text:
|Publication number
|Publication type
|Application number
|Publication date
|Oct 27, 1981
|Filing date
|Jul 17, 1980
|Priority date
|Oct 27, 1978
|Also published as
|Publication number
|Artur Reischl, Kuno Wagner
|Original Assignee
|Bayer Aktiengesellschaft
|Export Citation
|BiBTeX, EndNote, RefMan
|Patent Citations (10), Referenced by (12), Classifications (42)
|External Links: USPTO, USPTO Assignment, Espacenet
This application is a continuation-in-part of copending application Ser. No. 88,800 filed Oct. 29, 1979 and now abandoned.
Considerable quantities of relatively high molecular weight, crosslinked, secondary products are formed in the production of isocyanates on an industrial scale. These secondary products are obtained in the form of a tar-like, non-distillable residue during the working up, by distillation, of the crude isocyanate solutions obtained in the phosgenation of amines. These residues are generally unsuitable for the conventional applications of polyisocyanates (production of polyurethane plastics). In order to avoid a total loss of the non-distillable residue, it is possible in some cases (for example, in the phosgenation of diamines of the diphenylmethane series) to isolate only part of the pure monomeric isocyanate from the crude phosgenation product, i.e. to leave a considerable proportion of monomeric isocyanate in the sump phase, in order to keep the relatively high molecular weight secondary products in solution. For the liquid polyisocyanate mixture enriched with relatively high molecular weight products obtained in this way (so-called "crude MDI"), it has been possible in recent years to find a number of potential applications in special plastics.
All attempts, however, to use tolylene diisocyanate enriched with relatively high molecular weight secondary products (crude "TDI") and having a low, but still economically acceptable content of monomeric tolylene diisocyanate have so far failed. During distillation of the phosgenation product of tolylene diamines, relatively high molecular weight insoluble products containing uretdione, isocyanurate, carbodiimide, uretone imine, urea and biuret groups are formed under the conditions used in practice. Depending on the o-tolylene diamine content of the starting product, methyl benzimidazolones can also be formed during phosgenation and, with time, are biuretized with the free isocyanate groups present, accompanied by formation of insoluble, crosslinked products. Although crude TDI distillation residues which still have a high monomer content (above 80% by weight) and which contain virtually no methyl benzimidazolone or its derivatives, are soluble, they are not sufficiently stable in storage. The content of free NCO-groups decreases during storage, even at room temperature, accompanied by an increase in viscosity.
Numerous processes have also been proposed (U.S. Pat. No. 3,634,361, German Offenlegungsschrift No. 2,123,183, German Offenlegungsschrift No. 2,333,150, U.S. Pat. No. 3,455,836, and German Offenlegungsschrift No. 2,423,594) for dissolving TDI distillation residues, which still have a considerable content of free NCO-groups (preferably above 20% by weight), in an organic solvent in the presence of monomeric diisocyanates, optionally at high temperatures. These residue solutions may then be used as the isocyanate component for the polyisocyanate polyaddition process. In practice, however, this method of utilizing the TDI residues fails because of the inadequate stability during storage and the inability to standardize the solutions (if, in fact, solutions were obtained at all) or because of the sedimentation of insoluble constituents.
In recent years, TDI distillation residues have been partly utilized by means of alkaline hydrolysis. Unfortunately, only relatively small proportions of tolylene diamines can be recovered.
More success in maximizing the yield of 2,4-TDI ("T 100") or of isomer mixtures of 80% of 2,4-TDI and 20% of 2,6-TDI ("T 80") or 65% of 2,4-TDI and 35% of 2,6-TDI ("T 65"), based in each case on the tolylene diamine used, has been achieved by using the so-called long-tube vertical evaporators (U.S. Pat. No. 3,897,314) which have been adopted for use on a wide scale in the commercial production of tolylene diisocyanate, and by continuous thermolysis of the liquid TDI residue tar. In the above process, the residue is substantially free from monomers, but still contains free isocyanate groups. This residue has to be stirred into water (quenching) in the form of a hot (approximately 150� to 300� C.) tar-like mass immediately after separation of the pure monomeric TDI in order to avoid smoldering fires and for physiological reasons. During this quenching process, the majority of the free isocyanate groups still present react with the water to form additional polyurea groups (hereinafter called denaturing). This reaction is accompanied by the evolution of carbon dioxide. Only a very small percentage, generally around 1 to 10% by weight, of included isocyanate groups are left unreacted. Storage in water or in moist form causes the isocyanate content to undergo a further gradual reduction over a prolonged period.
These slag-like TDI residues contain polyurea and isocyanurate groups and are substantially insoluble in all the usual solvents. At temperatures above 250��30� C. they begin to melt to some extent, decomposing and giving off gasses.
No commercially or economically interesting possibilities have been found for utilizing these TDI residue slags. This is particularly true for the extremely high-temperature-resistant infusible T 80-residue slag. It is mainly this T-80 residue slag which accumulates in the production of TDI.
The vast majority of TDI distillation residues accumulating world-wide in the production of TDI is either dumped or burned in furnaces, with considerable difficulty. These TDI residue slags amount to approximately 10% of the total TDI production. In cases where TDI residue slags are burned, deposits of firmly adhering, substantially incombustible tarry masses accumulate on the bottom of the combustion chamber, and, in many cases, decompose explosively at temperatures above about 500� C.
The object of the present invention is, therefore, to provide commercially feasible possibilities for recycling TDI distillation residue slags, particularly the TDI residue slags quenched and denatured in water.
It has now, surprisingly, been found that the TDI distillation residues may be converted into high quality reactive fillers by very fine grinding. Optionally, the grinding process can be accompanied by or followed by simple chemical modification reactions in the heterodisperse phase. These reactive fillers may be used in the production of a variety of different plastics by polyaddition, polycondensation or polymerization. The present invention relates to a process for working up tolylene diisocyanate distillation residues into useable starting products for the production of plastics. This invention comprises taking a substantially monomer-free, crosslinked, distillation residue, insoluble in inert organic solvents, and which cannot be melted without decomposing, of the type accumulating as slag in the removal of monomeric tolylene diisocyanates by distillation and by grinding it into a powder having a mean particle size of less than 800 mμ, preferably less than 350 mμ, more particularly less than 100 mμ, and with particular preferance, less than 10 mμ. The instant invention can also use TDI residues which have been water quenched and denatured. This invention also, optionally, comprises chemically modifying these residues at the same time as grinding and/or afterwards by reaction of the functional groups of the distillation residue, particularly the isocyanate groups with known compounds.
As explained above, the distillation residues used in the process according to the present invention are by-products in the production of 2,4- and/or 2,6-tolylene diisocyanate on an industrial scale. They are in the form of relatively high molecular weight residue slags crosslinked through main valency bonds. These by-products amount to about 10% by weight, based on the calculated quantitative yield of monomeric diisocyanates of the distillation process. To make them easier to handle, they are generally introduced into water heated beyond 150� C., with the formation of a coarse-grained, irregularly shaped, insoluble slag where a large number of the free isocyanate groups react with water to form polyurea groups. This slag still has a small content of free NCO-groups (generally less than 15% by weight and in most cases from 1 to 10% by weight). However, it is substantially free of monomeric diisocyanates. By "substantially free of monomeric diisocyanates" is meant a residue containing less than 7.5% by weight of monomeric diisocyanates. In many cases, the residue of the instant invention will have monomeric contents of less than 3.0% and in some instances lower than 1.5% by weight. In addition, the TDI residue slags also contain urea, biuret, uretdione, isocyanurate, carbodiimide, uretone imine and, in some cases, even methyl benzimidazolone groups and their biuretization products in varying quantitative ratios. These slags are so highly crosslinked through these functional groups that, even after size-reduction to a mean particle size of less than 5 mμ, they are substantially insoluble in inert organic solvents. Methylene chloride, cyclohexane, cyclohexanone, toluene, xylene and dichlorobenzene are examples of these inert solvents. Boiling these slags in the above solvents has no dissolution effect either. Even in boiling dimethyl formamide, the residue powders are only partly swollen, but not dissolved. On heating, only a very small proportion, if any, of the TDI distillation residues soften at temperatures above about 250� C. Above about 280� C., the distillation residues decompose without melting, giving off gasses in the process.
The very coarse-grained TDI residue slag is preferably first precomminuted to less than 3 mm in a comminuting machine, for example in a cutting granulator or a hammer mill. It is then brought to the final particle size required using known wet or dry grinding processes. The present invention can be used in particular on TDI residue slags that have been quenched and denatured in water.
Where the TDI residues accumulate in water, as for example, in the above-described quenching process, any planned further modifying reactions can be carried out in an aqueous phase. It is particularly economical and environmentally sound to carry out final size-reduction by wet fine-grinding or superfine-grinding in batch-type or continuous machines arranged one behind the other in one or two stages. The solids concentrations during wet grinding are preferably between 15 and 45% by weight. In addition to tube and ball mills, it is particularly advantageous to use toothed colloid mills, trigonal gear ring mills, corundum disc mills and stirrer-equipped ball mills. A combination of a toothed colloid mill and a stirrer-equipped ball mill is suitable, for example, for particularly fine grain sizes.
In special cases, NH-addition reactions may even be carried out during the quenching process, for example, by directly stirring the viscous TDI residue melt into water to which NH-compounds have been added.
It is best, depending on the particle size, to use a deficit of NH-compounds in heavy, aqueous dilution and to stir the reaction mixture with intense turbulence to produce a more fine-grained TDI residue. This process can also be used during the grinding process.
In this way, for example, where denaturing is carried out in an aqueous ammonia solution or in ammonia-yielding solutions, such as an ammonium (bi)carbonate solution, a TDI residue slag is obtained which has an increased content of external urea groups, some of which are only monosubstituted. This slag is particularly readily accessible for subsequent condensation reactions.
Denaturing in the presence of ionomeric amines leads directly to TDI residues containing salt groups or groups capable of salt formation.
Size reduction in the aqueous phase may be controlled in such a way that, under the effect of the heat generated during grinding (which may optionally be regulated by cooling) and because of the formation of fresh cut surfaces accompanied by a considerable increase in the surface area, the TDI residue slag reacts with the water, even in the absence of externally applied heat. It is also possible, in cases where grinding is carried out in an aqueous medium, to effect other reactions by the addition of reactive compounds, for example, polyaddition reactions with NH-compounds or polycondensation reactions with carbonyl compounds. In special cases, it is possible during the grinding operation to replace some or all of the water by another liquid (optionally containing NCO-reactive groups) selected according to the particular application planned for the powdered residue.
The TDI residue slags obtained after wet grinding are used either in the form of very finely divided suspensions or pastes. Alternatively, after isolation of the suspending agent, they may be used as powders in the same way as the TDI residue powders obtainable by dry grinding.
TDI residue slags useable for dry grinding have been preground to less than 2-3 mm and predried, preferably at temperatures below 50� C. and have a moisture content of not much more than 10% by weight and preferably less than 5% by weight. The choice of the particular machines used for dry grinding is governed by the final particle size and particle size distribution required and the grinding costs. In comparison with plastics, the residue slags, being very hard by virtue of their high degree of crosslinking, may be ground without softening at temperatures of up to about 220�-300� C. This grinding can be done in conventional size-reducing machines free from any cooling problems. This is of particular importance in obtaining very fine particle sizes in the range of from less than 1 mμ to 5 mμ.
Grinding may be carried out, for example, in pinned-disc mills, ball mills or baffle plate mills. It may also be done in air-stream mills, such as cross-beater mills, gear ring mills or turbine mills. It is particularly advantageous to use steam-jet or air-jet mills because, in these mills, size reduction is primarily obtained by interparticle collisions, rather than by wall collisions. This results in very fine particle sizes in a single passage.
Dry grinding may also be carried out by singlestage and multistage, batch-type or continuous grinding processes. It is possible to produce commercial quantities of very fine TDI residue powders. These powders may contain free isocyanate groups or very fine-grained derivatives of TDI residue slag. The latter results by adding liquid, preferably low boiling reaction components effecting a modification reaction even in the gaseous phase during grinding.
Surprisingly size reduction of the TDI residue slag may also be carried out in conventional mixing devices equipped with ploughshare-like mixing elements and (preferably multistage) cutter heads. Apparatus of this kind are commercially available on both a laboratory and a technical scale. These mixers are both as a mill and a reactor for the modification reactions mentioned above.
It is only after wet or dry size reduction that the residual reactive groups in the residue slag are made available for a variety of different chemical reactions. Accordingly, before they are used as a reactive filler, the TDI residue powders obtained in accordance with the present invention may be subjected to a variety of different chemical modifications. These modification reactions may be carried out using a gas phase reactant and/or also in the presence of a liquid reaction medium.
In the above-mentioned modification reactions, it is primarily the small quantities of free isocyanate groups still present in the TDI residue powders which are reacted. Thus, it is possible, for example, to pass ammonia gas or gaseous amines through the finely ground TDI distillation residue, quickly reacting the free isocyanate groups in an exothermic reaction. The preferable method uses the counter-current principle and, therefore, needs no mechanical mixing. The reaction time can be as short as less than one minute. This gives rise to the formation in the TDI distillation residue of additional urea groups. These groups in turn can, particularly easily, enter into condensation reactions with carbonyl compounds, particularly formaldehyde. The carbonyl compounds can be passed through the powder at the same time as, or after, the reactions with ammonia or amines. Instead of using formaldehydeammonia mixtures, it is also possible to use urotropin under hydrolyzing conditions to form methylene-urea bridges. Suitable volatile amines are, for example, ethylamine, diethylamine, dimethylamine, butylamine, dibutylamine, ethylene diamine and propylene diamine. In addition to formaldehyde, suitable carbonyl compounds are, for example, acetaldehyde, propionaldehyde, butyraldehyde, acetone or methylethyl ketone.
Another modification reaction involving a gas phase reactant is the reaction with steam. The reaction of the free isocyanate groups in the finely powdered residue slag takes place slowly with steam at temperatures below 100� C. Quantitative polyurea formation may be quickly obtained, however, by applying reaction temperatures distinctly above the boiling point of water and preferably above 130� C. Providing adequately size-reduced TDI residue slag is used, it is sufficient to expose it to the above-mentioned temperatures wetted with water without any further mixing. Similarly, it is possible to use aqueous ammonia, aqueous amine solutions, or alcohols and carboxylic acids, optionally in gaseous form for modification reactions with the free NCO-groups. Examples of these are methanol, ethanol, propanol, isopropanol, butanol, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, formic acid and acetic acid.
Reactions particularly suitable for modifying the TDI residue powder in water or in an organic inert solvent are the catalyzed reactions of the free isocyanate groups with one another, for example, in the formation of uretdione groups in the presence of dimerization catalysts, such as trisubstituted phosphines, or the formation of carbodiimide groups in the presence of phospholine oxide. Another possible modification reaction is the addition reaction of the free isocyanate groups with weakly acid compounds (for example, bisulphite or other isocyanate donors) which may subsequently be split off, by applying elevated temperatures with the resulting liberation of the isocyanate groups. It is also possible to carry out a variety of different modification reactions in the liquid phase using compounds which contain groups reactive primarily with the isocyanate groups of the residue powder. Particularly preferred are hydroxyl, amino and/or carboxyl groups. Anionic and/or cationic groups or groups capable of salt formation may also be introduced into the residue powder by modification reactions of this type. Most of these compounds not only react with the free NCO-groups of the residue, but also with its carbodiimide bonds. Suitable monohydric and polyhydric alcohols, amines and carboxylic acids which may optionally contain further functional groups (for example, ionic groups and/or groups capable of salt formation) are described, for example, in Canadian Pat. No. 1,081,385 and U.S. Pat. No. 4,147,680, as reactants for polyisocyanates in the in situ production of polyisocyanate polyaddition products in polyhydroxyl compounds. Amines suitable for modification reactions are also described in U.S. Pat. No. 4,192,927. Suitable carboxylic acids are described in U.S. Pat. No. 4,192,926 (in connection with the addition of these compounds with carbodiimide groups). It is also possible in accordance with U.S. Pat. No. 4,192,925, to add phosphites with the carbodiimide bonds of the TDI residue powder to form phosphonoformamidine groups. It is also possible to carry out the above-described modification reactions using carbonyl compounds in a liquid reaction medium. Suitable carbonyl compounds are described, for example, in U.S. Pat. No. 4,206,109.
In addition to water, suitable reaction mediums for the above-mentioned modification reactions are the known organic solvents which boil at temperatures preferably below 150� C. Particularly preferred are those that boil at temperatures below 130� C. These liquids, as mentioned above, are essentially non-solvents for the powdered TDI-distillation residue, i.e. merely act as suspending agents.
Examples of such organic solvents are methylene chloride, acetone, petroleum ether, cyclohexanone, ethylacetate, tetrahydrofuran, benzene, toluene and xylene. After the modification reaction, the liquid reaction medium may be removed by filtration and drying or by distillation. In many cases, it is sufficient to use only very small quantities of the liquid reaction medium (frequently less than 10% by weight, based on the residue powder) in order to dissolve the modifying agent or to disperse it uniformly in the TDI residue powder. In cases where it is required to use temperatures above the boiling point of the solvent, the above-mentioned modification reactions can be carried out in a pressure vessel.
In one particular variation of the process according to the present invention, copolymerizable unsaturated groups are introduced into the finely powdered TDI distillation residue. This may be done by any of the above-described modification reactions. An example of this variation of the process is reacting the residue powder with an unsaturated carbonyl compound (i.e. acrolein, crotonaldehyde or methyl vinyl ketone), an unsaturated hydroxyl compound (for example, allyl alcohol or hydroxyethyl acrylate or methacrylate) and/or unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, maleic acid or fumaric acid). Residue powders modified in this way are particularly suitable for use in radical polymerization reactions.
The very finely ground NCO-containing or NCO-free TDI residue slags may also be converted into hydrophilic aromatic polysulphonic acid derivatives, for example, in suspension in chlorinated hydrocarbons, by reaction with sulphur trioxide or chlorosulphonic acid, followed by hydrolysis. In the above reaction, some of the sulphonic acid groups enter into addition reactions with the carbodiimide groups present.
With amines, ammonia or alkali, the corresponding aryl sulphonic acid salts are formed. If compounds containing tertiary nitrogen have been introduced into the residue powder, the sulphonic acid TDI residue powders can form amphoteric systems where both the positive charge and also the negative charge are situated in the same molecule. Separately produced anionic and cationic TDI residue powders may be mixed in any ion-equivalent ratio and used, for example, as ion exchangers.
In special cases, when the reaction mixture passes a pasty transition state, the above-mentioned modifying reactions may advantageously be carried out in self-cleaning screw machines. Suitable extruders are described e.g. in "Schneckenmaschinen in der Verfahrenstechnik" by H. Hermann, Springer Verlag, Berlin/Heidelberg/New York, 1972, and in U.S. Pat. Nos. 3,963,679 and 3,993,641, incorporated herein by reference.
It is known in the art that chemical reactions may be carried out in extruders. Generally, however, thermoplastic polymers are produced or worked up in such screw machines, temperatures above the softening point of the material being applied. Surprisingly, even the modification reactions according to the invention wherein non-meltable cross-linked TDI residue slags after denaturing with water are used may be carried out in the above-mentioned extruders, free-flowing, very finely divided powders being directly obtained at the head of the extruder.
The TDI residue powders may also be mixed at any time with powder-form polymeric hydrocyanic acids (so-called azulmic acids). Azulmic acids also contain reactive groups (particularly amino groups) which are capable of reacting both with the addable groups of the TDI residue (for example, NCO-groups and carbodiimide groups) and also with the modifying agents (for example, carbonyl compounds) optionally used in the working up of the residues. Processes for producing azulmic acids and for stabilizing them against the elimination of hydrocyanic acid are described, for example, in Houben-Weyl, Methoden der Organ. Chemie (1952), Volume 8, page 261, in Angew. Chem. 72 (1960), pages 379-384, in German Pat. Nos. 662,338 and 949,600 and in U.S. application Ser. Nos. 11,554 and 11,542, both filed Feb. 12, 1979.
The TDI distillation residues worked up in accordance with the present invention may be worked up into cellular or homogeneous sheets or molded bodies under pressure at elevated temperatures, optionally in a mold. They may also be used as a reactive filler in a variety of different plastics obtainable by polyaddition, polycondensation and/or polymerization reactions. They can be used in any quantity; generally in quantities of from 2 to 60% by weight, preferably in quantities of from 10 to 50% by weight, and, with particular preference, in quantities of from 15 to 40% by weight, based on the total quantity of modified plastic.
The TDI residue powders are preferably used as a filler in aminoplast and phenoplast resins. In this case, they are advantageously present during the production of these resins and are chemically incorporated into the polymer being formed through their numerous reactive groups. These resins are made using known methods, from carbonyl compounds and aminoplast or phenoplast monomers. Examples of these compounds are formaldehyde, urea, melamine and phenol. Carbonyl compounds and aminoplast and phenoplast monomers suitable for this purpose are described, for example, in U.S. Pat. Nos. 4,225,481; 4,206,109 and 4,160,754.
These TDI distillation residues may also be used as a reactive filler in the production of epoxide resins.
The free isocyanate groups of the very finely divided TDI residue may react both with the hydroxyl groups always present in commercial epoxide resins and also, at elevated temperatures, preferably above 160� C., with the epoxide groups to form oxazolidone rings. In addition, hardeners containing amino or carboxyl groups may also react with the carbodiimide groups present in the TDI residue slag. These carbodiimide groups are present in up to about 17% by weight in the TDI residues.
Very fine TDI residue powders having a mean particle size of less than 50 mμ, preferably less than 10 mμ, are preferably mixed homogeneously into liquid diepoxides either at room temperature or at elevated temperatures. The hardener (for example, an amino compound, dicarboxylic acid or a dicarboxylic acid anhydride) is then reacted under process conditions known per se. In many cases, it is possible to partially react the polyfunctional TDI residue powders simultaneously with both the epoxide resin and with the hardener during polyaddition of the epoxide. The reactive filler is incorporated into the hardened cast resin through main valency bonds in this case.
The TDI residue powders added increase the hardness and reduce the flammability of the epoxide-based resins and, in addition, reduce their shrinkage. The TDI residue powders are added in amounts up to 50% by weight. In the case of large castings, hardening is accompanied by a smaller increase in the internal temperature than in the case of unfilled castings.
In special cases, the epoxide resins and the very finely powdered TDI residues may even be combined with phenol, melamine and/or formaldehyde (i.e. for the production of abrasives for grinding or polishing wheels).
These TDI residue slags may also be used as a reactive filler in the production of cyanate resins. See, for example, the starting compounds described in German Offenlegungsschrift No. 2,260,487.
TDI residue powders may also be advantageously used in the production of plastics, using a known method, by the polymerization or copolymerization of monomers containing olefinically unsaturated groups. The TDI residue powders containing copolymerizable groups can be used also. Examples of such monomers are acrylonitrile, styrene, butadiene, acrylic acid, methacrylic acid, vinyl chloride, vinylacetate and unsaturated polyesters.
The polymerization reactions are preferably carried out in a liquid medium, for example, in water or an organic solvent (in the presence of the finely divided TDI powder).
The very finely divided TDI residue powders, with or without free NCO-groups, may readily be coated by polymerization reactions. This coating may be done, for example, by copolymerizing monomeric or oligomeric vinyl compounds in the presence of the very finely powdered residue slag, optionally in a solvent which is inert to isocyanate groups. Depending on the melting range of the polymer coatings, indefinitely storable isocyanate residue powders of this type may be used, at any time, as a reactive filler at elevated temperatures to form main valency bonds. Optionally, further H-acid components may also be used. Depending on the quantity and compatibility of the polymer coatings with the TDI residue powders and the components optionally added, combinations such as these may be brought into the required form under pressure. The above process wherein blowing agents above the softening point of the polymer are used is also possible. Where linear polymers are used, forming or shaping may even be carried out using injection molding machines.
In cases such as these, the optionally modified finely divided TDI residue powders are used in quantities of from 5 to 80% by weight, preferably in quantities of from 20 to 60% by weight, based on the total weight of the mixture.
TDI residue powders having been modified by reaction with an excess of glycol as described above are stable in storage for any desired time and surprisingly may be manufactured like thermoplastic materials into molded bodies, preferably at a temperature of from 150� to 230� C., most preferably 170� to 200� C., and at a specific pressure of from 5 to 100 bar/cm2, most preferably 10 to 40 bar/cm2. The bulk weight of the residue powders modified by means of glycols generally is from 430 to 800 g/l (depending on the particle size), homogeneous molded bodies with a gross density of about 1.2 to 1.3 g/cm3 being obtained or even products with a cellular structure and a density of about 0.7 to 1.2 g/cm3.
Since TDI residue slags modified only by denaturing with water behave like duromers, it is believed that the glycol-modified residue powders under the pressing conditions partly are linearized. Scrap material from the moldings may be processed repeatedly under the conditions given above although their softening point under normal pressure is well above 270� C. As a consequence, the moldings may be demolded without any cooling.
If an extremely finely ground TDI residue modified with an excess of glycol is used, metal surfaces may be coated by a melt sintering process in a fluid bed reactor, preferably at temperatures above 250� C. These coatings are flameproof.
The TDI distillation residues worked up using the present invention are also important as reactive fillers and binding agents in the production of boards or moldings in high-temperature pressures by bonding ligno-cellulose-containing fibers, chips or layers. Additional binders used are preferably the condensation products of formaldehyde with urea, melamine or phenol known per se for this purpose, particularly in the form of their aqueous solutions or dispersions. It is already known from German Offenlegungsschrift No. 1,669,759 and from German Auslegeschrift No. 1,653,169 that, in addition to or instead of binders such as these, it is also possible to use polyisocyanates in the production of pressed materials based on vegetable starting materials containing ligno-cellulose.
It has now been found that the modified TDI residue slags of the present invention are highly suitable as binding agents or additional binding agents. In this connection they are used in quantities of at least 2% by weight, generally of from 2 to 90% by weight and preferably from 5 to 60% by weight, based on the total weight of the molding.
Suitable starting materials containing ligno-cellulose which may be bound in this way are, for example, wood, bark, cork, bagasse, straw, flax, bamboo, alfa grass, peanut and rice husks, sisal and coconut fibers. The material may be in the form of granulates, chips, fibers or powder. It may have a water content of from 0 to 35% by weight, preferably from 5 to 25% by weight. Optionally, from 1 to 50% by weight, preferably from 5 to 20% by weight of formaldehyde or a formaldehyde resin (expressed as solids, based on the total weight of the molding) and the above-mentioned quantity of TDI residue powder are added to it. This is followed by processing (generally under the effect of heat and pressure) to form boards or moldings.
Laminating boards or moldings may also be produced in the same way from veneers, papers or fabrics. Additionally, laminated boards or moldings may also be produced in this way from veneers and strip-form, bar-form or rod-form center layers (so-called cabinet making boards). This is done by treating these veneers with the TDI residue powder and the conventional binder and subsequently pressing them with the center layers, generally at elevated temperature and pressure. It is preferred to apply temperatures in the range of from 100� to 250� C., and, with particular preference, in the range of from 130� to 200� C. The initial pressure applied is preferably between 5 and 150 bars. The pressure subsequently falls, generally towards zero, in the course of the pressing operation. It is, of course, also possible to use organic or inorganic fungicides, insecticides, or flameproofing agents known per se. These additives are usually in quantities of from about 0.05 to 30% by weight, preferably in quantities of from 0.5 to 20% by weight.
Therefore, the present invention also relates to a process for the production of boards or moldings by the hot pressing of starting materials containing ligno-cellulose with a binder comprising at least 2% by weight, based on the total weight of the molding, of the modified TDI residue slags and optionally with formaldehyde resins as an additional binder.
The residue slags of the present invention may also be added as a reactive filler in lacquers and coatings of various kinds. These fillers are generally in quantities of from about 2 to 70% by weight, preferably in quantities of from about 5 to 40% by weight, based on the total solids content. Examples of lacquers and coatings such as these are roof or floor coverings, gap-filling and trowelling compounds known per se. Optionally, bitumen or tar compositions may also be added. Another potential application is in the modification of thermoplastic plastics. Here, the residue powders are mixed with the thermoplast in a quantity of from 3 to 200% by weight, preferably of from 10 to 100% by weight, based on the thermoplast, using techniques known per se (for example, co-extrusion). In this way, it is possible, for example, to considerably increase the hardness of flexible thermoplasts, such as flexible PVC. It is also possible, however, to add the residue powders to plasticized rigid polymers, such as rigid PVC. By adding the residue powders to plasticized rigid polymers, the amount of expensive rigid polymer needed can be reduced.
The TDI residue powders which preferably have been modified chemically may also be mixed with scrap plastics (preferably polyurethane foam material) and molded under pressure at above 100� C., preferably above 160� C., optionally in the presence of additional binding agents. Depending on thermoplastic properties of the plastic scrap and the pressing conditions, homogeneous or cellular products with excellent mechanical properties are obtained.
Materials of this type may be used, for example, in the production of structural components or furniture.
In all the above-mentioned applications, the TDI residue powders of the present invention may also be used with powder-form azulmic acids. The azulmic acids may be used in a quantitative ratio range of from 90:10 to 10:90.
The TDI residue powders may also be used in combination with other organic and/or inorganic fillers such as chalk, clay, calcium sulphate, silica, sand, charcoal and powdered plastic scrap.
The present invention is illustrated by, but is in no way limited to, the following Examples wherein the quantities quoted represent parts by weight or percent by weight, unless otherwise indicated.
TABLE 1______________________________________Characterization of the TDI residues used in the Exampleswhich accumulate as distillation residues, insolublein inert solvents, in the production of monomeric tolylenediisocyanates. Begin- Part-Nature NCO- Type of ning of icleof the content size-reducing decomp. sizeTDI- % machines used �C. mμ1 2 3 4 5 6 7______________________________________I 80 D 7.2 -- HM + 280 130 KZMII 80 D 4.7 HM 295 400III 80 D 8.4 HM + LSM 275 20IV 80 D 9.9 HM + LSM 270 4V 80 13.9 SG + TM 265 150VI 65 D 6.8 -- HM + 270 85 IZMVII 65 D 11.6 HM + TM 255 110______________________________________ Key to Table 1 Column 1: Serial No. (in Roman numerals) of the TDIdistillation residue used in the Examples Column 2: Nature of the TDI residue 80 or 65 = isomer ratio of the monomeric diisocyanate mixtures isolated from the crude product by distillation (2,4TDI, 2,6TDI = 80:20 or 65:35). D = quenching after isolation of the monomeric TDI by introducing the hot (150-200� C.), tarlike extremely viscous TDI pan residue into waterfilled stirrerequipped vessels with formation of a very coarsegrained TDI residu slag, evolution of CO2 and polyurea formation (see below). Column 3: NCOcomponent in % by weight, based on TDI residue (solids). The NCOcontent is determined immediately after sizereduction at 50� C. in acetone using a sample additionally ground to less than 60 Column 4: Type of rough and fine grinding machines used in dry grinding: HM = hammer mill LSM = airjet mill SG = cutting granulator TM = turbine mill Column 5: Type of rough and fine grinding machines used in wet grinding: HM = hammer mill KZM = colliod toothed ring mill TZM = trigonal toothed ring mill Column 6: Beginning of decomposition in �C. Column 7: Particle size in mμ of approximately 50% by weight of the ground material.
Isolation of the TDI pan residue in pure form (i.e. without quenching) is only possible providing special precautionary measures are taken, i.e. providing the hot melt (150�-200� C.) is immediately subjected to intensive cooling in the absence of oxygen to prevent exothermic self-ignition. The hard tar-like mass is infusible, even in powder form.
The phosgenation residue remaining in the sump during the production of tolylene diisocyanates, i.e. approximately 10% by weight of the theoretical monomer yield, is run off in a hot (approximately 150� to 180� C.), highly viscous form into a stirrer-equipped vessel containing at least twice the quantity of water. A large number of the free isocyanate groups react to form polyurea groups. The reaction is accompanied by the evolution of carbon dioxide. This quenching and denaturing process is accompanied by intense heating of the water. This results in the formation of a coarse-grained, very irregularly shaped, porous residue slag. The water is run off into a trough until the water content still present in the slag has fallen to below 10% by weight, and more advantageously, for subsequent size reduction in a hammer mill, to below 5% by weight.
In order to determine the included isocyanate content, a sample has to be size-reduced to less than 60 mμ and heated in acetone to 50� C. By way of comparison, only about half the free NCO-groups are observed at room temperature. In the case of coarse-grained TDI residue slag, it is only possible to determine a fraction of the NCO-groups. Depending on the particle size, the NCO-content of the quenched and denatured residue slag wetted with water gradually decreases over a period of days (<500 mμ) to weeks (>2-3 mm) at room temperature. The reduction in the content of free isocyanate groups is prevented by drying the quenched and denatured TDI residue slag. This is done by pregrinding to a grain size of less than 3 mm, then drying in a recirculating air cabinet at temperatures below 50� C. until the water content has fallen to below 0.2%, followed by storage in the absence of air.
Gas-phase polyaddition reactions
The TDI residue I is size-reduced in water to 200 mμ undersize (30%), then dewatered in a suction filter. It is spread out on enamel plates in approximately 2 cm thick layers and dried for about 3 hours at 130�-145� C. in a recirculation cabinet, or until the 7.2% by weight of free isocyanate groups still present before the heat treatment have quantitatively reacted, primarily with the steam, to form additional polyurea groups.
The dry, free-flowing powder has an apparent density of 560 g/l. Above 310� C., the powder gradually decomposes without melting, becoming dark brown in color.
The dry-ground TDI residue II (Example 2) and VI (Example 3), characterized in Table 1, are treated with gaseous ammonia in a vessel equipped with a paddle stirrer. The ammonia is introduced from below. Depending on the NCO-content and particle size, a temperature of from 40� to 60� C. is reached in an exothermic reaction. The free isocyanate content falls towards zero after addition of a substantially equivalent quantity of ammonia.
The extremely light-colored, infusible addition products, modified by free terminal urea groups, may be used as high-temperature-resistant reaction components for condensation reactions with carbonyl compounds, particularly formaldehyde, optionally using urea(s) or phenol(s). The powder densities are 650 g/l (Example 2) and 510 g/l (Example 3).
A mixture of 100.0 parts by weight of dry-ground TDI residue IV (particle size <10 mμ) and 28.6 parts by weight of ε-caprolactam is heated to 120�-140� C. for about 90 minutes, or until the NCO-content has fallen to zero.
The light-colored, finely divided powder has a powder density of 365 g/l.
Polyaddition reactions using small additions of inert solvents.
100 parts by weight of TDI residue III and a solution of 10 parts by weight of acetone and 12 parts by weight of ethanolamine are thoroughly mixed. The resulting mixture is kept at 55� C. for 1 hour in a reaction vessel, after which the acetone is evaporated off. A very finely powdered, NCO-free TDI residue modified by terminal hydroxy ethyl urea groups is quantitatively formed.
100 parts by weight of TDI residue III are mixed with 6 parts by weight of urea in 12 parts by weight of ethylacetate. The resulting mixture is heated to 140� C. in a pressure vessel. After 60 minutes, the solvent is distilled off and the biuretized TDI residue is isolated.
Polyaddition reactions in relatively large quantities of inert solvents in which the TDI residue is suspended.
100 parts by weight of TDI residue IV, 165 parts by weight of acetone and 11.9 parts by weight of N-methyl diethanolamine are boiled under reflux in a stirrer-equipped vessel until no more free isocyanate groups can be detected.
The TDI residue modified by incorporated tertiary nitrogen groups is isolated from the organic suspending agent in the form of a finely divided powder by filtration under suction and drying.
The polyaddition reaction according to Example 7 is immediately followed by methylation with a 5 equivalent percent deficit of dimethyl sulphate in acetone suspension at boiling temperature. The extremely finely divided TDI residue containing quaternary nitrogen groups is isolated in the same way as described above. It is a water-insoluble cationic polyelectrolyte which, in contrast to the extremely hydrophobic starting product, can easily be suspended in water without the formation of a supernatant phase.
Instead of dimethyl sulphate, 1,2-dichloropropane, 1,4-dichlorobutene, a mineral acid or phosphoric acid may be used for quaternization. In these cases, the degree of quaternization is not quite as high.
In the same manner as in Example 7, 100 parts by weight of TDI residue IV having a particle size of less than 10 mμ, 150 parts by weight of toluene and 11 parts by weight of allyl alcohol are heated with stirring at the boiling temperature of the suspending agent until the unsaturated alcohol has been added to the free isocyanate groups, about 3 to 4 hours.
After the NCO-free suspension has been cooled, the modified, very finely divided TDI residue may be filtered under suction and dried (cf. Example 16). It may also be subjected without isolation to copolymerization in another reaction step.
100 parts by weight of TDI residue IV having a particle size of less than 10 mμ are suspended in 158 parts by weight of acetone, followed by the slow addition, at approximately 50� C., of 22 parts by weight of a diamine sulphonate corresponding to the following formula:
H2 N--CH2 CH2 --NH--CH2 --CH2 --SO3 Na
dissolved in 28 parts by weight of water.
The reaction mixture is then boiled under reflux for about 1 hour until no more free NCO-groups can be detected.
This anionic TDI modified residue sulphonate is suitable for use as a dispersion aid in the production of aqueous polyurethane dispersions.
100 parts by weight of TDI residue IV (particle size less than 10 mμ) and 100 parts by weight (particle size <10 mμ, obtained from hydrocyanic acid by Th. Volker's method, Ang. Chem. 72 (1960)) are suspended in 300 parts by weight of acetone and boiled for about 3 hours until the isocyanate groups have completely reacted with the amino groups of the polymeric hydrocyanic acid.
The isolated, NCO-free, very finely powdered polyadduct has an organic nitrogen content of 32% by weight.
100 parts by weight of TDI residue VII, 200 parts by weight of toluene and 90 parts by weight of a diepoxide corresponding to the following formula: ##STR1## are kept for approximately 2.5 hours at approximately 110� C. in a stirrer-equipped vessel until the isocyanate groups have quantitatively reacted. After cooling, the finely powdered polyaddition product is isolated by filtration and drying under reduced pressure.
100 parts by weight of TDI residue VII and 150 parts by weight of the diepoxide according to Example 11 diluted with 50 parts by weight of acetone are thoroughly mixed at room temperature. The diluent is distilled off in vacuo at a temperature below 50� C.
The residual mixture is heated for 15 minutes at about 150� C./20 bars in a steel mold. The molding, containing oxazolidone rings, is removed from the mold after cooling.
25 parts by weight of sodium bisulphite dissolved in 37 parts by weight of water are added to 100 parts by weight of TDI residue IV (particle size less than 10 mμ) suspended in 150 parts by weight of acetone in a stirrer-equipped vessel. This mixture is heated to boiling temperature over a period of about 3 hours.
After the suspending agent has been removed, a modified, indefinitely storable TDI residue is obtained from the NCO-free suspension. The bisulphite may be removed from the TDI residue at temperatures above 120� C. with the recovery of free isocyanate groups.
Catalytically initiated reactions of TDI residues
100 parts by weight of TDI residue V (R 80) having a particle size of less than 300 mμ are suspended in 150 parts by weight of anhydrous toluene, followed by the addition of 1 part by weight of phospholine oxide.
The free NCO-group content falls to zero over a period of from about 3 to 4 hours at reflux temperature with the elimination of CO2.
The isolated, finely divided TDI residue has a carbodiimide group content of approximately 20% by weight.
The procedure is as described in Example 14, except that the phospholine oxide is replaced by a total of 3 parts by weight of tributyl phosphine added in 3 portions at intervals of 1 hour.
The TDI residue modified by uretdione groups liberates isocyanate groups at temperatures above 180� C. In the presence of amino groups, the isocyanate groups are liberated even at temperatures above 100� C.
Polymerization reactions with TDI residues.
A total of 4 parts by weight of azodiisobutyrodinitrile and 45 parts by weight of monomeric acrylonitrile are alternately added in portions at from 60� to 90� C. to the NCO-free suspension of the TDI residue containing terminal allyl urethane groups obtained in accordance with Example 8. As the polymerization reaction progresses, the temperature is gradually increased to approximately 110� C. After cooling, the monomer-free suspension is filtered under suction, and the filter cake is washed with a little acetone and dried.
The extremely light-colored, finely divided reaction product has a powder density of 450 g/l. It is particularly suitable for use as a readily homogenizable organic filler.
100 parts by weight of TDI residue IV (particle size less than 10 mμ) are suspended in 370 parts by weight of toluene. This is followed by the addition of 40 parts by weight, of an unsaturated polyester containing 1.4% by weight of terminal hydroxyl groups (acid number 1.4) of adipic acid, fumaric acid and 1,4-butane diol (molar ratio 13:13:29), 79 parts by weight of acrylonitrile, 30 parts by weight of styrene and a total of 3 parts by weight of azodiisobutylrodinitrile.
The hydroxyl groups of the polyester are initially polyadded with the free isocyanate groups of the TDI residue at 110� C., followed by polymerization in accordance with Example 16 as soon as no more free NCO-groups can be detected. The solvent-free, finely divided reaction product may be stirred at any time into polyethers or polyesters containing hydroxyl groups without any sedimentation and may be used as an active organic filler.
Isocyanate addition reactions during wet grinding.
Immediately after preliminary grinding in a hammer mill (mean particle size approximately 0.8 mm; NCO-content 13.4% by weight), a TDI residue slag (65 D) is suspended in water at room temperature to form a 30% suspension. This is followed by the addition of 15 parts by weight of a 25% aqueous ammonia solution per 100 parts by weight of TDI residue solids.
The TDI residue is wet-ground in a trigonal toothed ring mill to a particle size of less than 160 mμ in this dilute, ammoniacal-aqueous phase, the temperature rising during grinding to around 70� C.
After at least 3 hours or more, the aqueous suspension is dewatered in a pressure filter and the filter cake (approximately 65% fine-grained) is washed and isolated.
The T 65 residue containing free terminal urea groups has an NCO-content of less than 0.2% by weight. It is particularly suitable for condensation reactions with carbonyl compounds or for mixed condensation reactions with carbonyl compounds and aminoplast or phenoplast formers.
100 parts by weight of the preground TDI slag (mean particle size 800 mμ) of Example 18 is suspended in water with 20 parts by weight of a 30% aqueous ethylene diamine solution to form a suspension having a solids content of approximately 30% by weight. As described in Example 18, this suspension is continuously pumped through a trigonal toothed ring mill. The NCO-free TDI residue containing additional polyurea groups is freed from the water by filtration under suction and drying at 100� C. in a recirculating air cabinet.
The powder density is 535 g/l.
100 parts by weight of the TDI slag corresponding to residue I are suspended in water with 10 parts by weight of a 25% aqueous ammonia solution to form a suspension having a solids content of 35%. As in Example 19, the suspension thus formed is ground in a colloid toothed ring mill to a grain size of less than 160 mμ. This is followed by condensation in a stirrer-equipped vessel for 3 hours at from 60� to 80� C./pH 3 with 12% by weight of formalin solution (containing 30% CH2 O) in the presence of phosphoric acid.
After cooling the condensation product is filtered under suction and washed once with 0.5% of ammonia water and twice with ion-free water, followed in each case by pressing.
The NCO-free TDI residue modified by polymethylene urea groups may be used for stabilizing plastics against heat.
Size reduction and reactions in a mixer reactor.
In a horizontally arranged cylindrical container comprising ploughshare-like mixing elements with a multistage cutter head, the TDI-residue preground to less than 33 mm is three-dimensionally brought into a state of intensive movement in a weak stream of nitrogen and heated to 90�-100� C. Further size reduction is obtained both by means of the cutter head, which rotates at high speed, and by intercollision of the very hard residue particles or by impact on the wall of the drum. During this fine size-reduction the glycols used are sprayed in under pressure in the quantities indicated in the Table in such a way that they are atomised into the fluidised material at an acute angle to the cutters. At a reaction temperature of around 100� C., the greater part of residual isocyanate content which may still be present in the TDI-residue powder reacts in 30 minutes to 2 hours, depending on the particle size, a corresponding equivalent quantity of the glycol used reacting to form urethane groups and, optionally, polyurethane compounds containing terminal hydroxyl groups. Under the described conditions, excess glycol is distributed uniformly in very thin layers over a very large area of the surface of the TDI-residue powder. If, in cases where TDI-residues denatured with water are used, a very small amount of residual moisture is still present, the highly hydrophilic glycols may partially penetrate into the often finely porous particles. In this way, it is possible to obtain free-flowing, very finely divided and non-dusting powders which, in the case of very fine particles, absorb up to 25 or even 35% by weight of glycols which are liquid at room temperature and, inspite of this, have a dry appearance.
TABLE 2______________________________________Example No. 21 22 23 24 25______________________________________TDI-residue (parts) 85 II 88 II 83 III 80 VII 85 VIIDG (parts) 10 -- 17 20 10EG (parts) 5 -- -- -- --EGR (parts) -- 12 -- -- --PPG (parts) -- -- -- -- 5Pressing conditions�C. 220 185 180 170 170Kp/m2 40 50 50 30 10min./mm. 0.3 0.5 0.3 0.2 0.2______________________________________ DG = diethylene glycol EG = ethylene glycol EGR = EGresidue (sump residue of mono to pentaethylene PPG = polypropylene glycol (molecular weight 600)
A coarse-grained sample from the rough size-reduction of TDI-residue II having a coarse-grain fraction of 45% in the particle size from 0.5 to 3 mm is reacted with diethylene glycol in a ratio by weight of 90:10 in the mixing and size-reducing reactor and, after cooling, is further size-reduced for 1 to 2 hours in the mixer or ground to a particle size of less than 0.5-1 mm in an air stream mill.
In the case of the glycol-modified TDI-residues of Examples 21 to 25, subsequent size reduction is not necessary because the finely divided TDI-residues are not agglomerated under the test conditions applied.
The TDI-residue powders modified with low molecular weight glycols obtained in accordance with Examples 21 to 26 may be pressed under a specific pressure of from 10 to 50 bars and at temperatures of from 170� to 220� C. to form sheets which have ball indentation hardness of from 9 to 16 kp/mm2 and high impact strength. The fire-retarding effect is particularly remarkable. 2 to 5 mm thick sheets may be heated to red heat with an oxygen blast flame which produces surface foaming with an increase in volume. Following removal of the flame, the sheets are immediately self-extinguished.
Although the invention has been described in detail for the purpose of illustration, it is to be understood that such detail is solely for that purpose and that variations can be made therein by those skilled in the art without departing from the spirit and scope of the invention except as it may be limited by the claims.
|Cited Patent
|Filing date
|Publication date
|May 9, 1960
|Apr 27, 1965
|Bayer Ag
|Polyurethane plastics
|Oct 10, 1966
|Jul 15, 1969
|Allied Chem
|Polyisocyanate compositions
|Feb 27, 1969
|Jan 11, 1972
|Allied Chem
|Polyisocyanate compositions
|Dec 16, 1968
|Jan 18, 1972
|Du Pont
|Recovery of aromatic dhsocyanates from still residues
|Feb 7, 1974
|Jul 29, 1975
|Bayer Ag
|Process for removing distillation residue from crude isocyanates
|Jul 17, 1974
|Jun 15, 1976
|Bayer Aktiengesellschaft
|Process for the production of polyurethane elastomers
|Oct 17, 1975
|Nov 23, 1976
|Bayer Aktiengesellschaft
|Process for the production of polyisocyanates containing uretdione groups
|Jun 2, 1975
|Dec 27, 1977
|Sumitomo Bayer Urethane Co., Ltd.
|Purification of organic isocyanates
|Nov 3, 1975
|Feb 28, 1978
|Basf Wyandotte Corporation
|Process for the separation of residues of toluenediisocyanate production
|Jul 14, 1977
|Mar 6, 1979
|Allied Chemical Corporation
|Novel adhesive, molding and filler composition incorporating toluene diisocyanate residue
|Citing Patent
|Filing date
|Publication date
|Dec 29, 1983
|Dec 18, 1984
|Olin Corporation
|Isocyanate-reactive compounds from TDI distillation residue and polyurethanes prepared therefrom
|Dec 22, 1988
|Feb 27, 1990
|The Dow Chemical Company
|Rigid foams prepared from treated toluene diisocyanate residue
|Jun 1, 1990
|Aug 27, 1991
|The Lubrizol Corporation
|Process for distillation of crude isocyanate concentrates
|Dec 15, 1992
|Oct 11, 1994
|Bayer Aktiengesellschaft
|Process for the production of isocyanates and for working up the residue
|Dec 13, 1993
|Apr 9, 1996
|Bayer Corporation
|Treatment of isocyanate residue
|Dec 27, 1996
|May 19, 1998
|Bayer Corporation
|Toluene diisocyanate residue-based compositions as fillers for polyisocyanates
|Dec 27, 1996
|May 26, 1998
|Bayer Corporation
|Isocyanate prepolymers produced from toluene diisocyanate residue dissolved in toluene diisocyanate
|Dec 27, 1996
|Sep 8, 1998
|Bayer Corporation
|Toluene diisocyanate residue-based compositions and the use of such compositions as fillers for hydroxyl compounds
|Oct 27, 1997
|Nov 17, 1998
|Bayer Corporation
|Toluene diisocyanate residue-based compositions having reduced acid values
|Jun 14, 2002
|Dec 19, 2002
|Gunter Hofmann
|Substance precipitation
|Jun 14, 2006
|Sep 9, 2010
|Basf Aktiengesellschaft
|Method for preparing isocyanate adducts
|Feb 21, 1990
|Sep 7, 1990
|The Lubrizol Corporation
|A process for distillation of crude isocyanate concentrates
|U.S. Classification
|International Classification
|Cooperative Classification
|European Classification


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Virgin and hermit, also known as Afreda, Alfritha, Aelfnryth, and Etheldreda. She was the daughter of King Offa of Mercia, in England, and was either betrothed to or loved by St. Ethelbert, the king of the East Angles. Ethelbert went to Offa's court to ask for Alfreda but was murdered by Offa's queen, Cynethritha. Horrified by the deed, Alfreda departed the court and retired to the marshes of Crowland. There she lived as a hermitess until her death. Her sister, Aelfreda, also lost a husband to the political intrigue of Offa and his queen.
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John Gonzales de Castrillo was born at Sahagun, Leon Spain. He was educated by the Benedictine monks of Fagondez monastery there and when twenty, received a canonry from the bishop of Burgos, though he already had several benefices. He was ordained in 1445; concerned ... continue reading
In the year 1400, a young man came to the door of the largest hospital in Siena. A plague was raging through the city so horrible that as many as twenty people died each day just in the hospital alone. And many of the people who died were those who were needed to tend ... continue reading
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China sentenced three people to death on Monday for a deadly attack at Beijing's Tiananmen Square last October, state television reported, an incident blamed by the government on Islamist militants.
Another attacker was given a life sentence, and four others received jail terms ranging from five to 20 years.
Five people were killed and 40 hurt when a car plowed into a crowd at the northern edge of Tiananmen Square and burst into flames. Those killed included two bystanders and three people in the car.
Two of those sentenced, named in a state media report, appeared to have ethnic Uighur names.
The western province of Xinjiang is the traditional home of the Turkic-speaking Uighurs, and China has blamed previous knife and bomb attacks on separatists who seek to establish an independent state there called East Turkestan.
China has been on edge since a suicide bombing last month killed 39 people at a market in Xinjiang's capital of Urumqi.
Police in Xinjiang have arrested or tried dozens of suspects in recent weeks for spreading extremist propaganda, possessing banned weapons and other crimes.
Knife-wielding attackers in western China wounded four people in a crowded chess hall in the city of Hotan on Sunday, state broadcaster China Central Television (CCTV) said in a separate report on Monday.
Two of the attackers died from serious injuries and a third was arrested.
The motive for Sunday's attack was not immediately clear.
Rights activists and exile groups have charged that the government's own repressive policies in Xinjiang have sowed the seeds of unrest, a claim Beijing denies.
In March, 29 people were stabbed to death at a train station in the southwestern city of Kunming.
- Reuters
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0226284670 / 978-0226284675 / Going for Jazz: Musical Practices and American Ideology / Nicholas Gebhardt
0226267911 / 978-0226267913 / Mayors and Money: Fiscal Policy in New York and Chicago (American Politics and Political Economy Series) / Ester R. Fuchs
0226268969 / 978-0226268965 / Thomas Kuhn: A Philosophical History for Our Times / Steve Fuller
0226269566 / 978-0226269566 / Unsettled: The Culture of Mobility and the Working Poor in Early Modern England / Patricia Fumerton
0226273369 / 978-0226273365 / In the Workshop of History / Francois Furet
0226273938 / 978-0226273938 / Managing to Make It: Urban Families and Adolescent Success (The John D. and Catherine T. MacArthur Foundation Series on Mental Health and De) / Jr., Frank F. Furstenberg, Thomas D. Cook, Jacquelynne Eccles, Jr., Glen H. Elder
0226276473 / 978-0226276472 / Science and Salvation: Evangelical Popular Science Publishing in Victorian Britain / Aileen Fyfe
0226278743 / 978-0226278742 / Fire and Desire: Mixed-Race Movies in the Silent Era / Jane M. Gaines
0226278786 / 978-0226278780 / Tournament of Lawyers: The Transformation of the Big Law Firm / Marc Galanter, Thomas Palay
0226278794 / 978-0226278797 / Created Unequal: The Crisis in American Pay / James K. Galbraith
0226279146 / 978-0226279145 / How Experiments End / Peter Louis Galison
0226280616 / 978-0226280615 / The Making of the New Deal Democrats: Voting Behavior and Realignment in Boston, 1920-1940 / Gerald H. Gamm
0226280853 / 978-0226280851 / Logic, Language, and Meaning, Volume 1: Introduction to Logic / L. T. F. Gamut
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Israeli Defense minister Avigdor Lieberman likens Palestinian icon Mahmoud Darwish to Hitler, and in its coverage, The New York Times continues to bury the battle inside Israeli leadership over fascistic and Nazi currents in the country's politics.
Category Archives: Israel/Palestine
My family's Nakba story
Mondoweiss intern Tamara Nassar shares a lyrical and haunting account of her family's story during the Nakba: "The tragedy of the Nakba is that it perpetually reproduces itself with every refugee born in exile and until the last refugee returns. The Palestinian in diaspora gives birth to Nakba; her children become walking embodiments of abandonment."
Coexistence in the land of 'Hatikvah'
Growing up in the US, the Israeli national anthem held special meaning for Steven Davidson. But after living with a Palestinian family in Hebron, the song gained a different meaning: "Hatikvah didn't feel so close to my heart any more. Its solemn melody still aroused that sense of belonging through wandering, only now, this sense felt betrayed by the song's words. Everyone singing Hatikvah in this room felt like they belonged in a state they barely knew of— to the exclusion of so many whose home this had once been."
My Name is Saleh: Notes on Palestinian childhood
Ahead of this week's House of Lords debate about the health and well being of Palestinian children, Juliana Farha reports from a sold-out presentation by Defense for Children International-Palestine at the University of London's School of Oriental and African Studies: "Ayed tells us that physical torture of Palestinian children was common a few years ago, but interrogators observed that those being tortured often call up reserves of strength to resist, rendering it counter-productive. Instead, they discovered, psychological terror can be more effective: threatening to arrest the child's family members, for instance, or to revoke his father's work permit."
Palestinian boy of 12 in occupied West Bank is killed by rubber-coated steel bullet
A 12-year-old Palestinian boy, Muhye Muhammad Sidqi al-Tabbakhi, was killed Tuesday evening during clashes with Israeli soldiers in the occupied village of al-Ram in the West Bank after he was struck in the heart by a rubber-coated steel bullet. Police had raided the village and youths responded with bottles and stones, which were met by live fire, rubber bullets, and tear gas.
Poet on Trial: A visit to an Israeli court
Kim Jensen reports from Nazareth at the third hearing in the Israeli government's case against Dareen Tatour, the 33-year old Palestinian poet who is being prosecuted for "incitement to violence" on the basis of a YouTube clip and two alleged Facebook status updates. Jensen writes, "The wheels of justice grind slowly in the State of Israel, at least for Palestinian activists who endure de facto and de jure inequality under the law."
Israel's opposition parties plan to filibuster bill to expel Hanin Zoabi
Members of Israel's opposition coalition will filibuster overnight to stall a vote on a controversial bill to expand the Knesset's power to oust one of their own. The expulsion bill, formerly called the suspension bill, grants parliamentarians the authority to permanently kick their peers out of office, without loose criteria for disqualification. It is aimed at one member: Hanin Zoabi of the Joint List.
Explaining Israel's separate and unequal education system
Haaretz has run a series of articles on Israel's "separate and unequal" education system that allocates more funds to Jewish students than Palestinian students. Hatim Kanaaneh says it's old news. It's been this way for the four decades he's been advocating for Palestinian citizens of Israel. In a state that defines itself as Jewish, what do you expect?
Gaza couples struggle with financial difficulties amidst social crisis
After nine years of Israel's blockade and consistent assaults on Gaza, Gazans are faced with a financial crisis that impedes on daily and personal decisions leading to disastrous social consequences: young couples lack basic resources to marry and sustain families.
Israeli human rights organizations push back against law designed to 'silence opposition'
Israel's human rights NGOs pushed back this week after the Knesset passed a transparency law that critics say was the most recent attempt by Israeli Prime Minister Benjamin Netanyahu's coalition to persecute the country's left. Leading Israeli settlement watchdog Peace Now vowed to wage legal war against the new law, which requires NGOs that receive more than half of their funding from foreign donors to declare their funding sources prior to addressing Knesset committees, speaking with public officials, as well as on publications and websites.
Video: Palestinian swimmer overcomes Israeli restrictions to prepare for Rio Olympics
Palestinian swimmer Mary al Atrash, 22, is one of six Palestinians competing this year in Rio as part of the largest delegation Palestine has ever sent to the Olympics Games. Al Atrash will compete in the 50 meters freestyle, but her training has been difficult due to the fact that she does not have an Olympic-size pool to train in. Nearby Jerusalem has better facilities, including several Olympic-sized pools, but because of the Israeli occupation al Atrash is unable to travel to Jerusalem to train.
Prisoner Bilal Kayid rushed to hospital on 33rd day of hunger strike
Palestinian prisoner Bilal Kayid was rushed to a hospital in Ashkelon, Israel, after his health suddenly deteriorated, as he entered his 33rd day of hunger strike, according to the Palestinian Committee for Prisoners' Affairs. Meanwhile, some 37 Palestinians prisoners have begun open hunger strikes in solidarity with Kayid.
Palestinian youth was shot 9 times 'accidentally,' Israeli army says
Yahya Hisham Hijazi, 24, from Shu'fat refugee camp in occupied Jerusalem, who was injured by nine Israeli army bullets [on Thursday 14 July], became the latest victim of Israel's security obsession and paranoia, under allegations that became known to the Palestinians, claims of "carrying a knife," that continue to be used as a direct justification of the military's open fire orders.
Israelis take on Facebook 'monster' with claims it knowingly incites Palestinian attacks
Relatives of four Israeli-Americans and one American tourists killed in Israel and the occupied West Bank between 2014 and June 2016 are suing Facebook for $1 billion in damages, claiming the social media site promotes "terrorism" and "knowingly and intentionally assisted" in the deaths.
Powerful new game 'Liyla and The Shadows of War' dramatizes 2014 Israeli attack on Gaza
A Palestinian computer engineer has put together a chilling game for smartphones, which shows the struggle of Gazan civilians to survive Israel's 2014 onslaught. Rasheed Abueideh, creator of "Liyla and The Shadows of War" says he wants to provoke an emotional reaction from players. "[The purpose of the game is] to make people cry," he says. "It's to show the facts in the war and the effect of war on the civilians and on children."
Bible justifies rape in times of war, despite rabbis' efforts to spin or hide the teaching
Rabbis from Rashi to Ramban have long tried to hide or apologize for bible teaching that a soldier must "satisfy his lust" with a captive women. Now the Israeli chief army rabbi Eyal Qarim's comments have exposed the hideous point for all to see.
Israeli army blows up three Palestinian wells in occupied Hebron
'I Am a Human Being': A visit with Dareen Tatour
Israeli police initiate 'friction activity' on quiet streets in East Jerusalem
Israeli rabbi who advocated rape of 'comely gentile women' during war becomes chief army rabbi
After attack, Netanyahu gov't pours money into rightwing settlements
Israel's security cabinet said Sunday it will spend $13 million to expand social and education programs in West Bank settlements "in order to make it easier" for residents "to deal with the effects of the security situation and minimize its impact on the daily routine." Peace Now said the funding was a backdoor policy to build up settlements under the cover of responding to the recent bout of violence.
Israeli forces shoot five Palestinians during raid of Sa'ir as siege of southern West Bank continues
Ma'an reports: "Israeli forces shot and injured at least five Palestinians and detained three others in the southern occupied West Bank district of Hebron overnight Saturday, as Israeli forces continued to impose a strict siege on the village of Sair after an Israeli man was shot and injured while driving his car around midnight near the nearby illegal Israeli settlement of Teqoa."
US media fail to report video of soldiers shooting desperate Palestinian girl holding knife overhead
Video of helmeted Israeli soldiers shooting a slender Palestinian girl holding a knife in the occupied territories would show Americans the overwhelming imbalance of forces in the conflict. If only US media would give it the attention that Gideon Levy does in the Israeli press.
900 Gazans are still in need of care for injuries sustained in 2014 war
UN: "In early July 2014, the Palestinian Ministry of Health (MoH) and the World Health Organization (WHO) warned that Gaza's struggling health sector was near to collapse due to the severe shortages of medicines, medical disposables and fuel, and the lack of capacity to expand services to meet population needs. In the days and weeks following that warning, the health sector was confronted with over 11,200 injuries, among them more than 3,800 children, which is the highest number of injuries for such period of time it had ever faced. The challenge to the health system posed by the 2014 hostilities has extended into the present; approximately 900 of those injured sustained some form of permanent disability and require continued attention, while a significant part of the health infrastructure was damaged."


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Definition of "public prosecutor" - English Dictionary
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a type of heavy cloth that has a pattern woven into it that is the same colour as the cloth


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Fantastic Pokémon and Where to Find Them at AU
Answer: Pretty much everywhere on campus.
Office of the Vice President of Campus Life
Fax: 202-885-1769
Butler Pavilion, Room 400
Monday-Friday 9:00a.m. - 5:00p.m.
Answer: Pretty much everywhere on campus.
AU history professor discusses Brexit and the new British prime minister.
Office of Campus Life staff share what they are working on while on campus, and their summer plans away from the office.
American University Museum summer shows explore North & South Korean art, the African influence in Brazil, and artist immigrants of Washington, D.C.
Maria Rose Belding and Zoey Jordan Salsbury were recognized for their work with MEANS Database, a nonprofit that uses technology to connect food pantries to each other and to local donors.
Student awardees are the best of AU's academic achievers and servant-leaders.


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The U.S. Federal Trade Commission (FTC) is on the brink of launching a fresh antitrust probe into Google, over alleged misconduct over how it handles its display advertising business, Reuters reported.
An unnamed source confirmed the news to Reuters late last week, adding that the investigation is still in its early stages and that the FTC had not yet sent out civil investigative demands ordering Google to hand over data.
The probe will focus on the tools Google purchased from display ad company Doubleclick in 2007. The FTC reportedly began the investigation following demands from a number of unnamed competing display advertising companies, which accused Google of using its position in the display ads market to favor its own services.
The FTC has mounted antitrust probes against Google in the past. The FTC previously mounted an investigation into whether Google was using its search dominance to promote its own services more than those of its competitors. That antitrust probe ended in January, with Google only making a couple of minor changes.
Elsewhere on the antitrust front, Google's business in Canada is also about to face a formal inquiry from Canada's Competition Bureau, the Financial Post reported May 17. The agency has yet to reveal the scope of the investigation or asked for any documentation from Google.
This article was originally published on V3.
Related reading
What the evolution of search can teach marketers about digital transformation
For years, search engines have proved themselves as the gateway to the web, an entry point to the content of webpages people wanted to read.
Four key digital transformation trends you must pay attention to right now
Last week ClickZ Intelligence held its webinar on The What, Why and How of Digital Transformation in association with Marketo.
Google launches imported call conversions
If the internet killed the phone call, the smartphone has revived it.
Will Pokémon GO become a marketing platform for local businesses?
Nintendo's Pokémon Go, a free augmented reality (AR) mobile game, is on fire.


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Marijuana Blog
Granddaddy Purple Trichomes
Granddaddy Purple Trichomes - Hybrid
Green bud nuggets begin to show purple hues as they mature on Granddaddy Purple cannabis plants. This all-Indica marijuana strain is known worldwide for its many phenotypes that include Grape Ape, Grandaddy Grape Ape and Purple Erkel to name just a few. The strain hails from the Northern Californian hills as it has for more than 20 years. It grows very well indoors, either in water, air or soil. It has a predisposition to be short in bushy, as Indicas will. A euphoric effect about the same as the Purple Urkle is produced, a devastating Indica. This is a great night time strain because it%u2019s such a heavy indica buzz, with a very pleasant upper head body and warmth buzz which fades into droopy red eyes, munchies and complete pain relief and sedation.
Sockeye, a Portland ad company, takes on marijuana client
Stoner Secret Menu
What strain are you smoking on today?
Legal US High Times Cannabis Cup Coming To Seattle
Half Baked - Thurgood Goes to Rehab
Grand Daddy Purple bud shots
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Gearing up for Belmont Stakes
Horses and their jockeys tread the track prior to the 145th Running of the Belmont Stakes. Videojournalist: Jim Staubitser (June 1, 2013)
Newsday.com now uses Facebook for our comment boards. Please read our guidelines and connect your Facebook account to comment.
Clark Gillies visits young patients at Cohen Children's Medical Center Hey Harold: Andre Ward vs. Alexander Brand Police Release Football Player Search Video HBO 'Real Sports' looks at sewage issue in Rio HBO's 'Real Sports' on hospitals in Rio Cowboys team bus involved in fatal crash US Ping Pong Prodigy Ready for Rio N..C. Gov.: NBA All-Star Move 'PC B.S.' Safe at Home Foundation Fundraiser Obama Honors KC Royals at White House Terence Crawford's greatest hits Inquiry Finds Russian Cheating Went Beyond Sochi


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...I don't have math materials in Spanish like a school teacher would receive in their classes. I only meet clients in public libraries, not in their homes. I have return customers, and I prearrange days and times to meet in certain Southeast Houston area public libraries after school is out on a daily basis as well as on Saturdays.
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...When tutoring, I enjoy receiving questions from students, so that I can provide instruction according to specific needs. My approach is to teach from the student's perspective, in order for students to gain a personal understanding and enjoyment of the subject. Please feel free to inform me of topics of study and specific needs so that I can more effectively prepare for each lesson.
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The Jets have added some depth to their depleted wide receiving and defensive back core. With a recent rash of "soft tissue" injuries the team worked out some free agents during this morning's training camp practice at Cortland. They have signed wide receivers Wes Kemp (6'3", 223 LB) out of Missouri and Chris Forcier (6'3", [...]
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By Glenn Naughton It took a lot longer than all parties involved would have liked, but the New York Jets now have their starting quarterback under contract for the 2016 season according to N…


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Tags » Wicca
WOTC Extra - What Exactly is Paganism?
What Exactly is Paganism?
Paganism recognizes that throughout all things — from the atom to the universe — there is a duality. Night and day, love and hate— the ancient Oriental concept of Yin and Yang which was long matched by similar concepts in what we now call Europe. 508 more words


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Mason's retirement vaults Clayton's value
And what of Flacco's fantasy value? Mason was still one of the league's most reliable possession receivers, a security blanket Flacco used to the tune of 121 targets, 80 receptions and 1,037 yards (for a relatively modest 12.9 yards per catch) in 2008. The Ravens have spoken this offseason about opening up their offense a bit to take advantage of Flacco's big arm and presumably more advanced knowledge of the pro game, but that's a bit harder to envision now. In truth, both Clayton and Williams are better cast as outside threats who might not always be in the perfect place but who can occasionally make a huge play. It's possible that a smaller guy such as Yamon Figurs could see more time out of the slot as a possession guy, that new tight end L.J. Smith now becomes a more important target, or that Marcus Smith, an '08 fourth-rounder Baltimore likes a lot, could pick up some slack. But certainly this news doesn't help Flacco's fantasy value in a system where the rushing triumvirate of Ray Rice, Willis McGahee and Le'Ron McClain was already expected to get a big amount of the workload.
The final question worth asking here is whether the Ravens' hands are completely tied, or whether they still might be able to acquire a new No. 1 receiving target. Brandon Marshall is disgruntled in Denver, Anquan Boldin hates his contract in Arizona and, of course, there's Plaxico Burress, who is still in legal limbo. Maybe GM Ozzie Newsome decides it's time to take care of what has been a pretty shaky receiver situation for several years, and makes one of those teams and/or players an offer they can't refuse. If that winds up happening, and the Ravens essentially "trade" Mason for someone such as Marshall or Boldin, it would probably mean a pretty severe Flacco upgrade. Stay tuned.