对叔丁基苯甲酸改性超支化聚酯的合成和性能

以三羟甲基丙烷(TMP)为核,二羟甲基丙酸(bis-MPA)为AB2型单体,合成超支化聚酯(HBPE)。采用对叔丁基苯甲酸(PTBA)对其进行改性,得到PTBA取代度为10%~75%的超支化聚酯(HBP-10M~HBP-75M,统称HBP-Ms)。通过傅里叶变换红外光谱(FTIR)、核磁共振氢谱(1HNMR)和凝胶渗透色谱(GPC)对产物结构和相对分子质量(简称分子量,下同)进行表征,并考察HBP-Ms的溶解性和涂膜性能。研究结果表明,合成了支化度为0.47的HBPE,改性后的HBP-Ms具有良好的溶解性,可溶解在丙酮、DMF、乙酸乙酯、乙醚、苯和二甲苯,不溶于正己烷。HBP-Ms涂膜具有较高的硬度、光泽度和柔韧性,其中HBP-10M和HBP-25M具有更优异的溶解性和涂膜性能。TGA分析表明,PTBA可提高改性树脂涂膜的热稳定性。     

二元醇为核单体的超支化聚酯的合成与性能

分别以乙基丁基丙二醇(BEPD)、1,4-丁二醇(BDO)和新戊二醇(NPG)为核单体,二羟甲基丙酸为AB2型单体,对甲苯磺酸为催化剂,采用准一步法合成了第三代超支化聚酯(HBP-1、HBP-2和HBP-3)。采用FT-IR、1H-NMR和GPC对其结构和分子量进行表征并测定了超支化聚酯的特性黏度。以甲苯二异氰酸酯加成物为固化剂,研究了超支化聚酯的固化涂膜性能,使用热重分析仪(TGA)考察了超支化聚酯涂膜的热稳定性能。结果表明,三种核单体成功合成了超支化聚酯,以BEPD为核单体的超支化聚酯HBP-1具有最高的支化度达到0.55。GPC测得的分子量与理论分子量接近,且以BEPD为核的HBP-1分子量分布最低为1.68。超支化聚酯在极性溶剂中有较好的溶解性能,在非极性溶剂中不溶,其中HBP-1具有更好的溶解性能和较低的特性黏度(4.24 mL g 1)。超支化聚酯的固化涂膜具有较好的热稳定性、优异的附着力、柔韧性和较高的硬度。     

含柔性长链的超支化聚酯的合成及表征

以三羟甲基丙烷和己内酯为原料,辛酸亚锡为催化剂,经开环聚合得到含柔性长链的液态聚己内酯多元醇(PCLs)。再以PCLs为核单体,二羟甲基丙酸为臂,对甲苯磺酸为催化剂,经缩聚反应合成了两代超支化聚酯(HBPEs)。采用FT-IR、1H-NMR、GPC对HBPEs进行结构表征,结果表明:HBPE-2的支化度为0.44,相对分子质量与理论相对分子质量比较接近,HBPE-1和HBPE-2的相对分子质量分布系数分别为1.70和1.82,聚酯的代数增加后相对分子质量分布有所变宽。以TDI三聚体为固化剂,对超支化聚酯HBPEs涂膜性能进行测试。结果证明:根据结构设计所合成的超支化聚酯(HBPEs)的涂膜,与同类产物相比,涂膜耐冲击性和柔韧性更佳。其中第2代超支化聚酯的综合性能更优异,耐冲击性50 cm,柔韧性1 mm,铅笔硬度HB。     

以缩水甘油醚为核的星形羟基聚酯的合成及其涂膜性能

以三羟甲基丙烷三缩水甘油醚（TMPGE）为核分子,利用AB₂型单体2,2-二羟甲基丙酸与ε-己内酯开环反应产物及一元羧酸的羧基与TMPGE的环氧基反应,合成了系列星形羟基聚酯（SHPs）,研究了一元羧酸种类及原料配比对SHPs性能的影响。采用FTIR、¹H NMR对SHPs的分子结构进行表征,用GPC对其相对分子质量及分布进行了测试,并考察了其溶液黏度和特性黏度。测试了以甲苯二异氰酸酯/三羟甲基丙烷（TDI/TMP）加成物为固化剂制备的SHPs漆膜性能。SHP-2的溶液黏度低至220 mPa·s（80%固含）,用其制备的高固含涂料VOC低于320 g·L^-1,其漆膜具有优异的附着力、柔韧性和较高的硬度。     

核分子比例对超支化聚酯结构和涂膜性能的影响

以双季戊四醇为核,二羟甲基丙酸为单体合成了不同代数的超支化聚酯。采用了IR、GPC、13C NMR、DSC和化学滴定等方法对产物进行了表征和分析。试验结果表明聚合物具有较小的多分散性指数(拟两代超支化聚酯M—w/M—n=1.159,拟四代超支化聚酯M—w/M—n=1.028)。通过聚合物的13C NMR分析了超支化聚酯的支化度,表明在超支化聚酯中,端羟基的反应活性大于线性单元中羟基的活性。并用油酸对聚合物进行改性,研究了固含量与黏度的关系及其涂膜的性能;结果表明该树脂具有良好的成膜性和涂膜性能。     

一种用于喷墨墨水的超支化聚合染料的合成研究(英文)

本论文采用一步法,以季戊四醇作为B4核单体、2,2-二羟甲基丙酸作AB2型单体合成了超支化聚酯内核(HBPE),并对产物进行表征,计算超支化聚酯的支化度为0.41;探讨并建立了超支化聚酯的缩聚反应动力学方程-d[COOH]/dt=K[COOH][OH],该缩聚反应属于二级反应,反应速率由羧基浓度和羟基浓度共同决定。采用月桂酸改性超支化聚酯合成了新的长链烷基化的超支化聚合物(LHBP),并用红外和核磁共振谱图进行结构表征。溶解性质表明月桂酸改性超支化聚酯溶解于极性较弱的溶剂中,较未改性的超支化聚酯具有更好的有机溶剂溶解性。采用改性后的超支化聚酯内核(LHBP)和2-羟乙胺基蒽醌,通过IPDI偶联法合成了超支化聚合染料(R-LHBP)。     

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。     

以季戊四醇为核的超支化树脂的研究

以季戊四醇(B4)、2,2-二羟甲基丙酸(AB2)和对甲苯磺酸通过准一步熔融缩聚反应合成了常温为玻璃态的不同代数脂肪族超支化聚酯.采用13C NMR、FI-IR、GPC、DSC等方法对其结构和性能等进行了表征与分析.结果表明得到了高转化率、相对分子质量分布较窄、支化度较高且Tg在60～80℃的超支化聚酯.以甲基丙烯酸为反应试剂,对超支化聚酯进行部分端基改性,得到了粉末状改性超支化树脂,可以进一步为合成UV涂料主体树脂提供指导.     

超支化不饱和树脂改性不饱和聚酯涂料的制备及性能研究

为了进一步提高不饱和聚酯涂料的固化能力和涂膜的综合性能,用三羟甲基丙烷二烯丙基醚与异佛尔酮二异氰酸酯加成物对端羟基超支化聚酯进行改性制得超支化的不饱和树脂,再用所得的超支化不饱和树脂对线性不饱和聚酯进行改性,用傅里叶变换红外(FT-IR)、核磁共振(1H-NMR)、凝胶渗透色谱(GPC)、扫描电子显微镜(SEM)、热重分析(TG)等对产物进行表征与分析,结果表明,当超支化不饱和树脂添加量为30%时,所得涂料具有最优异的综合性能,表干时间39 min,铅笔硬度2H,柔韧性3 mm,耐冲击性45 cm,拉伸强度10.15 MPa,断裂伸长率13.06%,耐热性最好。     

超支化聚酯接枝剑麻微晶制备改性形状记忆聚氨酯

<正>本发明公开了一种超支化聚酯接枝剑麻微晶制备改性形状记忆聚氨酯的方法。分别制备剑麻微晶和端羧基超支化聚酯,二者反应制备超支化聚酯接枝剑麻微晶,将聚己内酯二元醇在氮气气氛下加热至80℃,磁力搅拌直至融化,然后加入N,N-二甲基甲酰胺和二月桂酸二丁基锡,加热至105℃保温15 min以脱     

Synthesis and characterization of PBTCA-modified hyperbranched polyether corrosion and scale inhibitors

In this study, hyperbranched polyether (HBP) with terminal hydroxyl was synthesized from tetrahydrofuran and glycidol by cationic open-loop polymerization and then modified by 2-phosphono-butane-1,2,4-tricarboxylic acid to introduce carboxyl and phosphorus to improve corrosion and scale inhibition. The structure of the products (HBPs) was determined by FTIR and ¹H-NMR. The scale inhibition efficiency (E) of calcium carbonate and calcium sulfate reached 99.74 and 97.10% at a concentration of 20 mg/L. X-ray diffraction and scanning electron microscopy were used to examine crystal type and morphology. The addition of scale inhibitors can inhibit the growth of the calcium scale crystal and destroy the crystal structure. The corrosion inhibition rate of HBPs can reach 72.98% when dosage was 150 mg/L. Polarization curve showed that HBPs was a kind of mixed corrosion inhibitor. The adsorption of HBPs on the surface of carbon steel conformed to Langmuir adsorption, which formed physical adsorption film and inhibited the corrosion process. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 48041.     

Synthesis and Characterization of Hyperbranched Linear Surfactants

A series of hyperbranched linear surfactants (HLS) was prepared by using oleic acid modifying the first generation hydroxyl-terminated hyperbranched polymer (HBP-1), which was obtained through a step synthesis method using trimethylolpropane and N,N-dihydroxyethyl dodecylamine -3-amine-methyl propionate (AB₂-type monomer). AB₂—type monomer was obtained through the Michael addition reaction of methyl acrylate and diethanol amine. Single-factor experiments were conducted to investigate the influences of reaction conditions such as temperature, oleic acid dosage, and reaction time on the synthesis of HLS. Results indicate that the optimal temperature and time of the esterification reaction were 130 °C and 3 h, respectively. The structures of HLS were characterized by Fourier transform infrared spectrophotometry (FT-IR) and the results indicate that HBP-1 had been successfully modified by oleic acid. Furthermore, the surface tension and the critical micelle concentration (CMC) of the HLS solution show that HLS can significantly reduce the surface tension of water.     

Cyclodextrin-based hyperbranched polymers by acyclic diene metathesis polymerization of an AB<Subscript>n</Subscript> monomer: molecule design,synthesis, and characterization

A novel cyclodextrin-based hyperbranched polymer (HBP) was synthetized via acyclic diene metathesis (ADMET) polymerization in homogeneous water/organic mixtures. A modified α-cyclodextrin (α-CD) molecule with one electron-rich terminal alkene and many electron-poor acrylates was first prepared through the esterification reaction, and then utilized as an AB_n-type monomer for subsequent ADMET polymerization between alkene and acrylate using the second generation Hoveyda-Grubbs catalyst, yielding HBP with the reaction time prolonged. The chemical structures of monomer and HBP were characterized by elemental analysis, IR, gel permeation chromatography with multiangle laser light scattering, and NMR measurements. The degree of branching was determined by using ¹H NMR spectroscopy and the values ranged from 0.51 to 0.42. Influence of the molecular weight on the properties (thermal stability and solubility) was also investigated. The resulting HBPs showed the good thermal stability, and higher molecular weight resulted in higher decomposition temperature from 361 °C to 383 °C. These thermally stable HBPs also displayed the excellent solubility in aprotic polar solvents.     

新型涂料用超支化聚酯酰胺聚合物的应用研究

以六氢苯酐和含氮二元醇为原料,合成了AB2单体和超支化聚酯酰胺聚合物。采用FT-IR、DSC-50、GC/MS和化学滴定等方法对得到的单体和聚合物的结构分别进行了表征和分析。实验表明合成的超支化聚合物是非结晶的,其玻璃化转变温度为67℃;聚合物的数均相对分子质量为1 689.04～3 752.6。进一步用油酸对聚合物进行改性,并研究油改性树脂溶液的流变性和以聚氨酯为固化剂配制成的涂料的涂层性能,结果表明该涂料在室温下快速固化,得到的涂层具有良好的涂膜性能。     

Fluorinated ?-caprolactone: Synthesis and ring-opening polymerization of new α-fluoro-?-caprolactone monomer

Fluorinated polyester was synthesized from a novel α-fluoro-?-caprolactone monomer (α-FCL). The monomer was synthesized from commercially available cyclohexene oxide in three steps. Baeyer-Villiger reaction using 3-chloroperoxybenzoic acid of the corresponding 2-fluorocyclohexanone resulted in formation of two isomeric lactones α-and-?-fluoro-?-caprolactones in 1:1.2 molar ratio, respectively. Poly(α-fluoro-?-caprolactone) was synthesized by bulk ring-opening polymerization of α-fluoro-?-caprolactone monomer (α-FCL) catalyzed by stannous octanoate, Sn(Oct)₂ at 120 °C for 6 h. Relationships between reaction time, polymer yield, and molecular weight were established. The ring-opening polymerization of ?-fluoro-?-caprolactone (?-FCL) produce geminal fluorohydrin, which is not stable and it is subsequently dehydrofluorinated to give the corresponding aldehyde. Copolymerization of α-FCL with ?-caprolactone (?-CL) in various feed ratios was also investigated. Detail microstructure analyses of the copolymers were accomplished from ¹H, ¹³C and 2-D NMR data. Presence of fluorine atoms is expected to regulate the chemical and physical properties of the polyester.     

Novel poly(ε-caprolactone)s bearing amino groups: Synthesis,characterization and biotinylation

A novel functional ε-caprolactone monomer containing protected amino groups, γ-(carbamic acid benzyl ester)-ε-caprolactone (γCABεCL), was successfully synthesized. A series of copolymers [poly(CL-co-CABCL)] were prepared by ring-opening polymerization of ε-caprolactone (CL) and γCABεCL in bulk using tin (II)-2-ethylhexanoate [Sn(Oct)₂] as catalyst. The morphology of the copolymers changed from semi-crystalline to amorphous with increasing γCABεCL monomer content. They were further converted into deprotected copolymers [poly(CL-co-ACL)] with free amino groups by hydrogenolysis in the presence of Pd/C. After deprotection, the free amino groups on the copolymer were further modified with biotin. The monomer and the corresponding copolymers were characterized by ¹H NMR, ¹³C NMR, FT-IR, mass, GPC and DSC analysis. The obtained data have confirmed the desired monomer and copolymer structures.     

双尾型丙烯酰胺类疏水缔合共聚物的合成与表征

通过光引发自由基聚合的方式,将双尾型丙烯酰胺类疏水单体(N-苯乙基-N-十四烷基甲基丙烯酰胺,PETMAM),与丙烯酰胺(AM)、丙烯酸(AA)等水溶性单体进行共聚,制备出双尾型疏水缔合水溶性共聚物(DTHAP),来解决丙烯酰胺类聚合物耐温抗盐性以及稳定性差的难题。通过测定聚合物溶液的表观黏度作为评价其性能的主要手段,考察了丙烯酸加量、盐、表面活性剂(SDS)含量、疏水单体含量等因素对聚合物性能的影响,从而确定了比较理想的反应条件。实验中发现:丙烯酸加量和表面活性剂含量的变化会影响聚合物的临界缔合行为;盐的引入能够显著降低表面活性剂的用量,提高聚合物的增黏效果;疏水单体含量较低时[0.35%～0.45%(mol)],聚合物可以表现出明显的增黏效果。当聚合物浓度为1 g·L^-1时,聚合物的黏度可以达到141.5 mPa·s,其临界缔合浓度(CAC)为0.75 g·L^-1左右。聚合物在120 g·L^-1的NaCl溶液和120 g·L^-1 NaCl、0.4 g·L^-1 CaCl₂溶液中,80℃下老化90 d,黏度分别为47.6 mPa·s和45.9 mPa·s。采用红外光谱、扫描电镜两种手段,表征了聚合物的结构。     

Hyperbranched polyurethane acrylates synthesized via copolymerization of monomers A2 and B3 with monofunctional compound BR added gradually at different rates

A kinetic model was proposed to describe hyperbranched polymers (HBPs) formed by the polymerization of monomers A₂ and B₃ with monofunctional compound (BR) added gradually in a semibatch reactor. The dependences of the degree of polymerization (DP) and the degree of branching on the reaction time and the monomer compositions were calculated. The DP of the HBPs could be increased by the slow addition of BR in the reactor. If the monomers B₃ and A₂ were mixed at a molar ratio of B₃:A₂ = 1:3, and the BR was fed slowly into the reactor, the HBPs with weight average DP were approximately 3200 and 16 700 at conversion of 0.95 and 0.99, respectively, which were higher than those prepared by the batch system. This theory was further verified by an experimental demonstration. Hyperbranched polyurethane acrylate can be synthesized with a higher DP in a semibatch system than in a batch reactor.     

Bio-based hyperbranched polyurethanes for surface coating applications

High performance vegetable oil based hyperbranched polymers are not only interesting but also very useful with respect to current scenario of advanced coating materials. So in the present study hyperbranched polyurethanes have been synthesized from the monoglyceride of Mesua ferrea L. seed oil, poly(?-caprolactone)diol, 2,4-toluene diisocyanate and glycerol without using any catalyst by a two-step one pot A₂ + B₃ approach. The linear analog (neglecting little possible branching due to different components of monoglyceride) of the hyperbranched polyurethane has also been prepared by the same method without using glycerol, just to compare with hyperbranched polymer. The formation of polymers was confirmed by FTIR, ¹H NMR, UV and SEM studies and measurements of hydroxyl value, solubility and viscosity. TGA results indicated the high thermal stability of hyperbranched and linear polymers (210–220 °C). The properties like tensile strength, impact strength, hardness, adhesion, flexibility, gloss, elongation at break and chemical resistance were influenced by the hard segment content of the polymers. The hyperbranched polyurethane with 30% hard segment content showed the optimum properties. The values of hydrodynamic diameter of hyperbranched polymers compared to the linear analog support the hyperbranched formation. Thus it confirms the formation of mechanically strong and thermally stable hyperbranched polyurethane coating materials from a vegetable oil.     

Thiol–ene networks and reactive surfaces via photoinduced polymerization of allyl ether functional hyperbranched polymers

A series of allyl ether functionalized hyperbranched (HB) polyester of three generations was synthesized from commercially available Boltorn^®. These modified HB polymers were homopolymerized to form films with a large number of residual allyl ether groups available for post film formation reactions. Additionally, the polyester multifunctional molecules were cured with a di and tetrathiol monomer in a one to one molar ratio to determine the effect of conversion on the resulting network thermal and physical properties. The same UV-cure chemistries were carried out with a similar second generation polyester dendrimer for comparison. This was in an effort to determine if there is any significant difference in the film chemical conversion and properties with dendrimers in comparison to HB molecules. The highly crosslinked films were obtained and characterized with respect to physical (DMTA) and thermal (DSC and TGA) properties.