Influence of interchange reactions on the miscibility of polyesterurethanes/polycarbonate binary blends

A series of thermoplastic polyurethane elastomers (TPUs) with various hard-segment contents was prepared using 4,4′-diphenylmethane diisocyanate and 1,4-butanediol as the hard segment and poly(ethylene adipate)diol or poly(butylene adipate)diol, whose number-average molecular weight is 2000, as the soft segment. The miscibility of TPU/polycarbonate (PC) blends observed by differential scanning calorimetry was enhanced by the interchange reaction at high temperature. Both hard and soft segments were suggested to be involved in the interchange reaction with PC. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 64: 2363–2369, 1997     

Thermoplastic urethane elastomers. I. Effects of soft-segment variations

A series of thermoplastic urethane elastomers with soft segments of varying sequence length was prepared and their dynamic mechanical properties were characterized over a wide temperature range. The polymers were prepared using various molecular weight polycaprolactone diols as the soft segment and 4,4′-diphenylmethane diisocyanate and 1,4-butanediol as the hard segment. The urethane elastomer exhibited soft-segment crystallization when a polycaprolactone diol greater than 3000 M?_n was used. The glass transition temperature of these materials progressively shifted to lower temperatures as the chain length of the soft segment was increased. This dependence was interpreted in terms of a molecular weight relationship similar to that associated with amorphous homopolymers. The dynamic mechanical properties of these polyurethanes appear to be consistent with responses observed for compatible copolymers.     

Influence of soft segment content and chain length on the physical properties of poly(ether ester) elastomers and fabrication of honeycomb pattern and electrospun fiber

Different series of poly(ether ester) (PEE) thermoplastic elastomers were synthesized using dimethyl-2,6-naphthalene dicarboxylate as hard segment, 1,4-butanediol as the chain extender, and three different soft segments of different molecular weights (MW), namely polycaprolactone diol (MW: 530 and 2000), poly(tetramethylene ether glycol) (MW: 1000 and 1800), and polycaprolactone-block-polytetrahydrofuran-block-polycaprolactone (MW: 2000). The composition of soft segment was changed from 30% to 50% with respect to the hard segment. The characteristic studies were focused to analyze the influence of the concentration and length of the soft segment content. In each series, 50:50 compositions of the hard and soft segments were found to show the best mechanical properties. In addition the physical properties of the elastomer were very sensitive to the type of soft segment. The elastomers prepared in this study were systematically characterized using various spectroscopic studies and thermal and mechanical analyses. As a means of discovering the feasibility of PEE elastomers as new functional materials honeycomb patterns and nanofibers have been fabricated by applying breath figures method and electrospinning, respectively, yielding uniform honeycomb structures and nanofibers of their diameter ranging from about 100 to 800 nm depending on the type of elastomer and the electrical potential employed .     

Thermoplastic polyurethane elastomers based on polycarbonate diols with different soft segment molecular weight and chemical structure: Mechanical and thermal properties

A series of thermoplastic polyurethane elastomers based on polycarbonate diol, 4,4′‐diphenylmethane diisocyanate and 1,4‐butanediol was synthesized in bulk by two‐step polymerization varying polycarbonate diol soft segment molecular weight and chemical structure, and also hard segment content, and their effects on the thermal and mechanical properties were investigated. Dynamic mechanical analysis termogravimetric analysis, differential scanning calorimetry, Fourier transform infrared‐attenuated total reflection spectroscopy and mechanical tests were employed to characterize the polyurethanes. Thermal and mechanical properties are discussed from the viewpoint of microphase domain separation of hard and soft segments. On one hand, an increase in soft segment length, and on the other hand an increase in the hard segment content, i.e., hard segment molecular weight, was accompanied by an increase in the microphase separation degree, hard domain order and crystallinity, and stiffness. In phase separated systems more developed reinforcing hard domain structure is observed. These hard segment structures, in addition to the elastic nature of soft segment, provide enough physical crosslink sites to have elastomeric behavior. POLYM. ENG. SCI., 2008. © 2007 Society of Plastics Engineers     

IPDI／PEPA型热塑性聚氨酯的合成及表征

以异佛尔酮二异氰酸酯(IPDI)、聚己二酸乙二醇丙二醇酯二醇(PEPA)和1,4-丁二醇(BDO)为原料,用熔融预聚合两步法,后聚合温度60-90℃,合成硬段含量为50％的IPDI／PEPA型热塑性聚氨酯。采用凝胶渗透色谱仪测试其数均相对分子质量为78 650,重均相对分子质量为125 446,相对分子质量分布为1．59。红外光谱分析表明聚合较为完全,聚合物不存在支链结构,为热塑性材料。DSC分析表明聚合物软段和硬段的玻璃化转变温度分别为-34℃和48℃,透射电镜照片进一步说明该材料存在一定的相分离。     

PPDI型热塑性聚氨酯弹性体的制备与性能研究

以对苯二异氰酸酯(PPDI)、低聚物二元醇和1,4-丁二醇为原料合成PPDI型热塑性聚氨酯弹性体(TPU),考察了软段种类和相对分子质量、硬段含量、R值(n(NCO)∶n(OH))等对其性能的影响,并与MDI型TPU的动态力学性能作比较.结果表明,聚ε-己内酯(PCL)体系TPU具有良好的性能,硬段含量和R值的提高均可...     

New thermoplastic segmented polyurethanes with hard segments derived from 4,4′‐diphenylmethane diisocyanate and methylenebis(1,4‐phenylenemethylenethio)dialcanols

New thermoplastic poly(ether–urethane)s and poly(carbonate–urethane)s were synthesized by a one‐step melt polymerization from poly(oxytetramethylene) diol (PTMO) and poly(hexane‐1,6‐diyl carbonate) diol (PHCD) as soft segments, 4,4′‐diphenylmethane diisocyanate, and 2,2′‐[methylenebis(1,4‐phenylenemethylenethio)]diethanol, 3,3′‐[methylenebis(1,4‐phenylenemethylenethio)]dipropan‐1‐ol or 6,6′‐[methylenebis(1,4‐phenylenemethylenethio)]dihexan‐1‐ol as unconventional chain extenders. The effects of the kind and amount of the polymer diol and chain extender used on the structure and properties of the polymers were studied. The polymers were examined by Fourier transform infrared (FTIR) spectroscopy, X‐ray diffraction analysis, atomic force microscopy, differential scanning calorimetry, thermogravimetric analysis (TGA), TGA coupled with FTIR spectroscopy, and Shore hardness and tensile testing. The obtained high‐molecular‐weight polymers showed elastomeric or plastic properties. Generally, the PTMO‐based polymers exhibited significantly lower glass‐transition temperatures (up to ?48.1 vs ?1.4°C), a higher degree of microphase separation, and ordering in hard‐segment domains in comparison with the corresponding PHCD‐based ones. Moreover, it was observed that the polymers with the PTMO soft segments showed poorer tensile strengths (up to 36.5 vs 59.6 MPa) but higher elongations at break. All of the polymers exhibited a relatively good thermal stability. Their temperatures of 1% mass loss were in the range 270–320°C. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

可生物降解热塑性聚氨酯弹性体的合成与性能研究

以中等分子量聚碳酸亚丙酯多元醇作为软段,并与过量的甲苯二异氰酸酯生成预聚物,用1,4–丁二醇进行扩链制备热塑性聚氨酯弹性体,整个反应体系保持—NCO/—OH=1.2。研究了硬段含量变化对材料结构与性能的影响。结果表明,所得弹性体的拉伸性能随着硬段含量的增加而增大,这是微相分离变化的结果;弹性体具有较好的生物降解性,可用于潮湿恶劣环境。     

Contribution of soft segment entanglement on the tensile properties of silicone–urea copolymers with low hard segment contents

Novel, segmented thermoplastic silicone–urea (TPSU) copolymers based on rather high molecular weight aminopropyl terminated polydimethylsiloxane (PDMS) soft segments (<M_n> 10,800 and 31,500 g/mol), a cycloaliphatic diisocyanate (HMDI) and various diamine chain extenders were synthesized. Copolymers with very low urea hard segment contents of 1.43–14.4% by weight were prepared. In spite of very low hard segment contents, solution cast films showed very good microphase separation and displayed reasonable mechanical properties. Tensile strengths of TPSU copolymers showed a linear dependence on their urea hard segment contents, regardless of the structure of the diamine chain extender used. The modulus of silicone–urea copolymers is dependent on the urea concentration, but not on the extender type or PDMS molecular weight. When silicone–urea copolymers with identical urea hard segment contents were compared, copolymers based on PDMS-31,500 showed higher elongation at break values and ultimate tensile strengths than those based on PDMS-10,800. Since the critical entanglement molecular weight (M_e) of PDMS is about 24,500 g/mol, these results suggest there is a significant contribution from soft segment chain entanglement effects in the PDMS-31,500 system regarding the tensile properties and failure mechanisms of the silicone–urea copolymers.     

Synthesis and characterization of biodegradable poly(ester‐urethanes) based on bacterial poly(R‐3‐hydroxybutyrate)

A series of poly(R‐3‐hydroxybutyrate)/poly(ε‐caprolactone)/1,6‐hexamethylene diisocyanate‐segmented poly(ester‐urethanes), having different compositions and different block lengths, were synthesized by one‐step solution polymerization. The molecular weight of poly(R‐3‐hydroxybutyrate)‐diol, PHB‐diol, hard segments was in the range of 2100–4400 and poly(ε‐caprolactone)‐diol, PCL‐diol, soft segments in the range of 1080–5800. The materials obtained were investigated by using differential scanning calorimetry, wide angle X‐ray diffraction and mechanical measurements. All poly(ester‐urethanes) investigated were semicrystalline with T_m varying within 126–148°C. DSC results showed that T_g are shifted to higher temperature with increasing content of PHB hard segments and decreasing molecular weight of PCL soft segments. This indicates partial compatibility of the two phases. In poly(ester‐urethanes) made from PCL soft segments of molecular weight (M_n ≥ 2200), a PCL crystalline phase, in addition to the PHB crystalline phase, was observed. As for the mechanical tensile properties of poly(ester‐urethane) cast films, it was found that the ultimate strength and the elongation at the breakpoint decrease with increasing PHB hard segment content. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 703–718, 2002     

Synthesis and properties of polyester-based TPUs prepared by solution polymerisation

Abstract

The polyester based thermoplastic polyurethane elastomers (TPUs) were prepared by one-step solution polymerisation to obtain a product with completely linear molecular structure and with excellent solubility. The synthesis technique was determined by investigation of the influence of solvent and catalyst on the viscosity of the reaction system and the mechanical properties of the resulting product. The effects of the molecular structure on the mechanical, damping and crystallisation properties of TPUs were studied in terms of the type of diisocyanate, mass fraction of hard segment, type and molecular weight of soft segment, and type of chain extender. The structure and morphology of TPUs were characterised by FTIR, GPC and AFM analysis. There was microphase separation in the molecules of TPU, in which the hard-segment phase was dispersed in the soft-segment phase.     

Evaluation of nanoparticulate fillers for development of shape memory polyurethane nanocomposites

The effects of nano-size fillers on shape memory (SM) properties of polyurethane (PU) nanocomposites were evaluated. Organoclay, carbon nanofiber (CNF), silicon carbide (SiC), and carbon black (CB) were selected as the fillers in an attempt to reinforce the PU and to obtain significantly increased shape recovery stress. The shape memory PU was synthesized from diphenylmethane diisocyanate, 1,4-butanediol, and poly(caprolactone)diol, the latter with a molecular weight of 4000 g/mol. The composites were prepared by melt mixing of extended chain PU with the fillers. The shape memory behavior was triggered by heating the specimen above the melting point of the crystalline soft segment. Our results indicate that exfoliated organoclay significantly augments SM performance, while CNF and SiC diminish it by interfering with crystallization of the soft segment. CB destroys the shape memory properties beyond a certain loading. Better SM performance with organoclay can be attributed to mechanical reinforcement without much interference with the soft segment crystallinity. The reduction of soft segment crystallinity in the presence of CNF and SiC was analyzed. It was found that the extent of crystallinity, as well as the crystallization temperature, was significantly reduced in the presence of these fillers.     

Structural characterization and mass transfer properties of polyurethane block copolymer: influence of mixed soft segment block and crystal melting temperature

An attempt has been made to investigate the influence of mixed soft segment on structure and mass transfer properties of segmented polyurethane (SPU). For this purpose polyurethane block copolymer containing soft segment such as polycaprolactone glycol (number‐average molecular weight 3000, PCL 3000), PCL 3000–polypropylene glycol (number‐average molecular weight 3000, PPG 3000), PCL 3000–polytetramethylene glycol (number‐average molecular weight 2900, PTMG 2900), PPG 3000–PTMG 2900, were synthesized using a two‐step or three‐step synthesis process. All the SPUs were modified with the hydrophilic segment, i.e. diol‐terminated poly(ethylene oxide) (number‐average molecular weight 3400, PEG 3400). Fourier‐transform infrared, wide‐angle X‐ray diffraction, differential scanning calorimetry, and dynamic mechanical thermal analysis were used to characterize the polyurethanes. The mass transfer properties were measured by equilibrium sorption and water vapor permeability measurements. Mixed blocks loosen the inter‐chain interaction due to phase mixing which decreases the crystallization of the soft segment in the resulting SPU. The crystallinity of mixed polyol block SPU increases when both polyols are crystallizable in the pure state. Highest loss tan δ value was observed for the sample containing PTMG 2900–PPG 3000 mixed soft segment due to their flexible and phase mixed structure which increases the chain mobility; this sample performed best among all four SPUs in equilibrium water sorption as well as water vapor permeability owing to their loose and nearly amorphous structure. Soft segment crystal melting further enhances the water vapor permeability significantly, which would make the membrane suitable for breathable textiles, packaging and medical applications. Copyright © 2006 Society of Chemical Industry     

Synthesis and characterization of radiation curable polyurethanes containing pendant acrylate groups

A series of radiation sensitive and relatively high molecular weight poly(tetramethylene adipate) polyurethanes containing pendant acryfate functionality was synthesized. These radiation curable materials possess good mechanical properties and behave like common thermoplastic elastomers prior to chemical crosslinking which further enhances their strength and insolublizes them. Both the precursor and the cured materials were characterized by stress-strain, differential scanning calorimetry. and dynamic mechanical testing. It was found that the poly-(tetramethylene adipate) soft segments with molecular weight of 2000 or higher were crystallizable in the cross-linked network. The soft segment molecular weight and the diisocyanate type were found to be important in determining the tensile and thermal properties of these male-rials. The crosslinking process was found to depress crystallization of the soft segments and to improve tensile properties. Increasing the soft segment molecular weight resulted in an Increased elongation al break bill a decreased ultimate stress for both the precursor linear polymers and the crosslinked materials.     

Syntheses and characterization of novel biostable polyisobutylene based thermoplastic polyurethanes

The synthesis of polyisobutylene (PIB) based thermoplastic polyurethanes (TPU) with enhanced mechanical properties have been accomplished using poly(tetramethylene oxide) (PTMO) as a compatibilizer. PIB TPUs with Shore 60-100 A hardness were prepared by employing PIB diols (hydroxyallyl telechelic PIBs) for the soft segment and 4,4′-methylenebis(phenylisocyanate) (MDI) and 1,4-butanediol (BDO) for the hard segment. The TPUs exhibited number average molecular weight (M_n) in the range of 83,000-110,000 g/mol with polydispersity indices (PDIs) = 1.8-3.1. These TPUs, however, were inferior compared to commercial TPUs such as Pellethane™ (Dow Chemical Co.) as they exhibited low tensile strength (6-15 MPa) and/or ultimate elongation (30-400%). Processing of the harder compositions was also difficult and some could not be compression molded into flat sheets for testing. Differential Scanning Calorimetry (DSC) showed the presence of high melting (≥200 °C) crystalline hard segments suggesting longer - MDI-BDO - sequences than expected based on the stoichiometry. Easily processable TPUs with excellent mechanical properties (tensile strength up to 40 MPa, ultimate elongation up to 740%) were obtained by incorporating PTMO in the soft segment. Examination of PIB-PTMO TPUs with varying hard: soft compositions (20:80, 35:65 and 40:60 wt:wt) and Shore hardness (60 A, 80 A and 95 A) indicated that substituting 10-30 wt% of PIB diol with PTMO diol is sufficient to reach mechanical properties similar to Pellethanes.     

Fluorescently labeled degradable thermoplastic polyurethane elastomers: Visual evaluation for the degradation behavior

Thermoplastic polyurethane elastomers (TPU) were synthesized with isophorone diisocyanate (IPDI) as the rigid segment, poly(lactic‐co‐glycolic acid) (PLGA‐PEG‐PLGA) diol as soft segment, and 1,4‐butanediol (BDO) as the chain extender. During the chain extension process, three kinds of fluorescent monomers 4‐(2‐hydroxyethylamino)?1,8‐naphthoyl‐(2‐hydroxyethyl)imide (HNHI), 1,5‐dihydroxy naphthalene (DHN), and dicoumarin (DIC) were introduced to get the fluorescently labeled degradable TPUs. The structure and degradation properties of the TPUs were characterized in detail. The results showed that there was no significant effect found on average molecular weight, mechanical properties, and glass transition temperature of polyurethane by introducing 0.001% (wt) weight percent of fluorescence monomers. The degradation behavior of fluorescent‐tagged thermoplastic elastomer has been characterized with fluorescence microscopy. Results showed that polyurethane elastomers, in which fluorescence monomers especially HNHI were introduced by chemical reaction, had more homogeneous and stable fluorescence intensity than that with fluorescence monomers introduced by post blending. This work also provides a promising visual characterization approach to monitor degradation behavior of degradable TPUs for tissue engineering applications or drug delivery system. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42519.     

Structure‐property relationship of L‐tyrosine‐based polyurethanes for biomaterial applications

The structure‐property relationship of L ‐tyrosine‐based polyurethanes was demonstrated by using different polyols and diisocyanates. L ‐tyrosine‐based chain extender, desaminotyrosyl tyrosine hexyl ester (DTH), was used to synthesize a series of polyurethanes. Polyethylene glycol (PEG) or poly caprolactone diol (PCL) was used as the soft segment and hexamethylene diisocyanate (HDI) or dicyclohexylmethane 4,4′‐diisocyanate (HMDI) was used with DTH as the hard segment. The polyurethanes were characterized to investigate the effect of structure on different polyurethane properties. From FTIR and DSC, these polyurethanes exhibit a wide range of morphology from phase‐mixed to phase‐separated structure. The decreasing molecular weight of the PEG soft segment leads to relatively more phase mixed morphology whereas for PCL‐based polyurethanes the extent of phase mixing is less with decreasing PCL molecular weight. Results show that PCL‐based polyurethanes are mechanically stronger than PEG‐based polyurethanes but PCL‐based polyurethanes degrade slower and absorb less water compared with PEG‐based polyurethanes. The HMDI‐based polyurethanes are less crystalline and comparatively more hydrophobic than HDI‐based polyurethanes. The characterization results show that the polyurethane properties are directly related to the structure and can be varied easily for a different set of properties that are pertinent for biomaterial applications. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Thermal and dynamic mechanical properties of polyurethaneureas

Measurements were made of the thermal and dynamic mechanical properties of 22 polyurethaneureas of varying diol molecular weight, type of aromatic chain extender, diol molecular weight distribution, and chain extender stoichiometry. The dynamic mechanical data, obtained as a function of temperature and frequency (in the kHz region), were used to construct master curves of shear modulus and loss factor over a wide range of reduced frequencies. Based on these master curves, interpreted in conjunction with the thermal analysis results, it was found that: Soft segment crystallization occurs at the higher diol molecular weights, dynamic mechanical properties are well correlated with the soft segment glass transition, diol molecular weight influences dynamic mechanical properties by affecting the degree of phase separation and hence glass transition temperature, and neither diol molecular weight distribution nor chain extender stoichiometry have a significant effect, in the ranges studied, on transition temperatures or dynamic mechanical properties.     

Synthesis and characterization of a novel poly(ester‐urethane) containing short lactate sequences and PEG moieties

A novel poly(ester‐urethane) with tailor‐made structure was prepared by using lactic acid (LA) as starting material through a combination of two facile common reactions. First, a diol was prepared via the esterification between LA and poly(ethylene glycol) (PEG) with low molecular weight. Subsequently, the poly(ester‐urethane) was synthesized through the addition polymerization of the LA‐based diol and toluene 2,4‐diisocyanate with 1,4‐butanediol as chain extender. The structure, morphology, and properties of intermediate and the poly(ester‐urethane) were analyzed with Fourier transform infrared spectroscopy, proton nuclear magnetic resonance, gel permeation chromatography (GPC), X‐ray diffraction, differential scanning calorimetry, polarizing optical microscopy, and thermogravimetric analysis. The results indicated that the intermediate was a diol of conjugating quite short lactate sequences with PEG oligomer, and the structure of the poly(ester‐urethane) was as expected. The thermal transition, thermal decomposition temperature, and crystallinity of the polymer samples depended on the molecular size of PEG. In vitro degradation property of the poly(ester‐urethane) also relied on the molecular weight of PEG. The weight loss percentages varied from 11 to 36% after 12‐days immersing in phosphate‐buffer saline at 37°C. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Thermoplastic polyurethanes from renewable resources: effect of soft segment chemical structure and molecular weight on morphology and final properties

The effect of soft segment molecular weight and chemical structure on the morphology and final properties of segmented thermoplastic polyurethanes containing various hard segment contents has been investigated from the viewpoint of the degree of microphase separation. Vegetable oil‐based polyesters and corn sugar‐based chain extender have been used as renewable resources. The synthesis has been carried out in bulk without catalyst using a two‐step polymerization process. Physicochemical, thermal and mechanical properties, and also morphology, have been studied using Fourier transform infrared spectroscopy, differential scanning calorimetry, dynamic mechanical analysis, atomic force microscopy, X‐ray diffraction and mechanical testing. Chemical structure and molecular weight of polyols strongly affect the properties of the synthesized segmented thermoplastic polyurethanes. An increase in soft segment molecular weight leads to an increase of the degree of soft segment crystallinity and microphase separation, thus giving enhanced mechanical properties and higher thermal stability. Copyright © 2012 Society of Chemical Industry