生漆/氨基硅氧烷/环氧桐油复合涂料的 制备与性能研究

以生漆为原料,先采用γ-氨乙基氨丙基三甲氧基硅烷(AATMS)与漆酚的酚羟基发生醇解反应,再通过AATMS的氨基与环氧桐油的环氧基发生开环反应,得到了一种复合涂料。该涂料的干燥成膜过程是在漆酶作用下,通过空气自氧化聚合得到高度交联的聚合膜。固定AATMS用量为生漆质量分数10%不变,讨论了环氧桐油用量对生漆的物理机械性能的影响,结果发现环氧桐油用量为生漆质量分数的30%时,漆膜的性能最佳,柔韧性、耐冲击性、硬度、附着力分别提高到2mm、40kg·cm-1、6H和1级。利用红外光谱分析(FT-IR)证实了复合涂膜的结构。利用热分析(TG-DTG)研究了复合涂膜和生漆涂膜的热稳定性,结果表明复合涂膜比生漆涂膜的热稳定性高。研究测试了复合涂膜和生漆涂膜的耐溶剂性能、耐化学介质性能和耐老化性能,结果表明复合涂料的漆膜比生漆涂膜性能都大幅提升。     

聚合马来松香乙二醇酯Ca(Ⅱ)、Ni(Ⅱ)配合物固定化淀粉酶研究

将松香改性合成聚合马来松香乙二醇酯(简称MEEP),使之分别与CaCl2、NiCl2、MgCl2和CuCl2反应,制备聚合马来松香乙二醇酯Ca(Ⅱ)、Ni(Ⅱ)、Mg(Ⅱ)和Cu(Ⅱ)配合物,再对淀粉酶进行固定化,比较了固定化酶和游离酶的性能.实验结果表明,4种聚合马来松香乙二醇酯配合物固定化酶使用5次后,固定化酶保留活力均在50%以上,其中MEEPCa(Ⅱ)和MEEPNi(Ⅱ)固定化酶的效果较好,固定化酶保留活力均在70%以上;固定化酶最适温度50℃,较游离酶高10℃;聚合马来松香乙二醇酯Ca(Ⅱ)、Ni(Ⅱ)固定化酶的最适pH值分别为5.24、6.86,米氏常数分别为1.47×10-4kg/L和2.64×10-4kg/L,游离酶为2.69×10-5kg/L.     

聚合松香的制备及其含量测定

以工业松香为原料,用硫酸-无水氯化锌作催化剂制备聚合松香.在70℃下,用甲苯溶解松香(松香和甲苯的重量比为1∶1),加入n(H2SO4)∶n(ZnCl2)=0.6的催化剂,120℃温度聚合反应10 h和270℃减压蒸馏(200 Pa)的条件下,所得一级聚合松香的二聚松香的含量≥90.5%,软化点182℃,酸值150.6 mg KOH/g,收率≥74%;二级聚合的二聚松香的含量≥65%,软化点135℃,酸值157 mg KOH/g,收率≥95%.用GC-MS分离出二聚体中的14个异构体;通过测定松香单体和二聚体的相对校正因子,采用面积归一法测定产品二聚体的含量.     

生漆与二异氰酸酯的反应及漆膜性能

本文用红外光谱（IR）、动态机械热分析（DMTA）、扫描电镜等仪器和物理、化学手段,研究生漆和2,4-甲苯二异氰酸酯（TDI）的反应特性、聚合成膜机理及漆膜性能等。结果表明,在漆酶和TDI共同作用下,生漆／TDI混合物的固化成膜速率比生漆快得多。当生漆与TDI混合后,生漆乳液的连续相中的漆酚迅速与TDI发生加成反应并生成聚氨酯化合物;在漆酶的催化作用下,该化合物的漆酚基上不饱和侧链双键进一步发生氧化聚合;所得的生漆／TDI涂膜具有优良的物理机械性能。     

漆酚铁聚合物的制备及性能研究

以生漆和三氯化铁反应制备漆酚铁聚合物,用红外光谱、涂膜鲜映性仪和光泽度仪等对聚合物结构和漆膜性能进行表征.结果表明,反应温度65℃,反应时间3h,漆酚和三氯化铁物质的量比为8∶1,所生成的漆酚铁聚合物性能较好.     

有机硅改性UV固化水性环氧树脂的研究

以环氧树脂E-51、甲基三乙氧基硅烷为原料,用接枝共聚的方法合成了有机硅改性水溶性UV固化环氧树脂,该方法有效地改善了环氧树脂的柔韧性、水溶解性,提高了成膜物的机械性能,其拉伸强度达到53.5 MPa,断裂伸长率为46.5%,耐冲击性大于50 kg/cm。通过红外光谱、热重分析表征产物的结构和性能,结果表明,有机硅已经成功接枝到环氧树脂的分子上。有机硅改性后环氧树脂在400℃的分解率由之前的60%降至40%。文章同时讨论了有机硅改性水性UV固化环氧树脂合成中反应温度、有机硅种类以及加入量等对UV固化水性环氧树脂成膜物的附着力、耐水性及耐碱性的影响,以此获得最佳反应条件:质量分数为14.4%的甲基三乙氧基硅烷与羧酸改性的环氧树脂在90℃下反应5～6 h。     

光点击化学修饰石油树脂研究

为改善传统石油树脂改性方法能耗高、效率低等缺陷,本文应用点击化学,在常温下,以甲苯为溶剂,以Darocur1173为光引发剂,在UV-LED灯辐照下,通过3-巯基丙酸与DCPD石油树脂发生巯基-烯加成反应,制备的产物命名为DCPD-COOH。以三苯基膦为催化剂,用甲基丙烯酸缩水甘油酯(GMA)与DCPD-COOH反应,制备了可光固化的丙烯酸酯石油树脂,命名为DCPD-A。固化漆膜的设计配方:DCPD-A(50份)、活性稀释剂甲基丙烯酸羟乙酯(HEMA,50份),光引发剂Darocur1173(5份)。在该配方下制得的固化漆膜其附着力达到0级,铅笔硬度为2H。制备的DCPD-A与极性溶剂或者极性树脂的相容性较好,可应用于光固化涂料和光固化油墨等领域。     

新型光固化环氧丙烯酸酯乳液的制备及其防腐性能研究

将环氧树脂和非离子型表面活性剂在一定温度下与丙烯酸反应合成出改性环氧丙烯酸酯树脂,再利用相反转乳化法制备得到光固化水性环氧乳液。对该反应的原料种类、反应条件、以及乳化工艺进行了优化研究,并对不同条件下得到的乳液进行了综合性能评价。着重考察了环氧树脂的种类以及光引发剂的种类对乳液粒径、清漆膜电化学防腐性能和耐盐雾性能的影响。结果表明:选取环氧树脂E20,光引发剂IRGACURE651,酯化反应温度为105℃,反应时间3h,乳化温度为25℃~30℃,搅拌速度为800r/min时,制得的乳液稳定性和漆膜性能(包括漆膜的力学性能、电化学防腐性能和耐盐雾性能)最佳。     

改性丙烯酸乳液合成及性能研究

通过核壳乳液聚合法合成了烷基丙烯酸酯磷酸酯改性的丙烯酸乳液,讨论了聚合温度、乳化剂、磷酸酯的加入方式和用量、pH值等因素对乳液合成以及涂膜性能的影响。结果表明:聚合温度控制在75～80℃之间较为合适,使用了烷基丙烯酸酯磷酸酯进行改性的乳液,单体转化率和固含量提高,凝胶率以及涂膜吸水率明显下降,乳液的稳定性得到提升。当聚合温度为78℃,磷酸酯占单体总质量0.5%(wt)、反应体系pH值在5左右以及采用延后滴加磷酸酯单体的方式时,能够提高乳液耐水等性能以及涂膜的交联度,合成性能优异的磷酸酯改性丙烯酸乳液。     

3-氨丙基三乙氧基硅烷对聚氨酯/Al-Sm_2O_3复合涂层自然老化性能的影响

通过硅烷偶联剂3-氨丙基三乙氧基硅烷(KH550)改性聚氨酯(PU)/Al-Sm_2O_3复合涂层,从功能特性和力学性能角度系统研究了改性前后涂层自然老化性能的变化规律。结果表明,改性后PU/Al-Sm_2O_3复合涂层的红外发射率对自然老化的稳定性得到明显增强,在同等条件下改性后的涂层发射率要明显低于未改性的涂层发射率。改性后涂层表面的Sm_2O_3颗粒分散更加均匀,对近红外光的吸收强度有所增强,从而使改性后涂层对1.06μm近红外光的反射率要明显低于未改性涂层。改性前后涂层的硬度对自然老化具有良好的稳定性,其硬度可保持在3 H;未改性涂层的附着力和耐冲击强度受自然老化影响明显,但改性后涂层的附着力和耐冲击强度得到明显加强,经自然老化4个月后仍然可保持在1级和50 kg·cm。     

Structural study of oriental lacquer films during the hardening process

Oriental lacquer is the natural resin obtained by tapping lac trees. It hardens into a tough and insoluble film. The extreme hardness and insolubility are some of the most important functions, which are required for industrial coating materials. In this study, two kinds of oriental lacquer films, traditionally named Kiurushi (raw urushi) and Kuromeurushi produced by two different pretreatments, were analyzed during hardening with Fourier transform infrared spectroscopy (FT-IR), thermogravimetry/differential thermal analysis-mass spectrometry (TG/DTA-MS) and pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS) to investigate their functional expression process. Typical functional groups of the lacquer films were detected by FT-IR. The TG/DTA-MS curves clarified that the thermal degradation of the lacquer films gradually began at around 200 °C, and reached the fastest rate at 400-500 °C. Apparently, FT-IR and TG/DTA-MS could not reveal any difference between the films. On the other hand, Py-GC/MS revealed differences between the films in the peak area ratios of 3-pentadecenylcatechol to 3-pentadecylcatechol and 3-pentadecadienylcatechol to 3-pentadecylcatechol. The ratios of Kiurushi lacquer film were higher than those of Kuromeurushi lacquer film. Both ratios, furthermore, decreased during hardening due to polymerization of the alkenylcatechols into an urushiol polymer skeleton comprising nucleus-side chain and side chain-side chain cross-linkages with 3-pentadecylcatechol at the terminal. The present results suggest that the reaction rate of these cross-linkages in Kuromeurushi lacquer film is faster than that in Kiurushi lacquer film. A good correlation was found between the peak area ratios obtained by Py-GC/MS and hardness obtained by pencil hardening testing. Oriental lacquer expresses the functions - an extreme hardness and insolubility - accelerating the nucleus-side chain and side chain-side chain cross-linkages. Furthermore, it has become clear that the traditional treatments called Nayashi and Kurome effectively accelerate the hardening rate by activating the cross-linkages.     

基于二氧化碳共聚物的紫外光固化高分子材料的制备与性能

普通低分子量的二氧化碳共聚物由于预聚体中含有较多的亲水性端羟基, 在紫外光辐照下不能交联而降低材料的耐水性. 为降低亲水性端羟基对材料耐水性的影响, 本文利用锌钴双金属氰化物(Zn-Co DMC)催化剂实现了CO₂与4-乙烯基环氧环己烷、 环氧环己烷的三元无规共聚, 制备出分子量在40000以上, 含C=C双键的脂环族聚碳酸酯; 采用四(3-巯基丙酸)季戊四醇酯为固化剂, 基于紫外光诱导的双键-巯基点击反应制备了紫外光固化高分子材料. 研究发现, 在5.0 mJ/cm²的紫外光辐照剂量下即可制备出高透明硬化涂层, 在可见光(400~750 nm)波段内透光率达到97.5%, 铅笔硬度达到3H, 对马口铁等基体附着力达到0级. 值得指出的是, 该紫外光固化薄膜的玻璃化转变温度超过110 ℃, 与双酚A型环氧树脂相当, 而且不含苯环等结构, 具有更优异的耐紫外光老化性能.     

Preparation and evaluation of high-transparent scratch-resistant thin films on plasma treated polycarbonate substrate

New simple aqueous sol–gel procedure has been used for producing hard transparent organic–inorganic coatings on polycarbonate (PC). Sol-gel thins films were prepared by mixing Si and Al aqueous alkoxides and applied on the plasma treated PC. Tetraethyl orthosilicate (TEOS), 3-glycidoxypropyltrimethoxysilane (GPTMS) and aluminum tri sec-butoxide were used as main precursors. Before applying coatings PC were treated by Dielectric Barrier Discharge (DBD) system being conducted at atmosphere pressure. The effects of temperature, sols volume ratios and aging time on the coatings properties were scrutinized. Chemical, structural, morphological, optical and mechanical analyses of the samples were done by ATR-FTIR, EDS, XRD, FE-SEM, TEM, UV/vis spectroscopy, ellipsometry, pencil hardness and eraser scratch methods. TEM results showed well-dispersed nano-particles in the liquid sol. All of the films showed higher average transmittance (89 %) than the raw PC (86 %) that was stemmed from the lower refractive index (1.481) than raw PC (1.58). Films indicated good adhesion onto the plasma treated substrates (5B). The pencil hardness of the PC substrate (4B) improved to 3H (8 pencil grade increment) with just a single layer coating (775 nm thickness) due to the preparation of new hard structures of interlocked Si and Al atoms.     

Analysis and Characterization of Korean Lacquer

Three kinds of Korean lacquer saps were analyzed including chemical composition, enzymatic activity, molecular weight distribution, unsaturated degree of side chain, and drying property. The results were compared with Chinese and Japanese lacquer saps all collected in the same month (August 2012 and 2013) to investigate similarities and differences. Compared with Chinese and Japanese saps, the Korean lacquer sap contains the most lipids (84.9%) and urushiol triene (56.1%) components and the second highest enzyme activity after Chinese lacquer sap. In the drying and film hardness test, Korean and Chinese film reached a stronger hardness sooner than Japanese lacquer film; in 21 days the former reached 2H and the latter only H. The results of IR, NMR, and GC-MS analysis showed slight differences due to different growing conditions.     

羧基化含氟聚芳醚的合成及涂层性能

以四烯丙基联苯二酚(TABP)、 双酚A和十氟联苯为原料, 通过室温缩聚制得含氟聚芳醚(FPAEs), 再将其与3-巯基丙酸进行加成, 制得羧基化含氟聚芳醚(CFPAEs). 通过改变TABP的投料量来调节产物的羧基含量. 以N-甲基吡咯烷酮(NMP)为溶剂, 将CFPAE涂层喷涂在马口铁上. 研究发现, CFPAE涂层具有优异的热稳定性和机械强度, 羧基的引入可显著提高含氟聚芳醚涂层的附着力. 当羧基含量为0.265 mmol/g时, 涂层的黏附力等级为0级, 铅笔硬度为6H, 不引起涂层破坏的最小轴棒直径为0.5 mm, 水接触角为103.9°. 此外, CFPAE涂层还具有优异的耐酸、 耐盐、 抗紫外老化和防腐蚀等性能. 研究结果表明, 羧基化是拓展含氟聚芳醚在特种氟碳涂料上应用的一种有效途径.     

有机硅氧烷改性St/BA/AA三元共聚乳液的制备

采用核壳乳液聚合法,制备了乙烯基三乙氧基硅烷（VTES）改性的St/BA/AA三元共聚乳液,其结构经FT IR确证。研究了VTES用量、乳化剂用量及配比和引发剂用量对单体转化率和粒径的影响。结果表明：在最优条件［48%St, 48%BA, 4%AA, 1%N-MA, 4%VTES, 8%乳化剂（OP-10/SDS=1/3）, 0.8%引发剂］下,单体转化率为95.8%,平均粒径242 nm。并研究了改性St/BA/AA乳胶膜(1)的耐溶剂性和铅笔硬度。结果表明：1具有良好的耐溶剂性,铅笔硬度为2H。