单组分湿固化聚氨酯密封剂的制备、固化特性及开发应用

介绍了单组分湿固化聚氨酯密封剂的制备、固化特性及该产品的国内外发展概况，并就其开发工作提出了看法。     

紫外光固化丙烯酸阴极电泳涂料的制备

通过合成侧链含有苄基和羟基的丙烯酸树脂，然后在侧链上引入光敏性基团，以有机酸中和并加入光引发剂后进行乳化，制备得到电泳涂料，最后通过电泳技术制备涂层。采用红外对树脂结构进行表征，研究了不同功能性单体含量、不同中和度、不同双键接枝率和不同施工工艺对涂层的影响。结果表明：在优化后的条件下，制备的 UV丙烯酸阴极电泳涂层光滑致密，有良好的附着力、硬度、光泽、耐冲击性和柔韧性等性能。     

环氧树脂固化用腰果酚型酚醛胺的制备及其固化动力学研究

以腰果酚、甲醛和二乙烯三胺为原料通过曼尼希反应合成了腰果酚醛胺固化剂，通过红外光谱和凝胶渗透色谱分别对其化学结构和相对分子质量进行了分析，并研究了腰果酚醛胺固化剂对环氧树脂的固化动力学。结果表明：制备的腰果酚醛胺固化剂的数均、重均相对分子质量均在 1 250左右，且相对分子质量分布较窄。通过将非等温 DSC曲线数据拟合 Kissinger方程、 Ozawa方程、 Crane方程，得到环氧树脂 /二乙烯三胺固化体系表观活化能为 71. 40 kJ/mol，环氧树脂 /腰果酚醛胺固化剂的表观活化能低于前者为 56. 72 kJ/mol，固化反应级数没有变化，均为 0. 93。因此，相比于传统固化剂二乙烯三胺，腰果酚型酚醛胺能使得环氧树脂在更低的温度下，更快地进行固化，符合研究预期结果。     

咪唑盐的合成、固化反应及性能研究

本文合成了三种咪唑盐，并就其固化反应特点及对固化物性能的影响作了初步探讨。     

高性能不流动半固化片的研究

选择电子级玻纤布为支撑载体，浸入以耐高温环氧树脂为主体树脂的胶粘剂中，制备出一种综合性能优良的半固化片。通过对所制备的半固化片的粘接强度、回流焊、热应力、介质电阻、介质耐电压、介电常数、溢胶量和热膨胀系数等测试项目进行系统研究。研究结果表明：所制备的高性能不流动半固化片具备优良的性能，能够满足下游客户生产刚挠结合板的需求。     

湿固化单组份聚氨酯密封胶的研制

用甲苯二异氰酸酯、聚酯和聚醚通过二步法制备了湿固化单组份聚氨酯密封胶。研究了聚酯和聚醚种类、反应温度和时间、填料和催化剂等对密封胶性能的影响，确定了制备工艺条件和配方。     

紫外光固化粉末涂料

主要介绍了紫外光固化粉末涂料的组成、固化原理以及制备工艺，具体描述了紫外光固化粉末涂料的优势及现在存在的技术壁垒。     

微胶囊型单组分室温固化压敏胶的制备及性能表征

采用原位聚合法，以三聚氰胺-甲醛（MF）为壁材分别制备了包覆环氧树脂与硫醇的微胶囊，并将两种微胶囊混合制备成单组分环氧压敏胶。当外力使微胶囊囊壁破裂后，由于两种芯材具有良好的互溶性，有利于其释放后的相互扩散和均质化，实现快速均匀固化。对微胶囊的微观形貌、尺寸分布、化学结构、热稳定性进行了表征，并研究了单组分压敏胶的固化放热过程与粘接性能。研究结果表明：所制备的微胶囊都呈规则球形，表面光滑，平均粒径在8～10μm左右，包封率都在70%以上；所制备的微胶囊具备良好的储存稳定性，室温下可长期储存而不发生质变，升温到150℃时皆能高效适用；将活性组分进行微胶囊化包覆不会破坏芯材的反应活性，且该胶粘剂在室温甚至低温下都有较好的固化效果；将两种微胶囊混合制备成单组分胶粘剂，并对其进行粘接强度测试，结果表明该微胶囊型单组分室温固化压敏胶十分具有发展潜力。     

阴极电泳涂料用新型交联剂的制备

采用ε－己内酰胺为封闭物，制备了二苯甲烷二异氰酸酯交联剂，用于阴极电泳涂料，以提高阴极电泳涂料的泳透力和降低固化温度。阐述了交联剂和阴极电泳涂料的制备工艺，并通过泳透力和固化分率的测定来验证该交联剂的作用。     

紫外光固化亚光涂料的研究

快速固化的紫外光固化亚光涂料的关键是选择适宜的固化速度与氧阻聚时间。通过对活性树脂、活性单体、光引发剂、光引发协同剂等的选择,确定了最佳涂料配方,制备了可快速固化、光泽稳定的亚光漆。     

含氟丙烯酸酯橡胶的合成及性能

以丙烯酸乙酯、丙烯酸丁酯、含氟丙烯酸酯为单体,采用半连续乳液聚合法合成了含氟丙烯酸酯橡胶(ACM),用傅里叶变换红外光谱表征了其微观结构,考察了含氟单体种类及用量对含氟ACM亲水性、玻璃化转变温度及硫化特性的影响,以及交联剂二乙烯基苯(DVB)用量对含氟ACM硫化胶拉伸性能的影响。结果表明,丙烯酸六氟丁酯或丙烯酸十二氟庚酯(简称G 05)的转化率均超过90%;随着含氟单体用量的增加,ACM乳液涂膜的接触角逐渐增大,当加入质量分数为5%的G 05时,涂膜变为疏水性表面;含氟ACM只有1个玻璃化转变温度,且随着含氟单体用量的增加而逐渐下降;含氟ACM的操作安全性高,在硫化初期具有良好的流动性能;当DVB质量分数为3%时,含氟ACM的拉伸强度达到11.2 MPa。     

γ-癸内酯的合成

以正庚醇,丙烯酸甲酯为原料,过氧化二叔丁基为催化剂合成γ 癸内酯。考察了各因素对产品收率的影响,合理的反应条件为:反应温度170～172℃、回流反应时间4h、混合液n(丙烯酸甲酯)∶n(正庚醇)=1∶4、w(催化剂)=6%(相对于丙烯酸甲酯)。生成的甲醇从分馏柱顶端分出。在此条件下,γ 癸内酯的收率达75 5%。     

有机硅改性丙烯酸酯的合成及应用

以八甲基环四硅氧烷、甲基丙烯酸甲酯、丙烯酸正丁酯、丙烯酸为原料,采用预乳化连续滴加法制得了有机硅-丙烯酸酯乳液。探讨了乳化剂种类、乳化剂配比等因素对有机硅乳液的影响。结果表明,采用非离子型表面活性剂AEO-3、AEO-7、AEO-9和阴离子表面活性剂十二烷基苯磺酸钠(SDBS)制备乳液,且当m(SDBS)∶m(AEO)为1∶1.82时,乳液稳定性好。通过Fox方程设计聚丙烯酸酯的玻璃化温度(理论值)确定各类丙烯酸单体的配比,对有机硅丙烯酸酯性能进行了讨论分析,Tg=-10℃的有机硅改性丙烯酸酯性能较好。     

双组分丙烯酸酯胶粘剂的研制

丙烯酸酯压敏胶粘剂作为A组分,含有-NCO的聚氨酯预聚物作为B组分,把A组分和B组分混合,制备双组分丙烯酸酯胶粘剂。丙烯酸酯压敏胶粘剂则是由丙烯酸羟乙酯、丙烯酸羟丙酯、GMA(甲基丙烯酸缩水甘油酯)等单体通过溶液聚合而成的。研究了自交联丙烯酸酯的用量及A组分与B组分的配比对双组分丙烯酸酯胶粘剂性能的影响。     

Solubility in the binary and ternary system for poly(alkyl acrylate)-supercritical solvent mixtures

Experimental cloud-point data to 210 ‡C and 2,200 bar are presented for binary and ternary mixtures of poly(methyl acrylate)-CO₂-methy acrylate and poly(ethyl acrylate)-CO₂, propylene, and 1-butene-ethyl aerylate systems. The accuracy of the experimental apparatus was tested by comparing the measured pressure-temperature phase behavior data of the poly(ethyl acrylate)-CO₂ system obtained in this study with those of Rindfleisch et al. [1995]. The phase behaviors for the system poly(methyl acrylate)-CO₂-methyl acrylate were measured in changes of pressure-temperature slope, and with cosolvent concentrations of 0, 5.0, 13.7, 25.3, and 43.3 wt%, respectively. With 48.3 wt% methyl acrylate to the poly(methyl acrylate)-CO₂ solution significantly changes, the phase behavior curve takes on the appearance of a typical lower critical solution temperature (LCST) boundary. The impact of ethyl acrylate on the cloud-point for the poly(ethyl acrylate)-CO₂ system shows the change of slope of the phase behavior curves from negative to positive with ethyl acrylate concentration of 0, 8.2, and 25.0 wt%. The cloud-point behavior for the poly(ethyl acrylate)-CO₂-39.5 wt% ethyl acrylate system shows an LCST curve. The solubility curve to ∼150 ‡C and 1,650 bar for poly(ethyl acrylate)-propylene-ethyl acrylate system shows the change of pressure-temperature diagram and with ethyl acrylate concentration of 0, 7.2 and 21.0 wt%. Also, when 41.1 wt% ethyl acrylate was added to the poly(ethyl acrylate)-propylene solution, the phase behavior curve showed the LCST region. The high pressure phase behavior of poly(ethyl acrylate)-1-butene-0, 3.1, 8.1, 18.5 and 30.7 wt% ethyl acrylate system presented the change of pressure-temperature curve from the UCST region to U-LCST region as the ethyl acrylate concentration increased.     

保护胶体在高固含量弹性丙烯酸酯乳液聚合中的应用

为了降低高固含量弹性丙烯酸酯乳液聚合的凝聚率,选择了聚甲基丙烯酸钠作为丙烯酸酯乳液聚合的保护胶体,研究了其用量对乳液聚合和乳液性能的影响,探讨了它对丙烯酸酯乳液的稳定机理。研究结果表明,聚甲基丙烯酸钠增加了乳液聚合的稳定性,其用量仅为0.2%就可使凝聚率降到;提高了乳液胶膜的耐水性;保持了较低的乳液黏度。     

Studies on the polyblends of poly(vinyl chloride) with various methacrylate copolymers,melt rheological properties. II

Studies have been made on the melt rheological properties of poly(vinyl chloride) (PVC) with copolymers of methyl methacrylate (MMA) and methyl acrylate (MA), ethyl acrylate (EA), butyl acrylate (BA), and 2-ethyl hexyl acrylate (EHA) at a blending ratio of 80:20. Effect of blend composition on shear stress–shear rate, melt viscosity, melt elasticity, and extrudate distortion have been studied. A significant decrease in the melt viscosity is observed on incorporation of low T_g, acrylate copolymers such as those with BA and EHA, thereby reducing the processing temperature. First normal stress and die swell ratio also decreases with an increase in the side chains of acrylate copolymer. PVC blended with P(MMA-co-BA) and P(MMA-co-EHA) is sensitive to both temperature and shear stress.     

The effect of interpenetrating polymer network formation on polymerization kinetics in an epoxy‐acrylate system

The kinetics of thermally initiated cationic epoxy polymerization and free radical acrylate photopolymerization were studied using photo-differential scanning calorimetry. The reactions of the neat monomers and diluted monomers as well as interpenetrating polymer networks (IPNs) were studied as a function of dilution by the other monomer and temperature. The reaction sequence was also varied to study its effect on the kinetics of formation of the simultaneous IPN's. Both reactions quickly become diffusion controlled. The effects of increasing temperature and dilution on the acrylate polymerization rate profiles are similar, leading to reduced polymerization rate and longer polymerization times. The dilution effect on the epoxy polymerization is similar to that of the acrylate. However, unlike the acrylate reaction the epoxy polymerization rate increases strongly with temperature. The preexistence of one polymer has a significant effect on the polymerization of the second monomer. This effect is larger for the acrylate than for the epoxy polymerization. New kinetic models are needed to capture these complex behaviors.     

核壳型丙烯酸酯乳液的制备与性能研究

采用甲基丙烯酸甲酯／丙烯酸丁酯作复合单体,丙烯酸为功能单体,通过预乳化半连续种子乳液聚合工艺合成了核壳型丙烯酸酯乳液,讨论了反应温度、乳化剂用量、核壳单体质量比以及丙烯酸加入量对乳液性能以及漆膜力学性能的影响,并用TEM对乳胶粒子进行了表征。结果表明：采用预乳化半连续滴加法,当复合乳化剂SDS与OP-10质量比为2：1且总用量为4％,核、壳层中甲基丙烯酸甲酯与丙烯酸丁酯的质量比分别为3：7和4：1,核壳总单体质量比为1：1,丙烯酸质量分数为4％,核层和壳层反应温度分别为70℃和80％时,可以合成黏度适中、乳胶粒粒径分布均匀、稳定性好和漆膜力学性能优良的核壳型丙烯酸酯乳液。     

影响丙烯酸丁酯收率因素的分析研究

在丙烯酸丁酯生产的过程中,精制过程是影响丙烯酸丁酯（AEB）收率的最主要的部分。影响精制系统的因素包括系统压力、系统温度、回流/进料、冷却水、蒸汽等。通过分析得到,系统压力和系统温度是影响丙烯酸丁酯装置精制系统收率的最主要因素,而其他因素又分别对精制系统有着不同程度的影响。若要提高AEB收率,可以通过对这些影响因素进行调整;给出了精馏系统的最佳操作条件,达到提高丙烯酸丁酯收率的效果。