Thermal degradation studies of methacrylonitrile polymers and copolymers—3. Polymers capable of chain end-initiated colouration

Polymethacrylonitrile (PMAN) prepared by free-radical polymerisation with the initiator 4,4′-azo-bis(4-cyanovaleric acid) (ACVA) has chain ends from the initiator fragment which incorporate carboxyl groups. These ends are found to act as reactive sites for initiation of colouration in the polymer at temperatures from 140 °C. Several polymers, with different chain-end concentrations, have been made and the thermal degradation behaviour has been studied under programmed heating in the absence of air to 500 °C, with full product characterisation. In contrast with pure PMAN prepared with 2,2′-azo-bis(isobutyronitrile) (AIBN) as initiator, which degrades quantitatively to monomer, these ACVA-initiated polymers give very much reduced monomer yields, an important tar/wax fraction and a substantial amount of residue, amounting to 32–48% of the sample weight, dependent on the initial molecular weight of the polymer. The infrared spectral changes at the onset of the colouration reaction have been examined at 160 °C. Mechanisms are suggested to account for the observed products.     

Halloysite nanotubes/polystyrene (HNTs/PS) nanocomposites via in situ bulk polymerization

Serials of halloysite nanotubes/polystyrene (HNTs/PS) nanocomposites with different contents of organo-modified halloysite nanotubes (organo-HNTs) were successfully prepared by the in situ bulk polymerization of styrene with the organo-HNTs as macromonomers. The percentage of grafting (PG%) of more than 230% was achieved, calculated from the results of the thermogravimetric analysis (TG). The TG results also showed that the thermal stabilities of the HNTs/PS nanocomposites prepared via the bulk polymerization were better than the pure polystyrene. And the maximum thermal degradation temperature of the nanocomposites increased with the increasing of the amount of the HNTs fillers added.     

Block polymethacrylonitrile copolymers based on a central polyether or polyacetal block: A study of the salt/copolymer complexes

Some block copolymers based on polymethacrylonitrile (PMAN) and polyethers or polyacetals were synthesized in an anionic way. To appreciate the salt/polymer interactions, polymer electrolytes were prepared by the dissolution of lithium imide or lithium perchlorate in PMAN homopolymer and copolymers. The investigation of the triblock copolymer complexes allowed the solvating competition between nitrile‐ and ether‐ or acetal‐functional groups to be highlighted. The polydioxolane solvating ability was equivalent to that of PMAN but lower than that of polyoxyethylene or polyoxypropylene. Moreover, we were interested in the salt effect as block compatibilization was concerned. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 3665–3673, 2005     

Thermogravimetric characterisation of poly(methyl methacrylate) photopolymerised by colloidal cadmium sulphide

The thermal stability of poly(methyl methacrylate) (PMMA) photopolymerised using colloidal cadmium sulphide as the photoinitiator was studied by thermogravimetry (TG) and differential TG (DTG).The thermal stability of the CdS initiated PMMA was greater than that of conventional radically polymerised PMMA and approached that of anionically prepared PMMA. The DTG curve of the CdS initiated PMMA was a composite of four peaks, three of which correspond to the three peaks observed in the DTG curve of standard radically prepared PMMA. It is suggested that the additional peak arises from a new mode of depolymerisation initiation, that is, from chain end unsaturation introduced into the polymer chain during polymerisation initiation with the colloidal CdS.     

乙烯基三甲基硅烷等离子体聚合物膜的结构与性能

采用外部电极电容耦合高频等离子体装置对乙烯基三甲基硅烷(VTMS)进行等离子体聚合。用IR、XPS、PGC/MS、X-ray、ESR和元素分析等方法对聚合物结构进行表征,并推断聚合反应历程。应用TG研究聚合物的热性能。通过X-ray证实聚合物为非晶结构。在无添加气体存在时聚合,XPS测试结果表明产物中有氧嵌入,且聚合物的C/Si比总的说来比单体的C/Si比低。TG的测试结果表明聚合物膜具有优良的热稳定性。     

三氯环硼氮烷和聚硼氮烷的合成与表征

以三氯化硼和氯化铵为原料,甲苯为溶剂,高产率(98%)地合成了具有硼和氮的六元环结构的三氯环硼氮烷(1);1分别与正丙胺(Ⅰ)和异丙胺(Ⅱ)反应制得正丙胺基环硼氮烷(1~Ⅰ)和异丙胺基环硼氮烷(1~Ⅱ);1~Ⅰ和1~Ⅱ经过脱胺和热聚合反应制得聚硼氮烷先驱体(2和3).用IR,NMR和XRD等对2和3的组成与结构进行了分析,探讨了聚硼氮烷的胺基取代基对聚硼氮烷聚合反应性及产物结构的影响.研究结果表明,3具有更强的热聚合特性.     

Synthesis and Investigation of Monoesters of Polymaleic Acids with Azo Group

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聚乙炔热氧化过程的研究

本文测定了聚乙炔在氮气、空气和氧气中的等速升温热重曲线,测定了不同聚乙炔样品热氧化的恒温热重曲线,比较了聚合体系和顺反结构等对热氧化行为的影响。观察到钕催化聚乙炔的热氧化诱导现象。动力学分析表明,氧化反应对聚乙炔和氧气浓度都接近表观一级反应,顺式聚乙炔的表观活化能为42±6ki/mol,反式聚乙炔为51±6kJ/mol。用红外光谱跟踪氧化过程,表明含氧基团可分两类,分属于中间和最终产物,由此推断了可能的氧化反应。     

Novel propylmethacrylate-monofunctionalized polyhedral oligomeric silsesquioxanes homopolymers prepared via radical bulk free polymerization

Novel propylmethacrylate-monofunctionalized polyhedral oligomeric silsesquioxanes (POSS-PMA) homopolymers were obtained, in good yield, by free bulk radical polymerizations of the low melting macromer heptaisobutylpentacyclooctasiloxan-1-(yl)propylmethacrylate [(PMA)(i-Bu)₇T₈], 1, by using different initiator/macromer molar ratios. Their characterization was accomplished by TG, DTG and DSC analyses, Gel permeation chromatography (GPC) and MALDI-TOF mass spectrometry. The results indicate that both macromolecular as well as the thermal properties of the new materials are dependent on the initiator/macromer molar ratio used in the polymerization process. By increasing the amount of initiator, polymers with lowest molecular masses, highest molecular weight distributions (MWD) and lowest thermal stability were obtained. High value of MWD was found for all the samples. The different thermal behavior observed for the sample prepared by using the highest amount of initiator is explained by the formation of polymer branched chain, induced by chain transfer to polymer processes. MALDI-TOF mass spectra resulted diagnostic of the homopolymers compositions displaying a series of peaks corresponding to oligomeric structures present in the polymeric samples. The thermal polymerization of 1 performed without employing catalyst was also investigated. Only low yields (4%) of short oligomers (from dimer to pentamer), bearing degraded POSS cages, were isolated.     

Chlorinated thermal stabilizer for optically clear PMMA

Optically clear poly(methyl methacrylate) (PMMA) blends with HET‐EG oligoester (synthesized by condensation of chlorendic acid with ethylene glycol) at six different compositions were prepared by bulk polymerization. The effect of HET‐EG in the PMMA matrix on the optical clarity of PMMA blend was measured using ultraviolet‐visible spectroscopic study. The thermal stability of PMMA blends was investigated using differential scanning calorimetric (DSC) and thermogravimetric (TG) analyses. The parameters to deduce the thermal stability of pure PMMA and PMMA blends were calculated from DSC and TG results. The thermal stability of PMMA was found to increase effectively by loading 5% of HET‐EG oligoester without marring optical clarity. The probable physical and chemical actions of HET‐EG oligoester on the thermal stability of PMMA are discussed. Copyright © 2011 John Wiley & Sons, Ltd.     

不同热引发剂对凝胶态聚合物电解质性能的影响

采用热重/差热分析方法研究了两种热聚合引发剂: AIBN和BPO. 它们通常用于制备锂离子二次电池凝胶态聚合物电解质. 采用不同引发剂制备的凝胶态聚合物电解质具有不同的特性并影响聚合物锂离子二次电池的性能, 例如倍率性能, 高低温性能和循环性能. 为凝胶态聚合物电解质体系选择了一种合适的热引发剂.     

Surface effects on phase transition behavior and thermal polymerization of long-chain diynoic acids in micro DSC measurements

Effects of metal surfaces, such as aluminium, silver and gold, on the melting behavior and thermal polymerization of long-chain diynoic acids having a diacetylene group at different positions were investigated by thermal analyses using DSC, TG and other methods. The surface effects of metals were significant in the order of Ag, Al and Au. These effects are attributable to the anchoring of carboxyl group on the surface by chemisorption, which leads to unfavorable condition for polymerization of heptadeca-2,4-diynoic acid. In the case of tricosa-10,12-diynoic acid, containing a flexible methylene chain, inserted between COOH and C≡C?C≡C groups, the anchoring of COOH on the metal surface causes rather favorable effect on the polymerization.     

基于催化链转移聚合法MMA/MPS共聚物的制备及其表观催化链转移常数测定的研究

以钴Ⅱ肟氟化硼络合物(CoBF)为催化剂,2,2′-偶氮二异丁腈(AIBN)为引发剂,实现了甲基丙烯酸甲酯(MMA)与γ-甲基丙烯酰氧基丙基三甲氧基硅烷(MPS)在60℃甲苯体系中的催化链转移聚合(catalytic chaintransfer polymerization,CCTP),制备出末端含有双键的共聚物.利用核磁共振证明了其末端双键的存在,并通过热重分析证明CCTP产物与自由基聚合产物的结构区别.用凝胶渗透色谱(GPC)对7种单体组成下不同催化剂CoBF用量的聚合产物进行分子量表征,结果表明以催化链转移聚合合成的共聚物具有分子量低及分子量分布较窄,且聚合物的分子量随着催化剂CoBF的增加呈明显下降趋势.又分别采用了基于DPn(数均聚合度)、DPw(重均聚合度)的Mayo方程和基于ΛP、ΛH的链长分布方程计算出催化剂的表观链转移常数,发现基于DPw的Mayo方程和基于ΛP的链长分布方程的计算结果最为接近.并通过对共聚体系中不同单体组成的研究发现,催化剂表观链转移常数随着单体组成中MPS的增加而增加.     

带有功能侧链的聚马来酸单酯类聚合物的合成

利用聚合物直接制备LB膜引起了人们广泛的兴趣,为了采用於不同挂膜方法制备均匀的功能LB膜,要求聚合物除了是双亲性的、带有特定的功能基团之外,还应具有适当的分子量,为此,一般都采用含功能基的单体与亲水性单体共聚的方法来制备。     

高分子固体电解质LiNO_3-LiOOCCH_3/聚丙烯酸锂的合成与性能研究

以丙烯酸和氢氧化锂为原料用反相乳液聚合法合成聚丙烯酸锂 (PAALi) ,将其熔于低共熔盐 (一定比例的LiNO3 LiOOCCH3混合物 )中得到新型高分子固体电解质 (SPE) ,用XRD、IR、DTA、TG DTG等技术进行了表征 ,讨论了影响合成PAALi工艺及新型固体电解质电阻率的主要因素 ,在LiNO3 LiOOCCH3摩尔比为 1∶1时 ,将其按质量百分比 80∶2 0与聚丙烯酸锂混合均匀并熔融 ,得到的电解质其室温离子电导率可达 2× 10 - 5S·cm- 1 ,大量低共熔盐的加入可明显提高SPE的离子导电率 .XRD、DTA及TG DTG结果表明低共熔盐与聚丙烯酸锂形成了新的配合物     

Methyl Methacrylate–Ethyleneglycol Dimethacrylate–Acrylic Acid Surface as Stationary Phase for Stir Bar Sorptive Extraction

A novel poly(methyl methacrylate–ethyleneglycol dimethacrylate–acrylic acid) film has been introduced for coating on stir bars to sorptive extraction (SBSE). The effects of different contents of porogen, monomer, cross-linker, modifier and initiator during the solvent or bulk polymerization step on the mechanical property and solvent resistant of prepared sorptive stir bars were investigated. The evaluation of results were caused to obtain the four prepared sorptive stir bars with good mechanical stability and excellent resistance to organic solvents. The extraction efficiency of these prepared sorptive stir bars were investigated by liquid desorption-liquid chromatography-ultraviolet detection (LD-LC-UV) using N-Nitrosodiphenylamine as target analyte. SBSE assays showed the sorptive stir bar that prepared using solution polymerization method had the better recovery for N-Nitrosodiphenylamine in water samples. This sorptive stir bar showed good linearity and acceptable recoveries, as well as advantages such as sensitivity, simplicity, low cost and high feasibility. Based on atomic force microscopy (AFM) results, the average pore size of optimum prepared stir bar using solvent polymerization method was obtained ~9 nm. The thermal gravity (TG) and differential scanning calorimetric (DSC) results showed this polyacrylate film has high thermal stability.     

乳液聚合法制备聚苯乙烯/Mg-Al层状双氢氧化物纳米复合材料

采用乳液聚合法制备阻燃性聚苯乙烯MgAl层状双氢氧化物(LDHs)纳米复合材料.通过对不同合成条件下复合材料的XRD谱,讨论了纳米复合材料的形成过程;经SEM图证实了LDHs是以剥离的纳米级层片分散在基体中的;TG和DSC谱图揭示了LDHs纳米层板可有效提高PS的热稳定性,并可使PS的玻璃化转化温度明显提高;当层状双氢氧化物在插层复合材料中含量为14.92%时,纳米复合材料的氧指数可达23.5%,其用量比在PS中直接添加纳米LDHs时要少约一倍.文中还分析了纳米复合材料的形成过程.     

Synthesis and degradation profile of cast films of PPG-DMPA-IPDI aqueous polyurethane dispersions based on selective catalysts

Waterborne polyurethane (WBU) dispersions synthesized from poly(propylene glycol) (PPG), dimethylolpropionic acid (DMPA), and isophorone diisocyanate (IPDI) with catalysts of different selectivity were prepared via by the conventional prepolymer isocyanate process. Two types of chain extenders were used, ethylene glycol (EG) and propylene glycol (PG), producing polyurethanes. The dispersions were neutralized by the addition of triethylamine. The thermal stability of the materials, obtained as cast films prepared from aqueous dispersions was evaluated by thermogravimetry (TG). It was observed that initial degradation temperatures were above 140 °C, with two-step degradation profiles. The use of a more selective catalyst in the formulations led to materials with higher thermal stability. DTG curves exhibited stages not perceptible in the curves of weight loss, which were mainly influenced by the differences in the formulations. Thermal decomposition of the obtained polyurethanes was followed by TG coupled with FTIR spectroscopy.     

六羟基化合物为骨架的高分子固-固相变材料的合成与性能

分别使用三种含6个羟基的化合物(山梨醇、双季戊四醇和肌醇)作为分子骨架,聚乙二醇(PEG)作为相变功能链,4,4'-二苯基甲烷二异氰酸酯(MDI)为交联剂,合成了3种具有不同交联结构的新型固-固相变储能材料。通过傅里叶变换红外光谱(FT IR)、X-射线衍射(XRD)、偏光显微镜(POM)、示差扫描量热法(DSC)和热重量分析法(TG)分别对合成材料的分子结构、结晶性能、相变行为和热稳定性进行了研究。结果显示,所制备的材料在30~70℃温度范围内具有典型的固-固相变特性,其升温和冷却过程的相变焓最高可达107.5J/g和102.9J/g。此外,通过热重分析发现所合成材料具有较好的可重复使用性和热稳定性。因此,合成的新型固-固相变材料在热能储存和控温领域具有巨大的应用潜力。     

Laccase‐catalyzed polymerization of lignocatechol and affinity on proteins of resulting polymers

For the synthesis of a new biologically functional polymer from a natural resource by an environment‐friendly method, the laccase‐catalyzed polymerization of a lignin‐based macromonomer, lignocatechol, was carried out for the first time in ethanol–phosphate buffer solvent system to give crosslinked polymers in good yields. Lignocatechol was prepared by the phase separation system of lignin and catechol in aqueous sulfuric acid. The copolymerization was also performed with urushiol to afford the corresponding copolymers in high yields. The polymerization mechanism was estimated by the IR and pyrolysis GC‐MS measurements, suggesting that the polymerization proceeded mainly at the catechol ring through a quinone radical intermediate. The thermal properties were measured by the DSC, TG, and TMA analyses, indicating that the polymers had high thermal stabilities because of the crosslinked structures. In addition, it was found that the resulting polymers had the affinity of bovine serum albumin (BSA) and glucoamylase. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 824–832, 2009