Selective removal of polyethylene or polypropylene from their blends based on difference in their adsorption behaviour

The adsorption of polyethylene and polypropylene on zeolites depends on the nature of zeolite, the solvent as well as the molar mass of the polymer sample. For example, linear polyethylene is strongly retained on zeolite SH-300 from decalin, while isotactic, syndiotactic or atactic polypropylene is fully eluted in this system. On the other hand, polypropylene is retained on zeolite CBV-780 from diphenylether, while linear polyethylene is eluted. These differences in the elution behaviour have been utilised for selective removal of either linear polyethylene or polypropylene from blends of both polymers. The desorption of the retained polymer is difficult, or at times impossible. However, the selected adsorption systems have complimentary character, i.e. either one or second component is eluted or fully retained. Thus these sorbent/solvent systems, identified herein, are the first isocratic chromatographic systems, which enable selectively to remove polyethylene or polypropylene from their mixture. Moreover, decalin/SH-300 enables the removal of both linear and branched polyethylene from mixtures with random ethylene/propylene copolymers (polyethylene fully retained, ethylene/propylene copolymers eluted).     

Adsorption of polypropylene from dilute solutions on a zeolite column packing

Faujasite type zeolite CBV-780 was tested as adsorbent for isotactic polypropylene by liquid chromatography. When cyclohexane, cyclohexanol, n-decanol, n-dodecanol, diphenylmethane, or methylcyclohexane was used as mobile phase, polypropylene was fully or partially retained within the column packing. This is the first series of sorbent-solvent systems to show a pronounced retention of isotactic polypropylene. According to the hydrodynamic volumes of polypropylene in solution, macromolecules of polypropylene should be fully excluded from the pore volume of the sorbent. Sizes of polypropylene macromolecules in linear conformations, however, correlate with the pore size of the column packing used. It is presumed that the polypropylene chains partially penetrate into the pores and are retained due to the high adsorption potential in the narrow pores.     

Adsorption of polyethylene from thermodynamically good solvents on a zeolite stationary phase

Adsorption of linear polyethylene and isotactic polypropylene on columns packed with zeolites ZSM‐5, Y, and silicalite was studied using high‐temperature liquid phase chromatography. Linear polyethylene was fully retained on a column packed with ZSM‐5 zeolite from non‐polar solvents, such as 1,1,2,2‐tetrachloroethane and 1,3,5‐trimethylbenzene at a temperature of 140°C. Partial adsorption on ZSM‐5 zeolite was found for polyethylene in 1,2,4‐trichlorobenzene and on silicalite from 1,2,4‐trichlorobenzene and 1,3,5‐trimethylbenzene. On the other hand, adsorption of polyethylene was not found from polar liquids, such as 2‐ethylhexyl acetate, cyclohexyl acetate, and cyclohexanone. Isotactic polypropylene was not adsorbed on any tested sorbent.     

HPLC Study of the Kinetics of Intramolecular Cyclization of Two New Phenyldiazene Molecules. Analytical Properties of the Resulting Liquid Crystals

A group of zeolites and a 3D nanoporous metal-organic material RPM-1 were tested as column packings for adsorption of isotactic polypropylene and linear polyethylene from dilute solutions. It was found that polyethylene is fully or partially retained from thermodynamically good solvents (1,1,2,2-tetrachloroethylene, 1,4-dimethylbenzene, diphenylether, 1,2-dichlorobenzene and 1,3-dichlorobenzene) at temperatures of 115 °C or 140 °C, when a specific type of zeolite with pore sizes 5–6 Å has been used as the column packing. Polypropylene was fully retained in another type of zeolite with pores of 7–12 Å, when diphenylether was used as the mobile phase. As far as known, this is the first system sorbent - mobile phase, where adsorption of polypropylene was observed.     

Elution behavior of polyethylene in polar mobile phases on a non-polar sorbent

Linear polyethylene standards in the range of 1-500 kg/mol, dissolved in 1,2,4-trichlorobenzene, were injected into a column packed with oligo(dimethylsiloxane) modified silica gel. Fifteen polar solvents (cyclohexanone, cyclohexylacetate, cyclohexanol, nonylalcohol, dimethylformamide, dimethyl sulfoxide, ethylene- and diethylene glycol monobutyl ether, benzylalcohol, hexylacetate, bis(2-ethyl-hexyl)phthalate, N,N-dimethylacetamide, propylene carbonate, dipropylene glycol and N-methyl-pyrrolidone) were evaluated as mobile phases. Depending on the type of mobile phase evaluated, different elution behaviors are observed for polyethylene: (1) polyethylene was eluted in the size exclusion mode, (2) polyethylene was eluted together with the sample solvent peak at constant elution volume, (3) polyethylene was partially or fully retained on the column. The retained polymer was easily removed from the column by injecting a small volume of trichlorobenzene. The use of ethylene glycol monobutyl ether as the mobile phase enabled separation of the polyethylene from polypropylene. In this case polypropylene is eluted in the size exclusion mode, while polyethylene is eluted at a constant elution volume or remains in the column.     

Carbonaceous sorbents for high‐temperature interactive liquid chromatography of polyolefins

The elution behavior of polyethylene (PE) and the three stereoisomers of polypropylene (PP) was studied on porous graphite along with three other carbon‐based sorbents, carbon‐clad zirconia particles, activated carbon, and exfoliated graphite in a systematic way in this work. Decahydronaphthalene, 1,2,3,4‐tetrahydronaphthalene, 1,3,5‐trimethylbenzene, tetrachloroethylene, xylene and p‐xylene were used as mobile phases. While PE is adsorbed to various extents on all the tested carbonaceous sorbents from the majority of the solvents, PP is fully adsorbed only in selected cases. Testing alcohols (C7–C9) as mobile phase with Hypercarb? indicates that all stereoisomers of PP are selectively adsorbed and desorbed when a solvent gradient alcohol→1,2,4‐trichlorobenzene is used at 160°C. The retention of all stereoisomers of PP increases with the polarity of the alcohol. Linear PE is retained on Hypercarb? even from 1,2‐dichloro‐ and 1,2,4‐trichlorobenzene, when a temperature below 120°C is applied, while it is not retained from these solvents at higher temperatures. All stereoisomeric forms of PP are not adsorbed under the same conditions. Some of the tested new sorbent/solvent systems have potential to be applied in routine analysis of industrially synthesised polyolefins.     

Elution behavior of polyethylene and polypropylene standards on carbon sorbents

The elution behavior of linear polyethylene and isotactic, atactic and syndiotactic polypropylene was tested using three different carbon column packings: porous graphite (Hypercarb), porous zirconium oxide covered with carbon (ZirChrom-CARB), and activated carbon TA 95. Several polar solvents with boiling points above 150°C were selected as mobile phases: 2-ethyl-1-hexanol, n-decanol, cyclohexylacetate, hexylacetate, cyclohexanone, ethylene glycol monobutyl ether and one non-polar solvent, n-decane. Polyethylene standards were completely or partially adsorbed in all tested sorbent/solvent systems. Polypropylene standards were partially adsorbed on Hypercarb and carbon TA95, but did not adsorb on ZirChrom-CARB. ZirChrom-CARB retained polyethylene pronouncedly when 2-ethyl-1-hexanol, cyclohexylacetate or hexylacetate were used as mobile phases at temperature 150 or 160°C, while all three basic stereoisomers of polypropylene eluted in size exclusion mode in these sorbent/solvent pairs. This is very different from the system Hypercarb/1-decanol, which separated polypropylene according to its tacticity. The opposite elution behavior of polyethylene and polypropylene in system ZirChrom-CARB/2-ethyl-1-hexanol (polypropylene eluted, polyethylene fully adsorbed) enabled to realize separation of blends of polyethylene and polypropylene. Ethylene/1-hexene copolymers were separated according to their chemical composition using system Hypercarb/2-ethyl-1-hexanol/1,2,4-trichlorobenzene.     

Adsorption of Linear Polyethylene and Isotactic Polypropylene from 1,1,2,2-Tetrachloroethane and 1,2,3-Trichloropropane on to Polar Adsorbents

Linear polyethylene and isotactic polypropylene samples were dissolved in 1,1,2,2-tetrachloroethane or 1,2,3-trichloropropane and injected at 135 °C into columns packed with porous particles of hydroxyapatite, aluminium oxide, zirconium oxide, Florisil, or silica gel. Both polymers were retained, to different extents, within the columns. It is hypothesized that the polymers interact with the surfaces of the adsorbents and are adsorbed. Retention of isotactic polypropylene from 1,1,2,2-tetrachloroethane was in the order aluminium oxide > hydroxyapatite ≈ zirconium oxide ≈ Florisil ≈ silica gel. Recovery of polyethylene from 1,1,2,2-tetrachloroethane was almost the same on aluminium oxide, hydroxyapatite, zirconium oxide, and Florisil; it was more retained by silica gel. Polyethylene was usually more retained than polypropylene. Recovery of polyethylene from both chlorinated solvents was similar whereas recovery of polypropylene was better from 1,2,3-trichloropropane than from 1,1,2,2-tetrachloroethane. Both chlorinated solvents are toxic and may attack seals in a Waters 150C chromatograph. Moreover, the polymers may be chlorinated in these solvents. For these reasons they are not optimum solvents for routine analysis. This is the first time polyethylene and polypropylene have been found to be retained by adsorbents with pore diameters in the range 60–300 Å. Desorption of the retained polymers is possible with some polar solvents.     

Adhesion of a pair of polyethylene moldings by polyethylene gels

It was found that polyethylene gels in solvents such as benzene, toluene, xylene, decalin, tetralin, tetrachloroethylene, 1,1,2,2-tetrachloroethane, and chlorobenzene are effective for adhesion of a pair of polyethylene plates. In particular, the adhesion strength of polyethylene gels in decalin, tetralin and tetrachloroethylene was strong enough for practical use.Adhesive effect appears due to local dissolution of the surface of polyethylene plate in contact with the gel with increasing temperature, and subsequent recrystallization.     

Biodiesel Synthesis via Esterification of Feedstock with High Content of Free Fatty Acids

The objective of this work was to study the synthesis of ethyl esters via esterification of soybean oil deodorizer distillate with ethanol, using solid acid catalysts and commercial immobilized lipases, in a solvent-free system. Three commercially immobilized lipases were used, namely, Lipozyme RM-IM, Lipozyme TL-IM, and Novozym 435, all from Novozymes. We aimed for optimum reaction parameters: temperature, enzyme concentration, initial amount of ethanol, and its feeding technique to the reactor (stepwise ethanolysis). Reaction was faster with Novozym 435. The highest conversion (83.5%) was obtained after 90 min using 3 wt.% of Novozym 435 and two-stage stepwise addition of ethanol at 50°C. Four catalysts were also tested: zeolite CBV-780, SAPO-34, niobia, and niobic acid. The highest conversion (30%) was obtained at 100°C, with 3 wt.% of CBV-780 after 2.5 h. The effects of zeolite CBV 780 concentration were studied, resulting in a conversion of 49% using 9 wt.% of catalyst.     

Adhesive effect of linear low-density polyethylene gels on polyethylene moldings

Adhesive effect of linear low density polyethylene (LLDPE) gels in organic solvents such as decalin, tetralin, and o-dichlorobenzene on high density polyethylene (HDPE) moldings has been investigated by shearing tests, and DSC measurements. For all of the gels the temperature at which the heated gel starts to exhibit the adhesive effect was about 70 °C, which is similar to the result of LDPE gel. In particular, when heated at 110 °C, LLDPE gel in tetralin showed such a strong bond strength that polyethylene plates of 3 mm in thickness and 20 mm in width gave rise to necking. It was found that LLDPE gel behaved as though it added LDPE gel to HDPE gel namely LDPE-like components in LLDPE resin exerted the adhesive effect at lower heating temperature, HDPE-like components exerted the strong adhesive effect at higher heating temperature.     

Adhesive effect of high density polyethylene gels on polyethylene moldings

Adhesive effect of polyethylene moldings by use of high density polyethylene gels in organic solvents such as decalin, tetralin, ando-dichlorobenzene was investigated by shearing tests, electron microscope, and DSC measurements. All of the gels showed such a strong adhesive strength over 36 kg/cm² that polyethylene plates of 3 mm in thickness gave rise to necking sufficient for practical use, when heated at 120 °C for 2 h. In particular, the gel in tetralin showed a strong adhesive strength when heated at 110 °C. It was found that adhesive strength increases with the heating temperature; the temperatures at which adhesive strength begins to increase differ depending on the type of polyethylene sample and solvent. It is apparent that polyethylene gels exhibit an adhesive effect when they are heated at higher temperatures than the gel melting temperatures, and that the closer the SP values of solvents used for the gelation are to the molded polyethylene, the stronger the adhesion of the polyethylene molding.     

The kinetics of flow-induced crystallization from solution

In situ birefringence measurements of the seeded growth in a tubular flow geometry of 0.01 wt% solution of a polyethylene fraction in xylene have been used to determine the flowinduced crystallization kinetics as a function of temperature and flow rate. In contrast to earlier reports on higher molecular weight polyethylene and polypropylene systems, orientational properties of the crystallized fibers do not show a clear correlation with growth conditions (i.e., temperature and flow rate). The combined kinetic data from these experiments and our earlier studies of higher molecular weight polyethylene—xylene and polypropylene—tetralin systems are analyzed in terms of a modified from of the Avrami equation which provides a basis for separately correlating temperature and flow rate effects. The observed temperature dependency of the crystallization process can be interpreted in terms of nucleation and growth models while the flow rate dependency can be interpreted on the basis of entanglement formation arguments. Results showing liquid phase precursor formation in an atactic polystyrene system are also presented to further document the liquidphase separation which can be induced in polymers under flow.     

A Comparison of Silica C and Silica Gel in HILIC Mode: The Effect of Stationary Phase Surface Area

In order to assess the effect of silica gel structure on retention in hydrophilic interaction chromatography, a test system was developed which used quaternary ammonium ions as probes with tetramethylammonium acetate (TMAA) as the counter-ion competing against the interaction of the test probes with ionised silanols in the stationary phase. Four silica gel columns and a silica hydride column were examined. Retention times were obtained for the test probes at 20, 40, 60, 80 and 90 % acetonitrile (ACN) with all the mobile phase mixtures containing 10-mM TMAA buffer at pH 6.0. All phases gave “U”-shaped plots for log k against percentage of ACN with the steepest rise in retention occurring between 80 and 90 % ACN. Benzyltrimethylammonium, the smallest quaternary ammonium ion, was the most strongly retained probe at 90 % ACN and was most retained on a high surface area 60 Å Kromasil column and least retained on a 300 Å ACE silica gel column. The ionic strength of the mobile phase was varied at 80 and 90 % ACN and plots of log k against the inverse of buffer strength followed by fitting of second-order polynomial curves allowed an assessment of the contribution from HILIC to the mixed HILIC/ion-exchange retention mechanism. Toluene and pentylbenzene were used to assess the decrease in accessible pore volume due to water absorption in HILIC mode.     

New small-scale cross-axis coil planet centrifuge. Partition efficiency and application to purification of bullfrog ribonuclease

The new small-scale cross-axis coil planet centrifuge (X-axis CPC) previously designed and fabricated in our laboratory has a distinctive feature such that four separation columns of similar weight are mounted symmetrically around the rotary frame to achieve stable balancing of the centrifuge under a high revolution speed. In this column layout, neighboring columns must be rotated in the opposite direction if viewed from the center of the centrifuge to avoid twisting the interconnecting flow tubes. The effect of rotational direction of the columns on the partition efficiency was evaluated with separation of a set of test samples such as cytochrome c, myoglobin, and lysozyme using an aqueous-aqueous polymer phase system composed of 12.5% (w/w) polyethylene glycol (PEG) 1000 and 12.5% (w/w) dibasic potassium phosphate under 1000 rpm of column revolution. A series of experiments was performed using a set of two diagonally located columns (connected in series) each consisting of five coiled layers of 1 mm I.D. with a total capacity of 27.0 mL. Both right- and left-handed coils were tested each under the optimized conditions for choice of mobile phase and direction of the column rotation so that the satisfactory volume of the mobile phase was retained in the column by the aid of Archimedean screw effect. The results of these studies showed that one particular combination of handedness of the coil and direction of the rotation yielded the best peak resolution for each mobile phase. In order to demonstrate the capability of the apparatus, the purification of ribonuclease (RNase) from the extract of bullfrog egg, sialic acid binding lectin (cSBL), was carried out using both organic-aqueous and aqueous-aqueous polymer phase systems. When using the 16.0% (w/w) PEG 1000-6.3% (w/w) dibasic potassium phosphate-6.3% (w/w) monobasic potassium phosphate system, cSBL was successfully separated from other proteins present in the extract while commercial RNase A was eluted at near the solvent front by the lower phase mobile. The cSBL retained its native RNase activity. The overall results demonstrated that the present new small-scale X-axis CPC is useful for the purification of bioactive compounds without loss of their native activities.     

Enantiomeric separations of cationic and neutral compounds by capillary electrochromatography with monolithic chiral stationary phases of beta-cyclodextrin-bonded negatively charged polyacrylamide gels

Enantiomeric separation by capillary electrochromatography with beta-cyclodextrin-bonded negatively charged polyacrylamide gels was examined. The columns used are capillaries filled with a negatively charged polyacrylamide gel, a so-called monolithic stationary phase, to which allyl carbamoylated beta-CD (AC-beta-CD) derivatives covalently bind. The capillary wall is activated first with a bifunctional reagent to make the resulting gel bind covalently to the inner surface of the fused-silica tubing. Enantiomeric separations of 15 cationic compounds were achieved using the above-mentioned columns and mobile phases of 200 mmol l(-1) Tris-300 mmol I(-1) boric acid buffer (pH 7.0 or 9.0) or 200 mmol l(-1) Tris-300 mmol l(-1) boric acid buffer (pH 7.0) containing an achiral crown ether (18-crown-6). Enantiomeric separations of two neutral compounds were also achieved using 200 mmol l(-1) Tris-300 mmol l(-1) boric acid buffer (pH 9.0) as a mobile phase. High efficiencies of up to 150,000 plates m(-1) were obtained. Both the within- and between-run reproducibilities of retention time and separation factor were good. The reproducibilities of retention time and separation factor for three different columns prepared from a different batch of monomers were acceptable. The gel-filled capillaries were stable for at least 3 months with intermittent use, utilizing the mobile phase of 200 mmol I(-1) Tris-300 mmol I(-1) boric acid buffer (pH 9.0).     

溶剂特性对淖毛湖煤加氢液化中间产物反应行为的影响

为探究溶剂特性对煤加氢液化中间产物反应行为的影响,以新疆淖毛湖煤作为原料,四氢萘、循环溶剂及十氢萘作为供氢溶剂,在高压搅拌釜中进行直接加氢液化实验,并运用电子顺磁共振手段分析了中间产物-沥青质的自由基浓度的变化。结果表明,四氢萘溶剂中沥青质随反应温度的升高在大量生成的同时又被转化,产率从290℃的12.92%到350℃的最大34.13%再到430℃的15.98%;循环溶剂中沥青质产率先持续上升,290℃即有31.89%,400℃达到最大47.96%,之后由于结焦反应降低至33.90%。十氢萘溶剂中沥青质产率变化趋势与四氢萘一致。三种溶剂中沥青质自由基浓度的变化趋势相同,均在350℃达到最大值,分别是1.778×10¹⁸、2.323×10¹⁸和1.930×10¹⁸/g,整体上看循环溶剂数值要高于四氢萘,十氢萘介于两者之间。而四氢萘及循环溶剂中沥青质的g值在2.00323-2.00403,变化趋势与液化气体产物中CO_x含量变化相吻合。     

Adhesive effect of low-density polyethylene gels on polyethylene moldings

Adhesive effect of low density polyethylene (LDPE) gels in organic solvents such as decalin, tetralin, ando-dichlorobenzene on high density polyethylene (HDPE) moldings has been investigated by shearing tests, electron microscopy, and DSC measurements. When heated at 110°C for 2 h, all of the gels showed strong adhesive strengths around 30 kg/cm², which is sufficiently strong for practical uses. It has been found that the adhesive strength increases with the heating temperature and that the temperature at which the heated gel begins to exhibit the adhesive effect depends upon solvents and is about 30° lower than that of the HDPE gels.     

The chromatographic behavior of arsenic compounds on anion exchange columns with binary organic acids as mobile phases

Summary Identification and quantification of arsenic compunds was performed with high- performance liquid chromatography (HPLC) and flame atomic absorption spectrometry (FAAS) as element-specific detector. Arsenous acid, methylarsonic acid, dimethylarsinic acid, arsenic acid, arsenobetaine, and arsenocholine were separated on two anion-exchange columns (Synchropak Q 300 and PRP-X 100) with different binary organic acids as mobile phases. The infleunce of chromatographic parameters, such as pH and the concentration of the mobile phase were investigated. An unusual chromatographic behavior of arsenous acid was observed when tartaric acid was used as mobile phase.     

The hydrophilic interaction like properties of some reversed phase high performance liquid chromatography columns in the analysis of basic compounds

The hydrophilic interaction chromatography (HILIC) like properties of an ACE cyano (CN) HPLC column was studied for the separation of some basic compounds. Good separation of a test mix of basic compounds was obtained with a mobile phase consisting of acetonitrile/water (95:5) containing 3.25 mM ammonium acetate. The retention times of the basic compounds decreased with increased ionic strength or with increased water content in the mobile phase. When Trishydroxymethyl aminomethane (Tris) (pK(a) 8.0), which is a weaker amine than ammonia (pK(a) 9.3), was used as an additive in the mobile phase retention of the basic compounds was increased. The ACE CN column gave excellent peak shapes for all the basic compounds. The utility of the column for impurity profiling of two basic drugs was tested and some impurities in oxprenolol were characterised by interfacing with Fourier transform mass spectrometry. It was also observed that ACE butyl and ACE phenyl columns retained basic compounds when the columns were eluted with a mobile phase consisting of acetonitrile/water (95:5) containing 3.25 mM ammonium acetate.