BTCA交联Col/PVA复合纤维的结构与性能研究

在胶原蛋白(Col)与聚乙烯醇(PVA)共混纺丝原液中,加入丁烷四羧酸(BTCA)作为交联剂,经湿法纺丝得到初生纤维,经热拉伸和热定型、缩醛化处理得到Col/PVA复合纤维;分析了Col/PVA复合纤维的结构和性能。结果表明:BTCA可以使纤维内部形成交联结构,提升纤维内部Col的稳定性,红外光谱分析表明,BTCA与PVA上的羟基反应生成了酯键;经扫描电子显微镜观察发现BTCA交联处理后复合纤维内部致密,孔洞和缺陷少;差示扫描量热法分析表明BTCA的交联作用会抑制纤维内PVA的结晶,使结晶度有所下降;BTCA添加质量分数为3%的复合纤维的断裂强度、断裂伸长率、Col保留率分别为4.94 cN/dtex,12.56%,91.09%,水中软化点为106℃,具有优良的综合性能。     

甲阶酚醛树脂酯催化反应动力学及产物热分析

利用凝胶转化率的测定,研究了醋酸甘油酯(三醋酸甘油酯、二醋酸甘油酯、一醋酸甘油酯)对甲阶酚醛树脂交联反应的催化动力学,并对交联产物进行了热分析。结果表明,醋酸甘油酯对甲阶酚醛树脂的催化交联反应是一级动力学反应,三醋酸甘油酯、二醋酸甘油酯、一醋酸甘油酯等作催化剂时该反应的表观活化能分别为:11.45 kJ/mol、22.53 kJ/mol和29.27 kJ/mol;交联反应主要由甲阶酚醛树脂中的羟甲基引起,其酯催化交联产物比热固化产物更容易发生热分解。     

促进剂种类对EP/PN体系固化反应动力学的影响

在一定比例的环氧树脂(EP)和线型酚醛树脂(PN)固化剂中加入丁酮溶解好的促进剂,制备了EP/PN体系。研究了不同促进剂对于EP/PN体系的固化反应动力学的影响。研究结果表明,2-乙基-4-甲基咪唑(2E4MZ)和三苯基膦(TPP)均可加速EP/PN体系的固化。使用外推法确定两体系的凝胶温度、固化温度和后处理温度等特征温度,发现2E4MZ促进的固化体系其凝胶温度较低,而固化温度和后处理温度略高。同时利用Kissinger方程和Ozawa方程计算出2E4MZ促进体系的平均表观活化能为74.92 kJ/mol,TPP促进体系的平均表观活化能为78.59 kJ/mol。     

BTCA改性PEG/PVA相变储能纤维的结构与性能

将聚乙二醇(PEG)与聚乙烯醇(PVA)溶液混合,加入丁烷四羧酸(BTCA)作为交联剂配制纺丝原液,采用干法纺丝制得BTCA改性PEG/PVA相变储能纤维;研究了BTCA含量、热处理条件对交联程度的影响,并对纤维的结构、形态、储能性能及力学性能进行了分析。结果表明:在热处理温度为180℃,热处理时间为12 min时,纤维可达到良好的交联效果,纤维的交联程度随BTCA含量的增加呈上升趋势,BTCA质量分数为3%时达到平衡;改性纤维中PEG以独立微相区形式存在,而经热处理后可保留在交联网络中;热处理后的改性纤维力学性能随BTCA含量增加而提高,储能性能也增加且稳定;当BTCA质量分数为6%时,热处理后的纤维断裂强度达3.49 cN/dtex,再经沸水处理后纤维相变焓值可达23.01 J/g,PEG保留率达80%。     

不饱和聚酯/复合引发体系非等温固化动力学研究

采用非等温DSC法研究了不饱和聚酯/复合引发体系在不同升温速率下的固化行为,通过T-Φ外推法确定了该体系的凝胶温度、固化温度和后固化温度分别为102.7℃,124.0℃和196.5℃。通过Kissinger和Crane方程对DSC数据进行处理,获得了固化反应的表观活化能E=116.88 kJ/mol,碰撞因子A=7.35×1014,反应级数n=0.945,并由此得到了该体系的固化动力学方程。     

交联壳聚糖复合微球对F-的吸附性能研究

以壳聚糖(CTS)包合氧化铝经戊二醛交联反应制备了复合微球作为氟离子吸附剂。主要研究了复合微球对F-的吸附模型和吸附动力学,并考察了再生次数对吸附容量的影响。结果表明复合微球对F-有很强的吸附作用和较快的吸附速率;吸附行为符合Freundlich模型,为吸热过程,吸附表观活化能△E=53.71kJ/mol;复合微球经碱液洗脱再生后能够多次使用。     

2-巯基吡啶镉(Ⅱ)、汞(Ⅱ)配合物的热分解动力学研究

采用TG-DTG技术研究了2-巯基吡啶镉(Ⅱ)、汞(Ⅱ)配合物在氮气气氛中的热分解机理及非等温动力学。采用积分法(Coats-Refern方程,HM方程,MKN方程)和微分法(Achar方程)对非等温动力学数据进行了分析,得到了配合物第一步热分解反应的机理函数、动力学参数和热分解动力学方程。结果表明:其热分解过程属F2(化学反应)机理控制,非等温热分解的动力学方程为dα/dT=A/β.e-E/RT(1-α)2,其中镉(Ⅱ)配合物的表观活化能E=86.35 kJ/mol,指前因子A=4.72×107s-1;汞(Ⅱ)配合物的表观活化能E=189.67 kJ/mol,指前因子A=3.79×1018s-1。     

柔性UPR树脂/粉煤灰非等温固化动力学

用差示扫描量热法(DSC)研究了柔性不饱和聚酯树脂/粉煤灰体系的非等温固化过程,利用T-β外推法确定了体系的固化工艺温度:凝胶温度257.625K、固化温度374.275K、后处理温度406.565K。用Flynn-Wall-Ozawa法和Friedman-Reich-Levi法获得了柔性UPR固化反应表观活化能为Ea=83.94kJ·mol-1。由ASTME698-79标准方法求得指前因子,lnA=25.27;结合Crane方程分析知,复合体系的固化反应接近于一级反应。最终建立了复合体系固化反应动力学方程为ln(ddαt)=25.27-10096.22T+ln(1-α)0.9126。     

盐酸四环素的非等温降解

研究了盐酸四环素的降解动力学模型。通过不同的升温速率(β=5、10、20、25K/min)下进行热重量分析得到降解数据,并根据无模型动力学方法,得到降解活化能E及其与反应转化率α之间的关系(在转化范围0<α<0.3内,E的平均值为200kJ/mol;当α>0.3时,E值随着α变化而变化)。     

聚乙二醇-聚乙烯醇相变储能纤维的制备及其性能

以聚乙二醇(PEG)为相变物质,聚乙烯醇(PVA)为纤维基体,加入少量丁烷四羧酸(BTCA)作为交联剂,采用干法纺丝制备相变储能纤维,利用原位交联法在纤维拉伸热定形过程中使BTCA与PVA、PEG发生交联,将PEG接枝在PVA上。研究了BTCA、PEG合适的添加量以及最佳热定形温度对PEG保留率的影响,并通过差示扫描量热法、扫描电镜对纤维的热性能和形貌进行了分析。结果表明:当PEG添加量为30%(占PVA质量的百分数)、BTCA添加量为5%(占PVA质量的百分数)时,纤维充分交联,200℃下热处理10 min所得纤维PEG的保留率98%;制得的纤维的相变热焓可达34 J/g,拉伸强度可达3.26 cN/dtex;在升降温循环400次后仍具有良好的储能性。     

Properties of electrospun poly(vinyl alcohol) hydrogel nanofibers crosslinked with 1,2,3,4‐butanetetracarboxylic acid

ABSTRACT: Electrospun nanofibrous hydrogel membranes have been gaining significant importance due to the combination of unique physical properties of nanofibers and biocompatibility of hydrogels. Thus, they are considered as potential candidates for medical textile applications. This study deals with electrospinning of poly(vinyl alcohol) (PVA) hydrogel nanofibrous membranes. The chemical crosslinking of PVA with proportionate quantities of 1,2,3,4 butanetetracarboxylic acid (BTCA) was undertaken to form hydrogel structures. Cross‐linked membranes were characterized by scanning electron microscopy, FT‐IR and thermogravimetric analysis, water swelling, and durability tests. FT‐IR analysis demonstrated the formation of ester linkages between PVA and BTCA and thermogravimetric analysis showed that crosslinking improved the thermal stability of the nanofibrous structure. Furthermore, the results indicated that crosslinking with BTCA improved water stability of PVA membranes and the nanofibrous structure was preserved after water treatment. It is envisaged that use of BTCA as a cross‐linker to form hydrogel nanofibers could be a practical and a promising method for medical textile applications, especially for wound dressings given its nontoxicity and immiscibility with polymer solutions. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Crosslinking reaction of poly(vinyl alcohol) with poly(acrylic acid) (PAA) by heat treatment: Effect of neutralization of PAA

The crosslinking reaction of poly(vinyl alcohol) (PVA) by esterification using poly(acrylic acid) (PAA) as a crosslinking reagent was investigated to obtain highly insoluble PVA materials. Blend films of PVA and PAA (PVA/PAA = 8/2) were prepared to examine the effect of degree of neutralization (DN) in PAA and heat‐treatment conditions on the degree of crosslinking reaction. The degree of crosslinking reaction varied significantly when the DN of PAA changed. The optimum DN for the crosslinking reaction was in the range of 5 to 10 mol %. In the case of unneutralized PAA, the degree of crosslinking reaction was at most 15 mol % by heat treatment for 20 min at 200°C. Applying partially neutralized PAA (DN = 10 mol %) raised the degree to about 40 mol % under the same heat‐treatment conditions. FTIR analysis revealed that the hydroxyl group of PVA in the film blended with unneutralized PAA was degraded to a greater degree than that with partially neutralized PAA as a result of heat treatment. It was found that heat treatment at a low pH condition enhances the degradation of the hydroxyl group of PVA, resulting in a decrease of the number of crosslinking sites by esterification. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 2420–2427, 2003     

苯氨基甲酸甲酯热解制备苯基异氰酸酯的非等温动力学

采用热分析与红外联用技术对苯氨基甲酸甲酯(MPC)热解历程进行分析,结果表明,苯氨基甲酸甲酯的热解过程是一步生成苯基异氰酸酯同时释放出甲醇气体. 进一步对该热解反应进行了非等温动力学研究,对MPC的热解数据采用Flynn-Wall-Ozawa法计算得到反应活化能. 采用5种方法考察反应动力学参数,结果表明,MPC热解机理为相边界反应模型,机理函数为G(a)=a1/3,热解反应活化能E=20.52 kJ/mol,指前因子lgA=2.23,动力学方程为a1/3= 169.82exp[20.52′103/(8.314T)]t.     

Development of a novel PPTA/cellulose composite insulation paper with low dielectric constant and improved mechanical properties by BTCA crosslinking

This study investigates the effect of 1,2,3,4-butane tetracarboxylic acid (BTCA) crosslinking treatment on the electrical properties of poly-p-phenylene terephthalate (PPTA)/cellulose insulation paper to prepare a novel composite insulation paper with low dielectric constant and good electrical performance. Three-layer PPTA/cellulose composite paper crosslinked by BTCA under various conditions, composite paper without crosslinking, directly mixed composite paper, and conventional Kraft paper are prepared. The morphology and surface chemical composition of the paper samples are characterized. Dielectric, mechanical, and thermal properties are investigated. Results show that the BTCA concentration of 0.2 mol L⁻¹ with a 180°C curing temperature is the relatively superior crosslinking condition to prepare a novel composite with low dielectric constant and good comprehensive performance. The dielectric constant and loss of the novel composite paper decrease to 3.21 and 0.392 at 50 Hz. The tensile strength of the BTCA crosslinked three-layer PPTA/cellulose composite paper (thickness: 130 μm) has reached 10.01 kN m⁻¹, increased by 41.6% than the directly mixed composite paper. The novel BTCA crosslinked composite paper also shows improved thermal stability. The BTCA crosslinking proves to be a promising method to improve the dielectric properties and electrical performance of the PPTA/cellulose composite paper.     

改进Freeman_Carroll法求算氢氧化镁热分解动力学参数研究

Freeman-Carroll法是用来计算固体物质热分解反应动力学参数较为常用的方法,本文对该法进行了改进,对转化率d求算公式进行了微分变换,发现dα/dT与dα/dw,满足一简单的数学关系式,而通过这一关系式可解决Freeman-Cart011求算动力学参数不准确的问题,对于一般的固体热分解动力学参数的计算具有普遍的意义。采用改进后的方法计算Mg（OH）：热分解活化能E为122kJ／mol,反应级数n为0．68。     

Morphology and mechanical properties of pullulan/poly(vinyl alcohol) blends crosslinked with glyoxal

We prepared pullulan/poly(vinyl alcohol) (PVA) blend films by casting the polymer solution in dimethyl sulfoxide. Their morphology and mechanical properties were investigated. Scanning electron micrographs revealed that the pullulan was immiscible with PVA over the entire composition range. The tensile strength and modulus of the blend films were lower than those predicted by the upper bound composite equation. To improve the mechanical properties, we investigated the reaction of the 40/60 blend with glyoxal. The infrared spectral change and the increase in the glass‐transition temperature (corresponding to the PVA component) accompanying the reaction indicated that crosslinking with glyoxal had proceeded. The crosslinked films were homogeneous and had higher tensile strengths and moduli than the simple blend. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 2273–2280, 2001     

Effect of postcrosslinking modification with glutaraldehyde on the properties of thermoplastic starch/poly(vinyl alcohol) blend films

Thermoplastic starch (TPS)/poly(vinyl alcohol) (PVA) blend films were modified by crosslinking through soaking the films in glutaraldehyde aqueous solution and then heating in an oven. The effects of the concentration of the glutaraldehyde aqueous solution, soaking time, reaction temperature, and time on the crosslinking reaction were investigated. The moisture absorption and mechanical properties of the films were measured to characterize the influence of the crosslinking modification. It was found that the crosslinking modification significantly reduced the moisture sensitivity of the TPS/PVA blend films and increased the tensile strength and Young's modulus but decreased the elongation at break of the TPS/PVA blend films. The described method could be used for posttreating TPS/PVA‐based products to optimize their properties. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012