Biobased hyperbranched shape‐memory polyurethanes: Effect of different vegetable oils

Hyperbranched polyurethanes were synthesized from poly(ε‐caprolactone) diol as a macroglycol, butanediol as a chain extender, a monoglyceride of a vegetable oil (Mesua ferrea, castor, and sunflower oils separately) as a biobased chain extender, triethanolamine as a multifunctional moiety, and toluene diisocyanate by a prepolymerization technique with the A₂ + B₃ approach. The structure of the synthesized hyperbranched polyurethanes was characterized by ¹H‐NMR and X‐ray diffraction studies. M. ferrea L. seed‐oil‐based polyurethane showed the highest thermal stability, whereas the castor‐oil‐based one showed the lowest. However, the castor‐oil‐based polyurethane exhibited the highest tensile strength compared to the other vegetable‐oil‐based polyurethanes. All of the vegetable‐oil‐based polyurethanes showed good shape fixity, although the castor‐oil‐based polyurethane showed the highest shape recovery. Thus, the characteristics of the vegetable oil had a prominent role in the control of the ultimate properties, including the shape‐memory behaviors, of the hyperbranched polyurethanes. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39579.     

Evaluation of viscosity and printing quality of chitosan‐based flexographic inks: The effect of chitosan molecular weight

Inks composed of renewable resources are important for the environment protection. We report preparation of a new type of edible chitosan‐based flexographic ink. The performance of three inks, containing three different molecular weight (MW) chitosan, was analyzed by the different experimental techniques. The Ink viscosity was investigated from the parameters shear rate, time, temperature, and flexographic printing simulation. The printing quality on coated paper was studied by the scratch resistance, contact angle, print fastness, chromatic aberration, and dot gain. Viscosity recovery rate reached 69% after 6 s, and the print fastness was up to 91%. The experimental ΔE is 0.97, the dot gain is 23%, and contact angle is 69° for the best ink. Experimental results indicate that the developed ink is suitable for the flexographic printing with good application prospects. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43997.     

酰胺改性氢化蓖麻油在平版印刷油墨中的应用研究

通过试验,在传统平版印刷油墨体系(松香改性酚醛树脂、醇酸树脂)中添加酰胺改性氢化蓖麻油,考察其对油墨流动性及应用性能的影响。     

Ionic liquids as performance additives for water‐based printing inks

For the first time, the use of ionic liquids as additives for printing inks in order to improve the wettability of the printing base by the ink is presented. The aim of this work was to study the influence of ionic liquids on the selected properties of water‐based printing ink and the prints. The contact angles of the printing inks on the printing base were measured. Modified flexographic inks were laboratory printed on polypropylene plastic film. The impact of small amounts of various ionic liquids on printing ink colour was examined in terms of the optical density of the full‐tone area, the colour parameters (L*, a*, b*, CIE), the total colour difference, and the gloss of the dried ink film. The influence of ionic liquids on the ink contact angle, the optical density, and the L*a*b* coordinates is discussed. In general, the investigated ionic liquids improve the wettability of water‐based flexographic printing ink, with an acceptable total colour difference. The optical density is increased for printing inks containing ionic liquids in comparison with the original flexographic printing ink, Process.     

蓖麻油常压催化氢化的研究

使用混合价态的氧化镁／蛋白质／钯催化剂对蓖麻油的常压催化氢化具有使用寿命长（连续使用３０次仍有较高的活性）、活性高（氢化速度为５１０ｍｌ／ｍｍｏｌ·ｍｉｎ）、氢化彻底（氢化蓖麻油的碘值小于４）等优点，在７０℃用正丙醇作溶剂且与蓖麻油投料比为５．７７ｍｌ／ｇ时氢化活性最高。     

Synthesis and Properties of Polyurethane Elastomers with Castor Oil as Crosslinker

Castor oil–polyurethane elastomers were prepared by reacting poly (1,4-butane diol) (Terathane 1400) with aliphatic 1,6-hexamethylene diisocyanate. The prepolymers were chain-extended with bifunctional precursor chains and/or with castor oil as a trifunctional crosslinker at stoichiometric ratios. These resulted in a series of crosslinked polyurethane elastomers with different structures of the hard segment. The properties of the material were measured by differential scanning calorimetry, thermogravimetric analysis, atomic force microscopy, as well as tensile properties measurements. The effect of stoichiometric balance (i.e., OH/NCO molar ratio) on the final properties was evaluated. The formation of hydrogen bonds was observed by Fourier transform infrared.spectroscopy The measured properties were found to be strongly influenced by the molar ratio of chain extenders to the diisocyanate component. The glass transition temperatures (T _g) for the polyurethanes with OH_polyol/NCO/OH_{chain extender} having molar ratios of 1:2:1 and 1:4:3 were found to be −70 and −57 °C, respectively. The polyurethanes networks with a OH/NCO molar ratio of 1:2:1 had excellent mechanical properties, indicating that this is the optimum ratio to be used in castor oil polyurethane elastomer formulations. The objective of this work was to study the effect of the castor oil crosslinker on the morphology of the resulting crosslinked polyurethanes and to correlate the morphology with the properties of these bio-based crosslinked polyurethanes.     

Preparation of high‐tack value adhesive for offset printing inline cold foil stamping and its performance characterization

A high‐tack‐value adhesive for offset printing inline cold foil stamping was prepared using rosin‐modified phenolic resin, terpene resin, industrial soybean oil, and solvent oil. The prepared adhesive can overcome the low accuracy of cold foil stamping and reproduction of existing conventional adhesives. The tack value, viscosity, ink (adhesive) thread length, ink flow, viscoelasticity, thixotropy, emulsification rate, and solid content of the prepared adhesives were characterized. The adhesive was applied on a MAN ROLAND 700 eight‐color offset printing cold foil stamping press. Stamping quality was evaluated. Results showed that the prepared adhesive has high tack value and the increment of the tack value is small with increasing test time. To achieve good stamping quality, the tack value of the adhesive should be controlled between 20 to 30, and its viscosity and emulsification rate should be kept at approximately 80 Pa·s and within the range of 30% to 40%, respectively. Appropriate levels of viscoelasticity, thixotropy, and ink flow were also necessary. POLYM. ENG. SCI., 59:139–144, 2019. © 2018 Society of Plastics Engineers     

Morphology–properties relationship in high‐renewable content polyurethanes

The effect of diisocyanate nature and hard segment content on the morphology and properties of high‐renewable content segmented thermoplastic polyurethanes was studied. Vegetable oil‐based polyether diol and corn sugar derived chain extender were used as renewable reactants together with an aliphatic (1,6‐hexamethylene diisocyanate, HDI) or aromatic (4,4′‐diphenylmethane diisocyanate, MDI) diisocyanate as hard segment. Segmented thermoplastic polyurethanes were synthesized by two‐step bulk polymerization. Morphology and physicochemical, thermal and mechanical properties were analyzed by Fourier‐transform infrared spectroscopy, differential scanning calorimetry, dynamic mechanical analysis, atomic force microscopy, and mechanical testing. The effect of mechanical deformation over the microstructure was also analyzed. Changes in crystallinity and hard segment hydrogen bonding after mechanical testing were evaluated by Fourier‐transform infrared spectroscopy and differential scanning calorimetry. The increase of physical crosslinking sites by aromatic diisocyanate and chain extender ratio in the polyurethane results in hard segment crystalline domains with spherulitic morphology, which enhance the stiffness and hardness whereas percentage elongation at break diminish. The flexible, linear aliphatic nature of HDI favors the arrangement of urethane groups thus creating strong hard segment interactions and hard segment crystal microdomains composed of fibrillar morphology are observed. POLYM. ENG. SCI., 54:2282–2291, 2014. © 2013 Society of Plastics Engineers     

Tailoring the properties of deposited thin coating and print features in flexography by application of UV-ozone treatment

Printed functional materials are a rapidly growing area of interest for low-cost high-speed device manufacture with flexographic printing seen as a route to achieving this. The relationship between surface tension of the ink and surface free energy (SFE) of the photopolymer plate is a key for optimum performance. However, traditional methods of surface tension modification of the ink/coating often cannot be employed for functional inks. In this research, rapid, permanent modification of flexographic printing plate’s SFE is achieved through controlled UV-ozone treatment, and the effects of the treatment on the polar and dispersive component of SFE are analyzed by Fourier transform infrared attenuated total reflectance spectroscopy, swelling experiments, and roughness measurements. Printing trials using the modified printing plates reveal improved print uniformity and control of deposited ink layer thickness, as well as improved print features—particularly track and pad junctions which can be problematic for printed electronic applications. The ability to rapidly tailor printing plate SFE is of benefit to all volume printing applications. Furthermore, it is of critical importance for functional printing and printed electronics where surface tension of the ink is determined by the functional material and chemical modification is not possible or desirable.     

UVA and UVC modification of photo polymeric surface and application for flexographic deposition of thin coatings

The object of this research was to perform, characterize, and apply the functional modification of flexographic photo polymeric printing plate surface by UVA and UVC post‐treatments. Photo polymeric printing plates have an important application in functional printing, where new printing inks/coatings and substrate formulations are used and the specific qualitative requirements must be met. The limitations of materials and processes often require expensive reformulations of the functional inks to achieve printability. Results of this research showed that the modification of the photo polymeric printing plate surface at the end of its production process can be used to precisely adjust the printing ink transfer to the printing substrate and thus eliminate the need for changing the ink/coating composition. By applying specific UV post‐treatment, one can create a flexographic coating deposition system of tailored properties adjustable to variable reproduction systems with high quality requirements. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43526.     

A simple one‐step synthesis and polymerization of plant oil triglyceride iodo isocyanates

In this study, a novel and simple route for the synthesis of the iodine isocyanate (INCO) adduct of soybean oil triglycerides is described. Soybean oil iodo isocyanate (ISONCO) was synthesized by the reaction of iodine isocyanate and soybean oil at room temperature. ISONCO was then polymerized with polyols, such as, castor oil, pentamethylene glycol, and glycerol to give the corresponding polyurethanes and with polyamines, such as, ethylene diamine, hexamethylene diamine, and triethylene tetramine to give corresponding polyureas. The structures of the monomer and the polymers were determined by FTIR and ¹H‐NMR analyses. Thermal properties of the polymers were determined by DSC and TGA. Thermal degradation of the polyurethanes started at 150°C. Stability of the polyureas was higher than polyurethanes. Almost all polymers showed a T_g around ?50°C. The mechanical properties of the polymers were determined by tensile tests. Among the polymers synthesized, castor oil polyurethane showed the highest elongation at break and the lowest tensile strength of 140 KPa. The highest tensile strength of 900 KPa was observed in the pentamethylene glycol polyurethanes. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Modified Castor Oil Based Polyurethane Elastomers for One-Shot Process

Studies have been carried out on polyurethane elastomers based on modified castor oil in combination with different molecular weights of polyethylene glycol and polymeric methylene diphenyl-4,4′-diisocyanate (PMDI). The resulting polymers were cast into molds and the moldings were characterized by scanning electron microscopy and thermogravimetric analysis. Mechanical properties such as tensile strength, elongation at break, hardness, abrasion resistance, and compression set were measured. There is an increase in the flexibility of polyurethanes with increase in molecular weight of PEGs added to modified castor oil.     

环保型大豆油墨的制备

采用大豆油衍生物大豆油甲酯为溶剂,制备环保型大豆油墨,并与矿物油溶剂制备油墨的性能进行比较。试验结果表明:大豆油墨的总体性能与矿物油油墨相当,而在黏性、稳定性和光泽方面,大豆油墨更优于矿物油油墨。     

Chain‐extended polyurethanes—Synthesis and characterization

Chain‐extended polyurethanes (PUs) were prepared using castor oil and different diisocyanates such as toluene‐2,4‐diisocyanate and 4,4′‐methylene bis(phenylisocyanate) as a crosslinker and different aromatic diamines like 4,4′‐diaminodiphenyl methane and 4,4′‐diaminodiphenyl sulphone as chain extenders. The effect of aromatic diamines on the swelling and thermal degradation behavior of PU have been discussed. A thermogravimetric analyzer (TGA) curve shows that all the chain‐extended PUs are stable up to 194°C and that maximum weight loss occurs at 490°C. The TGA thermograms show that the thermal degradation of the PUs was found to proceed in two steps. The average molecular weight between crosslinks (M?_c) was determined by swelling studies. The properties imparted by the aromatic chain extenders are explained on the basis of groups present in the diamines. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 359–369, 2002; DOI 10.1002/app.10347     

Synthesis and characterization of flame retardant hyperbranched polyurethanes for nano-composite and nano-coating applications

Flame retardant hyperbranched polyurethanes were prepared by reacting phosphorous containing triol, tris(bisphenol-A) mono phosphate, castor oil, and polyethylene glycol with different diisocyanates like TDI, IPDI and HMDI via A₂+B₃ method. In this method A₂ reactants were diisocyanates along with castor oil and polyethylene glycol whereas phosphorous containing triol was used as B₃ reactant and dibutyltin dilaurate (DBTDL) was used as catalyst. Synthesized polyurethans were characterized by gel-permeation chromatography (GPC), elemental analysis, Fourier transform infrared spectroscopy (FTIR) and ¹H NMR spectroscopic techniques. Neat polyurethanes were used for preparing films. Nano-clay composites were prepared with various concentration of organomodified montmorillionite nano-clay. Flame retardant, Thermal and mechanical properties of these hyperbranched polyurethanes and their nano-composites were found out. The polyurethanes and their formulations with nano-clay were also used for the coating of mild steel panels. Scratch, pencil, and impact hardness, flexibility and adhesion properties of coated panels were also determined. Observations show an increase in the scratch hardness and flexibility with the introduction of clay. All the coatings show excellent chemical resistance properties compare to their linear counterpart.     

Solvent-Cast 3D Printing of Biodegradable Polymer Scaffolds

3D printing is a popular fabrication technique because of its ability to produce complex architectures. Melt-based 3D printing is widely used for thermoplastic polymers like poly(caprolactone) (PCL), poly(lactic acid) (PLA), and poly(lactic-co-glycolic acid) (PLGA) because of their low processing temperatures. However, traditional melt-based techniques require processing temperatures and pressures high enough to achieve continuous flow, limiting the type of polymer that can be printed. Solvent-cast printing (SCP) offers an alternative approach to print a wider range of polymers. Polymers are dissolved in a volatile solvent that evaporates during deposition to produce a solid polymer filament. SCP, therefore, requires optimizing polymer concentration in the ink, print pressure, and print speed to achieve desired print fidelity. Here, capillary flow analysis shows how print pressure affects the process-apparent viscosity of PCL, PLA, and PLGA inks. Ink viscosity is also measured using rheology, which is used to link a specific ink viscosity to a predicted set of print pressure and print speed for all three polymers. These results demonstrate how this approach can be used to accelerate optimization by significantly reducing the number of parameter combinations. This strategy can be applied to other polymers to expand the library of polymers printable with SCP.     

全色彩环保油墨

通过分析油墨的基本组成可知：溶剂对环境的影响最大。与矿物油、植物油相比，源于木材加工业的松浆脂肪酸酯在油墨中作溶剂，其化学结构、黏度及挥发性能具有很多优点。而且，所制成的植物油型油墨在胶印性能、生物降解、气味、提高印刷效率方面效果极佳。目前，在环保要求与资源可再生性利用的压力下，植物油型油墨必将越来越受青睐。     

Synthesis and curing of millable polyurethanes based on castor oil

This paper presents the results of studies on the synthesis and curing of millable polyurethanes based on castor oil. To facilitate the preparation of millable urethanes, the hydroxy number of castor oil was modified to about two by acetylation. It was then used with tolylene diisocyanate (NCO/OH-ratios 1:0.9, 1:1 and 1:1.1, resp.) for polyurethane preparation. The dynamic curing of the synthesized polyurethanes was studied in a Brabender Plasticorder using various sulfur vulcanizing systems. The effect of stoichiometric ratio and choice of chain extenders on the dynamic curing behaviour was also studied. An NCO/OH ratio of 0.9 and 1,4-butanediol (30 wt.-%) as chain extender were found to favour the formation of a crosslinkable polyurethane. It was observed that a cure system containing sulfur, N-cyclohexyl-2-benzothiazole sulfenamide and mecraptobenzothiazole was a possible choice for the preparation of a sulfur-crosslinked polyurethane.     

Biobased polyisocyanates from plant oil triglycerides: Synthesis,polymerization, and characterization

In this study, an easy and efficient synthesis of unsaturated plant oil triglycerides having isocyanate groups is reported. In the first step of the synthesis, the triglyceride was brominated at the allylic positions by a reaction with N‐bromosuccinimide, and in the second step, these brominated species were reacted with AgNCO to convert them to isocyanate‐containing triglycerides. At the end of the reaction, approximately 60–70% of the bromine was replaced by NCO groups, and the double bonds of the triglyceride were not consumed. When the amount of AgNCO was increased, the yield also increased. The final products were characterized with IR and ¹H‐NMR, and polyurethanes and polyureas were obtained from these fatty isocyanates with alcohols and amines, respectively. The polymers were characterized by differential scanning calorimetry and thermogravimetric analysis. Differential scanning calorimetry curves showed that glycerin polyurethane showed a glass‐transition temperature at 19°C, castor oil polyurethane showed two glass‐transition temperatures at ?43 and 36°C, and triethylene tetraamine polyurea showed a glass‐transition temperature at 31°C. Some properties of the polymers, such as the tensile strength and swelling ratios, were also determined. The swelling rate of glycerin polyurethane was higher than that of castor oil polyurethane in dichloromethane. The equilibrium swelling ratio was highest for the castor oil polyurethane. The polyurethanes synthesized in this study had a Young's modulus around 50 kPa and a tensile strength around 0.01 N/mm² (100 kPa). The tensile strength of glycerin polyurethane was higher than that of castor oil polyurethane. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Polymers containing sulfur in the side chain

We synthesized new thiodicarboxylic acids, p-tolylmethylthiomethylsuccinic acid and 1-naphthylmethylthiomethylsuccinic acid, and thiodiols, 2-(p-tolylmethylthiomethyl)-1,4-butanediol and 2-(1-naphthylmethylthiomethyl)-1,4-butanediol, by the addition of dimethyl itaconate with p-tolylmethanethiol or 1-naphthylmethanethiol, followed by hydrolysis or reduction, respectively, of the resultant dimethyl esters. These difunctional monomers were used for the synthesis of new linear polyesters and polyurethanes containing sulfur in the side chain. The polyesters were synthesized by melt polycondensation of the obtained acids with 2,2′-oxydiethanol. We found reduced viscosity, molecular weight (by GPC), and softening temperature for the reaction products. Low molecular weights, low softening temperature, and very good solubility in organic solvents are their characteristics. The polyurethanes were prepared by polyaddition diols with hexamethylene diisocyanate and tolylene diisocyanate in benzene. They were characterized by reduced viscosity and some tensile properties. The polyurethane derived from 2-(p-tolylmethylthiomethyl)-1,4-butanediol and hexamethylene diisocyanate (η_red. 1.17 dL/g) behaves like a high elasticity thermoplastic elastomer. Thermal stability of all polymers was determined by thermogravimetric analysis. The structure of the monomers and polymers were confirmed by elemental analysis and FTIR and ¹H-NMR spectroscopy. © 1996 John Wiley & Sons, Inc.