Preparation of polyamines

[Detailed Description of the Invention]

This invention relates to polyamine. It is in the object of this invention providing the compound which is in agreement with the following general formula:<img file="JPH03379B2_D0001.tif" />Among a formula, R of same or different intermediary Stomach is also good, and shows the Al Killen machine preferably tetra, Hexa, Octa, Deca, undeca and a dodeca methylene machine, more preferably a hexamethylene machine. The compound may be built with corresponding publicly known biuret Reiso cyanate. These biuret tri-isocyanate contains the biuret polyisocyanate of higher functionality which usually contains the biuret machine beyond two pieces and it of quantity with which a small quantity (abbreviation &lt;10% weight) decreases. Therefore, the polyamine built from now on contains amine of high functionality rather than having a biuret machine beyond two pieces and it of a little decreasing quantity too. The NCO pre polymer to which a certain fatty series primary amine which contains a biuret machine in a surprising thing corresponds is slightly mixed with a superfluous aqueous base or the water solvent blend of a base (for example, dropped into alkaline fluid), And it is I and It was which are directly obtained when the obtained Cava (alkali) mate is processed by the acid ion exchange object. This, therefore polyamine by this invention are how to manufacture the polyamine which has a biuret machine by hydrolysis of a compound which has an end isocyanate group, and are Then, (1) the NCO pre polymer which has a corresponding biuret machine in the 1st step -- Then -- what was arbitrarily dissolved in the inactive organic solvent of water miscibility -- solution of a base, or the water solvent blend of a base -- arbitrary -- 40degreeC from about 0, Preferably in 10 to 20 degreeC, it is converted into the Cava mate corresponding by being mixed so that the equivalent ratio of hydroxide to a NCO basis may be 0.3:1 to 1.3:1, preferably 1.01:1 to 1.30:1, (2) In the 2nd step, the Cava mate is CO by a reaction with the acid ion exchange object of the amount of these at least.₂being directly converted into amine of isolation, Occurred(ing) -- and (3) Amine of isolation may be manufactured by the method (this gentleman method is said to below as the "new method".) characterized by what is separated by the publicly known way. Polyamine of this invention, (A) Polyisocyanate (B) On polyamine and an arbitrary target (C) About what has a Then isocyanate reactivity machine with other low-molecular quantity and/or amount compounds of polymers, it is arbitrarily. (D) In existence of a publicly known auxiliary agent and an additive agent, it may be arbitrarily used as an ingredient (B) in manufacture of cell-like polyurethane plus Chikusu and a poly-urethan form by making it react. Compared with an old method, the new method has the following surprising advantage. (1) In manufacture of NCO pre polymer from the compound containing polyisocyanate and a NCO reactivity H atom, the isocyanate of a little monomers often remains in pre polymer. Only polyamine of a corresponding low-molecular quantity built the ionic exchanger and the connective in the new method, and it was shown that these may be removed from a reaction mixture with them. However, since this does not happen to a surprising thing about polyamine of the amount of polymers, according to the new method, it has the molecule homogeneity which was easy to get polyamine of the amount of polymers directly rather rather than having passed through the stage of mineral acid salt, and has been improved considerably. (2) To add an ionic exchanger to Cava mate solution or suspension or its opposite method can be chosen. (3) The process conditions of the new method are very mild, polyamine is generally slightly built by this as a colorless thru/or yellow output, and, moreover, the result that these oxidize substantial more late for the absence of impurities is brought about. (4) Since it is proved that the process conditions of the new method are very mild, sensitive polyamine containing a biuret machine can be built easily, and the thing of the new class of biuret polyamine may be obtained by the new method in this way. (5) It can be used, without being converted into the salt in which the amount polyamine of polymers corresponds many acid ion exchange objects from the amount of these based on H atom. By production of the unnecessary subliving thing of salt, corresponding salt requires still a procedure stage. In a publicly known way, the NCO pre polymer used in the new method is built by making water react to superfluous isocyanate. The Al Kyren polyisocyanate which does not have a basis which may be hydrolyzed in principle for this reason (as a NCO basis being another), for example, it is described by Wae G Soul (W. Siefken) at "Yusutsu Liebig's chemicals yearbook (Justus Lievigs Annalen der Chemie), 562, the 75th, or 136 pages" -- as -- for example, following general formula: Q(NCO)_o(n shows among a formula the Al Killen machine with which 2 and Q have two to 18 pieces, preferably six to ten carbon atoms.) It is alike and a corresponding thing, for example, 1, 4 ―Tetra methylene di-isocyanate, 1, 6-hexamethylene di-isocyanate, 1, and 12-Dodecane diisocyanate are contained. The biuret containing a NCO basis is built by the reaction of the reaction of a NCO compound and superfluous water to urea, and a NCO compound. The NCO content of the NCO compound which shifts to polycarbamate and polyamine by the new method, respectively is between about 0.5% weight and 37.5% weight, preferably between 0.7 % of the weight and 27% weight. All the substances which have an acid hydrogen atom which can move into an insoluble polymer matrix are suitable as an acid ion exchange object in the new method. It has styrene / divinylbenzene frame as a matrix of a polymer, and the ion-exchange resin which a sulfonic group combines with this as an acid function is suitable especially as polymer acid in the new method. In the new method, pre polymer is usually first dissolved in the inactive solvent of water miscibility. For example, a suitable solvent is dimethoxyethane (DME), a tetrahydro franc, or dioxane. In this stage, one to 400 of pre polymer copies may be used per 100 copies of a solvent. Pre polymer is the alkaline metal or alkaline-earth-metals hydroxide in water and/or a water solvent, tetra-alkylammonium hydroxide, or a strong base like sodium aluminate, agitating, Preferably it is adjusted by about 0 to 40 degreeC, and the concentration of a base is suitably mixed with the solution preferably calculated by 1 weight section of a base to 5 to 20 of water and/or a water solvent weight sections slowly (preferably he is a cotton intermediary in 120 minutes after 30) (for example). It is dropped into the solution of a base. Hydroxide (for example, tetra-alkylammonium hydroxide) of organic and inorganic ammonium is suitable again. having the lowest possible viscosity to about 5000mpa.s desirable, if a method is performed without a solvent In the form where the NCO (to for example, 30 to 90 degreeC) pre polymer heated beforehand arbitrarily was distributed as finely as possible (for example, introduced by pouring in through a nozzle), It is added at a high churning speed, and in order to agitate easily, it is arbitrarily increased by the quantity of the water introduced (for example, 1.1 to 100 times). measurement supply may be carried out with a base again all over a reaction room (a static mixer (static mixer) or a churning room mixture device -- like), and it may be stopped in a container until a reaction completes NCO pre polymer or its solution. Quantity of hydroxide of a base preferably an alkaline metal, or alkaline-earth metals, It is adjusted so that the base of a little isolation may remain in addition at least, when a reaction is completed, and use of the ratio of NCO/OH from 1:1.01 to 1:1.30 and hydroxide of an alkaline metal is preferred in this reaction. In order to improve the homogeneity of solution, the emulsifier which can be obtained commercially preferably is added in the quantity (based on a 100-weight section reaction mixture) of 0.1 to 2 weight sections, preferably about 0.5 weight section. In order to avoid the difference in local concentration, powerful churning is recommended when mixing a NCO ingredient with a hydroxide ingredient. After pre polymer is added desirable, a mixture is further agitated in 0 during 180 minutes after further about 15 to 20 degreeC. However, it is also possible to use the relation between NCO/hydroxide ion which has fewer bases of the relation of 1:0.3 to 1:0.99, for example. Thereby, it is beforehand elongated by a urea machine and the amount of [ which has the amount of polymers and hyperviscosity ] drawing of polycarbamate and polyamine will increase. In the 2nd step, Cava mate solution or dispersion liquid are mixed with an ionic exchanger. In the new method, it is not a problem whether it is whether it is that acid ion exchange resin is added to Cava mate dispersion liquid or solution (method A) and that the reverse procedure is adopted (method B). In the ratio permitted with the strength of generating of gas, and the size of a device, ion-exchange resin and the Cava mate ingredient are mixed (10 to 300 minutes). However, only after [ the whole ion-exchange resin ] 4 [ about 1-/] is added, generating of gas occurs. When an ingredient was mixed, the rise of temperature took place, and it was proved that the temperature of 10 to 70 arbitrarily adjusted by external heating degreeC is convenient. An ionic exchanger is added until generating of gas stops. The dissolved carbon dioxide is driven out by heating to 60 between short time to 100 degreeC. The reverse method (method B) of introducing an ionic exchanger is preferred, when the data of the reaction is known, and especially when it is a continuous magnetization method. At the terminal point of a reaction, a reaction mixture is base, as it Suitables in the amine content of isolation, and its basic strength. Easy processing is composed as follows: (1) Supposing amine is soluble, another [ of it ] will be carried out and the solution of amine will be separated from a solvent by distillation. (2) Supposing amine is soluble slightly, a suitable solvent will be added until amine dissolves, and a method will be performed as mentioned above. (3) Supposing amine is insolubility, it is The past(ed) from a fluid medium, a residual substance will be processed with a suitable solvent until amine dissolves, and a method will be performed as mentioned above. A suitable solvent is an aprotic bipolar water miscible solvent at the time, such as N-methyl pylori boss, Dimethylform amide, and dimethyl sulfoxide. It is reproduced by a publicly known method, and the loaded ion-exchange resin (neutralized type) may be re-used easily. No obtained polyamine contains the volatilization ingredient of a trace in 80degreeC and 0.013 to 0.13 mb from 60. Because of the low steam pressure of the polyamine obtained by this invention, they are these, It sets to manufacture of cell-like polyurethane plus Chikusu arbitrarily, It is preferably used as a reaction object over the polyisocyanate arbitrarily mixed with other low-molecular quantity (molecular weight: from 32 to 399), and/or the compound which has an isocyanate reactivity machine of the amount of polymers (molecular weight: from 400 to about 15000) comparatively. or [ that the suitable start ingredient for manufacture of polyurethane plus Chikusu is described above with regards to pre polymer manufacture ] -- or the following German patent publication before examination No. 2302564, It is stated to No. 2432764 (U.S. Pat. No. 3963679), No. 2639083, No. 2512385, No. 2513815, No. 2550796, No. 2550797, No. 2550833, No. 2550860, and No. 2550862 again. The reference to the additive in which these publications should be arbitrarily used for polyurethane manufacture again, or an auxiliary agent is included. Using polyamine by this invention, polyurethane urea may be manufactured. Application of everything but polyamine by this invention includes the hardening agent for the EPO Xide and phenyl resin like other publicly known reactions of all the amine at the time, such as a coupling ingredient for diazo dye, amide, or imide formation, for example. The following example illustrates the present invention while showing the new method. Quantity should be understood as a weight section or weight %, if there is no indication specially. Mersolato (Mersolat H is a registered trademark of a Beyer company, and is Alkyl sulfonate, i.e., paraffine sulfonate.) Example 1 (The Cava mate's manufacture) The solution in 200 ml of the dioxane of compound 200g (1.12 mol of NCO is included and it is NCO value =23) obtained by biuret-ization of 1 and 6-diisocyanate hexane sets to 10 to 15 degreeC, It crosses in 30 minutes and is 67.2 g (1.2 mol) and Mersolato (Mersolat) of KOH. It is dropped while external intercooling is needed for the solution in 200 ml of 0.1 g of water of H. A mixture is re-agitated for 30 minutes at this temperature. (Manufacture of amine (method A)) Ruwatit which carried out humidity (Lewatit) Little by little, over 150 minutes, 680 g of SC 108 is added, while the temperature of 60 to 70 degreeC is maintained. Between this process, it is CO.₂20 ml of of occur. Considerably, at the time of weak Matsuta, a mixture is mixed with 1 of dioxane and the generation of gas is heated by 90 degreeC for 10 minutes. It is CO as a result with which all the gas yields (98.8% of the amount of = theories) of 25.1 are built between this procedure.₂of 5.1 occurs again. the suction fault of the hot mixture is carried out, it is only yellow slightly, and exact¹80 g (46.8%) of the resin-like output which has a H-NMR spectrum is obtained.<img file="JPH03379B2_D0002.tif" />[Ruwatit (Lewatit) It is SO in the divinylbenzene / styrene matrix (thing which has the particle size of 0.5 thru/or 1.5 mm and which was crosslinked 8%) like SC 108 (Beyer company)] gel.₃The highly acidic cation exchange object which has H basis. The amount of whole picture is [ resin / humid ] 4.5 mval(s)/1g about 2 mval(s)/1 ml or dry resin. Useful capacity is about 1.3 mval(s) or 3 mval/g. In the same method, the following ion-exchange resin is used in the method of Example 1, and it is obtained in the yield and purity with which polyamine may rank. 1 Ruwatit (Lewatit) It is SO in S100 (Beyer company) styrene / divinylbenzene matrix.₃The highly acidic cation exchange object which has H basis. The amount of whole picture is 2.2 mval(s)/ml about humid resin. Useful capacity is (humid resin of 900g[ from appearance weight 800 ]/) to 1.8 mval/ml. 2 Ruwatit (Lewatit) It is SO in the styrene / divinylbenzene matrix of SP112 (Beyer company) huge porosity and the quality of fine pores.₃The highly acidic cation exchange object which has H basis and average bridge construction. The amount of whole picture is about 1.9 mval(s)/ml about humid resin. Useful capacity is (humid resin of 800g[ from appearance weight 700 ]/) to 1.3 mval(s)/ml. 3 Ruwatit (Lewatit) They are viaduct density and SO in SP120 (Beyer company) huge porosity, and large porous styrene / divinylbenzene matrix.₃The highly acidic cation exchange object which has H basis. The amount of whole picture is 1.9 mval(s)/ml about humid resin, and useful capacity is (humid resin of 800g[ from appearance weight 700 ]/) to 30 g CaO/ about humid resin. 4 Ruwasolve (Lewasorb) A10 (Beyer company) -- this -- &lt; -- it is an exchange object of the type (H form) of Ruwatit 100 ground by the particle size of 0.2 mm. The information on others about the ion-exchange resin used is found out by the following publication by a Beyer company. OC/I 1379, OC/I 1350, OC/I 20026, OC/I 20031, OC/I 20303 and OC/I 20333. It is beforehand converted into H form, and all the ionic exchangers used are washed by distilled water until they stop containing acid. (Comparative example) If the salt which the above-mentioned Cava mate was processed with mineral acid, and was obtained is neutralized by KOH, solid output will be about 30 to 50% of CO.₂It is obtained only with gas yield, the output is large, and it is insolubility (urea generation).