由两种单体借助酯交换反应制备三元共聚物

本文讨论了甲基丙烯酸羟乙酯和甲基丙烯酸在乙醇中进行溶液聚合时,借助酯交换反应,在该亲水体系中引入第三疏水组分,从而制备三元共聚物的可行性.     

SYNTHESIS OF ALKYL AND ARYL 1-PROPENYL ETHER MONOMERS: A NEW APPROACH

A new, convenient synthesis of alkyl and aryl 1-propenyl ether monomers in good to excellent yields has been developed. Alkyl and aryl allyl ethers can be smoothly isomerized to the desired 1-propenyl ethers by refluxing in a basic ethanolic solution containing pentacarbonyliron as a catalyst. A simplified two-step, one-pot procedure has also been developed which consists of combining an alcohol with allyl bromide in the presence of base and then adding pentacarbonyliron to isomerize the in-situ generated allyl ether to directly give the 1-propenyl ether. Good yields of alkyl 1-propenyl ethers were obtained using this process. Factors affecting the isomerization reaction were investigated and a mechanism was proposed.     

新型螺环交联剂的合成及其交联聚合反应

合成了一种新型螺环环丙烯酸酯交联剂 ３，１１ 二亚甲基 ２，１０ 二酮 １，４，９，１２ 四氧二螺［４，２，４，２］十四烷（２）．在过氧化苯甲酰（ＢＰＯ）引发下，在苯溶液中进行了它与甲基丙烯酸甲酯（ＭＭＡ）的自由基聚合反应．得到的交联聚合物是具有螺环交联结构的聚甲基丙基酸甲酯．交联聚合物分别在酸性和碱性条件下水解．结果表明，此交联离聚物在酸碱条件下都很稳定，特别是在酸性条件下，具有极好的稳定性     

甲基丙烯酸2-(N-吖啶酮基)乙酯的合成及其敏化的烯类单体光聚合

我们曾报道过4-甲基丙烯酰氧基二苯甲酮(MABP)与甲基丙烯酸N,N-二甲氨基乙酯(DMAEMA)构成的氧化还原引发体系敏化丙烯腈的光聚合。由于MABP及DMAEMA是可聚合的二芳基酮和脂肪叔胺,因而既能参与引发又能参与聚合而进入聚合物链中。一般二苯甲酮要同三级胺,如三乙胺等一起在紫外光照条件下形成光氧化还原引发体系才能有较好的引发效果。同一分子中既含二苯甲酮基又含三级胺基的光敏剂,     

Acrylate based anticorrosion films using novel bis‐phosphonic methacrylates

Two novel phosphonated methacrylate monomers were successfully synthesized and subsequently incorportated into adhesion/anticorrosive coatings. Specifically, they were propyl N,N‐tetramethyl‐bis(phosphonate)‐2‐hydroxyl‐bis(methylene) amine methylmethacrylate (MAC₃NP₂) and 2‐[2,2‐bis(diisopropoxyphosphoryl)ethoxy]‐methylmethacrylate, (MAC₃P₂). The phosphonic forms of each monomer were blended with ～85% w.w acrylates (tripropyleneglycol‐diacrylate and hexanediol‐diacrylate) and 6% w.w of the photo sensitive initiator Darocur®. Along with a monophosphonic monomer synthesized in a previous publication (MAC₃P), they were polymerized on Q‐panels under ultraviolet light, and then subject to the salt spray test (ca. 0.5 mol/L NaCl at 35 °C) for a duration of up to 50 days. The results indicate that acrylate blends with low concentration of the bisphosphonic compound MAC₃P₂ have excellent resistance to corrosion, thus excellent adhesive properties. Importantly, these coatings were formed without the use of a hydrophobic polymer matrix or solvents. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 7972–7984, 2008     

含胺基功能性单体的聚合研究——ⅫⅠ.丙烯腈在N-丙烯酰-N′-苯基哌嗪及其聚合物作为增感剂下的光聚合

关于含有芳香叔胺基的烯类单体,我们曾报道过N,N-二甲氨基苯乙烯,N-(4—N′,N′-二甲氨基苯基代丙烯酰胺(DMAPAA),N-(4-N′,N′-二甲氨基苯基代甲基丙烯酰胺(DMAPMA),甲基丙烯酸-4-N,N-二甲氨基苄脂(DMABMA),8-丙烯     

NOVEL TRIMETHACRYLATES: SYNTHESIS,CHARACTERIZATION, AND EVALUATION OF NEW MONOMERS FOR IMPROVED DENTAL RESTORATIVES

ABSTRACT

Two novel trimethacrylates, i.e., 1,1,1-tri-[4-(methacryloxyethoxy)-phenyl] ethane (TMPE) and 1,1,1-tri-[4-(2-methyl-2-methacryloxyethoxy)-phenyl]ethane (TMMPE), have been synthesized by reacting methacryloyl chloride with the corresponding hydroxyl intermediates. Both trimethacrylate monomers, having a low viscosity of 11.5 and 13.1 Pa.S, respectively, were blended with TEGDMA at three different weight ratios, i.e., 90/10, 70/30, and 50/50. The mixtures were made visible light-curable (VLC) by the addition of camphorquinone (0.5 wt%) and N,N-dimethyl-aminoethyl methacrylate (1.0 wt%). In addition to evaluation as cured neat resins, VLC formulations with 70% by wt. of silanated microfiller were also prepared and evaluated. The control in both cases was a VLC formulation of BisGMA/TEGDMA (70/30 and 50/50 wt/wt). These new, formulated resins have both improved physical properties and higher double bond conversion than the BisGMA control, as well as decreased linear polymerization shrinkage (LPS). The neat resin having 70/30 (wt/wt) ratio of TMPE/TEGDMA (T7T3, Table 2) exhibited a compressive strength (CS) of 496 (±51) MPa compared to the 70/30 (wt/wt) ratio of BisGMA/-TEGDMA control having 425(±27) MPa. A filled resin having a 90/10 (wt/wt) ratio of TMPE/TEGDMA exhibited a flexural strength (FS) of 122.6(±23) MPa, compared with a similar filled BisGMA/TEGDMA (70/30, wt/wt) resin exhibiting 112.7(±19) MPa. These and other results suggest that these new trimethacrylates have potential application in formulating dental composites with improved performance.     

新型热反应大分子单体的合成与表征

溶液法合成了一些低分子量的羟端基低聚苯醚砜,并由相转移催化剂将之转为热反应大分子单体——α,ω-双甲基丙烯酸聚苯醚砜酯;用FTIR、~1H-NMR对其结构进行了表征,GPC、VPO对其分子量进行了分析和测定;用DSC、DTA对聚苯醚砜双烯大分子单体的转变温度、热反应过程进行了测定和分析。     

含次环己基的有机硅单体及其低聚体的合成

硅氯仿和环己二烯-1,3进行硅氢加成反应,生成1,3-双(三氯硅基)环己烷,经醇解制得1,3-双(三乙氧硅基)环己烷,与溴化甲基镁反应,制得1,3-双(二乙氧甲硅基)环己环、1-(乙氧二甲硅基)-3-(二乙氧甲硅基)环己烷和1,3-双(乙氧二甲硅基)环己烷,它们在盐酸溶液中分别进行水解,得到各种含次环己基的有机硅低聚体,其中2,2,4,4,11,11,13,13-八甲基-3,12-二氧(杂)-2,4,11,13-四硅(杂)三环[11,3,1,1~(5,9)]十八烷和D_4相似,可能经开环聚合得到聚硅次环己基硅氧烷。     

手性乙烯基二联苯单体的合成与螺旋选择性聚合反应

设计、合成了一系列含有手性烷氧基末端的乙烯基二联苯单体,进行了普通自由基、原子转移自由基以及负离子聚合反应.所有单体中,只有手性烷氧基苯基位于乙烯基邻位的聚合物的比旋光度与其单体相比有比较大的区别,且在对应于其侧基的紫外吸收处呈现明显不同于单体的Cotton效应,说明可能形成了某一方向占优的螺旋构象.在所研究范围内,聚合条件和聚合物分子量对聚合物的旋光度没有明显的影响.比较负离子聚合和自由基聚合所获得聚合物的比旋光度发现,负离子聚合有利于增加聚合物螺旋链构象的完整性.切除能形成螺旋链的聚合物侧基上的手性烷氧基,所得到的聚合物虽然不含手性原子但依然表现出光学活性,说明其具有一定的手性记忆效应.     

ADVANCES IN THE SYNTHESIS AND POLYMERIZATION OF METAL-CONTAINING MONOMERS

Abstract

Polymerization and copolymerization of metal-containing monomers (MCM) is a unique method of synthesizing metal-containing polymers wherein practically all functional groups are bound to the metal.     

用含偶氮基的聚苯乙烯大分子引发剂合成两亲性嵌段共聚物

采用含偶氮基的聚苯乙烯预聚物（ＰＳ ＡＣＰＣ）作为引发剂，合成了苯乙烯（Ｓｔ）分别与甲基丙烯酸（ＭＡＡ）、甲基丙烯酸（β 羟丙酯）（ＨＰＭＡ）的嵌段共聚物，考察了ＰＳ ＡＣＰＣ引发第二单体的聚合反应行为，以及影响第二单体转化率和均聚物含量、共聚物组成的因素．用溶解性、凝胶渗透色谱（ＧＰＣ）、红外光谱（ＩＲ）、核磁共振（ＮＭＲ）、动态接触角（ＤＣＡ）等表征了嵌段共聚物．     

新双硫代甲酸盐衍生物的合成

双硫代甲酸盐可用作抗菌剂,橡胶硫氏剂,也是过渡金属的良好配位体。但是大多数研究都只限于脂肪族一元胺衍生物,本文报道芳香族及脂肪族多元胺的双硫代甲酸盐的合成。产物的红外光谱,核磁共振谱和元素分析结果列于附表。     

合成醇催化剂中组分间的相互作用

近年来,CO/H_2催化合成低碳混合醇的研究受到广泛的关注。低碳混合醇可作为掺合汽油的助溶剂、燃料和代油品,一经分离则是非常重要的化工原料,应用价值很大。催化剂是合成过程的关键,七十年代以来该领域研究取得很大进展,如美国Dow公司开发的MoS_2体系,意大利Sham公司研制的“甲基燃料”合成催化剂及法国IFP开发的混合氧化物型“乙基燃料”合成催化剂等,引起人们的极大重视。催化剂的表面     

A CONVENIENT SYNTHESIS OF ALKYLPHOSPHONIUM SALTS

Abstract

The reaction of methanol and its homologs with Ph₃ P in 48% aqueous hydrobromic acid provides alkyltriphenylphosphonium salts in quantitative yields.     

一些新拟除虫菊酯化合物的合成

本文采用几种不同于速灭菊酯的醇组份合成了十七个新拟除虫菊酯化合物。分别用红外光谱、核磁共振谱、质谱及元素分析等方法确定了它们的结构,并选择了家蝇、蚜虫、粘虫、拟谷(虫甲)、红蛛蜘等昆虫作了生物活性的测定。其中,醇组份为和的新拟除虫菊酯化合物具有较好的杀虫、杀螨活性。     

合成气制低碳燃料醇工业侧线模试

在接近工业操作条件下,综合考察催化剂制备放大、工业粒度催化剂、反应器放大及工业合成气等放大效应对合成气制低碳燃料醇催化反应的影响。在模试反应器中采用多段蛇管换热及移热与催化剂床层合理稀释,从而保证反应温度均匀。在模试中较系统地考察了温度、压力、空速及合成气中CO_2含量对合成低碳燃料醇反应的影响。在400—405℃,14—15MPa,尾气空速4000h~(-1)条件下进行了1000小时寿命试验,结果良好。低碳燃料醇的时空产率为0.21—0.25升醇/升催化剂/小时。在燃料醇中,甲醇占74—77%,异丁醇12—15%。本工作为合成气制低碳燃醇料工业试验装置的基础设计提供数据。     

新型聚乙烯醇系亲和吸附剂的制备及其在糖蛋白纯化中的应用 (I)基质合成

以醋酸乙烯酯（ＶＡＣ）和甲基丙烯酸缩水甘油酯（ＧＭＡ）为单体,甲基丙烯酸烯丙酯（ＡＭＡ）为交联剂,在致孔剂正庚烷／乙酸丁酯的存在下,悬浮聚合,制得了一系列大孔共聚物;醇解后得到一种新型聚乙烯醇系亲和层析基质。依据单体的Ｑ、ｅ值,计算了体系的竞聚率,讨论了不同交联度、ＧＭＡ含量、致孔剂用量及配比对基质孔结构和性能的影响。     

复合床层中合成低碳醇的研究(英文)

研究了复合催化剂床对合成低碳醇反应行为的影响。结果表明,采用复合床可以提高反应产物中低碳醇的选择性。第一段催化床层的反应产物的分布和第二段催化床层的反应条件直接影响最终的反应结果。第一段催化剂床层中ＣＯ的转化率或甲醇的选择性过高都不利于提高反应产物中低碳醇的选择性。