UV辐照辅助下聚合物固载引发剂的合成与应用研究
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摘要
本论文以P(S-DVB)微球、P(S-DVB)磺酸钠微球和聚丙烯无纺布为基体材料,通过UV辐照接枝反应制备了P(S-DVB)丙烯酸接枝微球,P(S-DVB)磺酸钠丙烯酸接枝微球和丙烯酸接枝聚丙烯无纺布,探讨了浸泡液配方、辐照时间及辐照距离等条件对辐照接枝聚合反应的影响。得出P(S DVB)磺酸钠微球UV辐照接枝反应体系的最佳浸泡液配比为:分散剂和溶剂体积比为1:1,丙烯酸浓度为50%,引发剂A浓度为25 g/L,引发剂B浓度为0.75 g/L,在G灯辐照下,以d_3距离辐照接枝反应t_3,最大接枝率可达68.3%;P(S-DVB)微球UV辐照接枝反应体系的最佳浸泡液配比为:分散剂和溶剂比例为3:2,丙烯酸浓度为50%,引发剂A浓度为25 g/L,引发剂B浓度为0.75g/L,在G灯辐照下,以d_2距离辐照接枝反应t_2,最大接枝率可达52.6%;PP无纺布UV辐照接枝反应体系的最佳浸泡液配比为:分散剂和溶剂比例为1:1,丙烯酸浓度为50%,引发剂A浓度为25 g/L,引发剂B浓度为0.50 g/L,在H-1汞灯辐照下,以四层堆叠的形式,d_2辐照距离接枝反应t_3,最大平均接枝率可达1321%。在双氧水和过酸化促进剂的混合液中,将三类UV辐照接枝产物上所引入的羧基转化为过羧基,使其具有进一步引发聚合反应的活性。比较了过酸化促进剂用量对固载过酸含量的影响,结果表明双氧水和过酸化促进剂体积比为25:18时,所得固载过酸含量最高。对三类固载过酸引发剂引发单体的接枝反应做了研究,比较了丙烯酸、丙烯酰胺及丙烯酸/丙烯酰胺混合单体的接枝聚合反应。
本文重点研究了PP无纺布固载过酸氧化还原体系引发丙烯酰胺的接枝聚合反应,探讨了反应温度、反应时间、单体浓度、固载过酸含量等因素对接枝聚合反应的影响。对其反应机理进行了深入探讨,得出接枝聚合反应的动力学方程为:R_g=K[M][RCOOOH]~(1/2),接枝聚合反应表观活化能E=8.103KJ/mol,在单体浓度或固载过酸浓度恒定是,接枝聚合反应速率常数分别为K=5.100×10~(-3)L/mol·s及K'=5.125×10~(-3)L/mol·s。
本文对三种基体材料的接枝产物进行了羧基含量测定、傅立叶变换红外光谱(FTIR)和扫描电镜(SEM)分析,结果表明聚合物固载过酸引发接枝聚合反应成功地在各基体材料表面引入了预定单体的聚合物长链,引起基体材料表面形貌发生了较大改变。
本文对PP无纺布固载过酸引发的接枝产物在不同温度、盐及pH值的水溶液中的溶胀性能进行了研究,各接枝产物的溶胀比对温度的变化表现出一定的响应性(呈热缩性);其溶胀比随盐及pH值的改变有明显的变化,随盐及pH值的循环改变时,表现出溶胀-收缩-溶胀的规律性变化,各接枝产物尤其是丙烯酸的接枝产物其溶胀比对盐和pH值的响应性尤为明显。
本文还对三种基体材料的接枝产物对重金属及亚甲基蓝的吸附性能进行了研究,发现丙烯酸单体的接枝产物对Cu~(2+)和Pb~(2+)有较好的吸附性。吸附性最好的PP无纺布固载过酸引发丙烯酸接枝产物对金属离子的最大吸附容量分别达到99.6mg(Cu~(2+))/g、343.8mg(Pb~(2+))/g,而PP无纺布固载过酸引发丙烯酸/丙烯酰胺混合单体接枝产物对亚甲基蓝的吸附效果最佳,最大吸附容量可达1185mg(亚甲基蓝)/g,吸附反应速率遵循Ho准二级吸附速率方程,表观吸附活化能Ea=40.24kJ/mol;其等温吸附符合Langmuir方程,吸附过程为化学吸附的吸热吸附。
In the current paper,polyacrylic acid was grafted onto backbone of several polymer substrate,such as P(S-DVB)microspheres,P(S-DVB)sodium sulfonate mierospheres and polypropylene non-woven fabrics,by the surface grafting polymerization induced by UV radiation.Several effect factors of the radiation grafting were investigated,including formulation of soaking solution,time and distance of the radiation.The optimum condition could be given as follow:①ratio of dispersant and solvent 1/1,concentration of acrylic acid 50%,concentration of initiator A 25 g/L,concentration of initiator B 0.75 g/L, radiated by using 700W metal halide lamp(radiation distance 20cm,and radiation time 1.5h), the maximum grafting rate for the P(S-DVB)microspheres could approach 68.3%;②ratio of dispersant and solvent 3/2,concentration of acrylic acid 50%,concentration of initiator A 25 g/L,concentration of initiator B 0.75 g/L,radiated by using 700W metal halide lamp (radiation distance 15cm,and radiation time 1h),the maximum grafting rate for the sodium sulfonate microspheres could approach 52.6%;③ratio of dispersant and solvent 1/1, concentration of acrylic acid 50%,concentration of initiator A 25 g/L,concentration of initiator B 0.5 g/L,radiated by using 500W mercury lamp(radiation distance 15cm,and radiation time 1.5h),the maximum grafting rate for the polypropylene non-woven fabrics could approach 1321%,the grafted polymers obtained by UV radiation could be changed to polymer supported peroxy acid in mixture of hydrogen peroxide and peroxy acid accelerator,as initiators for the subsequent grafting polymerization.The results showed that the concentration of polymer-supported peroxyacid could approach maximum value when the ratio of hydrogen peroxide and accelerator was 25:18.We also research the grafting polymerization of several monomers,such as acrylic acid(AA),acrylamide(AM)and mixture of AA and AM,initiated by polymer-supported initiators synthesized in preceding step.
The polymerization of acrylic acid and acrylamide grafted onto polypropylene non-woven fabrics by using the polymer-supported peroxyacid redox system as an initiator were studied emphatically.The influences of reaction time,reaction temperature, concentration of monomer and polymer-supported peroxyacid on graft polymerization were discussed in depth as well.Finally,the polymerization kinetics of acrylamide grafted onto polymer was also discussed,the graft polymerization rate could be expressed as R_g= K[M][RCOOOH]~(1/2)in the early stage of the reaction,the apparent activation energy of graft polymerization is 8.103KJ/mol,the rate costant of graft polymerization is 5.100×10~-~3L/mol·s and 5.125×10~(-3)L/mol·s when the concentration of monomer and polymer supported preoxyacid mantainning a constant,respectively.
The content of carboxyl group were determined for all the resultant grafted polymer, and some of them were characterized by using FTIR and SEM techniques.The results revealed that the predetermined monomers were grafted onto the corresponding polymer substrate,and causing more changes of surface morphlogy in the substrates.
Swelling behaviors of resultant grafted polymers were investigated in different aqueous solution by varying its temperature、pH value and type of dissolved salts,the swelling ratios of the grafted polymers changed with solution temperature,followed the laws of pyrocondensation.And all the grafted polymers,especially that of acrylic acid,had obvious response to the changes of pH value and type of salts in solution.
The adsorption of heavy metalions and methylene blue(MB)by grafted polymer was also studied in this work.Some of resultant graft polymers adsorb heavy metal and methylene quickly,the resultant polymer for the polypropylene non-woven fabrics grafted with acrylic acid on its backbone have the best effect in adsorption of Cu~(2+)and Pb~(2+),the maximum adsorbing capacity is 99.6mg(Cu~(2+))/g and 343.8mg(Pb~(2+))/g,respectively.The polypropylene non-woven fabric grafted with AA/AM mixture have the best adsorbing effect of MB,the maximum adsorbing capacity is 1185mg(MB)/g,the adsorption speed rate followed the laws of the second order kinetics model of Ho,apparent activation energy of adsorption is 40.24KJ/mol,the isothermal adsorption followed the isothermal adsorption equations of langmuir,the adsorption process was an endothermic chemisorption.
本文重点研究了PP无纺布固载过酸氧化还原体系引发丙烯酰胺的接枝聚合反应,探讨了反应温度、反应时间、单体浓度、固载过酸含量等因素对接枝聚合反应的影响。对其反应机理进行了深入探讨,得出接枝聚合反应的动力学方程为:R_g=K[M][RCOOOH]~(1/2),接枝聚合反应表观活化能E=8.103KJ/mol,在单体浓度或固载过酸浓度恒定是,接枝聚合反应速率常数分别为K=5.100×10~(-3)L/mol·s及K'=5.125×10~(-3)L/mol·s。
本文对三种基体材料的接枝产物进行了羧基含量测定、傅立叶变换红外光谱(FTIR)和扫描电镜(SEM)分析,结果表明聚合物固载过酸引发接枝聚合反应成功地在各基体材料表面引入了预定单体的聚合物长链,引起基体材料表面形貌发生了较大改变。
本文对PP无纺布固载过酸引发的接枝产物在不同温度、盐及pH值的水溶液中的溶胀性能进行了研究,各接枝产物的溶胀比对温度的变化表现出一定的响应性(呈热缩性);其溶胀比随盐及pH值的改变有明显的变化,随盐及pH值的循环改变时,表现出溶胀-收缩-溶胀的规律性变化,各接枝产物尤其是丙烯酸的接枝产物其溶胀比对盐和pH值的响应性尤为明显。
本文还对三种基体材料的接枝产物对重金属及亚甲基蓝的吸附性能进行了研究,发现丙烯酸单体的接枝产物对Cu~(2+)和Pb~(2+)有较好的吸附性。吸附性最好的PP无纺布固载过酸引发丙烯酸接枝产物对金属离子的最大吸附容量分别达到99.6mg(Cu~(2+))/g、343.8mg(Pb~(2+))/g,而PP无纺布固载过酸引发丙烯酸/丙烯酰胺混合单体接枝产物对亚甲基蓝的吸附效果最佳,最大吸附容量可达1185mg(亚甲基蓝)/g,吸附反应速率遵循Ho准二级吸附速率方程,表观吸附活化能Ea=40.24kJ/mol;其等温吸附符合Langmuir方程,吸附过程为化学吸附的吸热吸附。
In the current paper,polyacrylic acid was grafted onto backbone of several polymer substrate,such as P(S-DVB)microspheres,P(S-DVB)sodium sulfonate mierospheres and polypropylene non-woven fabrics,by the surface grafting polymerization induced by UV radiation.Several effect factors of the radiation grafting were investigated,including formulation of soaking solution,time and distance of the radiation.The optimum condition could be given as follow:①ratio of dispersant and solvent 1/1,concentration of acrylic acid 50%,concentration of initiator A 25 g/L,concentration of initiator B 0.75 g/L, radiated by using 700W metal halide lamp(radiation distance 20cm,and radiation time 1.5h), the maximum grafting rate for the P(S-DVB)microspheres could approach 68.3%;②ratio of dispersant and solvent 3/2,concentration of acrylic acid 50%,concentration of initiator A 25 g/L,concentration of initiator B 0.75 g/L,radiated by using 700W metal halide lamp (radiation distance 15cm,and radiation time 1h),the maximum grafting rate for the sodium sulfonate microspheres could approach 52.6%;③ratio of dispersant and solvent 1/1, concentration of acrylic acid 50%,concentration of initiator A 25 g/L,concentration of initiator B 0.5 g/L,radiated by using 500W mercury lamp(radiation distance 15cm,and radiation time 1.5h),the maximum grafting rate for the polypropylene non-woven fabrics could approach 1321%,the grafted polymers obtained by UV radiation could be changed to polymer supported peroxy acid in mixture of hydrogen peroxide and peroxy acid accelerator,as initiators for the subsequent grafting polymerization.The results showed that the concentration of polymer-supported peroxyacid could approach maximum value when the ratio of hydrogen peroxide and accelerator was 25:18.We also research the grafting polymerization of several monomers,such as acrylic acid(AA),acrylamide(AM)and mixture of AA and AM,initiated by polymer-supported initiators synthesized in preceding step.
The polymerization of acrylic acid and acrylamide grafted onto polypropylene non-woven fabrics by using the polymer-supported peroxyacid redox system as an initiator were studied emphatically.The influences of reaction time,reaction temperature, concentration of monomer and polymer-supported peroxyacid on graft polymerization were discussed in depth as well.Finally,the polymerization kinetics of acrylamide grafted onto polymer was also discussed,the graft polymerization rate could be expressed as R_g= K[M][RCOOOH]~(1/2)in the early stage of the reaction,the apparent activation energy of graft polymerization is 8.103KJ/mol,the rate costant of graft polymerization is 5.100×10~-~3L/mol·s and 5.125×10~(-3)L/mol·s when the concentration of monomer and polymer supported preoxyacid mantainning a constant,respectively.
The content of carboxyl group were determined for all the resultant grafted polymer, and some of them were characterized by using FTIR and SEM techniques.The results revealed that the predetermined monomers were grafted onto the corresponding polymer substrate,and causing more changes of surface morphlogy in the substrates.
Swelling behaviors of resultant grafted polymers were investigated in different aqueous solution by varying its temperature、pH value and type of dissolved salts,the swelling ratios of the grafted polymers changed with solution temperature,followed the laws of pyrocondensation.And all the grafted polymers,especially that of acrylic acid,had obvious response to the changes of pH value and type of salts in solution.
The adsorption of heavy metalions and methylene blue(MB)by grafted polymer was also studied in this work.Some of resultant graft polymers adsorb heavy metal and methylene quickly,the resultant polymer for the polypropylene non-woven fabrics grafted with acrylic acid on its backbone have the best effect in adsorption of Cu~(2+)and Pb~(2+),the maximum adsorbing capacity is 99.6mg(Cu~(2+))/g and 343.8mg(Pb~(2+))/g,respectively.The polypropylene non-woven fabric grafted with AA/AM mixture have the best adsorbing effect of MB,the maximum adsorbing capacity is 1185mg(MB)/g,the adsorption speed rate followed the laws of the second order kinetics model of Ho,apparent activation energy of adsorption is 40.24KJ/mol,the isothermal adsorption followed the isothermal adsorption equations of langmuir,the adsorption process was an endothermic chemisorption.
引文
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