On the issue of urea phase connectivity in formulations based on molded flexible polyurethane foams

Lithium chloride was added to systematically alter the phase separation behavior, and hence, the nature of urea phase connectivity, in a series of plaques based on molded flexible polyurethane foam formulations. The plaques prepared were found to possess varied levels of urea phase connectivity that was examined at different length scales using several characterization techniques. SAXS, TEM, and t‐AFM were used to show that addition of LiCl systematically reduced the formation of the urea aggregate structures typically observed in flexible polyurethane foam formulations and thus led to a loss in urea phase connectivity at the macrolevel. SAXS, DSC, and DMA revealed that formulations with and without LiCl exhibited similar interdomain spacings and soft segment glass transitions, suggesting that incorporation of LiCl did not prevent the plaques from undergoing partial microphase separation. WAXS demonstrated that addition of LiCl led to a loss in the local ordering of the hard segments within the microdomains, i.e., it led to a reduction of microlevel connectivity or the regularity in segmental packing of the urea phase. High‐magnification t‐AFM images showed that increasing the LiCl content dispersed the urea component more homogeneously and in a more uniform manner in the polyol matrix, and thus altered the connectivity of the urea phase at the microdomain level. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 2956–2967, 2002     

Effect of miscibility and forced compatibility on damping properties of CIIR/PAc blend

In this study, a kind of novel damping materials was prepared based on the blend of chlorinated butyl rubber (CIIR) and polyacrylate (PAc) synthesized by different molar ratio of butyl methacrylate and ethyl acrylate. Research results from experiments and analyses by employing DMA, TEM, and FTIR show that whether at a cocured system or noncocured system, it can be achieved to shift a loss peak of CIIR towards a higher temperature region and to keep the damping value from markedlly decreasing, which broadens the effective damping function area of CIIR to the vicinity of ambient temperature. In the former system, the thermodynamical miscibility of CIIR and PAc, to some extent, is predominated by the molecular design of PAc, while in the latter system, covulcanized networks play a more significant role in improving compatibility and abating the peak split, though the suppression effect of thermal stress on the transition of CIIR T_ll transition still can not be neglected. Furthermore, transition state derived from the cocuring CIIR and PAc cannot make the phase separation completely take place, and consequently results in the deformation of phase morphology of the cocured CIIR/PAc blend. It is the influence of thermodynamics miscibility and forced compatibility in different size that makes the suppression effect of foreign PAc on CIIR T_ll transition be controllable. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 3127–3133, 2006     

氟化硅氧烷改性环氧树脂的制备与性能

首先,以全氟(2-甲基-3-氧杂己基)氟化物(六氟环氧丙烷二聚体)和N-(β-氨乙基)-γ-氨丙基三甲氧基硅烷(KH792)为原料制备一种氟化硅氧烷,用FTIR和1HNMR表征其结构.然后,将氟化硅氧烷与聚醚胺共同固化环氧树脂DGEBA(双酚A型二缩水甘油醚),测试了改性环氧树脂复合材料的性能.结果表明,与未改性环氧树脂相比,加入氟化硅氧烷使含氟量1％(以DGEBA质量计)改性环氧树脂复合材料的表面静态水接触角由72.0°增至103.2°,表面能由(42.08±2.17)mN/m降至(20.55±1.45)mN/m,40 d吸水率由1.75％降至1.38％,有效提高了材料的疏水性;介电常数由3.83降低至3.63;材料热分解5％温度由339℃升高至347℃;拉伸及弯曲力学性能分别提高了8.5％及7.7％.含氟量为1％时,改性环氧树脂复合材料的综合性能最佳,差式量热扫描和动态力学性能测试结果表明,少量改性剂可以促进环氧树脂的固化反应,提高固化度和交联密度;当氟化硅氧烷添加量增加时,材料内部发生显著的微相分离并导致性能逐渐下降.     

The Influence of Diphenyl Siloxane on Morphology and Physical Properties in the Poly(Imide Siloxane)(PIS) Copolymer

Various numbers of diphenyl-siloxane groups were incorporated in α,ω-bis(aminopropyl)polydimethylsiloxane (APPS) to prepare α,ω-bis(aminopropyl)-polydimethyldiphenylsiloxane (APPPS) oligomers of three different number-average molecular weights(Mn = 547,772,1210 g mol⁻¹).These APPPS oligomers were than used, together with 3,3′,4,4′-bezonphenone tetracarboxylic dianhydride (BTDA) and 2-2′-bis[4-(3-aminophenoxy)phenyl] sulfone (m-BAPS), to synthesize a series of APPPS containing poly(imide siloxane) (PIS) copolymers. Microstructural studies showed that at certain APPPS content, a critical microphase separation point existed, beyond which, microphase separation began to develop. This critical point of microphase separation was found to be affected by the Mn of the APPPS oligomers (8.0, 4.3 and 2.1 mol% for Mn of 547, 772 and 1,210 g mol⁻¹, respectively). Diphenyl-siloxane significantly improved compatibility between polyimide and polysiloxane segments. Physical studies showed that the introduction of diphenyl siloxane changed the thermal stabilities and mechanical properties of the PIS copolymers. These findings have potential applications for design purposes in engineering polymers.     

聚酯型聚氨酯乳液的合成及性能

以异佛尔酮二异氰酸酯（ IPDI）、六亚甲基二异氰酸酯（HDI）和聚己二酸 1,4-丁二醇酯二醇（ PBA）为主要原料制备系列水性聚氨酯乳液（ WPU）。采用红外光谱仪、差式扫描量热仪、 X-射线衍射仪、电子拉力机等对 WPU进行结构表征;为了从聚集状态上对聚氨酯结晶性有更深层次的探究,对 WPU进行了定伸情况下的测试。结果显示：随着硬段含量的增加,硬段 -软段间的氢键相互作用减小,微相分离程度增加,结晶性能降低;随着伸长率的增加,氢键相互作用和结晶性能都表现出先减小后增大的趋势。当硬段含量为 14. 73%时,聚氨酯胶膜拉伸强度达到 40. 11 MPa,剥离强度为 93. 7 N/（25 mm）。     

Acoustic damping flexible polyurethane foams: Effect of isocyanate index and water content on the soundproofing

High-efficiency sound absorbing flexible polyurethane foams (FPUFs) are manufactured using nonpolar polyester resin, methylene diphenyl diisocyanate, and other reagents by one-shot bulk polymerization. In this study, the impact of the isocyanate index (90, 100, and 110) and water content (2.5 and 5%) on the microphase separation and soundproofing behavior of FPUFs are examined using atomic force microscopy, Fourier transform infrared spectroscopy, optical microscope, and an impedance tube device. The results reveal that the increase of the isocyanate index and water content leads to the increase of the cell size, cell size distribution, open-cell content, cell wall roughness, and microphase separation. Also, maximum sound absorption coefficient (α) reaches to 0.98 and the average of α in the frequency range of 1500–4000 Hz increases from 0.7 to 0.87 by increasing the water content from 2.5 to 5% and isocyanate index from 90 to 110; therefore, acoustic damping performance enhances up to 26.24% due to the synergic effects of microphase separation on the viscose media formation, open-cell content, cell wall roughness, cell size, and cell size distribution. In conclusion, FPUFs with an optimal amount of microphase separation and drainage flow can be a promising candidate for sound insulating materials. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47363.     

Widely Tunable Morphologies in Block Copolymer Thin Films Through Solvent Vapor Annealing Using Mixtures of Selective Solvents

Thin films of block copolymers are extremely attractive for nanofabrication because of their ability to form uniform and periodic nanoscale structures by microphase separation. One shortcoming of this approach is that to date the design of a desired equilibrium structure requires synthesis of a block copolymer de novo within the corresponding volume ratio of the blocks. In this work, solvent vapor annealing in supported thin films of poly(2‐hydroxyethyl methacrylate)‐block‐poly(methyl methacrylate) [PHEMA‐b‐PMMA] by means of grazing incidence small angle X‐ray scattering (GISAXS) is investigated. A spin‐coated thin film of a lamellar block copolymer is solvent vapor annealed to induce microphase separation and improve the long‐range order of the self‐assembled pattern. Annealing in a mixture of solvent vapors using a controlled volume ratio of solvents, which are chosen to be preferential for each block, enables selective formation of ordered lamellae, gyroid, hexagonal, or spherical morphologies from a single‐block copolymer with a fixed volume fraction. The selected microstructure is then kinetically trapped in the dry film by rapid drying. This paper describes what is thought to be the first reported case where in situ methods are used to study the transition of block copolymer films from one initial disordered morphology to four different ordered morphologies, covering much of the theoretical diblock copolymer phase diagram.     

Synthesis and characterization of advance PA6‐b‐PDMS multiblock copolymers

Advance polyamide‐6‐b‐polydimethylsiloxane (PA6‐b‐PDMS) multiblock copolymers were first synthesized via the polymerization in bulk. Binary carboxyl terminated PA6 was served as the hard segment and PDMS modified with hexamethylene diisocyanate (PDMS‐NCO) was the soft segment. A series of PA6‐b‐PDMS copolymers based on different content and length of soft segments were obtained. Interestingly, Differential scanning calorimetry (DSC) studies revealed no obvious change in melting temperature after introducing PDMS segments to copolymers. The high melting temperatures indicated these copolymers possess potential applications in automotive industry that require high continuous use temperatures. DSC and transmission electron microscopy studies both demonstrated increasing the length and the content of the soft segment contributed to increasing of the degree of microphase separation. However, the improvement of thermal stability resulting from PDMS segments was also observed by thermo gravimetric analysis. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 41114.     

乙烯脲改性水性聚氨酯脲的制备与性能

采用一种新型的扩链剂乙烯脲(EU),在聚氨酯硬段引入具有刚性环状二取代脲基团,通过控制脲含量、交联度以及软段相对分子质量来制备一系列的EU改性水性聚氨酯脲(PUU-EU),并利用透射电镜(TEM)、广角X射线衍射(WAXD)、动态力学机械分析(DMA)、热失重分析(TGA)等测试方法,系统地研究PUU-EU微观结构与氢键化程度、微相分离、耐热性、力学强度的关系,并与1,4-丁二醇(BDO)扩链制备的水性聚氨酯(WPU)进行对比。结果表明,在一定范围内,PUU-EU随脲含量增加,其氢键化程度愈发完善,微相分离程度随之增加,力学强度逐步提高。     

可生物降解聚癸二酸丙三醇酯弹性体的组成及结晶性能

在不同摩尔比条件下,利用丙三醇和癸二酸通过熔融共缩聚反应方法合成了可生物降解的聚癸二酸丙三醇酯弹性体(PGS)。通过溶胀实验、X射线衍射分析及差示扫描量热分析对其组成和结晶性能进行了表征。结果表明,PGS是一种由溶胶和凝胶组成的低交联度聚酯,其中溶胶含量大于75%;PGS的玻璃化转变温度低于-25℃;当癸二酸用量增加时,PGS中存在着结晶,具有以非晶相为软区、晶相为硬区的微观相分离结构。