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.

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.

Solvent-free esterification of poly(vinyl alcohol) and maleic anhydride through mechanochemical reaction

A solid-state mechanochemical processing, that is, pan-milling, was used to conduct the esterification of poly（vinyl alcohol） （PVA） with maleic anhydride （MA） through stress-induced reaction. FTIR spectrum study indicated the presence of ester linkages and olefinic double bonds in maleic anhydride cross-linked PVA. Thermal properties of the cross-linked product were characterized by DSC. The results showed its glass transition temperature was 20 ℃ higher than the original linear PVA and the thermal stability was also improved.

Synthesis and Characterization of Styrene-Maleic Anhydride-Butyl Acrylate Terpolymer

A novel surface modifying agent and internal compatilizer of inorganic and macromolecule composite materials,P(St/MAH/BA)terpolymer,was synthesized in butanone by solution polymerization method using styrene(St),maleic anhydride(MAH),and butyl acrylate(BA)as monomers and azobisisobutyronitrile(AIBN)as an initiator.Some affecting factors on terpolymers yields such as polymerization time,reaction temperature,solvent volume,initiator content,and reactants ratios were studied.Furthermore,the structure and thermal properties of terpolymers were primarily characterized and determined by Fourier Transform Infrared Spectroscopy(FTIR),nuclear magnetic resonance(NMR),thermogravimetric analysis(TGA),and gel permeation chromatography(GPC).The results indicate that the terpolymers are random polymers and the yields are low,but the thermal decomposed temperature of terpolymers P(St/MAH/BA)is around 220 ℃ and the average molecular weights(Mw)achieve 1.189×105 g·mol-1.

A STUDY OF SILICA-SUPPORTED CROSS-LINKED POLY (MALEIC ACID-CO-STYRENE)-PLATINUM COMPLEX IN THE HYDROGENATION OF p-CRESOL

A silica-supported cross-linked poly(maleic acid -co- styrene)-platinum complex (PMS-Pt) has been prepared and found to be active in the hydrogenation of p-cresol under mild conditions (303-323K, 1.01 x 10(5)Pa). In this hydrogenation system water serves as a solvent and p-cresol can be converted to 4-methylcyclohexanol quantitatively via 4-methylcyclohexanone as intermediate.

SYNTHESIS AND CHARACTERIZATION OF A NEW COMBLIKE POLYMER BASED ON POLY (VINYL METHYL ETHER-ALT-MALEIC ANHYDRIDE) BACKBONE

A new comblike polymer host for polymer electrolyte was synthesized by reacting monomethyl ether of poly(ethylene glycol) with poly(vinyl methyl ether-alt-maleic anhydride) and endcapping the residual carboxylic acid with methanol. Butanone was selected as a solvent for the esterification in order to obtain a completely soluble product. The synthesis process was traced through by LR. Compared with the model compounds, the presumed structure of this comblike polymer has been proved to be valid by C-13 NMR The comb polymer is a white rubbery solid. It can be dissolved in butanone and THF, and manifests good film forming ability.

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.

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.

FABRICATION AND AFM/FFM STUDIES OF C_(60)-CONTAINING POLYELECTROLYTE SELF-ASSEMBLED FILMS

An initial investigation on the roughness and frictional properties of the self-assembled thin films from polyelectrolytes is presented. Star-shaped C-60-Poly(styrene-maleic anhydride) was successful prepared. The multilayer thin films have been fabricated on mica with diazoresin as the cationic polyelectrolyte and hydrolyzed star-shaped C-60-poly(styrene-maleic anhydride) as the anionic polyelectrolyte via self-assembly technique. The crosslinking structure of the films is formed from the conversion of ionic bond to covalent bond after UV irradiation. AFM/FFM investigations provide insights into the roughness and frictional properties on a microscale. The roughness depends strongly on the number of film layers in the case of C-60-containing films. The frictional forces of the films exhibited a well behaved non-linear relationship in response to the change of applied load. It supports the prediction of enhanced load-bearing property Of C60-containing thin films.

Synthesis and characterization of biodegradable materials:PDLLA-(MAh-Diol)_n-PDLLA copolymer

The novel biodegradable copolymer PDLLA-（MAH-Diol）n-PDLLA with unsaturated bond was synthesized by copolymefizing lactide and prepolymer, which was prepared by the polycondensation of maleic anhydride and poly（ethylene glycol）, using ptoluene sulphonic acid as catalyst. The new copolymer has improved hydrophilicity and flexibility. The structure and properties of the novel polymers were studied by FTIR, NMR, GPC-MALLS and DSC.

The Characterization of Comblike Polymer Electrolyte by Means of NMR

The comblike polymers based on poly (styrene-co-maleic anhydride) backbone with poly (ethylene glycol) methyl ether as side chains were synthesized and characterized by H-1 NMR. with the result compared with that of 1R. It is found that it is both feasible and simple to synthesize this kind of compounds with the help of H-1 NMR.

Preparation and characterization of porous titania-grafted poly(styrene-divinylbenzene)/maleic anhydride nanocomposite microspheres

Mesoporous titania-grafted poly(styrene-divinylbenzene)/maleic anhydride [P(St-DVB)/MA] nanocomposite microspheres were prepared by an open ring reaction method.The titania nanoparticles were first modified by attachment of amino groups to their surface to prevent particle aggregation,and to allow the nanoparticles to covalently bond the polymer microspheres,the surface of which was modified by attachment of MA functional groups to enable the polymer to retain their porous structures and to react with the amino groups on the surface of the titania particles.The porous nanocomposite microspheres were detected by FTIR,SEM,TEM,XRD and UV-Vis spectrophotometry.The results indicated that the nanocomposite microspheres were composed of nanosized titania uniformly distributed on the surface,and exhibited better UV absorbing property than pure polymer microspheres or unmodified titania.Furthermore,compared with pure porous polymer microspheres,the nanocomposite microspheres showed more efficient UV protection and slow release of Parsol-1789(a photo-reactive and cosmetic agent) held inside the porous network of the microspheres.

SUPERCRITICAL CARBON DIOXIDE ASSISTED SYNTHESIS OF AMPHIPHILIC GRAFT COPOLYMERS BASED ON POLY(STYRENE-CO-MALEIC ANHYDRIDE) WITH METHOXYL POLY(ETHYLENE GLYCOL) SIDE CHAINS

Supercritical carbon dioxide （scCO2） was used as a reaction medium in synthesizing amphiphilic graft copolymers composed of poly（styrene-co-maleic anhydride） （SMA） backbones and methoxyl poly（ethylene glycol） （MPEG） side chains via esterification. The synthesized copolymers were characterized by Fourier transform infrared spectroscopy （FTIR）, gel permeation chromatography （GPC）, IH-NMR, thermo-gravimetric analysis （TGA） and differential scanning calorimetric analysis （DSC）. The gelation phenomenon was suppressed effectively by tuning reaction conditions. The influences of scCO2 temperature and pressure on the conversion of anhydride were investigated. It was found that the highest conversion ratio occurred at 80~C under a constant pressure of 14 MPa or 26 MPa. With the increase of scCO2 pressure, the conversion ratio increased first, and then leveled off. The conversion ratio of anhydride could be controlled by regulating the reaction conditions. It was also revealed that using low molecular weight MPEG brought a high conversion ratio of anhydride.

COORDINATION COPOLYMERIZATION OF STYRENE WITH MALEIC ANHYDRIDE BY RARE-EARTH COORDINATION CATALYSTS

The study on coordination copolymerization of styrene (S) with maleic anhydride (MA) by rare-earth coordination catalysts, NdL_3-Al(i-Bu)_3, has been successfully carried out for the first time. Some features, kinetic behavior, and mechanism of the SMA copolymerization by Nd(naph)_3-Al(i-Bu)_3 system are described and discussed. The copolymex of styrenemaleic anhydride prepared by the NdL_3-Al(i-Bu)_3 systems in benzene at 50℃ is an alternating-rich white powder having high number-average molecular weight of 6—8.5×10~5. The overall activation energy for the polymerization was found to be 10.5KJ/mol. The polymerization was not suppressed by addition of hydroquinone. The catalytic activity of various ligands in NdL_3 for the copolymerization decreases in the following order: Nd (naph)_3>Nd-(P_(507))_3～NdCl_3-6H_2O>Nd(P_(204))_3>Nd(acac)_3. 3H_2O. The experimental results are explained based on a mechanism to be the coordination-type copolymerization in terms of the participation of a monomer-monomer complex in propagation.

超临界CO_2协助多单体接枝改性聚丙烯

利用超临界CO2作为溶胀剂和携带剂,使小分子单体马来酸酐和苯乙烯单体(MAH与St)及引发剂过氧化苯甲酰(BPO)插嵌进入聚丙烯(PP)基质中,然后在100℃条件下反应4 h得到接枝产物。研究了不同超临界CO2条件及引发剂浓度对接枝率的影响,固定超临界流体压力,改变温度,42℃为最佳温度,接枝率达到2.2%;固定温度,改变压力,10 MPa为最佳条件,接枝率为2.3%。对样品的FT-IR和SEM分析表明,共单体确实接枝到了PP分子链上,而DSC分析表明,随着接枝率的提高,材料的熔点(Tm)及表观结晶度(Ca)下降。这可能是接枝破坏了PP链结构的规整性,同时扩大了分子链间的距离所致。

超临界CO_2中两亲共聚物的合成及其对PVDF膜亲水化改性

以超临界CO2流体为反应介质,通过固相接枝反应合成了具有PEG侧链的聚(苯乙烯-马来酸酐)(SMA)功能化梳状两亲共聚物(SMA-g-MPEG),用1 H NMR和FT-IR表征了SMA-g-MPEG的结构和组成。并以SMA-g-MPEG为亲水改性材料通过非溶剂诱导相分离法制备PVDF共混复合膜。表面元素分析结果表明SMA-g-MPEG共聚物中的PEG侧链在膜表面形成富集;纯水接触角测定和BSA吸附试验表明膜的亲水性和抗蛋白质污染性能得到明显的提高。

聚丙烯与马来酸酐和苯乙烯在超临界CO_2中的双组分接枝

在超临界CO2 介质中 ,颗粒状的聚丙烯与马来酸酐、苯乙烯通过自由基接枝聚合生成了聚丙烯 g (马来酸酐 苯乙烯 )。探讨了双组分单体的摩尔比 ,溶胀温度和时间 ,反应压力和时间等对接枝率的影响。结果表明 ,苯乙烯作为一种共聚单体能够明显提高双组分的接枝率。在 5 0℃和 10MPa压力下溶胀 2h后 ,升温至 12 5℃、17MPa时反应 4h ,双组分接枝产物的最大接枝率为 10 5 8% ,比在同样条件下聚丙烯接枝马来酸酐的接枝率大 1倍。用FTIR和DSC表征了接枝共聚物的结构和热性能。聚丙烯支链中引入苯乙烯的结构单元 ,使产物的Tm由 15 8℃降低到 15

超临界CO_2中马来酸酐与苯乙烯的聚合

在超临界CO2中进行了马来酸酐(M A)与苯乙烯(S t)的沉淀聚合反应,研究了反应时间、反应压力等条件对聚合反应的影响。用FT-IR、GPC、DSC和TG对产物进行了表征。结果表明,聚合反应的转化率可以达到96%,产物的数均分子量M-n可以达到4.6×104g/m o l。DSC和产物溶解性分析表明所合成的产物为交替共聚物。

不同改性剂对PP/CaCO_3复合材料结晶和动态力学性能的影响

以马来酸酐(MAH)、聚丙烯蜡(PPW)为主要原料,采用原位固相接枝改性法制得PP/Ca-CO3-MAH-PPW复合材料,对改性CaCO_3进行表面性能分析,并与PP/PP-g-MAH/CaCO_3复合材料进行结晶、动态力学和耐热性能的比较.结果表明,CaCO_3经原位固相接枝改性后,表面极性减弱,与PP的界面张力降低、相容性提高; CaCO_3表面的PPW层虽会阻碍CaCO_3的异相成核作用,但其可使复合材料形成适宜的界面粘接,有利于材料韧性的提高; CaCO_3-MAH-PPW可降低基体分子链的缠绕程度,增加其柔顺性,使复合材料玻璃化转变温度下降. PP-g-MAH的存在有助于提高PP/PP-g-MAH/CaCO_3复合材料的结晶温度,与基体形成较强的界面粘接,提高复合材料的模量、强度以及耐热性能.