HET acid based oligoesters - TGA/FTIR studies

One of the important reactive halogenated dicarboxylic acids used in the synthesis of flame retardant unsaturated polyester resins is 1,4,5,6,7,7-hexachlorobicyclo [2.2.1] hept-5-ene-2,3-dicarboxylic acid (HET acid). In the present investigation four different oligoesters are synthesized using HET acid as the diacid component and 1,2-ethane diol, 1,2-propane diol, 1,3-propane diol and 1,4-butane diol as the aliphatic diols. Melt condensation technique in vacuum is used for the synthesis of the oligoesters. The number average molecular weights of the oligoesters are determined using end group analysis. The degree of polymerization is estimated to be 3-5. The structural characterization is done using FTIR and NMR (¹H and ¹³C) techniques. In the present investigation, TGA-FTIR studies for the different oligoesters are carried out in nitrogen atmosphere. The materials are heated from ambient to 600 °C at a heating rate of 20 °C/min. The main volatile products identified are CO, HCl, H₂O, CO₂, hexachlorocyclopentadiene and HET acid/anhydride. The evolution profile of these materials with respect to the structure of the oligoesters is discussed in detail and presented. The importance of β-hydrogens in the diol component and the plausible mechanism for the flame retardant behavior of these oligoesters are presented.     

Thermal degradation studies on PMMA–HET acid based oligoesters blends

Imparting thermal stability to polymethyl methacrylate (PMMA) without affecting its optical clarity is attempted by incorporating HET acid based oligoesters. Pure PMMA and PMMA containing five and 20 wt% of four different oligoesters are separately prepared using bulk polymerization. The thermal properties of the materials studied using DSC, TG, TG–FTIR and Pyr–GC–MS are presented. The main volatile degradation products identified are CO, HCl, CO₂, H₂O, hexachlorocyclopentadiene, hexachloroendomethylene tetrahydrophthalic acid/anhydride and methyl methacrylate. A detailed mechanism for the influence of the degradation products of HET acid based oligoesters on the thermal degradation of PMMA is also presented.     

Effect of structure on the thermal degradation and flame retardancy of hexolic anhydride based polyesters

Based on the anhydrides like hexolic (5,6,7,8,10,10-hexachloro -3a,4,4a,5,8,8a,9,9a-octahydro-5,8-methanonaphtho-[2,3-c]-furan-1,3-dione), maleic and phthalic and diols like 1,4-butanediol, cis-2-butene-1,4-diol and 2,3-dichloro-2-butene-1,4-diol, a family of polyesters has been synthesized using azeotropic condensation technique. The structural characterizations of the polyesters have been carried out using infra-red, 1^H - and ¹³C- nuclear magnetic resonance spectroscopic methods. The thermal properties of the polyesters have been studied using thermogravimetric technique. The off-line pyrolysis of these materials was done. The qualitative and semi-quantitative analyses of the volatiles as well as the heavy mass fractions of the degradation products were carried out using a gas chromatograph coupled to a mass selective detector (GC-MSD). Thermogravimetric data indicate that the thermal stability and the char residue of the polyester resins decrease in the order 1,4-butanediol based>cis-2-butene-1,4-diol based>2,3-dichloro-2-butene-1,4-diol based polyesters. The GC-MSD data indicate that the amount of flame cooling agents (hexa-, isomeric penta-, tetra- and isomeric tri-chlorocyclopentadienes) produced during the pyrolysis of the polyesters increases in the order 2,3-dichloro-2-butene-1,4-diol based<cis-2-butene-1,4-diol based<1,4-butanediol based polyesters. The trends observed in these two parameters which are contributing factors to the flame retardancy of the polyester materials were suitably explained on the basis of the effect of the structural changes in the diol part of the polyesters on the primary degradation mechanism, the β-chain scission process.     

Hydrolytic stability of oligoesters: comparison of steric with anchimeric effects

A comparison of steric and anchimeric effects on the hydrolytic stability of polyesters was studied. Twelve monomers were selected based on their propensity toward steric and anchimeric interactions: adipic acid, isophthalic acid, phthalic anhydride, hexahydrophthalic anhydride, 1,4-cyclohexanedicarboxylic acid, maleic anhydride, ethylene glycol, 1,2-propanediol, 1,3-propanediol 1,4-butanediol, 1,5-pentanediol, and neopentyl glycol. Hydroxyl terminated oligoesters consisting of one diacid and one diol and one hydroxyl terminated oligoester consisting of two diacids and one diol were prepared. The hydrolytic stability was evaluated in an acetone/water solution. The acid number was monitored as a function of time. It was found that telechelic groups favor anchimeric interactions, while steric groups determine the rate of hydrolysis for the main chain.     

Synthesis and Characterization of Polyurethanes Based on Oligo(ϵ-caprolactone) Prepared by Free-Metal Method

The oligoester diols were synthesized via ring-opening polymerization of ?-caprolactone in the presence of creatinine and diethylene glycol or 1,4-butanediol as initiator systems. Thus, obtained oligomers were successfully used in the synthesis of segmented polyurethanes. The oligoester diols (poly(?-caprolactone) and dihydroxy(polyethylene adipate)) were reacted with 4,4′-methylenebis(phenyl isocyanate) in the presence of 1,4-butanediol as the chain extender to obtain polyurethanes. The physical and mechanical properties of polyurethanes were determined. The structures of the oligoesters and polyurethanes were elucidated by means of NMR, IR and MALDI-TOF MS studies.     

偏蓝相干法聚氨酯合成革的制备工艺

本文研究了溶剂型聚氨酯在合成革中的展色性能,以4,4-二苯基甲烷二苯基甲烷二异氰酸酯、己二酸、乙二醇、1,4-丁二醇、甲基丙二醇、N,N-二甲基甲酰胺及乙酸乙酯为主要原料。考察了多元醇组成、扩链剂种类及溶剂组成等因素对干法聚氨酯合成革展色性影响规律。结果表明,当己二酸系聚酯二元醇中乙二醇与1,4-丁二醇的摩尔比为1∶1时、所用扩链剂组成为乙二醇与甲基丙二醇的摩尔比为1∶0.5,所使用的溶剂中N,N-二甲基甲酰胺与乙酸乙酯的质量比为2∶1时,制备得到的干法聚氨酯合成革的展色性能最佳(偏蓝相)。     

Solubilities,thermostabilities and flame retardance behaviour of phosphorus-containing flame retardants and copolymers

Thirteen phosphorus-containing flame retardants were synthesized in this work. The solubilities of flame retardant [(6-oxide-6H-dibenz[c,e][1,2]oxaphosphorin-6-yl)-methyl]-butanedioic acid (DDP) in selected solvents are measured. TGA measurements of the 13 phosphorus-containing flame retardants were carried out and thermal stabilities of three flame-resistant PET (FRPET) resins were investigated. A FRPET incorporated by DDP with terephthalic acid and ethylene glycol reported in literature was also discussed and compared. The thermal stability of the FRPET is improved by the incorporation of phosphorus-containing flame retardants. The LOI values of all phosphorus-containing polyesters are higher than 27%. The improvement of the flame-resistant ability is due to the formation of the char that is not only caused by the existence of phosphorus elements in the resin but also by the relative large number of carbon atoms of the phenyl group in the flame retardants.     

Preparation and Study of Some Copolyesters

Terephthalate unsaturated copolyesters with ethylene glycol and 2-butene-1,4-diol, with ethylene glycol and 2-butyne-1,4-diol, with ethylene glycol and diethylene glycol, and with 2-butyne-1,4-diol were synthesized by trans-esterification reactions. Proton nuclear magnetic resonance spectroscopy was used to elucidate the structures of the copolyesters. The intrinsic viscosities of the copolyesters were measured in o-chlorophenol at 30°C. The number-average molecular weights of these copolyesters were determined by using a vapor pressure osmometer. The thermal behaviors of the copolyesters were studied by differential thermal analysis and are discussed in terms of structural differences.     

Chlorinated thermal stabilizer for optically clear PMMA

Optically clear poly(methyl methacrylate) (PMMA) blends with HET‐EG oligoester (synthesized by condensation of chlorendic acid with ethylene glycol) at six different compositions were prepared by bulk polymerization. The effect of HET‐EG in the PMMA matrix on the optical clarity of PMMA blend was measured using ultraviolet‐visible spectroscopic study. The thermal stability of PMMA blends was investigated using differential scanning calorimetric (DSC) and thermogravimetric (TG) analyses. The parameters to deduce the thermal stability of pure PMMA and PMMA blends were calculated from DSC and TG results. The thermal stability of PMMA was found to increase effectively by loading 5% of HET‐EG oligoester without marring optical clarity. The probable physical and chemical actions of HET‐EG oligoester on the thermal stability of PMMA are discussed. Copyright © 2011 John Wiley & Sons, Ltd.     

New type of thermoplastic multiblock elastomers––poly(ester-block-amide)s––based on oligoamide 12 and oligoester prepared from dimerized fatty acid

Multiblock poly(ester-block-amide)s (PEA) elastomers comprising hard blocks of oligoamide and oligoester soft segments were prepared and their structure-property relations were analysed. The polycondensation reaction of oligoesters (prepared from 1,4-butanediol and dimerized fatty acid) with oligolaurolactam (PA12) gave copolymer series with variable blocks content (the soft segments content was varied from 24 to 60 wt.%). PEAs are the phase system composed of crystallised sequences of oligoamide (hard segment phase) as well as oligoesters (soft segment phase). Mixing between the hard and soft phases was studied by thermal and mechanical measurements (DSC, DMTA). These results have indicated on a multiphase structure of investigated materials. The relationship between the observed thermal and tensile properties and the soft/hard segments content indicated on an increase of the phase separation with soft segments content.     

Effect of different polyethers on surface and thermal properties of poly(urethane-siloxane) copolymers modified with side-chain siloxane

Poly(urethane-dimethylsiloxane) (PU-PDMS) copolymers with 4,4′-methylenebis(cyclohexyl isocyanate), different polyethers i.e., poly(oxytetramethylene)diol, poly(ethylene glycol), poly(propylene glycol), and α,ω-dihydroxy terminated polydimethylsiloxane extended with 1,4-butanediol in two-step solution polymerization were obtained. The PU-PDMS were modified using 1.25 mol% of polydimethylsiloxane which was incorporated into main polyurethane backbone as a side chain. The structure of the synthesized PU-PDMS was confirmed by FTIR as well as ¹H and ¹³C-NMR spectroscopy. The effect of different soft segments on free surface energy (FSE) components and thermal stability of poly(urethane-siloxane) copolymers was investigated. The activation energy of the thermal degradation of PU-PDMS using isoconversional methods (Ozawa–Flynn–Wall and Friedman) was calculated. It was concluded that molecular mass, thermal stability, and FSE of PU-PDMS copolymers depend on polyol used. The apparent activation energy at first step of degradation in nitrogen generally increases with the extent of conversion which may result from complex mechanism related to formation of decomposition products. Hydrophobic character of side-chain siloxane on surface properties of the PU-PDMS coatings was confirmed. The obtained coatings are generally soft with the relative hardness in the range of 0.120–0.027.     

聚酯的序列结构对聚氨酯弹性体形貌的影响

以己二酸(AA),1,4-丁二醇(BDO),乙二醇(EG)分别采用一步法、二步法合成分子量为3000的聚酯PAEB-R和聚酯PAEB-A.再分别与二苯基甲烷二异氰酸酯(MDI)、扩链剂1,4-丁二醇(BDO),乙二醇(EG)反应分别合成固含量30%与粘度为20000的聚氨酯(PAEB-R)-MDI-TPU和聚氨酯(PAEB-A)-MDI-TPU.SEM、AFM表明不同工艺所合成的聚氨酯均存在微相分离,且聚氨酯(PAEB-R)-MDI-TPU微相分离程度高于(PAEB-A)-MDI-TPU.     

Synthesis and characterization of some halogen-containing poly(esterurethane)s

A series of halogen-containing poly (esterurethane)s was synthesized from the prepolymers, i.e., hydroxy-terminated polyesters containing chlorine and fluorine and the diisocyanates such as toluene diisocyanate (TDI) and hexamethylene diisocyanate (HMDI). Polyesterification of halogenated phthalic anhydride with an excess of diols such as ethylene glycol, 1,2-propanediol, and 1,4-butanediol in the presence of trifluoroacetic anhydride (TFAA) was carried out to prepare prepolymers. The prepolymers and the poly (esterurethane)s were characterized by infrared (IR), ¹H nuclear magnetic resonance (NMR), viscosity, end-group analysis, solubility and thermal analysis namely thermogravimetric analysis (TGA), and differential scanning calorimetry (DSC). Kinetics of thermal degradation was also studied. Resistance of the polymers to alkaline agents and combustion was also tested.     

A novel phosphorus-containing copolyester/montmorillonite nanocomposites with improved flame retardancy

A novel phosphorus-containing flame-retardant copolyester/montmorillonite nanocomposite (PET-co-HPPPA/O-MMT) was synthesized by the in situ intercalation polycondensation of terephthalic acid, ethylene glycol, and 2-carboxyethyl(phenylphosphinic) acid (HPPPA) with montmorillonite (O-MMT). The morphology was characterized by wide-angle X-ray diffraction, scanning electron microscopy and transmission electron microscopy. The effects of organoclay on the thermal properties and melting behaviors of the nanocomposites were investigated by thermogravimetric analysis and differential scanning calorimetry. The flammability of the nanocomposites was characterized by the limiting oxygen index test and the UL-94 vertical test. The results showed that a small amount of organoclay was able to improve the thermal stabilities and the flame retardancy of PET-co-HPPPA copolyesters, and however there was no significant increase in the melting points of nanocomposites when the content of diethylene glycol was controlled as a certain value. The overall crystallization rate of the nanocomposites is greater than that of neat copolyester. The nanocomposites have better flame retardancy than PET-co-HPPPA.     

Mechanical Properties and Thermal Degradation Kinetics of a Novel Thermally Stable Thermoplastic Poly(ester-ether) Elastomer Containing N′N-Bis(2-carboxymethyl) Pyromellitimide Unit

A novel thermally stable thermoplastic poly(ester-ether) (PEE) elastomer containing imide units was prepared from poly(tetramethylene glycol) (PTMG1000), 1,4-butanediol (BD) and a new imide dicarboxylic acid based on pyromellitic dianhydride (PMDA) and glycine through a traditional chemical two-step method. The structures of the synthesized imide dicarboxylic acid and novel PEE were confirmed by FT-IR spectroscopy. The mechanical properties of the novel PEE were investigated. Thermal stability and thermal degradation kinetics of the novel PEE were investigated by thermogravimetric analysis (TGA) under different heating rates. The kinetic parameters of the degradation process were determined by using Kissinger, Flynn–Wall–Ozawa and Friedman methods. The Coats–Redfern method was also used to discuss the probable degradation mechanism of this PEE. The results showed that introduction of the imide units into the poly(ester-ether) endowed the PEE with excellent thermal stability and good mechanical properties. The activation energy obtained by using the Kissinger method was in agreement with that using the Flynn–Wall–Ozawa method. The reaction order (n) and pre-exponential factor (A) were obtained by using the Friedman method. Analysis of the experimental results suggests that the decomposition reaction mechanism of the PEE was a F₃ type (random nucleation with three nuclei on the individual particle).     

气相色谱法检测工业用乙二醇纯度及杂质

以Rtx-624色谱柱（30 m×0.32 mm×1.8 μm）为分析柱进行分析，采用校正面积归一化法，建立了检测工业用乙二醇纯度及其中有机杂质的气相色谱分析法。该法可检测传统乙烯法制得的乙二醇中固有杂质二乙二醇、三乙二醇和1，3-二氧杂烷-2-甲醇，同时也适用于检测草酸酯加氢法制得的乙二醇中的新杂质（1，2-丁二醇、1，4-丁二醇、1，2-己二醇、碳酸乙烯酯等）。结果表明，该法具有良好的重复性和较高的检测灵敏度，检出限最低可达0.0002%（质量分数），回收率在91.2%~105.4%之间。该法在乙二醇生产控制、产品检测、市场贸易等过程中具有良好的应用前景。     

PREPARATION OF EVOH MICROPOROUS MEMBRANES via THERMALLY INDUCED PHASE SEPARATION USING BINARY SOLVENTS

Microporous ethylene-vinyl alcohol copolymer （EVOH） flat membranes and hollow-fiber membranes with 38 mol% ethylene content were prepared via thermally induced phase separation （TIPS） using the mixture of 1,4-butanediol and poly（ethylene glycol）（PEG400） as diluents. Effects of the ratio of 1,4-butanediol to PEG400 on the phase diagrams, phase separation mechanism and membrane morphology were studied by small angle light scattering （SALS） measurements, differential scanning calorimetry （DSC）, and scanning ele~：tron microscopy （SEM）. It was found that by varying the composition of the binary solvent, the phase diagrams and membrane morphology can be controlled successfully. Moreover, the phase diagrams showed that broader regions of Liquid-Liquid （L-L） phase separation were obtained, as well as closer distances between L-L phase separation lines and Solid-Liquid （S-L） phase separation lines, Interconnected structures observed both in the flat membrane and hollow fiber membrane consist with the above results.     

Thermal degradation of wood treated with flame retardants

Wood, one of the most flammable materials, was treated with various compounds containing nitrogen, phosphorus, halogens, and boron. For a study of flame retardance from the standpoint of thermal degradation, the samples were subjected to thermogravimetry (TG), differential thermal analysis (DTA) and differential thermogravimetry (DTG) in nitrogen to determine if there were any characteristic correlations between thermal degradation behaviors and the level of flame retardance. From the resulting data, kinetic parameters for different stages of thermal degradation are obtained using the method of Broido. The energies of activation for the decomposition of samples are found to be from 72 to 109 kJ mol^–1. For wood and modified wood, the char yields are found to increase from 10.2 to 30.2%, LOI from 18 to 36.5, which indicates that the flame retardance of wood treated with compounds is improved. The flame retardant mechanism of different compounds has also been proposed.     

A method for simultaneously improving the flame retardancy and toughness of PLA

In order to modify the brittleness and flame retardant properties of poly(lactic acid) (PLA), a series of flame retardant toughened PLA composites were prepared using poly(ethylene glycol) 6000 (PEG6000) as a toughening and charring agent together with ammonium polyphosphate (APP) as an acid source and blowing agent. The fire and thermal behavior of PLA/PEG/APP composites was evaluated by limiting oxygen index (LOI), UL‐94, cone calorimeter, and thermogravimetric analysis (TGA). The results showed that the PLA/PEG/APP system had good charring ability and could improve the flame retardancy of PLA. When the content of APP in the composites was more than 5 wt%, all samples could reach UL‐94 V‐0 rating. The results of mechanical property tests demonstrated that the brittleness of PLA was also improved after blended with PEG6000. All the PLA/PEG/APP composites with an APP content of less than 10 wt% showed an obvious neck and fracture behavior, that is, the tensile behavior of PLA was changed from brittle to ductile. Copyright © 2010 John Wiley & Sons, Ltd.     

Synthesis and studies of homopolycyanurates based on 2-carbazol-4,6-dichloro-s-triazine

Eight homopolycyanurates have been synthesized by interfacial polycondensation of 2-carbazol-4,6-dichloro-s-triazine with 1,7-dihydroxynaphthalene, 1,4-dihydroxyanthraquinone, ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propanediol, 1,4-butanediol and 1,8-dihydroxyanthraquinone. All the homopolycyanurates synthesized were characterized for their solubility, density, viscosity, IR, NMR spectral and thermogravimetric parameters.