聚乙二醇改性聚乳酸的合成与表征

以乳酸为原料,聚乙二醇为改性剂,氯化亚锡为催化剂,采用熔融缩聚法合成了聚乙二醇-聚乳酸接枝共聚物(PLEG),讨论了反应温度、反应时间、催化剂用量和聚乙二醇用量对产物黏均摩尔质量的影响。研究表明,最佳反应条件为:反应温度155℃,反应时间8 h,催化剂质量分数0.8%,聚乙二醇质量分数2.5%。通过红外光谱对共聚物化学结构进行分析,并通过X射线衍射(XRD)研究共聚物的结晶性能。     

马来酸酐改性端羟基乳酸预聚体的合成及性能研究

采用聚乙二醇（PEG）与乳酸反应,合成了端羟基乳酸预聚体（PLEG）。然后将PLEG与马来酸酐进行直接熔融缩聚得到改性聚乳酸（MPLA）。采用正交分析法探讨了原料比、反应温度、反应时间等工艺条件对MPLA相对分子质量的影响,并研究了MPLA的亲水性能、力学性能和在体外模拟生物环境中的降解特性。结果表明：马来酸酐与PLEG的质量比为1:15,在130 ℃反应15 h,MPLA的黏均相对分子质量最大为61564。相较于PLEG,MPLA的拉伸强度、弹性模量和断裂伸长率明显提高,亲水性得到改善。MPLA在体外模拟生物环境中的降解性能较好,其降解速率与马来酸酐含量有关。     

端羟基聚乳酸的扩链改性研究

乳酸与2,2-(1,3-亚苯基)-二恶唑啉(1,3-PBO)直接熔融缩聚成端羟基乳酸预聚物(PLBO),以聚乙二醇(PEG)和六亚甲基二异氰酸酯(HDI)聚合制得的端异氰酸酯基聚乙二醇(PEG-NCO)为扩链剂,以二月桂酸二丁基锡为催化剂,对PLBO进行扩链以制备可完全生物降解的聚酯氨酯(PEU)。采用乌氏黏度法、FTIR、DSC、XRD、TG、SEM等方法对各聚合物的结构和性能进行了表征。结果表明:以n(—OH)/n(—NCO)=1的比例投料、反应温度165℃、反应压力0.096 MPa、反应时间20 min为PLBO扩链反应的最佳条件;PEU的最大黏均分子量为44 700;PEG的引入使得PEU的玻璃化转变温度均小于PLA与PLBO,且柔韧性提高;PEU热稳定性提高,分解过程分为两步,第一步为PEU链段中的PLA失重,第二步为PEG-NCO链段的降解;PEU的结晶度降低,进一步说明扩链后聚合物的柔韧性增强。     

阳离子水性聚氨酯的合成及其在染整中的应用

采用逐步聚合法,选用异佛尔酮二异氰酸酯（IPDI）和聚乙二醇（PEG1000）为预聚单体,自制的端羟基季铵盐为阳离子扩链剂,利用亚硫酸氢钠对异氰酸酯基封端处理后对体系进行去离子水分散乳化,合成了一种反应型阳离子水性聚氨酯（WPU）固色剂,考察了预聚反应温度、nNCO／nOH比值以及扩链剂用量对阳离子WPU性能的影响。结果表明,当预聚反应nNCO／nOH比值为2．0、温度70℃,季铵盐扩链剂质量分数为9％（相对于预聚物）时,合成阳离子WPU性能较好;将其用于活性染料或直接染料染色棉织物的固色处理,耐皂洗牢度及耐摩擦色牢度效果良好,其中湿摩擦牢度能够达到4级。     

4，4-二苯基甲烷二异氰酸酯扩链聚乳酸的制备及表征

以D,L-乳酸单体为原料,使用无毒催化剂辛酸亚锡,通过熔融缩聚合成粘均分子质量接近5000的外消旋聚乳酸（PDLLA）后,再加入4,4-二苯基甲烷二异氰酸酯（MDI）对制得的低分子质量聚乳酸进行扩链。研究了反应时间、反应温度、催化剂用量及扩链剂用量对分子质量的影响,得出了最佳合成条件。     

间苯二胺扩链剂酰基化合成聚脲反应动力学研究

采用酰基化方法对扩链剂间苯二胺进行了改性,以减缓聚脲的高反应活性来研究合成反应的动力学方程。以间苯二胺、冰乙酸为原料,磷酸为催化剂合成了新型位阻型扩链剂二乙酰间苯二胺,并用红外光谱、高分辨质谱、凯氏定氮法和核磁共振氢谱分析确定了合成产物的化学结构。将它和端氨基聚醚、4,4’-二苯甲烷二异氰酸酯(MDI)通过两步溶液法合成了新型聚脲,考察了改性二胺扩链剂对聚脲性能的影响,并用傅里叶变换红外光谱仪(FTIR)跟踪该固化反应过程,得到了不同温度下的反应速度常数。实验结果表明,当用改性扩链剂代替原扩链剂合成聚脲时,凝胶时间大大延长。该反应体系表现为良好的一级动力学关系,并得出该反应的活化能。     

多官能度聚乙二醇的合成研究

以D-山梨醇为引发剂,二甲亚砜为溶剂,氢氧化钾为催化剂,环氧乙烷为单体,阴离子开环聚合合成了多官能度聚乙二醇。详细考察了催化剂、引发剂、溶剂、聚合温度等因素对聚合产物的性能影响。初步确定了聚合条件,聚合温度100～110℃,聚合时间6h。通过官能度的理论计算和测试证明合成的聚合物为多官能度聚乙二醇。     

L-乳酸低聚物的异氰酸酯扩链反应工艺研究

采用直接熔融缩聚法制备L-乳酸低聚物。在氮气氛围下,使用六亚甲基二异氰酸酯(HDI)、二苯基甲烷二异氰酸酯(MDI)作扩链剂,研究了反应时间、温度、反应官能团配比、低聚物粘均相对分子质量(Mη)等对扩链反应的影响,对扩链产物进行了红外光谱表征及差示扫描量热分析。结果表明:HDI和MDI对L-乳酸低聚物均有较好的扩链效果,扩链反应规律基本相同;HDI的扩链效果优于MDI,扩链反应速率快,扩链时间短,扩链产物Mη高、熔点高、热性能好;较佳扩链反应工艺参数:nNOC∶nOH为1:1,反应温度165℃,HDI扩链时间20 min、MDI扩链时间30 min,L-乳酸低聚物M越高,扩链产物M越高。     

不同投料比对直接熔融聚合法生物降解材料聚乳酸-聚乙二醇的影响

以氧化亚锡为催化剂(mc／mLA=0．005),以外消旋乳酸(D,L-LA)单体为原料,使其与数均相对分子质量为1000的聚乙二醇(PEG)共聚,通过直接熔融共聚法,在1650℃、70Pa下反应15h,合成了生物降解材料聚乳酸-聚乙二醇(PLEG)。发现最佳投料比为mu／mPEG=9时,可顺利地得到共聚产物PLEG,且其特性黏数[η]可达最高(0．4009dL/g),产物的亲水性能也得到改善,有利于PLEG作为药物缓释载体的应用。     

端羟基乳酸预聚物的合成

聚乳酸是一种性能优良的完全生物降解高分子材料,近年来被广泛应用于生物材料。实验以L 乳酸作为原料,采用直接熔融缩合聚合法制备扩链反应的端羟基乳酸预聚物。研究探讨二醇或聚乙二醇和催化剂种类及其用量等聚合条件对预聚物分子量的影响,并采用IR,GPC和1HNMR等测试手段对预聚物进行了表征。     

Degradation of poly(D,L‐lactic acid)‐b‐poly(ethylene glycol) copolymer and poly(L‐lactic acid) by electron beam irradiation

This article investigated the effects of electron beam (EB) irradiation on poly(D ,L ‐lactic acid)‐b‐poly(ethylene glycol) copolymer (PLEG) and poly(L ‐lactic acid) (PLLA). The dominant effect of EB irradiation on both PLEG and PLLA was chain scission. With increasing dose, recombination reactions or partial crosslinking of PLEG can occur in addition to chain scission, but there was no obvious crosslinking for PLLA at doses below 200 kGy. The chain scission degree of irradiated PLEG and PLLA was calculated to be 0.213 and 0.403, respectively. The linear relationships were also established between the decrease in molecular weight with increasing dose. Elongation at break of the irradiated PLEG and PLLA decreased significantly, whereas the tensile strength and glass transition temperature of PLLA decreased much more significantly compared with PLEG. The presence of poly(ethylene glycol) (PEG) chain segment in PLEG was the key factor in its greater stability to EB irradiation compared with PLLA. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

聚乳酸基离聚物的合成与表征

聚乳酸是一种绿色环保高分子材料。以丙交酯为单体,辛酸亚锡为催化剂,N-甲基二乙醇胺为引发剂通过丙交酯的开环聚合法制备了聚合物分子链中含有氨基官能团的双端羟基聚乳酸,然后以异佛尔酮二异氰酸酯作为扩链剂进行溶液扩链反应制备了聚乳酸基聚氨酯,然后再与冰醋酸、碘甲烷、溴乙烷反应,制备了以聚乳酸基聚氨酯为基体的离聚物。并采用特性粘数测定、GPC、差示扫描量热法、热重分析法、X射线衍射等方法对聚合物进行了表征。结果表明,聚乳酸基聚氨酯离聚物的特性粘数高于聚乳酸基聚氨酯,离聚物的热稳定性优于聚乳酸及聚乳酸基聚氨酯。     

Reaction Factors Influencing the Synthesis of Polystyrene-Polyurethane-Polystyrene Triblock Copolymer

Polystyrene-polyurethane-polystyrene (PS-PU-PS) triblock copolymer was synthesized by two-step polymerization. The first step, polyurethane (PU) prepolymers based on 2,4-toluene diisocyanate (TDI), hydrophilic poly(ethylene glycol) (PEG), hydroxyethyl acrylate (HEA), and ethylene glycol (EG), were prepared with ethylene glycol as a chain extender, dibutyltin dilaurate as a catalyst, and toluene as a solvent. The next step, polystyrene-polyurethane-polystyrene (PS-PU-PS) triblock copolymers, were prepared by free radical copolymerization between PU prepolymer and styrene (ST) monomer. Toluene and 2,2′-azobisisobutyronitrile (AIBN) were used as solvent and initiator, respectively. Fourier transform infrared spectroscopy (FT-IR) spectroscopy was used to characterize the structure of the copolymer. Influences of reaction temperature, reaction time, catalyst sorts, isocyanate monomer sorts, solvent sorts, and the concentration of initiator on the synthesis of the triblock copolymer were studied.     

熔融扩链反应制备PLA／PBAT多嵌段共聚物

以六亚甲基二异氰酸酯(HDI)为扩链剂,在催化剂辛酸亚锡作用下,通过熔融扩链反应制备了聚乳酸(PLA)/聚(己二酸丁二酯/对苯二甲酸丁二酯)(PBAT)多嵌段共聚物.研究了反应时间、温度、扩链剂用量等工艺条件对PLA/PBAT共聚物结构、相对分子质量的影响.用红外光谱仪、核磁共振仪、偏光显微镜等分析手段对PLA、PBAT和PLA/PBAT共聚物进行了分析表征.结果表明,通过扩链反应,PLA的分子链中引入了新的嵌段,其相时分子质量及柔韧性大幅度提高.     

阳离子可染聚酯酯型改性剂的合成研究

以质量分数15%的硫酸为催化剂,将己二酸与乙二醇进行酯化反应,合成了阳离子可染聚酯的改性剂己二酸乙二醇酯,对催化剂用量、反应温度、反应时间、投料比等因素进行了探讨,采用红外光谱法对产物进行了表征。结果表明:当催化剂质量分数为0.05%,乙二醇:己二酸(摩尔比)为3.2:1,反应温度115~120℃,反应时间3.5 h时,其酯化率超过90%,且粘度低于0.05 Pa.s。红外光谱分析表明,产物中含有酯键,说明己二酸与乙二醇发生了酯化反应。     

Syntheses of poly(lactic acid)‐poly(ethylene glycol) serial biodegradable polymer materials via direct melt polycondensation and their characterization

Directly starting from lactic acid (LA) and poly(ethylene glycol) (PEG), biodegradable material polylactic acid‐polyethylene glycol (PLEG) was synthesized via melt copolycondensation. The optimal synthetic conditions, including prepolymerization method, catalyst kinds and quantity, copolymerization temperature and time, LA stereochemical configuration, feed weight ratio m_LA/m_PEG and M_n of PEG, were all discussed in detail. When D ,L ‐LA and PEG (M_n = 1000 Da) prepolymerized together as feed weight ratio m_{D ,l‐LA}/m_PEG = 90/10, 15 h copolycondensation under 165°C and 70 Pa, and 0.5 wt % SnO as catalyst, gave D ,L ‐PLEG1000 with the highest [η] of 0.40 dL/g, and the corresponding MW was 41,700 Da. Using L ‐LA instead of D ,L ‐LA, 10 h polymerization under 165°C and 70 Pa, and 0.5 wt % SnO as catalyst, gave L ‐PLEG1000 with the highest [η] of 0.21 dL/g and MW of 15,600 Da. Serial D ,L ‐PLEG with different feed weight ratio and M_n of PEG were synthesized via the simple and practical direct melt copolycondensation, and characterized with FTIR, ¹H NMR, GPC, DSC, XRD, and contact angle testing. D ,L ‐PELG not only had higher MW than PDLLA, PLLA and L ‐PELG, but also better hydrophilicity than PDLLA. The novel one‐step method could be an alternative route to the synthesis of hydrophilic drug delivery carrier PLEG instead of the traditional two‐step method using lactide as intermediate. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 577–587, 2006     

Glycolyzed products from PET waste and their application in synthesis of polyurethane dispersions

Soft drinks poly(ethylene terephthalate) (PET) bottles were depolymerized by glycolysis with different molar ratio of glycol, such as propylene glycol (PG), triethylene glycol (TEG) and poly(ethylene glycol) (PEG 400), in the presence of a zinc acetate catalyst. These glycolyzed products were characterized by hydroxyl value (HV) determinations. The obtained glycolyzed products were reacted with isophorone diisocyanate (IPDI), dimethylol propionic acid (DMPA), as potential ionic center for water dispersibility, and mixed with ethylene diamine (EDA) as extender chain to prepare polyurethane dispersions. The PET glycolyzed products and polyurethane formation were characterized using Fourier transform infrared spectroscopy (FTIR). The molecular masses distribution of oligoester polyol and polyurethane dispersions were determined by using gel permeation chromatography (GPC). The effect of different PET/glycol molar ratio, on the physico-mechanical properties, such as hardness, adhesion test and gloss of polyurethane films were investigated. Thermal properties were investigated by thermogravimetric analysis (TG) and differential scanning calorimetry (DSC).     

ATRP法合成两亲性聚乙二醇-聚丙烯酸叔丁酯嵌段共聚物

以mPEG-Br为大分子引发剂,CuBr/PMDETA为催化体系,采用原子转移自由基聚合法(ATRP)合成了两亲性嵌段共聚物聚乙二醇-聚丙烯酸叔丁酯(mPEG-b-PtBA),并采用FT-IR,1H-NMR和GPC等表征了聚合物的结构.考察了单体与引发剂的配比、反应时间、反应温度及催化剂与配体的比例等因素对产物的分子量...