超高相对分子质量PPTA树脂及其高模量芳纶的研究

对高相对分子质量聚对苯二甲酰对苯二胺(PPTA)树脂进行了表征,开展了添加超高相对分子质量PPTA树脂与普通相对分子质量PPTA树脂共混进行液晶纺丝得到高强度和高模量芳纶的结构表征与性能试验,同时对芳纶的力学性能与其PPTA树脂相对分子质量的关系进行了研究。结果表明,芳纶的力学性能与其PPTA聚合体的相对分子质量紧密相关,如果PPTA树脂的相对分子质量不够高,加上液晶纺丝和高模量热处理过程分子链的进一步降解,高模量芳纶的制备就无法实现。在系统研究PPTA聚合反应规律,特别是聚合诱导相互转变规律及其影响因素研究基础上,通过调控连续聚合的反应条件,在1 000 t/a连续聚合生产线上制备出比浓对数粘度高达9.2 dl/g的超高相对分子质量PPTA树脂;用超高相对分子质量PPTA树脂与通用级PPTA树脂(比浓对数粘度6.8 dl/g)混合进行纺丝,制备出高强度的芳纶,并进一步热处理得到高强度和高模量的芳纶。     

用直接纺丝法制芳纶短纤维

研究了直接纺丝制取芳纶短纤维的新方法。讨论了纤维长度、直径及力学性能与纺丝条件的关系。发现影响纤维长度的主要因素是空气层高度和喷丝速度,影响纤维直径的主要因素为喷口直径及喷丝速度。此外,还用PPTA短纤维制成了均匀的PPTA"浆粕"纤维。     

复合溶剂NMP/CaCl2热稳定性对PPTA树脂黏度的影响

研究了影响PPTA树脂比浓对数黏度的NMP/CaCl_2复合溶剂,NMP/CaCl_2复合溶剂的热稳定性直接影响PPTA树脂比浓对数黏度及相对分子质量分布,一般PPTA树脂黏度较高可以提高纺丝强度,PPTA树脂黏度平均提高一个单位对位芳纶纤维强度提高3～4 g/D,PPTA树脂相对分子质量分布较窄有利于纺丝的稳定。重点研究了复合溶剂的热稳定性对PPTA树脂黏度及相对分子质量分布的影响。     

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。     

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浆液的配置及其纺丝性能探讨

以低黏度聚对苯二甲酰对苯二胺(PPTA)为原料,工业浓硫酸为溶剂,采用干喷湿纺法制备对位芳纶,探讨了PPTA浆液的配制及其纺丝性能。结果表明:选择PPTA树脂比浓对数黏度(ηinh)为6.0 d L/g,浆液中PPTA质量分数为19.3%,对纺丝性能非常重要;控制PPTA树脂灰分含量小于100μg/g,浓硫酸中的杂质含量小于100μg/g,可以提高PPTA浆液的可纺性和纤维的强度;配浆螺杆温度分8区,设置温度前低后高,可以减少浆液的降解,浆液粘稠度均匀;配制的PPTA浆液在8 h内纺丝,所得纤维都有较高的断裂强度,大于18.3 c N/dtex。     

聚合工艺参数对PPTA树脂黏度的影响

研究了对芳纶(PPTA)树脂在聚合过程中影响黏度的因素,采用Ca Cl2/NMP复合溶剂,通过单因素实验得到PPTA树脂黏度最大时的工艺条件为:PPD∶TPC物质的量比1∶1. 003,复合溶剂中水分130×10-6,盐含量8.4%,双螺杆聚合反应器转速70 r/min;采用两次投料方式可有效减少PPTA树脂黏度值的波动。     

3，4′-ODA改性PPTA对结构及性能影响的分析

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，能够使其在极性有机溶剂中聚合并得到聚合物纺丝原液。用元素分析、红外光谱和热重分析的方法来验证和分析聚合体的结构和热性能。实验结果表明：3，4′-ODA的加入量对共聚体的结构和性能均有明显的影响。     

对位芳香族聚酰胺共缩聚工艺研究

聚对苯二甲酰对苯二胺(PPTA)是一种全芳香族聚酰胺,由其制备的纤维具有高强、高模、耐高温等优异的性能而广泛应用于特种服装、航空航天、通讯电缆以及复合材料中。但PPTA树脂难溶难熔,只能在浓硫酸中溶解,纺丝工艺复杂。通过添加第三单体对其进行改性,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。本实验采用3,4'-二氨基二苯醚(3,4'-OD A)为第三单体,分别在N,N-二甲基乙酰胺(DMAc)/CaCl和N-甲基-2-吡咯烷酮(NMP)/CaCl溶剂体系中,对其共聚合工艺进行了研究。探讨了反应时间、反应温度、单体摩尔浓度、CaCl含量以及3单体含量和初始投料比对共聚物比浓对数粘度的影响。     

原位缩聚合成含聚芳酰胺／酯的微相复合物 Ⅲ．全芳聚酰胺与聚酯-聚醚体系的研究

对于聚对苯二甲酰对苯二胺(PPTA)和PBT-PTMG体系,比较了溶剂配比(CH2Cl2／NMP)、聚合物浓度、强极性溶剂的用量和加料方式对缩聚反应的影响。发现溶剂配比、基体聚合物PBT-PTMG影响PPTA的转化率和PPTA的分子质量。通过FTIR研究发现PPTA中的酰胺键-NH-和PBT-PTMG的醚键特征吸收均向低渡数位移;通过用PBT-PTMG 的良溶剂二氯甲烷对复合物进行产抽提,结果发现,刚性链PPTA与PBT-PTMG分子链有较强的氢键相互作用,从而改进了分子间的相容性,获得了PPTA／PBT-PTMG的微相复合物。PPTA／PBT-PTMG的微相复合物有较好的力学性能。     

Ca2+/H2O2降解水中孔雀石绿

在中性条件下,研究了Ca2++H2O2降解水中孔雀石绿(MG)过程. 结果表明,加入Ca2+明显促进了MG降解,可使其脱色率由20%升至98%. 随着H2O2加入量的增加,MG的脱色率在最初的10 min内显著上升,当H2O2/Ca2+(摩尔比)>5时,2 h后Ca2++H2O2降解MG脱色率均能达到98%. 随着温度的升高,MG的脱色率显著上升. 抗氧化剂(抗坏血酸)的加入抑制了Ca2++H2O2降解MG,当抗坏血酸浓度达到1 mg/L时,降解率为0,说明在Ca2++H2O2降解MG体系中存在着氧化作用. 在避光和光助条件下,加入Ca2+均能明显缩短MG的降解时间,说明Ca2+对其降解有催化作用.     

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。     

Some parameters of spinning poly-p-phenylene terephthalamide fibres through an air gap

The spinneret draw ratio for jets of LC solutions of PPTA (range of 1 to 10) is a basic parameter in spinning of high-strength fibres through an air gap. The strength of the fibres is a function of the conditions of intense spinneret drawing of the jets of LC solutions of PPTA and the spinning speed. Most of the sulfuric acid (solvent) passes into the spinning bath as a result of brief contact of the jet of LC PPTA solution and fibres with it during spinning. Translated from Khimicheskie Volokna, No. 2, pp. 12–14, March–April, 1998.     

High strength and high toughness aromatic polyamide fiber. I. Preparation and properties of block poly(p-phenylene and 4,4′-diphenyl ether terephthalamide) fiber

High strength and high toughness organic fibers can be prepared by molecular design of a suitable block copolymer with mixed segment of rigid and flexible molecular chains. In this paper, the synthesis of fiber forming high molecular weight block copolymer of poly(p-phenylene terephtalamide) (PPTA) and poly(4,4′-diphenyl ether terephthalamide) (DPETA) was studied by the low temperature solution polycondensation method. The high molecular weight block copolymer could be obtained in the mixed solution of 1,3-dimethyl1-2-imidazolidone (DMI) and N,N′-dimethyl acetamide (DMAc) in the presence of triethylamine. The copolymer structures were characterized by elemental analysis and IR spectra. The thermal stability of the block copolymer was better than that of PPTA homopolymer and the ordered copolymer. The wet spinning of the block copolymer was performed using the reaction solution as the spinning dope. The maximum tensile strength and elongation were observed for the filament containing 50% PPTA. The block copolymer had high strength and high Yound's modulus but had a low elongation compared with the ordered copolymer.     

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%.     

恶草酮生产废水的化学氧化法处理研究

对恶草酮生产废水处理的双氧水氧化工艺进行了研究,为解决恶草酮生产废水处理提供技术参考。结果表明,氧化前添加Ca(OH)2的效果优于NaOH,且Ca(OH)2的添加量在1%~3%(w/v)范围内,废水COD下降值基本相同,而超过3%(w/v)时,不降反增;在双氧水处理240 min之内,废水的COD呈线性递减,而后几乎不变。采用优化的工艺:添加1%的Ca(OH)2预处理后,加入5%(v/v)H2O2氧化4 h,并用适量Ca(OH)2控制pH为5,而后添加适量的活性炭;恶草酮生产废水的COD由38 000 mg/L降至18 000 mg/L左右,COD的去除率约为55%。     

Ozonation of Phenol-Containing Wastewater Using O3/Ca(OH)2 System in a Micro Bubble Gas-Liquid Reactor

The degradation of phenol in aqueous solution was investigated in an integrated process consisting of O₃/Ca(OH)₂ system and a newly developed micro bubble gas-liquid reactor. The effects of operating parameters such as Ca(OH)₂ dosage, reactor pressure, liquid phase temperature, initial phenol concentration and inlet ozone concentration on degradation and mineralization (TOC removal) were studied in order to know the ozonation performance of this new integrated process. It is demonstrated that the degradation and TOC removal efficiency increased with increasing inlet ozone concentration and increasing Ca(OH)₂ dosage before 2 g/L, as well as decreasing initial phenol concentration. The optimum Ca(OH)₂ dosage should exceed Ca(OH)₂ solubility in liquid phase. The reactor pressure and liquid phase temperature have little effects on the removal and TOC removal efficiency. When Ca(OH)₂ dosage exceeded 3 g/L, the degradation and TOC removal of phenol almost reached 100% at 30 and 55 min, respectively. The intensification mechanism of Ca(OH)₂ assisted ozonation was explored through analysis of the precipitated substances. The mechanism for Ca(OH)₂ intensified mineralization of phenol solution is the simultaneous removal of CO₃^2- ions, as hydroxyl radical scavengers, due to the presence of Ca²⁺ ions. Results indicated that the proposed new integrated process is a highly efficient ozonation process for persistent organic wastewater treatment.     

A new nanocluster polyoxomolybdate [Mo_(36)O_(110)(NO)_4(H_2O)_(14)]·52H_2O:Synthesis,characterization and application in oxidative degradation of common organic dyes

Polyoxomolybdate [Mo_(36)O_(110)(NO)_4(H_2 O)_(14)]·52 H_2 O was synthesized by a simple one-pot procedure through reducing an acidified mixture of Na_2 MoO_4·2 H_2 O and NH_2 OH·HCl. In order to create a heterogeneous catalyst system, the polyoxomolybdate was pillared with MgAl-LDH-NO_3 by direct ion exchange. These novel materials were carefully analyzed by various chemico-physical methods. The catalytic degradation of methylene blue(MB) and rhodamine B(RB) as common dyes in the presence of MgAl-LDH-1 nanoparticles with aqueous hydrogen peroxide, H_2 O_2, as an oxidizing agent was studied in aqueous solution at room temperature. More importantly, the catalyst can be recovered and reused efficiently up to five consecutive cycles with negligible loss of catalytic activity.     

烟气气相组分及Ca(OH)_2对KMnO_4氧化NO的影响机理

在固定床反应器中考察了KMnO₄氧化烟气中NO的过程,分析了烟气组分H₂O、O₂及SO₂对NO氧化过程的影响规律,得到了Ca（OH）₂对KMnO₄氧化NO的影响机理。实验结果表明,H₂O是KMnO₄氧化NO的必要条件;在含H₂O条件下,O₂可以提高NO氧化率。SO₂与氧化剂反应生成无水钾镁钒类复盐K₂Mn₂（SO₄）₃对NO氧化具有负面作用;Ca（OH）₂的加入提高了氧化剂表面的固体碱度从而促进氧化过程进行;通过添加Ca（OH）₂可以降低SO₂对NO氧化过程的负面影响。根据气体成分和产物分析可知,KMnO₄在钙基吸收剂表面氧化烟气中NO的机理可能是KMnO₄以离子态将吸附在氧化剂表面的NO和SO₂氧化为NO₂和SO₃,生成的NO₂、SO₃再传递到氧化位临近的碱性位被吸收。     

α-FeO(OH)微球在光催化降解甲基橙中的应用

α-FeO(OH)在光催化降解偶氮染料方面已突显出其独特的优势。采用水热法制备α-FeO(OH)微球,并以此为催化剂,以甲基橙为目标降解物,考察α-FeO(OH)微球对甲基橙的吸附作用及α-FeO(OH)/H₂O₂/Vis体系对甲基橙的降解,探讨在α-FeO(OH)/H₂O₂/Vis体系中催化降解甲基橙的机理。采用XRD和SEM对催化剂进行表征,研究pH和H₂O₂浓度对催化性能的影响。结果表明,pH为6.5和H₂O₂浓度为1.2 mol·L^-1时,催化效果最佳,α-FeO(OH)微球和工业级α-FeO(OH)对甲基橙降解率分别为94.3%和28.6%,制备的α-FeO(OH)微球的催化效果明显优于工业级α-FeO(OH),α-FeO(OH)的性质与其结构和形貌关系较大。