超高分子量聚丙烯腈混合溶剂沉淀聚合等理论研究及原丝制备工艺的探索
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摘要
碳纤维因其拥有高强，高模，密度小等极优越的机械性能及化学稳定性广泛应用于航空、航天领域。聚丙烯腈（PAN）原丝是目前生成碳纤维最主要的原料。在碳纤维的生产过程中，原丝的性能是制约碳纤维性能的主要因素。影响原丝性能的因素主要有聚合体中共聚单体类型、分子量、立构规整性、纺丝方法及工艺、牵伸工艺、干燥致密化程度、上油工艺等。采用高平均分子量聚丙烯腈树脂进行纺丝是生产高强度聚丙烯腈原丝的有效途径。
基于此我们对于高分子量聚丙烯腈的合成以及纺丝做了大量的工作，研究了混和溶剂沉淀聚合的机理，以及分子量，转化率和沉淀颗粒形貌与反应体系中水含量的关系。利用高分子量聚丙烯腈纺丝，利用落球粘度法研究了纺丝液的流变性质，最终制的了强度1GPa的优质碳纤维原丝。以下是具体研究内容：
1.本文利用二甲基亚砜（DMSO）与沉淀剂水的非均相混合溶剂沉淀聚合合成高分子量聚丙烯腈。在50℃，55℃，60℃以及65℃4个不同的温度下研究了水含量由0-90%对于转化率的影响，并通过对于转化率的分析对PAN混合溶剂沉淀聚合反应过程的机理进行了探讨。
2.利用SEM研究了沉淀颗粒微观结构，由于是混合溶剂的沉淀聚合，溶剂DMSO可以与沉淀可以发生溶剂化作用，溶剂DMSO的含量对于沉淀颗粒的结构有着很大的影响。本文应用第四统计力学分析了在混合溶剂沉淀聚合中沉淀颗粒形貌随着沉淀剂水含量以及温度的变化
3.混合溶剂沉淀聚合中，在水含量很少的时候趋向于溶液聚合方式，而水含量高时倾向沉淀聚合，在这样的体系中，分子量的贡献是来自2部分的，一个是液相的贡献，另一部分是沉淀颗粒表面以及间隙的原位聚合的贡献，我们这里称之为固相的贡献。本文通过固液相聚合反应的动力学方程首先推得两相各自分子量分布的表达式， f_L(X)和f_S(X)，进而求出数均分子量的表达式，最后利用实验来求得液-固相贡献之比R值,通过R值可知随水含量的增加，沉淀聚合过程中固相中的聚合逐渐占主导地位。
4.从沉淀聚合的亚微观聚集过程出发，建立初生态沉淀聚合聚合体凝聚过程模型，推导出了丙烯腈沉淀聚合体的分子量与H_2O/DMSO的关系。在H_2O/DMSO的不同配比条件下进行实验，得出的实验结果与理论推导相吻合。最终可以得到：聚丙烯腈的分子量随H_2O/DMSO比例增加而线性递增的结论。
5.利用扫描电子显微镜和强度测试仪，研究了普通分子量PAN原丝生产过程中，聚合纺丝工艺以及高温高压牵伸对原丝表面形态及力学性能的影响，并利用群子统计理论，成功预测了高强度纤维的理论牵伸倍数。结果表明：原丝质量的好坏与纺丝液的质量和纺丝工艺密切相关，高温高压蒸汽牵伸，牵伸倍数增大，纤维直径减小，取向提高，纤维表面越光滑，强度和拉伸功率增大；阶段升温聚合方法，干燥致密化效果提高对原丝性能改进具有至关重要的作用；特定工艺下，根据群子统计理论成功预测了纤维强度为1.0GPa时，纤维的理论牵伸倍数为11.16。
6.高分子聚丙烯腈溶解困难，且制得的纺丝液粘度高。高分子聚丙烯腈的溶解是纺丝中的一个主要难题。我们通过落球法测粘度研究了高分子量聚丙烯腈共聚物的流变性能。论文详细的研究了剪切速率，水含量、温度、浓度与粘度的关系。并求出了不同温度下的粘流活化能。通过研究确定了最佳的湿法纺丝条件，并由此制的纤维直径小于10微米，强度达1GPa的原丝。
PAN fiber is one of the most commonly used precursors for makingcarbon fibers. Since carbon fibers generally have the inherentcombination of high strength, high stiffness, light weight, and chemicalstability, they are uniquely qualified for use in the aerospace industry.
The Properties of carbon fibers are directly influenced by thequality of PAN precursor fibers. The type of the copolymers,molecularweight of PAN, the stereoregularity and spinning methods arethe mian factors influence the performance of PAN fibers. It is aneffective way using high molecular weight polymer to enhance thestrength of PAN precursor fibers.
We have done a lot of work on synthesis of high molecular weightpolyacrylonitrile and making PAN fibers with wet-spinning. This paperstudies the mechanism of mixed solvent radical polymerization of PAN.We have studied the relationships between molecular weight, conversionrate, precipitation particle morphology and the content of water in thereaction system. We got the PAN precursor with the strength is1GPa by using high molecular weight polyacrylonitrile resin. The rheologicalproperty of high molecular weight PAN spinning solution was studied byusing falling ball method. The main work we have done are as follows:
1. We got the high molecular weight PAN by using mixed solventradical polymerization. The precipitation polymerization of acrylonitrile(AN) was carried out in a mixture solvent of dimethyl sulfoxide (DMSO)and water at50-65℃. We studied the effect of water content from0to90%(w/w) on the conversion of aggregation in the precipitationpolymerization. The mechanism of mixed solvent radical polymerizationwas also studied.
2. The morphologies of PAN precipitates of were investigated bySEM analysis measurement. The solvent content of DMSO have greatimpact on the morphology of precipitation particle. According tosub-cluster statistical theory, we stduied the relationship of precipitationparticle morphology with the content of water and the reactiontemperature.
3. We synthesis PAN by mixed solvent radical polymerization, thewater content affects the polymerization a lot. When the water content islow the polymerization tends to the solution polymerization, and whenwater content is high it tends to precipitation polymerization. Thecontribution of molecular weight of the PAN is from two parts, one isthe contribution of solution polymerization which we called the contribution of liquid phase. The other is the particle surface andprecipitation polymerization gap contributions which we called thecontribution of solid phase. Though the kinetic equation of two phasepolymerization which we metioned above, we get the expressionmolecular weight distribution of two-phase polymerizations f_L(X)(theexpression molecular weight distribution of the liquid phase) and f_S(X)(the expression molecular weight distribution of the solid phase). Thenwe deduce the expression of the number average molecular weight. Weobtain the values of R which is the ratio of liquid-solid phasecontributions from the data of the number molecular weight. The valueof of R show that the soild-phase polymerization play the main role forthe contribution of the number molecular weight with the increase ofwater in the reaction system.
4. The purpose of this study is experimental and theoreticalinvestigations of PAN molecular weight increase in precipitationpolymerization as functions of H_2O/DMSO ratio and intrinsic viscosity.To obtain the purpose, precipitation polymerization of acrylonitrile wascarried outby changing the solvent ratio of H_2O/DMSO at differenttemperature, molecular weight and intrinsic viscosity ofthe obtainedpolymer were measured in DMF solution, and model mechanism ofprecipitation polymerization was suggested in relation betweenmolecular weight increases of PAN and H_2O/DMSO ratio.
5. By using scanning electron microscopy (SEM) and electric singlefiber strength tester, effects of different spinning processes, especiallypressured stream drawing, were investigated on the mechanicalproperties and morphologies of precursor in the preparation of PANprecursor. The empirical relationship between fiber strength and drawratio was studied by using the sub-cluster statistical theory, with whichthe corresponding draw ratio of higher-strength precursor wassuccessfully predicted. The results indicated that: the property ofPAN-based precursor is closely related with the quality of spinning dropand spinning process. During the pressured-stream drawing, as theincrease of draw ratio, fiber diameter decreased, the degree oforientation raised, the surface of precursor became smoother and thestrength and tensile power increased. Polymerization temperaturecontrolled by stage and the results of drying collapse play a importantrole in the improvement of mechanical property of the precursor.According to sub-cluster statistical theory, it was predicted successfullywhen fiber strength was1.0GPa under a certain experimental conditionof the fiber were11.16.
6. The high molecular weight PAN is difficut to dissolve, and theviscosity of the spinning solution which produced by the high molecularweight PAN and DMSO is high. The rheological behavior ofPAN/DMSO solution was studied with falling ball rheometer. We studied the relationship between the shear rate, water content,temperature, concentration and viscosity of the spinning solution.According to Arrhenius equation, the viscous flow activation energydecrease with the inerease the concentration of the water in the spinningsolution from0-3wt%. We got the PAN precursor with the diameter lessthan10μm and the intensity more than1Gpa.
基于此我们对于高分子量聚丙烯腈的合成以及纺丝做了大量的工作，研究了混和溶剂沉淀聚合的机理，以及分子量，转化率和沉淀颗粒形貌与反应体系中水含量的关系。利用高分子量聚丙烯腈纺丝，利用落球粘度法研究了纺丝液的流变性质，最终制的了强度1GPa的优质碳纤维原丝。以下是具体研究内容：
1.本文利用二甲基亚砜（DMSO）与沉淀剂水的非均相混合溶剂沉淀聚合合成高分子量聚丙烯腈。在50℃，55℃，60℃以及65℃4个不同的温度下研究了水含量由0-90%对于转化率的影响，并通过对于转化率的分析对PAN混合溶剂沉淀聚合反应过程的机理进行了探讨。
2.利用SEM研究了沉淀颗粒微观结构，由于是混合溶剂的沉淀聚合，溶剂DMSO可以与沉淀可以发生溶剂化作用，溶剂DMSO的含量对于沉淀颗粒的结构有着很大的影响。本文应用第四统计力学分析了在混合溶剂沉淀聚合中沉淀颗粒形貌随着沉淀剂水含量以及温度的变化
3.混合溶剂沉淀聚合中，在水含量很少的时候趋向于溶液聚合方式，而水含量高时倾向沉淀聚合，在这样的体系中，分子量的贡献是来自2部分的，一个是液相的贡献，另一部分是沉淀颗粒表面以及间隙的原位聚合的贡献，我们这里称之为固相的贡献。本文通过固液相聚合反应的动力学方程首先推得两相各自分子量分布的表达式， f_L(X)和f_S(X)，进而求出数均分子量的表达式，最后利用实验来求得液-固相贡献之比R值,通过R值可知随水含量的增加，沉淀聚合过程中固相中的聚合逐渐占主导地位。
4.从沉淀聚合的亚微观聚集过程出发，建立初生态沉淀聚合聚合体凝聚过程模型，推导出了丙烯腈沉淀聚合体的分子量与H_2O/DMSO的关系。在H_2O/DMSO的不同配比条件下进行实验，得出的实验结果与理论推导相吻合。最终可以得到：聚丙烯腈的分子量随H_2O/DMSO比例增加而线性递增的结论。
5.利用扫描电子显微镜和强度测试仪，研究了普通分子量PAN原丝生产过程中，聚合纺丝工艺以及高温高压牵伸对原丝表面形态及力学性能的影响，并利用群子统计理论，成功预测了高强度纤维的理论牵伸倍数。结果表明：原丝质量的好坏与纺丝液的质量和纺丝工艺密切相关，高温高压蒸汽牵伸，牵伸倍数增大，纤维直径减小，取向提高，纤维表面越光滑，强度和拉伸功率增大；阶段升温聚合方法，干燥致密化效果提高对原丝性能改进具有至关重要的作用；特定工艺下，根据群子统计理论成功预测了纤维强度为1.0GPa时，纤维的理论牵伸倍数为11.16。
6.高分子聚丙烯腈溶解困难，且制得的纺丝液粘度高。高分子聚丙烯腈的溶解是纺丝中的一个主要难题。我们通过落球法测粘度研究了高分子量聚丙烯腈共聚物的流变性能。论文详细的研究了剪切速率，水含量、温度、浓度与粘度的关系。并求出了不同温度下的粘流活化能。通过研究确定了最佳的湿法纺丝条件，并由此制的纤维直径小于10微米，强度达1GPa的原丝。
PAN fiber is one of the most commonly used precursors for makingcarbon fibers. Since carbon fibers generally have the inherentcombination of high strength, high stiffness, light weight, and chemicalstability, they are uniquely qualified for use in the aerospace industry.
The Properties of carbon fibers are directly influenced by thequality of PAN precursor fibers. The type of the copolymers,molecularweight of PAN, the stereoregularity and spinning methods arethe mian factors influence the performance of PAN fibers. It is aneffective way using high molecular weight polymer to enhance thestrength of PAN precursor fibers.
We have done a lot of work on synthesis of high molecular weightpolyacrylonitrile and making PAN fibers with wet-spinning. This paperstudies the mechanism of mixed solvent radical polymerization of PAN.We have studied the relationships between molecular weight, conversionrate, precipitation particle morphology and the content of water in thereaction system. We got the PAN precursor with the strength is1GPa by using high molecular weight polyacrylonitrile resin. The rheologicalproperty of high molecular weight PAN spinning solution was studied byusing falling ball method. The main work we have done are as follows:
1. We got the high molecular weight PAN by using mixed solventradical polymerization. The precipitation polymerization of acrylonitrile(AN) was carried out in a mixture solvent of dimethyl sulfoxide (DMSO)and water at50-65℃. We studied the effect of water content from0to90%(w/w) on the conversion of aggregation in the precipitationpolymerization. The mechanism of mixed solvent radical polymerizationwas also studied.
2. The morphologies of PAN precipitates of were investigated bySEM analysis measurement. The solvent content of DMSO have greatimpact on the morphology of precipitation particle. According tosub-cluster statistical theory, we stduied the relationship of precipitationparticle morphology with the content of water and the reactiontemperature.
3. We synthesis PAN by mixed solvent radical polymerization, thewater content affects the polymerization a lot. When the water content islow the polymerization tends to the solution polymerization, and whenwater content is high it tends to precipitation polymerization. Thecontribution of molecular weight of the PAN is from two parts, one isthe contribution of solution polymerization which we called the contribution of liquid phase. The other is the particle surface andprecipitation polymerization gap contributions which we called thecontribution of solid phase. Though the kinetic equation of two phasepolymerization which we metioned above, we get the expressionmolecular weight distribution of two-phase polymerizations f_L(X)(theexpression molecular weight distribution of the liquid phase) and f_S(X)(the expression molecular weight distribution of the solid phase). Thenwe deduce the expression of the number average molecular weight. Weobtain the values of R which is the ratio of liquid-solid phasecontributions from the data of the number molecular weight. The valueof of R show that the soild-phase polymerization play the main role forthe contribution of the number molecular weight with the increase ofwater in the reaction system.
4. The purpose of this study is experimental and theoreticalinvestigations of PAN molecular weight increase in precipitationpolymerization as functions of H_2O/DMSO ratio and intrinsic viscosity.To obtain the purpose, precipitation polymerization of acrylonitrile wascarried outby changing the solvent ratio of H_2O/DMSO at differenttemperature, molecular weight and intrinsic viscosity ofthe obtainedpolymer were measured in DMF solution, and model mechanism ofprecipitation polymerization was suggested in relation betweenmolecular weight increases of PAN and H_2O/DMSO ratio.
5. By using scanning electron microscopy (SEM) and electric singlefiber strength tester, effects of different spinning processes, especiallypressured stream drawing, were investigated on the mechanicalproperties and morphologies of precursor in the preparation of PANprecursor. The empirical relationship between fiber strength and drawratio was studied by using the sub-cluster statistical theory, with whichthe corresponding draw ratio of higher-strength precursor wassuccessfully predicted. The results indicated that: the property ofPAN-based precursor is closely related with the quality of spinning dropand spinning process. During the pressured-stream drawing, as theincrease of draw ratio, fiber diameter decreased, the degree oforientation raised, the surface of precursor became smoother and thestrength and tensile power increased. Polymerization temperaturecontrolled by stage and the results of drying collapse play a importantrole in the improvement of mechanical property of the precursor.According to sub-cluster statistical theory, it was predicted successfullywhen fiber strength was1.0GPa under a certain experimental conditionof the fiber were11.16.
6. The high molecular weight PAN is difficut to dissolve, and theviscosity of the spinning solution which produced by the high molecularweight PAN and DMSO is high. The rheological behavior ofPAN/DMSO solution was studied with falling ball rheometer. We studied the relationship between the shear rate, water content,temperature, concentration and viscosity of the spinning solution.According to Arrhenius equation, the viscous flow activation energydecrease with the inerease the concentration of the water in the spinningsolution from0-3wt%. We got the PAN precursor with the diameter lessthan10μm and the intensity more than1Gpa.
引文
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