Well-defined crosslinked materials via ring opening metathesis polymerisation

The work reported here is part of our ongoing programme of work directed. towards the synthesis and characterisation of polymeric materials via ROMP-RIM and ROMP-RTM. It describes the synthesis and characterisation of well-defined linear and crosslinked polymeric materials via ROMP-RTM. The process involves in-mould polymerisation of monofunctional imidonorbornene monomers, with different alkyl side chain lengths, to give a range of linear polymers. The process also involves in-mould copolymerisation of monofunctional imidonorbornene monomers, with different alkyl side chain lengths and difunctional monomers with different alkylene spacer lengths, to produce well-defined crosslinked polymers. The glass transition temperature (T_g) of the linear polymers was found to depend on the length of the alkyl side chain. For the crosslinked materials the results show that as the percentage of the difunctional, crosslinking unit, is increased (1, 5 and 10 molar percentage of the difunctional monomer) the glass transition shifts to a higher temperature, the height of the tanδ peak decreases and the plateau shear modulus above T_g increases. These results are as expected for an increase in the crosslink density of a polymer.     

非交联组份对端乙烯基聚环氧丙烷/聚苯乙烯网状共聚物粘弹性的影响

本文描述了端乙烯基聚环氧丙烷/聚苯乙烯网状共聚物的合成及表征。研究了非交联组份对共聚物的玻璃化转变温度T_g,贮能模量E'、耗能模量E'和阻尼系数tanδ等动态力学性能的影响,计算了试样的粘弹性参数。结果表明,非交联组份对交联网有明显塑化作用,使其T_g降低,自由体积分数和阻尼系数增大。     

Preparation of high damping elastomer with broad temperature and frequency ranges based on ternary rubber blends

Based on the blends of chlorinated butyl rubber (CIIR), nitrile butadiene rubber (NBR) and chloroprene rubber (CR), a kind of high damping elastomer with broad temperature and frequency ranges is prepared. CIIR/NBR binary blend is prepared to take advantage of the immiscibility and the large difference in cross‐link density of the different phases caused by the curatives and accelerators migration. The dynamic mechanical analysis reveals that the binary blend was immiscible and its loss factor (tanδ) versus temperature curves show two separated and expanded loss peaks when compared with those of pure cured CIIR and NBR. In order to improve its damping properties at room temperature, the third component CR with the polarity between CIIR and NBR was blended into the binary blend. The resulted CIIR/NBR/CR ternary blend has gained effective damping properties (tanδ > 0.3) in the temperature range of ?86.4 to 74.6°C and the frequency range of 10^?2 to more than 10⁹ Hz. Other effects on the damping properties of the ternary rubber were also studied. Copyright © 2013 John Wiley & Sons, Ltd.     

Polymeric sulfated surfactants with varied hydrocarbon tail: I. Synthesis, characterization, and application in micellar electrokinetic chromatography

The influence of surfactant hydrocarbon tail on the solute/pseudostationary phase interactions was examined. Four anionic sulfated surfactants with 8-, 9-, 10-, and 11-carbon chains having a polymerizable double bond at the end of the hydrocarbon chain were synthesized and characterized before and after polymerization. The critical micelle concentration (CMC), polarity, and aggregation number of the four sodium alkenyl sulfate (SAIS) surfactants were determined using fluorescence spectroscopy. The partial specific volume of the polymeric SAIS (poly-SAIS) surfactants was estimated by density measurements and capillary electrophoresis (CE) was employed for determination of methylene selectivity as well as for elution window. The CMC of the monomers of SAIS surfactants decrease with increase in chain length and correlated well when fluorescence method was compared to CE. The physicochemical properties (partial specific volume, methylene selectivity, electrophoretic mobility, and elution window) increased with an increase in chain length. However, no direct relationship was found between the aggregation number and the length of hydrophobic tail of poly-SAIS surfactants. These polymeric surfactants were then used as pseudostationary phases in micellar electrokinetic chromatography (MEKC) to study the retention behavior and selectivity factor of 36 benzene derivatives with different chemical characteristics. Although variation in chain length of the polymeric surfactants significantly affects the retention of nonhydrogen bonding (NHB) benzene derivatives, these effects were less pronounced for hydrogen bond acceptor (HBA) and hydrogen bond donor (HBD) benzene derivatives. Therefore, hydrophobicity of poly-SAIS surfactants was found to be a major driving force for retention of NHB derivatives. However, for several benzene derivatives (NHB, HBA, and HBD) significantly higher selectivity factor was observed with longest chain polymeric surfactant (e.g., poly(sodium 10-undecenyl sulfate), poly-SUS) compared to shorter chain polymeric surfactant (e.g., poly(sodium 7-octenyl sulfate), poly-SOcS). In addition, the effect of the surfactant hydrophobic chain was also found to have some impact on migration order of NHB, HBA, and HBD benzene derivatives.     

Damping elastomer with broad temperature range based on irregular networks containing hyperbranched polyester and dangling chains

Elastomer is one of the important materials for vibration and noise reduction. However, its narrow effective damping temperature range (tanδ ≥ 0.3) remains to be a major issue that hinders its application as a damping material. Herein, we precisely design and synthesize a polyurethane structure where specific dangling chains with both electron‐donating group and electron‐absorbing group were introduced into prepolymers, generating more hydrogen bonding interaction with the main chain to hinder microphase separation. At the same time, hyperbranched polyester as a cross‐linking agent increases its free volume effectively. The synergy effect of enhancement of hydrogen bonding, decrease of microphase separation, and increase of free volume results in a higher damping polyurethane elastomer with a great wider effective damping temperature range up to 175°C (−60°C‐115°C), which provides a new idea for the preparation of damping elastomer.     

BaTiO3 / (PU/UP-IPNS)复合材料的相容性、力学性能和阻尼性能研究(英)

以水热法合成的BaTiO3纤维和同步法制备的互穿聚合物网络为原料，采用原位分散聚合法获得了一系列BaTiO3/(PU／UP-IPNs)复合材料。采用傅立叶交换红外分光光度计跟踪考察了IPNs的聚合过程，用透射电镜观测了IPNs及其复合物的形貌。结果表明，IPNs中两相相畴尺寸在纳米级范围内，在此基础上，实现了BaTiO3纤维状的复合。动态力学性能的检测结果表明，相较纯IPNs，复合材料的阻尼损耗模量和阻尼损耗因子值均有所提高，且在低温区均出现了肩峰。复合物的最大损耗因子值均大于0．4，在约50℃范围内，E’值提高100MPa。力学性能检测结果表明，IPNs中的连续相是决定材料力学性能的主要因素；有机／无机组分间混溶性的降低，使BaTiO3/IPNs复合材料的抗张强度和断裂伸长率均下降。     

Novel Methods for Obtaining High Modulus Aliphatic Polyamide Fibers

Super high modulus polyethylene fibers can be created by converting high molecular weight flexible PE chains into highly oriented and extended chain conformations. However, unlike polyethylene, aliphatic polyamides have very high cohesive energy and therefore cannot be easily drawn and highly oriented. This review addresses this fundamental problem by analyzing various novel approaches that can be used to suppress hydrogen bonding in these types of polyamides. Plasticization of such polymers with ammonia, iodine, salts, and Lewis acids, as well as dry spinning, wet spinning, and gel spinning, are discussed. Specialized techniques that involve vibrational zone drawing and annealing as well as laser heating zone drawing and annealing are also reviewed. Some of these methods definitely lead to remarkable improvements in initial modulus and other mechanical properties. The development of recombinant spider silk proteins as well progress in spinning these materials is also reported. The advantages and disadvantages of all of these processes are then summarized.     

Non-linear Viscoelastic Rheological Properties of PCC/PEG Suspensions

The shear thinning and shear thickening rheological properties of PCC/PEG suspension were investigated with the increase of oscillatory amplitude stress at different constant frequencies. The results show that the complex viscosity was initially independent of stress amplitude and obvious shear thinning occurred, then dramatic shear thickening took place after reaching the minimum viscosity. Typically, in a constant frequency of 5 rad/s, the elastic modulus, viscous modulus, and tanδ （δ is the out-of-phase angle） vs. the stress amplitude was investigated. It is found that the elastic modulus initially appeared to be independent of stress amplitude and then exhibited a rapid decrease, but the viscous modulus was independent of amplitude stress at lower amplitude stress. After reaching the minimum value the viscous modulus showed a rapid increase. On the other hand, tanδ increased from 0.6 to 92, which indicates that the transition from elastic to viscous had taken place and tanδ showed a steep increase when shear thickening occurred. Lissajous plots are shown for the dissipated energy vs. different maximum stress amplitude in the shear thinning and shear thickening regions. The relationship of dissipated energy vs. maximum stress amplitude was determined, which follows a power law. In the shear thinning region the exponent was 1.91, but it steeply increases to 3.97 in the shear thickening region.     

PMPS/PMAc相容性与同步互贯聚合物网络的阻尼性能研究

互贯聚合物网络是一种聚合物合金 ,其组分的热力学性质决定组分间的相容性和微相结构 ,从而影响材料的阻尼性能 .采用同步互贯聚合物网络 (SIN)技术制备了一种新型的聚苯基硅氧烷 (PMPS) 聚甲基丙烯酸酯 (PMAc)阻尼材料 ,用DMA和AFM等表征研究了其玻璃化温度转变行为与微观相态结构 .结果表明 ,由相容性好的组分制备的SIN材料阻尼值最高 ,tanδmax 可达 1 4,只有一个玻璃化温度转变峰 ,其微相结构为双相连续 ;组分介于相容与不相容之间时 ,所构成的SIN样品的tanδ≥ 0 3的温度区间最宽 ,可达 170℃ ,微相结构为单相连续 ;由相容性差的组分制得的SIN阻尼材料的内耗峰裂分为两个区间 .PMPS PMAcSIN材料的阻尼性能可以通过调节组分的相容性进行控制 .     

CRYSTALLIZATION AND MECHANICAL PROPERTIES OF BLENDS OF METALLOCENE SHORT CHAIN BRANCHED POLYETHYLENE WITH CONVENTIONAL POLYOLEFINS

Metallocene-catalyzed short chain branched polyethylene (SCBPE) was blended with LDPE, HDPE, PS, EPDM and iPP in the weight proportions of 80 and 20. The crystallization and mechanical properties of these blends were studied by PLM, DSC and DMA. It has been observed in PLM that SCBPE/LDPE, SCBPE/HDPE and SCBPE/EPDM can form band spherulites whose band width and size are both smaller than that of the pure SCBPE. Tiny crystallites are observed in the completely immiscible SCBPE/PS blend. The crystallites in SCBPE/iPP are very small and only irregular spherulites are seen. The crystallization kinetics and mechanical properties of SCBPE are greatly affected by the second polyolefin, but in a different way, depending on the phase behavior and the modulus of the second components. SCBPE may be phase miscible in the melt with HDPE, LDPE and EPDM and co-crystallize together with HDPE or LDPE during cooling. A big change of crystal morphology and crystallization kinetics is seen in SCBPE/iPP blend compared with pure SCBPE and the lowest tanδ is also seen for this system. DMA results show that the tensile modulus of the blends has nothing to do with phase behavior, but only depends on the modulus of the second component.     

A five-parameter fractional derivative temperature spectrum model for polymeric damping materials

To capture viscoelastic behavior of polymeric damping materials based on limited dynamic mechanical analysis tests, a simple fractional temperature spectrum model representing the viscoelastic materials is proposed in this paper and experimental tests aims at stressing the validity of the model. The storage modulus, the loss modulus, and the loss factor, are established based on the five-parameter fractional derivative model and the time–temperature superposition principle. The dynamic mechanical tests of two polymeric materials are carried out to verify this temperature spectrum model. Results indicate a good agreement between the temperature spectrum model and experimental tests at various temperature conditions. Furthermore, thermodynamic coupling of the viscoelastic material is investigated by temperature rise calculation and vibration experiment test. Comparison analysis shows that the temperature rise model can simulate the temperature rise process for the shear vibration of the constrained damping, which provide references for the damping capability, thermal damage and failure of viscoelastic material.     

Towards advanced circuit board materials: adhesion of copper foil to ultra‐high molecular weight polyethylene composite

Polyethylene based composites are attractive materials for advanced circuit board applications because of their unique combination of properties: low dielectric constant and loss factor, light weight, high flexural modulus and low thermal expansion coefficient controlled in all spatial directions. This investigation describes a process to consolidate chopped fibers of ultra‐high molecular weight polyethylene concurrently with its bonding to a copper foil. Bonding is affected by a thin sheet of low‐density polyethylene, incorporating a crosslinking agent with a concentration gradient across the sheets thickness. In this single step process, the composite material is formed and bonded to the metal foil, achieving good adhesion without the use of extraneous glue. Copyright © 2002 John Wiley & Sons, Ltd.     

热塑性聚氨酯微孔发泡材料的表观密度与其力学性能的关系

用高压CO2流体通过升温发泡法制备了一系列不同表观密度的热塑性聚氨酯(TPU)微孔发泡材料,探究了TPU发泡材料的表观密度与其力学性能的关系.微孔发泡材料的泡孔结构和表皮结构由扫描电子显微镜表征;不同表观密度材料的力学性能利用万能材料试验机和旋转流变仪表征.研究发现:TPU微孔发泡材料的表观密度主要是由材料皮层厚度占比和泡孔层密度决定的,皮层厚度占比越小和泡孔面积占有率越高,泡沫的表观密度越小;微孔发泡材料在线性应变区的压缩模量E与材料表观密度ρ的关系为:E∝ρ1.7,符合泡沫材料压缩模量与表观密度呈指数关系的基本结论;循环压缩实验中,随微孔发泡材料表观密度减小,损耗百分比增大,残余应变减小;流变实验中,微孔发泡材料的模量随表观密度变化没有明显的变化,阻尼因子tanδ随泡沫表观密度变化不呈单一的规律性.同时,阐明了微孔发泡材料的压缩模量E和损耗百分比随表观密度变化的机理.     

Thermomechanical investigation of a thick film of aniline-formaldehyde copolymer and poly(methyl methacrylate)

A thick film of aniline-formaldehyde copolymer and PMMA is synthesized via dispersion of aniline-formaldehyde copolymer powder as filler particles in PMMA with two different concentrations. Variation of the complex elastic modulus and mechanical loss factor (tanδ) with temperature is studied. It is observed that the complex elastic modulus decreases with temperature owing to thermal expansion of films. On the other hand, tanδ increases up to a characteristic temperature beyond which it shows a decreasing trend toward melting. Transition temperature T _g of sample S₁ (pure PMMA) is found to be 80°C. In sample S₂ (1 wt % aniline formaldehyde copolymer), the peak of tanδ at a lower temperature (66°C) corresponds to glass transition temperature T _g of the PMMA matrix, while the peak of tanδ at a higher temperature (107.8°C) corresponds to T _g of a polymer chain restricted by filler particles of aniline-formaldehyde copolymer. A further increase (10 wt % aniline-formaldehyde copolymer) in the concentration of filler particles of aniline-formaldehyde copolymer results in a more compact structure and a shift of T _g to a higher temperature, 122.2°C. This shift in the glass transition temperature of thick films of aniline-formaldehyde copolymer and PMMA is dependent upon the concentration of filler particles in the sample.     

Quadruple Hydrogen Bond-Containing A-AB-A Triblock Copolymers: Probing the Influence of Hydrogen Bonding in the Central Block

This work reveals the influence of pendant hydrogen bonding strength and distribution on self-assembly and the resulting thermomechanical properties of A-AB-A triblock copolymers. Reversible addition-fragmentation chain transfer polymerization afforded a library of A-AB-A acrylic triblock copolymers, wherein the A unit contained cytosine acrylate (CyA) or post-functionalized ureido cytosine acrylate (UCyA) and the B unit consisted of n-butyl acrylate (nBA). Differential scanning calorimetry revealed two glass transition temperatures, suggesting microphase-separation in the A-AB-A triblock copolymers. Thermomechanical and morphological analysis revealed the effects of hydrogen bonding distribution and strength on the self-assembly and microphase-separated morphology. Dynamic mechanical analysis showed multiple tan delta (δ) transitions that correlated to chain relaxation and hydrogen bonding dissociation, further confirming the microphase-separated structure. In addition, UCyA triblock copolymers possessed an extended modulus plateau versus temperature compared to the CyA analogs due to the stronger association of quadruple hydrogen bonding. CyA triblock copolymers exhibited a cylindrical microphase-separated morphology according to small-angle X-ray scattering. In contrast, UCyA triblock copolymers lacked long-range ordering due to hydrogen bonding induced phase mixing. The incorporation of UCyA into the soft central block resulted in improved tensile strength, extensibility, and toughness compared to the AB random copolymer and A-B-A triblock copolymer comparisons. This study provides insight into the structure-property relationships of A-AB-A supramolecular triblock copolymers that result from tunable association strengths.     

Improved mechanical properties of epoxy composites reinforced with surface‐treated UHMWPE fibers

The surface treatment of ultra‐high molecular weight polyethylene fiber using potassium permanganate and the mechanical properties of its epoxy composites were studied. After treatment, many changes were happened in the fiber surface: more O‐containing groups (―OH, ―C═O, and ―C―O groups), drastically decreased contact angles with water and ethylene glycol, slightly increased melting point and crystallinity, and formed cracks. Different contents (0.1–0.5 wt%) ultra‐high molecular weight polyethylene fibers/epoxy composites were prepared. The results indicated that the surface treatment decreased the tensile strength of epoxy composites, but increased the bending strength. When the fiber content was 0.3 wt%, the above properties reached the maximum. At the same fiber content, the interlaminar shear strength of the composites was increased by 26.6% up to the as‐received fiber composites. Dynamic mechanical analysis of the composites suggested the storage modulus and tanδ were decreased due to the surface treatment. Fractured surface analysis confirmed that the potassium permanganate treatment was effective in improving the interface interaction.     

Thermorheological analysis of PVC blends

The effect of temperature on dynamic viscoelastic measurements of miscible poly (vinyl chloride) (PVC)/ethylene‐vinyl acetate–carbon monoxide terpolymer (EVA‐CO) and immiscible PVC/high‐density polyethylene (HDPE) and PVC/chlorinated polyethylene (CPE) molten blends is discussed. PVC plasticized with di(2 ethyl hexyl) phthalate (PVC/DOP) and CaCO₃ filled HDPE (HDPE/CaCO₃) are also considered for comparison purposes. Thermorheological complexity is analyzed using two time–temperature superposition methods: double logarithmic plots of storage modulus, G′, vs. loss modulus, G″, and loss tangent, tan δ, vs. complex modulus, G*, plots. Both methods reveal that miscible PVC/EVA‐CO and PVC/DOP systems are thermorheologically complex, which is explained by the capacity of PVC to form microdomains or crystallites during mixing and following cooling of the blends. For immiscible PVC/HDPE and PVC/CPE blends the results of log G′ vs. log G″ show temperature independence. However, when tan δ vs. log G* plots are used, the immiscible blends are shown to be thermorheologically complex, indicating that the morphology observed by microscopy and constitued by a PVC phase dispersed in a HDPE or CPE matrix, is reflected by this rheological technique. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 469–477, 2000     

The effect of radiation on the physical and chemical properties of polyethylene containing an antioxidant and/or other additives

This paper describes the effect of an antioxidant, a monomer and fillers (silica or carbon black), alone or in certain combinations with each other, on the mechanical and chemical response of a low density polyethylene to exposure to ionizing radiation. If chain scission is a significant factor in the radiolysis of a polymer, then the relation between sol fraction and Young's modulus or ultimate elongation (both at 160°C) should change depending on whether an additive inhibits or enhances crosslinking. Such additives do not significantly or consistently alter the relation between these properties in a low density polyethylene, indicating that chain scission is not a significant feature of the radiolysis of this polymer.     

New soybean oil‐Styrene‐Divinylbenzene thermosetting copolymers—IV. Good damping properties

New polymeric materials have been prepared by the cationic copolymerization of regular soybean oil, low saturation soybean oil, i.e. LoSatSoy oil, or conjugated LoSatSoy oil with styrene and divinylbenzene, norbornadiene or dicyclopentadiene initiated by boron trifluoride diethyl etherate (BF ₃·OEt ₂) or related modified initiators. The effects of the stoichiometry, the type of soybean oil and the alkene comonomer on the damping behavior of the resulting polymers have been investigated. The damping properties have been quantitatively evaluated by the loss tangent maximum (tan δ) _max, ­the temperature range ΔT for efficient damping (tan δ > 0.3), and the integrals of the linear tan δ v. temperature curves (tan δ area, TA). These bulk materials are composed primarily of soybean oil‐styrene‐divinylbenzene random copolymers with considerable variability in the backbone compositions. The good damping properties of the soybean oil polymers are presumably determined by the presence of fatty acid ester side groups directly attached to the polymer backbone and the segmental heterogeneities resulting from crosslinking. In general, crosslinking reduces the (tan δ) _max and the TA values, but broadens the region of efficient damping (ΔT). Soybean oil polymeric materials with appropriate compositions and crosslink densities are capable of efficiently damping over a temperature region in excess of 110 °C and provide noise and vibration attenuation over broad temperature and frequency ranges. Copyright © 2002 John Wiley & Sons, Ltd.     

PCL/SiO2杂化纳米相微结构与晶态成核生长特性

The nano-phase microstructure of high molecular weight poly(ε-caprolactone) (PCL) /silica hybrid materials, in which polymeric and inorganic component are coupled by hydrogen bonding, and nucleation and growth of PCL chain in the hybrids were studied by scanning electronic microscopy, wide-angle X-ray diffraction and differential scanning calorimetry. The results show that the micro-phase separation in the hybrids occurs at the nano-meter scale. The average scale of the polymeric domain is about 70 nm. The morphological structure of the inorganic component appears as irregular particles. The uniform distribution of two phases relates to the bonding strength of hydrogen bonding between components in the hybrids. After a PCL is hybridized, the relative degree of crystallinity decreases and the corresponding scale of microlite change. In addition, with inorganic content increasing, the equilibrium melting points of the PCL in hybrids decrease. The energy that polymeric chains fold to form crystals on the surface of crystal nucleus increases. This result is due to the influence of silica and the bonding strength in hybrids.