Temperature dependence of the zero-shear melt viscosity of oligomeric epoxy resins

The melt viscosities of a homologous series of five epoxy resins based on bisphenol A and epichlorohydrin have been measured over a wide range of temperatures. It is shown that the temperature dependence of the zero-shear viscosity can be well described by the three-parameter Vogel equation. The Vogel parameters B and T_o were found to increase with increasing glass transition temperature, T_g, of the resin, while the ratios $\text{B}\text{T}{}_{\mathrm{<mtext>g</mtext>}}$ and $\text{T}{}_{\mathrm{<mtext>o</mtext>}}\text{T}{}_{\mathrm{<mtext>g</mtext>}}$ remained approximately constant. This constancy of the reduced Vogel parameters implies that T_g can be used as a corresponding states parameter to superimpose the viscosity-temperature data of all five resins onto a single master curve. The existence of such a master curve is of practical use, as it enables melt viscosities of epoxy resins to be predicted over a fairly extensive temperature range from only two quantities, viz. the value of T_g and one single viscosity value at a given temperature.     

Polymer molecular weight,zero shear viscosity,steady state compliance and binary blending law

Viscoelastic properties of binary blends of polystyrenes with a narrow distribution of low and high molecular weights (M₂ > M₁ > M_c) were examined. By combining the theoretical work of Montfort et al., Kurata, and Schausberger, a binary blending law was developed and was used to calculate the zero shear viscosity and steady state compliance of the blend of two monodisperse polymers. The blending law was also used to calculate the molecular weight distribution of a polydisperse polymer. The calculated results were compared with those obtained from viscoelastic ] and GPC measurements, with good agreement.     

Practical relationship between apparent viscosity and molecular weight of urea-formaldehyde resin adhesives

The proper viscosity of urea-formaldehyde (UF) resin adhesive for optimum adhesion depends on the type of a raw wood material for wood-based composite panels. This study investigated the practical relationship between apparent viscosity and molecular weight (MW) of UF resin adhesives during the control of their synthesis. The UF resins were synthesized at various formaldehyde/urea (F/U) mole ratios ranging from 0.8 to 1.5 with different apparent viscosities. In addition, low- and high-viscosity UF resins with 1.0 and 1.2 F/U mole ratios, respectively, were mixed at five different blending ratios of 100:0, 75:25, 50:50, 25:75, and 0:100 to obtain different viscosities. The MW of each resin was measured by gel permeation chromatography, and the relationship between apparent viscosity and MW was derived using the Mark-Houwink (M-H) equation. The results showed a good relationship between the two parameters, allowing the prediction of the MW of UF resins based on their apparent viscosity after synthesis. The weight average molecular weight (Mw) values fit well with the M-H equation, while the number average molecular weight (Mn) values did not. For the first time, this paper has reported that k and α, constants of the M-H equation based on Mw of the UF resin, ranged from 0.015 to 0.017 and 1.172 to 1.276, respectively. These suggest that the relationship between apparent viscosity and Mw should be considered for the synthesis of UF resin adhesives.     

A relationship between steady-state shear melt viscosity and molecular weight distribution in polystyrene

A model that relates to the molecular weight distribution (MWD) of high-density polyethylene to the steady-state shear melt viscosity has been applied to polystyrene melts. Relations are developed for predicting the rheological flow curve from the molecular weight distribution. Relationships are also developed to predict the MWD from the flow curve, although practical limitations to this procedure are given. From a consideration of predictions of the model and experimental data, it is concluded that the transition for a given molecular species from Newtonian to non-Newtonian flow is sharp. Additionally, the calculated empirical parameter that partitions the MWD into molecules that act in a Newtonian fashion and those that do not is shown to be equivalent to the largest molecular weight homolog that can still undergo Newtonian flow at a given shear rate for monodisperse fractions. The temperature dependence of the relaxation times is found to be somewhat higher than that predicted by the Rouse theory. An activation energy of 30 kcal/mole for η0 was used to fit the experimental viscosity data adequately at 190° and 225°C. The terminal relaxation spectrum for a narrow-MWD polystyrene standard is calculated and found to agree well for long relaxation times with that reported in the literature.     

Dependence of intrinsic viscosity and molecular size on molecular weight of partially hydrolyzed polyacrylamide

As a typical water-soluble polymer, ultra-high molecular weight (UHMW) partially hydrolyzed polyacrylamide (HPAM) has been widely used in various industries as thickeners or rheology modifiers. However, precise determination of its critical physical parameters such as molecular weight, radius of gyration (R_g) and hydrodynamic radius (R_h) were less documented due to their high viscosity in aqueous solution. In this work, the molecular structure of five UHMW-HPAM samples with different MW was elucidated by ¹H and ¹³C NMR spectroscopy, and their solution properties were characterized by both static and dynamic light scattering. It is found that all the second virial coefficient (A₂) values are positive and approaching zero, indicating of a good solvent of 0.5 M NaCl for UHMW-HPAM. The weight-average molecular weight (M_w) dependence of molecular size and intrinsic viscosity [η] for these series of HPAM polymers with MW ranging from 4.81 to 15.4 × 10⁶ g·mol⁻¹ can be correlated as R_g = 3.52 × 10⁻²M_w^0.51, R_h = 1.97 × 10⁻²M_w^0.51, and [η] = 6.98 × 10⁻⁴ M_w^0.91, respectively. These results are helpful in understanding the relationship between molecular weight and coil size of HPAM polymers in solution, and offer references for quick estimation of molecular weight and screening of commercial UHMW-HPAM polymers for specific end-users.     

Comments on the accuracy of zero shear intrinsic viscosity of high molecular weight polyacrylamide

The intrinsic viscosity of a polymer is traditionally measured with a capillary tube viscometer where the shear rate range is moderately high. Such method is valid when the polymers are non-ionic and have low to moderate molecular weight. The viscosity-shear rate curves obtained for dilute aqueous solutions of two high molecular weight polyacrylamides using two rotational viscometers indicate a strong shear-dependent viscosity in the medium to high shear rate regions. The zero shear intrinsic viscosity of the polymers determined by extrapolation from the high shear rate region to the zero shear condition may result in large errors. Its implication in predicting the molecular weight of polymers using the Mark-Houwink-Sakurada equation is discussed. A rheological equation for intrinsic viscosity as a function of shear rate is proposed.     

含侧氨基聚二甲基硅氧烷MHS方程的订正

通过测定含侧氨基聚二甲基硅氧烷聚合物的数均分子量和特性粘数,对MHS方程中的常数K和α进行了订正,得到的MHS方程表述为:[η]=3.21×10-4Mn0.66。     

The dependence of shear and elongational viscosity on the molecular weight of poly(vinylidene fluoride)

The dependence of shear and elongational viscosity on the molecular weight of poly(vinylidene fluoride) has been studied using a capillary rheometer. The elongational viscosity was evaluated based on Cogswell's method with two types of capillaries: capillary length (L)/capillary diameter (D) = 10 mm/1 mm and L/D = 0 mm/1 mm. We used the ratio P₀/P_L that indicates the contribution of elongational flow to the total flow involving both the shear and elongational flows. P_L and P₀ are the pressure losses in the capillary and the converging flows, respectively. P₀/P_L increased with molecular weight and shear rate. This corresponds to decreasing the number of entanglements of molecular chain under a large displacement, especially high shear. Thus, we suggest using P₀/P_L as the parameter of the entanglement interaction on the molecular chain under a large displacement. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 2381–2384, 1999     

Characteristic molecular weights in the dynamics of polymer melts: n.m.r. and zero-shear viscosity

As shown in previous papers, chain fluctuations in polymer melts can be analysed into three consecutive components (local segment re-orientation, reptation within the tight tube and tube renewal). The intensity function derived on this basis leads to a series of limiting cases, which can be realized by frequency and/or molecular weight variation. The occurrence of the characteristic molecular weights M_AB, M_BC and M_C separating these limits have been verified by the aid of nuclear magnetic relaxation of linear polyethylene and atactic polystyrene melts. The M_C-values are equivalent to the critical molecular weights as known from rheology. An expression for the zero-shear viscosity in the whole range of molecular weights has been derived.     

氯化聚丙烯甲苯溶液的特性黏数及其黏均分子量

分别用乌氏黏度计和旋转黏度计测定了氯化聚丙烯甲苯溶液的特性黏数和黏度,把特性黏数和黏度进行关联,发现ηsp/C与浓度C(ml/g)的关系用多项式ηsp/C=[η]+k1[η]2C+k2[η]2C2拟合,可以得到很好的结果。并且用特性黏数和Mark-Houwink方程求出了不同氯化聚丙烯(CPP)的黏均分子量。     

Benzoxazine–epoxy copolymers: effect of molecular weight and crosslinking on thermal and viscoelastic properties

Bisphenol‐A‐based benzoxazine was copolymerized with epoxy and chain‐extended epoxies in order to study the effect of molecular weight on cured resin properties. Cure behaviour of the copolymers was studied using differential scanning calorimetry, which indicated a single exothermic curing peak at 248 °C. Dynamic mechanical thermal analysis was used to study the viscoelastic properties of the cured resins. A decrease in tan δ peak position and an increase in storage modulus and tan δ peak height were observed due to chain extension. Higher char yield was observed for the copolymer chain extended with tetrabromobisphenol‐A. Copyright © 2005 Society of Chemical Industry     

Semi-empirical model for polyelectrolyte intrinsic viscosity as a function of solution ionic strength and polymer molecular weight

Elements of Odijk-Skolnick-Fixman and Yamakawa-Fujii polymer solution theories have been modified to create a new model that correlates flexible coil polyion intrinsic viscosity behavior with solvent and polymer properties. A new dimensionless viscosity is derived and is successfully related to the dimensionless ratio of Debye-Hückel screening length to polyion charge spacing and the degree of polymerization. The model has been applied to intrinsic viscosity data reported in the scientific literature and to data collected in our laboratory, all using sodium chloride solutions ranging in ionic strength. Multiple molecular weight fractions of six compositionally different polyelectrolytes were used to obtain 73 intrinsic viscosity versus ionic strength data points for model analysis. Regression analysis was applied to empirically determine the relationships between the dimensionless groups. The resulting model equation was found statistically adequate in describing the entire data set.     

Determination of steady-state elongational viscosity for rubber compounds using bell-mouthed dies

A bell-mouthed die geometry was designed to cause convergent flow at a constant, uniform, elongational strain rate. An equation was derived, which showed that steady-state elongational viscosity could be calculated from a plot of pressure drop due to elongation against a simple function of die length. To obtain values of pressure drop due to elongation, it was necessary to correct the total pressure drop measured across the bell-mouthed dies for the contribution from shear occurring near the die wall. For this purpose, a simplified shape for the bell-mouthed dies was assumed, comprising several parallel sided segments. Applying a formula to pressure drop data measured across straight dies corresponding to these segments gave an estimate of the pressure drop due to shear across the bell-mouthed dies. Pressure drops due to elongation were determined by subtracting the pressure drop due to shear from the total pressure drop measured across the bell-mouthed dies. Measurements were also carried out with lubrication to validate the shear correction method. The results indicate that for the compound used in this study, a combination of bell-mouthed and straightsided dies can be used in a conventional capillary rheometer to determine steady-state elongational viscosity. An elongational viscosity of 190 kPa s at 90°C and at a strain rate of 10 s⁻¹ was determined for a simple styrene-butadiene rubber compound. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 66: 1139–1150, 1997     

偏氯乙烯-氯乙烯悬浮共聚树脂的分子质量及分布

在5L聚合釜中合成了偏氯乙烯(VDC)-氯乙烯(VC)悬浮共聚树脂,研究了聚合温度、转化率、单体配比和助剂对分子质量及分布的影响．结果表明,共聚树脂的分子质量与聚合温度的关系符合Arrhenius方程,其综合活化能为-32．877kJ／mol;聚合物的特性黏数在高转化率阶段基本不变;分子质量随着单体配比中VC含量的增加而降低、分子质量分布也有一定的波动;聚合前加入助剂对共聚树脂的分子质量及分布影响不大。     

聚丙烯熔体流动指数与分子量及其分布的关系

研究了聚丙烯(PP)的熔体流动指数(MI)与聚合物不同分子量之间的关联性,对于分子量分布较窄的PP,数均分子量(Mn)、重均分子量(Mw)和粘均分子量(Mv)均能较好的关联;反之,MI与Mn关联性下降,而MI与Mn和Mv的关联性仍很好,尤其是MI与Mv的关联性受分子量分布的影响很小;MI与Z均分子量的关联性很差。同时．确定了MI与各种分子量之间的关联式,该式用于本体PP工艺反应器内氢气浓度的计算和MI的预测,与实验测量结果吻合良好。     

Effect of molecular weight of epoxidized‐natural rubber on viscosity and tack of pressure‐sensitive adhesives

The effect of molecular weight of rubber on viscosity and loop tack of rubber‐adhesives were studied using two grades of epoxidized‐natural rubber, i.e., ENR 25 and ENR 50. Coumarone–indene resin, gum rosin, and petro resin were used as tackifiers. Toluene was used as the solvent throughout the experiment. The adhesive was coated on polyethylene terephthalate (PET) substrate using a SHEEN hand coater. Viscosity was determined by a HAAKE Rotary Viscometer, whereas loop tack was measured by a Llyod Adhesion Tester operating at 10 cm/min. Results show that viscosity increases gradually upto a critical molecular weight of 6.8 × 10⁴ and 3.9 × 10⁴ for ENR 25 and ENR 50, respectively, before a rapid increase in viscosity is observed. Loop tack indicates maximum value at the respective critical molecular weights for the three tackifiers investigated suggesting the culmination of wettability. For both rubbers, loop tack increases with coating thickness due to the concentration effect of adhesive. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Relationship between molecular structure and zero‐shear viscosity of polymers

The relationship between molecular structure and zero‐shear viscosity of polymers was studied. In this study we propose a new equation, which is based on Berry and Fox's equation. This new equation is constructed from some molecular parameters, such as mean square length and average molecular weight of statistical skeletal unit, characteristic ratio, entanglement molecular weight, glass‐transition temperature, free volume fraction at glass‐transition temperature, and thermal expansion coefficient of free volume. It is proposed that some of these molecular parameters could be predicted by group contribution methods, except for the free volume parameters. We also propose new empirical relations between free volume parameters and molecular structures of polymers, which make it possible for free volume parameters to be obtained from molecular structure. Using these relationships, it is possible that the zero‐shear viscosity and its temperature dependence are obtainable from the molecular structure of polymers. We applied this formula to some polymers, including both amorphous and semicrystalline polymers. Comparison between the measured and calculated zero‐shear viscosity showed quite good agreement. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 1609–1618, 2001     

超高分子量抗盐型聚合物的合成及性能评价

以丙烯酰胺(AM)和衣康酸(IA)为原料,采用自由基溶液聚合法合成了共聚物(IAPAM),用FTIR、1HNMR、元素分析和GPC对其结构进行表征,并对其抗一价、二价阳离子降黏性能及抗氧化还原物质能力进行评价.结果表明,IAPAM黏均相对分子质量高达1.716×107.与部分水解聚丙烯酰胺(HPAM)相比,IAPAM有...     

Effect of recovery methods and conditions on the yield,solubility, molecular weight,and creep compliance of regenerated chitosan

The objective of this study is to explore the effect of using different recovery methods and conditions on the yield, solubility, molecular weight, and creep compliance of the regenerated chitosan. The results show that yields obtained by dialysis were higher than those using recovery medium of alkali solutions, organic solvents, or alkali–alcohol–water mixtures. For those chitosans employing alkali solutions as the recovery medium, the higher the alkali concentration used, the higher the yields obtained, although the total quantity of alkali in the solution were the same. Solubilities of regenerated chitosans were similar and independent at the methods of using alkali solution, organic solvent or alkali–alcohol–water mixture or at different concentrations of alkali solution. The molecular weight of regenerated chitosan decreased from 2.37 × 10⁷ to 1.68 × 10⁷ Da proportionally with the concentration of the alkali solution of the recovery medium from 1N to 8N. Creep compliance of regenerated chitosan gel obtained from 65% degree of deacetylation (DD) chitosan was lower than that of either 72 or 89% DD chitosan gel. Of the same DD chitosan, compliance of regenerated chitosan gels obtained by using a higher concentration of alkali solution was lower than that of a lower concentration ones. Hydrogels regenerated from different DD chitosans and/or different recovery mediums have different structure and tactile properties. Therefore, they can be used as wound dressings suited to different applications. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 193–202, 2002; DOI 10.1002/app.10296     

无机盐对两性聚丙烯酰胺特性粘度的影响

用红外吸收光谱对两性聚丙烯酰胺结构进行了表征,表明分子链上丙烯酰胺(AM)、甲基丙烯酰氧乙基三甲基氯化铵(MADQUAT)和丙烯酰胺基甲基丙磺酸钠(NaAMPS)链节的存在。随后研究了NaCl、CaCl2浓度及pH值对不同阴阳离子度的聚合物特性粘度的影响。结果表明,AM-MADQUAT-NaAMPS共聚物特性粘度受CaCl2浓度影响较NaCl大,但总的来说耐盐性比单性离子聚合物好,且其特性粘度在很大范围内(除等电点附近)不受pH值的影响。