CA2065256A1 - Use of at least partly water-soluble polymers for removing printing ink from printed waste paper and or recycling water in the papermaking industry - Google Patents
Use of at least partly water-soluble polymers for removing printing ink from printed waste paper and or recycling water in the papermaking industryInfo
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- CA2065256A1 CA2065256A1 CA 2065256 CA2065256A CA2065256A1 CA 2065256 A1 CA2065256 A1 CA 2065256A1 CA 2065256 CA2065256 CA 2065256 CA 2065256 A CA2065256 A CA 2065256A CA 2065256 A1 CA2065256 A1 CA 2065256A1
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Classifications
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
- D21C5/00—Other processes for obtaining cellulose, e.g. cooking cotton linters ; Processes characterised by the choice of cellulose-containing starting materials
- D21C5/02—Working-up waste paper
- D21C5/025—De-inking
- D21C5/027—Chemicals therefor
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/64—Paper recycling
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- Health & Medical Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Toxicology (AREA)
- Paper (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Polyamides (AREA)
- Detergent Compositions (AREA)
- Paints Or Removers (AREA)
Abstract
A b s t r a c t The invention relates to the use of at least partly water-soluble polymers having weight average molecular weights of 2,000 to 500,000, prepared by reaction of poly-mers containing carboxyl, ester and/or anhydride groups with amino alcohols and/or diamines, for the removal of printing inks from printed wastepaper and/or recycling water in the paper making industry.
Description
~r ~r~
~8E~ OF A~ hE~A8~ PARq~IALLY WATElE~-8~LllBLE POLYMER~ FOR
REMOVING PP~INq!IN~: IN}~ FROM PRINTE:l:! WAl:TB PAP13R AND/Ol~
RECYCLIN~ WAT~R I~l TIIE PAP~R ~A}tING INDU8~RY
This invention relates to the use of at least partly water-soluhle polymers having weight average molecular weights in the range from 2,000 to 500,000, prepared by reaction of polymers containing carboxyl, ester and/or anhydride groups with amino alcohols and/or diamines, for the removal of printing inks from printed wastepaper and/or recycling water in the paper making industry.
Today, wastepaper is used in large quantities for the production of, for example, newsprint and sanitary paper.
Lightness and color are important quality features for pa-pers of this type. To achieve this, the printing inks have to b~ removed from the printed wastepaper. This is normal-ly done by deinking processes essentially comprising two steps, namely:
J ~
1. refining the wastepaper, i.e. fiberizing in water in the presence of the chemicals re~uired for detachment of the printing ink particles and 2. removal of the detached printing ink particles from the fiber suspension.
The second step can be carried out by washing or flotation (Ullmanns Encyclopadie der tecbnischen Chemie, 4th Edition, VolO 17, pages 570 - 571 (1979)). In flo-tation, whi~h utilizes the difference in wettability be~
~0 tween printing inks and paper fibers, air is forced or drawn through the fiber suspension. Small air bubbles at-tach themselves to the printing ink particles and form a froth at the surface of the water which is removed by clarifiers.
The deinking of wastepaper is normally carried out at alkaline pH values in the presence of alkali hydroxides, alkali silicates, oxidative bleaches and surfactants at temperatures in the range from 30 to 50 o C. Soaps and/or fatty alcohol polyglycol ethers are often used as surfac-tants which are responsible for the detachment and separa-tion of the printing ink particles ~Ullm2nns Encyclopadie der technischen Chemie, 4th Edition, Vol. 17, pages 571-572 (1979)).
European patent EP 172 684 describes copolymers of acrylamide and dimethyl diallyl ammonium chloride having molecular weights preferably in the range from 2,000,000 to lO,OOO,Ooo which are used for the deinking of cellulose ~a-terial. However, the papers treated ~n this way have very poor degrees of whiteness.
In recent years, conventional printing ink systems, for example based on nitrocellulose, maleate resins and/or shellac, which contain esters and/or ketones, for example ethyl acetate and/or methyl ethyl ketone, or alcohols as solvent, have been increasingly replaced by water-dilutable printing inks for reasons of pollution control. Another reason for the increasing use of water-dilutable printing inks lies in the non-inflammability of water which elimin~
2 0 ~
ates the need for the expensive safety systems ~hich nor-mally have to be installed in the printing factories where solvent-containing printing inks are used. Most water-dilutable printing inks contain as binder component anionic polymers, for example polymers containing carboxyl groups, of which the neutralization with bases makes the printing inks dilutable with water. How~ver, water-dilutable print-ing inks have the major disadvantage that they can only be removed completely inadequately, if at all, with the sur-factants typically present in the deinking liquor (Wochen-blatt fUr PapierfAbrikation 13, 537-538 (1988)). The re-sult of this is that, hitherto, the wastepaper printed with water-dilutable printing inks, which is accumulating in ever-increasing ~uantities, is not recycled and, hence, is also not available as a wastepaper raw material for news-print and sanitary papers.
Accordingly, the problem addressed by the present in-vention is to provide a deinking process by which it is possible to deink wastepaper. In particular, it should be possible by this deinking process to deink wastepaper con-taining constituents printPd with water-dilutable printing inks.
It is alr~ady known from German patent application DE
~8E~ OF A~ hE~A8~ PARq~IALLY WATElE~-8~LllBLE POLYMER~ FOR
REMOVING PP~INq!IN~: IN}~ FROM PRINTE:l:! WAl:TB PAP13R AND/Ol~
RECYCLIN~ WAT~R I~l TIIE PAP~R ~A}tING INDU8~RY
This invention relates to the use of at least partly water-soluhle polymers having weight average molecular weights in the range from 2,000 to 500,000, prepared by reaction of polymers containing carboxyl, ester and/or anhydride groups with amino alcohols and/or diamines, for the removal of printing inks from printed wastepaper and/or recycling water in the paper making industry.
Today, wastepaper is used in large quantities for the production of, for example, newsprint and sanitary paper.
Lightness and color are important quality features for pa-pers of this type. To achieve this, the printing inks have to b~ removed from the printed wastepaper. This is normal-ly done by deinking processes essentially comprising two steps, namely:
J ~
1. refining the wastepaper, i.e. fiberizing in water in the presence of the chemicals re~uired for detachment of the printing ink particles and 2. removal of the detached printing ink particles from the fiber suspension.
The second step can be carried out by washing or flotation (Ullmanns Encyclopadie der tecbnischen Chemie, 4th Edition, VolO 17, pages 570 - 571 (1979)). In flo-tation, whi~h utilizes the difference in wettability be~
~0 tween printing inks and paper fibers, air is forced or drawn through the fiber suspension. Small air bubbles at-tach themselves to the printing ink particles and form a froth at the surface of the water which is removed by clarifiers.
The deinking of wastepaper is normally carried out at alkaline pH values in the presence of alkali hydroxides, alkali silicates, oxidative bleaches and surfactants at temperatures in the range from 30 to 50 o C. Soaps and/or fatty alcohol polyglycol ethers are often used as surfac-tants which are responsible for the detachment and separa-tion of the printing ink particles ~Ullm2nns Encyclopadie der technischen Chemie, 4th Edition, Vol. 17, pages 571-572 (1979)).
European patent EP 172 684 describes copolymers of acrylamide and dimethyl diallyl ammonium chloride having molecular weights preferably in the range from 2,000,000 to lO,OOO,Ooo which are used for the deinking of cellulose ~a-terial. However, the papers treated ~n this way have very poor degrees of whiteness.
In recent years, conventional printing ink systems, for example based on nitrocellulose, maleate resins and/or shellac, which contain esters and/or ketones, for example ethyl acetate and/or methyl ethyl ketone, or alcohols as solvent, have been increasingly replaced by water-dilutable printing inks for reasons of pollution control. Another reason for the increasing use of water-dilutable printing inks lies in the non-inflammability of water which elimin~
2 0 ~
ates the need for the expensive safety systems ~hich nor-mally have to be installed in the printing factories where solvent-containing printing inks are used. Most water-dilutable printing inks contain as binder component anionic polymers, for example polymers containing carboxyl groups, of which the neutralization with bases makes the printing inks dilutable with water. How~ver, water-dilutable print-ing inks have the major disadvantage that they can only be removed completely inadequately, if at all, with the sur-factants typically present in the deinking liquor (Wochen-blatt fUr PapierfAbrikation 13, 537-538 (1988)). The re-sult of this is that, hitherto, the wastepaper printed with water-dilutable printing inks, which is accumulating in ever-increasing ~uantities, is not recycled and, hence, is also not available as a wastepaper raw material for news-print and sanitary papers.
Accordingly, the problem addressed by the present in-vention is to provide a deinking process by which it is possible to deink wastepaper. In particular, it should be possible by this deinking process to deink wastepaper con-taining constituents printPd with water-dilutable printing inks.
It is alr~ady known from German patent application DE
3~ 39 479 that both solvent-containing and also water di-lutable printing inks can be removed from printed waste-paper in the presence of at least partly water-soluble pol-ymers and/or copolymers having number average molecular weights of 2,000 to 500,000. The polymers and/or copoly-mers are obtained by polymerization of monomers containing amino groups, for example dimethyl aminoethyl methacrylate or by copolymeri~ation of monomers containing amino groups with unsaturated acids, ~or example acrylic acid and/or methacrylic acid, unsaturated carboxylic acid esters, ~or example ethyl acrylate and/or methyl methacrylate, amides of acrylic acid and/or methacrylic acid and/or N-vinyl pyrrolidone. It has surprisingly been found that the good deinking results already achieved with the polymers and/or 2 ~ ~
copolymers described in DE 38 39 479 can be considerably improved both in regard to solvent-containing printing inks and in regard to water-dilutable printing inks by using at least partly water-soluble polymers having weight average molecular weights of 2,000 to 500,000 which are prepared by reaction of polymers containing car~oxyl, ester and/or an-hydride groups with aminoalcohols and/or diamines. It has also been found that water-dilutable and/or solvent-con-taining printing inks can also be removed from recycling water in the paper making industry with ~hese polymers.
Ac¢ordingly, the present invention relates to the use of at least partly water-soluble polym~rs having weight average molecular weights of 2,000 to 500,000, prepared by reaction o~ polymers containing carboxyl groups and/or ester groups corresponding to the general formula -COOR, in which R is a C1_8 alkyl group or an aromatic group, and/or -CO-o-Co- groups, with - based on the carboxyl, ester and/or latent carboxyl groups present in the polymers -B1. 0 to 1 equivalent of amino alcohols corresponding to general formula I
HO - (CnH2nO)X R - N
in which R5 is a Cl 8 alkyl group or an aromatic group, R~ and R7 are the same or dif~erent and repres~nt C1_ 4 alkyl groups or aromatic groups or R6 and R7 together represent CH2CH2-O-CH2CH2, n = 2, 3 and/or 4 and x is a number of 0 to 10, B2. 0 to 1 equivalent of diamines corresponding to general Xormula II
N - R8 _ N/
\ 11 ~ R
in which R8 is a Cl 8 alkyl group or an aromatic group, R9 is H or a Cl_4 alkyl group and R10 and R11 may be the same or di~ferent and represent C1_4 alkyl groups or R10 and R11 together r2present -CH=CH-N=CH-, B3. 0 to 0.5 equivalent of alcohols corresponding to gen-eral formula III
H0 - (CmH2mO)y - Rl2 in which ~12 is a C6_22 alkyl group or an aromatic group, m ~ 2, 3 and/or 4 and y is a number of 0 to 30 and B4. 0 to 0.5 equivalent of amines corresponding to general formula IV
H
N Rl4 in which R13 i5 H or a C1_4 alkyl group and R14 is a C6_2~ alkyl group or an aromatic group, with the proviso that the sum of the equivalents of compo-nents ~l and B2 is not 0, for the removal of printing inks :Erom printed waste paper and/or recycling watar in the paper making industry.
Anhydride groups which may be present in the polymers according to the invention contalin two latent carboxyl groups p~r anhydride group.
At least partly water-soluble polymers having weight average molecular weights of 5,000 ts 300,000 are pre~er-ably used, polymers having weight average molecular weights of lO,000 to lO0,000 being particularly preferred.
"At least partly water~soluble" means that more than 0.01% by weigh~ of the polym~rs dissolves in water at the in-use p~ value to form clear or clouded solutions in water.
Printed wastepaper is pre~erably refined in the pres-ence of, and recyclin~ watsr in the paper making industry is preferably treated by addition of, at lea~t partly water-soluble polymers prepared by reaction of polymers containing carboxyl, ester and/or anhydride groups with -based on the carboxyl, ester and/or latent carboxyl groups 3 2 3~
present in the polymers -Bl. 0 to 1 equivalent of amino alcohols, B2. 0 to 1 equivalent of diamines, B3. 0 to 0.2 equivalent o~ alcohols and B4. 0 to 0.2 equivalent of amines, with the proviso that the sum of the equivalents of compo-nents B1 and B2 is from 0.7 to 1.
Polymers containing carboxyl, ester and/or anhydride groups preferably contain structural units corresponding to the general formulae Al~
--CRl_CR2--C=O
oR3 and/or A2. 2 ~ \O/ ~O
and/or ~3- 1 2 fR - CR -C=O C=O
OR OR
in which Rl and R2 may be the same or di~ferent and repre-~ent H or a methyl group and R3 and R4 may be the same ordifferent and represent ~, C1_~ alXyl groups vr aromatic groups~
Polymers containing only structural units correspond-ing to general formula A1 are particularly preferred.
The polymers containing carboxyl, ester and/or anhy-dride groups required for the preparation of polymers to be used in accordance with the invention may be prepared by known polymerization processes in organic solvents, such as hexane, octane, toluene, xylene and/or ketones. Suitable monomers are, ~or example, acrylic acid, methacrylic acid, ~ 3~
ids, aryl esters of the above-mentioned acids, maleic an-hydride, maleic acid, ~umaric acid, mono-C1_8 alkyl esters of the above-mentioned acids, di-Cl_8-alkyl esters o~ the above-mentioned acids and also the corresponding aryl est-ers. The alkyl group of the alsohol radicals in the estersmay be linear, branched or cyclic. A monomer or mixture of monomers may ~e used. Acrylic acid, methacrylic acid, ac-rylates and/or methacrylates are preferred as monomers.
Other suitable monomers are styrene, alkyl styrenes, 4-vin-yl pyridine, N-vinyl pyrrolidone, acrylonitrile, acryl-amide~ methacrylamide, vinyl chloride and/or vinylidene chloride. The polymerizations are carried out in the pres-ence of radical-forming agents, for example dibenzoyl per-oxide and/or azo-bis-i~obutyronitrile, under normal pres-sure at temperatures in the range from 60 to 150 D C.
The reactions of the polymers containing carboxyl, ester and/or anhydride groups with amino alcohols and/or diamines and, optionally, alcohols and/or amines are car-ried out in the presence or absence of organic solvents, preferably in the presence of catalysts, such as sulfuric acid, p-toluene sulfonic acid, dibutyl tin dilaurate, tin and/or alkali alcoholates, at temperatures in the range from 100 to 230 C. The water formed during the esterifi-cation and/or amidation reaction and/or the alcohols formed are removed by distillation. Suitable organic solvents are, ~or example, aliphatic and/or aromatic hydrocarbons having boiling points above 100 C.
Suitable amino alcohols corresponding to general form-ula I are, for example, 2-dimethylaminoethanol, 2-diethyl-aminoethanol, 3-dimethylamino-2,2-dimethyl-1-propanol, 4-(dimethylamino)-l-butanol, 6-(dimethylamino)-1-hexanol, 2 [2-(dimethylamino)-ethoxy~-ethanol, 2-dibutylaminoethanol, 3-dimethylamino-1-propanol~ 3-diethylamino-1-propanol, 4-dimethylaminophenol, 3-diethylaminophenol, N-hydroxyethyl-N-methyl aniline, N-hydroxyethyl-N-ethyl aniline, N-n-butyl-N-hydroxyethyl aniline and/or 4-(2-hydroxyethyl)-morpholine. Examples of diamines corresponding to general formula II are N,N-dimethylaminopropylamine, N,N-diethyl-aminopropylamine, N,N-diethylaminoethylamine, 1-diethyl-amino-4-aminopentane,N,N-dimethyl p-phenylenediamine,N,N-diethyl-p-ph~nylenediamine and/or 1-(3-aminopropyl)-imida-zole.
The reactions oP polymers containing carboxyl, ester and/or anhydride groups with amino alcohols andtor diamines may be carried out in the presence of alcohols correspond-ing to general formula III and/or amines corresponding to general formula IV. The alkyl groups which may be present in the alcohols and/or amines may be linear, branched and/
or cyclic. Examples of alcohols correspondiny to general formula III are cyclohexanol, 2-ethyl hexanol, octanol, do-decanol, tetradecanol, hexadecanol, octadecanol, docosanol, tallow alcohol containing 12 moles ethylene oxide and/ or benzyl alcohol. Examples of amines corresponding to general formula IV are hexyl amine, 2-ethyl hexyl amine, octyl amine, decyl amine, dodecyl amine, tetradecyl amine, hexadecyl amine, octadecyl amine, docosyl amine, coconut oil amine and/or tallow amine.
Printing inks can be removed particularly effectively from printed wastepaper and/or recycling water in the paper making industry in the presence of at least partly water-soluble polymers prepared by reaction of polymers consisting of structural units corresponding to general formula Al, in which Rl is H, R2 is H or a methyl group and R3 is H or a Cl_4 alkyl group, with amino alcohols corr~
sponding to general formula I and/or diamines corresponding to general formula II, preferably with amino alcohols.
The at least partly water-soluble polymers to be used in accordance with the invention are preferably present as aqueous solutions or a~ueous dispersions and have polymer contents of 1 to 20% by weight and prePerably 1 to 5% by weight.
The polymers to be used in accordance with the inven-tion are prePerably added to paper stock suspensions in quantities o~ 0.02 to 2% by weight and more preferably in Ji~, quantities of 0.1 to 0.5~ by weight, based on air-dry paper stock. Air-dry paper stock means that an equilibrium state of internal moisture has been established in the paper stock. This equilibrium state depends on the temperature and relative humidity of the air.
In many cases, the deinking result, i.e. the removal of printing inks from printed wastepaper, can be improved if the polymers to be used in accordance with the invention are used in combination with, for example, Cl0_22 ~atty acids, such as OlinorR4010, OlinorR4020 and/or Olinor~DG40 (all products of Henkel KGaA), ethoxylated alcohols con-taining 6 to 22 carbon atoms, ethoxylated alkyl phenols, polymers, such as polyacrylamides and/or polydimethyl aminoethyl methacrylates, and/or copolymers, for example of the type described in DE 38 3g 479, in quantities of 0.01 to 1% by weight, based on air-dry paper stock, and/or with layer compounds precipitated in situ having the following general composition M(~ xM(III)x(OH)2(A )x/z nH20 in which M(II) represents divalent metal cations, M(III) represents trivalent metal cations and AZ~ represents anions of monobasic and/or polybasic acids, x is a number of 0.01 to 0.5 and n is a number of 0 to 20, ; described in DE 39 09 568. The molar ratio of divalent metal cations to trivalent metal cations in layer compounds precipitated in ~itu is preferably between 20:1 and 1:1.
Trivalent metal cations may be useclin quantities of 0.3 to ; 2~ by weight, based on air-dry paper stock.
In the presence of polymers according to the inven-tion, water-dilutable and/or solvent-containing printing inks, preferably water-dilutable printing inks, either on their own or in combination with solvent-containing print-ing inks, for example rotary newsprint inks, book printing inks, offset printing inks, illustration intaglio printing inks, flexographic printing inks, laser printing inks and/
or packaging intaglio printing inks, may be removed from printed wastepaper, for example newspapers, magazines, com-2 ~J ~
puter paper, journals, brochures, forms, telephone direc-tories and/or catalogues. ~he ~einked wastepaper obtained is distinguished by very high degrees of whiteness.
Printed wastepaper is refined at 20 to 60 c in a pulper in an aqueous solution typically con~aining 0.5 to 1.5% by weight of hydrogen peroxide (100%), 0 to 2.5% by weight of 99~ by weight NaOH and O to 4.0% by weight of soda water glass having a solids content of 35% by weight (37 to 40Bè) - all percentages by weight are based on air-dry wastepaper - at pulp densities of, for example, 1 to 5%
by weight. The paper stock suspensions ar~ then stirred into water or wa~er is added to them so that 0.6 to 1.6% by weight paper stock suspensions are obtained. After a resi-dence time of 60 to 120 minutes at temperatures in the range from 20 to 60 C, 0.02 to 2% by weight, based on air-dry paper stock, of the polymers to be used in accord-ance with the invention are added to the paper stock sus-pensions. The detached printing ink particles are then re-moved from the fiber suspensions in known manner by washing or flotation. Flotation is preferably carried out in known manner, for example in a Denver ~lotation cell.
If one or more of the substances mentioned above, for example fatty acids, ethoxylated ~altty alcohols and/or al-kyl phenols, polymers, copolymers and/or layer compounds precipitated in situ, are used, they may be added to the paper stock suspensions before or during disintegration of the paper stock or togethex with the compounds according to the invention.
Where the compounds according to the invention are used, printing inks are removed both from the wastepaper and from the recycling water. The compounds according to the invention may also be used for the separate treatment of recycling water in the paper making industry. In cases such as these, the printing ink particles are removed, Por example by filtration or flotation, after the addition of 2 to 100 mg of the compounds according to the invention per liter oP recycling water.
2 ~ $ ~
E x a ~ p ~_e s Preparation o~ polymer I acco~di~g_to ~he lnven~i2~
100 g of xylene were introduced into and heated to 100 C in a rQaCtiOn flask equippsd wi~h a stirrer, a re flux condenser and two dropping funnels. 100 g of ethyl acrylate was added dropwise from one droppinq funnel and, at the same time, 1 g of dibenzoyl peroxide dissolved in 20 g of xylene was ad~ed dropwise ~rom the other dropping fun nel over a total period of 2 hours at the temperature of 100 C. After the monomer~ had been added, the mixture was stirred ~or another hour at 100 C. A polyethyl acrylate having a specific viscosity ~ of 1.40 at 25C (10% by weight in toluene) was formed.
117 g of 2-diethyl aminoethanol and 6.6 g of sodium methylate were then added and the temperature was increased to 130 to 140 C, ethanol being distilled off at the same time. After the reaction, xylene was removed by distilla-tion in vacuo and the polymer obtained was dissolved in water containing acetic acid. A solution having a polymer content of 1% by weight was obtained.
Pre~aration of polymer_II accordinq to the invention In the ~ame way as for the production of polymer I ac-cording to the invention, 100 g of ethyl acrylate was poly-merized in the presence of 0.5 g of dibenzoyl peroxide.
~he polyethyl acrylate obtained had a specific viscosity of 1.69 at 25 C (10~ by weight in toluene).
The subsequent reaction with 2-diethyl aminoethanol and the preparation of an aqueous solution having a polymer content of 1~ by weight were carried out in the same way as for the preparation of polymer I according to the inven-tion.
~c~tion of ~olyELer TII accor~ tA t~e ~n~e~ti~
In the same way as for preparation of polymer I ac-cording to the invention, 100 g of ethyl acrylate and 1 g of dibenzoyl peroxide dis~olved in 20 g o~ xylene were add-ed to 100 g of xylene over a period of 2 hours at 80 C.
2 J~
After the monomers had been added, the mixture was stirred for another hour at 90- C. The polyethyl acrylate obtained had a specific viscosity ~ of 2.54 at 25C (10% by weight in toluene).
The subsequent reaction with 2-diethyl aminoethanol and the preparation of an aqueous solution having a polymer contant o~ 1% by wei~ht were carried out in the same way as for the preparation of polymer I according to the inven-tion.
Application Examples 20 g of air-dry (= 18.4 g of bone-dry for 8.3% mois-ture) printed wastepaper (100~ newspapers) printed with flexographic inks were disintegrated for 10 minutes at 45 C in a Starmix, stage 2, in 520 ml of an aqueous solution containing 2.0% by weight of soda waterglass, solids con-tent 35% by weight (37 - 40B~), 2.33% by weight hydrogen peroxide, 30% by weight, and 1.0% by weight sodium hydrox-ide, 99% by weight (all percentages by weight are based on air-dry paper stock). The pulp was then diluted with water to 1.84 1 and left standing for 1.5 hours at 45 C. 0.2%
by weight, based on air-dry paper stocX, of the polymers according to the invention was added with stirring to 600 ml of this fiber suspension which was then flotated for 12 minutes at 45 C in a Denver laboratory flotation cell (600 ml~ at 300 revolutions per minute. After flotation, the pulp was separated from the water (circulating water) on a suction filter, Pormed into a sheet between two filter pa-pers on a photo dry press and dried ~or 90 minutes at 100 C.
The deinking results are shown in Table. 1. The deink-ability value (DE~) was calculated from the reflection fac-tors R4s7~ (whiteness) of the printed (BS), deinked (DS) and unprinted (US) paper stock in accordance with the following formula:
whiteness (DS) - whiteness (BS~
DEM (%) a - - X 100 whiteness (US) - whiteness (BS) 2~t32~)~
(0% means no deinking, 100~ means quantitative deinking).
The quality of the circulating water was determined by transmission measurement (Photometer 662, manufactured by Metro of Herisau, Switzerland; the higher the transmission T i.n %, the better the quality of the circulating water:
100% T means clear circulating water3.
-- . . . . . , ~ _ Table 1 Polymer used R457 R457 R457 DEM (%) T (%) (US3 (BS) (DS) 1 51.227.2 44~1 70 98 2 51.227.2 43.8 69 100 3 51.227.2 42.3 63 99 _ _ _
copolymers described in DE 38 39 479 can be considerably improved both in regard to solvent-containing printing inks and in regard to water-dilutable printing inks by using at least partly water-soluble polymers having weight average molecular weights of 2,000 to 500,000 which are prepared by reaction of polymers containing car~oxyl, ester and/or an-hydride groups with aminoalcohols and/or diamines. It has also been found that water-dilutable and/or solvent-con-taining printing inks can also be removed from recycling water in the paper making industry with ~hese polymers.
Ac¢ordingly, the present invention relates to the use of at least partly water-soluble polym~rs having weight average molecular weights of 2,000 to 500,000, prepared by reaction o~ polymers containing carboxyl groups and/or ester groups corresponding to the general formula -COOR, in which R is a C1_8 alkyl group or an aromatic group, and/or -CO-o-Co- groups, with - based on the carboxyl, ester and/or latent carboxyl groups present in the polymers -B1. 0 to 1 equivalent of amino alcohols corresponding to general formula I
HO - (CnH2nO)X R - N
in which R5 is a Cl 8 alkyl group or an aromatic group, R~ and R7 are the same or dif~erent and repres~nt C1_ 4 alkyl groups or aromatic groups or R6 and R7 together represent CH2CH2-O-CH2CH2, n = 2, 3 and/or 4 and x is a number of 0 to 10, B2. 0 to 1 equivalent of diamines corresponding to general Xormula II
N - R8 _ N/
\ 11 ~ R
in which R8 is a Cl 8 alkyl group or an aromatic group, R9 is H or a Cl_4 alkyl group and R10 and R11 may be the same or di~ferent and represent C1_4 alkyl groups or R10 and R11 together r2present -CH=CH-N=CH-, B3. 0 to 0.5 equivalent of alcohols corresponding to gen-eral formula III
H0 - (CmH2mO)y - Rl2 in which ~12 is a C6_22 alkyl group or an aromatic group, m ~ 2, 3 and/or 4 and y is a number of 0 to 30 and B4. 0 to 0.5 equivalent of amines corresponding to general formula IV
H
N Rl4 in which R13 i5 H or a C1_4 alkyl group and R14 is a C6_2~ alkyl group or an aromatic group, with the proviso that the sum of the equivalents of compo-nents ~l and B2 is not 0, for the removal of printing inks :Erom printed waste paper and/or recycling watar in the paper making industry.
Anhydride groups which may be present in the polymers according to the invention contalin two latent carboxyl groups p~r anhydride group.
At least partly water-soluble polymers having weight average molecular weights of 5,000 ts 300,000 are pre~er-ably used, polymers having weight average molecular weights of lO,000 to lO0,000 being particularly preferred.
"At least partly water~soluble" means that more than 0.01% by weigh~ of the polym~rs dissolves in water at the in-use p~ value to form clear or clouded solutions in water.
Printed wastepaper is pre~erably refined in the pres-ence of, and recyclin~ watsr in the paper making industry is preferably treated by addition of, at lea~t partly water-soluble polymers prepared by reaction of polymers containing carboxyl, ester and/or anhydride groups with -based on the carboxyl, ester and/or latent carboxyl groups 3 2 3~
present in the polymers -Bl. 0 to 1 equivalent of amino alcohols, B2. 0 to 1 equivalent of diamines, B3. 0 to 0.2 equivalent o~ alcohols and B4. 0 to 0.2 equivalent of amines, with the proviso that the sum of the equivalents of compo-nents B1 and B2 is from 0.7 to 1.
Polymers containing carboxyl, ester and/or anhydride groups preferably contain structural units corresponding to the general formulae Al~
--CRl_CR2--C=O
oR3 and/or A2. 2 ~ \O/ ~O
and/or ~3- 1 2 fR - CR -C=O C=O
OR OR
in which Rl and R2 may be the same or di~ferent and repre-~ent H or a methyl group and R3 and R4 may be the same ordifferent and represent ~, C1_~ alXyl groups vr aromatic groups~
Polymers containing only structural units correspond-ing to general formula A1 are particularly preferred.
The polymers containing carboxyl, ester and/or anhy-dride groups required for the preparation of polymers to be used in accordance with the invention may be prepared by known polymerization processes in organic solvents, such as hexane, octane, toluene, xylene and/or ketones. Suitable monomers are, ~or example, acrylic acid, methacrylic acid, ~ 3~
ids, aryl esters of the above-mentioned acids, maleic an-hydride, maleic acid, ~umaric acid, mono-C1_8 alkyl esters of the above-mentioned acids, di-Cl_8-alkyl esters o~ the above-mentioned acids and also the corresponding aryl est-ers. The alkyl group of the alsohol radicals in the estersmay be linear, branched or cyclic. A monomer or mixture of monomers may ~e used. Acrylic acid, methacrylic acid, ac-rylates and/or methacrylates are preferred as monomers.
Other suitable monomers are styrene, alkyl styrenes, 4-vin-yl pyridine, N-vinyl pyrrolidone, acrylonitrile, acryl-amide~ methacrylamide, vinyl chloride and/or vinylidene chloride. The polymerizations are carried out in the pres-ence of radical-forming agents, for example dibenzoyl per-oxide and/or azo-bis-i~obutyronitrile, under normal pres-sure at temperatures in the range from 60 to 150 D C.
The reactions of the polymers containing carboxyl, ester and/or anhydride groups with amino alcohols and/or diamines and, optionally, alcohols and/or amines are car-ried out in the presence or absence of organic solvents, preferably in the presence of catalysts, such as sulfuric acid, p-toluene sulfonic acid, dibutyl tin dilaurate, tin and/or alkali alcoholates, at temperatures in the range from 100 to 230 C. The water formed during the esterifi-cation and/or amidation reaction and/or the alcohols formed are removed by distillation. Suitable organic solvents are, ~or example, aliphatic and/or aromatic hydrocarbons having boiling points above 100 C.
Suitable amino alcohols corresponding to general form-ula I are, for example, 2-dimethylaminoethanol, 2-diethyl-aminoethanol, 3-dimethylamino-2,2-dimethyl-1-propanol, 4-(dimethylamino)-l-butanol, 6-(dimethylamino)-1-hexanol, 2 [2-(dimethylamino)-ethoxy~-ethanol, 2-dibutylaminoethanol, 3-dimethylamino-1-propanol~ 3-diethylamino-1-propanol, 4-dimethylaminophenol, 3-diethylaminophenol, N-hydroxyethyl-N-methyl aniline, N-hydroxyethyl-N-ethyl aniline, N-n-butyl-N-hydroxyethyl aniline and/or 4-(2-hydroxyethyl)-morpholine. Examples of diamines corresponding to general formula II are N,N-dimethylaminopropylamine, N,N-diethyl-aminopropylamine, N,N-diethylaminoethylamine, 1-diethyl-amino-4-aminopentane,N,N-dimethyl p-phenylenediamine,N,N-diethyl-p-ph~nylenediamine and/or 1-(3-aminopropyl)-imida-zole.
The reactions oP polymers containing carboxyl, ester and/or anhydride groups with amino alcohols andtor diamines may be carried out in the presence of alcohols correspond-ing to general formula III and/or amines corresponding to general formula IV. The alkyl groups which may be present in the alcohols and/or amines may be linear, branched and/
or cyclic. Examples of alcohols correspondiny to general formula III are cyclohexanol, 2-ethyl hexanol, octanol, do-decanol, tetradecanol, hexadecanol, octadecanol, docosanol, tallow alcohol containing 12 moles ethylene oxide and/ or benzyl alcohol. Examples of amines corresponding to general formula IV are hexyl amine, 2-ethyl hexyl amine, octyl amine, decyl amine, dodecyl amine, tetradecyl amine, hexadecyl amine, octadecyl amine, docosyl amine, coconut oil amine and/or tallow amine.
Printing inks can be removed particularly effectively from printed wastepaper and/or recycling water in the paper making industry in the presence of at least partly water-soluble polymers prepared by reaction of polymers consisting of structural units corresponding to general formula Al, in which Rl is H, R2 is H or a methyl group and R3 is H or a Cl_4 alkyl group, with amino alcohols corr~
sponding to general formula I and/or diamines corresponding to general formula II, preferably with amino alcohols.
The at least partly water-soluble polymers to be used in accordance with the invention are preferably present as aqueous solutions or a~ueous dispersions and have polymer contents of 1 to 20% by weight and prePerably 1 to 5% by weight.
The polymers to be used in accordance with the inven-tion are prePerably added to paper stock suspensions in quantities o~ 0.02 to 2% by weight and more preferably in Ji~, quantities of 0.1 to 0.5~ by weight, based on air-dry paper stock. Air-dry paper stock means that an equilibrium state of internal moisture has been established in the paper stock. This equilibrium state depends on the temperature and relative humidity of the air.
In many cases, the deinking result, i.e. the removal of printing inks from printed wastepaper, can be improved if the polymers to be used in accordance with the invention are used in combination with, for example, Cl0_22 ~atty acids, such as OlinorR4010, OlinorR4020 and/or Olinor~DG40 (all products of Henkel KGaA), ethoxylated alcohols con-taining 6 to 22 carbon atoms, ethoxylated alkyl phenols, polymers, such as polyacrylamides and/or polydimethyl aminoethyl methacrylates, and/or copolymers, for example of the type described in DE 38 3g 479, in quantities of 0.01 to 1% by weight, based on air-dry paper stock, and/or with layer compounds precipitated in situ having the following general composition M(~ xM(III)x(OH)2(A )x/z nH20 in which M(II) represents divalent metal cations, M(III) represents trivalent metal cations and AZ~ represents anions of monobasic and/or polybasic acids, x is a number of 0.01 to 0.5 and n is a number of 0 to 20, ; described in DE 39 09 568. The molar ratio of divalent metal cations to trivalent metal cations in layer compounds precipitated in ~itu is preferably between 20:1 and 1:1.
Trivalent metal cations may be useclin quantities of 0.3 to ; 2~ by weight, based on air-dry paper stock.
In the presence of polymers according to the inven-tion, water-dilutable and/or solvent-containing printing inks, preferably water-dilutable printing inks, either on their own or in combination with solvent-containing print-ing inks, for example rotary newsprint inks, book printing inks, offset printing inks, illustration intaglio printing inks, flexographic printing inks, laser printing inks and/
or packaging intaglio printing inks, may be removed from printed wastepaper, for example newspapers, magazines, com-2 ~J ~
puter paper, journals, brochures, forms, telephone direc-tories and/or catalogues. ~he ~einked wastepaper obtained is distinguished by very high degrees of whiteness.
Printed wastepaper is refined at 20 to 60 c in a pulper in an aqueous solution typically con~aining 0.5 to 1.5% by weight of hydrogen peroxide (100%), 0 to 2.5% by weight of 99~ by weight NaOH and O to 4.0% by weight of soda water glass having a solids content of 35% by weight (37 to 40Bè) - all percentages by weight are based on air-dry wastepaper - at pulp densities of, for example, 1 to 5%
by weight. The paper stock suspensions ar~ then stirred into water or wa~er is added to them so that 0.6 to 1.6% by weight paper stock suspensions are obtained. After a resi-dence time of 60 to 120 minutes at temperatures in the range from 20 to 60 C, 0.02 to 2% by weight, based on air-dry paper stock, of the polymers to be used in accord-ance with the invention are added to the paper stock sus-pensions. The detached printing ink particles are then re-moved from the fiber suspensions in known manner by washing or flotation. Flotation is preferably carried out in known manner, for example in a Denver ~lotation cell.
If one or more of the substances mentioned above, for example fatty acids, ethoxylated ~altty alcohols and/or al-kyl phenols, polymers, copolymers and/or layer compounds precipitated in situ, are used, they may be added to the paper stock suspensions before or during disintegration of the paper stock or togethex with the compounds according to the invention.
Where the compounds according to the invention are used, printing inks are removed both from the wastepaper and from the recycling water. The compounds according to the invention may also be used for the separate treatment of recycling water in the paper making industry. In cases such as these, the printing ink particles are removed, Por example by filtration or flotation, after the addition of 2 to 100 mg of the compounds according to the invention per liter oP recycling water.
2 ~ $ ~
E x a ~ p ~_e s Preparation o~ polymer I acco~di~g_to ~he lnven~i2~
100 g of xylene were introduced into and heated to 100 C in a rQaCtiOn flask equippsd wi~h a stirrer, a re flux condenser and two dropping funnels. 100 g of ethyl acrylate was added dropwise from one droppinq funnel and, at the same time, 1 g of dibenzoyl peroxide dissolved in 20 g of xylene was ad~ed dropwise ~rom the other dropping fun nel over a total period of 2 hours at the temperature of 100 C. After the monomer~ had been added, the mixture was stirred ~or another hour at 100 C. A polyethyl acrylate having a specific viscosity ~ of 1.40 at 25C (10% by weight in toluene) was formed.
117 g of 2-diethyl aminoethanol and 6.6 g of sodium methylate were then added and the temperature was increased to 130 to 140 C, ethanol being distilled off at the same time. After the reaction, xylene was removed by distilla-tion in vacuo and the polymer obtained was dissolved in water containing acetic acid. A solution having a polymer content of 1% by weight was obtained.
Pre~aration of polymer_II accordinq to the invention In the ~ame way as for the production of polymer I ac-cording to the invention, 100 g of ethyl acrylate was poly-merized in the presence of 0.5 g of dibenzoyl peroxide.
~he polyethyl acrylate obtained had a specific viscosity of 1.69 at 25 C (10~ by weight in toluene).
The subsequent reaction with 2-diethyl aminoethanol and the preparation of an aqueous solution having a polymer content of 1~ by weight were carried out in the same way as for the preparation of polymer I according to the inven-tion.
~c~tion of ~olyELer TII accor~ tA t~e ~n~e~ti~
In the same way as for preparation of polymer I ac-cording to the invention, 100 g of ethyl acrylate and 1 g of dibenzoyl peroxide dis~olved in 20 g o~ xylene were add-ed to 100 g of xylene over a period of 2 hours at 80 C.
2 J~
After the monomers had been added, the mixture was stirred for another hour at 90- C. The polyethyl acrylate obtained had a specific viscosity ~ of 2.54 at 25C (10% by weight in toluene).
The subsequent reaction with 2-diethyl aminoethanol and the preparation of an aqueous solution having a polymer contant o~ 1% by wei~ht were carried out in the same way as for the preparation of polymer I according to the inven-tion.
Application Examples 20 g of air-dry (= 18.4 g of bone-dry for 8.3% mois-ture) printed wastepaper (100~ newspapers) printed with flexographic inks were disintegrated for 10 minutes at 45 C in a Starmix, stage 2, in 520 ml of an aqueous solution containing 2.0% by weight of soda waterglass, solids con-tent 35% by weight (37 - 40B~), 2.33% by weight hydrogen peroxide, 30% by weight, and 1.0% by weight sodium hydrox-ide, 99% by weight (all percentages by weight are based on air-dry paper stock). The pulp was then diluted with water to 1.84 1 and left standing for 1.5 hours at 45 C. 0.2%
by weight, based on air-dry paper stocX, of the polymers according to the invention was added with stirring to 600 ml of this fiber suspension which was then flotated for 12 minutes at 45 C in a Denver laboratory flotation cell (600 ml~ at 300 revolutions per minute. After flotation, the pulp was separated from the water (circulating water) on a suction filter, Pormed into a sheet between two filter pa-pers on a photo dry press and dried ~or 90 minutes at 100 C.
The deinking results are shown in Table. 1. The deink-ability value (DE~) was calculated from the reflection fac-tors R4s7~ (whiteness) of the printed (BS), deinked (DS) and unprinted (US) paper stock in accordance with the following formula:
whiteness (DS) - whiteness (BS~
DEM (%) a - - X 100 whiteness (US) - whiteness (BS) 2~t32~)~
(0% means no deinking, 100~ means quantitative deinking).
The quality of the circulating water was determined by transmission measurement (Photometer 662, manufactured by Metro of Herisau, Switzerland; the higher the transmission T i.n %, the better the quality of the circulating water:
100% T means clear circulating water3.
-- . . . . . , ~ _ Table 1 Polymer used R457 R457 R457 DEM (%) T (%) (US3 (BS) (DS) 1 51.227.2 44~1 70 98 2 51.227.2 43.8 69 100 3 51.227.2 42.3 63 99 _ _ _
Claims (20)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A process for separating printing ink from aqueous liquids wherein the ink is suspended together with paper fibers derived from waste paper or from recycling water in the paper making industry, wherein the improvement comprises the presence in the suspension of ink and water to be separated during the separation process of at least partly water-soluble polymers having weight average molecular weights of 2,000 to 500,000, said polymers being prepared by reaction of intermediate polymers containing carboxyl groups; ester groups corresponding to the general formula -COOR, in which R is a C1-8 alkyl group or an aromatic group; or -CO-O-CO- groups with - based on the total of the carboxyl, ester, and latent carboxyl groups present in the polymers (B1) 0 to 1 equivalent of amino alcohols corresponding to general formula I
in which R5 is a C1-8 alkyl group or an aromatic group; R6 and R7 are the same or different and represent C1-4 alkyl groups or aromatic groups, or R6 and R7 together represent CH2CH2-O-CH2CH2; n = 2, 3, or 4 and may be the same or different for each of the x CnH2nO groups present; and x is a number of 0 to 10;
(B2) 0 to 1 equivalent of diamines corresponding to general formula II
in which R8 is a C1-8 alkyl group or an aromatic group: R9 is H or a C1-4 alkyl group; and R10 and R11 may be the same or different and represent C1-4 alkyl groups, or R10 and R11 together represent -CH=CH-N=CH-;
(B3) 0 to 0.5 equivalent of alcohols corresponding to general formula III
HO - (CmH2mO)y-R12 in which R12 is a C6-22 alkyl group or an aromatic group; m = 2, 3, or 4 and may be the same or different for each of the y CmH2mO groups present;
and y is a number of 0 to 30; and (B4) 0 to 0.5 equivalent of amines corresponding to general formula IV
in which R13 is H or a C1-4 alkyl group and R14 is a C6-22 alkyl group or an aromatic group, with the proviso that the sum of the equivalents of compo-nents B1 and B2 is not 0.
in which R5 is a C1-8 alkyl group or an aromatic group; R6 and R7 are the same or different and represent C1-4 alkyl groups or aromatic groups, or R6 and R7 together represent CH2CH2-O-CH2CH2; n = 2, 3, or 4 and may be the same or different for each of the x CnH2nO groups present; and x is a number of 0 to 10;
(B2) 0 to 1 equivalent of diamines corresponding to general formula II
in which R8 is a C1-8 alkyl group or an aromatic group: R9 is H or a C1-4 alkyl group; and R10 and R11 may be the same or different and represent C1-4 alkyl groups, or R10 and R11 together represent -CH=CH-N=CH-;
(B3) 0 to 0.5 equivalent of alcohols corresponding to general formula III
HO - (CmH2mO)y-R12 in which R12 is a C6-22 alkyl group or an aromatic group; m = 2, 3, or 4 and may be the same or different for each of the y CmH2mO groups present;
and y is a number of 0 to 30; and (B4) 0 to 0.5 equivalent of amines corresponding to general formula IV
in which R13 is H or a C1-4 alkyl group and R14 is a C6-22 alkyl group or an aromatic group, with the proviso that the sum of the equivalents of compo-nents B1 and B2 is not 0.
2. A process as claimed in claim 1, wherein the at least partly water-soluble polymers have weight average molecu-lar weights of 5,000 to 300,000.
3. A process as claimed in claim 2, wherein the at least partly water-soluble polymers are prepared by reaction of the intermediate polymers with a total of components (B1) - (B4) that includes a total of from 0.7 to 1 equivalent of components from components (B1) and (B2) and no more than 0.2 equivalents from each of components (B3) and (B4) for each equivalent of the total of carboxyl, ester, and anhydride groups in the intermediate polymers.
4. A process as claimed in claim 3, wherein the intermediate polymers contain structural units corresponding to at least one of the following general formulae:
(A1) and (A2) and (A3) in which R1 and R2 may be the same or different and repre-sent H or a methyl group and R3 and R4 may be the same or different and represent H, a C1-8 alkyl group or an aromatic group.
(A1) and (A2) and (A3) in which R1 and R2 may be the same or different and repre-sent H or a methyl group and R3 and R4 may be the same or different and represent H, a C1-8 alkyl group or an aromatic group.
5. A process as claimed in claim 4, wherein the intermediate polymers contain structural units corresponding to gen-eral formula A1.
6. A process as claimed in claim 5, wherein the at least partly water-soluble polymers are prepared by reaction of intermediate polymers consisting of structural units corresponding to general formula A1 when R1 is H, R2 is H
or a methyl group and R3 is H or a C1-4 alkyl group with amino alcohols.
or a methyl group and R3 is H or a C1-4 alkyl group with amino alcohols.
7. A process as claimed in claim 2, wherein the at least partly water-soluble polymers have weight average molecular weights of 10,000 to 100,000.
8. A process as claimed in claim 7, wherein the at least partly water-soluble polymers are prepared by reaction of the intermediate polymers with a total of components (B1) -(B4) that includes a total of from 0.7 to 1 equivalent of components from components (B1) and (B2) and no more than 0.2 equivalents from each of components (B3) and (B4) for each equivalent of the total of carboxyl, ester, and anhydride groups in the intermediate polymers.
9. A process as claimed in claim 1, wherein the at least partly water-soluble polymers are prepared by reaction of the intermediate polymers with a total of components (B1) -(B4) that includes a total of from 0.7 to 1 equivalent of components from components (B1) and (B2) and no more than 0.2 equivalents from each of components (B3) and (B4) for each equivalent of the total of carboxyl, ester, and anhydride groups in the intermediate polymers.
10. A process as claimed in claim 9, wherein the inter-mediate polymers contain structural units corresponding to at least one of the following general formulae:
(A1) and (A2) and (A3) in which R1 and R2 may be the same or different and represent H
or a methyl group and R3 and R4 may be the same or different and represent H, a C1-8 alkyl group or an aromatic group.
(A1) and (A2) and (A3) in which R1 and R2 may be the same or different and represent H
or a methyl group and R3 and R4 may be the same or different and represent H, a C1-8 alkyl group or an aromatic group.
11. A process as claimed in claim 8, wherein the inter-mediate polymers contain structural units corresponding to at least one of the following general formulae:
(A1) and (A2) and (A3) in which R1 and R2 may be the same or different and represent H
or a methyl group and R3 and R4 may be the same or different and represent H, a C1-8 alkyl group or an aromatic group.
(A1) and (A2) and (A3) in which R1 and R2 may be the same or different and represent H
or a methyl group and R3 and R4 may be the same or different and represent H, a C1-8 alkyl group or an aromatic group.
12. A process as claimed in claim 7, wherein the inter-mediate polymers contain structural units corresponding to at least one of the following general formulae:
(A1) and (A2) and (A3) in which R1 and R2 may be the same or different and represent H
or a methyl group and R3 and R4 may be the same or different and represent H, a C1-8 alkyl group or an aromatic group.
(A1) and (A2) and (A3) in which R1 and R2 may be the same or different and represent H
or a methyl group and R3 and R4 may be the same or different and represent H, a C1-8 alkyl group or an aromatic group.
13. A process as claimed in claim 2, wherein the inter-mediate polymers contain structural units corresponding to at least one of the following general formulae:
(A1) and and (A3) in which R1 and R2 may be the same or different and represent H
or a methyl group and R3 and R4 may be the same or different and represent H, a C1-8 alkyl group or an aromatic group.
(A1) and and (A3) in which R1 and R2 may be the same or different and represent H
or a methyl group and R3 and R4 may be the same or different and represent H, a C1-8 alkyl group or an aromatic group.
14. A process as claimed in claim 1, wherein the inter-mediate polymers contain structural units corresponding to at least one of the following general formulae:
(A1) and (A2) and (A3) in which R1 and R2 may be the same or different and represent H
or a methyl group and R3 and R4 may be the same or different and represent H, a C1-8 alkyl group or an aromatic group.
(A1) and (A2) and (A3) in which R1 and R2 may be the same or different and represent H
or a methyl group and R3 and R4 may be the same or different and represent H, a C1-8 alkyl group or an aromatic group.
15. A process as claimed in claim 14, wherein the in-termediate polymers contain structural units corresponding to general formula A1.
16. A process as claimed in claim 15, wherein the at least partly water-soluble polymers are prepared by reaction of intermediate polymers consisting of structural units corre-sponding to general formula A1 when Rl is H, R2 is H or a methyl group and R3 is H or a C1-4 alkyl group with amino alcohols, diamines, or both.
17. A process as claimed in claim 13, wherein the at least partly water-soluble polymers are prepared by reaction of intermediate polymers consisting of structural units coheir-sponding to general formula A1 when R1 is H, R2 is H or a methyl group and R3 is H or a C1-4 alkyl group with amino alcohols, diamines, or both.
18. A process as claimed in claim 12, wherein the at least partly water-soluble polymers are prepared by reaction of intermediate polymers consisting of structural units corre-sponding to general formula A1 when R1 is H, R2 is H or a methyl group and R3 is H or a C1-4 alkyl group with amino alcohols, diamines, or both.
19. A process as claimed in claim 11, wherein the at least partly water-soluble polymers are prepared by reaction of intermediate polymers consisting of structural units corre-sponding to general formula A1 when R1 is H, R2 is H or a methyl group and R3 is H or a C1-4 alkyl group with amino alcohols, diamines, or both.
20. A process as claimed in claim 10, wherein the at least partly water-soluble polymers are prepared by reaction of intermediate polymers consisting of structural units corre-sponding to general formula A1 when R1 is H, R2 is H or a methyl group and R3 is H or a C1-4 alkyl group with amino alcohols, diamines, or both.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3928841A DE3928841A1 (en) | 1989-08-31 | 1989-08-31 | THINKING OF WASTE PAPER |
| DEP3928841.2 | 1989-08-31 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2065256A1 true CA2065256A1 (en) | 1991-03-01 |
Family
ID=6388287
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA 2065256 Abandoned CA2065256A1 (en) | 1989-08-31 | 1990-08-22 | Use of at least partly water-soluble polymers for removing printing ink from printed waste paper and or recycling water in the papermaking industry |
Country Status (12)
| Country | Link |
|---|---|
| EP (1) | EP0494152B1 (en) |
| JP (1) | JPH05500690A (en) |
| KR (1) | KR927003916A (en) |
| AT (1) | ATE117748T1 (en) |
| AU (1) | AU638049B2 (en) |
| CA (1) | CA2065256A1 (en) |
| DE (2) | DE3928841A1 (en) |
| FI (1) | FI98935C (en) |
| PL (1) | PL286683A1 (en) |
| RU (1) | RU2008384C1 (en) |
| WO (1) | WO1991003598A1 (en) |
| YU (1) | YU162990A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106883479A (en) * | 2017-04-11 | 2017-06-23 | 南昌印钞有限公司 | A kind of rubber and preparation method thereof |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3909568A1 (en) * | 1989-03-23 | 1990-09-27 | Henkel Kgaa | METHOD FOR RECYCLING PAPER |
| DE4442056A1 (en) * | 1994-11-25 | 1996-05-30 | Henkel Kgaa | Process for removing printing inks from printed waste paper |
| JP3262517B2 (en) * | 1996-10-02 | 2002-03-04 | 花王株式会社 | Deinking method |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4786364A (en) * | 1984-08-02 | 1988-11-22 | Calgon Corporation | DMDAAC/AM copolymers as deinkers |
| DE3627407C2 (en) * | 1986-08-13 | 1994-05-19 | Steinbeis Temming Papier Gmbh | Process for cleaning water circuits in pulp and paper production |
| DE3839479A1 (en) * | 1988-11-23 | 1990-06-07 | Henkel Kgaa | THINKING OF WASTE PAPER |
-
1989
- 1989-08-31 DE DE3928841A patent/DE3928841A1/en not_active Withdrawn
-
1990
- 1990-08-22 WO PCT/EP1990/001397 patent/WO1991003598A1/en active IP Right Grant
- 1990-08-22 AT AT90912114T patent/ATE117748T1/en not_active IP Right Cessation
- 1990-08-22 DE DE59008381T patent/DE59008381D1/en not_active Expired - Fee Related
- 1990-08-22 EP EP19900912114 patent/EP0494152B1/en not_active Expired - Lifetime
- 1990-08-22 JP JP2511593A patent/JPH05500690A/en active Pending
- 1990-08-22 AU AU61735/90A patent/AU638049B2/en not_active Ceased
- 1990-08-22 CA CA 2065256 patent/CA2065256A1/en not_active Abandoned
- 1990-08-22 KR KR1019920700469A patent/KR927003916A/en not_active Application Discontinuation
- 1990-08-27 YU YU162990A patent/YU162990A/en unknown
- 1990-08-30 PL PL28668390A patent/PL286683A1/en unknown
-
1992
- 1992-02-25 FI FI920829A patent/FI98935C/en not_active IP Right Cessation
- 1992-02-28 RU SU5011456 patent/RU2008384C1/en active
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106883479A (en) * | 2017-04-11 | 2017-06-23 | 南昌印钞有限公司 | A kind of rubber and preparation method thereof |
| CN106883479B (en) * | 2017-04-11 | 2018-11-20 | 南昌印钞有限公司 | A kind of rubber and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| PL286683A1 (en) | 1991-08-26 |
| RU2008384C1 (en) | 1994-02-28 |
| KR927003916A (en) | 1992-12-18 |
| FI920829A0 (en) | 1992-02-25 |
| EP0494152B1 (en) | 1995-01-25 |
| AU6173590A (en) | 1991-04-08 |
| FI98935B (en) | 1997-05-30 |
| FI98935C (en) | 1997-09-10 |
| DE59008381D1 (en) | 1995-03-09 |
| JPH05500690A (en) | 1993-02-12 |
| DE3928841A1 (en) | 1991-03-07 |
| EP0494152A1 (en) | 1992-07-15 |
| WO1991003598A1 (en) | 1991-03-21 |
| YU162990A (en) | 1992-07-20 |
| ATE117748T1 (en) | 1995-02-15 |
| AU638049B2 (en) | 1993-06-17 |
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