Studies on photocrosslinkable-cum-flame retardant poly(benzylidene phosphoramide ester)s

Four series of photocrosslinkable-cum-flame retardant poly(benzylidene phosphoramide ester)s were synthesized from bis(4-hydroxy-3-methyoxybenzylidene) acetone, 2,5-bis(4-hydroxy-3-methoxybenzylidene)cyclopentanone, 2,6-bis(4-hydroxy-3- methoxybenzylidene)cyclohexanone and 2,7-bis(4-hydroxy-3-methoxybenzylidene) cycloheptanone with various arylphosphorodichloridates by interfacial polycondensation using a phase transfer catalyst. The resultant polymers were characterized by gpc, FTIR, ¹H, ¹³C and ³¹P-NMR spectroscopy. Thermal behavior of the polymers was evaluated by differential scanning calorimetry and thermogravimetry. Flame retardant properties were ascertained by Limiting Oxygen Index. The photocrosslinking ability of the polymers was studied by ultraviolet spectroscopy. The crosslinking proceeds via 2π + 2π cycloaddition reaction of the benzylidene groups. The rate of crosslinking decreases with increase in the size of cycloalkanone ring, while the thermal stability increases with increase in the size of the alkanone ring. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 3285–3291, 1999     

New rigid-rod poly(benzoxazole-imide)s containing chloro-substituted p-phenylene units in the main chain

A series of new poly(o-hydroxy amide-imide)s with high molecular weights were synthesized by low-temperature solution polycondensation from a preformed imide ring and chloro- or dichloro-substituted p-phenylene-containing diacid chlorides of 2,5-bis(trimellitimido)chlorobenzene or 1,4-bis(trimellitimido)-2,5-dichlorobenzene and three bis(o-amino phenol)s. All the poly(o-hydroxy amide-imide)s were readily soluble in a variety of organic solvents such as N-methyl-2-pyrrolidone and N,N-dimethylacetamide. Transparent and flexible films of these polymers were cast from their solutions. The cast films had tensile strengths ranging from 88 to 102 MPa and elongations at break of 8–12%. Subsequent thermal cyclodehydration of the poly(o-hydroxy amide-imide)s afforded novel poly(benzoxazole-imide)s. The poly(benzoxazole-imide)s exhibited glass-transition temperatures in the range of 310–338 °C and were stable up to 500 °C in nitrogen, with 10% weight-loss temperatures recorded between 550 and 570 °C in nitrogen. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 4151–4158, 1999     

蜜蜂外激素9－ODA和9－HDA的合成

６－溴－２－己酮在Ｌｉ２ｃｕＣｌ４催化下与γ－溴代巴豆酸甲酯进行格氏偶联，合成了蜂王物质９－羰基－（Ｅ）－２－癸烯酸（９－ＯＤＡ），将其还原得到另一蜂王物质９－羟基－（Ｅ）－２－癸烯酸（９－ＨＤＡ）。该法是合成９－ＯＤＡ和９－ＨＤＡ的新路线。     

1－N－（苯并咪唑－1－乙酰基）－4－苯基－3－氨基硫脲金属配合物的合成及结构表征

合成了新配体１－Ｎ－（苯并咪唑－１－乙酰基）－４－苯基－３－氨基硫脲（ＢＰＭＳ），将其与Ｍｎ（Ⅱ）、Ｃｏ（Ⅱ）、Ｎｉ（Ⅱ）、Ｃｕ（Ⅱ）、Ｃｄ（Ⅱ）、Ｚｎ（Ⅱ）、ＵＯ２（Ⅱ）等金属的醋酸盐反应，合成了７个新配合物。所有化合物均经元素分析、ＩＲ、１ＨＮＭＲ和热重分析等表征。红外光谱表明，配体以四齿方式通过烯醇式羰基氧原子、烯醇式硫羰基硫原子以及Ｃ＝Ｎ１和Ｃ＝Ｎ２的氮原子与金属配位     

二茂钛苄氧基衍生物的合成及性质研究

Ｃｐ２ＴｉＣｌ２及（ＭｅＣｐ）２ＴｉＣｌ２在Ｅｔ３Ｎ或ＮａＮＨ２存在下与苄醇类化合物反应，高产率地合成了６个未见文献报道的二茂钛（Ⅳ）苄氧基衍生物，甲基二茂钛（Ⅳ）苄氧基化合物，经元素分析，ＨＮＭＲ和ＩＲ光谱确定了化合物的结构，并对其部分性质进行了讨论。     

芳香聚醚酮酮晶体结构及其晶型变化的研究（Ⅰ）

利用Ｘ射线及热分析技术研究了聚醚酮酮（ＰＥＫＫ）的溶剂诱导结晶及从玻璃态结晶和从熔融态结晶的行为。发现ＰＥＫＫ有两种晶型结构（Ⅰ和Ⅱ），晶型Ⅱ的形成与热历史和溶剂诱导有关，其熔点始终低于Ⅰ型１０℃左右。ＰＥＫＫ的低温熔融峰与其分子链极化有关，而与热历史无关，此低温熔融峰热焓占总热焓２％～１０％，其平衡熔点为４０９℃。     

含间苯基聚芳醚酮的合成与性能研究

含间苯基聚芳醚酮的合成与性能研究林权，张万金，吴忠文，尹玖梅（吉林大学化学系，长春，１３００２１）（中国科学院长春应用化学研究所）关键词聚芳醚酮，间苯基，熔点，结晶度聚芳醚酮作为一类耐高温特种工程塑料，由于具有优异的热、电、机械性能，已被广泛应用于电...     

Synthesis and characterization of a family of biodegradable poly(ester amide)s derived from glycine

A series of aliphatic poly(ester amide)s derived from 1,6-hexanediol, glycine, and diacids with a variable number of methylenes (from 2 to 8) have been synthesized and characterized. Infrared spectroscopy shows that the studied polymers present a unique kind of hydrogen bond that is established between their amide groups. Thermal properties as melting, glass transition, and decomposition temperatures are reported. The data indicate that all the polymers are highly crystalline. Thus, different kinds of spherulites (positive and/or negative) were obtained depending on the preparation conditions and on the polymer samples. Moreover, all the polymers crystallized from dilute diol solutions as ribbonlike crystals where a regular folding habit and a single hydrogen bond direction could be deduced. A test of enzymatic hydrolysis was employed to assess the potential biodegradability of these polymers. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 1271–1282, 1998     

Comparative study of the thermal properties of related aromatic polyhydrazides and poly(1,3,4-oxadiazole)s

Studies were undertaken to ascertain the thermal behavior of several new types of aromatic polyhydrazides and poly(1,3,4-oxadiazole)s containing different functional groups. Results of thermal analysis investigations indicate that all the polyoxadiazoles are remarkably heat-resistant when heated in nitrogen at elevated temperature but somewhat less heat-resistant than fully aromatic polyoxadiazoles. Most of the new polyoxadiazoles decompose when heated to about 450°C. The incorporation of tetraphenyl silane, hexafluoroisopropylidene, phthalido or phenoxytherephthalic groups into the main chain decrease the glass transition temperature of aromatic poly(1,3,4-oxadiazole)s. In the case of the silicon-containing polymers the glass transition temperature is independent of the other groups incorporated in the same macromolecule. The cyclization process of all investigated polyhydrazides takes place in the range between 320 and 390°C.     

含氰基侧基聚芳醚砜的合成与表征

汉２，６－二卤苯甲腈、４，４′－二氯二苯砜、４，４′－二羟基二苯砜、间苯二酚、对苯二酚、酚酞及双酚Ａ为主要原料，合成了含不同结构单元和不同氰基含量的含氰基侧基的聚芳醚砜，并采用ＩＲ、＾１３ＣＮＭＲ等分析手段对其结构进行了表征，同时研究了结构单元和氰基含量对聚芳醚砜性能的影响。