Cyclic hyperbranched polyesters derived from 4,4-bis(4′-hydroxyphenyl)valeric acid

Three monomers were prepared from 4,4-bis(4′-hydroxyphenyl)valeric acid (BHVA) namely its methylester (BHVAM), its bis-acetylated methylester (BAVAM) and its 4,4-bis(4′-acetoxyphenyl)valeric acid (BAVA). All three monomers were polycondensed in bulk at various temperature profiles using Ti(OBu)₄, Co(OAc)₂, Mn(OAc)₂, Sn(OAc)₂ or Bu₂Sn(OAc)₂ as transesterification catalysts. The structure of the resulting ‘hyperbranched’ polyesters were characterized by ¹H NMR spectroscopy, MALDI-TOF mass spectroscopy and in selected cases by SEC. Regardless of the reaction conditions only low oligomers almost free of cycles were obtained from the methylesters BHVAM and BAVAM. Higher molecular weights and high contents of cycles were obtained from polycondensations of BAVA. The content of cycles increased with the conversion. Hyperbranched polyesters with cyclic core were detected up to masses around 10,000 Da. The reactivities of the three hyperbranched monomers were compared with those of bisphenol-A plus dimethyl sebacate or acetylated bisphenol-A plus sebacic acid in ‘linear polycondensations’ and close analogies were found.     

Synthesis and characterization of hyperbranched aromatic polyesters used for polymeric graded‐index materials

A series of hyperbranched aromatic polyesters, with different numbers of terminal naphthyl groups per molecule, were synthesized from 5‐hydroxyisophthalic acid as an AB₂ type monomer and ethylenediaminetetraacetic acid as an ‘initiator core’ molecule via an ‘one‐step’ approach, to be modified with β‐naphthol. These polyesters had polydispersities in the range 1.78–2.13, indicated by gel permeation chromatography, and degrees of branching between 0.45 and 0.60 by ¹H NMR using model compounds. Characterization indicated intense absorption bands in the near‐UV spectral region and one fluorescence centre with emission at 365 nm. The refractive index increased with the number of naphthyl groups up to a value of 1.6205. The diffraction efficiency was about 8.7% for diffraction grating of cured films. Copyright © 2003 Society of Chemical Industry     

Hyperbranched polyesters based on hydroxyalkyl‐lactones via thiol‐ene click reaction

The preparation of AB₂ monomers via thiol‐ene click reaction from six‐ and seven‐membered unsaturated lactones is described. The hydroxyl‐functionalized valerolactone was prepared by use of Michael thiol‐ene‐addition reaction starting from 2‐mercaptoethanol and 3‐methylenetetrahydro‐2H‐pyran‐2‐on. The hydroxyl‐functionalized caprolactone was prepared radically from 2‐mercaptoethanol and 7‐allyloxepan‐2‐one. Both AB₂ monomers were polymerized via ring opening in the presence of tin(II)‐2‐ethylhexanoate (Sn(Oct)₂) as a catalyst yielding the hyperbranched polyesters. The new hyperbranched polyesters were analyzed by ¹³C NMR spectra to determine the degree of branching. © 2014 Society of Chemical Industry     

Facile and efficient synthesis of hyperbranched polyesters based on renewable castor oil

Hyperbranched polyesters with thioether linkages were facilely prepared from methyl 10‐undecenoate, a castor oil‐derived renewable chemical. The monomer was obtained in excellent yield through thiol–ene click chemistry in the presence of catalytic amounts of photoinitiator under UV irradiation. Subsequent bulk polycondensation via a transesterification process catalyzed by Ti(OBu)₄, Sb₂O₃ or Zn(OAc)₂ gave hyperbranched polyesters with high molecular weights and unusual crystalline properties. The degree of branching in the range 0.45 ? 0.54 calculated from quantitative ¹³C NMR spectroscopy and low inherent viscosities of 0.16 ? 0.25 dL g^?1 strongly confirmed the hyperbranched structures of the resultant polymers. © 2012 Society of Chemical Industry     

Synthesis and characterization of a thermotropic liquid crystalline hyperbranched polyester

BACKGROUND: Hyperbranched polymers have received increasing attention in the fields of medicine, homogeneous catalysis and materials science. Hydroxyl‐functional aliphatic polyesters are one of the most widely investigated families of hyperbranched polymers. The research reported here is based on the preparation of a novel hyperbranched polyester and the modification of its terminal hydroxyl groups by biphenyl mesogenic units. RESULTS: 2,2,6,6‐Tetramethylolcyclohexanol as a core and 8‐[4′‐propoxy(1,1‐biphenyl)yloxy]octanoic acid as a mesogenic unit were synthesized. A hyperbranched polyester (HPE) was synthesized in one step and subsequently substituted by reaction of its terminal hydroxyl groups with the biphenyl mesogenic units to yield a novel liquid crystalline hyperbranched polyester (HPE‐LC). The chemical structures of all compounds were confirmed using Fourier transform infrared, ¹H NMR and ¹³C NMR spectroscopy. The thermal behavior and the mesogenic properties of the biphenyl mesogenic unit and HPE‐LC were investigated using differential scanning calorimetry, polarized optical microscopy and wide‐angle X‐ray diffraction. The results demonstrated that the degree of branching of the HPE is ca 0.63. Both HPE‐LC and the biphenyl mesogenic unit exhibit mesomorphic properties, but HPE‐LC has a lower isotropic transition temperature and a wider transition temperature range than the biphenyl mesogenic unit. CONCLUSION: A novel liquid crystalline hyperbranched polyester was successfully synthesized, which exhibits mesomorphic properties. This polymer has good solubility in highly polar solvents and good thermal stability. Copyright © 2009 Society of Chemical Industry     

超支化聚酯的端基改性及其涂膜性能

以三羟甲基丙烷为核多元醇,二羟甲基丙酸为AB₂型单体,对甲苯磺酸为催化剂准一步法合成了第二代超支化聚酯(HBP-0)。HBP-0分别经己内酯和月桂酸改性得到改性超支化聚酯(HBPs)。采用FT-IR、¹H NMR和GPC对HBP-0的结构和相对分子质量进行表征,发现超支化聚酯的支化度为0.43,相对分子量与理论相对分子量比较接近, 相对分子质量分布系数只有1.72。以甲苯二异氰酸酯加成物为交联剂,考察了改性超支化聚酯交联涂膜性能,结果表明,3种改性超支化聚酯的涂膜性能在光泽度、耐冲击性、附着力和柔韧性方面表现十分优异。其中HBP-3同时用己内酯和月桂酸改性具有最佳性能,黏度最低为7500 mPa·s,涂膜表干40 min,且硬度达到F。而单独用己内酯或月桂酸改性的HBP-1和HBP-2的相应数据分别为7×10⁵ mPa·s、20 min和HB及17500 mPa·s、90 min和2B。     

Synthesis and characterisation of star branched polyesters with dendritic cores and the effect of structural variations on zero shear rate viscosity

A series of branched polyesters consisting of poly(ε-caprolactone) (PCL) (degree of polymerisation: 5-200) initiated from hydroxy-functional cores and end-capped with methylmethacrylate have been prepared. The cores were third-generation hyperbranched polyester, Boltorn, with approximately 32 hydroxyl groups, a third-generation dendrimer with 24 hydroxyl groups and a third-generation dendron with eight hydroxyl groups. Finally, a linear PCL was synthesised as a reference material. All initiators were based on 2,2-bis(methylol) propionic acid (bis-MPA). ¹³C NMR spectra of the polymers showed that those with shorter arms contained unreacted hydroxyl groups on the core. Rheological measurements of zero shear rate viscosity, η₀, showed that the branched polyesters had a considerably lower η₀ than linear polyester with similar molecular weight. The low melt viscosity and the crystallity produced a rheological behaviour suitable for the film formation process for powder coatings. Measurements of mechanical properties of cured films showed that those with low arm molecular weight, M_a, were amorphous while those of high M_a were crystalline.     

Synthesis and crystallization behaviors of highly fluorinated aromatic polyesters

Studies on fluorine containing condensation polymers are limited compared to that of fluorine containing addition polymers. In this report, highly fluorinated aromatic polyesters were synthesized by a polycondensation reaction of tetrafluorophthalic anhydride with ethylene glycol. Viscosity, solubility, thermal properties and crystallization behaviors of fluorinated polyesters were investigated using IR, ¹⁹F NMR, DSC, GPC, polarized optical microscope and rheometer. The fluorinated polyester is insoluble in most organic solvents, such as acetone, ethyl acetate, chloroform, THF, and trichloromethane. However, it is soluble in highly polar solvents, such as dimethylsulfoxide, dimethylformamide and dimethylacetamide. The fluorinated polyester (o-PETF) is a crystalline polymer with a crystallization enthalpy of 35.2 J/g and a broad crystallization temperature range from 54 to 130 °C. Average crystalline growth rate is 4.2 μm/min at 110 °C in the preliminary 30 min. Spherulite growth was observed at the temperature when the dendrites begin to melt. Crystallization property of o-PETF may be ascribed to the higher mobility of fluorinated polyester chains and dipolar contribution of carbon-fluorine bonds.     

Development of moisture cure polyurethane–urea coatings using 1,2,3-triazole core hyperbranched polyesters

This article reports the development of moisture cure polyurethane–urea coatings. The coating has been developed using different generations of novel 1,2,3-triazole core containing hyperbranched polyester polyols (THBP). For the synthesis of THBP, the core molecule, tetra hydroxyl-terminated di-triazole (THTD), has been synthesized by click reaction involving ethylene diazide and 2-butyne-1,4-diol. The polycondensation reaction between the core THTD and 2,2-bis (hydroxymethyl) propionic acid (Bis-MPA) at different mole ratios has been used to get first (THBPG-1), second (THBPG-2), and third (THBPG-3) generations of triazole core hyperbranched polyesters. The structural investigations of these THBPs have been carried out by ¹H NMR, ¹³C NMR, and FTIR spectroscopy. The different generations of THBPs were further reacted with 1-isocyanato-4-[(4-isocyanatocyclohexyl) methyl] cyclohexane (H₁₂-MDI) at OH:NCO ratio of 1:1.2 to get –NCO terminated triazole core hyperbranched polyurethanes. They were cured under atmospheric moisture to get hyperbranched polyurethane–urea coatings and were named as THBPUG-1, THBPUG-2, and THBPUG-3. FTIR has been used to confirm the formation of polyurethane coatings. The TGA and DMTA have been used to determine the thermal stability and dynamic mechanical properties of the coatings, respectively. The corrosion resistance properties of the coatings have been studied by salt spray and electrochemical test. The coatings were also evaluated for microbial resistance. The results indicate that the thermal stability, glass transition temperature, and corrosion resistance properties increase with an increase in generation number of THBPs used for coating development. All three generations of coating films show excellent antimicrobial activity. Based on overall combined structure–property relationship study, these types of coatings will be useful as multifunctional applications in marine and moist environments.     

Synthesis and characterization of hyperbranched aromatic poly(ester-imide)s

The synthesis and characterization of hyperbranched aromatic poly(ester-imide)s are described. A variety of AB₂ monomers, N-[3- or 4-bis(4-acetoxyphenyl)toluoyl]-4-carboxyl-phthalimide and N-{3- or 4-[1,1-bis(4-acetooxyphenyl)]ethylphenyl}-4-carboxy phthalimides were prepared starting from condensation of nitrobenzaldehydes or nitroacetophenones with phenol and used for synthesis of hyperbranched poly(ester-imide)s containing terminal acetyl groups by transesterification reaction. These hyperbranched poly(ester-imide)s were produced with weight-average molecular weight of up to 6.87 g/mol. Analysis of ¹H NMR and ¹³C NMR spectroscopy revealed the structure of the four hyperbranched poly(ester-imide)s. These hyperbranched poly(ester-imide)s exhibited excellent solubility in a variety of solvents such as N,N-dimethylacetamide, dimethyl sulfoxide, and tetrahydrofuran and showed glass-transition temperatures between 217 and 255 °C. The thermogravimetric analytic measurement revealed the decomposition temperature at 10% weight-loss temperature (T_d¹⁰) ranging from 365 to 416 °C in nitrogen.     

Structure–property correlation study of hyperbranched polyurethane–urea (HBPU) coatings

This paper deals with the structure–property relation of different HBPU coatings based on the variation of parameters like, NCO/OH ratio, generation number and type of diisocyanates used. For this, the NCO terminated HBPU prepolymers were synthesized first by reacting the different generation hyperbranched polyesters (HBPs) with excess diisocyanates. In the next step, these HBPU prepolymer coated films were completely moisture cured to get the desired HBPU coatings. The synthesized polymers were confirmed by ¹H, ¹³C NMR and FT-IR spectroscopy methods whereas structure–property relation was drawn from the FT-IR peak deconvolution technique. The degree of branching (DB) and percent composition of different structural units present in the HBPs were calculated from the ¹H and ¹³C NMR data by using Fretch equation. The melt viscosity study of different HBP samples suggests that most polyester sample showed Newtonian behavior. The coating film properties were studied by DMTA, TGA, UTM, and contact angle measurement instruments. DMTA and TGA data shows that the increase of NCO/OH ratio and generation number had a favorable impact on storage modulus (E′), glass transition temperature (T_g), onset degradation temperature (T_1ON) and char residue values of the coatings. The contact angle and UTM data suggest that the hydrophobicity and tensile strength increases but flexibility decreases with increasing the NCO/OH ratio.     

Study on hyperbranched polyesters as rheological modifier for Spandex spinning solution

The rheological behavior of polyurethane (PU)/N,N‐dimethylformamide (DMF) spinning solutions with various contents of hyperbranched polyesters was studied using a RS150L‐controlled stress rotational rheometer. The results showed that the viscosity of the spinning solutions could be greatly reduced by adding hyperbranched polyesters even at 0.5 wt% loading. The zero‐shear viscosity of solutions with hyperbranched polyesters was much lower than that of pure PU/DMF solution, which indicated a lower degree of entanglement when solutions were in a static state. The apparent activation energy of viscous flow and the critical shear rate for shear thinning of solutions with hyperbranched polyesters were much lower than that for pure PU/DMF solution, which indicated a weaker entanglement structure formed. In addition, the effect of hyperbranched polyesters on the mechanical properties of Spandex fiber was discussed. Copyright © 2006 Society of Chemical Industry     

Preparation of hyperbranched copolymers of maleimide inimer and styrene by ATRP

Novel hyperbranched copolymers were prepared by the atom transfer radical copolymerization of N-(4-α-bromobutyryloxy phenyl) maleimide (BBPMI) with styrene in 1-methyl-2-pyrrolidone (NMP) using the complex of CuBr/2,2′-bipyridine as catalyst. The copolymerization behavior was investigated by comparison of the conversion of double bond of BBPMI determined by ¹H NMR with that of styrene. The hyperbranched structure of resulting copolymers was verified by gel permeation chromatography (GPC) coupled with multi-angle laser light scattering (MALLS). The influences of dosage of catalyst and monomer ratio on the polymerization rate and structure of the resulting polymers were also investigated. The glass transition temperature of the resulting hyperbranched copolymer increases with increasing mole fraction of BBPMI, f_BBPMI. The resulting copolymers exhibit improved solubility in organic solvents; however, they show lower thermal stabilities than their linear analogues.     

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)。     

Effect of generation number on properties of fluoroalkyl-terminated hyperbranched polyurethane latexs and its films

The 1–3 generations of hyperbranched polyesters (HBPE-1/2/3) were synthesized from trimethylolpropane (TMP) and 2,2-dimethylol propionic acid (DMPA) by “quasi-one-step method.” Then, isophorone diisocyanate (IPDI), polybutylene adipate (CMA-1044), DMPA and 1,4-butanediol (BDO) were utilized to prepare the urethane prepolymer (PU), which was reacted with HBPE to synthesize hyperbranched polyurethanes (HBPU). Finally, 1–3 generations of fluoroalkyl-end-capped hyperbranched polyurethanes (FHBPU) latexes were obtained by the reaction of perfluorohexyl ethanol (S104) and HBPU as well as the self-emulsification process. Structure of the products, the properties of different FHBPU emulsions and its films were investigated by FTIR, ¹H NMR, TEM, DLS, TGA, XPS, XRD, SEM, AFM and static contact angle measuring instrument. Results showed that the particle size of FHBPU latexes increased gradually with the increase of generation number. SEM and XRD results verified that an amount of the crystal particles was increased with the increase of generation number. XPS and AFM demonstrated that degree of microphase separation and film roughness was increased with the increase of branching degree. Static water contact angles could attain 95.9°, 100.3°, and 107.0°, respectively on the 1–3 generations of FHBPU films, compared to that on PU (75.1°).     

Boltorn型超支化聚酯的合成与表征

以季戊四醇(PEL)、三羟甲基丙烷(TMP)和2,2-二羟甲基丙酸(DMPA)为原料,合成了3种端羟基超支化聚酯(HBPE),即分别是以PEL为核的HBPE、以TMP为核的HBPE和无核的HBPE。采用FTIR、13C NMR、GPC等方法对其结构进行了表征,3种HBPE的Fréchet支化度分别为41.86%,41.49%和39.77%,而Frey支化度分别为32.29%,31.37%和23.11%。研究了中心核分子对HBPE的溶解性、特性黏度的影响。结果表明,随着核分子官能度的增加,HBPE的溶解性变好,特性黏度增加,支化度(DB)增加,分子量多,分散系数(PD I)变小。     

Hyperbranched polymers containing oxazoline monomers and succinic anhydride: Applications in fast drying,low solvent coating formulations

Melt-polycondensation of succinic acid anhydride with oxazoline-based diol monomers gave hyperbranched polymers with carboxylicacids terminal groups. ¹H NMR and quantitative ¹³C NMR spectroscopy coupled with DEPT-135 ¹³C NMR experiment showed high degrees of branching (over 60%). Esterification of the acid end groups by addition of citronellol at 160 °C produced novel white spirit soluble resins which were characterized by Fourier transform-infrared (FTIR) spectroscopy, gel permeation chromatography (GPC), differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). Blends of the new hyperbranched materials with commercial alkyd resins resulted in a dramatic, concentration dependent drop in viscosity. Solvent-borne coatings were formulated containing the hyperbranched polymers. Dynamic mechanical analysis studies revealed that the air drying rates of the new coating systems were enhanced compared with identical formulations containing only commercial alkyd resins.     

Preparation,characterization and modification of hyperbranched polyester-amide with core molecules

The synthesis of hyperbranched polyester-amides based on pentaerythritol (PETL) as a core molecule and AB₂ monomer containing one carboxylic group and two hydroxylic groups using core-dilution/slow monomer addition strategy have been studied. The AB₂ monomer was prepared by diisopropanolamine (DIPA) and cis-1,2-clyclohexane-dicarboxylic anhydride (HHPA). Two types of hyperbranched polyester-amide (1G-HP, 2G-HP) were obtained with the molar ratio of AB₂ monomer and pentaerythritol (PETL) was 4 and 8, respectively. The structures of products were characterized by IR, ¹³C NMR, GPC and viscosity measurement. It was shown that the hyperbranched polymers prepared had high degree of branching (DB) and narrow molecular weight distribution. As for 1G-HP and 2G-HP, the intrinsic viscosity [η] was 4.32 ml/g and 5.29 ml/g, and the viscometric radius R_V was1.28 nm and 1.67 nm, respectively. The results of viscosity measurement indicated that the structures of 1G-HP and 2G-HP were compacted and had a spherical conformation. In addition, the reactions of hydroxyl end-groups with polyethylene glycol monomethyl ether (mPEG550) and glycidyl methacrylate (GMA) were conducted to provide amphiphilic and UV-curable properties of resulting polymers. The properties of the modified hyperbranched polyester-amide were also investigated initially.     

High-toughening modification of polylactic acid by long-chain hyperbranched polymers

The hyperbranched polyester synthesized by “one-step method” was grafted with stearic acid to obtain long-chain hyperbranched polymers (LCHBPs) with a large number of long stearic acid chains at the end. By means of FTIR and ¹³C-NMR characterization, it was proved that stearic acids were grafted onto hyperbranched polyesters (HBPE) to yield LCHBPs successfully. It was determined by GPC and hydroxyl value titration that the number average molecular weight of HBPE was 4.86 × 10³ and the grafting rate of stearic acid was 47%. Polylactic acid (PLA)/LCHBPs blends were prepared by melt processing method. The results showed that comparing with neat PLA, the tensile strength of PLA/LCHBPs blends decreased slightly with the increase of LCHBPs, but still maintained a high level, while the elongation at break and the impact strength of the PLA with 3.0 phr LCHBPs were greatly improved by 1360.0% and 119.8%, respectively. In addition, the impacted fracture characteristics of PLA changed significantly from brittle fracture to ductile fracture after LCHBPs incorporation, with the formation of a large number of filamentous structures. Thus, LCHBPs was an excellent toughening modifier for PLA and the resulting blends with improved performance possess wider applications.     

Phosphorus based indole and imidazole functionalized hyperbranched polyester as antimicrobial surface coating materials

Third generation of hyperbranched polyester (HP) synthesized via melt condensation and end-capped with bis indole and imidazole phosphoryl chloride. The modified polyesters subjected to different characterization viz., FTIR, ¹H and ¹³C NMR, GPC and elemental analysis. NMR analysis was used for the determination of OH conversion that demonstrates linear units had a lower reactivity as compared to terminal OH groups in HP. The thermogravimetric analysis (TGA) and differential scanning calorimetric (DSC) studies indicated that the HP was stable up to 276 °C and the glass transition temperature was 79.6 °C. After modification of HP, thermal stability was increased for indole modified HP, but the glass transition temperature was decreased. The flame retardance of the hyperbranched polyester was also evaluated with the help of TGA analysis and showed higher value of limiting oxygen index (LOI) for modified polyesters. Morphology of the modified polyester showed more roughness than unmodified HP and this nature positive correlated with bacterial zone of inhibition value. Biological studies showed that the HP and modified HP are able to inhibit the reproduction of gram-positive and gram-negative bacteria. Indole modified HP is showed good activity compared to imidazole modified HP.