水性双组分丙烯酸-聚氨酯的合成与表征

使用相转化法,即将水溶性丙烯酸树脂和HDI缩二脲混合,然后加水稀释转相,制备了水性双组分丙烯酸聚氨酯。研究了丙烯酸树脂配方对双组分聚氨酯性能的影响,并用红外光谱(FTIR)对涂膜固化进行了表征。结果表明,以丙二醇甲醚醋酸酯为溶剂,在羟值为120 mgKOH·g-1、酸值为30 mgKOH·g-1的水溶性丙烯酸树脂中,添加10 %的甲基丙烯酸异冰片酯,获得的双组分聚氨酯乳液粒径小。室温干燥12 h,固化反应完成,涂膜交联密度高。     

影响阴离子聚丙烯酸羟基树脂包覆HDI缩二脲乳胶粒粒径的因素

采用转相法制备了阴离子聚丙烯酸羟基树脂包覆HDI缩二脲乳胶粒.用TEM观察了包覆乳胶粒形态结构,分析了影响包覆乳胶粒粒径的影响因素.结果表明,乳胶粒呈现明显的核-壳结构,HDI缩二脲被聚丙烯酸羟基树脂包覆.聚丙烯酸羟基树脂分子量越大、溶剂极性越强,乳胶粒粒径越小.增加苯乙烯用量,乳胶粒粒径随之先减小后增加,苯乙烯质量分数为10%时粒径最小.乳胶粒粒径随羟基含量的增加而增大.当羟值为60 mg KOH•g^-1时,乳胶粒粒径随着丙烯酸含量的增加而减小;当羟值在90 mg KOH•g^-1以上时,降低丙烯酸含量有利于乳液粒径的减小.降低聚丙烯酸链间的氢键作用力,增加羟基和HDI缩二脲间的氢键作用力,能获得粒径小而均匀的包覆粒子.     

氟改性双组分水性丙烯酸聚氨酯涂料性能研究

以甲基丙烯酸十二氟庚酯（DFMA）、丙烯酸（AA）、甲基丙烯酸羟乙酯（HEMA）、甲基丙烯酸甲酯（MMA）和丙烯酸丁酯（BA）为原料,采用溶液聚合法合成了一系列氟含量不同的水性羟基丙烯酸树脂。将含氟水性羟基丙烯酸树脂、亲水性异氰酸酯固化剂和助剂混合制备氟改性双组分水性丙烯酸聚氨酯（2K—WPU）涂料。利用傅里叶变换红外光谱（FT-IR）对其结构进行了表征,并对涂料的接触角、吸水率和清漆性能分别进行了测试。结果表明,该水性树脂粒径在28．2～68．1nm之间,粒径分布均匀。当水性羟基丙烯酸树脂组成中DFMA质量分数从0增加至20％时,所制备氟改性2K-WPu涂料的水接触角从70．3。增大到97．6。,吸水率从11．4％降低至6．31％,涂膜的耐水性显著提高。清漆性能测试表明,所制氟改性2K．WPu的各项性能优异。     

聚合方法对水性羟基丙烯酸树脂及相应2K-WPU性能的影响

分别通过溶液聚合、乳液聚合和两步聚合法制备了3种水性羟基丙烯酸树脂(PAS、PAE、PAT),采用傅里叶变换红外光谱(FT-IR)、动态光散射(DLS)和示差扫描量热法(DSC)对所合成树脂进行了表征。在无催化剂存在的条件下,分别将3种水性树脂与异氰酸酯固化剂Bayhydur XP 2655以及助剂混合得到双组分水性聚氨酯清漆,通过红外光谱对固化后清漆结构进行了表征,并对3种水性清漆的性能进行了研究。实验结果表明基于PAT的水性清漆综合性能较优。     

水性环氧乳液稳定性研究及分析

介绍了使用相反转法制备双酚A型环氧树脂水基乳液,研究表面活性剂类别及其用量、乳化温度、树脂分子量、溶剂的种类等各种因素对环氧树脂乳液颗粒度大小和稳定性的影响。得出结论:乳化剂类别及其用量对乳液的粒度及其分布影响明显;溶剂对乳液稳定性影响很大,合适的溶剂能提高其稳定性而不合适的溶剂反而使稳定性变差;乳化工艺尤其乳化温度是影响乳液稳定性的重要因素;双酚A环氧树脂的分子量越大,采用相反转法制备稳定的环氧乳液越困难。     

常温酮肼自交联纳米环氧树脂乳液的制备与表征

以环氧树脂E-20合成了环氧月桂酸酯, 以丙烯酸单体与双丙酮丙烯酰胺(DAAM)对其进行接枝改性, 添加己二酸二酰肼(ADH)制备了常温酮肼自交联纳米环氧树脂乳液。以红外光谱仪表征了合成过程中各步产物及乳液固化后的结构, 结果表明得到了设计结构的树脂, 干燥后涂膜的FTIR谱图表明酮羰基与酰肼基发生交联反应生成了腙;DSC分析表明合成的树脂具有两个玻璃化温度(T_g), 分别为丙烯酸接枝环氧树脂和纯丙烯酸树脂的T_g, 前者低于常温, 表明可以实现常温自交联。在改性环氧树脂乳液的合成过程中, 以粒径分析和综合性能分析对功能性单体配比进行了研究, 结果发现当MAA与E-20质量比为11.0%~14.7%、DAAM的用量为2%~3%、m(ADH)/m(DAAM)为0.8~1.0时, 制得的乳液具有良好的储存稳定性和涂膜性能。透射电镜及粒径测试表明乳液粒径为纳米级, 约88 nm, 且粒径分布均匀, 基本呈稳定的球形结构。将所制备的纳米乳液配制成防腐涂料, 性能测试表明该涂料具有良好的综合性能。     

聚氨酯固化丙烯酸树脂与水性PVDF的共混相容性研究

分析了一种新型水性PVDF氟碳树脂乳液(FCF-301)的粒径、SEM、红外及核磁氢谱特征,分析表明氟碳乳液为核壳型。为进一步提升其应用性能,采用双组分水性丙烯酸树脂对核壳型水性PVDF进行复合改性。其中,树脂的共混相容性是复合改性的关键要素。通过SEM、FT-IR、DSC对溶液铸膜法制备的共混薄膜表征结果对比可知:聚氨酯固化丙烯酸树脂A2470与水性PVDF树脂FCF-301共混呈部分相容:其海岛结构相分离现象少,且相界面模糊;与碳氟键相关的红外吸收峰有一定程度迁移;共混薄膜材料中水性PVDF树脂FCF-301熔点向低温方向迁移-5 ℃,为备选双组分共混相容体系中最优。     

水性异氰酸酯交联剂/VAE复合胶粘剂的制备与应用

将六亚甲基二异氰酸酯(HDI)三聚体在自制的丙烯酸树脂乳液中乳化,制得水性异氰酸酯交联剂乳液;然后将交联剂乳液与VAE乳液(醋酸乙烯-乙烯共聚乳液)复配,制得木材用胶粘剂。结果表明:当m(丙烯酸树脂)∶m(异氰酸酯)=2∶1、m(水性异氰酸酯交联剂乳液)∶m(VAE乳液)=1∶2、施胶量为300 g/m2和热压温度为110～130℃时,细木工板的胶接强度(0.85 MPa)、横向静曲强度(22.6 MPa)和耐水性(80℃热水中浸泡10 h不开胶)均达到较佳值,并且均符合GB/T 9 846-2004标准。     

Influence of temperature on the phase inversion of chlorinated polypropylene

In this study, the maleic anhydride modified chlorinated polypropylene (MCPP) resin was emulsified by mixed ionic surfactants comprising sodium dodecyl sulfate (SDS) and sulfonated castor oil (SCO). The influence of temperature on the morphology of emulsion was studied through transitional and catastrophic inversion methods. The transitional inversion of emulsion from water‐in‐oil (W/O) to oil‐in‐water (O/W) was triggered by decreasing the temperature and the catastrophic inversion was achieved by increasing the weight fraction of water. The results of transitional and catastrophic inversion both indicated that the phase inversion of “ionic surfactant–MCPP–water” system is easier to trigger at low temperatures than at high temperatures, which could be interpreted by the thermodynamic and hydrodynamic theory. Incomplete phase inversion occurred at low temperatures when the volume of water phase was small and emulsions with small particle size and narrow particle size distribution could only be obtained at an intermediate temperature. These results are of great importance for the preparation of stable polymer emulsions in food, cosmetics and paints industry. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40325.     

环氧/丙烯酸/弹性聚酯—聚氨酯抗风沙磨蚀涂料的研制

以环氧树脂、羟基丙烯酸树脂、弹性聚脂树脂混拼改性作基料树脂,添加颜填料及助剂组成A组分,以HDI缩二脲N-75为B组分,二者以5∶1质量比混合后施工,涂层具有弹性好、韧性优、强度高、附着力好、耐磨耐候耐腐蚀、抗风沙撞击等特点。     

丙烯酸乳液酸值测定方法研究

国标测定树脂酸值的溶剂体系适用于非水系或溶剂法合成水性丙烯酸树脂体系，其溶剂体系不适用于乳液聚合法制得的丙烯酸乳液酸值测定。研究选用百里酚蓝作为指示剂，采用乙醇和水的混合溶剂溶解乳液样品进行酸值测定，讨论了醇水比和稀释比对乳液粒径和酸值的影响，结果显示：采用醇水比为1．5的混合溶剂，总体积为50～200mL且稀释比小于200的条件溶解不同类型的丙烯酸乳液样品，乳液状态稳定且可得到较准确稳定的酸值结果。     

改性水性硝化纤维素乳液研究

采用醇酸树脂转相乳化法和丙烯酸酯类单体互穿聚合物网络聚合法制备改性硝化纤维素乳液。研究了醇酸树脂、丙烯酸酯类单体乳化剂用量等因素对乳液性能的影响。结果表明，丙烯酸酯类单体改性互穿聚合物网络聚合法制得的乳液效果好.     

Effect of mixing protocol on formation of fine emulsions

Emulsions are usually stabilised with a mixture of surfactants with different hydrophilicity. The initial partitioning of surfactants between the dispersed phase and continuous phase, and how these phases are brought into contact, can significantly affect the emulsification processes. Dynamic-phase behaviour maps were prepared to allow for a systematic investigation of the effects of emulsification routes on emulsion properties. Six semibatch modes of additions with constant surfactant concentration across the routes were selected. For a target cyclohexane-in-water emulsion using a pair of polyoxyethylene nonylphenyl ether surfactants with a specified HLB and water volume fraction, fine droplets could form only if water dissolving the water-soluble surfactant was added to the oil dissolving the oil-soluble surfactant. This route allowed the transitional inversion to occur and as a result fine droplets were formed due to an ultra-low interfacial tension. The addition of water dissolving the water-soluble surfactant to oil dissolving the oil-soluble surfactant, direct emulsification method, produced by far large droplets because of a rather high interfacial tension. In a series of experiment, the semibatch direct and phase-inversion emulsification method, were assimilated in situ. The impeller location was used as a variable that controls which phase is added as the dispersed phase. The location of impeller in relation to the interface did not affect the emulsion drop size at a high agitation rate, but it did at a low agitation rate. Under low agitation speed and when the impeller was placed in the oil phase, the oil layer progressively, but slowly, dragged the water phase and eventually inverted to an oil-in-water emulsion, indicating that transitional-phase inversion has locally occurred in the oil layer. At a high agitation speed the mechanical energy provided by the impeller homogenised the emulsion instantaneously and did not allow the optimum formulation and the associated ultra-low interfacial tension to be reached regardless of location of the impeller. A high impeller speed increased drop size by transforming the transition inversion mechanism to a catastrophic mechanism under which the size of drops is mainly determined by the mechanical energy provided. This paper aims to show how some of the complexities involved in emulsification processes can be explained by consulting with dynamic-phase maps.     

Role of operating conditions in determining droplet size and viscosity of tackifier emulsions formed via phase inversion

Water‐based pressure‐sensitive adhesives are formulated by combining a polymer latex with a tackifier emulsion. The latter is an oil‐in‐water emulsion made by the process of phase inversion. The phase inversion itself is carried out in a stirred tank fitted with a heating jacket by progressively adding water to a water‐in‐oil emulsion. The point of onset of phase inversion and the characteristics of the emulsion that is formed depend on process conditions; these include temperature, rate of water addition, and agitation speed. The role of these operating conditions is elucidated here. Increasing temperature delayed the onset of phase inversion slightly, but it did not affect emulsion particle size, provided it remained below a critical value. Agitation speed had to be increased upon increasing the water flow rate to prevent increasing the particle size. Finally, the point of onset of phase inversion could be predicted reasonably well using a model available in the literature. © 2010 American Institute of Chemical Engineers AIChE J, 57: 96–106, 2011     

天然松香改性苯丙乳液的制备及其性能研究

以苯乙烯(St)、甲基丙烯酸甲酯(MMA)、丙烯酸-2-乙基己酯(2-EHA)、丙烯酸-2-羟基乙酯(HEA)和丙烯酸(AA)为反应单体,利用天然松香乳液作为改性剂,通过乳液聚合的方式制备了松香-苯丙复合乳液。研究了乳化剂用量、引发剂用量、松香乳液用量和单体配比对乳液性能的影响。并通过TGA、DLS、TEM对所制备的复合乳液进行了表征。结果表明:当乳化剂用量为单体质量的5%、引发剂用量为单体质量的0.8%、松香乳液用量为单体质量的30%、m(硬单体)∶m(软单体)=2.5∶1时,制得的乳液呈白色泛蓝光,粒径为131 nm。成膜后,漆膜光滑透明,硬度(1H)、耐水性(接触角97.05°)和附着力(1级)等性能良好。     

防结露乳胶涂料的研究

防结露乳胶涂料由丙烯酸酯乳液、无机多孔物质、各类助剂、钛白、去离子水配制而成，除具有防结露性外，还具有隔音、隔热功能。简述了丙烯酸酯乳液的聚合工艺和防结露涂料的配方。讨论了乳化剂用量对丙烯酸酯乳液性能，以及树脂／多孔物质用量比和乳液粒径对涂层防结露性的影响。     

秸秆基环氧树脂乳液的制备及其涂膜性能

以脂肪醇聚氧乙烯醚(AEO-9)和十二烷基硫酸钠(SDS)复配为乳化剂,通过相反转技术乳化秸秆基环氧树脂,考察了复配乳化剂的HLB值、用量以及乳化温度和搅拌速率对乳液临界含水量Rf值、粒径及稳定性的影响,获得了如下较佳的乳化工艺条件:HLB值17,复合乳化剂用量8%,乳化温度35°C,搅拌速率800 r/min。以此工艺制得的乳液稳定性较好,平均粒径为1.57μm。以水性聚酰胺为固化剂,将此乳液制成清漆,固化后所得漆膜综合性能良好。     

相反转法合成一种水性环氧树脂乳液的研究

用环氧树脂E-44和表面活性剂OP-10合成水性环氧树脂乳化剂,然后在表面活性剂的作用下,采用相反转法,将油包水状态环氧树脂转化成水包油状态的水性环氧树脂。探讨了乳化剂用量、反应温度等对水性环氧树脂粒径和结构的影响。结果表明,合成水性环氧树脂的最佳工艺条件是:以三乙醇胺为催化剂,乳化剂用量为20%时,反应温度为60℃,反应时间为6 h。     

常温固化水性环氧树脂乳液的研制

将环氧树脂与亚麻酸进行酯化反应,再与丙烯酸类单体进行加成,中和后加水分散制得的水性环氧树脂乳液。采用红外光谱仪(FTIR)、粒度分布仪、透射电镜(SEM)等研究了环氧树脂的种类,反应物配比,酯化反应过程中反应温度、反应时间对产物水溶性、稳定性及涂膜性能的影响。结果表明:选用环氧树脂E-20,亚麻酸与环氧树脂物质的量比为2∶1,120℃反应5 h所制得的水性环氧树脂乳液性能最好。     

木器高光面漆用丙烯酸酯树脂的制备与性能研究

以甲基丙烯酸甲酯(MMA)和丙烯酸丁酯(BA)为主单体,多种交联体系为功能单体,采用水性固体丙烯酸树脂(SR-675、QZ-7001、QZ-7002)和聚合型乳化剂NRS-10搭配作为体系的表面活性剂,通过预乳化半连续乳液聚合工艺合成了木器高光面漆用丙烯酸酯树脂。探究了水性固体丙烯酸树脂酸值、T_g、相对分子质量以及用量;NRS-10用量、引发剂(APS)用量和树脂T_g对树脂及涂膜性能的影响。结果表明:当采用水性固体丙烯酸树脂SR-675且用量占单体总量的20%(下同)、NRS-10占0.5%、APS占0.75%,树脂T_g设计为40 ℃时,合成的丙烯酸酯树脂制备成木器面漆,涂膜光泽高、附着力好、耐水性好,铅笔硬度可达2H。