Properties of polyisobutylene polyurethane block copolymers: 2. Macroglycols produced by the ‘inifer’ technique

The structure-property relationships of a series of 4,4′-diphenylmethane diiscoyanate (MDI) based polyisobutylene (PIB) polyurethanes were investigated. The PIB glycol was synthesized via the ‘inifer’ technique and had a narrow functionality distribution with a number average functionality of 2.0. The use of a PIB glycol with improved functionality and solution polymerization of the polyurethane led to improved mechanical properties compared with previously studied PIB polyurethanes. However, the mechanical properties were still low compared with conventional polyurethanes; the absence of soft segment strain-induced crystallization and compositional heterogeneity due to reactant incompatibility are cited as possible causes of low mechanical properties. Sample compositions were designed for independent investigation of the effects of hard segment content and soft segment molecular weight on the properties of the materials. Increasing hard segment content resulted in improved dynamic and tensile modulus, lower elongation at break, and larger hard segment domains. Increasing soft segment molecular weight led to larger domains and reduced mechanical properties. The degree of phase separation as measured by the soft segment T_g and the amount of interfacial mixing measured by small angle X-ray scattering (SAXS) were unaffected by hard segment content and soft segment molecular weight and were indicative of a high degree of phase separation compared with conventional polyurethanes.     

Properties of polyisobutylene polyurethane block copolymers: 3. Hard segments based on 4,4′-dicyclohexylmethane diisocyanate (H12MDI) and butane diol

A series of polyisobutylene (PIB) polyurethanes based on 4,4′-dicyclohexylmethane diisocyanate (H₁₂MDI) have been synthesized and their structure-property relationships have been investigated. The PIB glycol was synthesized by the ‘inifer’ technique. Sample compositions were designed for independent investigation of the effects on physical properties of hard segment content and soft segment molecular weight and for comparison with corresponding 4,4′-diphenylmethane diisocyanate (MDI) based PIB polyurethanes. Increasing hard segment content resulted in improved dynamic and tensile modulus while elongation at break was unaffected. Increasing soft segment molecular weight led to decreased mechanical properties attributed to larger domain sizes as indicated by small angle X-ray scattering (SAXS). Both the soft segment T_g and the extent of interfacial mixing as measured by SAXS were unaffected by hard segment content and soft segment molecular weight suggesting that the materials were highly phase separated. In comparison with corresponding MDI based materials the H₁₂MDI based polyurethanes exhibited less hard segment ordering, slightly less interfacial mixing, smaller domain sizes, and slightly better ultimate tensile properties.     

Mechanical,thermal, and electric properties of polyurethaneimide elastomers

Linear polyurethaneimide elastomers (PUI) were obtained from polyether- or polyester-diols, diphenylmethane diisocyanate or bitolylene diisocyanate and pyromellitic acid dianhydride. It was found that these polymers have considerably better mechanical properties than typical linear polyurethanes (PU). The elastic modulus and stress at break increase with contents of the hard polyimide segments. The softening temperatures and thermal stability of the PUI at 500°C were higher than the ones of PU with similar hard segment contents. Electric properties of PUI were close to the ones of conventional PU. It was shown that cellular PUI had considerably lower dielectric constant. T_g's of the soft segments PUI were less than T_g's corresponding to PU. It is connected with greater phase separation of the hard imide segments from the soft polyether– or polyester–urethane matrix.     

Thermal and mechanical properties of linear segmented polyurethanes with butadiene soft segments

A series of segmented polyurethanes based on a hydroxyl terminated polybutadiene soft segment (HTPBD) have been prepared with varying hard segment content between 20 and 60 weight percent. These materials are linear and amorphous and have no potential for hydrogen bonding between the “hard” and “soft” segments. The existence of two-phase morphology was deduced from dynamic mechanical behavior and thermal analysis. Both techniques showed a soft segment glass transition temperature, T_gs, at ?56°C and hard segment transitions between 20 and 100°C, depending on the urethane content. The low value of T_g, only 8° higher than the T_g of free HTPBD and independent of hard segment concentration indicated nearly complete phase segregation. Depending on the nature of the continuous and dispersed phases, the urethanes behaved as elastomers below 40 weight percent hard segment or as glasslike materials at higher hard segment contents. The effect of thermal history on transitions of the HTPBDurethanes was also investigated and the results suggest that the absence of hydrogen bonding to the soft segment must account for the extraordinary insensitivity to thermal history in dynamic mechanical, thermal and stress-strain behavior. Comparisons are made to the more common polyurethanes containing polyether and polyester soft segments.     

Effects on properties of varying the cis/trans isomer distribution in polyurethane elastomers made with 1,4-cyclohexane diisocyanate

Polyurethane elastomers have been made using 1,4-cyclohexane diisocyanate (CHDI), 1,4-butanediol (BDO) and a 2000 M_n polyether diol soft segment. The cis/trans isomer distribution of the CHDI was varied between 23% and 100% trans. This variation in isomer distribution had significant effects on the polyurethane's thermal and physical properties. Decreasidng the trans CHDI content gives polyurethanes with lower hardness, lower thermal stability, higher Coefficient of Linear Thermal Expension (C.L.T.E.) values and decreased modulus values. Morphology studies showed good phase separation between the hard and soft segment blocks as well as a block copolymer morphology between the cis and trans CHDI/BDO blocks in the hard segment. The polyurethanes made were compared to polyurethanes made with MDI and H₁₂MDI, the leading aromatic and aliphatic diisocyanates respectively.     

Thermal and mechanical properties of solution polymerized segmented polyurethanes with butadiene soft segments

A series of HTPBD containing polyurethanes of high molecular weight have been synthesized in solution. The value of the soft segment T_g is very close to that of the free HTPBD and independent of hard segment content indicating complete or very nearly complete phase segregation. Since the hard segments of TDI/BDO are amorphous, the driving force for phase segregation must arise from the large degree of incompatibility between the polar hard segment and nonpolar soft segment. Furthermore, in these samples there is also no opportunity for hydrogen bonding between hard and soft segments to enhance compatibility.The values of the hard segment glass transition increase with the average hard segment length following a Fox-Flory type relationship. In contrast to the segment T_g observed in bulk polymerized samples, only a single hard segment T_g occurred in the present study. This indicates that the double T_g behaviour is a result of the heterogeneous nature of the bulk polymerization.With increasing hard segment content, the properties vary from soft to rigid elastomers, and rubber roughened plastics. This variation in properties is caused by changes in the sample morphology which depends upon the relative fractions of hard and soft segments. Mechanical properties show marked improvement over the corresponding bulk polymerized samples. Unlike polyester and polyether urethanes, these materials evidence no change in the soft segment T_g following thermal treatment and no effect of thermal history on the mechanical properties.     

Block copolyetheresters. V. Low-temperature properties of thermotropic block copolyetheresters

The low-temperature properties of block copolyetheresters with hard segments of poly(alkylene p,p′-bibenzoate) and soft segments of poly(tetramethylene ether) were investigated by differential scanning calorimetry (DSC) and dynamic mechanical analysis (DMA). In the temperature range of −100 to 60°C, two transition temperatures, a glass transition temperature (T_g) and a melting temperature (T_m), were found by DSC and are attributed to the polyether segments. The T_g monitored by DSC of the polyether segments of the block copolyetheresters is around −68°C and independent of the composition and the type of polyester segment. Thus, the amorphous parts of the polyether segments should be immiscible with the amorphous parts of the polyester segments. The polyether segments of the block copolyetheresters exhibit a lower T_m and a lower crystallinity than those of the poly(tetramethylene ether)glycol due to the presence of the polyester segments. The crystallizability of the polyether segments is dependent on the composition to some extent. The DMA data show that the dynamic modulus drops more abruptly around −10 to 15°C, indicating that the mechanical properties may change significantly due to the melting of the polyether segments. © 1996 John Wiley & Sons, Inc.     

Effect of the degree of soft and hard segment ordering on the morphology and mechanical behavior of semicrystalline segmented polyurethanes

The hierarchical microstructure responsible for the unique energy-absorbing properties of natural materials, like native spider silk and wood, motivated the development of segmented polyurethanes with soft segments containing multiple levels of order. As a first step in correlating the effects of crystallinity in the soft segment phase to the hard segment phase, we chose to examine the morphology and mechanical behavior of polyurethanes containing polyether soft blocks with varying tendencies to crystallize and phase segregate and the evolution of the microstructure with deformation. A series of high molecular weight polyurethanes containing poly(ethylene oxide) (PEO) (1000 and 4600 g/mol) and poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) (PEO-PPO-PEO) (1900 g/mol) soft segments with varying hard segment content were synthesized using a two-step solution polymerization method. The presence of soft segment crystallinity (PEO 1000 g/mol) was shown to improve the storage modulus of the segmented polyurethanes below the T_m of the soft block and to enhance toughness compared to the PEO-PPO-PEO soft segment polyurethanes. We postulate that this enhancement in mechanical behavior is the result of crystalline soft regions that serve as an additional load-bearing component during deformation. Morphological characterization also revealed that the microstructure of the segmented polyurethanes shifts from soft segment continuous to interconnected and/or hard domain continuous with increasing hard segment size, resulting in diminished ultimate elongation, but enhanced initial moduli and tensile strengths. Tuning the soft segment phase crystallinity may ultimately lead to tougher polyurethane fibers.     

Preparation and properties of transparent thermoplastic segmented polyurethanes derived from different polyols

Various segmented polyurethanes of different soft segment structure with hard segment content of about 50 wt% were prepared from 4,4′‐diphenylmethane diisocyanate (MDI), 1,4‐butanediol and different polyols with a M_n of 2000 by a one‐shot, hand‐cast bulk polymerization method. The polyols used were a poly(tetramethylene ether)glycol, a poly(tetramethylene adipate)glycol, a polycaprolactonediol and two polycarbonatediols. The segmented polyurethanes were characterized by gel permeation chromatography (GPC), UV‐visible spectrometry, differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), X‐ray diffraction, and their tensile properties and Shore A hardness were determined. The DSC and DMA data indicate that the miscibility between the soft segments and the hard segments of the segmented polyurethanes is dependent on the type of the soft segment, and follows the order: polycarbonate segments > polyester segments > polyether segments. The miscibility between the soft segments and the hard segments plays an important role in determining the transparency of the segmented polyurethanes. As the miscibility increases, the transparency of the segmented polyurethanes increases accordingly. The segmented polyurethanes exhibit high elongation and show ductile behavior. The tensile properties are also affected by the type of the soft segment to some extent. POLYM. ENG. SCI., 47:695–701, 2007. © 2007 Society of Plastics Engineers.     

Thermal and mechanical properties of polyisobutylene‐based thermoplastic polyurethanes

We investigated thermal and mechanical properties of thermoplastic polyurethanes (TPUs) with the soft segment comprising of both polyisobutylene (PIB) and poly(tetramethylene)oxide (PTMO) diols. Thermal analysis reveals that the hard segment in all the TPUs investigated is completely amorphous. Significant mixing between the hard and soft segments was also observed. By adjusting the ratio between the hard and soft segments, the mechanical properties of these TPUs were tuned over a wide range, which are comparable to conventional polyether‐based TPUs. Constant stress creep and cyclic stress hysteresis analysis suggested a strong dependence of permanent deformation on hard segment content. The melt viscosity correlation with shear rate and shear stress follows a typical non‐Newtonian behavior, showing decrease in shear viscosity with increase in shear rate. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 891‐897, 2013     

Thermal transition behavior of polybutadiene containing polyurethanes

The thermal transition behavior of a series of hydroxy terminated polybutadiene (HTPBD) containing segmented polyurethanes has been studied by differential scanning calorimetry (DSC) and thermal mechanical analysis (TMA). Four transition regions are observed; the soft segment T_g, at ?74°C, two hard segment transitions T₁, at 40°C and T₂ at 103°C and a softening region by TMA at 180°C, presumed to arise from the dissociation of allophonate bonding, The low T_g, only 7°C higher than the T_g of free HTPBD, indicates nearly complete phase segregation despite the amorphous nature of the hard segment structure. The dependence of T₁, on hard segment length and thermal cycling suggests that it represents domains consisting primarily of shorter hard segments units. Factors contributing to the rather low mechanical properties of HTPBD polyurethanes are also discussed.     

Engineering plastics from lignin. VII. Structure property relationships of poly(butadiene glycol)-containing polyurethane networks

Hydroxypropyl lignin-based thermosetting polyurethanes containing polybutadiene (PBD) glycol soft segments (M_n of 2800 g M^?1) were synthesized with excess hexamethylene diisocyanate (HDI) and tolylene diisocyanate (TDI) by solution casting. Miscibility of the glycol with the lignin derivative was found to be poor as expected, and phase separation between the two polyol components in polyurethanes was detected by thermal and mechanical analysis, and by electron microscopy. This study examines the effect of concentration of polybutadiene glycol on the thermal and mechanical properties of the polyurethanes. The two-phase network system displayed significantly different properties than either the poly(ethylene glycol)-containing polyurethanes or their soft segment-free counterparts described previously. Macrophase separation was observed at nearly all degrees of mixing and was found to affect thermal and mechanical properties. The glass transition temperature (T_g) of the lignin phase in the TDI-based networks increased with poly(butadiene glycol) content rising from 3.6 to 71.4% of polyurethane, and this was attributed to the employment of a constant diisocyanate weight fraction which gave rise to a variable NCO/OH ratio and crosslink density. Distinct phase separation was evidenced by scanning electron microscopy (SEM) at above 3.6 and 7.1% glycol content for HDI- and TDI-based films, respectively. The polyurethane films behaved like rubber-toughened lignin networks when PBD was the discrete phase, and like lignin-reinforced rubber when the lignin derivative was discrete. This behavior was evidenced by the Young's modulus decreasing from 2000 to 50 MPa and ultimate strain rising from 6 to greater than 150%, with soft segment content increasing from 0 to 71.4%.     

Structural and mechanical properties of polybutadiene-containing polyurethanes

A series of segmented polyurethanes based on hydroxylterminated polybutadienes (HTPBD) and their hydrogenated derivatives (HYPBD) has been synthesized. Thermal, mechanical, and spectroscopic studies were carried out over a wide temperature range to elucidate the structure-property relationships existing in these polymers. Both thermal and dynamic mechanical response showed a soft segment T_g at ?74°C for the unsaturated polyurethanes and at ?69°C for the hydrogenated samples. In addition, two hard segment transitions are observed by differential scanning calorimetry (DSC) at 40 and 75°C and a softening region by thermal mechanical analysis (TMA) at 190°C. The low T_g, very close to that of the free HTPBD and HYPBD and independent of hard segment content, indicated that these polymers were well phase separated. Results of infrared analysis revealed that at room temperature, 90-95 percent of the urethane N-H groups formed hydrogen bonds. Since hydrogen bonding resides only within the hard segment domain in these butadiene-containing polyurethanes the extent of H-bonding served as additional evidence for nearly complete phase segregation. From dynamic mechanical studies, the plateau modulus above the soft segment T_g and stress-strain behavior depended upon the concentration of hard segments. A slight increase in the modulus, a moderate increase in stress (σ_b), and decrease in elongation accompanied a higher hard segment content. The thermal and mechanical response of these polyurethanes appears to be consistent with behavior observed for other phase segregated systems. Variations in behavior resulting from hydrogenation of the precursor prepolymer are discussed.     

Incidence of the polyol nature in waterborne polyurethane dispersions on their performance as coatings on stainless steel

Three waterborne polyurethane dispersions derived from polyester, polyether and polycarbonate diols with molecular weight of 1000 Da were synthesized by the acetone method and used as coatings on stainless steel 304 plates. The properties of the dispersions and the polyurethane films were influenced by the polyol nature. The polyurethanes obtained with polyether or polyester showed higher degree of phase separation between the soft and the hard segment. The higher adhesive strength under shear stresses was obtained in the joints produced with the waterborne dispersion obtained with polycarbonate diol. The properties of the polyurethane coating obtained with polycarbonate diol on stainless steel 304 were significantly higher as compared with the others. Improved performance of coatings obtained with polycarbonate diol was ascribed to the higher polarity of the carbonate groups that contributed to additional hydrogen bond formation between soft segments with respect to those obtained with polyether or polyester     

聚醚/聚酯型亲水性聚氨酯防水透湿性能研究

以4,4’-二苯基甲烷二异氰酸酯(MDI)和1,4-丁二醇(BDO)为硬单体,制备了6组聚醚与聚酯或不同聚醚混合单体为软链段的嵌段型亲水性聚氨酯防水透湿涂层剂。研究了聚氨酯材料的微结构和软段结构对其防水、透湿性能的影响。结果表明,亲水性聚氨酯软链段的结构、组成、相对分子质量和含量及软、硬段相区间的微相分离程度对材料防水透湿性能的影响较大,亲水性聚氨酯的防水透湿性能主要取决于其中亲水性软链段的亲水性及其活动性。     

Transition behavior and phase segregation in TDI polyurethanes

Prior studies of two series of segmented polyurethanes based on 2, 4 toluene cliisocyanate (2, 4 TDI) or 2, 8 TDI, butanediol, and a 1000 molecular weight polytetramethyleneoxide (PTMO-1000) soft segment revealed a rapid increase in soft segment glass transition temperature (T_g) with increasing urethane content in the 2, 4 TDI series. The change in T_g couldbe correlated with estimates of hard segment-soft segment phase mixing obtained by infrared analysis of the urethane NH and carbonyl bands. In the present paper, the infrared data have been reevaluated using improved procedures for resolving the carbonyl band into H-bonded and nonbonded components, and the relation between the estimated extent of phase mixing and T_g has been reexamined. The transition behavior in an extensive series of related polymers has also been determined, including 2, 4 TDI arid 2, 6 TDI samples with PTMO2000 as well as polybutyleneadipate (PBA-1000 and PBA-2000) soft segments. The results indicate the effectiveness, of increased soft segment molecular weight in promoting phase segregation, imply that much greater phase mixing occurs in polyester than polyether samples, suggest that anchoring the ends of the soft segments has only a small effect on T_g, and provide some evidence that H-bonding not only increases T_g but can also impede soft segment crystallization.     

Surface and bulk properties of waterborne polyurethane modified with fluorinated siloxane

Two series of polyester and polyether waterborne polyurethanes (WPUs) modified with poly[(3,3,3‐trifluoropropyl)methylsiloxane] (PTFPMS) were synthesized by prepolymerization method and the effect of PTFPMS on surface and bulk properties were investigated by a variety of experimental methods. FTIR and DSC results showed that the polyester WPU has better compatibility between soft segments and hard segments than polyether WPU in bulk and the degree of phase separation increased in polyester WPU but decreased in polyether WPU with increasing PTFPMS. ARXPS analysis revealed the migration of PTFPMS to WPU surface and the migration ability of Si element was better than F element. AFM images demonstrated that the surface of WPU films became rougher as PTFPMS content increased. The enrichment of PTFPMS with low surface energy and roughened surface imparted good hydrophobicity and oleophobicity to WPU films and polyether WPU has better surface properties compared with polyester WPU. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46473.     

Phase separation and phase inversion of polyurethane networks

A series of polyurethane networks were prepared from MDI (4,4¹-diphenyl methane diisocyanate), ethylene glycol and a polyoxyethylene-tipped polyoxypropylene triol. The phase separation and phase inversion phenomena of these polyurethane networks were investigated by differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA) and measurement of their tensile properties. The DSC and DMA data indicate that the segmented copolyurethanes possess a two-phase morphology comprising soft and hard segments. It can be found from DSC data that the polyether soft segments exhibit a T_g (glass transition temperature) of –60 °C, and the aromatic hard segments display a T_g of about 128 °C. Two T_gs corresponding to the comprised segments can also be found by DMA for some segmented polyurethanes. Varying the content of aromatic hard segments over the range from 0 to 80 wt% changes the material behavior from a soft rubber through a highly extensible elastomer to a brittle semi-ductile glassy material. Based on the property-composition plots, phase inversion appears to occur at a hard segment content of about 50 wt%.     

聚氨酯弹性体的动态力学性能的影响因素

综述了聚氨酯弹性体动态力学性能的多种影响因素,讨论了软段类型(聚酯和聚醚)、软段相对分子质量、硬段类型(二异氰酸酯和扩链剂)、硬软段质量分数对PU弹性体动态力学性能的影响。在PU弹性体中,聚酯软段比聚醚软段的Tg高,弹性模量依PPG、PEG、PTMG软段顺序增加。     

Structure-property relationships in thermoplastic elastomers: I. Segmented polyether-polyurethanes

Segmented poly(ether-b-urethanes) have been synthesized with 2000 MW polypropylene oxide coupled with diisocyanates and diol type chain extenders. The diisocyanates used were symmetric rigid 4, 4′-diphenylmethane diisocyanate (MDI), linear aliphatic hexamethylene diisocyanate (HDI), and unsymmetric rigid toluene-2, 4-diisocyanate (TDI). The chain extenders were symmetric N, N′-bis(2-hydroxyethyl) terephthalamide (BT) and N, N′-bis(2-hydroxyethyl)-hydroquinone (BH) unsymmetric N, N′-bis(2-hydroxyethyl)isophthalamide, and linear aliphatic 1, 4-butanediol (B). Hard segment contents ranged from 20 to 40 wt percent. The thermal behavior of these materials is consistent with phase separation into separate hard and soft domains, In order of increasing temperature above the soft segment T_g, there are transitions which occur in the regions ?56 to ?36°C (T_a), 70 to 90°C (T_b), and 138 to 168°C (T_m). The former is probably associated with soft segment change from a viscoelastic to an elastomeric state. Values of T_a are ～ ?51 C and ?56°C for the MDI-BT and HDI-BT polymers, respectively, and are independent of hard segment content. Microscopy showed that the former polymers have spherulitic morphology, so these materials have good microphase separation and exhibit crosslinked elastomeric properties. The TDI-BT or BI and MDI-B polyurethane have composition-independent T_a values of ?41 and ?36°C, respectively. These materials probably have considerable “domain-bound-ary-mixing”. At low hard segment content the MDI-B polymers behave as non-crosslinked elastomers. Only the MDI-BI polymers have _Ta values, which are strongly affected by composition, increasing in magnitude with increasing of hard segment content. This is interpreted as significant “mixing-in-domains” and is supported by morphology observed by microscopy. The next higher transition, T_b, probably involves dissociation of interdomain hydrogen bonding. In the case of the MDI-BT polyurethanes, the spherulites associated with the hard domains had disappeared at 141°C and the few small spherulites in the MDI-BI polymers disappeared at 130°C. The T_b values are 70, 83 to 90, and 100°C for the MDI-B, HDI-BT, and HDI-BI polymers, respectively. The melting transitions occurred between 138 to 168°C for the various polyurethanes except for the MDI-BT systems which decompose before melting. Thermal decomposition is a two-stage process. Hard segments decompose between 200 and 300°C. The initial decomposition temperatures are lowered in the presence of strong acid. Soft segments decompose at higher temperatures. The mechanical properties of the MDI-BI polyurethanes are charateristic of crosslinked elastomer, the results of which will be presented in a subsequent paper.