摘要
稳定性是合成聚合物胶乳研究中人们关注的重点之一,但达到稳定性可调控、实现胶乳的可逆凝聚与再分散非常困难,目前尚无解决方法。究其原因,影响问题解决的关键是表面活性剂。目前使用的表面活性剂所制备的胶乳,一旦稳定性遭受破坏、发生凝聚,表面活性剂就失去恢复胶乳稳定性的能力。近几年,虽然有用于调控油水乳液体系稳定性的可切换表面活性剂的相关报道,但可逆凝聚与再分散胶乳在相关领域尚属空白,其研究与开发将对乳液聚合工业技术进步、节能减排有着十分重要的科学意义和重大的应用价值。
围绕着可逆凝聚与再分散胶乳的制备,本论文选择简便且环境友好的CO2/N2为控制稳定性的触发条件,通过设计可切换乳液聚合表面活性剂,以期将表面活性剂牢固结合在乳胶粒表面,实现胶乳可逆凝聚与再分散。为此,本论文定制了对CO2刺激响应敏感的N-脒基乙基十一烯酯((N-amidino)ethyl undec-10-enoate, UEm)可切换表面活性剂、2-甲基-1-对乙烯基苄基-1,4,5,6,-四氢嘧啶(2-methyl-1-(4-vinylbenzyl)-1,4,5,6-tetrahydropyrimidine, SCm)可切换共聚单体、N-脒基十二烷基丙烯酰胺((N-amidino)dodecyl acrylamide, DAm)可切换反应型表面活性剂以及甲基丙烯酸二甲胺基乙酯(DMAEMA)和甲基丙烯酸甲酯(MMA)的嵌段共聚物(PDMAEMA10-b-PMMA,4, PDM)大分子表面活性剂,并进行了苯乙烯(St)或甲基丙烯酸甲酯(MMA)的乳液(共)聚合研究,制备得到通N2加热或极少量碱发生凝聚、通CO2超声可再分散且上述过程可逆的PSt或PMMA(共聚)胶乳。
本论文主要涉及:
(1)设计合成了7种脒类化合物:十二烷基脒(N-dodecyl amidine, C12Am)、 UEm、N-脒基乙基十一烯酰胺((N-amidino)ethyl undec-10-enamide, UAm)、N-脒基已基甲基丙烯酰胺((N-amidino)hexyl methacrylamide, M6Am)N-脒基已基甲基丙烯酸酯((N-amidino)hexyl methacrylate, M6Em)、1,2-二甲基-1,4,5,6,-四氢嘧啶(1,2-dimethyl-1,4,5,6-tetrahydropyrimidine, DM6Cm)和N,N-二甲基乙脒(N,N-dimethyl ethyl amidine, DMEm)。通过电导测试,发现除UAm和M6Am因分子中含有易与脒基团形成氢键的活泼氢而没有C02/N2切换能力,其他几种脒类化合物都对CO2/N2触发敏感,且环脒DM6Cm的切换效果最明显。稳定性研究表明环脒DM6Cm和2-甲基咪唑啉(2-methyl-2-imidazoline, MeIMD)以及含有酰胺基团的M6Am和UAm较稳定,在实验测试条件下未发生水解,而直链烷基脒C12Am、UEm和DMEm都发生不同程度的水解。
(2)使用UEm为可切换表面活性剂,通过乳液聚合,成功制备了稳定的PSt胶乳。该表面活性剂有很好的重复可切换能力。合成的PSt胶乳在通N2、45℃加热条件下发生凝聚,凝聚的乳胶粒经通C02、超声能实现再分散,且凝聚得到的胶乳淤浆与室温烘干的干粉也能经通C02、超声实现再分散。
(3)使用SCm为可切换共聚单体,通过无皂乳液聚合成功制备了稳定的PSt、St/丙烯酸丁酯(BA)、St/MMA和St/丙烯腈(AN)(共聚)胶乳。该共聚单体有很好的重复可切换能力,耐热和耐水解稳定性也很突出。使用极少量碱,合成的胶乳能发生凝聚,凝聚的乳胶粒经通C02、超声能实现再分散,且凝聚得到的胶乳淤浆与室温烘干的干粉也能经通C02、超声实现再分散。
(4)使用DAm为可切换反应型表面活性剂,通过乳液聚合,成功制备了稳定的PSt胶乳。该表面活性剂有良好的重复可切换能力。合成的PSt胶乳在加热通N2条件下发生凝聚,凝聚的乳胶粒经通C02、超声能实现再分散,该凝聚—再分散过程可逆。同时,合成的PSt胶乳具有突出的抗电解质稳定性。
(5)使用PDM为大分子表面活性剂,将其用于MMA的乳液(共)聚合成功制备了稳定的PMMA(共聚)胶乳。该大分子表面活性剂是由两步法RAFT溶液聚合制得,数均分子量为2360g/mol,PDI为1.10。合成的胶乳可用极少量的碱凝聚,凝聚后的胶乳淤浆可通C02、超声能再分散,再分散的胶乳又可通N2在40℃下实现再凝聚,且N2凝聚-C02再分散过程可逆。
Stability is one of the key issues in the study of polymeric latexes. It is great challenging to produce latexes which can be reversibly coagulated and redispersed. There is no such latex existed so far. The latex stability strongly relies on surfactants. The latexes prepared by generic surfactants can not be re-stablized after coagulation. Although a few switchable surfactants have been reported lately, none of them can be applied for emulsion polymerization. Research and development in this area is believed to have important scientific and industrial impact on the progress of emulsion polymerization technology, energy saving and environmental protection.
In this study, CO2/N2was chosen to trigger the reversible coagulation and redispersion of latexes synthesized with switchable surfactants. The switchable surfactants were readily bonded on the surface of latex particles, thus making the latex reversibly coagulatable and redispersible. Herein, a CO2-responsive switchable surfactant of (N-amidino)ethyl undec-10-enoate (UEm), a switchable monomer of2-methyl-1-(4-vinylbenzyl)-1,4,5,6-tetrahydropyrimidin (SCm), a switchable reactive surfactant of (N-amidino)dodecyl acrylamide (DAm), and a polymeric surfactant of poly(2-(dimethylamino)ethyl methacrylate)10-b-poly(methyl methacrylate)14(PDM) were synthesized. Emulsion (co)polymerizations of styrene (St) or methyl methacrylate (MMA) with these switchable surfactants were studied. The resulted latexes, which could be reversibly coagulated by trace amount of caustic soda or bubbling N2with heat, and redispersed by CO2bubbling with ultrasonication, were first developed in this study.
The following were covered in this thesis:
(1) Seven amidine compounds were synthesized. They were N-dodecyl amidine (C12Am), UEm,(N-amidino)ethyl undec-10-enamide (UAm),(N-amidino)hexyl methacrylate (M6Em),(N-amidino)hexyl methacrylamide (M6Am), N,N-dimethyl ethyl amidine (DMEm), and1,2-dimethyl-1,4,5,6-tetrahydropyrimidine (DM6Cm). Conductivity tests showed there was no CO2/N2switchability with UAm and M6Am bearing amide groups due to formation of hydrogen bond with amidine, while other compounds were CO2/N2-responsive with DM6Cm having most significant switchability. The cyclic amidine DM6Cm and2-methyl-2-imidazoline (MeIMD), as well as UAm and M6Am bearing amide groups were more stable without hydrolysis under experimental conditions. Hydrolysis occurred with the acyclic amidines C12Am, UEm, and DMEm.
(2) Stable PSt latexes were produced by emulsion polymerization of St using UEm as a switchable surfactant. The surfactant had a good repeatable CO2/N2switchablity. The PSt latexes could be readily coagulated by bubbling N2at45℃, and the coagulated latex particles were redispersible by CO2bubbling with ultrasonication. The washed and dried latex particles could also be reversibly coagulated and re-dispersed.
(3) Soap-free emulsion copolymerizations of St with SCm as a switchable comonomer were conducted. Stable PSt, St/butyl acrylate, St/MMA, and St/acrylonitrile latexes were obtained. The comonomer SCm possessed a good repeatable CO2/N2switchablity and outstanding stabilities against heat and hydrolysis. The resulted latexes could be coagulated by trace amount of caustic soda, and the coagulated latex particles were redispersible by CO2bubbling with ultrasonication, as well as the washed and dried latex particles.
(4) By using DAm as a switchable reactive surfactant, stable PSt latexes were produced during emulsion polymerization of St. The surfactant DAm was found to have a good repeatable CO2/N2switchablity. The resulted PSt latexes could be coagulated by bubbling N2with heat, and the coagulated latex particles were redispersible by CO2bubbling with ultrasonication. The coagulation and redispersion processes were repeatable by the CO2/N2bubbling. Moreover, the PSt latexes possessed good stability against electrolyte.
(5) Emulsion (co)polymerizations of MMA were carried out with an acidified switchable polymeric surfactant PDM. The surfactant was synthesized by RAFT solution polymerization. The PDM had a number-average molecule weight of2360g/mol and PDI of1.10. The resulted PMMA latexes could be coagulated by trace amount of caustic soda, and the coagulated latex particles after washing with deionized water could be redispersed into fresh water to form stable latexes again by CO2bubbling with ultrasonication. The recovered latexes could then be coagulated by N2bubbling with gentle heating. These coagulation and redispersion processes could be repeated with alternatively CO2/N2bubbling.
引文
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