Polyätherester-Block-Copolymere – Eine Gruppe neuartiger thermoplastischer Elastomerer

High melting polyether esters can be prepared by ester interchange from readily available starting materials such as dimethyl terephthalate, polyalkylene ether glycols and linear short chain diols. The resulting block copolymers exhibit a continuous two-phase domain structure consisting of amorphous polyether ester soft segments and crystalline short chain polyester hard segments. By proper selection of the relative amounts of polyether and polyester segments, polymers ranging from fairly soft elastomers to impact resistant elastoplastics may be obtained. The preparation, morphology and physical characterization of polyether esters as well as the effect of the structures of the soft and hard segments on polymer properties are described. Polytetramethylene terephthalate based on polyether esters are particularly suited as thermoprocessable high performance elastomers offering an unusual combination of physical and chemical properties characterized by high abrasion, tear and solvent resistance as well as excellent low and high temperature properties. Because of their good melt stability, low melt viscosity and high crystallization rates, these polymers can be processed within a wide temperature range by all methods commonly used in the plastics industry.     

偶氮嵌段共聚物合成、自组装与光响应性

含偶氮苯基团的嵌段共聚物兼具偶氮聚合物和嵌段共聚物的特点,可自组装形成具有特殊光响应性能的各种纳米/亚微米结构,在光信息存储、传感器、药物输送、光控智能材料等领域有重要的应用前景。本文对本课题组近年来在含强推拉电子型偶氮生色团的嵌段共聚物合成、自组装与光响应性方面的研究工作进行简要综述。     

Solid-state thermochromism and piezochromism in the polysilylenes

The polysilylenes exhibit complex solid-state structures and electronic properties. In this report the solid-state conformational structures of symmetrically substituted poly(di-n-alkylsilylenes) are described. Comparisons between the different structures and their respective UV absorption characteristics demonstrate that the relationship is complex and aspects of molecular geometry beyond chain conformation must be considered. The thermochromic and piezochromic behavior of several of these polysilylenes is discussed. The all-trans conformation of the silicon backbone is associated with both phenomena. The properties of several polysilylene copolymers have also been investigated. We find that some of the copolymers form a well-ordered structure and exhibit absorption characteristics similar to the crystalline phases of the corresponding homopolymers.     

Role of chain symmetry and hydrogen bonding in segmented copolymers with monodisperse hard segments

Thermoplastic segmented polyurethane and polyurea copolymers whose monodisperse hard segments are based on only a single diisocyanate molecule are discussed. The solid-state structure-property behavior of these materials demonstrates that a proper selection of the level of symmetry and/or cohesiveness of the hard microdomains may allow elimination of the traditional requirement of chain extension to obtain melt processable segmented urethanes, and more specifically, urea copolymers with useful structural properties.     

The effect of soft‐segment structure on the properties of novel thermoplastic polyurethane elastomers based on an unconventional chain extender

Thermoplastic polyurethane elastomers (TPUs) are now widely used because of their excellent properties that include high tensile and tear strength, and good abrasion, impact and chemical resistance. TPUs are multiblock copolymers with alternating sequences of hard segments composed of diisocyanates and simple diols (chain extenders) and soft segments formed by polymer diols. Commonly used hard segments for TPUs are derived from 4,4′‐diphenylmethane diisocyanate (MDI) and aliphatic diols. The aim of our research was to examine the possibility of obtaining TPUs with good tensile properties and thermal stability by using an unconventional aliphatic‐aromatic chain extender, containing sulfide linkages. Three series of novel TPUs were synthesized by melt polymerization from poly(oxytetramethylene) diol, poly(ε‐caprolactone) diol or poly(hexane‐1,6‐diyl carbonate) diol of number‐average molecular weight of 2000 g mol^?1 as soft segments, MDI and 3,3′‐[methylenebis(1,4‐phenylenemethylenethio)]dipropan‐1‐ol as a chain extender. The structure and basic properties of the polymers were examined using Fourier transfer infrared spectroscopy, X‐ray diffraction, atomic force microscopy, differential scanning calorimetry, thermogravimetric analysis, Shore hardness and tensile tests. It is possible to synthesize TPUs from the aliphatic‐aromatic chain extender with good tensile properties (strength up to 42.6 MPa and elongation at break up to 750%) and thermal stability. Because the structure of the newly obtained TPUs incorporates sulfur atoms, the TPUs can exhibit improved antibacterial activity and adhesive properties. Copyright © 2011 Society of Chemical Industry     

Synthesis of polyurethane–imide (PU–imide) copolymers with different dianhydrides and their properties

This study reports the synthesis of polyurethane–imide (PU–imide) copolymers using 4,4′-diphenylmethane diisocyanate (MDI) polytetramethylene glycols (PTMGs) and different aromatic dianhydrides. Differential scanning calorimetry (DSC) results indicate that PU–imide copolymers had two phase structures containing four transition temperatures (T_gs, T_ms, T_gh and T_mh). However, only PU–imide copolymers were formed by soft PTMG(2000) segments possessing a T_ms (melting point of soft segment). When different aromatic dianhydrides were introduced into the backbone chain of the polyurethane, although the T_gs (glass transition temperature of the soft segment) of some of PU–imide copolymers did not change, the copolymers with long soft segments had low T_gs values. The T_gh (glass transition temperature of hard segment) values of PU–imide copolymers were higher than that of polyurethane (PU). In addition, the high hard segment content of PU–imide copolymer series also had an obvious T_mh (melting point of hard segment). According to thermogravimetric analysis (TGA) and differential thermogravimetric analysis (DTGA), the PU–imide copolymers had at least two stages of degradation. Although the T_di (initial temperature of degradation) depended on the hard segment content and the composition of hard segment, the different soft segment lengths did not obviously influence the T_di. However, PU–imide copolymers with a longer soft segment had a higher thermal stability in the degradation temperature range of middle weight loss (about T_d 5%–50%). However, beyond T_d 50% (50% weight loss at temperature of degradation), the temperature of degradation of PU–imide copolymers increased with increasing hard segment content. Mechanical properties revealed that the modulus and tensile strength of PU–imide copolymers surpassed those of PU. Wide angle X-ray diffraction patterns demonstrated that PU–imide copolymers are crystallizable. © 1999 Society of Chemical Industry     

不同结构水性聚氨酯分散体的合成与性能研究

用不同结构不同分子质量的聚酯多元醇合成一系列水性聚氨酯分散体,探讨了其力学性能、黏度、粘附力和贮存稳定性,还分析了结晶性、扩链剂和硬段含量对水性聚氨酯性能的影响.结果表明,用PBA和PHA合成的水性聚氨酯具有较好的性能,适度的结晶性有利于提高粘附力,扩链交联剂在一定的比例范围才能保持分散液的稳定性,40%～46%硬段含量可以保证水性聚氨酯既有较好的力学性能和黏度,又有满足使用要求的干燥速度.     

Comparative evaluation of different methods of inclusion of silver into sulfadiazine‐based polyurethane urea composites

This paper approaches two series of composites: one series incorporating silver nanopowder in sulfadiazine‐based polyurethane urea through a solution‐dispersion method, and another series of composites incorporating silver sulfadiazine in the hard domain of the main chains of the polyurethane. The morphology, structure, and physical properties of these silver composites with different hard segment structures were characterized and compared. It was found that using silver sulfadiazine as a chain extender causes an orderly dispersion of the silver ions along the backbone chain. This leads to an improvement in all properties for these composites, as opposed to composites which incorporated silver nanopowder. Thus, this paper expands on the development of a new and simple method of including silver during the synthesis reaction of the polymer matrix, by chain extension with silver sulfadiazine. Using silver sulfadiazine as a chain extender ensures the repartition of the silver on the molecular backbone chain which allows the silver ions to retain specific properties, unlike other composites which tend to lose silver over time through surface migration. POLYM. COMPOS., 38:2156–2165, 2017. © 2015 Society of Plastics Engineers     

浇注型聚氨酯弹性体耐酸碱性能研究

以不同种类二异氰酸酯和各种多元醇为主要原料,通过预聚法合成了一系列结构不同的聚氨酯弹性体(PUE),研究了软硬链段的化学结构及硬段含量对PUE耐酸碱性能的影响。结果表明,聚四氢呋喃醚多元醇作为软段具有更加稳定的化学结构,有利于PUE耐酸碱性的提高。选用刚性较大的二异氰酸酯4,4’-二苯基甲烷二异氰酸酯(MDI-100),以刚性对称的氢醌-双(β-羟乙基)醚(HQEE)为扩链剂,有利于聚氨酯分子链硬段的规整排列从而产生结晶,可提高PUE的耐酸碱性。     

Benzoin‐terminated polyurethane as macrophotoinitiator for synthesis of polyurethane–polymethyl methacrylate block copolymers

Macromolecular photoinitiators have attracted much attention in the recent years. They combine the properties of polymers with those of low‐molecular weight photoinitiators. These are polymers having side‐ or main‐chain photoreactive groups and can be used to make tailor‐made graft and block copolymers. Benzoin is an important photoinitiator, and polymers containing terminal photoactive benzoin group can initiate polymerization of vinylic monomers to give block copolymers. In the present case, we report the synthesis of polyurethane macrophotoinitiator with benzoin end group, which was subsequently used to synthesize polyurethane–polymethyl methacrylate block copolymers. The block copolymers were characterized by FTIR, ¹H NMR, TGA, scanning electron microscopic analysis, and solution viscometry studies. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Synthesis and characterization of poly(siloxane-urethane)s

A series of polyurethane block copolymers based on hydroxy-terminated polydimethylsiloxane and poly(propylene glycol) soft segments of molecular weights 1818 and 2000, respectively, were synthesized. The hard segments consisted of 4,4′-diphenylnethane diisocyanate and 1,4-butanediol as the chain extender. Samples with different molar ratios were prepared. We tried to synthesize polydimethylsiloxane-based polyurethanes (PDMS-PU) containing a hard block as major fraction and a soft block as minor fraction for preparing toughened rigid systems. After a study of the pure polydimethylsiloxane-based polyurethane and poly(propylene glycol)-based polyurethane (PPG-PU), (mixed polyol)-based block copolymers and blends of PDMS-PU and PPG-PU were synthesized, and characterized by means of differential scanning calorimetry, tensile testing and scanning electron microscopy. In (mixed polyol)-based copolymers and lower hard-segment content blends, macro-phase separation occurred, but blends with higher hard-segment contents showed significant reduction in amounts of phase separation.     

Stimuli-responsive tertiary amine methacrylate-based block copolymers: Synthesis,supramolecular self-assembly and functional applications

In the past decade, responsive polymers exhibiting reversible or irreversible changes in physical properties and/or chemical structures in response to external stimuli have been extensively investigated. Among them, tertiary amine methacrylate-based block copolymers represent a unique category considering their responsiveness to multiple external stimuli (e.g., pH, temperature and salts), which are essentially relevant to the biological milieu. These intriguing properties allow for their applications in a variety of fields ranging from drug or gene delivery, imaging, diagnostics, antibacterial coatings, catalysis, and bio-separations. This review article highlights tertiary amine methacrylate-based block copolymers, focusing on recent advances in the synthesis of tertiary amine methacrylate-based block copolymers with varying chemical structures and chain topologies, their supramolecular self-assembly in aqueous media as well as in the bulk state, and the emerging functional applications.     

Mechanical properties and fractography of block copolymers based on NR and MDI-based polyurethanes

Five series of block copolymers were synthesized from hydroxyl-terminated liquid natural rubber (HTNR) and polyurethane (PU) oligomers, from various diols and diphenyl methane-4,4′-diisocyanate (MDI). They were characterized by mechanical testing and fracture studies (SEM analysis). The block copolymer characteristics were assessed on the basis of the composition and the type of extender diols. Mechanical properties were found to be strongly dependent on the copolymer composition in all the series. Tensile properties were found to improve with the hard segment content. At low hard segment content samples resemble flexible elastomers whereas at high hard segment content they behave as rigid plastics. Where bisphenol A (BPA) is used as the extender diol sample rigidity was higher compared to the samples with aliphatic diols which is attributed to the presence of aromatic ring system in the former samples. Fracture mechanism was found to vary from ductile fracture to rigid and brittle fracture as the hard segment content increased. Fractography also shows the presence of some beads disposed on the sample surface which could be the uncombined polyurethane homopolymer fractions.     

Block architecture influence on the structure and mechanical performance of drawn polyurethane elastomers

Some natural biopolymers such as spider silk exhibit superb mechanical properties, characterised by their great toughness. Synthetic polyurethane (PU) copolymers also endow great toughness but lack silk's stiffness and strength. The aim of this work was to elucidate the role of segment block architectural features that influence PU stiffness and strength after cold drawing. For this purpose PUs with varied soft segment character, crystalline versus rubbery, as well as with different hard segment chemistries, 4,4′‐diphenylmethane diisocyanate/1,4‐butanediol versus 1,6‐hexamethylene diisocyanate/1,4‐butanediol, were synthesised by a two‐step polymerisation method. We found that the architecture of both block segments has a dramatic influence on drawn PU mechanical performance, in which PUs with crystallisable soft segments and crystalline hard segments are shown to have a greater impact on developing stiffer and stronger materials. © 2013 Society of Chemical Industry     

Self-healing supramolecular waterborne polyurethane dispersions with quadruple hydrogen bonds in main chain

A facile method for preparing supramolecular waterborne polyurethane (WPU) based on quadruple hydrogen bonds (4H-WPU) is reported. Herein, 4H-WPU with quadruple hydrogen bonds in main chain were synthesized by poly (1,4-buthylene-neopentylene adipate glycol) as soft segment, 2-ureido-4[1H]-pyrimidinone (UPy) functionalized monomer, isophorone diisocyanate, 2,2-Bis(hydroxymethyl)propionic acid (hydrophilic monomer), isophorondiamine, triethylamine (neutralizer), and monoethanolamine (blocking agent) as hard segment. The molecular weight of 4H-WPU was controlled around 18,000 consistently. The properties of 4H-WPU with different content of hydrophilic group, hard segment, and UPy units were characterized and the results could provide the reference for preparing supramolecular WPU with high mechanical and self-healing performance while maintaining dispersion stability. The tensile strength of 4H-WPU was 10 times of the blank sample. The healing time of scratched 4H-WPU film was inversely proportional to the content of UPy- functionalized monomer and the shortest healing time is 2.5 hr at 80°C. Mechanical performance of healed films can be restored to more than 90%.     

Facile synthesis of multiblock copolymers composed of poly(tetramethylene oxide) and polystyrene using living free-radical polymerization macroinitiator

A facile synthetic strategy for well-defined multiblock copolymers utilizing ‘living’ free-radical polymerization macroinitiator has been presented. Polyurethane composed of alkoxyamine initiating units and poly(tetramethylene oxide) (PTMO) segments was prepared by polyaddition of tolylene 2,4-diisocyanate terminated PTMO with an alkoxyamine-based diol. Polymerization of styrene with the polyurethane macroinitiator was carried out under nitroxide-mediated free-radical polymerization (NMRP) condition. GPC, NMR, and IR data revealed that the polymerization was accurately controlled and well-defined polystyrene chains were inserted in the main chain of macroinitiator to give the poly(tetramethylene oxide)-b-polystyrene multiblock copolymers. The synthesized multiblock copolymers were characterized by tensile test, differential scanning calorimetry, and dynamic mechanical analysis. Mechanical properties of the multiblock copolymers can be tuned by the sufficient molecular weight control of PS chains. Soft segment of PTMO and hard segment of PS were apparently compatible due to the multiblock structure of low molecular weight segments and polar urethane groups.     

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

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

The effect of chain extenders structure on properties of new polyurethane elastomers

Two series of polyurethane elastomers were synthesized to investigate what effect does the incorporation of various new chain extenders have on the mechanical and thermal properties of polyurethane elastomers. The polyurethane soft segments were based on poly(ε-caprolactone) polyol. The hard segment was based on 1,6-hexamethylene diisocyanate in combination with 2,5-dimethyl-3-hexine-2,5-diol (DHD), hexaethylene glycol, glycerin, or castor oil. The results showed that the degradation rate and mechanical properties of the final products can be controlled through the structure of diol chain extenders or/and hard segment cross-linking present in the polyurethane elastomers. The DHD-based polyurethane displayed a relatively low glass transition temperature of −57 °C and a tensile strength of 11–14 MPa and elongation at break of 600–700%. These kinds of materials have potential application in many domains.     

Properties of random and block copolymers of butadiene and styrene. I. Dynamic properties and glassy transition temperatures

The effect of monomer sequence on physical properties was investigated for butadienestyrene solution copolymers made by organolithium initiation. The polymers varied from random copolymers of uniform composition along the polymer chain to ideal block polymers of specific block sequence arrangement and included rubbers of intermediate degrees of randomness. Uniform composition random copolymers exhibit a single glass transition temperature and a very narrow dynamic loss peak corresponding to this transition. The glass transition can be predicted from the styrene content and the microstructure of the butadiene portion of the rubber. Random copolymers in which composition varies along the polymer chain, and to some extent between molecules, exhibit a single glass transition, but the dynamic loss peak is broadened. The extent of this broadening is shown to be compatible with the sequence distribution, polymer segments of various compositions losing mobility at different temperatures. This indicates a tendency for association between segments of different temperatures. This indicates a tendency for association between segments of different chains which are similar in composition. Block copolymers display two transitions, corresponding to T_g for each type of block. The position and width of the dynamic loss peaks are related to block length and compositional purity of the blocks.     

Influence of the hydroquinone ether moieties and Bisphenol A glycerolate diacrylate on the UV stability behavior of new polyurethane materials

A series of the polyurethane materials with different ratios of hydroquinone ether derivatives and bisphenol A glycerolate diacrylate were synthesized using a two-step polymerization procedure. The structures of the obtained polyurethanes were characterized by Fourier transform infrared spectroscopy (FTIR). The influence of the hard segments structure on the thermo-mechanical properties were studied by TGA and stress-strain testing. It was found that with the increase in bisphenol A glycerolate diacrylate content, the new polyurethane materials had improved thermo-mechanical properties, due to the fact that the material develops a crosslinked structure. The durability of the polyurethane films when exposed to ultraviolet radiation was tracked by mechanical behavior and changes in chemical structure. Bisphenol A glycerolate diacrylate-based polyurethane elastomers exhibit improved behavior under UV radiation exposure compared with conventional polyurethanes that are chain-extended with butanediol.