有机锡化合物引发D,L-丙交酯的开环聚合

D,L-丙交酯在有机锡化合物四苯基锡(Ph4Sn)、三正丁基醋酸锡(Bu3SnOAc)、辛酸亚锡(SnOct2)等催化剂引发下开环聚合,得到高分子量的聚D,L-乳酸,讨论了聚合单体D,L-丙交酯纯度、聚合温度、聚合时间、聚合体系真空度以及引发剂有机锡催化剂与聚合单体D,L-丙交酯的比例对聚D,L-乳酸合成的影响,通过红外光谱和核磁共振光谱对聚D,L-乳酸的结构进行了表征。实验结果表明,D,L-丙交酯开环聚合反应的较佳工艺路线是:D,L-丙交酯重结晶5次,聚合温度140℃,聚合时间24 h,聚合体系真空度13.3~133.3 Pa,引发剂有机锡催化剂与单体D,L-丙交酯比例0.2‰~0.5‰,此时聚D,L-乳酸的粘均分子量最高,分别达到32.46×104,33.43×104和41.36×104。     

萘钾及乙醇钾引发L-丙交酯开环聚合研究

分别以萘钾和乙醇钾为引发剂成功地引发了L-丙交酯的开环聚合,考查了不同的单体/引发剂(M/I,物质的量比)在不同的反应时间下对聚L-乳酸(PLLA)相对分子质量及其分布的影响。以FT-IR1、H-NMR、GPC和粘均相对分子质量测试等对所得PLLA进行了表征,结果表明,通过改变M/I,2种引发剂都能够有效地控制PLLA的相对分子质量;PLLA的相对分子质量分布随反应时间的增加而变宽,其中乙醇钾的引发活性比萘钾的高,得到PLLA的相对分子质量比萘钾引发时大,相对分子质量分布也较窄。     

Dispersion polymerization of L-lactide in supercritical carbon dioxide

Triblock (A-B-A) oligomers of ε-caprolactone (ε-CL) (A) and poly(ethylene glycol) with an average molecular weight of 400 (PEG400) (B) were synthesized with three different molecular weight in the range of 2–6 kDa by changing the ratio of PEG400/ε-CL. These oligomers were then used in dispersion polymerization of L-lactide in supercritical carbon dioxide (scCO₂) as stabilizers. 5% stabilizer in the polymerization recipe allowed synthesis of poly(L-lactide) (PLLA) in scCO₂ in the powder form with a weight average molecular weight of around 60 kDa with polymerization yields around 80%. Interestingly, there was almost no effect of stabilizer molecular weight on polymerization. L-lactide polymerization in scCO₂ without any stabilizer was also possible but both the PLLA molecular weight and polymerization yield were lower, and the product was as aggregates instead of powders. A stabilizer concentration of 5% in the polymerization recipe was found adequate. Further increases in the stabilizer load resulted lower molecular weights and lower yields.     

不同催化体系下L-丙交酯的合成及表征研究

以乳酸为单体,采用先缩聚后解聚的方法制备了L-丙交酯。首先通过正交实验较系统的研究了合成工艺,包括三种不同催化剂(锌粉、乙酸铜及辛酸亚锡)用量、脱水温度及裂解温度对产物收率的影响；进而考察了提纯方法对丙交酯最终产率及杂质(乳酸、水)含量的影响,并利用红外、热分析及核磁共振技术对产物结构进行了详细表征。结果表明,在辛酸亚锡催化下,脱水及裂解温度分别为130℃及190℃时,L-丙交酯单体的产率达到80%；通过多次重结晶可以得到较高纯度产物。     

Synthesis of Poly-L-Lactide for Scaffold Materials by Melt-Solid Polycondensation

Poly-L-lactide (PLLA) with low viscosity average molecular mass for scaffold materials was synthesized by melt-solid condensation polymerization and characterized by IR, XRD, and ¹H-NMR. The influences of catalyst (LaCl₃/C₇H₈SO₃) concentration, polymerization temperature and polymerization time on the viscosity average molecular mass of poly-L-lactide acid (PLLA) were investigated. Poly-L-lactide with a viscosity average relative molecular mass of about 7.2 × 10⁴ was obtained when melt-solid polycondensation was conducted with first preheating at 110°C for 4 h and solid polycondensation at 150°C for 20 h; the catalyst concentration was 0.4 wt. %. PLLA was made into porous materials by using sodium hydrogen carbonate particulates as the porogen to foam. Scanning electron microscope observation indicates that the sample is highly porous and well distributed with good interconnections between pores and the pore size of porous materials in the range of 300–500 μm and it can be used as scaffold for bone tissue engineering.     

Calcium methoxide initiated ring-opening polymerization of ε-caprolactone and L-lactide

Summary A commercial calcium dimethoxide and an in-situ generated calcium methoxide prepared from bis(tetrahydrofuran)calcium bis[bis(trimethylsilyl)amide] and methanol, were investigated as initiators for the ring-opening polymerization of ε-caprolactone and L-lactide. Commercial calcium dimethoxide initiated rapid ε-caprolactone polymerization at 120°C in bulk to give quantitatively a polymer with a polydispersity index around 1.3. Significant racemization was observed for L-lactide polymerization. The In-situ formed calcium methoxide promoted the solution polymerization of both ε-caprolactone and L-lactide to high conversion at room temperature over a short time period, yielding the corresponding polyesters with narrow molecular weight distribution. NMR spectra showed that the poly(L-lactide) isolated had a purely isotactic microstructure. The initiator efficiency could be tuned by varying the molar ratio of methanol and bis(tetrahydrofuran)calcium bis[bis(trimethylsilyl)amide]. Received: 11 August 2000/Revised version: 21 December 2000/Accepted: 3 January 2001     

低真空条件下D,L-丙交酯的合成研究

为了提高D,L-丙交酯的收率,研究了D,L-乳酸为单体,低真空条件下使乳酸单体先缩聚后解聚制备D,L-丙交酯的工艺条件。考察了制备过程中脱水温度、脱水率、催化剂量、聚合温度和解聚温度对丙交酯产率的影响。结果表明,以ZnO为催化剂,用量为1.2%,在全程低真空条件下,乳酸分别在120~160℃脱水和220~250℃解聚,以无水乙醇和乙酸乙酯作为溶剂改进了粗产品的提纯方法,可得到产率达40.2%的丙交酯。毛细管熔点法测定了产物的熔点,并用红外光谱、差示扫描量热法、X-射线衍射分析对产物进行了分析表征。所得产物为高纯的环状丙交酯。     

Preparation of high molecular weight poly(N‐vinylcarbazole) in high yield by low‐temperature precipitation polymerization of N‐vinylcarbazole

To produce high molecular weight poly(N‐vinylcarbazole) (PVCZ) with high conversion, N‐vinylcarbazole (VCZ) was heterogeneously polymerized in methanol at 30, 40 and 50 °C using a low temperature initiator, 2,2′‐azobis(2,4‐dimethylvaleronitrile) (ADMVN), and the effects of polymerization temperature and concentration of initiator and solvent on the polymerization behaviour and molecular parameters of PVCZ investigated. Globally, experimental results correspond to predicted ones. Low polymerization temperature using ADMVN and a heterogeneous system using methanol proved to be successful in obtaining poly(N‐vinylcarbazole) (PVCZ) of high molecular weight and high conversion with small temperature rise during polymerization, although free radical polymerization by azoinitiator was used. The polymerization rate of VCZ in methanol at 30 °C is proportional to the 0.88th power of ADMVN concentration. The molecular weight is higher and the molecular weight distribution is narrower with PVCZ polymerized at lower temperatures. For PVCZ produced in methanol at 30 °C using an ADMVN concentration of 0.0001 mol/mol of VCZ, a weight average molecular weight of 1 750 000 g mol⁻¹ is obtained, with a polydispersity index of 1.82 © 2000 Society of Chemical Industry     

Modeling of poly(L‐lactide) thermal degradation: Theoretical prediction of molecular weight and polydispersity index

A mathematical model to describe the molecular weight and polydispersity index (Q) in poly(L ‐lactide) (PLLA) thermal degradation has been developed. Based on the random chain scission mechanism, effects of temperature and time on the molecular weight and polydispersity index are included in this model. It incorporates the degradation and recombination reaction of PLLA thermal degradation, while taking into account the equal probability assumption. The developments of molecular weight and polydispersity index of PLLA polymer in the thermal degradation process were investigated at temperature ranging from 180–220°C, the experimental data show PLLA reaches its thermal degradation equilibrium in 2 h. The simulated results of this model are compared with the measured molecular weight and polydispersity index of the PLLA polymer. The changes of the molecular weight and polydispersity index in the PLLA thermal degradation can be predicted by this model. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 2557–2562, 2003     

Effect of soft segment on degradation kinetics in polyethylene glycol/poly(l-lactide) block copolymers

Summary The hydrolytic degradation of polyethylene glycol(PEG)/poly (L-lactide)(PLLA) copolymers with various PEG wt% contents at 37°C and pH=7 was studied by differential scanning calorimetry(DSC) and gel permeation chromatography(GPC). The effect of PEG contents in PEG/PLLA copolymers on the crystalline morphology and hydrolytic degradation rate was investigated. Due to the hydrophilic PEG segments in PEG/PLLA copolymers, the exothermic recrystallization and the shoulder portion of melting endotherm appear immediately following the hydrolysis of copolymers. Moreover, after a period of hydrolysis of 100 h. the molecular weight distribution turn to a bimodal shape from a unimodal in the original, and the polydispersity becomes greater with a value from 1.5 up to 5, which are not observed for PLLA homopolymer. The rate constants of hydrolysis for the first-order auto-catalytic kinetics, increase with the PEG content over 0 to 18.3 wt%, ranging from 1 to 6x10^-4hr^-1.     

沉淀聚合制备低分子量聚丙烯酸及残液循环利用

以偶氮二异丁腈(AIBN)为自由基引发剂,石油醚为溶剂,异丙醇为链转移剂,通过沉淀聚合制备了低相对分子质量(简称分子量,下同)的聚丙烯酸。考察了引发剂用量、链转移剂用量、单体质量浓度对聚合收率的影响,确定最佳聚合条件为:AIBN用量为单体质量的10%,链转移剂用量为单体质量的100%,单体质量浓度100g/L,反应温度80℃,反应时间4 h。反应结束后产品在底部沉淀析出,溶剂可循环利用,在最佳聚合条件下,残液循环利用5次,单体的累计转化率达到92.6%。凝胶渗透色谱(GPC)分析表明,通过残液循环制备的产品重均分子量(Mw)变化不大,保持在1 000～1 300,多分散性(PDI)为1.92～3.38。     

Solution polymerization behavior of N‐vinylcarbazole by low‐temperature azoinitiator

N‐Vinylcarbazole (VCZ) was solution polymerized in 1,1,2,2,‐tetrachloroethane (TCE) at 30, 40, and 50°C using a low‐temperature initiator, 2,2'‐azobis(2,4‐dimethylvaleronitrile) (ADMVN); the effects of polymerization temperature and concentrations of initiator and solvent were investigated. On the whole, the experimental results corresponded to predicted ones. Low‐polymerization temperature using ADMVN proved to be successful in obtaining poly(N‐vinylcarbazole) (PVCZ) of high molecular weight with smaller temperature rise during polymerization, nevertheless of free radical polymerization by azoinitiator. The polymerization rate of VCZ in TCE was proportional to the 0.46 power of ADMVN concentration. The molecular weight was higher and the molecular weight distribution was narrower with PVCZ polymerized at lower temperatures. For PVCZ produced in TCE at 30°C using ADMVN concentration of 0.00005 mol/mol of VCZ, weight‐average molecular weight of 271 000 was obtained, with polydispersity index of 1.66. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 76: 1558–1563, 2000     

甲基丙烯酸二甲氨基乙酯的ATRP聚合

2-溴代异丁酸-Ⅳ-丁二酰亚胺酯（NHS—BIBA酯）由2-溴代异丁酸和,v-羟基丁二酰亚胺通过酯化反应制得。以它为引发剂,2,2＇-联吡啶（bpy）／CuBr为催化体系、水为溶剂,采用原子转移自由基聚合（ATRP）合成了带有功能基团的聚甲基丙烯酸二甲氨基乙酯（PDMAEMA）高分子。研究了引发剂、温度、反应时间、pH值和浓度对聚合产率的影响,利用凝胶渗透色谱（GPC）和核磁共振（1HNMR）测定了聚合物的分子量、多分散指数（PDI）和链结构。由GPC可知在最高产率下,Mn和Mw／Mn分别为8674和1．59,结果表明,NHS-BIBA酯引发的PDMAEMA实际数均分子量高于理论分子量,并具有低分散度,链结构上氢原子出峰符合特有的化学位移。     

High-pressure polymerization of ethylene using methyl isobutyl ketone peroxide as initiator

An investigation was carried out into the suitability of methyl isobutyl ketone peroxide (MIKP) as initiator for the high pressure polymerization of ethylene. For this purpose, polymerization tests were carried out in a stirred autoclave at a pressure of 1000 to 2000 bar and a temperature of 195 to 310°C. The initiator concentration of the feed was varied between 6.5 and 42 mol ppm while the residence time was kept at a constant 30 s. Apart from the rate of polymerization, the conversion and the initiator consumption were also determined. The characteristic properties of polyethylene (PE) were determined by measuring the melt flow index, the density and, in some cases, the molecular weight distribution. Conversion levels of 5 to 27% were achieved with rates of polymerization between 1 and 5.5 kg PE l^?1 h^?1. The initiator consumption at 1700 bar was in the region of 1 to 2 g I kg^?1 PE^?1 over a temperature range of 220 to 315°C. In view of these results, MIKP can be considered as suitable to initiate ethylene high pressure polymerization at 220 to 310°C, particularly in the tubular reactor. The density of the polyethylene thus prepared is ranging between 0.910 and 0.927 g ml^?1. Without the addition of modifiers or cross-linking agents, the melt flow index varies considerably. The polydispersity of the polymers prepared at a pressure of 1700 to 2000 bar was between 6 and 8 and therefore within the range to be expected for stirred autoclaves. Reducing the pressure to 1000 bar resulted in surprisingly low polydispersity values of 2.4 to 3.7.     

Tert‐butyl peroxyacetate initiated semibatch polymerization of 1,1‐difluoroethylene in supercritical carbon dioxide

Due to its inertness and solubility in vinylidene fluoride, (VF2), supercritical carbon dioxide is used as a replacement solvent for producing polyvinylidene fluoride (PVDF). tert‐butyl peroxyacetate (TBPA) was evaluated for the first time as a free radical initiator for radical chain polymerization of VF2 producing PVDF without use of a dispersion agent in a semibatch reactor using supercritical carbon dioxide. Diethyl peroxydicarbonate (DEPDC) at 75°C has been evaluated in many publications as an initiator in batch and continuous reactors for polymerization of VF2 in supercritical carbon dioxide. The effects of monomer and initiator concentration, agitation, and reaction time upon average molecular weight and polydispersity were evaluated using TBPA as an initiator at 104°C and compared with DEPDC initiated polymerization. It was found that as agitation rate, monomer concentration, and reaction time increased, the average molecular weight of PVDF using TBPA as an initiator increased. Lower concentrations of TBPA were needed compared to DEPDC to produce comparable molecular weights of PVDF. Using TBPA as an initiator at the conditions investigated resulted in lower polydispersity at similar monomer concentrations compared to DEPDC. Average molecular weights using TBPA ranged from 49,900 g/mol to 1.3 million g/mol and polydispersity ranged from 1.3 to 5.4. POLYM. ENG. SCI., 56:435–440, 2016. © 2016 Society of Plastics Engineers     

Properties of stereo multi-block polylactides obtained by chain-extension of stereo tri-block polylactides consisting of poly(L-lactide) and poly(D-lactide)

Stereo multi-block polylactides (multi-sb-PLA) having controlled block sequences of poly(L-lactide) (PLLA) and poly(D-lactide) (PDLA) were synthesized by chain-extension of stereo tri-block polylacitdes (PLLA-PDLA-PLLA) that were readily synthesized by two-step ring-opening polymerization (ROP) of D- and L-lactides. The weight-average molecular weight of the resultant multi-sb-PLAs reached about 14.3?×?10⁴ Da. These multi-sb-PLAs were found to exclusively form stereocomplex (sc) crystals without homo-chiral (hc) crystallization occurring because the quickly formed sc crystals effectively suppressed the hc crystallization as cross-linkers. Their thermal properties could be tuned by controlling the block lengths of PLLA-PDLA-PLLA in the two-step ROP. Particularly, the multi-sb-PLAs consisting of longer PLLA and PDLA blocks in 1:1 ratio exhibited higher sc crystallinity and thermo-mechanical properties after thermal annealing.     

生物可降解聚乳酸的制备及其性能研究

以L-乳酸(LLA)为原料合成L-丙交酯,通过L丙交酯开环聚合制备高分子量的聚乳酸(PLA)。考察反应温度、反应时间以及催化剂用量对PLA的影响,获得优化的聚合工艺条件。GPC测得PLA的重均分子量可达21.9×104g/mol。FTIR和旋光度测试表明产物为聚L-乳酸(PLLA)。DSC和XRD测试证明:PLLA为结晶性材料,熔点为170℃,属于α'-和α-相共存的混合晶型。拉伸测试表明:高分子量的PLLA具有良好的力学性能。     

Stannous octoate-versus zinc-initiated polymerization of racemic lactide

Summary Racemic lactide (D,L-lactide) was bulk-polymerized comparatively using stannous octoate and zinc metal as initiators. A two-level fractional factorial design was used to assess the influence of selected experimental variables with respect to intermolecular transesterification, whose extent in the resulting high molecular weight poly(D,L-lactide)s (PLA50) was investigated by¹³C NMR. Five variables, namely polymerization temperature, monomer-to-initiator ratio, polymerization time, nature of the initiator and monomer degassing-time, were found significant and were ranked according to their average effect on transesterification. A significant interaction of polymerization temperature and polymerization time was also detected. Zinc led to lower stereoregularity than stannous octoate.     

聚D,L-丙交酯合成方法研究

以辛酸亚锡为催化剂,研究开发了环境友好材料聚D,L-丙交酯(PDLLA)的合成方法。探讨了单体丙交酯纯度、催化剂辛酸亚锡用量、反应时间、反应温度及真空度对聚合物相对分子质量的影响。实验结果表明,重结晶4次后的丙交酯作为单体,在辛酸亚锡摩尔分数为0.1%—0.18%,真空度0.098 MPa,聚合温度150—160℃下聚合6—8 h可获得粘均相对分子质量Mη大于20×104的聚D,L-丙交酯。分别采用FTIR和1H-NMR对产物的结构进行了表征。     

Multifunctional Initiator with Platinum-Acetylide Dendritic Core for Living Polymerization of Isocyanides

A novel multifunctional initiator has been developed by peripheral modification of a Pt-acetylide dendrimer. Pd–Pt μ-ethynediyl units were introduced to the first-generation dendrimer by a divergent method. The dendritic initiator was applicable to the living polymerization of aryl isocyanides, producing high molecular weight polymers with a narrow polydispersity index in quantitative yields. The ³¹P NMR spectrum of the resulting polymer suggested that all Pd–Pt μ-ethynediyl units in the dendritic molecule actually functioned as an initiator.