CA1271004A - Cationic sizing agents for paper - Google Patents
Cationic sizing agents for paperInfo
- Publication number
- CA1271004A CA1271004A CA000521098A CA521098A CA1271004A CA 1271004 A CA1271004 A CA 1271004A CA 000521098 A CA000521098 A CA 000521098A CA 521098 A CA521098 A CA 521098A CA 1271004 A CA1271004 A CA 1271004A
- Authority
- CA
- Canada
- Prior art keywords
- weight
- styrene
- cationic
- emulsifier
- sizing agent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
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Classifications
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/20—Macromolecular organic compounds
- D21H17/33—Synthetic macromolecular compounds
- D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D21H17/41—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups
- D21H17/44—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups cationic
- D21H17/45—Nitrogen-containing groups
- D21H17/455—Nitrogen-containing groups comprising tertiary amine or being at least partially quaternised
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F257/00—Macromolecular compounds obtained by polymerising monomers on to polymers of aromatic monomers as defined in group C08F12/00
- C08F257/02—Macromolecular compounds obtained by polymerising monomers on to polymers of aromatic monomers as defined in group C08F12/00 on to polymers of styrene or alkyl-substituted styrenes
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/20—Macromolecular organic compounds
- D21H17/33—Synthetic macromolecular compounds
- D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D21H17/35—Polyalkenes, e.g. polystyrene
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/20—Macromolecular organic compounds
- D21H17/33—Synthetic macromolecular compounds
- D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D21H17/37—Polymers of unsaturated acids or derivatives thereof, e.g. polyacrylates
Abstract
Cationic sizing agents for paper A b s t r a c t Cationic sizing agents for paper, obtainable by a process in which a water-soluble cationic terpolymer com-pound, built up in a chemically uniform manner, of a) 7 to 40% by weight of N,N-dimethylaminoethyl acrylate and/or methacrylate, b) 40 to 80% by weight of styrene and c) 4 to 50% by weight of acrylonitrile, the sum of components a) to c) always being 100% by weight and at least 10% of the dimethylamino groups of the terpolymer being quater-nized with monoepoxides, with the exception of epihalo-genohydrins, and the remainder being protonated, is dissolved in an aqueous medium and, in the presence of 10 to 70% by weight - based on the following monomer mixture -of this emulsifier, d) 5 to 95% by weight of acrylonitrile, meth-acrylonitrile or styrene or mixtures thereof and e) 5 to 95% by weight of acrylic acid ester and/or methacrylic acid ester with 1 to 12 C atoms in the alcohol radical -the sum of components d) and e) always being 100% by weight -are emulsified and the emulsion thus obtained is subjected to emulsion polymerization, initiated by free radicals, at temperatures of 20 to 150°C.
Description
~7~()4 The present invention relates to aqueous, collo;d-ally disperse sizing agents for paper which have improved stability properties and a reduced tendency to foam and are based on copolymers of acrylonitrile, methacrylo-nitrile or styrene and acrylic acid esters or methacrylicacid esters which are polymerized in the presence of quaternized terpolymers, built up in a chemically uniform 0anner, of N,N-dimethylaminoethyl (meth)acrylate, styrene and acrylonitr;le, as emulsifiers.
It is known (compare European Patent 0,058,313) that cationic sizing agents for paper can be prepared in the form of relatively stable, colloidally disperse, usually transluscent solution by polymerizing acrylo-nitrile or methacryloni~rile with acrylic acid esters or methacrylic acid esters in the presence of particular poly-meric cationic emulsifiers in an aqueous system. These emulsifiers are quaternization products of terpolymers, built up in a chemically uniform manner, of N,N-dimethyl-aminoethyl (meth)acrylate, styrene and acrylonitrile with contents of basic comonomer of not more than ~0% by weight.
The average particle diameters of these colloidally dis-perse solutions are between 15 and 200 nm, preferably bet~een 20 and 150 nm.
German Offenlegungsschr;ft 3,401,573 describes the preparation of sizing agents for paper which are ~ikewise colloidally disperse and are particularly effective for wrapping paper, by polymerizing either mixtures of (meth)-acrylonitrile~ styrene and acrylic acid esters or meth-acrylic acid esters or mixtures of styrene and acrylic acid esters or methacrylic acid esters in the presence of the abovementioned quaternized terpolymers built up in a chemically uniform manner.
A disadvantage of these colloidally disperse sizing agents is that in practice they are ~requently not com-pletely satisfactorily stable in the presence of Le A 24 141 . .
7~)0
It is known (compare European Patent 0,058,313) that cationic sizing agents for paper can be prepared in the form of relatively stable, colloidally disperse, usually transluscent solution by polymerizing acrylo-nitrile or methacryloni~rile with acrylic acid esters or methacrylic acid esters in the presence of particular poly-meric cationic emulsifiers in an aqueous system. These emulsifiers are quaternization products of terpolymers, built up in a chemically uniform manner, of N,N-dimethyl-aminoethyl (meth)acrylate, styrene and acrylonitrile with contents of basic comonomer of not more than ~0% by weight.
The average particle diameters of these colloidally dis-perse solutions are between 15 and 200 nm, preferably bet~een 20 and 150 nm.
German Offenlegungsschr;ft 3,401,573 describes the preparation of sizing agents for paper which are ~ikewise colloidally disperse and are particularly effective for wrapping paper, by polymerizing either mixtures of (meth)-acrylonitrile~ styrene and acrylic acid esters or meth-acrylic acid esters or mixtures of styrene and acrylic acid esters or methacrylic acid esters in the presence of the abovementioned quaternized terpolymers built up in a chemically uniform manner.
A disadvantage of these colloidally disperse sizing agents is that in practice they are ~requently not com-pletely satisfactorily stable in the presence of Le A 24 141 . .
7~)0
- 2 -electrolytes and at elevated temperatures tabove 60C) when shearing forces are applied, and they have a tendency to foam. Larger amounts of electrolytes may occur in the paper processing operation if enzymatically degraded starch is included in the sizing liquor as an additive.
After degradation has taken place, the enzyme activity is stopped by addition of acid (for example sulphuric acid or hydrochloric acid); the electrolytes are then formed by the addition of a base, which neutralizes the excess acid.
Since the enzymatic degradation of starch is fre-quently also carried out at elevated temperatures (about 80C to 100C) and the starch solution is usually added immediately to the sizing liquor, an increase in temperature of the sizing liquor to temperatures of not more than 80C is in general to be expected. Under these extreme conditions, the colloidally disperse sizing agents described above partly or completely agglomerate and coagulate; deposits are formed on the paper machine and the sizing effect is drastically reduced. Shearing forces, which likewise may occur during paper processing, lead to similar effectS. Another disadvantage of the sizing agents described above is, in some cases, a tendency to foam beyond the normal degree, which can likewise lead to trouble in the paper processing operation.
It has now been found, surprisingly, that colloid-ally disperse sizing agents for paper which are stable towards electrolytes, shearing forces and heat and have little tendency to foam are obtained by polymerizing mix-tures of (meth)acrylonitrile and/or styrene and acrylic acid ester or methacrylic acid ester in the presence of terpolymers, built up in a chemically uniform manner, of dimethylaminoethyl (meth)acrylate, styrene and acrylo-nitrile which have been quaternized with monoepoxides.
The sizing agent for paper, according to the invention, is obtained as a colloidally disperse solution Le A 24 141 _._
After degradation has taken place, the enzyme activity is stopped by addition of acid (for example sulphuric acid or hydrochloric acid); the electrolytes are then formed by the addition of a base, which neutralizes the excess acid.
Since the enzymatic degradation of starch is fre-quently also carried out at elevated temperatures (about 80C to 100C) and the starch solution is usually added immediately to the sizing liquor, an increase in temperature of the sizing liquor to temperatures of not more than 80C is in general to be expected. Under these extreme conditions, the colloidally disperse sizing agents described above partly or completely agglomerate and coagulate; deposits are formed on the paper machine and the sizing effect is drastically reduced. Shearing forces, which likewise may occur during paper processing, lead to similar effectS. Another disadvantage of the sizing agents described above is, in some cases, a tendency to foam beyond the normal degree, which can likewise lead to trouble in the paper processing operation.
It has now been found, surprisingly, that colloid-ally disperse sizing agents for paper which are stable towards electrolytes, shearing forces and heat and have little tendency to foam are obtained by polymerizing mix-tures of (meth)acrylonitrile and/or styrene and acrylic acid ester or methacrylic acid ester in the presence of terpolymers, built up in a chemically uniform manner, of dimethylaminoethyl (meth)acrylate, styrene and acrylo-nitrile which have been quaternized with monoepoxides.
The sizing agent for paper, according to the invention, is obtained as a colloidally disperse solution Le A 24 141 _._
- 3 - 23189-6381 with average particle diameters oE preferably 15 to 200 nm by a process in which a water-soluble cationic terpolymer com-pound, built up in a chemically uniform manner, of a) 7 to 40, preferably 8 to 30% by weight of N,N-dimethylaminoethyl acrylate and/or methacrylate, b) ~0 to 80% hy weight of styrene and c) 4 to 50, preferably 5 to 40% by weight of acrylonitrile, the sum of components a) to c) always being 100% by weight and at least 10% of the dimethylamino groups of the terpolymer being quaternized with monoepoxides, with the exception of epihalo-genohydrins, and the remainder being protonated, is dissolved in an aqueous medium, and, in the presence of 10 to 70% by weight - based on the following monomer mixture - of this emulsi-fier, d) 5 to 95, preferably 20 to 80% by weight of acrylonitrile, methacrylonitrile or styrene or mixtures thereof and e) 5 to 95, preferably 20 to 80% by weight of acrylic acid ester and/or methacrylic acid ester with 1 to 12 C-atoms in the alcohol radical - the sum of components a ) and e) always being 100% by weight - are emulsified, and the emulsion thus obtained is subjected to emulsion polymerizati.on, initiated by free radicals, at temperatures of 20 to 150C, wherein the terpolymer is quater-nized with a monoepoxide of the formula R-~H-CH-RI
' ~ ' O
wherein R and R' are idential or different radicals and repre-sent hydrogen, Cl-C16-alkyl which may be substituted by OH, cycloal]cyl with 5-12 C~atoms or an aryl group with 6-12 C-atoms1t ' ~l5 ,~
'71t)0~
- 3a - 23189-6381 The weigh-t ratio between the polymeric, ca-tionic emulsifier and monomer mixture of d) and e) is pre:Eerab]y 1:4 to 1:1.
The sizing agent for paper, according to the inven-tion, is also obtained when, in addition to the cationic emulsi-Eier meht:ioned, a cationic and/or non-ionic auxiliary emulsi-fier is ernployed in amounts of 1 to 40% by weight, preferably 3 to 20% by weight, based on the above cationic emulsifier, the non-ionic emulsifier having the formula Rl-X-(CH2-CH2-O) -H (II) wherein ~27~
l, X denotes 0, NH or C00, R1 is a higher aliphatic, cycloaliphatic, arali-phatic or aromatic hydrocarbon radical with 6-30 C atoms and n is an integer > 2, and the cationic auxiliary emulsifier having the formula R2 ~3 \ ~i3 /
N
wherein R2 and R3 represent higher aliphatic or araliphatic hydrocarbon radicals with 6 to 20 C atoms, R~ and Rs represent lower aliphatic hydrocarbon radicals with 1 to 6 C atoms and Y represents a halide ion~
The terpolymer, built up in a chemically uniform manner, of N,N-dimethylaminoethyl tmeth)acrylate, styrene and acrylonitrile is quaternized in an organic medium, after partial or complete neutralization with acid, with monoepoxides of the general formula R-~-CH-R
20 wherein R and R' represent identical or different radicals and denote hydrogen, an alkyl group with 1 to 16 carbon atoms, a cycloalkyl group with S to 12 carbon atoms or an aryl group with 6 to 12 carbon atoms, it being possible for the substituents mentioned also to contain hetero atoms or func-tional substituents, in particular hydroxyl sub~
stituents, but excluding epihalogenohydrins. Lxamples of monoepox-ides which are particularly suitable are ethylene oxide, Le A 2lt 1~,1 ~L27~00~
propylene oxide, 1,2-butylene o~ide, 2,3-butylene oxide, isobutylene oxide, 1,2-epoxyhexane, 1,2-epoxydecane, 1,2-epoxydodecane~ styrene oxide, cyclohexene oxide and gly-cidyl alcohol. The hydrophilic-hydrophobic properties of the polymeric cationic emulsifier can be influenced within wide limits both via the nature of the epoxide and via the degree of quaternization.
The quaternization of homo- or copolymers contain-ing dialkylamino groups with ethylene oxide, propylene oxide or styrene oxide is known from French Patent Speci-fication 1,173,575 and British Patent Specification 1,281,683 and from German Offenlegungsschrift 2,258,868.
However, monoepoxides with longer alkyl chains are not claimed. Furthermore, nothing is reported of a use of such products as sizing agents for paper which are stable towards electrolytes, heat and shearing forces and have favourable foaming properties.
After the quaternizat;on, the remaining acid is added and the components are dissolved to form aqueous solutions with a concentration of 10 to 30% by weight, preferably 15 to 25% by weight. The emulsifier solutions thus obtained can now also be freed from the organic sol-vent by distillation; however, the removal of the organic solvent is not necessary, since the solvent in general does not interfere with the emulsion polymerization in the subsequent course of the reaction.
For the emulsification, it is sufficient for the quaternized cationic terpolymers to be employed for the emulsion polymerization without further additives. In some cases, however, it proves to be quite advantageous for oligomeric non-ionic and/or low molecular weight cationic auxiliary emulsifiers to be employed together with the polymeric cationic emulsifier in proportions of 1 to 40% by weight, preferably 3 to 20% by weight, based on the cationic emulsifier.
Suitable non-ionic auxiliary emulsifiers are reac-Le A 24 141 7~
tion products of aliphatic, araliphatic, cycloaLiphatic or aromatic carboxylic acids, alcohols, phenol derivatives or amines with epoxides, such as, for example, ethylene oxide.
Examples of these are reaction products of ethyl-ene oxide with carboxylic acids, such as, for example, lauric acid~ stearic acid, oleic acid, the carboxylic acids of castor ~il or abietic acid, with longer chain alcohols, such as oleyl alcohol, lauryl alcohol or stearyl alcohol, with phenol derivatives, such as, for example, substituted benzyl- or phenylphenols or nonylphenol and with longer chain amines, such as, for example, dodecyl-a0ine and stearylamine. The reaction products with ethyl-ene ox;de are ol;go- or polyethers with degrees of poly-merization of between 2 and 100, preferably from 5 to 5û.
Suitable cation;c low molecular we;ght auxiliaryemulsifiers are quaternized ammonium salts, such as, for example, benzyldodecyl dimethyl-ammonium chloride. The auxiliary emulsifiers mentioned effect additional emulsi-fication of the monomer mixture and in some cases increase the stability of the colloidally disperse sizing agents.
However, it is not advisable to use too high an amount of these auxil;ary d;spersing agents, since undesirable foaming can otherwise readily occur.
Suitable acrylic acid esters or methacrylic acid esters which are employed as comonomers in the free radi-cal emulsion copolymerization are preferably those com-pounds which form copolymers with film-form;ng tempera-tures belc,~ 1û0C with ~meth)acrylonitrile or styrene or mixtures thereof.
Copolymers which, because of the position of their glass transition point, have higher film-forming tempera-tures possess only an inadequate sizing action. Compounds which are suitable in principle are acrylates, such as methyl, ethyl, n-butyl and 2-ethylhexyl acrylate, and methacrylates, such as methyl methacrylate and n-butyl Le A 24 1_ 3L~ 3 methacrylate. They can be copolymerized individually or as a mixture with methacrylonitrile, acrylonitrile or styrene or with mixtures of the two comonomers last men-tioned or with mixtures of all three monomers. The con-tent of styrene, acrylonitrile or methacrylonitrile ormixtures of these components can be between 5 and 95, preferably 2D and 80% by weight. Formulations containing too little styrene, acrylonitrile or methacrylonitrile in the copolymer may cause trouble during paper production because of their tackiness, and sizing of the paper is inadequate with formulations with a very large amount of styrene, acrylonitrile or methacrylonitrile.
Possible initiators for the emulsion polymeriza-tion are, preferably, water-soluble non-ionic Peroxides which supply free radicals, such as hydrogen peroxide and t-butyl hydroperoxide, as well as water-soluble azo com-pounds, such as are described, for example, in German Offenlegungsschrift 2,841,045. Redox systems which con sist of peroxidic initiators and reducing agents, such as amines, polyamines, thiourea, iron-II salts and the like, are furthermore suitable. Possible initiators are also water-insoluble initiators, such as azoisobutyronitrile and benzoyl peroxide. The latter are then dissolved vir-tually only in the organic phase. The initiators men-tioned are added in amounts of 0.1 to 5% by we;ght, prefer-ably 0.3 to 3.0% by weight, based on the monomer mixture.
Customary chain regulators, for example n-dodecyl-mercaptan, t-dodecylmercaptan, diisopropylxanthogene di-sulphide, thioglycol and thioglycerol, can also be employed to regulate the molecular weights of the polymers.
They are added in amounts of 0.1 to 2% by weight, based on the monomer mixture.
The emulsion polymerization in an aqueous medium can be carried out by known polymerization processes, either discontinuously or continuously or by the feed pro-cess. The continuous process and the feed process are Le A 24 141 7~
particularly preferred. ln the latter, water, together with some or all of the emuls;fier system and, if approp-riate, some of the monomer mixture, is taken under a nitrogen atmosphere and is heated to the polymerization temperature of 20 to 150C, preferably 50 to 100C, and the monomer mixture and initiator and, if appropriate, emulsifier are added dropwise in the course of 0.5 to 10 hours, preferably 1 to h hours.
After some time, the mixture is post-activated and the reaction is brought to completion up to a conversion of about 99.0% to 99.9%. The weight ratio of emulsifier to polymer here is 1:9 to 7:3, preferably 1:4 to 1:1.
Residual monomers and any organic solvent still present are removed by distillation in vacuo after the emulsion copolymerization. Water is then added until an approxi-mately 10 to 35% strength by weight aqueous colloidally disperse solution results. The viscosity of these dis-persions, measured in a rotary viscometer at 20C, is in general below 50 mPa.s. The average particle diameters, measured by means of laser scattered light spectroscopy, are between 15 and 200 nm, preferably bet-ween 20 and 150 nm, depending on the reaction conditions.
Dispersions with particle sizes below 50 nm appear trans-parent, whilst those with larger particles appear more cloudy. The stability of the dispersions with particle sizes belo~ 100 nm is also better than that of those with particle sizes above 100 nm, which can be demonstrated, for example, by exposure to heat at temperatures above 80C. The content of sediments is usually considerably higher in dispersions with coarser particles than in fine-particled dispersions.
The stability of the colloidally disperse sizing agents according to the invention is also increased by grafted-on portions of the polymer on the polymeric emul-sifier present in relatively large amounts. Such graftingreactions, which are triggered off by transfer reactions Le A 24 141 7~
by the emulsifier, are known in the literature (compare H. Gerrens, Fortschritte der Hochpolymer-Forschung (Advances in High Polymer Research), Volume I, (1959) page 300).
S The sizing agents for paper according to the invention can be used in all the working methods customary in papermaking for surface and beater sizing~
In addition to the substantial pH independence of their sizing effect and the generally very high degree of sizing industrially, the improved stability towards electrolytes, shearing forces and heat and the reduced tendency to foam in comparison with the sizing agents for paper in European Patent 0,058,313 and German Offenlegungsschrift 3,401,573 should be emphasized again, and are illustrated in the following examples.
Example 1 Preparation of the cationic emulsifiers 5,720 9 of isopropanol are taken in a 40 litre autoclave. The autoclave is flushed thoroughly with nitrogen and then warmed to 80C. Mixtures I and solu-tions II of Table I are metered in at this temperature in the course of 4 hours, with exclusion of air. The mixture is then subsequently stirred for 1 to 2 hours and there-after post-activated with so~ution III. The mix-ture is then stirred at 80C for about 6 to 12 hours.After the terpolymerization, the amount of acetic acid (IV) stated in Table I is metered into the polymer at an unchanged temperature. The monoepoxide (V) is subsequently metered ;n as the quatern;z;ng agent ;n the course of about 15 minutes and the mixture ;s st;rred for about 1 hour. Thereafter, the remainder of the acetic acid (VI) ;s added. About 63-65 litres of deionized water at a temperature of about 60C are taken in a 120 litre stock vessel equipped with a stirrer, and the contents of the 40 litre autoclave are combined with this. A homogeneous aqueous solution is prepared in a short time by stirring Le A 24 141 ~73L~O~
;ntensively. The aqueous solutions, which also contain organic solvent, have the properties likewise recorded in Table I.
Table I
Emulsifier A a C D E
Polymer;zation and quaternizat;on temperature (C) 80 80 80 80 80 I. N,N-dimethylaminoethyl methacrylate (g) 3217 3217 2257 3217 3217 styrene (g) 10244 10244 10608 1024410244 acrylonitrile (g)2644 2644 3219 2644 2644 II. Azoisobutyronitrile (9) 500 500 550 500 500 acetone (g) 3000 3000 3000 3000 3000 III. Azoisobutyronitrile (9) 50 50 50 50 50 acetone (g) 300 300 300 300 300 IV. acetic ac;d (9) 1229 984 690 984 984 V. 1,2-epoxydodecane (9)1131 - - - -1,2-epoxyhexane (9) - 1025 719 1,2-epoxybutane (9) - - - 885 propylene oxide (g) - - - - 891 VI. Acetic acid (9) 1230 1475 1035 1475 1475 Concentration (~)20.3 20.1 20.2 20.0 19.9 Viscos1ty (at 20C) 50-100 30-70 300-500 20-50 20-50 [mPa.s]*
pH value: 4.2 4.2 4.1 4.2 4.2 Appearance of the emulsifier solution: slightly clear clear clear clear cloudy *) Viscosity is not constant since the samples have structural viscosity Examples 2_ to 4 9,720 9 of deionized water are taken in a 40 litre stirred autoclave. The water is then boiled up thoroughly under a nitrogen atmosphere and cooled to 70C. There-after, the emulsions I (compare Table I) are added to the initial water, with exclus;on of a;r. 12 9 of a 35 Le A 24 141 strength hydrogen peroxide solution are then added~ After about 15-30 minutes~ che monomer mixtures II and the initiator mixtures III are metered in over a period of about 4 hours. Thereafter, the mixture is subsequently stirred for a further 2 to 5 hours and is then post-activated with mixture IV and after-polymerized for about a further 2 to 10 hours. About 1.5 to 2 litres of a mix-ture of water, organic solvent (isopropanol and acetone) and residual monomers are then distilled off under a waterpump vacuum of about 200 to 400 mbar and are replaced by the same amount of deionized water. The physico-chemical properties of the colloidally disperse solutions thus obtained are likewise recorded in Table II.
Table II.
Example 2 3 4 I. Emulsifier A
(compare Table I) (9) 12400 12400 12400 Styrene (9) 124 - -Acrylonitrile (9) - 124 Methacrylonitr;le (9) - - 124 n-Butyl acrylate (9) 124 124 124 II. Styrene (9) 2356 Acrylonitrile (9) - 2356 Methacrylonitrile (9) - - 2356 n-Butyl acrylate (9) 2356 2356 2356 III. Hydror~en peroxid e (35% strength) (9) 198 198 198 Deionized water (9~ 2480 2480 2480 IV. Hydrogen peroxide (35% strength) (g) 25 25 50 Deionized water (9) 100 100 100 Concentration (% by weight) 24.8 25.0 24.9 Viscosity (at 23C) [mPa.s] <50 <50 <50 pH value 4.3 4.4 4.3 Appearance of the colloidally disperse sl;ghtly slightly slightly solution cloudy cloudy cloudy Average particle diameter d [nm] 67 48 52 L_ A 24 141 Examples 5 and 6 The colloidally disperse sizing agents 5 and h are prepared in the same way as the corresponding sizing agents 2 and 3, but emulsifier A is replaced by emulsifier 5 8 (compare Table I).
Table III
Example 5 I. Emulsifier B
(compare Table I) (9)12400 12400 Styrene (9) 124 Acrylonitrile (9) - 124 n-Butyl acrylate (9)124 124 II. Styrene (9) 2356 Acrylonitrile (9) - 2356 n-Butyl acrylate (9)2356 2356 Concentration (/~ by weight) 24.7 24.6 Viscosity (at 23C) [mPa.s] <50 <50 pH value 4.2 4.3 Appearance of the colloidally disperse solution transparent transparent Average particle diameter dz [nm] 39 35 ~C~
The collo;dally disperse sizing agents 7 and 8 are prepared ;n the same way as the corresponding sizing agents 2 and 3, but emulsifier A is replaced by emulsif;er C (compare Table I).
Le A 24 1~1 Table IV
Example 7 8 _ I. Emulsifier C
tcompare Table I) (9)12400 12400 Styrene (9) 124 Acrylonitrile (9) - 124 n-Butyl acrylate (9)124 124 II. Styrene (9) 2356 Acrylonitrile (9) - 2356 n-Butyl acrylate (g)2356 235b Concentration (% by ~eight) 25.2 25.1 ' Viscosity (at 23C) [mPa.s] <50 <50 Appearance of the colloidally disperse solution transparent transparent Average particle diameter dz [nm] ~5 37 Examples 9 and 10 The colloidally disperse sizing agents 9 and 10 are prepared in the same way as the corresponding sizing agents 2 and 3, but emulsifier A is replaced by emulsi-fier D (compare Table I).
Le A 24 141 ~L~7i~)~4 Table V
Example 9 10 I. Emulsifier D
(compare Table I) (9)12400 12400 Styrene (9) 124 Acrylonitrile (9) - 124 n-Butyl acrylate (9) 124 124 II. Styrene (9) 2356 Acrylonitrile (9) - 2356 n-Butyl acrylate (9)2356 2356 Concentration (% by weight) 25.3 25.1 Viscosity (at 23C) [mPa.s] <50 <50 Appearance of the colloid-ally disperse solution transparent transparent Average particle diameter d (nm) 48 43 Examples 11 and 12 The colloidally disperse sizing agents 11 and 12 are prepared in the same way as the corresponding sizing agents 2 and 3, but emulsif;er A ;s replaced by emulsi-f;er E (compare Table I).
Le A 24 141 ~710~34 Table VI
Example 11 12 .
. EmuLsifier E
(compare Table I) (9) 12400 12400 Styrene (9) 124 Acrylonitrile (9) - 124 n-Butyl acrylate (9) 124 124 II. Styrene (g) 2356 Acrylonitrile (9) - 2356 n-~utyl acrylate (g) 2356 2356 Concentration (% by weight)25.4 24.8 Viscosity (at 23C) (mPa.s) <50 <50 Appearance of the colloidally disperse solution transparent transparent Average particle diameter dz [nm] 32 28 A solution of 5% by weight of starch (PerfectamylR
A 4692 from AvEsE)~ 0.4% by weight of sodium sulphate and 0.20 or 0.25% by weight o~ the sizing agent to be tested (calculated as the active substance) in 94.40 or 94.35%
by weight of water is used as the sizing liquor for sur-face sizing. ~efore use in the siz;ng press, the sizing liquors are warmed at 75C in a waterbath for 30 minutes.
A laboratory slzing press from Werner Mathis, Zurich, type HF is used for the sizing. The siz;ng l1quor has a tem-perature of about 25C in the sizing press. The paper is drawn through at a speed of 4 m/minute. The surface-sized paper is dried on a clrying cylinder in the course of about 45 seconds at about 100C. Pefore testing the sizing, the paper is acclimatized at room temperature for 2 hours.
Le A ~4 141 ~Z73L()(~
.
The sizing is tested in accordance with DIN 53 132. In this, the water uptake in g/m2 is determined after a testing time of 60 seconds (Cobb60).
Use Example 1 This example demonstrates the good activity of some sizing agents after exposure to heat and electrolytes on paper free from aluminium sulphate. The base paper used has the following composition and properties:
50% by weight of conifer cellulose, 50% by weight of hard-wood cellulose and 9.5~ by weight of clay ash, pH in the headbox: 7.5; wet uptake in the laboratory sizing press:
about 80% by weigh~, paper weight: 80 g/m2.
Two sizing agents according to European Patent 0,058,313 (sizing agents 3 and 10) - called here M and N -were used as the comparison substance.Table VII
Surface sizing on paper free from aluminium sulphate after exposure to heat and electrolytes.
Sizing agent Water uptake in g/m2 on addit;c~n of 20 from Example 0.20% by weight 0.25% by weight of sizing agent (based on the pure active substance) to the liquor 3 37.8 35.3 35.3 33.1 6 34.1 32.4 8 35.2 33.5 34.7 32.3 11 35.8 33.6 12 33.2 31.3 M 45.2 40.5 N 65.5 61.3 Without a sizing agent, the water uptake is 89.0 g/m2 .
Use Example 2 This example demonstrates the low tenclency of the sizing agents according to the invention to foam in com-Le ~ 24 141 t~LO~
- ~7 --parison with sizing agents M and N according to European Patent 0,058,313. The tendency to foam is, in this exampLe, measured in the absence of additives such as, for example, additional emulsifiers and antifoaming agents.
In this example 0.4% by weight of active compound is dissolved in a sizing liquor of 5% by weight of com-mercially available starch (Perfectamyl A 4692R) and the solution is warmed to bOC. 200 ml of this sizing liquor are passed from an aluminium vessel, ~hich has a circular opening 4 mm in diameter (Ford cup) on its underside, from a height of 60 cm into a graduated glass beaker under gravity. The volume (in ml) of the foam which forms over the surface of the liquid is determined once immediately and alsoafter standing in air for one minute. The first vaLue gives information on the tendency of the sizing agent to foam, and the second value gives information on the speed at which the foam is degraded and the stability of the foam.
Table VIII Tendency of sizing agents t~ foam 20 Sizing agent Foam volume in ml from Exampleimmediatelyafter 1 minute 2û
1~ 15 Le A 24 141
' ~ ' O
wherein R and R' are idential or different radicals and repre-sent hydrogen, Cl-C16-alkyl which may be substituted by OH, cycloal]cyl with 5-12 C~atoms or an aryl group with 6-12 C-atoms1t ' ~l5 ,~
'71t)0~
- 3a - 23189-6381 The weigh-t ratio between the polymeric, ca-tionic emulsifier and monomer mixture of d) and e) is pre:Eerab]y 1:4 to 1:1.
The sizing agent for paper, according to the inven-tion, is also obtained when, in addition to the cationic emulsi-Eier meht:ioned, a cationic and/or non-ionic auxiliary emulsi-fier is ernployed in amounts of 1 to 40% by weight, preferably 3 to 20% by weight, based on the above cationic emulsifier, the non-ionic emulsifier having the formula Rl-X-(CH2-CH2-O) -H (II) wherein ~27~
l, X denotes 0, NH or C00, R1 is a higher aliphatic, cycloaliphatic, arali-phatic or aromatic hydrocarbon radical with 6-30 C atoms and n is an integer > 2, and the cationic auxiliary emulsifier having the formula R2 ~3 \ ~i3 /
N
wherein R2 and R3 represent higher aliphatic or araliphatic hydrocarbon radicals with 6 to 20 C atoms, R~ and Rs represent lower aliphatic hydrocarbon radicals with 1 to 6 C atoms and Y represents a halide ion~
The terpolymer, built up in a chemically uniform manner, of N,N-dimethylaminoethyl tmeth)acrylate, styrene and acrylonitrile is quaternized in an organic medium, after partial or complete neutralization with acid, with monoepoxides of the general formula R-~-CH-R
20 wherein R and R' represent identical or different radicals and denote hydrogen, an alkyl group with 1 to 16 carbon atoms, a cycloalkyl group with S to 12 carbon atoms or an aryl group with 6 to 12 carbon atoms, it being possible for the substituents mentioned also to contain hetero atoms or func-tional substituents, in particular hydroxyl sub~
stituents, but excluding epihalogenohydrins. Lxamples of monoepox-ides which are particularly suitable are ethylene oxide, Le A 2lt 1~,1 ~L27~00~
propylene oxide, 1,2-butylene o~ide, 2,3-butylene oxide, isobutylene oxide, 1,2-epoxyhexane, 1,2-epoxydecane, 1,2-epoxydodecane~ styrene oxide, cyclohexene oxide and gly-cidyl alcohol. The hydrophilic-hydrophobic properties of the polymeric cationic emulsifier can be influenced within wide limits both via the nature of the epoxide and via the degree of quaternization.
The quaternization of homo- or copolymers contain-ing dialkylamino groups with ethylene oxide, propylene oxide or styrene oxide is known from French Patent Speci-fication 1,173,575 and British Patent Specification 1,281,683 and from German Offenlegungsschrift 2,258,868.
However, monoepoxides with longer alkyl chains are not claimed. Furthermore, nothing is reported of a use of such products as sizing agents for paper which are stable towards electrolytes, heat and shearing forces and have favourable foaming properties.
After the quaternizat;on, the remaining acid is added and the components are dissolved to form aqueous solutions with a concentration of 10 to 30% by weight, preferably 15 to 25% by weight. The emulsifier solutions thus obtained can now also be freed from the organic sol-vent by distillation; however, the removal of the organic solvent is not necessary, since the solvent in general does not interfere with the emulsion polymerization in the subsequent course of the reaction.
For the emulsification, it is sufficient for the quaternized cationic terpolymers to be employed for the emulsion polymerization without further additives. In some cases, however, it proves to be quite advantageous for oligomeric non-ionic and/or low molecular weight cationic auxiliary emulsifiers to be employed together with the polymeric cationic emulsifier in proportions of 1 to 40% by weight, preferably 3 to 20% by weight, based on the cationic emulsifier.
Suitable non-ionic auxiliary emulsifiers are reac-Le A 24 141 7~
tion products of aliphatic, araliphatic, cycloaLiphatic or aromatic carboxylic acids, alcohols, phenol derivatives or amines with epoxides, such as, for example, ethylene oxide.
Examples of these are reaction products of ethyl-ene oxide with carboxylic acids, such as, for example, lauric acid~ stearic acid, oleic acid, the carboxylic acids of castor ~il or abietic acid, with longer chain alcohols, such as oleyl alcohol, lauryl alcohol or stearyl alcohol, with phenol derivatives, such as, for example, substituted benzyl- or phenylphenols or nonylphenol and with longer chain amines, such as, for example, dodecyl-a0ine and stearylamine. The reaction products with ethyl-ene ox;de are ol;go- or polyethers with degrees of poly-merization of between 2 and 100, preferably from 5 to 5û.
Suitable cation;c low molecular we;ght auxiliaryemulsifiers are quaternized ammonium salts, such as, for example, benzyldodecyl dimethyl-ammonium chloride. The auxiliary emulsifiers mentioned effect additional emulsi-fication of the monomer mixture and in some cases increase the stability of the colloidally disperse sizing agents.
However, it is not advisable to use too high an amount of these auxil;ary d;spersing agents, since undesirable foaming can otherwise readily occur.
Suitable acrylic acid esters or methacrylic acid esters which are employed as comonomers in the free radi-cal emulsion copolymerization are preferably those com-pounds which form copolymers with film-form;ng tempera-tures belc,~ 1û0C with ~meth)acrylonitrile or styrene or mixtures thereof.
Copolymers which, because of the position of their glass transition point, have higher film-forming tempera-tures possess only an inadequate sizing action. Compounds which are suitable in principle are acrylates, such as methyl, ethyl, n-butyl and 2-ethylhexyl acrylate, and methacrylates, such as methyl methacrylate and n-butyl Le A 24 1_ 3L~ 3 methacrylate. They can be copolymerized individually or as a mixture with methacrylonitrile, acrylonitrile or styrene or with mixtures of the two comonomers last men-tioned or with mixtures of all three monomers. The con-tent of styrene, acrylonitrile or methacrylonitrile ormixtures of these components can be between 5 and 95, preferably 2D and 80% by weight. Formulations containing too little styrene, acrylonitrile or methacrylonitrile in the copolymer may cause trouble during paper production because of their tackiness, and sizing of the paper is inadequate with formulations with a very large amount of styrene, acrylonitrile or methacrylonitrile.
Possible initiators for the emulsion polymeriza-tion are, preferably, water-soluble non-ionic Peroxides which supply free radicals, such as hydrogen peroxide and t-butyl hydroperoxide, as well as water-soluble azo com-pounds, such as are described, for example, in German Offenlegungsschrift 2,841,045. Redox systems which con sist of peroxidic initiators and reducing agents, such as amines, polyamines, thiourea, iron-II salts and the like, are furthermore suitable. Possible initiators are also water-insoluble initiators, such as azoisobutyronitrile and benzoyl peroxide. The latter are then dissolved vir-tually only in the organic phase. The initiators men-tioned are added in amounts of 0.1 to 5% by we;ght, prefer-ably 0.3 to 3.0% by weight, based on the monomer mixture.
Customary chain regulators, for example n-dodecyl-mercaptan, t-dodecylmercaptan, diisopropylxanthogene di-sulphide, thioglycol and thioglycerol, can also be employed to regulate the molecular weights of the polymers.
They are added in amounts of 0.1 to 2% by weight, based on the monomer mixture.
The emulsion polymerization in an aqueous medium can be carried out by known polymerization processes, either discontinuously or continuously or by the feed pro-cess. The continuous process and the feed process are Le A 24 141 7~
particularly preferred. ln the latter, water, together with some or all of the emuls;fier system and, if approp-riate, some of the monomer mixture, is taken under a nitrogen atmosphere and is heated to the polymerization temperature of 20 to 150C, preferably 50 to 100C, and the monomer mixture and initiator and, if appropriate, emulsifier are added dropwise in the course of 0.5 to 10 hours, preferably 1 to h hours.
After some time, the mixture is post-activated and the reaction is brought to completion up to a conversion of about 99.0% to 99.9%. The weight ratio of emulsifier to polymer here is 1:9 to 7:3, preferably 1:4 to 1:1.
Residual monomers and any organic solvent still present are removed by distillation in vacuo after the emulsion copolymerization. Water is then added until an approxi-mately 10 to 35% strength by weight aqueous colloidally disperse solution results. The viscosity of these dis-persions, measured in a rotary viscometer at 20C, is in general below 50 mPa.s. The average particle diameters, measured by means of laser scattered light spectroscopy, are between 15 and 200 nm, preferably bet-ween 20 and 150 nm, depending on the reaction conditions.
Dispersions with particle sizes below 50 nm appear trans-parent, whilst those with larger particles appear more cloudy. The stability of the dispersions with particle sizes belo~ 100 nm is also better than that of those with particle sizes above 100 nm, which can be demonstrated, for example, by exposure to heat at temperatures above 80C. The content of sediments is usually considerably higher in dispersions with coarser particles than in fine-particled dispersions.
The stability of the colloidally disperse sizing agents according to the invention is also increased by grafted-on portions of the polymer on the polymeric emul-sifier present in relatively large amounts. Such graftingreactions, which are triggered off by transfer reactions Le A 24 141 7~
by the emulsifier, are known in the literature (compare H. Gerrens, Fortschritte der Hochpolymer-Forschung (Advances in High Polymer Research), Volume I, (1959) page 300).
S The sizing agents for paper according to the invention can be used in all the working methods customary in papermaking for surface and beater sizing~
In addition to the substantial pH independence of their sizing effect and the generally very high degree of sizing industrially, the improved stability towards electrolytes, shearing forces and heat and the reduced tendency to foam in comparison with the sizing agents for paper in European Patent 0,058,313 and German Offenlegungsschrift 3,401,573 should be emphasized again, and are illustrated in the following examples.
Example 1 Preparation of the cationic emulsifiers 5,720 9 of isopropanol are taken in a 40 litre autoclave. The autoclave is flushed thoroughly with nitrogen and then warmed to 80C. Mixtures I and solu-tions II of Table I are metered in at this temperature in the course of 4 hours, with exclusion of air. The mixture is then subsequently stirred for 1 to 2 hours and there-after post-activated with so~ution III. The mix-ture is then stirred at 80C for about 6 to 12 hours.After the terpolymerization, the amount of acetic acid (IV) stated in Table I is metered into the polymer at an unchanged temperature. The monoepoxide (V) is subsequently metered ;n as the quatern;z;ng agent ;n the course of about 15 minutes and the mixture ;s st;rred for about 1 hour. Thereafter, the remainder of the acetic acid (VI) ;s added. About 63-65 litres of deionized water at a temperature of about 60C are taken in a 120 litre stock vessel equipped with a stirrer, and the contents of the 40 litre autoclave are combined with this. A homogeneous aqueous solution is prepared in a short time by stirring Le A 24 141 ~73L~O~
;ntensively. The aqueous solutions, which also contain organic solvent, have the properties likewise recorded in Table I.
Table I
Emulsifier A a C D E
Polymer;zation and quaternizat;on temperature (C) 80 80 80 80 80 I. N,N-dimethylaminoethyl methacrylate (g) 3217 3217 2257 3217 3217 styrene (g) 10244 10244 10608 1024410244 acrylonitrile (g)2644 2644 3219 2644 2644 II. Azoisobutyronitrile (9) 500 500 550 500 500 acetone (g) 3000 3000 3000 3000 3000 III. Azoisobutyronitrile (9) 50 50 50 50 50 acetone (g) 300 300 300 300 300 IV. acetic ac;d (9) 1229 984 690 984 984 V. 1,2-epoxydodecane (9)1131 - - - -1,2-epoxyhexane (9) - 1025 719 1,2-epoxybutane (9) - - - 885 propylene oxide (g) - - - - 891 VI. Acetic acid (9) 1230 1475 1035 1475 1475 Concentration (~)20.3 20.1 20.2 20.0 19.9 Viscos1ty (at 20C) 50-100 30-70 300-500 20-50 20-50 [mPa.s]*
pH value: 4.2 4.2 4.1 4.2 4.2 Appearance of the emulsifier solution: slightly clear clear clear clear cloudy *) Viscosity is not constant since the samples have structural viscosity Examples 2_ to 4 9,720 9 of deionized water are taken in a 40 litre stirred autoclave. The water is then boiled up thoroughly under a nitrogen atmosphere and cooled to 70C. There-after, the emulsions I (compare Table I) are added to the initial water, with exclus;on of a;r. 12 9 of a 35 Le A 24 141 strength hydrogen peroxide solution are then added~ After about 15-30 minutes~ che monomer mixtures II and the initiator mixtures III are metered in over a period of about 4 hours. Thereafter, the mixture is subsequently stirred for a further 2 to 5 hours and is then post-activated with mixture IV and after-polymerized for about a further 2 to 10 hours. About 1.5 to 2 litres of a mix-ture of water, organic solvent (isopropanol and acetone) and residual monomers are then distilled off under a waterpump vacuum of about 200 to 400 mbar and are replaced by the same amount of deionized water. The physico-chemical properties of the colloidally disperse solutions thus obtained are likewise recorded in Table II.
Table II.
Example 2 3 4 I. Emulsifier A
(compare Table I) (9) 12400 12400 12400 Styrene (9) 124 - -Acrylonitrile (9) - 124 Methacrylonitr;le (9) - - 124 n-Butyl acrylate (9) 124 124 124 II. Styrene (9) 2356 Acrylonitrile (9) - 2356 Methacrylonitrile (9) - - 2356 n-Butyl acrylate (9) 2356 2356 2356 III. Hydror~en peroxid e (35% strength) (9) 198 198 198 Deionized water (9~ 2480 2480 2480 IV. Hydrogen peroxide (35% strength) (g) 25 25 50 Deionized water (9) 100 100 100 Concentration (% by weight) 24.8 25.0 24.9 Viscosity (at 23C) [mPa.s] <50 <50 <50 pH value 4.3 4.4 4.3 Appearance of the colloidally disperse sl;ghtly slightly slightly solution cloudy cloudy cloudy Average particle diameter d [nm] 67 48 52 L_ A 24 141 Examples 5 and 6 The colloidally disperse sizing agents 5 and h are prepared in the same way as the corresponding sizing agents 2 and 3, but emulsifier A is replaced by emulsifier 5 8 (compare Table I).
Table III
Example 5 I. Emulsifier B
(compare Table I) (9)12400 12400 Styrene (9) 124 Acrylonitrile (9) - 124 n-Butyl acrylate (9)124 124 II. Styrene (9) 2356 Acrylonitrile (9) - 2356 n-Butyl acrylate (9)2356 2356 Concentration (/~ by weight) 24.7 24.6 Viscosity (at 23C) [mPa.s] <50 <50 pH value 4.2 4.3 Appearance of the colloidally disperse solution transparent transparent Average particle diameter dz [nm] 39 35 ~C~
The collo;dally disperse sizing agents 7 and 8 are prepared ;n the same way as the corresponding sizing agents 2 and 3, but emulsifier A is replaced by emulsif;er C (compare Table I).
Le A 24 1~1 Table IV
Example 7 8 _ I. Emulsifier C
tcompare Table I) (9)12400 12400 Styrene (9) 124 Acrylonitrile (9) - 124 n-Butyl acrylate (9)124 124 II. Styrene (9) 2356 Acrylonitrile (9) - 2356 n-Butyl acrylate (g)2356 235b Concentration (% by ~eight) 25.2 25.1 ' Viscosity (at 23C) [mPa.s] <50 <50 Appearance of the colloidally disperse solution transparent transparent Average particle diameter dz [nm] ~5 37 Examples 9 and 10 The colloidally disperse sizing agents 9 and 10 are prepared in the same way as the corresponding sizing agents 2 and 3, but emulsifier A is replaced by emulsi-fier D (compare Table I).
Le A 24 141 ~L~7i~)~4 Table V
Example 9 10 I. Emulsifier D
(compare Table I) (9)12400 12400 Styrene (9) 124 Acrylonitrile (9) - 124 n-Butyl acrylate (9) 124 124 II. Styrene (9) 2356 Acrylonitrile (9) - 2356 n-Butyl acrylate (9)2356 2356 Concentration (% by weight) 25.3 25.1 Viscosity (at 23C) [mPa.s] <50 <50 Appearance of the colloid-ally disperse solution transparent transparent Average particle diameter d (nm) 48 43 Examples 11 and 12 The colloidally disperse sizing agents 11 and 12 are prepared in the same way as the corresponding sizing agents 2 and 3, but emulsif;er A ;s replaced by emulsi-f;er E (compare Table I).
Le A 24 141 ~710~34 Table VI
Example 11 12 .
. EmuLsifier E
(compare Table I) (9) 12400 12400 Styrene (9) 124 Acrylonitrile (9) - 124 n-Butyl acrylate (9) 124 124 II. Styrene (g) 2356 Acrylonitrile (9) - 2356 n-~utyl acrylate (g) 2356 2356 Concentration (% by weight)25.4 24.8 Viscosity (at 23C) (mPa.s) <50 <50 Appearance of the colloidally disperse solution transparent transparent Average particle diameter dz [nm] 32 28 A solution of 5% by weight of starch (PerfectamylR
A 4692 from AvEsE)~ 0.4% by weight of sodium sulphate and 0.20 or 0.25% by weight o~ the sizing agent to be tested (calculated as the active substance) in 94.40 or 94.35%
by weight of water is used as the sizing liquor for sur-face sizing. ~efore use in the siz;ng press, the sizing liquors are warmed at 75C in a waterbath for 30 minutes.
A laboratory slzing press from Werner Mathis, Zurich, type HF is used for the sizing. The siz;ng l1quor has a tem-perature of about 25C in the sizing press. The paper is drawn through at a speed of 4 m/minute. The surface-sized paper is dried on a clrying cylinder in the course of about 45 seconds at about 100C. Pefore testing the sizing, the paper is acclimatized at room temperature for 2 hours.
Le A ~4 141 ~Z73L()(~
.
The sizing is tested in accordance with DIN 53 132. In this, the water uptake in g/m2 is determined after a testing time of 60 seconds (Cobb60).
Use Example 1 This example demonstrates the good activity of some sizing agents after exposure to heat and electrolytes on paper free from aluminium sulphate. The base paper used has the following composition and properties:
50% by weight of conifer cellulose, 50% by weight of hard-wood cellulose and 9.5~ by weight of clay ash, pH in the headbox: 7.5; wet uptake in the laboratory sizing press:
about 80% by weigh~, paper weight: 80 g/m2.
Two sizing agents according to European Patent 0,058,313 (sizing agents 3 and 10) - called here M and N -were used as the comparison substance.Table VII
Surface sizing on paper free from aluminium sulphate after exposure to heat and electrolytes.
Sizing agent Water uptake in g/m2 on addit;c~n of 20 from Example 0.20% by weight 0.25% by weight of sizing agent (based on the pure active substance) to the liquor 3 37.8 35.3 35.3 33.1 6 34.1 32.4 8 35.2 33.5 34.7 32.3 11 35.8 33.6 12 33.2 31.3 M 45.2 40.5 N 65.5 61.3 Without a sizing agent, the water uptake is 89.0 g/m2 .
Use Example 2 This example demonstrates the low tenclency of the sizing agents according to the invention to foam in com-Le ~ 24 141 t~LO~
- ~7 --parison with sizing agents M and N according to European Patent 0,058,313. The tendency to foam is, in this exampLe, measured in the absence of additives such as, for example, additional emulsifiers and antifoaming agents.
In this example 0.4% by weight of active compound is dissolved in a sizing liquor of 5% by weight of com-mercially available starch (Perfectamyl A 4692R) and the solution is warmed to bOC. 200 ml of this sizing liquor are passed from an aluminium vessel, ~hich has a circular opening 4 mm in diameter (Ford cup) on its underside, from a height of 60 cm into a graduated glass beaker under gravity. The volume (in ml) of the foam which forms over the surface of the liquid is determined once immediately and alsoafter standing in air for one minute. The first vaLue gives information on the tendency of the sizing agent to foam, and the second value gives information on the speed at which the foam is degraded and the stability of the foam.
Table VIII Tendency of sizing agents t~ foam 20 Sizing agent Foam volume in ml from Exampleimmediatelyafter 1 minute 2û
1~ 15 Le A 24 141
Claims (9)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A cationic sizing agent for paper, obtainable by a process in which a water-soluble cationic terpolymer compound, built up in a chemically uniform manner, of a) 7 to 40% by weight of N,N-dimethylaminoethyl acrylate and/or methacrylate, b) 40 to 80% by weight of styrene and c) 4 to 50% by weight of acryloni-trile the sum of components a) to c) always being 100% by weight and at least 10% of the dimethylamino groups of the terpolymer being quaternized with a mono-epoxide of the formula wherein R and R' are identical or different radicals and represent hydrogen, C1-C16-alkyl which may be substituted by OH, cycloalkyl with 5-12 C-atoms or an aryl group with 6-12 C-atoms, with the exception of epihalogenohydrins, and the remainder protonated, is dissolved in an aqueous medium and, in the presence of 10 to 70% by weight - based on the following monomer mixture - of this emulsifier, d) 5 to 95% by weight of acryloni-trile, methacrylonitrile or styrene or a mixture thereof and e) 5 to 95% by weight of acrylic acid ester and/or methacrylic acid ester with 1 to 12 C-atoms in the alcohol radical - the sum of components d) and e) always being 100% by weight - are emulsified and the emulsion thus obtained is subjected to emulsion polymer-ization, initiated by free radicals, at a temperature of 20 to 150°C.
2. A sizing agent for paper according to Claim 1, wherein the cationic terpolymer compound, built up in a chemically uniform manner, consists of a) 8 to 30% by weight of N,N-di-methylaminoethyl acrylate and/or methacrylate/ b) 40 to 80% by weight of styrene and c) 5 to 40% by weight of acrylonitrile, the sum of components a) to c) always being 100% by weight.
3. A sizing agent for paper according to Claim 1, wherein the monomer mixture consists of d) 20 to 80% by weight of acrylonitrile, methacrylonitrile or styrene or a mixture thereof and e) 20 to 80% by weight of acrylic acid ester and/or metha-crylic acid ester with 1 to 12 C-atoms in the alcohol radical, the sum of components d) and e) being 100% by weight.
4. A sizing agent for paper according to Claim 1, wherein, in addition to the polymeric cationic emulsifier accor-ding to Claim 1, a cationic and/or non-ionic auxiliary emulsifier is employed in amounts of 1 to 40% by weight, based on the above cationic emulsifier, the non-ionic emulsifier having the formula R1-X-(CH2-CH2-O)n-H (II) wherein X denotes O, NH or COO, R1 is a higher aliphatic, cycloaliphatic, araliphatic or aromatic hydrocarbon radical with 6-30 C-atoms and n is an integer ? 2, and the cationic auxiliary emulsifier having the formula Y(-) wherein R2 and R3 represent higher aliphatic or araliphatic hydrocarbon radicals with 6 to 20 C-atoms, R4 and R5 represent lower aliphatic hydrocarbon radicals with 1 to 6 C-atoms and Y- represents a halide ion.
5. A sizing agent according to Claim 1, wherein the weight ratio between the polymeric cationic emulsifier and monomer mixture of d) and e) is 1:4 to 1:1.
6. A sizing agent according to Claim 1, wherein the emulsion polymerization is initiated with a water-soluble non-ionic peroxide and/or an azo compound which supply free radicals in an amount of 0.1 to 5% by weight, based on the monomer mixture.
7. A sizing agent according to Claim 1, in the form of a colloidally disperse solution with average particle diameter of 15-200 nm.
8. A sizing agent according to Claim 1, in the form of a colloidally disperse solution with average particle diameter of 20-150 nm.
9. A sizing agent according to Claim 1, wherein the terpolymer, built up in a chemically uniform manner, of N,N-dimethylaminoethyl (meth)acrylate, styrene and acrylonitrile is quaternized with the monoepoxide in an organic medium, after partial or complete neutralization with acid.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19853537824 DE3537824A1 (en) | 1985-10-24 | 1985-10-24 | CATIONIC SIZE FOR PAPER |
| DEP3537824.7 | 1985-10-24 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1271004A true CA1271004A (en) | 1990-07-03 |
Family
ID=6284338
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000521098A Expired - Lifetime CA1271004A (en) | 1985-10-24 | 1986-10-22 | Cationic sizing agents for paper |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US4806591A (en) |
| EP (1) | EP0221400B1 (en) |
| JP (1) | JPS62104999A (en) |
| CA (1) | CA1271004A (en) |
| DE (2) | DE3537824A1 (en) |
Families Citing this family (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ES2048779T3 (en) * | 1988-08-06 | 1994-04-01 | Giulini Chemie | CATIONIC SIZING AGENT FOR PAPER. |
| JP2681053B2 (en) * | 1989-02-27 | 1997-11-19 | 三井サイテック株式会社 | Paper manufacturing method |
| EP0406461B1 (en) * | 1989-07-05 | 1994-01-05 | Giulini Chemie GmbH | Paper sizing agent containing a cationic dispersant |
| US5367009A (en) * | 1990-04-12 | 1994-11-22 | Arakawa Chemical Industries Ltd. | Aqueous rosin emulsion and dispersant composition useful therein |
| DE4200715A1 (en) * | 1992-01-14 | 1993-07-15 | Bayer Ag | Vinyl polymer DISPERSIONS |
| DE4320433A1 (en) * | 1993-06-21 | 1994-12-22 | Wolff Walsrode Ag | Process for the preparation of cationic, water-soluble polymers and their use |
| DE4324568C2 (en) * | 1993-07-23 | 1997-09-11 | Leuna Harze Gmbh | Cationic paper sizes |
| DE19601267A1 (en) * | 1996-01-16 | 1997-07-17 | Bayer Ag | Recording material for inkjet printing processes |
| US7939601B1 (en) | 1999-05-26 | 2011-05-10 | Rhodia Inc. | Polymers, compositions and methods of use for foams, laundry detergents, shower rinses, and coagulants |
| ATE410455T1 (en) * | 1999-05-26 | 2008-10-15 | Rhodia | BLOCK POLYMERS, COMPOSITIONS AND METHODS FOR USE IN FOAM, DETERGENT, SHOWER CLEANER AND COAGULANT |
| US20050124738A1 (en) * | 1999-05-26 | 2005-06-09 | The Procter & Gamble Company | Compositions and methods for using zwitterionic polymeric suds enhancers |
| US7241729B2 (en) * | 1999-05-26 | 2007-07-10 | Rhodia Inc. | Compositions and methods for using polymeric suds enhancers |
| JP4645927B2 (en) * | 2000-03-15 | 2011-03-09 | 星光Ｐｍｃ株式会社 | Cationic emulsion type surface sizing agent |
| ATE292643T1 (en) * | 2000-08-16 | 2005-04-15 | Bayer Chemicals Ag | CATIONIC POLYMER DISPERSIONS FOR PAPER SIZING |
| JP5136862B2 (en) * | 2009-01-27 | 2013-02-06 | 荒川化学工業株式会社 | Paper-making surface sizing agent, coating liquid containing paper-making surface sizing agent, and paper obtained using these |
| NL1039825C2 (en) * | 2012-09-27 | 2014-03-31 | Stichting Dutch Polymer Inst | Graft copolymer, method for producing such graft copolymer and composition comprising such graft copolymer. |
| CN103334339B (en) * | 2013-07-02 | 2015-05-20 | 浙江理工大学 | Positive ion styrene-acrylic emulsion surface sizing agent with high reactivity for papermaking and synthetic method thereof |
| CN108276520A (en) * | 2018-02-01 | 2018-07-13 | 威尔（福建）生物有限公司 | Auxiliary agent and preparation method thereof for handling paper mill sludge |
| CN111608010B (en) * | 2020-04-17 | 2021-12-31 | 仙鹤股份有限公司 | Preparation method of high-strength low-static CTP lining paper |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2980634A (en) * | 1954-10-08 | 1961-04-18 | Rohm & Haas | Quaternary ammonium compounds of polymers of aminoalkyl vinyl ethers |
| DE1073854B (en) * | 1956-04-10 | 1960-01-21 | Rohm &. Haas Company, Philadelphia, Pa. (V. St. A.) | Process for the production of filled papers and the like |
| GB1281683A (en) * | 1968-07-04 | 1972-07-12 | Ici Ltd | Cationic polymers and their preparation and use |
| DE2058120A1 (en) * | 1970-11-26 | 1972-05-31 | Basf Ag | Cationic copolymers of ethylenically unsaturated cpds - used as paper sizings and textile dressings |
| JPS546902A (en) * | 1977-06-10 | 1979-01-19 | Seiko Kagaku Kogyo Co Ltd | Sizing agent for paper making |
| DE3103917A1 (en) * | 1981-02-05 | 1982-08-19 | Bayer Ag, 5090 Leverkusen | CATIONIC SIZING AGENT FOR PAPER AND METHOD FOR THE PRODUCTION THEREOF |
| DE3401573A1 (en) * | 1984-01-18 | 1985-07-25 | Bayer Ag, 5090 Leverkusen | CATIONIC SIZING AGENT FOR PAPER AND METHOD FOR THE PRODUCTION THEREOF |
-
1985
- 1985-10-24 DE DE19853537824 patent/DE3537824A1/en not_active Withdrawn
-
1986
- 1986-10-13 DE DE8686114129T patent/DE3663949D1/en not_active Expired
- 1986-10-13 EP EP86114129A patent/EP0221400B1/en not_active Expired
- 1986-10-17 JP JP61245610A patent/JPS62104999A/en active Granted
- 1986-10-20 US US06/921,173 patent/US4806591A/en not_active Expired - Fee Related
- 1986-10-22 CA CA000521098A patent/CA1271004A/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| EP0221400B1 (en) | 1989-06-14 |
| JPH0577798B2 (en) | 1993-10-27 |
| DE3537824A1 (en) | 1987-04-30 |
| DE3663949D1 (en) | 1989-07-20 |
| US4806591A (en) | 1989-02-21 |
| JPS62104999A (en) | 1987-05-15 |
| EP0221400A1 (en) | 1987-05-13 |
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