超支化聚酯的合成及改性

以三羟甲基丙烷为核分子,二羟甲基丙酸为单体,合成了超支化聚酯。采用了IR、GPC、特性黏数和化学滴定等方法对产物进行了表征和分析。实验表明合成的超支化聚酯具有较窄的分子质量分布和较小的大分子流体力学半径,有类似球形的分子结构;得到的支化聚酯Mn=4.68×103g/mol,Mw=5.4×103g/mol,Mw/Mn=1.15,[η]=5.28 mL/g。进一步用油酸对聚合物进行改性,并研究了固含量与黏度的关系及其漆膜的性能;结果表明该树脂具有良好的成膜性和涂膜性能。     

二茂铁端基修饰的超支化聚（胺-酯）的合成与表征

首先以二乙醇胺和丙烯酸甲酯为原料,通过Michael加成反应制备A2B型前驱单体N,N-二羟乙基-3-氨基丙烯酸甲酯,然后以三羟甲基丙烷为反应中心核,采用有核准一步法合成羟端基超支化聚(胺-酯)(HPAE);最后利用二茂铁甲酸对HPAE进行端基改性,得到了二茂铁端基修饰的超支化聚(胺-酯)(HPAE-Fc)。HPAE-Fc的合成条件:w(催化剂)=2.5%(相对于反应物总质量),反应温度为140℃,反应物投料比n(OH)∶n(二茂铁甲酸)为1∶0.8,反应时间为4 h。采用FTIR、1HNMR、UV-vis、DSC和羟值等手段对HPAE-Fc的结构进行了表征,表明二茂铁基团成功地接枝到了HPAE分子表面,接枝率达70%。     

马来酸酯烯类支化单体合成及其与甲基丙烯酸的共聚

采用三羟甲基丙烷(TMP)和马来酸酐(MA)制备多官能度烯类支化单体单三羟甲基丙烷三马来酸单酯(MTPTM)。MTPTM与甲基丙烯酸(MAA)在水溶液中通过自由基聚合,制备超支化聚合物。采用NMR表征了MTPTM和超支化聚合物的结构。考察了MAA和MTPTM单体摩尔比对超支化聚合物相对分子质量、水溶液黏度、热稳定性以及玻璃化转变温度的影响。结果表明,随MAA单体用量增加,聚合物相对分子质量及其分布先降后升,n(MTPTM)∶n(MAA)=1∶9时出现最小值(Mw=2.09×104,Mw/Mn=1.66),产物水溶液黏度也呈现先降后升的趋势,并在n(MTPTM)∶n(MAA)=1∶6时出现最小值。而玻璃化转变温度则先升后降,n(MTPTM)∶n(MAA)=1∶9时出现最大值(Tg=274.5℃),MAA单体比例增加,有助于超支化聚合物热稳定性提高。     

酯端基超支化聚(胺-酯)的合成与表征

以乙醇胺和丙烯酸甲酯为原料,通过Michael加成反应合成了N-羟乙基-3-胺基-N,N-二丙酸甲酯AB2单体,并采用FT IR1、H NMR和元素分析对单体的结构进行了表征;以丁二酸酐为反应中心核,N-羟乙基-3-胺基-N,N-二丙酸甲酯为单体,制得了1~5代酯端基超支化聚(胺-酯)。采用核磁共振法对1~5代酯端基超支化聚(胺-酯)的支化度进行了表征,结果表明,由于采取的是加入中心核并逐步加入单体的有核准一步缩聚法,所合成的超支化聚(胺-酯)具有较高的支化度;凝胶渗透色谱测定的结果表明,超支化聚(胺-酯)的相对分子质量分布较窄,具有单分散性;超支化聚(胺-酯)的粘度较低且在多种溶剂中均有较好的溶解性,分解温度均高于170°C,具有良好的热稳定性。     

端羟基超支化聚合物的合成及对铬鞣革复鞣性能的影响

以二乙醇胺(DEA)和丙烯酸甲酯(MA)为原料,通过Michael加成反应制得AB2型单体;由"一步法"使单体与核(三羟甲基丙烷,TMP),在对甲苯磺酸(P-TSA)催化下,通过酯交换反应制得一种端羟基超支化聚(胺-酯)(HPAE)。经单因素实验筛选出了HPAE的最优合成条件:反应温度120℃、w(P-TSA)=2%(相对于单体与核的总质量)、反应时间4~5 h。用IR、GPC等手段对聚合物的分子结构进行了表征,并将HPAE应用于绵羊皮蓝湿革的复鞣。结果表明,HPAE-Ⅰ(第一代端羟基超支化聚合物)对皮样漂白作用明显,白度值增幅为19.8%;HPAE-Ⅲ(第三代端羟基超支化聚合物)可以显著提高铬鞣革撕裂强度,增幅为23.3%,抗张强度增幅为11.3%。     

支化型水性聚氨酯胶黏剂的合成及性能

采用异佛尔酮二异氰酸酯(IPDI)、聚四氢呋喃醚二醇2000(PTMG2000)为原料,二月桂酸二丁基锡、1,4-丁二醇和2,2-二羟甲基丙酸分别为催化剂、小分子扩链剂和亲水单体,制得水性聚氨酯预聚体(PPU);接着以丙烯酸甲酯、二乙醇胺和三羟甲基丙烷为原料合成了超支化聚(胺-酯)(HPAE);最后制备出不同HPAE含量(以IPDI与PTMG2000的总质量为基准,下同)的支化型水性聚氨酯(WPU)胶黏剂.采用FTIR和1HNMR对HPAE及胶黏剂的结构进行了表征;通过TGA、多功能材料试验机考察了胶膜的热力学性能和机械性能.结果表明,HPAE用量为IPDI与PTMG2000的总质量的1.0％时,制备的WPU2乳液及胶膜综合性能较好,其乳液固含量为33.67％,胶膜吸水率为11.22％,水接触角为90.32°;胶膜机械拉伸强度为10.33 MPa,断裂伸长率为533.73％;其粘结性能良好,剥离强度为4.063 N/mm.     

超支化界面剂的制备及其对PVC阻燃输送带粘合性能的影响

合成含有大量端羟基的超支化聚酰胺酯,用硅烷偶联剂KH560对其封端改性制成超支化界面剂,用超支化界面剂处理涤棉帆布带芯,制成聚氯乙烯(PVC)阻燃输送带。研究超支化界面剂对PVC输送带粘合性能的影响。结果表明:随着超支化界面剂浓度增大,输送带覆盖层与帆布带芯的层间粘合强度提高;第3代超支化界面剂(AB2型单体与核分子三羟甲基丙烷以物质的量比21∶1合成第3代超支化聚酰胺酯,第3代超支化聚酰胺酯与硅烷偶联剂KH560以物质的量比24∶1合成第3代超支化界面剂),其浓度为0.003 mol·L-1时输送带的层间粘合强度最高;使用超支化界面剂的输送带耐高温性能良好,在100℃时层间粘合强度保持率仍能达到75%以上;超支化界面剂的成本比硅烷偶联剂低,推荐浓度为2%~2.5%,超支化界面剂具有良好的经济性和工业化应用前景。     

超支化聚合物的研究及应用

以二异丙醇胺（DIPA）及酸酐为原料合成了含有一个羧基、两个羟基的AB2型单体,采用AB2型单体自缩聚的方法合成了超支化聚酰胺酯,然后用甲基丙烯酸对超支化聚酰胺酯的端基功能改性。然后将超支化单体与马来酸酐、甲基丙烯酸共聚合成阻垢分散剂。     

超支化聚(酰胺-酯)的合成及性能研究

以丁二酸酐和二乙醇胺为起始原料经加成反应合成新型AB2型单体,在溶液中采用“准 一步法”自缩聚反应合成超支化聚(酰胺-酯),使用傅里叶变换红外光谱、乌式粘度计、差热-热重联 用分析仪等测试分析超支化酰胺类聚合物的结构、粘度及热性能,红外光谱图分析进一步证实了聚合 物的超支化结构。实验表明封端剂对超支化聚合物的粘度有较大影响,封端产品粘度在0．019- 0．057 dL／g范围之间,而未封端产品粘度为0．146 dL／g。热分析中,超支化聚(酰胺-酯)的Td(热分 解温度)为316．3℃,Tg(玻璃态转化温度)为270℃;结果表明,超支化聚(酰胺-酯)具有较低的比浓 对数粘度、良好的溶解性和热稳定性等特点。     

超支化聚酯型环氧树脂的合成及表征

用多元酸酐与环氧氯丙烷开环聚合制备了端羟基超支化聚酯,在碱作用下对羟基封端的超支化聚酯进行了闭环反应合成了超支化聚酯型环氧树增,研究了碱及碱的用量对闭环反应的影响,通过DSC考察了超支化聚酯型环氧树脂/邻苯二甲酸酐固化体系的固化行为,计算出固化过程的2个固化反应活化能Ea分别为64 35kJ/mol和91 12kJ/mol,频率因子lnA分别为21 8和26 8。     

Photopolymerizable hyperbranched (meth)acrylated poly(amine ester)

A hyperbranched (meth)acrylated poly(amine ester) (HPAE‐2‐A) was synthesized by the modification of the hydroxyl end groups of the second generation of a hyperbranched poly(amine ester) with acryloyl chloride and methacrylic anhydride. The photopolymerization kinetics were investigated with photo‐differential scanning calorimetry and Fourier transform infrared. The properties of HPAE‐2‐A, including the dynamic viscosity, pendulum hardness, and shrinkage, were also studied in comparison with those of a hyperbranched methacrylated poly(amine ester) (HPAE‐2‐MA) prepared in the laboratory and traditional epoxy acrylate and epoxy methacrylate. HPAE‐2‐A polymerized rapidly under UV irradiation in the presence of a photoinitiator and had a higher final conversion of double bonds. The thermomechanical properties of UV‐cured HPAE‐2‐MA films were compared with those of EB‐cured films measured with a dynamic mechanical thermal analyzer. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 168–173, 2003     

Preparation and properties of hyperbranched poly(amine‐ester) films using acetal cross‐linking units

Novel films based on cross‐linked hyperbranched poly(amine‐ester) (HPAE) were prepared by cross‐linking the terminal hydroxyl groups of HPAE using glutaraldehyde (GA). The cross‐linking process was monitored by measuring the intrinsic viscosity of HPAE/GA in N,N‐dimethylacetamide. The surface structures of the cross‐linked HPAE films obtained from different HPAE/GA ratios were imaged using atom force microscopy, and their properties were characterized in terms of hydrophilicity, solvent swelling, mechanics, and protein adsorption. It was found that the static contact angle was <32.9°, tensile strength was >0.35 MPa, elongation at break was >9.2%, swelling degree was >63% in water, and bovine serum albumin adsorption was relatively low. The results indicate that cross‐linked HPAE films have a strong application potential in many areas. Copyright © 2005 Society of Chemical Industry     

Preparation and characterization of novel hyperbranched poly(amine‐ester) films crosslinked by glutaraldehyde

Novel films based on hydroxyl terminated hyperbranched poly (amine‐ester) (HPAE‐OH) of different generation were prepared by crosslinking the terminal hydroxyl groups of HPAE with glutaraldehyde (GA). The progress of crosslinking reaction was characterized by Fourier transform infrared (FTIR) and viscosity measurement. The surface morphology of the crosslinked HPAE films was characterized by field emission scanning electron microscope (FE‐SEM) and atomic force microscopy. The results suggested that the films have homogenously dense interior matrices and smooth surface. The hydrophilicity/hydrophobicity of the crosslinked HPAE films was characterized by the water contact angle measurement. Variable swelling behavior in different solvents was also studied. The in vitro biocompatibility of the film was investigated by the bovine hemoglobin (Hb) adsorption measurement. And these results showed that these crosslinked HPAE films had excellent hydrophilicity, variable swelling behavior in different solvents, and relative low protein absorption. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Reaction and characterization of crosslinking hyperbranched poly(amine-ester) with succine anhydride

Basing on hydroxyl terminated hyperbranched poly(amine-ester)s (HPAEs), the cross-linking reactions and preparation of ester-crosslinked HPAE films were investigated using succine anhydride (SA) as crosslink reagent. It was proved that the cross-linking reaction between HPAE and SA followed a two-step mechanism. This mechanism provides an efficient route to prepare HPAE/SA cross-linked films, in which, the precursor films were prepared by casting HPAE/SA solution at a lower temperature, and then curing the films at a higher temperature. By varying SA content, the solid HPAE/SA films with different cross-linking degrees were prepared successfully. The highest tensile strength of the cross-linked film could reach 59.60 MPa. With all water contact angle smaller than 74.3°, the crosslinked films demonstrated good hydrophilic properties. __________ Translated from Journal of East University of Science and Technology (Natural Science Edition), 2006, 32(10): 1,164–1,168 [译自: 华东理工大学学报 (自然科学版)]     

Micelles formed by self‐assembly of hyperbranched poly[(amine‐ester)‐co‐(D,L‐lactide)] (HPAE‐co‐PLA) copolymers for protein drug delivery

BACKGROUND: The aim of the work presented was to synthesize a series of amphiphilic hyperbranched poly[(amine‐ester)‐co‐(D ,L ‐lactide)] (HPAE‐co‐PLA) copolymers and study the formation of copolymeric micelles. These copolymeric micelle systems are expected to be potential candidates for applications in protein drug delivery. RESULTS: The chemical structures of the copolymers were confirmed by Fourier transform infrared spectroscopy, ¹³C NMR and thermogravimetric analysis. Fluorescence spectroscopy and dynamic light scattering confirmed the formation of copolymeric micelles of the HPAE‐co‐PLA copolymers. The maintenance of stability of bovine serum albumin (BSA) during release from micelles in vitro was also measured using circular dichroism and fluorescence spectrometry. CONCLUSION: Novel hyperbranched HPAE‐co‐PLA copolymers have been synthesized. Conjugation of PLA to HPAE was proved to be an available method for the preparation of micelles for protein delivery. The BSA‐loaded micelles showed enhanced encapsulation efficiency and the structural stability of BSA was retained during the release process. The hyperbranched polymeric micelles could be useful as drug carriers for protein drug delivery systems. Copyright © 2008 Society of Chemical Industry     

Synthesis and characterization of an amphiphilic hyperbranched poly(amine‐ester)‐co‐D,L‐lactide (HPAE‐co‐PLA) copolymers and their nanoparticles for protein drug delivery

A series of hyperbranched poly(amine‐ester)‐co‐D ,L ‐lactide (HPAE‐co‐PLA) copolymer were synthesized by ring‐opening polymerization of D ,L ‐lactide with Sn(Oct)₂ as catalyst to a fourth generation branched poly(amine‐ester) (HPAE‐OHs4). The chemical structures of copolymers were determined by FTIR, ¹H‐NMR, ¹³C‐NMR, and TGA. Double emulsion (DE) and nanoprecipitation (NP) method were used to fabricate the nanoparticles of these copolymers encapsulating bovine serum albumin (BSA) as a model. DSC thermo‐grams indicated that the nanoparticles with BSA kept stable below 40°C. Different factors which influence on particular size and encapsulation efficiency (EE) were investigated. Their EE to BSA could reach 97.8% at an available condition. In vitro release behavior of NPs showed a continuous release after a burst release. The stability maintenance of BSA in the nanoparticle release in vitro was also measured via circular dichroism and fluorescence spectrometry. The results showed that the copolymer nanoparticles have a promising potential in protein delivery system. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Synthesis,characterization, and properties of PCDL aliphatic hyperbranched polyurethane coatings

The isocyanate‐terminated polyurethane pre‐polymer (PPU) was synthesized via the step‐growth polymerization approach by using polycarbonate diol (PCDL, Mn = 2000) and isophorone disocyanate (IPDI) as monomers, dibutyltin dilaurate (DBTDL) as the catalyst. Subsequently, the hyperbranched polyurethane (HBPU) was synthesized by graft copolymerization using PPU, hyperbranched poly(amide–ester) polyol (HPAE) and 1,4‐butanediol (BDO). The molecular structure of HBPU was characterized by means of FTIR, ¹H‐NMR, and ¹³C‐NMR. It was observed that HBPU was synthesized as anticipated. The thermal and mechanical properties, the microstructure, and morphologies of the filmed HBPU and LPU (linear polyurethane) were tested, respectively. The filmed HBPU, revealed better thermal stability, and higher T_g accompanied with lower viscosity than those of filmed LPU. Additionally, the mechanical experiment showed that the filmed HBPU exhibited enhanced mechanical properties because it contained certain amounts of HPAE. Compared with its linear analog (LPU) specimen, the tensile strength of the filmed HBPU containing 10 wt % HPAE increased by 1.9 times (up to 28.15 MPa), and its elongation at break increased by 1.5 times (up to 543.8%), resulting from the dual effects of the hydrogen bonding and the crosslinking density in the HBPU system. The morphologies of filmed HBPU were characterized by means of WAXD and SEM, which indicated that increasing the content of HPAE lowers the crystallinity of HBPU. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 2671–2679, 2013     

Supramolecular Hyperbranched Poly(amino ester)s with Homogeneous Electron Delocalization for Multi‐Stimuli‐Responsive Fluorescence

Nonconventional luminogens without conjugated chromophores have attracted much interest for their intriguing fluorescence and potential wide applications. Their emission mechanism, however, remains an open question. Herein, hyperbranched poly(amino ester) (HPAE) with novel structure is synthesized through a simple one‐pot polycondensation reaction. The HPAE exhibits strong fluorescence and aggregation‐induced emission (AIE) characteristic. Transmission electron microscopy and theoretical calculation results demonstrate that the fluorescence is attributed from electron delocalization in the supramolecular self‐assemblies of HPAE. Meanwhile, supramolecular self‐assemblies, induced by the synergy effect of inter/intramolecular hydrogen bond and amphipathicity of HPAE, rigidify the molecule conformation, leading to enhanced fluorescence. Furthermore, the HPAE exhibits single‐color emission due to its generation of homogeneous electron delocalization. Interestingly, such HPAE shows multi‐stimuli‐responsive fluorescence to solvent, temperature, pH, and Fe³⁺. Therefore, this work not only provides an important step forward in exploring the emission mechanism of nonconventional luminogens, but also develops a multi‐functional unconjugated AIE probe.     

Reaction and characterization of crosslinking hyperbranched poly (amine-ester) with succine anhydride

Basing on hydroxyl terminated hyperbranched poly (amine-ester)s (HPAEs), the cross-linking reactions and preparation of ester-crosslinked HPAE films were investigated using succine anhydride (SA) as crosslink reagent. It was proved that the cross-linking reaction between HPAE and SA followed a two-step mechanism. This mechanism provides an efficient route to prepare HPAE/SA cross-linked films, in which, the precursor films were prepared by casting HPAE/SA solution at a lower temperature, and then curing the films at a higher temperature. By varying SA content, the solid HPAE/SA films with different cross-linking degrees were prepared successfully. The highest tensile strength of the cross-linked film could reach 59.60 MPa. With all water contact angle smaller than 74.3°, the crosslinked films demonstrated good hydrophilic properties.