Difunctional Alcohols Research Articles

Phytic acid oligomers as bio-based crosslinkers for epoxy and polyol resins

AbstractIn recent years, the chemical industry is not only striving to produce the best possible products for various applications, but the new products should ideally be based on renewable resources. The ideal case of "cradle to cradle" is generally not achievable in the coatings industry, as maximizing product life and preventing product degradation in the environment is usually one of the main goals of the coatings industry. Therefore, if the coatings industry wants to act sustainably, its efforts should be focused on renewable raw materials. This paper presents a process that makes the renewable raw material phytic acid easily accessible for conventional epoxy and polyol resin coating systems through hydrophobization- and oligomerization. Phytic acid, as a phosphorus reservoir in plants and with beneficial properties for corrosion protection and as a flame retardant, could be a new base for various coatings. In this work, a simple one-pot oligomerization of phytic acid with green mono- and difunctional alcohols is investigated. The aim of this work is to create a phytic acid hardener system based on renewable raw materials that can produce coatings with solvent-based epoxy and polyol binders as well as water-based epoxy binders. The successful reaction was observed by infrared, 1H-NMR, and 31P-NMR spectroscopy and the acid equivalent weight was determined by conductivity titration. The renewable curing agent was then used equivalently with different binder systems to prepare coatings. Crosslinking and glass transition temperature were monitored using oscillatory rheology. The coatings were applied to glass plates and the pendulum hardness was measured. A simple heating test followed by 31P-NMR and IR spectroscopy was also performed to demonstrate the stability of phytic acid under reaction conditions.

Synthesis and Characterization of Anionic Polyurethane Dispersants for Waterborne Paints

Anionic polyurethane dispersants APUDs were used as dispersing agents in formulation of waterborne paints. The APUDs were synthesized by three steps. In the first step, macromonomer diisocyanate having carboxylic acid was prepared by isophorone diisocyanate IPDI, dimethylol propionic acid DMPA in presence of acetone as solvent and dibutyltin dilaurate DBTDL as catalyst. Then, carboxylic polyurethane was prepared by reaction macromonomer diisocyanate having carboxylic acid groups with alcohols. In this work, alcohols were 1,4-butanediol and 1,6-hexanediol as difunctional alcohols, trimethylol propane as trifunctional alcohol and pentaerythritol as tetrafunctional alcohol. The final step involved neutralization and dispersion in water, where acidic polyurethane was neutralized by the addition of triethylamine TEA. The polymers have been characterized with 1H-NMR and FT-IR. The dispersion of APUDs depends on their molecular weights and chemical structures. Dispersion of titanium dioxide in typical waterborne acrylic resin has been investigated.

Investigation of a spiro to ansa rearrangement with di-functional alcohols in cyclotriphosphazene derivatives

A spiro to ansa rearrangement has been investigated by the reactions of cyclotriphosphazene derivatives having five-membered spiro rings, N3P3Cl4[O(CH2)2NH], (1) and N3P3Cl4[O(CH2)2O], (2) with disodium salts of 1,3-propanediol and 2,2,3,3-tetrafluoro-1,4-butanediol. Compounds 1 and 2 with the strong nucleophile, 1,3-propapanediol, give rearrangement reactions to form stable ansa–ansa compounds, whereas reaction of compounds 1 and 2 with the fluorinated alkoxide results in normal nucleophilic substitution at the PCl2 groups and no rearrangement takes place with the weaker nucleophile. The synthesised compounds (3a, 3b, 4b, 5a–d, 6c and 6d), have been fully characterised by elemental and mass (MS) analysis, and by 1H and 31P NMR spectroscopy. Crystal structures of 3b, 4b, 5b–d and 6c have been characterised by X-ray crystallography. It is found that 1,3-propapanediol is a sufficiently strong nucleophile to cause a spiro to ansa rearrangement in the mono-spiro cyclotriphosphazenes compounds 1 and 2, even though crystallographic evidence shows that formation of the seven- and eight-membered ansa–ansa rings in compound 3b results in distortion and compression of the cyclophosphazene ring. A possible mechanism, which depends on attack of the anionic oxygen nucleophile at spiro-bearing phosphorus atom, was used to help understand the spiro-to-ansa rearrangement reaction.

Synthesis, Structure, and Reactivity of Dinuclear Nickel Amino-Thiophenolate Complexes Bearing Bridging VO2(OH)2–and VO2(OR)2– Coligands

A series of novel mixed ligand dinickel complexes of the type [Ni(II)(2)L(μ-L')](+), where L' is a tetrahedral oxo-alkoxo vanadate (L' = [O(2)V(V)(OR)(2)](-), R = H or alkyl) and L a macrocyclic N(6)S(2) supporting ligand, have been prepared, and their esterification reactivity has been studied. The orthovanadate complex [Ni(2)L(μ-O(2)V(OH)(2))](+) (2), prepared by reaction between [Ni(2)L(μ-Cl)]ClO(4) with Na(3)VO(4) and a phase transfer reagent in CH(3)CN, reacts smoothly with MeOH and EtOH forming the vanadate diesters [Ni(2)L(μ-O(2)V(OMe)(2))](+) (3) and [Ni(2)L(μ-O(2)V(OEt)(2))](+) (4). The dialkyl orthovanadate esters in 3 and 4 are readily transesterified with mono- and difunctional alcohols. Complex 3 can also be generated from 4 by transesterification with MeOH. Complexes 3 and 4 react with diols (ethylene glycol, propylene glycol and diethylene glycol) as well to afford the complexes [Ni(2)L(μ-O(2)V(OH)(OCH(2)CH(2)OH))](+) (5), [Ni(2)L(μ-O(2)V(OCH(2))(2)CH(2))](+) (6), and [Ni(2)L(μ-O(2)V(OCH(2)CH(2))(2)O)] (7). The crystal structures of the tetraphenylborate salts of complexes 3-7 reveal in each case four-coordinate O(2)V(V)(OR)(2)(-) groups bonded in a μ(1,3)-bridging mode to generate trinuclear complexes with a central N(3)Ni(μ-S)(2)(μ(1,3)-O(2)V(OR)(2))NiN(3) core. The stabilization of the four-coordinate V(V)O(2)(OR)(2)(-) moieties is a consequence of both the two-point coordinative fixation to and the steric protection of the bowl-shape binding pocket of the [Ni(2)L](2+) fragment. Cyclic voltammetry experiments reveal that the encapsulated vanadate esters are not reduced in a potential window of -2.0 to +2.5 V vs SCE. The spins of the nickel(II) (S(i) = 1 ions) in 3 are weakly ferromagnetically coupled (J = +23 cm(-1), (H = -2JS(1)S(2))) to produce an S = 2 ground state.

Surface Modification of ZnO Nanoparticles

The synthesis and surface modification of ZnO nanoparticles, achieved through a controlled precipitation reaction using NaOH as precipitating agent with a 0.2 molar ratio were studied. The surface modification was carried out through a chemical hydrolysis reaction at 80°C for 6 h, in order to promote better adhesion between inorganic particles and a polymer matrix when they were used in composite materials. Both 3-aminopropyltrimethoxysilane (APTMS) and difunctional alcohol spiroorthocarbonate (SOC DIOL) were used as modifying agents in a 0.5:1 ratio with respect to ZnO nanoparticles. According to x-ray diffraction (XRD), electron transmission microscopy with scanning modulus (STEM) and infrared spectroscopy (FTIR), the ZnO crystalline structure did not change after treatment. Surface modification was performed in order to subsequently use ZnO nanoparticles in medical antimicrobial devices.

Cycloaliphatic polyester based high solids polyurethane coatings: I. The effect of difunctional alcohols

High-solids polyesters were synthesized with two cycloaliphatic diacids, 1,4- cyclohexanedicarboxylic acid (1,4-CHDA) and 1,3-cyclohexanedicarboxylic acid (1,3-CHDA); and with five diols, 1,4-cyclohexanedimethanol (CHDM), neopentyl glycol (NPG), hydroxypivalyl hydroxypivalate (HPHP), 2-butyl-2-ethyl-1, 3-propanediol (BEPD), and 1,6-hexanediol (HD). The viscosity of the polyesters was dependent on the structures of diols. The viscosity of polyesters is lower with the diol HD, intermediate with BEPD and HPHP, and higher with the diols CHDM and NPG. The polyesters were crosslinked with hexamethylene diisocyanate isocyanurate (HDI isocyanurate) affording polyurethane coatings. The mechanical properties, tensile properties, fracture toughness, and viscoelastic properties were investigated for the polyurethane films with five different diols. The cyclohexyl structure of the CHDM provides the polyurethane with rigidity which is manifested in high tensile modulus, hardness, and fracture toughness. In contrast, the linear diol, 1,6-hexanediol provides polyurethane with very high flexibility, but these coatings suffer with respect to low hardness and tensile modulus.

Synthesis and photoreactions of polyesters containing triazene and cinnamylidene malonyl units

The synthesis and photoreactions of polyesters containing the photolabile triazene group (Ph-N=N-NR 2 ) as well as photocrosslinkable units based on substituted cinnamylidene malonyl moieties are reported. The polyesters were obtained by reacting a triazene containing difunctional alcohol with different substituted cinnamylidene malonic acid dichlorides. Irradiation at A > 395 nm enables selective photocrosslinking of the cinnamylidene malonyl ester units via [2 + 2] π-cycloaddition without affecting the triazene units. The photocrosslinking reaction of the triazene containing polyesters as well as triazene-free reference polyesters were investigated by UV and IR spectroscopy. After selective photocrosslinking the irradiated polymers became insoluble and no longer exhibited a T g below decomposition temperature. The crosslinked triazene containing polyesters show strong absorption at A = 308 nm and are therefore interesting candidates for applications using XeCl excimer laser ablation.

ChemInform Abstract: Functionalized Ozonides by Substitution Reactions of Chlorinated Ozonides with Difunctional Alcohols.

AbstractChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

Functionalized Ozonides by Substitution Reactions of Chlorinated Ozonides with Difunctional Alcohols

AbstractSubstitution of 3‐chloro‐3,5‐bis(chloromethyl)‐5‐methyl‐1,2,4‐trioxolane (3) with allyl alcohol gave the corresponding diastereomeric allyloxy‐substituted ozonides 4, which were converted into diozonides 7 by ozone treatment. Substitutions of 3 with ethanediol or with 1,3‐propanediol gave the corresponding hydroxyalkoxy‐substituted ozonides 8, 14, which were oxidized to the corresponding aldehydes 10, 16. Reaction of 3,5‐dichloro‐3,5‐bis(chloromethyl)‐1,2,4‐trioxolane (1a) with ethanediol gave the corresponding bis(hydroxy)‐substituted ozonide 19 as well as a bicyclic ozonide 18 by reaction of 1a with ethanediol in a ratio of 1:1.

New polyesters with photosensitive backbones based on the triazene unit

The synthesis of photosensitive polymers that contain the triazeno group (Ph-N=N-NR 2 ) as a sensitive unit in their backbone is reported. The synthesis pathway consists of difunctional alcohols incorporating the photosensitive unit that react with diacyl derivatives to give the respective polyesters. Upon irradiation, the photosensitive chromophores both in monomeric and polymeric surroundings are cleaved fast and irreversibly, as shown in photolytic studies and their kinetic evaluations. Thermogravimetrical investigations indicate the loss of nitrogen being the initial thermal decomposition step and exhibit stabilities sufficient for the requirements in applications as photoresists.

Effect of monofunctional and trifunctional modifiers on a phase mixed polyurethane system

AbstractThe dynamic mechanical behavior of a phase mixed polyurethane system modified with trifunctional and monofunctional alcohols was investigated and compared with a typical polyurethane system with a difunctional alcohol. Of interest was verifying that the average functionality of the alcohol would determine the dynamic mechanical properties and not whether that functionality was achieved by an equimolar blend of trifunctional and monofunctional alcohols or by a purely difunctional alcohol. The base system consisted of poly(tetramethylene ether)glycol (PTMG) cured with 4,4′‐diphenylmethane diisocyanate (MDI). The trifunctional alcohol was trimethylol propane (TMP). The monofunctional alcohol was decyl alcohol (DA). Samples with a typical difunctional alcohol, 2,2‐dimethyl‐1,3‐propanediol (DMPD), were prepared and their properties compared with those of the above samples. To a first approximation, the properties of TMP‐DA modified polymers are identical to those of DMPD polymers of the same hard segment concentration. These results confirm our hypothesis that the dynamic properties obtained from a combination of a trifunctional alcohol with a monofunctional alcohol are essentially equivalent to those of a difunctional alcohol.

Synthesis of transannular- and spiro-substituted cyclotriphosphazenes: x-ray crystal structures of 1,1-[N3P3(OCH2CF3)4{O2C12H8}], 1,3-[N3P3(OCH2CF3)4{O2C12H8}], 1,1-[N3P3(OCH2CF3)4{O2C10H6}], and 1,3-[N3P3(OCH2CF3)4}O2C10H6}

A cyclic triphosphazene with four trifluoroethoxy side groups and two nongeminal chlorine atoms, 1,3-[N 3 P 3 (OCH 2 -CF 3 ) 4 Cl 2 ], reacts with difunctional alcohols or amines to give transannular derivatives. Examples of the difunctional reagents used include catechol, 2,2'-biphenol, 1,8-dihydroxynaphthalene, 1,8-diaminonaphthalene, 1,3-propanediol, 1,3-diaminopropane, and 2,2'-dilithiobiphenyl.

ChemInform Abstract: Phosphorus‐Nitrogen Compounds. Part 63. The Reactions of 6,6‐Bis‐t‐butylamino‐2,2,4,4‐tetrachlorocyclotriphosphazatriene (I) with Difunctional Alcohols, Amines, and Aminoalcohols. The 31P and 1H NMR Spectra of the Products.

ChemInformVolume 21, Issue 39 Organoelement Compounds ChemInform Abstract: Phosphorus-Nitrogen Compounds. Part 63. The Reactions of 6,6-Bis-t-butylamino-2,2,4,4-tetrachlorocyclotriphosphazatriene (I) with Difunctional Alcohols, Amines, and Aminoalcohols. The 31P and 1H NMR Spectra of the Products. W. F. DEUTSCH, W. F. DEUTSCH Dep. Chem., Birkbeck Coll., Univ. London, London WC1E 7XH, UKSearch for more papers by this authorR. A. SHAW, R. A. SHAW Dep. Chem., Birkbeck Coll., Univ. London, London WC1E 7XH, UKSearch for more papers by this author W. F. DEUTSCH, W. F. DEUTSCH Dep. Chem., Birkbeck Coll., Univ. London, London WC1E 7XH, UKSearch for more papers by this authorR. A. SHAW, R. A. SHAW Dep. Chem., Birkbeck Coll., Univ. London, London WC1E 7XH, UKSearch for more papers by this author First published: September 25, 1990 https://doi.org/10.1002/chin.199039240AboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onFacebookTwitterLinked InRedditWechat No abstract is available for this article. Volume21, Issue39September 25, 1990 RelatedInformation

Dielectric measurements on liquid crystalline polymers derived from PETP

Poly(ethylene terephthalate) PETP has been modified with a difunctional alcohol and acid in the molar relation 1:1. By dielectric relaxation measurements could be shown that the modification increases the segmental mobility (α-process). The local mobility (β-process) increases at smaller and decreases at higher concentrations of the modificators. A separation of the α-relaxation from the common relaxation process α+β could be observed with decreasing temperature.

ChemInform Abstract: Phosphorus‐Nitrogen Compounds. Part 55. The Reactions of 2,2,4,4‐Tetrachloro‐6,6‐diphenylcyclotriphosphazatriene with Aliphatic Difunctional Alcohols, Amines, and Aminoalcohols. 1H and 31P NMR Spectroscopic Studies of the Products.

ChemInformVolume 19, Issue 43 Organoelement Compounds ChemInform Abstract: Phosphorus-Nitrogen Compounds. Part 55. The Reactions of 2,2,4,4-Tetrachloro-6,6-diphenylcyclotriphosphazatriene with Aliphatic Difunctional Alcohols, Amines, and Aminoalcohols. 1H and 31P NMR Spectroscopic Studies of the Products. W. F. DEUTSCH, W. F. DEUTSCH Dep. Chem., Birkbeck Coll., London WC1E 7HX, UKSearch for more papers by this authorR. A. SHAW, R. A. SHAW Dep. Chem., Birkbeck Coll., London WC1E 7HX, UKSearch for more papers by this author W. F. DEUTSCH, W. F. DEUTSCH Dep. Chem., Birkbeck Coll., London WC1E 7HX, UKSearch for more papers by this authorR. A. SHAW, R. A. SHAW Dep. Chem., Birkbeck Coll., London WC1E 7HX, UKSearch for more papers by this author First published: October 25, 1988 https://doi.org/10.1002/chin.198843270Read the full textAboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onFacebookTwitterLinked InRedditWechat No abstract is available for this article. Volume19, Issue43October 25, 1988 RelatedInformation

Phosphorus–nitrogen compounds. Part 55. The reactions of 2,2,4,4-tetrachloro-6,6-diphenylcyclotriphosphazatriene with aliphatic difunctional alcohols, amines, and aminoalcohols. Proton and phosphorus-31 nuclear magnetic resonance spectroscopic studies of the products

The reactions of geminal N3P3Ph2Cl4 with aliphatic difunctional alcohols, amines, and aminoalcohols have been investigated. A series of monospiro derivatives, N3P3Ph2[X(CH2)nY]Cl2[X = Y = O or NH, n= 2–4; X = O, Y = NH, n= 2–4; X = Y = NMe, n= 2 or 3; X = NH, Y = NMe, n= 2 or 3; X = O, Y = NMe, n= 2] were obtained and the 31P and 1H n.m.r. spectra investigated. The field and temperature dependences of the 31P n.m.r. spectra were used in the study of degenerate spectra. Non-equivalence of methylene protons in the spiro rings is observed in the 1H n.m.r. spectra of these compounds.