Polyurethane cationomers. II. Phase inversion and its effect on physical properties

The three series of polyether polyurethane cationomers based on MDI, HDI, and TDI that are the subject of Part I, undergo emulsification (or phase inversion) on addition of water to solutions in MEK. The phase inversion mechanism depends on the structure of hard segment, ionic content, and dispersion temperature. The dispersion process can be divided into three stages involving a separation of hard segment aggregates due to adsorption of water on their surface, water entering into disordered and then ordered hard domains, and finally a rearrangement of agglomerates to form microspheres. The extent of penetration of water into the disordered hard domains decreases with increasing glass transition temperature; while in ordered hard domains, penetration depends on the dissociation temperature of urethane–urethane hydrogen bonds. Thus the penetration of water into the hard domains is strongly dependent on the dispersion temperature. Films cast from the emulsions have both ordered and disordered hard segment regions, this is also true of films cast directly from solution. The dispersion can disrupt the order in hard domains, leading to an increased phase separation for the MDI system and to a slightly increased phase mixing for the HDI and TDI systems. Films cast from solutions have a morphology with soft domains as a continuous phase and hard domains as a fibrillar network dispersed in the continuous phase. After dispersion, the hard segments originally distributed in the dispersed phase can be inverted to become a hard domain network or a continuous phase.     

Polyurethane cationomers. I. Structure-property relationships

Polyether polyurethane cationomers are prepared using poly (tetramethylene oxide) of molecular weight 2000 as soft segments, N-methyl-diethanolamine as chain extender, glycolic acid as quaternization agent, methyl ethyl ketone as solvent, and three different diisocyanates. The three diisocyanates are 4,4′-diphenylenemethylene diisocyanate (MDI), hexamethylene diisocyanate (HDI), and toluene diisocyanate (TDI). Properties of the films cast from solutions of the three series of ionomers are studied by infrared spectroscopy, dynamic mechanical analysis, thermogravimetric analysis, differential scanning calorimetry, wide angle x-ray diffraction, and tensile elongation testing. In the un-ionized and ionized systems, the hard segments exhibit disordered and ordered arrangements, respectively. Ionization disrupts the order and produces increased cohesion in the hard domains, which have opposing effects on the tensile elongation properties. In the MDI and TDI systems, cohesion is predominant, leading to an increased tensile strength and modulus and decreased elongation at break. But in the HDI system, the disruption of the order is predominant, leading to decreased tensile strength and only insignificant reduction in the elongation at break. In the TDI system, the tensile strength is rather low, which is attributed to the poor order in the hard domains resulting from the high content of the asymmetric 2,4-isomer of the urethane.     

Segmented polyurethanes with 4,4′-bis-(6-hydroxyhexoxy)biphenyl as chain extender. Part 2. Synthesis and properties of MDI-polyurethanes in comparison with 2,4-TDI-polyurethanes

Linear segmented polyurethanes based on poly(butylene adipate)s (PBA) of different molecular weight (M_n 2000, 1000, and 600), 4,4′-diphenylmethane diisocyanate (MDI) and the mesogenic diol 4,4′-bis-(6-hydroxyhexoxy)biphenyl (BHHBP) as well as the unsegmented polyurethane consisting of MDI/BHHBP units have been synthesized and characterized by elemental analysis, ¹³C-NMR and SEC. The thermal behavior and the morphology were studied by DSC, polarizing microscopy, and DMA. The properties of the MDI-polyurethanes were discussed in relation to the BHHBP chain extended 2,4-TDI-polyurethanes and common 1,4-butanediol chain-extended MDI products. MDI polyurethanes based on PBA (M_n 2000) exhibit a glass transition temperature T_g of about −40°C independent of the hard segment content up to ∼50% hard segments. At higher hard segment contents increasing T_gs were observed. Polyurethanes, based on the shorter polyester soft segments PBA (M_n 1000 or 600), reveal an increase in the glass transition temperatures with growing hard segment content. The thermal transitions caused by melting of the MDI/BHHBP hard segment domains are found at 50 K higher temperatures in comparison with the analogous TDI products with mesogenic BHHBP/TDI hard segments. Shortening of the PBA chain length causes a shift of the thermal transitions to lower temperatures. Polarizing microscopy experiments indicate that liquid crystalline behavior is influenced by both the content of mesogenic hard segments and the chain length of the polyester. © 1996 John Wiley & Sons, Inc.     

用WAXD和SAXS研究新型聚醚－聚酯－聚脲浇铸型弹性体的形态

用ＷＡＸＤ和ＳＡＸＳ研究了一种新型的聚醚－聚酯－聚脲浇铸型弹性体的形态结构．ＷＡＸＤ的结果表明：用三种不同的二异氰酸酯,其硬段中的结晶度依次是ＨＤＩ＞ＭＤＩ＞ＴＤＩ．对于ＨＤＩ和ＭＤＩ混合合成的体系、由于与“Ｐｏｌａｍｉｎｅ”的反应速度不同,形成三相体系．ＳＡＸＳ的结果表明：增加“Ｐｏｌａｍｉｎｅ”分子量,有利于软、硬段的微相分离．对于不同的二异氰酸酯,相分离度依次是ＨＤＩ＞ＭＤＩ＞ＴＤＩ．     

用WAXD和SAXS研究新型聚醚－聚酯－聚脲浇铸型弹性体的形态

 用ＷＡＸＤ和ＳＡＸＳ研究了一种新型的聚醚－聚酯－聚脲浇铸型弹性体的形态结构．ＷＡＸＤ的结果表明：用三种不同的二异氰酸酯,其硬段中的结晶度依次是ＨＤＩ＞ＭＤＩ＞ＴＤＩ．对于ＨＤＩ和ＭＤＩ混合合成的体系、由于与“Ｐｏｌａｍｉｎｅ”的反应速度不同,形成三相体系．ＳＡＸＳ的结果表明：增加“Ｐｏｌａｍｉｎｅ”分子量,有利于软、硬段的微相分离．对于不同的二异氰酸酯,相分离度依次是ＨＤＩ＞ＭＤＩ＞ＴＤＩ．     

High performance bio-based polyurethane elastomers: Effect of different soft and hard segments

In this work, a series of high performance bio-based polyurethanes(bio-PUs) were synthesized from polylactide(PLA)-based diols, different diisocyanates(TDI, MDI, HDI, IPDI) and chain extender 1,4-butanediol, in which different soft and hard segments are used to adjust their transition temperatures and mechanical properties. Poly(lactide-co-caprolactone)copolymer diols(co-PLAols) instead of PLA diols as the soft segment improved the thermal stability and mechanical properties of the synthesized bio-PUs. Among them, MDI-based bio-PUs have the highest T_g(43.8 °C), tensile strength(23.5 MPa) and modulus(380.8 MPa), while HDI-based bio-PUs have the lowest T_g(21.4 °C) and highest elongation at break(580%). Especially, the bio-PUs synthesized from co-PLAols and MDI demonstrate better mechanical properties,closed to petroleum-based commodities. Furthermore, the obtained bio-PUs display good shape memory properties at body temperature and cytocompatibility. Therefore, these bio-PUs are promising for applications in biomedical fields.     

Preparation and properties of imide‐containing elastic polymers from elastic polyureas and pyromellitic dianhydride

A new approach to obtain imide‐containing elastic polymers (IEPs) via elastic and high‐molecular‐weight polyureas, which were prepared from α‐(4‐aminobenzoyl)‐ω‐[(4‐aminobenzoyl)oxy]‐poly(oxytetramethylene) and the conventional diisocyanates such as tolylene‐2,4‐diisocyanate(2,4‐TDI), tolylene‐2,6‐diisocyanate(2,6‐TDI), and 4,4′‐diphenylmethanediisocyanate (MDI), was investigated. IEP solutions were prepared in high yield by the reaction of the polyureas with pyromellitic dianhydride in N‐methyl‐2‐pyrrolidone (NMP) at 165°C for 3.7–5.2 h. IEPs were obtained by the thermal treatment at 200°C for 4 h in vacuo after NMP was evaporated from the resulting IEP solutions. We assumed a mechanism of the reaction via N‐acylurea from the identification of imide linkage and amid acid group in IEP solutions. NMR and FTIR analyses confirmed that IEPs were segmented polymers composed of imide hard segment and poly(tetramethylene oxide) (PTMO) soft segment. The dynamic mechanical and thermal analyses indicated that the IEPs prepared from 2,6‐TDI and MDI showed a glass‐transition temperature (T_g ) at about −60°C, corresponding to T_g of PTMO segment, and suggested that microphase‐separation between the imide segment and the PTMO segment occured in them. TGA studies indicated the 10% weight‐loss temperatures (T₁₀) under air for IEPs were in the temperature range of 343–374°C. IEPs prepared from 2,6‐TDI and MDI showed excellent tensile properties and good solvent resistance. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 715–723, 2000     

Structure-property relationship of polyurethane ionomer

Polyurethane (PU) ionomers were prepared using various types of polyol (PTAd, PCL, PTMG, and PPG) and isocyanate (MDI, HDI, and IPDI), together with different extender (DMPA) contents, degree of neutralization, and number average molecular weight (M _n) of polyol. Modulus (E), strength (_b), and glass transition temperature (T _g) significantly increased with the increased amount of extender and extender neutralization. Among three of the iocyanate used, PU from MDI gave the highest modulus, strength, andT _g. With regard to theM _n of PTAd (600, 1000, 2000), PU from PTAd 600M _n gave the highest modulus, strength, andT _g, due probably to the highest hard segment content and phase mixing. On the other hand, PU from PTAd 2000M _n gave significantly improved strength over PTAd 1000M _n, and the highest elongation. The results were interpreted in terms of soft-segment crystallization, and soft-hard phase separation, which was concluded from the lowered softT _g.     

UV-curable poly(ethylene glycol)–based polyurethane acrylate hydrogel

Poly(ethylene glycol) (PEG) with molecular weight (M_n) of 1000, 2000, 3000, and 4000 g/mol, four types of diisocyanate [hexamethylene diisocyanate (HDI), 4,4′-dicyclohexylmethane diisocyanate (H₁₂MDI), isophorone diisocyanate (IPDI), and toluene diisocyanate (TDI)], two types of comonomers [acrylamide (AAm) and acrylic acid (AAc)] that comprised up to 60% of the total solid were used to prepare UV-curable PEG–based polyurethane (PU) acrylate hydrogel. The gels were evaluated in terms of mechanical properties, water content as a function of immersion time and pH, and X-ray diffraction profiles of dry and swollen films. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 2703–2709, 1999     

Polyurethane Ionomers from Cycloaliphatic Diisocyanate and Polytetramethylene Glycol

Abstract

Segmented polyurethane (PU) ionomers were prepared from cycloaliphatic diisocyanate [methylene bis(4-cyclohexyl isocyanate) (H₁₂MDI) and isophoron diisocyanate (IPDI)] and polytetramethylene glycol (PTMG) by using an anionic-type chain extender, viz., dimethylol propionic acid (DMPA). The effect of ionic content and butanediol (BD) on the state of dispersion and physical properties of emulsion-cast film was determined using Autosizer, transmission electron microscopy (TEM), Instron, and Rheovibron. With increased incorporations of DMPA in PU, particle size of emulsion decreased asymptotically, tensile modulus and strength increased, and the glass transition temperature (T _g) moved toward the higher temperature. On the other hand, with increased incorporation of BD in PU, particle size of emulsion, tensile modulus, and strength of the emulsion cast film increased, and the major transition of soft segment moved toward higher temperature. With regard to the structural effect of the isocyanate, H₁₂MDI gave finer dispersion and better mechanical properties over IPDI.     

Structure analysis of polyether-based thermoplastic polyurethane elastomers by FTIR, 1H NMR and 13C NMR

One kind of unknown structure sequence and composition ratio of thermoplastic polyurethane elastomers were characterized by nuclear magnetic resonance spectroscopy, Fourier transformed infrared spectroscopy, and gel permeation chromatography (GPC). The results showed that the polyurethane (PU) was obtained from poly(tetramethylene glycol) (PTMG) as soft segment, 1,4-butanediol (BDO) as chain extender, and 4,4′-methylenediphenyl diisocyanate (MDI) as hard segment. Furthermore, the composition ratio of MDI:PTMG:BDO was 2.07:1.22:1.00. At last, the molecular weight of PU was determined by GPC, and the number average molecular weight (M_n) and weight average molecular weight (M_w) are 63,300 and 133,800?g?mol^?1, respectively.     

The influence of hard‐segments on two‐phase structure and shape memory properties of PCL‐based segmented polyurethanes

Poly(ε‐caprolactone)‐based segmented polyurethanes (PCLUs) were prepared from poly(ε‐caprolactone) diol, diisocyanates (DI), and 1,4‐butanediol. The DIs used were 4,4′‐diphenylmethane diisocyanate (MDI), 2,4‐toluenediisocyanate (TDI), isophorone diisocyanate (IPDI), and hexamethylene diisocyanate (HDI). Differential scanning calorimetry, small‐angle X‐ray scattering, and dynamic mechanical analysis were employed to characterize the two‐phase structures of all PCLUs. It was found that HDI‐ and MDI‐based PCLUs had higher degree of microphase separation than did IPDI‐ and TDI‐based PCLUs, which was primarily due to the crystallization of HDI‐ and MDI‐based hard‐segments. As a result, the HDI‐based PCLU exhibited the highest recovery force up to 6 MPa and slowest stress relaxation with increasing temperature. Besides, it was found that the partial damage in hard‐segment domains during the sample deformation was responsible for the incomplete shape‐recovery of PCLUs after the first deformation, but the damage did not develop during the subsequent deformation. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 557–570, 2007     

Oxygen permeability in thermoplastic polyurethanes

The thermal and oxygen transport properties of a series of thermoplastic polyurethanes (TPUs) based on 4,4′‐methylene diisocyanate (MDI) and 1,4‐butanediol (BD) as hard segments, and poly(tetramethylene glycol) (PTMG) or poly(butylene adipate) (PA) as soft segments, are studied. Oxygen permeabilities (P) of both polyester‐based and polyether‐based TPUs increase with decreasing hard segment fractions. Oxygen solubility (S) and diffusivity (D) can be derived from permeation curves. S correlates with the amount of excess free volume as determined by the difference between glass‐transition and testing temperatures (i.e., the degree of super cooling) and decreases with the increased T_g in polyester‐based TPUs. The intensity of low temperature gamma transition reflects the activation energy for D; the higher the intensity is, the lower D is annealed TPU samples exhibited higher oxygen permeabilities as well as lower storage moduli at room temperature, despite modest increases in overall crystallinity. Dedensification of the soft segment phase during annealing/crystalline phase growth is the most likely explanation for loss of mechanical and barrier properties after annealing as partially confirmed by Fourier transform infrared spectroscopy. © 2012 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2012     

Structure and properties of segmented poly(urethaneurea)s with relatively short hard‐segment chains

We report the structure and properties of segmented poly(urethaneurea) (SPUU) with relatively short hard‐segment chains. The SPUU samples comprised poly(tetramethylene glycol) prepolymer as a soft segment and 4,4′‐diphenylmethane diisocyanate (MDI) units as a hard segment that were extended with ethylenediamine. To discuss quantitatively the conformation of the soft‐segment chain in the microphase‐separated domain space, we used SPUU samples for which the molecular weights of the hard‐ and soft‐segment chains are well characterized. The effects of the cohesive force in the hard‐segment chains on the structure and properties of SPUU were also studied with samples of different chain lengths of the hard segment, although the window of x_H, the average number of MDI units in a hard‐segment chain, was narrow (2.38 ≤ x_H ≤ 2.77). There were urethane groups in the soft segments and urea groups in the hard segments. Because of a strong cohesive force between the urea groups, we could control the overall cohesive force in the hard‐segment chains by controlling the chain lengths of the hard segment. First of all, microphase separation was found to be better developed in the samples with longer hard‐segment chains because of an increase of the cohesive force. It was also found that the interfacial thickness became thinner. The long spacing for the one‐dimensionally repeating hard‐ and soft‐segment domains could be well correlated with the molecular characteristics when the assumption of Gaussian conformation was employed for the soft‐segment chains. This is unusual for strongly segregated block copolymers and might be characteristic of multiblock copolymers containing rod–coil chains. The tensile moduli and thermal stability temperature, T_H, increased with an increase of the cohesive force, whereas the glass‐transition temperature, the melting temperature, and the degree of crystallinity of the soft‐segment chains decreased. The increase in T_H especially was appreciable, although the variation in the chain length of the hard segment was not profound. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 1716–1728, 2000     

Preparation of high‐temperature polyurethane by alloying with reactive polyamide

A series of novel poly(urethane amide) films were prepared by the reaction of a polyurethane (PU) prepolymer and a soluble polyamide (PA) containing aliphatic hydroxyl groups in the backbone. The PU prepolymer was prepared by the reaction of polyester polyol and 2,4‐tolylenediisocyanate and then was end‐capped with phenol. Soluble PA was prepared by the reaction of 1‐(m‐aminophenyl)‐2‐(p‐aminophenyl)ethanol and terephthaloyl chloride. The PU prepolymer and PA were blended, and the clear, transparent solutions were cast on glass substrates; this was followed by thermal treatments at various temperatures to produce reactions between the isocyanate group of the PU prepolymer and the hydroxyl group of PA. The opaque poly(urethane amide) films showed various properties, from those of plastics to those of elastomers, depending on the ratio of the PU and PA components. Dynamic mechanical analysis showed two glass‐transition temperatures (T_g's), a lower T_g due to the PU component and a higher T_g due to the PA component, suggesting that the two polymer components were phase‐separated. The rubbery plateau region of the storage modulus for the elastic films was maintained up to about 250 °C, which is considerably higher than for conventional PUs. Tensile measurements of the elastic films of 90/10 PU/PA showed that the elongation was as high as 347%. This indicated that the alloying of PU with PA containing aliphatic hydroxyl groups in the backbone improved the high‐temperature properties of PU and, therefore, enhanced the use temperature of PU. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 3497–3503, 2002     

Synthesis and characterization of poly(urethane‐benzoxazine) films as novel type of polyurethane/phenolic resin composites

Poly(urethane‐benzoxazine) films as novel polyurethane ( PU )/phenolic resin composites were prepared by blending a benzoxazine monomer ( Ba ) and PU prepolymer that was synthesized from 2,4‐tolylene diisocyanate (TDI) and polyethylene adipate polyol (MW ca. 1000) in 2 : 1 molar ratio. DSC of PU/Ba blend showed an exotherm with maximum at ca. 246 °C due to the ring‐opening polymerization of Ba, giving phenolic OH functionalities that react with isocyanate groups in the PU prepolymer. The poly(urethane‐benzoxazine) films obtained by thermal cure were transparent, with color ranging from yellow to pale wine with increase of Ba content. All the films have only one glass transition temperature (T_g ) from viscoelastic measurements, indicating no phase separation in poly(urethane‐benzoxazine) due to in situ polymerization. The T_g increased with the increase of Ba content. The films containing 10 and 15% of Ba have characteristics of an elastomer, with elongation at break at 244 and 182%, respectively. These elastic films exhibit good resilience with excellent reinstating behavior. The films containing more than 20% of Ba have characteristics of plastics. The poly(urethane‐benzoxazine) films showed excellent resistance to the solvents such as tetrahydrofuran, N,N‐dimethyl formamide, and N‐methyl‐2‐pyrrolidinone that easily dissolve PU s. Thermal stability of PU was greatly enhanced even with the incorporation of a small amount of Ba . © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 4165–4176, 2000     

Basic structure–property behavior of polyurethane cationomers

Polyurethane (PU) cationomers were synthesized from polytetramethylene adipate glycol (PTAd), isophorone diisocyanate (IPDI), and N-methyl diethanolamine (MDEA) according to a prepolymer mixing process. Basic structure-property behavior of the emulsion (obtained by adding water to the ionomer solution) and emulsion cast film was studied with regard to the molecular weight (M_n) of PTAd, MDEA content, degree of neutralization, and extender functionality. Particle size decreased asymptotically with increasing M_n of PTAd due to the increased chain flexibility, and with the degree of neutralization due to the increased hydrophilicity of the PU. Emulsion viscosity generally showed the opposite tendency with particle size dependence. The major transition temperature, corresponding to the glass transition (T_g) of phase mixed PU or hard segment-rich phase of the PU monotonically increased with MDEA content, degree of neutralization, and with increasing extender functionality. However, with increasing M_n of PTAd, T_g first decreased (M_n = 1000) and then increased (M_n = 1500, 2000), due respectively to the increased hard fraction of phase mixed PU, and soft segment crystallization. Tensile strength increased and elongation at break decreased with MDEA content, degree of neutralization, and extender functionality. © 1994 John Wiley & Sons, Inc.     

Polyisobutylene‐based polyurethanes X: PU nanocomposites with s‐containing soft segments

Sulfur‐containing polyisobutylene (PIB)‐based polyurethane nanocomposite (PIB_s‐PU/NC) was synthesized using HO? CH₂CH₂? S? PIB? S? CH₂CH₂? OH for the soft segment, conventional hard segments of MDI and BDO, and organically modified montmorillonite (OmMMT) nanolayers. The properties of PIB_s‐PU/NC containing 72.5% PIB and 0.5% OmMMT were studied and contrasted with unmodified PIB_s‐PU. PIB_s‐PU/NC produces colorless optically clear films exhibiting enhanced tensile strength, elongation, oxidative–hydrolytic stability, and creep resistance relative to that of PIB_s‐PU. FTIR spectroscopy indicates H bonded S atoms between soft and hard segments, and OmMMT nanolayers. DSC and XRD suggest randomly dispersed low‐periodicity crystals and urea groups between galleries. We propose that minute amounts of OmMMT nanolayers become covalently attached to polyurethane chains and beneficially affect properties by acting as co‐chain extender/reinforcing filler. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 2760–2765     

Liquid crystalline polyurethane. Polyurethanes containing bis-(p-oxymethylphenyl) terephthalate

Several polyurethanes based on bis-(p-oxymethylphenyl) terephthalate (BOPT) were synthesized and studied with respect to some of their thermal properties. BOPT exhibits a mesomorphic phase at 252–264°C. Polymerization was carried out by equimolar reaction with hexamethyl-ene diisocyanate (HDI), 4,4-dicyclohexylmethane diisocyanate (H₁₂MDI) α,α'-diisocyanate-1,3-dimethylcyclohexane (H6 XDI), 4,4′-diphenylmeth-ane diisocyanate (MDI), 2,4-tolylene diisocyanate (TDI), and phenylene diisocyanate (PDI). It became clear that polyurethanes obtained from BOPT with HDI, H₁₂MDI, H₆XDI, and TDI have mesomorphic phases at 243–291, 214–250, 172–229, and 180–234°C, respectively, as determined by DSC and polarized microscopy, and that all polyurethanes are crystalline as evidenced by x-ray diffraction.     

Chlorine degradation of polyether-based polyurethane

The tensile properties of polyether-based polyurethane (PU) filaments decrease with increasing chlorine concentrations as well as with treatment times. Fourier transform infrared (FTIR) results show the formation of quinoid, azo, and aldehyde groups in the chlorine-treated PU, and increased hydrogen bonding between the C O C in the soft segment and the N H in the hard segments. A breakdown mechanism involving chain cleavages along the ether linkages in the soft segments as well as at the urethane linkages of the hard–soft segment interfaces is proposed. Chlorine-treated PU showed increased solubility in tetrahydrofuran (THF). The molecular weight data of the THF-soluble portion of treated PU also support the proposed locations of chain scissions. The increased soft segment T_g and T_m with increasing chlorine concentrations are results of increased phase-mixing and hydrogen bonding. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 3263–3273, 1997