FI84196B - FOERFARANDE FOER FRAMSTAELLNING AV PAPPER ELLER PAPPERSLIKNANDE MATERIAL. - Google Patents

Abstract

1. Use of basic amides from amine mixtures which are obtained as tetramine bottom product in the industrial synthesis of dialkylenetriamines, in particular, dipropylenetriamine and more particularly diethylenetriamine from dihalogenoalkanes and ammonia after the triamine fraction has been distilled off or which are obtained in the industrial synthesis of diethylenetriamine and ethylenediamine from 1,2-dichloroethane and ammonia and long-chain fatty acids or fatty acid mixtures which have a melting point below 30 degrees C, for enhancing the porosity of paper or paperlike materials.

Description

Method for making paper or paper-like materials 1 84196

The invention relates to a method for producing paper and paper-like materials.

For technical reasons, papers are often desired which have a higher opacity, porosity or even higher volume than papers made from the same starting material by conventional procedures.

10 In the past, attempts have been made to meet these requirements by changing the degree of grinding, which has been an advantage, at least in terms of opacity, but has required additional grinding problems and raw material stocks. Attempts have also sometimes been made to add fillers or special fillers from the plastic backing material, but in general this has improved the opacity or only the volume, but not all three paper properties, i.e. opacity, porosity and volume.

It has now surprisingly been found that a new process for the production of paper or paper-like materials is characterized by the addition to the stock of basic amides of long-chain fatty acids or fatty acid mixtures fusible below 30 ° C (under normal conditions) using more polyethylene polyamides. than 3 amino groups in the molecule, results in papers or paper-like materials that have higher porosity, higher opacity, and higher ti-30 volume compared to paper-like materials made without amides.

It is known to add salts and quaternization products of basic amides of long-chain fatty acids with a melting point above 30 ° C as an adhesive to the stock, but compared to the excipients used in the process according to the invention, the potential effect observed with such adhesives is insignificant and costlier. In contrast, the porosity excipients used according to the invention have a barely perceptible, insignificant sizing ability. In addition, prior art sizing preparations only reach their sizing ability after the quaternization reaction. As adhesives based on potentially quaternized, long-chain fatty acid amides already exist, it could not be concluded that basic amides of long-chain fatty acids or fatty acid mixtures melting below 30 ° C could be used as paper blowing agents.

The basic amides used in the process of the invention are added to the pulp in connection with papermaking, preferably in the form of aqueous preparations.

Preferably, amides are used which can be prepared by reacting fatty acids with polyalkylene polyamines such that 50 to 100% of the primary amino groups react to form an amide. Particularly useful are, for example, triethylenetetramine, tetraethylenepentamine and pentaethylenehexamine, which can be used in the form of technically pure fractions.

It is preferred to use amine mixtures formed in the polyamine synthesis of dihaloalkanes and ammonia.

The composition of the amine mixtures is preferably as follows: A. from about 3% to about 27% by weight of diamines B. from about 10% to about 22% by weight of triamines C. from about 15% to about 25% by weight of tetramines D. from about 10% to about 20% by weight -% pentamines 30 E. about 5 to about 10% by weight of hexamines F. about 15 to about 25% by weight of water and G. about 3 to about 30% by weight of other ingredients, the sum of components A to G being 100% by weight. %.

Depending on the starting alkane, the diamine component A may contain monoalkylenediamines, such as 1,3-propylenediamine, butylenediamines or diaminohexanes, such as 1,6-diaminohexane and especially ethylenediamine.

3 84196

Preferably, amine mixtures are used which are formed by the so-called as reactor base mixtures in the technical synthesis of di-propylene triamine and propylenediamine starting from dichloropropane and ammonia.

Particularly preferably, amine mixtures are used which are formed by the so-called as reactor base mixtures in the technical synthesis of diethylenetriamine and ethylenediamine starting from 1,2-dichloroethane and ammonia.

The advantage of these mixtures is that their use does not require laborious distillation and other further purification steps, although, for example, coarse purification with activated carbon, diatomaceous earth, ion exchangers, drying, etc. is entirely possible. Due to the characteristic color, it may be possible, for example, to distill the reactor base continuously to remove any high-molecular, usually dark-colored resin components. But in principle, such an operation is not necessary.

The technical base mixture 20 formed in the synthesis of polyethylene polyamine using dichloroethane as a starting material contains e.g. In addition to these, for example, tetraethylenepentamine, pentaethylenehexamine, hexaethyleneheptamine and their branched and cyclic isomers as well as oligomeric and polymeric amine resins of unknown structure are found.

In addition to ethylenediamine, the "technical" triamine part of the reactor bottom consists largely of diethylenetriamine, while the tetramine part contains small amounts of unspecified impurities and the main component is essentially 4 tetramine isomers, i.e. 1 linear and 1 branched (main) isomers, and in addition it contains (in addition to unspecified impurities and isomers less than 3%) pentamines of about 5 isomeric forms and about 14% 4 84196 hexamines of about 9 isomeric types that are linear, branched, or cyclic. Naturally, other higher amine types and other impurities are also present. Diamines, triamine, tetramines, pen-5 amines and hexamines account for about 95-99% of the anhydrous reactor bottom.

The proportion of linear, unbranched anhydrous compounds must be at least 40% by weight and preferably more than 60% by weight. According to the process, in addition to the above, mixtures of technical alkylene polyamines with a different boiling range and amine content can also be used.

The reactor base from the preparation of ethylene polyamines, as technically formed and very well suited for the preparation of blowing agents according to the invention, has the following composition determined by fractional distillation and gas chromatography (concentration limits indicate conventional production variations): 20-15% by weight of water (17-25% by weight) ) 3-20 "ethylenediamine (7) 0.1-0.5" piperazine (0.2) 0.0-0.8 "tricyclic diamine (0.1) 0.0-0.3" ethanolamine (0, 1) 25 10-20 "triamine (14) 0.5-2" aminoethylpiperazine (1) 15-25 "tetramine (19) 10-20" pentamine (16) 5-10 "hexamine (7) 30 3-9" heptamine (5,6) 5-15 "higher boiling resinous ingredients (9) 1-6" salts, ash (4) 101,4 35

The figures in parentheses illustrate a typical reactor bottom, which is also used in the example section below.

5 84196

Numerical values are rounded and the reported value may vary by approximately ± 10%.

Also preferred are amine mixtures formed by the so-called as a tetramine distillation residue, synthesizes on a technical scale dialkylene triamines, in particular dipropylene triamine and in particular diethylene triamine from dihaloalkanes and ammonia, after removal of the triamine fraction by distillation.

In this way, amine mixtures are formed which contain, for example: A) less than 10% by weight, preferably less than 1% by weight of triamines, B) from about 50% to about 60% by weight, preferably from about 52% to about 55% by weight tetramines, 15 C) about 25 to about 35% by weight, preferably about 29 to about 32% by weight of pentamines, D) about 10 to about 20% by weight, preferably about 12 to about 15% by weight of hexamines, and E) about 1 to about 15% by weight, preferably about 2 to about 20% by weight of other ingredients, the sum of components A + B + C + D + E being 100% by weight.

Particularly preferably, the process according to the invention uses basic amides consisting of oleic acid or fatty acid mixtures containing oleic acid and an amine mixture formed as a tetramine distillation residue.

As aqueous preparations of basic amides, it is preferred to use basic amides whose amine groups have been partially or completely converted into a salt form and which have been dispersed or dissolved in an aqueous medium. Acetates and / or formates of basic amines are preferably used.

The invention further relates to papers and paper-like materials produced by the method according to the invention, e.g. especially cardboard.

6 84196

The opacifiers used in the process of the invention are prepared and transported mainly in the form of an aqueous formulation of 10-35%. However, when used in stock, the concentration can be diluted to less than 1%. From Toi-5, it is also possible to add only basic amides to the stock, whereby an aqueous dispersion of the excipient can be formed in situ and act in the stock itself.

The advantage of the blowing agents used according to the invention is e.g. the fact that the porosity of the paper no longer needs to be changed by other means and that the amount of blowing agents compatible with the adhesives is very small, i.e. 0.05 to about 5, preferably 0.2 to 0.8% by weight, based on the solids and the pulp .

As long-chain fatty acids and fatty acid mixtures 15, in principle all fatty acids having more than 9 and preferably more than 15 carbon atoms and melting below 30 ° C (under normal conditions) can be used. These are mainly natural fatty acids, such as oleic acid, elaidic acid, linseed fatty acids or soybean fatty acids and other vegetable fatty acids, e.g. tall oil fatty acid, but also fatty acids with mineral deposits or petroleum oil, also synthetic, preferably monofunctional, long-chain fatty acids obtained by the oxosynthesis or Fischer-Tropsch method or by the oxidation method or the dimerization or oligomerization method. Preferably, oleic acid or (technical) fatty acid mixtures containing mainly oleic acid are used.

The reaction between the fatty acids and the polyalkylene polyamines takes place by methods known in the art, preferably by heating the components with water splitting, possibly excluding air or in a shielding gas atmosphere (N2). Although other proportions lead to products with some potency in the preparation, the best results are obtained by combining amides in the preparation of amides with amounts of fatty acids and polyalkylene polyamines that 40-100% of the primary amino groups of the amine or amine mixture can be converted to the amide by carboxyl groups. The use of superciometric amounts of fatty acids can also be considered.

Due to the poor availability of amides, polybutylene or polypropylene polyamines are not so much used as polyalkylene polyamines, but preferably polyethylene polyamines. Such amines can in principle be prepared by reacting α, β-dihaloethane with ammonia. All polyamines formed in this synthesis, provided that about 50% or more of the primary amino groups can be converted to the amide, can in principle be considered as starting amines for use in the process according to the invention. However, since ethylenediamine and di-15 ethylenediamine are highly desirable technical intermediates, it is preferred according to the invention to use polyethylene polyamines containing more than 3 amino groups, as these are inexpensive by-products of di- and triamine synthesis. Such amines include triethylene-20 tetramine fractions and tetraethylene pentamine and pentaethylene hexamine fractions.

Particularly interesting and surprisingly very effective in the blowing agents used according to the invention are the mixtures formed as a residue, the so-called distillation of the tetramyl-25 ni residue remaining after removal of the di- and triamines from the reaction mixture by distillation.

Not only is it surprising that such a non-specific mixture consisting of a wide variety of linear, branched and cyclic amines of the most basic basicity and molecular weight can be used with excellent results to provide porosity instead of the well-defined amine fraction. .

Particularly surprising was the finding that, for example, compared to a pure tetramine fraction, such broad-split polyamine blends provide blowing agents with an improved level of action, which in itself and β 84196 combined with the need to fractionate polyalkylene polyamines represents a significant technical advance.

It has surprisingly been found that the process described here can be decisively improved by using not only the technical fraction from e.g. triethylenetetramine, which still contains isomers of this amine and impurities having the same boiling range, as polyamines, but that the reaction with fatty acids uses 10 as the starting amine as a whole reaction products formed during the synthesis of polyethylene polyamines from α, β-dihaloalkane and ammonia, which are removed by distillation only of alkylenediamine (ethylenediamine) and optionally dialkylenetriamine (diethylenetriamine-15). This technical amine mixture, which contains many different amine components, mainly containing 4 or more nitrogen atoms in its molecule, is obtained by the so-called as a "tetramine distillation residue" in the synthesis of dipropylene triamine or especially diethylenetriamine. This 20 amine mixture is particularly readily available. It is called a "tetramine distillation residue" and has the advantage that its use does not require laborious distillation or other additional purification steps, although, for example, coarse purification with activated carbon, diatomaceous earth, ion exchanger or other cleaning aids is entirely possible. Due to the characteristic color, it may be possible, for example, to fractionally distill the tetramine distillation residue to remove any high-molecular, usually dark-colored resin components. But in principle, such an operation is not necessary.

In the preparation of basic fatty acid amides, technical amine mixtures are preferably technical polyethylene polyamines, i.e. a tetramine distillation residue obtained from the synthesis of technical diethylenetriamine.

Corresponding technical polypropylene polyamine fractions are also suitable in principle. Of particular interest is the technical triethylenetetramine distillation residue, i.e. the 9,819,166 triethylenetetramine remaining after distillation of the diethylenetriamine fraction and the distillation residue material containing all other amines.

Suitable components for the technical tetramine distillation residue are, for example, aminoethylpiperazine, trisaminoethylamine, Ν, Ν'-bisaminoethylpiperazine, aminoethylated N-aminoethylpiperazines in the form of various isomers and a number of other unidentified impurities. In addition to these, the residue contains, for example, tetraethylenepentamine, pentaethylenehexamine, hexaethylene-heptamine and their branched and cyclic isomers, as well as oligomeric and polymeric amine resins of unknown structure.

As a tetramine fraction, the "technical" triethyleneamine contains, in addition to small, unspecified amounts of impurity-15, essentially 4 tetramine isomers, i.e. one linear, one branched and two isomer containing piperazine rings, while the so-called in addition to these impurities and isomers in excess of 1 to 3%, the tetramine distillation residue still contains (about 30%) 20 pentamines of about 9 isomeric types which are linear, branched or cyclic, and of course higher amine types and other impurities . Tetramines, pentamines and hexamines account for about 91-97% of the tetramine distillation residue.

The proportion of linear compounds must be at least 20% by weight and preferably more than 40% by weight. According to the process, mixtures of technical polyalkylene amines with a lower boiling range and a lower amine content can also be used.

Based on the amount of amine fraction or tetramine distillation residue used, fatty acids are used to prepare the amide precursor of the blowing agents used in accordance with the invention in such amounts that 50-100% of the available primary amino groups can be converted to 35 amides. This means that the basic amide formed preferably still contains on average at least 2 basic amino groups per molecule.

ίο 84196 These requirements may be met by reacting, for example, 150 parts by weight of a technical residue of tetramine distillation and about 1,5 moles of oleic or fatty acid or ricinoleic acid and acetylating the basic amides according to the 5 OH number method to give an OH number of 150 to 210, in which case the acid number must be less than 10.

The basic amides can be prepared by various methods known to those skilled in the art, e.g. simply by heating the calculated amounts of tall oil-10 fatty acid and amine, optionally in a type-protected temperature of 180-220 ° C, and removing the water formed by amide formation by distillation. The acidification product must have an acid number of less than 15, preferably less than 8.

The molten base amides then formed, after cooling to a suitable temperature range, e.g. near the melting point of the amides in the range of about 30-70 ° C, can be dispersed in water and then allowed to react with good stirring, optionally with a dispersing aid. with. This takes 0.5 to 10 hours to 20 hours and then, preferably, the still warm dispersion is prepared into a solution, suspension or emulsion of 5 to 40% by weight, preferably 10 to 25% by weight, optionally with further addition of water and cooling. and continuing stirring at 10 to 80 ° C for 0.1 to 10 hours. This is usually done by stirring alone, but mechanical emulsifiers may also be used.

It is also possible to react the amide melt with small amounts of inorganic or organic acid as dispersing aid (preferably less than 20% and in particular 0-10% of the amount required for neutralization) before dispersing in water to facilitate the dispersing step.

When the amount of water present in the dispersing step is less than the amount of water contained in the final aqueous preparation, it has proved expedient to optimally combine the control of the desired blowing agent concentration with the possible additional viscosity-reducing electrolyte (e.g. NaCl) used in the invention.

The dispersing aid for the aqueous preparations used in the process of the basic fatty amide according to the invention is not only to be used in an amount of 0 to about 15% by weight of conventional dispersing aids, such as anionic, cationic or nonionic salt colloids and / or emulsifiers, but also quaternizing agents such as esters and amides of haloacetic acid, e.g. chloroacetamide, propanesulfonate, dimethyl sulphate, benzyl chloride, alkyl chloride, methyl chloride and other α-haloalkanes, ethylene oxide, preferably ethylene oxide, , preferably 0.1 to 1 equivalents based on the amino groups of the basic amide. However, preferred dispersing aids which do not adversely affect the porosity or bulking effect of the additives used according to the invention are, in particular, inorganic and, above all, organic acids, such as hydrohalic acids, phosphoric, sulfuric or nitric acid or fumaric, maleic, citric, malic or succinic acid or toluenesulfonic acid, in particular because of its relatively low corrosivity, and formic acid and / or acetic acid, which are volatile.

These acids, the amount of which is preferably such that the reaction of the aqueous formulation is neutral (pH about 7), form the an emulsifying or dispersing salt with a basic amide which stabilizes an aqueous formulation of basic fatty amines active as blowing agents for use in accordance with the invention. It is also conceivable to use smaller or larger acid additions, e.g. when the reaction of the stock has to be kept in a slightly basic or acidic range.

35 When the solids content is more than 10% by weight, the consistency of the described aqueous preparations used in the invention can sometimes be porridge-like, which may cause processing difficulties. In this case, 0.05 to 5, preferably 0.1 to 1% by weight of electrolytes (based on solids) can be added to the preparations, which improves the flowability. The addition is preferably carried out in the last dilution step of the blowing agent preparation, so that the desired amount of electrolyte, e.g. sodium chloride, is dissolved in the water reserved for the final dilution and thus added.

Although it is also possible to add the electrolyte in advance or already during the first or second addition of water, the most effective way has proved to be to mix the electrolyte as late as possible in the dilution process. In this way, preparations are obtained which, with a solids content of more than 10% by weight, are easily flowable and which do not subsequently thicken.

Suitable electrolytes are, in addition to organic salts, such as ammonium or alkali formates, acetates, benzoates, phosphonates or sulfonates, preferably inorganic salts, such as ammonium chloride, potassium chloride, calcium chloride, zinc chloride, in particular aluminum chloride, magnesium chloride or magnesium chloride. chloride, although in principle soluble chlorides, nitrates, sulphates, phosphates and carbonates of other elements and also the acids or bases themselves may also be used.

The resulting ready-to-use aqueous preparations containing blowing agents have a solids content of 5 to 40% by weight, preferably 10 to 35% by weight. For use, these preparations are further diluted to the required concentration, e.g., to a concentration of less than 5% by weight, which is conventional in paper expression.

The excipients used in the process according to the invention have the advantage that they are very effective and almost indefinitely stable in the form of their water-soluble preparations and do not require the addition of alum (adhesives) or cationic or anionic excipients, although it is conceivable and also possible to add i3. 841 96 Fillers or such excipients based on, for example, cationic starch, quaternized polyamines, quaternized polyamidamines, quaternized basic formaldehyde resins, methylcellulose, carboxymethylcellulose, polycanthylcellulose, lignin sulfonic acid, lignin sulfonic acid, various , polymers or copolymers of (meth) acrylic acid, maleic acid, fumaric acid and itaconic acid or other polymers and copolymers optionally containing carboxylic or sulphonic acid groups in the form of a salt, collagen, gelatin, alginates and carrageenans or m night substantive or reactive dyes.

White tones do not impair the effectiveness of the excipients used according to the invention. Aqueous preparations 15 can be prepared without the use of emulsifiers.

Blowing agents, alone or in admixture with adhesives, are well suited for opalescence, porosity and bulking of paper, but can of course also be used for other paper modifications. They can be used not only in connection with wood, chalk or kaolin-containing papers, low-quality waste paper or recycled paper which do not contain fillers or contain other types of fillers, such as talc or gypsum, but are also suitable for cellulose-based and other materials such as cardboard. for the modification of textile materials, leather, cardboard or particle board or insulation boards or gypsum or gypsum board.

The essential advantage of the new blowing agents is that it is not necessary to change the porosity of the paper in any other way and that blowing agents compatible with the adhesives can be used in very small amounts, i.e. 0.05 to about 5, preferably 0.2 to 0.8 % by weight based on solids and paper pulp.

The invention is further illustrated by the following Examples 35; parts and percentages are by weight unless otherwise indicated.

i4 841 96

Examples 1 and 2 (comparative examples)

An adhesive (excipient A) according to DE application 2 838 270 was prepared.

Preparation of dibasic amide A 170 parts of stearic acid were melted and 43.8 parts of technically pure triethylenetetramine (molar ratio about 2: 1) were added with stirring. The temperature was then raised to 190 ° C under nitrogen and the volatiles were removed by distillation. After 6 hours, an acid number of 1.9 had been reached. The melting range of the amide was 87-107 ° C.

Excipient A

201.6 parts of basic amide and 3.7 parts of epichlorohydrin were stirred for 30 minutes at 120 ° C. Then 70 parts of water were added followed by 32.3 parts of epichloro-15 rhydrin and stirred for one hour at 100-120 ° C. Finally, 1,182 parts of water preheated to about 95 ° C were added, and the resulting emulsion was stirred at reflux for about an hour. After cooling to about 40 ° C, 1.2 parts of NaCl in 92 parts of water were added to the porridge-like emulsion to form an easy-to-flow adhesive preparation of about 15%.

The following comparative example (which is excipient B) was then carried out using oleic acid instead of stearic acid.

The experimental results shown in the table show that the excipient A achieves a relatively low porosity effect and a good sizing effect, while the excipient B does not achieve any sizing effect, but the caking effect is moderate.

Example 3 This example clearly shows the good effect of the blowing agents used according to the invention compared to the excipients A and B.

The procedure was as for the preparation of amide A, but 35 stearic acid was replaced by oleic acid. The basic amide, melting at about 64 ° C, was worked up as auxiliary A, but instead of the total amount of epi-chlorohydrin, i.e. 36 parts, 16 parts of formic acid were used. A neutral blowing dispersion with a solids content of about 13% was obtained.

is S4'96

Example 4 The procedure was as in Example 3, except that pure oleic acid was used instead of pure oleic acid, - technical tetramine distillation residue with an approximate composition of less than 1% by weight of triamines, 52% by weight of tetramines, 30% by weight of pentamines was used instead of triethylenetetramine, 13% by weight of hexamines and 4% by weight of other ingredients, and - instead of 16 parts of formic acid, 24 parts of acetic acid were used.

A dispersion of about 13% of the blowing agent was obtained. 15 The experimental results in the table show the good effect of the tetramine distillation residue used in the preparation of the amide.

Example 5

In analogy to the preparation of amide A or B, an amide was prepared from 5,100 parts of tall oil fatty acid and 1,314 parts of a tetramine distillation residue having an approximate composition similar to that of Example 4. The amide formed had a melting point of about 41 ° C and an acid number of 6.3. 202 parts of amide and 29 parts of acetic acid 25 were melted together so that the temperature did not rise above 80 ° C. The melting point of the salt formed was about 63 ° C. This salt may be added to the stock in comminuted form and optionally stabilized with kaolin, silicic acid or talc powder, or pre-dissolved as such to an aqueous excipient formulation to a solids content of 15%, dispersing 150 parts of the optionally comminuted salt with 85 parts of 80 ° C water with good stirring. .

The 15% dispersion thus obtained can be used as such as a blowing agent.

16,841 96

Example 6

The procedure was as in Example 5, but instead of pine fatty acid, fish oil fatty acid containing about 60-70% C22 fatty acid was used.

5 The following table compares Examples 1 to 6 using the following tests:

bonding

The so-called gluing evaluation criterion was the so-called ink penetration test, which is performed by placing a strip of paper containing the test substance in DIN

53 126 on the surface of the container filled with the standard ink and the time taken for the ink to penetrate the upper surface of the paper placed on the surface is calculated. Under standardized conditions, 15 different adhesives can be evaluated very well with this test.

opacity

The opacity was evaluated according to the method DIN 53 146, where the opacity is expressed as a percentage so that a high percentage value means better opacity. 20 The thickness of the paper in the comparison and examples was 0.11 mm.

Porosity

Porosity was evaluated according to DIN 53 120 and permeability was expressed in ml air / min.

25 The thickness of the paper in the comparison and examples was 0.11 mm.

Volume change

The density was determined with said paper thickness of 0.11 mm per basis weight and was expressed as kg / dm 3, i.e. when using a given amount of solids, the weight per unit volume is a measure of any change in volume.

Testing of the porous materials used according to the invention, e.g. with alum-free chalk-containing paper: i 8 841 96 5 g of a mixture of 50 g of spruce sulphite pulp and 25 g of chalk were slurried in 200 ml of tap water. Then x% blowing agent (solids calculated from the sum of pulp and filler) was added. It was then filled with water to about 1 liter without the addition of a fixing agent, and a sheet of paper in a sheet mold was prepared. The sheet was sucked and squeezed out of water and dried in a tumble dryer for 5 minutes at 90-100 ° C. For testing, sample pieces, e.g., strips for the ink penetration test (2 cm x 6 cm), were cut from the sheet, and the tests.

The test results are shown in the following table. For comparison, the products of Examples 1 and 2 and, as Example No. 0, unglued and non-porous paper were used.

15 Opacity and porosity were also evaluated on papers made on a laboratory paper machine.

Table comprising the evaluation of different blowing agent preparations 20 _

Example No. A B C D E F G

Product from example No. 1 2 3 4 5 6 0 25 Bonding s 900 12 8 10 9 11 2

Opacity approx.% 72 77 80 82 81 82 71

Porosity ca. ml / min 380,410,620,790,800,768,300

Volume +15 +15 +35 +49 +51 +50 ± 0 30 Application rate% 0.6 0.6 0.6 0.6 0.6 0.6

The table shows the superiority of non-crystalline fatty acids at 30 ° C, as well as the negative effect of quaternization and the particularly positive effect of the amine mixture contained in the tetramine distillation residue.

84196 BC

Example 7 (according to the invention)

In analogy to the preparation of dibasic amide A, the amide was prepared from 5,500 parts of technical oleic acid and 1,500 parts of reactor bottom having an approximate composition (wt%) of: 17% water, 7% ethylenediamine, 0.2% piperazine, 1% tricyclic diamine, 0.1% ethanolamine, 14% triamine, 1% aminoethylpiperazine, 19% tetramine, 16% pentamine, 7% hexamine, 5.6% heptamine, 9% higher boiling 10 resinous ingredients and 4 % salt and ash.

Numeric values are rounded and the reported value may vary by ± 10%.

The amide formed had a melting point of about 45 ° C and an OH number of 128 and an acid number of 5.0.

200 parts of amide and 35 parts of acetic acid were melted together, so that the temperature did not rise above 80 ° C. The melting point of the salt formed was about 63 ° C. This salt can be added to the stock in a comminuted form and optionally stabilized with kaolin, starch, silicic acid or talc powder, or pre-dissolved as such to an aqueous excipient formulation at a solids content of about 15%, dispersing the salt with good stirring (at 80 ° C) 1000 part of 80 ° C water and cooled to 50 ° C. A solution of 1.15 parts of common salt in 100 parts of water is then added and stirred with cooling to 20-25 ° C.

The experimental results shown in the table clearly show the improvement in porosity achievable according to the invention.

Example 8 (according to the invention)

The procedure was as in Example 7, but tall oil was used instead of oleic acid.

The following table compares Examples 1, 7 and 8: 9 841 96

bonding

The so-called gluing evaluation criteria were the so-called an ink penetration test carried out by placing a strip of paper containing the test substance on the surface of a container filled with standard ink in accordance with DIN 5 53 126 and calculating the time taken for the ink to penetrate the upper surface of the paper placed on the surface. Under standardized conditions, this test can very well evaluate different adhesives.

10 Opacity

The opacity was evaluated according to the method DIN 53 146, where the opacity is expressed as a percentage so that a high percentage value means better opacity.

The thickness of the paper in the comparison and examples was 0.11 mm.

Porosity

Porosity was evaluated according to DIN 53 120 and permeability was expressed in ml air / min.

The thickness of the paper in the comparison and examples was 20.11 mm.

Volume change

The density was determined by said paper thickness of 0.11 mm per basis weight and expressed as kg / dm 3, i.e. when a given amount of solids is used, the weight per unit volume is a measure of any change in volume.

Testing of blowing agents according to the invention, e.g. on alum-free, chalk-containing paper: 5 g of a mixture of 50% birch sulphate pulp and 50% pine sulphate pulp (degree of grinding 35 ° SR) were slurried in 200 ml of tap water. X% blowing agent (solid calculated from the sum of pulp and filler) was then added. It was then filled with water to about 1 liter without the addition of an adhesive and made into a sheet of paper in a 35-sheet sheet mold (Rapid-Köthen). The sheet was sucked and squeezed out of water and dried in a vacuum drier for 5 minutes at 90 ° C. For testing, 20,841,96 specimens of the sheet, e.g., strips (2 cm x 6 cm) for the ink penetration test, were cut and subjected to the test. tests. The basis weight was about 100 g / m2.

The test results are shown in the following table. The product of Example 1 (excipient A) and paper No. 0, which was not glued and was not treated with blowing agents, were used as a control.

Opacity and porosity were also evaluated on papers made on a laboratory paper machine.

10

A table comprising a review of various blowing agent preparations; the values shown are the means of 5 experiments

15 Example No. A B C D

Product from example 1 7 8 0

Bonding s 900 56 2

Opacity approx.% 83 88 88 83 20 Porosity approx. Ml / min 145 225 218 140

Volume (relative) +2.9 +8.0 +7.1 ± 0 Operating volume% 0.7 0.7 0.7 0.7 25 The table shows the superiority of non-crystalline fatty acids at 30 ° C, as well as the superiority of the reactor bottom. excellent healing effect of the amine mixture.

Example 9

In a paper machine, a blend of recycled paper stock containing 0.075% polyamideamine-based retention aid was made into a paper having a basis weight of about 100 g / m 2.

If 0.3% of the blowing agent of Example 7 (based on solids 35) was added to the pulp before entering the machine, the volume of paper leaving the machine dry increased by 7.5%.

Claims (9)

2i 84196 A process for the preparation of paper or paper-like materials, characterized in that basic amides of long-chain fatty acids or fatty acid mixtures melting below 30 ° C are prepared in 5 stocks using polyethylene polyamines having more than 3 amino groups in the molecule. Process according to Claim 1, characterized in that the basic amides are used in the form of an aqueous preparation. Process according to Claim 1 or 2, characterized in that amides are used which can be prepared by reacting long-chain fatty acids or mixtures of fatty acids melting below 30 ° C with polyethylene polyamines in such a way that 50 to 100% of the primary amino groups react. Process according to one of Claims 1 to 3, characterized in that triethylenetetramine, tetraethylenepentamine or pentaethylenehexamine, preferably in the form of technically pure fractions, are used in the amide formation. Process according to one of Claims 1 to 4, characterized in that amine formation uses mixtures of amines which are formed as a tetramine distillation residue in the technical synthesis of dialkylenetriamines, in particular dipropylene triamine and in particular diethylenetriamine, distillation. Process according to Claim 1, characterized in that amine mixtures are used in the amide formation, which are formed in the technical production of diethylenetriamine and ethylenediamine from 1,2-dichloroethane and ammonia. 22 841 96 Process according to one of Claims 1 to 6, characterized in that oleic acid and fatty acid mixtures containing oleic acid are used. Process according to one of Claims 1 to 7, characterized in that basic amides dispersed or dissolved in an aqueous medium are preferably used in the form of acetates and / or formates. Papers and paper-like materials, in particular cardboard, made according to one of Claims 1 to 8. 23 841 96