第5期 曾晓翘等：丙烯酸酯系互穿网络聚合物乳液的微观形貌 ·617。 [4 Li XQ.Chen PZ.Qin C H.et al.The application study of PTA 3结论 on TEM technic in characterization:the structure of core shell 本研究利用磷钨酸负染法，使用透射电镜表征 emulsion.Polym Mater Sci Eng.1999,15:129 (李小琴，陈沛智，秦昌华，等.磷钨酸在核壳型乳液TEM表 了丙烯酸酯系互穿网络聚合物乳液的微观形貌.研 征技术中的应用研究.高分子材料科学与工程，1999.15： 究表明：在制备P(MMA-St)/P(BA一EA)互穿网络 129) 聚合物乳液的过程中，可以通过调节网络质量配比 [5 Joy D C.Joy C S.Low voltage scanning ebctmon microscopy. 和溶胀工艺，来改变乳液粒子的微观形貌，从而影响 Micron,1996.27:247 乳液成膜性能.在相同的反应条件下，随着网络Ⅱ [6 Tajma A.Higuchi T.Yabu H,et al.Hemispherical polymer nane partices of polisoprene poly methyl methacrylate)blend 含量的递增和网络I含量的递减，乳液粒子体积逐 with cone-shell structu re.Collaids Surf A.2008.313:333 渐递减，两网络互穿得更加致密.采用反向溶胀方 [7 Qian J.Yuan J.Tuo X L,et al.Characterization of com-shell 式和适当的网络质量配比，可以获得互穿程度更强、 polysty meneacryicacid (PS-AA)copolymer namspheres and the 成膜性能更好的乳液粒子，延长溶胀时间可以增加 selective dissolution of the pore structure.J Chin Ekctron Mi- 互穿网络壳部分的厚度，但是溶胀时间超过2h后， crascS0c,2007,26(02):124 (钱骏，袁俊，庹新林，等.聚苯乙烯丙烯酸共聚物胶体纳米 乳液粒子微观形貌不会再有明显的改变. 球核壳结构及其选择性溶解过程的表征.电子显微镜学报 2007.26:124) 参考文献 [8 Zhu C S.Analysis of Polymer Structures.Beijing:Science [1]Maekaw a T.Quntitative characterizations of styrene-butadiene Pes5,2004 coreshell latexes by TOF-SIMS and pyrolysis GCMS.Appl (朱诚身.聚合物结构分析.北京：科学出版社，2004448) Surf Sci,2006.252:7019 9Cedric G.Gilbert F.Christopher JG P.et al.The morphology [2]Harris J R.Roos C.Djalli R.et al.Application of the negative of submicron sized com-shell latex particles:An electron mi- staining tech nique to bot h aqueous and organic solvent soutions of croscopy study.Micron,2007.38:524 polymer particles Micron,1999,30:289 [10 Yun X Y.Huo D X.Zhang L.et al.Effect of temperature on [3]Ferrera GG.Sancheza M S,RibellesaJ LG,et al.Nanodomains film format ion of the cor-shell latex and properties of the com- in a hydrophilic-hydrophobic IPN based on poly 2-hydroxyethyl psite film.Paym Mater Sci Eng.2007.23(3):126 acrylte)and poly(ethyl acrylate).Eur Polym J,2007,43: (袁显永，霍东霞，张丽，等.温度对核壳胶乳涂膜形成及性 3138 能的影响.高分子材料科学与工程，2007,23(3)：126 (上接第611页) [5]Luo J F,Domfeld DA.Material removal mechanism in chemical film wafers.J Tribol.2004.126(1):185 mechanical polishing:theory and modeling.Trans Semiond [8 Gitis N V.Xiao J.Kumar A.et al.Advanced specification and Manu f,2001,142):112 tests of CMP retaining rings //Proceedings of the 2004 CMP-MIC [6]Thakurta D G.Borst C L Schw endeman D W.et al.Three-di- Conference.Marina De Ray.2004.252 mersional chemical mechanical planarization surry flow modd [9Muldow ney G P.James D B.Characterization of CMP pad sur based on lubrication theory.J Ekctrochem Soc,2001,148(4): face texture and pad-wafer contact.Mater Res Soc Symp Proc. 207 2004,816:147 [7]Lin J F,Chen J D.Chang Y H.et al.Analysis of the tribological [10 Moinpour M,Trgub A,Oehler A.et al.Advances in charac- mechanism arising in the chemical mechanical polishing of copper terization of CMP consumables MRS Bull,2002.27:7663 结论 本研究利用磷钨酸负染法, 使用透射电镜表征 了丙烯酸酯系互穿网络聚合物乳液的微观形貌 .研 究表明 :在制备 P( M MA-St)/P( BA-EA) 互穿网络 聚合物乳液的过程中, 可以通过调节网络质量配比 和溶胀工艺, 来改变乳液粒子的微观形貌, 从而影响 乳液成膜性能.在相同的反应条件下, 随着网络 II 含量的递增和网络 I 含量的递减, 乳液粒子体积逐 渐递减, 两网络互穿得更加致密 .采用反向溶胀方 式和适当的网络质量配比, 可以获得互穿程度更强 、 成膜性能更好的乳液粒子 .延长溶胀时间可以增加 互穿网络壳部分的厚度, 但是溶胀时间超过 2 h 后, 乳液粒子微观形貌不会再有明显的改变 . 参 考 文 献 [ 1] Maekaw a T .Quantitative characterizations of styrene-butadiene core-shell lat exes by TOF-SIMS and pyrolysis GC-MS.Appl Su rf Sci, 2006, 252:7019 [ 2] Harris J R, Roos C, Djalali R, et al.Application of the negative st aining t ech nique to both aqueous and organic solvent solu tions of polym er particles.Micron , 1999, 30:289 [ 3] Ferrera G G, Sa ′ ncheza M S, Ribellesa J L G, et al.Nanodomains in a hydrophilic-hydrophobic IPN based on poly ( 2-hydroxyethyl acrylate) and poly ( ethyl acrylat e) .E ur Polym J , 2007, 43: 3138 [ 4] Li X Q, Chen P Z, Qin C H, et al.The application study of PTA on TEM t echnic in characterization:the structure of core/ shell emulsion.Polym Mater Sci E ng, 1999, 15:129 ( 李小琴, 陈沛智, 秦昌华, 等.磷钨酸在核壳型乳液 TEM 表 征技术中的应用研究.高分子材料科学与工程, 1999, 15: 129) [ 5] Joy D C, Joy C S .Low volt age scanning electron mi croscopy . Micron, 1996, 27:247 [ 6] Tajima A, Hi guchi T , Yabu H, et al.Hemispherical polymer nano-particles of polyisoprene-poly ( methyl methacrylate) blend with core-shell structu re .Colloids S urf A, 2008, 313:333 [ 7] Qian J, Yuan J, Tuo X L, et al.Characterization of core-shell polysty rene-acryli c acid ( PS-AA) copolymer nanospheres and the selective dissolution of the pore structure.J Chin E lectron Mi￾crosc S oc, 2007, 26( 02) :124 ( 钱骏, 袁俊, 庹新林, 等.聚苯乙烯-丙烯酸共聚物胶体纳米 球核壳结构及其选择性溶解过程的表征.电子显微镜学报, 2007, 26:124) [ 8] Zhu C S .Analysis of Polymer Structures.Beijing :S cience Press, 2004 ( 朱诚身.聚合物结构分析.北京:科学出版社, 2004:448) [ 9] Cédric G, Gilbert F, Christopher J G P .et al.The morphology of submi cron sized core-shell lat ex particles:An electron mi￾croscopy study.Micron , 2007, 38:524 [ 10] Yuan X Y, Huo D X, Zhang L, et al.Effect of temperatu re on film formation of the core-shell latex and properties of the com￾posit e film .Pol ym Mater S ci Eng , 2007, 23( 3) :126 ( 袁显永, 霍东霞, 张丽, 等.温度对核壳胶乳涂膜形成及性 能的影响.高分子材料科学与工程, 2007, 23( 3) :126) ( 上接第 611 页) [ 5] Luo J F, Domf eld D A .Mat erial removal mechanism in chemi cal mechanical polishing :theory and modeling .Trans Semi cond Manu f, 2001, 14( 2) :112 [ 6] Thakurta D G, Borst C L, Schw endeman D W, et al.Three-di￾mensional chemical mechanical planarization slurry flow model based on lubrication theory .J E lectrochem S oc, 2001, 148 ( 4) : 207 [ 7] Lin J F, Chen J D, Chang Y H, et al.Analysis of the tribologi cal mechanism arising in the chemical mechanical polishing of copper￾film w afers.J Tribol, 2004, 126( 1) :185 [ 8] Gitis N V, Xiao J, Kumar A, et al.Advanced specification and tests of CMP ret aining rings∥Proceedings of the 2004 CMP-MIC Conf erence .Marina Del Ray, 2004:252 [ 9] Muldow ney G P, James D B.Charact erization of CMP pad sur￾face t exture and pad-wafer con tact.Mater Res Soc Sym p Proc, 2004, 816:147 [ 10] Moinpour M, T regub A, Oehler A, et al.Advances in charac￾terization of CMP consumables.MRS Bu ll, 2002, 27:766 第 5 期 曾晓翘等:丙烯酸酯系互穿网络聚合物乳液的微观形貌 · 617 ·