Preparation of epoxy‐ended hyperbranched polymers with precisely controllable degree of branching by thiol‐ene Michael addition

Epoxy‐ended hyperbranched polymers (EHPs) have a wide range of applications due to their outstanding performances. Because their microstructures are not positively identified, it is very difficult to ascertain the reinforcing and toughening mechanisms of EHPs and their interface interaction with other matrixes. Controllable synthesis of EHPs with precise degree of branching (DB) remains to be a major challenge. Here, a method for preparing novel nitrogen‐phosphor skeleton epoxy‐ended hyperbranched polymers (NPEHP) with controllable DB by a thiol‐ene Michael addition between thiol‐ended hyperbranched polymers (NPHSH) and glycidyl methacrylate have been firstly reported. NPHSH is synthesized by an esterification between hydroxyl‐ended hyperbranched polymers (NPHOH) and 3‐mercaptopropionic acid. NPHOH is prepared by a thiol‐ene Michael addition between methacrylate group of a monomer and thiol group of linear monomer (AB) and/or branched monomer (AB₂). The molar ratio between the AB and AB₂ monomers controls the DB of the products. The ¹H NMR spectra analysis of NPHOH shows that their experimentally determined DBs are very close to their theoretical values, indicating good controllability of their DBs. The narrow molecular weight distributions of NPHOH, NPHSH, and NPEHP suggest high efficiency of the thiol‐ene Michael addition. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 44277.     

Conformational and hydrodynamic parameters of hyperbranched pyridylphenylene polymers

Hydrodynamic and optical methods were applied to study conformational and physical properties of hyperbranched pyridylphenylene polymers in dilute solutions. The samples were synthesized using Diels–Alder polycyclocondensation. It was demonstrated that hydrodynamic properties of the studied macromolecules were typical for compact non‐percolated spheres. Optical and electro‐optical methods revealed information regarding the shape and asymmetry of the macromolecules (p ≈ 1.4). The contributions of optical shape effect to the observed flow birefringence of polypyridylphenylene solutions and intrinsic anisotropy of polarizability were evaluated and analysed. It was shown that varying the polymer composition (i.e. the degree of branching) caused considerable changes in the anisotropy of optical polarizability of the polymers. Dramatic difference of the electro‐optical properties in non‐polar (toluene) and polar (tetrachloroethane) solvents was found; this difference was related to the orientational correlation of polar solvent molecules with respect to the macromolecules. Dynamic properties were studied by non‐equilibrium electric birefringence which had a reasonable agreement with the dimensions estimated from hydrodynamic data. © 2016 Society of Chemical Industry     

Synthesis,characterization and properties of TAP‐6FDA hyperbranched polyimides with different branching degrees

A series of hyperbranched polyimides were successfully synthesized by condensation polymerization of A₂‐type dianhydride monomer 2,2‐bis(3,4‐dicarboxylphenyl) hexafluoropropane dianhydride (6FDA) and B′B₂‐type triamine monomer 2,4,6‐triaminopyrimidine (TAP). Polymers with different branching degrees (DB) and terminated groups were obtained by changing the monomer addition order and the monomer molar ratio. Fourier transform infrared spectroscopy and ¹H NMR were used to verify the structure of the prepared polyimides, which indicated that the amino group still existed in all the products. The DB of the polymers indicated by ¹H NMR increased from 30% to 79% with the molar ratio of TAP:6FDA decreasing from 1:1 to 1:2. The absolute molecular weights were measured by size‐exclusion chromatography with multi‐angle laser light‐scattering detection, which suggested that the highest molecular weight would be obtained when the molar ratio of amino groups:anhydride groups of the monomers was 3:3.2. With the DB increasing, the d‐spacing values indicated by wide angle X‐ray diffraction increased from 5.15 Å to 5.68 Å and the UV ? visible spectra of the polymers exhibited decreasing cut‐off wavelengths. The 5% weight loss temperature in nitrogen increased with decreasing content of TAP monomer, and the glass transition temperatures of the obtained polyimides decreased from 282 °C to 258 °C with increasing DB. © 2013 Society of Chemical Industry     

Influence of branching on the thermal behavior of poly(butylene isophthalate)

The thermal behavior of linear and randomly branched poly(butylene isophthalate) samples was investigated by thermogravimetric analysis and differential scanning calorimetry. As to the thermal stability, it was found to be good and similar for all the samples. The thermal analysis carried out using DSC technique showed that the melting temperature of the polymers decreased with increasing branching unit content, although the glass‐transition temperature was practically not affected by ramifications. The multiple endotherms typical of linear PBI were also observed in branched samples and were found to be influenced both by temperature and degree of branching. By applying the Hoffman‐Weeks' method, the equilibrium melting temperatures of the polymers were obtained. The presence of a crystal‐amorphous interphase was evidenced only for the branched samples and the interphase amount was found to increase as the branching unit content was increased. Isothermal melt crystallization kinetics was analyzed according to Avrami's treatment. The introduction of branching points was found to decrease the overall crystallization rate of poly(butylene isophthalate). Values of Avrami's exponent n close to 3 were obtained for all the samples, in agreement with a crystallization process originating from predetermined nuclei and characterized by three dimensional spherulitic growth. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 2001–2010, 2002; DOI 10.1002/app.10517     

Rheology and thermal behavior of long branching polypropylene prepared by reactive extrusion

Long‐chain branching polypropylene (LCB‐PP) was achieved by reactive extrusion in the presence of bifunctional monomer [1,6‐hexanediol diarylate (HDDA)] and peroxide of dicumyl peroxide (DCP). Influences of HDDA and DCP concentrations on the branching efficiency were comparatively evaluated. Fourier transformed infrared spectroscopy (FTIR) results indicated that the grafting reaction took place, and HDDA has been grafted on PP skeleton. In comparison with initial PP, some modified samples showed lower melt flow index because of a large number of LCB in their skeleton. Several rheology plots were used to investigate the rheological properties of the initial PP and modified PPs, and the rheological characteristics confirmed the LCB in modified PPs skeleton. DSC results showed that the crystallization temperatures of modified PPs were higher than those of initial PP and degraded PP, suggesting that the modified PPs had long‐chain branched structure. The contrastive investigation in the rheology of modified PPs suggested that proper concentrations of HDDA and DCP were more beneficial to producing LCB during reactive extrusion. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

The effect of random branching on the balance between flow and mechanical properties of polyamide-6

The rheological and mechanical properties of a series of linear and randomly branched polyamide 6 samples, with varying molar mass and varying degree of moderate branching, have been investigated.As expected, it was found that random long-chain branching has a pronounced effect on the rheological behaviour of the materials in both shear and extensional flow. The zero shear viscosity increases with branching while the flow curve becomes more shear thinning. Randomly branched materials have an enhanced melt strength in elongational flow. Although branched, the materials show perfect melt stability in their rheology.The mechanical properties show minor differences between the linear and the moderately branched samples and are mainly dependent on the weight average molar mass. A small increase in modulus, yield stress and failure stress and a decrease in the strain at break are found, which is probably due to increased molecular orientation in the plane of injection moulding. The IZOD impact strength is similar to what is normally found for linear polyamide-6, and independent of branching. Also the fracture toughness K_IC is not affected by the incorporation of random branching. However, it is clearly dependent on the weight average molar mass.By using random branched polyamide-6, molecular weights and related mechanical properties can be obtained that are out of reach for linear polyamide-6.     

Rheological behavior in the molten state and solution of hyperbranched polyester of fourth and fifth generation

The rheological behavior in the molten state and solution of hyperbranched polyol polyesters (HBPs) obtained by one step (HBP4, HBP5), step by step (HBP4P, HBP5P), and combination of both (HBP1‐4, HBP1‐5) was studied. Under conditions of dynamic oscillatory shear, all HBPs presented a shear‐thinning behavior and under steady shear they showed a Newtonian behavior. Also, the steady shear viscosities decreased with increasing temperature. The behavior of HBPs was mainly viscous, except for the HBP4P that showed higher storage modulus and reduction of complex viscosity when increasing the angular frequency. The HBPs presented higher complex viscosity than steady shear and they did not follow the Cox‐Merz rule. The HBPs in solution presented a plateau region at shear rate lower than 40 s⁻¹ but a shear‐thickening behavior at shear rate higher than 40 s⁻¹. The viscosities of HBPs in solution (in the plateau region) and molten state increase in the following order: HBP5P > HBP1‐5 > HBP4P > HBP1‐4 > HBP4 > HBP5. These results are not in agreement with the values of the number average molar mass obtained by vapor pressure osmometry due to different interaction between HBPs molecules. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Effects of the excluded volume interactions on the conformational properties of star polymers

The effects of the excluded volume interactions on the conformational properties of star polymers have been studied. First order calculations at the critical dimensionality d = 4 yield the critical exponents of the average quantities up to first order in ε = 4-d. We thus find the partition function, the probability of the end of a branch to reach the central core and the probability of contact of the ends of two branches. The size of the macromolecule, expressed by the mean square radius of gyration 〈s²〉_star is studied in the region where the interactions between the polymeric units repel one another and in the region where the units attract one another. The results are compared with the results of previous works and with experiments.     

Assessment of branching in polymers from small angle X-ray scattering (SAXS): SAXS from model comb-branched polystyrenes

Comb-branched polystyrenes having both fixed backbone length and number of branches but variable branch lengths were prepared anionically. Small angle X-ray scattering of the model polystyrenes from methyl ethyl ketone (MEK) solutions at 25°C was examined and it is shown that the mass per unit length and cross-sectional radius of gyration increase with increasing branch length. A maximum appears in the Kratky plot for the branched polymers. While the linear polymer displays an essentially Gaussian segment distribution in solution, the branched polymers deviate considerably from the behaviour of the linear polymer under the same conditions.     

分批加入溶剂及引发剂对聚醋酸乙烯酯支链的影响

研究了以甲醇为溶剂,偶氮二异丁腈( AIBN)为引发剂的醋酸乙烯酯聚合过程,采用多检测凝胶渗透分析仪和黏度测定的研究方法,比较醇解前后聚醋酸乙烯酯( PVAc)和聚乙烯醇(PVA)聚合度的变化和差异研究过程参数如溶剂和引发剂分批加入以及反应时间对PVAc支链化程度的影响.结果表明,在溶剂总质量分数为20％、引发剂总质量...     

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。     

PP链结构对反应挤出制备长链支化PP的影响

以过氧化二异丙苯(DCP)为引发剂、1,4-丁二醇二丙烯酸酯(BDDA)为接枝单体,通过反应挤出制备长支链聚丙烯(PP),研究了PP链长及主链中乙烯嵌段含量对PP长链支化程度的影响。随着PP树脂分子链长度降低以及乙烯嵌段含量增加,PP大分子自由基发生接枝和双基偶合扩链反应的几率增大,导致BDDA在PP主链上的接枝率提高,反应挤出产物的熔体弹性效应增强以及在Cole-Cole曲线出现上翘所对应的动态黏度降低。黏度降低表明分子链松弛时间增加,PP长链支化程度增大。。     

Impact of fillers and counterface topography on wear behavior of PTFE polymers for ultrasonic motor

Aimed to study the effects of reinforcing or functional fillers on mechanical and tribological properties of PTFE‐based friction materials of ultrasonic motor, carbon fibers reinforced PTFE composites modified with different functional fillers with differences in dimension, size, and hardness are fabricated. The tribological performances of PTFE‐based friction materials are comparatively investigated under different sliding velocities and normal loads on different surface morphologies, respectively. The experimental results reveal that nano‐SiO₂ shows excellent performance in improving friction stabilities and wear resistance in different operating conditions. It is believed the silica‐based tribofilms, higher deformation resistance, and bearing capacity play a key role in improving friction stabilities. Furthermore, the results also show that the surface topography plays an important role in wear properties. The lower wear rate (sliding against with the disordered surface) is believed to be attributed to wear debris easy‐store characteristic of the topography, which promotes transfer films formation and decreases the wear rate effectively. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44835.     

门尼粘度及支化程度对三元乙丙橡胶性能的影响

通过无转子硫化仪、橡胶加工分析仪、核磁交联密度仪等分析手段研究三元乙丙橡胶(EPDM)的门尼粘度、长链支化程度对过氧化物硫化EPDM的硫化特性及其硫化胶性能的影响。结果表明,门尼粘度的增加,有助于交联密度和硫化速率的提高,横向弛豫时间不断减小。高支化程度对EPDM胶料硫化速度不利。EPDM门尼粘度越高,初始储能模量G′0越大,储能模量迅速下降的临界应变值越小;不同长链支化度的EPDM硫化胶的储能模量大致相等,但长支化链的损耗因子值相对较高。门尼粘度对EPDM硫化胶拉伸强度变化影响较小;而长链支化程度的提高,使硫化胶拉伸强度和断裂伸长率略微降低。     

A novel approach using differential scanning calorimetry to investigate the dissolved state in aqueous solutions of polymers used for papermaking

The size and conformations of dissolved polymer molecules of polyethylene glycol (PEG) in 5% aqueous solutions were examined through the use of differential scanning calorimetry (DSC). As long as the freezable bound water is considered to be the water enclosed by the entangled polymer chains in the solution, the appearance of the characteristics of a polymer begins to occur at a degree of polymerization (DP) between 11 and 21 and is largely completed at a DP of about 50. Assuming that the peak temperature of the DSC curve for the freezable bound water indicates the size of the entangled molecular coil, the lowering of the peak temperature with a decrease of molecular weight (MW) suggests a decrease in the size of the entangled molecular coil. The linear relationship between the peak temperature and the reciprocal of the number‐average MW suggests melting point depression as a plausible mechanism for the peak temperature lowering. Mixing of two polymers with different MWs—and thus, entangled molecular coils of different sizes—causes a kind of polymer–polymer interaction and the coil sizes change as follows. If the difference in the values of the two MWs is large, the sizes of the entangled molecular coil of each MW are brought closer to each other. The extent of approach is roughly proportional to the mixing ratio. If the difference in the values of the two MWs is not large, the original entangled molecular coils disappear and a single molecular coil of intermediate size appears instead. The size of the single intermediate molecular coil varies roughly according to the simple mixing law for the values of the two MWs. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 2798–2807, 2003     

聚合度对纤维素表面性能的影响

根据Washburn浸渍理论和van Oss-Good-Chaudhury组合理论及应用柱状灯芯技术测试了具有不同聚合度(DP)的纤维素的表面性能,同时与已报道的纤维素的表面能进行了比较。结果表明:纤维素的表面能随分子量的增加而增大,但主要是其Lifshitz-van der Waals力在起主导作用。研究还发现纤维素的表面能γS与聚合度DP之间的关系大致可以描述为:γS=37.56+0.02 DP,而纤维素的极性率P与聚合度DP之间的关系则是一种非线性关系,如:P=11.88-0.02 DP+9.10 DP2。     

Study on the molecular behavior of hydrophobically modified poly(acrylic acid) in aqueous solution and its emulsion‐stabilizing capacity

In this article, molecular conformation and aggregation behavior of partly hydrophobically modified poly(acrylic acid) (HMPAA) in aqueous solution has been studied by mesoscale simulation approach dissipative particle dynamics for the purpose to find out how the chemical structure and environmental conditions effect its capacity. It has been found that, as a kind of pH‐sensitive polymer, the chemical structure variation of HMPAA carried by adjusting pH and grafting degree influence the taking place of intermolecular and intramolecular associations, which induced the formation of molecular network and help to maintain high bulk phase viscosity of its aqueous solution in larger pH range or under higher salinity comparing with PAA. There exists an optimum grafting degree, above which the increase of the possibility of the intramolecular associations enhance the coiling of the polymer chain and result in destroy of the network. The experimental determination of properties of aqueous solutions of poly(acrylic acid) (U10) and poly alkyl acrylate (U20), such as the bulk phase viscosity and oil/water interface tension, accord well with the molecular simulation conclusion, by which the mechanisms of elevated stability of surfactant‐free O/W emulsion stabilized by the HMPAA comparing with PAA has been discussed. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Influence of the degree of substitution on the solution properties of chloromethylated polysulfone

The conformational behavior and unperturbed dimensions of polysulfone and chloromethylated polysulfone with different degrees of substitution were investigated by viscometry in N,N‐dimethylformamide; we intended to use these results with more complicated structures with different properties and applications. The effects of concentration and temperature on the coil densities and dimensions and of chlorine content on the unperturbed dimension parameters are discussed. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 524–531, 2006     

Effects of aluminium content on the molecular structure and properties of polyaluminocarbosilane for SiC fibre fabrication

Polyaluminocarbosilane (PACS) is an important precursor for silicon carbide (SiC) fibres and ceramics. Much work has focused on the sintering effect of elemental Al, and it was found to increase density and inhibit grain growth during the pyrolysis of the SiC_xO_y phase at high temperatures. In addition to the sintering effect, Al may also affect the detailed molecular structure and the related properties of the precursor. In this work, PACS with different Al contents are prepared by a high-pressure method. The structural forms of the component elements are quantitatively determined by ¹H NMR, ²⁹Si NMR, DEPT, ²⁷Al MAS NMR and elemental analysis, and a method of determining the relative branching degree of PACS is proposed. It is found that increasing the Al content in the precursor leads to an increase in the weight percentage of the SiC₃O, CH₂ and CH groups, while the content of the SiC₄ groups remains almost unchanged, which consequently causes a rise in the relative branching degree of the molecular structure. The rheological properties of the precursors are investigated on a monofilament spinning device. It is found that the apparent viscosity rises, and the spinnability of the precursor weakens, with increasing Al content, while the non-Newtonian index becomes larger, indicating a decrease in the pseudo-plasticity of the precursor. In addition, the ceramic yield becomes higher, which is definitely correlated to the more branched and ring molecular structures.     

Anomalous rheological behavior of polyethylene melts in the gross melt fracture regime in the capillary extrusion: Effect of long‐chain branching

During a capillary extrusion with several different polyethylenes, we observe an abnormal rheological behavior. The nominal viscosity of some polyethylene melt in the gross melt fracture regime does not change with the temperature. Several metallocene‐catalyzed linear low density polyethylene are investigated. Among them, polyethylenes, which have long‐chain branches in their main chain, show this abnormal rheological behavior. By capillary extrusion experiments with various dies of different L/D ratios, it is inferred that the abnormal rheological behavior is originated in the die land, not die entrance nor die exit. From various experiments, we notice that this abnormal phenomenon may be used to detect long‐chain branch of PE. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008