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     

High performance UV cured polyurethane dispersion

Imide groups were introduced in the hard segment of UV cured polyurethane dispersion (UV-PUD) by extending the NCO terminated prepolymers with pyromellitic dianhydride (PMDA) where the soft segments were prepared from PTMG, H₁₂MDI, HDI and DMBA. It was found that imide hard segment, as compared with conventional urethane hard segment gave remarkably high mechanical properties as well as thermal stability in terms of decomposition temperature and dynamic mechanical properties at elevated temperatures, and the results were interpreted based on the partial mixing of soft segments and imide hard segments.     

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.     

FTIR STUDIES ON THE MODEL POLYURETHANE HARD SEGMENTS BASED ON A NEW WATERBORNE CHAIN EXTENDER DIMETHYLOL BUTANOIC ACID （DMBA）

Three model polyurethane hard segments based on dimethylol butanoic acid (DMBA) and 1,6-hexane diisocyanate (HDI), toluene diisocyanate (TDI) and 4,4‘-diphenylmethane diisocyanate (MDI) were prepared by the solution method.Fourier Infrared (FTIR) spectroscopy was employed to study the H-bonds in these model polyurethanes. The model polyurethane hard segment prepared from HDI and 1,4-butanodiol (BDO) was used for comparison. It was found that the incorporation of the pendent carboxyl through DMBA into the model hard segments weakens the original NH…O=C H-bond but gives more H-bond patterns based on the two H-bond donors, urethane NH and carboxylic OH. The carboxylic dimer is one of the main H-bond types and is stronger than another main H-bond type NH…O=C. In addition, the H-bond in aromatic model hard segments is stronger than that of aliphatic hard segments. The appearance of the free C:O and the fact that almost all N-H is H-bonded suggest that there possibly exist either the third H-bond acceptor or the H-bond formed by one acceptor with two donors.     

液晶型聚氨酯弹性体的固体高分辨核磁共振研究

采用固体高分辨＾１３Ｃ核磁共振谱以及溶液碳谱、氢谱的方法对以聚四氢呋喃（ＰＴＭＯ）为软段、４，４＇－二苯基甲烷二异氰酸酯（ＭＤＩ）为硬段、４，４＇－二羟已氧基联苯（ＨＢ６）为扩链剂的液晶型聚氨酯弹性体的相态结构、分子运动、氢键相互作用等问题进行了研究。探讨了样品的化学结构与上述问题间的关系。     

端羟基芳香酯二醇扩链的聚氨酯－酯的DSC研究

端羟基芳香酯二醇扩链的聚氨酯－酯的ＤＳＣ研究陈静，余学海，杨昌正（南京化工学院应化系南京２１０００９）（南京大学化学系南京２１００９３）关键词嵌段聚醚聚氨酯－酯，结晶性，微观相结构，差示扫描量热法，形态结构众所周知，聚氨酯嵌段共聚物是一类结构特殊、用...     

端羟基芳香酯二醇扩链的聚氨酯－酯的DSC研究

端羟基芳香酯二醇扩链的聚氨酯－酯的ＤＳＣ研究陈静，余学海，杨昌正（南京化工学院应化系南京２１０００９）（南京大学化学系南京２１００９３）关键词嵌段聚醚聚氨酯－酯，结晶性，微观相结构，差示扫描量热法，形态结构众所周知，聚氨酯嵌段共聚物是一类结构特殊、用...     

Synthesis and characterization of polydimethylsiloxane polyurea-urethanes and related zwitterionomers

A series of segmented polyurea urethane and polyurea block copolymers based on a hexane diisocyanate (HDI) modified aminopropyl terminated polydimethylsiloxane soft segment was synthesized. The hard segments consisted of 4,4′-methylene diphenylene diisocyanate (MDI) which was chain extended with 1,4-butanediol (BD), N-methyldiethanolamine (MDEA), or ethylene diamine. Zwitterionomers were prepared by quaternizing the tertiary amine of the MDEA extended material with γ-propane sultone. The effect of chemical structure on the extent of phase separation and physical properties was studied using a variety of techniques including thermal analysis, dynamic mechanical spectroscopy, tensile testing, and small-angle x-ray scattering. It was observed that the compatibility between the nonpolar polydimethylsiloxane soft segments and the polar urethane hard segments was improved by inserting HDI linkages into the polydimethylsiloxane soft segments. The aggregation of hard segments was enhanced by increasing hard-segment content or by the introduction of ionic functionality. The tensile strength and modulus of these materials was higher than those of polyurethanes containing soft segments based on polydimethylsiloxane and its derivatives.     

Synthesis and properties of polycyanoethylmethylsiloxane polyurea urethane elastomers: A study of segmental compatibility

A series of polyurea urethane block polymers based on either aminopropyl-terminated polycyanoethylmethylsiloxane (PCEMS) soft segments or soft segment blends of PCEMS and polytetramethylene oxide (PTMO) were synthesized. The hard segments consisted of 4,4′-methylenediphenylene diisocyanate (MDI) chain-extended with 1,4-butanediol. The hard segment content varied from 11 to 36%, whereas the PTMO weight fraction in the soft segment blends varied from 0.1 to 0.9. The cyanoethyl side group concentration was also varied during the synthesis of the PCEMS oligomer. The morphology and properties of these polymers were studied by differential scanning calorimetry, infrared spectroscopy, dynamic mechanical and tensile testing, and small-angle x-ray scattering. These materials exhibited microphase separation of the hard and soft segments; however, attaching polar cyanoethyl side groups along the apolar siloxane chains promoted phase mixing in comparison with polydimethylsiloxane-based polyurethanes. The increased phase mixing is postulated to lead to improved interfacial adhesion and thus can account for the observed improvement in ultimate tensile properties compared with polydimethylsiloxane-based polyurethanes. Both hard segment content and cyanoethyl concentration are important factors governing the morphological and tensile properties of these polymers.     

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.     

Model MDI/butanediol polyurethanes: Molecular structure,morphology, physical and mechanical properties

Model butanediol–MDI–polypropylene oxide polymers have been synthesized to explore the structure–property relationships in urethane/polyether polymers. The results of mechanical, thermal, and spectroscopic analyses agree remarkably well. The phase mixing in these polymers decreases with increasing hard-segment length, while the hard-segment stability increases with increasing hard-segment length. This is demonstrated clearly by dynamic mechanical, differential scanning calorimetry, infrared, and NMR studies. The importance of hydrogen bonding to the stability of the hard segment is strongly supported by the variable-temperature infrared experiments. The critical hard-segment size for phase segregation was shown to be two butanediols per hard segment. The temperature limit of the flatness of the storage modulus was tied to the thermal stability of the hard-segment hydrogen bonding which is controlled largely by the length of the hard segment and the extent of the hydrogen bonding.     

Synthesis and Characterization of Thermoplastic Polyurethaneureas based on Polyisobutylene and Poly(tetramethylene oxide) Segments

New thermoplastic polyurethaneureas (TPUU) based on polyisobutylene (PIB) and poly(tetramethylene oxide) (PTMO) segments have been synthesized possessing tensile properties comparable to conventional PTMO based TPUs. PIB based TPUU containing 35 weight (wt)% hard segment was synthesized by chain extension of H₂N-Allyl-PIB-Allyl-NH₂ with 4,4′ -methylene bis(phenylisocyanate) (MDI) and 1,4-butanediol (BDO) in toluene. The ultimate tensile strength (UTS) = 12 MPa and ultimate elongation = 70% were inferior to PTMO based polyurethane (UTS = 35 MPa, elongation at break = 600%). H₂N-Allyl-PIB-Allyl-NH₂ and HO-PTMO-OH in different proportions were chain extended in presence of MDI and BDO to obtain TPUUs containing 35 wt% hard segment. The polymers exhibited M _ns = 84000–138000 with polydispersity indices (PDIs) = 1.7–3.7. The UTS = 23–32 MPa and elongation at break = 250–675% was comparable to that of PTMO based polyurethane and significantly higher than the PIB based TPUU with the same Shore hardness. The Young's modulus of the polymers was strongly dependent and directly proportional to the PIB wt% in the SS of the TPUUs.     

Structure-property relationships in polycaprolactone-polyurethanes

The structure-property relationships of polycaprolactone-based segmented polyurethanes were studied using differential scanning calorimetry (DSC), small-angle x-ray scattering (SAXS), wide-angle x-ray diffraction (WAXD), dynamic mechanical, and stress-strain testing. The materials studied varied in hard-segment type [4,4′-diphenylmethane diisocyanate/butanediol (MDI/BD) or 4,4′-dicyclohexyl methane diisocyanate/butanediol (H₁₂MDI/BD)], soft-segment molecular weight (830 or 2000 MW polycaprolactone), hard-segment content (23–77% by weight), and thermal history. The materials with aromatic (MDI/BD) hard segments had semicrystalline hard-segment domains, while the materials with aliphatic (H₁₂MDI/BD) hard segment had mostly amorphous domains. Materials with the shorter polycaprolactone soft segment (830 MW) exhibited thermal and mechanical behavior which indicated a considerable degree of hard- and soft-segment compatibility. The materials which contained a 2000-MW polycaprolactone soft segment exhibited better-defined microphase separation. SAXS was used to characterize the microphase structure of each system. The effects of hard-segment content and soft-segment molecular weight were similar for the aromatic (MDI) and aliphatic (H₁₂MDI) hard-segment-based block copolymers. Changing the hard segment from aromatic to aliphatic gave materials with larger interfacial area and slightly higher tensile strength. A range of morphologies between isolated hard domains in a rubbery matrix and isolated rubbery domains in a hard matrix was observed.     

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．     

Microphase separation in RIM polyureas as studied by solid-state NMR

The microphase separation (MPS) in polyureas based on methylene diphenyl diisocyanate (MDI) hard segment, diethyltoluenediamine chain extender, and amino-terminated polypropylene glycol soft segment prepared by reaction injection molding (RIM) was studied by advanced solid-state NMR spectroscopy. Incomplete microphase separation leads to the presence of mobilized hard segments dispersed in the soft segment domains as well as immobilized soft segments residing in the hard domains. This is detected by ¹H-NMR spectra recorded under spinning at the magic angle (MAS) as well as two-dimensional wide-line separation (WISE) NMR spectra. The sizes of the various domains as well as the interfaces between them are quantified by spin diffusion measurements. In this way the impact of annealing, method of polymerization, and hard segment content on MPS is studied. Whereas annealing at temperatures up to 170°C results in improving the MPS, major changes are observed after annealing at higher temperatures (190°C), where the system changes from “soft-in-hard” to “hard-in-soft” behavior. The MPS decreases with increasing hard segment content. The highest MPS is observed for solution polymerized samples. The various NMR experiments clearly reveal the nonequilibrium nature of RIM systems. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 693–703, 1998     

SOLID-STATE VARIABLE-TEMPERATURE NMR STUDY ON THE PHASE SEPARATION OF POLYETHER POLYURETHANE ZWITTERIONOMERS

Polyether-polyurethane zwitterionomers based on 4, 4'-diphenylmethane diisocyanate(MDI), methyl diethanolamine (MDEA), and polytetramethylene oxide glycol (PTMO) werestudied with variable-temperature wide-line ~1H NMR. It is found that upon ionization, degree ofphase separation in the polymer system decreased at first due to the loss of hard segmentregularity, while further ionization increased the degree of phase separation through increasinghard phase cohesion and difference of polarity between hard and soft segments.     

Studies on thermoplastic polyurethanes based on new diphenylethane-derivative diols. II. Synthesis and characterization of segmented polyurethanes from HDI and MDI

Various new thermoplastic segmented polyurethanes were synthesized by a one-step melt polymerization from aliphatic-aromatic α,ω-diols containing sulfur in the aliphatic chain, including 4,4′-(ethane-1,2-diyl)bis(benzenethioethanol), 4,4′-(ethane-1,2-diyl)bis(benzenethiopropanol) and 4,4′-(ethane-1,2-diyl)bis(benzenethiodecanol) as chain extenders, hexane-1,6-diyl diisocyanate (HDI) or 4,4′-diphenylmethane diisocyanate (MDI) and 20-80 mol% poly(oxytetramethylene)diol (PTMO) with molecular weight of 1000 g/mol as a soft segment. The reaction was conducted at the molar ratio of NCO/OH = 1 and 1.05, and in the case of the HDI-based polyurethanes in the presence of dibutyltin dilaurate as a catalyst. The effect of the diisocyanate used on the structure and some physicochemical, thermal and mechanical properties of the segmented polyurethanes were studied. The structures of these polyurethanes were examined by FTIR and X-ray diffraction analysis. The thermal properties were investigated by differential scanning calorimetry and thermogravimetric analysis. Shore hardness and tensile properties were also determined. All the synthesized polymers showed partially crystalline structures. The MDI-based polyurethanes were products with lower crystallinity, higher glass-transition temperature (T_g) and better thermal stability in comparison with the HDI-based ones. The MDI series polymers also exhibited higher tensile strength (up to ∼36 MPa vs. ∼23 MPa) and elongation at break (up to ∼3900% vs. ∼900%), but lower hardness than the analogous HDI series polyurethanes. In both series of the polymers an increase in PTMO soft-segment content was associated with decreased crystallinity, T_g, hardness and tensile strength. An increase in PTMO content also involved an increase in elongation at break.     

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.     

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.