EP0000706B1 - Utilisation de sels de polyimideamines comme agents d'encollage superficiel cationiques pour le papier - Google Patents

Utilisation de sels de polyimideamines comme agents d'encollage superficiel cationiques pour le papier Download PDF

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Publication number
EP0000706B1
EP0000706B1 EP78100381A EP78100381A EP0000706B1 EP 0000706 B1 EP0000706 B1 EP 0000706B1 EP 78100381 A EP78100381 A EP 78100381A EP 78100381 A EP78100381 A EP 78100381A EP 0000706 B1 EP0000706 B1 EP 0000706B1
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Prior art keywords
sizing agents
copolymers
parts
acid
paper
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EP78100381A
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German (de)
English (en)
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EP0000706A1 (fr
Inventor
Günter Dr. Kolb
Friedhelm Dr. Müller
Joachim Dr. Probst
Günter Dr. Sackmann
Wulf Dr. Von Bonin
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Bayer AG
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Bayer AG
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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
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
    • C08F8/32—Introducing nitrogen atoms or nitrogen-containing groups by reaction with amines

Definitions

  • the present invention relates to the use of salts of polyimidamines with organic or inorganic acids for the surface sizing of paper.
  • the corresponding polyimidamines are derived from copolymers of maleic anhydride and 2,4,4-trimethylpentene-1.
  • polyimidamines To produce paper sizing agents, such polyimidamines must either be mixed with non-cationic polymers in accordance with German Patent 1,621,688, or converted into graft polymers with special, olefinically unsaturated graft monomers in accordance with German Patent 1,621,689. As can be seen from the comparative tests of German patent 1,621,688, the polyimidamines alone have a significantly lower, inadequate sizing effect.
  • DE-OS 25 44 948 discloses cationic sizing agents based on copolymers of maleic anhydride and alpha-olefins with 10-26 carbon atoms, which are obtained by converting the copolymers into polyimidamines and subsequent salt formation. To produce suitable polyimidamines, the copolymers must also be reacted with a low molecular weight polyamine in addition to monoprimary mono-tertiary aliphatic diamines.
  • polyimidamines of the type mentioned derived from copolymers of maleic anhydride and 2,4,4-trimethylpentene-1 by reaction with a mixture of a diamine with tertiary and primary amino groups and a primary monoamine, directly in the form of a aqueous solution of their salts with organic or inorganic acids can be used as an excellent surface sizing agent for paper.
  • the copolymers of maleic anhydride with 2,4,4-trimethylpentene-1 are preferably of equimolar and alternating structure.
  • the average molecular weights are between 8,000 and 500,000, preferably between 10,000 and 60,000, determined by membrane osmometry.
  • the preferred copolymers have intrinsic viscosities of 0.08 to 0.3 dl / g, measured in N, N-dimethylformamide at 25 ° C.
  • Copolymers with intrinsic viscosities below 0.08 dl / g lead to considerably less effective sizing agents for paper. Products that are too high in molecular weight result in viscosities of the sizing agent that are too high and thus poorer processability.
  • the molar ratio of diamine (A) to monoamine (B) is 1: 0.3 to 1: 2.0.
  • Diamines are those of the general formula and as monoamines those of the general formula used.
  • R denotes a linear or branched aliphatic chain containing 2 to 12, preferably 2 to 6 carbon atoms, which may optionally also contain oxygen or sulfur atoms.
  • the substituents R 1 and R 2 of the tertiary amino group can be the same or different and represent aromatic radicals, such as phenyl, toluyl, xylyl, chlorophenyl, nitrophenyl, 4-dimethylaminophenyl, preferably phenyl, toluyl, xylyl, araliphatic radicals, such as benzyl, 2- Phenylethyl, preferably benzyl; Alkyl radicals with 1 to 12, preferably 1 to 6 carbon atoms, or the two substituents together represent a 5- or 6-membered cyclic ring which may contain an oxygen or sulfur atom.
  • diamines whose primary and tertiary amino groups are separated from one another by a linear alkylene chain from 2 to 6 methylene groups and whose tertiary amino group is substituted by linear C 1 -C 4 -alkyl radicals.
  • 1-Amino-3-dimethylaminopropane is particularly preferred.
  • the substituent R 3 represents an aliphatic or cycloaliphatic, saturated or unsaturated, optionally substituted hydrocarbon radical.
  • Preferred monoamines are ammonia and / or aliphatic primary monoamines with 1 to 18 carbon atoms or cycloaliphatic monoamines with 5 to 8 carbon atoms.
  • Particularly preferred monoamines are, for example, methylamine, ethylamine, n-propylamine, n-butylamine, sec. Butylamine, iso-butylamine, tert. Butylamine, n-hexylamine, 2-ethylhexylamine, cyclohexylamine and dehydroabietylamine.
  • 1-Amino-3-dimethylaminopropane and ethylamine in a molar ratio of 1: 1 to 1: 1.6 are particularly preferably used as the amine mixture.
  • the mixture of the diamines (A) and the monoamines (B) is used in an approximately equimolar amount, but preferably in a slight excess based on the anhydride groups of the starting polymer; the amine mixture used should preferably contain 1.0-1.5 mol of primary amino groups, based on one mol of anhydride groups of the polymer.
  • the excess of amine is therefore added in order to achieve the most complete possible imidization, which should be at least 80%, preferably more than 85%. Lower imidized reaction products are poorly water-soluble and show insufficient sizing effects on paper.
  • the molar ratio of diamine to monoamine should be between 1: 0.3 and 1: 2.0.
  • Suitable solvents include organic, alkyl and halogen-substituted aromatic solvents such as benzene, toluene, m-, o- or p-xylene or mixtures thereof. They are capable of both the maleic anhydride-2,4,4-trimethylpentene-1 copolymers and their reaction products, the. Polyimidamines to solve.
  • Inorganic and organic acids are suitable for this, of which 100 to 500 mol percent, based on the tertiary amino groups contained in the chemically bound amine mixture, are added. Particularly suitable acids are formic acid, acetic acid, propionic acid, lactic acid, hydrochloric acid, nitric acid and sulfuric acid, preferably formic acid and acetic acid. Water is generally used as the solvent.
  • the polyimidamine salts are present in a 5 to 30% solution. No gelling of the products is observed, as is described in the Belgian patent specification 654 889 in the higher molecular weight range above 5000.
  • the copolymer of maleic anhydride and 2,4,4-trimethylpentene-1 is advantageously imidized in two stages.
  • the copolymer is suspended or dissolved in the organic solvent at temperatures between 0 ° C. and 50 ° C. and the amine mixture is added dropwise at these temperatures with stirring. Monoamide is predominantly formed in this reaction stage.
  • the reaction mixture is brought to a temperature of 130 ° C. to 200 ° C. with stirring.
  • This stage is carried out thermally, if necessary with the aid of catalysts, e.g. p-toluenesulfonic acid, pyridine etc., with elimination of water, the imide formation from at least 80%, preferably more than 85% of the original anhydride group.
  • the organic polymer solution can, for example, be converted into an aqueous solution are carried out in such a way that the organic solution is continuously added to a heated receiver with dilute aqueous acid while the organic solvent is distilled off.
  • the copolymers of maleic anhydride and 2,4,4-trimethylpentene-1 converted to polyimidamine salts are used as surface sizing agents for paper, which have excellent sizing effects directly in aqueous solution without any additives.
  • sizing agents are products that ensure that paper is labeled with ink but prevent it from bleeding.
  • water repellents are water-repellent and water-insoluble
  • the sizing agents according to the invention are water-soluble.
  • German patent 1 162 688 in which cationic sizing agents are used in the form of dispersion, is the use according to the invention of the sizing agents in homogeneous aqueous solution. They are easy to process, guarantee, in contrast to heterogeneous sizing systems, absolute homogeneity of the sized paper and show excellent sizing efficiency on all papers, with particular emphasis being placed on chalk-containing paper.
  • the sizing agents used according to the invention are clearly superior to all conventional sizing agents.
  • Example B As in Example B, except that a mixture of 15 parts of hexylamine and 39 parts of 1-amino-3-dimethylaminopropane is added dropwise without solvent instead of the amine mixture there.
  • the aqueous solution has a solids content of 13.5% by weight. 96.
  • a laboratory size press from Werner Mathis, Zurich, type HF was used for the sizing.
  • the size liquor had a temperature of approx. 20 ° C in the size press.
  • the paper was fed at a speed of 4 m / min. pulled through.
  • the surface-sized papers were dried on a drying cylinder within 45 seconds at approx. 100 ° C. Before the sizing test, the papers were air-conditioned for 2 hours at room temperature. Sections of the paper were then pre-weighed, immersed in water at 20 ° C. for 1 minute, pressed once between filter paper using a 10 kg rolling weight and weighed back. The value for the water absorption on both sides in g / m 2 was calculated from the weight difference. The lower the water absorption, the better the effect of the tested sizing agent. Sizing is good when water absorption of approx. 40 g / m 2 and below is achieved.
  • This example is intended to show that good sizing effects can be achieved with the described sizing agents on unsized papers from bleached cellulose.
  • the base paper used was made from bleached sulfite pulp with the addition of 3% china clay (calculated as ash) at pH 6.8 and had a basis weight of 70 g / rri2.
  • This example shows the good effectiveness of the sizing agents described on pulp-containing papers.
  • the base paper used was made from 50% bleached wood pulp and 50% bleached sulfite pulp with the addition of 11% china clay (calculated as ash) at pH 5 and had a weight per unit area of 70 g / m 2 .
  • the base paper used was made from 50% bleached spruce sulfite and 50% bleached beech sulfate pulp with the addition of 14% precipitated calcium carbonate (calculated as ash) at pH 6.8 and had a weight per unit area of 70 g / m 2 .
  • sizing agent I is compared with a cationic "sizing agent M", which represents the prior art and whose composition corresponds to the products described in DT-OS 1 621 688, namely the sizing agent 2 there , a mixture of A) 30 parts of a 0.25% strength aqueous solution of the acidic salt of a reaction product of 1 mol of an alternating styrene / maleic anhydride copolymer with 0.5 mol of 1-dimethylaminopropylamine and 0.5 mol of cyclohexylamine and B) 70 Share a 0.25% emulsion of a copolymer of 60% by weight butyl acrylate and 40% by weight styrene.
  • the degree of sizing against ink was determined using the Hercules Sizing Tester, in accordance with the operating instructions of the manufacturer Hercules Inc., Wilmington, Delaware, USA. The time is measured in seconds until the remission drops to 75% of the remission value of paper when the test ink is applied to the paper and penetrates through the paper. The longer the measured time, the better the degree of sizing.
  • This example shows the usability of the sizing agents described in the pulp.
  • paper sheets were formed on a laboratory sheet former, which were dried at 100 ° C. and had a weight per unit area of approx. 100 g / m 2 .
  • the sizing effect was determined by the "ink float sample” common in the paper industry, i.e. by placing the papers on test ink (Pelikan 4001).

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Paper (AREA)

Claims (5)

1. Utilisation de sels d'acides organiques ou inorganiques avec des polyimidamines formées à partir de copolymères d'anhydride d'acide maléique avec des monomères hydrocarbonés et un mélange comprenant:
A) une diamine comportant un groupe amino tertiaire et un groupe amino primaire, et
B) de l'ammoniac ou une monoamine primaire,

comme agents d'encollage superficiel pour le papier, caractérisée en ce que ces sels dérivent de copolymères d'anhydride d'acide maléique et de 2,4,4-triméthylpentène-1 ayant des poids moléculaires moyens de 8.000 à 500.000, tandis qu'ils sont obtenus à partir de ces copolymères par réaction en milieu organique anhydre à des températures de 0 à 200°C avec le mélange d'amines, le rapport molaire entre la diamine (A) et l'ammoniac ou la monoamine (B) étant de 1:0,3 à 1:2, tandis qu'au moins 80% des groupes anhydrides sont transformés en groupes imides correspondants.
2. Utilisation d'agents d'encollage du papier suivant la revendication 1, caractérisée en ce que ces agents dérivent de copolymères d'anhydride d'acide maléique et de 2,4,4-triméthylpentène-1 à structure équimolaire et alternée avec des poids moléculaires moyens de 10.000 à 60.000, les viscosités limites de ces copolymères étant de 0,08 à 0,3 dl/g (mesuré dans du diméthylformamide à 25°C).
3. Utilization d'agents d'encollage du papier suivant la revendication 1, caractérisée en ce que les polyimidamines sont obtenues par réaction avec un mélange d'amines comprenant:
A) une diamine de formule:
Figure imgb0010
dans laquelle
R représente une chaîne alkylène linéaire de 2 à 6 groupes méthylène, et R, et R2 représentent des groupes alkyle linéaires contenant 1 à 4 atomes de carbone, et
B) une monoamine primaire choisie parmi le groupe comprenant la méthylamine, l'éthylamine, la n-propylamine, la n-butylamine, la n-hexylamine, la cyclohexylamine, la 2-éthylhexylamine et la déhydroabiétylamine.
4. Utilisation d'agents d'encollage du papier suivant la revendication 3, caractérisée en ce qu'on utilise un mélange d'amines comprenant le 1-amino-3-diméthylaminopropane et l'éthylamine dans un rapport molaire de 1:1 à 1:1,6.
5. Utilisation d'agents d'encollage du papier suivant la revendication 1, caractérisée en ce qu'on emploie des sels des polyimidamines avec l'acide formique, l'acide acétique, l'acide propionique, l'acide lactique, l'acide chlorhydrique, l'acide nitrique ou l'acide sulfurique.
EP78100381A 1977-07-21 1978-07-12 Utilisation de sels de polyimideamines comme agents d'encollage superficiel cationiques pour le papier Expired EP0000706B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19772732851 DE2732851A1 (de) 1977-07-21 1977-07-21 Verwendung von polyimidaminsalzen als kationisches oberflaechenleimungsmittel fuer papier
DE2732851 1977-07-21

Publications (2)

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EP0000706A1 EP0000706A1 (fr) 1979-02-21
EP0000706B1 true EP0000706B1 (fr) 1981-04-01

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EP78100381A Expired EP0000706B1 (fr) 1977-07-21 1978-07-12 Utilisation de sels de polyimideamines comme agents d'encollage superficiel cationiques pour le papier

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EP (1) EP0000706B1 (fr)
JP (1) JPS5423709A (fr)
AT (1) ATA522478A (fr)
CA (1) CA1119758A (fr)
DE (2) DE2732851A1 (fr)
IT (1) IT7850367A0 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP4459704A4 (fr) * 2021-12-27 2026-01-14 Kao Corp Agent de dispersion pour électrode de dispositif de stockage électrique

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6045642B2 (ja) * 1980-09-19 1985-10-11 電気化学工業株式会社 熱可塑性樹脂の製法
JPS60184875A (ja) * 1984-03-05 1985-09-20 Fuji Photo Film Co Ltd 感熱記録紙
GB8817085D0 (en) * 1988-07-18 1988-08-24 Int Paint Plc Coating compositions
EP0353899B1 (fr) * 1988-07-18 1993-12-29 Courtaulds Coatings (Holdings) Limited Compositions de revêtement
CA2212407A1 (fr) 1996-08-20 1998-02-20 Theodore Tysak Compositions de revetement aqueuses contenant des latex acide-amine
AU736677B2 (en) * 1996-08-20 2001-08-02 Rohm And Haas Company Process for preparing polymer compositions containing both acid and amine functionality

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1621693B2 (de) * 1968-02-23 1975-06-19 Bayer Ag, 5090 Leverkusen Anionische Papierleimungsmirtel
DE2544948C3 (de) * 1975-10-08 1978-11-16 Akzo Gmbh, 5600 Wuppertal Verfahren zur Herstellung von kationischen Leimungsmitteln für Papier

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP4459704A4 (fr) * 2021-12-27 2026-01-14 Kao Corp Agent de dispersion pour électrode de dispositif de stockage électrique

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DE2732851A1 (de) 1979-02-08
EP0000706A1 (fr) 1979-02-21
IT7850367A0 (it) 1978-07-19
ATA522478A (de) 1981-04-15
CA1119758A (fr) 1982-03-16
DE2860576D1 (en) 1981-04-23
JPS5423709A (en) 1979-02-22

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