NMR SPECTROSCOPIC STUDY ON COPOLYMER OF ETHYLENE-NORBORNENE

A series of ethylene-norbornene copolymers were synthesized using VO (Oft) Cl-2/Al2Et3Cl3 catalytic system and their structure was characterized by H-1-NMR, H-1-H-1 COSY NMR and C-13-NMR. Assignments of NMR spectra were given and discussed in detail.

Synthesis of Polynorbornene-Poly(ethylene-co-propylene)Diblock Copolymer

Transformation of living ring-opening metathesis polymerization into coordination polymerization by converting the titanacyclobutane group attached to a polynorbornene chain into titanocene alkoxide has been used for the synthesis of polynorbornene-poly(ethylene-co-propylene) block copolymer. Preliminary characterizations of the copolymerization products by solvent extraction and C-13 NMR spectrum are reported.

Selective swelling of polysulfone/poly(ethylene glycol) block copolymer towards fouling-resistant ultrafiltration membranes

Fouling resistance of ultrafiltration(UF) membranes is critical for their long-term usages in terms of stable performance, so convenient approaches to prepare fouling-resistant membranes are always anticipated. Herein, we demonstrate the facile fabrication of antifouling polysulfone-block-poly(ethylene glycol)(PSF-b-PEG, SFEG)composite membranes. SFEG layer was coated onto macroporous supports and cavitated by immerging them in acetone/n-propanol following the mechanism of selective swelling induced pore generation. Thus-produced SFEG membranes possessed high permeance and excellent mechanical strength. Meanwhile, the structures and separation performances of the SFEG layers can be continuously tuned through simply changing swelling durations. More importantly, the hydrophilic PEG chains were spontaneously enriched onto the pore walls through swelling treatment, endowing intrinsic antifouling property to the SFEG membranes. Bovine serum albumin(BSA)/humic acid(HA) fouling tests proved the prominent fouling resistance of SFEG membranes, and the fouling resistance is expected to be long-standing because of the firm connection between PEG chains and PSF matrix by covalent bonding.

Copolymerization of Ethylene with Dicyclopentadiene Using a Constrained Geometry Cyclopentadienyl-phenoxytitanium Catalyst

The copolymerization of ethylene with dieyclopentadiene （DCP） in the presence of a constrained geometry tetramethylcyclopentadi-enyl-phenoxytitanium catalyst [ 2,4-＇ Bu2-6-（ 2,3,4,5-Me4 -Cp ） -PhO ] TICl2, combined with AI（ iBu）3/Ph3C^＋ B（ CsF5 ）4^- cocatalyst system was studied. The copolymers that were formed were characterized by ＇ H and ,3 C NMR, differential scanning calorimetry （ DSC）, SEM, and X-ray diffraction （XRD） analyses. The re- suits of the analysis indicate that the copolymers of ethylene with dicyclopentadiene are amorphous and display two or more melting temperatures in their DSC diagrams. Moreover, the morphologies of the copolymers are quite different from that of polyethylenes.

Poly(L-lactide)-Poly(ethylene glycol) Multiblock Copolymers: Synthesis and Properties

Poly (L-lactide)-poly(ethylene glycol) multiblock copolymers with predetermined block lengths were synthesized by polycondensation of PLA diols and PEG diacids. These copolymers presented special properties, such as better miscibility between the two components, low crystallinity and better hydrophilicity, which can be modulated by adjusting the block lengths of the two components.

PREPARATION OF HIGH DENSITY POLYETHYLENE/POLYETHYLENE-BLOCK-POLY(ETHYLENE GLYCOL)COPOLYMER BLEND POROUS MEMBRANES VIA THERMALLY INDUCED PHASE SEPARATION PROCESS AND THEIR PROPERTIES

High density polyethylene （HDPE）/polyethylene-block-poly（ethylene glycol） （PE-b-PEG） blend porous membranes were prepared via thermally induced phase separation （TIPS） process using diphenyl ether （DPE） as diluent. The phase diagrams of HDPE/PE-b-PEG/DPE systems were determined by optical microscopy and differential scanning calorimetry （DSC）. By varying the content of PE-b-PEG, the effects of PE-b-PEG copolymer on morphology and crystalline structure of membranes were studied by scanning electron microscopy （SEM） and wide angle X-ray diffraction （WAXD）. The chemical compositions of whole membranes and surface layers were characterized by elementary analysis, Fourier transform infrared spectroscopy-attenuated total reflection （FTIR-ATR） and X-ray photoelectron spectroscopy （XPS）. Water contact angle, static protein adsorption and water flux experiments were used to evaluate the hydrophilicity, antifouling and water permeation properties of the membranes. It was found that the addition of PE-b-PEG increased the pore size of the obtained blend membranes. In the investigated range of PE-b-PEG content, the PEG blocks could not aggregate into obviously separated domains in membrane matrix. More importantly, PE-b-PEG could not only be retained stably in the membrane matrix during membrane formation, but also enrich at the membrane surface layer. Such stability and surface enrichment of PE-b-PEG endowed the blend membranes with improved hydrophilicity, protein absorption resistance and water permeation properties, which would be substantially beneficial to HDPE membranes for water treatment application.

Y-shaped block copolymers of poly(ethylene glycol) and poly(N-isopropylacrylamide) synthesized by ATRP

Novel Y-shaped block copolymers of poly（ethylene glycol） and poly（N-isopropylacrylamide）, PEG-b-（PNIPAM）2, were successfully synthesized through atom transfer radical polymerization （ATRP）. A difunctional macroinitiator was prepared by esterification of 2,2-dichloroacetyl chloride with poly（ethylene glycol） monomethyl ether （PEG）. The copolymers were obtained via the ATRP ofN-isopropylacrylamide （NIPAM） at 30℃ with CuCl/Me6TREN as a catalyst system and DMF/H2O （v/v = 3：1） mixture as solvent. The resulting copolymers were characterized by gel permeation chromatography （GPC） and ^1H NMR. These block copolymers show controllable molecular weights and narrow molecular weight distributions （PDI 〈 1.15）. Their phase transition temperatures and the corresponding enthalpy changes in aqueous solution were measured by differential scanning calorimetry （DSC）. As a result, the phase transition temperature of PEG45-b-（PNIPAM55）2 is higher than that of PNIPAM, however, the corresponding enthalpy change is much lower, indicating the significant influence of the macromolecular composition and architecture on the phase transition.

SYNTHESIS AND CHARACTERIZATION OF AMPHIPHILIC GRAFT COPOLYMER CONTAINING MICROPHASE SEPARATED AND LONG POLY(ETHYLENE OXIDE) SIDE CHAIN STRUCTURES

Acryloyl terminated Poly (ethyleneoxide)macromonomers (PEO-A) with different PEO chain lengths have been prepared by deactivation of PEO alkoxide with acryloyl chloride. A new kind of amphiphilic polystyrene-g-poly (ethylene oxide)graft copolymer containing both microphase separated and PEO side chain structures has been synthesized from radical copolymerization of PEO-A macromonomer with styrene. After careful purification by a newly-developed method called 'selective dissolution', the well-defined structure of the purified copolymers was confirmed by IR, ~1H-NMR and GPC. Various experimental parameters controlling the copolymerization were studied in detail. The results indicated that the feed ratio of styrene to macromonomer(S/M) was the most important determining factor for the composition of the copolymers. A detailed 'comb- model' was proposed to describe the molecular structure of the graft copolymers. Finally, this amphiphilic graft copolymers may readily form microphase separated structures as clearly indicated by transmission electron microscopy.

THERMALLY STIMULATED SHAPE MEMORY BEHAVIOR OF(ETHYLENE OXIDE-BUTYLENE TEREPHTHALATE)SEGMENTED COPOLYMER

The thermally stimulated shape memory behavior of ethylene oxide-butylene terephthalate (EOBT) segmented copolymers with different soft segment molecular weight and hard segment content was investigated. The deformation recovery ratio R-f of the EOBT samples increases with the soft segment molecular weight and the hard segment weight content, while the average overall deformation recovery speed V-r increases with the hard segment content. The temperature of maximum deformation recovery speed (T-M) is determined by the melting temperature of the soft segment crystals and the stability of the crystallized hard segment domains.

Ethene／norbornene copolymerization by[Me2Si（3—^tertBuCp）（N^tertBu）]TiCl2／MAO—catalyst

?Ethene/norbornene copolymerization by the catalyst system [Me_2Si( 3- tertBuCp)(N tertBu)]TiCl_2/MAO was investigated in detail at 30 ℃, 60℃, and 90℃. A mass flow controller was used in this work to obtain kine tic data and investigate tempera ture's effects on activity, norbornene incorporation, copolymerization parameter , microstructure, glass transition temperature, and molar masses were described. H igh copolymerization values r_E and high alternation are determined. The n umber of isotactic alternating sequences is much higher than that of the syndiot actic alter nating sequences.

IMPACT PROPERTIES OF METALLOCENE - CATALYZED ETHYLENE-α-OLEFIN COPOLYMERS

The impact properties of two selected metallocene-catalyzed ethylene-butene copolymers and one conventionalcopolymer were evaluated using Izod impact test. It is found that the metallocene-catalyzed copolymer shows superior impactproperties. This result was explained on the basis of the more homogeneous inter-molecular composition distribution andnarrower molecular weight distribution, which leads to more homogeneous morphology with fewer defects. Stepwisecrystallization improves the impact properties, especially in the crack propagation process, to a large extent. This is due to thedecrease of entanglements by stepwise crystallization, which is advantageous for the chain slip and shear. The polymer withheterogeneous intra-molecular composition distribution exhibits a more evident improvement of impact properties understepwise crystallization.

SIMULTANEOUS SAXS/WAXS/DSC STUDIES ON MICROSTRUCTURE OF CONVENTIONAL AND METALLOCENE-BASED ETHYLENE-BUTENE COPOLYMERS

The fractions of one metallocene-based (mPE) and one conventional (znPE) ethylene-butene copolymer eluted at from temperature rising elution fractionation were selected for DSC and time-resolved small angle X-ray scattering (SAXS) and wide angle X-ray scattering (WAXS) characterization. The DSC and WAXS results show that two crystal structures exist in both mPE and znPE: structure A with higher melting temperature and structure B with lower melting temperature. It was found that original znPE (s-znPE) contains more highly ordered structure A than original mPE (s-mPE) in spite of the higher comonomer content of znPE. Another structure C is also identified because of higher crystallinity measured by WAXS than by DSC and is attributed to the interfacial region. The SAXS data were analyzed with correlation function and two maxima were observed in s-mPE and s-znPE, in agreement with the conclusion of two crystal populations drawn from DSC and WAXS results. These two crystal populations have close long periods in s-mPE, but very different long periods in s-znPE. In contrast, freshly crystallized mPE and znPE (f-mPE and f-znPE) contain only a single crystal population with a broader distribution of long period

Sound Absorption Properties of Discarded Feathers/Ethylene Vinyl Acetate Copolymer Thermoplastic Composite Materials

The discarded feathers / ethylene vinyl acetate copolymer( EVA) thermoplastic composite materials was obtained with discarded feathers as reinforced material and EVA powders as matrix material by hot pressing method. Sound absorption properties were studied by changing mass ratio of discarded feathers and EVA,thickness of composite materials,hot pressing pressure and hot pressing temperature. It was found that the sound absorption properties of composite materials were good when the mass ratio of discarded feathers and EVA was 1: 1,thickness of composite materials was 30 mm,hot pressing pressure was 8 MPa,and hot pressing temperature was 80 ℃. Under the optimum conditions,the effect of composite density on sound absorption property was analyzed. In a certain range,the sound absorption property was enhanced with the decrease of the composite density.When the composite density was 0. 1g /cm^3, the maximum absorption coefficient was 0.96. Finally,the capillary theory was used to calculate the maximum sound absorption coefficient of discarded feathers / EVA thermoplastic composite materials. The good agreements of experimental results and calculated results proved the validity of the theoretical models.

COMPOSITIONAL HETEROGENEITY OF ETHYLENE OXIDE-BUTYLENE TEREPHTHALATE SEGMENTED COPOLYMER

A series of ethylene oxide-butylene terephthalate (EOBT) segmented copolymers with different soft segment length and hard segment content were synthesized. The compositional heterogeneity was studied by solvent extraction. The results show that the compositional heterogeneity increases when soft segment length and hard segment content increase. The compositional heterogeneity is also reflected in the crystallization behavior and morphology of soft and hard segment in EOBT segmented copolymer. The more compositional heterogeneous the EOBT segmented copolymer is, the more different the morphology and the crystallization behavior between separated fractions. Compared with ethylene oxide-ethylene terephthalate (EOET) segmented copolymer, compositional heterogeneity in EOBT segmented copolymer is weaker. But the compositional heterogeneity in EOBT segmented copolymer with long soft segment and high hard segment content is still obvious.

ETHYLENE OXIDE-ETHYLENE TEREPHTHALATE SEGMENTED COPOLYMER SOLID ELECTROLYTE

A series of ethylene oxide-ethylene terephthalate segmented copolymers (EOET) weresynthesized and complexed with LiClO_4 to form some new polymer electrolytes. The EOET-LiClO_4 electrolytes exhibit not only high ionic conductivity, but also good mechanical strengthand toughness. The EOET 3400--25--LiClO_4 complex possesses the highest conductivity (4. 65×10^(-5)s·cm^(-1) at room temperature when the ratio [Li^+]/[EO] equals 1/16. The structures of these electrolytes were examined with FTIR analysis, X-ray diffractionand DSC thermograms, and the results of high ionic conductivity of the segmented copolymerswere discussed.

POLYCAPROLACTONE-POLY (ETHYLENE GLYCOL) BLOCK COPOLYMER Ⅲ DRUG RELEASE BEHAVIOR

The drug release behavior of degradable polymer--polycaprolactone-poly (ethyleneglycol)block copolymer(PCE) in vitro was investigated by using 5-Fluoro-uracil (5-Fu) asa model drug under a condition of pH 7. 4 at 37C. It is found that the release rate of 5-Fufrom PCE increased with increasing polyether content of the copolymer. The results showthat the increasing polyether content of the copolymer caused increasing hydrophilicity anddecreasing crystallinity of the PCE copolymer. Thus, the drug release behavior and thedegradable property of the PCE can be controlled by adjusting the composition of thecopolymer.

CHARACTERIZATION OF AMPHIPHILIC AND MICROPHASE SEPARATED GRAFT COPOLYMERS Ⅱ SURFACE CHARACTERIZATION AND IN VITRO BLOOD-COMPATIBILITY ASSESSMENT OF POLYSTYRENE-GRAFT-ω-STEARYLPOLY (ETHYLENE OXIDE)

This paper reported the research results concerning the surface characterization ofpolystyrene-graft-w-stearyl poly(ethylene oxide) (PS-g-SPEO) by means of XPS,contactangle measurement and TEM, and its in vitro blood compatibility assessment by measuringthe plasma recalcification time (RT) and partial thromboplastin time (PTT). The XPSresults demonstrated that the surface and bulk composition of the PS-g-SPEO graftcopolymers differ remarkably from each other,and that SPEO component was constantlyenriched at the copolymer/air interface. Contact angle studies indicated that the surfacewater wettability can be adjusted effectively by changing the composition of the copolymer.PS-g-SPEO graft copolymers can undergo microphase separation as clearly illustrated byTEM photographs. The relationship between the surface properties of PS-g-SPEO graftcopolymer and its blood compatibility was also discussed.

SYNTHESIS OF NOVEL BLOCK COPOLYMERS OF POLY(3-HYDROXYBUTYRIC ACID)WITH POLY(ETHYLENE GLYCOL)THROUGH ANIONIC POLYMERISATION

A novel kind of copolymer with ABA-type block structure was synthesized by anionic ring-opening polymerization of beta-butyrolactone (beta-BL) in the presence of a PEG-based dicarboxylates as macroinitiators which were prepared by the esterification of aliphatic cyclic anhydride and poly(ethylene glycol) (PEG) oligomers (M-n = 2000, 4000 and 6000) and conversion of potassium dicarboxylates. The resultant copolymers as well as the intermediates were characterized by IR, H-1-NMR and GPC.

Enzymatic Synthesis and Characterization of Novel Amphiphilic Triblock Copolymer Poly(p-dioxanone-co-5-benzyloxytrimethylene carbonate)-block-poly(ethylene glycol)

Novel amphiphilic triblock copolymer poly（p-dioxanone-co-5-benzyloxytrimethylene carbonate）-block-poly（ethylene glycol）-block-poly（p-dioxanone-co-5-benzyloxytrimethylene carbonate） （p（PDO-co-BTMC）-b-PEG-b-p（PDO-co-BTMC）） was successfully synthesized using immobilized porcine pancreas lipase on porous silica particles （IPPL） as the catalyst for the fLrSt time. 1H NMR, 13C NMR and GPC analysis were used to confirm the structures of resulting copolymers. The molecular weight （Mn） of the copolymer with feed ratio of 69：20：11 （BTMC： PDO： PEG ） was 31300 g/mol and the polydispersity was 1.85, while the Mn decreased to 25000 g/mol and polydispersity of 1.93 with the feed ratio of 50：40：10.

SYNTHESIS OF POLY(ETHYLENE TEREPHTHALATE)-POLYCAPROLACTONE BLOCK COPOLYMER BY DIRECT COPOLYMERIZATION

Po ly(ethylene terephthalate)-polycaprolactone block copolymer (PCL-b-PET) is a polyester with improved biodegradability. In the present paper, a new direct copolymerization method of epsilon-caprolactone (epsilon-CL) and bishydroxyethylene terephthalate (BHET) in the presence of Ti(OBu)(4) was proposed for the synthesis of PCL-b-PET. The PCL-b-PET copolymer was characterized by IR, GPC and H-1-NMR techniques, and the effects of synthesis conditions, such as temperature, reaction time and concentration of catalyst on the copolymerization were discussed.