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A series of α,ω-telechelic polydimethylsiloxanes (PDMS), with predetermined molecular weights of about 2500 g mol-1, was synthesized by siloxane equilibration reaction. Syntheses were performed using octamethylcyclotetrasiloxane (D4) and various disiloxanes: hexamethyldisiloxane (HMDS), 1,1,3,3-tetramethyldisiloxane (TMDS), 1,3-divinyltetramethyldisiloxane (DVTMDS), 1,3-bis(3-carboxypropyl)tetramethyldisiloxane (DCPTMDS) and 1,3-bis(3-aminopropyl)tetramethyldisiloxane (DAPTMDS). The role of the disiloxane was to introduce terminal functional groups at the end of the polymer chains and to control the molecular weight of the polymers. Polymers with trimethyl, hydrido, vinyl, carboxypropyl and aminopropyl end-groups were obtained in this way. The structure of the α,ω-telechelic PDMSs was confirmed by NMR and IR spectroscopy. The molecular weights of the polymers were determined by 1H-NMR, gel permeation chromatography (GPC) and dilute solution viscometry. Thermogravimetric analysis (TGA) under nitrogen and air showed that the type of the terminal groups significantly influenced the thermal and thermo-oxidative stability, as well as the degradation mechanism of the α,ω-telechelic PDMSs. [Project of the Serbian Ministry of Education, Science and Technological Development, Grant no. 172062]

Two series of crosslinked poly(urethane-ester-siloxane)s were synthesized from α,ω-dihydroxy-(ethylene oxide-poly(dimethylsiloxane)-ethylene oxide) (EO-PDMS- -EO), 4,4'-methylenediphenyl diisocyanate and Boltorn® hyperbranched polyesters of the second and third pseudo generation, by two-step polymerization in solution. The effect of the EO-PDMS-EO content and functionality of the applied crosslinking agent on the morphology and surface properties of the prepared poly(urethane-ester-siloxane)s was investigated by FTIR spectroscopy, small-angle X-ray scattering (SAXS), atomic force microscopy (AFM), scanning electron microscopy (SEM) and water absorption measurement. Different techniques (FTIR peak deconvolution, SAXS and AFM) revealed that decrease of the crosslinking agent functionality and EO-PDMS-EO content promotes microphase separation in the synthesized poly(urethane-ester-siloxane)s. SEM analysis and water absorption experiments showed that, due to the hydrophobic character of EO-PDMS-EO and its ability to migrate to the surface of poly(urethane-ester-siloxane)s, samples synthesized with higher EO-PDMS-EO content and crosslinking agents of lower functionality had more hydrophobic surfaces and better waterproof performances. The obtained results indicate that the synthesis of poly(urethane-ester-siloxane)s based on EO-PDMS-EO and Boltorn® hyperbranched polyesters leads to the creation of networks with interesting morphological and surface properties, which can be easily tailored by changing the content of EO-PDMS-EO segment or functionality of hyperbranched polyester. U ovom radu sintetisane su dve serije umreženih poli(uretan-estar-siloksana) (PUS) korišćenjem α,ω-dihidroksi-(etilenoksid-poli(dimetilsiloksan)-etilenoksida) (EO-PDMS-EO), 4,4'-diizocijanatodifenilmetana i dva Boltorn® hiperrazgranata poliestra (HRP) druge i treće pseudo generacije kao umreživača. Svaka serija se sastoji od uzoraka koji imaju različiti udeo mekog segmenta (EO-PDMS-EO). Uticaj funkcionalnosti korišćenog HRP i udela mekog segmenta na morfologiju i površinska svojstva PUS ispitan je primenom FTIR spektroskopije, SAXS, AFM i SEM analize i merenjem količine apsorbovane vode. Pokazano je da sa smanjenjem funkcionalnosti umreživača i udela EO-PDMS-EO dolazi do povećanja stepena mikrofaznog razdvajanja kod sintetisanih PUS. Pored toga, uzorci PUS sa većim udelom mekog segmenta i sintetisani primenom HRP niže funkcionalnosti pokazuju bolju otpornost na vodu.

A series of novel polyurethane crosslinked structures (PUs) was prepared from α,ω-dihydroxy-(ethylene oxide-poly(dimethylsiloxane)-ethylene oxide) (EO-PDMS-EO), 4,4'-methylenediphenyl diisocyanate and Boltorn ® hyperbranched polyester of the third pseudo generation. The hydroxyfunctional hyperbranched aliphatic polyester with 26 end groups was used as a crosslinking agent. In order to improve the compatibility of all the reactants during the synthesis, the PU samples were prepared by two-stage, step-growth polymerization in solution. The content of the soft EO-PDMS-EO segments was varied in the range from 15 to 40 wt. %. The influence of the EO-PDMS-EO content on the swelling behavior, crosslink density, hardness, and the thermal and surface properties of the synthesized PUs was investigated. The structure of the synthesized polyurethanes was confirmed by the presence of specific bands in the Fourier transform infrared spectra. Swelling studies were performed to determine the crosslink density and polyurethane networks with lower EO-PDMS-EO contents had higher crosslink densities. The glass transition temperature of the synthesized PUs, determined by differential scanning calorimetry, slightly increased from 50 to 58°C on decreasing the EO-PDMS-EO content because of the higher crosslink density of the samples. Increasing the EO-PDMS-EO content led to better thermal stability, as was evidenced by the onset temperature of weight loss. The surface of the polyurethane networks became more hydrophobic with increasing EO-PDMS-EO content. The surface morphology of synthesized polyurethanes was analyzed by scanning electron microscopy. U ovom radu prikazana je sinteza, struktura i neka svojstva novih umreženih poliuretana pripremljenih polazeći od α,ω-dihidroksi-(etilenoksid-poli(dimetilsiloksan)-etilenoksid) pretpolimera (EO-PDMS-EO), 4,4'-metilendifenildiizocijanata i Boltorn® hiperrazgranatog poliestra treće pseudo-generacije. Hiperrazgranati hidroksi funkcionalni alifatski poliestar sa 26 krajnjih grupa služio je kao umrežavajući agens pri sintezi poliuretana. U cilju poboljšanja kompatibilnosti reaktanata tokom sinteze, poliuretani su sintetisani dvostepenom polimerizacijom u rastvoru. Sadržaj mekog EO-PDMS-EO segmenta variran je u opsegu od 15 do 40 mas. %. Ispitan je uticaj EO-PDMS-EO sadržaja na ponašanje pri bubrenju, gustinu umrežavanja, tvrdoću, termička i površinska svojstva sintetisanih poliuretana. Struktura sintetisanih poliuretana potvrđena je FTIR spektroskopijom. Ponašanje pri bubrenju je ispitivano kako bi se odredila gustina umrežavanja i pokazano je da poliuretanske mreže sa nižim EO-PDMS-EO sadržajem imaju veću gustinu umrežavanja. Rezultati diferencijalne skenirajuće kalorimetrije pokazali su povećanje temperature ostakljivanja poliuretana od 50 do 58°C sa smanjenjem EO-PDMS-EO sadržaja kao posledicu veće gustine umreženosti uzoraka. Sintetisani poliuretani sa većim sadržajem EO-PDMS-EO segmenata pokazuju bolju termičku stabilnost, što je potvrđeno porastom početne temperature degradacije, određene TG analizom. Hidrofobnost površine poliuretana je rasla sa povećanjem sadržaja EO-PDMS-EO u odgovarajućem uzorku. Površinska morfologija sintetisanih poliuretana je analizirana skenirajućom elektronskom mikroskopijom.

Two series of thermoplastic elastomers (TPES), based on poly(dimethylsiloxane) (PDMS) as the soft segment and poly(butylene terephthalate) (PBT) as the hard segment, were analyzed by dynamic mechanical spectroscopy. In the first TPES series the lengths of both hard and soft segments were varied while the mass ratio of the hard to soft segments was nearly constant (about 60 mass%). In the second series, the mass ratio of hard and soft segments was varied in the range from 60/40 to 40/60, with a constant length of soft PDMS segments. The influence of the structure and composition of TPESs on the rheological properties, such as complex dynamic viscosity, μ*, the storage, G', and loss, G', shear modulus as well as the microphase separation transition temperature, TMST, was examined. The obtained results showed that the storage modulus of the TPESs increased in a rubbery plateau region with increase in degree of crystallinity. The rheological measurements of TPESs also showed that a microphase reorganization occurred during the melting process. The microphase separation transition temperatures were in the range from 220 to 234°C. In the isotropic molten state, the complex dynamic viscosity increased with increasing both the content and length of hard PBT segments. Dve serije termoplastičnih elastomera (TPES) na bazi poli(dimetilsiloksana) kao mekog segmenta i poli(butilentereftalata) kao tvrdog segmenta su analizirane dinamičko-mehaničkom spektroskopijom. U prvoj TPES seriji varirane su dužine tvrdih i mekih segmenata dok je njihov maseni odnos bio skoro konstantan (oko 60 mas%). U drugoj seriji, odnos tvrdih i mekih segmenata je variran u opsegu od 60/40 do 40/60, dok je dužina mekih PDMS segmenata bila konstantna. Ispitan je uticaj strukture i sastava TPES kopolimera na reološka svojstva, kao što su kompleksni dinamički viskozitet, μ*, moduli sačuvane, G', i izgubljene energije, G', i temperatura mikrofaznog razdvajanja, TMST. Dobijeni rezultati su pokazali da su uzorci sa većim stepenom kristaliničnosti imali i veće module sačuvane energije u gumolikom platou. Reološka merenja su takođe pokazala da svi TPES uzorci ispoljavaju mikrofaznu reorganizaciju u procesu topljenja. Temperature mikrofaznog razdvajanja su bile u opsegu od 220 do 234°C. U izotropskom rastopu, kompleksni dinamički viskoziteti su rasli sa povećanjem sadržaja i dužine PBT segmenata.

Segmented thermoplastic polyurethane copolymers (PURs) were synthesized using 4,4'-methylenediphenyl diisocyanate and 1,4-butanediol as the hard segment and α,ω-dihydroxy-poly(propylene oxide)-b-poly(dimethylsiloxane)-b-poly(propylene oxide) (PPO-PDMS) as the soft segment. The content of incorporated soft segments in PURs varied in the range from 40 to 90 wt.%. The structure, molecular weights and crystallinity of obtained copolymers were monitored by FTIR, 1H, 2D NMR spectroscopy, GPC and DSC analysis, respectively. Surface free energy analysis indicates the presence of hydrophobic (siloxane) groups on the surface, giving highly hydrophobic nature to the obtained PURs films. Water absorption measurements showed that the increase of the hydrophobic PPO-PDMS segment content, led to the decrease of percentage of absorbed water in copolymers. SEM and AFM analysis revealed that copolymers with lower content of PPO-PDMS segments have higher microphase separation between segments. The results obtained in this work indicate that synthesized PURs based on PPO-PDMS, demonstrated proper surface and morphological properties with a great potential for variety of applications such as hydrophobic coatings in biomedicine. [Projekat Ministarstva nauke Republike Srbije, br. 172062]

Segmented polyurethanes based on poly(dimethylsiloxane), currently used for biomedical applications, have sub-optimal biocompatibility which reduces their efficacy. Improving the endothelial cell attachment and blood-contacting properties of PDMS-based copolymers would substantially improve their clinical applications. We have studied the surface properties and in vitro biocompatibility of two series of segmented poly(urethane-dimethylsiloxane)s (SPU-PDMS) based on hydroxypropyl-and hydroxyethoxypropyl-terminated PDMS with potential applications in blood-contacting medical devices. SPU-PDMS copolymers were characterized by contact angle measurements, surface free energy determination (calculated using the van Oss-Chaudhury-Good and Owens-Wendt methods), and atomic force microscopy. The biocompatibility of copolymers was evaluated using an endothelial EA.hy926 cell line by direct contact assay, before and after pre-treatment of copolymers with multicomponent protein mixture, as well as by a competitive blood-protein adsorption assay. The obtained results suggested good blood compatibility of synthesized copolymers. All copolymers exhibited good resistance to fibrinogen adsorption and all favored albumin adsorption. Copolymers based on hydroxyethoxypropyl-PDMS had lower hydrophobicity, higher surface free energy and better microphase separation in comparison with hydroxypropyl-PDMS-based copolymers, which promoted better endothelial cell attachment and growth on the surface of these polymers as compared to hydroxypropyl-PDMS-based copolymers. The results showed that SPU-PDMS copolymers display good surface properties, depending on the type of soft PDMS segments, which can be tailored for biomedical application requirements such as biomedical devices for short-and long-term uses. Ministry of Education, Science and Technological Development of the Republic of Serbia {[}172062]

In this study, the synthesis, structure and physical properties of two series of thermoplastic polyurethanes based on hydroxypropyl-terminated poly(dimethylsiloxane) (HP-PDMS) or hydroxyethoxypropyl-terminated poly(dimethylsiloxane) (EO-PDMS) as soft segments, and 4,4'-methylenediphenyl diisocyanate and 1,4-butanediol as hard segments were investigated. The polyurethanes were synthesized by two-step polyaddition in solution. The effects of the type and content of PDMS segments on the structure, thermal and surface properties of copolymers were studied by H-1-, C-13-nuclear magnetic resonance (NMR) spectroscopy and two-dimensional NMR spectroscopies (heteronuclear multiple bond correlation (HMBC) and rotating-frame nuclear Overhauser effect (ROESY)), gel permeation chromatography (GPC), differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), wide-angle X-ray scattering (WAXS), scanning electron microscopy (SEM) and water contact angle and water absorption measurements. Thermal properties investigated by DSC indicated that the presence of soft PDMS segments lowers the glass transition and melting temperatures of the hard phase as well as the degree of crystallinity. SEM analysis of the copolymers with a lower soft segment content confirmed the presence of spherulite superstructures, which arise from the crystallization of the hard segments. When compared with polyurethanes prepared from HP-PDMS, the copolymers synthesized from EO-PDMS with the same content of the soft segments had a higher degree of crystallinity, better thermal stability and a less hydrophobic surface. The obtained results showed that the synthesized polyurethanes had good thermal and surface properties, which could be further modified by changing the type or content of the soft segments.

Two series of polyurethane films based on hyperbranched polyester of the second pseudogeneration (Boltorn?), 4,4'-methylenediphenyl diisocyanate and two different siloxane prepolymers, ?,?-dihydroxy-(ethylene oxide-poly(dimethylsiloxane)-ethylene oxide) (EO-PDMS-EO) and ?,?-dihydroxypropyl-poly(dimethylsiloxane) (HP-PDMS), were prepared by two-step polymerization in solution. The influence of the type and content of soft segment on the morphology, thermomechanical and surface properties of the synthesized polyurethanes was studied by atomic force microscopy (AFM), small-angle X-ray scattering (SAXS), scanning electron microscopy (SEM), dynamic mechanical thermal analysis (DMTA) and water absorption measurements. It was found that these techniques confirmed existence of microphase separated morphology. Synthesized polyurethanes exhibited two glass transition temperatures and one second relaxation process. The results showed that polyurethanes based on HP-PDMS had higher surface roughness, better microphase separation and waterproof performances. Samples synthesized with lower PDMS content had less hydrophobic surface, but higher crosslinking density and better thermomechanical properties. (Projekat Ministarstva nauke Republike Srbije, br. 172062]

A series of novel thermoplastic urethane-siloxane copolymers (TPUSs) based on a α,ω-dihydroxy-[poly(ε-caprolactone)-b-poly(dimethylsiloxane)-b- -poly(ε-caprolactone)] (α,ω-dihydroxy-PCL-PDMS-PCL) triblock copolymer, 4,4'-methylenediphenyl diisocyanate (MDI) and 1,4-butanediol (BD) was synthesized. The effects of the content (9-63 mass %) of hard urethane segments and their degree of polymerization on the properties of the segmented TPUSs were investigated. The structure, composition and hard segment degree of polymerization of the hard segments were examined using 1H- and quantitative 13C-NMR spectroscopy. The degree of crystallinity of the synthesized copolymers was determined using wide-angle X-ray scattering (WAXS). The surface properties were evaluated by measuring the water contact angle and water absorption. In the series of the TPUSs, the average degree of polymerization of the hard segments was varied from 1.2 to 14.4 MDI-BD units. It was found that average values from 3.8 to 14.4 MDI-BD units were effective segment lengths for crystallization of hard segments, which resulted in an increase in the degree of microphase separation of the copolymers. Spherulite-like superstructures were observed in copolymer films by scanning electron microscopy (SEM), which are believed to arise from the crystallization of the hard segments and/or PCL segments, depending on the content of the hard segments. The surface of the copolymers became more hydrophobic with increasing weight fraction of PDMS. The synthesized copolymers based on a PCL-PDMS-PCL segment showed good thermal stability, which increased with increasing content of soft PDMS segments, as was confirmed by the value of the starting temperature of thermal degradation. U ovom radu prikazana je struktura i neka svojstva serije novih termoplastičnih uretan-siloksanskih kopolimera (TPUSs) na bazi α,ω-dihidroksi-[poli(ε-kaprolakton)-b-poli(dimetilsiloksan)-b-poli(ε-kaprolakton)] triblok kopolimera (α,ω-dihidroksi-PCL-PDMS-PCL), 4,4'-metilendifenildiizocijanata (MDI) i 1,4-butandiola (BD). Ispitan je uticaj sadržaja uretanskog tvrdog segmenta (9-63 mas. %) i njegove dužine, tj. stepena polimerizacije, izražene preko broja MDI-BD ostataka, na svojstva segmentiranih TPUSs. Struktura, sastav i stepen polimerizacije tvrdog segmenta su ispitani pomoću 1H- i kvantitativne 13C-NMR spektroskopije. Stepen kristaliničnosti kopolimera je određen metodom difrakcije X-zraka na velikim uglovima (WAXS). Površinska svojstva kopolimera su ispitana određivanjem kontaktnih uglova sa vodom i merenjem apsorpcije vode. U seriji kopolimera dužina tvrdog segmenta izražena preko broja ponavljajućih MDI-BD jedinica je varirana od 1,2 do 14,4. Utvrđeno je da tvrdi segmenti sa 3,8 do 14,4 ponavljajućih MDI-BD jedinica efikasno kristališu, što je rezultovalo u povećanju stepena mikrofazne separacije kopolimera. SEM analiza je pokazala prisustvo sferulitne strukture u kopolimernim filmovima, koja najverovatnije potiče od kristalizacije tvrdih i/ili PCL segmenata, zavisno od sadržaja tvrdih segmenata. Hidrofobnost površine kopolimera je rasla sa povećanjem masenog udela PDMS-a u odgovarajućem uzorku. Sintetisani poliuretani na bazi PCL-PDMS-PCL pokazuju povećanje termičke stabilnosti sa povećanjem sadržaja mekih PDMS segmenata, što je potvrđeno porastom početne temperature degradacije, određene TG analizom.