丙烯酸乳液的合成及其在塑料基材上的应用

以苯乙烯(St)、甲基丙烯酸甲酯(MMA)和丙烯酸-2-乙基己酯(2-EHA)为主单体,甲基丙烯酸羟乙酯(HEMA)、甲基丙烯酸(MAA)、双丙酮丙烯酰胺(DAAM)和己二酸二酰肼(ADH)为功能性单体,通过功能单体MAA和HEMA来改善合成的乳液成膜时与塑料基材的界面接触,提高附着力。由实验得出:当乳液设计种子用量占预乳液的3%,Tg为60℃,MAA用量占单体总量的3%,HEMA用量占单体总量的3%,DAAM用量为单体总量的4%时,合成的交联型丙烯酸酯乳液配制成塑料涂料在PC、ABS板上具有硬度高、附着力优异和耐乙醇擦拭性能好等优点。     

金属防腐漆用双重自交联丙烯酸乳液的制备及其性能研究

以甲基丙烯酸甲酯(MMA)和丙烯酸2-乙基乙酯(2-EHA)为主单体,甲基丙烯酸(MAA)、乙烯基三乙氧基硅烷(A-151)、双丙酮丙烯酰胺(DAAM)和己二酸二酰肼(ADH)的酰肼交联体系以及丙烯酸磷酸酯(PAM-100)为功能单体,采用反应型乳化剂SE-10N,通过预乳化乳液聚合工艺合成了金属防腐漆用双重自交联丙烯酸酯乳液。考察了乳液Tg、MAA、SE-10N、A-151、DAAM/ADH和PAM-100对乳液及其金属防腐漆涂膜的影响。结果表明:当乳液设计Tg为30℃、MAA用量为单体总量的3%、反应型乳化剂SE-10N用量为单体总量的2.5%、A-151用量为单体总量的2%、DAAM用量为单体总量的2%、PAM-100用量为单体总量的3%时,所制备的自交联丙烯酸酯乳液配制成的金属防腐涂料,具有附着力好、耐盐水、耐酸碱、耐盐雾等特点。     

双丙酮丙烯酰胺改性水性环氧树脂的制备

以双丙酮丙烯酰胺(DAAM)和丙烯酸单体改性月桂酸与环氧树脂E-20的开环反应产物,并以己二酸二酰肼(ADH)为交联剂,制备了室温自交联水性环氧乳液,采用红外光谱、粒度分析仪及透射电镜等表征了乳液结构,研究了DAAM用量及其与ADH质量配比对乳液性能的影响。结果表明,合成的乳液粒径88 nm,DAAM添加质量分数为2%~3%,ADH与DAAM的质量比为0.8~1.0∶1时乳液性能最优,稳定性优异。     

高性能户外水性木器涂料用纯丙乳液的制备与研究

使用甲基丙烯酸甲酯(MMA)、丙烯酸正丁酯(BA)以及丙烯酸异辛酯(2-EHA)为主要单体,以甲基丙烯酸(MAA)、γ–甲基丙烯氧基丙基三甲氧基(A-174)、双丙酮丙烯酰胺(DAAM)和己二酸二酰肼(ADH)为功能性单体,通过核壳、自交联技术合成了户外水性木器涂料乳液。研究了乳化剂、交联单体、硅烷偶联剂用量以及玻璃化转变温度对乳液性能的影响。结果表明:当乳液的玻璃化转变温度设计为10℃、乳化剂质量分数为1.5%、A-174质量分数为3%、DAAM质量分数为3%时,合成的水性户外木器涂料用乳液具有优异的贮存稳定性、干燥速度、打磨性、抗回黏性、耐水性、柔韧性以及耐黄变性,完全可以满足水性户外木器涂料的使用。     

VAc/VoeVa/DAAM三元共聚乳液的制备与性能研究

以VAE[醋酸乙烯酯(VAc)-乙烯共聚物]为种子乳液、聚乙烯醇(PVA)为保护胶体、叔碳酸乙烯酯(VoeVa10)为VAc的共聚单体、OP-10为乳化剂、己二酰肼(ADH)/双丙酮丙烯酰胺(DAAM)为交联体系和叔丁基过氧化氢/甲醛次硫酸钠为氧化还原型引发剂,采用种子乳液聚合法制备了VAc/VoeVa10/DAAM共聚乳液;然后在反应后期加入后交联剂(ADH),得到改性聚醋酸乙烯酯(PVAc)乳液。结果表明:当w(PVA1788+PVA1799)=3%、m(PVA1788)∶m(PVA1799)=1∶1、m(VoeVa10)∶m(VAc)=(10～15)∶100、w(氧化剂)=0.3%、w(VAE)=10%、w(OP-10)=2%、m(ADH)∶m(DAAM)=(0.5～1.5)∶1.0且w(DAAM)=2%时,相应乳液具有优异的耐水性和稳定性,并且其涂膜柔韧性和粘接性能俱佳。     

DAAM对室温自交联纯丙乳液性能的影响

以衣康酸二丁酯(DBI)为第1功能单体、双丙酮丙烯酰胺(DAAM)为第2功能单体,合成了固含量为45%的纯丙乳液,并在室温与己二酰肼(ADH)交联。通过控制DAAM的用量,制备了一系列的室温自交联乳液,研究了DAAM用量对乳液和乳胶膜性能的影响。结果表明,DAAM的加入对乳液和胶膜的各项性能均有一定改善,DAAM的适用量为3%。     

用苯-丙乳液制成的水性可剥涂料

合成了苯–丙乳液。研究了软、硬单体对乳液涂膜性能的影响。加入增韧剂和脱膜剂及其它助剂对苯–丙乳液进行了改性。讨论了增韧剂和脱膜剂用量对涂膜性能的影响。结果发现,当m(软)∶m(硬)=13∶20,w(增韧剂)=4.5%,w(脱膜剂)=0.7%时,涂膜具有较好的附着力、柔韧性和伸长率。获得了具有较佳的涂膜可剥性水性涂料。该涂料具有以下性能:固含量30%,D=18~23nm,Tg=–5°C,附着力7级,伸长率300%,柔韧性1mm,铅笔硬度2H,δ=30~40μm,η=55~64mP·s,冲击强度>50kg·cm。     

一种高光泽聚丙烯酸酯乳液的制备及性能研究

以St(苯乙烯)为硬单体、BMA(甲基丙烯酸丁酯)为软单体、HEMA(甲基丙烯酸羟乙酯)为功能单体、自制A-35(水溶性丙烯酸酯树脂)为乳化剂、DAAM(双丙酮丙烯酰胺)和ADH(己二酸二酰肼)为交联单体,采用种子乳液聚合法制备了一种新型水性上光涂料用聚丙烯酸酯乳液。研究结果表明:当m(St)∶m(BMA)=50∶42~45∶52、w(A-35)=20%~30%(相对于乳液总固含量而言)、w(HEMA)=2%和w(DAAM)=2.5%(均相对于单体总质量而言)时,该乳液的硬度、附着力和储存稳定性相对最佳,并且涂膜可室温固化,而且其光泽度、耐水性、耐溶剂性及耐磨性均满足水性上光涂料的使用要求。     

高性能水性木器漆用PUA树脂的制备及漆膜性能研究

以水性PU乳液为原料,通过与丙烯酸酯单体共聚制备了稳定的PUA复合乳液。重点考察了PU的加料方式、PU用量以及丙烯酸酯单体的配比对聚合过程和乳液性能的影响。研究表明,在种子乳液聚合基础上采用核壳两层预乳化工艺,PU用量为20%,丙烯酸酯单体配比m(MMA)∶m(BA)∶m(2-EHA)=6∶2∶2时可得到性能优异的PUA复合乳液。漆膜性能的测试结果表明,该PUA乳液配制的水性木器清漆具有优异的性能,可满足高档木器对漆膜的高性能要求。     

氟碳铝型材保护膜用压敏胶的制备与性能

以丙烯酸丁酯(BA)和丙烯酸异辛酯(2-EHA)为软单体、甲基丙烯酸甲酯(MMA)为硬单体、丙烯酸(AA)和丙烯酸羟丙酯(HPA)为功能单体,采用降低PSA(压敏胶)的Tg(玻璃化转变温度)和预乳化半连续乳液聚合法合成了丙烯酸酯PSA乳液。研究结果表明:当m(软单体)∶m(硬单体)∶m(功能单体)=90∶5∶5、m(BA)∶m(2-EHA)=1∶2、w(AA)=1.0%、w(HPA)=5%、w(缓冲剂)=0.25%、w(引发剂)=w(复合乳化剂)=0.6%且m(阴离子型乳化剂)∶m(非离子型乳化剂)=1∶1时,PSA乳液的综合性能相对最好,用该PSA制成的保护膜对氟碳铝型材具有良好的附着力,并且其耐湿热老化性能和耐热老化性能俱佳。     

Synthesis and characterization of low-temperature self-crosslinkable acrylic emulsion for PE film ink

A low-temperature self-crosslinkable acrylic emulsion was synthesized by semi-continuous emulsion polymerization technology using methyl methacrylate (MMA), butyl acrylate (BA), acrylic acid (AA) and diacetone acrylamide (DAAM) as monomers and adipic dihydrazide (ADH) as crosslinker. Transmission electron microscope (TEM) micrograph disclosed spherical emulsion particles possess core–shell structure. Fourier transform infrared (FTIR) spectrogram showed that crosslinking reaction between CO groups of DAAM and NHNH₂ groups of ADH can occur during coating film formation at low temperature, even at room temperature. Differential scanning calorimeter (DSC) analysis indicated that glass transition temperature (Tg) of the crosslinked film is increased by 5 °C. Thermogravimetric analysis (TGA) curves demonstrated that self-crosslinking reaction improves thermal stability of film. As DAAM content increased from 0% to 2%, water absorption ratio of film decreased from 26.2% to 7.4%, adhesion ratio on the PE thin film increased from 0% to 97%. While the n(ADH)/n(DAAM) ratio increased from 0:1 to 0.8:1, crosslinking density of films was increased from 0% to 88%, water absorption ratio decreased from 36.5% to 7.4% and adhesion ratio on the PE thin film increased from 0% to 97%. The optimal DAAM content and n(ADH)/n(DAAM) ratio was 2% and 0.8:1 in this experiment. The emulsion has good potential application in water-based ink for PE film.     

自交联封闭性乳液的合成与性能

以双丙酮丙烯酰胺（DAAM）、甲基丙烯酸甲酯（MMA）、丙烯酸丁酯（BA）和甲基丙烯酸（MAA）为共聚单体,采用半连续种子乳液聚合工艺合成自交联封闭性聚丙烯酸酯乳液（PAE）,考察了DAAM和复合乳化剂对乳液聚合稳定性以及涂膜性能的影响。研究发现：随着DAAM含量的增加,乳液聚合稳定性下降,粒径增大,涂膜的耐介质性能和交联度提高,合适的DAAM加入量为总单体质量的3.0%,DAAM和己二酰肼(ADH)的最佳摩尔比为2∶1。采用SDBS+OP-10+OP-40为复合乳化剂体系,选用乳化剂的含量为2.35%,阴/非离子乳化剂质量比为1∶1.25;复合乳化剂在种子、核、壳比例为1.5∶1∶2,制备的乳液具有较好的聚合稳定性（乳液凝胶率低和单体转化率高）,乳液耐电解质（钙离子）稳定性好,涂膜具有优异的封闭性。傅里叶红外光谱（FTIR）表明在涂膜形成过程中DAAM的酮羰基与ADH的酰肼基反应生成腙（C=N）,TEM分析显示乳液的乳胶粒子呈核壳结构,TGA分析发现DAAM改性的PAE降低了涂膜的热稳定性。     

水性丙烯酸酯乳液的合成及性能研究

以双丙酮丙烯酰胺（DAAM）为功能性单体,采用预乳化半连续种子乳液聚合法合成水性丙烯酸酯乳液,添加己二酸二酰肼（ADH）为交联剂,构成室温自交联体系。考察了DAAM、ADH用量对乳液及其乳胶膜性能的影响。用傅里叶红外光谱仪（FT-IR）对交联反应进行了表征。通过差示扫描量热法、力学性能和耐溶剂性能的测试等方法研究了乳液和乳胶膜的性能。结果表明,当DAAM用量为2.4%~3.5%,ADH与DAAM的当量比为1~1.2时,乳液和乳胶膜的综合性能较好。     

热压型水性干法复膜胶的研制

以丙烯酸酯和苯乙烯(St)为主要原料、CO-459为阴/非离子型复合乳化剂、H-843为水性增黏剂和双丙酮丙烯酰胺(DAAM)/己二酰肼(ADH)为特殊交联体系,采用半连续预乳化种子乳液聚合法制备热压型水性干法苯丙乳液复膜胶,并探讨了乳化剂、DAAM、ADH、增黏剂和生产设备等对苯丙乳液的聚合稳定性、使用性能等影响。结果表明:当w(总CO-459)=0.9%、w(DAAM)=0.8%、w(ADH)=0.5%和w(H-843)=0.5%(均相对于总投料的质量而言)时,相应乳液的聚合稳定性良好、剥离强度较大,并且其复膜后可进行模切、凹凸、压纹和热压等工艺操作,具有良好的应用前景。     

Rheological and curing behavior of aqueous ambient self‐crosslinkable polyacrylate emulsion

An aqueous ambient crosslinkable polymer acrylic (AACPA) emulsion was obtained by adding adipic acid dihydrazide (ADH) to the polyacrylate emulsion incorporating diacetone acrylamide (DAAM), and this emulsion was synthesized by two feeding materials methods. The AACPA emulsion and its paint film were characterized with rheological measurements, laser light scattering, Fourier transform infrared, torsional braid analysis (TBA), DTA, and so on. The results showed that AACPA emulsion was pseudoplastic fluid and pseudoplasticity increased with increasing of DAAM content. The results also showed that water resistance, solvent resistance, and thermotacky temperature of AACPA paint film increased with increasing of the content of DAAM. The results dealing with curing behavior of the paint film showed that adding organic swelling solvent and organic acid to the AACPA emulsion can accelerate the curing speed of the paint film. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

酮肼交联对涂料印花用聚丙烯酸酯乳液的影响

以双丙酮丙烯酰胺(DAAM)作为官能单体,制备了含有酮羰基的聚丙烯酸酯乳液。将此乳液与己二酸二酰肼(ADH)混合,制得涂料印花用粘合剂。涂膜经红外光谱测试表明,乳液成膜时酮羰基与肼发生了交联反应。另外讨论了DAAM的用量与添加方式、DAAM与ADH的质量比以及固化温度等对织物印花各种性能的影响。     

室温交联聚丙烯酸酯乳胶膜的制备及其渗透性能

以双丙酮丙烯酰胺（DAAM）为官能性单体合成了带酮羰基的聚丙烯酸酯核壳乳液,将其与己二酸二酰肼（ADH）在室温下交联制备了聚丙烯酸酯多孔乳胶膜,考察了乳液壳层组成、ADH用量、致孔剂用量及种类对乳胶膜渗透性能的影响。研究结果表明,当壳层组成BA/(MMA+AA+DAAM)质量比为2.5/2.5时,乳胶粒子没有完全变形,粒子间相互融接堆积,结合致孔剂的作用,形成了内部呈疏松多孔结构的乳胶膜,膜的渗透量较高;研究进一步揭示,限制大分子链段的热运动有利于维持乳胶膜的多孔结构,从而获得较高的渗透量;此外,发现以葡萄糖、聚乙二醇300（PEG300）为致孔剂时可使乳胶膜获得较高的渗透量。     

The diacetone acrylamide crosslinking reaction and its control of core‐shell polyacrylate latices at ambient temperature

Self crosslinkable core‐shell polyacrylate latices (PAs) cured at ambient temperature were synthesized by semicontinuous‐seeded emulsion polymerization with diacetone acrylamide (DAAM) and adipic dihydrazide (ADH) as crosslinkable monomers. The influences of DAAM monomer mass content, neutralizer, and curing temperature on the properties of self crosslinkable core‐shell latices and the keto‐hydrazide crosslinking were discussed. The spectroscopic techniques such as Fourier transform infrared spectroscopy (FTIR), differential scanning calorimeter (DSC), atomic force microscopy (AFM), transmission electron microscopy (TEM), and contact angle instruments were used to determine the structure and properties of PAs. The water evaporating rate during the film‐forming process of self crosslinkable core‐shell latices was also investigated. FTIR analyses demonstrate that the keto‐hydrazide crosslinking reaction does not occur in the latex environment but occurs at ambient temperature with the evaporation of water during the film‐forming process. The results of DSC show that the core‐shell crosslinkable PAs have two glass transition temperatures (T_g), and T_gs of crosslinked film are higher than that of non crosslinked fim. Moreover, the keto‐hydrazide reaction is found to be acid catalyzed and favored by the loss of water and the simultaneous decrease in pH arising from the evaporation of ammonia or amines during film‐forming process. Hence, in the volatile ammonia or amines neutralized latices, the latex pH value adjusted to 7–8, which not only ensure the crosslinkable latex with good storage stability but also obtain a coating film with excellent performances by introducing the keto‐hydrazine crosslinking reaction. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

长烷基链对水性聚氨酯在非极性基材上附着力的影响

以聚己二酸新戊二醇酯（PNA）、二聚酸聚酯多元醇（BY3026）、异佛尔酮二异氰酸酯（IPDI）为主要原料制备了一系列侧链含长链烷基的水性聚氨酯（WPU）乳液并制成胶膜。通过FTIR、DSC表征了胶膜的结构和热性能，测试了乳液粒径及胶膜的力学性能、吸水率、接触角以及其在双向拉伸聚丙烯薄膜（BOPP）上的附着力。结果表明，当m(BY3026)∶m(PNA)从0∶1增加到3∶5,WPU乳液粒径增大，胶膜的耐水性增强，表面能先减小后增大，拉伸强度和断裂伸长率从52.6 MPa和2607.2%分别降低至38.7 MPa和1911.2%。当m(BY3026)∶m(PNA)=2∶5时，制备的WPU胶膜表面能为35.43mJ/m2,WPU乳液在BOPP薄膜上的T-剥离强度为2.98 N/25 mm。     

Control of adhesive properties through structured particle design of water-borne pressure-sensitive adhesives

The concept of using structured particles and the mechanism of film formation from latexes to produce pressure-sensitive adhesive (PSA) films with controlled sub-micron and nanometre scale morphology has been investigated with the objective of enhancing adhesive performance. Structured particle acrylate-based latexes were synthesised by seeded semi-continuous emulsion polymerisation procedures. Aliquots removed at intervals during the polymerisations were analysed for conversion and z-average particle diameter; the results confirm that the particles grew without secondary nucleation or coagulation. Three-layer particles were studied first and comprised a core whose composition was the same for all particles, an interlayer between core and shell which was crosslinked during synthesis (using 1,6-hexanediol diacrylate, HDDA) and a shell which contained diacetone acrylamide (DAAM) repeat units that provided for interfacial crosslinking between particles during film formation by reaction with post-added adipic acid dihydrazide (ADH). The three-layer latexes produced adhesive films with high shear resistance when ADH was added, but peel adhesion was generally low and further reduced by increasing either the thickness or HDDA concentration of the interlayer. Thus two-layer latexes with shell layers containing DAAM but no pre-crosslinked interlayer were the main focus of the study. The effects of core:shell ratio and amount of DAAM on adhesive performance were optimum with a core:shell ratio of 80:20 and 2 wt% DAAM in the shell copolymer, for which interfacial crosslinking using the stoichiometric amount of ADH led to a marked increase in shear resistance with only a slight reduction in peel adhesion. Increasing the level of n-dodecylmercaptan (DDM) chain transfer agent used in synthesis of the core increases peel adhesion and reduces shear resistance in the absence of ADH, but high shear resistance can be recovered through interfacial crosslinking with ADH. Adhesive performance can be optimised by using a high DDM level in the core and a low DDM level in the shell, a combination that enables both high peel adhesion and shear resistance to be achieved with the addition of ADH. The results from this study define guiding principles for development of commercial water-borne PSAs that can compete with solvent-borne PSAs in high-performance applications.