松香树脂酸乙烯酯合成新方法

松香树脂酸乙烯酯合成新方法哈成勇袁金伦夏建汉（中国科学院广州化学研究所广州５１０６５０）松香树脂酸及其衍生物的乙烯酯是一类含活性乙烯基的物质；歧化松香树脂酸乙烯酯［主要成分为去氢枞酸乙烯酯（简称ＶＤｅＨＡ）和二氢枞酸乙烯酯（简称ＶＤｉＨＡ）］和马来海...     

歧化松香树脂酸乙烯酯组成与结构的研究

本文研究了国产歧化松香乙烯酯的组成与各组分的分子结构，结果表明国产歧化松香乙烯酯的主要成分是二氢枞酸和脱氮枞酸的乙烯酯，二者重量比为3∶4；其乙烯酯上的乙烯基在核磁共振谱图中呈现为很好的ABX系统；因为二氢枞酸有三个异构体，所以仅用光谱方法无法确定二氧枞酸乙烯酯环内双键的位置。     

GPC法测定歧化松香树脂酸乙烯酯-苯乙烯共聚物相对分子质量及其分布

利用凝胶渗透色谱仪测定了新型高分子材料（歧化松香树脂酸乙烯酯－苯乙烯）的数均和重均相对分子质量及其分布，测试结果表明由于分子链中松香树脂酸乙烯酯链段的影响，共聚物数均相对分子质量随２个组分的比例变化，分布于６７００～５４７００，重均相对分子质量分布于１６３００～１１５０００，标准偏差为００７８，相对标准偏差为３３６％。     

松香树脂酸异构化反应研究

以松香为原料、盐酸为催化剂、95%乙醇为重结晶溶剂进行超声波强化松香树脂酸异构化反应研究.通过正交优化实验考察了反应温度、反应时间、超声波频率、搅拌转速、盐酸用量对枞酸单离收率和纯度的影响,确定最佳异构化反应条件为: 超声频率47.2 kHz,反应温度55℃,盐酸用量0.06 mL盐酸·(g松香)-1 ,反应时间40 min,搅拌转速300 r·min-1,枞酸单离收率为31.76%,纯度为97.32%.采用气相色谱仪和圆盘旋光仪对枞酸产品进行了分析鉴定,实验值与文献值吻合.     

导数光谱法测定歧化松香中树脂酸异构体

用紫外（UV）导数光谱法建立了同时测定歧化松香中五种树脂酸异构体的新方法。通过选择合适的求导阶数（n）、微分波长差（△λ）、扫描速度和定量方法,对不同批号的歧化松香中的主成分脱氢枞酸和微量组分枞酸、新枞酸、左旋海松酶及长叶松酸进行了测定（其中左旋海松酸和长叶松酸测定的是合量）,实验结果令人满意。该法可消除树脂酸各异构体及同系物的背景干扰,对迭加的树脂酸的检出和定量很有效。方法的平均回收率为99．0％,相对标准偏差小于0．2％。     

松香中枞酸型树脂酸的MNDO研究

应用半经验MNDO量子化学计算方法确定了松香中4种枞酸型树脂酸的优化几何构型及相对能量，据此对该类树脂酸分子的构象及相对稳定性作了分析与预测，并与已知的实验结果作了对比。     

松香催化加氢过程中树脂酸组成变化的跟踪分析

利用自行改进的DEAE-Sephadex离子交换色谱和气相色谱-质谱-计算机联用(GC-MS-DS)技术研究了在Raney Ni 存在下脂松香催化加氢反应过程中各类树脂酸组成的变化。证实在本实验条件下松香催化加氢过程中的主体反应是树脂酸的二氢化,只伴随少量的四氢化和极少量的脱氢反应。发现在二氢海松酸/异海松酸型树脂酸的分子间存在因双键移位而引起的异构现象。在整个跟踪分析过程中,共检出7种二氢枞酸型树脂酸、5种二氢海松酸/异海松酸型树脂酸及3种四氢树脂酸。     

核磁共振法测定松香中树脂酸总量及枞酸与脱氢枞酸含量

本文用吡嗪作分子间内标，利用氢核磁共振（＾１Ｈ－ＮＭＲ）积分法对松香中枞酸，脱氢枞酸及树脂酸总量进行了测定，并对该方法的可靠性进行了研究和比较，结果令人满意。该法不仅可以克服松香中各异物体及同系物的干扰，而且不必用极难制备和保存的天然纯纵酸和脱氢枞酸作标样。     

以Pd/C为催化剂的松香加氢反应机理

松香是由松树分泌的松脂经蒸馏而得,其主要成分为枞酸型树脂酸(C19H29COOH)[1]。由于枞酸型树脂酸含有共轭双键,易与大气中的氧作用,使松香的颜色加深、质变脆、热稳定性差、品级下降。松香经催化加氢反应,改变了枞酸型树脂酸的双键结构,使其趋于脂环的稳定结构,消除了松香因共     

自制氢化松香主要化学组成的GC-MS法测定

利用自行改进的DEAE－Sephadex离子交换色谱从以玉米松香为原料制备的氢化松香中分离出主要化学组成部分－酸性部分，然后采用DB－5毛细管柱和GC－MS技术对酸性部分进行定性和相对含量测定；共鉴定出6种二氢枞酸型树脂酸，4种二氢海松酸／异海松酸型树脂酸，1种四氢枞酸型树脂酸，2种四氢海松酸／异海松酸型树脂酸；其主要成分为13－二氢枞酸、8－二氢枞酸、13β－7－二氢枞酸、8α，13β－四氢枞酸及8（14）－二氢海松酸等。     

Polymers from vinyl esters of perhydrogenated rosin

Vinyl esters of tetrahydro acids from perhydrogenated rosin have been homopolymerized; copolymerized with vinyl chloride, vinyl acetate, butadiene; and terpolymerized with styrene and acrylonitrile. Materials containing such vinyl esters of tetrahydro acids can be readily crosslinked with peroxide.     

Preparation and characterization of rosin glycerin ester and its bromide

Rosin glycerin ester and its bromide were prepared from natural renewable rosin, glycerin and liquid bromine which were first subjected to an esterification reaction, followed by an addition reaction. Their structures were characterized by an infrared (IR) spectrum and their thermal resistance was conducted with thermal gravity (TG) and differential scanning calorimetry (DSC). It showed that the bromide in the rosin glycerin ester decomposed faster than the ester; hence it may be used as fire-resistant material.     

(Meth)acrylate vinyl ester hybrid polymerizations

In this study, vinyl ester monomers were synthesized by an amine catalyzed Michael addition reaction between a multifunctional thiol and the acrylate double bond of vinyl acrylate. The copolymerization behavior of both methacrylate/vinyl ester and acrylate/vinyl ester systems was studied with near‐infrared spectroscopy. In acrylate/vinyl ester systems, the acrylate groups polymerize faster than the vinyl ester groups resulting in an overall conversion of 80% for acrylate double bonds in the acrylate/vinyl ester system relative to only 50% in the bulk acrylate system. In the methacrylate/vinyl ester systems, the difference in reactivity is even more pronounced resulting in two distinguishable polymerization regimes, one dominated by methacrylate polymerization and a second dominated by vinyl ester polymerization. A faster polymerization rate and higher overall conversion of the methacrylate double bonds is thus achieved relative to polymerization of the pure methacrylate system. The methacrylate conversion in the methacrylate/vinyl ester system is near 100% compared to only ～60% in the pure methacrylate system. Utilizing hydrophilic vinyl ester and hydrophobic methacrylate monomers, polymerization‐induced phase separation is observed. The phase separated domain size is in the order of ～1 μm under the polymerization conditions. The phase separated domains become larger and more distinct with slower polymerization and correspondingly increased time for diffusion. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 2509–2517, 2009     

Polymers from the vinyl ester of dehydroabietic acid

The vinyl ester of dehydrogenated abietic acid has been homopolymerized, copolymerized with vinyl chloride, vinyl acetate, and butadiene and terpolymerized with styrene and acrylonitrile. Both in the homopolymerization and the copolymerization, the vinyl ester of dehydroabietic acid has given lower molecular weight polymers than were obtained with the vinyl ester of tetrahydroabietic acid. Polymers containing the vinyl ester of dehydroabietic acid can be readily crosslinked with peroxide.     

氢化松香与HEMA酯化物自聚与共聚研究

用氢化松香(HR)与甲基丙烯酸-2-羟乙酯(HEMA)进行酯化反应,得到了酯化物(HRH),然后对其进行了在甲苯中的自由基自聚反应、以及与甲基丙烯酸甲酯(MMA)或与苯乙烯(St)的共聚反应,制备了自聚物和共聚物,用IR和核磁共振氢谱(1HNMR)对产物进行了表征,用综合热分析仪表征了产物的热稳定性和玻璃化转变温度.结果表明:成功合成了HRH自聚物(PolyHRH)、以及共聚物[Poly(HRH-co-St)和Poly(HRH-co-MMA)].产物的热稳定性顺序为:HRH>PolyHRH>Poly(HRH-co-St)>Poly(HRH-co-MMA).     

基于纳米镍催化的松香加氢研究--树酯酸组成的研究

松香的主要成份是枞酸型树脂酸,其因共轭双键的存在而易被氧化,大大降低了其附加值。经氢化后的松香具有抗氧性好、脆性小、热稳定性高、颜色浅等特点,因而广泛应用于胶粘剂、合成橡胶、涂料、油黑、造纸、电子、食品等工业部门[1]。采用催化加氢的方法可使枞酸型树脂酸中的共轭双键消除[2]。以枞酸为代表的反应式为:松香催化加氢主要有熔融法[3]和溶剂法[4],所用催化剂主要是Pd和N i。熔融法制氢化松香,当反应温度低于200℃时,枞酸加氢速度较慢,反应不完全。温度升高,氢化松香中枞酸含量显著地减少,但温度高于250℃时,树脂酸脱羧严重,甚至…     

Chemically functionalized clay vinyl ester nanocomposites: Effect of processing parameters

The primary objective of this study was to improve montmorillonite clay‐platelet separation in vinyl ester resin matrix by organically modifying the nanoclay platelet with a partially reactive onium salt. The reactive onium salt (ω‐undecylenyl amine hydrochloride) was synthesized from commercial ω‐undecylenyl alcohol through a series of synthetic conversions. Nonreactive onium salt (undecyl amine hydrochloride) was made from commercial undecyl amine. These salts were characterized with ¹H and ¹³C NMR and Fourier transform infrared techniques. The relative amounts of exfoliated, intercalated, and as‐treated clay and the size of the clay particle aggregates depended significantly on the composition of clay and the processing conditions. When the clay was ion‐exchanged with a mixture of reactive and nonreactive onium salts, a partially exfoliated vinyl ester resin polymer nanocomposite was formulated. The addition of a comonomer styrene and high‐intensity ultrasonic mixing produced vinyl ester nanocomposite with the highest degree of clay‐platelet exfoliation. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 1310–1321, 2004     

Influence of the type of epoxy hardener on the structure and properties of interpenetrated vinyl ester/epoxy resins

The morphology–toughness relationship of vinyl ester/cycloaliphatic epoxy hybrid resins of interpenetrating network (IPN) structures was studied as a function of the epoxy hardening. The epoxy was crosslinked via polyaddition reactions (with aliphatic and cycloaliphatic diamines), cationic homopolymerization (via a boron trifluoride complex), and maleic anhydride. Maleic anhydride worked as a dual‐phase crosslinking agent by favoring the formation of a grafted IPN structure between the vinyl ester and epoxy. The type of epoxy hardener strongly affected the IPN morphology and toughness. The toughness was assessed by linear elastic fracture mechanics, which determined the fracture toughness and energy. The more compact the IPN structure was, the lower the fracture energy was of the interpenetrated vinyl ester/epoxy formulations. This resulted in the following toughness ranking: aliphatic diamine > cycloaliphatic diamine ≥ boron trifluoride complex > maleic anhydride. For IPN characterization, the width of the entangling bands and the surface roughness parameters were considered. Their values were deduced from atomic force microscopy scans taken on ion‐etched surfaces. More compact, less rough IPN‐structured resins possessed lower toughness parameters than less compact, rougher structured ones. The latter were less compatible according to dynamic mechanical thermal and thermogravimetric analyses. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 5471–5481, 2004     

Synthesis and photopolymerization of novel multifunctional vinyl esters

Novel mono‐ and multifunctional vinyl ester monomers containing thioether groups were synthesized via an amine‐catalyzed Michael addition reaction between vinyl acrylate and multifunctional thiols. Using photo‐differential scanning calorimetry and real‐time Fourier transform infrared (RTIR) spectroscopy, the polymerization kinetics and oxygen inhibition of the homopolymerizations of the vinyl ester monomers were investigated. The effect of the vinyl ester and thioether group on acrylate/vinyl ester and thiol/vinyl ester copolymerizations was determined using real‐time IR spectroscopy to monitor polymerization rates of acrylate, vinyl, and thiol groups simultaneously. Polymerization of the vinyl esters used was found to be relatively insensitive to oxygen inhibition. We propose that the thioether group is responsible for reducing oxygen inhibition by a series of chain transfer/oxygen‐scavenging reactions. In polymerization of a acrylate/vinyl ester mixture both in nitrogen and in air, the vinyl ester monomer significantly enhances the polymerization rates and the conversion of the acrylate double bonds via plasticization of the crosslinked matrix and reduction of inhibition by oxygen. Ultimately, the vinyl ester monomer is incorporated into the polymer network. Thiol/vinyl ester free‐radical copolymerization is much faster than either thiol/allylether copolymerization or vinyl ester homopolymerization. The electron‐rich vinyl ester double bonds ensure rapid copolymerization with thiol. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 4424–4436, 2004