聚对苯二甲酸乙醇酯和聚对苯二甲酸丁二醇酯化学扩链反应

综述了用于聚对苯二甲酸乙二醇酯和聚对苯二甲酸丁二醇酯聚对苯二甲酸丁二醇酯化学扩链反应的羧基加成型和羟基加成型扩链剂，以及缩合型扩链反应，羧基加成型扩链反应和羟基加成型扩链反应、羟羟基同时加成型扩链反应。     

双■唑啉化合物偶联聚酯的研究Ⅱ.聚对苯二甲酸乙二酯的偶联反应

用特性粘度（［η］）和羧值为参数，研究了双唑啉化合物（ＢＯＺ）对聚对苯二甲酸乙二酯（ＰＥＴ）的扩链反应动力学过程，表明ＢＯＺ是与ＰＥＴ中羧基反应，考察了不同工艺生产的ＰＥＴ的扩链效果，结果说明达到的［η］极大值取决于原始ＰＥＴ的［η］与羧值之比     

聚对苯二甲酸乙二醇酯切片的固相聚合规律

简要介绍了制备高分子量聚对苯二甲酸乙二醇酯的三种方法,重点介绍了其固相聚合的基本原理及主要副反应规律,固相聚合的各种影响因素,如预聚体原料路线、端羟基和羟基平衡、切片形状和尺寸、催化剂、反应副产物等。最后介绍了聚对苯二甲酸乙二醇酯固相滞反应动力学,如温度、时间对固相聚合反应速度的影响,低温固相聚合反应动力学等。     

双恶唑啉化合物偶联聚酯的研究：II.聚对苯二甲酸乙二酯的偶联反应

用特性粘度（［η］）和羧值为参数，研究了双恶唑啉化合物（ＢＯＺ）对聚对苯二甲酸乙二酯（ＰＥＴ）的扩链反应动力学过程，表明ＢＯＺ是与ＰＥＴ中羧基反应，考察了不同工艺生产的ＰＥＴ的扩链效果，结果说明达到的［η］极大值取决于原始ＰＥＴ的［η］与羧值之比。     

取向态聚对苯二甲酸乙二酯膜热弛豫过程的偏振红外光谱研究

用升温在位偏振红外光谱测量方法，研究了不同取向态的聚对苯二甲酸乙二酯（ＰＥＴ）膜在热弛豫过程中的尺寸变化以及分子链构象和取向的变化．结果说明，ＰＥＴ小尺度取向链段的热弛豫较大尺度取向分子链的热弛豫在较低的温度下发生，取向ＰＥＴ膜的热收缩主要与分子链大尺度取向的弛豫有关，而其后的自发伸长是结晶过程引起的，分子链的取向程度对结晶伸长的幅度有着重要影响．     

聚对苯二甲酸乙二酯的非等温结晶行为

用付里叶变换红外光谱法、示差扫描量热、广角Ｘ 射线衍射和密度法等手段，研究了聚对苯二甲酸乙二酯（ＰＥＴ）的非等温结晶行为．在１１０℃以上，ＰＥＴ的结晶度随温度的升高而增加；在１６０～２３０℃温度区间，ＰＥＴ的结晶度随温度的升高变化不大．但在其后的降温过程中，其结晶度显著增加．从高温缓冷试样的结晶度明显地比淬火试样的高．实验结果有力地支持了高聚物在结晶前链的折叠就已经形成的观点．     

聚对苯二甲酸乙二酯／热致液晶聚合物共混体系中液晶组分的诱导结晶效应

用差示扫描量热法对聚对苯二甲酸乙二酯（ＰＥＴ）／热致液晶高分子（ＬＣＰ）共混体系的等温和非等温结晶行为进行了研究．结果表明，由于液晶组分的加入，共混体系中ＰＥＴ的结晶速率和结晶度均得到提高．说明ＬＣＰ具有ＰＥＴ结晶成核剂的作用．在较低的ＬＣＰ组分含量下（～２ｗｔ％），这一效果最为明显，说明ＬＣＰ是以很小的微区或某些ＬＣＰ分子链介晶微束的形式对ＰＥＴ的结晶起成核剂的作用．     

聚对苯二甲酸乙二酯溶剂诱导结晶研究 Ⅲ．溶剂对聚对苯二甲酸乙二酯玻璃化转变温度的影响

应用动态力学方法测定了聚对苯二甲酸乙二酯ＰＥＴ／溶剂体系的粘弹谱，从实验上证实溶剂对ＰＥＴ进行增塑，使其玻璃化转变温度降低，导致ＰＥＴ在低于通常的结晶温度下结晶，甚至在室温便进行结晶，证明溶剂诱导结晶是由于玻璃化转变温度降低的机理是正确的，可接受的．     

聚对苯二甲酸丁二酯/聚对苯二甲酸乙二酯固态缩聚的研究

研究了聚对苯二甲酸丁二酯（ＰＢＴ）／聚对苯二甲酸乙二酯（ＰＥＴ）共混物的固态缩聚反应，从反应动力学过程的测定结果，表明与纯ＰＥＴ或ＰＢＴ不同，其反应速度较快，并呈超加和的相对分子质量（以特性粘数［η］表征）增长。从反应发生在液相的基本观点出发，说明温度、共混等使液相增多，将加速反应的进行，加上共混物之间的相互缩聚和酯交换，生成嵌段共聚物的结果，导致超加和效应。     

聚对苯二甲酸丁二酯/聚对苯二甲酸乙二酯固态缩聚的研究

研究了聚对苯二甲酸丁二酯(PBT)/聚对苯二甲酸乙二酯(PET)共混物的固态缩聚反应,从反应动力学过程的测定结果,表明与纯PET或PBT不同,其反应速度较快,并呈超加和的相对分子质量(以特性粘数[η]表征)增长。从反应发生在液相的基本观点出发,说明温度、共混等使液相增多,将加速反应的进行,加上共混物之间的相互缩聚和酯交换,生成嵌段共聚物的结果,导致超加和效应。     

Chain extension of polyesters PET and PBT with N,N′-bis (glycidyl ester) pyromellitimides. I

Three N,N′-bis (glycidyl ester imide) of pyromellitic acid (diepoxides) were prepared and were used as chain extenders for poly (ethylene terephthalate) (PET) and poly (butylene terephthalate) (PBT). The typical reaction conditions for the coupling of the polyester macromolecules were heating with the chain extender under argon atmosphere above the melting temperature (280°C for PET and 250°C for PBT) for several minutes. The Characterization of the samples, obtained at variable residence times in the reactor, was based on solution viscosity measurements and carboxyl and hydroxyl end-group determinations. Two of the diepoxides used gave satisfactory results. Starting from a PET having intrinsic viscosity [η] = 0.60 dL/g, and carboxyl content CC = 42 eq/10⁶ g, one could obtain PET with [η] = 1.15 dL/g and CC = 16 eq/10⁶ g within 30 min at 280°C. Analogous results were observed for PBT. The hydroxyl content of polyester in all cases was increased. When the quantity of the chain extender used was higher than that theoretically required for its reaction with all carboxyl end groups of the polyester, this resulted in some gel formation indicative of crosslinking. © 1995 John Wiley & Sons, Inc.     

Effect of Exogenous Carboxyl and Hydroxyl Groups on Pyrolysis Reaction of High Molecular Weight Poly(L-Lactide) under the Catalysis of Tin

The effect of exogenous hydroxyl, carboxyl groups and/or Sn~(2+) on pyrolysis reactions of poly(L-lactide)(PLLA) was investigated by thermogravimetric analysis(TGA). The activation energy(E_a) of pyrolysis reactions was estimated by the Kissinger-Akahira-Sunose method. The kinetic models were also explored by the Malek method, and the random degradation behavior was determined by comparing the plots of ln{-ln[1-(1-w)~(0.5)]} versus 1/T for experimental data from TGA with model reactions. The pyrolysis reaction rate of PLLA was affected slightly by exogenous hydroxyl and carboxyl groups at lower levels of Sn with 65-70 mg·kg~(-1) but increased appreciably in the presence of extraneous Sn~(2+), ―COOH/Sn~(2+), or ―OH/Sn~(2+). The E_a values for the pyrolysis reactions of the PLLAs that provided lactide were different under the catalysis of Sn~(2+) in different chemical environments because Sn~(2+) can form the new Sn-carboxylate and Sn-alkoxide with exogenous carboxyl and hydroxyl groups, which were different in steric hindrance for the formation of activated complex between Sn~(2+) and PLLA. Under the catalysis of Sn~(2+), a lactide molecule can be directly eliminated selectively at a random position of PLLA molecular chains, and the molecular chain of PLLA cannot change two PLLA fragments at the elimination site of lactide. However, it was regenerated into a new PLLA molecule with the molecular weight reduced by 144 g·mol~(-1).     

钯催化合成新型聚合物聚亚胺酮

以二溴化芳香酮和芳香二胺为单体,通过钯催化的胺化缩聚反应合成了新型聚合物——聚亚胺酮,其结构经1HNMR,IR和元素分析确认。     

HDI作为扩链剂合成含PLLA和PBS链段的聚酯氨酯

以数均分子量为6350g/mol端羟基聚L-乳酸(PLLA-OH)与10500g/mol端羟基聚丁二酸丁二酯(PBS-OH)为预聚物,六亚甲基二异氰酸酯(HDI)为扩链剂,通过熔融反应制备了分子量高达30×104g/mol的可完全生物降解聚酯氨酯(PEU).研究了异氰酸根(NCO)与羟基比例对扩链反应的影响.结果表明,当[NCO]/[OH]=1∶1时,扩链效果最好,PEU分子量最大;PEU分子量随着预聚物中PBS含量增大而提高.通过核磁共振谱(1H-NMR)确定了PEU的结构与组成,并对聚酯氨酯进行了凝胶渗透色谱(GPC)、差示扫描量热(DSC)、热重分析(TGA)以及拉伸性能测试.DSC结果显示,扩链后PEU的结晶主要由PBS链段产生,而PLLA链段几乎不结晶;TGA结果表明,PEU的热降解分两步进行,第一步为PEU中PLLA链段的热降解,第二段为其中PBS链段的降解;拉伸测试结果表明,PBS与PLLA的共聚能够制备拉伸强度与断裂伸长率优异的聚合物材料.     

Heat-Resistant Polymer-Grafted Carbon Black: Grafting of Poly(Amide-Imide) Onto Carbon Black

Aromatic poly(amide-imide) with terminal isocyanate groups (PAINCO) was prepared by the polycondensation of trimellitic anhydride and a slight excess of 4,4′-diphenylmethane diisocyanate in N-methyl-2-pyrrolidone (NMP) at 160°C for 20 h. PAI was effectively grafted onto the surface by the reaction of PAI-NCO with carbon black: the percentage of grafting onto FW 200 and Neospectra II was determined to be 41.2 and 39.5%, respectively. When the carboxyl and phenolic hydroxyl groups on carbon black were blocked by treatment with diazomethane, the grafting of PAI-NCO onto the treated carbon black does not proceed. Therefore, it is concluded that PAI-NCO reacts with the carboxyl and phenolic hydroxyl groups on carbon black and PAI is grafted through amide and urethane bonds, respectively. The reaction of PAI-NCO with carbon black was accelerated by the addition of amines as catalyst and by raising of the reaction temperature. Thermogravimetric analysis indicated that PAI-grafted carbon black was stable in air up to about 300°C. The PAI-grafted carbon black was found to give a stable colloidal dispersion in NMP.     

Poly{ [4-（hydroxyl）（tosyloxyl）iodo]styrene} Promoted Halotosyloxylation Reaction of Alkynes

Halotosyloxylation reaction of alkynes with iodine or NBS or NCS was efficiently promoted by the poly { [4-(hydroxyl)(tosoyloxyl)iodo]styrene }.     

Chain extension of polyesters PET and PBT with two new diimidodiepoxides. II

Two new diglycidyl ester compounds containing preformed imide rings for better thermal stability were prepared to be used as chain extenders for PET and PBT. The preparation of these compounds was carried out in two steps. In the first step, diimidodiacids were prepared from pyromellitic anhydride and 3-aminopropanoic acid or 4-(aminomethyl)benzoic acid. From these diimidoacids, in a second step, diimidodiepoxides were obtained by reaction with epichlorohydrin. The aforementioned diimidodiepoxides were used as chain extenders for poly(ethylene terephthalate) (PET) and poly(butylene terephthalate) (PBT) with satisfactory results. The polyester samples obtained from various residence times in the reactor, were characterized by solution viscosity measurements, carboxyl, and hydroxyl end-group determination. Starting from a PET having intrinsic viscosity ([η]) of 0.60 dL/g and carboxyl content (CC) of 42 equiv/10⁶ g, one could obtain PET with [η] of 1.16 and CC below 5 equiv/10⁶ g. The typical reaction condition for the coupling of PET was its heating with the chain extender under argon atmosphere above its melting temperature (280°C) for several minutes. Analogous results were obtained for PBT. The hydroxyl content in all cases was increased. © 1996 John Wiley & Sons, Inc.     

PET/PEN共混物的相容性与酯交换反应

通过用1H-NMR对聚对苯二甲酸乙二酯(PET)与聚2,6-萘甲酸乙二酯(PEN)、PET/PEN共聚物的共混物酯交换反应的研究,测得了反应速率常数、反应活化能和诱导期.根据酯交换反应程度和不同反应温度下的诱导期探讨了酯交换反应与相容性的关系,认为PET与PEN的相容导致或增强了酯交换反应,即相容性是酯交换的必要条件;同时酯交换的发生又促进了PET与PEN的相容.酯交换和相容是聚酯共混物熔融时相互关联的两个过程.     

The thermal degradation of poly(-(d)-β-hydroxybutyric acid): Part 2—Changes in molecular weight

Changes in molecular weight occur in poly(-(d)-β-hydroxybutyric acid) in the temperature range 170–200°C, at which latter temperature evolution of volatile products of degradation becomes significant. Two processes are involved in these changes in molecular weight. The more important is random chain scission at ester groups, which results in the formation of carboxyl and vinyl groups. Although this ultimately results in a drastic reduction in the molecular weight of the polymer, this is delayed in the early stages of the reaction by a condensation reaction between the terminal hydroxyl groups present in the original polymer and the terminal carboxyl groups, which were either originally present or formed in the chain scission process. This delay could have relevance to the industrial processing of this material.     

银离子与聚酰胺-胺型树形高分子配位作用的研究

The complexation between poly(amidoamine) (PAMAM) dendrimers and silver ion was studied in this paper. The results showed that generations and surface groups of dendrimers， reaction time， pH value， mole ratio of Ag⁺/PAMAM dendrimers， as well as reaction temperature strongly influence complexation between Ag⁺ and PAMAM dendrimers. The maximum complexing number of Ag⁺ that amino-， hydroxyl- and carboxylate- terminated PAMAM dendrimers could bind has been obtained. It has been found that the measured value of amino- and hydroxyl- ter-minated PAMAM is almost similar to the theory value， but to carboxylate- terminated PAMAM， there is a dis-crepancy between the measured value and theory value because of the electrostatic interaction between the silver ion and carboxyl group.