Effect of thermal treatment on the structure and the biomedical properties of polyetherurethane film containing dipeptides of L-serine

Prepolymers which were obtained by the reaction of 4,4'-diphenylmethane diisocyanate (MDI) with polytetramethylene glycol (PTMG) and polyethylene glycol (PEG) were chain-extended by the reaction with the linear or cyclic dipeptide of L-serine to yield a novel polyetherurethane containing dipeptide segments. In these polyetherurethanes, spherulites, fibrous structures, and needle-like crystals were formed according to the conditions used. Polyetherurethanes containing the cyclic dipeptide segments exhibit a thermally stable conformation when cast from solution at room temperature. On the other hand, polyetherurethanes containing the linear dipeptide segments exhibit a thermally stable conformation only after annealing. The properties of polyetherurethanes were elucidated by investigation of their morphology by electron microscopy, surface composition by electron spectroscopy for chemical analysis, hydrogen-bonding properties by i.r. spectroscopy, and degree of crystallinity by differential scanning calorimetry. The antithrombogenicity of polyetherurethane films containing linear dipeptides was increased by annealing. Their oxygen permeability was controlled by the linear or cyclic dipeptide segments or by annealing. The urea permeability of hydrophilic polyetherurethane film was easily controlled by the casting conditions and molecular weight of the polyether component. The relationship between the morphology and biomedical properties of these polyetherurethane films is discussed.     

医用含离子嵌段聚醚氨酯的合成、精细结构与性能的研究

合成了新的扩链剂8-二(2-羟乙基)胺基-1-辛磺酸钠和新的大分子单体——含烷基磺酸钠的端烃基丙二酸二聚醚酯,并由此合成了一系列精细结构明确的、分别在硬段或软段上悬挂有正辛基磺酸钠侧链的阴离子型聚醚氨酯,通过FTIR、粘弹谱及透射电镜的研究、血液相容性的评价,阐述了精细结构、分子中的相互作用、微相分离和性能的关系。     

Synthesis and nonthrombogenicity of fluoroalkyl polyetherurethanes

New polyetherurethanes carrying fluoroalkyl substituents in the side chains were synthesized from N,N-di(hydroxyethyl)heptadecafluorooctyl-sulfonamide (a chain extender), 4,4'-disocyanatodiphenylmethane, and poly(tetramethylene glycol). Various kinds of polyetherurethanes having different tensile properties were prepared by changing the content of fluoroalkyl chain extender or the molecular weight of poly(tetramethylene glycol). The surface of a film made from the fluoroalkyl polyetherurethane was strongly water-repulsive. The in vitro thrombus formation on the fluoroalkyl polyetherurethanes was reduced by increasing the content of chain extender for the same molecular weight of poly(tetramethylene glycol). Protein adsorption, platelet adhesion, and platelet activation on the fluoroalkyl polyetherurethanes were also investigated.     

Thermal and mechanical properties of poly(ether urethane) modified by copolyamide segments

Thermoplastic polyurethane elastomers (TPUs) from diol-terminated poly(tetramethylene glycol) (PTMG), 1,4-butanediol (BD), and 4,4′-methylenediphenyl diisocyanate (MDI) were modified by copolymerizing diamine-terminated nylon-6/6,6 copolyamide oligomer. In TPUs modified by the copolyamide segment, the hard segment showed decreased crystallinity and melting point depression as the content of copolyamide segment was increased, which is probably due to mixing and strong interaction between copolyamide and hard segments. As some of the hard segments were replaced by copolyamide segments, the crystallinity of PTMG segments increased. This suggests that the copolyamide-PTMG segment interaction is weaker than the interaction between hard and PTMG segments. Tensile properties of TPUs are discussed based on the thermal properties.     

以PEG和PTMG为混合软段的聚氨酯的合成、表征及血液相容性研究

我们用4,4'-二苯基甲烷二异氰酸酯(MDI),扩链剂1,4-丁二醇(BDO)为硬段,聚乙二醇(PEG)与聚四氢呋喃醚二元醇(PTMG)为混合软段,在不同PEG、PTMG配比下,采用二步法,合成了一系列聚醚聚氨酯(PU)。对所合成的材料进行了傅立叶变换红外光谱、力学性能测试、水接触角、吸水率、溶血试验和静态血小板粘附试验。结果表明,本研究成功合成了机械强度高、亲水性好、血液相容性良好的新型混合软段的聚氨酯,是一种有着巨大应用前景的生物医用材料。     

PDMS-based polyurethanes with MPEG grafts: synthesis, characterization and platelet adhesion study.

Polyurethane (PU), based on poly(dimethyl siloxane) (PDMS) as a soft segment, with monomethoxy poly(ethylene glycol) (MPEG) grafted onto it, was synthesized as a new polymeric biomaterial for coating PDMS-based biomedical devices. Two different chain extenders, ethylene glycol (EG) and diethyl bis(hydroxymethyl) malonate (DBM), were used for the synthesis of PDMS-based PUs and then MPEG was grafted onto them by allophanate and esterification reactions, respectively. Their molecular structures were confirmed qualitatively and quantitatively using FT-IR and 1H-NMR measurements. PDMS-based PU was more hydrophobic than Pellethane, which is a commercial biomedical-grade poly(ether urethane), due to the PDMS-rich phase at the polymeric surface. However, the incorporation of MPEG in PDMS-based PU induced an increase in hydrophilicity. Analyses of their morphology using dynamic mechanical analysis and differential scanning calorimetry showed that the degree of phase separation increased with the content of hard segments. It also showed that MPEG is compatible with a hard segment consisting of 4,4'-diphenylmethane diisocyanate (MDI) and DBM, while being incompatible with one consisting of MDI and EG. Platelet adhesions with PDMS-based PUs were significantly reduced when compared with Pellethane. It was also observed from a platelet adhesion experiment that the incorportion of MPEG further reduced platelet adhesion. PDMS-based PUs with MPEG grafts, which have few hard segments and a distinct PEG phase, exhibited the least platelet adhesion among the polymer samples tested.     

Influence of surface morphology and chemistry on the enzyme catalyzed biodegradation of polycarbonate-urethanes

Polycarbonate based polyurethanes were synthesized with varying hard segment content as well as hard segment chemistry based on three different diisocyanates,1,6-hexane diisocyanate (HDI), 4.4'-methylene bisphenyl diisocyanate (MDI) and 4,4-methylene biscyclohexyl diisocyanate (HMDI). The surface chemistry and morphology were characterized using X-ray photoelectron spectroscopy (XPS) and atomic force microscopy (AFM). The polymers were incubated with cholesterol esterase (CE) in a phosphate buffer solution at 37 degrees C over 10 weeks. XPS results showed that the surface chemistry changed as the size and chemistry of the hard segment varied within the materials. AFM images exhibited distinctive surface morphologies for all polymers, and this was particularly apparent with changes in the hard segment chemistry. The results showed that the surface of HDI polymers consisted of relatively stiff rod-like structures, which corresponded to the soft segment domains. Polymers with a higher HDI content exhibited a dense top layer containing a relatively higher hard segment component, covering the sub-surface matrix of rod like structures. The MDI based polyurethane had large aggregates on its top surface, which corresponded to the aggregation of harder components. The HMDI based polycarbonate-urethane presented a relatively homogeneous surface where no phase separation could be detected. The relative differences in hard and soft segment content in their surface structure was supported by XPS findings. The analysis of the biodegradation results, concluded that enzyme catalyzed biodegradation within these materials was initiated in amorphous soft segment regions located in the region of the interface between hard and soft segments. A higher hard segment content at the surface contributed significantly to an increase in biostability. The findings provided an enhanced understanding for the role of surface molecular structure in the enzyme catalyzed biodegradation of polyurethanes.     

Potassium ion-based polyurethane anionomers: effects of emulsification on structure and physical properties

A polyurethane was prepared using poly(oxytetramethylene) as soft segments, 4,4′-methylenedi(phenyl isocyanate) as diisocyanate and 2,2-bis(hydroxymethyl)propionic acid as chain extender, and then ionized with potassium hydroxide to yield the potassium ion-based PU anionomer. The resulting PU anionomer solution in ethyl methyl ketone was emulsified by continuous addition of water. In the unionized film, soft segment crystallites are not present. Ionization creates soft segment crystallites and produces increased cohesion in the hard domains, which leads to an increase in both tensile strength and elongation at break. Emulsification of the PU ionomer solution leads to slightly increased phase separation. During the emulsification, conductivity and viscosity variations show that water is first adsorbed on the surface of the hard-segment microionic lattices and then enters into the disordered hard domains. The morphology of the unionized film shows that the hard domains are dispersed in the soft domains and tha the size of hard domains increases greatly after the ionization. After dispersion, the hard segments originally distributed in the dispersed phase undergo phase inversion and adopt a morphology of interwoven soft and hard domains. Compared with other PU anionomers, the present system is branched rather than linear, as reflected in the good mechanical properties of the present system.     

Synthesis and antithrombogenicity of anionic polyurethanes and heparin-bound polyurethanes

Two kinds of novel antithrombogenic polyurethane materials were synthesized. One of them is a polyetherurethane with anionic charges on the film surface, and the other is a polyetherurethaneurea to which heparin was covalently bound. The mechanism of their antithrombogenicity was investigated. The anionic polyetherurethane selectively adsorbed albumin, did not cause a conformational change of plasma proteins adsorbed, and suppressed the adherence and deformation of platelets but did not deactivate the blood-clotting system, thus leading to a moderate antithrombogenicity. The heparin-bound polyetherurethaneurea was not favorable for the selective adsorption of albumin, caused the denaturation of plasma proteins adsorbed, and induced the adherence and deformation of platelets but deactivated the blood-clotting system, leading to excellent antithrombogenicity. For the investigation of blood-material interaction, the importance of a multiparameter estimation of the activation of platelets and the blood-clotting system was indicated.     

Poly(ε‐caprolactone) and Pluronic Diol‐Containing Segmented Polyurethanes for Shape Memory Performance

A series of novel segmented linear and crosslinked polyurethanes (PUs) are synthesized from poly(ε‐caprolactone) (PCL) (25 kg mol^?1), methylene diphenyl diisocyanate (MDI), and various polyether diols (Pluronic (PLU) and polyethylene glycol (PEG)). The basic structures of the highly deformable PUs are PLU/PEG–MDI–PCL–MDI–PLU/PEG and PLU–MDI–PCL–MDI–PLU, respectively. The linear and crosslinked PUs are characterized. Changes in the tensile behavior are attributed to the effects of compositional variables and alterations in the crosslink density. Additional information on the morphology of the segmented PUs is deduced from differential scanning calorimetry, as well as transmission and scanning electron microscopy investigations. Both the linear and the crosslinked PUs exhibit a broad rubbery plateau above the melting temperature of the crystalline PCL phase, which is highly beneficial for shape memory function. This work highlights that the chemical build‐up of soft segments containing high‐molecular‐weight crystallizable chain units is a proper tool to tailor the morphology and mechanical properties of PUs, and thus also their shape memory properties.

     

Physicochemical and Biological Properties of Nano-hydroxyapatite-Reinforced Aliphatic Polyurethanes Membranes

Polymer nano-composite membranes, based on aliphatic biodegradable polyurethane (PU) elastomers and nano-hydroxyapatite (n-HA), were prepared by solvent casting and freeze-drying. The PU matrix was synthesized from 4,4′-dicyclohexylmethane diisocyanate (H₁₂ MDI), poly(ethylene glycol) (PEG), castor oil (CO) and 1,4-butandiol (BDO). The n-HA/PU membranes were characterized by SEM, XRD, IR, TG, mechanical test and in vitro biocompatibility. The results revealed that incorporation of 30 wt% n-HA into the PU matrix increased the tensile strength nearly by 186% and the elongation-at-break by 107% compared to pure PU. The addition of n-HA had the slight positive effect on the thermal stability of PU. Cell culture and MTT assays showed that the incorporation of n-HA into the PU matrix provided a favourable environment for initial cell adhesion, maintained cell viability and cell proliferation. These results suggested that the n-HA/PU composite membrane might be a prospective biodegradable guided bone regeneration (GBR) membrane for future applications.     

Influence of surface morphology and chemistry on the enzyme catalyzed biodegradation of polycarbonate-urethanes

Abstract —Polycarbonate based polyurethanes were synthesized with varying hard segment content as well as hard segment chemistry based on three different diisocyanates,1,6-hexane diisocyanate (HDI), 4,4′-methylene bisphenyl diisocyanate (MDI) and 4,4-methylene biscyclohexyl diisocyanate (HMDI). The surface chemistry and morphology were characterized using X-ray photoelectron spectroscopy (XPS) and atomic force microscopy (AFM). The polymers were incubated with cholesterol esterase (CE) in a phosphate buffer solution at 37°C over 10 weeks. XPS results showed that the surface chemistry changed as the size and chemistry of the hard segment varied within the materials. AFM images exhibited distinctive surface morphologies for all polymers, and this was particularly apparent with changes in the hard segment chemistry. The results showed that the surface of HDI polymers consisted of relatively stiff rod-like structures, which corresponded to the soft segment domains. Polymers with a higher HDI content exhibited a dense top layer containing a relatively higher hard segment component, covering the sub-surface matrix of rod like structures. The MDI based polyurethane had large aggregates on its top surface, which corresponded to the aggregation of harder components. The HMDI based polycarbonate-urethane presented a relatively homogeneous surface where no phase separation could be detected. The relative differences in hard and soft segment content in their surface structure was supported by XPS findings. The analysis of the biodegradation results, concluded that enzyme catalyzed biodegradation within these materials was initiated in amorphous soft segment regions located in the region of the interface between hard and soft segments. A higher hard segment content at the surface contributed significantly to an increase in biostability. The findings provided an enhanced understanding for the role of surface molecular structure in the enzyme catalyzed biodegradation of polyurethanes.     

Synthesis, characterization, and platelet adhesion studies of novel aliphatic polyurethaneurea anionomers based on polydimethylsiloxane-polytetramethylene oxide soft segments

Two novel aliphatic polyurethaneurea anionomers were synthesized based on polydimethylsiloxane (PDMS)-polytetramethylene oxide (PTMO) soft segments. The hard segments consisted of either 4,4'-methylene dicyclohexyl diisocyanate (H12MDI), sulfonic acid-containing diol and 1,4-butandiol (BD) or H12MDI, carboxylic acid-containing diol and BD. The nonionic counterpart chain extended with BD was prepared. In addition, the base nonionic polyurethaneurea containing a pure PDMS soft segment, which is denote H-D-BD, was also studied for comparison. The effects of soft segment type and ion incorporation on the physical properties, surface properties, and plateled adhesion are discussed. The ionic polyurethaneureas exhibited poor phase separation, a smaller fraction of PTMO present at the surface, and a smaller contact angle. On the other hand, it also showed a larger fraction of PDMS present at the surface and a higher water absorption value than its nonionic counterpart. H-D-BD had more phase-separated structure, a larger fraction of PDMS present at the surface, and larger contact angle but lower water absorption value than the PTMO-containing polyurethaneureas. The in vitro platelet adhesion experiments indicated that the ionic groups, especially for carboxylate, and surface enrichment PDMS soft segment could effectively inhibit platelet adhesion.     

Synthesis and characterization of L-tyrosine based polyurethanes for biomaterial applications

The use of amino acid based polymers for biomaterial applications enhance biocompatibility and ensure biodegradability. Two polyurethanes based on L-tyrosine based diphenolic dipeptide, desaminotyrosyl tyrosine hexyl ester as chain extender are synthesized with polyethylene glycol (PEG) and polycaprolactone diol (PCL) as soft segment and hexamethylene diisocyanate as diisocyanate. The chemical structure and molecular characteristics of the polymers were studied by 1H NMR, FTIR, and gel permeation chromatography. Results of DSC and TGA analysis were used for examining the thermal behavior of the polyurethanes. In addition, DSC results were used to analyze the morphology of the polymers, which shows characteristic microphase behavior of the polyurethanes. The tensile properties of the polyurethanes are primarily controlled by the soft segment and are higher in PCL based polymers. Contact angle, water vapor permeation, release of model drug, and water absorption characteristics of the polymers were studied and analyzed in terms of structure of the polyurethanes. In vitro degradation studies show that PEG based polyurethane is more degradable than PCL based polyurethane. The difference in the soft segment structure offers significant variation in the properties of the polyurethanes. These polyurethanes show the potential for use in a variety of biomaterial applications including tissue engineering.     

Biodegradable polyurethanes for implants. II. In vitro degradation and calcification of materials from poly(epsilon-caprolactone)-poly(ethylene oxide) diols and various chain extenders

Linear, biodegradable, aliphatic polyurethanes with various degrees of hydrophilicity were synthesized in bulk at 50-100 degrees C. The ratios between the hydrophilic and hydrophobic segments were 0:100, 30:70, 40:60, 50:50, and 70:30, respectively. The hydrophilic segment consisted of poly(ethylene oxide) (PEO) diol (molecular weight = 600 or 2000) or the poly(ethylene-propylene-ethylene oxide) (PEO-PPO-PEO) diol Pluronic F-68 (molecular weight = 8000). The hydrophobic segment was made of poly(epsilon-caprolactone) diol (molecular weight = 530, 1250, or 2000). The chain extenders were 1,4-butane diol and 2-amino-1-butanol. The diisocyanate was aliphatic hexamethylene diisocyanate. The polymers absorbed water in an amount that increased with the increasing content of the PEO segment in the polymer chain. The total amount of absorbed water did not exceed 2% for the poly(ester urethane)s and was as high as 212% for some poly(ester ether urethane)s that behaved in water like hydrogels. The polymers were subjected to in vitro degradation at 37 +/- 0.1 degrees C in phosphate buffer solutions for up to 76 weeks. The poly(ester urethane)s showed 1-2% mass loss at 48 weeks and 1.1-3.8% mass loss at 76 weeks. The poly(ester ether urethane)s manifested 1.6-76% mass loss at 48 weeks and 1.6-96% mass loss at 76 weeks. The increasing content and molecular weight of the PEO segment enhanced the rate of mass loss. Similar relations were also observed for polyurethanes from PEO-PPO-PEO (Pluronic) diols. Materials obtained with 2-amino-1-butanol as the chain extender degraded at a slower rate than similar materials synthesized with 1,4-butane diol. All the materials already manifested a progressive decrease in the molecular weight in the first month of in vitro aging. The rate of molecular weight loss was higher for poly(ester ether urethane)s than for poly(ester urethane)s. For poly(ester ether urethane)s, the rate of molecular weight loss was higher for materials containing Pluronic than for those containing PEO segments. All polymers calcified in vitro. The susceptibility to calcification increased with material hydrophilicity. The progressive deposition of calcium salt on the film surfaces resulted in the formation of large crystal aggregates, the structure of which depended on the chemical composition of the calcified material. Needle-like aggregates, resembling brushite, formed on the hydrophobic polyurethane, and plate-like crystals formed on the highly hydrophilic material. The calcium-to-phosphorus atomic ratio of the crystals growing on the samples was dependent on the chemical composition of the material and varied from 0.94 to 1.55.     

Synthesis and characterization of iodinated polyurethane with inherent radiopacity

The synthesis and characterization of polyurethane (PU) with excellent radiopacity for medical and allied applications are reported. Bisphenol-A (BPA) was iodinated to obtain 4,4′-isopropylidinedi-(2,6-diiodophenol) (IBPA) which was used as a chain extender for the preparation of a radiopaque PU. The PU was prepared by reacting 4,4′-methylenebis(phenyl isocyanate) (MDI), poly(tetramethylene glycol) (PTMG) and IBPA in 2.2:1.2:1 molecular ratio and is characterized by infrared spectroscopy (IR), thermogravimetry (TGA), dynamic mechanical analysis (DMA), energy dispersive X-ray analysis (EDX), gel permeation chromatography (GPC) and X-radiography. X-ray images showed that the PU prepared using IBPA as the chain extender is highly radiopaque. An in vitro cytotoxicity test using L929 mouse fibroblast cells shows that the PU is non-cytotoxic. The outlined synthesis of a PU with radiocontrast properties opens up the possibility of synthesizing many different kinds of radiopaque PUs with desirable range of physical properties exploiting the versatility in their chemical synthesis.     

Effect of aggregation state of hard segment in segmented poly(urethaneureas) on their fatigue behavior after interaction with blood components

Characterization of microphase separated structure, interaction with blood components, such as lipids, and fatigue behavior after immersion in blood components were carried out for segmented poly(urethaneureas). The materials studied were Biomer and segmented poly(urethaneurea) (TU-Mn) composed of hard segment with 4,4'-diphenylmethane diisocyanate (MDI)-ethylenediamine (EDA) or 4,4'-diaminodiphenylmethane (DAM) and soft segment with MDI-polytetramethylene glycol (PTMG) [Mn of 856, 1350, and 2000]. Small-angle x-ray scattering, wide-angle x-ray diffraction, and dynamic viscoelastic measurements revealed that these materials showed the state of microphase separation. TU-Mn with PtMG of Mn = 856 shows the partial phase mixing between hard and soft segments, and phase separation was improved with an increase of Mn of PTMG. Biomer has the characteristics of stronger aggregation of hard segment than that of TU-Mn. All the specimen showed lipid absorption, but the amount of absorption decreased remarkably after precoating on the specimen surface with serum albumin. Lipid absorption of the specimen was confirmed by dynamic viscoelastic and IR measurements. In the case of segmented poly(urethaneurea) which did not immersed in lipids solution, their fatigue strength are sufficient for application to artificial heart systems. However, fatigue strength of the TU-Mn series was decreased drastically after absorption of lipids. On the other hand, Biomer did not show a decrease of fatigue strength after lipid absorption. The reduction of fatigue strength in the TU-Mn series after lipid absorption will be attributed to the weak aggregation of hard segment domain. This reduction of fatigue strength in the TU-Mn series is characterized by formation of microcrack and mirror zone in fatigue fractured specimen. As the precoating of the specimen surface with serum albumin inhibits the absorption of lipids, the reduction of fatigue strength was not observed for the specimen precoated with serum albumin even after immersing the TU-Mn series in lipids solution for 96 days.     

Synthesis,characterization, and platelet adhesion studies of novel aliphatic polyurethaneurea anionomers based on polydimethylsiloxane-polytetramethylene oxide soft segments

Two novel aliphatic polyurethaneurea anionomers were synthesized based on polydimethylsiloxane (PDMS)-polytetramethylene oxide (PTMO) soft segments. The hard segments consisted of either 4,4'-methylene dicyclohexyl diisocyanate (H₁₂MDI), sulfonic acid-containing diol and 1,4-butandiol (BD) or H₁₂MDI, carboxylic acid-containing diol and BD. The nonionic counterpart chain extended with BD was prepared. In addition, the base nonionic polyurethaneurea containing a pure PDMS soft segment, which is denote H-D-BD, was also studied for comparison. The effects of soft segment type and ion incorporation on the physical properties, surface properties, and plateled adhesion are discussed. The ionic polyurethaneureas exhibited poor phase separation, a smaller fraction of PTMO present at the surface, and a smaller contact angle. On the other hand, it also showed a larger fraction of PDMS present at the surface and a higher water absorption value than its nonionic counterpart. H-D-BD had more phase-separated structure, a larger fraction of PDMS present at the surface, and larger contact angle but lower water absorption value than the PTMO-containing polyurethaneureas. The in vitro platelet adhesion experiments indicated that the ionic groups, especially for carboxylate, and surface enrichment PDMS soft segment could effectively inhibit platelet adhesion.     

Usefulness of polyurethane for small-caliber vascular prostheses in comparison with autologous vein graft

 For long-term patency of small-caliber vascular prostheses, antithrombogenicity and microporous structure are very important. We have developed a new technique to give a microporous structure to a polyurethane vascular prosthesis that has favorable antithrombogenicity. A solution of tetrahydrofuran/dimethylformamide (1 : 1) containing 13 wt% of segmented polyurethane (PTMG + MDI) and calcium carbonate (mean particle size, 8 μm) was dipcoated on a glass mandrel 3 mm in diameter and placed into distilled water. After the glass mandrel was removed, the polyurethane tube was placed into hydrochloric acid, and a microporous polyurethane vascular prosthesis was produced. Prostheses made in this fashion, and autologous jugular vein grafts were implanted into the femoral artery and the carotid artery of mongrel dogs. Patency was recognized on the arteriogram and duplex scanning (ultrasonography), and the removed grafts were inspected macroscopically and microscopically. This prosthesis was similar in elasticity to a vein graft. Patency was defined 8 weeks after implantation, and this prosthesis showed less intimal hyperplasia than the autologous vein graft. The new polyurethane prosthesis might be useful for small-caliber vascular reconstruction. Received: December 18, 2000 / Accepted: January 28, 2002     

Polyurethane ionomers: Order in 4,4′-methylenedi(phenyl isocyanate)- and hexamethylene diisocyanate-based poly(ether-urethane) cationomers

Polyurethane cationomers from poly(oxytetramethylene) of molecular weight 2000 as soft segments, 2,2′-methyliminodiethanol as chain extender, glycolic acid as quaternization agent, and 4,4′-methylenedi(phenyl isocyanate) (MDI) and hexamethylene diisocyanate (HDI) as diisocyanates are synthesized and characterized by using wide-angle X-ray diffraction, dynamic mechanical analysis, differential scanning calorimetry and tensile-elongation testing. It is found that, in the unionized and ionized cases, the hard segments exhibit a disorder and short- and long-range order, but no crystallinity. The ordered hard segments in the hard domains aggregate so tightly as to act as crosslinks, such that crystallization of soft segments occurs during elongation. Such disorder and order are also found to exist in the solutions of ethyl methyl ketone as reflected in variations of conductivity and viscosity during addition of water at 20°C. Ionization by insertion of the acid can disrupt the order in MDI and HDI systems, but can increase the cohesion between the neighbouring hard segments, the latter being predominant over the former. Dispersion is apt to disrupt the long-range order in HDI systems but has only an insignificant effect on the order in MDI systems.