DE1241615B - Process for the production of neutral or basic solutions of water-soluble, nitrogen-containing, high-molecular compounds - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

EDITORIAL

Int. CL:

C08g

German class: 39 c-15

Number: 1 241 615

File number: B 72573IV d / 39 c

Filing date: July 6, 1963

Open date: June 1, 1967

• It is already known to use alkylenimines with epoxy compounds in the presence of solvents at elevated temperatures to water-soluble products to be implemented (see German patent specification 651 797).

It is also known to react epichlorohydrin with ammonia or amines or polyamines. Included Depending on the conditions, viscous water-soluble ones are formed Condensation products (French Patent 771 836, German Auslegeschrift 1 010 736) or -v fully crosslinked, water-insoluble products suitable as ion exchangers (USA patents 2,469,683 and 2,515,142).

From the German patent 665 791 it is also known to use ethyleneimine in the presence of 'acidic catalyst' to polymerize catalysts.

It has now been found that neutral or basic solutions of water-soluble, nitrogen-containing, high molecular weight organic compounds through conversion of

(I) ethylene imine or 1,2-propylene imine with ^ao

(II) Hydrocarbon compounds which have at least one epoxy group and at least one not reactive chlorine, bromine or iodine atom bonded to the carbon atoms of the epoxy group or at least two reactive chlorine, bromine or reactive atoms bonded to different carbon atoms Contains iodine atoms,

in solvents at elevated temperatures until the viscosity of a 1 percent strength by weight solution of the reaction ^{product is at least IcP at 2O 0} C and the product is still water-soluble, if the molar ratio of component (I) to component (II) is 3 to 100: 1, is preferably 5 to 30: 1.

In the present context, reactive chlorine, bromine and iodine atoms are understood to mean those which are in the / or / S position of an epoxy group, or those which are formed by splitting an epoxy group with hydrogen chloride, bromine or hydrogen iodide, that is are in the vicinity of a hydroxyl group.

As component (II) suitable hydrocarbon compounds with at least one epoxy group and at least one reactive chlorine, bromine or reactive chlorine group not bonded to the carbon atoms of the epoxy group Examples of iodine atoms are l-chloro-2,3-epoxypropane (epichlorohydrin), 2-chloro-3,4-epoxyhexane, l-chloro ~ 3j4-epoxybutane, l, 4-dichloro-2,3-epoxybutane, l, l-dichloro-2,3-epoxypropane, l-chloro-3,4-epoxycyelohexane, l-bromine ^^ - epoxypropane, l-iodine-2,3-epoxypropane and l-bromo-2,3-epoxycyelohexane.

Process for producing neutral or
basic solutions of water-soluble,
nitrogen-containing, high molecular weight compounds

Applicant:

Aniline & Soda Factory in Baden

Aktiengesellschaft, Ludwigshafeh / Rhine

Named as inventor:

Dr. Uwe Sönksen, Ludwigshafen / Rhine

Also suitable as component (II) are reaction products obtained from polyepoxide compounds Reaction of one or more epoxy groups with hydrogen chloride, bromine or hydrogen iodide is formed. Therefor suitable polyepoxide compounds are, for example, the diepoxides of butadiene, vinylcyclohexene, Dicyclopentadiene and dipentene, also for example cyclododecantriepoxide, l, 2-6,7-diepoxy-3-methylhepten-4, l, 2-4,5-6,7-triepoxy-3-methylheptane and 1,2-9,10-diepoxyphenyldecane.

Hydrocarbon compounds suitable as component (II) which contain at least two different Containing reactive chlorine, bromine or iodine atoms bonded to carbon atoms are, for example, such Compounds obtained by reacting the monoepoxide compounds listed above with chlorine, bromine or Hydrogen iodide is formed, for example: 1,3-dichloro-2-hydroxypropane, 1,4-dichloro-2,3-dihydroxybutane, 1,4-dichlorobutanol-2, 2,4-dichlorohexanol-3, l-chloro-3-bromo-2-hydroxypropane and l-iodo-4-chloro-2-hydroxybutane.

The implementation of components (I) and (II) is carried out in solvents such as water, acetone, alcohols, Dimethylformamide or dioxane, or in mixtures of water with organic solvents. It is most convenient to work in water. You can use water and component (II) and add component (I) as such or in solution with stirring, or water is added and / or the organic solvent alone and adds both components at the same time.

It is also immaterial whether component (II), for example ljS-dichloro ^ -hydroxypropane, as such is used or whether it is only in situ from the starting compounds, such as epichlorohydrin and Hydrochloric acid.

709 588/352

3 4

During the reaction, the amount of solvent is greater than that of a known flocculant

! by means of expediently dimensioned in such a way that they can be seen from the following comparative tests:

Final concentration of the solution 2 to 50 percent by weight - 400 mg of unbleached, ground sulfite pulp,

.cent, preferably 6 to 20 percent by weight. So-called mucilage, were found in 11 drinking water

If the dilution is too great, it will be suspended during reaction 5 of the degree of hardness 14 ° dH (German hardness),

the solutions are not sufficiently viscous, while the pH of this suspension was with a

when working in too concentrated solution the final mixture of 2 parts of 10% sulfuric acid and

product becomes partially or completely insoluble very easily. 3 parts of 10% aluminum sulfate solution to 4.5

After the reactants have been added, it is established.

stirred until the desired viscosity is reached, io This mucilage suspension was being placed in a viscosity, based on a l ° / oi§ ^e solution, 1-1-standing cylinder and with so much milliliter after the reaction is at least 1 cP (at ⁰ C) must be a 0, l ° / ₀ aqueous solution of a 20-flocculation. The subsequent stirring time can vary depending on the fact that the suspension after a single concentration between a few minutes and several ----- shaking and 60 seconds clearing time by off hours. 15 flocculation of the solid was clarified. The clarifying effect

In order to obtain the most viscous solutions possible, this was assessed visually.

It is often expedient to start the reaction with essentials. To achieve the clarification were required (1 mg

less solvent than for a stable final solution solid substance corresponds to 1 ml of the solution):

It would be necessary to begin by working on this _{4 deg product according to at iel 1}

Wise given close spatial proximity of the ao ",", "". ·., "

Molecules, a particularly strong mixture of 2 mg of the product according to Example 2 is achieved

networking. The resulting highly viscous solutions - 5 mg of the product according to Example 3

6 mg of the product according to Example 4 are then added for stabilization with further solution

medium to a concentration below 50, preferably 3 mg of the product according to Example 5

diluted below 20 percent by weight _a5 '5 mg of the product according to Example 6

The one suitable for the appropriate reaction -, ",, .." "..,"

The temperature range is between room temperature ^{7 m} S of ^the product according to Example 7

and the boiling range of the solvent, preferably ⁴ mg of the product according to Example 8

above 70 ^° C., the heat of reaction is more expedient - 5 mg of the product according to example 9

wisely removed by cooling to a certain 30 x 4 _{mg of} the product according to Example 10

Maintain temperature. Sometimes it is useful to _{6 of the product according to example n}

the reaction at a lower temperature than the _d hi _n2eeen

desired to begin and the solution through the ' _ΛΛ . , \ , ....., _TT , ..,,

The heat of reaction developed slowly to the final ^ ¹ . ^m S % ?? commercial homopolyethylene

to let come valid temperature. By a 35 " ¹ ^ ⁸ ( ^{volume of the io} / o» gen solution 1.9 cP)

Such temperature control can be used, as can the parts and percentages mentioned in the examples

by changing the concentration, the running-in time is weight units,

or the temperature itself, the reaction in a '

control the desired meaning. B e 1 s ρ 1 e 1 1

Heating the molar ratio in which the component (T), and 40 800 parts of water at 8O ⁰ C, 23 parts of

the component (II) have reacted with one another, epichlorohydrin (0.25 mol) is added and slowly

at the end of the reaction between 3 and 100, preferably 107 parts while maintaining the temperature of 80 ° C

wisely between 5 and 30. Nevertheless, the viscosi- (2.5 mol) ethyleneimine are added. The duration of the addition

activities of the solutions, based on a l f _o ° i§ß solution is about 22 minutes. The 14% solution has

still considerably above those of for example 45 after 2 hours of stirring at 80 ⁰ C a viscosity,

by the method of German patent related to a l ° / ^e oig solution and 20 ⁰ C, of 2.8 cP.

665,791 obtained, prepared in a known manner. · 1 -7

Polyäthyleniminen, so that it can be assumed that the example 2

Component (II) not only catalytically acid donating, 500 parts of water are heated to 7O ⁰ C, 23 parts of

but mainly crosslinking and increasing the size of the molecule 50 (0.25 mol) epichlorohydrin was added and slowly

acts and thus 86 parts (2 mol) of ethyleneimine are added dropwise directly to the formation of the molecule. One lets

is involved. the temperature to 9O ⁰ C rise, and keeps it

According to the method according to the invention, by cooling between 85 and 90 ^° C. After about

highly viscous, mix with water in any ratio- 8 minutes of stirring, the reaction mixture is like this

Obtainable solutions. When the solutions have become highly viscous, they contain 1000 parts of water

are diluted enough to be diluted by a slight thickening. The solution is just under 7%

apart from that, stable and remain water-soluble. With viscosity on a 1% solution at 20 ° C

increasing concentration decreases the stability of the 3.6 cP.

sings. Completely dehydrated products are water- Example 3

insoluble. 60

The solutions of 400 parts of water produced according to the invention are ^{heated to 70 °} C., 1 part

High molecular weight compounds are excellent in epichlorohydrin added and slowly, while about excellent as a textile auxiliary. In particular one hour, at the same time 430 parts of 60% ethylene can they increase the wet tensile strength of imine (6 mol) and 10.5 parts of epichlorohydrin (total paper and as a clarifying agent for the removal of suspended matter 65 amount 0.125 mol) was evenly added. The tempe-

used by sewage. temperature is maintained by cooling at 70 to 8O ⁰ C.

Unexpected technical advantages of the after stirring after about an hour, the solution

Solutions obtained according to the invention as flocculants are so viscous that a further 2200 parts of water are added

will. The resulting solution is 6% ig · The viscosity of a l% solution at 2O ⁰ C is 5.4 cps.

Example 4

100 parts of water are heated to 70 ° C, 23 parts (0.25 mole) of epichlorohydrin was added and then under stirring 114 parts (2 moles) of 1,2-propylene imine at 70 to 80 ⁰ C was added uniformly. After half an hour of stirring at 8O ⁰ C. for a further 450 parts of water are added and again 1,000 parts of water were added after a further half hour of stirring. The solution is then about 8%. The viscosity at 20 ° C, based on an L ° / _o solution is 1.1 cP.

Example5

490 parts of water are ^{heated to 80 °} C., 32 parts (0.25 mol) of dichlorohydrin are added, and 86 parts (2 mol) of ethyleneimine are added uniformly over the course of about 21 minutes. The temperature is allowed to rise to 85 ⁰ C and then holds it by cooling between 80 and 85 ° C. After stirring for about 40 minutes, a further 500 parts of water are added. An almost 11% solution is obtained. Its viscosity at 20 ⁰ C, based on a l% ig ^e solution is 2.9 cP.

Example 6

A mixture of 300 parts of water and 50 parts concentrated hydrochloric acid is heated to 50 ⁰ C. 23 parts (0.25 mol) of epichlorohydrin and slowly 55 parts (1.28 mol) of ethyleneimine are added uniformly. The temperature is allowed to rise to 85 ° C and then holds it by cooling between 80 and 85 ⁰ C. After about an hour of stirring at 80 to 85 ° C, the solution quickly becomes viscous. An approximately 13% solution is prepared by adding 300 parts of water. Its viscosity at 2O ⁰ C, based on a l% solution, is 2.7 cP.

Example 7

100 parts of dimethylformamide and 33.8 parts (0.0625 mol) of a 70% strength aqueous suspension of the reaction product of dimethyl-di - [(p-2,3-epoxypropyl) phenyl] methane with 1 mol of hydrochloric acid (prepared by 1 hour stirring at 60 to 70 ⁰ C until no ionic chloride is no longer detectable) are heated to 100 ⁰ C and uniformly (1.25 mol) of ethylenimine was added over 30 minutes 53.5 parts. The temperature rises to about 130 ⁰ C. After stirring for 30 minutes at 125 to 130 ° C., 350 parts of water are added. The resulting solution is 14 ° / ₀ ig · The viscosity of a l ° / oig ^s solution at 20 ° C is 1.6 cps.

Example 8

A mixture of 650 parts of water and 250 parts of ethyl alcohol is heated to 70 ⁰ C. 23 parts (0.25 mol) of ₁ epichlorohydrin are then added and 107 parts (2.5 mol) of ethyleneimine are added uniformly over a period of about 25 minutes. The heat of reaction is partly cooled by external cooling and partly by refluxing the alcohol. After stirring for 2 hours at reflux temperature, an approximately 13% solution is obtained. Its viscosity at 2O ⁰ C, based on a l ° / ^e oig solution is 3.2 cP.

Example 9

A mixture of 650 parts of water and 250 parts of acetone is heated to reflux temperature. 23 parts (0.25 mol) of epichlorohydrin are added and 107 parts (2.5 mol) of ethyleneimine are added uniformly over 30 minutes. The temperature is maintained while both by evaporative cooling, such as by external cooling to about 60 to 70 ° C !, After 2.5 hours stirring at reflux temperature, the approximately 13% solution has a viscosity, based on a l% solution and 2O ⁰ C , of 2.8 cP.

Example 10

500 parts of water are heated to 70 ° C., 36 parts (0.25 mol) of epibromohydrin are added, and 86 parts (2 mol) of ethyleneimine are slowly added dropwise. The temperature is allowed to rise to 90 ⁰ C and then holds it by cooling between 85 and 90 ° C. After about 6 minutes of stirring has become highly viscous, the reaction mixture. It is diluted with 1100 parts of water. The solution is then about 7 ° / oig · The viscosity of a l ° / o solution at 20 ⁰ C is 3.8 cps.

Example 11

400 parts of water are heated to 70 ° C., 55 parts (0.25 mol) of the reaction product of 1 part of epichlorohydrin and 1 part of hydriodic acid are added, and 107.5 parts (2.5 mol) of ethyleneimine are slowly added dropwise. The temperature is allowed to rise to 85 ° C. and is then kept at 85 ° C. by cooling. After stirring for about 20 minutes, a further 900 parts of water are added to the highly viscous contents of the flask and the mixture is stirred for a further 1 hour. The solution is about ll% ig · The viscosity of a l ° / _o by ^weight: solution at 20 ° C is 2.7 cps.

Claims (1)

Claim: Process for the preparation of neutral or basic solutions of water-soluble, nitrogen-containing, high molecular weight compounds Implementation of (I) ethylene imine or 1,2-propylene imine with
(JJ) 1 mol of a hydrocarbon compound which contains at least one epoxy group and at least one reactive chlorine, bromine or iodine atom not bound to the carbon atoms of the epoxy group or at least two reactive chlorine, bromine or iodine atoms bound to different carbon atoms, is in solvents at elevated temperatures, until the viscosity of a lgewichtsprozentigen solution at 20 ⁰ C for at least 1 cP and the product is still water soluble, characterized in that the molar ratio of component (I) to component (II) 3 to 100: 1. - Considered publications:
German patent specification No. 651 797.