iPB-g-MAH反应挤出工艺及性能

采用反应挤出工艺制备聚丁烯-1接枝马来酸酐改性材料,研究了挤出机温度、螺杆转速及原料放置时间对引发剂过氧化二异丙苯(DCP)、共单体苯乙烯(St)、接枝单体马来酸酐(MAH)反应体系的影响,分析了接枝物iPB-g-MAH-co-St在挤出机工业化制备中的适宜条件。结果表明,反应挤出温度对制备iPB-g-MAH的影响较大,在170~210℃区间内,接枝率最高可达3.05%,最低仅为1.29%,适宜的反应温度范围为180~200℃;螺杆转速对反应挤出制备iPB-g-MAH的接枝率影响较小,在60~140 r/min转速区间内,接枝率最大与最小值之间的差值低于40%,适宜的反应转速为120 r/min;配置好的原料放置时间过长导致过氧化二异丙苯(DCP)降解iPB-1,接枝物的接枝率与力学性能显著降低,在实际生产中需严格控制物料的放置时间。

Effect of Residual Maleic Anhydride in PP-g-MAH on the Thermo-Oxidative Aging Properties of RGF-PP

The mechanical, morphological and thermo-oxidative aging properties of the glass fiber reinforced polypropylene (RGF-PP) were studied based on four different maleic anhydride grafted polypropylene (PP-g-MAH) compatibilizers with different content of residual maleic anhydride (MAH). It was shown that PP-g-MAH compatibilizer could significantly improve the mechanical properties of RGF-PP, while from thermal and morphological analysis results, the content of residual MAH had negative influence on long term thermo- oxidative aging properties of RGF-PP with adding PP-g-MAH compatibilizer;the lower the residual content of MAH is, the better the thermo stability of the PP-g-MAH is, and also the better the thermo-oxidative aging properties was obtained.

PE/SEBS-g-MAH/SEBS的制备及防污性能

以聚乙烯(PE)网衣为基材,苯乙烯-乙烯/丁烯-苯乙烯嵌段共聚物接枝马来酸酐(SEBS-g-MAH)和苯乙烯-乙烯/丁烯-苯乙烯嵌段聚合物(SEBS)为原料,通过浸涂法制备得到PE/SEBS-g-MAH/SEBS(PSMS);分析讨论了不同SEBS附着率时PSMS的力学性能、表面形貌、表面性质、抗蛋白吸附和抗大肠杆菌吸附等性能。结果表明,PSMS表面呈大小不一的泡孔形貌,且随着SEBS附着率的增大,PSMS表面泡孔密度增大,拉伸强度先增加后降低。当SEBS附着率为46.1%时,PSMS的拉伸强度和表面自由能分别为6.045 MPa和14.055 mN/m,抗蛋白吸附率达93.21%,同时兼具良好的抗大肠杆菌吸附性能。除此之外,PSMS在海洋挂板实验中也表现出良好的防污性能。

TPAS/PLA/PLA-g-MAH共混材料制备及性能

使用熔融和注塑工艺制备热塑性醋酸淀粉(TPAS)/聚乳酸(PLA)/聚乳酸接枝马来酸酐(PLA-g-MAH)共混材料,考察PLA-g-MAH的增容效果,并对共混材料的力学性能、热性能、熔体流变性能和亲水性进行分析。结果表明:PLA-g-MAH提高TPAS在PLA中的分散程度,显著增强了两者的界面结合力;随着PLA-g-MAH含量的增加,共混材料的拉伸强度、断裂伸长率和缺口冲击强度均先升高后降低,含量为15%时达到最大值,较未增容体系分别增加17.9%、18.5%和138.5%;添加PLA-g-MAH导致共混材料结晶能力减弱,表面疏水性提高,共混材料熔体黏弹性增强,加工性能提高。

LLDPE-g-MAH接枝率的测定方法的建立与分析

本文通过酸碱滴定法和红外分析法建立了一种快速检测线型低密度聚乙烯接枝马来酸酐(LLDPE-g-MAH)接枝率的方法。首先,通过酸碱滴定法得到不同接枝率LLDPE-g-MAH样品的接枝率,然后通过红外分析法得到该样品的马来酸酐特征峰与LLDPE内标峰的峰高比值,通过滴定法得到的接枝率与红外特征峰峰高比值的拟合出标准曲线。该标准曲线可以用于快速测定未知LLDPE-g-MAH的接枝率。此方法操作快速便捷,对工业投产具有指导意义。

Ni/Al_2O_3 catalysts derived from spinel NiAl_2O_4 for low-temperature hydrogenation of maleic anhydride to succinic anhydride

Ni/Al2O3 catalysts were derived from spinel NiAl2O4 with different Ni content ((2.5, 5 and 7.5) wt%). The catalysts were obtained by H-2 reduction and were investigated for the low-temperature hydrogenation of maleic anhydride (MA) to produce succinic anhydride (SA). The characterization results showed that Ni-0 active sites were mainly derived during the H2 reduction from spinel NiAl2O4 Among the catalysts studied, employing the optimum preparation and reaction conditions with Ni(5%)/Al2O3 yielded the highest catalytic performance. A near-100% conversion of MA and similar to 90% selectivity to SA were achieved at 120 degrees C and 0.5 MPa of H-2 with a weighted hourly space velocity (MA) of 2 h(-1). (C) 2017, Dalian Institute of Chemical Physics, Chinese Academy of Sciences. Published by Elsevier B.V. All rights reserved.

Synthesis and Characterization of a Novel Biomaterial: Maleic Anhydride-modified Poly(dl-lactic acid)

A novel modified poly(dl-lactic acid) (PDLLA) was obtained by covalently grafting of maleic anhydride onto the backbone of PDLLA, attempting to improve PDLLA’s hydrophilicity and cell affinity and to provide reactive groups for further chemical modification. FTIR, 13C NMR and DSC were used to characterize the maleic anhydride-modified PDLLA.

Solid-Liquid Equilibria of Several Binary and Ternary Systems Containing Maleic Anhydride

Solid-liquid equilibria (SLE) of three binary systems and seventernary systems containing maleic an- hydride (MA) are measured byvisual method. The experimental data are compared with the calculatedones with modified universal quasichemical functional group activitycoefficient (UNIFAC) method in which the interaction parametersbetween groups come from two sources, dortmund data bank (DDB), ifthere's any, and correlations based on our former presentedexperimental SLE data of twenty binary systems.

Insights into the thermochemical evolution of maleic anhydride-initiated esterified starch to construct hard carbon microspheres for lithium-ion batteries

Starch,as a typical polysaccharide with natural spherical morphology,is not only a preferred precursor for preparing carbon materials but also a model polymer for investigating thermochemical evolution mechanisms.However,starch usually suffers from severe foaming and low carbon yield during direct pyrolysis.Herein,we report a simple and eco-friendly dry strategy,by maleic anhydride initiating the esterification of starch,to design carbon microspheres against the starch foaming.Moreover,the infuence of ester grafting on the pyrolytic behavior of starch is also focused.The formation of ester groups in precursor guarantees the structural stability of starch-based intermediate because it can promote the accumulation of unsaturated species and accelerate the water elimination during pyrolysis.Meanwhile,the esterification and dehydration reactions greatly deplete the primary hydroxyl groups in the starch molecules and thus the rapid levoglucosan release is inhibited,which well keeps the spherical morphology of starch and ensures the high carbon yield.In further exploration as anode materials for Lithium-ion batteries,the obtained carbon microspheres exhibit good cyclability and rate performance with a reversible capacity of 444 m Ah g^(-1)at 50 m A g^(-1).This work provides theoretical fundamentals for the controllable thermal transformation of biomass towards wide applications.

Ni-loaded Catalyst Containing Activated Clay for Maleic Anhydride Hydrogenation to Succinic Anhydride

In this work, the hydrogenation of maleic anhydride to succinic anhydride in the presence of 5 m%Ni/clay catalysts was investigated. These catalysts were characterized by X-ray diffraction （XRD）, H2 temperature programmed reduction （TPR） and thermogravimetric analysis （TGA） techniques. The XRD and TPR studies showed that Ni was present as Ni2＋ on the support, which indicated that there were no elemental nickel （Ni^0） and Ni203 species in the unreduced samples. Increasing of calcination temperature to 650 ℃ leads to destruction of the support structure observed in TGA, while the catalyst sample calcined at 550 ℃ exhibits better performances than other samples. The ideal conversion of maleic anhydride （97.14%） and selectivity of succinic anhydride （99.55%） were realized at a reaction temperature of 180 ℃ and a weight hourly space velocity of 4 h^-1 under a reaction pressure of 1 MPa.

CONTROLLED RADICAL COPOLYMERIZATION OF STYRENE AND MALEIC ANHYDRIDE UNDER GAMMA RADIATION IN THE PRESENCE OF BENZYL DITHIOBENZOATE

The copolymerization of styrene (St) with maleic anhydride (MAh) under gamma radiation at room temperature in the presence of benzyl dithiobenzoate (BDTB) was found to display 'living' nature evidenced by constant concentration of chain radicals during the copolymerization, linear evolution of molecular weights with conversion and narrow molecular weight distribution (M-w/M-n = 1.23-1.35). The compositional analysis and the sequence structural information of the copolymers obtained from DEPT (Distortionless Enhancement by Polarization Transfer) experiments demonstrate that the copolymers obtained also possess strictly alternating structure.

Safety evaluation of long-term vas occlusion with styrene maleic anhydride and its non-invasive reversal on accessory reproductive organs in langurs

Aim:To evaluate the safety of the long term vas occlusion with styrene maleic anhydride (SMA) and its non-invasive reversal at the level of accessory reproductive glands (ARGs) in langurs.Methods:The morphology of seminal vesicle and ventral prostate was evaluated by light as well as transmission electron microscopy.Serum clinical chemistry and urine albumin were evaluated in an autoanalyzer using reagent kits.Fructose,acid phosphatase and zinc in the seminal plasma were evaluated spectrophotometrically according to the WHO manual.Serum testosterone, prostate specific antigen and sperm antibodies were evaluated by enzyme-linked immunosorbent assays (ELISA) using reagent kits and hematology was estimated according to standard procedures.Results:The morphological features and secretory activity of the seminal vesicle and prostate were normal as evidenced by the presence of well- developed mitochondria,rough endoplasmic reticulum,Golgi bodies,secretory granules and normal nuclear charac- teristics throughout the course of investigation.Serum testosterone and prostate specific antigen remained unaltered and serum antisperm antibodies level presented negative titres.Urine albumin was nil.Total red blood corpuscles (RBC),white blood corpuscles (WBC),hemoglobin (Hb) and red cell indices,serum protein,glucose,cholesterol, creatinine,creatine kinase (CK),serum glutamate oxalate transaminase (SGOT),serum glutamate pyruvate transami- nase (SGPT),lactate dehydrogenase (LDH),bilirubin,urea,triglycerides and high-density lipoprotein (HDL) did not show appreciable changes following vas occlusion and after its non-invasive reversal.Although fructose,acid phos- phatase (ACP) and zinc in the seminal plasma showed a significant reduction following vas occlusion,it could not be related to the morphology of seminal vesicle and prostate.Conclusion:SMA vas occlusion and its non-invasive reversal do not damage the accessory reproductive organs.

Surface Modification of Waste Tire by Grafting with Styrene and Maleic Anhydride

Waste tire powder, as waste rubber WR was subjected to grafting with styrene (St) and maleic anhydride (MA). Hydrogen peroxide H2O2 was used to initiate the free radical copolymerization of St onto WR. A thermal initiation was used in case of grafting of MA onto WR. Effect of initiator and monomer concentrations together with the influence of reaction temperature and reaction time were investigated. The grafting was estimated by weight, and the grafted copolymers were characterized by FT/IR, DSC and SEM to prove the grafting. It has found that the grafting increases with increase monomer and initiator concentrations. The increase in the reaction temperature and time also causes increasing levels of the grafted St and MA.

The UV Aging Properties of Maleic Anhydride Esterified Starch/Polylactic Acid Composites

Esterified starch/polylactic acid（ES/PLA） blending composite was prepared by melting extrusion with maleic anhydride esterified starch and PLA as the raw materials. The composite was accelerated aging by using UV aging box, and its properties were characterized by Fourier transform infrared spectroscopy（FT-IR）, scanning electron microscopy（SEM）, X-ray diffraction（XRD）, thermo gravimetric analysis（TGA） and mechanical testing machine. FT-IR and SEM results show that the infrared absorption peak intensities of C-O, C-H, and C=O in aged samples decrease gradually with increasing aging time. The damage degree of surface and internal of aged samples increases gradually. XRD analysis results show that after aging treatment, the crystalline diffraction peak of thermoplastic esterified starch at 2θ = 21° disappears and the diffraction peaks of PLA at 2θ = 16.5° appear, indicating that the hydrolysis rate of esterified starch is greater than that of PLA. The crystallinity of PLA in aged sample shows an increasing trend at first followed by a decreasing one along with the increasing time of aging treatment, suggesting that the hydrolysis of amorphous regions of PLA is more preferential than its crystalline regions. Because of the influence of crystal structure and the change of composition structure, the initial decomposition temperature of aging test specimen gradually increases with the extension of aging time. The maximum decomposition rate temperature and residual mass increases at first, and then decrease after the aging time extending to 1600 h. As the aging time increases, the damage degree of combination interface between esterification starch and PLA is exacerbated, resulting in the tensile strength and bending strength of aged specimen decreasing gradually.

GRAFTING OF PEROXIDE-INITIATED MALEIC ANHYDRIDE ON SPHERICAL PE/PPIN-REACTOR BLEND GRANULES

Spherical polyethylene/polypropylene (PE/PP) in-reactor blend granules with various ethylene/propylene molar ratios and high porosity were synthesized using a high yield TiCVMgCl2 supported catalyst. A solution of benzoyl peroxide (BPO)/maleic anhydride (MAH)/xylene (interfacial reagent) or BPO/MAH/St (comonomer) was absorbed onto the PE/PP in- reactor blend granules, and solid phase graft polymerization of MAH on PE/PP was conducted. The amount of grafted MAH on PE/PP was measured through chemical titration. The results showed that solid phase graft polymerization of MAH in PE/PP in-reactor blend granules produced graft copolymer with high amount of grafted MAH, and the amount of grafted MAH was raised slightly when St was introduced as comonomer. The graft in-reactor blend was fractionated into five fractions through temperature-gradient extraction fractionation (TGEF), and the fractions were analyzed by FTIR. The results revealed that MAH is mainly grafted on the PE segments, whereas MAH was predominantly grafted on the PP segments when St was present in the graft polymerization system. In addition, the final product is still in the form of regular spherical granules, which is beneficial for industrial processing.

Selective Hydrogenation of Maleic Anhydride to Succinic Anhydride over Nickel Catalyst Supported on Carbon Microspheres

The colloidal carbon microspheres(CMS)were prepared by the hydrothermal method.The nickel catalysts supported on carbon microspheres(Ni/CMS)were further prepared and were characterized by the Fourier transform infrared spectroscopy(FTIR),the X-ray diffraction(XRD),the scanning electron microscopy(SEM),the transmission electron microscopy(TEM),and the N_(2)adsorption technique.The selective hydrogenation of maleic anhydride(MA)to succinic anhydride(SA)over the Ni/CMS catalysts was investigated.The results indicated that the Ni/CMS catalyst,which was prepared with glucose as carbon source and calcined at 500℃,exhibited the best performance.The hydrogen pressure,reaction temperature,and reaction time could significantly affect the conversion of maleic anhydride during the hydrogenation reaction.A 98.4%conversion of MA and an 100%selectivity to SA were achieved over the Ni/CMS catalyst in acetic anhydride solvent under mild conditions covering a temperature of 90℃,a H2 pressure of 1.0 MPa,and a reaction time of 3 h.

PHOTOCOPOLYMERIZATION OF MALEIC ANHYDRIDE AND VINYL ACETATE IN TETRAHYDROFURAN~*

The copolymerization of maleic anhydride and vinyl acetate in tetrahydrofuran was studied. Results show that the maximum copolymerization rate is in 0.6 mole fraction of maleic anhydride, indicating the involvement of maleic anhydride-tetrahydrofuran charge transfer complex in the chain initiation process. ESR study provides collateral evidence for the formation of maleic anhydride radical and tetrahydrofuran radical.

SYNTHESIS OF MESOPOROUS POLY(STYRENE-co-MALEIC ANHYDRIDE)/SILICA HYBRID MATERIALS VIA A NONSURFACTANT-TEMPLATED SOL-GEL PROCESS

Mesoporous poly(styrene-co-maleic anhydride)/silica hybrid materials have been prepared. The synthesis was achieved by the HCl-catalyzed sol-gel reactions of tetraethyl orthosilicate (TEOS) and styrene-maleic anhydride copolymer in the presence of 3-aminopropyl triethoxysilane (APTES) as a coupling agent and citric acid as a nonsurfactant template or pore-forming agent, followed by ethanol extraction. Characterization results from nitrogen sorption isotherms and powder X-ray diffraction indicate that polymer-modified mesoporous materials with large specific surface areas (e.g. 900 m(2)/g) and pore volumes (e.g. 0.6 cm(3)/g) could be prepared. As the citric acid concentration is increased, the specific surface areas, pore volumes and pore diameters of the hybrid materials increase.

PE-g-MAH粘接剂的制备及其在阻隔膜中的粘接性能研究

采用双螺杆熔融挤出法制备了马来酸酐接枝聚乙烯(PE-g-MAH)。探讨了在以基体树脂为线型低密度聚乙烯(LLDPE)的基础上,添加不同种类引发剂含量、不同接枝单体马来酸酐(MAH)含量对制备出PE-g-MAH的性能的影响。同时也探究了不同接枝率、熔融指数以及晶点个数的PE-g-MAH粘接剂在乙烯-乙烯醇共聚物(EVOH)阻隔膜上粘接性能的影响。通过傅里叶变换红外光谱对接枝产物进行定性表征并分析接枝物接枝率,通过熔体流动速率测试分析其流动性,通过180°剥离强度测试分析粘接剂的性能。研究结果表明:当引发剂为过氧化二异丙苯(DCP)且添加0.05份,MAH添加1份时,PE-g-MAH接枝率为0.68%,熔融指数为0.94 g·(10 min)^(-1),晶点个数为12,此时材料粘接性能最佳;选择EVOH作为阻隔层粘接,当接枝率为0.68%时,PE-g-MAH的剥离强度达到最大值为69.0 N/cm,PE-g-MAH粘接剂的粘接性能达到相对最佳。

Promotional Effect of CoO(OH) on Selective Hydrogenation of Maleic Anhydride to γ-Butyrolactone over Supported Ruthenium Catalyst

A decorated ruthenium catalyst was prepared by the coprecipitation method and used for the selective hydrogenation of maleic anhydride(MA) to γ-butyrolactone(GBL). The as-prepared catalyst was characterized by XRD, TGDTG and N2 adsorption techniques. The characterization tests revealed that the catalyst carrier was composed of monoclinic zirconia(m-ZrO2) and hydroxyl cobalt oxide(CoO(OH)). The hydrogenation results showed that the content of CoO(OH), the reaction temperature, the hydrogen pressure and the reaction time significantly affected the catalytic selectivity to GBL. The promotional effect of CoO(OH) was remarkable, which led to an obvious increase in GBL selectivity. An 100% MA conversion and 92.0% selectivity to GBL were achieved over the Ru/ZrO2-CoO(OH)(35%) catalyst in water solvent under the conditions involving a reaction temperature of 180 ℃, a hydrogen pressure of 3.0 MPa, and a reaction time of 6 h.