合成革生产废水具有成分复杂、COD高、色度高、有毒性、难降解的特点.根据废水来源和水质特点,对废水进行分质预处理,碱减量废水、DMF废水首先单独进行预处理,再与染色废水和生活污水混合,统一进入后续处理系统.主工艺采用"絮凝沉淀+A2O+生物接触氧化+终沉淀"的处理工艺.系统出水水质达到《纺织染整工业水污染物排放标准》(GB 4287—2012)表2中的间接排放标准,并满足所在工业园区污水处理厂的排水纳管要求.本系统工艺设计合理,处理效果好,抗冲击负荷能力强,工程自投运以来,出水水质及系统运行长期稳定,对同类废水项目具有较好的借鉴意义.

The rare earth (RE) salts Eu(AA)3 (AA: acrylic acid group) and the macromonomers of polyurethane acrylate (MPUA) containing vinyl groups at the end of the chain are prepared for achieving a novel transparent Eu(AA)3-polyurethane acrylate (Eu-PUA) materials by copolymerization. The structure and properties of the Eu(AA)3 and the Eu-PUA have been systematically characterized by infrared spectroscopy (FTIR), proton and carbon nuclear magnetic resonance (1H-NMR, 13C-NMR), thermogravimetric analysis (TGA), dynamic mechanical analysis (DMA), and fluorescence spectrophotometer. It is proved that the Eu(AA)3 have been successfully bonded onto the molecular chains of the polyurethane acrylate and the glass transition temperature (Tg) of the polyurethane acrylate increases at the presence of Eu(AA)3. In addition, the Eu-PUA materials show favorable thermal stability and transparence. Typically, the fluorescence spectra show that the strongest fluorescence emission peak of the Eu-PUA material appears at 614 nm at the excitation wavelength of 395 nm. This demonstrates that such material can be applied to functional optical materials in the future. (C) 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012

P(n-butyl acrylate-co-styrene)/poly(vinyl chloride)[P(nBA-co-St)/PVC]composite resins were prepared via seeded emulsion copolymerization of vinyl chloride(VC) using n-butyl acrylate(nBA) and styrene copolymer latex as seeds.Diameters and morphology of latex particles were characterized by laser particle size analyzer,SEM and TEM.The results demonstrate that the PVC chains successfully covered onto the P(nBA-co-St) seeds.A phenomenon of retardation polymerization appeared in VC graft copolymerizing the P(nBA-co-St) was reasonably explained.Pure PnBA core greatly influenced Tg of the composite resin in the low-temperature transition region.This result should stem from the different degrees of PnBA-or PSt-grafted PVC to cause the difference of the graft copolymer content in the resin.The fractured surface for the P(nBA-co-St)/PVC sample with 75/25 mass ratio of nBA to St units showed a "root or beard" morphology.SEM analysis confirms that toughening mechanism in the materials derives from the shear yielding of the PVC matrix.

Micron sizes BaSO4 modified by aluminate coupling agent was used as fillers.PP/BaSO4 composite materials were prepared through melt blending.Mechanical properties,morphology of fractured surfaces,processing rheology and crystalline behaviors of the composite materials were studied.The results show that there is improved interfacial-adhesion between the modified BaSO4 and the PP matrix.The interfacial debonding occurs under an action of certain external force.Consequently,some caves form.This ensures the inorganic particles to transfer and relieve the stress formed in the materials,and makes plastic deformation of the matrix to occur after the particles' debonding.Consequently,the forming crazes at the initial stage of the deformation don't expand.The rigidity and toughness of the composite materials are improved.The modified interface between the BaSO4 particles and PP increases nucleating ability of the fillers,and retards the movement of the PP macromolecular chains.This leads to the formation of less smaller sizes of PP crystals with in complete structure.

PVC-based thermoplastic elastomer(TPVC) was prepared by in-situ polymerization with acrylate monomers and PVC resin. The influences of the plasticizer and acrylic rubbers on the mechanical properties,the dynamic mechanical properties and the processing rheological properties of the PVC-based thermoplastic elastomer were studied. The results show that with the increase of the plasticizer dioctyl phthalate (DOP),the elongation at break of TPVC materials gradually increases,and its tensile strength shows a decreased trend. While the glass transition temperature (Tg) of the used poly (acrylate) rubber is much lower,the elongation at break and the processing rheological properties of TPVC are much better than pure PVC materials,however the tensile strength of the TPVC is decreased.

N,N,N',N'-tetrahydroxyethylurea was produced using reaction of urea with diethanolamine.Dendrimeric carbamates with eight hydroxyls(8-OH) and sixteen hydroxyls (16-OH) can be synthesized by reaction of N,N,N',N'-tetrahydroxyethylurea with urea and diethanolamine alternatively,which is an eco-friendly route.The obtained products were analyzed by means of nuclear magnetic resonance(1H-NMR and 13C-NMR).The testing of surface tension shows that 16-OH has good surface activity.The critical micelle concentration,the saturation surface excess and the surface tension values of 16-OH are 3.502 mmol/L,0.0015 mmol/m2 and 35.7 mN/m,respectively.The results show that this green synthetic route is feasible.

The properties and morphology of nano-calcium carbonate (nano-CaCO3) modified with the titanate coupling agent isopropyl trioleoyl titanate (IPTT) were characterized by Fourier transform infrared, thermogravimetric analyses, surface tension, and transmission electron microscopy. The results showed that the grafting ratio of IPTT on the surface of nano-CaCO3 (IPTT-Ca) increased with IPTT content. IPTT-Ca/PBA/PMMA (IPTT-Ca/ACR, PBA/PMMA core-shell polymer, referred to ACR) latexes were prepared by seeded emulsion polymerization. They were then used to mix with PVC resin. The outer layer (PMMA) enhanced the dispensability of IPTT-Ca/ACR in the PVC matrix by increasing the interfacial interaction of these composite particles with PVC. The notched impact strengths of the blends were influenced by the weight ratio of IPTT-Ca to BA/MMA monomers, the weight ratio of BA/MMA. The relationships between the mechanical properties and the core-shell composite structures were elaborated. (C) 2009 Wiley Periodicals, Inc. J Appl Polym Sci 115: 1336-1346, 2010

Synthesis of poly(butyl acrylate-co-ethylhexyl acrylate)core/poly(vinyl chloride)-shell [P(BA-EHA)/PVC] used as a modifying agent of PVC via semicontinuous seeded emulsion copolymerization is reported here. Diameter distributions and morphology of the composite latex particles were characterized with the aid of particle size analyzer and transmission electron microscopy (TEM). The grafting efficiency (GE) and grafting ratio (GR) of vinyl chloride (VC) grafted onto the P(BA-EHA) with varying content of crosslinking agent and core-shell ratios were investigated. TEM studies indicated that the P(BA-EHA)/PVC latex particles have core-shell structure, and the P(BA-EHA) rubbery particles in blending materials were uniformly dispersed in PVC matrix. Dynamic mechanical analysis (DMA) results revealed that the compatibility between the P(BA-EHA) and the PVC matrix was significantly improved due to the presence of the P(BA-EHA)-grafted-VC copolymer. The notched impact strength of the blending material with 3 wt% of rubber content was seven times that of the PVC. Linear regressions of mechanical properties as loading of the modifier were made. The resulting data of notched impact strength and elongation at break for the blending materials deviated significantly from regression lines within 3-4.5 wt% of the P(BA-EHA) content. The PVC blends modified by the modifier exhibited good toughness and easy processability. POLYM. ENG. SCI., 50:1085-1094, 2010. (C) 2009 Society of Plastics Engineers

Poly(butadiene-styrene) rubber latexes (SBRL) modified by poly(n-butyl acrylate) (PBA) were used as seeds (SBA) then SBA/PVC composite resins were prepared through seeded emulsion copolymerization with vinyl chloride monomer. Diameter distributions, morphological structure of the latex particles and morphology of composite materials were characterized with the aid of particle diameter analyzer and transmission electron microscope (TEM). Dynamic mechanical properties of the samples and breaking surfaces' morphology of the notched bars were determined and characterized via a dynamic mechanical analyzer (DMA) and scanning electron microscope(SEM), respectively. TEM and particle diameter analysis showed that the PVC was assuredly coated onto the SBA particles, and the SBA/PVC particles presented clearly core-shell morphology. TEM studies indicated that the composite particles of the SBR modified by the PBA were uniformly dispersed in the PVC matrix. DMA results revealed that the SBA/PVC sample showed a weak and extensive glass-transition in low-temperature range. It was suggested that there should be a transition layer of microstructure where the SBA-grafted PVC macromolecules were embedded. The mechanical properties' research showed that the SBA/PVC composite resin had good impact strength at a low level of the PBA. SEM studies showed that the fractured surface of the composite sample exhibited better toughness than that of the SBR/PVC sample.

Silica-sol/acrylate copolymer composite latexes were prepared by semicontinuous emulsion polymerization.The hard monomer,methyl methacrylate(MMA),was distributed with a gradient concentration in the radial direction,and its effects on polymerization process and adhesive properties were researched.Dynamic light scattering(DLS)was used to monitor the particle diameters and showed that the particles have grown without significant secondary nucleation occurring.The molecular parameters were characterized by gel permeation chromatography(GPC),dynamic mechanical analysis(DMA).Adhesive properties measured were loop tack force,peel strength and shear resistance according to FINAT test methods.The relationship between pressure-sensitive properties and molecular parameters,such as gel content and molecular weight,was evaluated.

1,4-Butanediol-dicarbamate was synthesized by the reaction of butanediol with urea.Structure of the product was confirmed by IR,elemental analysis,1H NMR and 13C NMR.On this base,a novel nonisocyanate approach for the synthesis of polyurethanes was preliminarily investigated starting from urea,PEG400 and 1,6-diaminohexane.The obtained polyurethane was analyzed by means of IR and GPC.The weight-average molecular weight of the product is 4266.

A preparation method of isocyanate-free polyurethane was proposed using dimethylhexane-1,6-dicarbamate(HDU)as a curing agent.The structure of the obtained polyurethane was confirmed by means of IR,NMR,and GPC.When the molar ratio of HDU to polyether glycol 3000 was 1∶1,the reaction temperature was 180 ℃,a weight-average molecular weight of 8.5×104 was obtained after 1 hour.

以碳酸二甲酯和1,6-己二胺为原料制备1,6-六亚甲基二氨基甲酸甲酯（HDU）;再以HDU与聚醚二元醇（EPO3000）为原料合成无异氰酸酯聚氨酯。产物用红外光谱、核磁共振氢谱、热失重以及凝胶色谱表征。结果表明,n（HDU）/n（EPO3000）为1∶1,在180℃下反应1h,产物特性黏数达208.4 mL/g,重均分子量为1.1×10~5。

Dispersion copolymerization of glycidyl methacrylate(GMA),methyl methacrylate(MMA) and butyl acrylate(BA) was investigated using poly(N-vinylpyrrolidone)(PVP) as a steric stabilizer and 2,2'-azobisisobutyronitrile(AIBN) as an initiator in an ethanol/water medium.In this paper,comonomers' conversion on reaction time and morphology of the copolymer particles with different monomer ratios were investigated.The glass-transition temperature(Tg) and the epoxy equivalent mass(EEW) of acrylic resin were determined.The acrylic powder coatings were prepared by blending the synthesized resin,matrix polyester resin and suitable assistants.The synthesized acrylic resin was well suitable for powder coating application.

Liquid crystalline bismaleimide copolymers containing methyl side-group(MBMI) were synthesized by using 4,4’-diaminodiphenyl ether(DDE) as chain extending reactant,and the molecular ratios of MBMI to DDE used were 1:1,2:1 and 3:1,respectively.The chemical structure,thermal properties and mesomorphic phase behaviors of the copolymers synthesized were characterized by FT-IR,1H-NMR,TGA,DSC and HSPM,respectively,and the reaction mechanics were investigated by FT-IR integral intensity method.The results show that,during the synthesizing process,the mechanism of double bonds additive reaction takes place.Comparing with MBMI,the melting transition temperatures(Tm) of the copolymers synthesized decrease,while their thermogravimetic properties change only a little.Among those synthesized copolymers,the copolymer synthesized with MBMI to DDE molecular ratio of 1:1 has the largest Tm decrease which is 64℃ lower than that of MBMI.Since it was found that the incorporation of DDE has no effect on the liquid crystal behavior of MBMI,and the liquid crystalline characters could be retained in the crosslinked networks,the liquid crystalline network materials based on bismaleimide were obtained in this study.

In view of bond rotation flexibility and the additivity of stiff energy, a new equation containing mole fractions of sequences and glass transition temperatures (Tg's) of periodic copolymers was proposed. Meanwhile, the effect of stereochemical sequences was also taken into account. Even for the case of all substitutions on primary (C1), second (C2), and third (C3) carbon atoms adjoining to the given bond (triad sequences effect) to be considered, no intractable parameters exist in the new equation if the periodic copolymers of poly[AB], poly[AAB], and poly[BBA] could be acquired. This may facilitate its convenient application in comparison with the Ham equation (Ham, G. E. J. Macromol. Sci. Chem. 1975, A9, 461), which also concerned triad contributions. The new equation was applied to methyl methacrylate-styrene, ethylene-methyl methacrylate, and ethylene-vinyl acetate copolymers, and excellent fittings were obtained. The parameters obtained may predict Tg values of periodic copolymers that have not been acquired as well as provide useful information on the bond rotation flexibility.

DSC was used to study the curing behavior of AEN and BMD.The Kienetic analysis was performed by means of Kissinger,Crane and Ozawa methods at heating rates of 5,10,15 and 20 ℃/min between 30 ℃～400 ℃.By Kissinger and Crane equation, The analysis shows that reaction average activation energy is 109 kJ/mol,reaction order is 0.94,Tgel?is 79.68 ℃,Tcure?is 121.93 ℃.By Ozawa method the analysis shows the reaction activation energy ΔE is increasing function with curing transition degree α.Apparent activation energy ΔE is more reasonable than the constant activation nenergy.

Combining the advantages of thermoset and order of liquid crystal,liquid crystalline epoxy resin(LCER) is a kind of function material which has potential applications in many fields.Due to relatively easy to synthesis and the convenient structure controllability,the one containing ester mesogen becomes the most important class of LCERs.The synthesis,mesogenic property and curing of LCER containing ester mesogen were introduced in this paper.The advances in the study overseas and the future application of LCER containing ester mesogen were also depicted.

A kind of liquid crystalline bismaleimide containing bisphenol-s group was synthesized.The chemical structure was confirmed by FT-IR and 1H-NMR spectra and the mesomorphic phase behavior was investigated by differential scanning calorimetry(DSC),hot stage polarized light microscopy(HSPM).The results show that the liquid crystalline bismaleimide containing bisphenol-s group exhibits broad range of liquid crystalline phase at moderate temperature.Ball granul texture,typical of nematic phase can be observed in the liquid crystalline state during heating/cooling process.