| 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.
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