Ring-opening Copolymerization of ε-Caprolactone and δ-Valerolactone Catalyzed by a 2,6-Bis(amino)phenol Zinc Complex

In combination with methyllithium,a 2,6-bis(amino)phenol zinc complex 1 was used in the ring-opening polymerization ofδ-valerolactone in the absence or presence of benzyl alcohol and showed high efficiency,mainly producing cyclic and linear polyvalerolactones,respectively.On the basis of homopolymerization,the ring-opening copolymerization ofε-caprolactone andδ-valerolactone was investigated.The P(CL-co-VL)random copolymers,PCL-b-PVL and PVL-b-PCL diblock copolymers,were prepared by varying the feeding strategy(premixing or sequential feeding).The copolymer composition was adjusted by varying the feeding ratio of two monomers.The structure and thermal properties of obtained polymers were characterized by GPC,1 H-NMR,13 C-NMR,MALDI-TOF mass spectroscopy,and DSC,respectively.     

PREPARATION OF LOW MOLECULAR WEIGHT POLY（GLYCIDYL METHACRYLATE） BY PHOTOPOLYMERIZATION

Low molecular weight poly（glycidyl methacrylate）s （PGMAs） were prepared by photopolymerization in ethyl acetate, with benzophenone （BP） as photoinitiator, and triethylamine （TEA） as hydrogen donor. The existence of semipinacol dormant end groups in PGMA was confirmed by FT-IR and ^1H-NMR, and the content of the semipinacol dormant groups was determined quantitatively by ^1H-NMR measurement. The effects of various thctors, such as reaction time, BP concentration and monomer concentration on the synthesis of the polymers were investigated systematically. The molecular weights of the polymers were also investigated with GPC. It is shown that increasing BP concentration and decreasing irradiation time and monomer concentration led to a significant decrease of the molecular weights.     

Cationic surfmers with benzyl groups: Synthesis and copolymerization with acrylamide

A series of cationic surfmers with benzyl groups（QARBCs）with different R groups on the benzene ring were synthesized and characterized by IR,¹H-NMR,¹³C-NMR.The aggregation of QARBCs was studied by the steady-state fluorescence technique.It turned out that QARBCs had surface activity and their critical micelle concentration（CMC）values varied in the range of 10^-2—10^-3mol/L with slight increase with temperature.The copolymerization of acrylamide（M₁）and QARBCs（M₂）was studied below and above CMC,their reactivity ratios were determined by the Finemann-Ross method.It was found that below CMC,copolymerization took place in a homogeneous system and reactivity ratios of acrylamide and QARBCs were less than 1;while above CMC,reactivity ratios of QARBCs were greater than 1.The copolymerization mechanism of QARBC was observed to be similar to that of micellar polymerization.QARBCs tended to homopolymerization,which gave rise to micro-blocky sequences in the polymer backbone.The Q and e values of QARBCs were calculated according to the Alfrey-Price equation by using r_1（AM）and r_2（qarBC）.Samples of poly（AM-co-QARBC） were prepared above and below CMC and their hydrophobic associations were studied by the steady-state fluorescence spectra and 2D NOESY spectra,and their critical associating concentrations（CAC）were estimated.The results showed that samples of poly（AM-co-QARBC）prepared above CMC had stronger hydrophobic association in aqueous solution than those prepared below CMC.     

Morphological studies on Sn-O coordination driving self-assembly of well-defined organotin-containing block copolymers

A tin-oxygen coordination driving self-assembly was developed in the block copolymers containing organotin, which were prepared by the radical addition-fraction transfer（RAFT） method and characterized by the gel-permeation chromatography（GPC） and 1H-NMR. And the self-assemblies of these block copolymers with various chain length ratios in the different concentrations in CHCl3 were stable according to the results of DLS and TEM. Additionally, it was also given an insight investigation on the regulation of self-assembly of the block copolymers by adding dibutyltin dichloride and a possible mechanism was proposed.     

以对-(4-烯丙氧基苯甲酰氧基)苯甲酸对-甲氧基苯酚酯为单体的液晶聚硅氧烷的合成与表征

A liquid crystalline polysiloxane has been prepared by a hydrosilation reaction of poly (methylhydrosiloxane) with (p-((4-allyloxy)benzoxy)benzoxy)-4-methoxyphenyl. The chemical structure of the monomer and polymer was confirmed by IR and 1H-NMR analysis, and as many as 13% α-addition isomeric side chains were found from the NMR spectrum of the polymer. In addition ,the phase behavior of the monomer and polymer were studied by optical polarized microscopy and DSC measurements.     

Ring-opening polymerization of L-lactide with rare earth aryloxides substituted by various alkyl groups

<正>Rare earth aryloxides substituted by various alkyl groups[Ln(OAr)_3]such as methyl,isopropyl and tertbutyl,were used as single component catalysts to affect ring-opening polymerization of L-lactide(LLA).The catalytic activity, polymerization characteristics,polymerization kinetics and the mechanism were studied.It was found that the catalytic activity of rare earth aryloxides is influenced by both the structure and the number of alkyl groups on the phenyl ring.The stronger the electron-donation ability of the alkyl group,the higher the catalytic activity will be.An increase in the number of the substitute group will result in a higher catalytic activity.Lanthanum tris(2,4,6-tri-tert-butylphenolate)[La(OTTBP)_3] exhibits the highest activity among all lanthanum aryloxides.According to the ~1H-NMR data,it was proposed that the LLA polymerization proceeded via a coordination-insertion mechanism involving cleavage of acyl-oxygen bond of the lactide.     

A novel photo-initiated approach for preparing aluminum diethylphosphinate under atmospheric pressure

A novel preparation of aluminum diethylphosphinate（AlPi） was carried out with free-radical addition reaction by means of UV-irradiation under atmospheric pressure.A solution of sodium hypophosphite was treated with ethylene and irradiated with ultraviolet light in the presence of an amount of photoinitiator effective to initiate the free-radical reaction between the hypophosphite anion and the double bond of the ethylene molecule.The ethylene was micro-bubbled into the reaction mixture with the addition of the photoinitiator,and the gas-liquid contact surface and the photoinitiator concentration in the gas-liquid interface were increased largely.The yield of the final product could be improved to about 96%.The contents of P,Al in samples were detected by ICP,and the molecular structure of the samples was confirmed by ³¹P NMR,¹H NMR and FTIR spectroscopic analysis.Thermal stability of the final products was investigated in detail by TG-DTA.     

Sonochemical Preparation of Micro- and Nanometer Cu2O

Cu2O particles with different morphologies and scales were prepared sonochemically on the solid-liquid interface of CuCl and water, by adjusting the reaction factors. The products were characterized by powder X-ray diffraction（XRD） and scanning electron microscopy（SEM）. The formation and morphology of Cu2O crystals were influenced by high-intensity ultrasound, reaction temperature, and addition of CuCl. The results indicate that micrometer Cu2O was crystallized in cubic and octahedral shapes, whereas, nanometer Cu2O was not produced in well-shaped crystals.     

Optical and mechanical properties of polyurethane/surface-modified nanocrystalline cellulose composites

in order to improve the optical and mechanical performances of waterborne polyurethane （WPU）, nanocrystalline cellulose （NCC）/WPU composites were synthesized in this study. NCC （prepared by acid hydrolysis of cotton fiber） was modified by （3-aminopropyl）triethoxysilane （APTES） to enhance its compatibility with WPU, and the surface-modified NCC was characterized by grafting ratio, crystallinity and contact angle （CA）. NCC/WPU composites were examined by scanning electron microscopy （SEM）, X-ray powder diffraction （XRD） and thermogravimetric analysis （TG）. The anti-yellowing property, specular gloss, pencil hardness, and abrasion resistance of NCC/WPU composites were investigated by the methods of Chinese National Standards GB/T 23999-2009, GB/T 9754-2007, GB/T 6739-2006 and GB/T 1768-2006, respectively. The results showed that the grafting ratio of NCC modified by 6% APTES was 36.01% and the crystallinity of modified NCC was decreased with the enhancement of APTES. CA of the modified NCC was decreased by 28.8% and the nanoparticles were homogeneously dispersed in the WPU matrix. The XRD patterns of the NCC/WPU composites were relatively steady, while the thermal stability of the composites was enhanced by 6.7% with 1.0 wt% modified NCC. Modified NCC affected the specular gloss of NCC/WPU composites more obviously than the anti-yellowing property. The pencil hardness of NCC/WPU composites was increased from 2H to 4H by addition of NCC and the abrasion resistance of the composites was enhanced significantly. In general, NCC/WPU composites showed significant improvements in the optical and mechanical performances.     

Studies on crystal transition of polyamide 11 nanocomposites by variable-temperature X-ray diffraction

Polyamide I1 （PAll） and its nanocomposites with different organoclay loadings were prepared by melt-compounding and subsequent pelletizing. The crystal phase transitions of PAl 1 and its clay nanocomposites were investigated by variable-temperature X-ray diffraction. It was found that the Brill transition of the nanocomposite was 20 K higher than that of the neat PAl 1 for both heating and cooling processes. The PAl 1 d-spacings of the nanocomposites were observed to be smaller than those of the neat PAl 1 for melt crystallization. The constraints imposed by the addition of layered clay, restricting the thermal expansion of the polymer chains, are probably responsible for such a reduction of the d-spacing.     

SYNTHESIS AND POLYMERIZATION OF α-METHACRYLYOXYLETHYLOXYCARBONYLMETHYL-ω-(N,N-DIETHYLDITHIOCARBAMYL)POLYSTYRENE MACROMONOMERS

Polystyrene macromonomers with different molecular weight were prepared by radical polymerization of styrene(St) in benzene using β-methacryloxylethyl 2-N,N-diethyldithiocarbamylacetate (MAEDCA) as a monomer-iniferter.Characterization of the macromonomer by ~1H-NMR showed that the end groups were α-methacrylyoxylethyloxycarbonyl-methyl and ω-(N,N-diethyldithiocarbamyl). The macromonomer was difficult to homopolymerize, but it was easilycopolymerized with methyl methacrylate (MMA) initiated by AIBN to form graft copolymers (PMMA-g-PSt) with PStbranches randomly distributed along the PMMA backbone. Copolymerization reaction and the structure of the graftcopolymers were strongly affected by M_n and concentration of the macromonomer. The composition and M_n of the purified graft copolymer were determined by ~1H-NMR and GPC analysis.     

Ring-opening polymerizaion of 2,2-dimethyltrimethylene carbonate initiated by <Emphasis Type="Italic">in situ</Emphasis> generated,tetrahydrosalen stablized yttrium borohydride complex and random copolymerization with <Emphasis Type="Italic">ɛ</Emphasis>-caprolactone

The poly（2,2-dimethyltrimethylene carbonate）（PDTC）with one hydroxyl and one formate terminal functions was synthesized by in situ generated,tetrahydrosalen stabilized yttrium borohydride complex.The influences of monomer/initiator molar ratio,temperature and reaction time on polymerization of DTC were investigated.Under the condition:[DTC]/[I]=500,55℃,toluene:0.5 mL,DTC:0.6 g,PDTC with M_n=15600 and PDI=2.15 was obtained. Through ¹H-NMR and ¹³C-NMR analyses,the structure of PDTC was characterized and a coordination-insertion mechanism was proposed.In addition,the random copolymerization of DTC and caprolactone（CL）initiated by rare-earth borohydride compound was studied.The microstructure of PDTC-co-PCL includes four diads:DTC-CL,CL-CL,DTC-DTC and CL-DTC, which were determined by the specific signals in ¹H-NMR spectra.Based on the typical signals of the formate（δ= 8.08）and hydroxyl（δ=3.34）end groups of PDTC-co-PCL,a mechanism involving DTC monomer inserts before CL during the initiation process was presumed.Furthermore,the thermal properties of amorphous copolymer were characterized by differential scanning calorimetry（DSC）.The results support the random structure of PDTC-co-PCL.     

Copolymerization of ethylene and 1-hexene with TiCl4/MgCl2 catalysts modified by 2,6-diisopropylphenol

A supported TiCl4/MgCl2 catalyst without internal electron donor (O-cat) was prepared firstly. Then it was modified by 2,6-diisopropylphenol to make a novel modified catalyst (M-cat). These two catalysts were used to catalyze ethylene/1-hexene copolymerization and 1-hexene homopolymerization. The influence of cocatalyst and hydrogen on the catalytic behavior of these two catalysts was investigated. In ethylene/1-hexene copolymerization, the introduction of 2,6-iPr2C6H3O-groups did not deactivate the supported TiCl4/MgCl2 catalyst. Although the 1-hexene incorporation in ethylene/1-hexene copolymer prepared by M-cat was lower than that prepared by O-cat, the composition distribution of the former was narrower than that of the latter. Methylaluminoxane (MAO) was a more effective activator for M-cat than triisobutyl-aluminium (TIBA). MAO led to higher yield and more uniform chain structure. In 1-hexene homopolymerization, the presence of 2,6-iPr2C6H3O-groups lowered the propagation rate constants. Two types of active centers with a chemically bonded 2,6-iPr2C6H3O-group were proposed to explain the observed phenomena in M-cat.     

KINETICS STUDY ON MELT GRAFTING ACRYLIC ACID ONTO LLDPE USING REACTIVE EXTRUSION

The kinetics of melt grafting acrylic acid(AA)onto linear low density polyethylene(LLDPE)by using reactive extrusion was investigated.The polymeric peroxides(POOP and POOH)generated by electron beam irradiation were used to initiate the graft reaction.The samples taken out from the barrel at five ports along screw axis were analyzed by FTIR.The spectra show that both the graft copolymerization and homopolymerization proceed in two stages:the graft degree(or mass of homopolymer)increases linearly with the reaction time in the initial stage,and then gradually in the second stage.The rate of graft copolymerization R_g is always faster than that of homopolymerization R_h in the present system and the activation energy is 131 kJ·mol~(-1) for graft copolymerization and 127 kJ·mol~(-1) for homopolymeirzation.These results were interpreted in terms of solubility and diffusion of monomer,as well as the reactivity and the concentration of reactive species. The relationships between reaction rate and monomer concentration and peroxide concentration were found to he:R_g ∝ [M]~(1.46)[POOP+POOH]~(0.53) and R_h ∝[M]~(1.08)[POOH]~(0.51),which indicate that the addition of monomer to polymeric radicals is a slow step for the graft copolymerization.     

NOVEL HYPERBRANCHED POLY（PHENYLENE OXIDE）S WITH PHENOLIC TERMINAL GROUPS： EFFECTS OF REACTION TIME AND CORE MOLECULES ON THE MOLECULAR WEIGHT AND POLYDISPERSITY

A novel hyperbranched poly（phenylene oxide） （HPPO） with phenolic terminal groups was prepared from 4-bromo-4＇,4＂-dihydroxytriphenylmethane as AB2 monomer in dimethylsulfoxide （DMSO） via a modified Ullmann reaction. The molecular weight and polydispersity （PD） of the resulting polymers increased with increasing reaction time. In the presence of core molecules （bisphenol A and 1,3,5-trihydroxybenzene）, which have the similar molecular backbones to the reactive monomer, the molecular weight could be controlled by varying the core-to-monomer ratio. Incorporation of a very small amount of core molecules could lead to a higher molecular weight as compared with that without the addition of core molecules. However, when the core content reached certain extent, the molecular weight would decrease with the further increase in the core content. A new similar behavior of control over the PD was also obtained. The resulting polymers were characterized by ^1H-NMR, ^13C-NMR, FT-IR, and GPC.     

Preparation and Enantioseparation Property of Chiral Stationary Phases Based on Cellulose Tris(3,5-dimethylbenzoate)——A New Way to Prepare Polysaccharide-coating Type Chiral Stationary Phases

A new method to prepare polysaccharide-coating type chiral stationary phases （CSPs） was developed in this work. As a typical example, naked silica gel was coated by cellulose, which was then derivatized with 3,5-dimethylbenzoyl chloride to afford cellulose tris（3,5-dimethylbenzoate）-silica gel （CTDBS） complex. The silanols on CTDBS were end-capped with 3- aminopropyltriethoxysilane to obtain CSP 1. The amino groups on CSP 1 were further end-capped with 3,5-dimethylbenzoyl chloride to give CSP 2. The silanols on CTDBS were end-capped with methyltrimethoxysilane to yield CSP 3. CSPs 1-3 were characterized by FTIR, solid-state 13C-NMR and elemental analysis. The enantioseparation abilities of CSPs 1-3 were evaluated with structurally various chiral analytes. The enantioseparation results demonstrated that the end-capping moieties on CSPs 1 and 2 significantly affected enantioseparation. In addition, the effect of the structures of chiral analytes and end- capping moieties on the retention factors and the resolutions was discussed.     

Synthesis,insecticidal activity and molecular docking study of clothianidin analogues with hydrazide group

A series of novel neonicotinoid analogues were designed and synthesized by introducing a hydrazide group into clothianidin. Their structures were confirmed by IR, 1H NMR, and HRMS （ESI）. Preliminary bioassay showed that some compounds, Sb and Sg, exhibited good activity against soybean aphids （Aphis glycines） at 100 mg L ^-1. In addition, molecular docking with receptor was carried out to explain their different activity from clothianidin.     

Effect of Monomer Feeding Mode on thePreparation of Hollow Latexes with High MAA Content in the Core Latex Preparation简

In order to prepare hollow latex particles with optimum morphology based on osmotic swelling principle, three- layer core/shell latex particles with 40 wt% MAA in the core were first prepared via multistep seeded emulsion copolymerization, in which monomers were added by a semi-continuous process with monomer addition under two different forms： pure monomers＇ mixture （monomer addition）, and pre-emulsified monomers （pre-emulsion addition）. Then, the hollow latex particles with different morphologies were obtained after alkali post-treatment. Influences of the monomer feeding mode on the emulsion polymerization and the particle morphology were investigated. Results showed that the pre- emulsion addition could significantly improve the polymerization stability in each step, and greatly enhance the uniformity of shell encapsulation. The sizes of the core and core/shell latex particles obtained by the pre-emulsion addition were smaller and more uniform than those synthesized by the monomer addition, and the hollow latex particles with intact morphology were generated by alkali post-treating of the core/shell latexes prepared from the pre-emulsion addition. As the core size increased, the morphology of the post-treated particles underwent evolution from hollow to collapse. Moreover, the mechanism of the particle morphological evolution was proposed.     

Interaction of Ethylene-N,N＇-dianthranilate to Ni（Ⅱ）： Binding Properties and Coordination Mode Studies

The binding properties of ethylene-N,N＇-dianthranilate （EDA） and Ni（II） were studied by difference UV-Vis in 0.05 M Tris-HCl buffer （pH 7.4）. The stoichiometric ratio of EDA to nickel （1：1） was confirmed and the conditional binding constant （IogKNi-EDA = 12.33 ± 0.06） was obtained. In addition, an interesting tetranuclear complex [Nin（EDA）4]·2CH3CH2OH-9H2O was obtained unexpectedly in alcohol-water solution and characterized by X-ray crystallography and electrospray ionization mass spectra （ESI-MS）. It is found that EDA acts as a pentadentate ligand and performs a chelating-bridging coordination mode.     

ELECTROCHEMICAL COPOLYMERIZATION OF 3-（4-FLUOROPHENYL）THIOPHENE AND 3-METHYLTHIOPHENE IN BORON TRIFLUORIDE DIETHYL ETHERATE

The copolymer poly（3-（4-fluorophenyl）thiophene-co-3-methylthiophene） was successfully prepared from mixtures of 3-（4-fluorophenyl）thiophene （FPT） and 3-methylthiophene （MET） via electrochemical oxidation in boron trifluoride diethyl etherate （BFEE） and its mixed electrolytes with acetonitrile （ACN）. The influence of monomer concentration ratios on the copolymerization was investigated by using linear sweep voltammetry and cyclic voltammetry. The structure and morphology of these copolymer films were elucidated by UV-Vis, infrared spectroscopy, elemental analysis, thermal analysis and scanning electron microscopy （SEM）, respectively. The results showed that the molar ratio of FPT and MeT units, when copolymer was electrodeposited from feed ratio of FPT：MeT = 1：2, was about 1.08：1. In addition, the introduction of ACN into BFEE has little effect on the properties of as-formed copolymers.