Study on preparation and properties of polyether polytriazole elastomers

To explore the application of click chemistry in the field of elastomer materials, propargyl-terminated ethylene oxide-tetrahydrofuran copolymer(PTP(E-co-T)) was prepared from hydroxyl-terminated ethylene oxide-tetrahydrofuran copolymer(P(E-co-T)) by end-etherisation modification. FTIR and 13C-NMR results indicate that P(E-co-T)-terminated hydroxyl was etherified thoroughly, yielding the target product PTP(E-co-T), and the content of terminated alkynyl of PTP(E-co-T) was evaluated to be 0.428 mmol·g-1. Using a polyazide compound as a cross-linker, polytriazole elastomers with various functional molar ratio(R) values were prepared from PTP(E-co-T) by virtue of the Cu AAC reaction. Mechanical property tests indicate that with the increase in R, the modulus E and stress σb of the polytriazole elastomers first increase and subsequently decrease, whereas the strain first decreases and later increases. The mechanical properties of the polytriazole elastomers show a parabolic dependence on the R value. Near the stoichiometric ratio, E and σb show maxima and the strain εb shows a minimum. Swelling tests demonstrate that the apparent molecular weight of polytriazole elastomer strands also first decreases and subsequently increases. At the stoichiometric ratio, the network structure possesses strands with a minimum apparent molecular weight and a maximum apparent density. Dynamic mechanical analysis reveals that the polytriazole elastomers presented damping peaks at approximately-64 °C, corresponding to the glass transition of copolyether strands, and the elastomer exhibited the lowest dissipation factor tanδ at the stoichiometric ratio. Thermal analysis suggests that the weight-loss process of the polytriazole elastomer is characteristic of one-step decomposition, and the elastomer begins to decompose from polyether strands, not triazole groups.     

CO_2共聚物为基的新型聚氨酯弹性体的合成与性能

本文报道一类以ＣＯ＿２共聚物为基的新型聚碳酸亚丙酯聚氨酯（ＰＰＣＰＵ）弹性体。探讨了这类弹性体的最佳台成方法．讨论了不同配比，不同的扩链交联剂对弹性体的力学性能的影响。研究了弹性体的热性能及耐水性与不同配比的依赖关系。发现控制适当的配比．能获得耐水住能和耐热性能良好的弹性体。     

Synthesis and nonlinear optical properties of hyperbranched polytriazole containing second‐order nonlinear optical chromophore

The hyperbranched polytriazole (hb‐PTA) containing second‐order nonlinear optical chromophore was synthesized through “A₂ + B₃” approach based on “click reaction.” Its corresponding linear analogue (l‐PTA) was prepared for comparison. The hb‐PTA has better solubility in common organic solvents than the l‐PTA. Both the polymers exhibit good thermal stability with 5% weight loss temperatures over 260 °C. The poled film of hb‐PTA exhibits much higher second‐harmonic coefficient (96.8 pm/V) than that of l‐PTA (23.5 pm/V). The three‐dimensional spatial isolation effect resulting from the highly branched structure and the crosslinking of the terminal acetylene groups at moderate temperature play important roles in the enhancement of optical nonlinearity. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 1140–1148, 2008     

Studies on thermotropic liquid crystalline polyurethanes. II. Synthesis and properties of liquid crystalline polyurethane elastomers

Three series of novel thermotropic liquid crystalline polyurethane elastomers (TLCPUEs) were studied. Hard segments were formed by using hexamethylene diisocyanate (HDI) reacted with a mesogenic unit, benzene-1,4-di(4-iminophenoxy-n-hexanol), which also acted as a chain extender. Three diols: 1,10-decanediol,poly(oxytetramethylene) glycol (PTMEG) M _n = 1000 and PTMEG M _n = 2000 were used as the soft segments. The effects of soft segments of polyurethanes on the liquid crystalline behavior were studied. Higher molecular weight TLCPUEs were obtained by adding 30?50 mol % of mesogenic segments to diisocyanates. In contrast to a conventional chain extender such as 1,2-ethylene glycol or 1,4-butyl glycol, the synthesized polyurethane elastomers exhibited a mesophase transition by using a mesogenic unit as the chain extender. Mesophase was found for all synthesized LC polyurethanes except of polymers H2-A-12 and H2-A-7. The structures and the thermal properties of all synthesized TLCPUEs were studied by using FTIR spectroscopy, wide-angle x-ray diffraction (WAXD) and DSC measurements, a polarizing microscope equipped with a heating stage, dynamic mechanical analysis (DMA), and thermogravimetric analysis (TGA). Mechanical properties were also examined by using a tensilemeter. © 1995 John Wiley & Sons, Inc.     

Aggregation structure and mechanical properties of functionally graded polyurethane elastomers

Functionally graded polyurethane elastomers (FGPUEs) were prepared with two molds fixed at different temperatures (30 and 150 °C). The effects of the molar ratio of the curing agent (60/40, 75/25, or 97/3 1,4‐butane diol/1,1,1‐trimethylol propane) and the molecular weight of the polymer glycol (number‐average molecular weight = 2000 or 3000) on the molecular aggregation state and mechanical properties of the FGPUEs were investigated with differential scanning calorimetry, polarized optical microscopy, dynamic viscoelastic measurements, and tensile tests. The aggregation state of the FGPUEs was changed continuously from the one side (lower temperature side) to the other side (higher temperature side); for example, the glass‐transition temperature gradually increased in this direction. Also, the number of spherulites formed in the FGPUEs increased in the same manner. In the mechanical tests, the tensile strength and elongation at break of the lower temperature side were higher than those of the higher temperature side. This was correlated with the strong phase separation of the lower temperature side. The poly(oxytetramethylene glycol)‐based FGPUE with a chain extender of 75 wt % showed the largest degree of the temperature gradient. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 2355–2363, 2003     

Synthesis of transparent thermoplastic polyurethane elastomers

Thermoplastic polyurethanes were synthesized from poly(propylene glycol)‐block‐poly(ethylene glycol) polyols and hybrid hard segments that combined at least two different chain extenders. The combination of hard segments allowed for modification of elastomer performance and processing not achievable by any single hard segment. The combination of hard segments modulated hard‐segment energies that were directly related to elastomer performance. Special attention is paid to obtaining optically transparent elastomers with this technique. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 271–278, 2004     

Studies on thermotropic liquid crystalline polyurethanes. III. Synthesis and properties of polyurethane elastomers by using various mesogenic units as chain extender

Four series of thermotropic polyurethane elastomers (TPUEs) were synthesized in this study. The hard segments were formed by using 4,4′-methylenedicyclohexyl diisocyanate (H₁₂MDI) reacted with various mesogenic units, such as benzene-1,4-di(4-iminophenoxy-n-hexanol), benzene-1,4-di(4-iminophenol), and 3,3′-(4,4′-biphenylene)dipropanol, which also acted as the chain extender. Poly(oxytetramethylene)glycols (PTMEGs), PTMEG-2000 (M_n 2,000) and PTMEG-1000 (M_n 1,000) were used as a soft segment. The structures of all synthesized thermotropic liquid crystalline polyurethanes (TLCPUs) were characterized by FTIR spectroscopy. The effects of mesogenic units on the LC properties and elastic behaviors of LCPUs were studied. It was difficult to show LC behaviors for the PU elastomers derived from the mesogenic units with a lower aspect ratio, such as 3,3′-(4,4′-biphenylene)dipropanol, or the long soft segments, PTMEG-2000. In addition, these PU elastomers show better elastic properties by using a higher aspect ratio mesogenic unit as the chain extender, such as benzene-1,4-di(4-iminophenoxy-n-hexanol and benzene-1,4-di(4-imino-phenol)). The thermal properties were investigated by DSC measurements, thermal optical polarized microscopy, wide angle X-ray diffraction, dynamic mechanical analysis, and thermogravimetric analysis. The mechanical properties were measured by a tensilemeter. © 1996 John Wiley & Sons, Inc.     

Anti‐vibration and vibration isolator performance of poly(styrene‐butadiene‐ styrene)/ester‐type polyurethane thermoplastic elastomers

This investigation presents novel thermoplastic elastomers (TPEs) based on poly(styrene‐butadiene‐styrene) (SBS) and ester‐type polyurethane (TPU‐EX) materials were prepared with varying compositions. A series of investigations were conducted on the relationships between mechanical properties, dynamic mechanical properties, anti‐vibration and vibration isolator properties given, and the different compositions. The experimental results show incompatibilities between SBS and TPU‐EX. SBS mechanical properties, dynamic mechanical properties, anti‐vibration and vibration isolator properties are improved with an increase in the amount of TPU‐EX, suggesting that the blending of SBS with TPU‐EX was consistent with the compound rule. Based on the obtained results, the viscoelasticity of SBS materials, their capacity to isolate vibration, and their anti‐vibration performance can be adjusted by controlling the proportion of TPU‐EX. Copyright © 2009 John Wiley & Sons, Ltd.     

Amphiphilic thermoset elastomers from metal‐free,click crosslinking of PEG‐grafted silicone surfactants

The hydrophobicity of silicone elastomers can compromise their utility in some biomaterials applications. Few effective processes exist to introduce hydrophilic groups onto a polysiloxane backbone and subsequently crosslink the material into elastomers. This problem can be overcome through the utilization of metal‐free click reactions between azidoalkylsilicones and alkynyl‐modified silicones and/or PEGs to both functionalize and crosslink silicone elastomers. Alkynyl‐functional PEG was clicked onto a fraction of the available azido groups of a functional polysiloxane, yielding azido reactive PDMS‐g‐PEG rake surfactants. The reactive polymers were then used to crosslink alkynyl‐terminated PDMS of different molecular weights. Using simple starting materials, this generic yet versatile method permits the preparation and characterization of a library of amphiphilic thermoset elastomers that vary in their composition, crosslink density, elasticity, hydrogel formation, and wettability. An appropriate balance of PEG length and crosslink density leads to a permanently highly wettable silicone elastomer that demonstrated very low levels of protein adsorption. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 1082–1093     

Preparation of polyurethane elastomers (PUEs) in a high‐throughput workflow

High‐throughput experimentation (HTE) represents a promising and versatile approach for polyurethane (PU) research as a tool to rapidly screen and characterize a large number of samples in an automated way. To realize a unique HTE workflow for the research and development of PU elastomers (PUEs), the use of parallel automated formulation and coating platforms at Flamac were explored. To evaluate the applicability of HTE for PUEs, four different PU systems were investigated with different reactivities and viscosities. All prepared PUEs were evaluated by conventional physical testing methods measuring the E‐modulus, tensile‐elongation and the hardness properties revealing similar trends as conventionally prepared PUEs indicating the viability of the HTE approach. In addition, the properties of the PUEs were also investigated using downscaled microtensile bars as well as depth‐sensing indentation, again, revealing similar trends. With this proof of principle study, we demonstrated for the first time that HTE can also be extended to polymeric materials based on high reactive and viscous raw materials in combination with complex technologies. The reported results provide a basis for the use of HTE approaches for preparing, screening and characterizing large numbers of PUEs for R&D purposes. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

聚酯的序列结构对聚氨酯弹性体形貌的影响

以己二酸(AA),1,4-丁二醇(BDO),乙二醇(EG)分别采用一步法、二步法合成分子量为3000的聚酯PAEB-R和聚酯PAEB-A.再分别与二苯基甲烷二异氰酸酯(MDI)、扩链剂1,4-丁二醇(BDO),乙二醇(EG)反应分别合成固含量30%与粘度为20000的聚氨酯(PAEB-R)-MDI-TPU和聚氨酯(PAEB-A)-MDI-TPU.SEM、AFM表明不同工艺所合成的聚氨酯均存在微相分离,且聚氨酯(PAEB-R)-MDI-TPU微相分离程度高于(PAEB-A)-MDI-TPU.     

Synthesis, characterization and mechanical properties of polyester-based aliphatic polyurethane elastomers containing hyperbranched polyester segments

Aliphatic polyester-based polyurethane (PU) elastomers with hyperbranched polyester segments were synthesized from polyester diol, hydroxyl-terminated hyperbranched polyester (HB-20), isophorone diisocyanate (PDI) and 1,4-butanediol. The crosslinking density of the PU elastomer was calculated by using Flory-Rehner equation. The degree of hydrogen bonding, the microstructure and the morphologies of these PU materials were characterized by means of FT-IR, WAXD and DSC, respectively. The experimental results showed that the PU elastomers containing small amount of HB-20 exhibited the enhanced hydrogen bonding and mechanical properties. As compared with the comparable PU specimen, the tensile strength of the polyester-based aliphatic PU containing 6 wt% HB-20 increased by 71.2 times, up to 36.1 MPa, and the elongation at break was still as high as 333.1%, resulting from the dual effects of the hydrogen bonding and the crosslinking density in the PU system.     

Crack growth in medical-grade silicone and polyurethane ether elastomers

One major problem with ball and socket artificial discs is the migration of wear particles to the surrounding tissues. This debris can cause inflammation that can lead to implant loosening. Encapsulating the artificial disc with an elastomer sheath could prevent this problem by retaining the wear particles within the disc. The encapsulation sheath will face millions of tensile cycles during the implant life and, therefore, it must have the ability to withstand large strains without fracture. Using cyclic displacement, crack nucleation was applied on dumbbell specimens and crack growth was applied on rectangular specimens with an initial crack. Both tests were performed on Silex silicone and polyurethane ether elastomer specimens, both with a Shore durometer hardness of 40 shore A. No samples completely failed during the crack nucleation tests after five million cycles. The polyurethane ether elastomer showed a slower rate of crack growth life (421 k cycles to reach 70 mm crack length) than silicone elastomer (221 k cycles to reach the same crack length) in the control group. Accelerated ageing decreased the hardness and the crack growth rate of the polyurethane elastomer but had the opposite effect for the silicone elastomer. Gamma sterilization increased the crack growth rate and did not affect the hardness of the polyurethane elastomer. The hardness and the crack growth rate of the silicone elastomer were increased after gamma sterilization.     

Synthesis and optical properties of new polyurethane cationomers with anchored stilbene chromophores

An ionic diol bearing a one‐sided urethane‐stilbene group located on the ammonium quaternary structure was prepared and proposed as an intermediate for polyurethane ionomer synthesis. Polyurethane cationomers with stilbene ionic groups based on poly(tetramethylene oxide) diols, 4,4′‐diphenylmethane diisocyanate and the aforementioned ionic diol, were synthesized and characterized. Some aspects of the trans–cis photoisomerism and fluorescent emission of the stilbene chromophore in polyurethane cationomers were studied comparatively with the urethane‐stilbene diol. The stilbene polycations absorbed at λ_A = 316 nm and emitted violet‐blue light with an emission maxima at λ_F = 444 nm (dimethylformamide solution) and λ_F = 465 nm (film). These polymers are known for their elastomeric properties and are assumed to be of great interest for some future applications. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 1918–1928, 2002     

Synthesis and properties of sulfonated polyurethane ionomers with anions in the polyether soft segments

A series of polyether (PTMO, PEO) polyurethane ionomers having different contents of sodium sulfonate groups in the soft segments have been synthesized. The reaction of transesterification was involved in the incorporation of the sodium sulfonate groups in the polyether. The polyurethane ionomers were characterized by means of dynamic mechanical thermal analysis, differential scanning calorimetry, and small-angle x-ray scattering. Solid-state ionic conductivity was also measured. As the ionization level increased, the compatibility of the hard and soft segments increased and the glass transition region of the soft segment became broader. These samples had relatively higher moduli and good film-forming ability. Moreover, this kind of ionomer provides a very promising ionic conductive multiphase polymer with a single ion transport mechanism. © 1997 John Wiley & Sons, Inc.     

Dynamic elastomers based on bio-derived crosslinker

Petroleum-derived monomers are the most common building blocks for ester-based thermosets. Bio-derived thermoset elastomers are becoming viable alternatives to conventional thermosets. Herein, we developed a biobased vitrimer-type thermoset elastomers using abundant and sustainable raspberry ketone as feedstock. We utilize raspberry ketone to create building blocks for dynamic oxime chemistry and crosslinked these through free radical polymerization with poly(ethylene glycol) methyl ether methacrylate as a comonomer. In contrast to other dynamic networks based on ester bonds, which need catalysts, this is undesirable since catalyst deactivation or leaching lowers its effect over time and may impair reuse. This network incorporates catalyst-free bond exchange reactions in catalyst-dependent polyester networks by substituting oxime-esters for typical ester linkages. The elastomer exhibits stress relaxation, a low glass transition temperature (T_g) (−55 to −40.2°C) and tensile strength up to 5.2 ± 3.0 kPa. Furthermore, the dynamic oxime transesterification exchange mechanism allows elastomers to be reprocessed using a hot press at 160°C and 8 × 10³ kPa pressure. After reprocessing, the tensile strength of elastomers can be recovered up to 78.1 ± 10.9%. This work integrates the principles of catalyst-free dynamic exchange process and mechanical recycling coupled with biobased components to provide a rational solution towards conventional elastomers. In the future, these elastomers can be exploited for the development of hydrogels, recyclable elastomers, and commodity plastics.     

Synthesis and properties of fluorinated thermoplastic polyurethane elastomer

A series of fluorinated thermoplastic polyurethane elastomers (FTPU) based on self-synthesized fluorinate polyether diol (PFGE) were prepared by two-step polymerization. For the purpose of improving the molecular weight and mechanical property of FTPU, polybutylene adipate (PBA) was used to be compounded with PFGE as the soft-segment of FTPU. Effects of the mass ratio of PFGE/PBA and the mass fraction of hard-segment on the mechanical property of FTPU were investigated. The structure and morphology of FTPU were characterized by FTIR, GPC, DMA, surface tension and AFM analysis.     

Studies on multistep thermal decomposition behavior of polytriazole polyethylene oxide‐tetrahydrofuran elastomer

Polytriazole polyethylene oxide‐tetrahydrofuran (PTPET) is an energetic propellant elastomer that is prepared using glycidyl azide polymer and trifunctional alkynyl‐terminated polyethylene oxide‐tetrahydrofuran. Its thermal decomposition, determined using thermogravimetic analysis, showed two mass‐loss peaks largely related to the decomposition of azide groups and the main chain. Flynn‐Wall‐Ozawa and Kissinger‐Akahira‐Sunose methods were deployed to obtain kinetic triplet parameters of PTPET thermal decomposition by the traditional model‐free method; the Coats‐Redfern approach was used as the model‐fitting method. Kinetics analysis indicated that the mechanism of the two‐step reactions were the primary‐reaction of first order and the power‐law phase reaction of the 2/3 order. The first decomposition stage of PTPET had an activation energy (E_a) of 113 to 116 kJ/mol while the second was 196 to 210 kJ/mol. The thermal decomposition of PTPET with different heating rates and mechanisms showed good kinetic compensation effects, the gas products being further studied with TG‐FTIR.     

Structure of the hard segments in trans,trans-diisocyanato dicyclohexylmethane based PU elastomers

A model for the structure of the hard segments and the hydrogen bonded network in the hard domains of segmented polyurethane elastomers with trans,trans-diisocyanato dicyclohexylmethane (tt-HMDI)/1,4-butanediol (BDO) based hard segments is proposed. The structure of the bis(methylurethane) oftt-HMDI (Me-ttHMDI-Me) has been determined by single crystal x-ray diffraction analysis and the conformation and packing of the polyurethane hard segments are constructed by connecting the successive Me-ttHMDI-Me units via –CH₂–CH₂– groups using the principle of isomorphic substitution. The conformation and hydrogen bonds of the monomer units are retained. The resulting polyurethane structure is highly crosslinked by a three-dimensional hydrogen bond network. The special packing principle may explain the high melting point as compared to the well-known structure of 4,4-diisocyanato diphenylmethane (MDI)-BDO hard segments and the differences in the material properties.     

Mesomorphic properties of side-chain cholesteric liquid-crystalline elastomers

New monomer cholesteryl 4-(10-undecylen-1-yloxybenzoyloxy)-4′-ethoxybenzoate (M₁), crosslinking agent biphenyl 4,4′-bis(10-undecylen-1-yloxybenzoyloxy-p-ethoxybenzoate) (M₂) and a series of side-chain cholesteric elastomers were prepared. The chemical structures of the monomers and elastomers obtained were confirmed by element analyses, FT-IR, and ¹H NMR. The mesomorphic properties and thermal stability were investigated by differential scanning calorimetry, thermogravimetric analysis, polarizing optical microscopy, and X-ray diffraction measurements. The influence of the content of the crosslinking unit on the phase behavior of the elastomers was examined. M ₁ showed cholesteric phase, and M ₂ displayed nematic phase. The elastomers containing less than 12 mol% of the crosslinking units revealed reversible mesomorphic phase transition, wide mesophase temperature ranges, and high thermal stability.