Synthesis and Characterization of Novel Colored Polyurethanes

ABSTRACT

Azo disperse dyes containing N, N-diethylol group have been prepared and each dye was polycondensed with 4,4′ -Diphenyl methane diisocyanate. The resultant colored polyurethanes were characterized by nitrogen content, IR spectral studies, number average molecular weight ([Mbar]n), estimated by conductometric titration, and thermogravimetry. The electrical conductivity of all the polyurethanes was measured at room temperature.     

Synthesis,Characterization, and Glass Reinforcement of Poly(Amido-Imide)s-Part-3

Poly(amido-imide)s (PAI) were prepared by the intermolecular Diels-Alder (DA) reaction of 1,1-(sulfonyldi-4,1-phenylene) bis[(2-furanyl methylamino) acetamide] (SPBFA) with various bis(maleimide)s. The DA reaction was carried out in tetrahydrofuran as a solvent, as well as in bulk, followed by aromatization of sodium acetate intermediates in the presence of acetic anhydride. All the polymers were characterized by elemental analysis, infrared (IR) spectral studies, and thermogravimetry. The PAI exhibit moderate thermal stability. The SPBFA and bis(maleimide)s were polymerized (at 145±10°C) by in situ DA intermolecular reaction into moderately thermally stable PAI-glass fiber composite laminates and were characterized by their chemical resistance and mechanical properties.     

Synthesis,Characterization and Glass Reinforcement of Poly(Ester Amido Imide)s

Poly(ester amido imide)s (PEAI)s (IIIa–e) were prepared by the intermolecular Diels-Alder (DA) reaction of bismaleimide (II) having epoxy resin segment with various bisfurans (Ia–e) having amide bridge. The DA reaction was carried out with tetrahydrofuran as a solvent, as well as in bulk, followed by aromatization of DA polyadduct intermediates in the presence of acetic anhydride. All the resultant polymers, designated as poly(ester amido imide)s (PEAI)s, were characterized by elemental analysis, number average molecular weight, IR spectral studies and thermogravimetry. The PEAIs exhibit good thermal stability. Bismaleimide (II) and bisfurans (Ia–e) were polymerized (at 150 ± 10°C) by in situ DA intermolecular reaction into moderately thermally stable PEAIs. The glass fiber-reinforced composites (i.e., laminates) of all PEAIs were prepared and characterized by their chemical resistance and mechanical properties.     

Synthesis,Characterization and Properties of New Semifluorinated Poly(arylene ether phosphine oxide)s

Bis(4‐fluoro‐3‐trifluoromethylphenyl)phenylphosphine oxide is synthesized and six new poly(arylene ether)s are prepared by nucleophilic displacement of the fluorine atom on the benzene ring by several diphenols under basic conditions. The products show very high glass transition temperatures of up to 252 °C and very good thermal stabilities of up to 490 °C for 5% weight loss. The polymers display very low heat release rates in the microscale combustion calorimeter test, suggesting good flame retardance. All polymers are soluble in a wide range of organic solvents. Transparent thin films cast from dichloromethane exhibit tensile strengths up to 54 MPa, a modulus of elasticity up to 0.97 GPa and elongation at break up to 47% depending on their exact repeating unit structures.

     

低分子量聚N-乙烯基甲酰胺-co-乙烯胺的合成

以N-乙烯基甲酰胺为单体,N,N-二甲基甲酰胺和乙酸乙酯为混合溶剂,偶氮二异丁腈为引发剂,十二硫醇为链转移剂,通过沉淀聚合法制备了低分子量的聚N-乙烯基甲酰胺。详细研究了单体质量分数、混合溶剂配比、引发剂用量、链转移剂用量、反应温度及反应时间对聚合反应的影响。在最佳聚合条件下,聚合物收率可达93.1%、聚合物的数均分子量(Mn)为2 975.2,PDI=2.64,且聚合残液可循环利用。然后将所得聚合物在酸性条件下水解,制备了不同胺化度的聚N-乙烯基甲酰胺-co-乙烯胺,产品的数均分子量为1 000~1 400,PDI为1.34~1.40。     

New Thermally Stable Poly(Ester-Imide)s Containing Phenoxymethyl Moieties as Flexible Groups in the Main Chain: Synthesis and Characterization

Several new poly(ester-imide)s were prepared by direct polycondensation reaction of 1,1-bis[4-(trimellitimido)phenoxy]methane 6 with various aromatic diols 7a-f in a system of tosyl chloride (TsCl), pyridine (Py), and N,N-dimethylformamide (DMF). The reactions with TsCl were significantly promoted by controlling alcoholysis with diols, in the presence of catalytic amounts of DMF, to give a series of poly(ester-imide)s. The resulted polymers were characterized by FTIR and ¹H-NMR spectroscopy. Also, thermal properties of the PEIs 8a-f were investigated using thermal gravimetric analysis (TGA) and differential scanning calorimetry (DSC).     

Synthesis and spectral,thermal, and photocrosslinking studies of poly(benzylidene phosphoramide ester)s

A new class of poly(benzylidene phosphoramide ester)s containing a photoreactive benzylidene chromophore in the main chain were synthesized from bis(4-hydroxy-3-methoxy benzylidene) acetone with various substituted N-aryl phosphoramidic dichlorides by an interfacial polycondensation technique. The synthesized polymers were characterized by inherent viscosity, IR, and ¹H-, ¹³C-, and ³¹P-NMR spectroscopy. The molecular weights of these polymers were determined by gel permeation chromatography. These polymers were studied for their thermal stability and photochemical properties. Thermal properties were evaluated by thermogravimetric analysis and differential scanning calorimetry. It was found that halogen-containing polymers show a higher thermal stability than that of nonhalogenated polymers. The photocrosslinking property of these polymers was studied by ultraviolet spectroscopy. The photoreactive benzylidene chromophore in the main chain dimerizes via 2π + 2π cycloaddition reaction to form a cyclobutane derivative and leads to crosslinking. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 65: 2151–2157, 1997     

聚（癸二酸-1,3-丙二醇）酯低聚物的合成与表征

在无催化剂、相对较低温度下合成了聚(癸二酸-1,3-丙二醇)酯低聚物。GPC色谱显示,过量1,3-丙二醇常使粗产物呈现多组分,但随其用量减少,粗产物逐渐变均一。FTIR光谱表明,低聚物主链为酯键结构,且羟基含量随单体摩尔比降低及第二阶段反应进行而趋于减小。1H NMR分析发现,低聚物实际摩尔组成远低于初始单体摩尔比;低聚物摩尔质量为967.14～3970.49g/mol,1,3-丙二醇封端度为38%～66%。该低聚物期望在口香糖制备中用作无毒、环境友好、可生物降解型增塑剂。     

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.     

低代数聚丙烯亚胺树形分子的合成与表征

对聚丙烯亚胺树形分子的合成进行了研究。通过优化反应条件 ,如提高反应温度、增大反应物浓度、加入少量醋酸作为催化剂、选择氨 甲醇作为还原溶剂 ,提出了一条合成结构较为精确 ,可以最大程度减少或避免副反应的聚丙烯亚胺树形分子的合成路线。红外光谱表明优化条件下所得 0 5代聚丙烯亚胺树形分子反应完全 ,有利于结构增长 ;滴定法表明在氨 甲醇溶剂下还原所得 1 0代聚丙烯亚胺树形分子中伯胺基的摩尔分数为x (NH2 ) =85 % ,比在甲醇条件下所得结果 [x(NH2 ) =76 % ]有较大提高。1H核磁共振、元素分析也表明所合成的低代数聚丙烯亚胺树形分子结构精确 ,达到了分子设计的目的。     

聚氧乙烯链封端的聚酰胺-胺树状聚合物的合成与表征

采用酰氯法,用丙烯酰氯和不同相对分子质量的聚乙二醇为原料,制备出一系列具有丙烯酰端基的聚氧乙烯大单体(PEO-A)。实验证明,较佳的原料摩尔比n(PEG)∶n(CH2CHCOCl)∶n〔(CH3CH2)3N〕=2∶1∶1。然后以聚氧乙烯大单体为端基改性剂,在氮气保护下50℃四氢呋喃溶液中分别与G1.0～G4.0聚酰胺-胺树状聚合物进行Michael加成反应96h,合成出了聚氧乙烯(PEO)链封端的非离子型聚酰胺-胺树状聚合物,并用傅立叶变换红外光谱(FTIR)、核磁共振波谱(1HNMR,13CNMR)对其组成和结构进行了表征。     

新型含氰侧基聚芳醚酰胺的合成及表征

在DMAC为溶剂,叔胺为HCl吸收剂的条件下,将间苯二胺与自制的2,6-二(4-氯甲酰苯氧基)苯甲腈进行低温缩聚反应,合成得到了新型含氰侧基聚芳醚酰胺(C-PEAMI)。用IR、TG等方法对其结构和性能进行了表征。     

Synthesis,Characterization and Material Application of Poly(Urea-Imide)s,Part 1

Poly(urea-imide)s (PUIs) were prepared by Diels-Alder (DA) intermolecular polymerization of hexamethylenebis(2-furanmethylurea) (BFU) (1) with various bismaleimides (2a-f). The DA reaction was carried out using 1,4-dioxane as solvent, as well as in bulk, followed by aromatization (dehydration) of poly(tetrahydro phthalimide) intermediates (3a-f) in the presence of acetic anhydride. All the PUIs (3a-f, 4a-f and 5a-f) were characterized by elemental analysis, IR spectral studies and thermogravimetrically. BFU (1) and bismaleimides (2a-f) were polymerized (at 145 ± 10°C) by in situ DA intermolecular reaction into moderately thermally stable PUIs (5a-f), glass fiber and carbon fiber composites without evolution of any byproducts. The prepared composites were characterized by chemical resistance and mechanical properties.     

Synthesis,Characterization and Properties of Novel Poly(urethane‐imide) Networks as Electrical Insulators with Improved Thermal Stability

Summary: A new series of thermoplastic poly(urethane‐imide)s (TPUI1‐4) containing hydroxyl groups in the backbone was synthesized from the reaction of epoxy‐terminated polyurethane prepolymers (EPU1‐4) and an imide containing diacid (DIDA) chain extender under optimized reaction conditions. EPU1‐4 was prepared through end‐functionalization of NCO‐terminated polyurethanes based on polyester polyol (CAPA) and hexamethylene diisocyanate with glycidol. A blocked isocyanate (BIC) was made from the reaction of trimethylol propane (TMP), toluene diisocyanate (TDI) and N‐methylaniline (NMA). Polymer networks were prepared from the reaction of librated isocyanate groups of BIC with hydroxyl groups of TPUIs. The starting materials and polymers were characterized by conventional spectroscopic methods and the physical, thermal and electrical properties of crosslinked networks were studied. Investigation of the recorded properties for these samples showed considerable improvement in thermal and electrical properties in comparison to common polyurethanes.

Synthetic route for preparation of TPUIs.     

Poly(ether urethane)s from aromatic diisocyanates based on lignin‐derived phenolic acids

A series of new bio‐based aromatic diisocyanates, namely bis(4‐isocyanato‐2‐methoxyphenoxy)alkane and bis(4‐isocyanato‐2,6‐dimethoxyphenoxy)alkane, were synthesized starting from lignin‐derived phenolic acids, namely vanillic acid and syringic acid, via the Curtius rearrangement. The diisocyanates were employed to synthesize poly(ether urethane)s by reacting them with potentially bio‐based aliphatic diols, namely 1,10‐decanediol and 1,12‐dodecanediol. The chemical structures of diisocyanates and poly(ether urethane)s were confirmed using Fourier transform infrared, ¹H NMR and ¹³C NMR spectroscopy. Inherent viscosities and number‐average molecular weights of the poly(ether urethane)s were in the ranges 0.58–0.68 dL g^?1 and 32 100–58 500 g mol^?1, respectively, indicating the formation of reasonably high molecular weight polymers. The poly(ether urethane)s exhibited 10% weight loss in the temperature range 304–308 °C. The glass transition temperatures of the poly(ether urethane)s were in the range 49–74 °C and were dependent both on the number of methylene units in the diols and on the number of methoxy substituents on the aromatic rings of the diisocyanate component. © 2017 Society of Chemical Industry     

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。     

Poly(ester-ether)s: I. Investigation of the Properties of Blend Films of Polydioxanone and Poly(methyl dioxanone)

This study aimed at examining the properties of blends of semi-crystalline polydioxanone (PDX) and amorphous poly(methyl dioxanone) (PMeDX). The authors show that low amounts of PMeDX, within 15 wt% acts as plasticizer to high molar mass PDX as confirmed by an increase in Young's modulus of films. The plasticizing effect on blends increased with decreasing reduced viscosity of PMeDX. Mechanical tests showed overall reduced tensile properties of the blends. Viscosity analysis coupled with SEM and AFM indicated immiscibility of the blends over the whole range of compositions. Blend samples with higher PMeDX contents degraded at faster rates with profiles differing from PDX.