Polyisocyanate crosslinking composition and its preparation
(57) Abstract:The invention relates to the production of a mixture of polyfunctional isocyanates and use it as an isocyanate component and simultaneously cross-linking agent when receiving both hard and flexible foams. It is claimed a method of obtaining a polyisocyanate cross-linking composition to obtain a polyurethane foam containing a polyisocyanate and 2,4,6-triisocyanate, namely, that the solution of phosgene in chlorobenzene was added a solution of fused mixture polyamine with 2,4,6-triaminotoluene in chlorobenzene at mass ratio 85-98 : 2-15, respectively, at 0-10°C, followed by postironium with increasing temperature up to 130°C until the disappearance formed in the reaction of a suspension of the amine hydrochloride. The invention allows to obtain a mixed isocyanate component, corresponding to the existing norms and standards, without the increased cost of production. 7 table. The invention relates to the production of a mixture of different polyfunctional isocyanates and use it as an isocyanate component and simultaneously cross-linking agent upon receipt of polyurethane foams, namely politician is="ptx2">Isocyanate mixture consists of MDI (PIZ) and 2,4,6-triisocyanate (TICT). PIZ is a mixture of isocyanates: 4,41-metaldependent, triisocyanate and MDI. The present three - and polyisocyanates create the mesh structure, thereby acting as cross-linking agents, however, each additional functional group in the PIZ leads to an increase in molecular weight. The presence of a mixture trifunctional monomer (2,4,6-TEST) allows to obtain more regular structure, and varying the amount enables you to predict and correlate the physico-mechanical properties of the polymer.As the prototype was selected polyisocyanate composition which is a mixture of PIZ and triisocyanate obtained by partial trimerization PIZ [U.S. patent No. 4382125, MKI class. C 08 G 18/14, NCI 521/160. Isocianurate-modified polymethylen polyphenylene polyicocyanate compositions. //Narayan T., Kan, P. T., J. T. Patton - States. 30.11.81. Publ. 03.05.83]. The mixture PIZ and Tris-2,4,6-(isocyanatomethyl)-1,3,5-triazine is obtained by transformation of a part of PIZ under the action of tertiary amines at a temperature of 30-60°C for 1-12 h in the above-mentioned triazine containing the latter from 19.7 to 32.3%. Before applying isocyanate polyisocyanate compositions containing triisocyanate crosslinking agent requires additional chemical stage of trimerization with subsequent deactivation of the catalysts, which complicates the process of obtaining the isocyanate component of the polyurethane foam and, in addition, this method is unsuitable for obtaining the proposed kopazicii containing PIZ and TEST.To obtain 2,4,6-triisocyanate, which is an integral part of the composition, there are several ways. The most Mature and commonly used are: a method of hot-vosganian hydrochloride triaminotoluene in the environment of chlorobenzene [Application Germany No. 3132923, MKI class. C 07 C 119/048. Verfahren zur Herstellung von 2,4,6-Triisocyanato-toluol. //L. Schuster - AV. 20.08.81. Publ. 03.03.83], the second method is a two-stage vosganian of triaminotoluene, and the first stage is carried out at temperatures close to 0°C and the second at boiling solvent [W. Siefken Mono - und Polyisocianate. //Annalen der Chemie, - 1949, - Bd.562, Heft 2. - S. 75-136]. Due to the poor solubility of triaminotoluene in organic solvents commonly used for the reaction of vosganian, the two-stage method is not suitable.As a prototype obtain a polyisocyanate cross-linking composition was chosen as the method of formation of 2,4,6-triisocyanate who sees getting clean TEST, carried out at a temperature of 110-130°C with constant bubbling phosgene within 36-48 hours until complete disappearance of sediment (hydrochloride of triaminotoluene). Then dispersing the reaction mixture. The length of the process, as well as the formation of significant quantities of products resinification complicate the process. The implementation of the method requires acquisition of amine hydrochloride, which is unnecessary technological stage. To the listed drawbacks and the fact that TEST is a solid product, so its direct use in polyurethane foam (PUF) compositions, production technology which involves the dosing of liquid isocyanate component, it is impossible.The present invention is the creation of a new polyisocyanate crosslinking compositions and methods of its receipt of reducing the number of process steps, the acceleration reaction vosganian, reducing the formation of resinous products and at the same time the preparation of the solution TEST in the PITZ in liquid form suitable for processing in foam.This object is achieved polyisocyanate cross-linking composition comprising a polyisocyanate and polyisocyanate and is the compared components, wt.%:PIZ 97.5-82TEST 2.5-18and by the way it is received by vosganian mixture polyamine and polyamidoamine in chlorobenzene at a temperature of 0-10°C, followed by raising the temperature to 130°C; characterized in that as polyamidoamine take triaminotoluene and forgenerating subjected fused mixture polyamine and triaminotoluene at a ratio (wt.%) 98-85 : 2-15, respectively.The proposed method provides for immediately mixed isocyanate component method joint vosganian polyamine (PA) and 2,4,6-triaminotoluene (TAT). The mixture of amines are prepared by fusing the necessary quantities PA and TAT. The molten mixture was introduced in chlorobenzene and held vosganian first at a temperature of 0-10°C., and then gradually heated the reaction mass to 130°C and boiled it with constant bubbling phosgene. Then drove the solvent, and the product was subjected to "hardening" and analyzed in accordance with THE 113-03-413-89. Thus obtained product can be used for the synthesis of polyurethane foam without further processing. The proposed method allows to obtain a new isocyanate mixed component without additional technology development, as aesca the solvent in this case is not a hindrance for the implementation of the process, the addition of TAT to polyamino did not exceed 15% (the maximum number of cross-linking agent in recipes), a mixture of amines were completely dissolved in chlorobenzene. Received mixed isocyanate component liquid. We offer the use of a mixture of MDI with 2,4,6-triisocyanate, the receipt of which fits into the technology of the MDI without special complications of the process, does not lead to the appreciation of the isocyanate component.Example 1. Vosganian mixture of amines.Alloy 2.5 g TAT and 47.5 g PA. The melt is then poured into 350 ml of dry chlorobenzene. In chetyrehkolkoy flask equipped with a stirrer, thermometer and addition funnel, zakolerovat in an ice bath 150 ml of dry chlorobenzene and poured there 54 ml (79.5 g) condensed phosgene (1.5-fold excess). To a solution of phosgene in chlorobenzene with stirring is added dropwise freshly prepared solution of amines with such speed that the temperature of the reaction mixture did not rise above 10°C. After the addition is addition funnel is replaced with a bubbler and an ice bath - oil. The temperature of the reaction mixture is slowly raised to 130°C and serves phosgene. The completion of the reaction is determined by almost Klenow mass, otdovat excess phosgene dry nitrogen. Then under vacuum distilled chlorobenzene. The product received is "quenched", this heated bath to 90-100°C, put it under the reaction flask and gradually reduce the temperature to 20°C. the Operation of tempering reduces the ability of the isocyanate mixture to semipolitical and phase separation, stabilizing the quality of the product during storage. Next, analyze the resulting product at NCO-groups and chlorine (see table.1).The polyisocyanate produced at JSC "Corundum" method of mhti-GIAP [Production of isocyanates. Review details. ser. "Nitrogen industry - M., Niitekhim, 1976. - 35 S.] in accordance with THE 113-03-38-105-90 must have the characteristics shown in table 2.As you can see from the results table.1 and 2, the samples obtained by vosganian mixture of amines with the content of TAT to 7 wt.%, for all parameters meet the requirements of TU. Samples 5 and 6 correspond to THE content of NCO-groups and can also be used to obtain certain types of polyurethane foam (PUF).Using cross-linking agents, it is desirable to obtain foams with high load capacity [Flexible Polyurethane Foams. /by ed. R. Herrington, K. Hock. - Midland Dow Plastics, 1991. - 350 p.]. For procladius mesh structure.The obtained isocyanate mixed component (B), we used without any additives for the production of rigid foam on the example of two systems designed for the preparation of rigid polyurethane foam (GPU) SPU-N and SPU-17H. System brand SPU-N is used to obtain polyurethanes by spraying in the construction of houses, public and industrial buildings, for heat and sound insulation, sealing and insulation of joints of panels, window and door blocks, and other gaps and cracks.Component (A) was standard for these systems, and consisted of a complex mixture of polyester, foaming agent, fire-extinguishing additives, foam controller and catalyst.When developing recipes found that 2,4,6-TEST may be contained in the isocyanate component in an amount of 2-15% (wt.). Meanwhile, the technological uptake of foam remain within the standard.Process the sample is in the foaming SDA industrial component a (A-N) when the mass ratio a:B=1:1. According to the results of five parallel foaming was determined kinetic parameters PUF (start,heliopaths.,lifting). At the end of rise of the foam was visually determined the degree of filling (W, vol.%)and the structure of the slice of the sample. Apparent density (EACH.) was determined by cut a rectangular pattern.The results are presented in table 3.According to the requirements of SPU-N formed foam must have a uniform fine structure without cracks and cavities inside the sample. The presence of individual cells with a diameter up to 2 mmThe structure of all samples obtained using the mixed isocyanate with different content TEST meets the requirements.Recipe SPU-17H is used to obtain GPU the same destination, and SPU-N by spraying at ambient temperatures down to -15°C. the Possibility of using mixtures PIZ TEST in this case was assessed in the same way as for SPU-N. The ratio of components a:B=1:2 (hydroxyl-containing component, the standard for this recipe AND-17H), the temperature of the components prior to foaming was 23±1C, mixing time of the original components 5-7 C. Results in foaming is shown in table.4. The structure of the samples met the requirements.When testing the dimensional stability of the samples tested for technological sample.In addition to the hard polyurethane foam, a mixture of PIZ TEST were used in obtaining flexible foam. When choosing recipes isocyanate component was based on the physical mixture TDI/20 and PIZ in the ratio 2:1(B-222) and 3:1(B-221). To receive pins used samples of mixtures of isocyanates No. 5 and No. 6, containing TAT in the original mixture of amines 10 and 10-15 wt.% respectively. Component B was prepared by mixing data samples of TDI 80/20, after which it was determined isocyanate number. Testing process the test was conducted with industrial hydroxyl-containing component (HSC) A-222 for the ratio of TDI 80/20 mixture of PIZ TEST=2:1 and the ratio of 3:1 in the case of A-221. Foaming was conducted in an open manner. The ratio of components a:B was in the interaction with A-222 2.64:1 and a-221 - 2.78:1. A weighted mixture of the components was mixed with 6 turbine stirrer and transferred to the form. The temperature of the components before mixing was 22±2C. In the foaming process in three parallel tests were determined by the same parameters as in the case of GPU (ARTICLE.,TH.,BELOW., W, Yeach.). The samples were utverjdali for 10-15 min, after which they were removed from the forms and crimp for disclosure of cells and prevent shrinkage. Then the samples were cut and sample PIZ. The results are presented in tables 5 and 6.The observed shrinkage is partially removed after compression. The cellular structure of the samples is satisfactory. According to the requirements of THE 6-55-7-88 on the national system of the EPP at the free foaming governed by the following parameters: ARTICLE.=10-14 CTH.=65-70 CEACH.=42-45 kg/m3. The obtained data are consistent with the requirements of TU.Physico-mechanical properties (FMS) EPPS were determined on samples molded polyurethane foam obtained by the above formulas. The samples after aging were subjected to physical and mechanical tests according to the standard methods:determination of residual deformationThe OST.according to GOST 18268. Plastic mesh elastic. Method for determining the relative permanent deformation under compression;determination of compressive stress40according to GOST 26605-85. Plastic mesh elastic. The method of determining the compression of the sample;the specimens tensile testingPandPaccording to GOST 15873-70. Plastic mesh elastic. Method of tensile test.Test data are given in table.7. For comparison in the table.7 shows the values of PMI foam, polucen the positions using mixtures PIZ TEST allow you to get the foam, approaching, and in some ways surpassing the foam obtained from standard components.Thus, the products of the joint vosganian 2,4,6-triaminotoluene with polyamines can be included in formulations of both hard and elastic pen. In the first case, the product can be used directly as the isocyanate component, and the second in a mixture of TDI. With the introduction of a system of flexible foam product co vosganian physico-mechanical properties of the obtained foams conform to the norms and standards. A method of obtaining a polyisocyanate cross-linking composition to obtain a polyurethane foam containing a polyisocyanate and 2,4,6 - triisocyanate, namely, that the solution of phosgene in chlorobenzene was added a solution of fused mixture polyamine with 2,4,6-triaminotoluene in chlorobenzene at mass ratio 85-98:2-15, respectively, at 0-10C with subsequent postironium with increasing temperature to 130C to the disappearance formed in the reaction of a suspension of the amine hydrochloride.
FIELD: production of polyisocyanate compositions for manufacture of polymer-impregnated concrete, impregnation of reinforced-concrete, concrete, brick and wooden structures for enhancing their quality.
SUBSTANCE: coats made on base of these compositions posses enhanced decorative and mechanical properties, high resistance to freeze, water, acids, alkalis and petroleum products. Polyisocyanate composition is produced by blowing polyphenylene polymethylene polyisocyanates by ammonium air mixture content of ammonium of 0.01-0.1 vol-% synthesized by phosgenation of polyphenylene polymethylene polyamines followed by separation of main part of phosgene, hydrogen chloride and solvent at atmospheric pressure and temperature of up to 180°C diluted by toluene at subsequent introduction of 0-30 parts by mass of solid wastes formed at processing and storage of mixture of polyphenylene polymethylene polyisocyanates and 0-120 parts by mass of antipyrene per 100 parts by mass of polyisocyanate; solution is mixed with hardening agent added to toluene solution of polyisocyanate in the amount of 0.01-5 parts by mas per 100 parts by mass of polyisocyanate.
EFFECT: optimization of composition; improved characteristics; reduction of hardening time.
SUBSTANCE: invention relates to the method of obtaining diaminephenylmethane and its highest homologues by the condensation of aniline and formaldehyde in the presence of heterogeneous solid acid catalysts, which are characterised by the fact that the utilised catalysts are catalysts selected from (a) split zeolites and/or (b) alumo-silicate catalysts, which have the regulated hexagonal mesoporous structure with the size of 3-10nm.
EFFECT: it makes it possible to get diaminephenylmethane with the increased contents of primary amines.
4 cl, 4 ex
SUBSTANCE: invention relates to the method of producing polyisocyanate, which involves (a) formation of polyisocyanate in a reaction system through reaction of polyamine, on which polyisocyanate is based, in a solution of inert solvent with phosgene, optionally in a solution of inert solvent; (b) separation of solvent from polyisocyanate, formed at stage (a) by evaporation or fractional distillation; (c) bringing the separated solvent to temperature between 10°C and 150°C and subsequent processing of the separated solvent with isocyanate trimerisation catalyst for trimerisation of isocyanate impurities in the separated solvent; (d) transferring the processed solvent from stage (c) to the reaction system at stage (a).
EFFECT: repeated use of solvent in the process, free from trace amounts of isocyanate and with low level of impurities.
10 cl, 1 dwg
SUBSTANCE: invention relates to a method of producing arylisocyanates which can be used in organic synthesis, including production of physiologically active substances (PAS). The method involves phosgenation of the corresponding amine, which is dissolved in a polar solvent, with phosgene which is dissolved in a non-polar solvent at temperature ranging from 0 to 30°C and normal atmospheric pressure. When separating the desired product, the reaction mass is treated with N,N-dimethylformamide, preferably in amount of 1 to 5 vol % of amine put into the reaction. The method allows for production of isocyanates of the required quality for synthesis of physiologically active substances.
EFFECT: method is cheap, suitable for synthesis of preparative amounts of isocyanates using compact laboratory equipment.
2 cl, 3 ex
SUBSTANCE: invention relates to a method of producing diisocyanates of general formula R(NCO)n, in which R is a (cyclo)aliphatic hydrocarbon radical which contains up to 15 carbon atoms, preferably from 4 to 13 carbon atoms, under the condition that, there are at least two carbon atoms between two isocyanate groups NCO, and n equals 2, through phosgenation of corresponding amines of general formula R(NH2)n, in which R assumes values given above, in a gaseous phase in a tube reactor while feeding heated phosgene and amines into the said reactor. For phosgenation, a tube reactor is used, which has a double-wall guide tube which diverges centrally towards the axis of rotation of the tube reactor, where between the inner and outer walls of the said guide tube there is a concentric annular gap, and the ratio of the cross sectional area of the tube reactor, bounded the inner wall of the guide tube, to the cross sectional area of the tube reactor, bounded by the wall of the tube reactor and the outer wall of the guide tube, ranges from 1:0.5 to 1:4. Temperature of vaporous amines and phosgene which are separate from each other ranges from 200°C to 600°C; vaporous amines in a mixture with inert gas are fed into the tube reactor through a concentric annular gap with stream average velocity of 20-150 m/s, and phosgene is fed into the tube reactor into the remaining region of the cross section of the tube reactor with stream average velocity of at least 1 m/s.
EFFECT: reduced probability of back-mixing and formation of by-products due to improved mixture of educts.
9 cl, 1 dwg, 2 ex
SUBSTANCE: invention relates to a method for synthesis of isocyanates of general formula R(NCO)n (I), where R is a (cyclo)aliphatic or aromatic hydrocarbon residue containing 15 carbon atoms, preferably 4-13 carbon atoms, provided that between two NCO-groups there are at least two carbon atoms, and n equals 2 or 3, through phosgenation of corresponding amines of general formula R(NH2)n (II), where R is a (cyclo)aliphatic or aromatic hydrocarbon residue containing up to 15 carbon atoms, preferably 4-13 carbon atoms, provided that between two amine groups there are at least two carbon atoms, and n equals 2 or 3, in gaseous phase in a tube reactor, having a central nozzle and annular space between the central nozzle and walls of the tube reactor, characterised by that turbulence is generated in the central nozzle, and in particular, turbulence of the stream entering the central nozzle increased due to one or more built-in turbulence generating elements, where the eduction stream which contains amines is fed into the tube reactor through the central nozzle, and the eduction stream containing phosgene is fed into the tube reactor through the annular space, or the eduction stream containing amines is fed into the tube reactor through the annular space and the eduction stream containing phosgene is fed into the tube reactor through the central nozzle.
EFFECT: method enables much faster mixture of reagents.
13 cl, 3 dwg, 1 ex
SUBSTANCE: invention relates to a novel improved method for synthesis of diaminodiphenylmethane and poly(diaminodiphenylmethane), involving a step for reacting aniline with formaldehyde at temperature between 50 and 150°C in the presence of hydrogen chloride added in gas form. The method is characterised by that the aniline contains 0.1-7 wt %, preferably 2-5 wt % protonic compound selected from water and lower aliphatic alcohol.
EFFECT: method enables control of absorption of gaseous hydrogen chloride with aniline until formation of solid substances, as well as minimisation of expenses on modifying equipment.
6 cl, 4 ex
SUBSTANCE: present invention relates to a method of preparing mixtures which contain diphenylmethane diisocyanates and polyphenyl polymethylene polyisocyanates, used in preparing polyurethane compositions for producing plastics, insulation materials, adhesives, coatings etc. The method involves a step for reacting corresponding mixtures of diphenylmethane diamines and polyphenyl polymethylene polyamines with phosgene in the presence of at least one solvent in several steps. At the first step, corresponding carbomoyl chlorides and amine hydrochlorides are formed, and at the next step residual carbamoyl chlorides are dissociated to corresponding polyisocyanates and hydrogen chloride, and the amine hydrochlorides undergo phosgenation to form corresponding polyisocyanates in the end. At the step for removing excess phosgene, the remaining unreacted amount of solid amine hydrochlorides, which lies between 10 and 5000 parts per million, is monitored.
EFFECT: cheap method of producing polyisocyanate mixtures, having a brighter colour, usually having colour index L in HunterLab coordinates higher than 10, without addition of extra reagents which reduce brightening and/or use of additional equipment.
9 cl, 1 ex, 1 dwg
SUBSTANCE: method comprises the following steps: a) reaction of a primary aliphatic or aromatic amine with phosgene in the presence of a solvent to obtain the corresponding isocyanate and a stream containing hydrogen chloride, phosgene and solvent, low-boiling compounds and inert substances; b) separation of the stream containing hydrogen chloride, phosgene and solvent, low-boiling compounds and inert substances in at least a two-step sequence of absorption steps, comprising at least one isothermic absorption step and at least one adiabatic absorption step, to obtain (i) a stream of hydrogen chloride containing not more than 0.5 wt % phosgene in terms of the total weight of the stream of hydrogen chloride, and (ii) a stream of liquid phosgene; and c) recycling the stream of liquid phosgene (ii) to step (a). The phosgene is partially condensed from the stream containing hydrogen chloride, phosgene and solvent, low-boiling compounds and inert substances before said separation in at least a two-step sequence of absorption steps. The method enables to clean the stream which contains hydrogen chloride, phosgene and solvent, low-boiling compounds and inert substances coming from the amine phosgenation process such that the residual concentration of phosgene in the stream of hydrogen chloride remains not higher than 0.5 wt %, thereby minimising the loss of initial phosgene.
EFFECT: improved method.
8 cl, 4 dwg, 1 ex
SUBSTANCE: according to the disclosed method, in order to heat liquid amines, evaporation thereof and/or superheating the formed vapours one or more heat exchangers are used, said heat exchangers having specific heat-exchange surface area on the side where the amines pass through at least ranging from 1·103 m2/m3 to 1·105 m2/m3, where the heat exchangers are fitted with channels for passing streams of amines, the hydraulic diameter of which ranges from 1000 to 10000 mcm.
EFFECT: method enables to cut the dwelling time of initial diamines in the system, reduce the effect of temperature loads and reduce their decomposition, owing to which the desired products are obtained with higher output and quality, and the service life o the equipment is prolonged.
8 cl, 3 ex
FIELD: chemistry of polymers.
SUBSTANCE: invention relates to aromatic polyurethane polyols used as components of priming compositions. Invention describes the priming composition comprising aromatic polyurethane polyol including product of reaction: (a) at least one diol component among number of α,β-diols, α,γ-diols and their mixtures; (b) at least one triisocyanate; (c) at least one diisocyanate wherein at least one isocyanate is aromatic one, and molecular mass or aromatic polyurethane polyol is 3000 Da, not above, and a cross-linking agent also. Prepared aromatic polyurethane polyol shows viscosity value by Brookfield at the level 8260 centipoises, OH-number 192.6 KOH/g and the dispersity (Mn/Mw) at the level 3.0. Priming compositions prepared by using indicated aromatic polyurethane polyol are useful in finishing large means of transportation, for example, trains, trucks, buses and airplanes, in particular, in vehicle body works. Also, invention relates methods for applying priming compositions on support comprising applying indicated compositions, and to a method for finishing car in repairs comprising applying the indicated priming composition.
EFFECT: improved and valuable properties of composition.
11 cl, 5 tbl, 12 ex
FIELD: polymer materials.
SUBSTANCE: invention relates to compositions of molded polyurethane elastomers showing high physico-mechanical characteristics and providing high cyclic stability of products at alternate loadings within a wide operation temperature range. Invention may be used in rubber industry to manufacture cast tires and rolls for monorail vehicles. Composition according to invention contains polyoxytetramethylene glycol, mixture of 2,4-tolylenediisocyanate and 1,6-hexamethylenediisocyanate at molar ratio (0.8-0.9):0.1, and 3,3'-dichloro-4,4'-diaminodiphenylmethane in the form of solution in polyoxytetramethylene glycol at molar ratio (0.67-0.7):(0.29-0.30) as liquid hardener.
EFFECT: enabled use of polyurethane composition for molded elastomers.
2 cl, 2 tbl, 11 ex