摘要
以乳化性单体ZD、苯乙烯、丙烯酸羟乙酯和丙烯酸-2-乙基己酯为主要原料,通过溶液共聚法合成了一种用于丙烯酸酯水性涂料的高分子表面活性剂。使用FT—IR对合成产物的结构进行了表征,初步探讨了ZD对产物表面活性的影响。结果表明,共聚物的表观粘度(异丙醇溶剂,浓度85%)为100~530mPa·s,具有较低的CMC(4~9g/L),最低表面张力降至31.5mN/m(25℃)。
加入合成的高分子乳化剂,采用改进的无皂乳液连续聚合工艺,制备固含量40%丙烯酸酯无皂乳液,由TEM测得其粒径约90nm,粒子大小呈窄分布。确定最佳聚合工艺条件为:反应温度90℃,搅拌速率200~250r/min,引发剂用量为1.0wt%,高分子乳化剂用量7wt%。同时,研究了ZrO~(2+)对此类乳液的交联改性,按n(ZrO~(2+)):n(-COOH)为1:2的量加入碳酸锆铵,乳液涂膜硬度达2H,耐水性达72h以上。
以双丙酮丙烯酰胺(DAAM)为功能单体,合成含酮羰基的无皂纳米乳液,添加己二酰肼(ADH),组成室温交联型乳液。研究表明,DAAM含量高,乳液的粘度大,当乳液中DAAM用量为6wt%时,体系凝胶量少,且涂膜硬度为2H,吸水率2.5%,乳液贮存6个月后仍保持稳定。
A new polymeric surfactant for acrylate waterborne coatings was prepared by monomers ZD,styrene,hydroxyethyl acrylate and 2-Ethylhexyl acrylate.Structure of copolymer was signified by FT-IR.It was measured that, apparent viscosity of copolymeric solution were at the range of 100~630 mPa·s, critical glue bunches of density(CMC) appeared lower(4g/L~9g/L),and the minimum surface tension reaches 31.5 mN/m(25℃).
An soap-free acrylate emulsion with 40%solids content was synthesized by technology of continuous emulsion polymerization,inwhich using the new polymeric surfactant as emulsifier.And average particle size was characterized as 90nm by using TEM.Super emulsified properties have been studied at the optimized reaction condition: polymerization temperature 90℃,amount of initiator 1.0wt%,amount of polymeric surfactant 7wt%,whisking velocity of 200~250r/min.In corporation of crosslinking agent ZrO~(2+) will lead the chelation crosslinking between carboxylicion and metalion, which shows its pencil hardness 2H and water resistance over 72 h when adding n(ZrO~(2+)):n(-COOH) =1:2 to soap-free acrylate emulsion.
An ambient Crosslinkable soap-free nano-size acrylic polymer emulsion was obtained by adding adipic acid dihydrazide(ADH) to the acrylic polymer emulsion incorporated with diacetone acrylamide(DAAM).The results obvious showed that the apparent viscosity increased with increasing the DAAM content.It was reviewed that emulsion is stable after 6 month,Coagulation small,pencil rigidity 2H,and the water absorption 2.5%,with DAAM content 6wt%of latex films.
引文
[1]周铭,张玉兴,周树军.丙烯酸树脂的制备及其在涂料中的应用与研究现状[J].上海涂料.2005,37(2):25-29
[2]蔡斯让,郑田菱,丙烯酸酯无皂乳液聚合的研究[J].中国胶粘剂,(1997),6(5):4-6
[3]唐黎明,董汉鹏,新型无皂丙烯酸醋乳液的合成及性能研究[J].高分子材料科学与工程,(1998),14(1),17-19
[4]曹同玉,刘庆普,胡金生.聚合物乳液合成原理性能及应用[M].北京:化学工业出版社,2004
[5]张心亚,孙志娟,黄洪,蓝仁华,陈焕钦.乳液聚合技术最新研究进展[J].合成材料老化与应用,2006,35(1):38-42
[6]侯有军,任力,罗『F汤,曾繁森.乳液法制备聚合物纳米粒子及其结构表征与应用[J].离子交换与吸附,2001,17(2):178-186
[7]潘祖仁,高分子化学(第二版)[M].北京:化学工业出版社.1997,109-110
[8]张心亚,瞿金清,蓝仁华,涂伟萍,陈焕钦.核壳聚合与核壳结构聚合物乳液[J].现代化工,2002,22(9):58-61
[9]曾德芳,汪勇.无皂乳液聚合的技术进展[J].涂料技术与文摘,2004,25(1):10-ll
[10]青晨,徐建军,叶光斗,李守群.VAc/MA/从三元无皂乳液共聚的研究[J].中国胶粘剂,2006,15(4):1-5
[11]朱再盛,吕广镛.丙烯酸酯无皂乳液的研究[J].涂料工业,2004,34(6):4-6
[12]蒋笃孝,宋岭瑛.无乳聚合制备水溶性纸塑复膜胶的研究[J].中国胶粘剂,2000,12(15):4-6
[13]吴建一,陶洪滨,陈洁.无皂丙烯酸酯乳液涂料的研究[J].化学与粘合,2001,(3):110-114
[14]Stoffer J O,BoneT.Polymerization in water-in-oil microemulsion systems [J].J Poly Sci Polym Chem,1980,18(2):641-648
[15]董汉鹏,李效玉.乳液互穿网络型丙烯酸酯类热塑性弹性体的研究[J].高等学校化学学报,2004,25(4):774-777
[16]肖继君,赵俊芳,李彦涛,杨德钧,耿耀宗.LIPN聚氨酯/聚丙烯酸酯粒子形态结构的研究[J].河北科技大学学报,2002,23(1):14-18
[17]De Wet-Roos D,Knoetze J H,Cooray B.Emulsion polymerization of an epoxy -acrylate emulsion stabilized with polyacrylate.I.influence of salt,Initiator,neutralizing amine and stirring speed[J].J Appl Polym Sci.,1999,71:1347-1360
[18]何方岳.涂料用高分子表面活性剂的研究[J].浙江化工,2005,36(11):25-28
[19]隋卫平,李涛,王党生.高分子表面活性剂的制备与应用进展[J].现代化工,2004,(7):90-92
[20]沈一丁.高分子表面活性剂[M].北京:化学工业出版社,2002.32
[21]宋照斌,宋启煌.高分子表面活性剂在水处理剂中的应用[J].精细化工,2000,17(12):700-703
[22]Jialanella Gary L,Piirma Irja.Emulsion polymerization of methyl methacrylate using poly(methylmethacrylate-co-2-hydroxypropyl methacrylate)graft-polyoxyethylene as the stabilizer[J].J Appl Polym Sci.,1991,42:1423-1431.
[23]徐祖顺,易昌凤,程时远,封麟先,吴奇.聚甲基丙烯酸甲酯接枝聚氧乙烯共聚物溶液性质的研究[J].高分子学报,2000,(6)701-705
[24]曹亚,李惠林.CMC型高分子表面活性剂在稀溶液中分子聚集形态[J].四川大学学报(工程科学版),2005,37(2):51-54.
[25]Garti N,Aserin A.Advances in Colloid and Interface Sci.,1996,65:37-69
[26]汪地强,杜宗良,李瑞霞,吴大诚.聚丙烯酸丁酯丙烯酸的合成及其作为高分子乳化剂的应用[J].塑料工业.2001,29(4):3-11
[27]汪地强,刘若冰,杜宗良,吴大诚,刘白玲.聚丙烯酸丁酯丙烯酸的醇溶液聚合[J].塑料工业.2003,31(8):9-15
[28]王强,曹爱丽,黄积涛,孙继友,张嘉琪,王苹.以两亲聚合物为乳化剂研制高固含量乳液[J].高分子材料科学与工程,1999,15(2):35-37
[29]鲁德平,熊传溪.高分子乳化剂在丙烯酸酯乳液共聚物中的应用[J].高分子材料科学与工程,2000,1(2):262-8
[30]Robert M F.The homogeneous nucleation of polymer colloids[J].Br Polym J.,1973,5(5):467-483
[31]Smith W V,Chain initiation in styrene emulsion Polymerization[J].J.Am.Chem.Soc.,1949,71:4077-4082
[32]Goodwin JM,Hearn J,HoCC,Ottwill RH,Preparation and characterization of polymer lattices formed in the absence of surface active agents[J].Br Polym J.1973,5:437
[33]Hansen F K,Ugelstad J,Particle nucleation in emulsionpolymerization.I.A theory for homogeneous nucleation[J].J Polym Sci.Part A:Polym.Chem.,1978,16:1953
[34]irai M,Arai K,Saito S,Polymer particle formation in soapless emulsion polymerization[J].J Polym Sci.Polym Chem Ed.,1979,17:3655
[35]Feeney P,Napper D H,Gilbert R G,Surfactant-free emulsion polymerization:predictions of the coagulative nucleation theory[J].Macromolecules,1987,20:2922
[36]Goodwall A R,Wilkinson M C,Hearn J.Mechanism and emulsion polymerization of styrene in soap-free systems[J].J Polym Sci.,Part i:Polymer Chem.,1977,15(9):2193-2218.
[37]Chen S i,Lee S T.Kinetics and methanism of emulsifier-free emulsion polymerization styene/hydrophilic comonomer(acrylamide) system [J].Macromlecules,1991,24(6):3340
[38]Song Z Q,PoehleinGW,Particlenucleationinemulsifier-freeaqueous-phase polymerization:stage 1[J].J colloid and Int Sci.,1989,128:486
[39]Song Z Q,PoehleinGW,Kinetics of emulsifier-free emulsion polymerization of styrene[J].J Polym Sci.Polym.Chem.,1990,28:2359
[40]张茂根,翁志学,黄志明,潘祖仁.无皂乳液聚合中单分散粒子的形成过程[J].高等学校化学学报,1998,19(9):1518-1521
[41]张茂根,翁志学,黄志明,潘祖仁.MMA/BA无皂乳液聚合机理研究[J].高等学校化学学报,1999,20(11):1848-1852
[42]杨凌露,丛海林,曹维孝.无皂乳液聚合法制备P(St-MMA-SPMAP)单分散乳胶颗粒[J].高分子学报,2005,(2),223-226
[43]韩朝阳,龚兴宇,范晓东,秦华宇.有机硅改性聚丙烯酸酯无皂乳液的合成及性能 [J].高分子材料科学与工程,2004,20(5),81-84
[44]Aslamazova T R.Emulsifier-free latexes and polymers on their base[J].Prog Org Coat,1995,25:109-167
[45]Mahdavian A R,Abdollahi M.Investigation into the effect of carboxylic acid monomer on Particle nucleation and growth in emulsifier-free emulsion copolymerize-tion of styrene-butadiene-acrylic acid[J].Polymer.2004,(45),3233-239
[46]郝海涓,郝广杰,郭天瑛,宋谋道,张邦华.MMA/BA/AA/HEMA无皂乳液体系的合成与性能表征[J].离子交换与吸附,1999,15(6):453-459
[47]刘积灵,张玉坤,董薇.水性纯丙乳液及外墙涂料的研究[J].吉林化工学院学报,2003,20(2):10-12
[48]Guo T Y,Zhang B H.Studies on the preparation of stable and high solid content em ulsifier-free latexes and characterization of the obtained copolymers for MMA/BAsystemwiththeadditionofAHPS[J].J ApplPolym.Sci.,2001,79(1):21-28
[49]万波,王得宁.反应型乳化剂的合成及其在乳液聚合中的应用[J].合成橡胶工业,2003,26(2):94-97
[50]王继英,张荣珍,仇满德.无皂苯丙四元共聚乳液的合成及性能研究[J].河北大学学报(自然科学版),2004,24(2):153-155
[51]殷武,孔志元,朱柯.丙烯酸树脂无皂乳液的研究[J].涂料工业,2002(8):1-3
[52]任添斌,张洪涛.反应型表面活性剂的类型与应用[J].同用化学工业,2000,30(3):25-28
[53]Guyot A,Tauer K.Reaetive Surfactants in Emulsion Polymerization [J].Advances in Polymer Science,1994,111:43-65
[54]陈德铨,王坚,王晨.新型反应性乳化剂[J].精细化工,2001,18(8):435-442
[55]张洪涛,任天斌.可聚合乳化剂的类型及乳液聚合[J].粘接,1999,20(2):26-28
[56]JP6049108,Kinoshita Kouji,Production of core-shelle mulsion,1994
[57]彭顺金,张贵军,方华.反应性乳化剂及其乳液聚合[J].涂料工业,1999,(5):36-39
[58]Nakamae,Masato.Vinyl alcohol Polymer dispersion stabilizers for emulsion Polymerization of vinyl comPounds[P].APPI.JP:05,295,010,1992-4-17
[59]刘宇君,段晋星,俞开钰.甲醇存在下st-BA-HEA体系的无皂乳液聚合研究[J].化学工业与工程,2001,15(5):249-265
[60]刘宇君,程中虎.丙酮存在下St-BA-HEA体系的无皂乳液聚合[J].合成橡胶工业,2001,24(5):219-221
[61]Okubo M,Yamada A,Shihao S.Emulsifier-free emulsion Polymerization of styrene in acetone-WaterJ[J],Appl Polym Sci,1981,26(5):1675-1685
[62]黄志虹,谢志明,李卓美.丙烯酸酯无皂乳液在罩光油墨中的应用[J].中山大学学报,1999(6):64-67
[63]王莉明.辛醇在无皂乳液聚合中的应用[J].精细化工,2002,19(增刊):124-128
[64]李晓燕,马越,吴志明,王利明.挥发性乳化物在无皂乳液聚合中的应用[J].农机化研究,2005,(4):216-219
[65]李刚辉,沈一丁,任庆海.无皂乳液聚合的稳定方法和应用进展[J].化工进展,2005,24(5):489-492
[66]Kang K,Kan C,Du Y.Synthesis and ProPerties of soap-free Poly(methyl methacrylate-ethyl acrylate-methacrylic acid) latex Partieles PrePared by seeded emulsion Polymerization[J].European Polymer Jounal.2005,(41):439-445
[67]Kondo A,Kamura H,Higashitani K.Development and application of thermo-sensitive magnetic immunomicrospheres for antibody purification[J].APPlied Microbiology And Biotechnology,1994,41(1):99-105
[68]朱再盛,吕广镛.无皂乳液聚合的研究进展广州[J].化工,2001,29(4):7-12.
[69]韩朝阳,龚兴宇,范晓东,秦华宇.无皂型乳液聚合研究进展涂[J].料工业,2002,(9):28-30.
[70]常玉,梁剑锋.防水涂料用无皂乳液的制备[J].涂料工业.2004,34(8):21-24
[71]王金刚,张书香,孙昌梅,崔玉.高固含量无皂乳液的制备及应用研究进展[J].济南大学学报(自然科学版).2001,15(4):348-351
[72]Harui N,Agawa T.Novel ambient temperature curable two-component waterborne silicone acrylic coatings[J].J Coat Technol,1998,70(880):73-77
[73]蒋硕健.双丙酮丙烯酰胺与己二酰肼在水乳液与水溶性聚合物后交联中的应用[J].中国涂料,2003,(3):24-28
[74]付校坤.DAAM在建筑内外墙乳胶漆中的应用上[J].海涂料,2004,42(2),33-34
[75]Bakker P;Mestach D.Self cross-linknig acrylic dipsersinos for the wood industry[J].Surf Coat Intern.Part B:Coatings Transactions,2001,84(4),243-336.
[76]Michiel A J,ArieN.ALiquidCoating composition and a Process for a Substrate with Such Coating Composition.欧州专利,0199087.1986
[77]ArieN,J johannesPP.An Aqueous Coating Composition and a Process of Coating a Substrate with Such Coating Composition.欧州专利,264983,1988
[78]Arie N,Vandevoorde,et al.Liquid Coating Composition and a Process for Coating a Substrate with Such Coating composition.美国专利,4772680.1986
[79]J.E.Rechard;J.E.Devona;D.E.Setzke:L.Wagemans,Waterbasedcrosslinkable surface coatings[J].Prog Org Coat.1999,(36):45-52.
[80]孔祥正,阐成友.有机硅改性丙烯酸酯共聚乳液合成方法及胶膜性能的研究[J].高等学校化学学报,1995,16(11):1810-1813
[81]黄光速,李克友硅.氧烷一丙烯酸乙酯共聚物的结构与性能[J].合成橡胶工业.1994,17(5):288-291.
[82]Karlsson L E,Karlsson 0 J;Sundberg D C,None quilibrium particle morphology development in seeded emulsion polymerization[J].Appl PolymSci.,(2003),90(4):905-915
[83]武利民,于在璋.交联丙烯酸丁酯的乳液聚合研究[J].涂料工业,1992,(1):1-3
[84]Wiese H,Rupaner R.Influence of metal inos on the alkali-swelling behavior of carboxylated acrylic polymer latexes[J].Colloid Polym.Sci.,1999,277(4):372-375.
[85]徐坚.高分子表面活性剂的分子设计[J].高分子通报.1997,2(12):90-94
[86]Harkins W D.The Physical Chemistry of Surface Films[M].New York:Reinhold,1954,71.
[87]李学刚,王以和,张明晓,吴光权,刘发敏.测定表面张力装置的改进[J].分析测试仪器通讯,1995,(5):133-136.
[88]肖进新,罗妙宣.滴体积法测量表面张力装置的改进[J].实验室研究与探索,2000,(2):48-49.
[89]孟晶,李效玉.成膜温度对漆膜表面形态的影响[J].涂料工业,2005,35(4),1-4
[90]李秀艳,王平.乳液的最低成膜温度及其影响因素[J].涂料工业,2001,31(3),1-3
[91]柯昌美,汪厚植,周鹏,鄢永普,赵惠忠,李轩科.透明的纳米级纯丙微乳液的制备[J].中国胶粘剂,2005.14(5):14-17
[92]张心亚,蓝仁华,陈焕钦.水性涂料用苯丙微乳液的合成[J].石油化工.2003,32(5):410-413
[93]刘静,、彭慧,程时远,N一羟甲基丙烯酰胺对硅丙乳液及乳胶膜性能的影响[J].胶体与聚合物,2003,21(2):1-5
[94]刘金辉,李效玉,焦书科.以阳离子乳化剂进行丙烯酸丁酯一苯乙烯乳液共聚的动力学研究[I『].高分子学报,1995,4:472-476
[95]大森英三著,张育川等译,功能性丙烯酸树脂[M].北京:化学工业出版社,1993
[96]Hill L W,Wicks Z W.Amine solubilizers for water-soluble acrylic baking enamels[J].Progress in Organic Coating.1980,8(2):161-182
[97]Wang Z Yu,Paine A,Rudin A.A mass spectrometric investigation of the water-soluble oligomers remaining after the emulsion polymerization of methyl methacrylate[J].J Polym Sci Part A:Polym Chem.1995,33:1597-1616
[98]Paine A J,Pontes F M,Moffat K A.Starve fed emulsion PolymeriZation Proeess.US Patent,5444140,1995
[99]唐黎明,阚成友,杜弈.室温交联丙烯酸酯聚合物涂料的研制[J].中国涂料,2000,22(4):23-25
[100]余樟清,李伯耿,潘祖仁.涂料用可交联聚丙烯酸酯乳液的研究进展[J].高分子通报,1999,11(2):22-30
[101]COLEMAN L E,BORK J E,WYMAN D P.Synthesis and polymerization of N-[2-(2-methyl-4-oxopentyl)]-acrylamide-a new reactive vinylmonomer[J].J Polym Sci:PartA,1965,3(4):1601-1608
[102]Okanoto Y,Hasegawa Y,Yoshino F.Urethane/acrylic composite polymer emulsion[J].Prog Org Coat,1996,29(8):175-182
[103]叶扬祥,潘肇基.涂装技术实用手册,第2版[M].北京:机械工业出版社,2004
[104]查亿春,曹灿,曲刚.低成本环保型苯丙乳液的研制[J].涂料工业.2003,33(9):5-7
[105]张茂根,翁志学,黄志明,潘祖仁.表面活性单体存在下的MMA/BA乳液共聚合(Ⅱ)[J].高等学校化学学报.2000,21(1):148-15l
[106]赵从华,康芦笙,冉龙泉.影响外墙乳胶漆耐沾污性的因素[J].涂料工业.2003,33(1):17-19
[107]武利民.涂料技术基础,第1版[M].北京:化学工业出版社,1999
[108]Nagila R.Synthesis and characterization of zirconium ionomer dispersions [J].Polym Eng Sci.1999,39(3):543-549
[109]Rodgers J.Organic Film Former Compositions of Self Sensitive Systems.美国专利,3308078,1965