聚合条件对N-羧基-L-丙氨酸-环内酸酐开环聚合产物分子量的影响

用光气法制备了N-羧基-L-丙氨酸-环内酸酐(L-Alanine NCA).系统研究了L-Alanine NCA开环聚合反应过程中引发剂、溶剂、温度对聚合物分子量的影响.用硝基苯作溶剂,三乙胺作引发剂,所得聚合物特性粘度[η]=1.18.实验中发现,L-Alanine NCA可以顺利地进行热聚合反应。反应具有速率快,转化率高,分子量大的特点。甲苯溶剂中反应5小时所得聚合物[η]=2.35,高于采用引发剂的聚合体系产物的相应值。     

聚L-谷氨酸γ-苄酯的合成及其结晶结构的研究

利用L-谷氨酸苄酯与三光气反应制备了N-羧基-L-谷氨酸γ-苄酯-环内酸酐(NCA),以正已胺为引发剂,引发NCA开环聚合,合成了分子量为6700的聚L-谷氨酸γ-苄酯(PBLG).利用核磁共振仪(1 H-NMR)、凝胶渗透色谱(GPC)、傅里叶变换红外光谱(FTIR)以及一维大角X射线衍射仪(1D-WAXD)等表征手...     

ABA型聚L-丙氨酸-聚乙二醇嵌段共聚物的合成及其表征

利用L-α-丙氨酸和三聚光气反应制备了N-羧基-α-丙氨酸-环内酸酐(NCA).以聚乙二醇(PEG)为原料.制备了端氨基聚乙二醇(PEG-NH₂),并以此作为引发剂,引发NCA开环聚合.合成了不同组成和分子量的聚L-丙氨酸-聚乙二醇(PLAA-PEG-PLAA)嵌段共聚物.利用IR、¹H NMR、DSC、WAXD、CD等方法对共聚物结构进行了表征.结果表明,PEG-NH₂引发NCA开环聚合得到的是嵌段共聚物,通过¹H NMR谱得到共聚物组成及数均分子量;引入PEG的结果使聚L-丙氨酸的亲水性有所改善;CD测诚结果表明共聚物在水溶液中主链主要以α-螺旋构象存在.     

聚l-谷氨酸苄酯的制备及成膜

用三光气法合成了L-谷氨酸苄酯均聚物,讨论了N-羧基环内酸酐开环聚合的机理。用红外光谱、差示扫描量热测试技术分别对聚合产物进行了表征和分析。结果表明,N-羧基-L-谷氨酸-苄酯-环内酸酐开环聚合得到了聚L-谷氨酸苄酯。研究了不同温度和时间对聚合物分子量的影响。40℃是完成聚合反应的适宜温度。随着反应时间的增加,聚合产物分子量线性增加。用四氢呋喃作溶剂制备了PBLG薄膜,薄膜的密度为1.098 g/cm3。讨论了不同浸泡时间对聚合物吸水率的影响,结果显示,PBLG的吸水率随着时间的增加而增大,其变化范围为2.64%~5.58%,并且在48 h内逐渐趋于平稳;在相同状态下,断裂界面处的吸水率远高于其它部位。     

基于β-环糊精的多肽支臂星状聚合物的制备及性能

以β-环糊精(β-CD)为起始原料,通过磺酰化及乙二胺基取代等过程,制备具有端氨基的中间体β-环糊精(6-en-β-CD);再以6-en-β-CD为引发剂,通过赖氨酸N-羧基环内酸酐(Lys-NCA)和谷氨酸N-羧基环内酸酐(Glu-NCA)的混合开环聚合(ROP)和脱苄氧羰基(Cbz)保护等反应,制备了以β-CD为核、混聚多肽为支臂的星状聚合物[6-聚(谷氨酸-赖氨酸)-β-CD].以基质辅助激光解吸电离飞行时间质谱(MALDI-TOFMS)、核磁共振波谱(NMR)和傅里叶变换红外光谱(FTIR)等对星状聚合物及中间体结构进行表征;同时采用圆二色光谱(CD)和噻唑蓝(MTT)法对该聚合物的二级结构和体外毒性进行了考察.结果表明,所得星状聚合物的重均分子量(Mw)为4626,多分散系数(PDI)为1.10,平均聚合度(DP)为27.1;在水溶液中星状聚合物的二级结构是无规则线团;在5 mg/m L浓度下,细胞存活率可达到94%以上,没有呈现明显体外细胞毒性,具有潜在的药用前景.     

含芳香侧链聚类肽的合成与自组装

设计合成了一种侧链含有溴苯基团的新型N-取代-N-硫代环内羧酸酐(NNTA)单体,即N-4-溴苯基甘氨酸-N-硫代环内羧酸酐(NBrG-NTA).以聚乙二醇胺作为大分子引发剂,乙酸作为促进剂,实现了NBrG-NTA在DMAc中的可控开环聚合,以较高的产率(>80%)制备得到了不同嵌段长度的两嵌段共聚物聚(乙二醇)-b-聚(N-4-溴苄基甘氨酸)(PEG-b-PNBrG).体积排除色谱(SEC)测试表明产物具有较窄的分子量分布(?<1.06).示差扫描量热法(DSC)测试表明PNBrG嵌段具有良好的结晶性.系统研究了PEG-b-PNBrG在醇类溶剂中的自组装行为,利用透射电子显微镜(TEM)对组装体的形貌进行了详细表征,根据不同的退火温度和保温时间,获得了“竹叶”状、“海胆”状和“蒲公英”状等形貌的组装体.     

卟啉化聚(L-谷氨酸-γ-十八烷酯)的合成及其静电纺纤维膜制备

以单氨基卟啉作为引发剂,引发L-谷氨酸-γ-十八烷酯N-羧基内酸酐(SLGNCA)开环聚合合成卟啉化聚(L-谷氨酸-γ-十八烷酯)(PSLG),进一步通过静电纺丝制备其纤维膜.相比于自由氨基卟啉,金属氨基卟啉尤其是钴氨基卟啉引发得到的PSLG具有更高的分子量.紫外-可见光谱和荧光光谱研究表明,卟啉化PSLG依然具有卟啉独特的光谱性能,静电纺后可以制备具有均匀红色荧光的微米级纤维.     

叔丁氧羰基单端基保护己二胺的合成

以己二胺为原料，叔丁氧羰基酸酐(Boc2O)为保护剂，合成了Boc单端基保护己二胺。并用IR和^1H NMR对产物进行了表征。该化合物可用作氨基酸的N-羰基环内酸酐(NCA)开环聚合法合成结构明晰的两嵌段聚氨基酸的引发剂，因而具有良好的应用前景。     

AB型两亲聚L-谷氨酸-苄酯-聚乙二醇嵌段共聚物的合成与表征

利用L 谷氨酸和苯甲醇反应制备了L 谷氨酸 苄酯 ,然后将其与三聚光气反应制备了N 羧基 L 谷氨酸 环内酸酐 (NCA) .以聚乙二醇单甲醚 (MPEG)为原料 ,制备了端氨基聚乙二醇单甲醚 (MPEG NH2 ) ,并以此作为引发剂 ,引发NCA开环聚合 ,合成了不同分子量的聚L 谷氨酸 苄酯 聚乙二醇单甲醚 (PBGM )嵌段共聚物 .利用IR、1 H NMR、DSC、GPC等方法对共聚物结构进行了表征 .结果表明 ,MPEG NH2 引发NCA开环聚合得到的是嵌段共聚物 ,通过1 H NMR谱得到共聚物组成及数均分子量 ;随着共聚物中MPEG含量的增高 ,聚L 谷氨酸 苄酯的亲水性有所改善     

β-氯乙基乙烯基醚与柠康酸酐的共聚合反应的研究

衣文报导了用偶氮二异丁腈为引发剂,苯或甲苯为反应介质,β-氯乙基乙烯基醚与柠康酸酐共聚合反应的研究.红外光谱及核磁共振谱证明反应产物为共聚物,较详细地研究了反应条件对单体转化率、产物分子量及分子量分布的影响。     

Emulsion copolymerization of tribromophenyl maleimide with styrene

Emulsion copolymerization of Tribromophenyl Maleimide (TBPMI) and styrene was conducted by semi-batch and batch processes. The effects of monomer composition and copolymerization method on copolymerization rate, molecular weight and molecular weight distribution, latex particle size and size distribution, glass transition temperature (T_g), thermal stability and mechanical properties were investigated. A kinetic study has shown that the rate of copolymerization in the batch process increased with increasing TBPMI content in the monomer feed. For the semi-batch polymerized samples, molecular weight decreased and molecular weight distribution increased with increasing TBPMI content in the monomer feed. For the batch polymerized samples, molecular weight also decreased but no obvious tendency was observed for the molecular weight distribution when TBPMI content increased. Compared with the batch copolymers, the semi-batch copolymers have a higher molecular weight at the same initial monomer mixture composition. Latex particle size decreased, while particle size distribution slightly increased with increasing TBPMI content in both semi-batch and batch latices. The semi-batch samples exhibit only a single T_g, the value of which increses linearly with increasing TBPMI content. For the batch copolymers, two T_gs were found, reflecting a mixture of styrene-rich and TBPMI-rich copolymer chains. TGA results indicate that the thermal stability of the semi-batch copolymers increased with increasing TBPMI concentration. Young's and flexural moduli increased, while tensile and flexural strengths decreased by increasing the TBPMI content for both the semi-batch and batch specimens. The semi-batch specimens have higher tensile and flexural strenghts than the batch ones.     

Living radical copolymerization of styrene/maleic anhydride

Styrene/maleic anhydride (MA) copolymerization was carried out using benzoyl peroxide (BPO) and 2,2,6,6‐tetramethyl‐1‐piperidinyloxy (TEMPO). Styrene/MA copolymerization proceeded faster and yielded higher molecular weight products compared to styrene homopolymerization. When styrene/MA copolymerization was approximated to follow the first‐order kinetics, the apparent activation energy appeared to be lower than that corresponding to styrene homopolymerization. Molecular weight of products from isothermal copolymerization of styrene/MA increased linearly with the conversion. However products from the copolymerization at different temperatures had molecular weight deviating from the linear relationship indicating that the copolymerization did not follow the perfect living polymerization characteristics. During the copolymerization, MA was preferentially consumed by styrene/MA random copolymerization and then polymerization of practically pure styrene continued to produce copolymers with styrene‐co‐MA block and styrene‐rich block. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 2239–2244, 2000     

过硫酸铵-尿素引发丙烯酸甲酯与明胶接枝共聚

接枝共聚合反应;过硫酸铵-尿素引发丙烯酸甲酯与明胶接枝共聚     

Mechanism of graft copolymerization of styrene onto deproteinized natural rubber

High conversion and high grafting efficiency attained by graft copolymerization of styrene onto deproteinized natural rubber (DPNR) was investigated with respect to the molecular weight of grafted polystyrene. The graft copolymerization was performed with tert-butyl hydroperoxide/tetraethylenepentamine as an initiator after deproteinization of natural rubber with urea. Grafted polystyrene was isolated from the resulting graft copolymer by ozonolysis reaction. After the ozonolysis of the graft copolymer of DPNR and polystyrene (DPNR-g-PS), the molecular weight of grafted polystyrene was determined by size exclusion chromatography. Effects of initiator and monomer concentrations were investigated with respect to the molecular weight of the grafted polystyrene, which was found to depend on not only the number of active site generated on the rubber particle but also the feed of styrene. Deactivation and chain transfer of the active sites were attributed to effective amount of styrene used for the graft copolymerization.     

Novel approach to well‐defined polyester by living anionic alternating copolymerization of ethylphenylketene with 4‐methoxybenzaldehyde

A living anionic alternating copolymerization of ethylphenylketene (EPK) with 4‐methoxybenzaldehyde (MBA) was achieved. When n‐butyllithium was added to a mixture of EPK and MBA in tetrahydrofuran at ?40 °C in the presence of an excess amount of lithium chloride, the copolymerization of these monomers proceeded via complete 1:1 alternating manner to afford the polymer with a narrow molecular weight distribution. A linear relationship was observed between the molecular weight and the monomer/initiator ratio, keeping a narrow molecular weight distribution. The structure of the obtained polymer was determined to be a polyester by IR spectroscopy together with the reductive degradation of the polymer by lithium aluminum hydride, which quantitatively afforded the corresponding diol to the repeating unit of the expected polyester structure. Both conversions of EPK and MBA agreed to a first‐order kinetic equation with linear evolution between the molecular weight and conversion. These observations along with the successful results in two‐stage polymerization indicate that the present copolymerization proceeded through a living mechanism. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 2078–2084, 2001     

聚氯乙烯-丙烯酸丁酯接枝共聚物的结构表征

以通用聚氯乙烯(PVC)和脱氯化氢PVC树脂为基体,采用悬浮溶胀接枝共聚法合成聚氯乙烯-丙烯酸丁酯接枝共聚物,对脱氯化氢PVC和接枝共聚物的结构进行了表征.结果表明,以碱液为介质加热PVC能脱除少量氯化氢,得到以链节数为2,3,4的共轭双键为主的不饱和结构,而树脂的分子量变化不大;在相同接枝反应条件下,采用脱氯化氢PVC与丙烯酸丁酯接枝共聚可以提高接枝率和接枝效率;PVC接枝共聚物的特性粘度随接枝率增加而增加,其重均分子量和分子量分布指数均大于接枝所用的PVC树脂.     

Fe-Al络合催化苯乙烯-马来酸酐交替共聚

应用Ｆｅ（ａｃａｃ）３ Ａｌ（ｉ Ｂｕ）３（ａｃａｃ＝乙酰丙酮）催化苯乙烯 马来酸酐共聚,制得富于交替的白色粉末共聚物．共聚反应动力学研究表明,共聚反应与单体浓度呈一级关系,表观活化能为４８６ｋＪ／ｍｏｌ．     

乙烯砜型染料与丙烯腈的水相沉淀聚合

乙烯砜型染料与丙烯腈的水相沉淀聚合吴致宁，张雪松，杨锦宗大连理工大学精细化工系，大连，１１６０１２）关键词高分子染料、沉淀共聚合、乙烯砜型染料、丙烯腈近年来，随着人们对功能材料具有高附加值的认识的不断深人，特别是伴随各类功能性染料结构的开发，高分子染...     

PEB/MMA-AN悬浮接枝共聚反应机理

研究了乙烯-1-丁烯共聚物(PEB)弹性体与甲基丙烯酸甲酯(MMA)-丙烯腈(AN)悬浮接枝共聚反应行为及接枝共聚产物对SAN树脂增韧作用随反应时间的变化规律, 用凝胶渗透色谱法和傅里叶变换红外光谱法对接枝共聚产物进行了表征, 分析了接枝共聚反应机理, 推算了接枝链分子量. 结果表明, 体系首先发生链增长自由基向PEB转移终止形成非接枝共聚物(MAN_L)和PEB大分子自由基引发单体共聚形成接枝链(g-MAN)的反应, 接枝反应结束后体系发生明显的非接枝共聚形成非接枝共聚物(MAN_H)的反应; MAN_L的分子量低于g-MAN的分子量, 而g-MAN的分子量明显低于MAN_H的分子量; 在接枝共聚过程中发生已接枝和未接枝PEB断链并随机再接生成多嵌段共聚物的副反应; 在反应初期, 接枝链的AN单元含量接近于非接枝共聚物的AN单元含量, 在反应中后期前者远低于后者.     

Monte carlo simulation of copolymerization by ester interchange reaction in miscible polyester blends

The effects of reaction variables on the degree of randomness in copolymers formed by ester interchange reaction in miscible polyester melt blends were systematically investigated using a Monte Carlo method. Three reaction variables such as the molecular weight difference between two component polymers, the blend ratio, and the reaction ratio of end attack to bond flip, were particularly considered on the cubic lattice model. Ester interchange reactions were assumed to take place during reptational chain motions. It was found that the copolymerization was dependent upon the molecular weight difference and reaction ratio: As the molecular weight difference becomes smaller and when both end attack and bond flip reactions are involved simultaneously, the copolymerization is accelerated. However, the blend ratio does not affect the copolymerization process. This result is discussed in relation to the polymer chain conformation for the ester interchange reaction. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 1637–1645, 1998