DE2162567A1 - Process for the preparation of cationic, water-soluble, thermosetting, highly branched resins - Google Patents

Description

2Ί62567

Pcwiwofiwoif DipUng.P.Wii * Kpl.-Inn-G. Dannenberg Or. V. ScV i <J-Kowarzik Dr. P. WeinholJ, Dr. D. GucW

β FroaUurtfM ^ Gr. Eschenheimer Str. 3 *

SANDOZ Α.Θ. Basel, Switzerland

Case

Process for the production of cationic, water-soluble, thermosetting, highly branched resins.

The present invention relates to a process for the preparation of cationic, water-soluble, partially crosslinked, thermosetting, highly branched polyether (polyamide) polyalkylene-polyamine-epichlorohydrin resins. |

The present invention also relates to the use of these resins as an active ingredient in stabilized auxiliaries for the Paper industry, which are particularly suitable for increasing the strength of paper.

209830/0954

The present invention therefore relates to a method for the production of cationic, water-soluble, partially cross-linked, thermosetting, highly branched fibers (A), characterized in that a cationic, water-soluble, highly branched polyether (polyamide) polyalkylene polyamine, which from α) a polyether thread molecule with a terminal tert. Amino groups and quaternary ammonium groups in the chain and ß) to α) rare (polyamide) polyalkylene-polyamine residues, react with epichlorohydrin leaves.

Among highly branched polyether (polyamide) polyalkylene polyamines v / ground connections understood by implementation of polyether thread molecules of the schematic formula

RR ₁

R R,

V / ¹

Rg-N

(CH ₂ Cl) ₁

RR ₁

N-

R ₁ R

R ₂ -N-

IBI
■ ι-

R R,

X / ¹

-NO,

R _n R

N

(D

where R and R are an alkyl radical having 1-3 carbon atoms, R _{2 is} an alkylene radical having 2-k carbon atoms, each r, independently of one another, is an integer 2

up to 5,
s is an integer from 1 to 10,

209830/0954

2Ί62567

t O or 1
B.

-CH-O} -CH

CH ₂ -CH-CH ₂ - f 0-CH-CH ₂ JO- (CH ₂ ) ₂ ~ 0-fCHg

OH ^ I / X '^ I Sy OH

with (x + y) = r mean

with polyalkylene polyamines and / or polyamide-polyalkylene polyamines can be obtained. The polyether (polyamide) poly ™ alkylene polyamines and their production are not an issue of the present invention.

The polyether thread molecules (I) can be produced, for example, by practically complete reaction of a bivalent alcohol (II) (e.g. ethylene glycol) with epichlorohydrin in the presence of an etherification catalyst and subsequent reaction with an excess of a secondary amine (e.g. dimethylamine) and / or bitter . Diamines f (e.g. Ν, Ν, Ν ¹ , N'-tetramethylethylenediamine).

The polyamide-polyalkylene-polyamines can be obtained, for example, from (i) a polyalkylene-polyamine of the general formula

^H 2 ^N - ^C p ^H 2p PVQ

where ρ is an integer 2 to 4

and q is an integer 1 to K ,

209830/0954

and (ii) a C to C ₁₀ saturated aliphatic dicar-

bonic acid or a functional derivative of these dicarboxylic acids in a molsrem ratio (i): (ii) = 0.8: 1 to 1.5: 1, preferably 0.9: 1 to 1.2: 1.

As polyalkylene polyamines, for example, polyethylene polyamines, Polypropylene polyamines and polybutylene polyamines are used, of which the polyethylene polyamines are the are economically preferred. Not only can polyamines be used alone, but also Mixtures of the same and their raw products. Compounds recovered from still bottoms from refining of the lower Polyiithylen-polyamines are made and essentially Polyamines higher than tetraethylene pentamine can also be used.

Suitable dicarboxylic acids include malonic acid, succinic acid, Adipic acid or azelaic acid can be used. The saturated dibasic acids with 4 to 8 carbon atoms in the molecule are preferred. Mixtures of two or more saturated dicarboxylic acids can also be used.

I *

The dihydric alcohols (II) can increase branching of the polyether- (polyamide-) polyalkylene-polyamines (I) partly also by trivalent alcohols (e.g. glycerine) er-BotiiV uordon,

/ π 9 P: U) / 0 9 5 L

The Pjolyäther- (polyamide) polyalkylene polyamine (IV) according to the invention is reacted with epichlorohydrin at from 0 ° to 5O ⁰ C to obtain secondary amine group of the compound (IV) is about 0.6 to 1.8 moles of epichlorohydrin in the course of introducing 10 minutes to 2 hours and then further reacted at 30-80 ° C until the Umsetzungsgut, at 25 ⁰ C measured viscosity has been reached, which is greater than about 100 cP. The reaction is interrupted by rapid lowering of the pH to 6 and lower (eg 4), dilution with water and cooling to about 25 ⁰ C. The end product obtained is a cationic, water-soluble, partially crosslinked, heat-curable, low-viscosity, highly branched polyether- (polyamide) polyalkylene-polyamine-epichlorohydrin resin.

Another object of the present invention are the stabilized auxiliaries, which contain, as active substance produced according to the invention cationic resin in a preferred concentration of 5 ^Dis 25 percent by weight in aqueous solution.

Another object of the present invention is the use of these enhancement aids in the paper industry the strength of paper, the retention of powder and fines in paper production and for cleaning of sewage containing suspended matter.

209830/0954

Another object of the present invention is that Paper, which by using the auxiliary which contains the resin (A) prepared according to the invention as an active ingredient, is obtained.

Production of polyether-polyamide-polyalkylene-polyamine (not the subject of the present invention)

1. Manufacture of the polyether thread molecule

l86 g (3 mol) of ethylene glycol and 5 ml of boron trifluoride etherate, in a 4-necked flask which is equipped with a mechanical stirrer, a reflux condenser with calcium chloride tube, a thermometer and a dropping funnel, condenser and heated to 5O ⁰ C. Then, in the course of 90 minutes, with good stirring 1110 g (12 mol) of epichlorohydrin are added dropwise, keeping the temperature between 55 and 7O ⁰ C is maintained by cooling. The reaction mixture is then stirred for a further 6 hours at 65 ^° C. and then cooled to room temperature. The polyether-polychloride-bis-chlorohydrin is obtained as a pale yellowish, slightly viscous, clear liquid with a solids content of 100 %. 520 g (1.2 mol) of the polyether-polychloride-bischlorohydrin thus obtained are placed in a 4-necked flask equipped with a mechanical stirrer, a reflux condenser, a thermometer

209830/0954

and a dropping funnel is provided, mixed at room temperature with 180 g (1.6 mol) of a 40 # aqueous diethylamine solution. Then 107 g (0.8 mol) of a solution of JO $ aqueous sodium hydroxide solution are added dropwise so that the temperature does not exceed 6O ⁰ C. Subsequently is heated after a short stirring at 8O ⁰ C and further reacted for 3 hours. After addition of 316 g of water through the reaction 2.4 mol of chlorine ions is further stirred at 8O ⁰ C, were formed. It is cooled to room temperature and the polyether thread molecule is obtained as a pale yellowish, clear liquid with an active substance content of 50 #.

2. Production of the polyamide-polyalkylene-polyamine

1090 g (10.6 mol) Diathylentriamin be diluted in a vessel equipped with a stirrer, with external cooling so slowly with 400 g of water, that the internal temperature remains below 70 ^0C. 1460 g (10.0 mol) of powdered adipic acid are then introduced so slowly that the internal temperature can be kept at 50-90 ° C. by external cooling. The stirred vessel is closed and provided with a fractionation column to which a descending condenser is connected. With an oil bath under nitrogen innerhalt one hour at ⁰ C and then 120-1JO within 6 hours at 170-175 ° C

7 1: H 'n H »/ 0 9 S i>

Internal temperature heated. The water used for the solution and the water formed during the condensation is distilled off through the column, less than 4 g of diethylenetriamine being entrained by the water vapors. The mixture is stirred for a further 5 hours at 170-175 ° C. and the column with the descending condenser is then replaced by a reflux condenser. After cooling to 150-l60 ^o C to 328O g water is run in such a way that the inside temperature gradually falls under constant reflux at 100-105 ⁰ C. The mixture is refluxed for a further hour and, after cooling, a clear solution of the polyamide-polyalkylene-polyamine which contains 40 % of the particulate matter is obtained.

5. Manufacture of polyether-polyamide-polyalkylene-polyamine

94 g (corresponding to 0.2 mol of chloromethyl groups) of the polyether thread molecule obtained under 1., 24 g of water and 2180 g (0.2 mol) of the polyamide-polyalkylenepolyamine prepared in accordance with 2. are placed in a flask equipped with a stirrer, reflux condenser and thermometer mixed and ^{reacted at 100 0} C until all chloromethyl groups have reacted. It is then cooled to room temperature. The polyether-polyamide-polyalkylene-polyamine is obtained as a clear, yellowish aqueous solution with a dry matter content of 40%.

209 8 30/0 9 SU

The following examples illustrate the invention without this to restrict in any way.

example 1

400 g of the polyether-polyamide-polyalkylene-polyamine (which was obtained as described above) are mixed with 166.5 g of water in a flask equipped with a stirrer, reflux condenser and thermometer. Then, in the course of J50 minutes 111 g of epichlorohydrin are added dropwise (corresponding to 1.64 moles per secondary amine group of the polyamide-polyamine) at 20 to 25 ⁰ C ™ and weiterverrührt at this temperature for 60 minutes. Then is heated to 5O ⁰ C and reacted further until the viscosity of the reaction material, measured at 25 ⁰ C, 400-500 cP. By rapid addition of 668 g of water and 10 a 56.5 #igen hydrochloric acid, and while cooling to 20-25 ⁰ C g is interrupted the reaction. The pH is adjusted to 5.0 with additional hydrochloric acid. The end product is obtained as a pale yellowish, clear, low viscosity, aqueous solution with an active substance content of 20 %. The solution is stable at room temperature for more than 120 days.

209830/0954

Example 2

The procedure is as in Example 1, except that 600 g of the polyether-polyamide-polyalkylene-polyamine (instead of 400 g), 5II g of water (instead of 166.5 g) and I33 g of epichlorohydrin (corresponding to 1.31 mol per secondary amino group of the) are used. Polyamide-polyamine). If the viscosity of Umsetzungsgut'die I8O-25O cP, measured at 25 ⁰ C, has been reached, the reaction is stopped by rapid addition of 2490 g of water and 6 g of a 36.5 #igen hydrochloric acid, and while cooling to room temperature. The end product is obtained as a pale yellow, clear, aqueous solution with an active substance content of 10 % and a pH of 5.0. The solution is stable at room temperature for more than 120 days.

209830/0954

example

A slurry of bleached sulfite cellulose in water is ground to a degree of 55 ° C. Schopper-Riegler in a Dutch laboratory, type Valley. After adding the product prepared according to Example 1 in the amount indicated in the table (# based on dry cellulose), sheets are produced on a sheet-forming plant according to Rapid-Koethen and subjected to ^{a heat treatment at 105 ° C. for 2 hours.} Now 15 mm wide strips of paper are cut from it. These are placed in water at 20 ^° C. for 15 minutes, cooed between 2 sheets (3/4 glued) for 1 minute under a load of 10 g / cm and then tested for their wet breaking load.

The results are summarized in the table below:

% Resin based on
dry pulp Sheet weight
g / m ² Nas s break load
kg 0.0 (blind test) 135.2 0.3 0.5 135.6 1.8 1.0 134.8 2.3 1.5 I36.O 2.6 2.0 135.3 3.1

2098-30 / 0954

It is of course possible, without departing from the scope of the invention, to make changes, the principles given in the above description and in the claims for the person skilled in the art result. These changes relate in particular to the participants in the reaction, their character, their composition and their molar ratio, as well as the reaction conditions and the active ingredient content of the end products.

209830/0954

Claims (1)

Claims Y 11 Process for the preparation of cationic, water-soluble, partially crosslinked, thermosetting, highly branched resins (A), characterized in that a cationic, water-soluble, highly branched polyether (polyamide) polyalkylene polyamine, which is composed of α) a polyether Thread molecule with terminal tert. Ä ß) consists amino groups and quaternary ammonium groups in the chain and to α) pendant (polyamide) polyalkylene polyamine residues, with 0.2 to 2.0 moles of epichlorohydrin per secondary amine group of the (polyamide) polyalkylene polyamine to react. 2. The method according to claim 1, characterized in that 0.6 to 2.0 moles of epichlorohydrin per secondary Amino group of the polyamide-polyalkylene-polyamine and / or of the polyalkylene-polyamine is used. | J. Method according to claim 1, characterized in that the reaction is carried out with epichlorohydrin initially at a temperature between 0 to 50 ⁰ C and then at a temperature between 30 and 8O ⁰ C. 209830/0954 4. Aid on the basis of a stabilized, 5 to 25%, low-viscosity aqueous solution of the claim 1 prepared resin (A). 5. Use of the auxiliary claimed in claim 4 for the paper industry. 6. Use according to claim 5 to increase the strength of paper. 7. ^% use according to claim 5 ^to increase the retention of fillers and fines in papermaking. 8. Use according to claim 5 ^{for the} purification of wastewater containing suspended matter. 9. Paper produced by using the auxiliary claimed in claim 4. The patent attorney 209830/0954