Synthesis and characterization of antiseptic-based poly(anhydride-esters)

Summary Poly(anhydride-esters) were prepared from catechol, fenticlor and hexachlorophene. The molecular weights (M_w) of the polymers were typically >10,000 Da with glass transition temperatures (T_g) ranging from 23 to 84 °C. The thermal characteristics of the polymers paralleled the melting temperatures of the chemically incorporated antiseptic molecules. The in vitro release of the chemically incorporated antiseptic molecules were monitored over a 12 week period. For comparison, the in vitro release of physically admixed antiseptic molecules were also observed. After 12 weeks, the polymers were not completely degraded with drug release ranging from less than 1 to 55%. Sessile-drop contact angles indicated that the polymers were relatively hydrophobic, contributing to the slow polymer degradation rates.     

聚氨基三硝基苯撑的合成

以聚三硝基苯撑(PNP)为原料．合成了聚氨基三硝基苯撑(PATNP)。利用FTIR,DTA对其结构和性能进行了分析。PATNP的热稳定性要好于PNP。撞击感度比PNP低。是一种很有发展前景的热稳定性炸药。     

丙烯酰氧乙基三甲基氯化铵-丙烯酰胺共聚物的制备研究

以丙烯酰氧乙基三甲基氯化铵(DAC)和丙烯酰胺(AM)为单体,过硫酸铵和亚硫酸氢钠为引发剂,采用水溶液聚合合成阳离子高分子聚合物P(DAC-AM)。讨论了单体质量比、引发剂用量、温度等因素对聚合反应的影响,得到了合适的制备参数:反应温度55℃,引发剂0.035g,单体质量比m(AM):m(DAC)=3:14;并对产物进行了红外光谱和热失重分析,确定了聚合物为P(DAC-AM),热分解温度为230℃。     

聚戊二酸丙二醇酯的合成

合成了聚戊二酸丙二醇酯,其原料采用奇数碳原子的1,5-戊二酸和1,3-丙二醇。以钛酸四丁酯为催化剂,采用直接酯化、熔融缩聚工艺合成聚戊二酸丙二醇酯,经一系列配方试验,得到的最佳合成条件是:酯化反应不加催化剂,原料配比(mol)为戊二酸:丙二醇=1∶1.1;缩聚反应温度为250℃,催化剂用量占戊二酸质量1%,缩聚反应时间最短,为90 min,特性黏度可达到1.136 dL/g。实验采用水浴出料,产物经冷凝后得到固体丝条,再经切粒机造粒后得到固体颗粒。经红外测试,得到的合成产物为预期产物PPG。     

聚乙烯吡啶树脂的合成研究

聚乙烯吡啶树脂悬浮聚合中比表面积随交联度增加而增加,使用良溶剂较不良溶剂作为致孔剂,使树脂的表面积增加约１０％～３０％。在０５％的羟丙基甲基纤维素溶液中,加入７％ＮａＮＯ２盐析剂,以高于乙烯吡啶起始聚合温度（２ 乙烯吡啶＞６５℃;３ 乙烯吡啶＞８０℃;４ 乙烯吡啶＞７５℃）的温度,合成了交联度５％～４０％的聚乙烯吡啶系列树脂,对乙烯吡啶而言,产率＞９６％,产品粒度均匀,其中３０～６０目者可达８０％以上。     

Synthesis and Characterization of Poly(ethylene glycol) grafted Poly(ε-Caprolactone)

Summary A new graft copolymer, poly(ε-caprolactone) (PCL) grafted with poly(ethylene glycol) (PEG), was prepared by one-pot synthesis of ε-caprolactone and modified PEG. Aluminium isopropoxide or potassium tert-butoxide was used as a catalyst for the ring-opening polymerization. Polymerization using potassium tert-butoxide as a catalyst showed very effective graft reaction of PEG onto poly(ε-caprolactone). A slight decrease in the melting temperature was observed with the increase of the PEG graft frequency. Interestingly, considerable changes were observed on the surface property by the introducing PEG side chains compared to that of PCL homopolymer. Measurements of water contact angle showed that the hydrophilic surface of the polymer could be obtained even at a low graft frequency of PEG.     

Cryochemical Synthesis of Mn-Containing Poly(p-Xylylene)

A Mn-containing polymer was produced by solid-state photopolymerization of a cocondensated mixture of p-xylylene with Mn at 80 K. It was shown that during simultaneous deposition p-xylylene and Mn formed both σ- and π-complexes. Irradiation of the system by UV light resulted in polymerization of p-xylylene with the destruction of the unstable π-complexes, while the σ-bonded compounds were incorporated into the polymer chains. Complexes of Mn with benzyl-type radicals of the polymerized system were also observed. Prolonged storage of the polymerized material at ambient temperature under vacuum led to the gradual decomposition of the organomanganese compounds and complexes.     

聚间苯二甲酰间苯二胺树脂的合成研究

以间苯二胺为原料,在溶剂N,N-二甲基乙酰胺中与间苯二甲酰氯反应,聚合成间苯二甲酰间苯二胺树脂。通过在微通道反应器中进行聚合反应时,反应物配比有效控制在1.005~1.000,反应温度0~10℃,溶剂水份300×10~(-6)g/g以下,两种单体进料速率5∶4~5∶3,此条件下,聚合物粘度1.9~2.1,分子量分布稳定。     

聚d,l-乳酸的合成

本文分别以氧化锌、氯化亚锡和辛酸亚锡为催化剂，采用两部法合成了聚d,l-乳酸。用化学滴定法和粘度法测定了产物相对分子质量，并以红外光谱和DSC对产物进行了表征。结果表明所得到为无定形聚乳酸，Tg为53．3℃。     

聚N-乙烯基甲酰胺的合成与表征

以K2S2O8为引发剂由N-乙烯基甲酰胺(NVF)合成了聚N-乙烯基甲酰胺,并用红外光谱仪和X-射线光电子能谱仪对产物进行了表征。结果表明NVF的质量分数和反应温度对单体转化率和聚合物特性黏度的影响较大,在70℃时NVF的最佳单体质量分数为20%,NVF的转化率随温度的升高而增大,在80℃时单体的转化率可达到90%以上。     

聚乙烯己内酰胺的制备与表征

以乙烯己内酰胺单体(VCL)为原料,偶氮二异丁腈(AIBN)为引发剂,在水溶液中通过自由基聚合合成了聚乙烯己内酰胺. 考察了引发剂用量、溶剂用量、聚合反应时间和聚合反应温度对产物分子量和产率的影响,阐述了水溶液中自由基聚合的反应机理. 在VCL:AIBN:H2O=1:0.05:15(质量比),75℃下反应5 h的优化工艺条件下,产率能达到97%,并通过凝胶渗透色谱仪测定了聚合物的平均分子量. 以红外光谱和核磁共振对产品结构进行了表征,用分光光度计测定其临界溶解温度为32℃.     

聚对苯二甲酰对苯二胺的合成方法

分别介绍了聚对苯二甲酰对苯二胺的应用及界面缩聚法、酯交换法、气相聚合法、低温溶液缩聚法、直接缩聚法等几种合成方法的优缺点,分析了国内外聚对苯二甲酰对苯二胺的发展趋势。     

含醚间位芳香族聚酰胺共聚物的制备与表征

通过在芳香族聚酰胺化合物中引入4,4'-二氨基二苯醚制备含醚间位芳香族聚酰胺(PMIA)共聚物,并对其相关性能进行了检测。试验结果表明:通过反应成功将4,4'-二氨基二苯醚引入了共聚物,含醚PMIA共聚物溶液的表观黏度随剪切速率的升高而降低;制备的含醚PMIA共聚物起始分解温度低于PMIA;随着4,4'-二氨基二苯醚加入量的增加,含醚PMIA共聚物成纤能力降低;纤维断裂强度以及弹性模量降低,断裂伸长率升高,耐热持久性下降。     

聚己二酸-1,2-环己二醇酯的合成

聚酯多元醇是合成聚氨酯的主要原料,该文对1,2-环己二醇的衍生物聚己二酸-1,2-环己二醇酯的合成进行了较为详细的研究。考察了醇酸摩尔比、反应温度、反应升温方式、反应时间、减压时间、催化剂的用量和稳定剂的用量等因素对所合成的聚酯多元醇的酸值、羟值、相对分子质量和反应程度的影响。采用单因素优选法对合成工艺条件进行了优化,得到了合成聚己二酸-1,2-环己二醇酯的较佳工艺条件:缩聚反应温度180℃,反应时间3 h,n(1,2-环己二醇)∶n(己二酸)=1.6∶1,催化剂的用量为己二酸投料质量的0.8%,稳定剂用量为己二酸投料质量的0.3%。在此条件下合成出的聚己二酸-1,2-环己二醇酯为淡黄色、透明黏稠液体,酸值<9.3 mg/g,羟值50~70 mg/g,相对分子质量1 000~2 000。     

乙酰乙酰化聚乙烯醇的合成

通过酯交换反应将乙酰乙酰基引入聚乙烯醇(PVA),并采用红外光谱对产物进行了表征。重点讨论了反应温度、反应时间、乙酰乙酸酯用量等因素对酯交换反应的影响。试验发现:随乙酰乙酸酯用量的增加,乙酰乙酰化程度逐渐增大;随反应温度的升高,乙酰乙酰化程度先逐渐提高,后趋于稳定;随反应时间的延长,乙酰乙酰化程度提高,2.5h后趋于平衡。     

Synthesis and Thermal Characterization of Novel Poly(tetramethylsilanthrylenesiloxane) and Poly(tetramethylsilphenanthrylenesiloxane) Derivatives

Summary Novel poly(tetramethylsilarylenesiloxane) derivatives, i.e. poly(tetramethyl-2,6-silanthrylenesiloxane) (P1), poly(tetramethyl-9,10-silanthrylenesiloxane) (P2), and poly(tetramethyl-1,8-silphenanthrylenesiloxane) (P3), were synthesized by polycondensation of novel disilanol monomers, i.e. 2,6-bis(dimethylhydroxysilyl)-anthracene (M1), 9,10-bis(dimethylhydroxysilyl)anthracene (M2), and 1,8-bis(dimethylhydroxysilyl)phenanthrene (M3), respectively. P1 and P3 were soluble in common organic solvents, such as benzene, toluene, chloroform, dichloromethane, tetrahydrofuran, etc. whereas P2 was almost insoluble in common organic solvents. It was revealed that P1 and P3 were amorphous and that P2 exhibited the crystallinity, as deduced from differential scanning calorimetry (DSC) and X-ray diffraction measurements. The glass transition temperatures (T_g’s) of P1 (118 °C) and P3 (100 °C) were much higher than that of poly(tetramethyl-1,4-silphenylenesiloxane). The temperature at 5% weight loss (T_d5) of P3 was 500 °C, which was higher than those of P1 and P2, and comparable to that of poly(tetramethyl-1,4-silphenylenesiloxane). It would be speculated that the thermostability of the series of poly(tetramethyl-silarylenesiloxane) derivatives is dependent on the stability of arylene moieties incorporated.     

聚氧化苯乙烯的合成与表征

以丙酮为溶剂,采用不同引发剂BF3、H2SO4、KOH引发氧化苯乙烯聚合。结果表明,3种引发剂的聚氧化苯乙烯产率均较高,其中BF3作引发剂聚合条件要求最低,所得聚合产物的颜色略浅、粘度较大;丙酮用量增加,聚氧化苯乙烯产率降低、颜色变浅、粘度变小。NMR表征聚合产物结构具有多分散性。     

絮凝剂聚二甲基二烯丙基氯化铵的合成

二甲基二烯丙基氯化铵(DMDAAC)水溶液在过硫酸胺与亚硫酸氧钠组成的氧化还原引发体系中引发聚合.研究了不同引发剂及助剂作用下的聚合工艺条件,用印染废水验证聚合物的絮凝效果.数据表明:引发剂加入量以3 mg/L为佳;加入助剂能提高聚合产物分子量,添加量为0.35mg/L.聚合反应时间约6h;反应温度约60℃.聚合产物PDMDAAC在印染废水的絮凝实验中的最佳用量范围在35～45mg/L之间.     

聚亚苯基砜的合成与表征

以环丁砜为溶剂,用4,4'-二氯二苯砜和4,4'-联苯二酚为单体,无水碳酸钾为成盐剂,甲苯为脱水剂,采用"成盐"和"缩聚"两步反应合成出了我国长期依赖进口的特种工程塑料聚亚苯基砜(PPSU),并对产物进行了纯化。对比分析和测试了自制样品和美国Solvay公司产的PPSU样品的比浓对数黏度,C、H和K元素含量,核磁共振氢谱,傅里叶变换红外光谱,激光拉曼光谱,玻璃化转变温度和热分解温度。结果表明它们具有相同的化学结构、相近的分子量和纯度,自制PPSU的玻璃化转变温度比Solvay公司产的高约5℃,热稳定性相差不大。