain degree of biodegradability after incubation in aqueous buffer (pH 7.4 at 37 ºC) with porcine pancreas lipase.

  • Sugar-based aromatic copolyesters from cyclic galactitol and galactaric acid derivatives

     Lavilla Aguilar, Cristina; Alla Bedahnane, Abdelilah; Martinez de Ilarduya Saez de Asteasu, Antxon; Benito, Elena; García Martín, Maria de Gracia; Galbis Pérez, Juan Antonio; Muñoz Guerra, Sebastian
    International Symposium Frontiers in Polymer Science
    Presentation's date: 2013-05-21
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  • Complexes of poly(gamma-glutamic acid) and fatty acid choline

     Tolentino Chivite, Ainhoa; León Cabanillas, Salvador; Alla Bedahnane, Abdelilah; Martinez de Ilarduya Saez de Asteasu, Antxon; Muñoz Guerra, Sebastian
    International Symposium Frontiers in Polymer Science
    Presentation's date: 2013-05-22
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  • Sugar-based aromatic copolyesters: A comparative study regarding isosorbide and dicacetalized alditols as comonomers

     Lavilla Aguilar, Cristina; Martinez de Ilarduya Saez de Asteasu, Antxon; Alla Bedahnane, Abdelilah; García Martín, Maria de Gracia; Galbis Pérez, Juan Antonio; Muñoz Guerra, Sebastian
    European Polymer Congress
    Presentation's date: 2013-06-17
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  • Copolycarbonates of bisphenol a containing bicyclic D-glucitol

     Sánchez Clavería, Laura; Martinez de Ilarduya Saez de Asteasu, Antxon; Alla Bedahnane, Abdelilah; Muñoz Guerra, Sebastian
    European Polymer Congress
    Presentation's date: 2013-06-19
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  • Bio-based aliphatic polyesters from bicyclic D-mannitol

     Lavilla Aguilar, Cristina; Alla Bedahnane, Abdelilah; Martinez de Ilarduya Saez de Asteasu, Antxon; Muñoz Guerra, Sebastian
    European Polymer Congress
    Presentation's date: 2013-06-19
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  • Carbohydrate-based polyurethanes: A comparative study of polymers made from isosorbide and 1,4-butanediol

     Marin Bernabe, Romina; Alla Bedahnane, Abdelilah; Martinez de Ilarduya Saez de Asteasu, Antxon; Muñoz Guerra, Sebastian
    Journal of applied polymer science
    Date of publication: 2012-01-15
    Journal article

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    A set of linear polyurethanes containing isosorbide units were synthesized by polymerization in solution from HDI and MDI diisocyanates and 1,4-butanediol(BD), isosorbide (Is) or diisosorbide diurethanes (Is2HDI and Is2MDI) as diols. The thermal transitions, thermal stability, and crystal structure of the polyurethane homopolymers and copolymers containing isosorbide were evaluated and compared with those displayed by their polyurethane analogues entirely made of BD. It was found that incorporation of Is units in the polyurethane chain produced significant changes in Tg, Tm, and Td but no significant differences were noticed between copolymers made from Is or Is2 monomers. Degradation assays revealed that the presence of Is units increased slightly the hydrolysis rate of polyurethanes.

  • Biodegradable aromatic copolyesters made from bicyclic acetalized galactaric acid

     Lavilla Aguilar, Cristina; Alla Bedahnane, Abdelilah; Martinez de Ilarduya Saez de Asteasu, Antxon; Benito, Elena; García Martín, Maria de Gracia; Galbis Pérez, Juan Antonio; Muñoz Guerra, Sebastian
    Journal of polymer science. Part A, polymer chemistry
    Date of publication: 2012-08-15
    Journal article

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    Random poly(hexamethylene terephthalate-co-galactarate) s and poly(dodecamethylene terephthalate-co-galactarate) s copolyesters covering the whole range of compositions were obtained with weight-average molecular weights of 30,000–50,000 g mol 1 by melt polycondensation. They were thermally stable above 300 C, and displayed Tg in the þ20 to 20 C range with values steadily decreasing with the content in galactarate units. All the copolyesters were semicrystalline with Tm between 50 and 150 C and those made from dodecanediol were able to crystallize from the melt at a crystallization rate depending on composition. Copolyesters containing up to 50% of galactaric units retained the crystal structure of their respective polyterephthalate homopolyesters, whereas they adopted the structure of the respective polygalactarates when the content in Galx units reached 70%. Stress-strain essays revealed decay in the mechanical parameters as the aromatic units were replaced by Galx. Incubation in aqueous buffer revealed that hydrolysis of the polyesters were largely enhanced by copolymerization and evidenced the capacity of the Galx unit for making aromatic polyesters susceptible to biodegradation. A detailed NMR analysis complemented by SEM observations indicated that hydrolysis took place by preferred splitting of galactarate ester bonds with releasing of alkanediol and Galx-diacid.

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    Bio-based aromatic polyesters from a novel bicyclic diol derived from D-mannitol  Open access

     Lavilla Aguilar, Cristina; Martinez de Ilarduya Saez de Asteasu, Antxon; Alla Bedahnane, Abdelilah; García Martín, Maria de Gracia; Galbis Pérez, Juan Antonio; Muñoz Guerra, Sebastian
    Macromolecules
    Date of publication: 2012-10-23
    Journal article

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    2,4:3,5-Di-O-methylene-D-mannitol, abbreviated as Manx, is a D-mannitol-derived compound with the secondary hydroxyl groups acetalized with formaldehyde. The bicyclic structure of Manx consists of two fused 1,3-dioxane rings, with two primary hydroxyl groups standing free for reaction. A homopolyester made of Manx and dimethyl terephthalate as well as a set of copolyesters of poly(butylene terephthalate) (PBT) in which 1,4-butanediol was replaced by Manx up to 50% were synthesized and characterized. The polyesters had Mw in the 30 000−52 000 g mol−1 range and a random microstructure and were thermally stable up to nearly 370 °C. They displayed outstanding high Tg with values from 55 to 137 °C which steadily increased with the content in Manx. Copolyesters containing up to 40% of Manx were semicrystalline and adopted the crystal structure of PBT. Their stress− strain parameters were sensitively affected by the presence of carbohydrate-based units with elongation at break decreasing but tensile strength and elastic moduli steadily increasing with the degree of replacement.

  • Poly(ethylene terephthalate) terpolyesters containing 1,4-cyclohexanedimethanol and isosorbide

     Quintana Vicente, Roberto; Martinez de Ilarduya Saez de Asteasu, Antxon; Alla Bedahnane, Abdelilah; Muñoz Guerra, Sebastian
    High performance polymers
    Date of publication: 2012-02-01
    Journal article

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    A series of poly(ethylene terephthalate) terpolyesters containing varying amounts of both 1,4-cyclohexylenedimethylene and isosorbide units were prepared by melt phase polycondensation. These terpolymers were obtained with high molecular weights and polydispersities around 2.0-2.5. The nuclear magnetic resonance data revealed that they were all random terpolymers and that small amounts of isosorbide were lost during the polycondensation reaction. Thermal data showed that terpolymers with 90 mol% of ethylene units were crystalline, whereas the two other series containing 80 and 70 mol% were unable to crystallize from the melt. For the three series studied, it was observed that the glass transition temperature increased steadily with the content of isosorbide units, and that they had similar thermal stability.

    A series of poly(ethylene terephthalate) terpolyesters containing varying amounts of both 1,4-cyclohexylenedimethylene and isosorbide units were prepared by melt phase polycondensation. These terpolymers were obtained with high molecular weights and polydispersities around 2.0–2.5. The nuclear magnetic resonance data revealed that they were all random terpolymers and that small amounts of isosorbide were lost during the polycondensation reaction. Thermal data showed that terpolymers with 90 mol% of ethylene units were crystalline, whereas the two other series containing 80 and 70 mol% were unable to crystallize from the melt. For the three series studied, it was observed that the glass transition temperature increased steadily with the content of isosorbide units, and that they had similar thermal stability.

  • Carbohydrate-based copolyesters made from bicyclic acetalized galactaric acid

     Lavilla Aguilar, Cristina; Alla Bedahnane, Abdelilah; Martinez de Ilarduya Saez de Asteasu, Antxon; Benito, Elena; García Martín, Maria de Gracia; Galbis Pérez, Juan Antonio; Muñoz Guerra, Sebastian
    Journal of polymer science. Part A, polymer chemistry
    Date of publication: 2012-04-15
    Journal article

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    Mixtures of the dimethyl esters of adipic acid and 2,3:4,5-di-O-methylene-galactaric acid (Galx) were made to react in the melt with either 1,6-hexanediol or 1,12-dodecanediol to produce linear polycyclic copolyesters with aldarate unit contents varying from 10 up to 90 mole %. The copolyesters had weight–average molecular weights in the ∼35,000–45,000 g mol−1 range and a random microstructure, and were thermally stable up to nearly 300 °C. They displayed Tg in the -50 to -7 °C range with values largely increasing with the content in galactarate units. All the copolyesters were semicrystalline with Tm between 20 and 90 °C but only those made from 1,12-dodecanediol were able to crystallize from the melt at a crystallization rate that decreased as the contents in the two comonomers approached each other. Copolyesters containing minor amounts of galactarate units adopted the crystal structure characteristic of aliphatic polyesters but a new crystal polymorph was formed when the cyclic sugar units became the majority. Stress–strain parameters were sensitively affected by composition of the copolyesters with the mechanical behavior changing from flexible/ductile to stiff/brittle with the replacement of adipate units by the galactarate units.

  • Nanocomposites of comb-like ionic complexes of bacterial poly(glutamic acid) with nanoclays

     Tolentino Chivite, Ainhoa; Alla Bedahnane, Abdelilah; Muñoz Guerra, Sebastian
    European polymer journal
    Date of publication: 2012-12
    Journal article

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  • Bio-based poly(butylene terephthalate) copolyesters containing bicyclic diacetalized galactitol and galactaric acid: Influence of composition on properties

     Lavilla Aguilar, Cristina; Alla Bedahnane, Abdelilah; Martinez de Ilarduya Saez de Asteasu, Antxon; Benito, Elena; García Martín, Maria de Gracia; Galbis Pérez, Juan Antonio; Muñoz Guerra, Sebastian
    Polymer
    Date of publication: 2012-07-19
    Journal article

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    Copolyesters from 1,4-butanediol, dimethyl terephthalate and either 2,3:4,5-di-O-methylene-galactitol or dimethyl 2,3:4,5-di-O-methylene-galactarate with compositions of 10, 20, 30, 40 and 50% of either galactitol or galactarate units were prepared by melt-polycondensation. The copolyesters had Mw in the 32,000¿41,000 g mol-1 range and had a random microstructure. They displayed Tg from 20 to 70 °C with values steadily decreasing with the content in galactarate units but increasing with the content in galactitol units. All the copolyesters were semicrystalline with Tm between 115 and 210 °C and they adopted the crystal structure of PBT. Copolyesters containing up to 20% of galactitol units as well as all galactarate copolyesters were able to crystallize from the melt, at a crystallization rate that decreased with the content in carbohydrate-based units. Stress-strain essays revealed an increment in the tensile strength and elastic modulus with increasing contents in galactitol units whereas these parameters decreased when galactarate units were the replacing ones.

    Copolyesters from 1,4-butanediol, dimethyl terephthalate and either 2,3:4,5-di-O-methylene-galactitol or dimethyl 2,3:4,5-di-O-methylene-galactarate with compositions of 10, 20, 30, 40 and 50% of either galactitol or galactarate units were prepared by melt-polycondensation. The copolyesters had Mw in the 32,000–41,000 g mol−1 range and had a random microstructure. They displayed Tg from 20 to 70 °C with values steadily decreasing with the content in galactarate units but increasing with the content in galactitol units. All the copolyesters were semicrystalline with Tm between 115 and 210 °C and they adopted the crystal structure of PBT. Copolyesters containing up to 20% of galactitol units as well as all galactarate copolyesters were able to crystallize from the melt, at a crystallization rate that decreased with the content in carbohydrate-based units. Stress-strain essays revealed an increment in the tensile strength and elastic modulus with increasing contents in galactitol units whereas these parameters decreased when galactarate units were the replacing ones.

  • Bio-based aromatic copolyesters made from 1,6-hexanediol and bicyclic diacetalized D-glucitol

     Japu, Cristina; Alla Bedahnane, Abdelilah; Martinez de Ilarduya Saez de Asteasu, Antxon; García-Martín, M.G.; Benito, Elena; Galbis Pérez, Juan Antonio; Muñoz Guerra, Sebastian
    Polymer Chemistry
    Date of publication: 2012-08-01
    Journal article

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    Copoliésteres alifáticos derivados del ácido galactárico diacetalizado  Open access

     Lavilla Aguilar, Cristina; Alla Bedahnane, Abdelilah; Martinez de Ilarduya Saez de Asteasu, Antxon; Benito, Elena; García Martín, Maria de Gracia; Galbis Pérez, Juan Antonio; Muñoz Guerra, Sebastian
    Congreso Nacional de Jóvenes Investigadores en Polímeros
    Presentation's date: 2012-04-23
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  • Comb-like ionic complexes of pectinic and alginic acids with alkyltrimethylammonium surfactants

     Tolentino Chivite, Ainhoa; Alla Bedahnane, Abdelilah; Martinez de Ilarduya Saez de Asteasu, Antxon; Muñoz Guerra, Sebastian
    Carbohydrate polymers
    Date of publication: 2011-08-15
    Journal article

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    Ionic coupling of both polygalacturonic and alginic acids with alkyltrimethyl ammonium surfactants containing 18, 20 and 22 carbon atoms in the alkyl side chain was conducted in water solution to prepare non-soluble comb-like complexes. These amphiphilic complexes are arranged in a biphasic layered structure with the paraffinic phase made of alkyl side chains alternating with the hydrophilic phase made of polyuronic chains. The complexes displayed the thermal behaviour typical of comb-like systems carrying long polymethylene groups, which melt at temperatures between 40 and 80 ◦C without significant disruption of the layered arrangement. Melting temperature, crystallinity and thermal stability were slightly higher for the polygalacturonic complexes and all they increased almost steadily with the length of the alkyl chain within each series. The melting-crystallization process was followed by combined WAXS/SAXS and 13C CP-MAS NMR, which revealed that the transition involves an expansion-contraction of the structure that may attain up to 20% of the original dimension. The transition takes place without large conformational changes and is not fully reversible.

  • Compared structure and morphology of nylon-12 and 10-polyurethane lamellar crystals

     Fernandez Lopez, Carlos Eduardo; Bermúdez Hermida, Marta María; Alla Bedahnane, Abdelilah; Muñoz Guerra, Sebastian; Tocha, E.; Vancso, J.
    Polymer
    Date of publication: 2011-03-23
    Journal article

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    A comparative study of the structure and morphology of nylon-12 and 10-polyurethane (10-PUR) lamellar crystals, was carried out. Lamellar crystals were obtained by isothermal crystallization from diluted solution. Electron diffraction of lamellae combined with WAXS data recorded from crystal sediments indicated that nylon-12 crystallized in either α-form or γ-form according to the solvent chosen for crystallization. The α-form was the crystal modification predominant in doubly oriented films of nylon-12 prepared by epitaxial crystallization. On the contrary, 10-PUR invariably crystallized in α-form regardless crystallization conditions. The α-form of nylon-12 and 10-PUR shared the same crystal structure with hydrogen-bonded sheets made of antiparallel chains and stacked with progressive shifting along both b and c directions. Lamellar crystals of nylon-12 in γ-form and 10-PUR in α-form displayed similar morphological features but only the former appeared to be sensitive to temperature. Upon heating the nylon-12 crystals near to melting, the real-time WAXS analysis evidenced the occurrence of a partial γ-to-α crystal transition, and in situ AFM observations revealed the appearing of more or less regular ridges on the crystal surface. None of these changes were observed in 10-PUR crystals when subjected to similar treatment.

  • Polyterephthalates made from ethylene glycol, 1,4-cyclohexanedimethanol, and isosorbide

     Quintana, Robert; Martinez de Ilarduya Saez de Asteasu, Antxon; Alla Bedahnane, Abdelilah; Muñoz Guerra, Sebastian
    Journal of polymer science. Part A, polymer chemistry
    Date of publication: 2011-05-15
    Journal article

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    Three series of terephthalate polyesters (copolyesters and terpolyesters) containing 70, 80, and 90 mol % of ethylene glycol respectively, 1,4-cyclohexanedimethanol (CHDM) and isosorbide in varying ratios, were synthesized by melt polycondensation. It was found that only ~75 mol % of the feeding isosorbide was incorporated in the resulting polyesters and that their content in diethylene glycol oscillated between 2 and 4 mol %. The polyesters had weight-average molecular weights in the 25,000–33,000 g mol~1 range and polydispersities between 2 and 2.5. The combined 1H and 13C NMR analysis revealed that the microstructure of all these polyesters was at random. They showed good thermal stability with decomposition temperatures above 400ºC. Their glass-transition temperatures were observed to increase with the content in cyclic diols, this effect being more pronounced when isosorbide was the replacing comonomer. Only the series containing 90 mol% of ethylene terephthalate units was able to crystallize upon cooling from the melt. Compared isothermal crystallizations revealed that isosorbide was more effective than CHDM in repressing the crystallizability of PET.

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    Carbohydrate-based polyesters made from bicyclic acetalized galactaric acid  Open access

     Lavilla Aguilar, Cristina; Alla Bedahnane, Abdelilah; Martinez de Ilarduya Saez de Asteasu, Antxon; Benito, Elena; García Martín, Maria de Gracia; Galbis Pérez, Juan Antonio; Muñoz Guerra, Sebastian
    Biomacromolecules
    Date of publication: 2011-07-11
    Journal article

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    The dimethyl ester of 2,3:4,5-di-O-methylene-galactaric acid (Galx) was made to react in the melt with 1,n-alkanediols HO(CH2)nOH containing even numbers of methylenes (n from 6 to 12) to produce linear polycyclic polyesters. Two sets of poly(alkylene 2,3:4,5-di-O-methylenegalactarate) polyesters (PE-nGalx) with weight-average molecular weights in the ∼5000 - 10000 and ∼35000 - 45000 ranges were obtained using TBT and DBTO catalysts, respectively. For comparative purposes a set of poly(alkylene adipate) polyesters (PE-nAd) was also synthesized with molecular weights in the higher range using a similar procedure. The thermal stability of PE-nGalx was greater than that of PE-nAd although it notably decayed as molecular weight decreased. The replacement of Ad by Galx in the polyesters caused increases in Tg of up to 70ºC, and almost doubled the tensile mechanical parameters. All PE-nGalx were semicrystalline but only those made from 1,12-dodecanediol were able to crystallize from the melt with a crystallization rate that diminished as the molecular weight increased. In general, the galactarate containing polyesters displayed higher solubility and wettability than polyadipates, they hydrolyzed faster and exhibited comparable sensitivity to the action of lipases.

  • Biodegradation in compost of recycled low density polyethylene/polycaprolactone blends

     Bou Serra, Jorge; Marroyo Molina, Luis Miguel; Alla Bedahnane, Abdelilah; Olle Otero, Luis; Bacardit Dalmases, Anna; Santana Pérez, Orlando Onofre; Maspoch Ruldua, Maria Lluïsa
    European Polymer Congress
    Presentation's date: 2011-06-26
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  • Carbohydrate-based polyurethanes: a comparative study of polymers made from isosorbide and 1,4-butanediol

     Marín, Romina; Alla Bedahnane, Abdelilah; Martinez de Ilarduya Saez de Asteasu, Antxon; Muñoz Guerra, Sebastian
    European Polymer Congress
    Presentation's date: 2011-06-27
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  • Aromatic copolyesters containing diacetalized D-glucitol

     Japu, Cristina; Martinez de Ilarduya Saez de Asteasu, Antxon; Alla Bedahnane, Abdelilah; Benito, Elena; García Martín, Maria de Gracia; Galbis Pérez, Juan Antonio; Muñoz Guerra, Sebastian
    European Polymer Congress
    Presentation's date: 2011-06-27
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  • Thermal degradation of poly(hexamethylene terephthalate-co-dioxanone) copolyesters

     Giammanco, Giuseppe; Martinez de Ilarduya Saez de Asteasu, Antxon; Alla Bedahnane, Abdelilah; Muñoz Guerra, Sebastian
    European Polymer Congress
    Presentation's date: 2011-06-27
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  • Thermal degradation of polyuronic acids and their ionic complexes

     Tolentino Chivite, Ainhoa; Alla Bedahnane, Abdelilah; Martinez de Ilarduya Saez de Asteasu, Antxon; Muñoz Guerra, Sebastian
    European Polymer Congress
    Presentation's date: 2011-06-27
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  • Aliphatic polyesters from the carbohydrate-based bicyclic monomer methyl di-O-methylene-galactarate

     Lavilla Aguilar, Cristina; Alla Bedahnane, Abdelilah; Martinez de Ilarduya Saez de Asteasu, Antxon; Benito, Elena; Garcia Martin, M; Galbis Pérez, Juan Antonio; Muñoz Guerra, Sebastian
    European Polymer Congress
    Presentation's date: 2011-06-30
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  • Ionic complexes of polyacids and cationic surfactants

     Tolentino Chivite, Ainhoa; Martinez de Ilarduya Saez de Asteasu, Antxon; Alla Bedahnane, Abdelilah; Muñoz Guerra, Sebastian
    Macromolecular symposia
    Date of publication: 2010-10-01
    Journal article

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    Comb-like ionic complexes were prepared from polyuronic acids (pectinic and alginic acids) and alkyltrimethylammonium surfactants bearing linear alkyl chains with 18, 20 and 22 carbon atoms. In the condensed state, these complexes were able to self-assemble in ordered structures which were thermally stable up to ~200ºC. The complexes were analysed by DSC and WAXS/SAXS and compared to their analogous made from poly(γ-glutamic acid). They all adopt a biphasic layered structure in which the main chain and the alkyl side chain alternate with a nanometric periodicity. Alkyl side chains were partially crystallized in these complexes and they show reversible melting at temperatures within the 60-80ºC range depending on the length of the polymethylene segment.

  • Hydrolizable aromatic copolyesters of p-dioxanone

     Giammanco, Giuseppe; Martinez de Ilarduya Saez de Asteasu, Antxon; Alla Bedahnane, Abdelilah; Muñoz Guerra, Sebastian
    Biomacromolecules
    Date of publication: 2010-09-13
    Journal article

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    Entropically driven ring-opening copolymerization of mixtures of a fraction of cyclic oligo(hexamethylene terephthalate)s composed of cycle sizes from 2 to 5 and p-dioxanone was used to prepare random copolyesters covering a range of aromatic (HT) to aliphatic (DO) units ratios from 9 to 1.3. The composition and microstructure of the copolyesters were accurately determined by 1H and 13C NMR, respectively. The copolyesters showed thermal degradation and glass transition temperatures in good agreement with their comonomeric composition and microstructure, and they crystallized for contents in DO less than 30%, adopting the same crystal structure as poly(hexamethylene terephthalate). The copolyesters appeared to be sensitive to hydrolytic degradation, which was observed to take place superficially with the generation of non-water-soluble degraded fragments and with the release of water-soluble dioxanoic acid to the aqueous medium.

  • Crystallization Studies on Linear Aliphatic Polyamides Derived From Naturally Occurring Carbohydrates

     Fernandez Lopez, Carlos Eduardo; Bermúdez Hermida, Marta María; Alla Bedahnane, Abdelilah; Mancera Claveria, Manuel; Garcia Martin, M; Benito, Elena; Roffe, I.; Galbis Pérez, Juan Antonio; Muñoz Guerra, Sebastian
    Journal of applied polymer science
    Date of publication: 2010-06-05
    Journal article

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    Poly(ethylene terephthalate-co-isophthalate) copolyesters obtained from ethylene terephthalate and isophthalate oligomers  Open access

     Ubach, Joan; Martinez de Ilarduya Saez de Asteasu, Antxon; Quintana Vicente, Roberto; Alla Bedahnane, Abdelilah; Rudé, Elisabet; Muñoz Guerra, Sebastian
    Journal of applied polymer science
    Date of publication: 2010-02-05
    Journal article

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    A series of poly(ethylene terephthalate-co-isophthalate) copolyesters containing up to 50%-mole of isophthalic units were prepared by polycondensation from ethylene terephthalate and ethylene isophthalate fractions of linear oligomers containing from 5 to 6 repeating units in average. The polyesters were obtained in good yields and with high molecular weights. The microstructure of the copolyesters was studied as a function of reaction time by 13C-NMR showing that a random distribution of the comonomers was achieved since the earlier stages of polycondensation. The melting temperature and enthalpy of the copolyesters decreased with the content of isophthalic units so that copolyesters containing more than 25% of these units were amorphous. Isothermal crystallization studies made on crystalline copolyesters revealed that the crystallization rate of copolyesters decreased with the content in isophthalic units.

    Postprint (author’s final draft)

  • Sequence analysis of polyether-based thermoplastic polyurethane elastomers by 13C NMR

     Martinez de Ilarduya Saez de Asteasu, Antxon; Carvalho, Erica; Alla Bedahnane, Abdelilah; Muñoz Guerra, Sebastian
    Macromolecules
    Date of publication: 2010-04-27
    Journal article

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    In this Note we would like to report on the analysis of the microstructure of segmented polyurethanes by 13CNMRmaking use of the signals arising from nonprotonated aromatic carbons which appear to be sensitive to dyads sequence distribution. The polyurethanes here studied were obtained from poly(tetramethylene glycol) (PTMG) as macrodiol soft segment, 1,4-butanediol (BD) chain extender, and 4,40'-methylenediphenyl diisocyanate (MDI) as hard segment.The results obtained in this work provide a relatively simple and reliable method to determine the microstructure of MDI-based thermoplastic polyurethanes by means of the NMR technique.

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    Poly(ethylene terephthalate) terpolyesters containing 1,4-cyclohexanedimethanol and isosorbide  Open access

     Quintana Vicente, Roberto; Martinez de Ilarduya Saez de Asteasu, Antxon; Alla Bedahnane, Abdelilah; Muñoz Guerra, Sebastian
    Polycondensation Meeting
    Presentation's date: 2010-09-06
    Presentation of work at congresses

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    New PET derived terpolyesters have been synthesized y incorporation of CHDM and the biobased monomer isosorbide. It was observed that this incorporation repressed the crystallinity, increased the Tg improved the processability.