丙烯腈和醋酸乙烯酯水相沉淀连续共聚合研究
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摘要
丙烯腈(AN)共聚物(AN wt%＞85%)纤维即腈纶,在合成纤维中因其纺织服用性能类似羊毛,深受消费者欢迎,成为当今世界轻纺工业的重要原料。通常引入第二单体,如丙烯酸甲酯(MA)、醋酸乙烯酯(VAc)、衣康酸(IA)、丙烯酸(AA)等,以改善纤维的纺丝性能。目前国内工业化的腈纶共聚第二单体主要为丙烯酸甲酯(MA)和醋酸乙烯酯(VAc)两种。其中后者原料来源丰富,价格低,且高含量下还可提供纤维的高伸缩性,成为近年来研发的热点。
本文首先在模拟工业流程的连续小试装置上进行以VAc为二单AN水相沉淀共聚合研究。通过不同引发聚合体系和不同调控聚合体系pH值策略等实验表明,在线聚合体系pH值和聚合温度的实时反馈控制技术能快速确保聚合过程的稳定性,且重现性良好。在有种子开车的情况下一般聚合温度和体系pH值分别在半倍和二倍停留时间内趋于稳定,而离线测定的转化率、沉降值则在三倍停留时间后也达稳定。通过对比小试实验和工业生产的相关数据,可以证明连续小试装置模拟工业生产具有一定的代表性。同时,针对AN水相沉淀聚合中两种常见非稳态现象进行了初步分析。当聚合体系pH值超过3.0以后极易发生爆聚现象,而当体系pH值进一步上升超过4.0后则会导致失活现象。
其次,通过提高单体进料中二单VAc浓度配比及聚合体系pH值,可以顺利提高丙烯腈共聚物中VAc组成,聚合转化率也略有提高,达到高醋腈纶的目标。但测试结果发现,丙烯腈共聚合物粘均分子量明显增大,与理论分析相反,原因有待进一步剖析。分子量是决定纺丝原液粘度的关键因素。分子量过大,纺丝原液粘度会大大增加,不利于后加工和纤维的形成。为降低丙烯腈共聚物分子量,分别采用了增加链转移剂用量和调节引发体系的氧化剂还原剂比例。发现链转移剂TEG用量或氧化剂浓度提高5%,聚合转化率略有增加,共聚物VAc组成有明显下降,聚合物粘均分子量明显减小,但提高到10%时变化幅度减小。此外,平均停留时间从47min缩短到44min,聚合转化率、聚合物组成和粘均分子量均基本不变,可适度提高产能。
而且,共聚物中VAc%提高,体均和数均粒径均增大,粒径分布变窄,沉降值下降。值得注意的是,数均粒径增大幅度比较大,这说明小粒子之间凝聚速度加快。聚合体系pH值增加,体均粒径变化趋势是先增加后减小,数均粒径是先减小后增加;分布指数PDI是先增大后减小,分散系数C.V.则单边下降,而沉降值变化不明显。平均停留时间增加,数均粒径变化不大,体均粒径增加,粒径分布略变宽,沉降值略有下降。链转移剂用量或O/M比增加,体均和数均粒径都减小,粒径分布变宽,且小粒子增多,沉降值略有上升。
最后,探讨了丙烯腈共聚物的硫氰酸钠水溶液原液的流变特性,发现剪切应力与剪切速率在双对数坐标上呈线性关系,较好地符合幂律定律,属剪切变稀的非牛顿流体,即假塑性流体。共聚物组成VAc%相近的纺丝原液剪切粘度随分子量的升高而增加。其中,非牛顿指数n变化不明显,而共聚物分子量的增大将导致其表观粘度ηα及稠度系数κ_(sp)明显增大。相同分子量范围的丙烯腈共聚物,其纺丝原液剪切粘度随着二单VAc组成的提高而降低。其中,稠度系数κ_(sp)下降明显,而非牛顿指数n仍然变化不大。
Acrylic fiber is acylonitrile copolymer fiber with acylonitrile fraction more than 85wt%. It is welcomed very much due to the wool-like clothing properties compared to other synthetic fibers and has become one of the important raw materials in the world textile and other light industries. A second comonomer, such as methacrylate (MA), vinyl acetate (VAc), itaconic acid (IA), and acrylic acid (AA), is usually incorporated into acrylic fiber to modify the spinning properties of fiber. Up to now, methacrylate (MA) and vinyl acetate (VAc) are most used as second comonomers in domestic acrylic fiber industry. The resource of VAc raw material is abundant with low price, and the fiber with high VAc content can also perform the high retractility. Therefore, acrylic fiber with high VAc content has received a lot of attention.
In this work, the aqueous precipitation copolymerization of AN and VAc was investigated in a continuous pilot apparatus, which was scaled down from an industrial process. The experiments were carried out with different initiation systems and various pH values of polymerization system. It had been found that that the on-line monitor and control system of the polymerization temperature and pH could ensure stability and replicability of the polymerization process. For start-up with polymer seed, polymerization temperature and pH generally reach their stable state in half and two residence times respectively while the monomer conversion and sedimentation value became stable after three residence times. The comparison between pilot experimental and industrial process data has proven that the continuous pilot plant could repeat the industrial process. Meanwhile, two common unstable phenomena in AN aqueous precipitation polymerization had been analyzed. When the pH value of polymerization system was increased over 3.0, run away polymerization would take place very easily. On the other hand, when the pH value was further increased over 4.0, deactivation phenomenon would occur.
VAc content in Copolymers had been successfully increased by increasing VAc content in monomers feeding and pH value of polymerization system. The conversion was increased slightly correspondingly, which meet requirements for high VAc content acrylic fiber. However, the average molecular weight of copolymer was increased apparently, which contradict the results of theoretical analysis. Further investigation is necessary to reveal the reasons of this phenomenon. Molecular weight was the key factor determining the viscosity of spinning dope. If the molecular weight is increased excessively, the viscosity of spinning dope will be increased dramatically, which was not favorable for post-processing and fiber formation. In order to lower the molecular weight of AN copolymer, the amount of chain transfer agent (TEG) and the oxidant in initiation system were separately increased. It was found that with 5% increase in either chain transfer agent or oxidant concentration, polymerization conversion was increased slightly, while VAc composition content in copolymer and viscosity average molecular weight decreased significantly. However, further increase in either chain transfer agent or oxidant concentration did not have significant effects on resultant copolymer. In addition, when the average residence time was shortened from 47 minutes to 44 minutes, polymerization conversion, polymer composition and viscosity average molecular weight were not significantly affected, which might improve production capacity moderately.
When VAc content in the copolymer was increased, both volume average and number average particle sizes were increased, particle size distribution became narrow, and sedimentation value was declined. It is worth noting that the increase in number average particle size was greater, which indicated that cohesion rate between small particles was increased. When pH was increased, volume average particle size was increased first then decreased, while number average particle size was decreased first then increased. The distribution index of particle size (PDI) was increased first then decreased, while the coefficient of dispersibility (C.V.) was decreased and sedimentation value did not change significantly. When average residence time was increased, number average particle size was not changed, volume average particle size was increased, particle size distribution became broader slightly, and the sedimentation value was declined slightly. When the amount of chain transfer agent addition or oxidant was increased, both volume average and number average particle sizes were decreased, particle size distribution was broadened, the number of small particles was increased, and sedimentation value was increased slightly.
Rheological properties of acrylonitrile copolymer in NaSCN-aqueous solution have been investigated. It was found that the shear stress and shear rate showed a linear relationship in the double logarithmic coordinates, which meet with power-law. The solution is a shear thinning non-Newtonian fluid, also called pseudoplastic fluid. The shear viscosities of solution with similar Copolymers composition was increased with the increase of the molecular weight. The non-Newtonian index n was not obviously changed, while notable increase of apparent viscosityη_αand consistency coefficient k_(sp) have been found with the increase of copolymer molecular weight. The shear viscosities of solution of Copolymers with similar molecular weight were increased with the increase of the VAc content in copolymer. Consistency coefficient k_(sp) was decreased significantly, while non-Newtonian index n was not changed.
本文首先在模拟工业流程的连续小试装置上进行以VAc为二单AN水相沉淀共聚合研究。通过不同引发聚合体系和不同调控聚合体系pH值策略等实验表明,在线聚合体系pH值和聚合温度的实时反馈控制技术能快速确保聚合过程的稳定性,且重现性良好。在有种子开车的情况下一般聚合温度和体系pH值分别在半倍和二倍停留时间内趋于稳定,而离线测定的转化率、沉降值则在三倍停留时间后也达稳定。通过对比小试实验和工业生产的相关数据,可以证明连续小试装置模拟工业生产具有一定的代表性。同时,针对AN水相沉淀聚合中两种常见非稳态现象进行了初步分析。当聚合体系pH值超过3.0以后极易发生爆聚现象,而当体系pH值进一步上升超过4.0后则会导致失活现象。
其次,通过提高单体进料中二单VAc浓度配比及聚合体系pH值,可以顺利提高丙烯腈共聚物中VAc组成,聚合转化率也略有提高,达到高醋腈纶的目标。但测试结果发现,丙烯腈共聚合物粘均分子量明显增大,与理论分析相反,原因有待进一步剖析。分子量是决定纺丝原液粘度的关键因素。分子量过大,纺丝原液粘度会大大增加,不利于后加工和纤维的形成。为降低丙烯腈共聚物分子量,分别采用了增加链转移剂用量和调节引发体系的氧化剂还原剂比例。发现链转移剂TEG用量或氧化剂浓度提高5%,聚合转化率略有增加,共聚物VAc组成有明显下降,聚合物粘均分子量明显减小,但提高到10%时变化幅度减小。此外,平均停留时间从47min缩短到44min,聚合转化率、聚合物组成和粘均分子量均基本不变,可适度提高产能。
而且,共聚物中VAc%提高,体均和数均粒径均增大,粒径分布变窄,沉降值下降。值得注意的是,数均粒径增大幅度比较大,这说明小粒子之间凝聚速度加快。聚合体系pH值增加,体均粒径变化趋势是先增加后减小,数均粒径是先减小后增加;分布指数PDI是先增大后减小,分散系数C.V.则单边下降,而沉降值变化不明显。平均停留时间增加,数均粒径变化不大,体均粒径增加,粒径分布略变宽,沉降值略有下降。链转移剂用量或O/M比增加,体均和数均粒径都减小,粒径分布变宽,且小粒子增多,沉降值略有上升。
最后,探讨了丙烯腈共聚物的硫氰酸钠水溶液原液的流变特性,发现剪切应力与剪切速率在双对数坐标上呈线性关系,较好地符合幂律定律,属剪切变稀的非牛顿流体,即假塑性流体。共聚物组成VAc%相近的纺丝原液剪切粘度随分子量的升高而增加。其中,非牛顿指数n变化不明显,而共聚物分子量的增大将导致其表观粘度ηα及稠度系数κ_(sp)明显增大。相同分子量范围的丙烯腈共聚物,其纺丝原液剪切粘度随着二单VAc组成的提高而降低。其中,稠度系数κ_(sp)下降明显,而非牛顿指数n仍然变化不大。
Acrylic fiber is acylonitrile copolymer fiber with acylonitrile fraction more than 85wt%. It is welcomed very much due to the wool-like clothing properties compared to other synthetic fibers and has become one of the important raw materials in the world textile and other light industries. A second comonomer, such as methacrylate (MA), vinyl acetate (VAc), itaconic acid (IA), and acrylic acid (AA), is usually incorporated into acrylic fiber to modify the spinning properties of fiber. Up to now, methacrylate (MA) and vinyl acetate (VAc) are most used as second comonomers in domestic acrylic fiber industry. The resource of VAc raw material is abundant with low price, and the fiber with high VAc content can also perform the high retractility. Therefore, acrylic fiber with high VAc content has received a lot of attention.
In this work, the aqueous precipitation copolymerization of AN and VAc was investigated in a continuous pilot apparatus, which was scaled down from an industrial process. The experiments were carried out with different initiation systems and various pH values of polymerization system. It had been found that that the on-line monitor and control system of the polymerization temperature and pH could ensure stability and replicability of the polymerization process. For start-up with polymer seed, polymerization temperature and pH generally reach their stable state in half and two residence times respectively while the monomer conversion and sedimentation value became stable after three residence times. The comparison between pilot experimental and industrial process data has proven that the continuous pilot plant could repeat the industrial process. Meanwhile, two common unstable phenomena in AN aqueous precipitation polymerization had been analyzed. When the pH value of polymerization system was increased over 3.0, run away polymerization would take place very easily. On the other hand, when the pH value was further increased over 4.0, deactivation phenomenon would occur.
VAc content in Copolymers had been successfully increased by increasing VAc content in monomers feeding and pH value of polymerization system. The conversion was increased slightly correspondingly, which meet requirements for high VAc content acrylic fiber. However, the average molecular weight of copolymer was increased apparently, which contradict the results of theoretical analysis. Further investigation is necessary to reveal the reasons of this phenomenon. Molecular weight was the key factor determining the viscosity of spinning dope. If the molecular weight is increased excessively, the viscosity of spinning dope will be increased dramatically, which was not favorable for post-processing and fiber formation. In order to lower the molecular weight of AN copolymer, the amount of chain transfer agent (TEG) and the oxidant in initiation system were separately increased. It was found that with 5% increase in either chain transfer agent or oxidant concentration, polymerization conversion was increased slightly, while VAc composition content in copolymer and viscosity average molecular weight decreased significantly. However, further increase in either chain transfer agent or oxidant concentration did not have significant effects on resultant copolymer. In addition, when the average residence time was shortened from 47 minutes to 44 minutes, polymerization conversion, polymer composition and viscosity average molecular weight were not significantly affected, which might improve production capacity moderately.
When VAc content in the copolymer was increased, both volume average and number average particle sizes were increased, particle size distribution became narrow, and sedimentation value was declined. It is worth noting that the increase in number average particle size was greater, which indicated that cohesion rate between small particles was increased. When pH was increased, volume average particle size was increased first then decreased, while number average particle size was decreased first then increased. The distribution index of particle size (PDI) was increased first then decreased, while the coefficient of dispersibility (C.V.) was decreased and sedimentation value did not change significantly. When average residence time was increased, number average particle size was not changed, volume average particle size was increased, particle size distribution became broader slightly, and the sedimentation value was declined slightly. When the amount of chain transfer agent addition or oxidant was increased, both volume average and number average particle sizes were decreased, particle size distribution was broadened, the number of small particles was increased, and sedimentation value was increased slightly.
Rheological properties of acrylonitrile copolymer in NaSCN-aqueous solution have been investigated. It was found that the shear stress and shear rate showed a linear relationship in the double logarithmic coordinates, which meet with power-law. The solution is a shear thinning non-Newtonian fluid, also called pseudoplastic fluid. The shear viscosities of solution with similar Copolymers composition was increased with the increase of the molecular weight. The non-Newtonian index n was not obviously changed, while notable increase of apparent viscosityη_αand consistency coefficient k_(sp) have been found with the increase of copolymer molecular weight. The shear viscosities of solution of Copolymers with similar molecular weight were increased with the increase of the VAc content in copolymer. Consistency coefficient k_(sp) was decreased significantly, while non-Newtonian index n was not changed.
引文
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