CLAY CATALYZED SYNTHESIS OF BIO-DEGRADABLE POLY(GLYCOLIC ACID)

Glycolic acid was polymerized under vacuum in the presence and absence of nano sized clay.The added clay catalyzed the condensation polymerization which can be confirmed by recording FTIR spectroscopy and intrinsic viscosity (Ⅳ)values.The relative intensity of C=O/CH is increased while increasing the amount of clay.DSC showed the appearance of multiple endotherms of poly(glycolic acid).TGA showed the percentage weight residue remain above 750℃for polymer-nano composite system was 21% and hence proved the fl...

SURFACE MODIFICATION OF BLEND FILMS COMPOSED OF SILK FIBROIN AND POLY(ETHYLENE GLYCOL) MACROMER AND THEIR IN VITRO ANTITHROMBOGENICITY

In order to improve the blood compatibility of silk fibroin (SF), poly(ethylene glycol) macromer (PEGM) in different amounts was added to the SF film to incorporate C=C group into the surface of blend films which were then modified by SO2 gas plasma treatment. ATR-FITR and XPS were used to analyze the chemical change which had occurred on the film's surface. When the content of sulfur on the surface of blend films surpasses 1.59%, the antithrombogenicity of plasma treated films increases remarkably due to surface sulfonation. This result implies that SF with blend of PEGM after SO2 plasma treatment have potential use for making blood-contacting biomaterials.

THE STRUCTURE AND PROPERTIES OF CHITOSAN/POLYETHYLENE GLYCOL/SILICA TERNARY HYBRID ORGANIC-INORGANIC FILMS

The ternary hybrid films consisting of chitosan(CS),polyethylene glycol(PEG)and nano-sized silica which was surface-modified by amino groups(RNSA)were prepared.The structures of the blend membranes were characterized by attenuation total reflection-infrared spectroscopy(ATR-IR),X-ray diffraction(XRD),optical microscopy(OM)and differential scanning calorimetry(DSC).The results showed that the addition of silica affected not only the distribution and crystallinity of PEG on the sample surface,but also the pha...

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.

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.

Effect of Chitosan Coating on the Properties of Poly(glycolic acid-lactic acid)Thread-Embedding Material

Poly( glycolic acid-lactic acid)( PGLA) threadembedding material was modified by chitosan coating which could improve the rigidity,hydrophilicity and moisture absorption of the material,and produced better stimulation effect. Thus,this kind of thread-embedding materials which can be buried into acupuncture points to produce a long-time stimulation is popular in the acupuncture and moxibustion therapies. The variation tendencies of diameter,weight, hydrophilicity, and flexibility of the samples under the change of chitosan coating concentration,coating time and coating times were studied respectively. The results showed that the hydrophilicity,weight,and rigidity after coating rose in a certain range with the increase of coating time,coating times and coating concentration. The coating time had little influence on the diameter of fiber.

Mechanism of shales stabilization by hydrophobized poly(ethylene glycol)/K^(+) in water-base drilling fluids

The mechanism of the hydrophobized poly(ethylene glycol)(PEG)/K^(+) system inhibiting shale hydration was studied by laboratory experiment. The inhibition performance was evaluated through cuttings hot-rolling dispersion, bentonite inhibition and contact angle tests. The inhibition became stronger as contact angle and PEG concentration increased. A modified cuttings hot-rolling dispersion experiment suggested that these molecular systems did not act through the thermally activated mud emulsion(TAME) mechanism. The interaction of the PEG/K^(+) with clay samples was investigated through adsorption studies and by Fourier transform infrared spectroscopy(FT-IR), X-ray diffraction(XRD) and thermogravimetric analysis(TGA). The adsorption isotherms showed that the presence of K^(+) increased the PEG affinity for the clay surface. This inhibition effect was accompanied by a reduction of the bentonite hydration with PEG adsorption, evidenced by FT-IR, TGA and differential thermogravimetric(DTG) curves. XRD patterns were conclusive in showing that the presence of K^(+) ions limited the expansion of the clay interlamellar region to only one PEG layer, and the terminal hydrophobic segments of the PEG chains turned out to be determinant in enhancement of the inhibitory efficiency. The cuttings hot-rolling dispersion was carried out on water-base drilling fluid with PEG/K^(+), which proved the inhibition performance of PEG/K^(+) in oil field drilling.

Synthesis and Hydrophilic Performance of Poly(Lactic Acid)-Poly(Ethylene Glycol) Block Copolymers

Lactide was synthesized using lactic acid and stannous octoate as raw material and catalyst, respectively. Poly(lactic acid)-poly(ethylene glycol) (PLA-PEG) was prepared by lactide and poly (ethylene glycol) (PEG) via ring-opening polymerization. The most appropriate technological conditions of synthesis of lactide were researched in the paper. The copolymers were measured by Infrared spectroscopy (IR) and 1H nuclear magnetic resonance (1H NMR). The results proved that the lactide and PLA-PEG were synthesized successfully. Hydrophilic performance of the copolymer was measured by a water contact angle tester after prepared into a flat membrane. The water contact angle changed from 81.5? to 71.6?, which proved that the hydrophily of PLA-PEG was better than PLA.

Flotation of carbonaceous copper shale-quartz mixture with poly(ethylene glycol) alkyl ethers

The influence of different poly（ethylene glycol） alkyl ethers（CnH2n＋1O（C2H4O）mH, CnEm） on flotation of carbonaceous copper shale mixed with quartz as a gangue mineral was investigated. The results show that all of the ethers C4E1, C4E2, C4E3, C2E2, C6E2 investigated can be used for the flotation of carbonaceous copper shale. The best selectivity of separation in the flotation of the carbonaceous copper shale and quartz mixture is obtained with the C4E2 and C2E2 ethers. The obtained data can be used for developing separation of organic carbon present in carbonaceous shale at a rougher flotation stage on an industrial scale.

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.

Stereoselective Synthesis of Polysubstituted Cyclopropanes from Poly(ethylene glycol) Supported Pyridinium Ylide

Polysubstituted cyclopropanes were efficiently prepared with poly（ethylene glycol）（PEG） as soluble support. The reaction of PEG-supported pyridinium ylide with arylidenemalononitrile（R=CN） or ethyl arylidenecyanoa-cetate（R=COOEt） in the presence of triethylamine（TEA） afforded PEG-supported cyclopropanecarboxylates, which were cleaved by 1% KCN/EtOH to obtain polysubstituted cyclopropanes with exclusive trans-selectivity and good yields.

AN APPROACH TO SYNTHESIZE POLY(ETHYLENE GLYCOL)-b-POLY(ε-CAPROLACTONE) WITH TERMINAL AMINO GROUP via SCHIFF'S BASE AS AN INITIATOR

A new method to synthesize a degradable terminal amino group-containing copolymer,poly(ethylene glycol)-b- poly(ε-caprolactone)(MPEG-PCL-NH_2),was developed in the following three steps:(1)the ring-opening polymerization (ROP)ofε-caprolactone from the Schiff base prepared from benzatdehyde and ethanolamine(Ph-CH=NCH_2CH_2OH)used as an initiator to obtain heterobifunctional poly(ε-caprolactone)with one terminal Schiff base group and one hydroxyl group (HO-PCL-CH_2CH_2N=CH-Ph);(2)the coupling reaction of two ...

Exfoliation of poly(ethylene glycol)-intercalated graphite oxide composite in water without sonication

A novel method for exfoliating graphite oxide(GrO)was implemented through the mass water absorption of a GrO–poly(ethylene glycol)(GrO–PEG)composite.The GrO–PEG composite was prepared by intercalating PEG into the lamellae of GrO,and the variation of the basal spacing was measured by X-ray diffraction analysis.The yield of graphene was measured with an ultraviolet–visible spectrophotometer,and the properties of graphene oxide(GO)were characterized by atomic force microscopy,transmission electron microscopy(TEM),Raman spectrometry,and Fourier transform infrared spectroscopy.Increasing intercalation time was found to improve the yield of GO,whereas increasing the PEG molecular weight had the opposite effect.The GO sheets produced from the intercalation–absorption–exfoliation process were found to be a four-layer structure.TEM and Raman analyses indicate that the graphitized structure and oxygen groups of GO were preserved during the exfoliation process.Most importantly,the results show that good-quality GO could be prepared via a mild method involving water absorption of a GrO–PEG composite.

PROPERTIES OF SILK FIBROIN/POLY(ETHYLENE GLYCOL)400 BLEND FILMS

The blend film of silk fibroin (SF) and poly(ethylene glycol)400 (PEG400) with a blend ratio of 2/1 (wt/wt) wasprepared simply by dropping a little PEG400 into the SF solution and then casting the mixed aqueous solution at 50℃. Theresulting film exhibited much better mechanical properties in the dry and wet state than SF itself, owing to theconformational change of SF in the blends from the random coil to the β-sheet structure and intermolecular hydrogen bondformation between SF and PEG400. Thermogravimetric analysis showed that the initial thermal decomposition temperatureof the blend film was 170℃, which was 80℃ lower than that of SF (250℃) and 20℃ higher than that of PEG400 (150℃),and indicated a Strong interaction between two components of the blend. No crystalline peaks were observed in the X-raydiffraction curve of the blend film. Cell culture test showed that SF/PEG400 was a suitable substrate for the growth of humanumbilical vein endothelial cells (HUVEC).

POLYMERIZATION OF ETHYLENE METHYL PHOSPHATE IN THE PRESENCE OF SODIUM POLY(ETHYLENE GLYCOL)ATE

Poly(ethylene methyl phosphate)-poly(ethylene glycol)-poly(ethylene methyl phosphate) triblock copolymers carrying hydroxyl group at both chain ends were synthesized with sodium poly(ethylene glycol)ate as initiator. The effects of the factors such as solvent, amount of the initiator and reaction time were investigated. The copolymers were characterized by IR, H-1-NMR, H-1{P-31}-NMR, C-13-NMR, P-31{H-1}-NMR, and DSC. High molecular weight of the copolymer and high yield of the polymerization were achieved within 3 min at 25 degrees C. The polymerization process was studied by P-31{H-1}-NMR and transesterification was found during longer polymerization time.

High-gravity technology intensified Knoevenagel condensation-Michael addition polymerization of poly (ethylene glycol)-poly (n-butyl cyanoacrylate) for blood-brain barrier delivery

Poly(ethylene glycol)-poly(n-butyl cyanoacrylate)(PEG-PBCA)is a remarkable drug delivery carrier for permeating blood-brain barrier.In this work,a novel high-gravity procedure was reported to intensify Knoevenagel condensation-Michael addition polymerization of PEG-PBCA.A series of PEG-PBCA containing different block ratios were synthesized with narrow molecular weight distribution of polydispersity indexes less than 1.1.Furthermore,the reaction time reduced 60%compared to conventional stirred tank reactor process.Chemical structures of as-prepared polymers were characterized.In vitro drug delivery performance was evaluated.The cytotoxicity of PEG-PBCA to brain microvessel endothelial cells(BMVEC)decreases with the extension of the PEG chain and the shortening of the PBCA chain.The polymer cellular uptake to BMVECs was better after improving hydrophilicity by PEG block.Results of bloodbrain barrier permeability demonstrated that medium length of PBCA chain and short PEG chain are favorable for hydrophobic Nile red permeation,while long PEG chain and short PBCA chain are beneficial to delivery water-soluble doxorubicin hydrochloride(Dox).The average apparent permeability coeffi-cient increased 1.7 and 0.25 times than that of raw Nile red and Dox,respectively.High-gravity intensi-fied condensation polymerization should have great potential in brain drug delivery system.

Manipulating Zn^(2+)solvation environment in poly(propylene glycol)-based aqueous Li^(+)/Zn^(2+)electrolytes for high-voltage hybrid ion batteries

Compared with aqueous single-ion batteries,rechargeable aqueous hybrid ion batteries,especially Li^(+)/Zn^(2+)hybrid ion batteries,are receiving extensive interest owing to their low cost,high operating voltage,and energy density.However,their working voltage and lifespan are limited by the decomposition of water and the growth of Zn dendrites.Herein,detrimental side reactions induced by the water reduction and the Zn dendrite growth are successfully suppressed by a poly(propylene glycol)(PPG)-based hybrid ion electrolyte[(1 m Zn(TFSI)2+10 m LiTFSI)in PPG/H2O].The addition of PPG in the electrolyte can not only enhance the bonding strength of hydrogen-bond in water but also tailor the solvation sheath of Zn2+as revealed by synchrotron X-rays.The participated solvation of PPG with Zn^(2+)can weaken Zn-H_(2)O interactions and redistribute Zn^(2+)flux on the surface of the Zn anode,thus inducing favorably even deposition of Zn.In addition,the decomposition of TFSI-contributes a ZnF_(2)-enriched solid electrolyte interface at the Zn anode to further prevent water decomposition and restrain Zn dendrites.The PPG-based electrolyte enables 2.1 V LiMnO_(2)//Zn batteries to deliver high specific capacities(121.7 mAh g^(-1)for a coin cell and 90 mAh g^(-1)for a pouch cell),and maintain 80%of the capacity over 700 cycles at 0.5 C,suggesting a promising pathway for highly reversible aqueous hybrid ion batteries.

KINETICS OF NON-ISOTHERMAL CRYSTALLIZATION OF POLY (ETHYLENE TEREPHTHALATE) MODIFIED BY POLY (ETHYLENE GLYCOL)

The non-isothermal crystallization kinetics of poly(ethylene terephthalate) (PET) modified by poly (ethlene glycol) (PEG) were determined by DSC. The dual linear regression method was used to evaluate the relationship between the reciprocal of t 1/2 ( the half life of crystallization) and the appropriate temperature variable. The parameters such as the activation energy (Ed) for transport, the equilibrium melting temperature (T_m^0),the nucleation parameter (ψ),themaximum crystallization temperature (T_(e, max)), and the kinetic crystallizability (G) for the copolyesters were obtained. The influence of the PEG content in PET chains on the parameters characterizing crystallization kinetics and crystallization thermodynamics was discussed.

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 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.