胶束共聚合法合成丙烯酰胺/4-乙烯基吡啶共聚物

以十二烷基苯磺酸钠为表面活性剂 ,过硫酸钾 /亚硫酸氢钠为引发剂 ,进行丙烯酰胺 - 4-乙烯基吡啶胶束共聚合 ,合成了双亲共聚物 ,用1H NMR分析法、差示扫描量热量 ( DSC)对其进行表征 ,并分析了共聚物形成机理。     

脱水反应生成2-乙烯基吡啶的研究

研究了以2-羟乙基吡啶经脱水生成2-乙烯基吡啶的方法。采用酸碱两类脱水剂,对其反应效果分析比较,发现碱性脱水剂氢氧化钾,更有利于2-乙烯基吡啶合成;探讨了脱水剂用量、反应温度、反应时间等影响因素,得出了适宜的反应条件：n（2-羟乙基吡啶）：n（氢氧化钾）=5：2,在loo。C温度条件下,反应时间2h,反应收率80．2％,产物纯度可达98．1％,水分低于1％。     

用乙烯基吡啶改性苯乙烯-丁二烯-苯乙烯嵌段共聚物

通过采用1,1-二苯基乙烯作为降活剂降低苯乙烯-丁二烯-苯乙烯嵌段共聚物(SBS)活性大分子的活性,然后用2-乙烯基吡啶进行封端聚合,合成了苯乙烯-丁二烯-苯乙烯-2-乙烯基吡啶多嵌段共聚物,研究了降活剂和单体用量及反应条件对聚合的影响。结果表明,在降活剂用量控制为活性中心的1.0倍(摩尔比)、2-乙烯基吡啶质量分数控制为活性SBS的3%以下、反应温度在60～83℃及反应时间不少于35min时能够制得相对分子质量可控且分布较窄的嵌段共聚物。     

聚(丙烯酸钠-4-乙烯基吡啶)的表征

为了改善生物分解性能，在聚丙烯酸钠主链上引入了少量4-乙烯基吡啶，并对共聚产物进行了IR、UV、元素分析、热稳定性、螯合性能、分散性能等研究。结果表明，共聚产物中原来的吡啶环已经质子化，形成两性离子聚合物，聚合物的热稳定性随着原料中4-乙烯基吡啶含量的增加而下降，当4-乙烯基吡啶的物质的量分数为6％左右时，共聚物的粘均分子量大约1．3万，共聚物具有较好的螯合性能和分散性能。     

“一锅法”合成4-二甲氨基吡啶

以4-氰基吡啶、2-乙烯基吡啶和二甲胺为主要原料,一锅法合成了4-二甲氨基吡啶。得出的最佳工艺条件为:反应物配料比m(4-氰基吡啶)/m(2-乙烯基吡啶)=1.5,使用w(NaOH)=40%的水溶液回流2 h裂解中间体,反应产率达87.4%。目标化合物通过IR、1HNMR及MS确认。     

P2VP-b-PS-b-PI三嵌段共聚物的RAFT合成及表征

以S-十二烷基-S’-(α,α’-二甲基-α’’-乙酸)-三硫代碳酸酯(DDMAT)为链转移剂,通过可逆加成-断裂链转移自由基聚合(RAFT)方法制备了窄分布的聚2-乙烯基吡啶。再以该聚合物为大分子链转移剂,引发苯乙烯的RAFT聚合,得到聚2-乙烯基吡啶-b-聚苯乙烯(P2VP-b-PS)的两嵌段共聚物。以P2VP-b-PS为RAFT试剂,合成聚2-乙烯基吡啶-b-聚苯乙烯-b-聚异戊二烯(P2VP-b-PS-b-PI)的三嵌段共聚物。运用1H NMR、IR和凝胶渗透色谱(GPC)等技术对产物的结构和分子量及分子量分布进行表征,采用原子力显微镜(AFM)观察三嵌段共聚物薄膜的微相分离结构。结果表明,所得三嵌段共聚物P2VP72-b-PS136-b-PI300分子量分布较窄(PDI=1.69),合成过程具有活性/可控聚合特征,聚合物薄膜经溶剂退火处理后出现了明显的微观相分离结构。     

2-甲基吡啶合成2-乙烯基吡啶

以二苯胺生产过程中产生的副产物2-甲基吡啶为原料,以KOH改性的HZSM-5沸石分子筛为催化剂,气相一步法合成了2-乙烯基吡啶。考察了催化剂的焙烧温度、用于改性的钾含量、成型过程中的粘结剂的种类和含量,反应的工艺条件等因素对反应的影响。实验结果表明,催化剂焙烧温度为550℃,改性钾离子的质量分数为3%,以硅溶胶作为粘结剂进行催化剂成型,硅溶胶的用量为K-HZSM-5质量的50%,当反应温度为360~370℃,原料2-甲基吡啶和甲醛摩尔比为1∶3,质量空速0.75 h-1时,2-甲基吡啶的转化率可达到80.26%,2-乙烯基吡啶的选择性可达到97.59%,实现了副产物的有效利用。     

PP无纺布预辐射法固相接枝4-VP的研究

以预辐射聚丙烯无纺布为基材,4-乙烯基吡啶为单体,二乙烯基苯为交联剂,采用固相接枝聚合的方法制备接枝共聚物。讨论了反应温度、反应时间、阻聚剂、单体浓度和交联剂等对接枝率的影响。结果表明,接枝反应的最佳条件为:温度50℃,时间3 h,单体浓度10%,交联剂5%,阻聚剂(FeSO4.7H2O)0.08%,最佳条件下的接枝率为7.5%。     

2-乙烯基吡啶-甲基丙烯酸甲酯两嵌段共聚物的合成与表征

采用阴离子活性聚合方法合成了聚2-乙烯基吡啶(P2VP)-聚甲基丙烯酸甲酯(PMMA)两嵌段共聚物(P2VP-b-PMMA),并采用GPC、FT-IR、NMR等手段进行了结构表征.结果表明,聚合产物为数均分子量103166、多分散指数1.08的单分散P2VP-b-PMMA.     

2-乙烯基吡啶合成工艺研究

采用Re2O7负载ZSM-5沸石分子筛作为催化剂,以固定床为反应器,催化2-甲基吡啶合成2-乙烯基吡啶.系统地考查不同硅铝质量比的ZSM-5分子筛催化剂、反应温度、反应时间以及物料配比对2-乙烯基吡啶收率的影响,筛选出合适的反应条件.反应的最优条件为选取硅铝比为25的ZSM-5分子筛负载Re2O7,2-甲基吡啶∶甲醛为1∶4,反应温度为335℃,此时2-乙烯基吡啶的收率可达89.7％.该工艺操作简单,安全性高,条件温和,不易腐蚀管道,反应时间短,收率高,适合工业化生产.     

The effect of polystyrene-block-poly(4-vinylpyridine) prepared by a RAFT method in the dispersion polymerization of MMA

The dispersion polymerization of methyl methacrylate (MMA) has been carried out using polystyrene-block-poly(4-vinylpyridine) copolymer [P(S-b-4VP)], which was prepared by a reversible addition-fragmentation chain transfer (RAFT) method, as a steric stabilizer in an alcohol media. The stable polymer particles were obtained when the block copolymer concentrations increased from 1 to 10 wt% relative to the monomer and the average particle sizes decreased from 5.3 to 3.4 μm with the increasing concentration of the block copolymer. In particular, the incorporation of 2 wt% polystyrene-block-poly(4-vinylpyridine) produced 4.3 μm of monodisperse PMMA particles with 2.14% of C_v. Thus, the P(S-b-4VP) block copolymer prepared by the RAFT method is working not only as a steric stabilizer, but also in providing monodisperse micron-sized PMMA particles.     

Dipole moments of styrene/4-vinylpyridine copolymers—I: Relation to the fraction of polar component

Mean-square dipole moments for styrene/4-vinylpyridine (S4VP) random copolymers were determined at five different temperatures, 25–60°C, in 1,4-dioxane solution. The dipole moment behaviour was examined with respect to the increase in mole fraction of the polar monomer, 4-vinylpyridine (4VP), in the copolymer. The behaviour observed was different from the general behaviour of similar copolymers. The temperature coefficient of the dipole moment ratio was found to be zero, within experimental error, in the temperature interval 25–60°C.     

Anion exchange membranes prepared by amination of cross-linked membranes having chloromethyl groups with 4-vinylpyridine and trimethylamine

Copolymer membranes composed of chloromethylstyrene and divinylbenzene were reacted with 4-vinylpyridine and then trimethylamine to prepare highly tight anion exchange membranes. When 4-vinylpyridine reacted with chloromethyl groups of the copolymer membranes, 4-vinylpyridine polymerized in the membrane matrix to form a ladder-like polymer, of which one polymer was cross-linked. Consequently, relationships of ion exchange capacity and water content to electrical resistance of the obtained membranes were completely different from those of the anion exchange membranes with benzyl trimethylammonium groups cross-linked with divinylbenzene. With increasing reaction time of the copolymer membranes with 4-vinylpyridine, the electrical resistance of the membranes markedly increased with a small decrease in ion exchange capacity and with the decrease in water content. And fixed ion concentration of the membranes reacted with 4-vinylpyridine and then trimethylamine was higher than that of the membranes with benzyl trimethylammonium groups. These are thought to be because of the formation of a ladder-like polymer in the membrane matrix and the introduction of pyridine unit, which is more hydrophobic and bulkier than trimethylamine. The remarkable decrease in the pore size of the membranes was confirmed by the measurement of the diffusion coefficient of neutral molecules, urea and glucose, through the membranes.     

HEC-g-P4VP的pH值诱导胶束化行为

采用硝酸铈铵（CAN,Ce4+）自由基引发聚合合成了羟乙基纤维素接枝聚4-乙烯基吡啶（HEC-g-P4VP）聚合物。并用FTIR、1H NMR确证了共聚物结构。将这种纤维素接枝改性聚合物溶解在不同pH值的水溶液中,研究了它的胶束化行为。利用扫描电镜（SEM）和透射电镜（TEM）相结合,对胶束化行为进行了观察,结果表明HEC-g-P4VP能够形成清晰的核壳结构。在不同pH值条件下,所形成的核壳结构有所变化。说明HEC-g-P4VP在溶液中具有一定的pH值诱导胶束化行为。最后,采用滴体积法对HEC-g-P4VP在水溶液中的表面张力进行了研究,随着接枝率的提高,其表面张力有降低的趋势。     

Dipole moments of styrene/4-vinylpyridine copolymers—II: Relation to microstructure

Mean-square dipole moment values of styrene/4-vinylpyridine (S4VP) copolymers determined at 25–60°C in 1,4-dioxane solutions were related to the microstructure of the chains. Data on the synthesis and dipole moments of S4VP copolymers were used to calculate the distribution of triad fractions and effective dipole moments of styrene, S-centred, and 4-vinylpyridine, V-centred, fractions in the copolymer chains. The relative magnitudes of the effective dipole moment values calculated for each type of triad reflect the effect of dipole–dipole interactions on these values.     

An innovative approach for the chemical structural characterization of poly(styrene 4-vinylpyridine) copolymers by matrix-assisted laser desorption/ionization time of flight mass spectrometry

Poly(styrene-co-4-vinylpyridine) random copolymers with different molar composition were synthesized by nitroxide-mediated controlled-radical polymerization using 2,2,5-trimethyl-4-phenyl-3-azahexane-3-nitroxide (TIPNO) as a mediator. We record the matrix-assisted laser desorption/ionization time of flight (MALDI-TOF) spectra under various conditions, and we find (at last) that they show mostly intact ions [using 2(-4-hydroxyphenylazo-)benzoic acid as MALDI matrix]. Spectra are highly resolved, and thus they allow for the determination of all end-groups, even some less-abundant ones. Spectra are dominated by intact “dormant” copolymer chains terminated with TIPNO at one end and with (4-Bromo-phenyl)ethyl group (starting fragment) at the other one. Applying the mass analysis of copolymers (MACO) statistical model to the spectra, we show that the MACO/MALDI-TOF mass spectrometry (MS) analysis can be successfully applied to copolymers having a difference between the mass of the comonomers as small as 1 g mol⁻¹ (the styrene and 4-vinylpyridine units are 104.15 and 105.15 g/mol, respectively), which results in overlapping isotopic patterns. The results are accurate: chemical composition evaluated by means of MS agrees with that calculated by ¹H-nuclear magnetic resonance, for all copolymers investigated. This analytical method allows to extract detailed information on the composition of the copolymer samples and their structure. Glass transition temperatures of copolymers were also determined by differential scanning calorimetry. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 46976.     

Surface grafting polymerization of vinyl monomers on poly(tetrafluoroethylene) films by plasma treatment

Poly(tetrafluoroethylene) films were surface modified by argon plasma treatment followed by graft polymerization. Peroxidе groups were introduced on the surface of poly(tetrafluoroethylene) films after plasma treatment and the consequent contact with air when the films were taken out of the reactor. Grafting polymerization initiated by the surface peroxide (hydroxide) groups was performed on the poly(tetrafluoroethylene) film surface by using acrylic acid, 4-vinylpyridine and 1-vinylimidazole as monomers. Copolymers were obtained with grafting yield from 0.436 to 0.457 mg/cm² for poly(acrylic acid), from 0.299 to 0.390 mg/cm² for poly(4-vinylpyridine) and from 0.212 to 0.256 mg/cm² for poly(1-vinylimidazole), respectively. The free surface energies of the copolymers were determined. The chemical structures and the copolymer surfaces were characterized by IR, XPS and SEM analyses. High energy resolution X-ray photoelectron spectroscopy (XPS) confirmed the grafting of acrylic acid, 4-vinylpyridine and 1-vinylimidazole. The surface hydrophilicities of modified polytetrafluoroethylene films were significantly enhanced after plasma treatment and grafting modification. It is worth emphasizing that in this work acrylic acid, 4-vinylpyridine and 1-vinylimidazole were used as the reactive monomers for grafting on the poly(tetrafluoroethylene) film by plasma treatment. We believe that this vinyl monomers may be employable as functional groups, permitting a potentially wide range of applications: as ionomers, membranes, carriers for immobilization of biomolecules, for complex formation with heavy metals as catalysts.     

Supramolecular Assembly between Polystyrene-block-Poly(4-vinylpyridine) and 4-Dodecylbenzenesulfonic Acid

In this study, the desired polymer was prepared by complexing the surf molecule, i.e., 4-dodecylbenzenesulfonic acid (DBSA), with polystyrene-block-poly(4-vinylpyridine) (PS-P4VP) and a comb-coil A-block-(B-graft-C) type of copolymer can be generated through a supramolecular assembly route. On the block copolymer scale, the PS blocks are phase-separated from the P4VP(DBSA) _x block (x denotes the molar ratio between DBSA and pyridine groups) according to the relatively constant low-temperature glass transition (T _g) corresponding to the PS phase. In contrast, the high-temperature T _g increased with the DBSA content; a fact associated with the chain packing situation in the P4VP(DBSA) _x block. Both low and high T _g's became more visible if samples were subjected to a two-stage annealing process. Corresponding X-ray diffraction study also indicates that annealing enhanced the layered structure in the P4VP(DBSA) _x phase. The corresponding one-dimension correlation function suggests that both polymer and surfactant layers increased with the increasing DBSA content. In addition, amounts of the associated DBSA related to the formation of macroscopic anisotropic domains, that is, birefrigency can only be detected for copolymers of high P4VP(DBSA) _x content (>70 wt%).     

聚4-乙烯基吡啶氮氧化物的合成

以过氧化二苯甲酰(BPO)为引发剂，采用本体聚合方法制备了聚4-乙烯基吡啶(P4VP)，然后用冰醋酸为溶剂，钨酸钠为催化剂，过氧化氢为氧化剂，氧化聚4-乙烯基吡啶合成了聚4-乙烯基吡啶氮氧化物(PVNO)，探讨了反应条件对PVNO特性粘数的影响。另外，采用TG-DTA研究了氧化产物的热稳定性。     

The effects of the selectivity of the toluene/ethanol mixture on the micellar and the ordered structures of an asymmetric poly(styrene-b-4-vinylpyridine)

The effects of the solvent selectivity of toluene/ethanol mixtures on the micellar and ordered structures of an asymmetric diblock copolymer of PS(19.6 K)-b-P4VP(5.1 K) in the dilute (1 wt%) and semi-dilute (8 wt%) solutions, as well as in the gel and solid films, were studied using small angle X-ray scattering (SAXS), generalized indirect Fourier transform (GIFT), and transmission electron microscopy (TEM) methods. The solvent selectivity was controlled by ? (weight percentage of ethanol in toluene/ethanol mixture). Individual micelles, space-filled micellar structure (without three-dimensional order), and three-dimensionally ordered gel and solid structures were observed from the 1 and 8 wt% solutions, the gel, and the solid film, respectively. In the 1 wt% solution, the individual micellar structures were strongly dependent on ?; the spherical micelles with P4VP core at ? = 0, the unimer state at 10 ≤ ? ≤ 50, the spherical micelles with PS core at ? = 60, the cylindrical micelles with PS core at ? = 70 and 80, and precipitation at ? = 90 and 100 were observed. The 8 wt% solution was close to overlap concentration with the unimer state in the regions of 20 ≤ ? ≤ 40. In the gel, the ordered structure was observed in the sequence of bcc, hexagonal, gyroid, lamellar, reverse hexagonal and random as ? increased, and could be explained by the change of the relative volume fraction of each block as ? changed, similar to the phase sequence in the phase diagram of the diblock copolymer. The solid films showed the various kinetically frozen ordered microstructures such as randomly packed sphere, hexagonal, gyroid, hexagonally perforated lamella, reversed hexagonal, and randomly packed cylinder, which were controlled by the solvent quality in the gel before solidification. We believe that these results can be applied to photonic crystals, self-assembled nano-patterning, and functional nanoparticles in which the structural control is most important.