γ-丁内酯聚合研究新进展

综述了近年来采用金属络合物进行γ－丁内酯的开环聚合、γ－丁内酯的酶催化聚合、微生物发酵等及合成γ－丁内酯均聚共聚物的研究。     

Rapid Ring‐Opening Polymerization of D,L‐Lactide by Microwaves

Summary: Poly(D ,L ‐lactide) with a molar mass of 10⁵ g · mol⁻¹ and a yield over 90% was produced in 10 min by the ring‐opening polymerization of D ,L ‐lactide under microwave irradiation with forward power of 255 W. A degradation of the poly(D ,L ‐lactide) was also induced by microwaves with a power level over 340 W. The molar mass of poly(D ,L ‐lactide) was dependent upon the competition between the polymerization of D ,L ‐lactide and the degradation of the resulting polymer.

Profiles of molar mass versus microwave irradiation time (1.8 g DLLA, 0.1% Sn(Oct)₂).     

三(2,4,6-三甲基苯氧基)稀土配合物引发DL-丙交酯开环聚合特征与机理的研究

Tris(2,4,6-trimethylphenolate) lanthartide [Ln(OTMP)3] has been prepared and employed for ring-opening polymerization of D,L-lactide (LA) as single-component catalysts. The characteristics, kinetics and mechanism were examined. The polymerization is first-order with respect to monomer and initiator concentration, and the overall activation energy amounts to 62.9 kJ/mol. DSC curve disclosed the random structure of PLA. ^1H NMR spectrum analysis demonstrates that the polymerization of LA proceeded through acyl-oxygen bond cleavage.     

Cubane‐Type Polynuclear Zinc Complexes Containing Tridentate Schiff Base Ligands: Synthesis,Characterization, and Ring‐Opening Polymerization Studies of rac‐Lactide and ε‐Caprolactone

New polynuclear zinc complexes containing tridentate Schiff base ligands were successfully synthesized and fully characterized. The solid‐state structure of the complexes was determined using single crystal X‐ray diffraction. The complexes display a tetranuclear cubane‐like core structure [Zn₄O₄] and sowed good catalytic activity towards the ring‐opening polymerization (ROP ) of rac‐lactide (rac‐LA ) and ε‐caprolactone (ε‐CL ) under solvent‐free conditions. The polylactic acid (PLA ) obtained from rac‐LA showed isotactic enrichment, as proved by homonuclear decoupled ¹H‐NMR analysis. These complexes also showed good activity and superior control towards the ROP of rac‐LA and ε‐CL in the presence of benzyl alcohol as a co‐initiator. Furthermore, kinetic studies demonstrated that the ROP of rac‐LA and ε‐CL has a first order dependence on both monomer (rac‐LA and ε‐CL ) and catalyst concentration.     

Synthesis of poly(D,L‐lactic acid‐alt‐glycolic acid) from D,L‐3‐methylglycolide

D ,L ‐3‐Methylglycolide (MG) was synthesized via two step reactions with a good yield (42%). It was successfully polymerized in bulk with stannous octoate as a catalyst at 110 °C. The effects of the polymerization time and catalyst concentration on the molecular weight and monomer conversion were studied. Poly(D ,L ‐lactic acid‐co‐glycolic acid) (D ,L ‐PLGA50; 50/50 mol/mol) copolymers were successfully synthesized from the homopolymerization of MG with high polymerization rates and high monomer conversions under moderate polymerization conditions. ¹H NMR spectroscopy indicated that the bulk ring‐opening polymerization of MG conformed to the coordination–insertion mechanism. ¹³C NMR spectra of D ,L ‐PLGA50 copolymers obtained under different experimental conditions revealed that the copolymers had alternating structures of lactyl and glycolyl. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 4179–4184, 2000     

Alkyne Metathesis as a New Synthetic Tool: Ring‐Closing,Ring‐Opening,and Acyclic

Conceptually and mechanistically (!) the metathesis of disubstituted alkynes in the presence of molybdenum or tungsten catalysts (see scheme) is related to alkene metathesis. With skillful experimentation and careful selection of substrate, alkyne metathesis can result in both ring opening/ring closing and the formation of high molecular weight polymers.     

乙交酯与2-氢-2-氧-1,3,2-二氧磷杂环己烷的开环共聚研究

聚乙醇酸及其与乳酸的共聚物是一类无毒、有良好的生物相容性和生物可降解材料,它们广泛地用作药物控释体系的载体,牙科植入材料［１,２］．但由于聚乙醇酸的高度可结晶性,使其不溶于包括三氟乙酸在内的几乎所有的有机溶剂,因此通过共聚来改进其物化性质的研究一直方...     

Ring opening polymerization of tetrahydrofuran catalysed by maghnite-H+

The cationic ring-opening polymerization of tetrahydrofiiran using maghnite-H~+ is reported.Maghnite-H~+,is a non-toxic solid catalyst issued from proton exchanged montmorillonite clay.Polytetrahydrofuran,also called "poly(butandiol) ether",with acetate and hydroxyl end groups was successfully synthesized.Effects of reaction temperature, weight ratio of initiator/monomer and reaction time on the conversion of monomer and on the molecular weight are investigated.A cationic mechanism of the reaction was proposed.This chemistry can be considered as a suitable route for preparing poly(THF) as a soft segment for thermoplastic elastomers.     

己内酯和丙交酯的微波辅助开环聚合反应

己内酯和丙交酯在异辛酸亚锡存在下经微波辐照 5min可分别获得分子量 1 2 0kg·mol- 1的聚己内酯和 2 2 5kg·mol- 1 的聚乳酸。苯甲酸可作为己内酯微波辅助开环聚合的引发剂 ,所得聚己内酯的分子量达到 44 8kg·mol- 1 。通过混有布洛芬的己内酯的微波开环聚合可直接制备以聚己内酯为基质的药物控释系统。己内酯和丙交酯在微波辐照下的热行为对它们的开环聚合反应有重要影响。     

Phenylene‐Bridged Cyclic Siloxanes as Precursors to Nonshrinking Sol–Gel Systems and Their Use as Encapsulants

A new class of thermally robust sol–gel polymers have been prepared from the disilaoxacyclopentane derivative 1 by ring‐opening polymerization to form nonshrinking polysiloxanes. This reaction, which does not need solvent or water, can be used for, amongst other things, the encapsulation of an electronic microchip.     

基于β-环糊精的多肽支臂星状聚合物的制备及性能

以β-环糊精(β-CD)为起始原料, 通过磺酰化及乙二胺基取代等过程, 制备具有端氨基的中间体β-环糊精(6-en-β-CD); 再以6-en-β-CD为引发剂, 通过赖氨酸N-羧基环内酸酐(Lys-NCA)和谷氨酸N-羧基环内酸酐(Glu-NCA)的混合开环聚合(ROP)和脱苄氧羰基(Cbz)保护等反应, 制备了以β-CD为核、 混聚多肽为支臂的星状聚合物[6-聚(谷氨酸-赖氨酸)-β-CD]. 以基质辅助激光解吸电离飞行时间质谱(MALDI-TOF-MS)、 核磁共振波谱(NMR)和傅里叶变换红外光谱(FTIR)等对星状聚合物及中间体结构进行表征; 同时采用圆二色光谱(CD)和噻唑蓝(MTT)法对该聚合物的二级结构和体外毒性进行了考察. 结果表明, 所得星状聚合物的重均分子量(M_w)为4626, 多分散系数(PDI)为1.10, 平均聚合度(DP)为27.1; 在水溶液中星状聚合物的二级结构是无规则线团; 在5 mg/mL浓度下, 细胞存活率可达到94%以上, 没有呈现明显体外细胞毒性, 具有潜在的药用前景.     

环状芳香低聚物的合成及应用研究进展

综述了近年来环状芳香低聚物的合成及应用研究发展状况,对其合成方法和应用情况进行了综述和分析,并对今后的研究发展进行了预测。     

Synthesis and Immortal ROP of L-Lactide Using Copper Complex

In the present work, the -ONNO- tetradentate Schiff base ligand N, N′-bis (2-hydroxy-3-methoxybenzaldehyde) propylenediamine, [HMBPD] was synthesized. Further, complexation of this ligand with copper [HMBPD-Cu] was carried out and their reactivity for the ring-opening polymerization (ROP) of lactide (LA) has been studied. This monomeric copper complex is prepared by the reactions of copper solution with one molar equivalent of HMBPD Schiff-base ligand in ethanol under nitrogen atmosphere. This copper complex has been characterized by different spectroscopic methods, which showed square planner geometry. The copper complex is highly active towards ROP of LA. The rate of polymerization is heavily dependent on the initiator used. The copper complex allows controlled ring-opening polymerization as shown by the linear relationship between the percentage conversion and the number-average molecular weight. On the basis of literature reports, a mechanism for ROP of lactide has been proposed.     

Effect of ortho-Substituents on the Free-Radical Polymerization of N-Phenylmethacrylamides and on the Thermal Stability of the Polymers

Ceiling temperatures (T_c) and reactivities of N-phenylmethacrylamide (PMAm) and o-substituted PMAm's in free-radical polymerization and the thermal stability of the polymers obtained were investigated. Although PMAm and o-substituted analogs gave the same T_c, 123°C at 0.64 mol/L in N,N-dimethylformamide, that of 2,6-dimethyl-PMAm was found to be as low as 65°C. These findings are interpreted in terms of steric hindrance as a consequence of the bulkiness of the 2- and 6-substituents and of the rigid and planar structure expected for the polymers. In copolymerization with styrene, the o-monosubstituted PMAm's were estimated to be more reactive than PMAm by a factor of about 3 except for o-phenyl-PMAm. The enhanced reactivity of the PMAm with a relatively small o-substituent is explained by ground-state strain of the monomer tending toward a planar structure. 2,6-Dimethyl-PMAm and o-phenyl-PMAm showed lower and slightly higher reactivities than PMAm, respectively, probably due to the blocking effect of these substituents against the approaching polymer radical. Enhancement of thermal degradation owing to the substitution was confirmed by means of thermogravimetric analyses of the polymers. The polymers from the 2,6-dimethyl-substituted and the o-monosubstituted PMAm' exhibited similar maximum-degradation-rate temperatures.     

Synthesis of star‐shaped poly(D,L‐lactic acid‐alt‐glycolic acid)‐b‐poly(L‐lactic acid) with the poly(D,L‐lactic acid‐alt‐glycolic acid) macroinitiator and stannous octoate catalyst

Two types of three‐arm and four‐arm, star‐shaped poly(D,L ‐lactic acid‐alt‐glycolic acid)‐b‐poly(L ‐lactic acid) (D,L ‐PLGA50‐b‐PLLA) were successfully synthesized via the sequential ring‐opening polymerization of D,L ‐3‐methylglycolide (MG) and L ‐lactide (L ‐LA) with a multifunctional initiator, such as trimethylolpropane and pentaerythritol, and stannous octoate (SnOct₂) as a catalyst. Star‐shaped, hydroxy‐terminated poly(D,L ‐lactic acid‐alt‐glycolic acid) (D,L ‐PLGA50) obtained from the polymerization of MG was used as a macroinitiator to initiate the block polymerization of L ‐LA with the SnOct₂ catalyst in bulk at 130 °C. For the polymerization of L ‐LA with the three‐arm, star‐shaped D,L ‐PLGA50 macroinitiator (number‐average molecular weight = 6800) and the SnOct₂ catalyst, the molecular weight of the resulting D,L ‐PLGA50‐b‐PLLA polymer linearly increased from 12,600 to 27,400 with the increasing molar ratio (1:1 to 3:1) of L ‐LA to MG, and the molecular weight distribution was rather narrow (weight‐average molecular weight/number‐average molecular weight = 1.09–1.15). The ¹H NMR spectrum of the D,L ‐PLGA50‐b‐PLLA block copolymer showed that the molecular weight and unit composition of the block copolymer were controlled by the molar ratio of L ‐LA to the macroinitiator. The ¹³C NMR spectrum of the block copolymer clearly showed its diblock structures, that is, D,L ‐PLGA50 as the first block and poly(L ‐lactic acid) as the second block. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 40: 409–415, 2002     

Aluminium Complexes Bearing Pyrrolide Ligand as Efficient Catalysts for Ring‐Opening Polymerization of ε‐Caprolactone

Three aluminium complexes supported by a tetradentate pyrrolide ligand H₂L [H₂L = N,N′‐(2,2‐dimethylpropane‐1,3‐diyl)bis(1‐(1H‐pyrrol‐2‐yl)methanimine)], namely, Al(L)Me ( 1 ), Al(L)Cl ( 2 ), and Al(L)(OiPr) ( 3 ), were synthesized. The structures of 1 and 2 were established by X‐ray single crystal diffraction analysis, and the structure of 3 was characterized by NMR spectroscopy and element analysis. All complexes, containing different chemical bond forms (Al–C, Al–Cl, and Al–O), are good initiators for the ring‐opening polymerization (ROP) of ε‐caprolactone. The obtained polymers have high molecular weights (MWs) and relatively narrow molecular weight distributions (PDIs). Complexes 1 and 3 show dramatically high activities for the ROP of ε‐caprolactone. For complex 1 , when the monomer/initiator (M/I) ratio is 6400:1, a 40 % yield of the product could be obtained at 100 °C. The activity of 3 is higher than that of 1 , and 39 % yield of the polymers could be afforded at 70 °C, as the M/I value reaches 12800:1. The good activities of these complexes reveal their potential applications in industry.     

Bis(2‐cycloazylindolyl)titanium Complexes: Synthesis,Characterization, and the Catalytic Behaviors towards Hydroamination and Ring‐opening Polymerization of ϵ‐Caprolactone

The ligands 2‐pyrazol‐1‐yl‐1H‐indole (HL1) and 2‐ 1 , 2 , 4 ‐triazol‐1‐yl‐1H‐indole (HL2) individually reacted with Ti(NMe₂)₄ in tetrahydrofuran to form the corresponding complexes Ti(L1)₂(NMe₂)₂ ( 1 ) and Ti(L2)₂(NMe₂)₂ ( 2 ), respectively. The titanium complexes were fully characterized by NMR measurement and elemental analysis as well as the single‐crystal X‐ray diffraction of 1 and 2 . Both 1 and 2 exhibit high activities towards intermolecular hydroamination of terminal alkynes with high selectivity, and they also efficiently promote the ring‐opening polymerization of ?‐caprolactone.     

The Synthesis of Magnetic Core‐Shell Nanoparticles by Surface‐Initiated Ring‐Opening Polymerization of ε‐Caprolactone

Summary: The synthesis of core‐shell particles with a poly(ε‐caprolactone) (PCL) shell and magnetite (Fe₃O₄) contents of between 10 wt.‐% and 41 wt.‐% proceeds by surface‐initiated ring‐opening polymerization of ε‐caprolactone to give surface‐immobilized oligomers with between 1 400 g · mol⁻¹ and 11 500 g · mol⁻¹. The particles are dispersable in good solvents for the PCL shell. Magnetization experiments on the resulting superparamagnetic ferrofluids give a core‐size distribution with an average diameter, d_v, of about 9.7 nm.

TEM image of Fe₃O₄/PCL core‐shell particles cast from CHCl₃ dispersion.