CS212860B1 - Water soluble polymer - Google Patents

Description

The present invention is a stable, water-soluble polymer containing bound nitrogen and chlorine. Water soluble nitrogen-containing polymers are used in a variety of art and technology. Thus, some specific properties of such polymers such as cationic activity, surface tension reduction, increase in wettability and the like are advantageously utilized. Larger quantities of polymers of this type are known, but the most commonly used are the condensation products of low molecular weight polyaminoamide resins β epichlorohydrin, diohlorohydrin glycerin, diglycidyl ether, dichloroethane, glyoxal, divinyleulfone, acrolein and the like, (British Pat. 1,035,296? British Pat. U.S. Pat. No. 3,095,427; U.S. Pat. No. 3,240,664; U.S. Pat. No. 3,332,901, U.S. Pat. No. 3,733,290, U.S. Pat. No. 1,177,824, and the like). Known polyaminoamidových condensates with epichlorohydrin resins, optionally with additional acrylate * «au _in Kami (krartemizačními agents) rSak have serious drawback to impeding limiting their wider use. This is a very low stability, manifesting itself in storage at the beginning of a rather rapid increase in viscosity and then the formation of insoluble gel. Due to instability, the properties used subsequently change and the product loses its effectiveness or becomes unusable. The cause of low stability is the ongoing termination and propagation reactions between the primary and secondary amine groups of the polyaainoemide resin and the halomethyl groups of epichlorohydrin, which are slowed but not stopped by lowering the pH of the solution (acidification). No method of increasing etabili212 860 has been described in the literature

212 880 or water-soluble polymers, good storage.

We have now invented a water-soluble polymer containing nitrogen and possibly also chlorine, which has long-term stability even at elevated temperatures while retaining the desired cationic and other properties. The polymer according to the invention is prepared by polycondensation of 1 mol. parts of a polyaminoamide resin having an average molecular weight of 200 to 950 and an amine number of 350 to 980 mg KOH / g, obtained by reacting a dicarboxylic acid of 2 to 10 carbon atoms in the molecule or a mixture of these acids with a polyalkylene polyamine of 60 to 650; alkylene is ethylene or propylene, or mixtures of these polyalkylene polyamines in a molar ratio of 1: 1.9 to 2.1 with 0.9 to 1.6 mol. parts of dichlorohydrin glycerin and / or epichlorohydrin and 0.4 to 1.1 mol. parts of ethylene chlorohydrin or monochlorohydrin glycerin. The polymer according to the invention has an average molecular weight of 370 to 100, an amine number of 200 to 700 mg KOH / g and a bound hydrogen chloride content of 8.2 to 27.0% by weight.

The reaction product (polycondensate) is diluted with water to a suitable concentration, most often to a dry matter content of 30% by weight. Additions of acids to monitor pH are not necessary because the termination and propagation reactions in the polycondensate are complete. In addition, aqueous solutions at pH below 5 are subject to gradual degradation due to saponification of the amide bonds under proton catalysis. At the native pH (which is higher than 7), the melting takes place practically.

The water-soluble polymer of the invention can be prepared by several methods. The simplest is the process of condensing a polyaminoamide resin with epichlorohydrin (propagating agent) with mono-chlorohydrin (terminating agent) in the presence of boiling water at a temperature of usually 102-105 ° C, for 2.5-5.5 hours. The end of the reaction is detected by stopping the growth of the ionogenic chlorine (chloride) content. Other methods of preparation involve pre-condensing the propagation or termination reagent with polyamides, followed by reacting the product at elevated temperature with the dicarboxylic acid.

Due to the high functionality of the substances involved in the reactions and emerging intermediates, in the present state of analytical and computer technology it is not possible to accurately describe the structure of the polymer, which is probably formed by a mixture of polymerhomologists with unknown molecular weight distribution.

The polyaminoamide resin is prepared by known processes from dicarboxylic acids, in particular succinic, glutaric, adipic, sebaceous, cork and the like. or mixtures. Most often, the polyamide is carried out at temperatures of from 160 to 200 ° C, with gradual distillation of the reaction genus, until the acid number falls below 5 mg KOH / g. For easier handling, the polyaminoamide resin is used in the form of an aqueous solution. The water-soluble resin of the invention is then prepared by reacting a polyaminoamide resin with a mixture of epi-chlorohydrin (dichlorohydrin glycerin) with mono-chlorohydrin glycerin (ethylene chlorohydrin). Bplohlorohydrin reacts in two stages, firstly by alkylating the primary amino groups with an epoxy group. This reaction is already underway and is strongly exothermic. It is only in the second stage that the propagation and termination reactions take place simultaneously, in which the endothermic alkylaol of predominantly secondary amine groups occurs.

I 212 880 pin groups - CHgCl, wherein the neutral hydrogen chloride is neutralized by the tertiary nitrogen present. Chlorine therefore exists in the product in an ionized form (aqueous solution) and can easily be determined by argentome t-shirts or mercury meters. End of growth of ionized chlorine content End of propagation and termination reactions.

The dispersible polymers obtained by polycoadensating a polyaminoamide resin with eplchlorohydrin in a molar ratio higher than 1: 1.6 are virtually unusable for the extremely high viscosities or gel structure of polycondensates.

Example 1

By reacting 2 moles of diethylenetrlamine β with 1 mol of adipic acid, a polyaminoamide resin (PAAP) having an average molecular weight of 399 and an amine number of 611.1 mg KOH / g is prepared. The resin was dissolved in water to a 50% solution. The water-soluble polymer is prepared by reacting 1 mole of a polyaminoamide resin with epichlorohydrin and glycerine monochlorohydrin while boiling. The end of the reaction is detected by stopping the growth of the ionizable chlorine content. The product parameters vary depending on the molar ratio of the components according to Table 1, wherein m is the mass, n the amount of substance, V the viscosity at 20 ° C, the N amine number and the X content of chlorine.

Table 1

PAAP epichlor- hydrin monochlorr hydrin 30% aqueous solution m («) n (mol) m (g) n (mol) m (g) n (mel) V (mPa.s) R (mgKOH / g) X (% wt) 399.5 1.00 87.2 0,942 116.9 1,058 8.46 61.1 4.89 399.5 1.00 105.6 1,141 94.9 0,859 11.41 60.1 4.79 399.5 1.00 111.0 1,200 88.4 0,800 11.90 64.5 4.14 399.5 1.00 129.5 1,400 66.3 0,600 20.4 67.4 4.12 399.5 1.00 143.4 1,550 49.7 0.450 165.3 61.9 4.15

Example 2

Polyaminoamide resins were prepared as described in Example 1. 1 mole of a 50% aqueous solution (799 g) was reacted while boiling with 1.6 mole of glycerin dichlorohydrin (206 g) and 0.4 mole of ethylene chlorohydrin (32.2 g). Polycondensation is complete after 3 hours. The product has an average molecular weight of 638.1, an amine number of 351.7 mg KOH / g, and contains 11.11 wt. ionizable chlorine. The viscosity of the 30% solution in water is 55.6 mPa · s / 20 ° C.

Example 3

Reaction of 1 mole of sebacic acid (202.2 g) with 2 moles of polyamine provides a polyaminoamide resin. 1 mole of this resin is reacted with boiling with 1.5 mole epichlorohydrin and 0.50 mole monochlorohydrin glycerine for 2.5 hours. Depending on the polyamine used, a product with the parameters according to Table 2 is obtained, where M is the average molecular weight, the N amine number, the X content of the chlorine & V the viscosity at 20 ° C.

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Table 2

Polyamine PAAP Product ¹ - ¹ ...... i ? m (g) M N N M X (% wt) V (mPa.s)

Etylendi-

amine 120.2 281.3 389.9 236.1 475.3 14.93 43.6 Diethylene- triamine 206.2 368.8 608.6 398.8 562.8 12.60 57.2 Trio tyleatetramine 292.4 450.5 747.3 520.3 644.5 11.00 62.1 Tetraety- lenpentamine 378.4 542.8 825.2 605.8 736.8 9.63 65.8 Tetrapro- pylenpentamine 490.8 650.5 690.1 528.1 844.5 8.40 72.4

Example 4

Reaction of 1 mole of succinic acid (118.1 g) and 1.9 mole of diethylenetramine (195.9 g) to prepare a polyaminoamide resin having an average molecular weight of 275.9 and an amine number of 793.1 mg KOH / g. 1 mole of this polyaminoamide is reacted and boiled with 1 mole of epichlorohydrin (92.5 g), 0.5 mole of diohlorohydrin glycerin (64.5 g) and 0.5 mole of mono-chlorohydrin glycerin (55.3 g). After 3.5 hours of polycondensation, a product having an average molecular weight of 485.2, an amine number of 446.1 mg KOH / g, and a chlorine content of 18.2% by weight is obtained. and a 30% aqueous solution viscosity of 68.6 mPa · s / 20 ° 0.

Claims (2)

A water-soluble polymer capable of being prepared by polycondensation of 1 mol. % of a polyaminoalkid resin having an average molecular weight of 200 to 950 and an amine number of 350 to 980 mg KOH / g, obtained by reacting a dicarboxylic acid of 2 to 10 carbon atoms in the molecule or a mixture of these acids with a polyalkylene polyamine of 60 to 650; is ethylene or propylene, or mixtures of these polyalkylene polyamines in a molar ratio of? 2.1, with 0.9 to 1.6 mol. % of glycerol and / or epiohlerohydrin diohlorohydrin; and 0.4 to 1.1 mol. part of ethylenohlerhydrin or monoohlorohydrin glycerin.