Radiation-induced copolymerization of trioxane with tetrahydrofuran

Radiation-initiated copolymerization of solid trioxane (TOX) with tetrahydrofuran (THF) was investigated. The effects of radiation dose, THF concentration, and post-polymerization temperature and duration on copolymer yield and THF incorporation were studied. These results are compared with the results of TOX homopolymerization under identical conditions. Copolymer yield was lower than that of homopolymer. Only a fraction of charged THF entered into the polymer chain. THF content and radiation dose also altered the MW of the copolymer but it showed better thermal stability. The initial reaction rates of the copolymerization were determined and from these the activation energy was found to be 36.2 kcal mol^?1.     

Morphological effects on the bulk polymerization of trioxane in the solid state by γ-radiation

The solid-state polymerization by γ-radiation and postpolymerization of bulk samples of trioxane has been investigated. Different thermal treatment results in radically different initial morphologies of the melt-crystallized trioxane which in turn have a profound influence on the yield and morphology of the resulting poly(oxymethylene) (POM). The polymerization yield increases in the following series: melt-crystallized trioxane with an “opaque” (small grains) morphology, as-grown needles, trioxane with a “quasi-transparent” morphology, and finally thermally oriented crystals. Furthermore, little additional POM is formed during repeated polymerization cycles. The observation of an extensive nodulation of the polymer fibrils when the yield is high is consistent with a multiple-stage growth model for the solid-state polymerization of trioxane.     

New technology of vacuum trioxane crystallization from water solutions

The paper is focused on (i) kinetics of trioxane vacuum crystallization from solution in different apparatus volumes, (ii) vapour–liquid equilibrium and (iii) crystals hardness versus process temperature. It has been found that trioxane is a well-crystallized substance with relatively high effective growth rate and, simultaneously, to some extent, crystals are resistant to attrition. Unfortunately, their elongated shape promotes breaking in the forced magma circulation type crystallizers, but still it is easy to reach well-filtrated product. To meet the objective—a profitable technology for practical application, the studies in pilot scale using industrial solutions were performed. The discussed newly developed vacuum method seems to be a promising alternative for trioxane crystals production instead of a very energy-consuming and low-efficiency cooling crystallization. The additional advantages are simplicity of operation as well as lower capital cost.     

Creep rupture properties of homopolymer,copolymer, and terpolymer based on poly(oxymethylene)

Polyacetal copolymers were prepared by cationic ring‐opening copolymerizations of 1,3,5‐trioxane (TOX) with 1,3‐dioxolane (DOX), and polyacetal terpolymers were prepared by terpolymerizations of TOX, DOX, and 2‐ethylhexyl glycidyl ether (EHGE). Polyacetal polymers with three different structures such as polyacetal homopolymers, polyacetal copolymers, and polyacetal terpolymers were compared in the mechanical properties and the creep characteristics, and discussed from the view point of the polymer structure. The polyacetal copolymers and the polyacetal terpolymers were determined by ¹H‐MNR measurement. About 80 mol % of DOX and EHGE amounts in feed were incorporated randomly into the each polymer. From the plots of the degree of crystallinity (X_c) versus the tensile strength, the tensile strength and crystallintiy of the polyacetal homopoymers are higher than those of the polyacetal copolymers and the polyacetal terpolymers. However, the tensile strength does not decrease linearly with a decrease in the crystallinity among the polyacetal polymers with three different structures, the polyacetal homopolymer, the polyacetal copolymers, and the polyacetal terpolymers. Creep rupture was characterized by the activation volume, υ_c, value in Zhurkov's equation, which can be estimated from the slope in the plots of load versus log (rupture time) at 80°C. The polyacetal polymers with higher molecular weight have larger values of the activation volume than those with lower molecular weight. When the activation volume values are compared among the polyacetal polymers with the same molecular weights, they increase in the following order: the polyacetal homopolymers < the polyacetal copolymers < polyacetal terpolymers. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Poly(oxymethylene) crystals grown in the polymerization of trioxane initiated with perchloric acid in nitrobenzene

Summary Nascent crystalline poly(oxymethylene) (POM) was synthesized by cationic polymerization of trioxane with anhydrous perchloric acid in nitrobenzene solution. The high polarity of the solvent enabled to obtain high molecular weight polymer. Also the yield obtained indicates that the polymerization reached the expected thermodynamic ceiling-equilibrium. The participation of free oxy carbenium ions from growing POM-chains are relevant on the mecha nism of polymerization and crystallization. After an induction period, hexagonal single crystals of POM are formed whose macro conformation correspond to extended chain crystals. Thermal da ta is in agreement with this morphology, typical of a simultaneous polymerization and crystallization. The spiral growth of the crystals proceeds by a catalyzed crystal growth process.     

Synthesis and properties of macromer-grafted polymers for noncovalent functionalization of multiwalled carbon nanotubes

We prepared macromer-grafted polymers (MGPs) containing suitable polymer side chains for improving solubility and pyrene units for improving adsorption on multiwalled carbon nanotube (MWCNT) surfaces, and demonstrated that these MGPs act as MWCNT solubilizers that improve solubility of MWCNTs in typically poor solvents such as alkanes and that improve flowability of polymer/MWCNT composites. The polydimethylsiloxane (PDMS)-MGPs, synthesized using PDMS macromers and pyrene-containing monomers, improved solubility of MWCNTs not only in chloroform but also in hexane, which is a poor solvent for MWCNTs. Moreover, the addition of PDMS-MGP-adsorbed MWCNTs (MWCNT/PDMS-MGPs) to epoxy resin monomers or polybutylene terephthalate (PBT) drastically reduced the viscosity of the obtained epoxy resin monomer/MWCNT/PDMS-MGP mixtures and PBT/MWCNT/PDMS-MGP composites in comparison to the epoxy resin monomer/MWCNT mixtures and PBT/MWCNT composites, respectively. The viscosity of PBT/MWCNT/PDMS-MGP composites including ?1 vol% of MWCNTs, in particular, was almost equal to that of pristine PBT.     

Improvement of the mechanical stability of oak by radiation-induced in-situ copolymerization of allyl glycidyl ether with acrylonitrile and methyl methacrylate

This study deals with the improvement of the mechanical stability of oak, which belongs to the hardwoods, by radiation-induced in-situ copolymerization of certain monomers. Acrylonitrile (AN), methyl methacrylate (MMA), allyl glycidyl ether/acrylonitrile (AGE/AN), and allyl glycidyl ether/methyl methacrylate (AGE/MMA) monomers and monomer mixtures were employed to conserve and consolidate the wood. After impregnating oak with these monomer mixtures, polymerization was accomplished by γ-irradiation. The relationships between the mechanical properties of the wood/(co)polymer composites and the anatomic structure of the wood, the types and the quantity of the polymer and copolymer, the irradiation dose and the aging process were explored. The fine structure of the wood/(co)polymer composites and the compatibility of wood with polymer and copolymer were investigated by scanning electron microscopy. The existence of polymer and copolymer in the wood enhanced the mechanical durability of the wood. The results of the hardness and the compressive strength tests applied in the parallel and perpendicular directions to the fibers of the wood/(co)polymer composites show that P(AGE/MMA), P(AGE/AN) copolymers are effective in raising the mechanical durability. In the case of P(AGE/MMA), the increase in the compressive strength perpendicular to the fibers in the oak wood is 179% at highest conversion. Similar results were also acquired from hardness tests. The decrease in the mechanical durability after aging for 28 d was very little.     

Freeze‐drying method prepared UHMWPE/CNTs composites with optimized micromorphologies and improved tribological performance

Uniformly dispersed carbon nanotubes (CNTs) reinforced ultrahigh molecular weight polyethylene (UHMWPE) composites were successfully prepared by freeze‐drying method. Specifically, polymer powders were mixed with CNT aqueous paste, and then freeze‐dried. As a consequence, CNTs covered at the surface of UHMWPE powders evenly when CNT content was not very high, which improved the quantity of crystals and crystallinity of UHMWPE/CNTs composites by providing more nucleation sites during the upcoming compression‐molded process. Furthermore, optimized dispersion state of CNTs and concomitant higher crystallinity made freeze‐drying technique prepared composites display much lower wear rate when compared with pure UHMWPE and UHMWPE/CNTs composites fabricated by common heat‐drying method. In a word, our proposed method of freeze‐drying is simple and effective for mass production of UHMWPE/CNTs composites, and it is promising to be applied to fabricate many kinds of nanofillers modified polymer composites, for example, polymer/graphene material. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41885.     

Preparation and properties of some wood/(co)polymer composites

Beech and spruce samples which were impregnated with acrylonitrile (AN), methyl methacrylate (MMA), allyl glycidyl ether (AGE), AGE + AN, AGE + MMA monomers and monomer mixtures were subjected to (co)polymerization by gamma radiation. The dimensional stabilization and resistance against biodegradation of wood/(co)polymer composites was investigated. The water uptake capacities of wood/(co)polymer composites were observed to decrease by more than 70% as compared to untreated samples. There were no noticeable changes in the structure of the wood/(co)polymer composites after treatment with artifical acid rain. It was found that the wood/(co)polymer composites were stable against the biological attacks of microorganisms like mould and bacteria.     

Effect of coupling agent on polylactic acid/polypropylene and polylactic acid/polyamide 6 foam composites

The main part of polymer materials generated from fossil fuels do not degrade after completing their usage life and then begin to be waste in the environment. This situation has led to the emphasis on environmentally friendly, biodegradable, and bio-based polymers obtained from renewable sources as an alternative. In recent years, several studies are concentrated on especially lightweight and carbon dioxide (CO₂) emission limitations. In this work, the goal was to investigate at the same time environmentally friendly and lightweight polymer foam composites based on polylactic acid (PLA) polymer without lowering the performances of the materials. In this aim, polymer foam composites containing polypropylene (PP), polyamide 6 (PA6) and PLA were produced (PLA/PA6 (30:70) and PLA/PP (30:70)) with a chemical blowing agent (CBA) introduced at 1.5 wt.% to the polymer mixture. To improve the interpolymer compatibility and foaming activity maleic anhydride-grafted polylactic acid (PLA-g-MA) was utilized as coupling agent (CA) in different ratios (1, 3 and 5 wt.%). From the evaluation of the polymer mixtures in terms of their lightness, thermal and mechanical strength, the most appropriate CA ratios were determined as 1 wt.% for foamed PLA/PP (30:70) mixtures and 3 wt.% for foamed PLA/PA6 (30:70) mixtures.     

凹凸棒土/聚合物复合材料研究进展

综述了凹凸棒土在聚合物中的应用研究进展。研究表明，大多数情况下，常规的聚合物加工技术不足以将凹凸棒土解离为纳米短纤维，因此只能形成凹凸棒土／聚合物微米复合材料，但将凹凸棒土进行有机改性，可以明显提高其增强效果。采用原位聚合的方法可以制备出性能优异的凹凸棒土／聚合物纳米复合材料，或在高黏度和高极性的聚合物熔体中，凹凸棒土在剪切力下可以解离为纳米单晶，从而形成纳米复合材料。利用凹凸棒土／乳液共混共凝方式也可制备出凹凸棒土／橡胶纳米复合材料。     

Nematic–isotropic transition in polymer‐confined and polymer‐free liquid crystal mixtures

Depending on the processing conditions in liquid crystal (LC) display manufacturing, LC/polymer composite films may exhibit unusual properties with respect to the compositional and phase behavior of the LC constituents. In particular, we have observed extraordinary large shifts of phase transition temperatures in LC/polymer composites, which can not be explained by preferential solvation or adsorption. Therefore, the influence of real manufacturing conditions such as thermal stress, storage in vacuum, and UV irradiation on the nematic–isotropic (n–i) transition temperatures of commercial nematic mixtures was investigated. Shifts of the clearing temperature of up to 88 K, presumably due to partial evaporation or UV degradation, were observed. Furthermore, we found that annealing may lead to the replacement of the nematic phase by the smectic A phase at room temperature in both LC/polymer composites and pure LC samples. Among the tested commercial LC blends, the mixtures E7, MLC‐6650, and L101 showed the smallest stress effects. Practical consequences of our results are discussed. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Development of a new advanced process for manufacturing polyacetal resins. Part III. End-capping during polymerization for manufacturing acetal homopolymer and copolymer

Conventionally, acetal homopolymer or copolymer is obtained by the polymerization of formaldehyde or trioxane, following the end-capping using acetic anhydride or unzipping of the unstable polymer end fraction. First, Asahi Chemical developed a new process to obtain an end-capped polymer during polymerization of highly purified formaldehyde using acetic anhydride as the chain-transfer agent. Use of highly purified formaldehyde and endcapping during polymerization using acetic anhydride as a chain-transfer agent or an endcapping agent will provide a simple process for manufacturing acetal homopolymer. The polymerization mechanism was confirmed by infrared spectroscopy analysis and proton NMR analysis of the polymer obtained. Second, for the acetal copolymer, purified trioxane was copolymerized with ethylene oxide in the presence of methylal, which gave an endcapped polymer with high thermal stability. Two new intermediates from the initiation reaction of the copolymerization, 1,3,5,7-tetraoxacyclononane (TOCN) and 1,3,5,7,10-pentaoxacyclododecane (POCD), were isolated and a new initiation mechanism was proposed. © 1993 John Wiley & Sons, Inc.     

Polymer Inclusion Compounds: Model Systems for Ordered Bulk Polymer Phases and Starting Materials for Fabricating Polymer–Polymer Molecular Composites

Several small molecules can be cocrystallized with polymers to form inclusion compounds (ICs). Urea, perhydrotriphenylene and the cyclodextrins are examples, and serve to form the host crystalline lattice containing the guest polymer chains in their ICs. The guest polymer chains are confined to narrow, cylindrical channels created by the host, small-molecule lattice, where the polymers are highly extended as a consequence of being squeezed, and are separated from neighbouring polymer chains by the IC channel walls composed exclusively of the small-molecule lattice. The net result is a unique solid-state environment for polymers residing in IC channels, which can be utilized as model systems for ordered, bulk polymer phases. Comparison of the behaviour of polymer chains isolated and extended in IC crystals with the behaviour observed for ordered, bulk phases of polymers is beginning to permit an assessment of contributions made by the inherent, single chain and the cooperative, interchain interactions to the properties of ordered, bulk polymers. It is also possible to release and coalesce polymers from their IC crystals in a manner which leads to their consolidation with a chain-extended morphology. Embedding polymer IC crystals into a carrier polymer, followed by in situ release and coalescence of the included polymers from their IC crystals, offers a means to obtain polymer–polymer composites with unique morphologies. Several such polymer IC-generated composites are described and it is suggested that their unique morphologies might translate into useful, tailorable properties, as well as providing a means for addressing several questions that are fundamental to the behaviour of both phase-separated and homogeneous polymer solids. © 1997 SCI     

纳米粒子改性丙烯酸酯制备复合材料

作为分散相的纳米粒子以独立的相态形式通过改性,分散到作为连续相的丙烯酸酯聚合物基体中形成一种既保留无机材料的热稳定性与硬度,又兼具聚合物韧性与介电性能的复合材料,该过程不是无机相与有机相的简单混合,而是在纳米尺度内两相的有机复合。综述了近年来纳米粒子改性丙烯酸酯复合材料,重点介绍了纳米粒子种类、纳米粒子表面改性、复合材料制备方法及其工业应用等方面的研究成果,并对其发展方向进行了分析和展望。     

Enhanced fracture energy during deformation through the construction of an alternating multilayered structure for polyolefin blends

The effects of polymer blend components on the phase morphology, crystallization behavior and mechanical performance of materials processed by high speed thin‐wall injection molding (HSTWIM) and compression molding (CM) processes were investigated. High density polyethylene (HDPE) and polypropylene (PP) containing different ratios of rubber phase (0%, 18% and 21%) were selected to construct different blends. HSTWIM is shown to trigger the formation of a multilayered structure for these blends with oriented polymer crystals and epitaxial growth of HDPE crystals on PP. Such a layered structure is thought to provide a good template for morphological control of various functional polymer composites. Moreover, the addition of rubber in the multilayered structure with the rubber phase partially distributed between layers is observed. These issues are thought to be responsible for the much enhanced fracture energy compared with specimens from CM. The structural details and formation mechanism of these layered structures consisting of different compositions were investigated. Such a study could provide some guidelines for the preparation of high performance bio‐mimic materials or various functional polymer composites with alternating multilayered structure. © 2018 Society of Chemical Industry     

碳纳米管/热致液晶复合材料的研究进展

碳纳米管/聚合物复合材料是当代碳纳米管研究领域的前沿课题,也是一项多学科交叉、多技术集成的系统工程。由于液晶和碳纳米管的特殊性能和在光电领域的潜在应用,碳纳米管液晶复合体系已经引起人们的广泛关注。本文简单介绍了近年来碳纳米管/热致液晶复合材料的发展状况,阐述了其制备原理、工艺方法、存在的问题及潜在的应用领域。     

Morphology controlled synthesis zinc oxide and reinforcement in polyhydroxyalkanoates composites

Micro‐sized ZnO crystals with different shapes have been successfully synthesized by a simple solvothermal reaction in glycol‐water binary solution or citrate solution. The morphology and size of the ZnO are strongly depended on synthetic environment. The growth of ZnO crystals with tunable shape was controlled by a suppressed crystal growth of the nonpolar plane and polar plane, due to the Tris selectively adsorbed on the different plane facets. Systematic reactions in the presence of different environments were conducted to control the formation of various well‐shaped ZnO crystals. In addition, the porous three‐dimensional microspheres possess larger surface area, which make it improving the mechanical properties of polymer compound. The mechanical properties of ZnO reinforced polyhydroxyalkanoates (PHA) composites have been tremendously improved. The elongation to break and ultimate tensile strength are increased by 41.2 and 56% compared with the pure PHA, respectively. The Young's modulus of the composites is also further improved. The results demonstrate the effectiveness of ZnO as reinforcement applications in polymer composites. POLYM. COMPOS., 35:1701–1706, 2014. © 2014 Society of Plastics Engineers     

Effect of strain hardening of shape memory polymer fibers on healing efficiency of thermosetting polymer composites

Recently, shape memory polymer fibers (SMPFs) have been used in a biomimetic two-step (Close-Then-Heal) self-healing system for healing macroscopic cracks. The objective of this study was to investigate the effect of cold-drawing programming of SMPFs on the healing efficiency of conventional thermosetting polymer composites and the possibility of healing wide-opened crack by localized heating. To achieve the objective, continuous SMPF strand reinforced conventional epoxy composite beam specimens, which were dispersed with thermoplastic particles, were prepared. The SMPF strands were cold-drawn to various pre-strain levels before casting the polymer matrix. Repeated fracture/healing test was conducted by uniaxial tension. It is found that the composites were able to repeatedly heal macroscopic cracks. Strain-hardening by cold-drawing increased the healing efficiency considerably. It was demonstrated that healing can be achieved by heating locally surrounding the cracked region. The mechanism for the enhanced recovery stress was due to cold-drawing induced molecular alignment and formation of some perfect crystals in the hard segment domain of the SMPF.     

Structural properties and mechanical behavior of injection molded composites of polypropylene and sisal fiber

Composites based on isotactic polypropylene (PP) and sisal fiber (SF) were prepared by melt mixing and injection molding. The melt mixing characteristics, thermal properties, morphology, crystalline structure, and mechanical behavior of the PP/SF composites were systematically investigated. The results show that the PP/SF composites can be melt mixed and injection molded under similar conditions as the PP homo‐polymer. For the composites with low sisal fiber content, the fibers act as sites for the nucleation of PP spherulites, and accelerate the crystallization rate and enhance the degree of crystallinity of PP. On the other hand, when the sisal fiber content is high, the fibers hinder the molecular chain motion of PP, and retard the crystallization. The inclusion of sisal fiber induces the formation of β‐form PP crystals in the PP/SF composites and produces little change in the inter‐planar spacing corresponding to the various diffraction peaks of PP. The apparent crystal size as indicated by the several diffraction peaks such as L_(110)α, L_(040)α, L_(130)α and L_(300)β of the α and β‐form crystals tend to increase in the PP/SF composites considerably. These results lead to the increase in the melting temperature of PP. Moreover, the stiffness of the PP/SF composites is improved by the addition of sisal fibers, but their tensile strength decreases because of the poor interfacial bonding. The PP/SF composites are toughened by the sisal fibers due to the formation of β‐form PP crystals and the pull‐out of sisal fibers from the PP matrix, both factors retard crack growth.