Anionic graft polymerization of ethylene oxide on starch. I

Graft polymers of polyethylene oxide on various starches were obtained by anionic graft polymerization of ethylene oxide on the starch alkoxide derivatives. The polyalkoxides were prepared by reaction of potassium naphthalene with starch in DMSO solution. It was found that increase of monomer or alkoxide concentration led to transformation of the grafts from solids to syrups. Rice starch, having a more complex structure than soluble starch or wheat starch, led to graft polymers having higher melting ranges than the others. The graft polymers were very soluble in water or methanol.     

Anionic graft polymerization of methyl methacrylate on starch and dextrin

The anionic graft polymerization of methyl methacrylate on the potassium alkoxide derivative of starch or dextrin in DMSO was studied. The effects of monomer and alkoxide concentrations as well as temperature were investigated. The yield of graft polymer increased with increasing alkoxide concentration. With increasing monomer concentration and with increasing temperature the extent of homopolymer formation increased. The composition of the graft polymers was found to depend on the reaction conditions. Graft polymers having about 10–40% poly(methyl methacrylate) were obtained. There were quantitative differences in yield of isolated graft polymer between starch and dextrin and these were ascribed to differences in the solubility properties of the carbohydrates. Evidence on the structure of the graft polymers and on the mechanism of the graft polymerization was obtained from acid hydrolysis of the graft polymers and determination of the molecular weights of the cleaved side chains.     

Anionic graft polymerization of methacrylonitrile on potassium starch alkoxide

The anionic graft polymerization of methacrylonitrile on potassium starch alkoxide in dimethyl sulfoxide was studied. Factors affecting the graft polymerization such as monomer and alkoxide concentrations as well as temperature were investigated. The yield of the graft polymers was found to increase with alkoxide concentration, and it was possible to incorporate all the starch into graft polymer. On increasing the monomer concentration the graft polymer yield increased to a flat maximum. At the higher monomer concentrations, the efficiency of monomer in giving graft polymer decreased due to increased homopolymer formation. The composition of the graft polymers varied with increasing monomer concentration, graft polymers having about 40–65% of grafted starch were obtained. With increasing temperature (10 to 60°C), the yield of graft polymer decreased, there was more homopolymerization, but the amount of starch incorporated in the graft remained constant. The structure of the graft polymers was deduced from hydrolysis of the starch backbone of the graft polymers by dilute mineral acid and the determination of the molecular weights of the grafted side chains, and from oxidation by periodic acid, which showed the extent of grafting at the secondary hydroxyl groups. These results have shown that by anionic graft polymerization it is possible to obtain graft polymers having more densely packed grafted side chains of relatively low molecular weights than those obtained previously by free-radical graft polymerization.     

Amphiphilic graft copolymers - preparation and interfacial properties

Amphiphilic graft copolymers containing poly(ethylene oxide) (PEO) grafts have been prepared by various methods, for example, by coupling of reactive hydrophobic backbone polymers with end-functionalised PEO, by macromonomer copolymerisation, and by anionic graft polymerisation of EO onto polymer backbones carrying functional groups as initiator precursors. The graft copolymers are amphiphilic and were shown to accumulate at surfaces and interfaces in solution and in the solid state. Amphiphilic starch derivatives were prepared by reaction of amylose and starch with aliphatic α-epoxides.     

Anionic graft polymerization and homopolymerization of phenyl glycidyl ether

Phenyl glycidyl ether was found to react with potassium starch alkoxide in dimethyl sulfoxide (DMSO) to give graft polymers in almost quantitative yields, both the monomer and the starch being incorporated completely into the graft polymer. No transfer reactions to monomer or solvent leading to homopolymerization was found. For this reason this system was used as a model for the study of the rate of the graft polymerization of alkylene oxides on starch and other carbohydrates. Comparison of the rates of the graft polymerization of phenyl glycidyl ether on starch alkoxide with that of the homopolymerization by potassium naphthalene in DMSO under comparable conditions showed that the former reaction was much slower. Rates of the graft polymerizations on dextrin and sucrose under comparable conditions, were similar to those obtained with starch. On the other hand, the rates of polymerization on poly(ethylene oxide) alkoxides of different molecular weights were similar to those obtained in the corresponding homopolymerization by potassium naphthalene, showing that neither the molecular weight of the initiator nor the viscosity of the reaction medium were the governing factors. This suggested that the lower rates obtained by using the carbohydrate alkoxides as initiators were connected with the heterogeneity of these reaction systems, the polymeric alkoxide being insoluble in DMSO. The systematic study carried out on the homopolymerization by potassium naphthalene in DMSO showed that the effective initiator was dimsyl anion obtained by interaction of potassium naphthalene with DMSO. The reaction was bimolecular, being first order to monomer and to initiator. The molecular weights increased with increasing monomer concentration and decreasing catalyst concentration, in accordance with a “living” polymerization system.     

淀粉接枝丙烯酸乙酯及其增容性

研究了在挤出机中采用高温和剪切力的作用直接引发淀粉与丙烯酸乙酯的接枝共聚合反应．讨论了反应条件对接枝反应的影响，研究了接枝物在淀粉与聚乙烯共混物中的增容作用．实验结果表明，高温和剪切力可以引发淀粉与丙烯酸乙酯的接枝共聚合反应．接枝物作为增容剂，可以明显地改善淀粉与聚乙烯共混物的力学性能和流变性能．     

Synthesis of well‐defined comb‐like graft (co)polymers by nucleophilic substitution reaction between living polymers and polyhalohydrocarbon

A series of graft (co)polymers were synthesized by nucleophilic substitution reaction between iodinated 1,2‐polybutadiene (PB‐I, backbone) and living polymer lithium (side chains). The coupling reaction between PB‐I and living polymers can finish within minutes at room temperature, and high conversion (up to 92%) could be obtained by effectively avoiding side reaction of dimerization when living polymers were capped with 1,1‐diphenylethylene. By virtue of living anionic polymerization, backbone length, side chain length, and side chain composition, as well as graft density, were well controlled. Tunable molecular weight of graft (co)polymers with narrow molecular weight distribution can be obtained by changing either the lengths of side chain and backbone, or the graft density. Graft copolymers could also be synthesized with side chains of multicomponent polymers, such as block polymer (polystyrene‐b‐polybutadiene) and even mixed polymers (polystyrene and polybutadiene) as hetero chains. Thus, based on living anionic polymerization, this work provides a facile way for modular synthesis of graft (co)polymers via nucleophilic substitution reaction between living polymers and polyhalohydrocarbon (PB‐I). © 2013 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013     

Anionic graft polymerization of ethylene oxide on starch. II. Structure of the graft polymers

Starch–poly(ethylene oxide) graft polymers were prepared in DMSO at various monomer and starch alkoxide concentrations. Complimentary and varied information on the structure of the graft polymers was obtained from NMR and periodic acid oxidation of the polymers. From the NMR spectra of the graft polymers in pyridine containing a trace of HCl, which causes shifting of the resonance of the internal ? CH₂O? protons from the terminal ? CH₂OH protons, the polyethylene oxide content, the DP _n of the grafted side chains, and the efficiency of the alkoxides were calculated. With increase of the alkoxide concentration there was a small decrease in ? DP _n, and in the efficiency of the alkoxides in initiating graft polymerization. With increase of monomer concentration, there was only a small increase in ? DP _n but a large increase in the efficiency, indicating the existence of transfer reactions between the growing anions and the free hydroxyl groups on the starch. The results of he periodic acid oxidation showed that with increase of alkoxide concentration there was no significant change in the per cent oxidation of the graft polymers, but with increase of monomer, there was an increase in the participation of the secondary hydroxyl groups in initiation. This supports the NMR evidence for the existence of transfer reactions leading to ? DP _n values much lower than those calculated from [monomer]/[catalyst] ratios.     

Grafting of poly(ethylene oxide) on poly(methyl methacrylate) by transesterification

The grafting of the potassium alkoxide derivative of poly(ethylene oxide) on poly(methyl methacrylate) in homogeneous solution in toluene was studied. The alkoxide was prepared by reaction with potassium metal with methanolic potassium methoxide, or with potassium naphthalene. The last was the most suitable for the systematic investigation of the grafting process. Soluble graft polymers were formed, and essentially the initial poly(ethylene oxide) (PEO) and poly(methyl methacrylate) (PMMA) participated in the production of graft polymer. The composition of the graft polymers and the frequency of grafting of the side chains were determined by NMR. The solubility of the graft polymers in methanol and water increased with increasing PEO contents, while the melting ranges decreased. Fractionation of the crude graft polymers showed that the grafting reaction was random, and graft polymers containing one PEO side chain per about 10–170 MMA units were obtained.     

淀粉-醋酸乙酯-甲基丙烯酸甲酯接枝共聚物的合成及生物降解研究

用硝酸铈铵为引发剂,合成了淀粉 醋酸乙烯酯 甲基丙烯酸甲酯接枝共聚物,用质子核磁共振谱研究了接枝支链的化学组成,用Ｘ 射线粉末衍射研究了接枝共聚物的结晶结构变化,分别用实验室酶分解法和室外土壤掩埋法测定了接枝共聚物的生物降解性能,结果说明,仅接枝共聚物中的淀粉部分能被微生物降解,接枝支链部分不能被降解．     

原位制备淀粉接枝聚乳酸

研究了淀粉与乳酸的原位接枝反应.结果表明,利用乳酸中所含的水先将淀粉糊化,然后在95℃下减压反应,可直接得到淀粉-聚乳酸接枝共聚物.研究发现,上述反应体系中可原位生成丙交酯.该丙交酯的开环聚合是淀粉发生接枝反应的主要原因.利用定量核磁共振等方法对接枝产物的微结构进行了详细的解析.     

钻井液用交联-接枝淀粉的制备及性能

以N,N′-亚甲基双丙烯酰胺为交联剂,过硫酸铵为引发剂,采用“溶剂法”工艺合成了高粘度抗剪切丙烯酸钠接枝淀粉(St),考察了单体、引发剂和交联剂用量、丙烯酸中和度、反应时间及反应温度对合成交联丙烯酸钠接枝淀粉糊液粘度的影响。 结果表明,其优化反应条件为：m(淀粉)∶m(丙烯酸）=1∶1.5,乙醇质量分数为80%,过硫酸铵的用量为单体总质量的1%,交联剂为单体总质量的0.6%,反应时间2.5 h,反应温度为55 ℃,丙烯酸中和度为70%。 该交联接枝淀粉糊液具有良好的触变性,在4%盐水泥浆中的添加量为14.0 g/L时,表观粘度为26.0 mPa·s,滤失量为7.2 mL;在饱和盐水泥浆中添加量为23.5 g/L时,表观粘度为54.5 mPa·s,滤失量为3.1 mL;在80 ℃高温下老化16 h其表观粘度及滤失量等性能基本保持不变,表现出良好的增粘、降失水作用和抗盐、抗老化性能。     

Effects of water,methanol, and ethanol on the production of starch-g-polystyrene copolymers by cobalt-60 irradiation

Starch-g-polystyrene copolymers were made by simultaneous ⁶⁰Co irradiation of mixtures of wheat starch and styrene at room temperature. The extent of conversion of monomer to polymer is increased drastically with increasing water content up to a level of about 26 wt % on starch. Methanol had approximately the same effect as water at equivalent concentrations but ethanol was clearly less effective as a promoter of homo- and graft copolymerizations. Drying the starch reduced the conversion to polymer with all promoters but caused the greatest deterioration in the ability of ethanol to promote polymerization. The effects of physically swelling the starch by freeze drying the gelatinized material were also studied, as were preirradiation graft copolymerizations. The effects of promoters on graft polymerization parallel their abilities to scavenge stable radicals in irradiated starch. Water and methanol are better radical scavengers and polymerization promoters because they are better able to disrupt hydrogen bonds and permeate the starch structure. Radiolysis of the promoter is important in the grafting reaction.     

丙烯酸-2-乙基己酯改性玉米淀粉

接枝共聚合;丙烯酸-2-乙基己酯改性玉米淀粉     

氧化锌催化淀粉/乳酸接枝共聚物的制备与表征

以氧化锌为催化剂,采用原位聚合法制备了淀粉/乳酸接枝共聚物。由FT-IR、1H NMR、XRD和SEM对接枝产物进行了表征,且讨论了反应温度、淀粉与乳酸质量比、催化剂用量和反应时间对淀粉接枝率的影响,结果表明,当反应温度为95℃,淀粉与乳酸质量比为1∶5,催化剂用量为乳酸质量的1.0%,反应时间11 h时,产物的接枝率可达到14.20%。     

改性淀粉/PVA生物降解材料性能的研究

以BPO为引发剂、正庚烷为溶剂在66℃下制得马来酸酐接枝淀粉。将其与聚乙烯醇(PVA)、增塑剂及加工助剂等于HAAKE密炼机中共混,制备了可生物降解热塑性淀粉塑料。研究了接枝改性淀：粉／PVA共混物的力学性能、生物降解性能及热性能等,并用SEM研究了共混物的微观形态。结果表明接枝改性淀粉／PVA共混物拉伸强度为27．57Mpa,60d失重率达65．1％。     

Functional graft poly(N-isopropyl acrylamide)s using reversible addition-fragmentation chain transfer (RAFT) polymerisation

A series of NIPAM/4-vinyl benzyl chloride copolymers were substituted with 4(5)-imidazole dithioic acid or N-pyrrole dithioic acid to form multi-functional linear dithioate-functional polymers, which can be used as macromolecular transfer agents in a controlled radical polymerisation (RAFT) process. The presence of imidazole dithioate or N-pyrrole dithioate units along the NIPAM copolymer was determined by (1)H NMR, which showed broad CH-imidazole or CH-N-pyrrole resonances. Subsequent reaction of these multi-branch point polymers to produce graft polymers was achieved by reaction with NIPAM in the presence of AIBN. The graft polymers are produced as mixtures containing the desired product and linear polymer. The linear polymer is produced following transfer to the pendant dithioate group. Some of the branched polymers formed from the imidazole dithioate polymers were insoluble in water whilst others were found to be water soluble only in the presence of copper(II) ions. The use of N-pyrrole dithioate groups was found to substantially increase the solubility of the branched polymers in conventional solvents.     

焦磷酸络锰三价离子引发淀粉-丙烯酰胺的接枝共聚合

将带有极性基团的乙烯类单体通过化学接枝到淀粉或纤维素之类的天然多糖上,可作为絮凝剂、脱除剂和粘接剂^[1～3],近来已发展为高吸水性材料和石油分离剂^[4]。用Ce⁴⁺引发乙烯类单体接枝到淀粉和纤维素类已有报道^[5]。Rayonier用Mn³⁺的焦磷酸盐络合物引发接枝乙烯类单体至纤维素及其衍生物上^[6];Cenita等用Mn³⁺引发MMA、AN接枝淀粉^[7]。本文以焦磷酸络锰离子(Mn³⁺)作引发剂、丙烯酰胺(AM)为单体、淀粉为接枝基体进行接枝共聚,这一工作目前在国内外尚未见报道。     

Graft copolymerization of acrylamide onto carboxymethyl starch

Water absorption resins of carboxymethyl starch graft acrylamide (CMS-g-AM) were synthesized by copolymerization based on a free radical reaction. At first, CMS was prepared with starch and chloroacetic acid in an alkali-methanol media. Then, AM was grafted onto CMS by using ceric ammonium nitrate as an initiator. The resulting graft products were identified by infrared spectra. The effects of the preparation conditions on the substituent degree (SD) of starch and the water absorption capacities of CMS-g-AM were investigated. The results showed that SD of starch first increased remarkably and then decreased gradually with increased addition of sodium hydroxide, and the water absorption capacity of CMS-g-AM depended greatly on the SD of CMS and its maximum with 0.75 of SD of starch was 350 g/g.     

淀粉与丙烯酰胺流变相的微波辐射接枝共聚

微波辐射淀粉接枝乙烯基类单体的共聚反应，一般都采用溶液聚合，得到的产物含水量大，产物分离困难。本文将流变相反应法用于接枝共聚反应，探讨微波辐射下玉米淀粉与丙烯酰胺流变相态接枝共聚反应。