梳状P(MMA-co-MAh)-g-PEGME共聚物的合成及结构与性能

用自制的甲基丙烯酸甲酯和马来酸酐的共聚物P(MMA-co-MAh)为反应物,聚乙二醇单甲醚(PEGME)为接枝单体,合成了梳状P(MMA-co-MAh)共聚物多缩乙二醇酯(P(MMA-co-MAh)-g-MPEG).采用傅立叶红外光谱(FTIR)、核磁共振(NMR)13C谱、1H谱以及H,C-COSP谱对所合成的梳状共聚物结构进行表征;热失重分析(TGA)和示差扫描量热法(DSC)对所合成的共聚物的物理性能进行了分析.FTIR及NMR结果表明,聚乙二醇单甲醚通过酯化反应接枝到P(MMA-co-MAh)共聚物上,形成以MMA/MAh共聚物为主链,聚乙二醇单甲醚为侧链的梳状共聚物,其在马来酸酐上的接枝率大约为20%;热性能分析结果表明,合成的梳状共聚物热分解温度与共聚物P(MMA-co-MAh)的分解温度相差不大,接枝后的梳状共聚物也具有高的热稳定性,起始热分解温度在325.9℃左右,且该梳状共聚物具有两个玻璃化转变温度,一个是由于侧链的玻璃化转变引起的,温度为32℃左右;一个是主链的玻璃化转变引起的,温度为120℃左右.在主链玻璃化转变温度以下,侧链是可以移动的,有利于电活性物质和离子等在聚合物基体中的扩散和迁移.     

新型含酯基结构的具有低线膨胀系数和吸水性的聚酰亚胺的合成

将2种主链中含有酯基结构的二胺单体:二(4-氨基苯基)对苯二甲酸酯(BPTP)和4-氨基苯基-4-氨基对苯甲酸酯(APAB),与几种常见的酸酐聚合,合成了一系列主链中含有酯基结构的新型聚酰亚胺膜材料.结果表明,所制备的聚酰亚胺薄膜表现出优良的热稳定性、机械性能和低吸水性,其中聚合物的表观玻璃化转变温度高达526℃,在空气和N2气气氛下5%的热失重温度分别在498和507℃以上,表明薄膜具有非常优异的热性能.由于聚合物主链中引入酯基结构而表现出低的线膨胀系数和吸水率.     

由对苯二甲酰胺二醇合成聚酯酰胺及其扩链反应的研究

以N,N′-二(2-羟乙基)对苯二甲酰胺与己二酸及丁二醇缩聚,合成了同时带有端羧基与端羟基的聚酯酰胺预聚体,研究了不同扩链剂的扩链反应,获得了特性黏度达1.05 dL/g的聚酯酰胺.对预聚体及扩链后聚合物进行了红外与核磁表征,研究了聚合物的结构,并对聚合物进行了DSC与TG分析.     

含亚甲基链段苯并二(口恶)唑类聚合物的合成、表征及性能

通过溶液缩聚的方法合成了一系列含有不同长度亚甲基链段的聚苯并羟基酰胺(PHACx),然后在200～300 ℃下环化脱水制备了相应的聚多亚甲基苯并二唑(PBOCx),并对其结构进行了表征,探讨了聚合物的溶解性、热性能和光物理性能.研究表明:在主链上引入亚甲基提高了苯并二唑类聚合物在有机溶剂中的溶解性,其中PBOC3 和PBOC4具有较好的溶解性能,但随着亚甲基数量的进一步增加,溶解性有下降趋势.此外,所有的PBOCx聚合物均表现出良好的耐热性,在空气中的热分解温度可达到450 ℃以上.对聚合物光物理性能的初步研究表明:随着柔性链段的增加,电子共轭作用逐渐减弱,紫外吸收发生了蓝移.     

呋喃甲基缩水甘油醚与二氧化碳的共聚反应研究

采用糠醇和环氧氯丙烷反应制备了纯度较高的呋喃甲基缩水甘油醚,随后呋喃甲基缩水甘油醚与二氧化碳在稀土三元催化剂Y(CCl3COO)3-甘油-ZnEt2的催化下发生共聚反应,生成侧链为呋喃甲醚侧基的脂肪族聚碳酸酯.共聚物主链结构规整,主要为聚酯结构,数均分子量最高可达13.0×104,共聚物的玻璃化转变温度为-29～-30℃,5wt%起始热分解温度大于231℃.     

环氧丙烷聚醚三元醇/聚乳酸嵌段共聚物的合成与性能

以低不饱和度环氧丙烷聚醚三元醇与L型及DL型丙交酯为原料, 合成了不同单体物质的量比的聚醚与聚乳酸嵌段共聚物. 采用FTIR, 1H NMR, GPC对共聚物的结构进行了表征; 用DSC, DTA对共聚物的玻璃化转变温度、熔点及热分解温度进行了研究. 结果表明, 丙交酯在聚醚多元醇端羟基的引发下发生开环反应, 得到聚环氧丙烷L型乳酸(POLLA)或聚环氧丙烷DL型乳酸(PODLA)二嵌段共聚物. POLLA二嵌段共聚物具有结晶能力, 且随着L型聚乳酸链段的增长而增强. PODLA二嵌段共聚物为非晶态聚合物. 两种共聚物的玻璃化转变温度与共聚物的组成有关, 其值介于聚醚和聚乳酸玻璃化转变温度之间. 与聚醚三元醇相比, 二嵌段共聚物的耐热性得到提高, 其热分解温度提高了30～60 ℃, 约为235～262 ℃. 共聚物的结构和组成对材料的热降解机制有很大影响. PODLA在高温区发生热氧化降解.     

低分子量聚合物电解质的合成与性能

研究了低分子量梳状聚合物电解质的合成方法及结构，性能。首先合成了不同分子量的甲基丙烯酸聚乙二醇单甲醚酯，并进一步合成了分子量一万左右的梳状聚合物电解质，结果表明：反应严格按照反应方程进行，精制产物是非晶的梳状聚合物，本聚合物体系均存在两个玻璃化转变温度，一个在100℃左右，归属为梳状聚合物主链的玻璃化转变，另一个在－20摄氏度以下，归属于侧链玻璃化转变，在室温下侧链可以运动，有利于电活性物质的迁移和扩散，并用超微电极研究了该电解质的行为。     

生物降解脂肪族不饱和聚酯碳酸酯 2.生物降解

土埋法显示脂肪族不饱和聚酯碳酸酯(AUPEC)有良好的生物降解活性,单位面积失重(WPA)为其生物降解性能的较好指标,土埋三个月,AUPEC的WPA可达55mg·cm~(-2),失重达0.15质量分数,此外,实验表明生物降解主要在ALPEC的表面进行,聚合物的特性粘数、链结构、玻璃化转变温度及热分解温度不随聚合物的降解失重而变化。     

由脂肪族二酰胺二醇合成聚酯酰胺及表征

利用脂肪族二元酸酯与乙醇胺反应容易获得的对称二酰胺二醇,经缩聚合成聚酯酰胺预聚体,并针对端羧基和端羟基同时扩链来提高分子量,获得可生物降解的聚酯酰胺.首先将N,N′-二(2-羟乙基)草酰胺(HEOA)或N,N′-二(2-羟乙基)己二酰胺(HEHA)与己二酸和丁二醇缩聚,制备同时带有端羧基及端羟基的脂肪族聚酯酰胺预聚体,通过1,4-双(2-噁唑啉)苯及己二酰双己内酰胺混合扩链剂扩链,获得高分子量脂肪族聚酯酰胺,并通过红外、1H-NMR、DSC及TGA对其结构和热性能进行了表征.结果表明,预聚体在制备过程发生了一定的酯-酰胺交换反应;扩链后聚合物的熔点、熔融焓和热稳定性有所下降;但热稳定性仍接近或略高于聚己二酸丁二酯.     

主链含有非共轭结构的聚芴类蓝光聚合物的合成与性能研究

通过Suzuki偶合反应合成出了主链中含有非共轭烷氧基组分(-O-CH2-CH2-CH2-CH2-O-)的聚芴类衍生物聚- 2,7-(9,9-二辛基芴)-co-4,4’-丁氧基二苯(PFP)和聚-2,7-(9,9-二辛基芴)-co-4,4’-丁氧基二苯-co-N-苯基-4,4’-二苯胺(PFTP11)并通过相同的条件合成出主链由芴和三苯胺交替相连的聚合物聚-2,7-(9,9-二辛基芴)-co-N-苯基-4,4’-二苯胺(PFTPA)作为参比材料. 通过1H NMR和FT-IR分析对这些聚合物的化学结构进行了表征. 这三种聚合物在常用的有机溶剂中具有很好的溶解性, 可通过溶液加工的方式制备聚合物薄膜. 这些聚合物均具有较高的热分解温度(＞400 ℃), 聚合物PFP具有较高的玻璃化转变温度(～130 ℃)而PFTP11和PFTPA则未出现明显的玻璃化转变过程. 通过对聚合物的吸收特性进行测试得知它们具有较大的光学带宽(2.89～3.29 eV). 所有聚合物在固体薄膜状态下均发射出蓝色荧光, PFP, PFTP11和PFTPA的最大PL发射分别位于425, 437和440 nm. 通过对其电化学性能进行测试可知由于三苯胺基团的引入聚合物的HOMO能级明显提高, 这意味着聚合物的空穴传输能力得到了有效的改善.     

Synthesis,characterization of novel interacting blends of acrylated poly(ester-amide)s containing epoxy residues with vinyl ester resin

Unsaturated bisamic acids were prepared by reaction between maleic anhydride and different aromatic diamines. Unsaturated poly(ester-amide) resin (UPEAs) was prepared by reaction of diglycidylether of bisphenol-A (DGEBA) with unsaturated bisamic acids. Acrylation of Unsaturated poly(ester-amide)s (UPEAs) was carried out to afford acrylated UPEAs resin (i.e., AUPEAs). Interacting blends of Acrylated unsaturated poly(ester-amide)s (AUPEAs) with vinyl ester epoxy (VE) resin were prepared. APEAs and AUPEAs were characterized by elemental analysis, molecular weight determined by vapor pressure osmometer and by IR spectral study and by thermogravimetry. The curing of interacting blends was monitored on differential scanning calorimeter (DSC). Based on DSC data in situ glass reinforced composites of the resultant blends have been prepared and characterized for mechanical, electrical and chemical properties. Unreinforced blends were characterized thermo-gravimetrically (TGA).     

New Polymer Syntheses. 80. Linear,Star-Shaped,and Hyperbranched Poly(Ester-Amide)s from Silicon-Mediated One-Pot Condensations of 3-Acetoxy-, 3,5-Bisacetoxybenzoic Acid,and 3-Aminobenzoic Acid

Abstract

Acylation of N,O-bistrimethylsilyl-3-aminobenzoic acid with 3-acetoxybenzoylchloride yielded the trimethylsilylester of N-(3′-acetoxybenzoyl)-3-aminobenzoic acid, which was polycondensed in situ at 260 or 280°C. Cocondensation with acetylated tetraphenols yielded four-arm star copolymers with a random or preferentially alternating sequence of 3-hydroxy and 3-aminobenzoyl units. Due to ester-amide exchange detected by ¹H- and ¹³C-NMR spectroscopy, the sequences were never perfectly alternating. Methyl groups attached to the star centers allowed the determination of degrees of polymerization by ¹H-NMR spectroscopy. Acylation of N,O-bistrimethylsilyl-3-amino benzoic acid with 3,5-bisacetoxybenzoylchloride yielded a trifunctional monomer, the polycondensation of which yielded a hyperbranched poly(ester-amide). By cocondensation of the trifunctional monomer with acetylated tetraphenyl, star-shaped poly(ester-amide)s with four hyperbranched star arms were obtained. All these poly(ester-amide)s are amorphous materials with glass-transition temperatures in the 190–200°C range and good solubility in polar organic solvents.     

Soluble,thermally stable,flame retardant quinoline-based poly(ester amide)s

A new diamine was prepared via reaction between 8-hydroxy-5-nitroquinoline and 4-nitrobenzoyl chloride, followed by reduction of the nitro groups of the resulted compound. Novel quinoline-based poly(ester-amide)s were produced through polycondensation reactions of the prepared diamine with different diacid chlorides. The monomer and poly(ester-amide)s were characterized and properties of the polymers including solution viscosity, thermal behavior and stability, solubility, and crystallinity were studied.

High thermal stability and improved solubility was observed for the polymers, indicating successful designing of monomer and related polymers for overcoming the main issue of thermally stable polymers, i.e. the problem of increasing solubility versus high thermal stability.

Also, by changing the diacid chlorides for the preparation of poly(ester-amide)s, the structure-property relations were investigated.     

Synthesis, properties, and applications of urethane-modified acrylated poly(ester-amide)s

Epoxy resin-based unsaturated poly(ester-amide) resins (UPEAs) were treated with acryloyl chloride to afford acrylated UPEAs resins (AUPEAs). Urethane-based acrylated poly(ester-amide)s prepared by reaction with diisocyanate were characterized by elemental analysis, by molecular weight determination (by vapour pressure osmometry), by IR spectral study, and by thermogravimetry. The curing of interacting blends was monitored by differential scanning calorimetry (DSC). On the basis of DSC data in-situ glass-reinforced composites were prepared from the resulting materials and their mechanical, electrical, and chemical properties were characterized. Unreinforced blends were characterized by thermogravimetry.     

Synthesis and intrinsic blue fluorescence study of hyperbranched poly(ester-amide-ether)

A series of hyperbranched poly(ester-amide-ether)s (H-PEAEs) were synthesized via the A₂+CB₃ approach by the self-transesterification of ethyl ester-amide-ethers end-capped with three hydroxyl groups and ethyl ester group at two terminals. The molecular structures were characterized with ¹H NMR and FT-IR spectroscopy. The number average molecular weights were estimated by GPC analysis to possess bimodal wide distribution from 1.57 to 2.09. The strong inherent blue fluorescence was observed at 330 nm for excitation and 390 nm for emission. Moreover, the emission intensity and fluorescence quantum yield increased along with the incorporated ether chain length, as well as almost linearly with the H-PEAE concentration in an aqueous solution. For comparing the fluorescence performance, the linear poly(ester-amide-ether) (L-PEAE) and hyperbranched poly(ester-amide) (H-PEA) were synthesized. The results showed that the coexistence of ether bond and carboxyl group in the molecular chain was essential for generating the strong fluorescence. However, the compact backbone of H-PEAE would be propitious to the enhancement of fluorescence properties.     

Studies on novel interacting blends of acrylated poly(ester-amide)s having epoxy residues and vinyl ester of bisphenol-C

Novel unsaturated poly(ester-amide)s (UPEAs) were prepared by the reaction of Bisphenol-F based epoxy resin with bisamic acids. Acrylation of UPEAs were carried out using acryloyl chloride and the products are called Acrylated unsaturated poly(ester-amide)s (AUPEAs). These UPEAs were then treated with acrylol chloride to afford acrylated UPEAs resin (i.e., AUPEAs). Interacting blends of equal proportional AUPEAs and vinyl ester epoxy (VE) resin were prepared. APEAs and AUPEAs were characterized by elemental analysis, molecular weight determined by vapor pressure osmometer, IR spectral study and thermogravimetry. Curing of interacting blends was monitored on differential scanning calorimeter (DSC). Based on DSC data ‘in situ’ glass reinforced composites of the resultant blends have been prepared and characterized for mechanical, electrical and chemical properties. Unreinforced blends were characterized by thermogravimetry (TGA).     

Synthesis and characterization of aliphatic poly(esteramide)s containing symmetrical bisamide blocks

A series of symmetrical diols were synthesised through ring-opening of lactones with different ring sizes by alkane diamines in moderate to good yields. Ring-opening of the dilactones glycolide and lactide with a diamine in equimolar amounts afforded symmetrical diols in quantitative yield. Aliphatic poly(ester-amide)s were prepared by polycondensation of N,N′-bis(caproyl)butane diamide, dimethyl adipate and 1,4-butanediol. The structure of the diamide was retained in the polymer. The polymers synthesized are semi-crystalline materials that possess ordered structures in the solid phase over almost the entire copolymer range. Depending on thermal history and copolymer composition thermal analyses is in agreement with the presence of pseudo-hexagonal crystal structures below 75°C, a fast melting recrystallization at this temperature and a triclinic structure at higher temperatures.     

SYNTHESIS AND CHARACTERIZATION OF HYPERBRANCHED POLY(ESTER-AMIDE)S BASED ON GALLIC ACID AND DL-2-AMINOBUTYRIC ACID

INTRODUCTIONHighly branched macromolecules including dendrimers and hyperbranched polymers are interesting materialswith unique molecular structures and potential applications[1-5]. The two types of polymers have many analogousphysical and chemical properties such as high solubility, low viscosity and abundance of terminal groups. Theformer attracts much attention of researchers due to its perfect monodisperse architecture, but its preparation isgenerally tedious because of various protect…     

MULTIFUNCTIONAL HYDROPHILIC POLYMERS

ABSTRACT

Different types of multifunctional hydrophilic polymers were synthesized and characterized in view of their possible biomedical application. Several poly(amide)s and poly(ester-amide)s containing oligo(oxyethylene) segments and tartaric or succinic acid residues were prepared by activated polycondensation methods. New functional derivatives of β-cyclodextrin were obtained by reaction with glycidyl ether of protected polyols. The mechanism of β-cyclodextrin polymerization with epichlorohydrine was investigated by ¹³C-NMR spectroscopy.     

Whiskers. VIII. A convenient synthesis of poly(4-hydroxybenzoate) whiskers and their application in composites of nylon-6

Whiskers of poly(4-hydroxybenzoate) [poly(4-HBA)] were prepared by polycondensation of free 4-hydroxybenzoic acid with acetic anhydride and pyridine in a high boiling inert solvent. The purity of the monomer is decisive for the success of the synthesis. For a less pure 4-hydroxybenzoic acid, the preparation of acetylated oligomers with acetylchloride, followed by polycondensation of the isolated oligomers is a suitable alternative. Whiskers, with a solid-solid phase transition at 364°C were obtained, which is the highest temperature reported for this transition so far. Two batches of composites were prepared from nylon-6 using polyester whiskers with an alkaline or an acidic surface treatment. A third batch was prepared using poly(ester-amide) whiskers. The mechanical properties of these composites indicate that the surface treatment does not play any role, and that the poly(esteramide)s are inferior to the polyester whiskers, because they are not single crystals. © 1994 John Wiley & Sons, Inc.