Effects of Adding Unsaturated Polyester to the PVAC Adhesive on the Dimensional Stability of Laminated Veneer Lumber

Many properties of wood are affected by changes in moisture content below the fiber saturation point of wood. In this study, the dimensional stability of laminated veneer lumber (LVL), according to TSI EN 4084 and EN 4086, was evaluated. For this purpose Scots pine (Pinus sylvestris L.) and Oriental beech (Fagus orientalis L.) LVL panels were used. Panels of LVL were manufactured from cut veneers, and poly-vinyl acetate (PVAc), unsaturated polyester (uPE) and mixtures of them, as adhesives. Laminated veneer lumber panels with 4 plies and 5 mm in thickness were produced for each group. Depending on the adhesive type, the swelling and water absorption of the samples were measured by determining the weight increase in the two conditions of oven dried and being above the fiber saturation point. The lowest volumetric swelling of the Scots pine was measured as 10.4% bonded with 100% PVAc (control) and the highest volumetric swelling was measured as 13.8% bonded with 90% PVAc and 10% unsaturated polyester. The lowest volumetric swelling of the Oriental beech was measured as 17.2% bonded with 100% PVAc (control) and the highest volumetric swelling was found to be 21.8% bonded with 90% PVAc and 10% unsaturated polyester. Statistical analysis results show that adding unsaturated polyester to the PVAc increased the volumetric swelling and water absorption levels of both the Scots pine and Oriental beech LVL panels.     

Influence of processing conditions on shrinkage behavior of low profile unsaturated polyester resins. I: Systems without fillers

Blends of unsaturated polyester resin and polyvinylacetate (PVAc) were molded with a new instrument called the Plastoreactomat (PRM). The shrinkage and exothermic peak of polymerization were recorded during moding, and the influence of the processing conditions (pressure and temperature) on these phenomena and on the morphology was investigated for various PVAc contents. Within the limits of this study, it was found that shrinkage increases as the temperature and pressure increase. These results are discussed in terms of a competition between the phase separation and the reaction rates. In addition, it was verified that a co-continuous two-phase system consisting of the PVAc and the polyester network enhances the low-profile behavior.     

Rheology of unsaturated polyester resins. I. Effects of filler and low-profile additive on the rheological behavior of unsaturated polyester resin

Measurements were taken of the bulk rheological properties of concentrated suspensions of particulates in unsaturated polyester resins, using a cone-and-plate rheometer. The particulates used were clay, calcium carbonate, and milled glass fiber. With clay and milled glass fibers, shear-thinning behavior of suspensions was observed at low shear rates or low shear stresses as the concentration of particulates was increased, whereas concentrated suspensions of calcium carbonate exhibited Newtonian behavior over the range of shear stresses or shear rates investigated. The cone-and-plate rheometer was also used for measurements of the bulk rheological properties of various mixtures of polyester resin and low-profile additives. For low-profile additives, solutions, in styrene, of poly(vinyl acetate) (PVAc) and poly(methyl methacrylate) (PMMA) were used. It was found that the bulk viscosities of all mixtures of polyester resin and PVAc solution lie between those of the individual components, whereas the bulk viscosities of some mixtures of polyester resin and PMMA solution go through a minimum and a maximum, depending on the composition of the mixture. While all mixtures of polyester resin and PVAc solution exhibited negligible normal stress, some mixtures of polyester resin and PMMA solution exhibited noticeable normal stresses. It should be mentioned that polyester resin follows Newtonian behavior. It turned out that all mixtures of polyester resin and PVAc solution exhibited clear, homogeneous solutions, whereas mixtures of polyester resin and PMMA solution exhibited optical heterogeneity, i.e., turbidity. When polyethylene powders were used as low-profile additives, suspensions of polyester resin and polyethylene powders exhibited negative values of normal stress as the concentrations of suspension reached a critical value. When both filler and low-profile additive were put together in polyester resin, the rheological behavior became quite complex, indicating that some interactions exist between the filler and the low-profile additive.     

Chemorheology of thermosetting resins. III. Effect of low-profile additive on the chemorheology and curing kinetics of unsaturated polyester resin

An experimental study was conducted to investigate the effect of low-profile thermoplastic additives on the rheological behavior during cure and the curing kinetics of unsaturated polyester resin. For the study, a general-purpose polyester resin was used and two different types of thermoplastic additive, poly(vinyl acetate) (PVAc) and poly(methyl methacrylate) (PMMA), were used as low-profile additives. It has been found that, during cure, the resin/PMMA system exhibits shearthinning behavior even before the cure time reaches the critical value tη∞ whereas the resin/PVAc system does not. Also, both PVAc and PMMA help reduce the shrinkage of the resin during cure. However, our study shows that shrinkage control becomes effective only when the shear rate is greater than a certain critical value. The curing behavior determined with the aid of differential scanning calorimetry (DSC) shows that the rate of cure and the final degree of cure are decreased when the amount of low-profile additive is increased.     

Thermogravimetric analysis and morphological behavior of melamine‐formaldehyde filled polyvinyl acetate—Polyester nonwoven fabric composites

The objective of the present research work is to study the effect of different amounts of melamine‐formaldehyde (MF) viz., 0–20 parts by dry weight on the thermal stability of polyvinyl acetate (PVAc) latex impregnated polyester nonwoven fabric composites. From the thermogravimetric analysis, the improvement in thermal stability of the composites was noticed with increase in the MF content. Composites fabricated with five parts MF‐incorporated PVAc showed a drastic increase in the onset degradation temperature when compared with unfilled composites. It was found that the degradation of MF‐loaded PVAc‐polyester nonwoven fabric composites takes place in two steps. Degradation kinetic parameters were calculated for the composites using Broido and Horowitz‐Metzger methods. The tensile fractured composite specimens were analyzed using scanning electron microscope to know the morphological behavior. The increased percentage ash content also supports for the increased thermal stability of the composites with increasing the MF content in the system. The adhesion between the fiber and matrix can be seen from scanning electron microphotographs. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Tough low profile additives in sheet molding compound

Thermosetting polyester in a sheet molding compound (SMC) shrinks by 7 to 10% and causes fiber show-through and poor surface quality. Adding certain thermoplastics results in zero shrinkage and smooth surfaces; these are called low-profile additives (LPA). Poly(vinyl acetate) (PVAc), a highly effective LPA, decreases the fracture energy from 66.3 to 35.1 J/m² when present as 14 wt% of the matrix, even though the PVAc is tough. It produces a nodular three dimensional network; the crosslinked polyester nodules are interconnected by weak polyester bridges and the PVAc forms a thin coating on each nodule. The macroscopic crosslinking shrinkage is offset by void formation in the PVAc phase. Crack follows the void structure and cleaves the bridges between the nodules. Low matrix fracture toughness leads to high microcracking and early gross failure of the SMC. This paper presents alternative low profile additives that give excellent low profile effect with improved matrix fracture energy and SMC strength. Commercially available styrene-butadiene block copolymers were studied. These are less polar and form discrete cavitated domains of a few 100 μm in the solid polyester matrix. With this morphology, good low profile and toughening usually are contradictory, since the former requires small LPA particles for smooth surfaces and the latter requires large particles for crack bridging by the rubber. However, a good compromise was found in Epoxidized Kraton D1300X (a 50% diblock and 50% triblock copolymer of styrene and butadiene) with the compatibilizer Ricon 131MA17 (a maleic anhydride-polybutadiene adduct). This produces a low profile effect equivalent to PVAc, but with a higher matrix fracture energy of 70.7 J/m² and higher matrix modulus. With the epoxidized rubber, the flexural strength of the SMC increases by 13% over that with PVAc, with no sacrifice of the modulus or strain-to-failure.     

Phase‐separation mechanism and corresponding final morphologies of thermoset blends based on unsaturated polyester and low‐molar‐weight saturated polyester

The final morphology of cured blends based on unsaturated polyester, styrene, and low‐molar‐weight saturated polyester as a low profile additive (LPA) was investigated with atomic force microscopy and scanning electron microscopy. The observed structure was compared to those obtained with widely used poly(vinyl acetate) (PVAc). On the surface and in the bulk, a network of particles, ranging in size from 50 to 60 nm, was observed with saturated polyester as an LPA. The influence of the molar weight and LPA content was investigated. To determine the mechanism of formation of such a morphology, in situ experiments were carried out to elucidate the phase‐separation mechanism. Small‐angle laser light scattering and small‐angle neutron scattering experiments were performed on ternary blends containing PVAc and saturated polyester, respectively. The first stage of spinodal decomposition was observed in both cases. Within our experimental conditions, gelation froze further evolution and led to a two‐phase cocontinuous structure that imposed the final morphology characteristics. In particular, the period and amplitude of the concentration fluctuations generated during the phase separation played essential roles. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 95: 1459–1472, 2005     

Miscibility of biodegradable aliphatic polyester and poly(vinyl acetate) blends

We report miscibility behavior for synthetic biodegradable aliphatic polyester (BDP) and poly(vinyl acetate) (PVAc) blends by investigating their thermal, rheological, and mechanical properties. Two separate glass transition temperature peaks for the BDP/PVAc blends proved that these blend systems are immiscible. From the rheological measurement, the shear viscosity as a function of shear rate is observed to increase with increasing PVAc content in BDP/PVAc blends, since PVAc has a relatively high molecular weight compared to BDP. Moreover, BDP blends with 10 wt % PVAc have excellent mechanical properties. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 1348–1352, 2000     

Low‐profile mechanisms in a PVAc/polyester blend

The different steps associated with the curing of a PVAc/polyester blend are identified and correlated to the mechanism of shrinkage control in the presence of a low‐profile additive (LPA). Poly(vinyl acetate) (PVAc) is used as a LPA and is shown to induce a phase separation upon curing that leads to an interconnected globule morphology. This morphology strongly modifies the rheokinetics of the blend compared to that of the neat polyester resin. In particular, the presence of PVAc delays the cure kinetics and the gel time. A comparison between these delays, called shift times, demonstrates an increase in the gel conversion of polyester in the presence of PVAc. This, coupled to the thermal expansion of PVAc at the early stages of curing, contributes to the low‐profile effect. Microvoids in the LPA‐rich phase, which are believed to play a key role in the mechanism of shrinkage control, are efficient at the later stages of curing and during cooling and complete the low‐profile effect. However, it is also shown that the formation of microvoids may indirectly induce macroscopic voids that could be at the origin of pinholes at the surface of the parts molded with this material. POLYM. ENG. SCI. 46:303–313, 2006. © 2006 Society of Plastics Engineers     

Effects of poly(vinyl acetate) and poly(methyl methacrylate) low-profile additives on the curing of unsaturated polyester resins. I. Curing kinetics by DSC and FTIR

The effects of two low-profile additives (LPA), poly(vinyl acetate) (PVAc) and poly(methyl methacrylate) (PMMA) on the curing kinetics during the cure of unsaturated polyester (UP) resins at 110°C were investigated by using a differential scanning calorimeter (DSC) and a Fourier transform infrared spectrometer (FTIR). The effects of temperature, molar ratio of styrene to polyester CC bonds, and LPA content on phase characteristics of the static ternary systems of styrene–UP–PVAc and styrene–UP–PMMA prior to reaction were presented. Depending on the molar ratio of styrene to polyester CC bonds, a small shoulder or a kinetic-controlled plateau in the initial portion of the DSC rate profile was observed for the LPA-containing sample. This was due to the facilitation of intramicrogel crosslinking reactions since LPA could enhance phase separation and thus favor the formation of clearly identified microgel particles. FTIR results showed that adding LPA could enhance the relative conversion of polyester CC bonds to styrene throughout the reaction. Finally, by use of a microgel-based kinetic model and static phase characteristics of styrene–UP–LPA systems at 25°C, the effects of LPA on reaction kinetics regarding intramicrogel and intermicrogel crosslinking reactions, relative conversion of styrene to polyester CC bonds, and the final conversio have been explained. © 1995 John Wiley & Sons, Inc.     

Diffusion of electrolytes in hydrolyzable glassy polymers: Acetic acid in poly(vinyl acetate), poly(vinyl alcohol), and polyesters

Engineering materials containing poly(vinyl acetate) (PVAc) as the key component undergo hydrolytic degradation, which must be minimized or, at least, controlled. To characterize PVAc hydrolysis quantitatively, the diffusion of acetic acid (HAc) in PVAc, poly(vinyl alcohol) (PVA), unsaturated polyester (UPE), and a UPE/PVAc blend was studied in detail. The permeability cell earlier developed by the authors was modified here to reduce experimental error. As the diffusion and solubility coefficients of water and HAc in the above materials were measured at different temperatures, a mathematical model was developed, which takes proper account of the combined water and HAc diffusion in PVAc undergoing partial hydrolysis. The model was further validated by the experimental data obtained at 70°C for UPE/PVAc film, simulating a matrix of sheet‐molding compounds composite materials. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 1157–1166, 2002     

Phase separation of unsaturated polyester resin blended with poly(vinyl acetate)

The behavior of phase separation during the curing reaction of unsaturated polyester (UPE) resin in the presence of low profile additive, that is, poly(vinyl acetate) (PVAc), was studied by low-angle laser light scattering (LALS) and scanning electron microscopy (SEM). The experimental results revealed that the PVAc-rich phase was regularly dispersed in the cured styrene–UPE matrix for styrene–UPE resin blended with 5 wt % of PVAc. As the PVAc content was increased higher than 10 wt %, a cocontinuous PVAc and cured styrene–UPE phase was observed for the cured systems. The LALS observations were carried out in situ at a curing temperature of 100°C; thus, the effect of the rate of exothermic heat released from curing reaction on the morphology of curing system was investigated and reported in this work. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 2413–2428, 1999     

Comparison of the roles of two shrinkage‐controlled low‐profile additives in water aging of polyster resin–glass fiber composites

A model previously formulated or water sorption in polyester resin‐glass fiber composites has been applied to the kinetic analysis of experimental data for two composites containing a hydrolysable (polyvinyl acetate‐PVAc) and a non‐hydrolyzable (polystyrene‐PS) shrinkage‐controlling low‐profile additive (LPA) respectively. It was found that the equilibrium water uptake in the composites and their unreinforced matrix is not drastically affected by the type of LPA. The kinetics of water sorption in the composites, however, were substantially different. The PVAc composite displayed a two‐stage sorption process, the first stage being attributed to diffusion combined with hydrolysis, and the second to matrix swelling and plasticizing. A maximum in the kinetic curve was observed, and was due to changes in water solubility inside the matrix during sorption. In contrast, the PS composite displayed the typical kinetics of materials with slowly increasing hydrophilicity.     

Correlation between sizing formulation and compressive behavior of concentrated glass bundle suspensions

The correlation between sizing formulation, bundle mechanical characteristics, and bundle–matrix static and dynamic interactions are investigated. Two glass‐fiber sizing formulations are considered, one containing polyvinyl acetate (PVAc) and the other polyester/PVAc, as conventionally used in sheet molding compounds (SMC). Axial compression tests are conducted on dry two‐dimensional (2D) random suspensions. The forced packing is governed by the bending of fiber bundle segments between bundle‐bundle contact points. Benchmarking of the experimental curves with a modified theoretical model provides an estimation of the fiber bundle bending rigidity under forced packing conditions. This value is found to depend on the bundle sizing as well as on the interaction with solvents present in the matrix as is the case for SMC. Free flow and molding experiments are performed on planar SMC sheets using the two different fiber bundles as reinforcements. The results confirm the dependence of the molding energy and the SMC rheology on the bundles chemical and mechanical characteristics. POLYM. COMPOS., 26:370–376, 2005. © 2005 Society of Plastics Engineers     

新型玻纤毡用粉末粘结剂的研制

采用专门研制的PVAc树脂与中等数均分子量聚酯树脂混合制备得到新型的玻璃纤维原丝毡用粉末粘结剂。该粘结剂既保留了原有树脂的良好粘结力和理想的粒度分布,又有效地改善了贮存稳定性的问题,同时产品质量稳定性好。通过试验分析,选用的改性PVAc树脂要具有适合的软化点和较低的丙酮不溶物含量;聚酯树脂具有适合的软化点和分子量。进行两种树脂的不同配比试验,最后确定最适合的配方是GY-01-F。     

聚酯玻璃钢氙灯加速老化弯曲强度的分形现象研究

对聚酯玻璃钢进行实验室氙灯加速老化试验,测试了聚酯玻璃钢不同老化时间的弯曲强度。研究发现,弯曲强度与老化时间关系的现象是分形的,采用改变观察尺度计算方法对分形部分进行了分形维数的计算,得到聚酯的分形维数为1.24、含碳酸钙聚酯玻璃钢的分形维数为1.12、聚酯玻璃钢的分形维数为1.08,这说明氙灯加速老化下弯曲强度变化的复杂程度是按聚酯、含碳酸钙聚酯玻璃钢、聚酯玻璃钢顺序依次降低的。     

Thermokinetics of unsaturated polyester and vinyl ester resins

An experimental study was carried out to investigate the isothermal and non-isothermal curing kinetics of unsaturated polyester and vinyl ester resins, using differential scanning calorimetry (DSC). Emphasis was put on investigating the effect of low-profile additives on the curing kinetics of the thermo-setting resins. For the study, a general-purpose polyester resin and a vinyl ester resin were used, together with polyvinyl acetate (PVAc) as low-profile additive, benzoyl peroxide as initiator, and N,N-dimethyl aniline as promoter. It has been found that (1) the addition of the low-profile thermoplastic-additive decreases the rate of cure and, also, the final degree of cure of the resins, (2) the total heat of cure generated by isothermal cure is lower than that generated by non-isothermal cure, and (3) the resin/initiator mixture with promoter exhibits two major exotherm peaks during non-isothermal cure, but only a single exotherm peak during isothermal cure.     

Effect of curing temperature on the morphology of unsaturated polyester resin blended with poly(vinyl acetate)

Phase separation of unsaturated polyester/styrene (UPE/styrene) resin blended with 5 and 10 wt% of poly(vinyl acetate) (PVAc) cured at various temperatures ranging from 75°C to 150°C was studied using low angle laser light scattering (LALS) and scanning electron microscopy (SEM). For UPE/styrene resin blended with 5 wt% PVAc cured at a temperature below 90°C, a discrete phase‐separated structure was observed. As curing temperature was raised above 90°C, SEM micrographs revealed that more and more cured UPE globules fused together with increasing curing temperature. The LALS intensity profile became broader with increasing curing temperature, indicating a less discrete phase‐separated structure at a higher curing temperature. As PVAc content was increased to 10 wt%, SEM micrographs revealed a co‐continuous phase‐separated structure. The LALS intensity decayed slowly from the center of the scattering pattern to a high scattering angle without the appearance of maximum scattering peak intensity. The morphology of the cured sample did not change too much with curing temperature for UPE/styrene resin blended with 10 wt% of PVAc.     

不饱和聚酯树脂改性研究进展

综述了不饱和聚酯树脂(UPR)改性的研究进展。介绍了收缩率控制机理,低收缩研究发展的4个阶段,低收缩剂LSA的典型代表——聚苯乙烯(PS),聚甲基丙烯酸甲酯(PMMA),聚醋酸乙烯(PVAc),PVAc-PS共聚物。讨论了UPR增韧改性方法,提高分子主链对称性,在分子结构中引入长链醇与长链酸,长链醇包括一缩二乙二醇、二缩三乙二醇及聚乙二醇;长链二元酸如己二酸等。此外还可加入热塑性弹性体,如液体橡胶、液体聚氨酯等以形成互穿网络结构增韧UPR。论述了提高UPR阻燃性的2种途径,即选用本质阻燃性树脂和向UPR中添加阻燃剂。介绍了含卤有机阻燃剂、无机阻燃剂、主链或主链与侧链均含磷的阻燃剂和赋予阻燃性的影响因素。介绍了部分采用可降解的植物纤维——竹纤维制备的UP复合材料和木粉改善UPR的性能。这些方法使不饱和聚酯树脂在低收缩性能、力学性能、阻燃性能等方面得到了改善,扩展了其应用范围。     

Polyester molding compounds: Partial systems and related particulate composites

Several binary of ternary systems, consisting of an unsaturated polyester resin and one or two additives which are currently considered in formulating polyester molding compounds (such as BMC and SMC) were studied in relation to some of their relevant properties as a function of their composition. The additives were: MgO as a thickening agent; a thermoplastic polymer (PS or PVAc); and a fine CaCO₃ particulate filler. Measured quantities were, depending on the system physical state (fluid or crosslinked): viscosity, linear shrinkage, flexural modulus and strength, and fracture toughness and energy, besides SEM morphological characterization. Quantitative relations could in several instances be expressed; in particular, the relation between strength and filler volume fraction was found to follow the linear equation of the simplest area reduction “random model”.