【作者】 雷福厚；

【导师】 安鑫南；

【作者基本信息】 南京林业大学 ， 林产化学加工工程， 2005， 博士

【摘要】 大孔网状功能基高聚物广泛应用于天然药物分离、手性分子拆分、金属离子吸附、固定化酶以及高分子催化剂方面。本文以松香、马来松香、聚合松香、歧化松香胺为主要原料,采用三种途径合成功能基大孔网状松香聚合物,一是聚合松香的功能化,二是聚合松香的高分子化,三是先在松香上接枝聚合基团,再经聚合、交联、功能基化等步骤,实验结果表明,第一和第二种途径不能合成理想的功能基大孔网状松香聚合物,第三种是可行的方法,采用此方法合成了五个尚未见文献报道的功能基大孔网状松香聚合物,对聚合物的结构、性能进行了测试表征,初步探索了部分聚合物在酶的固定化、天然药物的分离及金属离子的吸附分离方面的应用情况。主要研究内容如下: 1、探讨了聚松香苯甲酯的合成反应情况。先以Lewis酸为催化剂,甲苯做溶剂,松香与苯甲醇进行酯化反应合成松香苯甲酯,经实验筛选了最佳反应时间、催化剂用量、产品分离纯化方法。再以酯化产物为原料,在50℃恒温下密封催化搅拌反应5小时合成聚合物,测定了聚合物的紫外、红外光谱、溶解度及分子量。聚松香苯甲酯的溶解度很小,和聚合松香比较而言,聚松香苯甲酯有更大的分子量,颜色浅,呈中性,反应条件温和。用碱性阴离子交换树脂作固定相、甲苯作流动相的柱层析方法可方便地分离松香苯甲酯。 2、研究了磺酸基聚松香苯甲酯的合成方法,该磺化反应的最适温度为20℃,树脂接枝率为每个松香苯甲酯结构单元接上1.58个磺酸基。用红外光谱对合成树脂进行了表征,分别用静态吸附法和动态吸附法测试了磺酸基聚松香苯甲酯对金属离子Co²⁺、Cu（²+）、pb²⁺的吸附性能,以及磺酸基聚松香苯甲酯吸附金属离子的重复使用性。结果显示,该树脂能与Co²⁺、Cu²⁺、pb²⁺等金属离子络合,尤其对Co²⁺、Pb²⁺的吸附比较明显,且该树脂还具有较好的重复使用性,用10%浓盐酸淋洗层析柱激活后,重复使用6次后,吸附能力仍保留80%以上。能用于金属离子的吸附分离。 3、以马来松香和乙二醇为原料,制备了聚合马来松香乙二醇酯,讨论了反应温度、反应时间对反应的影响:讨论不同催化剂对产品质量、色泽的影响,筛选出最佳反应温度,反应时间及最佳的反应物摩尔比,对产物的红外吸收光谱,紫外吸收光谱进行了分析,测定了聚合物的酸值,溶解度,交联度,热失重,分解温度。测定得到聚合马来松香乙二醇酯的交联度为56.2%,在无水乙醇中的溶解度为0.0738g/100ml,酸值为31.6mgKOH/g,没有明显的软化点,分解变化温度202-209℃,从差热图可知差热线比较平稳,没有吸热峰和放热峰,说明在30℃-550℃的温度范围内样品没有明显的软化点:BET法测定聚合马来松香乙二醇酯的比表面积、孔径分布微孔大部分分布在60-90nm;分析了聚合马来松香乙二醇酯聚合物的分子量,聚合马来松香乙二醇酯（1#）聚合物的分子量在27000以上。结果表明所合成的聚合物为大孔网状聚合物。 4、研究了聚合马来松香乙二醇酯与Cu（Ⅱ）、Ca（Ⅱ）、Mg（Ⅱ）的配合物固定化漆树漆酶情况,其中聚合马来松香乙二醇酯Cu（Ⅱ）配合物固定化漆树漆酶效果较好。在25℃下静置16h固定酶,聚合马来松香乙二醇酯Cu（Ⅱ）配合物固定化漆树漆酶的更多还原

【Abstract】 Functional macroreticular polymers have been widely applied for the separation of natural drugs, resolution of chiral molecules, adsorption of metal ions, immobilization of enzyme as well as polymer catalysts etc. In this paper, a series of macroreticular rosin polymers with function groups have been synthesized from rosin, maleated rosin, polymerized rosin and disproportionated rosin amine in three ways: A.: Graft functional groups for polymerized rosin; B: Synthesize high molecular polymer from polymerized rosin; C: Graft polymerisable groups on rosin first. Then synthesize the macroreticular rosin polymers with polymerization, cross-linking and functional group grafting. The research shows method A and B cannot get perfect function groups grafted macroreticular rosin polymers. Method C, however, is a feasible way. 5 new functional macroreticular rosin polymers have been synthesized. Their structure and performance have been investigated. The applications of synthesized polymers for immobilization of enzymes, separation of natural drugs and adsorption of metal ions have also been explored. The main contents includes:1. Synthesis of polymer of rosin benzylester were discussed as following: firstly, rosin benzylester was prepared from rosin and benzyl alcohol in the toluene with Lewis acid as catalyst. The optimum conditions, such as reaction time, dosage of catalyst and the method of purifying resultant, were selected in the experiments. Secondly, by using benzylester as raw material rosin benzylester polymer was synthesized in the closed flask for five hours stirring at 50℃by catalyst. IR and UV of the polymer were analyzed, and its solubility and molecular weight were measured too. Solubility of the polymer was low. To compare the polymer with polymerized rosin, the former had greater molecular weight and lighter color. Acid-groups degree is neutral. Preparing condition of rosin benzylester polymer was milder than that of polymerized rosin. Furthermore, rosin benzylester could be purified conveniently by column partition chromatography with anionexchange resin as immobilephase, and with toluene as mobilephase.2.Sulfonated rosin benzylester polymer was prepared. The optimum sulfonating temperature was 20(?), ratio of graft for resin is 1.58 sulphoacid groups to each rosin benzylester structural unit. IR and UV of the polymer were analyzed. Absorptive performance of sulfonated rosin benzylester polymer to cobalt( Ⅱ), copper(Ⅱ) and lead(Ⅱ) was determined by Static absorption and dynamic absorption. The repeatability of use to metal ion was also mensured. The result showed that the polymer could complexing with cobalt(Ⅱ), cuprum(Ⅱ) and plumbum(Ⅱ), especially for complexing to cobalt( Ⅱ) and plumbum(Ⅱ). It also had goodeffect of repetitive use. After using 5 times, it could still retain no less than 80% absorptive performance when it was rinsed with 10% hydrochloric acid, which could be used for separation of metal ion.3.The polymer of maleated rosin glycol ester was prepared from maleated rosin and glycol by using zinc oxide as catalyst. Effects of reaction temperature and time on preparation were discussed. Effects of the types of catalyst on the quality and color of products were also studies. The optimum reaction temperature, time and molar ratio of reactant were selected. IR and UV of the resultant were analyzed, and it’s acidity, solubility, degree of cross-linking, DTA and decompose temperature were measured. The degree of cross-linking of the polymer of maleated rosin glycol ester was 56.2%, solubility in anhydrous ethanol was 0.0738g/l00ml, acidity value was 31.6mgKOH/g, The polymer had no obvious softening point. Oxidized decompose temperature was 202-209 °C. Differential thermal curves from DTA spectrogram had neither thermopositive peak nor thermonegative peak, which showed that the sample had no obvious softening point was within 30°C-550 °C. Specific surface area, pore size and pore structure of the polymer were measured by BET method. The majority of pore size was between 60-90nm. Molecular weight of the polymer of maleated rosin glycol ester (l#sample) was analyzed. It is above 27000. Results showed that the polymer prepared was macroreticular resin.4.1mmobilizedRhusverniciferslaccasebyCu (QX Ca (□)> Mg (D) complexswith polymer of maleated rosin glycol ester were studies. Immobilized Rhus vernicifers laccase by Cu (D) complex with polymer of maleated rosin glycol ester had good effect, the relative activity was the highest among them after the enzyme was preserved 16 hours at 25 °C. Its relative remained activity was 69.1% ,and activity was 0.222 A OD ? g "’? mhv’after using 6 times.The feasible pH was at 6.86~9.23 which is wider than that of the free enzyme. The optimum pH descended about a unit. The optimum temperature was 60 °C, which was 30 °C higher than that of free enzyme. The results showed that method of immobilizing Rhus vernicifers laccase by Cu (D) complex with polymer of maleated rosin glycol ester was effective.5.Polymerized maleated rosin glycol ester was reacted with CaCb, NiCk, MgCb and O1CI2 individually to make polymerized maleated rosin glycol ester complexes of Ca ( II), Ni (II), Mg( II )and Cu( II ), Then, amylase was immobilized on polymer complexes of metal, and the performance of the immobilized enzyme was compared with that of the free enzyme. The results showed that the activities of enzymes immobilized remained over 50% after four times of use. The optimum temperature for the immobilized enzyme was 50 *C, which was 10 °C higher than that of free enzyme; the optimum pH for Polymerized maleated rosin glycol ester Ca (II )% Ni (II) were 5.24 and 6.86 respectively, and the optimum Michaels constants for them were 1.47 X 10-4kg/L and 2.64X10-4 kg/L respectively. Contrarily, Michaels constant for the free enzyme was 2.69 X 10-5kg/L.6.The separation and purification of natural products, such as berberine hydrochloride and momordica triterpene glucoside by cross-linking polymerized maleated rosin glycol ester macroporous resin was explored. The static absorption of berberine and momordica triterpene glucoside by the macroporous resin were 20.6 mg/g dry resin and 40.72 mg/g dry resin respectively. The results showed that the crosslinked polymerized maleated rosin glycol ester macroporous resin could separate and purify the berberine and momordica triterpene glucoside, but its structure and functional groups of the resin still needed to be optimized.7.Rosin has been oxygenated by potassium permanganate, potassium dichromate and H2O2. The effects of these oxidants on the oxygenation were compared respectively. The results showed that the oxygenation of rosin by H2O2 had good effect when using complex of disproportionated rosin amine Schiff base copper (H) to catalyze the reaction. The molecular weight, softening point and chirality of the oxygenated products which rosin oxidized by H2O2 were measured. They were also analyzed by infrared, ultraviolet spectra and GC/MS. The structures of four main products and three secondary products have been characterized.8.The synthesis of the disproportionated rosin amine Schiff base - copper (II) complex was investigated. The synthetic complex has been applied to catalyze oxidation of rosin with H2O2. The effects of H2O2 concentration, solvent, dosage of catalyst, and reaction temperature on the oxidation reaction were studied. The results showed that when using anhydrous ethanol as solvent and the dosage of rosin amine Schiff groups complex with copper (II) catalyst was 2%, the most effective factor was temperature, the secondary was the dosage of H2O2, and the reaction time was the least. The optimum conditions that were achieved by orthogonal experiments were as follows: the mass ratio of rosin to anhydrous ethanol was 1:5, 2% rosin amine Schiff base copper (II) complex catalyst, 7ml 35% H2O2 react at80°C forlh.9.The catalytic performances of disproportionated rosin amine Schiff base copper (II) complex that catalyzed oxygenation polymerization reaction of urushiol were investigated. First, disproportionated rosin amine was reacted with salicylaldehyde to form Schiff s base. Then, the synthesized Schiff s base was reacted with cupric acetate to make Schiff base copper (II) complex. Finally, the complex was used to catalyze oxygenation polymerization reaction of urushiol The effects of catalyst concentration, reaction time, substrate concentration and temperature on the reaction were discussed. It was found in our experiment that the optimum conditions were: 3% disproportionated rosin amine Schiff base copper (II) complex as catalyst and the urushiol concentration was 6.88g/100ml in ethanol. After reacting in room temperature for 48 hours, the precipitation yield of urushiol polymer was 51.3%.lO.Rosin glycol acrylate ester was synthesized from acrylic acid and rosin glycol ester, which was prepared from rosin and glycol with FeCU catalysis. Polymer of rosin glycol acrylate ester was made by polymerization of rosin elycol acrylate ester under the existence ofcatalyst. The synthesized polymer was then oxygenated by H2 0 2. The specific surface area, pore size, acidity, dissolvability and DTA analysis of polymer of rosin glycol acrylate ester and polymerized rosin glycol acrylate ester oxide were measured. BET method was used to measure the specific surface area and pore size, the specific surface area was measured as 0.3185 m /g for polymerized rosin glycol acrylate ester and 9.3669 m /g for its oxide. The pore size was 60-90nm for both for polymerized rosin glycol ester acrylate and its oxide. These results indicated that the polymer we synthesized was a macroporous resin. The solubility of polymerized rosin glycol acrylate ester and its oxide in ethanol was 0.0272g/100ml and 0.00482g/100ml respectively, which indicated that the polymer had a low solubility. The degree of cross-linking of polymerized rosin glycol acrylate ester was 12.3%. The temperatures of 5% weight loss for these two polymers were 259.8°C and 307.8 °C respectively. It was shown in DTA curves that the curve was steady without any thermalpositive and thermalnegative peaks, in other words, there was no obvious softening points in the temperature range from 30°C to 550 °C. Molecular weight of polymerized rosin glycol acrylate ester oxide was analyzed. It is above 25000. Results indicated the synthesized polymer was reticulated polymer.11.Polymer of rosin allyl alcohol ester was made by microwave polymerization and traditional polymerization methods. After analyzing the products with TGA, infrared and ultraviolet spectra, it was found that microwave polymerization was superior to traditional polymerization because it was simpler and quicker. The polymerized rosin allyl alcohol ester we made in these two ways both have cross-linking structure, the conjugated chemical bonds of rosin also took part in the reaction, and the softening points of them were over 300°C. Because the polymer cross-linked by curative could reserve more conjugated chemical bonds, its thermal stability was weakening. The TGA, infrared and ultraviolet spectroscopic analysis showed that the performances of the oxide of polymerized rosin allyl alcohol ester were superior to that of polymerized rosin allyl alcohol ester. The majority of pore size was between 5-100 nm. Molecular weight of Polymer of rosin allyl alcohol esterand its oxide was analyzed. Molecular weight of polymer of microwave polymerization is above 29305. Molecular weight of oxide of poly-rosin-allyl-alcohol ester by traditional methods is above25000. Results showed that the prepared polymer was a mesoporous and macroreticular resia.更多还原