Novel waterborne hyperbranched acrylated-maleinized alkyd resins

Different waterborne hyperbranched acrylated-maleinized alkyd resins (HBRAAM) were synthesized by modifying a hyperbranched alkyd resin (HBRA) with three different butylmethacrylate–maleic anhydride copolymers (BMA–MA) in the presence of p-toluenesulfonic acid (PTSA). The HBRAAM resins were characterized by using infrared analysis, iodine value, hydroxyl value, vapor pressure osmometry (VPO), dynamic light scattering (DLS), acid value, rheological analysis, differential scanning calorimetry, adhesion, flexibility, drying time, gloss, hardness and chemical resistance to solvents. The iodine value and hydroxyl value decreased with the amount of BMA–MA copolymer employed in the synthesis. Infrared analysis, VPO, and hydroxyl values allowed us to conclude that the reaction between HBRA resins and BMA–MA copolymers occurred. The viscosity of the HBRAAM resins was between 50.5 and 468 Pa s. All HBRAAM resins presented good properties of adhesion, flexibility, drying time, gloss, hardness and chemical resistance.     

Synthesis and characterization of hyperbranched and air drying fatty acid based resins

In this research four hyperbranched resins having fatty acid residues were synthesized. Dipentaerythritol, which was used as the core molecule of the resins, was twice esterified with dimethylol propionic acid. This resin was then esterified with the castor oil fatty acids. The hydroxyl group present in the ricinoleic acid which constitutes almost 87% of the castor oil fatty acids was then reacted with linseed oil fatty acids and benzoic acid. The linseed fatty acids were incorporated into the structure to esterify 0, 15, and 70% of the ricinoleic acid on mole basis. These resins were named as HBR-1, 2, and 3. A fourth resin (e.g. HBR-4) was synthesized by the incorporation of ‘15% linseed fatty acids + 55% benzoic acid’. The chemical characterization of the resins was achieved by FTIR spectroscopy and the thermal properties were determined by DSC. The physical and the mechanical properties of the resins were determined. The hardness value of the resins was measured as 24, 27, 25, and 68 Persoz for HBR-1, 2, 3, and 4, respectively. The viscosity of the resins was measured as 17.3, 9.7, 5.8, and 17.5 Pa·s at a shear rate of 200 s⁻¹. The increase in the amount of the linseed fatty acids increased the hardness, and decreased the viscosity of the resins. All resins showed excellent adhesion, gloss, and flexibility.     

Synthesis and Application of Palm Fatty Acid Distillate Based Alkyd Resin in Liquid Detergent

Palm fatty acid distillate (PFAD) is the by-product obtained during physical refining of crude palm oil, which mainly consists of free fatty acids along with minor amounts of glycerides, bioactive compounds such as tocopherols, tocotrienols, phytosterols, squalene, other hydrocarbons. In the present work, an eco-friendly alkyd resin was prepared using sustainable feedstock such as PFAD along with rosin. The various physico-chemical properties of PFAD-based alkyd resin (PFAD-AR) such as acid value, saponification value, viscosity and volatile matter were determined and compared to palm oil based alkyd resin (PO-AR). The structural properties of the alkyd resins were investigated using Fourier transform infrared (FTIR) and proton nuclear magnetic resonance (¹H NMR) spectroscopic techniques. The study presents the utilization of PFAD-based alkyd resin with sodium lauryl sulfate (SLS) and sodium lauryl ether sulfate (SLES) in the liquid detergent formulation. The performance properties of the PFAD-based alkyd resin liquid detergent formulations such as surface tension, wetting power and detergency were comparable with palm oil based alkyd resin liquid detergent formulations and with commercial liquid detergent (CLD). Surface tensions of liquid detergent formulations varied from 20 to 30 mN/m with decrease in concentration. The foaming properties of alkyd resin based liquid detergents are reduced with the increase in the amount of alkyd resin polymer in the formulations. Therefore, it has potential application as a foam reducer in detergent for washing machines.     

Effect of tall oil fatty acids content on the properties of novel hyperbranched alkyd resins

Hyperbranched alkyd resins (HBRA) were synthesized by modification of hydroxylated hyperbranched polyester (HBP1‐4) with tall oil fatty acids (TOFA). The core is a hydroxylated hyperbranched polyester of fourth generation with OH groups in the periphery (18), which is endcapped with tall oil fatty acids. The occurrence of these reactions, HBP1‐4 and TOFA, was determined by making use of acid value, nuclear magnetic resonance, and hydroxyl values. The effects of TOFA and HBP1‐4 on properties of the HBRA resins were investigated by vapor pressure osmometry, differential scanning calorimetry, thermogravimetric analysis, friction resistance, and hardness. The resins with higher modification percentage (HBRA4) presented the best thermal and hydrolytic stability, but lower friction resistance and hardness. All HBRA resins presented amorphous characteristics, OH groups, and double bonds in the periphery. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

水性苯丙共聚物改性醇酸树脂的制备及性能

以油酸、季戊四醇、邻苯二甲酸酐、苯甲酸为原料,采用丙二醇甲醚醋酸酯（PMA）为溶剂合成了基体醇酸树脂;用过氧化苯甲酰、过氧化苯甲酸叔丁酯双引发剂、分步引发烯类单体共聚,制备了一种苯丙烯树脂,并对醇酸树脂改性制得了水性醇酸树脂。考察了不同油度对水性醇酸树脂结构与性能的影响。通过FTIR、TGA、DLS分别对树脂的结构、稳定性和乳液性能进行了表征。测定了树脂的漆膜性能,包括耐水性、表干时间、硬度、电化学性能。结果表明,n（油酸）∶n（季戊四醇）∶n(邻苯二甲酸酐)∶n（苯甲酸）=1∶1∶1∶0.3,油度为47%时,聚合物乳液粒径为74.4 nm,PDI为0.262,胶膜的吸水率为14.5%,接触角为70.87?,有较好的耐水性。改性醇酸树脂的表干时间缩短为0.5 h,实干时间缩短为24 h,硬度达HB。     

Hyperbranched Polyether as a Modifying Agent for Urea-Formaldehyde Resins—Hardness and Strength Control Tool

A commercially available urea-formaldehyde (UF) resin was blended with a hyperbranched polyether (HBP) obtained from glycerol being a by-product in biodiesel production. The mechanical properties of the cured polymeric blends are described in this article. It was found that low addition (3 wt%) of the modifier significantly improves the hardness (16%) and the compressive shear strength (17%) of the polymer, whereas water absorption remains unaffected. It was also shown that blending UF resins with hyperbranched polyethers can be an effective tool for controlling mechanical properties and dimensional stability of the polymeric systems.     

Synthesis of oil based hyperbranched resins and their modification with melamine-formaldehyde resin

In this research hyperbranched resins containing fatty acid residues were synthesized. Dipentaerythritol which has six hydroxyl groups was used as the core molecule, and it was transesterified with (i) castor oil, and (ii) a mixture of castor oil and linseed oil at 240 °C. The resulting molecule had hydroxyl containing ricinoleic acid residue coming from castor oil. It was then esterified with dimethylol propionic acid at 140 °C in the presence of para-toluene sulfonic acid used as catalyst. The hyperbranched resin thus produced was then mixed with melamine-formaldehyde resin to improve its properties. The resins were characterized by FTIR spectroscopy, and the thermal properties were determined by DSC. The resins were thermally stable up to 316 °C. The viscosity of the resin that was synthesized by using only castor oil was 3.0 Pa s, while the one synthesized by using 50% linseed oil had a viscosity of 1.0 Pa s. When reacted with dimethylol propionic acid the viscosity of the former resin increased to 7.0 Pa s, and that of the second to 3.7 Pa s. The hyperbranched resins showed excellent adhesion, gloss, flexibility, and formability. The mixed resin (i.e. hyperbranched and melamine-formaldehyde) had higher hardness values but lower gloss, adhesion, and bending resistance. Both types of resins also had good impact and abrasion resistances.     

Preparation and properties of liquid crystalline alkyd resin with para-hydroxybenzoic acid mesogenic side chain

Liquid crystalline (LC) alkyd resins with mesogenic side chains are prepared with the following three methods: (a) grafting p-hydroxybenzoic acid (PHBA) to hydroxy-terminated alkyd resin, (b) grafting PHBA to carboxyl-terminated alkyd resin, and (c) grafting PHBA to an excess succinic anhydride-modified alkyd resin. Dicyclohexylcarbodiimide (DCC) is employed to react with formed water in promoting esterification of PHBA with alkyd at room temperature. Pyridine is used as a solvent, and the catalytic amounts of p-toluene-sulfonic acid (p-TSA) is added to suppress side reaction and to promote esterification. Grafting efficiency (% GE) is estimated to range from 70 to 95%. The character of liquid crystallinity is imparted only when at least two or more aromatic units of PHBA are connected to form the rodlike mesogenic side chain. At present, we have found that LC alkyd resins have the following merits: the polymer solution viscosity is reduced; the coating's dry-to-touch time is reduced; and the coating film is both hardened and toughened and has excellent resistance to water and acid. © 1992 John Wiley & Sons, Inc.     

Alkyd resins based on waste PET for water-reducible coating applications

Simultaneous glycolysis and neutral hydrolysis of waste PET flakes obtained from grinding post-consumer bottles was carried out in the presence of xylene and an emulsifier at 170 °C. The product was separated from ethylene glycol (EG), water, and xylene by filtration, and was extracted by water at boiling point thrice. The remaining solid was named water insoluble fraction (WIF). The filtrate was cooled to 4 °C, and the crystallized solid obtained by filtration was named water soluble crystallizable fraction (WSCF). These fractions were characterized by acid value (AV) and hydroxyl value (HV) determinations. WSCF and WIF were used for preparation of the water-reducible alkyd resins. Three long oil alkyd resins were prepared from phthalic anhydride (PA; reference alkyd resin) or depolymerization product of the waste PET (PET-based alkyd resin), glycerin (G), fatty acids (FA), and glycol (EG; reference alkyd resin) or depolymerization product of the waste PET (PET-based alkyd resin). Film properties and thermal degradation stabilities of these alkyd resins were investigated. Physical properties (drying times and hardness) and thermal degradation stabilities of the PET-based alkyd resin is better than these properties of the reference alkyd resin.     

Synthesis and characterization of novel alkyd-silicone hyperbranched nanoresins with high solid contents

Hyperbranched alkyd-silicone nanoresins (ASiHBRs) with high solid content were synthesized by etherification reaction between a hyperbranched alkyd resin (HABR) and Z-6018 silicone. ASiHBRs were characterized by nuclear magnetic resonance (NMR), gel permeation chromatography (GPC) and several other techniques. NMR spectra show the presence of aromatic rings, -Si-O and -C-O; grafting was successful. The molar masses of ASiHBRs determined by GPC are higher than that of HABR. The hydroxyl values decrease with increasing silicone content. ASiHBRs have low viscosities what allows easier film formation. Hydrodynamic dimensions, refractive indices, glass transition temperatures, gloss and hardness of ASiHBRs increase with increasing silicone contents. Low contents of volatile organic compounds provide more environmentally friendly coatings.     

Alkyd resins synthesized from postconsumer PET bottles

Simultaneous glycolysis and neutral hydrolysis of waste PET flakes obtained from grinding postconsumer bottles was carried out in the presence of xylene and an emulsifier at 180 °C. The product was separated from EG, water and xylene by filtration and was extracted by water at boiling point three times. The remaining solid was named water insoluble fraction (WIF). The filtrate was cooled to 4 °C and the crystallized solid obtained by filtration was named water-soluble crystallizable fraction (WSCF). These fractions were characterized by acid value (AV), hydroxyl value (HV) determinations. WSCF and WIF were used for preparation of the alkyd resins. Three long oil alkyd resins were prepared from phthalic anhydride (PA) (reference alkyd resin) or depolymerization product of the waste PET (PET-based alkyd resin), glycerin (G), sunflower oil fatty acids (SOFA) and glycol (EG) (reference alkyd resin) or depolymerization product of the waste PET (PET-based alkyd resin). Film properties and thermal degradation stabilities of these alkyd resins were investigated. Physical properties (drying times, hardness and abrasion resistance) and thermal degradation stabilities of the PET-based alkyd resins are better than these properties of the reference alkyd resin.     

Study of film properties of some urethane oils

In this study, sunflower oil-based urethane oils were obtained from three kinds of isocyanate components: toluene diisocyanate (TDI), hexamethylene diisocyanate (HMDI) and poly(1,4-butandiol) toluene 2,4-diisocyanate (PBTDI) terminated prepolymer. The polymers were prepared at four different ratios of isocyanate component/oil. Sunflower and linseed oil alkyd resin samples were also prepared as the comparative samples. The results suggest that the viscosity and the film properties of urethane oils depend on the amount and type of isocyanate component. The increase in isocyanate content of the urethane oils caused high viscosity. In comparison with the samples having the same oil content, PBTDI-based samples showed the highest viscosity. Viscosity of the polymers can dramatically affect some film properties. For example, high polymer viscosity caused short drying time. In comparison of alkali and water resistances of urethane oils with those of alkyd resins, better results were obtained depending on the structure of the urethane oils. On the other hand, alkyd resins and TDI-based polymers exhibited the best hardness properties. Chemical Engineering Dept, Maslak 80626Istanbul, Turkey; email: guners@itu.edu.tr.     

Synthesis and characterization of novel poly(aryl ether ketone)s containing both biphenylene and 1,4-naphthylene moieties

A novel epoxidized hydroxyl-terminated hyperbranched polymer (HPEEX) was formulated from epichlorohydrin and hydroxy-terminated hyperbranched polyester (HPE) based on trimethylol propane (TMP) and AB₂ monomer. The obtained HPEEX was characterized with FT-IR, ¹HNMR spectroscopy, TG, WAXD and GPC analysis. Results showed that the HPEEX was formulated as expected and its molecular weight and intrinsic viscosity were 3,789 g/mol and 3.96 mL/g, respectively. Meanwhile, the HPEEX was used as cross-linking agent in the preparation of waterborne epoxy resins. Performance of the HPEEX modified epoxy resin aqueous (EP-H) dispersions and their films was evaluated by various tests. It was found that with incorporation of hyperbranched polymer into the epoxy macromolecular chain, the EP-H films exhibited excellent hardness and water-proof performance: the hardness was as high as 96 (Shore A), and the contact angle of water on the surface of this kind of film was as high as 71°, resulting from branched structure, higher functionality of HPEEX, better cross-linking density and large number of hydrogen bonding in this epoxy system.     

Novel moisture-cured hyperbranched urethane alkyd resin for coating application

A hyperbranched polyol (HBP) was synthesized using dipentaerythritol as a core material and 2,2-bis(methylol) propionic acid as a chain extender. This was reacted with varying concentrations of soya fatty acid to make hyperbranched alkyd (HBA) resins. The HBA resins containing unreacted hydroxyl groups were reacted with isophorone diisocyanate at NCO/OH ratio of 1.6:1 to make high solid hyperbranched urethane alkyd (HBUA) resins. The excess NCO content in the HBUA resins was used to cure with atmospheric moisture, and thus moisture-cured HBUA coatings were formed. The resins were characterized by FTIR, and ¹³C NMR spectroscopic analysis. A series of such resins were made using different fatty acid/isocyanate ratios with respect to the hydroxyl groups present in the HBP. The effect of compositions on the mechanical and weathering properties of the cured resins was investigated. It was observed that there was an optimum fatty acid–isocyanate ratio in terms of the requirements of solvent, mechanical and weathering properties of the resin. The requirement of solvents for formulating HBUA coatings is much lower compared to linear alkyd-based coatings. The present study reveals that the moisture-cured HBUA resins can be used as a binder material in the field of low-pollution weather-resistance coatings.     

基于汽车修补漆用分散树脂的研究及应用

以ε-己内酯和含羟基丙烯酸酯合成的羟基丙烯酰氧基酯大单体及含氨基丙烯酸酯合成了一种含羟基和氨基的树脂,该树脂黏度较低,与其他树脂的相容性好,具有良好的干燥性能,适合用于制备汽车修补漆用通用色浆。优化了分散树脂的合成配方,并将该分散树脂和传统通用树脂进行了对比,探讨了对涂层的干燥、流平、硬度和柔韧性等物化性能的影响规律。     

用天然和可再生原料改性醇酸树脂研究进展

介绍了天然片状屏蔽型颜填料和可再生的多元醇-植物油脂肪酸为基础的高官能化合物改性醇酸树脂情况。片状云母氧化铁提高了醇酸树脂的耐候性,煅烧处理的片状高岭土和氧化铁红配合可使气干醇酸色漆涂膜具有耐水28 d的优良等性能。蔗糖多元醇-植物油脂肪酸化合制成多脂肪酸酯,具高官能度和低黏度,在气干性高固体醇酸涂料中具潜在应用前景;多脂肪酸酯进一步环氧化生成多酯多元醇,能代替羟基型醇酸和聚酯树脂在氨基醇酸和聚氨酯涂料中应用、提高固体分和改进性能。     

超支化聚合物的应用研究进展

对近几年超支化聚合物的应用研究进展进行了综述。超支化聚合物的性能介于线形聚合物和体形聚合物之间,目前主要用作聚合物共混改性剂、热固性树脂增韧剂、染色助剂、药物缓释剂、超支化液晶,并在涂料及聚合物薄膜方面获得较广泛应用。     

Hyperbranched unsaturated polyester resin for application in impregnation coatings

A new kind of water-soluble hyperbranched unsaturated polyester resin (HBUP) was prepared to enhance the rate of curing, to increase the adhesive strength and to decrease the dielectric constant of the water-soluble insulating impregnation coating comprising water-soluble unsaturated alkyd resin and amino resin. The HBUP was synthesized from pentaerythritol as the core molecule, which was then esterified with dimethylol propionic acid (DMPA). In addition, the terminal hydroxyl groups of HBUP were modified by acrylic acid and maleic anhydride. The hyperbranched structure and C=C double bonds of HBUP resin were investigated by Fourier transform infrared (FTIR) and nuclear magnetic resonance (¹³C-NMR and ¹H-NMR) spectroscopies. The reaction rate of the water-soluble insulating impregnation coating was accelerated by addition of HBUP which was demonstrated by the surface drying test and differential scanning calorimetry (DSC). The electrical and mechanical properties of the water-soluble insulating impregnation coating were also studied. It was shown that the addition of HBUP resin could reduce the permittivity of the coating which was at its lowest level when the HBUP content was 5 wt%, whereas the breakdown voltage, volume resistivity and adhesive strength of the coating were improved.     

Waterborne hybrid alkyd–acrylic dispersion: Optimization of the composition using mixture experimental designs

VOC-free waterborne hybrid alkyd–acrylic (50/50 wt/wt) dispersions were synthesized by melt condensation reactions between acrylic pre-polymers bearing carboxylic groups and medium-oil alkyd resins, followed by a self-emulsification through the neutralization of the carboxylic groups by an aqueous ammonia solution. A mixture experimental design was used to investigate how formulation components of the hybrid alkyd–acrylic resin affect the properties of the hybrid dispersion in terms of the viscosity of the dispersion, particle size, hydrolytic stability, and coating performance, namely gloss and film hardness. It was found that the content of ionizable monomers is the dominant factor controlling the particle size. This latter was shown to meaningfully affect the gloss of the coating after drying. The viscosity of the dispersion was mainly governed by the content of the soybean oil fatty acid which also controlled the hardness of the coating film after drying. An optimal composition that fits the requirement of paint formulation in terms of particle size, viscosity, hardness, and gloss was defined on the basis of the results of the mixture experimental design.     

紫胶改性水性醇酸树脂的合成工艺研究

从改进树脂综合性能着手,研究了水性醇酸树脂的合成工艺。确定了以熔融法和分步加料来制备醇酸树脂。以紫胶部分替代三羟甲基丙烷,顺丁烯二酸酐/偏苯三酸酐部分替代苯酐,所得水性醇酸树脂的干燥性能、硬度和柔韧性等性能得以提高。紫胶用量以5%为宜。