含苯并咪唑的芳香族聚酰胺共聚物的合成与表征

采用低温溶液缩聚法,在N-甲基吡咯烷酮(NMP)-氯化锂(LiCl)溶剂体系中加入2-(4-氨基苯基)-5-氨基苯并咪唑(DAPBI)作为第三单体,与对苯二胺(PPD)和对苯二甲酰氯(TPC)共聚得到改性对苯二甲酰对苯二胺(PPTA)共聚物。控制共聚单体投料顺序,设计合成出一系列序列结构不同的杂环段与PPTA硬段相间的嵌段聚合物。研究了序列结构和DAPBI含量对共聚物比浓对数黏度的影响,采用红外光谱、X射线衍射、热重分析仪等对共聚物结构和性能进行表征。试验结果表明:DAPBI成功引入到了PPTA分子链中,改性PPTA树脂为非晶结构,所得有规嵌段共聚物比无规共聚物拥有更好的有序性和结晶性能,共聚物能保持良好的耐热性能,溶解性能和力学性能得到了提升。     

聚乙烯吡咯烷酮对缩聚法制备芳纶浆粕工艺的影响(英文)

在对苯二胺 (PPDA)和对苯二甲酰氯 (TPC)在N -甲基吡咯烷酮 (NMP)—氯化钙 (CaCl2 )溶剂体系中进行低温溶液缩聚直接制备芳纶浆粕的过程中 ,加入高分子添加剂聚乙烯吡咯烷酮 (PVP) ,制得了较高相对分子质量的芳纶浆粕。结果表明 ,每 10 0mL溶剂的PVP最佳用量约为 6g ,最佳时间为TPC加料后 1～ 2min内 ,且以溶液加料方式更为有利。通过扫描电镜观察了所制浆粕的表面形貌。红外光谱和X -光衍射谱图证明了PVP没有连接到聚对苯二甲酰对苯二胺 (PPTA)分子链中 ,PVP不改变芳纶浆粕的化学结构     

聚对苯二甲酰对苯二胺共缩聚工艺研究

通过添加第三单体3,4'-二氨基二苯醚(3,4'-ODA)对聚对苯二甲酰对苯二胺(PPTA)进行改性,能够使其溶于一般的极性有机溶剂中,得到的聚合物溶液可以直接纺丝。研究了PPTA共聚合工艺,探讨了反应时间、反应温度、单体摩尔浓度、CaCl2含量以及第三单体含量和初始投料比对共聚物比浓对数黏度的影响。     

合成方法对共缩聚PPTA比浓对数粘度的影响

以4,4’-二氨基二苯醚(ODA)为第三单体对聚对苯二甲酰对苯二胺(PPTA)进行共缩聚改性,研究了共缩聚反应工艺条件对PPTA比浓对数粘度(ηinh)的影响。结果发现,当CaCl2用量为4%-6%时,单体摩尔浓度为0.35-0.45mol/L,爬杆后升温至80-85℃,总的反应时间30—40min,加入Ca(OH)2中和20min,制得的共缩聚PPTA的比浓对数粘度可达到2.50-3.37dL/g。不同的第三单体含量和不同的初始投料比对PPTA溶解性和ηinh有很大的影响。     

PPTA硫酸溶液流变性能及纺丝工艺的研究

采用旋转黏度计测定聚对苯二甲酰对苯二胺(PPTA)溶液的表观黏度,研究了PPTA相对分子质量、溶液浓度以及温度对PPTA溶液流变性能的影响,并对PPTA硫酸溶液进行纺丝,研究纺丝工艺对PPTA纤维性能的影响.结果表明:不同分子量的PPTA硫酸溶液表现出相同的流变行为,PPTA硫酸溶液随着溶液浓度的增大会出现一个临界浓度...     

PPTA树脂在甲磺酸中的溶解及其溶液性质初探

实验首次用甲磺酸(MSA)对聚对苯二甲酰对苯二胺(PPTA)树脂进行溶解制备PPTA/MSA溶液,并对所形成溶液性质进行研究并制备PPTA浆粕。通过偏光显微镜观察了PPTA树脂在MSA中的溶解规律,用树脂比浓对数粘度随时间的变化研究了树脂在MSA中的稳定性。并通过比表面积(BET)分析、X射线衍射(XRD)分析和热失重分析(TGA)研究了PPTA浆粕的比表面积、结晶度和热性能。结果表明:在低浓度下,PPTA树脂能与MSA混合均匀得到均一稳定的溶液,由所得溶液制备的PPTA浆粕性能优于同条件下用PPTA/硫酸溶液制备的浆粕性能。     

NMP-CaCl2体系中低温缩聚合成PPTA研究

采用低温溶液缩聚法将对苯二甲酰氯（TPC）和对苯二胺（PPD）在NMP-CaCl2溶剂体系中进行缩聚反应,制备了较高分子质量的聚对苯二甲酰对苯二胺（PPTA）树脂。研究了分子质量与反应时间的关系,考察了初始单体浓度、摩尔配比、起始反应温度、反应时间等影响缩聚反应的因素,获得了较优的聚合条件：初始单体浓度为0．35—0．4mol／L,对苯二甲酰氯和对苯二胺的摩尔配比为1．009～1．012,起始反应温度为-15～5℃,反应时间为35～60min。发现搅拌转速对于聚合分子质量的影响主要体现在低转速范围,当转速超过某一临界值时,转速对PPTA聚合分子质量几乎没有影响。     

溶致液晶聚对苯二甲酰对苯二胺的合成及性能

系统研究了影响聚对苯二甲酰对苯二胺（PPTA）对数比浓粘度的诸多因素,从而确定了最佳聚合工艺条件,并根据此工艺条件合成出了对数比浓粘度4．0以上的PPTA聚合体,用偏光显微镜,红外光谱、旋转粘度计和热失重分析对其结构及液晶性进行了研究和分析。结果表明,本实验所制得的聚合体确系PPTA结构,且属向列相液晶。用该聚合体初纺成的芳纶纤维（YS－AF1414）纤度为1．4旦,拉伸强度19．7克／旦,拉伸模量为450克／旦,性能指标接近美国Kevlar29的水平。     

PPTA及改性PPTA的合成与性能表征

通过在N-甲基吡咯烷酮（NMP）-氯化锂体系中,使用对苯二甲酰氯（TPC）、对苯二胺（PPD）和4,4’-二氨基二苯醚（DAPE）通过低温溶液聚合法合成了聚对苯二甲酰对苯二胺（PPTA）及改性PPTA。并考察了DAPE的用量对聚合体ηinh的影响,对制得的两种类型的芳香族聚酰胺进行了IR、TG、SEM等分析表征。     

3,4'-ODA改性PPTA共聚物溶液性质的研究

为了改善聚对苯二甲酰对苯二胺(PPTA)的溶解性能,在PPTA的聚合过程中添加第三单体3,4'-二氨基二苯醚(3.4'-ODA),得到了PPTA的共聚体溶液.主要讨论不同的溶剂体系(NMP或DMAc)中共聚物溶液的凝固性和稳定性,包括凝固剂的种类,溶剂的浓度,CaCl2的含量和温度对溶液的凝固值和临界浓度的影响.实验结果表明:水是非常强的凝固剂;随着凝固液中溶剂浓度的提高,凝固值增大;随着CaCl2含量的增大凝固值逐渐增大;温度影响不是太大,变化趋势比较缓和;共聚物溶液在室温和60℃下都具有非常好的稳定性.     

高黏度聚对苯二甲酰对苯二胺纺丝原液的制备

采用低温溶液缩聚的方法,在N-甲基吡咯烷酮(NMP)-氯化锂(LiC)l溶剂体系中,引入了4,4'-二氨基二苯醚(4,4'-ODA)作为第三单体,与对苯二胺(PDA)和对苯二甲酰氯(TPC)反应,得到可用于直接湿纺的均相共聚物原液。研究了单体浓度、第三单体用量、反应时间、反应温度、助溶剂及吡啶用量对纺丝原液黏度的影响。     

Studies on the semirigid chain polyamide—poly(1,4-phenyleneterephthalamide)

In this article, the polycondensation of terephthaloyl chloride and p-phenylenediamine was systematically studied, including the liquid–crystalline state of the solution and the spinning of poly(1,4-phenyleneterephthalamide) (PPTA). High-molecular-weight PPTA with ε_inh = 5–7 was prepared and the main factors influencing the solution polycondensation of 1,4-phenylenediamine with terephthaloyl chloride were studied in detail. Experimental results showed that the water content of the reaction system, reactant concentration, and volume ratio of mix solvents have a great influence on the inherent viscosity of the poly(1,4-phenyleneterephthalamide) obtained. The highest ε_inh was obtained at 0.3M/liter reactant concentration in a mixed solvent ratio HMPA/DMAC of 4/1 (by volume), at 0.35M/liter reactant concentration in a mixed solvent of HMPA/NMP = 7/3, and at 0.5M/liter of reactant concentration in a mixed solvent of HMPA/THF = 9/1. The water content must be controlled to less than 100 ppm in the polymerization system. In the early stage of the polycondensation process, the ε_inh of the polymer obtained increased rapidly with time. The system gelled within 2 or 3 min, while the monomer conversion reached about 100%. However, the reaction of polycondensation continued after gelation and the ε_inh of the polymer increased appreciably. We have studied the viscosity behavior at 20–155°C for the anisotropic solution of PPTA in 100% sulfuric acid (ε_inh of PPTA 2.5–4.9). Experimental results showed that, at low concentrations the viscosity of isotropic solution increases with the increase of polymer concentration to reach a maxium near the critical polymer concentration, beyond which the solution changes to an anisotropic liquid–crystalline solution. The appropriate spinning region was obtained as shown in the phase diagram determined by viscosity, degree of depolarization anisotropy, and region of thermal depolymerization. Fibers of PPTA with high modulus and high tenacity were obtained by dry-jet wet spinning. The fibers obtained have a tenacity of ～22 g/denier, a modulus of ～600 g/denier, and elongation at break ～3.5%.     

Novel poly(amide‐hydrazide)s and copoly(amide‐hydrazide)s from bis‐(4‐aminobenzyl) hydrazide and aromatic diacid chlorides: Synthesis and characterization

A new aromatic diamine, viz., bis‐(4‐aminobenzyl) hydrazide (BABH), which contains preformed hydrazide and methylene linkage, was synthesized starting from α‐tolunitrile. The BABH and intermediates involved in its synthesis were characterized by spectroscopic methods. Novel poly(amide‐hydrazide)s were synthesized by low temperature solution polycondensation of BABH with isophthaloyl chloride (IPC) and terephthaloyl chloride (TPC). Furthermore, two series of copoly(amide‐hydrazide)s, based on different mol % of BABH and bis‐(4‐aminophenyl) ether (ODA) with IPC/TPC were also synthesized. Poly(amide‐hydrazide)s and copoly(amide‐hydrazide)s were characterized by inherent viscosity [η_inh], FTIR, solubility, X‐ray diffraction (XRD), differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). The polycondensation proceeded smoothly and afforded the polymers with inherent viscosities in the range of 0.18–0.93 dL/g in (NMP + 4% LiCl) at 30°C ± 0.1°C. These polymers dissolved in DMAc, NMP or DMSO containing LiCl. The solubility of copolymers was considerably improved in line with less crystalline nature due to random placement of constituent monomers during the copolymerization. XRD data indicated that poly(amide‐hydrazide)s from BABH alone and IPC/TPC had higher crystallinity than the corresponding copoly(amide‐hydrazide)s derived from a mixture of BABH and bis‐(4‐aminophenyl) ether (ODA). Polymers showed initial weight loss around 160°C which is attributed to the cyclodehydration leading to the formation of corresponding poly(amide‐oxadiazole)s. Copolyamide‐hydrazides showed T_max between 400 and 540°C which is essentially the decomposition of poly(amide‐oxadiazole)s. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Synthesis and characterization of novel heat resistance poly(amide‐imide)s from N,N′‐[2,5‐bis(4‐aminobenzylidene) cyclopentanone] bistrimellitimide acid and various aromatic diamines

A new‐type of dicarboxylic acid was synthesized from the reaction of 2,5‐bis(4‐aminobenzylidene)cyclopentanone with trimellitic anhydride in a solution of glacial acetic acid/pyridine (Py) at refluxing temperature. Six novel heat resistance poly(amide‐imide)s (PAIs) with good inherent viscosities were synthesized, from the direct polycondensation reaction of N,N′‐[2,5‐bis(4‐aminobenzylidene)cyclopentanone]bistrimellitimide acid with several aromatic diamines, by two different methods such as direct polycondensation in a medium consisting of N‐methyl‐2‐pyrrolidone (NMP)/triphenyl phosphite (TPP)/calcium chloride (CaCl₂)/pyridine (Py) and direct polycondensation in a p‐toluene sulfonyl chloride (tosyl chloride, TsCl)/pyridine (Py)/N,N‐dimethylformamide (DMF) system. All of the above polymers were fully characterized by ¹H NMR, FTIR, elemental analysis, inherent viscosity, solubility tests, UV‐vis spectroscopy, differential scanning calorimeter (DSC), thermogravimetric analysis (TGA), and derivative of thermaogravimetric (DTG). The resulted poly(amide‐imide)s (PAIs) have showed admirable good inherent viscosities, thermal stability, and solubility. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

聚对苯二甲酰对苯二胺降解性研究

通过测量不同条件下聚对苯二甲酰对苯二胺(PPTA)溶液的比浓对数黏度,分析在PPTA纺丝前可能引起聚合物降解的因素,这些因素包括纺丝液浓度、残余的CaCl2、N-甲基-2-吡咯烷酮、水分和氢氧化钙等,最终得到水分和氢氧化钙对PPTA的降解影响很大,其余影响较小的结论。同时,分析了降解前后聚合物的结构和性能,发现降解结果是部分端胺基被氧化成硝基。     

New types of heat-resistant,flame-retardant ferrocene-based polyamides with improved solubility

A novel ferrocenyl diamine (FDA) was prepared by the condensation reaction of 1,1′-ferrocenedicarbonyl chloride with 2 mol of 2,6-bis(4-aminophenoxy)pyridine. A series of ferrocene-based polyamides was prepared via polycondensation reaction of FDA with various diacid chlorides in N-methyl-2-pyrrolidone (NMP) using trimethylchlorosilane (TMSCl) as activating agent. The monomer and polyamides were characterized and inherent viscosity, solubility, thermal stability and behavior, flame-retardancy, and crystallinity of the polymers were studied. The polymers showed good heat-resistant, flame-retardancy, and also improved solubility in polar aprotic solvents.     

Synthesis and properties of lyotropic liquid crystalline copolyamides containing phthalazinone moiety and ether linkages

A series of aromatic copolyamides containing phthalazinone moiety and ether linkages were prepared from 1,2-dihydro-2-(4-aminophenyl)-4-[4-(4-(aminophenoxyl)phenyl)](2H)phthalazin-1-one (DHPZ-DA), p-phenylenediamine (PPD), 4,4′-diaminodiphenylether (DAPE) and terephthaloyl dichloride (TPC) by low temperature solution polycondensation. The copolyamides had relatively high inherent viscosities, ranging from 1.86 to 5.30 dl/g. The copolyamides showed T_g values between 297 and 351 °C. Solubility of these copolyamides was improved in NMP, DMAc, NMP (1 wt% LiCl) and DMAc (1 wt% LiCl) by introducing phthalazinone moiety and ether linkages into the main chain. And they had good thermal stability, associated with 5 and 10% weight loss temperatures in the range of 480-516 and 501-532 °C in nitrogen, respectively. WAXD measures indicated these copolyamides were semicrystalline in nature. Some of these copolyamides exhibited lyotropic liquid crystalline behavior in concentrated H₂SO₄, NMP (1 wt% LiCl), and even in NMP solutions, as evidenced by polarizing light microscopy.