DE1595037C3 - Process for the production of high molecular weight polyamines - Google Patents

Description

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cine a larger amount of ethylene chloride dichloride to Another clear advantage of the invention possible, it is very preferred that the Reactive Procedure is that, if followed To cool the zone from the outside, for example by merely performing the process steps mentioned, the volume of the Enveloping this zone with a cooling jacket for the reaction vessel is almost completely used Water. In each case, whether external cooling can be used, and if the reaction is complete, one Will or not, the influx of ethylene dichloride will provide sufficient concentration of the desired orgaso adjusted so that the temperature is essentially present in the case of niche polyamine. With the known any point is maintained in the above- procedures involving amine and alkylene dihalide im mentioned temperature range falls. In the same way, certain molar ratio will work if it becomes an essential one Controlled supply of ammonia, namely io Licher part of the reactor volume of water a pressure regulator valve or through any fills. Accordingly, the verandere according to the invention expedient method, whereby the pressure driving in the unit of time achieves greater performance, it is held that e.r does not significantly exceed or result in a greater yield of organic rises or falls below the point that acts from the above polyamine per hour. So the size of the specified pressure range has been selected. 15 reaction vessel in each process up to his

After the reaction vessel has essentially been used with maximum power, in the sense of

Reaction product is filled, the Äthylendi- a useful yield.

chloride flow interrupted. The remaining, not by at least 10% of the weight of the total end-set ethylene dichloride will have to consist of water through further reaction. A consumed with ammonia, preferably at the 20 typical final solution, contains about 20 percent by weight of the same temperature and pressure as the water. In an approach involving ammonia and a previous operation. The ammonia supply ethylene dichloride is involved, in which the water is then terminated, and excess ammonia makes up the latter weight, based on the weight of the end reaction product released from the reaction vessel into the atmosphere, can be essentially vented or ver in a subsequent operation - 25 borrowed all the ammonium chloride easily through turns. This process, in which the traces of residual centrifugation borrowed from the organic polyamine phase, separate unreacted ethylene dichloride, which is preferably soluble in the water, is generally left depending on the work,
conditions carried out in 5 to 60 minutes. In a particular embodiment, a

When ammonia is reacted with ethylene dichloride, 30 remainder of ammonia is brought into the reaction vessel,

is, ammonium chloride is produced as a by-product in an amount just sufficient to produce a

forms. Surprisingly, stirring is made possible with closer contact. The residue is on a

following the above regulations, this secondary desired temperature is heated and brought to a certain

product brought from the aqueous reaction solution at the desired pressure, the. in the area of the

Salted out at room temperature. In this way is 35 named limits lie, and then ammo

a simple separation of ammonium chloride from nia and ethylene dichloride added. It will

the organic matter by centrifugation or taking care that the set temperature and

Filtration possible. It is particularly preferred that the set pressure be kept constant.

Ammonium chloride of that in the aqueous solution If the volume of the reaction vessel with .sub-

remaining organic polyamine is filled by centrifugal 40, the reaction is complete, and that

fugue to separate. 'Product is withdrawn.

The relatively high molecular weight polyamine The reaction itself can continue for a long time

even after the end of the reaction is within the time span to be carried out. This variable

mean in a polyamine hydrohalide form. naturally depends directly on the size of the educated

If the free base is desired, the neutral charge can vary depending on the temperature and pressure

sation by adding a strong base such as calcium ab. In general, however, the reaction takes from

hydroxide, sodium hydroxide, or potassium hydroxide, about ¹ _1/2 to about 20 hours, and most of the time it's in

respectively. This formed during the neutralization also ended in a time of 1 to 12 hours.

Salt can easily be removed from the free organic base. The following example serves as a further illustration

be separated. The term "polyamine" becomes 5 ° of the process according to the invention. "

for both the free base and the amine salt ...

or the mixtures of these two are used. Example!

Another extremely important advantage achieved by the process technology of the invention with external supply sources for anhydrous ammonia and ethy is that a relatively high level of lene dichloride was provided. A pressure regulator valve was formed in which concentrated product is formed. The reaction line arranged, the products from the ammonia source have an organic content of about led to the reaction vessel. First, the 20 to about 80%, and products, a polyamine reactor was charged with 15.88 kg of water. This amount of 40 to 80% is easy to achieve. 'Sufficient to permit good agitation with the ver-Da the final reaction product upon completion of the equipment used. The reaction reaction a relatively high content of container was heated to 100 ⁰ C and the system of organic solid substance, has each is then unnecessary with the anhydrous ammonia at 7 kg / cm ² · further concentration process. Generally is pressurized. In order to remove air, the concentration of the system in known processes was ventilated, brought back to a pressure of 7 kg / cm ² solution after the end of the reaction, for example 65, and heated ^{to 100 ° C.} The pressure was increased by boiling water, required to keep it at 7 kg / cm ² , by gradually producing the final gaseous product which was introduced from ammonia to the converted polyamine content. To replace ammonia.

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Then ethylene dichloride was fed into the container, the end product consisted of 43 ° / ₀ pumps and the cooling water was turned on. During the tetraethylene pentamine and lower polyamine reaction, the reaction ^{temperature was at 100 0} C fractions. From this it can be seen that he only persevered, namely by adjusting the amount of the introduction of a process with the ethylene dichloride described above. Through 5 process steps a sufficient polymerisation takes place such a careful measurement of the ethylenedi that the temperature of the exothermic products could lead to the formation of a higher molecular weight prochloride addition. With the known method, only one reaction can be kept constant at 100 ⁰ C. Little polymerization could be achieved, and it took about 2 hours for all of the * substantial portion of the final polyamine product to be added to ethylene dichloride:. . io composed of low molecular weight compounds.

After the loading has reached the capacity of the die by the method according to the invention

As the reaction vessel was approached, the pumping in of the products was extremely good as a coagulation of ethylene dichloride in the reaction zone, especially of rubber latex. The reaction was allowed to continue for ¹ _1/2 hours. In order to bring about the coagulation, the heated in order to convert the remaining ethylene dichloride, 15 polyamine produced according to the invention only in the and then the inflow of anhydrous am liquid was added, which terminated the suspended moniak. As a result, the system was cooled containing solids that should be removed. Through and vented. Subsequently, the polyamine action of the polyamine, these solids are centrifuged product and the ammonium chloride by-products are put together and then separated from the liquid waste product from the aqueous solution of the polymeric 20.

Amine separated. After centrifugation, comparative experiments were also made here,

the polyamine nuretwa ° / ₀ ammonium chloride 1 to 2. The separation of the undesired salt from the polyamines synthesized by known processes, the aqueous polyamine solution, was accordingly excellent. were compared. The corresponding coagulation effects of this particular approach 95 effects were shown on styrene-butadiene rubber are shown in the table: tested. The higher molecular weight products produced by the

processes according to the invention were obtained

Table I ^eme "^ ^ ' ^s ^ W ⁰ Io better effectiveness than coagu-

lating agents than the known polyamines.

Filled water .15.90 kg ₃₀ 'In the case of the polyamine syntheses, the molar ratio

Ammonia used 25 kg ratios of ammonia and ethylene dichloride as well

Ethylene dichloride 49.50 kg the other variables are the same in each case.

Total experiment time ^ 2 hours. When the total amounts of reactants increase

Pumped in amount of ethylene, the same time were put together and the

dichloride 23.57 1 / hour ₃₅ Reaction under high pressures and temperatures

Moles of NH ₃ per mole of ethylene were carried out, the polyamines did not reach

dichloride 2.49 the size of the molecular weights or the coagulation

Polyamine content in the end product 24% lation effects like the products after the

processes according to the invention have been produced.

Molecular quantities for good coagulation weight determinations were carried out on the polyamine mentioned. The molecular ■ effect can be in the range from 10 to about 1000 ppm, weight was over 300, and the product contained preferably between 10 and 100,
Substantially no lower mole polyamines- Excellent performance is observed when, one

kular weight, such as ethylenediamine, diethylenetriamine latex suspension, which is a copolymer of styrene and tetraethylene pentamine. 45 and contains butadiene suspended in water, with a

In a comparative experiment in which the polyamine produced according to the invention is treated container at the same time with the same number of moles. It becomes clear, floating on the water Ammonia and ethylene dichloride, as used above, get liquids and form them quickly filled and the reaction under essentially the flakes of copolymer, which continues in a under the same temperature and pressure conditions, agglomerate through easily removable solid mass.

Claims (1)

1 2 without sophisticated, costly and time-consuming patent claim: "to use separation processes. In many cases, however, there is such a separation Process for the production of high molecular weight essential, since only the organic polyamine is required in a polyamine by reacting ethylene dichloride 5 in a relatively pure state, and with ammonia at elevated temperatures and a substantial residue of inorganic salt concentrations under pressure, characterized, trations cannot be tolerated,
that 2 to 3 moles of ammonia per mole of ethylene- It is therefore an object of the invention to provide the above chloride in the presence of at least 10 weight disadvantages of the known method to eliminate percent water, based on the weight of the final ₁₀ and high molecular weight polycondensates to produce the product, at temperatures from 75 to 200 ⁰ C an excellent effect in promoting and under exhibit coagulation of suspended particles at a pressure of 5.27 to 70.3 kg / cm ^2,
be implemented, with ammonia for upright- This object is achieved by the invention maintenance of the reaction pressure slowly in the process, dissolved. Reaction zone introduced and at the same time under 15 The invention is a process for Maintaining the reaction temperature by producing high molecular weight polyamines Ethylene dichloride introduced into the reaction zone reaction of ethylene dichloride with ammonia and the reaction zone is continuously subjected to externally elevated temperatures and pressures which cool it down is, and after completion of the reaction is characterized in that 2 to 3 moles of ammonia By-products formed from the aqueous solution 20 per mole of ethylene dichloride in the presence of at least Polyamine can be removed. at least 10 percent by weight of water, based on the Weight of the end product, at temperatures of 75 to 200 ⁰ C and under a pressure of 5.27 to 70.3 kg / cm ^{2 are} implemented, with ammonia for 25 Maintaining the reaction pressure slowly in the reaction zone, introduced and simultaneously under Maintaining the reaction temperature the Ethy- The invention relates to a process for the production of lene dichloride introduced into the reaction zone and the of high molecular weight polyamines is continuously cooled from the outside by reacting the reaction zone, of ethylene dichloride with ammonia at elevated 30 and secondary temperatures formed after the reaction has ended and under pressure. products from the aqueous solution of the polyamine It is already known that ethylene chloride can be removed with Am-. monia in aqueous solution at 120 ⁰ C under pressure The reaction itself must be carefully controlled implement, the reactants being carried out in the conditions already lated. The tempe pressurized autoclave can be introduced. 35 temperature of the reaction is in the range of about 75 to Upon heating the reactants in the autoclave showed about 200 ⁰ C. The polymerization is carried out under a pressure therein rises slowly at first, then rapidly pressure from 5.27 to 70.3 kg / cm ^2. The implementation and drops on it quickly. At this moment itself, the autoclave is cooled and opened by slowly introducing Am. 'Moniak carried out in a reaction zone, wherein The known process for the production of poly-40 care must be taken that a certain amines by reacting a low "amine and fixed pressure within the above of an alkylene dihalide, however, certain post-limits have been maintained. At the same time will share. The most important is that, with such an ethylene dichloride introduced into the reaction zone, Process only end products with proportionate care must be taken that a certain low average molecular weight is set temperature within the above-mentioned will hold. For example, the response results in limits being sustained. At the beginning must of ammonia with ethylene dichloride under the loading, brought enough water into the reaction zone known process conditions are a mixture of, so that the organic product formed Polyamines in which a substantial proportion of · both at each point of polymerization and lower polyamines, such as ethylenediamine or 'Di- 50' then after the process is complete ethylenetriamine, is present. Attitude and release is. Change of certain variable process steps, if these reaction conditions are followed for example molar ratio, pressure or temperature polyamines with a relatively high molar removal obtained the kular weight adhering to the known processes. For example, if ammo shortcomings not. The same situation gives 55 niak implemented according to the above procedural steps when reacting with lower polyamines, the mixed polyamines have formed Alkylene dihalides. A large. Proportion of the average molecular weight over 300 Mixture of polyamine products consists only of and usually more than 500. Polyamines can also be used 2 or 3 units. 'Manufactured that even have a molecular weight Another disadvantage of the known production 60 up to 50000. Some polyamines have the difficulty of un- The polymerization is expedient at to separate desired salt by-products from the desired temperatures of about 80 to 140 ⁰ C and under organic polyamine phase. If at pressures in the range from 5.27 to 14 kg / cm ^2, a reaction between ammonia and performed. In these cases the products obtained are an alkylene dihalide, such as ethylene dichloride, in 65 clearer and less colored than those which are made under water, both the organic pro
duct -as also the ammonium chloride dissolved in water, the reaction described above is exothermic. Around and it is difficult to separate one from the other, therefore to control the implementation more precisely and