DE1595302A1 - Process for the production of water-soluble condensation products - Google Patents

Description

BAD ISCHE ANILIN- * S ODA-PABRIK AG ■ -— '

Our reference: O. Z. 24 094 Wed / Bö Ludwigshafen / Rh., February 7th. I966

Process for the preparation of water-soluble condensation products

The present invention relates to a process for the preparation of new water-soluble condensation products from ε-caprolaotam, alkylene polyamines and epiohlorohydrin,

US Pat. No. 2,720,508 describes the preparation of water-soluble and water-insoluble condensation products £ -Caprolaotae and alkylenepoly amines known. These condensation products leave in their property as textile and Paper auxiliaries, however, are to be desired, as they have only a moderate affinity for textiles and paper, see above that it was the object of the present invention to enrich the technology over more suitable means of this type su.

It has been found that valuable condensation products et al. for the purpose of textile and paper finishing, if one receives

a) each with 1 mole of an alkylenepolyamine

b) 1 mole to 1.3 mole of g-caprolactam

009810/1843

BATH ORIGINAL

—Ά— υ · ώ. et

reacted in a manner known per se, where r is the number of amino groups in the alkylene polyamine, and the resultant Intermediate condensation product in the aqueous medium with

c) 1 to 2.5 moles of epichlorohydrin per mole of basic amino groups present in the intermediate condensation product,

likewise in a manner known per se further allowed to react until a ,, # 15 aqueous solution at 2O ⁰ C a viscosity of between 30 and 100 cP, after which the solution is by addition of an acid to a powert below 6, the reaction üb cancel.

As alkylenepolyaines (a) come in the third line those of general? or »el I

H ₂ N- (R-NH) _n -H (I)

in consideration, in the R «in possibly duroh Aalno« or Substituted unbranched or branched hydroxyl groups Alkylene radical with 2 to 6 carbon atoms and η a value of 1 to 5 and where the total number of all carbon atoms is 2 to 12.

Examples of such compounds are ethylene diamine, 1,3-propylene diael, hexamethylene diamine, triaainopropane, 1,3-diamino-2-hydroxypropane, triethylenetetramine, pentaethylenehexamine, dihexamethylene triamine and, in particular, dir (i, 3-propylene) triamine, di- (I, 2-propylene) -triamine and above all

BATH

Diethyl triamine. Mixtures of different compounds (a) are also suitable.

The reaction of these alkylene polyamines (β) with the 6-caprolactam, which runs with elimination of water, can in a known manner an.sich DFTR by heating the components to temperatures between 150 and 280 advantageously 200 and 260 ⁰ C, take place.

It is useful here to remove the water from the reaction mixture to be removed continuously. It is also recommended to avoid unwanted discoloration. in the absence of air to work, e.g. under a nitrogen atmosphere.

The reaction of (a) with (b) is essentially complete, if no more water splits off, however, you can use them beyond this point in time to further increase the degree of condensation continue even longer. After that still unchanged remaining starting material is advantageous removed by distillation.

The Zwischenkond ens ati ons -is product thus obtained, regardless of ₉ ob.es is completely water-soluble or water-insoluble yet, Anteile'enthält _r ISS wässrige® medium in an initial! Consent rat ion you fo 20 to 50 in a known manner with 50 "bia 8ö% © it 'der iefiait quantity ρ-" preferably I ₀ 2 Ms 1 ^ 6 jS0JLä <pi ¥ © X © st © a aydrin weiteruHigeB et.2t ο

BAD 0RiQS ^ 5AL

-4- U. Δ. * 4

The amount of epichlorohydrin depends on the number of basic groups present in the intermediate condensation product, which are best determined by potentiometric titration happens with hydrochloric acid, depending on the polyamine used the transition point for the quantitative recording of the amino, groups is different. In the case of polyamines with weakly basic secondary amino groups, such as diethylenetriamine all amino groups only recorded through the consumption of HCl up to about p "2.0. The addition of the epichlorohydrin can be advantageous

may be done in portions. The gradual condensation with epichlorohydrin has an accelerating effect on the course of the condensation. During the condensation is diluted with additional water, in general, so that the final products in 10 to 20 ^ strength solution having a preferred viscosity of 30 to 100 cP at 2O ⁰ C are present. It is also advantageous to add up to 1 mole per mole of epichlorohydrin after the epichlorohydrin has acted on the intermediate alkali metal hydroxide, alkali metal carbonate or ammonia for a sufficiently long time. In order to prevent further condensation, the end products are brought to a p "value below 6 with an acid. Suitable acids are, for example, hydrochloric acid, sulfuric acid, acetic acid and toluenesulfonic acid.

The products of the process are available as aqueous solutions, as one it receives immediately in the implementation, the most diverse Uses, e.g. as a textile finishing agent, paper

-5- 009810/1643

-5- O.Z. 24 094

wet strength agent, filler retention agent for paper, Flocculants, fixatives or anchoring agents for Plastic films with cellulosic materials are supplied.

Examples

1 mole of an alkylene polyamine of the formula I.

H ₂ N- (R-NH) _n -H,

characterized by R and n, 'was heated with χ mol of f-caprolactam while passing nitrogen through. Of 200 ⁰ C to the reaction time t was measured and gradually further heated to 25O ⁰ C and held at 25O ⁰ G to give about y moles of water formed that were continuously distilled off from the "reaction mixture. The yields of higher molecular weight condensation products amounted after removal of up to 240 ⁰ C at 20 Torr volatile permitting re-use of play ρ #, based on the employed (Jesamtmaterial. the base equivalent of t moles of hydrochloric acid m gram were determined this intermediate condensation product, the strength at about 40 to 7O ⁰ C in 25 # aqueous solution the addition of the Epichlornydrins was reacted with epichlorohydrin per mole ζ Basenäcfuivalent. the lane involved in 2 portions with 0.75 moles first Epi chi Orhy it. After resolution of the relatively violent reaction with self-heating to about 9O ⁰ C, the temperature was by addition of water lowered to 60 ⁰ C and with the remaining amount (z - 0.75) mol of epichiorhydrin further

008810/1641

-6- 'O.Z. 24 094

condensed. With increasing conversion, the ^N reaction solution was continuously with the temperature of about 60 ^{0 C being maintained}
Water diluted to an approximately 15% solution. In addition, q mol of a base in aqueous solution were added to the reaction mixture after the reaction had progressed. After the viscosity V was reached, the solution was treated with concentrated hydrochloric acid
set to Ptt 3.5, as a result of which the final viscosity of the
obtained solution increased by about $ 10 to $ 20.

The viscosities of the products were V for 15 # aqueous solutions at 25 ⁰ C with the aid of Tausz viscometer.

The immediately obtained aqueous solutions of the process products were outstandingly suitable for use in
the textile and paper industry

The following table gives an overview of the individual examples

009810/1643

159530;

rH W. VO U.N. CU O CU co ·> Α O VO ON > ■ * ' l> - ■ ^ U.N. OS t * ~ Fir Ul O OS votr KNW ■ a ^ inc O KN ·> Β U.N. KNO
·> «J UN KN in ° ⁸ OS CU OS OS οπ = ρ OJ r-l U.N. U.N. t-H in in U.N. CU CU «\ • v · »■ U.N. ·> • Η N
Pl
M. rH CU t-H rH rH • ι rH •H VO O O CU ■ ■ O O ON t «- CU O Ί to rH • l • ι r-i * * ON co co O U.N. O iH VO KN E. in O KN KN C- rH KN O VO t-H rH iH U.N. CU t-H CO CU CU U.N. VO U.N. I. vo ■ st I - J VD KN U.N. Pl VO CO CU CU co VO in CU C- VO C- HO) C- C- O O U.N. O I. U.N. OJ, E ■ O C- in U.N. U.N. U.N. t-l CU ₍ ■ O O O O O co O O Cj co in U.N. I-J · » CU -P O VO VO KN £ $ ■ J * rH co E. CD ο VO «J in H ΤΤ · " ο ο t-H in m O O U.N. U.N. m Pi ' ^J
oJ X O CU CU U.N. KN CU CU CU Ö
• Η C3 CU in ι-Η O I. CU CVl CU CU CU rH CU rH CU Φ O I. I. I. H I. CU CVJ
te OJ
Ä CU
W. ϊχΓ I. I I
CU VO CHg O O O O VO I. I. I. I. I. I. CVl CU CU *
Pl CU CH ₂ O CHg CHg (CH ? O O M. O ^{1 1} I. I. I. I I • Η t-H I. α> CHg I. KN ■ = i- U.N. VO C- ON O t-H CU

ir6o 17S ^# Z '

ORIGINAL INSPECTED

810/1643

Claims (6)

-8- O.Z. 24 094 claims 1. A process for the preparation of water-soluble condensation products, starting from 6-caprolactam and alkylene polyamines, characterized in that a) each with 1 mole of an alkylenepolyamine. b) 1 mole to 1.3 mole of 6-caprolactam implemented in a manner known per se, where r is the number of Amino groups in the alkylenepolyamine, and that the intermediate condensation product thus obtained is in an aqueous medium with c) 1 to 2.5 moles of epichlorohydrin per mole of basic amino groups present in the intermediate condensation product are, can react further in a likewise known per se, until a 15- ^ aqueous solution at 20 ⁰ C a viscosity between 30 and 100 cP, after which the solution is adjusted by adding an acid to a _pH value below 6, to cancel the reaction. 2. The method of claim 1, characterized in that _t the extent the reaction of the alkylene polyamine (a) with the £ -caprolactam (b) about until this case no more water is eliminated. -9-009810 / 1643 -9- O.Z. 24 094 ■ 3. Process according to Claims 1 and 2, characterized in that the water formed in the reaction is continuously removed from the reaction mixture. 4. Process according to Claims 1 to 3, characterized in that one of an alkylenepolyamine (a) of the general formula I in the R one optionally by amino or hydroxyl groups substituted unbranched or branched alkylene radical having 2 to 6 carbon atoms and η is a value of 1 to 5, and the total number of all carbon atoms being 2 to 12. 5. Process according to Claims 2 to 4ι, characterized in that diethylenetriamine is used as the alkylenepolyamine. 6. Process according to Claims 1 to 5, characterized in that one starts from 1.2 to 1.6 mol of epichlorohydrin. BADISCHB ANILIN- & SODA-FABRIK AG 009 810/164