丙烯酸/丙烯酸-2-乙基己酯二元共聚物的序列分布研究
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摘要
以ABVN(偶氮二异庚腈)为引发剂、EAC(乙酸乙酯)为溶剂,采用溶液聚合法在55℃反应得到4组不同单体配比的AA(丙烯酸)/2-EHA(丙烯酸-2-乙基己酯)二元共聚物。通过核磁共振方法计算得到单体转化率。依据设计的反应单体投料比,EKT作图法处理数据,得到了AA和2-EHA的竞聚率分别为:r_1(AA)=1.47,r_2(2-EHA)=1.17。进而借助统计的方法分析了AA/2-EHA共聚物的链段序列和链节分布。研究结果表明:共聚物分子链中,不同长度的链段分布概率不一,且受到单体投料比的影响很大;当AA与2-EHA投料的质量比从5∶95到20∶80时,共聚物中AA的链段长度较短,而2-EHA的链段长度相对较长;AA的链节中以5个以内单体单元的链段长度为主,而2-EHA链节中以4～15单体单元的链段长度为主。
With 2,2'-azobis-(2,4-dimethylvaleronitrile)(ABVN)as initiator,ethyl acetate(EAC)assolvent,four groups of acrylic acid(AA)/2-ethylhexyl acrylate(2-EHA)copolymers with different monomer ratioswere synthesized by solution polymerization at 55 ℃. The monomer conversion was calculated by nuclear magneticresonance(NMR). According to the designed monomer feed ratio,the reactivity ratios of AA and 2-EHA wereobtained by EKT plotting method:r_1(AA) = 1.47,r_2(2-EHA)=1.17. Then the chain sequence and chaindistribution of AA/2-EHA copolymer were analyzed by statistical method. The results showed that the probabilities ofthe distribution of segments with different lengths were different in the copolymer chain,and were greatly influencedby the monomer feed ratio. When the mass ratio of w(AA)and w(2-EHA)was from 5∶95 to 20∶80,the chainlength of AA in the copolymer was shorter,while the chain length of 2-EHA was relatively longer. In AA chainsegments,the length of less than 5 monomers was dominant,while in 2-EHA chain segments,the length of 4-15 monomerswas dominant.
With 2,2'-azobis-(2,4-dimethylvaleronitrile)(ABVN)as initiator,ethyl acetate(EAC)assolvent,four groups of acrylic acid(AA)/2-ethylhexyl acrylate(2-EHA)copolymers with different monomer ratioswere synthesized by solution polymerization at 55 ℃. The monomer conversion was calculated by nuclear magneticresonance(NMR). According to the designed monomer feed ratio,the reactivity ratios of AA and 2-EHA wereobtained by EKT plotting method:r_1(AA) = 1.47,r_2(2-EHA)=1.17. Then the chain sequence and chaindistribution of AA/2-EHA copolymer were analyzed by statistical method. The results showed that the probabilities ofthe distribution of segments with different lengths were different in the copolymer chain,and were greatly influencedby the monomer feed ratio. When the mass ratio of w(AA)and w(2-EHA)was from 5∶95 to 20∶80,the chainlength of AA in the copolymer was shorter,while the chain length of 2-EHA was relatively longer. In AA chainsegments,the length of less than 5 monomers was dominant,while in 2-EHA chain segments,the length of 4-15 monomerswas dominant.
引文
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[2]李哲,李文刚,高亮,等.锂离子电池用水性丙烯酸酯胶粘剂的制备及性能研究[J].中国胶粘剂,2015,24(12):40-45.
[3]李铭杰.丙烯酸酯压敏胶的应用研究进展[J].粘接,2018,39(4):62-66+69.
[4]KUO C F J,CHEN J B.Synthesis of high-solid-content,acrylic pressure-sensitive adhesives by solvent polymerization[J].Journal of Applied Polymer Science,2018,135(19):46257.
[5]KIM S,LEE S W,LIM D H,et al.Fabrication of optically clear acrylic pressure-sensitive adhesive by photopolymerization:UV-curing behavior,adhesion performance,and optical properties[J].Journal of Adhesion Science and Technology,2013,27(20):2177-2190.
[6]KIM P S,LEE S W,PARK J W,et al.Kinetic and characterization of UV-curable silicone urethane methacrylate in semi-IPN-structured acrylic PSAs[J].Journal of Adhesion Science&Technology,2013,27(17):1866-1872.
[7]KAJTNA J,KRAJNC M.Solventless UV crosslinkable acrylic pressure sensitive adhesives[J].Internationa Journal of Adhesion&Adhesives,2011,31(8):822-831.
[8]CZECH Z,WESOLOWSKA M.Development of solventfree acrylic pressure-sensitive adhesives[J].European Polymer Journal,2007,43(8):3604-3612.
[9]郎爱华,申迎华,武根壮,等.AM/MADQUAT反相微乳液聚合及共聚物的序列分布[J].中北大学学报(自然科学版),2008,29(1):48-52.
[10]邓新华,孙元.聚(丙烯酸-丙烯酰胺)/聚乙烯醇共混高吸水性纤维中共聚物序列链段分布的研究[J].精细石油化工,2004(5):30-33.
[11]汤杰.尼龙6/66原位共聚物的序列分布、结晶行为及其反应动力学研究[D].上海:华东理工大学,2018:23-26.
[12]张晓勇.耐高温溶剂型丙烯酸酯压敏胶的研究[D].哈尔滨:哈尔滨工业大学,2017:16.
[13]张建军,孙娟,柯盛波,等.光学压敏胶的制备及其应用性能研究[J].中国胶粘剂,2017,26(8):29-32+47.
[14]王荣.改性丙烯酸酯乳液压敏胶的研究[D].广州:华南理工大学,2014:18.
[15]桂祖桐,达建文,张廷山,等.竞聚率及其测定技术的进展[J].齐鲁石油化工,1997,25(2):134-137.
[16]YILMAZ E,Kü?üKYAVUZ Z.Monomer reactivity ratios of styrene-4-vinylpyridine copolymers at low and high conversions[J].Polymer,1993,34(1):145-149.
[17]KENNEDY J P,KELEN T,TüD?S,et al.Analysis of the linear methods for determining copolymerization reactivity ratios.II.A critical reexamination of cationic monomer reactivity ratios[J].Journal of Polymer Science Polymer Chemistry Edition,1975,13(10):2277-2289.
[18]潘祖仁.高分子化学(第5版)[M].北京:化学工业出版社,2011:124.
[19]王子明,尹东杰,毛倩瑾.异丁烯醇聚氧乙烯醚与丙烯酸的竞聚率及共聚物链段分布[J].高分子材料科学与工程,2018,34(2):19-23.