Synthesis and Characterization of Melamine Formaldehyde Resins for Decorative Paper Applications

Melamine‐formaldehyde (MF) resins of improved environmental compatibility were synthesized at different molar ratios, temperature and pH. Five molar ratios of melamine and formaldehyde: 35:65, 36.5:63.5, 38.3:61.7, 41.1:58.9 and 42.4:58.6 were used to synthesize the corresponding resins. The prepared samples were characterized by using molecular weight determination viscometery, field emission scanning electron microscopy and thermogravimetric analysis. It was noticed that the solid content in the resin increases with an increase in pH. The maximum percentage of the solid content (51 %) was obtained for pH of 8.5 and temperature range of 95–98 ^oC. The refractive index of the final product was found increasing with an increase of melamine concentration in the resin. A similar trend was noticed in molecular weight of the resins with an increase in monomer yield. The maximum molecular weight of 114218 was obtained from the sample synthesized with MF molar ratio of 42.4:58.6.     

氨催化酚醛树脂的若干特征

采用核磁共振、元素分析、差热分析以及红外光谱等方法,对在不同反应条件下制备氨催化的酚醛树脂的反应过程、所得树脂的结构特征以及树脂的固化过程进行了研究,并对所得结果进行了讨论。     

Epoxidation of Alkyllithium Polybutadienes

Epoxidations with peracetic acid were effected on a series of alkyllithium and sodium polybutadienes, and the properties of the epoxy resins were compared. The alkyllithium and sodium polybutadienes differed in micro-structure and molecular weight distribution. The alkyllithium polybutadienes were more readily epoxidized, and epoxidation resulted in dramatically lower viscosity increases with increasing epoxy contents. Epoxidized alkyllithium polybutadienes varying in molecular weight and epoxy content were shown to be compatible, efficient, and permanent plasticizer-stabilizers for polyvinyl chloride.     

Adhesives and coatings based on phenolic/epoxy resins

Low molecular weight epoxy resin based on bis (4‐hydroxy phenyl) 1,1 cyclohexane was prepared and modified with various types of the prepared phenolic resins. Phenol–, cresol–, resorcinol–and salicylic acid–formaldehyde resins were used. The optimum conditions of formulation and curing process were studied to obtain modified wood adhesives characterized by high tensile shear strength values. This study indicated that the more suitable conditions are 1:2 weight ratio of phenol–or cresol–formaldehyde to epoxy resin in the presence of phthalic anhydride (20 wt%) of the resin content as a curing agent at 150°C for 80 min. Resorcinol–or salicylic acid–formaldehyde/epoxy resins formulated at 1:2 weight ratio were cured in the presence of paraformaldehyde (20 wt%) at 150°C for 60 min. The effect of the structure of phenolic resins on the tensile shear strength values of formulated resin samples, when mixed with the epoxy resins and cured under the previously mentioned optimum conditions for different times, was investigated. Metallic and glass coatings from the previous resins were also prepared and evaluated as varnishes or paints. Copyright © 1999 John Wiley & Sons, Ltd.     

Comparison of thermal curing behavior of liquid and solid urea–formaldehyde resins with different formaldehyde/urea mole ratios

This study was undertaken to compare thermal cure kinetics of urea–formaldehyde (UF) resins, in both liquid and solid forms as a function of formaldehyde/urea (F/U) mole ratio, using multi-heating rate methods of differential scanning calorimetry. The requirement of peak temperature (T _p), heat of reaction (ΔH) and activation energy (E) for the cure of four F/U mole ratio UF resins (1.6, 1.4, 1.2 and 1.0) was investigated. Both types of UF resins showed a single T _p, which ranged from 75 to 118 °C for liquid resins, and from 240 to 275 °C for solid resins. As the F/U mole ratio decreased, T _p values increased for both liquid and solid resins. ΔH values of solid resins were much greater than those of liquid resins, indicating a greater energy requirement for the cure of solid resins. The ΔH value of liquid UF resins increased with decreasing in F/U mole ratio whereas it was opposite for solid resins, with much variation. The activation energy (E _a) values calculated by Kissinger method were greater for solid UF resins than for liquid resins. The activation energy (E _α ) values calculated by isoconversional method which showed that UF resins in liquid or solid state at F/U mole ratio of 1.6 followed a multi-step reaction in their cure kinetics. These results demonstrated that thermal curing behavior of solid UF resin differed greatly from that of liquid resins, because of a greater branched network structure in the former.     

Physicochemical Characterization of Poly(vinyl chloride). II. Molecular Weight Distributions

Abstract

Molecular weight distributions in poly(vinyl chloride) resins have been determined from simple viscosity measurements. Ratio of 11% solution viscosity to intrinsic viscosity yielded a figure which has been correlated with molecular weight distributions obtained (1) from the ratio of weight-average to number-average molecular weights and (2) from gel permeation chromatography. Ratio of viscosities is thus a useful short-cut technique for obtaining approximate molecular weight distributions in poly(vinyl chloride) resins which have 0. 77 < [η] < 1.15 and 1. 6 < ROM < 2. 8.     

Analysis of resoles by gel-permeation chromatography

Resoles, the complex, heat-sensitive product mixture from the alkali-catalyzed reactions of phenol with formaldehyde were investigated by gel-permeation chromatography (GPC). The low molecular weight species of these resins which consisted of mono-and dinuclear methylol phenols were resolved into multiple peaks. Model compounds were used to identify the peaks of the specific methylol phenols or methylene etherbridged diphenols. Differences in the refractive index of individual species restricted the quantitative analysis of low molecular weight components in the resole. The effects of sodium and barium hydroxides and hexamethylene-tetramine as catalysts, reaction temperature, and time on the total composition of a resole are demonstrated with the gel-permeation chromatographic spectrum and with the aid of NMR. Formation of a “secondary” resole by methylolation of the bisphenol of formaldehyde was also monitored by GPC.     

Effect of Molecular Weight of WPU on the Heterogenic PUA Composite Latex Prepared by Soap-Free Emulsion Polymerization

Aqueous acrylic-polyurethane (PUA) composite emulsion was prepared by soap-free seeded emulsion copolymerization. Waterborne polyurethane (WPU) was used as the seeded emulsion and functioned as surfactant. The effect of molecular weight of WPU on the heterogenic was investigated. The molecular weight of WPU was controlled by varying the NCO/OH mole ratio. The GPC results confirmed that the molecular weight of WPU presented double distribution. And the molecular weight of WPU decreased with the increasing NCO/OH mole ratio. Surface tension test indicated that the molecular weight had little influence on the surface activity of WPU. However, after emulsion copolymerization of acrylic monomers, the morphology and properties of the PUA composite were impacted markedly by the molecular weight of WPU. With an increase in the NCO/OH mole ratio, the morphology of PUA composite latex changed from core-shell structures to fish bowl structure, and the mechanical properties of PUA films changed correspondingly.     

环氧树脂/聚砜共混体系相结构的调控研究——环氧预聚物分子量的影响

研究了不同分子量的环氧预聚物对双酚A型双官能团环氧树脂 /聚砜 (PSF) /固化剂 (二氨基二苯基砜 ,DDS)体系相分离结构的影响 .通过红外光谱 (FTIR)和动态热机械分析 (TMA)对反应转化率、玻璃化温度以及固化温度的关系的研究 ,表明环氧预聚物分子量较小时 ,凝胶点和玻璃化是影响相结构的关键因素 ;环氧分子量较大时 ,环氧扩链后粘度的变化则成为抑制相分离的重要因素 .电子显微镜 (SEM)结果表明改变环氧预聚物分子量可以达到调控相结构的目的 ,随着预聚物分子量的增大 ,体系的微区尺寸减小 .     

Hardness evaluation of cured urea–formaldehyde resins with different formaldehyde/urea mole ratios using nanoindentation method

To understand the influence of formaldehyde/urea (F/U) mole ratio on the properties of urea–formaldehyde (UF) resins, this study investigated hardness of cured UF resins with different F/U mole ratios using a nanoindentation method. The traditional Brinell hardness (H_B) method was also used for comparison. The H_B of cured UF resin films with different F/U mole ratios was determined after exposing the films to different post-curing temperatures. The nanoindentation method was employed for these films to measure Meyer hardness (H_M) and reduced modulus (E_r) which have been used to calculate the elastic modulus (E_s) of cured UF resins. As the F/U mole ratio decreased, the H_B decreased continuously, indicating a less rigid network structure in low F/U mole ratio UF resins. The higher the post-curing temperature, the greater the value of H_B. The H_M value also showed a similar trend as a function of F/U mole ratio. However, the E_r and E_s did not show a consistent trend as exhibited by H_M and H_B. Both H_M and E_r showed much greater variation in the coefficient of variation (COV) at lower F/U mole ratios 1.0 and 1.2, indicating a more heterogeneous composition of these resins. Linear relationships between H_M and E_r indicate that heterogeneity of the surface composition of samples contributes greatly to variations in the measured values. This variability is discussed in terms of crystal structures present in the cured UF resins of low F/U mole ratios.     

Synthesis,characterization, and curing of well-defined allyl ether-maleate functional ester oligomers: Linear versus nonlinear structures

A series of allyl ether-maleate functional star-shaped esters with from one to four arms has been synthesized. The structures that have been made are an analogous series with increasing molecular weight and functionality where the increase in molecular weight has been made nonlinear, i.e., star-shaped. The resins are monodisperse in the sense that each arm has a well-defined structure and that, within a certain sample, only one type of molecule exists. The viscosity and rheological behavior of the resins have been studied. The curing kinetics of the star-shaped (branched) resins and the properties of the films formed have also been studied. These properties have been related to differences in functionality and to differences in the molecular architecture of the resins. © 1992 John Wiley & Sons, Inc.     

Synthesis of symmetric macrocyclic diesterdihyrazides using successive [2+1]- and [1+1]-condensations

Potentially useful symmetric macrocyclic diesterdihydrazides were synthesized efficiently from available petrochemical products (tetrahydropyran and 4-methyltetrahydropyran) using successive [2+1]-condensation of 8-hydroxyoctan-2-one and its 6-methyl derivative with glutaric and adipic chlorides and [1+1]-condensation of the intermediate diketodiesters with glutaric dihydrazide.     

Simulation model for urea-formaldehyde reactors

A comprehensive simulation model for urea/formaldehyde (UF)-resins has been developed. The model utilizes kinetic results reported in the literature for low molecular weight systems and extends these to higher molecular weight systems by using a functional group approach. The model consists of - 9 functional groups, 5 urea groups and 4 formaldehyde groups. - 9 reactions, 5 methylolation reactions and 4 condensation reactions. In all these reactions both the formation and the decomposition reactions are included. All the kinetic constants are pH and temperature dependent. Two batch runs with different U/F ratios were used to adjust a couple of model parameters. Samples from these batch runs were analyzed with HPLC for low molecular weight compounds, and GPC for the average molecular weight. A run with continuous IR measurement showed excellent fit for the formaldehyde concentration. The model also estimates the viscosity from the functional groups.     

Splitting of the disulfide bonds in polysulfide polymers by hydrazine

The action of hydrazine on desulfurized tetrasulfide polymer obtained from bis-2-chloroethyl formal leads to S? S bond splitting and depolymerization. Our studies show that successful depolymerization can be initiated only in a strong alkali medium at 95–98°C. During this process cleavage of the disulfide bonds and the formation of polymers of lower molecular weight with ? SH end groups takes place. From the results of the experiments performed it can be seen that the degree of depolymerization increases with an increase in the amount of hydrazine, in the mole ratio of sodium hydroxide, and in the time of reaction. When 0.7–1.0 mole of hydrazine per segment of polymer and 4 mole of sodium hydroxide per mole of hydrazine are used, a polymer of low average molecular weight in the form of water-soluble sodium salt (fraction I) and a polymer in dispersion form (fraction II) are obtained. Similar results could be attained if the amount ot hydrazine were decreased and the mole ratio of sodium hydroxide were simultaneously increased to more than 4 mole per segment of hydrazine used. In a constant amount of sodium hydroxide with a smaller quantity of hydrazine or a shorter reaction time the amount of water-soluble polymer (as a sodium salt) decreases and the amount of polymer in dispersion form increases. If a portion of the polymer in dispersion is coagulated with a portion of the polymer in the mother liquid, the yield of the depolymerized product is higher, but the average molecular weight is also higher than those of fraction I. The influence of the average contents of sulfur on the efficiency of the depolymerization is tested in polymers that contain 2.5 (i.e., 3) atoms of sulfur per segment of polymer. The result is that the depolymerization of the polysulfide polymer could be carried out without previous desulfurization, but the molecular weights of the products obtained with an equivalent quantity of hydrazine are much higher than those obtained by depolymerization of the disulfide polymer.     

Ammeline–melamine–formaldehyde resins. Preparation and properties

Ammeline–melamine–formaldehyde resins (AMF Resins) containing 5–100 mol % of ammeline, were synthesized by polymerization of the preformed sodium salt of ammeline, melamine, and formaldehyde in basic medium by three methods. These resins, when cured, constitute a new class of thermosets. The rate of hydroxymethylation of the amino groups of the ammeline salt with formaldehyde was somewhat larger then that of the amino groups on melamine. At higher pH values ammeline insolubility was not a problem. The AMF resin composition was approximately equal to the mol ratio of the components originally charged. Both ammeline and melamine were consumed over the entire reaction period. Thus, it is possible to make approximately uniform random ammeline-melamine-formaldehyde resins (AMF) with any mol ratio of ammeline salt to melamine. By controlling the pH of the solution from which the resins were isolated, the (SINGLE BOND) O⁻ Na⁺/(SINGLE BOND) OH ratio could be varied. Resin melting points varied widely with the mol fraction of ammeline and the (SINGLE BOND) O⁻ Na⁺/(SINGLE BOND) OH ratio. AMF resin solubilities, shelf lives, cloud points, and water tolerance depended upon the method of preparation, pH, and other factors. The sodium salt of ammeline was hydroxymethylated in water more readily than ammeline. More highly methylolated ammeline species were readily formed in solution but upon precipitation only bis-N-hydroxymethylammeline was isolated. © 1996 John Wiley & Sons, Inc.     

Preparation of CoSe nanoparticles by microwave-assisted polyol method: effect of Se/Co ratio, support type and synthesis conditions on oxygen reduction activity

Highly methanol-tolerant CoSe nanoparticles supported on different carbon substrates were synthesized by microwave heating of glycerol solutions of cobalt(II) acetate and sodium selenite at different Se/Co mole ratios in the presence of different concentrations of acetic acid and ammonia. The resulting CoSe catalysts were used for the electrochemical oxygen reduction reaction (ORR) in acidic solution in the presence of methanol. The ORR activity of the catalyst was increased by increasing its Se content up to 50?mol%. The presence of acetic acid or ammonia in the synthesis solution significantly affects the electrocatalytic performance of the CoSe catalyst; highest activity was observed when the catalyst was synthesized at NH₃/Co(II) mole ratio of 6. Among the catalysts prepared on different supports including carbon black (Vulcan XC-72R), and nanoporous carbons synthesized from resorcinol-formaldehyde and phloroglucinol-formaldehyde resins, the one supported on the carbon prepared from the last resin exhibited highest electrocatalytic activity for ORR.     

Synthesis of Polymers by Using Divalent Metal Salts of Mono(hydroxyethyl)phthalate: Metal-Containing Unsaturated Polyesters with Pendent Methacrylate Groups

Syntheses of novel metal-containing unsaturated polyesters having pendent methacrylate groups obtained by use of divalent metal salts of mono(hydroxyethyl)phthalate-maleic anhydride (MA)-glycidyl methacrylate (GMA) reactions were investigated. The yields were generally high. The metal-containing polyesters obtained were slightly yellow-brown solids, and the molecular weights ranged from 1546 to 2174, depending on the mole ratio of feed. Among them, the polyesters obtained at a feed mole ratio of metal salt:MA:GMA of 1:8:8 were miscible with methyl methacrylate (MMA), giving homogeneous solutions suitable for copolymerization, and the polyesters could be easily cross-linked with MMA to give cured resins. The metal-containing cured polyester resins showed excellent physical properties. Resistance of the resins to chemical attack and boiling water and thermal behavior are also discussed.     

Formulation of an Environmentally Friendly Adhesive for Wood

Summary: Malaysia has over 4 million hectares of oil palm plantations that yield large amounts of empty fruit bunches (EFB) generated from palm oil milling operations. These forms of lignocellulosic residue pose an environmental hazard if their disposal is not managed in a systematic manner. One of the useful elements extracted from these EFBs is lignin. The general purpose of this study is to explore the potential uses of lignin extracted from soda black liquor (paper and pulping waste) derived from oil palm empty fruit bunches (EFB) in the formulation of a more environmentally friendly wood adhesive. In this work, the potential for replacing phenol with lignin in phenol formaldehyde resin formulation is examined. The quantity of phenol was reduced by synthesizing the resin at a lignin to phenol ratio of 1:1. The physical and chemical properties of lignin phenol formaldehyde resin (LPF) and commercial phenol formaldehyde resin (CPF) were then compared. The infrared spectrum revealed similarities in the functional groups of both LPF and CPF resins. Tensile strength comparisons between both resins revealed that the LPF resin had a higher bonding strength (11.60 MPa more in term of allowable maximum load). In addition, the kinematics viscosity test showed that the LPF resin had lower kinematic viscosity than the CPF resin after 21 days of storage. Finally, the scanning electron microscope images for both resins showed similarities in terms of penetration into wood vessels.     

一种用于快速成型工艺的红光光敏树脂的性能研究

合成了一种吸收波长为 6 80nm的菁染料 有机硼盐复合物光引发剂CDBC ,以 6 80nm激光二极管发射的激光作为光源 ,研究了由CDBC、EA6 12、POTMPTA组成的红光光敏树脂在快速成型工艺中的应用 ,考察了影响树脂几个主要性能即粘度、光固化速度、体积收缩率的因素 .结果表明 ,EA6 12含量高 ,POTMPTA含量低 ,树脂粘度大 ,体积收缩率小 ;相反 ,EA6 12含量低 ,POTMPTA含量高 ,则树脂粘度低 ,体积收缩率大 ;光引发剂CDBC含量 5 %以内时对树脂粘度和体积收缩率没有影响 ,CDBC含量增加 ,树脂的表固速度加快 ,但当CDBC含量大于 3%时 ,表固速度基本不变 .预聚物EA6 12质量分数 70 % ,单体POTMPTA质量分数 2 7% ,光引发剂CDBC质量分数 3%时 ,树脂粘度为 4 2 0mPa·s ,表固时间为 1 0s ,固化体积收缩率为 4 0 % ,具有较好的综合性能 .     

Synthesis from (+)-α-pinene of optically active macrocycles containing cyclobutane,ester, azine,or hydrazide groups

Optically active symmetric macrocyclic diesterazines and diesterdihydrazides were synthesized efficiently from the available natural monoterpene (+)-α-pinene (de 50%) using a [2+1]-reaction of 1′-[(1S,3S)-3-(2hydroxyethyl)-2,2-dimethylcyclobutyl]ethanone and glutaric and adipic acid chlorides followed by [1+1]condensation of the intermediate diketodiesters with hydrazine hydrate or glutaric acid dihydrazide.