含异氰脲酸酯结构聚醚多元醇的合成

以1,3,5-三羟乙基异氰脲酸酯（THEIC）为引发剂、三氟化硼乙醚络合物为催化剂,环氧化合物为环单体,进行了阳离子开环聚合反应的研究。发现THEIC与环氧单体可在非均相体系中平稳地进行阳离子开环聚合反应。在THEIC体系,就链引发而言,环氧氯丙烷的大于环氧丙烷、丁基醚环氧乙烷。调整环单体加料次序就可以获得嵌段共聚醚多元醇。     

异氰脲酸聚醚多元醇的合成

以环氧丙烷（PO）为原料,三（2-羟乙基）异氰脲酸酯（THEIC）为起始剂,采用实验室自制的双金属氰化配合物（DMc）为催化剂,合成具有类似于异氰酸酯三聚结构、本身具有可膨胀阻燃结构的异氰脲酸聚醚多元醇。考察了温度／压力与时间的关系,研究了原料中的水分、聚合温度及催化剂对聚合反应的影响。结果表明：诱导期中温度和压力均随时间的延长而升高;聚合期中压力和温度较为恒定,物料完全反应后釜内压力接近于0;水分在聚合反应体系中的阻聚作用是异常明显的;在温度为135℃,催化剂的质量分数为440×10^-6的条件下,催化剂的催化效率和产率最高,诱导期和反应时间缩短。     

异氰脲酸聚醚酯多元醇的合成及应用研究

采用双金属氰化配位物（DMC）催化三（2-羟乙基）异氰脲酸酯（THEIC）、环氧丙烷（PO）、邻苯二甲酸酐（PA）三元共聚反应,得到一种新型的三元聚合物。用核磁共振谱（1H-NMR）和红外（IR）表征了聚合物结构。并以此聚合物为原料制备了聚氨酯硬质泡沫塑料,研究了泡沫塑料的力学性能、热性能和阻燃特性等。结果表明：PA的引入可以有效提高硬质泡沫塑料的拉伸性能;随着PA与PO的摩尔比增大,泡沫塑料的热分解温度提高,氧指数也有所提高。     

异氰脲酸-苯酐基聚醚酯多元醇的合成及表征

以环氧丙烷（PO）、邻苯二甲酸酐（PA）为原料,三（2-羟乙基）异氰脲酸酯（THEIC）为起始剂,采用实验室自制双金属氰合配合物（DMC）为催化剂,合成具有类似于异氰酸酯三聚结构的异氰脲酸-苯酐聚醚酯多元醇。考察了聚合温度及催化剂的质量分数对聚合反应的影响。结果表明：在温度为135℃,催化剂的质量分数为440×10^-6的条件下,催化剂的催化效率和产率最高,诱导期和反应时间缩短,生产效率提高。通过对异氰脲酸-苯酐聚醚酯多元醇基与聚环氧丙烷聚醚基泡沫材料的氧指数测试,证明了异氰脲酸-苯酐聚醚酯多元醇能使制得聚氨酯泡沫材料的阻燃性提高。     

碳氮杂环型氯化聚醚多元醇的合成研究

以三羟乙基异氰脲酸酯与环氧氯丙烷按阳离子开环聚合成主链上具有碳氮杂环结构的氯化聚醚多元醇。从聚合方法、摩尔比、滴加速度、固液比等相关因素上进行了研究。     

三（2—羟乙基）异氰脲酸酯的合成及应用

本文简要介绍了三（２－羟乙基）异氰脲酸酯的合成方法，应用及在我国的开发利用前景。     

用三羟乙基异氰脲酸酯合成醇酸树脂

介绍了用三羟乙基异氰脲酸酯代替甘油合成油改性醇酸树脂的配方设计、工艺流程。用该树脂制备了清漆及色漆，列出了漆膜的性能指标。     

新型聚醚酯多元醇的研制

利用DMC催化环氧丙烷(PO)、马来酸酐(MA)与CO2三元共聚合成端羟基聚醚酯多元醇,并研究了MA的引入对聚合反应影响规律.实验发现,MA的引入可提高催化剂催化活性,缩短反应时间;适量的MA含量可减少副产物环碳酸酯的生成.另外,MA的引入会使聚合产物黏度明显增加,使得浇注聚氨酯材料时可操作性变差,聚合产物的相对分子质...     

多功能阻燃剂聚醚多元醇亚磷（膦）酸酯的合成

聚氨酯的阻燃防火技术研究与应用一直是人们关注的难题。特别是近年来，中国在加强国防建设，提高军事隐形化技术方面，十分迫切需要高强度、高阻燃性的PU软泡。对PU软泡的阻燃处理，目前一般是采用添加小分子阻燃剂如：甲基膦酸二甲酯     

端羟基聚醚酯多元醇的研制

利用DMC催化PO,邻苯二甲酸酐（PhA）与CO2三元共聚合成端羟基聚醚酯多元醇,并研究了PhA对聚合反应的影响规律。实验发现：PhA的引入可提高催化剂的催化活性,缩短反应时间;适量的PhA可减少副产物环碳酸酯的生成;另外,PhA的引入会使聚合产物的黏度明显增加,使得浇注聚氨酯材料时可操作性变差;聚合产物的相对分子质量分布较PO与CO2共聚物的变窄;合成较高相对分子质量的聚醚酯多元醇时（Mn〉4 000）,PhA的质量不要超过PO质量的15%。     

Synthesis and curing behavior of macrocycle‐terminated poly(aryl ether ketone)s

BACKGROUND: The introduction of poly(ether ether ketone)‐based carbon‐fiber composites accelerated the application of poly(ether ether ketone)s in advanced composite materials. In order to improve the compatibility and processability with reinforced components, polymers with low melt viscosity are preferable. RESULTS: Novel fully aromatic macrocycle‐terminated poly(aryl ether ketone)s (MCPAEKs) were prepared by condensation of macrocyclic aryl ether ketone dimers containing hydroxyphenyl groups and fluorine end‐capped poly(aryl ether ketone) oligomers. Compared with liner poly(aryl ether ketone)s, MCPAEKs showed much lower melt viscosities at low temperature. In the presence of caesium fluoride, the crosslinking reaction of MCPAEKs afforded fully aromatic thermoset poly(aryl ether ketone)s by ring‐opening reaction. CONCLUSION: The MCPAEKs exhibited high thermal stability due to their wholly aromatic structures. After crosslinking, the glass transition temperatures and complex melt viscosities of the polymers were increased greatly. Although there was some residual cesium fluoride or phenoxides produced by ring‐opening reaction, the thermoset poly(aryl ether ketone)s obtained had good thermal stability with temperatures at 5% weight loss above 475 °C. Copyright © 2009 Society of Chemical Industry     

Synthesis of poly(ether amide)s from p‐xylylene glycol and bis(ether nitrile)s

BACKGROUND: Poly(ether amide)s have been well studied in terms of improving the physical and thermal properties of aromatic polyamides. Poly(ether amide)s of high enough molecular weight to be useful for industrial purposes are generally difficult to prepare. The objective of this project was to introduce a simple and commercially feasible process to prepare poly(ether amide)s by a polymerization reaction at relatively low temperature. RESULTS: A series of poly(ether amide)s were prepared by direct polyamidation of p‐xylylene glycol with bis(ether nitrile)s via the Ritter reaction using concentrated H₂SO₄ in acetic acid. The synthesized poly(ether amide)s showed good solubility in polar aprotic solvents. The resultant poly(ether amide)s had inherent viscosities in the range 0.36–1.03 dL g^?1. The glass transition temperatures of the poly(ether amide)s were determined using differential scanning calorimetry to be in the range 190–258 °C. Thermogravimetric analysis data for these polymers indicated the 10% weight loss temperatures to be in the range 290–390 °C in nitrogen atmosphere. CONCLUSION: The Ritter reaction was applied for the synthesis of a variety of poly(ether amide)s with moderate to high molecular weights. This procedure provides a simple polymerization process for the convenient preparation of poly(ether amide)s in high yield at room temperature. Copyright © 2009 Society of Chemical Industry     

Synthesis of unsaturated poly(ether amide)s based on amine‐terminated poly(ethylene glycol)

Novel water‐soluble unsaturated poly(ether amide)s (PEAs) were synthesized by low‐temperature polycondensation of fumaryl chloride and amine‐terminated poly(ethylene glycol) (Jeffamine®). The unsaturated copolymers were further chemically modified with thiols to provide reactive pendant functional groups. Hydrogels based on these copolymers were prepared by copolymerization of the PEA with N‐vinyl pyrrolidone exposure to ultraviolet (UV) irradiation. The resulting hydrogels exhibited a high swelling ratio, and the magnitude of swelling depended on the molecular weight of Jeffamine®. The swelling ratio and equilibrium water content tended to increase with increasing chain length of the Jeffamine® used in copolymer synthesis. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 913–920, 1999     

含氯侧基聚芳醚酮醚酮酮的合成与表征

以α-萘酚为原料，通过和4，4′-二氟二苯酮在N，N-二甲基乙酰胺（DMAC）及K2CO3中的缩合反应制备了一种含萘环的新型芳醚单体4，4′-二（α-萘氧基）二苯酮（DNBP），将其分别与2，5-二氯对苯二甲酰氯（DCTPC）。对苯二甲酰氯（TPC）等芳二酰氯通过在NMP/AlCl3/ClCH2CH2Cl复合溶剂/催化剂体系中的低温溶液进行亲电共缩聚反应，合成了一系列在分子主链芳环上引入侧基氯原子的同时，又在主链中引入刚性萘环结构的新型聚芳醚酮醚酮酮无规共聚物。     

含芴可交联聚芳醚酮的合成

以4,4′-二氟二苯甲酮、双酚芴和二烯丙基双酚A为单体,调整双酚芴和二烯丙基双酚A的摩尔比,通过亲核取代逐步加成反应合成了一系列含芴可交联的聚芳醚酮（PAEK）;用红外光谱仪、核磁共振波谱仪、差示扫描量热仪、热重分析仪对所制备的含芴可交联PAEK的结构、热交联行为、热稳定性等进行了表征。结果表明,所制备的聚合物可通过热引发交联,交联后的聚合物具有优良的耐热性能,交联后聚合物的耐溶剂性能得到提高,最高凝胶含量达到97.5 %。     

Synthesis of polylactide/poly(ethylene glycol) diblock copolymers with functional endgroups

Amphiphilic polylactide/poly(ethylene glycol) (PLA–PEG) diblock copolymers with functional groups at the PEG chain ends were synthesized by coupling PLA and PEG homopolymers using different coupling agents. PLA precursors with different endgroups were synthesized by ring‐opening polymerization of l ‐lactide in the presence of different initiators such as octanol, acetic acid or benzoic acid, or water, using non‐toxic zinc lactate as catalyst. The mechanism of the ring‐opening polymerization of lactide initiated by carboxyl groups was investigated and discussed in comparison with the literature. N,N'‐carbonyldiimidazole was used to couple the two hydroxyl groups of PLA and PEG, using 4‐dimethylaminopyridine (DMAP) as catalyst. Dicyclohexylcarbodiimide (DCC) and DMAP were adopted to couple the carboxyl group and the hydroxyl group of PLA and PEG, respectively, while DCC and N‐hydroxysuccinimide were used to connect PLA and PEG by coupling their carboxyl and amine groups. Comparison of different coupling routes shows that the DCC/DMAP one exhibits the highest efficiency. A common tumor targeting ligand, folic acid, was attached to PLA–PEG with hydroxyl endgroups using the DCC/DMAP route. The resulting PLA–PEG copolymers bearing folic acid present great interest for targeted delivery of anti‐cancer drugs. © 2012 Society of Chemical Industry     

含三氟甲基聚芳醚酮的合成与表征

以六氟双酚A和4,4′–二氟二苯酮为原料,以N–甲基吡咯烷酮为溶剂采用新的合成工艺合成含三氟甲基聚芳醚酮,采用傅里叶变换红外光谱、核磁共振波谱及X射线衍射等对聚合物的结构和性能进行分析和表征。结果表明,采用新工艺合成的聚芳醚酮与传统工艺合成的树脂的热性能基本一致,具有良好的耐热性能,其玻璃化转变温度为162.6℃,氮气中5%热失重温度为517.1℃;80 kHz下含三氟甲基聚芳醚酮的介电常数为1.55,具有良好的电绝缘性;室温下能溶解于N–甲基吡咯烷酮、氯仿、四氢呋喃等有机溶剂。     

聚(芳基醚1,3,4-噁二唑)类聚合物的磺化及表征

为了探索影响芳香族聚噁二唑的磺化反应的因素,分别以发烟硫酸和氯磺酸为磺化试剂对几种含醚键聚芳噁二唑(PEODs)进行磺化,研究了以氯磺酸为磺化试剂时磺化反应时间、用量对磺化反应的影响,并分析了PEODs用于质子交换膜的潜在应用.磺化产物的结构与性能通过傅里叶红外(FT-IR)、氢谱(1H-NMR)、离子交换当量、热重分析(TGA)和溶解性等测试进行了表征.结果表明:发烟硫酸磺化产物磺化度不可控制,磺化度较氯磺酸的磺化产物高;采用氯磺酸磺化时,磺化时间对磺化反应没有影响,氯磺酸用量仅对侧苯基双酚A型聚噁二唑有影响;邻叔丁基型聚噁二唑的氯磺酸磺化产物有用于质子交换膜的潜力.     

新型含偶氮结构聚芳醚砜醚酮酮的合成与表征

在无水AlCl3及N-甲基吡咯烷酮(NMP)/1,2-二氯乙烷(DCE)复合溶剂的存在下,将含砜基芳二醚类单体与含偶氮苯结构芳二甲酰氯进行低温付-克缩聚反应,合成了一类新型含偶氮结构聚芳醚砜醚酮酮树脂。用IR、TG、WAXD及元素分析等技术进行了结构表征和性能测试。结果表明:所合成的聚合物树脂具有预期结构且为非晶态聚合物;在N2气氛中质量损失5%的温度(Td)分别为445～463℃;聚合物除了能在浓硫酸、CF3COOH/CHCl3等强极性质子型溶剂中溶解外,还能溶解于N-甲基吡咯烷酮(NMP)、N,N-二甲基甲酰胺(DMF)、二甲基亚砜(DMSO)等强极性非质子型溶剂中,也能在普通溶剂,如氯仿(CHCl3)、1,2-二氯乙烷(DCE)、四氢呋喃(THF)等中溶解。     

耐高温新型含杂萘联苯聚醚砜嵌段共聚物的性能

将氯端基聚醚醚砜齐聚物和杂萘联苯类双酚羟端基齐聚物通过溶液缩聚,成功地合成了一系列新型聚醚醚砜-聚醚砜(PEES-PPES)嵌段共聚物,并用IR、DSC、TGA、X-WAXD等测试手段对聚合物进行了表征。结果表明:PEES-PPES具有较高的热稳定性,较好的溶剂溶解性;砜基比例的变化对PEES-PPES的热性能有较大的影响,表明砜基对杂萘联苯聚醚砜改性效果明显。