Zoran S. Petrović

Pittsburg State University · Kansas Polymer Research Center

Development of waterborne polyurethanes (WPU) using bio-based sources represents a step towards sustainable materials science and industry. We synthesized bio-based cationic water-dispersed crosslinked polyurethanes from high oleic soybean oil (HOSO) polyol, isophorone diisocyanate, and methyldiethanol amine, with varying ionic group contents after...

There is an increasing awareness that materials and chemicals produced from fossil fuels are not sustainable, both in terms of the pollution caused by the extraction and production processes, and the fact that there is only a finite supply of these fossil fuels. Therefore, there is a strong incentive to find sources for chemicals and materials from...

Self-transesterification of castor oil was employed to prepare higher molar mass polyols possessing interesting properties that can be used without purification. The resulting structure of the polyols is complex due to the reversible nature of transesterification reaction, allowing formation and destruction of new polyols simultaneously. Detailed s...

One issue when utilizing natural oils as raw materials for preparing polymers in comparison with petrochemical starting materials is their complexity. Standard natural oils have typically very heterogeneous structure, which is reflected on properties of polymers. However, oils with regular structure such as high oleic oils, offer high degree of reg...

Preparing materials for technical applications made completely from natural oils is always a respectable goal. Epoxidized oils are an excellent platform for a range of new polymers, including cross-linked epoxy resins prepared by cationic ring-opening polymerization. Casts of glassy or rubbery epoxy resins were made from epoxidized algal, soybean,...

The direct conversion of natural products to useful engineering materials is desirable from both economic and environmental considerations. We describe the synthesis and properties of 100 % oil-based epoxy resins generated from three epoxidized oils. The catalyst, tris(pentafluorophenyl)borane (B(C6F5)3) in toluene, allowed for controlled cationic...

New materials were made by copolymerization of epoxidized linseed oil (ELO) and cyclohexene oxide (CHO) catalyzed by tris(pentafluorophenyl)borane (BCF). Pure polymerized ELO and polymerized CHO were prepared to study reactivity and properties of starting components in the presence of the selected catalyst. The catalyst furnished high conversion of...

We have found that B(C6F5)3 in toluene can be an effective initiator for cationic polymerization of epoxidized fatty acid methyl esters and epoxidized oils with cis-disubstituted oxirane groups. The reaction is relatively fast, but controllable. The polymerization product of epoxy methyl oleate was a mixture of linear and cyclic oligomers of molar...

The direct conversion of natural products to useful engineering materials is desirable from both economic and environmental considerations. We are describing the synthesis and properties of 100 % oil-based epoxy resins generated from three epoxidized oils. The catalyst, tris(pentafluorophenyl)borane (B(C 6 F 5 ) 3 ) in toluene, allowed for controll...

A new method for the synthesis of high molar mass, bio‐based polyols for elastic polyurethanes has been developed. This process is based on the self‐condensation of low molar mass polyols (Mn∼1000) and vacuum removal of the resulting glycerol. Self‐condensation products are hyperbranched estolide polyols with average molar masses close to 3000 and...

Thermosetting cast resins, filled with varying levels of silica, were prepared from epoxidized soybean oil (ESO) and epoxidized triolein (ETO) in order to study matrix-filler interactions and effects of cross-linking density on physical properties. While ESO is characterized by a highly heterogeneous composition, ETO had very regular structure but...

In order to cope with the resource crisis and environmental pollution that caused by the rapidly depletion of non-renewable petroleum resources, as well as to achieve the efficient and high value utilization of inedible green renewable oils were investigated. Bio-based polyols with different structures were prepared from microalgae oil, and the met...

Semi-interpenetrating polymer networks (SIPN) based on thermoresponsive poly(N-isopropylacrylamide) (PNIPA) and water-soluble sodium salts of linear hyaluronic acid (Na-HA) were physically cross-linked with synthetic nanoclay (laponite XLG). PNIPA hydrogels with different cross-linking densities and Na-HA concentrations were synthesized by in situ...

Rubber seed oil (RSO), extracted from the seeds of rubber trees, is inedible oil with high free fatty acid content. In order to add value to RSO, we prepared a polyol with primary OH groups via hydroformylation/hydrogenation. Free hydroxy fatty acids formed in the process were utilized as reactive diluents, viscosity reducers, and adhesion promoter...

Based on our experimental results and literature data, we propose a general mechanism of self‐condensation of glycerol to polyglycerol in the presence of alkaline catalysts. The mechanism involves the "in situ" formation of glycidol and oligo‐glycerols with terminal epoxy groups by intramolecular SN2 substitution reactions. We consider that termina...

Polymerization of soybean oil produces higher-viscosity liquids, which may serve as processing aids and plasticizers in certain rubbers as a replacement of petrochemical oils. Four polymerized soybean oils of different molecular weights showed good compatibility with ethylene-propylene-diene rubber (EPDM), but because of the presence of double bond...

Novel fast response shape-memory polyurethanes were prepared from bio-based polyols, diphenyl methane diisocyanate and butane diol for the first time. The bio-based polyester polyols were synthesized from 9-hydroxynonanoic acid, a product obtained by ozonolysis of fatty acids extracted from soy oil and castor oil. The morphology of polyurethanes wa...

Cardanol is a natural phenol which is obtained from high vacuum distillation of cashew nut shell liquid. It contains a hydrocarbon chain of 15 carbon atoms in the meta position, either with one, two or three non-conjugated double bonds. This article describes thermal thiol-ene reaction to synthesize new cardanol-based polyols for polyurethanes with...

The reactivity of internal epoxides, as in epoxidized fatty acids, with primary amines was investigated using primary amines and a model epoxide compound, which was a mixture involving cis‐ and trans‐isomers of 9,10‐epoxyoctadecane.The reactions were carried out at 100, 170, and 200°C for 24 h. It was observed that the reaction of an amine with an...

Two series of semiinterpenetrating networks (SIPN) based on linear hydrophilic poly(vinyl alcohol) (PVA) and thermo-responsive poly(N-isopropylacrylamide) (PNIPA), physically cross-linked with inorganic clay, are presented. The hydrogels with different cross-linking densities were prepared by varying the content of clay from 1 to 6 wt % and contain...

Rubber seed oil having high free fatty acid (FFA) content and high unsaturation was used to obtain high quality polyurethane resins through epoxidation and ring opening with methanol and free fatty acids. Two polyols prepared with free fatty acids and without, were cured with modified methylene diphenyl diisocyanate to obtain strong, high modulus g...

Novel high hydroxyl number and high functionality polyols were developed using thiol-ene reaction of castor oil with mercaptoethanol or mercaptanized castor oil with allyl alcohol (by photochemical reaction) and 2-hydroxyethyl acrylate (by Michael thiol-ene reaction). The polyols had OH numbers of 220-295 mg KOH/g and functionalities close to 6. Ca...

Rigid thiourethane foams were prepared from vegetable oil-based polythiols (polymercaptans) and compared with soy- and castor oil-based polyurethane reference foams. Three types of polymercaptans were tested, soybean oil-based one with thiol groups only, epoxidized soybean oil-based with vicinal thiol and hydroxyl groups and castor oil-based with h...

Blends with varied ratio of polylactic acid (PLA) and thermoplastic polyurethane (TPU) were prepared by melt blending. The PLA content in blends was 20, 40, 60 and 80 wt%. Samples of pure PLA and TPU that underwent the same thermal treatment were also prepared. Biodegradation was examined by respirometry. Pure TPU started to degrade immediately due...

Isosorbide, a renewable diol derived from starch, was used alone or in combination with butane diol (BD) as the chain extender in two series of thermoplastic polyurethanes (TPU) with 50 and 70% polytetramethylene ether glycol (PTMEG) soft segment concentration (SSC), respectively. In the synthesized TPUs, the hard segment composition was systematic...

Vegetable oils are sustainable and environmentally benign sources for new monomers and polymers. Here we report the preparation and use of polyacids derived from corn oil as curing agents for commercial epoxy resins (DER332). First, epoxidized corn oil (ECO) was polymerized by ring-opening polymerization in the presence of boron trifluoride diethyl...

A novel bio based Mannich polyol using limonene was synthesized. Mannich polyols are a group of amino polyols with aromatic structure which provide fire resistance, good thermal and superior physico-mechanical properties. The synthesized Mannich polyol was structurally characterized using wet methods (hydroxyl number, acid value and viscosity), gel...

Novel segmented polyurethane elastomers were successfully synthesized by a nonisocyanate route using dicyclic carbonates as precursors for both soft and hard segments. The hard segment was prepared from the dicyclic carbonate of bisphenol A and m-xylylenediamine as chain extender. The soft segment was poly(tetramethylene ether) glycol of molecular...

Isosorbide, a cyclic, rigid and renewable diol was used as a chain extender in two series of thermoplastic polyurethanes. Isosorbide was used alone or in combination with butane diol to examine the effects on the morphology of polyurethane (PU). Two series of materials were prepared – one with dispersed hard domains in the matrix of polytetramethyl...

Alkynated and azidated octadecane, synthesized from 9-octadecene, were used as model compounds for alkynated and azidated vegetable oils to study the kinetics of thermal Huisgen 1,3-dipolar cycloaddition. Alkyne and azide groups of alkynated and azidated octadecane possess low reactivity as they are branched in the middle of an 18-carbon chain. Rea...

Blends of two biocompatible polymers: thermoplastic polyester-urethane (TPU) and polylactic acid (PLA) were studied. The effect of the blending ratio on blend morphology and properties was examined by running a series of blends from 10 to 80 wt % of PLA. Increasing TPU concentration in the blends lowered the glass transition and melting point of PL...

Two novel potentially biodegradable thermoplastic polyurethane elastomers with unique structure and morphology were prepared from the modified oleic acid. The hardness and mechanical properties were controlled by adjusting soft segment concentration. Epoxidized methyl oleate was converted to methyl-9-OR-10-hydroxy stearate (hydroxystearate) by cata...

Water soluble epoxy resins were prepared from diglycidyl ethers of isosorbide (DGEI) and isosorbide diamine (ISODA). We investigated the effect of synthesis methods on the structure of DGEI and ISODA and their influence on properties of cured resins, and compared with bisphenol A commercial epoxy resins (DGEBA). DGEI and DGEBA were cured with dieth...

Novel renewable polyols based on limonene were synthesized using thiol-ene ‘‘click’’ chemistry. These limonene based polyols were structurally characterized using wet methods (hydroxyl number, acid value and viscosity), gel permeation chromatography and spectroscopic methods. The results indicated that high yield of polyols from limonene based mate...

A method of making a biobased-petrochemical hybrid polyol is provided. This method includes reacting a cyclic ether with a vegetable oil-based polyol in the presence of a cationic catalyst or a coordinative catalyst that includes a vegetable oil-based polyol ligand to form the biobased-petrochemical hybrid polyol. The biobased-petrochemical hybrid...

This paper examines the feasibility of using polyols from vegetable oils as base polyols (i.e. with 50% or more in a blend with petrochemical polyols) for flexible molded polyurethane foams. A series of hyperbranched (HB) polyols were synthesized by transesterification of hydroxy fatty acid methyl esters and different modifiers to control viscosity...

This paper reviews a part of the rich field of oleochemicals, their synthesis and applications as precursors for polymers by referring to published data rather than discussing details of different reactions. The hope is to help readers in finding leads in the vast research area carried out over a long period of time, to avoid traps and to inspire n...

The composition of crude algal oil was analyzed and determined by several methods. Oil was converted to polyols by ozonolysis, epoxidation, and hydroformylation. Ozonolysis gave a polyol with lighter color but a low OH number and was unsuitable for polyurethane applications. Epoxidation also improved the color and gave a polyol with an OH number ar...

Cashew nut shell liquid (CNSL) is a natural aromatic oil consisting of a mixture of phenolic structures with a carboxyl group in ortho position and substituted in meta position with a hydrocarbon chain of 15 carbon atoms. The major component of CNSL is anacardic acid (90 %), which is easily decarboxylated to cardanol by distillation. The present wo...

Enhanced oligomeric polyols are reported. The enhanced oligomeric polyols may be prepared by a method comprising the steps of: (a) providing an oligomeric polyol that comprises at least one glycerol fatty acid ester having at least one glycerol fatty acid ester bond; wherein at least 5% of the ethyldenyl groups (*C═C*) in the glycerol fatty acid es...

Polyurethanes were prepared via a nonisocyanate route, by reacting carbonated soybean oil (CSBO) with aromatic and cycloaliphatic diamines. Nonisocyanate polyurethanes prepared form CSBO and aliphatic diamines have relatively low tensile strength and one of the possible ways to increase strength and rigidity is to use diamines with rigid aromatic o...

Polymerized soybean oils of different molecular weights were used as plasticizers in NR/SBR compositions. The oils of different molecular weights and viscosities were synthesized by cationic polymerization using a proprietary technology. Because vegetable oils have double bonds, they are not only viscosity depressants but also active participants i...

Completely bio-based polyols, suitable for the preparation of rigid polyurethanes were synthesized from polyglycerol, lactic acid and fatty acids. Lactic units were introduced into the polyol structure by the ring opening addition of L-lactide to hydroxyl groups, in the presence of the titanium(IV) isopropoxide catalyst. To address the incompatibil...

Novel bio-based compounds containing phenols suitable for the synthesis of polyurethanes were prepared. The direct alkylation of phenols with different vegetable oils in the presence of superacids (HBF(4), triflic acid) as catalysts was studied. The reaction kinetics was followed by monitoring the decrease of the double bond content (iodine value)...

Polymerization of azidated castor, canola, corn, soybean, and linseed oils with two diynes under thermal click chemistry conditions (without a solvent or a catalyst) yielded fully cross-linked polymers (1–10) with similar density. The use of an aromatic diyne (1,4-diethynylbenzene) as a cross-linker resulted in polymers (1–5) that showed higher gla...

Structural studies on two segmented polyurethanes prepared from modified oleic acid soft segments and butane diol/diphenylmethane diisocyanate hard segments, were performed. Polyurethanes were thermoplastic elastomers with 50% and 70% soft segment concentration (SSC) for TPU-50 and TPU-70, respectively. DMA revealed the co-continuous morphology in...

Hydroformylation of methyl soyate produces a mixture of fatty acid methyl esters with zero, one, two, and three hydroxyl groups, the major component being with two hydoxyls (around 50%). Polymeriza-tion of methyl esters of hydroxy fatty acids gives a hyperbranched product with a different content of hydroxyl groups depending on the degree of conver...

We used multiple‐detection size exclusion chromatography and batch‐mode light scattering to follow the structural development of hydroxylated fatty acid methyl esters of soybean oil into hyperbranched (HB) polyol during polymerization by analyzing samples, collected at different times, in dilute solutions in tetrahydrofuran. The size of HB molecule...

Cashew nut shell liquid (CNSL) is a natural aromatic oil consisting of a mixture of phenolic structures with a carboxyl group in ortho position and substituted in meta position with a hydrocarbon chain of 15 carbon atoms. The major component of CNSL is anacardic acid (90 %), which is easily decarboxylated to cardanol by distillation. The present wo...

Hydroformylation of methyl soyate produces a mixture of fatty acid methyl esters with zero, one, two, and three hydroxyl groups, the major component being with two hydoxyls (around 50%). Polymerization of methyl esters of hydroxy fatty acids gives a hyperbranched product with a different content of hydroxyl groups depending on the degree of convers...

Two series of nanoclay reinforced, thermoresponsive hydrogels were prepared, one based on poly(N-isopropylacrylamide) (PNIPA) and the other on semi-interpenetrating networks containing PNIPA and poly(N-vinyl pyrrolidone) (PVP), designated as SIPNs. The gels were crosslinked with 1, 3, and 5 wt % inorganic clay (hectorite) and SIPN gels additionally...

New monomers were prepared by introducing the azide groups in castor, canola, corn, soybean, and linseed oils. Polymerization of the azidated oils with alkynated soybean oil under thermal "click" chemistry conditions (without using a solvent or a catalyst) yielded fully cross-linked elastomers (1-5) of almost the same density (1.05 × 10(-3) kg/m(3)...

A new class of biopolymers based on plant oils with allylic double bonds was prepared from vegetable oils by oxirane ring-opening. Investigation of model systems revealed that the main side reactions during ring-opening were formation of intramolecular cyclic ethers in epoxidized linoleic fatty ester and oligomerization. Side reactions in the epoxi...

The feasibility of using mineral nano- and micro-fillers as replacement of copolymer polyols in flexible foams was examined. Nano-fillers were nano-clays, a natural montmorillonite (Cloisite Na+) and montmorillonite modified with an organic quaternary ammonium salt (Cloisite 10A), and nano-silica dispersed in methylethylketone. Micro-fillers were m...

Novel bio-based compounds containing phenols suitable for the syn-thesis of polyurethanes were prepared. The direct alkylation of phenols with different vegetable oils in the presence of superacids (HBF 4 , triflic acid) as ca-talysts was studied. The reaction kinetics was followed by monitoring the de-crease of the double bond content (iodine valu...

Starting from a bio-based polyol through modification of soybean oil, BIOH™ X-210, two series of bio-based polyurethanes-clay nanocomposite foams have been prepared. The effects of organically-modified clay types and loadings on foam morphology, cell structure, and the mechanical and thermal properties of these bio-based polyurethanes-clay nanocomp...

Novel vegetable oil-based elastomers were prepared from hydrogenated ricinoleic acid methyl esters. Polyester polyol with molecular weight 2500 was synthesized by transesterification of methyl-12-hydroxy stéarate and 1,6-hexanediol. Segmented polyurethanes with 50 and 70% soft segment concentration (SSC) were prepared using the prepolymer method by...

Two series of segmented polyurethanes having soft segment concentration of 50 and 70 wt%, and different concentrations of nanometer-diameter silica were prepared and tested. Atomic force microscopy revealed a strong effect of nanoparticles on the large-scale spherulitic morphology of the hard domains. Addition of silica suppresses fibril formation...

Vegetable oils, fish oil and oils from algae are excellent raw materials for new polymers. These oils differ in the structure and unsaturation, but each offer specific advantages. Vegetable oils are inexpensive and offer different degrees of unsaturation. Fish oils may have a very high degree of unsaturation. Algal oils are new raw materials with s...

Kansas Polymer Research Center (KPRC) is a Kansas Technology Enterprise Corporation (KTEC) Center of Excellence, is involved primarily in the development of materials from renewable resources. The students have an opportunity to work on large machines for injection molding, extrusion, thermoforming, compression molding and blow molding as well as o...

Thermoplastic urethanes based on polyricinoleic acid soft segments and MDI/BD hard segments with varied soft segment concentration were prepared. Soft segment concentration was varied from, 40 to 70wt%. Biodegradation was studied by respirometry. Segmented polyurethanes with soft segments based on polyricinoleic acid degrade relatively slow losing...

Polyglycerol (PGL) is a polyhydroxyl compound obtained by selfcondensation of glycerol in the presence of alkaline catalysts. It is a very attractive polyol as a starter for the synthesis of polyether polyols for rigid polyurethane foams. It is liquid, easy to handle and has a very high average functionality of 4—20 (or more) hydroxyl groups/mol. B...

To our knowledge, this is the first description of the material properties of a high molecular weight linear polyester prepared from the methyl ester of 9-hydoxynonanoic acid (HNME). The HNME of high purity was prepared by ozonolysis of castor oil, followed by methanolysis of triglycerides. High molecular weight polyester prepared in bulk by transe...

Novel bio-based polyols were prepared from hydroformylated oleic acid (9/10-hydroxymethyl-octadecanoic acid) methyl esters (HFME) and trimethylolpropane by transesterification. Hydroformylation produces primary hydroxyls, which allow relatively lower transesterification temperatures and better yields than hydroxy fatty acids with secondary hydroxyl...

Polyglycerol (PGL) is a polyhydroxyl compound obtained by self-condensation of glycerol in the presence of alkaline catalysts. It is a very attractive polyol as a starter for the synthesis of polyether polyols for rigid polyurethane foams. It is liquid, easy to handle and has a very high average functionality of 4–20 (or more) hydroxyl groups/mol....

Novel thermoplastic polyurethane elastomers with different soft segment contents were prepared from bio-based polyols, diphenyl methane diisocyanate (MDI) and butane diol. The bio-based polyester polyol was synthesized from 9-hydroxynonanoic acid, a product obtained by ozonolysis of fatty acids. New polyols are similar in structure to polycaprolact...