Bulk material comprising a solid diisocyanate and a prepolymer containing urethane groups obtained therefrom.

Abstract

The present invention provides a bulk material used in a method for producing a prepolymer from solid diisocyanate in a simple, inexpensive manner with minimal by-product formation, a method for producing the same, and a method for producing the prepolymer. [Solution] A bulk material is provided that contains or consists of a diisocyanate solid at room temperature (25°C), characterized in that, in sieve analysis of the bulk material in a known style using a twin sieve array having mesh sizes of 0.1 mm and 4 mm, at least 90% by weight, preferably at least 95% by weight, of the bulk material is obtained in fractions of 0.1 mm to 4 mm. A method for producing the bulk material comprises a crystallization operation (i) and at least one step (ii) selected from the group consisting of classification, agglomeration, and grinding.

Description

Technical Field

[0001] The present invention relates to bulk materials containing solid diisocyanates, particularly naphthalene 1,5 - diisocyanate or p -phenylenediisocyanate, a process for their preparation, and a process for the preparation of isocyanate prepolymers using the bulk materials of the invention, the isocyanate prepolymers themselves, and their use for the production of polyurethane elastomers, particularly cast polyurethane elastomers.

Background Art

[0002] Cast polyurethane elastomers are usually used for the production of foams or solid molded articles. They are typically prepared by the reaction of an isocyanate component with a component having a hydrogen atom reactive with an isocyanate group. The latter component usually contains polyfunctional alcohols, amines and / or water.

[0003] In principle, there are two possible methods for the production of cast polyurethane elastomers, which differ by the order of addition of the co-reactants. In the so-called one-shot process, after weighing or volumetric measurement of the components, they are all mixed simultaneously and reacted while being molded. The disadvantage here is that intermediates formed from short-chain polyols (chain extenders) and isocyanates partially precipitate from the reaction melt and are thus removed from further reaction, which disrupts the further orderly increase in molecular weight, so that particularly when high melting point isocyanates are used, only inferior elastomers are obtained. A further disadvantage of the one-shot process is the rapid release of high reaction heat, which can often only be removed insufficiently. The resulting high temperature is isocy ​​This promotes side reactions such as anurate formation or carbodiimide formation, which is a characteristic of elastomers. It further diminishes sexuality.

[0004] For these reasons, the prepolymer method is primarily used for the production of cast elastomers. This method is established, and here, the long-chain diol component is first reacted with an excess of diisocyanate. This yields a liquid NCO prepolymer, which is then mixed with a short-chain diol (e.g., butane-1,4). -diol), or amine (e.g., methylenebis(o-chloroaniline) (MOCA) Alternatively, react it with diethyltoluenediamine (DETDA) and / or water. This is because some of the reaction heat is released and removed in advance during prepolymerization, and then the actual polymer is formed. The reaction in this case has the advantage of being easier to control. This promotes a regular increase in casting time, allowing for longer casting times, even with complex shapes. This makes blister-free filling easier.

[0005] The long-chain diol components used are polyether polyols and polycarbonate polyols. Polyol, preferably polyester polyol, comfortable poly-ε-caprolactone polyol It is a material. In particular, the isocyanate component used in high-quality cast elastomers is p - Phenylene diisocyanate (PPDI), 3,3-dimethyl-4,4'-biphenyl Diisocyanates (TODI), especially naphthalene 1,5-diisocyanate (NDI) Which high-melting-point diisocyanate is it?

[0006] For these high-quality cast elastomers, the preferred NCO content to be prepared first is... The prepolymer having a certain amount of free particles that tend to crystallize at low storage temperatures, However, since it still contains the monomer diisocyanate, the use of the prepolymerization method is problematic. However, storage at high temperatures can lead to undesirable reactions and associated increases in viscosity.

[0007] EP1918315A1 involves mixing a polyol with solid NDI at a temperature of 80-240°C. A method for producing NDI prepolymer is described. Here, the temperature is the temperature of the solid isocyanate The material is selected to melt during the exothermic reaction. After obtaining a transparent, homogeneous molten material, The prepared prepolymer is rapidly cooled.

[0008] For WO02081537A1, the polyol was first added at 140°C, followed by vigorous stirring. A method for preparing an NDI prepolymer by reacting it with solid NDI under mixing conditions is described.

[0009] DE10060473A1 contains naphthalene 1,4-diisocyanate or, as a comparison, The preparation of a prepolymer based on naphthalene 1,5-diisocyanate is described. Before adding the corresponding diisocyanate while stirring, first fill with polyol, 1 Dehydrate at 20°C and 20 mbar. Then, add the reaction mixture at 20 mbar and 125-1 Stir at 30°C for 15 minutes.

[0010] WO2015185659A1 contains a molten material of diisocyanate and polyol in a tubular inverted form. A method for the continuous preparation of NDI prepolymers, involving reaction in a reactor at 80-175°C, is described. This application, like EP1918315A1, concerns the chemical administration of diisocyanates. Engineering problems are also discussed. Therefore, for a controlled reaction in which the molecular weight increases uniformly, , heating is first required to enable rapid melting of the NDI, and then, after reaching the clearing point, rapid cooling is necessary so that the reaction temperature does not rise clearly above 127 °C during the course of the exothermic reaction. The continuous method can avoid some of the problems associated with the batch method, but ultimately it is less flexible and has not been established to date because of its inherently high chemical engineering complexity. In the described batch-like reverse prepolymer method, i.e., the method in which the polyol component is first charged and then the isocyanate is added, the reactor with each batch undergoes a change from OH- to NCO-functional content. This results in a more pronounced tendency of the method to fluctuations compared to the normal prepolymer

[0011] method where such a change does not occur. In such a regular prepolymer method, for example, by gradually metering in the lacking reactants, the latter is always supplied with an excess amount of reactants, thereby ensuring a very homogeneous reaction. This option for reaction control does not exist in the reverse prepolymer method where various excesses are inevitably present. To minimize problems, the change from the OH-dominant regime to the NCO-dominant regime must be carried out as quickly as possible, which means that the excess component, i.e., the isocyanate in this case, must be provided to the reaction very quickly. Nevertheless, as is clear from the prior art, the reverse prepolymer method has been established as an intermediate step in the production of high-quality cast elastomers. This is especially due to the use of solid isocyanates. When using the normal prepolymer method, these need to be charged first and melted at high temperature first, and the isocyanate In order to minimize problems, the change from the OH-dominant regime to the NCO-dominant regime must be carried out as quickly as possible, which means that the excess component, i.e., the isocyanate in this case, must be provided to the reaction very quickly. Nevertheless, as is clear from the prior art, the reverse prepolymer method has been established as an intermediate step in the production of high-quality cast elastomers. This is especially due to the use of solid isocyanates. When using the normal prepolymer method, these need to be charged first and melted at high temperature first, and the isocyanate This is especially due to the use of solid isocyanates. When using the normal prepolymer method, these need to be charged first and melted at high temperature first, and the isocyanate needs to be melted first at high temperature. ​​Undesirable side effects are already occurring.

[0012] A simple scale that can be used to indicate the extent to which side reactions have progressed during prepolymer formation. The degree is based on the NCO content of the prepolymer, i.e., the total mass of the prepolymer in percent. This is the mass of the isocyanate group. The stoichiometry of the main reaction of the two components is that which exists in the depletion state. Assuming that the reactive components for the NCO group are completely converted, the NC of the prepolymer It can be used to verify the theoretical value regarding the O content of the prepolymer. The further the O content deviates from this theoretical value, that is, the lower it is, the higher the NC The oxygen group reacts with other groups, for example, with a urethane group that gives allophanate, uretdione, Reaction with isocyanurates, or other isocyanate groups that form nylon 1, It has become more frequently involved in reactions with urea groups that form biuret. [Prior art documents] [Patent Documents]

[0013] [Patent Document 1] EP1918315A1 [Patent Document 2] WO02081537A1 [Patent Document 3] DE10060473A1 [Patent Document 4] WO2015185659A1 [Overview of the project] [Problems that the invention aims to solve]

[0014] The problem addressed by this invention is to produce a prepolymer from solid diisocyanate in a simple and inexpensive way. The goal was to manufacture the product legally and with minimal by-product generation. [Means for solving the problem]

[0015] Surprisingly, NCO prepolymers based on solid diisocyanates The base component consists of solid diisocyanate particles having a particle size between 0.1 mm and 4 mm. By using the essential bulk material, a simple and inexpensive method can be used to produce good quality It was then discovered that it could be prepared using low-level by-products.

[0016] The present invention relates to a batter containing or consisting of a diisocyanate solid at room temperature (25°C). A Luk material, comprising a twin sheave array having mesh sizes of 0.1 mm and 4 mm. In the sieve analysis of bulk materials using a known method, at least 90 times the weight of the bulk material It is particularly important that a certain percentage, preferably at least 95% by weight, is obtained in fractions of 0.1 mm to 4 mm. To provide a bulk material that is characteristic of the subject.

[0017] Sieve analysis was performed according to ASTM 1921-89, comparing the sieving time to the standard. The process will be shortened to 5 minutes.

[0018] The particles from this sieve fraction are used in the prepolymer by an industrially established reverse batch method. It is particularly suitable for preparation. As described above, the equivalence points cross in the reverse batch method, and long polymer chains To avoid the formation of a gel and the resulting increase in viscosity until gelation, this is done very carefully. It is known that crossover must occur rapidly. However, isocyanates alone Rapid addition is insufficient for this purpose. Instead, melting, dissolving, and mixing are necessary. The combination procedure ensures that the isocyanate group is truly available in the co-reactant. Both are necessary. Within larger particles, the temperature rises in the absence of the desired co-reactants. It is possible that isocyanate groups may already be undergoing side reactions with each other. Specifically, the upper limit of particle size in the bulk material of the present invention is the isocyanate in the reaction mixture. This results in rapid melting and mixing, and therefore, rapid achievement of the clear point and uniformity of molecular weight. This leads to an increase. The lower limit of the size is undesirable, firstly for occupational health reasons, and secondly This helps to significantly avoid dust that causes technical problems. Large surface dust particles The product promotes side reactions. For example, a reaction occurs between a normally hygroscopic isocyanate and moisture. This can lead to the formation of poorly soluble urea. Complete elimination of air, and therefore air humidity, is necessary on an industrial scale. And, from the standpoint of handling solids, it is almost impossible to achieve. In particular, the dust fraction is Depending on the mixture, it may be difficult to easily and completely disperse it in the reaction mixture, and it may adhere to the surface. Alternatively, it may remain as suspended matter in the gaseous space above the liquid surface for a while. This is because it affects the stoichiometry of the reaction and promotes undesirable side reactions.

[0019] The bulk material is preferably free-flowing. This is because Granu Heap (Gra Bulk with an angle of repose of ≤55°, preferably ≤50°, as measured by Nutools. It is understood to mean the material. The reason for the high fluidity of the bulk material of the present invention is essentially the main This refers to the particle size or particle size distribution. Preferably, the bulk material has a particle size of <0 in sieve analysis. The particles obtained in the 0.1 mm fraction should be 5% by weight or less, preferably 3% by weight or less, more preferably 3% by weight or less. It contains 2% by weight or less. Such bulk materials have good fluidity, making them suitable for transport containers. It enables optimal emptying and simple pneumatic transport of bulk materials.

[0020] Preferably, the bulk material of the present invention contains a diisocyanate solid at room temperature or This is a bulk material consisting of twin meshes with mesh sizes of 0.2 mm and 3 mm. In sieve analysis of bulk materials using a known method with a sieve array, at least 90 wt %, preferably at least 95% by weight of bulk material in fractions between 0.2 mm and 3 mm It is characterized by being obtained. The term "undersize" indicates the lower limit of the corresponding fraction. It is understood to mean particles smaller than defined. In sieving analysis, It is shaped to pass through a fine sieve and fall, or to be able to fall. The term "oversize" refers to a size larger than the upper limit specified for the corresponding fraction. It refers to particles. Therefore, in sieve analysis, coarser particles are found on higher sieves. It remains.

[0021] For analyses with a mesh size of 0.1-4 mm, 90% by weight of the bulk material is 0. When obtained in fractions of 1-4 mm, or when analysis with a mesh size of 0.2-3 mm is performed. In this case, if obtained in fractions of 0.2 to 3 mm, the bulk material is preferably 5% by weight or less. This includes oversized and undersized (5% or less by weight).

[0022] In a further preferred embodiment, the bulk material is ≥9 based on the total mass of the bulk material. 8% by weight, preferably ≥99% by weight, more preferably ≥99.5% by weight of solid diisocia It contains nates. Further components include, for example, by-products from the production of diisocyanates. It may be a monoisocyanate, solvent residue, or chlorination by-product.

[0023] A suitable solid diisocyanate is solid at room temperature, i.e., has a melting point above 25°C. These are diisocyanates. For example, methylene 2,2-diisocyanate, Methylene 2,4-diisocyanate, methylene 4,4-diisocyanate, naphthalene 1 ,4-diisocyanate, naphthalene 1,5-diisocyanate, naphthalene 1,8-di Isocyanates, phenylene 1,3-diisocyanate, phenylene 1,4-diisocyanate Isomers of tetralin 2,3-diisocyanate and tetralin 2,4-diisocyanate. Nate, tetralin 2,5-diisocyanate, tetralin 3,4-diisocyanate, o-Toluidine diisocyanate, durenidine diisocyanate, benzidine diisocyanate It is a compound and / or anthrylene 1,4-diisocyanate. It has a melting point of 80°C or higher. Diisocyanates containing naphthalene 1,5-diisocyanate or f Enium 1,4-diisocyanate is very, particularly preferred.

[0024] The present invention further provides a method for producing bulk material according to the present invention. For this purpose, Diisocyanates are first phosgenated by the corresponding amine in a known manner. It is prepared by [method]. A phosgene-free method, such as thermal urethane cleavage, is also possible, but these The preparation of solid diisocyanates has not been established on an industrial scale for various reasons. High melting point diisocyanates, for example, naphthalene 1,5-diisocyanate or phenyl One option for len-1,4-diisocyanate is described in WO2014044699. This is a suspension phosgenation as described. To separate the diisocyanate from the solvent, And methods available for further purification include methods known to those skilled in the art, for example, optionally Crystallization, sublimation, or distillation may be performed, possibly with the addition of seed crystals or azeotropes. In the context of pulses, the term "crystallization" is also understood to mean a simple coagulation process. Therefore, Obtaining crystalline materials is not absolutely necessary; for example, even amorphous solid precipitates are not required. It satisfies the requirements.

[0025] In the first embodiment, the method for producing the bulk material of the present invention is a crystallization operation (i) The following are selected from the group consisting of classification, agglomeration, and grinding. The process includes at least one step (ii), preferably step (ii) being aggregation and / or The process is grinding, and more preferably, step (ii) is grinding.

[0026] In a preferred embodiment of this method, the crystallization operation (i) is performed on a cooled surface, preferably a cooled surface. Cooled rotating drum flaker on a belt or rotating drum flaker, more preferably from the inside Crystallizing a molten solid diisocyanate on a raker, and then scraping it off after solidification. It is done by [the specified method].

[0027] The thickness of the crystallized solid diisocyanate layer on the cooled surface is determined here by the crystallization operation. Depending on the operating parameters, the temperature of the molten material and the cooled surface, as well as the cooling... This can be adjusted by the forward speed of the surface. Preferably, the thickness of the layer is ≥0.1 The range is mm and ≤4.0 mm, more preferably ≥0.2 mm and ≤3.0 mm. The range is, most preferably, ≥0.5mm and ≤2.5mm. Thus, particles that already have a favorable degree in one dimension are obtained in a later step, which is, Firstly, it has a positive effect on the melting properties of the finished bulk material, and secondly, the bulk according to the present invention Simplifies further processing required to provide the material.

[0028] Preferably, the crystallized diisocyanate is cooled using a scraper blade. It is removed from the surface. Here too, the shape of the particles is influenced by the positioning and shape of the blade. It is already possible to give it.

[0029] In the crystallization operation (i), one of the particles of the shape and size required for the bulk material according to the present invention is produced. Only the portion has already been obtained. Therefore, the method according to the present invention involves classification, agglomeration, and grinding. At least one further step is required, selected from the group consisting of the following.

[0030] In embodiments of this method in which classification is selected as step (ii), this is preferably By a dry method, that is, by separating a gas, preferably nitrogen or air, more preferably nitrogen Used as a separation medium, by means of sieving or by means of air sieving This is carried out. Classification by sieving is preferred. The particles are sieved by methods known in themselves. By means of this, it is separated into various fractions, thereby the bal according to the present invention One or more fractions containing the substance can then be selected. In the process, a certain proportion of the particles have a high aspect ratio, and therefore, in each case Exclude any sieves that are larger than at least one dimension of the mesh size used. This is impossible. This is not important for the bulk material of the present invention. Such particles only slightly impair the melting and mixing properties in the reverse prepolymerization method. This is because it does not. Excessively large particles or excessively small particles, that is, claim 1 Particles that cannot be obtained in the night sieve fraction can be recycled back into this method and recrystallized. Alternatively, or in addition to this, excessively large particles can be ground in the grinding device. .

[0031] In embodiments of the method according to the present invention in which aggregation is selected as step (ii), this is, Preferably, this is done in a drying form by sintering or molding press. This embodiment has a high crack The primary particles, i.e., the particles obtained after the crystallization operation, are used in the bulk material according to the present invention. This is particularly advantageous when the particle size is too small to be used for that purpose. Alternatively, this embodiment also, A sieve that yields small particles in a controlled manner, which are then aggregated to a desired size and returned to the surface. It is advantageous in combination with a separation or grinding process. In this way, very limited valve It is possible to manufacture the material. Compression molding, such as pelletizing or tableting, is preferred. This results in very uniform particles and good fluidity for the bulk material composed of them. Rasu.

[0032] In a preferred embodiment of the method according to the present invention in which grinding is selected as step (ii), this This is carried out in a grinding device. Preferably, one suitable for this purpose is one designed for dry operation. This is a conventional pulverizing device. For example, the roll gap through which the applied particles are pulverized is shared It is possible to use a grinding device consisting of two or more rotating rolls that form particles. This uses a so-called screw roll crusher, which crushes the material using a reverse-rotating screw mechanism. It is also possible to do this. The discharged crushed bulk material can be processed to achieve the desired particle size as needed. To that end, at least partially to a grinding device having a smaller grinding gap as needed. It can be reverted and reinstalled.

[0033] Preferred grinding devices are hammer mills or knife mills. A standard knife mill is, It typically has a cylindrical grinding space. The stator blade protrudes into this space from the outside, while, A rotary drum with outward-facing cutting blades rotates inside. Alternatively, a perforated screen is placed around the grinding space, and the ground particles leave the grinding space. On the other hand, it is preferable that excessively large particles are retained and further crushed. The material can be introduced into the grinding space in the axial or radial direction. It is particularly preferable to use a Marmill. The rotor rotates here within the grinding chamber, The hammer is equipped with a movable or fixed hammer. The impact of the hammer on the crushed material fragments is It is crushed, collides with the milling wall, and further crushing takes place there. About knife mills As already explained, here too, a sieve, preferably a perforated screen, is placed around the grinding space. This arrangement allows particles smaller than the maximum particle size to pass through and exit the grinding space. The process only involves upper particle limiting, and this is followed by blowing the bulk material if necessary. Dust removal is performed by sorting or sieving.

[0034] In a further preferred embodiment of this method, any existing oversize or undersize - The size is determined in process (iii) by classification from the bulk material obtained in process (iii) This is removed, at least partially, and classification is preferably done by sieving or wind sieving. This is more preferably done by sieving, and is not excessively large and / or excessively small. The sap particles are recycled in the method, at least partially, i.e., melted or dissolved and recycled. The material is then subjected to crystallization operation (i). If step (ii) involves grinding, excessively large particles are replaced. It can be recycled back into the crushing equipment.

[0035] The present invention further relates to the preparation of bulk materials according to the above description in NCO-terminated prepolymers. Provides the use of.

[0036] The present invention further comprises or comprises at least one isocyanate solid at room temperature. The reaction involves a reaction between one component (A) and at least one isocyanate-reactive component (B). or a method for preparing an NCO-terminated prepolymer consisting thereof, wherein component (A) is the above The present invention provides a method characterized by being equivalent to a bulk material.

[0037] The isocyanate-reactive component (B) preferably includes a polyol.

[0038] Suitable polyols for the production of prepolymers are, for example, 400-8000 g / mol, preferred More specifically, 600-6000 g / mol, more preferably 1000-3000 g / mol Average molecular weight M n It has the following properties. Their hydroxyl values ​​are 22-400 mgKOH / g, preferably More preferably, 30-300 mg KOH / g, and more preferably 40-250 mg KOH / g. These are OH tubes with a size of 1.5 to 6, preferably 1.7 to 3, more preferably 1.9 to 2.2. It has potential value.

[0039] Polyols for producing prepolymers are known organic polyols in polyurethane technology. These are hydroxyl compounds, such as standard polyester polyols and polyacrylates. Polyol, polyurethane polyol, polycarbonate polyol, polyether polyol Liol, polyester polyacrylate polyol and polyurethane polyacrylate Polyol, polyurethane polyester polyol, polyurethane polyether polyol Polyurethane polycarbonate polyol, polyester polycarbonate polyol Polyester, phenol / formaldehyde resins, or mixtures thereof. Polyols, polyether polyols, polyacrylate polyols, or polycarbonates Nat polyols are preferred, as are polyether polyols, polyester polyols and Polycarbonate polyols are particularly preferred. Polyester polyols are the most preferred. That is the case.

[0040] Examples of polyether polyols include styrene oxide, ethylene oxide, and propyl Fluorine oxide, tetrahydrofuran, butylene oxide, epichlorohydrin, and so These mixed addition and graft products, as well as polyaddition products of polyhydric alcohols or so Polyether polyols and polyhydric alcohols obtained by condensation of these mixtures, Polyether polyols obtained by alkoxylation of mine and amino alcohols It contains. Suitable hydroxy-functional polyethers are 1.5 to 6.0, preferably 1. Having an OH functional value of 7-3.0, more preferably 1.9-2.2, and 22-400, It has an OH value of 30 to 300, more preferably 40 to 250 mg KOH / g, and 400-8000g, preferably 600-6000g, more preferably 1000-3000g Molecular weight M / mol n These have, for example, the alkoxy functional starting molecules of hydroxyl functional starting molecules. Xylation products, for example, ethylene glycol, propylene glycol, butanediol , hexanediol, trimethylolpropane, glycerol, pentaerythritol, Sorbitol, or mixtures thereof, and also other hydroxy-functional compounds and ethyl It is a mixture with ammonium oxide, propylene oxide, or butylene oxide.

[0041] Examples of polyester polyols with good compatibility include di- and optionally tri- and Tetraols, as well as di- and optionally tri- and tetracarboxylic acids or hydroxycarboxylic acids. It is a known polycondensate of a carboxylic acid or lactone. Instead of a free polycarboxylic acid, To prepare the ester, use the corresponding polycarboxylic acid anhydride or the corresponding lower alcohol. It is also possible to use polycarboxylic acid esters of ethyl acetate. A suitable example of a diol is ethyl acetate. Glycol, butylene glycol, diethylene glycol, triethylene glycol, Polyalkylene glycols, such as polyethylene glycol, and propane-1,2- Diol, propane-1,3-diol, butane-1,3-diol, butane-1,4- Diols, hexane-1,6-diols and their isomers, neopentyl glycol or It is opentyl glycol hydroxypivalate, and the latter three compounds are preferred. In order to achieve an energy value > 2, in some cases, a polyol with a functional value of 3 in proportion is used, for example Trimethylolpropane, glycerol, erythritol, pentaerythritol, tri Methylolbenzene or trishydroxyethyl isocyanurate can be used. Useful dicarboxylic acids include, for example, phthalic acid, isophthalic acid, terephthalic acid, Tetrahydrophthalic acid, hexahydrophthalic acid, cyclohexanedicarboxylic acid, adipine Acids, azelaic acid, sebacic acid, glutaric acid, tetrachlorophthalic acid, maleic acid, fumaroles Glucosic acid, itaconic acid, malonic acid, suberic acid, 2-methylsuccinic acid, 3,3-diethylglycerin This includes taric acid and 2,2-dimethylsuccinic acid. The anhydrides of these acids are present in the presence of these acids. In that case, it can be used similarly. Therefore, for the purpose of the present invention, the anhydride is "acid" This is covered by the expression: If the average functional value of a polyol is ≥ 2, then benzoin Acids and monocarboxylic acids such as hexanecarboxylic acid can also be used. A saturated aliphatic or aromatic acid such as chlorophosphate or isophthalic acid is preferred. Here, a smaller amount An example of a polycarboxylic acid for optional additional use in any quantity is trimellitic acid. It can also be used as a co-reactant in the production of polyester polyols having a roxyl group. Examples of hydroxycarboxylic acids include hydroxycaproic acid, hydroxybutyric acid, and hydroxycaproic acid. It includes xydecanoic acid, hydroxystearic acid, etc. Usable lactones include ε- This includes caprolactone, butyrolactone and its congeners, as well as butanediol and / or Neopentyl glycol and / or hexanediol and / or ethyleneglycol Coal and / or diethylene glycol and adipic acid and / or phthalic acid and / or polyester polyols based on isophthalic acid are preferred. Butanediol Adipine and / or neopentyl glycol and / or hexanediol and adipine Polyester polyols based on acids and / or phthalates are particularly preferred. ε - Linear polyester diols based on caprolactone are also particularly preferred.

[0042] Useful polycarbonate polyols include carbon dioxide derivatives, such as diphenyl carbonate. It can be obtained by the reaction of dimethyl carbonate or phosgene with a diol. Useful diols of the species include, for example, ethylene glycol, propane-1,2- and 1,3-diol, butane-1,3- and 1,4-diol, hexane-1,6-diol All, octane-1,8-diol, neopentyl glycol, 1,4-bishydrox methylcyclohexane, 2-methylpropane-1,3-diol, 2,2,4-trimethyl Tylpentane-1,3-diol, dipropylene glycol, polypropylene glycol , dibutylene glycol, polybutylene glycol, bisphenol A, tetrabrom It contains sphenol A and lactone-modified diols. Preferably, the diol component This is 40% to 100% by weight of hexane-1,6-diol and / or hexanedi All derivatives, preferably those having not only terminal OH groups but also ether or ester groups. For example, 1 mole of hexanediol and at least 1 mole, preferably 1 to 2 moles of ε -The product obtained by reaction with caprolactone, or G or trihexylene The product obtained by the etherification of hexanediol, which gives recall, Contains. Polyether polycarbonate polyol can also be used. Tyl carbonate and hexanediol and / or butanediol and / or Polycarbonate polyols based on ε-caprolactone are preferred. Dimethyl caprolactone Polycarbonate and hexanediol and / or ε-caprolactone-based Recarbonate polyols are particularly preferred.

[0043] Suitable polyacrylate polyols include, for example, olefinic polyols having hydroxyl groups. By free radical polymerization of saturated monomers, or by olefins having a hydroxyl group. A olefinic unsaturated monomer and any other olefinic unsaturated monomer, for example, ethyl acrylate. acrylate, butyl acrylate, 2-ethylhexyl acrylate, isobornyl acrylate methyl methacrylate, ethyl methacrylate, butyl methacrylate, cyclomethacrylate Xyl methacrylate, isobornyl methacrylate, styrene, acrylic acid, acrylo Obtained by free radical copolymerization with nitriles and / or methacrylonitrile. A suitable olefinic unsaturated monomer having a hydroxyl group is, in particular, 2-hydroxy. Ethyl acrylate, 2-hydroxyethyl methacrylate, propyl acrylate on acrylic acid Mixture of hydroxypropyl acrylate isomers that can be obtained by the addition of an oxide The substance, and the hydr which can be obtained by adding propylene oxide to methacrylic acid It is a mixture of roxypropyl methacrylate isomers. A suitable free radical initiator is A Zo compounds, for example, those from the group azobis(isobutyronitrile), or peroxides, e.g. For example, it comes from the group of di-tert-butyl peroxides.

[0044] The polyols described can be used individually or in mixtures.

[0045] The isocyanate-reactive compound of component (B) is the isocyanate (single) of component (A) Reacting with (or multiple) isocyanate groups in excess of isocyanate reactive groups This yields an NCO-terminated prepolymer containing urethane groups. The quantitative ratio here is iso- The calculated (theoretical) NCO content of the anate component is preferably 2.5% to 6.0%, preferably It is an excess, in the range of 3.0% to 5.0%.

[0046] Additives may be used further in the preparation of the prepolymer. Suitable additives include catalysts. emulsifiers, UV and hydrolysis stabilizers, and preferably typical in polyurethane chemistry. It is a stabilizer used for general purposes. For example, see "Kunststoff Handbuc h[Plastics Handbook]vol.7, ed.G.Oertel,19 Seen in "83, Carl Hanser Verlag, Munich, Vienna" It is possible.

[0047] Examples of catalysts include trialkylamines, diazabicyclooctane, and dibutyltin dilaurate. N-alkylmorpholine, lead octanoate, zinc octanoate, calcium octanoate and magnesium octanoate, as well as the corresponding naphthenate, p-nitrophenoxide And so on.

[0048] Examples of suitable UV and hydrolysis stabilizers include 2,6-di-tert-butyl-4-methyl These are phenols and carbodiimides.

[0049] Suitable stabilizers include Brønsted acids and Lewis acids, such as hydrochloric acid and benzoyl chloride. Dibutyl phosphate, adipic acid, malic acid, succinic acid, pyruvic acid, citric acid, etc. Alkyl- and aryl sulfonic acids, for example, p-toluenesulfonic acid, and It is dodecylbenzenesulfonic acid.

[0050] This method preferably involves first adding the isocyanate-reactive component (B) as already described above. This is a reverse prepolymerization method in which an isocyanate component (A) is metered and supplied after filling. The nate-reactive component (B) is initially filled here in liquid form, i.e., in solution or melt. The mixture is filled, while component (B) is in the form of a bulk material, i.e., a solid, preferably stirred. While doing so, it is added to and mixed with the polyol component. This causes the bulk material to melt, It reacts with the polyol component. The reaction temperature here is preferably in the range of 80 to 160°C. More preferably, the temperature is in the range of 100 to 150°C.

[0051] More preferably, the NCO-terminated prepolymer is prepared in a batch manner using a reverse prepolymerization method. ru.

[0052] The NCO prepolymer prepared by the method of the present invention is preferably 2.5% to 6.0%. It has an NCO content of 3.0% to 5.0%, and a saturation level of 1000 to 12000 mPas / 70℃. Preferably 2000~10000 mPas / 70℃ according to DIN EN ISO 3219 It has a viscosity and can be advantageously used in the manufacture of solid or cellular elastomers. [Examples]

[0053] Examples raw materials: CAPA TM 2161A: Molecular weight 1600Da and OH functional value of 2 (OH value 70m) Poly-ε-caprolactone diol from PERSTORP, containing g KOH / g.

[0054] The theoretical NCO content of each prepolymer listed below was 4.07%.

[0055] Example 1 (Non-inventive, particles are too small): First, a typical bulk material containing 99.7% by weight of naphthalene 1,5-diisocyanate A sample was prepared using a twin sieve array (mesh diameter 4 mm, 0.1 mm square mesh). The samples were classified by method, divided into three fractions, and their weight ratios were determined. (0.1mm~4mm) This fraction accounts for 88% by weight of the total mass of the bulk material, and fractions exceeding 4 mm are Fractions with a weight of 1% were present, while fractions smaller than 0.1 mm had a weight of 11%.

[0056] First, put 100g of CAPA into a glass flask. TM Charge 2161A under a nitrogen atmosphere. Next, the mixture was heated to 125°C using an oil bath. Then, the mixture that had been previously analyzed by sieving was used. 25.94 g of Luk material was added while stirring. The reaction mixture reacted exothermically, reaching 135 The maximum temperature reached °C. After 30 minutes, the still cloudy mixture was rapidly cooled. The NCO content of the repolymer was 3.82%.

[0057] Example 2 (Invention): First, a typical bulk material containing 99.7% by weight of naphthalene 1,5-diisocyanate A sample was prepared using a twin sieve array (mesh diameter 4 mm, 0.1 mm square mesh). The material was classified by various methods, and the resulting fraction was divided into three parts. The fraction from 0.1 mm to 4 mm was the bulk material. It accounts for 96.6% of the total mass, and fractions exceeding 4 mm account for 1% of the total mass. Fractions smaller than 0.1 mm accounted for 2.4% by weight.

[0058] First, put 100g of CAPA into a glass flask. TM Charge 2161A under a nitrogen atmosphere. Next, the mixture was heated to 125°C using an oil bath. Then, the mixture that had been previously analyzed by sieving was used. 25.94 g of Luk material was added while stirring. The reaction mixture reached 134°C during the exothermic reaction. The reaction mixture reached its maximum temperature and became completely clear. After 30 minutes, the solution was rapidly cooled. The NCO content of the obtained prepolymer was 3.90%.

[0059] Example 3 (Non-inventive, 10% oversized particles): First, a typical bulk material containing 99.7% by weight of naphthalene 1,5-diisocyanate A sample was prepared using a twin sieve array (mesh diameter 4 mm, 0.1 mm square mesh). The fractions were classified by method and then divided into three parts. The fractions from 0.1 mm to 4 mm were divided into three parts. It has 88% by weight of the total mass of the material, and fractions exceeding 4 mm make up 10% by weight. Fractions of less than 0.1 mm had a proportion of 2% by weight.

[0060] First, put 100g of CAPA into a glass flask. TM Charge 2161A under a nitrogen atmosphere. Next, the mixture is heated to 125°C using an oil bath. Then, the mixture that was previously analyzed by sieving is used. Add 25.94g of the Luk material while stirring. The reaction mixture will reach 134°C during the exothermic reaction. It reaches its maximum temperature. After 30 minutes, the reaction mixture still contains solid flakes and rapidly The mixture was cooled. The NCO content of the prepolymer was 3.79%.

[0061] Example 4 (Invention): The fractions of 0.2 mm to 3 mm were treated with 99.7% by weight of naphthalene 1,5-diisocyanate. From bulk material including twin sieve arrays (square mesh with mesh diameters of 3 mm and 0.2 mm) Bulk material isolated by classification using a mesh (means) where more than 99% of the particles belong to this fraction. A material was obtained. Using this, a prepolymer was prepared as in Example 2. The NCO content of the rimar was 3.91%.

Claims

1. A bulk material containing a diisocyanate solid at room temperature (25°C), with mesh size For sieve analysis of bulk materials using a twin sieve configuration with sieves of 0.1 mm and 4 mm. In this process, at least 90% by weight of the bulk material is obtained in fractions between 0.1 mm and 4 mm. The bulk material is characterized in that sieve analysis is performed by the method described herein. Fee.

2. The claim is characterized by containing 5% by weight or less of particles obtained in a fraction of less than 0.1 mm. The bulk material described in item 1.

3. Sieve analysis using a twin sieve configuration with mesh sizes of 0.2 mm and 3 mm. In this process, at least 90% by weight of the bulk material is obtained in fractions between 0.2 mm and 3 mm. The bulk material according to claim 1 or 2, characterized in that it can be used.

4. It contains 5% or less by weight of oversize and 5% or less by weight of undersize. A bulk material characterized by any one of claims 1 to 3.

5. The bulk material is characterized by having a solid diisocyanate content of 98% by weight or more. The bulk material according to any one of claims 1 to 4.

6. The solid diisocyanate is a diisocyanate having a melting point of ≥80°C. A bulk material characterized by any one of claims 1 to 5.

7. Crystallization operation (i) and at least one selected from the group consisting of classification, agglomeration and grinding. A method for producing a bulk material according to any one of claims 1 to 6, comprising step (ii) of the above.

8. In the crystallization operation (i), the molten solid diisocyanate is brought to a low temperature surface, preferably It is characterized by crystallization on a cooling belt or rotating drum flaker, followed by scraping after solidification. The method according to claim 7.

9. As step (ii), the crystallized diisocyanate is crushed in a crushing device, preferably in The method according to claim 7 or 8, characterized in that it is carried out in a mill or knife mill. 。

10. Oversize and undersize are classified in process (iii) ii) At least partially separated from the bulk material obtained in ii), the classification is preferably This is done by sieving or wind sieving, and is not excessively large and / or excessively small. The particles are, at least partially, recycled back into the method, according to any of claims 7 to 9. A method using one of the following methods.

11. At least one component (A) containing or consisting of an isocyanate solid at room temperature The reaction involves or consists of a reaction with at least one isocyanate-reactive component (B). A method for producing an NCO-terminated prepolymer, wherein component (A) is described in any of claims 1 to 5. The method, characterized in that it corresponds to the bulk material shown.

12. The method according to claim 11, which is a reverse prepolymerization method.

13. The method according to claim 11 or 12, wherein the manufacturing is carried out in a batch manner.

14. An NCO-terminated prepolymer obtained by the method described in any one of claims 11 to 13.

15. Polyurethane elastomer obtained using the NCO-terminated prepolymer described in claim 14 —.