WO1991013924A1

WO1991013924A1 - Water-soluble or water-dispersible compounds containing polyether chains and quaternary ammonium groups

Info

Publication number: WO1991013924A1
Application number: PCT/EP1991/000375
Authority: WO
Inventors: Ralf Bohlander; Günter Uphues; Uwe Ploog; Maria Liphard
Original assignee: Henkel Kommanditgesellschaft Auf Aktien
Priority date: 1990-03-09
Filing date: 1991-03-01
Publication date: 1991-09-19
Also published as: AU7311091A; DE4007598A1

Abstract

The invention relates to water-soluble or water-dispersible compounds containing polyether chains and quaternary ammonium groups, a method for producing them and the use of these compounds to remove printing ink from printed waste paper and/or circulating water in the papermaking industry.

Description

"Hate-soluble or water-dispersible compounds containing polyether chains and quaternary ammonium groups"

The invention relates to water-soluble or water-dispersible compounds which contain polyether chains and quaternary ammonium groups, a process for their preparation and the use of these compounds for removing printing inks from printed waste paper and / or paper cycle water.

Waste paper is now used in large quantities for the production of, for example, newspaper printing and hygiene paper. The quality of these types of paper is determined by their brightness and color. In order to be able to produce high quality paper types, the printing inks have to be removed from the printed waste paper. This is usually done using deinking processes, which essentially take place in two steps:

1. opening the waste paper, that is to say defibrating in water with simultaneous action of the chemicals and. Required for the detachment of the printing ink particles

2. Elimination of the detached ink particles from the paper suspensions.

The second process step can be carried out by washing or flotation (Ull ann's Enzyclopadie der Technischen Chemie, 4th edition, volume 17, pages 570-571 (1979)). In flotation, in which the different wettability of printing inks and paper fibers is used, air is pressed or sucked through the paper stock suspensions. Small air bubbles combine with the ink particles and form a foam on the surface of the water, which is removed with fabric hangers.

The deinking of waste paper is usually carried out at alkaline pH values in the presence of alkali hydroxides, alkali silicates, oxidative bleaches and surface-active substances at temperatures between 30 and 50 ° C. Soaps and / or fatty alcohol polyglycol ethers are predominantly used as surface-active substances which bring about the detachment and separation of the printing ink particles (Ullmann's Enzyclopadie der Technischen Chemie, 4th edition, volume 17, pages 571-572 (1979)). The use of alkylamine polyethers to remove printing ink is described in German Offenlegungsschrift DE-0S 33 22 330 and in German Patent DE-PS 33 47 906. Furthermore, from JP 84/137587, referenced in Chem. Abstr. .102, 80638b (1985) Ethylem ^{'min-ethylene} oxide-propylene oxide copoly ere and from JP 82/25489, referenced in Chem. Abstr. 97, 57393n (1982) ethylene oxide-propylene oxide-alkyl (alkenyl) amine adducts known as deinking chemicals.

The classic printing ink systems, for example based on nitrocellulose, maleate resins and / or shellac, the esters and / or ketones, for example ethyl acetate and / or methyl ethyl ketone, or Alcohols as solvents have been increasingly replaced by water-thinnable printing inks in recent years for environmental reasons. Another reason for the increasing use of water-thinnable printing inks is the incombustibility of water, as a result of which the installation of expensive protective devices necessary when using solvent-containing printing inks is no longer necessary. Most water-thinnable printing inks contain anionic polymers as binders, for example polymers containing carboxyl groups, whose neutralization with bases makes the printing inks water-thinnable.

Although water-thinnable printing inks have decisive advantages over conventional solvent-based printing inks, there are still warnings about the introduction of processes using water-thinning printing inks (flexographic printing inks), since water-thinnable printing inks made from waste paper contain the usual surfactants from the deinking fleet - if at all - can only be removed completely inadequately (Das Papier 42 (10 A), V84-V88 (1988)). The consequence of this is that to date the waste paper that is being produced in ever larger quantities and that has been printed with water-thinnable printing inks has not been reused and is therefore not available as waste paper raw material for newsprint and hygiene paper.

The object underlying the invention was to provide connections for deinking waste paper with which it is possible, in particular water-dilutable printing inks. to be removed in satisfactory amounts from waste paper.

It has been found that water-thinnable and / or solvent-based printing inks can be found in printed waste paper The presence of previously unknown water-soluble or dispersible compounds which contain polyether chains and quaternary ammonium groups can be removed in large amounts.

The invention accordingly relates to water-soluble or water-dispersible compounds containing polyether chains and quaternary ammonium groups, obtainable by reacting compounds of the general formula I.

in the R a z-valent alkoxy radical, A0 1 to 100 alkylene oxide units, which are composed of 0 to 100 C2H4θ units, 0 to 50 C3HöO units and 0 to 30 C ^ gO units, shark chlorine and / or Bromine atoms, p is an integer between 0 and 3 and q is 0 or 1, with the proviso that the sum p + q is not equal to 0, and z is an integer from 1 to 10,

with ammonia, C22 alkylamines, aliphatic di- and / or polyamines and / or amino sugars in alkali metal hydroxides, aqueous or aqueous-alcoholic solutions up to a viscosity at 20 ° C between 200 and 15,000 mPas, then adding inorganic and / or organic acids up to a pH between 4 and 7 and then reaction with ethylene oxide and / or propylene oxide.

Another object of the invention is a process for the preparation of water-soluble or water-dispersible compounds containing polyether chains and quaternary ammonium groups, which is characterized in that compounds of the general formula I R-

in which R is a z-valent alkoxy radical, AO 1 to 100 alkylene oxide units, which are composed of 0 to 100 _2H4θ units, 0 to 50 C3Hö0 units and 0 to 30 C4HgO units, shark chlorine and / or bromine atoms, p is an integer between 0 and 3 and q is 0 or 1, with the proviso that the sum p + q is not equal to 0, and z is an integer from 1 to 10,

with ammonia, alkylamines Cι_22 ^_, aliphatic di- and / or polyamines and / or amino sugars contained in alkali metal hydroxides, aqueous or aqueous-alcoholic solutions to a Viskosi¬ ty at 20 ° C from 200 to 15,000 mPas is reacted, after anor¬ ganic and / or organic acids in amounts such that the pH of the solutions is between 4 and 7 and then reacted with ethylene oxide and / or propylene oxide at temperatures between 70 and 120 ° C and pressures between 10 ⁴ and 10 ⁵ Pa.

In contrast to the compounds according to the invention, the compounds described in DE-PS 38 03 213 have significantly lower molar masses and only have terminal quaternary ammonium groups and at least one oxirane group.

Compounds containing polyether chains and quaternary ammonium groups can be obtained by known processes from compounds of the general formula I by these in aqueous or aqueous-alcoholic solutions containing alkali metal hydroxides with ammonia, C22 -22-alkylamines, aliphatic di- and / or polyamines and / or amino sugars (NH compounds) are reacted at temperatures between 40 and 140 ° C (DE 22 46 434). Sodium hydroxide and / or potassium hydroxide, preferably sodium hydroxide. Ethanol and / or isopropanol are preferably used as alcohols in aqueous-alcoholic solutions. The alcohols can be present in any mixing ratio with water. Preferably, the weight ratio of water to alcohol is between 10: 90 and 90: 10. ^'The solutions contain 20 to 80 wt .-%, preferably 40 to 60 wt .-%, compounds of general formula I and NH- Verbinduπgen.

It may be appropriate to react compounds of the general formula I in a first process step with NH compounds at temperatures between 40 and 140 ° C. in the presence of alkali metal hydroxide solution without further addition of water and in a second process step the reaction product obtained with the same or with other NH To implement compounds at temperatures between 40 and 140 ° C. in aqueous solutions containing alkali metal hydroxides. Based on the content of halohydrin and / or epoxy groups in compounds of the general formula I, substoichiometric amounts of hydrogen atoms bonded to amine nitrogen atoms are used in the first process stage. Overall, based on halohydrin and / or epoxy group content, a 0.5 to 20-fold stoichiometric amount of hydrogen atoms bonded to amine nitrogen atoms is used, irrespective of whether NH compounds are added in one or in two stages.

When the viscosity of the reaction solutions, which increases in the course of the reaction, has reached 200 to 15000 mPas, preferably 1000 to 5000 mPas (in situ measurement with a 25 ml pipette; leakage method calibrated for Höppler at 20 ° C.), inorganic and / or organic acids, for example hydrochloric acid, sulfuric acid, acetic acid and / or lactic acid, up to a pH of the solutions between 4 and 7, preferably between 5 and 6. After that the reaction solutions in a known manner at temperatures between 70 and 120 ° C, preferably between 80 and 95 ° C, and pressures between 10 ⁴ and 10 ^ Pa, preferably between 10 ^ and 3 x 10 ^ Pa, with ethylene oxide and / or propylene oxide implemented (DE 35 26 600, DE 36 18 944). The alkylene oxides are used, based on amine nitrogen atoms, in amounts of 0.1 to 2 equivalents, preferably 0.3 to 1.2 equivalents.

The compounds of general formula I to be used as starting materials can be prepared from alcohols having 1 to 10 OH groups which are alkoxylated by known industrial processes with ethylene oxide, propylene oxide and / or butylene oxide ("Chemical Technology", volume 7, page 131 - 132, Carl-Hanser-Verlag, Munich - Vienna 1986)). The alkoxylated alcohols, if desired in a mixture with the corresponding non-alkoxylated alcohols, are mixed with epihalohydrins, preferably with epichlorohydrin, preferably in the presence of catalysts, for example boron trifluoride diacetic acid and / or tin tetrachloride, at temperatures between 50 and 150 ° C., preferably between 60 and 95 ° C. implemented. Epihalohydrins are used in amounts of 0.3 to 4 mol, based on an OH group. Suitable alcohols with 1 to 10 OH groups are, for example, linear, branched and / or cyclic, primary and / or secondary, monohydric alkyl alcohols with 1 to 22 C atoms, such as methanol, ethanol, butanol, isopropanol, cyclohexanol, 2-ethylhexanol and / or lauryl alcohol, dihydric alcohols of the general formula H0- (CH2) 2-12 ~ ° H, bisphenol A, glycerol, di-, tri- and / or tetraglycerol, trimethylolpropane, pentaerythritol, dipentaerythritol, sorbitol and / or mannitol. Alcohols with 2 to 4 OH groups are preferred.

Ammonia, C22-ATkylamines, for example dodecylamine, 2-ethylhexylamine, coconut amine and / or are suitable as NH compounds Talga in, linear, branched-chain and / or cyclic optionally partially alkoxylated, aliphatic di- and / or polyamines with optionally id groups in the aliphatic radicals, for example ethylenediamine, propylenediamine, hexamethylenediamine, diethylenetriamine, dipropylenetriamine, dihexaethylenetriamine, 1,2 - Dihydroxyethyldiaminoethane, piperazine, polyethylenei ine with average molecular weights between 200 and 10,000, bis- [3,3-aminopropyl] methylamine, N, N-dimethylaminopropylamine, N-stearylpropylenediamine and / or N-acylamidoamine, producible by aminolysis of natural Fats and / or oils or by amidating fatty acids with di- and / or polyamines, for example reaction products of beef tallow with tetraethylene pentamine or stearic acid with diethylene triamine, and / or sugar amines, for example glucamine. Alkoxylated, preferably ethoxylated, di- and / or polyamines must have at least one NH group. C 1 -C 22 -alkylamines and / or aliphatic di- and / or polyamines are preferably used as NH compounds.

The compounds according to the invention which are accessible by reacting compounds of the general formula I with NH compounds and then alkylene oxides are aqueous solutions or gels which form aqueous solutions with water and which contain the compounds according to the invention in amounts of 10 to 80% by weight, preferably 20 to 60% % By weight.

With the compounds according to the invention, printing inks, and in particular water-dilutable printing inks, can be removed particularly well from both printed waste paper and from paper circulation water. Accordingly, the invention further relates to the use of these water-soluble or water-dispersible polyether chains and quaternary ammonium groups Connections for removing printing inks from printed old papers and / or paper circulation waters.

^'The compounds of this invention are paper stock suspensions material preferably in amounts of from 0.02 to 2 wt .-%, particularly preferably from 0.1 to 0.5 wt .-%, based on air-dry Papier¬ added. Air-dry paper stock means that an equilibrium state of internal moisture has occurred in the paper stock. This state of equilibrium depends on the temperature and the relative humidity of the air.

In many cases, the deinking result, that is to say the removal of printing inks from printed waste paper, can be increased if the compounds according to the invention are used in combination with, for example, cio ^^ tartic acids, such as 01inor ^ 4010, 01inor ^ 4020 and / or 01inor ^R DG40 (Manufacturer of all products Henkel KGaA), ethoxylated alkyl alcohols with 6 to 22 carbon atoms, ethoxylated alkylphenols, polymers such as polyacrylamides and / or polydimethylaminoethyl methacrylates and / or copolymers, described for example in DE 38 39479, in quantities of 0.01 to 1 % By weight, based on air-dry paper stock, and / or with layer compounds of the general composition precipitated in situ

M (II) ₁ _ _x (III) _x (0H) 2 (A ^Z -) _x / _z -nH ₂ 0

where M (II) stands for divalent metal cations, M (III) for trivalent metal cations and A ^z "for anions of mono- and / or polybasic acids, the indices x a number between 0.01 and 0.5 and n is a number between 0 and 20, described in DE 39 09 568. The molar ratio of divalent metal cations to trivalent metal cations in layer compounds precipitated in situ is preferably between 20: 1 and 1: 1. Based on air-dry paper stock, trivalent metal cations can be used in amounts between 0.3 and 2% by weight.

In the presence of compounds according to the invention, water-thinnable and / or solvent-containing printing inks, preferably water-thinning printing inks, can be used alone or in combination with solvent-containing printing inks, for example newspaper rotary inks, letterpress inks, off-set printing inks, gravure printing inks, flexographic printing inks, laser printing inks and / or remove packaging gravure inks from printed waste paper, for example newspapers, magazines, computer papers, magazines, brochures, forms, telephone books and / or catalogs. The waste paper deinked using compounds according to the invention are distinguished by very high degrees of whiteness.

Printed waste papers are, for example, between 1 and 5% by weight in a cloth dissolver in aqueous solution, which typically contains 0 to 1.5% by weight hydrogen peroxide (100%), 0 to 2.5% by weight. 99% by weight NaOH and 0 to 4.0% by weight soda water glass with a solids content of 35% by weight (37 to 40 ° Be) - all% by weight information relates to air-dry paper stock , crushed at temperatures between 20 and 60 ° C. The pulp suspensions are then stirred into water or water is added, so that 0.6 to 1.6% by weight pulp suspensions are obtained. After a dwell time of between 60 and 120 minutes at temperatures between 20 and 60 ° C., 0.02 to 2% by weight of compounds according to the invention are added, based on air-dry paper stock, and the detached ink particles are then washed out or flotated in a manner known per se the pulp suspensions excreted. Flotation is preferably carried out in a manner known per se, for example in a Denver flotation cell. If one or more of the abovementioned substances, for example fatty acids, ethoxylated alkyl alcohols and / or alkylphenols, polymers, copolymers and / or layer compounds precipitated in situ, are used, these can be used before or during the size reduction of the paper stock or together with the compounds according to the invention be added to the pulp suspensions.

When using the compounds according to the invention, printing inks are removed both from the waste paper and from the circulating water. However, the compounds according to the invention can also be used for the separate purification of paper circulation waters. In these cases, the addition of 2 to 100 mg of compounds according to the invention per liter of circulating water removes the printing ink particles, for example by filtration or flotation.

Examples

Production of water-soluble or water-dispersible compounds containing polyether chains and guaternary ammonium groups

AI. 1400 g (1.75 mol) of bischlorohydrin ether, prepared by reacting polyethylene glycol with an average molecular weight of 600 with 2 mol of epichlorohydrin, 58.5 g (0.3 mol) of coconut amine and 195 g of 17% strength by weight sodium hydroxide solution were mixed. After stirring for one hour at 80 ° C., volatile constituents were removed by distillation in vacuo at 2 ^× 10 4 Pa and a temperature of up to 120 ° C. within 2 hours. The suspension obtained was cooled to 80 ° C. and insoluble constituents were removed by filtration.

74 g (0.57 mol) of dipropylenetria in, 1120 g of water and 115 g of 37% strength by weight sodium hydroxide solution were added to 1,300 g of the yellow filtrate obtained, and the mixture was then heated to 90 ° C. After 2 hours the viscosity had reached 3 500 mPas (in situ measurement with a 25 ml pipette; leakage method calibrated for Höppler at 20 ° C). The pH of the solution was adjusted to 5.3 by adding 90 g (1.5 mol) of acetic acid.

A2. 1,300 g of the clear, viscous, orange solution obtained according to AI were placed in a laboratory autoclave and reacted at 85 ° C. within 5 hours with 66 g (1.5 mol) of ethylene oxide at 10 ⁵ to 3 × 10 ⁵ Pa. A 50% by weight orange solution with a viscosity of 3,600 mPas (measured at 20 ° C. according to Höppler) was obtained.

A3. Analogously to A2, 1,300 g of the viscous orange solution obtained according to AI were reacted with 87 g (1.5 mol) of propylene oxide.

A 50% by weight, orange, milky-cloudy solution with a viscosity of 3,800 mPas (measured at 20 ° C. according to Höppler) was obtained.

Examples of use

20 g air-dry (= 18.4 g atro at 8.3% moisture; atro = absolutely dry) printed waste paper (100% daily newspapers), printed with flexographic printing inks in 520 ml aqueous solution, containing 2.0% by weight Soda water glass, solids content: 35% by weight (37 - 40 ° Be), 0.7% by weight 100% hydrogen peroxide and 1.0% by weight sodium hydroxide, 99% by weight (all% by weight - Information based on air-dry paper pulp) crushed in a star mix, stage 2 at 45 ° C for 10 minutes. The paper pulp was then diluted to 1.84 l with water and left to stand at 45 ° C. for 1.5 hours. Then, to each 600 ml of this paper stock suspension, based on air-dry paper stock, 0.2% by weight of compounds according to the invention were added with stirring and 12 minutes at 45 ° C. at a pH of 8.5 in a Denver laboratory flotation cell (600 ml) floated at 3,000 revolutions per minute. After the flotation, the paper pulp was separated from the water (circulating water) on a suction filter and formed into a sheet between 2 filter papers on a photo drying press and dried at 100 ° C. for 90 minutes. The deinking results are summarized in Table 1. The deinkability index (DEM) was calculated from the reflection factors R457 nm (whiteness) of the printed (BS), deinked (DS) and unprinted (US) paper stock using the following formula:

Whiteness (DS) - Whiteness (BS)

DEM (%) = x 100

Whiteness (US) - Whiteness (BS)

(0% means no ink removal, 100% means quantitative ink removal). The quality of the circulating water was determined with the aid of a transmission measurement (Photometer 662, Metrohm, Herisau, Switzerland) (the higher the transmission T in%, the better the circulating water can be assessed: 100% T means clear circulating water).

Table 1

used R457 R457 R457 DEM (%) T (%) according compounds (BS) (US) (DS) according to example

A2 28.2 55.0 44.3 61 99

A3 28.2 55.0 45.3 64 95

Claims

1. Water-soluble or water-dispersible compounds containing polyether chains and quaternary ammonium groups, obtainable by reacting compounds of the general formula I.

R-: (A0) —CH2-

in which R is a z-valent alkoxy radical, A0 1 to 100 alkylene oxide units which are composed of 0 to 100 C2H4θ units, 0 to 50 C3H6θ units and 0 to 30 C4Hs0 units, shark chlorine and / or bromine atoms, p a _. integer between 0 and 3 and q 0 or 1, with the proviso that the sum p + q is not equal to 0, and z means an integer from 1 to 10,

with ammonia, C22 alkylamines, aliphatic di- and / or polyamines and / or amino sugars in alkali hydroxides containing aqueous or aqueous-alcoholic solutions up to a viscosity at 20 ° C between 200 and 15,000 mPas, then addition of inorganic and / or organic acids up to a pH of the solutions between 4 and 7 and then reaction with ethylene oxide and / or propylene oxide.

2. Compounds according to claim 1, characterized in that in the general formula IR a 2- to 4-valent alkoxy radical, A0 1 to 100 alkylene oxide units, which are composed of 0 to 100 C2H4θ units, 0 to 50 C3Hö0 units and 0 to Put together 30 C4Hg0 units, shark chlorine atoms, p is an integer between 0 and 3 and q 0 or 1, with the proviso that the Sum p + q is not equal to 0, and z is an integer from 2 to 4.

3. A process for the preparation of water-soluble or water-dispersible compounds containing polyether chains and quaternary ammonium groups, characterized in that compounds of the general formula I

in which R is a z-valent alkoxy radical, AO 1 to 100 alkylene oxide units, which are composed of 0 to 100 C2H4θ units, 0 to 50 C3Hö0 units and 0 to 30 C4H8Ö units, shark chlorine and / or bromine atoms, p is an integer between 0 and 3 and q is 0 or 1, with the proviso that the sum p + q is not equal to 0, and z is an integer between 1 and 10,

with ammonia, C22 alkylamines, aliphatic di- and / or polyamines and / or amino sugars in alkali metal hydroxides, aqueous or aqueous-alcoholic solutions up to a viscosity of the solutions at 20 ° C. between 200 and 15,000 mPas, then inorganic and / or organic acids in amounts such that the pH of the solutions is between 4 and 7 and then reacted with ethylene oxide and / or propylene oxide at temperatures between 70 and 120 ° C. and pressures between 10 ⁴ and 10 ^ Pa .

4. The method according to claim 3, characterized in that compounds of the general formula I with ammonia, Cι_22-alkylamines, aliphatic di- and / or polyamines and / or amino sugars up to a viscosity of the solutions at 20 ° C between 1000 and 5000 mPas.

5. The method according to one or both of claims 3 to 4, characterized in that a pH of the solutions between 5 and 6 is adjusted by adding acid.

6. The method according to one or more of claims 3 to 5, da¬ characterized in that one carries out the reactions with ethylene oxide and / or propylene oxide at temperatures between 80 and 95 ° C and pressures between 10 ^ and 3 x 10 ^ Pa.

7. The method according to one or more of claims 3 to 6, da¬ characterized in that compounds of the general formula I are used in which R is a 2- to 4-valent alkoxy radical, A0 1 to 100 alkylene oxide units, which are from 0 to Assemble 100 C2H4θ units, 0 to 50 C3H6θ units and 0 to 30 C4H8θ units, shark chlorine atoms, p an integer between 0 and 3 and q 0 or 1, with the proviso that the sum p + q is not equal to 0 , and z represent an integer between 2 and 4.

8. Use of water-soluble or water-dispersible compounds containing polyether chains and quaternary ammonium groups, obtainable by reacting compounds of the general formula I.

in which R is a z-valent alkoxy radical, AO 1 to 100 alkylene oxide units which are composed of 0 to 100 C2H4θ units, 0 to 50 C3H5θ units and 0 to 30 C4H8θ units, shark chlorine and / or bromine atoms, p is an integer between 0 and 3 and q is 0 or 1, with the proviso that the sum p + q is not equal to 0, and z is an integer between 1 and 10,

with ammonia, C22 alkylamines, aliphatic di- and / or polyamines and / or amino sugars in alkali hydroxides containing aqueous or aqueous-alcoholic solutions up to a viscosity at 20 ° C between 200 and 15,000 mPas, then addition of inorganic and / or organic acids up to a pH between 4 and 7 and then ^" reaction with ethylene oxide and / or propylene oxide,

for removing printing inks from printed waste paper and / or paper circuit water.

9. Use according to claim 8, characterized in that in the general formula IR a 2- to 4-valent alkoxy radical, A0 1 to 100 alkylene oxide units, which are composed of 0 to 100 C2H4θ units, 0 to 50 CsHßO units and 0 to Compose 30 C4H8θ units, shark chlorine atoms, p is an integer between 0 and 3 and q 0 or 1, with the proviso that the sum p + q is not equal to 0 and z represent an integer between 2 and 4 .