Structural characterization and mass transfer properties of segmented polyurethane: influence of block length of hydrophilic segments

An attempt has been made to investigate the effect of the block length of hydrophilic segments on the structure and mass transfer properties of segmented polyurethane (HSPU). Three different block lengths of hydrophilic poly(ethylene glycol) (PEG) segments were used, namely PEG‐200, PEG‐2000 and PEG‐3400, where the numbers indicate the molecular weight of the PEG in g mol^?1. The HSPU were characterized using Fourier‐transform infrared (FTIR) spectroscopy, wide‐angle X‐ray diffraction (WAXD), differential scanning calorimetry (DSC), dynamic mechanical thermal analysis (DMTA) and tensile testing. Mass transfer properties were measured by sorption and water vapour flux (WVF) measurements. The control sample polyurethanes without PEG and a sample with PEG‐200 showed amorphous structure and an unclear phase separation as detected by WAXD, DSC and DMTA. There is evidence that the introduction of PEG blocks into the polyurethane matrix aids soft‐segment crystallization. The percentage crystallinity of soft segments was the highest with PEG‐2000 and an increase of PEG block length to 3400 g mol^?1 resulted in a decrease in crystallinity. Mechanically, polyurethane without PEG is tough while percentage strain at maximum load increased with increasing block length of PEG. In addition, sorption and WVF increased linearly with increasing PEG block length and with temperature. The permeability of such HSPUs is a function of temperature and showed a good fit to an Arrhenius form. Copyright © 2005 Society of Chemical Industry     

疏水花生壳/聚氨酯复合泡沫的制备与油水分离性能

为提高聚氨酯泡沫（PUF）的疏水性能，首先，采用十六烷基三甲氧基硅烷（HDTMS）对花生壳粉末（PSP）进行改性，得到疏水改性花生壳粉末（H-PSP）。水接触角测试结果表明，改性后H-PSP的水接触角由PSP的0°提高至145.2°。然后，采用预聚体法制备了PUF负载H-PSP复合材料[H-PSP-PUF-n,n为H-PSP占聚氨酯预聚体（PPU）质量的百分数]。对H-PSP-PUF-n的结构和性能进行了表征与测试。结果表明，H-PSP的负载提高了泡沫材料的表面粗糙度和力学性能，H-PSP的最佳负载量为PPU质量的10%（标记为H-PSP-PUF-10）。与PUF相比，H-PSP-PUF-10的静态水接触角达到142.4°，较PUF提高了50.4°。对二氯甲烷、石油醚、煤油、二甲苯、环己烷进行油水分离实验，结果表明，H-PSP-PUF-10对石油醚、煤油、二甲苯、环己烷的吸油倍率在7～9 g/g，而且具有良好的油水选择性。经15次吸附-脱附循环后，H-PSP-PUF-10对各油品的吸油倍率在6.5～8.0 g/g，具有良好的循环利用性。     

疏水花生壳/聚氨酯复合泡沫的制备与油水分离性能

为提高聚氨酯泡沫（PUF）的疏水性能,首先采用十六烷基三甲氧基硅烷（HDTMS）对花生壳粉末（PSP）进行改性,得到疏水改性花生壳粉末（H-PSP）。水接触角测试结果表明,改性后H-PSP的水接触角由PSP的0°提高至145.2°。然后采用预聚体法制备了PUF负载H-PSP复合材料（H-PSP-PUF-n,n为H-PSP占聚氨酯预聚体PPU的质量分数）。对H-PSP-PUF-n的结构和性能进行了表征与测试。结果表明,H-PSP的负载提高了泡沫材料的表面粗糙度和力学性能,H-PSP的最佳负载量为PPU质量的10%（H-PSP-PUF-10）。与PUF相比,H-PSP-PUF-10的静态水接触角达到142.4°,较PUF提高了50.4°。对二氯甲烷、石油醚、煤油、二甲苯、环己烷五种油品进行油水分离实验,结果表明,H-PSP-PUF-10对不同油品的吸油倍率在7~9 g/g,而且具有良好的油水选择性。经15次吸附-脱附循环后,H-PSP-PUF-10对各油品的吸油倍率在6.5~8.0 g/g,具有良好的循环利用性。     

Effects of a soft segment component on the physical properties of synthesized waterborne polyurethanes by using triblock ester-ether copolydiol as the soft segment

This paper examines the effect of an ester-ether soft segment structure on the physical properties of synthesized WBPUs. The CET series, CPT series, and CMT series anionic waterborne polyurethane (WBPU) were prepared with PCL-PEG-PCL, PCL-PPG-PCL, and PCL-PTMG-PCL triblock copolydiol as the soft segment. These copolydiols were synthesized from polyethylene glycol (PEG), polypropylene glycol (PPG), or polytetramethylene glycol (PTMG), respectively, by end capping with caprolactone (CL). Particle size and its distribution, solvent absorption, thermal properties, and the mechanical properties of the WBPUs were studied. The particle size of WBPU dispersion was in the sequence of CET > CPT > CMT series. The CET series WBPU had better phase mixing between the soft and hard segment, whereas the CMT series WBPU had good phase separation and better mechanical properties. In addition, both the phase mixing and mechanical properties increased with PCL content, except for the CMT series WBPU.     

Influence of the length of the chain extender on the properties of thermoplastic polyurethanes

Three polyurethane elastomers (PUs) were prepared using MDI (diphenylmethane-4,4'-diisocyanate), polyadipate of 1,4-butanediol, and three linear chain extenders with different lengths (ethylene glycol, 1,4-butanediol, and 1,6-hexanediol). The prepolymer procedure was used to prepare the PUs. The PUs were characterized using gel permeation chromatography, differential scanning calorimetry, wide angle X-ray diffraction, dynamic mechanical thermal analysis, and stress-controlled rheometry. The surface properties were evaluated from contact angle measurements. The PUs were used as raw materials for solvent-based adhesives, the adhesion properties of which were assessed from T-peel tests of solvent-wiped poly(vinyl chloride) (PVC)/polyurethane adhesive joints. The use of a short-chain extender produced phase separation, high crystallinity, and adequate rheological properties in the PUs. The length of the chain extender used in this study did not affect the surface properties of the PUs nor the T-peel strength of PVC/polyurethane adhesive joints but a change in the locus of failure was obtained: the decrease in the length of the chain extender, i.e. the improved crystallinity and the high degree of phase separation in the PUs, favoured the interfacial failure.     

PVDF中空纤维换热管亲/疏水组合表面强化蒸汽冷凝传热

针对塑料换热管热导率低的问题,采用非溶剂致相分离法（NIPS）,通过控制铸膜液中磺化聚醚砜（SPES）添加量,制备出具有致密层/非致密层复合结构,外表面接触角分别为49.8°、78.1°的中空纤维表面亲水（PVDF/SPES）、表面疏水（PVDF）换热管,在非致密层内填充水,从而提高换热管导热性能。将单根的表面亲水、疏水换热管编织,在列管式塑料换热器壳程,利用两根换热管的外表面,构建蒸汽冷凝用亲/疏水组合表面,研究该表面上蒸汽冷凝传热强化效果。研究表明,较熔融拉伸法制备的致密PVDF换热管疏水表面,NIPS法制备的亲水表面、疏水表面及亲/疏水组合表面上的蒸汽冷凝总传热系数分别提高46.6%、56.5%、99.7%。可见,较单一的亲水或疏水表面而言,亲/疏水组合表面能够显著强化蒸汽冷凝传热性能。     

Macroporous crosslinked hydrophobic/hydrophilic polystyrene/polyamide interpenetrating polymer network: Synthesis,characterization, and adsorption behaviors for quercetin from aqueous solution

In the present study, a novel hydrophobic/hydrophilic polystyrene/polyamide interpenetrating polymer network (PS/PAM IPN) was synthesized and its molecular structure was characterized by Fourier transform infrared ray (FT‐IR) spectrum, chemical analysis, swelling test, and N₂ adsorption‐desorption experiment. The obtained PS/PAM IPN was employed as a polymeric adsorbent to adsorb quercetin from aqueous solution, and the adsorption thermodynamics were calculated according to thermodynamic equations. It was found that no chemical bond was formed between PS and PAM and PS/PAM IPN held characters of amphiphilic polymer network (APN). The adsorption isotherms could be well fitted by Freundlich isotherm, and the adsorption was shown to be an exothermic, spontaneous, and more ordered process. The total adsorption capacity from the column adsorption experiment was measured to be 8.6 mg/mL wet resin, and the adsorbed quercetin on PS/PAM IPN could be easily desorbed by 10% of hydrochloric acid‐ethanol. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

软硬段比对磺酸盐型水性聚氨酯性能的影响

以聚己二酸乙二醇酯二醇(PBA)、异佛尔酮二异氰酸酯(IPDI)和六亚甲基二异氰酸酯(HDI)为主要原料,以乙二胺基乙磺酸钠为亲水性扩链剂,合成了固含量为50%的磺酸盐型水性聚氨酯(WPU)乳液。考察了软硬段比对乳液黏度、粒径及其分布、聚合物重均相对分子质量(Mw)、胶膜结晶性以及力学性能等影响。结果表明:当软硬段比值为2.96时,可以制得固含量为50%的磺酸盐型WPU乳液,其平均粒径为146.0 nm、黏度为143 mPa.s,聚合物Mw为128 488,结晶熔融温度为50℃,结晶性相对最好;此时WPU胶膜的拉伸强度(31.6 MPa)和断裂伸长率(1 702%)相对较大;WPU胶粘剂的初始剥离强度(118.6 N/cm)和最终剥离强度(156.3 N/cm)相对最高。     

Microphase separation and surface properties of segmented polyurethane-Effect of hard segment content

A series of segmented polyurethanes (SPU), based on 4,4′-diphenylmethane diisocyanate and 1,4-butanediol as hard segments (HS) and poly(propylene glycol) (Mn = 1000) as soft segments, were synthesized. Relationships between microphase separation and the surface and adhesive properties were characterized by thermal analysis, X-ray diffraction, contact angle, electron spectroscopy for chemical analysis, T-peel and tensile test measurements. Microphase separation occurred for SPU with an HS content of more than 50 wt% and influenced not only the bulk properties, but also the surface properties. Young's modulus and tensile strength increased abruptly for SPU with an HS content of more than 50wt%. Surface free energy also increased in a stepwise manner at an HS content of about 50wt%. The optimum HS content of SPUs for adhesion, based on T-peel test results, also gave good thermal and mechanical properties.     

软段结构对聚氨酯弹性体性能的影响

分别以聚四氢呋喃二醇(PTMG)、聚己内酯二醇(PCL)、高顺式端羟基聚丁二烯(HTPB)和自由基聚合制得的端羟基聚丁二烯(FHTPB)为软段,采用溶液聚合两步法制得了四种聚氨酯弹性体(PUE)。通过拉伸试验、动态力学性能分析(DMA)、差示扫描量热(DSC)和热重分析等手段,考察了软段结构对它们室温及低温下力学性能、热性能等的影响。结果表明,四种PUE低温(-30℃)下的拉伸强度和断裂伸长率均大于室温下的对应值。这不仅与低温下软段诱导结晶所产生的自增强效应有关,也与软、硬两段的微相分离程度增大有关。相较于其他三种PUE,HTPB-PUE软段不仅玻璃化温度(T _g)最低,而且极性也最弱,因而微相分离程度高,具有优异的柔性,-30℃下其断裂伸长率仍达660%以上。PCL-PUE和PTMG-PUE因软段易结晶,且软段与硬段的微相分离程度低,则刚性强。低温循环拉伸试验表明,-30℃下HTPB-PUE和FHTPB-PUE有较强的弹性恢复能力,而PCL-PUE和PTMG-PUE则相对较差。DSC和DMA结果显示HTPB-PUE的T _g远低于其他三种PUE,其T _g(DSC)低至-103℃。此外,四种PUE的初始分解温度十分相近,均在270℃左右。     

Effect of the hard segment on the properties of UV curable waterborne blocked polyurethanes

Two types of UV curable waterborne blocked polyurethanes (PUs) were obtained from 2,4-tolylene diisocyanate(TDI) and isophorone diisocyanate (IPDI), which had the same soft segments and different hard segments. The PUs contained both the UV curable C=C bond and the blocked NCO groups which could be de-blocked when heated. Effect of the hard segment on the properties of the two types of PUs was investigated. The FTIR spectra method was employed to confirm the structure of the PUs. The photo-DSC was used to study the photo-polymerization rate of the PUs under UV irradiation in the presence of a photo-initiator and the C=C conversion behaviors. Heating-up IR analysis was used to track the de-blocking process and the heat curing process. The thermal degradation analysis (TGA) was employed to investigate the thermal stability of the UV cured films before and after heat curing process. Dynamic mechanical properties of the UV and heat cured films were investigated by the dynamic mechanical thermal analysis (DMTA).     

Effect of novel aliphatic fluoro-diol content on synthesis and properties of waterborne polyurethanes

This study synthesized a waterborne polyurethane (WPU) prepolymer by using polytetramethylene glycol, isophorone diisocyanate, and 2,2,3,3,4,4,4-Heptafluoro-butynic acid 2,2-bis-hydroxymethyl-butyl ester (HFBA). Subsequently, a series of novel HFBA/WPUs were synthesized by adopting ethylenediamine as the chain extender. The results from Fourier transform infrared spectroscopy demonstrated that the CO groups of HFBA/WPUs shifted to lower wavenumbers as the HFBA content increased. Moreover, when the HFBA content of the synthesized HFBA/WPUs increased, the WPU initial decomposition temperature, glass transition temperature, tensile strength, and Young's modulus also increased. Furthermore, the results of atomic force microscopy identified a relatively high number of humpy protrusions and roughness levels in the HFBA/WPUs with a relatively high HFBA content, causing higher hydrophobicity of these HFBA/WPUs. Furthermore, in vitro platelet and erythrocyte adhesion experiments revealed that increasing the HFBA content lowered platelet and erythrocyte adhesion on the surface of the WPUs. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47356.     

Axial distribution of solids holdup for both hydrophilic and hydrophobic particles in three‐phase fluidized beds

The axial concentration distribution of the hydrophilic and hydrophobic particles, corresponding to poor and good attachment to rising bubbles in water, was investigated in a gas‐liquid‐solid fluidized bed. The sedimentation‐dispersion model depicted satisfactorily the axial distribution of solids holdup by modifying only the terminal settling velocity, which considered the effect of an additional drag force resulting from the attached rising bubbles. This model explained correctly the different phenomena, i.e. solids holdup decreased with increasing the axial height in the non‐attached system, but increased in the attached system.     

Studies on thermoplastic polyurethanes based on new diphenylethane‐derivative diols. III. The effect of molecular weight and structure of soft segment on some properties of segmented polyurethanes

Two series of poly(ether urethane)s and one series of poly(ester urethane)s were synthesized, containing, respectively, poly(oxytetramethylene) diol (PTMO) of M _n = 1000 and 2000 and poly(ε‐caprolactone) diol of M _n = 2000 as soft segments. In each series the same hard segment, i.e., 4,4′‐(ethane‐1,2‐diyl)bis(benzenethiohexanol)/hexane‐1,6‐diyl diisocyanate, with different content (～ 14–72 wt %) was used. The polymers were prepared by a one‐step melt polymerization in the presence of dibutyltin dilaurate as a catalyst, at the molar ratio of NCO/OH = 1 (in the case of the polymers from PTMO of M _n = 1000 also at 1.05). For all polymers structures (by FTIR and X‐ray diffraction analysis) and physicochemical, thermal (by differential scanning calorimetry and thermogravimetric analysis), and tensile properties as well as Shore A/D hardness were determined. The resulting polymers were thermoplastic materials with partially crystalline structures (except the polymer with the highest content of PTMO of M _n = 2000). It was found that the poly(ether urethane)s showed lower crystallinity, glass‐transition temperature (T_g), and hardness as well as better thermal stability than the poly(ester urethane)s. Poly(ether urethane)s also exhibited higher tensile strength (up to 23.5 MPa vs. 20.3 MPa) and elongation at break (up to ～ 1950% vs. 1200%) in comparison with the corresponding poly(ester urethane)s. Among the poly(ether urethane)s an increase in soft‐segment length was accompanied by an increase in thermal stability, tensile strength, and elongation at break, as well as a decrease in T_g, crystallinity, and hardness. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

The effect of fluorinated side chain attached on hard segment on the phase separation and surface topography of polyurethanes

It has been well established that polyurethanes exhibit a two-phase micro-structure due to the thermodynamic incompatibility between the soft segments and hard segments. In this work, we reported the effect of fluorinated side chain attached on hard segment on the phase separation and surface topography of polyurethanes. Two sets of fluorinated polyurethanes, namely, poly(ether urethane)s and poly(carbonate urethane)s containing various amounts of chain extender of fluorinated side chains, were investigated by DSC, XPS, DMA, AFM and FTIR. It was found that the phase separation in both bulk and surface increases in fluorinated poly(carbonate urethane)s and the phase mixing increases in fluorinated poly(ether urethane)s, with increasing amounts of fluorinated side chain. The increased degree of hydrogen bonding between hard segments and soft segments was observed by FTIR for fluorinated poly(ether urethane), which is believed to result in the enhanced phase mixing, and the enhanced association of domains with long-range order (hydrogen bonding) between hard segments was evident for fluorinated poly(carbonate urethane)s, which may correspond to the enhanced phase separation. The result is new and provides direct connection between surface topography and bulk phase separation of polyurethanes.     

硬段含量对脂肪族阴离子水性聚氨酯性能的影响

以异佛尔酮二异氰酸酯和聚酯多元醇为主要原料,用预聚混合法合成了一系列硬段含量不同的脂肪族阴离子水性聚氨酯纳米乳液。通过FTIR、GPC、DSC等,研究了硬段含量对产品结构和性能的影响。结果表明,随着硬段含量增加,乳液平均粒径逐渐增大但仍小于100nm,粒径分布逐渐变宽;分子结构中成氢键的脲键增多;数均相对分子量略有增加;DSC分析表明软段玻璃化温度向低温漂移,而硬段玻璃化温度向高温漂移,说明两相微相分离程度增加。硬段含量为30%时胶膜拉伸强度最高达52MPa,而断裂伸长率随硬段含量增加从2250%急剧减小到863%。耐水性在硬段含量最高时最佳。     

壁面亲水性对DMFC阳极通道内气液两相流影响的数值模拟

采用计算流体力学软件FLUENT对DMFC阳极通道内的气液两相流进行数值模拟,考察了阳极通道壁面的亲水性质对通道内气液两相流的影响.模拟结果表明:当流道侧壁面为憎水性时,CO2气体排出速度较快,但不利于反应物向扩散层方向迁移;当流道侧壁面和扩散层(GDL)表面均为亲水性时,有利于反应物向GDL方向迁移,但CO2气体排出阳极通道的速度较慢;当流道侧壁面为亲水性、GDL表面为憎水性时,既有利于反应物向GDL方向迁移,又有利于CO2气体排出通道.     

恒热流条件下亲疏水表面液滴蒸发特性

以恒热流方式结合高速摄影技术同步观察记录3 μl的小液滴在不同亲疏水表面的蒸发过程。通过一系列的对比实验观察记录了不同亲疏水表面液滴蒸发时接触角、接触直径、蒸发时间等的动态特性。从实验分析中可以看出亲水表面液滴蒸发速率比疏水表面上液滴蒸发速率快,并且随着热通量的增大,液滴蒸发速率增大。在恒热流条件下亲疏水表面液滴蒸发以CCR模式为主,在蒸发后期呈现混合蒸发模式,全程未出现CCA模式。     

软段对热塑性聚氨酯弹性体结构及性能的影响

以二苯基甲烷-4,4′-二异氰酸酯(MDI)和扩链剂1,4-丁二醇(BDO)为聚氨酯弹性体硬段(控制硬段质量分数32%),以实验室自制聚己二酸乙二醇酯二醇(PEA)和聚己二酸乙二醇丙二醇酯二醇(PEPA)为软段,经预聚体法合成不同结构的热塑性聚氨酯弹性体(TPU)。研究了弹性体软段部分对其硬度、力学性能和结晶性能的影响。结果表明,控制热塑性聚氨酯弹性体硬段部分不变,改变软段,材料硬度变化不大;软段聚酯二元醇随其相对分子质量的增加,TPU力学性能和结晶性能均增强;研究不同PG含量的软段PEPA-TPU发现,当PG质量分数为10%时,TPU力学性能与结晶性能最好。     

Thermoplastic polyurethanes from renewable resources: effect of soft segment chemical structure and molecular weight on morphology and final properties

The effect of soft segment molecular weight and chemical structure on the morphology and final properties of segmented thermoplastic polyurethanes containing various hard segment contents has been investigated from the viewpoint of the degree of microphase separation. Vegetable oil‐based polyesters and corn sugar‐based chain extender have been used as renewable resources. The synthesis has been carried out in bulk without catalyst using a two‐step polymerization process. Physicochemical, thermal and mechanical properties, and also morphology, have been studied using Fourier transform infrared spectroscopy, differential scanning calorimetry, dynamic mechanical analysis, atomic force microscopy, X‐ray diffraction and mechanical testing. Chemical structure and molecular weight of polyols strongly affect the properties of the synthesized segmented thermoplastic polyurethanes. An increase in soft segment molecular weight leads to an increase of the degree of soft segment crystallinity and microphase separation, thus giving enhanced mechanical properties and higher thermal stability. Copyright © 2012 Society of Chemical Industry