Poly(ethylene terephthalate) waste was depolymerised in the presence of diethylene- or tetraethylene glycol and manganese acetate as a catalyst. An epoxy resin was then prepared by the reaction of these oligomers with epichlorohydrin in presence of NaOH as a catalyst. The produced oligomers were condensed with maleic anhydride and ethylene glycol to produce unsaturated polyester. The chemical structures of the resulting epoxy and unsaturated polyester resins were confirmed by 1HNMR. The vinyl ester resins were used as cross-linking agents for unsaturated polyester resin diluted with styrene, using free radical initiator and accelerator. The 2-amino ethyl piprazine was used as hardener for epoxy resins. The curing behaviour of the unsaturated polyester resin, vinyl ester resins and styrene was evaluated at different temperatures ranged from 25 to 55 °C to calculate the curing activation energy of the system. The cured epoxy and unsaturated polyester resins were evaluated in coating application of steel. 相似文献
Oil-bearing formations often consist of loose sandy material. In the production of oil from these formations sand tends to be carried to the well bore along with the oil. The flow of sand can be prevented by consolidating or cementing together the sand particles of the formation around the well bore. The cementing has to be accomplished in such a manner that fluid flow channels between particles remain open. This paper describes a new three-step process that was developed to consolidate oil well sand. The steps in the process involve injection of: (1) resin, (2) inert fluid, and (3) inert fluid containing a catalyst. In the first step of the process, resin in injected into the formation where it fully saturates the interstices between sand grains. Permeability is established in the second step by displacement of the excess resin from the interstices, thereby leaving a thin film of resin on the sand grains. In the third step, polymerization is activated by migration of catalyst from the inert fluid into the thin resin film on the sand. The process has the advantage that resin is placed and permeability is established before the resin is catalyzed. This avoids premature polymerization of the resin which might cause plugging of the formation or the tubing string used to inject resin. Desirable characteristics of a resin for the three-step process are: (1) viscosity of 25–200 cp. at well bore temperature; (2) stability for several days at well bore temperature; (3) high adhesion to sand in the presence of an inert flushing fluid; (4) polymerization by less than 10% catalyst; (5) the polymerized resin binds sand together with a strong bond that is not affected by well fluids. Five different resin types have been tested for use in the three-step sand consolidation process. These are: (1) epoxy–anhydride cured with a tertiary amine; (2) epoxy–epoxy diluent cured with a primary–tertiary amine mixture; (3) furan; (4) unsaturated polyester–vinylpyrrolidone; (5) unsaturated polyester–styrene. The two epoxy resins give strong, permeable consolidated sand which is resistant to well fluids such as brine and crude oil. The furan resin gives a weak consolidation. The unsaturated polyester–vinylpyrrolidone gives good strength and oil resistance but is sensitive to brine. The unsaturated polyester–styrene is difficult to apply. Many oil wells have been successfully treated in the Gulf Coast area and in California with the two epoxy resins. Almost all of these wells are producing free of sand, and, to date, more than five million barrels of oil have been produced from these wells. 相似文献
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. 相似文献
An experimental study was conducted to investigate the effect of the chemical structure of low-profile additives on the curing behavior and chemorheology of unsaturated polyester resin during isothermal cure. For the study a general-purpose unsaturated polyester resin was cured in the presence of t-butyl perbenzoate as Initiator. The curing behavior of the resin was investigated using differential scanning calorimetry (DSC). Three different thermoplastic low-profile additives were used, namely poly(vinyl acetate) (PVAc), poly(styrene-co-butadiene), which is also known as KRATON DX-1300, and dehydrochlorinated Isobutylene/isoprene copolymer, often referred to as conjugated diene butyl (CDB) rubber. Each of the these additives, about 30 weight percent, was first dissolved in styrene. The solution was then mixed with unsaturated polyester resin and CaCO3. The CaCO3 particles helped stabilize the emulsions consisting of resin and KRATCN, and of resin and CDB. For each resin formulation, a series of isothermal DSC runs were made at various levels of cure pressure. It was found that for all three low-profile resins investigated, the final degree of cure went through a maximum as cure pressure was increased from atmospheric to 6.21 MPa (900 psi). We have observed evidence that in the presence of an initiator generating free radicals, the unsaturated double bonds in the KRATON and CDB undergo grafting reactions with the styrene monomers and unsaturated polyester resin, increasing the glass transition temperature of KRATON and CDB, to an extent which varies with the cure conditions employed. Both steady and oscillatory shearing flow properties were determined using a cone-and-plate rheometer. The rheological measurements indicate that the resin/CaCO3/KRATON and resin/CaCO3/CDB systems give rise to gel times shorter than the resin/CaCO3/PVAc system. It is concluded that both KRATON and CDB are more effective, both for enhancing the rate of cure of unsaturated polyester resin and imparting impact properties to the cured composites, than those thermoplastic low-profile additives that contain neither unsaturated double bonds nor a chemical structure that has rubber-like properties in the solid state. 相似文献
Summary: Synthesis and properties of amine modifiers for unsaturated polyester resins are presented. The modifiers were obtained by reacting 3‐azapentan‐1,5‐diol (diethanoloamine) with 2,4‐dichloro‐6‐methoxy‐1,3,5‐triazine, 2‐chloro‐4,6‐dimethoxy‐1,3,5‐triazine or with cyanuric chloride. They were incorporated into the structure of typical unsaturated polyester resins in the polycondensation stage, i.e. prior to dilution with styrene, in the amount of 0.25 through to 2.0 wt.‐%. The effect of the modifier presence on the curing behavior of the resulting resins is discussed.
Gelation times for unsaturated polyester resins modified with modifiers A , B , and C are shown with the curing system consisting of peroxide initiator and (?): 0.10 cm3, (?): 0.15 cm3, (?): 0.25 cm3, and (?): 0.50 cm3 of cobalt(II ) octenate solution per 25 g of resin. 相似文献
Abstract Waste polyethylene terephthalate (PET) flakes were depolymerized by using ethylene glycol (EG), propylene glycol (PG), diethylene glycol (DEG), and triethylene glycol (TEG) in the presence of zinc acetate as catalyst. All glycolysis products were reacted with maleic anhydride and mixed with styrene monomer to get unsaturated polyester (UP) resins. Molecular weights of all synthesized UP resins were determined by end-group analysis. The curing characteristics such as gel time and maximum curing temperatures, and mechanical properties such as hardness, tensile strength, and elastic module of these resins were investigated. The waste PET resins were compared with the reference resins prepared with the same glycols and the properties of the resins were found to be compatible with the properties of the reference resins. 相似文献
One method of reducing styrene emissions from vinyl ester (VE) and unsaturated polyester resins (UPE) is to replace some or all of the styrene with fatty acid-based monomers. Methacrylated fatty acid (MFA) monomers are ideal candidates because they are inexpensive, have low volatilities, and free-radically polymerize with vinyl ester. The viscosity of VE resins using these fatty acid monomers ranged from 700-2000 cP, which is considerably higher than that of VE/styrene resins (∼100 cP). In addition, the Tg of VE/MFA polymers were only on the order of 80 °C, which is significantly lower than that of VE/styrene polymers. Decreasing the length of the base fatty acid chains from 18 to 12 carbon atoms improved the Tg by 20 °C, while lowing the resin viscosity from ∼2500 to ∼1000 cP. Residual unsaturation sites on the fatty acid backbone decreased the cure rate of the resins thereby decreasing polymer properties. Ternary blends of VE, styrene, and fatty acid monomers also effectively improved the flexural, fracture, and thermo-mechanical properties and reduced the resin viscosity to acceptable levels, while using less than 15 wt% styrene, far less than commercial VE resins. 相似文献
Dimethacrylate oligomers diluted with styrene (commonly known as vinyl ester resins) are important matrix resins for fiber-reinforced composites used in construction, marine craft, and transportation vehicles. These comonomers react via free radical copolymerization to yield void-free thermosets. The inter-relationships among copolymerization kinetics, physical properties of the networks, and cure temperatures for a 700 g/mol dimethacrylate oligomer with systematically varied styrene concentrations were investigated. FTIR was used to monitor the reactions of the carbon-carbon double bonds of the methacrylate (943 cm−1) and styrene (910 cm−1). Reactivity ratios were determined via a non-linear method at four cure temperatures. The data were analyzed using the integrated form of the copolymerization equation and assuming a terminal reactivity model to predict copolymer compositions throughout the reactions. The results indicated that at early conversion more styrene was incorporated into the networks at lower cure temperatures. The experimental vinyl ester-styrene network compositions agreed well with those predicted by the integrated copolymer equation at early and intermediate conversion. Mechanical properties of dimethacrylate-styrene networks were determined for materials cured at room temperature and at 140 °C. Materials cured at room temperature were tougher and had lower rubbery moduli than those cured at 140 °C. 相似文献
The paper describes the effect of styrene on the properties of bis(methacryloxy) derivatives of epoxy resins (vinyl ester resins). The styrene concentration in the resin was systematically varied between 20–60 wt.-%. The curing characteristics of vinyl ester resins changed only marginally on dilution with styrene. Dilution with styrene resulted in a decrease in tensile modulus and increase in elongation of neat resin castings and glass fibre reinforced laminates. The glass transition temperature of laminates was determined by dynamic mechanical analysis and was found to decrease with increasing styrene content. 相似文献
Polyester resins were prepared by the reaction of p-carboxysuccinanilic acid ethyl ester with ethylene glycol and 1,4-butenediol. Also, unsaturated polyester resins were prepared by the copolymerization of p-carboxysuccinanilic acid ethyl ester and maleic anhydride with ethylene glycol, 1,6-hexanediol, 1,4-butenediol, and 2-butyne-1,4-diol. All the polyester resins and the copolyesters have been characterized and were found to cure with styrene, except those prepared in the absence of maleic anhydride. The properties of the cured products in the form of films were determined. Infrared and nuclear magnetic resonance (NMR) spectroscopy were used for both qualitative and quantitative analyses of the polyester resins and their hydrolyzate products after curing with styrene. 相似文献
ABSTRACT Novel flame retardant unsaturated poly(ester amide) resins (FR-UPEAs) were prepared by the reaction of brominated epoxy resins (BER) with unsaturated aliphatic bisamic acids using a base catalyst. These FR-UPEAs were characterized by elemental analysis and number average molecular weight determination by non-aqueous conductometric titrations. The curing of these FR-UPEAs was carried out by using benzoyl peroxide (BPO) as a catalyst and was monitored on a differential scanning calorimeter (DSC). Based on DSC data, the glass fiber reinforced composites (i.e., laminates) of these FR-UPEAs have been fabricated and their chemical, mechanical, and electrical properties have been evaluated. The composites were analyzed for their self-extinguishing time. The unreinforced cured samples of FR-UPEAs resins were analyzed thermogravimetrically. 相似文献
The rheological properties and curing kinetics of a vinyl ester resin have been determined during isothermal cure. Both steady and oscillatory shearing flow properties were determined using a cone-and-plate rheometer, and the curing kinetics were determined using a differential scanning calorimeter (DSC). Also determined were the rheological properties and curing kinetics of the resin when it had been thickened using magnesium oxide (MgO), in the presence of calcium carbonate (CaCO3) as filler and polyvinyl acetate (PVAc) as low-profile additive. The steady shearing flow behavior observed with the vinyl ester resin was found to be very similar to that observed with a general-purpose polyester resin, reported in Paper I of this series [C. D. Han and K. W. Lem, J. Appl. Polym. Sci., 28 , 3155 (1983)]. However, a significant difference in the oscillatory shearing flow behavior was found between the two resins. We have concluded that dynamic measurement is much more sensitive to variations in resin chemistry than steady shearing flow measurement. DSC measurement has permitted us to determine the degree of cure as a function of cure time. By combining the rheological and DSC measurements, we have constructed plots describing how the viscosity increases with the degree of cure, at various isothermal curing temperatures. 相似文献