【作者】 李彬；

【导师】 吕建平；

【作者基本信息】 合肥工业大学 ， 化学工程， 2012， 硕士

【摘要】 聚丙烯酸酯胶黏剂来源丰富，具有润湿性好，初粘力优，应用范围广泛等特点。但以此类胶黏剂用于氨酯键和聚烯烃类薄膜时，由于自身化学键的内聚能比较低，导致复合剥离强度较低。聚氨酯相比于丙烯酸酯，分子链上含有大量的键能极大的脲键，分子间的内聚力很大。但大部分的聚烯烃类薄膜都是非极性的，而氨酯键的极性非常大，所以聚氨酯胶黏剂通常很难在这种材料表面附着，导致剥离强度不高。且水性聚氨酯的固含量比较低，复合薄膜时，生产效率低，能耗较大。这些缺点阻止了水性聚氨酯在复膜胶领域的发展应用。但若将聚氨酯和丙烯酸酯结合起来，取长补短，采用科学的复合工艺，即可获得性能优异的水性复膜胶。本文先以二异氰酸酯、低聚物多元醇、二羟甲基丙酸（DMPA）等为主要原料，以甲基丙烯酸羟乙酯（HEMA）为封端剂，三乙胺（TEA）为中和剂，三羟甲基丙烷（TMP）、己二酸二酰肼(ADH)、二乙烯三胺（DETA）等为小分子扩链剂，合成端乙烯基水性聚氨酯乳液。依据预乳化种子乳液聚合工艺，合成丙烯酸酯乳液，以此乳液作种子，采用双滴加工艺，将已制备的水性聚氨酯引入聚合物中并聚合，从而制备出PUA复合乳液。并以此乳液作为复膜胶的基料，加入各种助剂如增粘剂、润湿剂、填料等制备出性能优异的水性复膜胶产品。分别研究了丙烯酸酯部分如软硬单体选择及配比，功能单体选择及用量，乳化剂类型及用量；聚氨酯部分如改性工艺、聚氨酯用量、HEMA、DMPA用量，R值大小，小分子胺类扩链剂；以及各种助剂对聚合物乳液性能的影响并介绍了用于聚烯烃薄膜复合用的PUA复膜胶的工艺及配方。实验表明：(1)采用反应型乳化剂SR-10制备的乳液，粘度小，耐水性好，剥离强度较高，且当其用量为2%时，剥离强度最大；(2)软单体为BA，硬单体为MMA，且当软硬单体比为3:1时，体系的剥离强度最大；(3)加入适量的功能单体如甲基丙烯酸（MAA）、丙烯酸羟乙酯(HEA)、双丙酮丙烯酰胺（DAAM）等，可以极大的提高体系的剥离强度；(4)采用种子乳液聚合工艺制备的PUA乳液剥离强度高、耐水性好、储存稳定性好，且当PU/PA=1:4时，体系的剥离强度最大；(5)当R值为1.3，DMPA用量为4.5%，HEMA用量为4%，ADH/DETA=2:1，且采用先加DETA，后加ADH的工艺，制备的PUA乳液剥离强度最好；(6)加入润湿剂可以降低接触角，提高剥离强度且当加入量为乳液总量的0.7%-0.8%时，剥离强度最大；(7)加入增粘树脂，可以提高乳液的初粘性，减小接触角，且当加入量为总量的15%时，剥离强度最大；(8)加入5%的纳米二氧化硅可以在不降低体系剥离强度的情况下，降低产品的成本。借助傅里叶红外光谱技术，证明乳液中确实合成了聚氨酯、丙烯酸酯的共聚物；通过热重及粒径测试，证明合成的PUA粒径较细，粒径分布较窄，热稳定性良好。更多还原

【Abstract】 With the features of abroad source,the polyacrylic adhesive show betterwetting property, excellent initial tack and widely adhesivity.However,theacrylic adhesive has low peeling strength because of its low cohesive energywhile bonding polyole substrate.Compared to the acrylic,the polyurethane hashigh cohesive energry,because the polyurethane molecular chain contains alarge number of urethane bond and urea bond whose bond energy are huge.Butit is too difficult to attach to the surface of the material for these urethanebond have large polarity,and most of the polyolefin films are non-polar,whichresult in low peeling strength. The water-based polyurethane has low solidcontent, low productivity, high energy consumption, which can prevent thedevelopment and application of water-based polyurethane in the field ofplastic plastic adhesive. Accordingly, we can combine advantage of bothpolyurethane and acrylic from each other, using the science compoundingprocess, and then get the performance of waterborne polyurethane-acryliclaminating adhesive.In this dissertation, side vinyl polyurethane emulsion was synthesizedusing diisocyanate,oligomer polyol,bis (hydroxymethyl) propionicacid(DMPA) as main raw material, methyl hydroxypropyl acrylate (HPMA) assealing side agent,triethyl-amine(TEA) as neutralizer,trimethylolpropane(TMP), adipic acid dihydrazide (ADH), diethylenetriamine(DETA) as small molecule chain extender.The polyacrylate emulsion wassynthesized based on the pre-emulsion seeded emulsion polymerizationprocess.After that,the polyurethane-acrylic emulsion was prepared using ofdual-dropwise added process,and using the acrylic emulsion as seed, sidevinyl waterborne polyurethane was leaded into the polymer and aggregated.Finally, excellen performance of water-based laminating adhesive product wasprepared by adding various additives such as increased viscosity, wettingagents, fillers to the PUA. The polyacrylate parts such as the type and dosage of the emulsifier, theselection and proportion of the flexible monomer and hard monomer, theselection and ratio of functional monomer;the polyurethane parts such as themodification process, dosage of polyurethane, amount of HEMA,and DMPA,R value size, and small molecules amine chain extender, and the influence ofvarious additives on the performance of polymer emulsion were studied, anddescribed the process and formulation of the laminating adhesive forpolyolefin film composite with the PUA were described too.The experment showed:(1)Emulsion prepared by reactive emulsifier SR-10, had low viscosity, good water resistance, high peeling strength, and whenthe amount of2%, the peeling strength was largest;(2) As Soft monomer BAand hard monomers MMA ratio of3:1, the system had the biggest peelingstrength;(3)Adding an appropriate amount of functional monomers such asmethacrylic acid (MAA), hydroxyethyl acrylate (HEA), diacetone acrylamide(DAAM), could greatly improve the peeling strength of the system;(4)PUAwhich was prepared by the way of seeded emulsion polymerization processhas high peeling strength, water resistance, good storage stability, and whenPU/PA=1:4, The polymer had the largest peeling strength;(5)When R=1.3,amount of DMPA4.5%, amount of HEMA4%, ADH/DETA=1:4, and theprocess of first joined the ADH, then added DETA, the PUA emulsion had thebest peeling strength;(6)The wetting agent could reduce the contact angle, andimporve the peeling strength.When the amount of0.7%-0.8%of the total oflotion, the peeling strength was largest.(7)By adding a tackifying resin, couldimprove the initial viscosity of the emulsion, reduce the contact angle, andwhen the amount of15%of the total emulsion, the peeling strength of syetemwas largest.(8)Adding5%nano-silica could be used to maintain sufficientpeeling strength, and reduce the cost of the product.The synthesis of polyurethane and acrylates copolymer were confirmed usingfourier spectrometer analysis;By using thermal gravimetric and particle size testproved that the synthesis of the PUA has smaller particle size, narrow particle sizedistribution, good thermal stability.更多还原