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.
• polyimidamines of the type mentioned which are derived from copolymers of maleic anhydride and 2,4,4-trimethylpentene-1 by reaction with a mixture of a diamine having 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 invention thus relates to the use of salts of organic or inorganic acids with polyimidamines, which differ from copolymers of maleic anhydride and 2,4,4-trimethylpentene-1 by reaction with a mixture of a diamine with tertiary and primary amino group and ammonia or derived from primary monoamine as a surface sizing agent for paper and paper-like materials.
• 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 copolymers of maleic anhydride and 2,4,4-trimethylpentene-1 are mixed with a mixture in an anhydrous organic medium A) a diamine with primary and tertiary amino group and B) ammonia or a primary monoamine implemented at temperatures from 0 ° to 250 ° C and thereby converting at least 80%, preferably more than 85%, of the anhydride groups of the copolymers into the corresponding imide groups.
• 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 able to solve both maleic anhydride-2,4,4-trimethylpentene-1 copolymers and their reaction products, the polyimidamines.
• 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 step carried out thermally, optionally with the aid of Katalysaroren, such as p-toluenesulfonic acid, pyridine, etc. elimination of water the imidization of at least 80%, preferably more than 85% of the original A nhy- dridement.
• the organic polymer solution can be converted into an aqueous solution, for example, in such a way that the organic solution is distilled off at the same time of the organic solvent continuously in a heated template with dilute aqueous acid.
• 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 1 621 688 in which cationic sizing agents are used in the form of dispersions, 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 an excellent sizing effect on all papers, with particular emphasis being placed on the chalk-containing paper.
• the used according to the invention Sizing agents are clearly superior to all conventional sizing agents.
• 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. testing, the papers were 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 weight per unit area of 70 g / m 2 .
• This example shows the good effectiveness of the sizing agents described on wood 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 (expressed as ash) of 50% of bleached spruce and 50% bleached sulphate pulp book with the addition of 14% precipitated calcium carbonate at pH 6.8 prepared and had a basis weight of 70 g / m 2.
• sizing agent J one of the products described, sizing agent J, is compared with a cationic "sizing agent M", which represents the prior art and corresponds in its composition to the products described in DT-OS 1 621 688.
• 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 about 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)

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Citations (2)

• 1977
  • 1977-07-21 DE DE19772732851 patent/DE2732851A1/de not_active Withdrawn
• 1978
  • 1978-07-12 DE DE7878100381T patent/DE2860576D1/de not_active Expired
  • 1978-07-12 EP EP78100381A patent/EP0000706B1/fr not_active Expired
  • 1978-07-19 IT IT7850367A patent/IT7850367A0/it unknown
  • 1978-07-19 AT AT522478A patent/ATA522478A/de not_active Application Discontinuation
  • 1978-07-19 CA CA000307675A patent/CA1119758A/fr not_active Expired
  • 1978-07-19 JP JP8721478A patent/JPS5423709A/ja active Pending

Patent Citations (2)

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