蒙脱石的有机化及其在不饱和聚酯中的试验

本文按正交法设计了18个制备有机蒙脱石的实验,优化了制备最大层间距的蒙脱石的最佳工艺条件,并对其进行了表征,最后制备了几种不同层间距蒙脱石／不饱和聚酯树脂复合材料。FTIR证实有机插层剂已进入蒙脱石;XRD结果表明蒙脱石层间距由1．44nm增加到3．98nm;通过对复合材料力学性能测试表明：层间距(3．98nm)最大的蒙脱石制得的复合材料各项性能最好,其中冲击强度提高了217％,弯曲强度提高了355％。     

Cure behavior of unsaturated polyester/modified montmorillonite nanocomposites

Dynamic rheology, differential scanning calorimetry and in situ Fourier transform infrared spectroscopy were used to study the cure behavior of unsaturated polyester/modified montmorillonite nanocomposites. The results showed that their gel times increased markedly at the same cure temperature, and that the activation energy of the nanocomposites was higher than that of the pure unsaturated polyester. Their peak temperatures of enthalpy increased as well. The total exotherm of the cure reaction declined and the cure rate decreased. In the curing process of pure unsaturated polyesters, the conversion of styrene was higher than that of the double bonds on unsaturated polyester macromolecular chains. The cure mechanism of the unsaturated polyester/modified montmorillonite changed because of the presence of double bonds in the layers of modified montmorillonite. However, the conversion of styrene in the nanocomposites was lower than that of double bonds on unsaturated polyester chains during cure at room temperature, and the conversion of styrene was increased after post‐curing and was higher than that of the double bonds on unsaturated polyester chains at the end of the cure reaction. Moreover, the degree of reaction of double bonds on unsaturated polyester chains of the nanocomposites was higher than that of unsaturated polyesters. Copyright © 2006 Society of Chemical Industry     

Water-containing resin based on unsaturated polyester

Unsaturated polyester resins containing water were prepared through two steps: formation of a stable W/O emulsion of polyester prepolymer and subsequent polymerization of the emulsion. In this paper, conditions for formation of the resins from the W/O type emulsion and the heat-protection properties of the resulting water-containing resins are reported. The stability of the emulsions was measured, and the results are discussed in relation to the gelation time, since the polymerization of the emulsions is required to proceed faster than their disintegration. It was found that with increasing viscosity of the emulsions their stability increases and the gelation time shortens. The above requirement is fulfilled at almost all regions of emulsifier concentration where stable W/O emulsions are formed. Water-containing unsaturated polyester resins exhibit a remarkable heat-protection effect at elevated temperatures (500 and 2500°C.) in comparison with polyester resins not containing water.     

Effect of reactive diluents on properties of unsaturated polyester/montmorillonite nanocomposites

Unsaturated polyester (UP)/montmorillonite (MMT) nanocomposite was prepared by using hydroxypropylacrylate (HPA) as a reactive diluent instead of conventional styrene monomer and the effect of polarity of reactive diluent on properties of nanocomposite was investigated. X‐ray and mechanical test data indicated that mixing for an extended period of time is essential to enhance the physical properties of nanocomposites in the UP/Cloisite 6A system. This was attributed to the high polarity of HPA that may disturb the preintercalation of UP resin into the galleries of MMT. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 238–242, 2004     

Gel time and polymerization kinetics of unsaturated polyester resin/clay montmorillonite nanocomposites

This article presents the variation of viscosity, gel point, and curing kinetic process of nanocomposites based on unsaturated polyester resin (UPR) and natural nano‐clay CloisiteNa^+® and organomodified Cloisite15A^® montmorillonites (MMT). Different amounts (1–10 wt%) of nanoclays were added homogeneously before the cross‐linking reaction of the thermoset polymer. The complex viscosity before curing was especially dependent on the CloisiteNa^+® content more than Cloisite15A^®. The G' and G'' slope also as the complex viscosity criterion were used to determine the nanocomposites gel time variation. Isothermal differential scanning calorimetry measurements were performed to calculate the reaction order and the rate constant using different empirical equations. These results demonstrated a catalytic effect of the clays on the UPR cure, with diffusion controlled phenomena predominating at high conversions. The X‐ray diffraction patterns were useful for identifying the nanocomposites formation, and gave information about the clays dispersion, which served to support the rheological and polymerization kinetic results. Finally, natural MMT CloisiteNa^+®decreased gel time and was more compatible with UPR than the organomodified Cloisite15A^®. POLYM. COMPOS., 36:1931–1940, 2015. © 2014 Society of Plastics Engineers     

Tensile properties of kenaf/unsaturated polyester composites filled with a montmorillonite filler

Kenaf/unsaturated polyester composites filled with montmorillonite (MMT) filler were produced. Overall, the study showed that, for samples with kenaf filler only, the strength properties decreased as the kenaf filler loading was increased from 40 to 60%. The increase in the kenaf filler loading reduced the amount of matrix material. This subsequently lowered the ability of the sample to absorb energy or distribute stress efficiently. However, with MMT, the tensile properties improved because of the high aspect ratio and surface area of the MMT. The study of the effect of kenaf filler size on the tensile properties showed that the samples with the smallest size (74 μm) displayed the lowest tensile properties compared to the larger ones. This was attributed to the agglomeration of the kenaf fillers. The addition of MMT resulted in an overall increase in the tensile strength of the composites compared to those without MMT. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

UV curing of composites based on modified unsaturated polyester

Synthesis and photocrosslinking of glass fiber-reinforced composites, based on epoxy acrylate-modified unsaturated polyester, have been investigated. The efficiency of the photocrosslinking process for glass fiber laminates of the polyesters that contain different comonomers has been evaluated by measuring mechanical properties. The data show (i) that 2 mm thick laminates, containing 30–40% glass fiber mats, are cured with UV irradiation for 15 sec at room temperature in air; (ii) that multifunctional acrylate or acrylether monomers added to the polyester resin improve the tensile and flexural properties of the photocured product to a greater extent than do added allylic monomers, due to the different photocrosslinking mechanisms; (iii) that the physical properties of the photocrosslinked laminates are well correlated with the molecular weight of the polyester, the amount of multifunctional monomer added, and the glass fiber content. © 1994 John Wiley & Sons, Inc.     

Synthesis and mechanical properties of unsaturated polyester based nanocomposites

Two classes of nanocomposites were synthesized using an unsaturated polyester resin as the matrix and sodium montmorillonite as well as an organically modified montmorillonite as the reinforcing agents. X‐ray diffraction pattern of the composites showed that the interlayer spacing of the modified montmorillonite expanded from 1.25 nm to 4.5 nm, indicating intercalation. Glass transition values of these composites increased from 72°C, in the unfilled unsaturated polyester, to 86°C in the composite with 10% organically modified montmorillonite. From Scanning Electron Microscopy, it is seen that the degree of intercalation/exfoliation of the modified montmorillonite is higher than in the unmodified one. The mechanical properties also supported these findings, since in general, the tensile modulus, tensile strength, flexural modulus, flexural strength and impact strength of the composites with modified montmorillonite were higher than the corresponding properties of the composites with unmodified montmorillonite. The tensile modulus, tensile strength, flexural modulus and flexural strength values showed a maximum, whereas the impact strength exhibited a minimum at approximately 3–5 wt% modified montmorillonite content. These results imply that the level of exfoliation may also exhibit a maximum with respect to the modified montmorillonite content. The level of improvement in the mechanical properties was substantial. Adding only 3 wt% organically modified clay improved the flexural modulus of unsaturated polyester by 35%. The tensile modulus of unsaturated polyester was also improved by 17% at 5 wt% of organically modified clay loading.     

Synthesis and applications of unsaturated polyester resins based on PET waste

Three types of unsaturated polyester resins were synthesized from the glycolysis of polyethylene terephthalate (PET) plastic waste, considering environment, cost and properties for their applications. These synthesized unsaturated polyester resins could be used for various construction processes and materials such as no dig pipelining (NDR-1), pultrusion (PLR-1) and polymer concrete (PCR-1). PET was taken from common soft-drink bottles, and ethylene glycol (EG), diethylene glycol (DEG) and MPdiol glycol mixtures were used for the depolymerization at molar ratios. The glycolyzed PET 1 ^st products (oligomers) were reacted with maleic anhydride, phthalic anhydride and dicyclopentadiene (DCPD) (especially for polymer concrete) to form unsaturated polyester resins with mixed styrene. The lab scale (1–5 kg) and pilot plant scale-up tests (200 kg) were experimented to evaluate the processing characteristics, viscosity, acid number and curing behaviors. The main properties such as hardness, flexural strength, tensile strength, heat distortion temperature, elongation, and chemical resistance were determined based on the various uses of the three resins. Furthermore, the applicability and the properties of these developed resins were verified through many real application tests.     

Nanocomposite systems based on unsaturated polyester and organo‐clay

Unsaturated polyester (UP) systems give rise to numerous possible approaches in synthesizing nanocomposites. A simultaneous mixing method was used to synthesize UP‐resin/organo‐clay nanocomposites. The effects of various mixing processes, using several organically‐modified clay types, were investigated. The incorporation of these organo‐clays resulted in an intercalated structure, the extent of which depended mainly on the type of the clay organic treatment. Organo‐clays that exhibited the highest intercalation levels were further studied using a sequential mixing method. The UP‐alkyd (without styrene) was mixed with different organo‐clays. Processing parameters such as mixing modes, applied shearing levels, clay contents, and mixing‐temperatures were investigated. Prolonged high shear levels promoted the intercalation and exfoliation of the silicate layers, resulting in a better dispersion of clay particles. The high shear levels effects were achieved by vigorous mechanical mixing and were intensified by using large amounts of clay and optimized matrix viscosity. Rheological studies of the nanocomposites were found complementary and in correlation with morphological and thermal characterization. This methodological approach provides a basis for understanding the structuring processes involving the formation of the UP/clay nanocomposites and establishing materials‐processing‐structure interrelations. Polym. Eng. Sci. 45:174–186, 2005. © 2005 Society of Plastics Engineers.     

Toughened interpenetrating polymer network materials based on unsaturated polyester and epoxy

Simultaneous interpenetrating polymer networks (IPNs) based on epoxy (diglycidyl ether of bisphenol A) and unsaturated polyester (UP) were prepared by using m‐xylenediamine and benzoyl peroxide as curing agents. A single glass transition temperature for each IPN was observed with differential scanning calorimetry, which suggests good compatibility of epoxy and UP. This compatibility was further confirmed by the single damping peak of the rheometric dynamic spectroscopy. Curing behaviors were studied with dynamic differential scanning calorimetry, and the curing rates were measured with a Brookfield RTV viscometer. It was noted that an interlock between the two growing networks did exist and led to a retarded viscosity increase. However, the hydroxyl end groups in UP catalyzed the curing reaction of epoxy; in some IPNs where the hydroxyl concentration was high enough, such catalytic effect predominated the network interlock effect, leading to fast viscosity increases. In addition, the entanglement of the two interlocked networks played an important role in cracking energy absorption and reflected in a toughness improvement. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 72: 585–592, 1999     

不饱和聚酯型人造大理石的力学性能

简述了不饱和聚酯(UPR)型人造大理石的制备工艺。研究了质量比为4∶1的Al(OH)3/Ca(OH)2复合填料用量对不饱和聚酯型人造大理石力学性能的影响,对制得的人造大理石的耐腐蚀性进行了测试,采用光学显微镜观察了试样腐蚀前后的表面形貌。结果表明,在复合填料与UPR质量比为1.86∶1时,弯曲强度、压缩强度达到最大,分别为55.88 MPa和96.04 MPa。甲苯对人造石的腐蚀作用最大,氢氧化钠次之,硫酸腐蚀作用较小,腐蚀介质主要对不饱和树脂聚合物产生腐蚀,从而导致人造石力学性能降低。     

Flame retardancy of unsaturated polyester composites with modified ammonium polyphosphate,montmorillonite, and zinc borate

Ammonium polyphosphate (APP) was modified using a new method, where the resulting modified APP (MAPP) was obtained by mixing APP with unsaturated polyester resin (UPR). MAPP was more effective in improving the flame retardancy of UPR than APP which was due to the improved dispersion of MAPP in UPR composite. Then, the UPR composites were prepared based on dimethyl methylphosphonate, MAPP, montmorillonite, and zinc borate. Finally, the flame-retardant and mechanical properties of the UPR composites were analyzed using the limited oxygen index (LOI), thermogravimetric analysis, UL-94 vertical burning test, scanning electron microscopy, cone calorimetry, mechanical tests, and viscosity measurements. The LOI and UL-94 tests showed that the flame-retardant properties clearly improved with the addition of fillers in the UPR composites compared to pristine UPR. The synergistic effect of Si- and P-containing flame retardants in this composite resulted in the LOI value increasing from 18.9 to 31.3% and achieved the UL-94 V-0 rating. Moreover, the heat release rate was lower than the pristine UPR. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47180.     

Preparation and properties of unsaturated polyester nanocomposites based on silylated sepiolite nanofibers

The novel surface‐modified sepiolite/unsaturated polyester (sepiolite/UP) nanocomposites were prepared by in situ polymerization. Sepiolite fibers were first organo‐modified by grafting of vinyltriethoxysilane (VTS) containing a double bond onto the surfaces and used as nanofillers. The morphology of sepiolites and nanocomposites were characterized by X‐ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), scanning electron microscope (SEM), and transmission electron microscope (TEM). Moreover, the thermal properties were determined by thermogravimetric analysis (TGA) and the thermal degradation mechanism was discussed. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

不饱和聚酯树脂微乳液的研究(Ⅰ)不饱和聚酯树脂的微乳化

合成了不同磺酸盐含量的三种不饱和聚酯，通过拟三元相图分析磺酸盐含量、苯乙烯、不同正构醇和水组成的体系对微乳区域的影响。研究结果表明，磺酸盐不饱和聚酯同苯乙烯互溶的前提下，磺酸盐含量越大，其微乳液增溶的水量越大；磺酸盐含量一定时，苯乙烯含量越小，其微乳液增溶的水量越大；正构醇质量分数为在2％～10％范围内，其微乳液增溶的水量最多；三种醇相比较，正丁醇体系的微乳区是W／O型向O／W型过渡的连续区域，正丙醇体系的O／W型微乳液区明显不同于正丁醇体系，正戊醇体系不能形成水包油型的微乳区。     

气干型不饱和聚酯树脂

论述了以烯丙基 (缩水 )甘油醚改善不饱和聚酯树脂的气干性 ,确定了气干性单体的最佳用量及树脂的稳定性酸值。     

Waterborne unsaturated polyester resins

The transformation of solvent soluble unsaturated polyester resins into resins able to form stable water dispersion is presented in this paper. The methods of modification are discussed, consisting of the introduction of polar hydrophilic groups such as carboxylic and sulfonic ones (sodium 5‐sulfonatoisophthalic acid) into the resin molecule, which ensure good tolerance with water. Instead of styrene, glycerol monoethers of allyl alcohol and unsaturated fatty alcohols were used as reactive built‐in crosslinking monomers for resin modification. The influence of the resin composition and method of synthesis on the dispersion stability and properties of photocurable lacquer coatings obtained from the waterborne resins were investigated.     

Preparation and testing of local polyester composites based on unsaturated polyesters as binder

A series of polymeric composites were prepared with sand/polyester ratio 92:8%. The sand used was local one. The polymeric composites were tested for their compressive strength, exterior volume, porosity, water uptake, specific gravity, volume of open pores and bulk density. The mechanical properties of these polymeric composites were within the range required for building bricks. No significant differences were observed between the polymeric composites made of glass sand and those from untreated sand except in exterior volume and compressive strength. Medium untreated sand was found to give better results in the mechanical properties.     

Improving glass transition temperature of unsaturated polyester thermosets: Conventional unsaturated polyester resins

Highly crosslinkable unsaturated polyester resins (UPR) have attracted many interests in the application as reinforced matrix materials. Here, we present a systematical study of the influence of different curing conditions and styrene concentrations on resin viscosity and dynamic-mechanical properties of the thermoset. The pure maleic Palapreg® P18-03 was selected as model UPR because of its broad industrial use. By applying newly developed thermal curing profiles (without thermal initiators) and by raising the styrene content, the T_g of the network could be increased up to 206/215°C (1/10 Hz). For the first time, a fast curable UPR based on propylene glycol and neopentyl glycol with a T_g of up to 215°C is described. A partial substitution of problematic styrene with methylmethacrylate, tert-butylacrylate, and maleic anhydride (MA) was studied as well. MA leads to significantly improved resin reactivity. A resin containing 42 wt% styrene and 8 wt% MA yields thermosets with remarkably improved mechanical properties and with a narrower glass transition range compared to the original P18-03.     

2步法合成双环戊二烯型不饱和聚酯树脂

采用2步法合成了原子灰用双环戊二烯(DCPD)型不饱和聚酯树脂,研究了原料用量对树脂性能影响,当n(顺酐)∶n(工业DCPD)∶n(精制DCPD)∶n(二元醇)=2.0∶0.7∶0.5∶1.75时,树脂性能稳定,原子灰综合性能如气干性、耐热性、打磨性、刮涂性、柔韧性等良好。