Rheology of epoxy networks near the gel point

Summary Curing and gelation of diglycidyl ether of Bisphenol A with poly(oxypropylene)-diamine (Jeffamine D 400) was followed using dynamic mechanical measurements. The gel point was determined rheologically and the characteristic value of the loss factor tan at the gel point, (tan)_gel, was found to depend on the structure of the polymer. A negative normal force is generated in the shear dynamic mechanical measurement at the gel point.Dedicated to Dr. Karel Duek on the occasion of his 60th birthday for his important contribution to polymer science     

Kinetics and flow of diallyl phthalate resins

The analysis of molding operations for thermosetting polymers requires knowledge of the rheology and reaction rates of the materials. The purpose of this research was to measure kinetic and rheological data on diallyl phthalate resins and to integrate these results into models describing the flow behavior. The chemical kinetics of the curing reactions were derived from calorimetric measurements taken with a differential scanning calorimeter. The rheological data were measured with a mechanical spectrometer equipped with eccentric rotating discs. A model based on the theory of ideal rubber elasticity was used to correlate the elastic storage modulus with reaction time and temperature. For the region below the gel point, the dynamic viscosity exhibited a power law dependence on angular frequency and an Arrhenius dependence on temperature.     

Polymerization of diallyl phthalate at high temperatures

The influence of high temperature (160–250°C) on diallyl phthalate polymerization has been investigated. Polymerization was carried out in a nitrogen atmosphere both with and without benzoyl peroxide as initiator, and also in a air atmosphere. A considerable increase in the conversion degree to the gelation point with a parallel increase in temperature has been established. Unsaturation degree of prepolymers remains unchanged independently of temperature and the way of polymerization initiation.     

Prediction of diallyl phthalate molding performance from laboratory tests I. Characterization and quality control of diallyl phthalate compounds

The purpose of this study was two-fold:

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邻苯二甲酸二烯丙基酯树脂固化特性的研究

运用示差扫描量热(DSC)法研究了邻苯二甲酸二烯丙基酯(DAP)树脂的固化反应历程。讨论了引发剂对DAP固化特性的影响,并由DSC曲线得到了DAP树脂的固化工艺和动力学参数。通过固化度、FT-IR的测试对DAP树脂在中温条件下的固化情况进行了研究。结果表明:在过氧化二异丙苯(DCP)固化体系中引入BPO可以使DAP树脂在更低温度下引发固化;在BPO、DCP用量均为2%的条件下,确定了体系的凝胶温度、固化温度、后处理温度分别为:100.5℃,124.3℃,137.8℃,表观活化能为129.3 kJ/mol,反应级数为0.950。固化度、FTIR的测试结果表明:DAP树脂在中温条件下可以固化得较完全。     

丙二酸二乙酯与邻苯二甲酸二烯丙酯复合改性酚醛树脂

以甲醛和苯酚为原料、有机酯[由丙二酸二乙酯和DAP(邻苯二甲酸二烯丙酯)组成]为改性剂,制备碱性PF(酚醛树脂);然后采用DMA(动态热机械分析)法、DSC(差示扫描量热)法、FT-IR(红外光谱)法和TGA(热失重分析)法等对改性PF的固化机制、反应动力学等进行了表征和分析。研究结果表明:随着有机酯用量的不断增加,改性PF的储能模量、损耗模量和损耗因子(tanδ)无明显的规律性,固化温度随之下降;有机酯可促进改性PF的凝胶固化,并且是通过快速促进PF分子的活性中间体亚甲基醌来实现的。有机酯用量虽对改性PF的耐热性影响不大,但相应胶合板的胶接强度有所降低;当m(有机酯)=12 g、m(丙二酸二乙酯)∶m(DAP)=1∶1时,改性PF的综合性能相对最好。     

Determination of cure of diallyl phthalate using differential scanning calorimetry

Kinetic parameters (reaction rate constant, activation energy, and frequency factor) were determined by differential scanning calorimetry using a linearly rising temperature program for the polymerization of diallyl phthalate monomer catalyzed with dicumyl peroxide. Cure times for specific degrees of cure at constant temperature were calculated and found to agree with the degree of cure measured by infrared spectroscopy. The relationship between non-isothermal and isothermal cure cycles is discussed.     

Rheology of polymers containing carbon black

In order to elucidate the flow behavior of electrophotographic toner systems, shear stress was measured as a function of shear rate in a cone and plate rheometer for polymer melts containing carbon blacks of surface area 24 and 625 m²/g at several concentrations and temperatures. Polymers included high and low molecular weight polystyrene and poly(butyl methacrylate). The addition of carbon black to the polymers caused a large increase in viscosity, especially at low shear rates and shear stresses. As the concentration of carbon black was increased, the viscosity at low shear rates became unbounded below a value of the shear stress designated the yield stress. The absolute magnitude of the yield stress depended primarily on the concentration and surface area of the carbon black and was independent of the polymer and temperature. Apparently, carbon black forms an independent network within the polymer at low shear rates which precludes flow. In some cases, the viscosity of polymers filled with carbon black was lower than that of the pure polymer. This effect was favored for polystyrene compared to poly(butyl methacrylate) and was facilitated by increasing the molecular weight of polystyrene, reducing the surface area and concentration of carbon black, and by increasing the temperature and shear rate.     

Rheology of core cross-linked star polymers

The rheological characterization for a set of structurally diverse core cross-linked star (CCS) polymers is presented. The influence of arm molecular weight (M_w(arm)) and CCS polymer molecular weight (M_w(CCSP)) on the steady- and dynamic-shear properties determined by plate rheometry will be discussed. Both these parameters dramatically affect the CCS polymer solution properties and determine its “molecular softness”; a key feature of star polymers. Data from light scattering and capillary viscometry analysis are also presented to relate the dimensional configuration of the CCS polymers to their rheological properties. The methodology for tuning the structure of the CCS polymer is provided and the implications on solution properties are discussed.     

Rubberwood–polymer composites based on diallyl phthalate and methyl methacrylate

Wood–polymer composites (WPC) of rubberwood (Hevea brasiliensis), were prepared by impregnating the wood with methyl methacrylate (MMA), and the combinations of MMA and diallyl phthalate (MMA/DAP). Polymerization was carried out by catalyst heat treatment. Impregnated samples showed significant improvements in compressive and impact strengths, hardness, and dimensional stability (toward water) over that the untreated rubberwood. © 1995 John Wiley & Sons, Inc.     

Rubberwood–polymer composites based on glycidyl methacrylate and diallyl phthalate

Wood–polymer composites (WPC) of rubberwood (Hevea Brasiliensis) were prepared by impregnating the wood with glycidyl methacrylate (GMA), combinations of glycidyl methacrylate and diallyl phthalate (GMA–DAP), or diallyl phthalate (DAP) alone. Polymerization was carried out by catalyst-heat treatment. The results showed that WPC based on GMA exhibited greater dimensional stability (results of antishrink efficiency after six days of soaking) about five times than those based on DAP alone. Flexural [Modulus of Elasticity (MOE), Modulus of Rupture (MOR), and toughnes], compressive, and impact properties for all the samples tested are improved, especially for those with higher chemical loading. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 67:1221–1226, 1998     

Estimation of crosslinking of diallyl phthalate prepolymer. An investigation by infrared spectroscopy

The cure of the dially phthalate prepolymer was studied by means of infrared spectroscopy. It was found that the C?C stretching band of the allyl group, which appears at 1647 cm^?1 in diallyl phthalate monomer, splits into two bands at 1645 and 1651 cm^?1 in both of the prepolymers and cured resins derived therefrom, the split band being found to be mostly useful to investigate the highly cured resin system of diallyl phthalate. On the basis of the split band, α is defined as a new parameter expressing a degree of residual unsaturation of diallyl phthalate prepolymers as well as highly crosslinked polymers, as revealed experimentally. Further, α proved to correlate closely with other parameters such as the iodine value measured for the prepolymers, and swelling weight ratio or Barcoal hardness (hot) measured for the cured resins, it becoming evidently a convenient parameter to examine the degree of crosslinking of diallyl phthalate resin system. The effect of metal molds employed upon cure of prepolymers was also elucidated from the measured α values.     

Mechanical and thermal properties of bisphenol A-based cyanate ester and diallyl phthalate blends

Cyanate ester resins are a high performance class of compounds. They have excellent mechanical properties, dielectric properties and thermal properties; however, their major drawback is their brittleness. An attempt was made to improve the impact strength of the cyanate ester resin. In the present study a commonly used cyanate resin, bisphenol A dicyanate (BADCy), was modified by the addition of diallyl phthalate (DAP) and was cured with benzoyl peroxide. The properties of the blends such as thermal and mechanical properties were investigated in detail by scanning electron microscope, dynamic mechanical analysis, thermogravimetric analysis, and mechanical measurement. The results indicate that the addition of the appropriate amount of DAP can effectively improve the impact toughness and the flexural strength while sacrificing the thermal properties of the blends. The maximum impact strength and flexural strength were observed on addition of 15 phr DAP content. However, the thermal stability of the blends was found to be lower than that of the unmodified BADCy resin.     

Preparation of functional polymer microspheres by suspension copolymerization of diallyl phthalate with carboxylic monomers

A study was made of the suspension copolymerization of diallyl phthalate (DAP) and acrylic and methacrylic acid (AAc and MAc, respectively, which were charged after delay to the suspension of partially prepolymerized DAP) and the structure of resulting gel particles. In the copolymerization of DAP with AAc, the conversion of AAc leveled off despite an appreciable amount of AAc remaining in the aqueous phase, whereas in DAP–MAc copolymerization most MAc was polymerized in the particles. The particle structure depended significantly on the mode of comonomer charge. Earlier charge of the comonomer to the reaction system resulted in the formation of particles having comonomer unit-rich surface layer. This was interpreted in terms of phase separation through loosely crosslinked structure in the particles and supported by an adsorption test using a dye and the observation of surface structure of the particles. The timing of comonomer charge changed the amount of comonomer units in the surface layer from 0.06 to 0.60 mmole/g particle.     

Studies on adhesion of allylic resin. III. Rheological treatment for the adhesion of diallyl phthalate resin

Rheological treatment was carried out for the joining system of diallyl phthalate resin and dichromate-treated copper foil. Rotational and diffusional segmental motions in the diallyl phthalate molecule are required to obtain the necessary bonding strength, and this consideration was confirmed by Kanamaru's setting rate theory. Furthermore, the bonding strength was dependent on the setting temperature and time, and these results were investigated by the dynamic properties of diallyl phthalate resin.     

Internal pressure behavior of polymers above and below the glass temperature

It has been well established in the literature that the internal pressure, P_i = (?E/?V)_T, of a polymer in the glassy state is about half the value expected from the behavior of the polymer just above the glass temperature, Tg. Consideration of this behavior in terms of a recent analysis of factors affecting internal pressures leads to the conclusion that the expression for the total energy of a glass must include a volume-dependent stored energy term, a term not present above Tg. This stored energy could be associated with actual bond and segment deformations in the glassy state. Brittleness and solvent cracking behavior of glasses will be strongly dependent on this stored elastic energy which can be modified by altering the molding conditions under which the glass is formed.     

Correlation between network structure and brittleness of triallyl isocyanurate resins as compared with diallyl phthalate resins

It is not possible to improve the toughness of triallyl isocyanurate (TAIC) resins by applying the procedures useful for diallyl phthalate (DAP) resins as typical allyl resins. The results obtained are discussed in connection with the network structure of TAIC resin. Thus, the polymerization of TAIC would provide a homogeneous network accompanied by the incomplete occurrence of intermolecular crosslinking reactions caused by the rigidity of polymer chains, although DAP resins would consist of the microheterogeneous networks as the agglomerate of colloidal particles.     

An analysis of the rheology of polypropylene below its melting point

Three sets of data for the deformation of crystalline poly-propylene in uniaxial tensile tests and uniaxial creep, in equal biaxial creep and in planar shear are examined. The methods of analysis used in the original papers, all based on variants of linear elasticity, are critically evaluated, and a constitutive equation based on the theory of a simple fluid with memory is proposed.