Thermal analysis of the structure of segmented polyurethane elastomers

Polyurethanes were prepared from 4,4′-methylenebis (phenyl isocyanate) (MDI), 1,4-butanediol (BD), and poly(tetrahydrofurane) polyether polyol (PTHF) by melt polymerization. The –OH functional group ratio of polyol/total diol was kept constant at 0.4, while the ratio of the isocyanate and hydroxyl groups (NCO/OH) changed between 0.940 and 1.150. The thermal analysis of the polymers by DSC and DMTA measurements indicated several transitions. The three glass transition temperatures observed were assigned to the relaxation of the aliphatic –CH₂– groups of the polyol, and to that of the soft and hard segments, respectively. The glass transition temperature of the soft and hard phase changed with the NCO/OH ratio indicating changes in phase structure and composition confirmed also by the maximum in the number of relaxing soft segments. Changes in the relatively small number of end-groups result in considerable modification of mechanical properties. Strength is determined by molecular mass and interactions, while stiffness depends mainly on phase structure. Surprisingly enough, –OH excess yields stiffer polymers, since the interaction of the –OH groups results in a decrease in the amount of the soft phase. A unique correlation was found between tensile modulus and the number of relaxing soft segments.     

Interpenetrating polymer networks from polyurethanes and methacrylate polymers. I. Effect of molecular weight of polyols and NCO/OH ratio of urethane prepolymers on properties and morphology of IPNs

Two types of reinforced elastomeric interpentrating polymer network (IPN) were prepared by simultaneous polymerization and crosslinking in solution. The first type consisted of polyurethane-poly(methyl methacrylate) (PU/PMMA), and the second, of polyurethane-poly(methyl methacrylate-methacrylic acid) PU/P(MMA–MAA) of constant composition (90/10) and (80/20) by weight, respectively. The members of each type differed in the NCO/OH ratio of the PU prepolymer and the molecular weight (MW) of the polyol in the PU component because we wished to investigate systematically the effect of changing the NCO/OH ratio and MW of the polyol on the mechanical properties and morphology of the resulting IPNs. The mechanical properties, particularly the modulus of both tyes of IPN, increased with increasing NCO/OH ratio and decreased with increasing MW of the polyol in the PU. The morphology of the IPNs was studied by differential scanning calorimetry (DSC) and scanning electron microscopy (SEM). Improved phase compatibility and decreasing extent of phase separation was observed in both types of IPN with increasing NCO/OH ratio and decreasing MW of the polyol used in the PU. These results may imply that improved interpenetration results from increasing the NCO/OH ratio and decreasing the MW of the polyol in the PU component. The fact that the effect is more pronounced with the type of PU-P(MMA–MAA) IPN can be rationalized as due to the additional hydrogen bonding between the carbonyl in the carboxyl groups and the urethane or urea groups in the PU component.     

Quantitative mapping of elastic moduli at the nanoscale in phase separated polyurethanes by AFM

The micro phase separated nanoscale morphology of phase separated polyurethanes (PUs) was visualized by atomic force microscopy (AFM) height and phase imaging of smooth surfaces obtained by ultramicrotonomy. PUs were obtained from 4,4′-methylenbis (phenyl isocyanate) (MDI), 1,4-butanediol (BD) and poly(tetrahydrofurane) polyether polyol (PTHF). The segmented polyether PUs with varying stoichiometric ratio of the isocyanate and hydroxyl groups were prepared to investigate the effect of molar mass, as well as the type and number of end-groups on their morphology and mechanical performance.The PU samples studied show characteristic “fingerprint” AFM phase images. Novel dynamic imaging modes of AFM, including HarmoniX material mapping and Peak Force Tapping were used to assess the mechanical performance of phase separated polyurethanes quantitatively as a function of their molecular structure. The values of surface elastic moduli were determined with nanoscale resolution and were in excellent agreement for both AFM modes. While tensile testing provides a bulk average value for the elastic modulus of the elastomers, the novel AFM based elastic moduli mappings introduced enable the study of surface stiffness with nanoscale resolution in a quantitative way.     

七(2,3,6-三-O-甲氧甲基)-β-环糊精的合成及其在气相色谱分离中的应用

将甲氧甲基引入β-环糊精的2,3,6-位合成了新的气相色谱手性固定相七(2,3,6-三-O-甲氧甲基)-β-环糊精,并采用静态法将其涂渍在毛细管内壁制备毛细管气相色谱柱。考察了毛细管柱的柱性能和分离性能。结果表明该固定相对Grob试剂、苯的二取代位置异构体(硝基甲苯、溴甲苯、二氯苯和二甲苯)及手性化合物(2-羟基丙酸甲酯、2-羟基丙酸乙酯和2-甲磺酰基丙酸甲酯)都具有良好的分离效果。与固定相2,3,6-三-O-甲基-β-环糊精的手性分离效果对比,结果显示两种手性固定相的分离能力各异,对一些手性脂类化合物对映体的分离存在互补性。     

Polyurethane cationomers with pendant trialkylammonium groups: Effects of ion content,alkyl group,and neutralizing anion

Diphenylmethane-4,4′-diisocyanate based polyether polyurethane cationomers were synthesized using 3-trialkylammonium-(1,2-propanediol)iodide (TAPI) as the chain extender. The ionic content was varied by substituting up to 100% of 3-dialkylamino-1,2-propanediol (DAP) for TAPI. Cationomers with bromine and chlorine ions were prepared from the iodine-based polymer via ion exchange. The morphology and properties of the cationomers were studied as a function of alkyl group, ion content, and anion type using small-angle x-ray scattering, tensile testing, dynamic mechanical thermal analysis, and differential scanning calorimetry. The bulky side groups of DAP and TAPI prevented crystallization in the hard domains, and consequently little or no phase separation was evident in the unionized materials. Polyurethanes with cationic functionality showed dramatic improvements in phase separation and tensile properties. Results suggest tht while ionic interactions are the primary driving force for phase separation, they produce a morphology not typical of ionomers, but rather akin to that of a conventional polyurethane with semicrystalline hard segments. © 1994 John Wiley & Sons, Inc.     

Thermal analysis of soybean oil based polyols

Soybean oil based polyols (5-OH polyol, 10-OH polyol and 15-OH polyol) were synthetised from epoxidized soybean oil. The melting peak of polyols and the relationship between melting peak and the number-average functionality of hydroxyl in polyols were investigated by differential scanning calorimetry (DSC). The thermal decomposition of polyols and some of their thermal properties by thermogravimetry (TG) and derivative thermogravimetry (DTG) were also studied. The thermal stability of polyols in a nitrogen atmosphere was very close hence they had a same baseplate of triglyceride for polyols. The extrapolated onset temperature of polyols in their thermal mass loss, first step had a decreasing order: 5-OH polyol>10-OH polyol>15-OH polyol due to the difficulty in forming multiple elements ring of them had the same order. The thermal behavior of polyols under non-isothermal conditions using Friedman’s differential isoconversional method with different heating rates indicated that the 5-OH polyol had the lowest activation energy in thermal decomposition amongst these polyols according to the same fractional mass loss because of the weakest intramolecular oligomerization. The 15-OH polyol was prior to reach the mass loss region because the six-member ring is more stable than the three-member ring from 10-OH polyol and more easily formed.     

聚醚聚氨酯/环氧树脂互穿网络聚合物的研究(Ⅱ)

合成了不同类型聚醚聚氨酯/环氧树脂(PU/EP)互穿网络聚合物(IPN),通过改变PU中聚乙二醇分子量、3OH/2OH及NCO/OH比值等,研究IPN组份间分子混合程度,采用电镜、动态力学分析及应力应变等测试方法表征。结果表明:聚乙二醇分子量降低及3OH/2OH、NCO/OH比的提高,可使相容性提高,材料力学性能增强。     

2，6-二-O-乙氧乙基-3-O-三氟乙酰基-β-环糊精气相色谱手性固定相的制备及应用

将β-环糊精的2,6-位引入乙氧乙基,3-位引入三氟乙酰基,合成了新的环糊精衍生物2,6-二-O-乙氧乙基-3-O-三氟乙酰基-β-环糊精,并采用静态法涂渍毛细管气相色谱柱,考察了毛细管柱的柱性能和分离性能。结果表明,该固定相对G rob试剂、苯的二取代位置异构体氯甲苯、硝基甲苯和溴甲苯以及10种手性化合物如α-取代丙酸酯化合物、1-(2′-硝基苯基)-乙醇、α-甲基-对氯苯乙腈和丙炔醇酮乙酸酯等具有良好的分离效果。其中,对α-甲磺酰基丙酸酯对映体的拆分效果最好;对α-取代丙酸的甲酯衍生物的分离效果优于乙酯衍生物;对α-羟基取代丙酸酯的分离效果优于α-卤代丙酸酯。     

Sound absorption behavior of flexible polyurethane foams including high molecular‐weight copolymer polyol

Noise pollution is an important issue for automotive industries. In this article, the high molecular‐weight copolymer polyol is blended in the polyol mixtures for fabricating flexible polyurethane foams to improve sound absorption efficiency. Changes of cavity size and material density of the foams are negligible by inclusion of copolymer polyol in the polyol mixture, but the closed pore ratio and specific airflow resistance increase for the copolymer polyol content higher than 20 wt% because of changes of phase separation behavior from drainage flow rate reduction that occurs with increased viscosity. Sound absorption efficiency increases with increasing copolymer polyol content up to 20 wt%, but it decreases beyond this point. The sound absorption property mainly results from the closed pore ratio, not from the cavity size. The compression strength increases with increasing copolymer polyol contents by increased amount of hard segments. Therefore, an optimum amount of high molecular‐weight polyol is recommended for enhanced sound absorption property.     

3-位烯丙基及甲基衍生的β-环糊精固定相的合成及气相色谱性能研究

制备了一种新的β-环糊精衍生物固定相2,6-二-O-戊基-3-O-[(甲基)5(烯丙基)2]-β-CD,并对其气相色谱分离性能进行研究。实验显示,该固定相具有良好的柱表面性能和较强的色谱分离能力,对一些芳香族位置异构体的分离能力优于2,6-二-O-戊基-3-O-烯丙基-β-CD衍生物,对10余种手性物质显示出较好的选择性能,且对α-位取代的丙酸酯类手性分离效果明显优于杂环类β-CD衍生物。与2,6-二-O-戊基-3-O-烯丙基-β-CD固定相的分离性能比较表明,β-CD 3位羟基部分甲基基团的引入能增强对芳香族位置异构体的选择能力,但不能明显改变烯丙基衍生物的手性分离能力。     

Design,polymerization, and properties of polyurethane elastomers from miscible,immiscible, and hybridized seed‐oil derived soft segment blends

Polyester seed‐oil derived polyols have been prepared and blended with conventional polyols for making polyurethane elastomers. Miscibility was complete for polypropylene oxide/polyethylene oxide and polytetramethylene oxide (PTMEG). Blends of polyester seed‐oil derived polyols with conventional polyester polyols (polybutylene adipate and ?‐polycaprolactone) were immiscible or nearly so. Furthermore, the phase behavior (miscible vs. immiscible) did not change appreciably for each blend composition explored as a function of temperature at relevant ranges (up to the polyether ceiling temperature). This counter‐intuitive result is found to be actually consistent with calculated solubility parameters for each polyol type and the phase diagrams computed on their basis. The phase behavior of the polyols is shown to have significant effects on the properties of polyurethane elastomers where immiscible polyols cause broadening of the glass transition distribution and significant reduction of ultimate tensile properties. However, here it is shown that immiscible systems containing polyester seed‐oil derived polyols can be transesterified with the appropriate polyol partner of interest to create a new single phase polyol or that the polyester polyol monomers can also be copolymerized to make new single phase polyols, both of which result in improved polyurethane elastomer properties. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 93–102     

Improving chemical recycling rate by reclaiming polyurethane elastomer from polyurethane foam

Flexible polyurethane foam was decomposed into a polyol mixture by an extruder with diethanolamine (DEA) as a decomposing agent. The resulting decomposed product could be used as an alternative virgin polyol in reclaiming polyurethane. In the case of reclaiming elastomer by using the decomposed product without any purification, virgin polyol could be alternated by the decomposed product up to 80%. It is a great improvement compared with the reclamation to foam, whose percentage was maximum 5%. Furthermore, the percentage could be improved up to 100% by purifying the decomposed product. We have found that physical properties of reclaimed polyurethane elastomer, such as tensile strength, hardness, and elongation, can be regulated by the ratio of unrefined/refined polyol. Whereas the tensile strength and the hardness increased as the content increased, the elongation decreased.     

HDPE/PP共混物在振动剪切作用下的力学性能与形态控制

采用高剪切引起的相容与振动剪切保压方式控制共混物的形态,结果表明,当共混体系中HDPE/PP为92/8时的试样拉伸强度为97.1MPa,而80/20试样的缺口冲击强度为45.5kJ/m₂,较静态试样分别提高4.3倍和9.5倍.采用振动剪切注射技术可以针对某一组分获得高强度、高韧性的HDPE/PP共混制件.     

The relationship between nanosilica dispersion degree and the tensile properties of polyurethane nanocomposites

The tensile properties and structure of silica-based polyurethane (PU) nanocomposites were parametrically studied as a function of silica type and weight concentration, polyol OH number, and mixing methods. The variation of the silica functionalization groups (from silanols to silazanes) had a relevant effect on dispersion. An elevated interparticle distance of the silica agglomerates improved substantially the tensile strength (from 44.3 to 82.8 MPa) and strain to failure (from 3.0 to 7.95) while maintaining elastic modulus (from 2.08 to 2.31 GPa) with respect to the neat PU matrix. Polyol’s with different OH numbers have shown to dramatically modify the silica dispersion degree by the modification of the stability of the colloidal dispersion. An increase of its value deteriorated dispersion and the tensile properties of the nanocomposites. The effect of three dispersion methods (ultrasonic dispersion, high shear mixing, and tip sonication) has shown to have a relative effect on the reduction of agglomerate size and the interparticle distance. High power sonication methods were more effective in reducing agglomerate size in contrast to shear methods. Classical theories of colloidal dispersion (Derjaguin, Landau, Verwey, and Overbeek) have been able to explain the correlation between the silica aggregation state and the final tensile properties of the nanocomposite.     

Robust isocratic liquid chromatographic separation of functional poly(methyl methacrylate)

The separation of telechelic poly(methyl methacrylate) (PMMA) prepolymers based on the number of end-groups under critical liquid chromatography (LC) conditions has been studied using a bare-silica column, which can interact with polar functional groups. The critical solvent compositions for non-functional, mono-functional and bi-functional PMMAs were determined in normal-phase LC using mixtures of acetonitrile and dichloromethane (DCM) of varying composition as the mobile phase. The telechelic prepolymers were successfully separated according to hydroxyl (OH) functionality (with zero, one, or two OH groups, respectively) under the critical conditions, in which fast (5 min), base-line separations were obtained independent of molecular weight. Changing the column temperature, flow rate, and mobile-phase composition within a certain range did not affect the functionality separation. Therefore this isocratic LC separation method is quite robust. Evaporative light-scattering detector (ELSD) calibration curves were used for the quantitative analysis of functional PMMA prepolymers.     

Mechanical and thermal properties of syndiotactic polystyrene blends with poly(p-phenylene sulfide)

Melt blends of syndiotactic polystyrene (sPS) and poly(p-phenylene sulfide) (PPS) have been prepared by using an internal mixer at 300 °C. The thermal, mechanical and morphological properties of binary blends of sPS with PPS have been investigated in this paper. The thermal and morphological properties show the immiscible binary blend evidences, which have a clear phase separation between the components at all compositions and a lack of adhesion at the interface. According to the X-ray diffraction patterns of blends, the crystalline structure of sPS in the blend is not altered from α form to β form. Indeed, the results for tensile test reveal that there is no synergism of the modulus of elasticity for sPS/PPS blend system.     

末端功能基团对聚（3-丁基噻吩）光电性能的影响

研究了4种带有不同末端基团的聚（3-丁基噻吩）（P3BT）的光电性能。 结果表明,末端基团对P3BT的结晶有一定的抑制作用,可以改变P3BT的表面能,从而有效调控P3BT∶PCBM共混体系相容性以及薄膜的形貌,并影响以P3BT为给体材料的聚合物光伏器件的性能。 其中,带有较短烷基链末端基团的烯丙基封端P3BT具有较高的结晶性,与PCBM具有适中的相容性,使得光伏器件的光敏层能够形成理想的微相分离结构,器件效率可以达到3.1%,较传统的溴封端P3BT器件效率提升35%以上。     

Synthesis and conformational property of tannin-like p-tert-butylcalix[4]arene 1,3-diesters stabilized by intramolecular hydrogen bonds.

Tannin-like p-tert-butylcalix[4]arene 1,3-digallate was synthesized, and its conformational property was investigated by dynamic (1)H NMR and X-ray crystallography. It was found that the 3-OH (or 5-OH) group of the galloyl group in p-tert-butylcalix[4]arene 1,3-digallate is placed at the position where an unusual nonbonded close contact is observed between the OH group and the aromatic ring of the galloyl group facing each other. The calixarene 1,3-diesters of various hydroxybenzoic acids were also prepared, and the conformational properties of those calixarenes were compared with that of p-tert-butylcalix[4]arene 1,3-digallate. A significant contribution of the 3- and 5-OH groups in pendant groups toward the close contact was found. It was suggested that the conformation of p-tert-butylcalix[4]arene 1,3-digallate was stabilized by intramolecular hydrogen bonds including OH.O and OH-pi interactions.     

Effect of filler shape on mechanical properties of rigid polyurethane composites containing plant particles

The effect of types of fillers on mechanical properties of rigid polyurethane composite samples was investigated. Polyurethane (PU) composites were prepared using a molasses polyol (MP, a mixture of molasses and polyethylene glycol, Mw=200) diphenylmethane diisocyanate (MDI) and fillers. The following plant particles, bamboo powder, roast bamboo powder, wood meal, coffee grounds, ground coffee bean parchment and cellulose powder, were used as fillers. The mixture of MP and fillers was reacted with MDI by adding an adequate amount of acetone as a solvent. The content of fillers was defined as the ratio of filler weight to total weight of polyol and fillers. The filler content was varied from 10 to 90 wt%. Polyurethane (PU) composites were prepared using fillers with MP. Lengths of major axis and minor axis for each particle regarded as an ellipse were measured using an optical microscope. Averages of diameter and aspect ratio were derived for each plant particle. The relationships between these average values and the mechanical properties, such as strength and elastic modulus, determined by the compression tests were investigated. The effect of filler content was estimated using the apparent volume ratio which is determined as the ratio of the apparent volume of fillers to the reciprocal values of the apparent density of samples. The master curves of the relationships between the specific values of mechanical properties and the apparent volume ratio were obtained. It was found that the compression strength and the elastic modulus for composite samples with different fillers showed maximum values at average aspect ratio around 3. It was also found that the apparent volume ratio, where the mechanical properties showed maximums, decreases with increasing aspect ratio. Using master curves, it is possible to evaluate the mechanical properties of plant particle filled polyurethane composites are described.     

Mechanical and biodegradation performance of short natural fibre polyhydroxybutyrate composites

The work outlined in this paper describes the evaluation of polyhydroxybutyrate (PHB) based natural fibre composites via an extrusion – injection moulding process. Virgin PHB was compounded with two different naturally occuring plant fibres, hemp and jute, and a third, regenerated cellulose fibre, lyocell. Composite materials containing 10–30 wt% of each type of fibre were obtained by twin screw extrusion and the resultant material was injection moulded to produce tensile samples suitable for mechanical characterisation. Mechanical properties were determined using tensile, impact and flexural testing. Melt flow index and water absorption studies were also carried out on the biocomposite materials, and Fourier transform infrared spectroscopy was used to examine the bonding between the polymer and each fibre type. The rate of biodegradation was also observed by placing composite samples in compost and measuring weight loss weekly. The biocomposites produced using this method were shown to have increased rates of biodegradation whilst exhibiting significantly improved flexural properties.