Synthesis,characterization, and curing of hyperbranched allyl ether–maleate functional ester resins

A model two-step synthesis of a saturated hyperbranched hydroxyl-terminated ester has been developed to show a synthesis route. Three different series of hyperbranched esters with different terminations have been synthesized to relate some of their properties to their structures. This route has then been used to synthesize three different allyl ethermaleate functional hyperbranched ester resins in a two-step procedure. The resins have been characterized with respect to rheology, structure, and properties, and the differences are discussed. The allyl ether-maleate functional resins have also been studied with respect to curing performance and final film properties. © 1993 John Wiley & Sons, Inc.     

Comparison of diffusion coefficients for matched pairs of macrocyclic and linear molecules over a drug-like molecular weight range

The diffusion coefficients of a series of closely matched pairs of macrocyclic and linear molecules have been compared using NMR spectroscopy. The macrocyclic series was designed both to overlap with and extend beyond the molecular weight range typically employed for drug-like molecules. The linear molecules each represent a carbogenic fission of their macrocyclic counterparts, designed to minimize differences in functionality and physicochemical properties. Each series of molecules was prepared using copper catalyzed azide-alkyne cycloaddition (CuAAC) reactions conducted in a flow using a copper tube. The macrocyclic series exhibited consistently higher diffusion across the entire molecular weight range studied. The fold difference in diffusion coefficients between the macrocyclic and linear analogues appeared to be independent of either solvent viscosity or dielectric environment.     

Cure study of addition-cure-type and condensation-addition-type phenolic resins

By the incorporation of propargyl and methylol groups on to novolac backbone, a series of addition-curable phenolic resins and condensation-addition dual-cure type phenolic resins (novolac modified by propargyl groups referred as PN, and novolac modified by propargyl and methylol groups simultaneously referred as MPN) were synthesized. The processing characteristics, thermal cure and catalytic cure behavior for both resins were investigated mainly by means of viscosity measurement and non-isothermal differential scanning calorimetry (DSC) techniques. The effect of propargyl and methylol content of PN and MPN, the molecular weight and the configuration of the parent novolac, on the processing and cure behavior was studied in details. Processing parameters and curing kinetic parameters were obtained. Both resins exhibit excellent processing properties. Thermal cure of PN resins possessed one cure mechanism and that of MPN resins possessed two cure mechanisms according to DSC analysis. The dual-cure-type mechanism made MPN resins superior to PN resins in terms of a mild and controllable cure process. Compared with thermal cure, catalytic cure of PN resins showed lower initiation temperature and cure temperature by about 60 °C. These novel resins have a bright prospect of application as matrix for thermal-structural composite materials.     

星形聚乳酸

星形聚乳酸以其独特的结构与性能引起了人们的广泛兴趣,通常使用“先核后臂”法进行合成。本文根据不同类型的“核”进行分类,如小分子多羟基醇（天然糖醇）、无机（杂环）化合物的衍生物、金属有机化合物、多元酚的衍生物和星形高分子等,综述了星形聚乳酸近年来合成（尤其是丙交酯开环聚合法合成）、性能与应用等方面的研究进展,指出星形聚乳酸高分子量、低黏度、良好溶解性和热稳定性等优点有利于其在药物缓释等生物医用材料中的加工应用。     

Multifunctional Polyesters for Bioartificial Vascular Prostheses

Aliphatic polyesters of controlled molecular weight and low molecular weight distribution were prepared via anionic ring-opening polymerization using a multifunctional star-shaped initiator. Functionalization results in star-shaped functional polyesters bearing methacrylate end groups. Novel biodegradable polyester resins were prepared by photochemical crosslinking of the functional polyesters. Three-dimensional microstructuring via UV replica molding shows the potential of this material as substrate for biomedical devices.     

Making polymer concrete and polymer mortar using synthesized unsaturated polyester resins from poly(ethylene terephthalate) waste

Depolymerization of poly(ethylene terephthalate), PET, waste was studied in the presence of manganese acetate catalyst and propylene glycol (PG) at different weight ratios. The glycolyzed products were analyzed for hydroxyl value and the amount of free glycol. A series of unsaturated polyesters based on the glycolyzed products, maleic anhydride and styrene, were prepared. Molecular weights and curing behavior of these polyesters were determined. Polymer concrete (PC) and polymer mortars (PM) made with these resins were investigated for their compressive strength. It has been found that the properties of PC and PM obtained from resins based on recycled PET are comparable to PC and PM made from virgin materials.     

Novel liquid crystalline resins based on MQ siloxanes

MQ siloxane resins containing Si-H functions have been made from tetramethyldisiloxane and tetraethoxysilane. Hydrosilylations with mesogenic alkenes give low molecular weight liquid crystal MQ resins with potentially useful properties.     

单组分聚氨酯清漆的制备与性能研究

不同的聚碳酸酯二元醇、聚四亚甲基醚二醇(PTMG)与二苯甲烷二异氰酸酯(MDI)、小分子二元醇反应,制得聚醚、聚碳酸酯型聚氨酯清漆。通过红外光谱分析结合其机械力学性能、耐水性等的测试结果,探讨聚碳酸酯型聚氨酯清漆的结构对形态和性能的影响。结果表明：随着硬段含量的增加,树脂涂膜的微相分离程度增加,机械性能提高;组分摩尔比例相同时,软段分子量的降低有利于提高树脂的软硬段相容性,增加树脂涂膜的物理机械性能;组分摩尔比例相同时聚酯型聚氨酯树脂的微相分离程度低于聚醚型聚氨酯树脂;MDI基溶剂型聚氨酯树脂的物理机械性能较好。     

Pot life extension of hydroxyl terminated polybutadiene based solid propellant binder system by tailoring the binder polymer microstructure

A possibility of extending the pot life of the HTPB-TDI based propellant binder system without adverse modification of mechanical properties is explored in the present study. It is proposed that by tailoring functionality distribution of the base HTPB polymer and changing the binder composition concurrently, the pot life of the binder system can be extended while the mechanical characteristics are kept within the acceptability window. Using an existing empirical relationship between fraction of high molecular weight (Fh) in HTPB and r-value corresponding to a more optimized set of mechanical properties, the r-values were calculated for different HTPB resins. HTPB resins with widely varying fractions of high molecular weight (Fh) were chosen and binder networks were prepared at different r values. Viscosity build up and chemical kinetics were studied for different formulations. From the studies, it is shown that the extension of pot-life is achievable by about 150 minutes without sacrificing the mechanical characteristics.     

Characterization of linear low-density polyethylene: Cross-fractionation according to copolymer composition and molecular weight

The structure of ethylene copolymers modified by α-olefins has become an area of intense investigation since the successful commercialization of so-called linear low-density polyethylene (LLDPE) resins. The molecular structure of a series of typical commercial LLDPE copolymers was investigated and compared to LDPE and HDPE. The commercial LLDPE resins studied contained about 7% by weight of butene-1. The resins were fractionated according to short-chain branching content by a technique called temperature rising elution fractionation. Size exclusion chromatography, x-ray diffraction, ¹³C nuclear magnetic resonance, intrinsic viscosity, and differential scanning calorimetry were used to fully characterize the whole polymers as well as fractions of a selected LLDPE resin. A broad set of data was assembled in this work to investigate the short-chain branching, long-chain branching, and the molecular-weight distribution of these commercial resins. The melting behavior of the LLDPE resins was found to be strikingly different from that of LDPE and HDPE. The broad and multimodal melting envelope of the LLDPE resins was found to be due to a broad and multimodal short-chain branching distribution. No significant long-chain branching was found in the LLDPE resins. The short-chain branching was found to decrease with the increase of molecular weight in a typical commercial LLDPE resin. The unique physical properties of these resins are certainly strongly controlled by the expression of the distinctive heterogeneous comonomer incorporation in the solid-state morphological structure. The physical and mechanical properties of these materials should be ultimately understandable on the basis of the unique morphology which results from the extremely heterogeneous incorporation of modifying α-olefin in these commercial LLDPE resins.     

Poly‐2‐oxazoline‐derived polyurethanes: A versatile synthetic approach to renewable polyurethane thermosets

2‐Nonyl‐2‐oxazoline and 2‐(9‐decenyl)‐2‐oxazoline have been copolymerized in different proportions by cationic ring‐opening polymerization to obtain a series of random linear copolymers with tailored molecular weight and double bond functionality in the side chains. Thiol‐ene addition of 2‐mercaptoethanol has been used to produce a set of polyoxazoline–polyols under mild conditions and with quantitative double bond transformation. The polyols obtained in this way were reacted with methylene‐bis(phenylisocyanate) to yield a series of amorphous and semicrystalline polyurethane networks. The thermal stability and the thermomechanical properties of these thermosets have been studied and related with the structure of the parent polyols. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Structural features of star-shaped fullerene (C60)-containing polystyrenes: Neutron scattering experiments

Structural features of star-shaped polyprotostyrene and polydeuterostyrene containing fullerene C₆₀ as a branching center have been studied by small-angle neutron scattering in benzene solutions. The results are compared with the corresponding characteristics of linear PSs, the molecular mass of which is equal to the molecular mass of one star arm in star-shaped macromolecules. The molecular masses of star-shaped polymers are estimated, and their branching center is shown to be hexafunctional. At relatively low concentrations of starshaped polymers in solutions, one can observe excluded volume effects, which are related by the presence of regions with higher densities at the center of a macromolecule. Using the Fourier transform of the scattering cross section, three-dimensional correlation functions are obtained, and the regular structure of stars is proved. Conclusions about the local correlations of units within one star arm and averaged correlations between units of neighboring arms within a given star are derived. An analysis of three-dimensional correlations shows that the centers of mass of all star arms are directed along orthogonal axes passing through the C₆₀ branching center of a star-shaped macromolecule.     

Synthesis and relationships between the structures and properties of monodisperse star-shaped oligofluorenes

[structure: see text] A convenient approach to a series of star-shaped pi-conjugated organic materials with oligofluorenes (OF) as the branches and a benzene ring as the core has been developed. The optical properties of these materials are liable to be tuned by introduction of more fluorene rings. The investigation of the structure-property relationship of these materials has indicated differences between star-shaped oligofluorenes and linear oligofluorenes, as well as polyfluorenes.     

Polyaryläther-Kondensationsprodukte des 4,4′-bis(chloromethylphenyl) äthers mit manchen diphenolen

Poly(aryl ethers) as products of the polycondensation of 4,4′-bis(chloromethylphenyl) ether with sodium salts of various phenols have been prepared in the Williamson reaction. The reaction was carried out at three different temperatures (78, 140, and 185°C.) in ethanol, xylene, and tetralin, respectively. The effect of the polycondensation and the nature and composition of initial components on the properties of the products has been studied. The molecular weights and the melting temperature of the synthesized resins increased with increasing reaction temperature. The structure and molecular weight have a pronounced effect on the properties of the resins. Resins prepared from 4,4′-dihydroxydinaphthyl had the highest melting temperature and were practically insoluble, while the resins prepared from 2,2′-dihydroxydinaphthlmethane had the lowest melting temperature and were soluble in practically all organic solvents. On the basis of the experimental data a reaction scheme appropriate for the synthesis of poly(aryl ethers) from the phenolates as well as from the free phenols in the presence of NaOH has been proposed. Some thermal and mechanical properties of poly(aryl ethers) have been determined. Thermal treatment of the resins above theri softening temperature resulted in an elevated softening point too. This is explained by the supplementary condensation of both chlorine or hydroxyl endgroups in the molten resins.     

Synthesis,cure, and composite properties of mixed allyl/propargyl cyclopentadiene resins

A series of thermosetting resins were synthesized via phase transfer reaction of allyl chloride and propargyl bromide with cyclopentadiene in the presence of a strong base. Feed ratios of 1 : 1, 3 : 1, and 5 : 1 allyl chloride to propargyl bromide were used to give resins with varying amounts of propargyl and allyl functionality. In all cases the resins could be thermally cured, without added catalyst, at temperatures below 275°C to give black, glassy, brittle materials with densities of 1.15. TGA evaluation of the resins, with heating to 1000°C, resulted in carbon yields ranging from 48 to 66% with increasing propargyl functionality causing increased values. Physical mixtures of ACP and PCP resins were also made and evaluated. Cure of the mixed materials also occurred below 275°C, and carbon yields were comparable to the corresponding APCP resin. APCP/carbon fiber composites gave good mechanical properties with flexural modulus values of 115–130 GPa and flexural strength values of 1000 MPa. Carbonization of 1 : 1 APCP/carbon fiber composites provided materials with interlaminar strength values of approximately 1.14 MPa. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 2869–2876, 1998     

Rational Design of Star-shaped Molecules with Benzene Core and Naphthalimide Derivatives End Groups as Organic Light-emitting Materials

A series of star-shaped molecules with benzene core and naphthalimides derivatives end groups have been designed to explore their optical,electronic,and charge transport properties as charge transport and/or luminescent materials for organic light-emitting diodes(OLEDs). The frontier molecular orbitals(FMOs) analysis has turned out that the vertical electronic transitions of absorption and emission are characterized as intramolecular charge transfer(ICT). The calculated results show that the optical and electronic properties of star-shaped molecules are affected by the substituent groups in N-position of 1,8-naphthalimide ring. Our results suggest that star-shaped molecules with n-butyl(1),benzene(2),thiophene(3),thiophene S?,S?-dioxide(4),benzo[c][1,2,5]thiadiazole(5),and 2,7a-dihydrobenzo[d]thiazole(6) fragments are expected to be promising candidates for luminescent and electron transport materials for OLEDs. This study should be helpful in further theoretical investigations on such kind of systems and also to the experimental study for charge transport and/or luminescent materials for OLEDs.     

Impact resistant resins based on olefinic terpolymers containing a system of conjugated double bonds—V. Influence of reaction solvent on the physico-chemical properties of ungrafted SAN and some technological properties of ATS resins

Radical induced grafting of styrene (S) and acrylonitrile (AN) on to an unsaturated ethylene-propylene based terpolymer (EPTM) in mixed solvents has been investigated. Molecular weight, molecular weight distribution, conversion of ungrafted poly(styrene-co-acrylonitrile) (SAN) with 25 w% of AN and its degree of graft on to EPTM have been reported as functions of composition of the toluene/η-heptane mixture used as solvent. Mechanical properties of ATS resins are strongly dependent on the degree of graft of SAN resins and the molecular parameters of the ungrafted SAN; both are influenced by toluene content in the solvent mixture.     

Radiation resistant amorphous–all aromatic polyarylene ether sulfones: Synthesis,characterization, and mechanical properties

The synthesis and characterization of amorphous, aromatic, polyaryl ethers has been investigated. Detailed synthesis procedures are provided. The main thrust of these activities was to synthesize polymers which could serve as castable amorphous matrix resins for carbonfiber composites and which would be highly resistant to radiation degradation. It was important that these polymers not contain any aliphatic groups in order to contrast their behavior with the commercially available Bisphenol-A polysulfones. The approach taken was to synthesize a series of statistical or random copolymers derived from hydroquinone and biphenol together with 4,4′-dichlorodiphenyl sulfone. In order to produce copolymers of high molecular weight, modified techniques were developed which utilized potassium carbonate as a weak base and N-methyl-2-pyrrolidone as the aprotic dipolar solvent. Detailed procedures are provided in this paper for the synthesis of high molecular weight copolymers of this type. In addition, stress-strain, dynamic mechanical properties and preliminary electron beam (e-beam) degradation studies are reported significantly. Improved mechanical property retention after e-beam exposure was observed with the all aromatic polyether sulfones.     

Linear and branched polyester resins based on dimethyl-2,5-furandicarboxylate for coating applications

In this study, novel bio-based hydroxyl-end-capped (co)polyesters from dimethyl-2,5-furandicarboxylate (DMF), 2,3-butanediol, and a variety of comonomers viz. glycerol, pentaerythritol or trimethylolpropane are prepared using a solvent-free, bulk polycondensation technique. Extensive molecular and thermal characterization was performed to elucidate the properties of these materials. The materials showed suitable properties for solvent-borne coating applications in terms of their molecular weight, functionality and thermal characteristics, and coatings were prepared using the isocyanurate of hexamethylene diisocyanate as a cross-linker. The resulting coatings, having thicknesses between 30 and 55 μm, were hard but rather brittle. All the coatings have good solvent resistance, pointing to sufficient network formation. It is clear that the presented DMF-based polyesters show promise as bio-based coating resins.     

Synthesis and characterization of novel polythiourethane hardeners for epoxy resins

A novel thiol-terminated polythiourethanes were synthesized from low-molecular-weight di- and multifunctional mercaptans and diisocyanates and employed as curing agent of epoxy resin. The curing reaction of epoxy resin and thermal properties of cured products were investigated with differential scanning calorimetry. Evaluation of climatic ageing resistance was made by the change in mechanical properties. Mechanical studies indicated that the application of polythiourethane has toughening effect and significantly increases ageing resistance of the cured resins. The results of this study indicate that molecular structure and functionality of polythiourethane oligomers are of critical importance in governing the curing mechanism, structure of the network and final properties of epoxy compositions.