CS245170B1 - Water-soluble cation active polyelectrolyte and method of its production - Google Patents

Description

This invention relates to water-soluble cationic polyelectrolyte, which can be applied to text him zu ^{il ŠL} echíov ^{tio n s P} ro increases ^and stain-elnosti ce ^ ^ l-voltage fibers zvytaváiní vabarvení fastness and dyeing reactive dye finishing ·

So far, Zn ^and m ^s for ^{alkyl or} rav zvyšovón ^s color.! ^{lo h} zovýc cell fibers ^were based on the use of quaternary ammonium compounds derived from tertiary amines and epichlorohydrin, with one reactive group

-CH 2 -CH-CH 2 v

or -CH ₀ -CH-CH ₀ III

OH Cl

Increased effects exhibit a quaternary ammonium compound derived from heterocyclic compounds ^{and no} en ns ^d VEMA ^du atoms having ^I to _L ^{to the} now obsolete maj ^{í ð} the realctivní Gr n ^{and y.} Two Reakt ^and HV ^and with ^the u ^p in the ^{y á} allow ZAT oximes in m ⁱ re ce ^l l to ^about ZOV ^á aa VLA simultaneously forge ce ^l l ^{a s} ZOV ^of Ret chain.

Have general formula (1)

Γϊ-μ-ϊ 1 ** * x ^r - (1) i Jr where Ϊ is a group

-CH ₀ -CH-CH ₉ or -CH 2 -CH-CH 2

Iv

OH C10 is an integer of 1, 2 or 3 k is an integer of 1 or 2

X is an anionic residue of a strong inorganic or organic acid

M is a heterocyclic radical derived from a heterocycle having two nitrogen atoms.

These compounds can also be used to increase the color fastness of substantive dyes. Their effect on dyeing with other anionic dyes is only moderate. They also have little effect on dyeing with reactive dyes.

Subsequent to dyeing or printing, the dye which is not sufficiently fastened to the fibers has to be removed from the textile materials, sorbed auxiliary chemicals have to be removed, and for some dye groups additional dye washability can be additionally reduced, for example.

Washing tex ^l them ^{al office} process textHníto echlovéín zu ^ ^ p e ^{of d eV} to ^b m · arven and print 'is a lengthy process that makes high demands on the consumption of process water and energy.

Washing is optional ^and Ste impor ^fo t ^{é é} and complicated ⁱⁿ dyeing and poti.stové ^í ^ u ce ^{l lo} ZOV ^ý c ^h materials reactive dyes. When coloring with this group of dyes, it is known that only part of the dye reacts with the cellulose fiber. A relatively large proportion of the dye hydrolyzes and must be removed. On m e ^ir perfection wash ^hyd ro ^{l b} yzovaného ARVs ^also depends on your color fastness or printing.

The solution to the problem of reactive dye washing has been - and is directed in several ways.

In particular, reactive systems and dye constitutions are sought which are fixed to the fiber with the highest yield so that the lowest possible amount of dye is removed by washing.

The second direction up atnujíc ^{l s} j m is also ^at a ^{LBE Iz} ^ cons tution dye is that the dye was hydrolyzed ce preferably washable. Other options are applied in the choice of washing procedure, both in terms of technology and machine choice.

An interesting technology is the use of sorbent suspensions. However, their use is prevented by a relatively high price and also the design modifications of the machinery have not yet been fully solved so that the sorbent property can be fully utilized.

Often is the use of ^{Gd and} NO and ^{H for} various type ation ^KTI vníc ^ ^h ^ ípirav ^to ter ^s and ^{p if} TO, THE final washing and have the purpose of blocking the radicals nevypraného dyes. This procedure is all Uve ^d enýc ^h ly ^from Wear them NEJM ^{s d d} Oru ^chit elný, or u in ^TS in color ^even in ^{y d} oc ^{HA s} healed light fastness.

^{Significantly EFFECTIVE} n ^{ky at} about ^d 8 ^t ra ^{NIVTE ck} h ^yd ro ^ly ionised ^{eh -p} o ^says lu reactive ^T IVN ^I No. ^HB arv ⁱ vs celulozovýc ^{h pickle} en ^{b r} arven ^greater than ^B o ^{p TI} Skov ^and N ^{and at} a ^{p l} e n ^e owls ^{and tal} axis ^t i v ^yb arven ^í ^ osta requires great especially substantive anionic dyes were produced using the newly created rows of cationic polyelectrolyte containing group of structural formula (2)

OH OH (2) where r is an integer of 1 to 3 which denotes the valency of rniion X k is an integer of 1 or 2 n is an integer of 2 to 10

X is the anionic residue of a strong inorganic or rrgnnic Pure s is an integer from 1 to 4

M is an effervescent residue

R is hydrogen or alkyl having 1 to 4 carbons

The formula of the polyelectrolytes can also be expressed in a complex manner, using the symbols for repeating parts of the chains and 8ubstatunn in the formula where the integer is 1 to 3 is an integer 1 or 2 is the integer 2 to 10 is an anionic residue strong inorganic or organic acids

X

A Is defined as

-CH ₂ -CH-CH ₂ -M ^{k +} -CH 2 ^- (R ₂ ^- ) -

M is a bifunctional heterocyclic radical as defined above

B is defined as for x = 1

or

- K- < ^CH 2) _n ] e - ^NR 3 ·

Τ ’

N- (CH _{2) n] 4} * -NR ₈ - ^<CH 2) n ^NR 3 ^j et

for values x = 2

R 1 are -Cl, -OH, or H-BR 2 is hydrogen, or -A-OH, -A-Cl, -A-B-H, -A-B-A-R,

R 4 R 4 are hydrogen or alkyl having a carbon number of 1 to 4 s is an integer of 1 to 4 ·

The continual polyelectrolyte is. obtainable by reaction of compounds of the general formula and multifunctional amines of the general formula (3) (1)

HN <“ ² >» - «

(3) wherein n, a, R1, R4 are as defined above.

0.1 to 2 moles of multifunctional amines of formula (3) can be used per mole of compound of formula (1). Particularly suitable properties have polyelectrolytes formed by the reaction of the compounds of formulas (1) and (3) in a molar ratio of 1: 0.5 to 1 µl.

The multifunctional amines of general formula (3) which can be used are preferably those available in the chemistry of epoxy resins and in the production of complexing agents. Such amines are, for example, ethylenediamine, diethylenetriamine, and triethylenetetremine.

The preparation of the compounds of formula (1) has already been described and protected. Usually, a salt of a strong acid and a heterocyclic compound with two nitrogen atoms is first prepared, and the aqueous solution of the salt is quaternized with epichlorohydrin so that 2 moles of epichlorohydrin are present per mole of salt. After the quaternization is complete, the process of the invention can be followed, the multifunctional amine of Formula 3 or an aqueous solution thereof can be added sequentially. ESPONDING ^R is ^H exotic erm ⁱ c ^p rot ^Ka> IHE ^on that lot ^{P and} Ch ^{10 and 100} ° ≤ preferably te ^r M ^{p-temperature} range ^{at 40} to 60 ° C.

After completion of the reaction, the resulting product was used without. other adjustments.

^EFFECTIVE concentration nn ^{e la} area in the mixture ^can ožadavk ^{P y P} mani Ulac ^when processed. It appears. It is advantageous to use aqueous solutions of the substances according to the invention having a concentration of 40 to 60%. Products with a higher concentration of active substance have too high a viscosity which makes processing difficult to handle.

Since the compounds of formula (1) are prepared as aqueous solutions having an active compound content of 70 to 85%, in order to maintain the above-mentioned condition for the concentration of the compound of the invention in the final product up to 50% ·

The resulting reaction products are at an active substance content of 40 to 60% yellow-brown viscous liquid with a specific gravity of 1.3 to 1.5 g.cm &lt; -1 &gt;

Some possible uses of the starting materials and their molar ratio in the reaction are shown in Table 1.

Table 2 shows the formulas of the basic structural units of these compounds.

Compounds of the invention exhibit a variety of properties applicable in refining technology * In alkaline conditions, they can react with alcoholic -OH groups of the cellulose macromolecule and cause cross-linking thereof. of formula (1) ·

Against these compounds, however, the compounds of the invention have a marked fixing effect on anionic dyes. Due to the appropriate arrangement of the -NH- and -OH groups, the cationic polyelectrolytes are capable of binding metal cations.

The process for producing a water-soluble cationic polyelectrolyte is explained in more detail in the following examples.

Example!

318 g of a 83% aqueous solution of 1,3-bis (3-chloro-2-hydroxypropyl) imidazolinium sulfate are poured into a glass four-necked flask equipped with a reflux condenser, stirrer, thermometer and a separatory funnel for dispensing. The temperature is adjusted to 25 ° C and 120 g of 50% ethylene amine are metered into the flask with stirring over 60 minutes. The temperature of the reaction mixture starts to rise spontaneously. The temperature is maintained at 65-70 ° C by cooling and at the rate of ethylenediamine. After the entire amount of ethylenediamine is metered in, the reaction mixture is allowed to react at the same temperature for 30 minutes. After cooling, the reaction mixture represents a tan, viscous liquid having a specific weight of 1.43 g / cm @ 2, which is miscible in any ratio with water.

Example 2

450 g of a 71% aqueous solution of 1,4-di (3-chloro-3-hydroxypropyl) -1-methylpiperazinium chloride are poured into the glass apparatus of Example 1. According to the procedure of Example 1, 120 g of 50% ethylenediamine are metered in. The resulting reaction mixture is a viscous liquid of a tan color with a specific weight of 1.35 g.cm &lt; -1 &gt;.

Instead of 1,4-di (3-chloro-2-hydroxypropyl) -1-methylpiperazinium chloride can be used

490 g of 1,3-bis (3-chloro-2-hydroxypropyl) pyrimidinediylium acetate 78%

432 g of 1,4-bis (3-chloro-2-hydroxypropyl) pyrazinediyl sulphate 84%

240 g of 1,3-bis (2,3-epoxypropyl) imidazolinium chloride 75%

Example 3

140 kg of an aqueous solution of 1,3-bis (3-chloro-2-hydroxypropyl) imidazolinium sulfate with an active substance content of 83% is metered into an enamelled duplicator equipped with a stirrer, a thermometer and a reflux condenser. A 50% aqueous solution of diethylenetriamine is started to be dosed at 25 ° C.

After the addition of 40 kg 50% aqueous solution of diethylenetriamine was allowed the reaction mixture ^P s te ^pl ol ^E 7 ⁰ C Jeet ⁴⁵ minutes ^ react and ^C o ^t OM oc ^hl and ^says · MMN ^Ikle in ^and skozn ^IH not ^made and ^P and ^{if P} has to ec ^ifi c ^{to h} ou ^t mo nose ^t 1, ⁴⁷ ^ g.cnT.

Dalfií compounds of the invention can be prepared in that 40 kg instead of diethylenetriamine ^p oužije ^{62 kg} hexamethylene diamine ^{y,. 10 kg of} N, N, N-methyl-phenylenediamine.

Table number Compound number ^{i, and} ______ · Starting materials ^{[υ-μ-ϊ] k +} 7 ^χΐ -

^1, 3-bis ^(c -chlóryhy roxy ^{d p} ro ^l -yl) imidazolinium sulfate of 1 mol 1 mol of ethylenediamine, ^ (^ З-СГ Ыо-гуМю ^ ^ го proryC) ryrazindiyCiumcrCprih mole

1,3- bis ^(2, 3-eroJO rrproC ^R) - mole imidazρliniumchCorid1

1,3-bibi-3-chloro- ² -hydroxypropyl) pyrimidinediyl sulphate (1,4-di-3-chloro- ^2- pyridopropyl) -1-methylrirerazinium acetate 1 mol

diethylenetriamine 0.8 mol triethylenetetramine 0.6 mol hexametolendiamine 1 mol N, N'-dimethylhexamethylenediamine ’1 mhl

1,4-di-Cr- ^2- aryl. C.opyl · ^p) -1, ^{4-diethyl p} i ^p e. , | razinium sulfate 1 mol ethylenediamine

0.6 mol

Table 2

Compound number

Basic structural unit

Oh

OH

H

CH ₂ N - (CH ₂ ) ₆ - N 4 ¹ 7

Table number 2 continued

Compound number

Basic structural unit

Claims (3)

A water-soluble cationic polyelectrolyte comprising a structural group of the general formula (2) OH -CH ₀ -CH-CH ₉ Where r k n X s M is an integer ^ 1, 2 or 3 is an integer 1 or 2 is an integer 2 to 10 is an anionic residue of a strong inorganic or organic acid is an integer 1 2,3 or 4 is a bifunctional heterocyclic residue ´ R is hydrogen or alkyl having 1 to 4 carbons 2. A process for the preparation of a water-soluble cationic polyelectrolyte according to claim 1, characterized in that 1 mole of a compound of the general formula (1) is reacted wherein Y is a group -CH ₂ -CH-CH ₂ OH Cl or (1) k is an integer of 1 or 2 X is an anionic radical of a strong inorganic or organic acid. M is a heterocyclic radical R is a hydrogen atom or an alkyl β number of carbons of 1 to 4 with 0.1 to 2 moles of the multifunctional amines of the formula? ^r Η-N ¹⁴ (CH ₂ ) _n -K 3- ^H (3) (3) wherein n is an integer of 2 to 10 s is an integer of 1, 2, 3 or 4 is hydrogen or alkyl and the number of carbons is 1 to 4 at a temperature of 10 to 100 ° C. A process according to claim 2, characterized in that it is used as a multifunctional mine of the general formula (3) of alkylenediamine, dialkylenetriamine or trialkylenetetraamine having 2 to 6 carbon atoms in the alkylene group.