两亲性超支化聚酯-酰胺的制备及其性能

引言 在同一分子中,既含有亲水性链段,又含有疏水性链段的聚合物称为两亲性聚合物,这种聚合物的凝聚态常具有多相结构,并对不同极性的化合物都具有一定的亲和力,这种独特的性质就使其既不同于低分子表面活性剂也异于一般的离子聚合物.带有亲水性支链的两亲性聚合物具有很大的应用潜能.可以用作乳液和分散体的稳定剂,颜料及塑料的表面改性剂,高分子材料的助剂及改性剂等[1-2].     

超支化聚(酯-酰胺)对超高摩尔质量聚乙烯的加工流动改性

采用超支化聚合物(HBP)改善超高摩尔质量聚乙烯(UHMWPE)的加工流动性。在摩尔质量为200万级的UHMWPE中加入3％的HBP，可使其熔融扭矩值下降约85％；对混合熔体的形态分析证明，HBP分子更易于在混合熔体的表面富集；初步认为HBP通过降低混合熔体的表观粘度来改善UHMWPE的加工流动性。     

Synthesis of poly(propylene-glycol-diacrylates) and properties of the photocured networks

A series of poly(propylene-glycol-diacrylates) (PPGDA) having molecular weights (MW) in the range 300–3,000 and an acrylic functionality near to two were synthesized by acrylation of the corresponding hydroxy-terminated oligomers with acrylic acid in the presence of p-toluensulphonic acid as a catalyst. The M¯_n of the acrylated products was found slightly lower than that of the starting oligomers, indicating the occurrence of an acidic degradation reaction which does not influence the acrylic functionality. The acrylated oligomers were ultraviolet (UV) cured until a complete double bond disappearance was obtained: only in the presence of tripropylene-glycol-diacrylate (TPGDA) were small amounts of residual unsaturations revealed. Rubbery materials were usually obtained, with the exception of TPGDA. The properties of the cured PPGDA were investigated by means of differential scanning calorimetry, thermomechanical analysis, and dynamic mechanical thermal analysis. The T_g values were found to decrease by increasing the MW of the used oligomers, that is, by increasing the length of the chain between the two acrylic double bonds. A good agreement with the Nielsen equation was found. Moreover, the equilibrium swelling values in water were measured; the obtained values were interpreted in terms of the solubility parameters of the oligomers and of the crosslinking density of the networks. Finally, some mixtures of PPGDA oligomers with a typical epoxy-acrylate resin were UV cured; their properties confirm the high flexibilizing effect of the PPGDA oligomers. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 65:491–497, 1997     

UV固化超支化聚酯的合成及性能研究

以马来海松酸(MPA),环氧氯丙烷(ECH)合成了超支化聚酯(HBPE),通过丙烯酸羟乙酯(HEA)对HBPE改性合成了涂料可用UV固化超支化聚酯。采用GPC,FT-IR,DSC等对产物结构进行了表征,研究了原料配比、加料方式和反应温度等对产物的影响,并考察了其光固化行为,测试了固化膜的性能。结果表明,HBPE合成最佳条件:n(MPA)∶n(ECH)=1∶1,反应温度90℃,HBPE与HEA最佳物质的量比为1∶2。该UV固化超支化聚酯固化膜附着力1级,抗冲击力40 kg/cm,铅笔硬度4H,耐甲乙酮100,可作为UV固化涂料中的主体树脂。     

Glass transition and structural relaxation in semi-crystalline poly(ethylene terephthalate): a DSC study

The aim of this work is to determine the relaxation times of the cooperative conformational rearrangements of the amorphous phase in semi-crystalline poly(ethylene terephthalate) (PET) and compare them with those calculated in amorphous PET. Samples of nearly amorphous polymer were prepared by quenching and samples with different crystallinity fractions were prepared from the amorphous one using cold crystallisation to different temperatures. The differential scanning calorimetry (DSC) thermograms measured on samples rapidly cooled from temperatures immediately above the glass transition show a single glass transition which is much broader in the case of high-crystallinity samples than in the amorphous or low-crystallinity PET. To clarify this behaviour, the samples were subjected to annealing at different temperatures and for different periods prior to the DSC measuring heating scan. The thermograms measured in samples with low crystallinity clearly show the existence of two amorphous phases with different conformational mobility, these are called Phases I and II. Phase I contains polymer chains with a mobility similar to that in the purely amorphous polymer, while Phase II shows a much more restricted mobility, probably corresponding to conformational changes within the intraspherulitic regions. The model simulation allows to determine the temperature dependence of Phase II relaxation times, which are independent from the crystallinity fraction in the sample and around two decades longer than those of the amorphous polymer at the same temperature.     

Preparation and properties of polymer/LDH nanocomposite used for UV curing coatings

The thermal and mechanical properties of UV curing coatings consisted of urethane acrylates as an oligomer and a diacrylate monomer were reinforced by using layered double hydroxide (LDH). The LDH was organically modified by an ion-exchange process, in which the nitrate anions were replaced by long alkyl sulfate anions. With organic modification, the d-spacing of inorganic LDH layers was greatly enlarged to 2.75 from 0.78 nm, leading the LDH to be organophilic. During in situ photopolymerization process, the d-spacing of LDH layers was further enlarged to 4.29 nm, indicating the intercalation of polymer chains. For comparison, polymer/LDH nanocomposite filled with un-modified LDH was also prepared, and showed less enhancement in thermal and mechanical properties.     

Upgrading the adhesion properties of a fast‐curing epoxy using hydrophilic/hydrophobic hyperbranched poly(amidoamine)s

A homologous series of hyperbranched polymers (HBPs) was prepared following a well‐defined method and their formation in a polymeric form bearing different extents of branching with amine functional groups at the terminals was verified using different techniques such as Fourier Transform Infrared, ¹H Nuclear Magnetic Resonance, Differential Scanning Calorimetry, and Gel Permeation Chromatography. Toughening of a commercially available fast cure epoxy was aimed through reactive blending with the formed HBPs that exhibit variation in polarity and branching according to the relevant synthesis strategy employed for each polymer. The mechanical properties (impact resistance, pull‐off adhesion, and bending) of the resulting coating films pertaining to each epoxy formulation after adhering to metal substrates revealed obvious progress in their performance with respect to a control sample that was hardened exclusively in absence of any HBP. The results were explained on the light of the ability of this class of materials to impose flexibility and dilute the intensive crosslink density associated frequently with the rapid curing of epoxy systems. The extent of gained enhancement for each formulation was accounted for by the molecular architecture of the HBPs, their degrees of branching, polarity, and relative reactive contents of primary amino groups in each case. In addition, the influence of these parameters on a proper wetting over the substrate and morphology of the films in each case was also studied using scanning electron microscopy. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

UV curing behavior of methacrylated hyperbranched poly(amine‐ester)s

Methacrylated hyperbranched poly(amine ester)s as oligomers in radiation curing resins have a lower viscosity and a higher cure speed. Their viscosity was reduced sharply when an amount of a monomer was added or the temperature was increased. Their polymerization rate and final conversion of the double bond differ with the variation of the chemical structure of the end group, molar mass, and monomer content. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 51–57, 2001     

Biodegradable and thermostable synthetic hyperbranched poly(urethane-urea)s as advanced surface coating materials

Aliphatic hyperbranched poly(urethane-urea)s with different weight percentages of branch generating moiety were synthesized by a one pot A₂ + BC₂ approach. Isophorone diisocyanate was used as the A₂ type monomer, while a tri-functional dihydroxyamine compound synthesized from ?-caprolactam and diethanol amine acted as the BC₂ monomer. Evidence supporting the hyperbranched structure of the synthesized poly(urethane-urea) was obtained from ¹H NMR spectra. FTIR study confirmed the nature and extent of hydrogen bonding present in this novel macromolecule. A Gaussian band fitting procedure of the IR band at amide-I region showed that the extent of hydrogen bonding increases with the increase of weight percentage of the tri-functional compound. The tensile strength, elongation at break, impact resistance, scratch hardness and gloss followed an increasing trend with the same. The thermal degradation of the hyperbranched poly(urethane-urea) was found to be dependent on the weight percentage of the BC₂ type moiety. The kinetics of thermal degradation studied by the Ozawa method showed that the activation energy required for thermal degradation of hyperbranched polymer is higher than its linear polyurethane analog. The synthesized polymer was found to be biodegradable by Pseudomonas aeruginosa bacteria. The study showed superiority of the hyperbranched structure over the linear one. Thus the results indicated the potential usage of the studied hyperbranched poly(urethane-urea) as an advanced surface coating material.     

Self-aggregates of poly(aspartic acid) grafted with long alkyl chains

Summary Biodegradable poly(aspartic acid) (PASP) containing octadecyl chain grafts has been synthesized by thermal polycondensation of aspartic acid, aminolysis by octadecylamine, and followed by hydrolysis of remaining succinimide in polymer backbone. The sonicated suspension formed self-aggregates in aqueous solution. Size exclusion chromatography and dynamic light scattering indicated that self-aggregates became compact and particle size was reduced as increasing the amount of substituted octadecyl chains. In the case of low degree of substitution, self-aggregates assembled loosely due to low hydrophobic interaction. In the concentration range of 0.05–1.0%, the stability of aggregates was maintained due to effective hydrophobic interaction and electrostatic repulsion. Below pH 3.2, macroscopic phase-separation appeared in aqueous solution due to attraction of protonated PASP backbone. Received: 3 April 2000/Revised version: 6 July 2000/Accepted: 7 July 2000     

Novel hyperbranched poly(phenylene oxide)s with phenolic terminal groups: synthesis, characterization, and modification

Novel hyperbranched poly(phenylene oxide)s (HPPOs) with phenolic terminal groups were prepared from 4-bromo-4′,4″-dihydroxytriphenylmethane via a modified Ullmann reaction. This monomer was treated with potassium carbonate or sodium hydroxide as a base and copper chloride as a catalyst in an aprotogenic solvent, either dimethylsulphoxide (DMSO) or sulfolane. The sulfolane/NaOH system at higher temperature led to more rapid polymerization, and a relative high molecular weight. The degrees of branching of these HPPOs from the DMSO/K₂CO₃ and sulfolane/NaOH systems were 71 and 48%, respectively, as determined by ¹H NMR integration experiments. The phenolic terminal groups underwent facile modification, furnishing hyperbranched polymers with a variety of functional chain ends. The nature of the chain-end groups had a significant influence on the solubility of the hyperbranched poly(phenylene oxide)s. The resulting polymers were characterized by NMR, Fourier transform infrared, gel permeation chromatography (GPC), thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC).     

Controlled synthesis and properties of degradable 3D porous lactic acid-based poly(ester-amide)

A novel 3D porous lactic acid-based Poly(ester-amide) (PLPEA) was synthesized via condensation polymerization of toluene diisocyanate (TDI) and dicarboxylic-terminated oligoester ELDA. Pores were generated in situ and the porous structure could be controlled with the feed ratio of reagents, which was examined with scanning electron microscopy (SEM). FTIR verified the structures of intermediate and PLPEA. It was found that the mechanical properties of the PLPEA were related well to the porous structure. The tensile strength and bend strength of PLPEA obtained with NCO/COOH of 1.5:1 could be 16.59 and 70.44 MPa, respectively. On the other hand, the thermal of PLPEA was mainly dominated with the chemical compositions. The glass transition temperature and thermal decomposition temperature of PLPEA were 3 and 427 °C (80 wt%), respectively. The weight loss percentage of PLPEA could be 8.5% after 124-days immersing in phosphate-buffer saline at 37 °C, suggested that PLPEA was degradable.     

Short poly(phenylene vinylene) chains grafted poly(organophosphazene)

Brominated poly(bis(4-methylphenoxyphosphazene) was allowed to react with 1,4-bischloromethylbenzene or 1,4-bischloromethyl-2,5-dimethoxybenzene in solution using phase transfer catalyst or potassium t-butoxide. Poly(p-phenylene vinylene) or poly(2,5-methoxy-1,4-phenylene vinylene) grafted organophosphazene copolymers were obtained. The UV-Vis absorption, photoluminescent, and thermal properties of the copolymers were measured. The copolymers are complete soluble in common organic solvents and fluoresce in the blue color range. The copolymers were used to build a series of organic light emitting diode (OLED). Only weak to nominated intensities with emission color from blue to red were obtained. The photoluminescent and electroluminescent (EL) spectra indicated there is a distribution in the PPV conjugated length. The compositions of the copolymers before and after the graft reaction were analyzed using NMR.     

Synthesis and properties of hyperbranched polyurethane acrylate used for UV curing coatings

The hyperbranched polyurethane acrylate (HPUA) was synthesized through the addition of hyperbranched polyurethane endcapped by hydroxyl groups (HPU-OH), with the semiadduct urethane monoacrylate (IPDI-HEA). The HPU-OH was prepared by the amidation reaction of diethanolamine with isophorone diisocyanate. The molecular structure of HPUA was characterized by FTIR and ¹H NMR analyses. The number average molecular weight and its polydispersity index were measured by GPC to be 7714 g mol⁻¹ and 1.24, respectively. The HPUA was blended with epoxy acrylate EB600 and difunctional monomer TPGDA in different ratios, and exposed to a UV lamp for photopolymerization in the presence of Runtecure 1104 as a photoinitiator at room temperature. The photopolymerization rate and final unsaturation conversion reached to the highest values with only 5 wt% HPUA addition, whereas decreased as further added. The tensile strength of UV-cured films was improved by adding less than 10 wt% HPUA without damaging the modulus, having the value of 62.56 MPa for EB₉₀HPUA₁₀ film. Besides, the elongation at break increased continuously with the addition of HPUA, reaching to 130% for EB₇₀HPUA₃₀ film. Moreover, the impact strength was greatly enhanced by the addition of HPUA, possessing nearly two times high for EB₇₀HPUA₃₀ film compared with pure EB600 film. However, the T_g decreased as HPUA was added from the DMTA measurements. According to the ratios of T_s/T_g the HPUA has good compatibility with EB600/TPGDA resin.     

涂料用聚(酯-酰胺)超支化聚合物合成与性能研究

以苯酐和含氮二元醇为原料，合成了聚(酯-酰胺)结构的超支化聚合物。对得到的聚合物的结构用红外光谱、差热分析等方法进行了表征，测定了聚合的相对分子质量，并用油酸与聚合物的端羟基反应，得到适用于涂料的树脂。研究了树脂溶液的流变性及以聚氨酯为固化剂配制成的涂料的涂膜性能，结果表明，该涂料可在室温下快速固化，得到的涂层具有很好的漆膜性能。     

新型聚三唑酯和聚三唑醚树脂的合成及性能

合成了三种含酯基和三种含醚键的炔单体,通过核磁共振氢谱(¹H NMR)、红外光谱(FT-IR)、质谱(MS)、液相色谱(LC)对其结构进行了表征。用这六种炔单体与叠氮单体反应制备了一系列新型聚三唑酯树脂(PTAE)和聚三唑醚树脂(PTAO)。利用差示扫描量热分析(DSC)、FT-IR、动态力学热分析(DMA)、力学试验机和热失重分析(TGA)表征了树脂的固化行为、固化树脂的力学性能、耐热性和热稳定性。结果表明PTAE和PTAO树脂易溶于有机溶剂,可低温(60℃)固化,固化树脂的弯曲强度超过了100 MPa,可达158 MPa,玻璃化转变温度(T _g)超过180℃,高者达251℃,热分解温度可达360℃。     

Flame retardancy and thermal property of novel UV-curable epoxy acrylate coatings modified by melamine-based hyperbranched polyphosphonate acrylate

A novel melamine-based hyperbranched polyphosphonate acrylate (MHPA), successfully synthesized via the Michael addition polymerization of 2-(2-amino-ethylamino)-4,6-bisethylamino-1,3,5-triazine with tri(acryloyloxyethyl) phosphate, was blended with the epoxy acrylate (EA) to prepare UV-cured flame retardant coatings. The study of their flammability revealed that MHPA can improve the flame retardancy and the sample with 45 wt% MHPA (EA3) showed a good intumescent behavior when combusted. The results of their thermal degradation displayed that MHPA had a dual effect on the thermal stability of EA: leading to its earlier degradation catalyzed by acidic species from the relatively weak phosphorus-bearing parts, but improving the thermal stability of the char layer at high temperature due to the formed intumescent phosphorus–carbon compounds. Besides, the total release amount of gas products of EA3 was much lower than that of pure EA and various flammable gases like hydrocarbons and highly toxic CO were also reduced     

In situ grafting of carboxylic acid-terminated hyperbranched poly(ether-ketone) to the surface of carbon nanotubes

Carboxylic acid-terminated hyperbranched poly(ether-ketone)s (HPEKs) were successfully grafted onto the surfaces of single-walled carbon nanotube (SWNT) and multi-walled carbon nanotube (MWNT) to afford HPEK-g-SWNT and HPEK-g-MWNT nanocomposites. They were prepared via in situ polymerization of 5-phenoxyisophthalic acid as an AB₂ monomer for the HPEK in the presence of SWNT or MWNT in polyphosphoric acid (PPA)/phosphorous pentoxide (P₂O₅) medium. The resultant nanocomposites were homogeneously dispersed in various common polar aprotic solvents as well as in concentrated ammonium hydroxide. The experimental results from Soxhlet extraction, solubility enhancement, elemental analysis (EA), thermogravimetric analysis (TGA), and scanning electron microscopy (SEM) provided clear evidences for grafting of hyperbranched polymers onto the surfaces of corresponding CNT's. Achieving enhanced solubility of CNT's in common organic solvents via the functionalization of CNT's is a key step for CNT's to be used in various application-specific purposes. The results could potentially envision to the area of CNT researches via the efficient introduction of three-dimensional globular dendritic macromolecules as increasing solubility, available multi-functionality, reactivity, processability, and also biocompatibility.     

Synthesis and characterization of hyperbranched poly(silyl ester)s

Hyperbranched poly(silyl ester)s were synthesized via the A₂ + B₄ route by the polycondensation reaction. The solid poly(silyl ester) was obtained by the reaction of di‐tert‐butyl adipate and 1,3‐tetramethyl‐1,3‐bis‐β(methyl‐dicholorosilyl)ethyl disiloxane. The oligomers with tert‐butyl terminal groups were obtained via the A₂ + B₂ route by the reaction of 1,5‐dichloro‐1,1,5,5‐tetramethyl‐3,3‐diphenyl‐trisi1oxane with excess amount of di‐tert‐butyl adipate. The viscous fluid and soft solid poly(silyl ester)s were obtained by the reaction of the oligomers as big monomers with 1,3‐tetramethyl‐1,3‐bis‐β(methyl‐dicholorosilyl)ethyl disiloxane. The polymers were characterized by ¹H NMR, IR, and UV spectroscopies, differential scanning calorimetry (DSC), and thermogravimetric analysis (TGA). The ¹H NMR and IR analysis proved the existence of the branched structures in the polymers. The glass transition temperatures (T_g's) of the viscous fluid and soft solid polymers were below room temperature. The T_g of the solid poly(silyl ester) was not found below room temperature but a temperature for the transition in the liquid crystalline phase was found at 42°C. Thermal decomposition of the soft solid and solid poly(silyl ester)s started at about 130°C and for the others it started at about 200°C. The obtained hyperbranched polymers did not decompose completely at 700°C. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 3430–3436, 2006     

Synthesis, optical and electrochemical properties of new hyperbranched poly(triphenylamine amide)s

A new triphenylamine-containing AB₂ type monomer with one carboxylic acid and two amino groups, 4-(bis(4-aminophenyl)amino)benzoic acid (3), was synthesized and used for the preparation of hyperbranched poly(triphenylamine amide)s. The self-polycondensation of the AB₂ monomer (3) afforded hyperbranched poly(triphenylamine amide) with amino end groups. The molecular weight of the hyperbranched poly(triphenylamine amide) was 21,000 Da determined by light scattering. End-capped hyperbranched polyamides were isolated by the chemical modification of unreacted amino groups with various acid chlorides. All the hyperbranched poly(triphenylamine amide)s exhibit excellent solubility in organic solvents such as NMP, DMF, DMSO, and DMAc at room temperature. The viscosities of hyperbranched poly(triphenylamine amide)s are as low as about 0.15 dL/g due to their dendritic structures. Poly(triphenylamine amide)s end-capped with rigid benzene ring have higher thermal stability than those with amino or aliphatic end groups. The photoluminescence of the hyperbranched polyamides is blue-yellow emissions around 430-510 nm. The energy gaps of the hyperbranched poly(triphenylamine amide)s with different end groups are about 2.93 eV and are independent on the end groups, but the HOMO and LUMO energy levels are dependent on the end groups.