CA1276415C - Process for preparing paper or paperlike materials - Google Patents
Process for preparing paper or paperlike materialsInfo
- Publication number
- CA1276415C CA1276415C CA000507692A CA507692A CA1276415C CA 1276415 C CA1276415 C CA 1276415C CA 000507692 A CA000507692 A CA 000507692A CA 507692 A CA507692 A CA 507692A CA 1276415 C CA1276415 C CA 1276415C
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- Prior art keywords
- process according
- paper
- fatty acid
- amide
- weight
- Prior art date
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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
- D21H17/03—Non-macromolecular organic compounds
- D21H17/05—Non-macromolecular organic compounds containing elements other than carbon and hydrogen only
- D21H17/07—Nitrogen-containing compounds
Landscapes
- Paper (AREA)
- Superconductors And Manufacturing Methods Therefor (AREA)
- Piezo-Electric Transducers For Audible Bands (AREA)
- Sampling And Sample Adjustment (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Abstract
Process for preparing paper or paperlike materials A b s t r a c t Process for preparing papers or paperlike mate-rials of high porosity, opacity and volume, characterized in that basic amides of long-chain fatty acids or fatty acid mixtures which have a melting point below 30°C are added to the paper-stuff.
Description
~7~41~
The invention relates to a process for preparing papers of paperlike materials.
Papers which, cornpared with the papers prepared by conventional processes, have increased opacity, porosity or even increased volume from the same starting material are frequently desired in industry.
Hitherto attempts have been made to meet these demands by changing the degree of beating, which was successful at least with regard to the opacity, but necessitated additional beatings and stockholdings. Even the addition of fillers or of plastics latexes which act as special fillers has been tried at times, but, if at all, was successful only with respect to the opacity or the volume alone but not with respect to all three paper properties:
opacity, porosity, volume.
According to the present invention there is provided in the making of paper from an aqueous pulp slurry, the improve-ment which comprises incorporating into such slurry an agent consisting essentially of a basic amide of a long-chain fatty acid haying a melting point below 30C, whereby the resulting paper exhibits increased porosity. As mentioned, the improvea process leads to papers or paperlike materi~ls which compared with papers or paperlike materials prepared in the absence of amides, have higher porosity, higher nontransparency (opacity) and higher volume.
It is admittedly known to add the salts and quater-nization products o basic amides of long-chain fatty acids having melting points above 30C as sizing agents to the paper-stuff, but compared with the auxiliaries according to the invention any ~Z~7~i415 -la- 23189-6244 obseryable effect with such sizing agents is insignificant and requires significantly more costly amounts. By contrast, the porosity auxiliaries according to the invention have only a small, negligible sizing agent action. Furthermore, the state of the art sizing agent preparations obtain their activity only 7~
through a quaternization reaction~ As a consequence, it was impossible to infer from the fact that there are sizing agents based on quaternized or non-quaternized long-chain fatty acid amides that basic amides of long-chain fatty acids or fatty acid mixtures which have melting points be-low 30C can be used as porositization agents for paper.
The basic amides used according to the invention are preferably added to the paper-stuff in the course of papermaking in the form of an aqueous preparation.
Preference is given to the use of such amides as are preparable by reacting the fatty acids with polyalky-lenepolyamines by converting 50-100% of the primary amino groups into amide groups. Use is made here in particular of polyethylenepolyamines having more than three amino groups in the molecule, such as triethylenetetramine, tetraethylenepentamine and pentaethylenehexamine, which can be used in the form of technical fractions.
Preference is also given to the use of such amine mixtures as are formed in the polyamine synthesis from dihalogenoalkanes and ammonia.
These amine mixtures preferably have the follow-ing composition:
A. about 3 to about 27% by weight of diamines B. about 10 to about 22% by weight of triamines 25 C. about 15 to about 25% by weight of tetramines D. about 10 to about 20% by weight of pentamines 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 constituents, where the sum of cDmponents A. - G. is 100% by weight.
Depending on the starting alkane, diamine compo-nent A. can contain monoalkylenediamines such as 1,3-propylenediamine, butylenediamines or diaminohexanes such as 1,6-diaminohexane and in particular ethylenediamine~
Preference is given to the use of such amine mix-tures as are obtained in the industrial dipropylenetriamine Le A 23 776 ~i~7~15 and propylenediamine synthesis from dichloropropane and ammonia as so-called reactor base mixtures.
Particular preference is given to the use of such amine mixtures as are obtained in the industrial diethy-lenetriamine and ethylenediamine synthesis from 1,2-di-chloroethane and ammonia as so-called reactor base mixtures.
These mixtures have the advantage that they can be used without expensive further distillation and other purification steps, although for exampLe coarse purifica-tion by means of activated carbon, siLica, exchangers, drying processes or similar purification aids is perfectly feasible. For example, because of the self-colour it may also be necessary to subject the reactor base to a non-fractional distillation so as to separa~e said base fromany higher-molecular, usually deeoly coloured resin con-stituents which may be present. However, this operation is basically not necessary.
The base mixture formed in the industrial poly-ethylenepolyamine synthesis based on dichloroethane con-tains for example the following constituents:
ethylenediamine, diethylenetriamine, triethylene-tetramine, aminoethylenepiperazine, trisaminoethylamine, N,N'-bisaminoethylpiperazine, aminoethyla~ed N-aminoethyl-piperazines in the form of various isomers and a number of unidentified other impurities. Plus, for example, tetra-ethyleneepentamine, pentaethylenehexamine, hexaethylene-heptamine and their branched and cyclic isomers and oligo-meric and polymeric amino resins of unknown structure.
While in addition to ethylenediamine in the reac-tor base the "technical" triamine content consists largely of diethylenetriamine, the tetramine content contains in addition to ill-defined small amounts of trace sub-stances essentially four tetramine isomers, namely one linear (main fraction), one branched and two isomers which contain piperazine rings; also present are (in addition Le A 23 776 ~7~ 5 to undefined trace substances and isomers in amounts below 3%) pentamines in the form of about S isomers and hexamines (about 14%) in the form of about 9 types of isomer which are linear, branched, or cyclic. And also of course higher amines and other trace substances. The diamines, tri-amines, tetramines, pentamines and hexamines account for about 95 to 99% of the water-free reactor base The linear unbranched water-free compounds should be present in an amount of at least 40% by weight and preferably above 60% by weightO It is also possible to include mixtures of technical alkylenepolyamines having different boiling ranges and amine contents in the process.
A reactor base from ethylenepolyamine production has in the state it is obtained in industry and in which it is particularly highly suitable for preparing porosi-tizing agents in accordance with the invention the follow-ing composition, determined by fractional distillation and gas chromatography:
(The compositions describe the customary produc-tion variations) 15 - 25 % by weight of water ( 17 ) 3 - 20 " ethylenediamine ( 7 ) 0.1 - 0.5 " piperazine ( 0.2) 0.0 - 0.8 " tricyclic diamine ( 0.1) 25 0.0 - 0.3 " ethanolamine ( 0.1) 10 - 20 " triamine ( 14 ) 0.5 - 2 " aminoethylpiperazine ( 1 ) 15 - 25 " tetramine ( 19 ) 10 - 20 " pentamine ( 16 ) 5 - 10 " hexamine ( 7 ) 3 - 9 " heptamine ( 5.6) 5 - 15 " higher-boiling, resinous constituents ( 9) 1 - 6 " salt, ash ( 4) 101.4 The numbers in brackets are those of a typical Le A 23 776 ~76415 reactor base as also used in the later illustrative section;
the numerical values have been rounded off and can fluc-tuate by about + 10% of their value.
Preference is also given to the use of surh amine mixtures as are obtained as the tetramine bottom product in the industrial synthesis of dialkylenetriamines, in particular dipropylenetriamine and especially diethylene-triamine, from dihalogenoalkanes and ammonia after the triamine fraction has been distilled off.
This gives amine mixtures which contain for example A) less than 10% by weight, preferably less than 1%
by weight, of triamines, B) about 50 to about 60% by weight, preferably about 52 to about 55% by weight, of tetramines, 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 20 E) about 1 to about 15% by weight, preferably about 2 to about 10% by weight, of other constituents, the sum of components A) + B) + C) + D) + E) being 100% by weight. Particular preference is given to the use in the process according to the inven-tion of basic amides of oleic acid or of fatty acid mixtures containing oleic acid and the amine mixture obtained as tetramine bottom product.
The aqueous preparations of the basic amides are preferably basic amides which are partly or wholly conver-ted at the amine groups in the salt form and are dispersed or dissolved in an aqueous medium; preference is given to the use of the acetates and/or formates of the basic amides.
The invention further relates to the papers and paperlike materials prepared using the process according 5 to the invention, such as, in particular, cardboards.
The porositizing auxiliaries according to the Le A 23 776 -~.~76~15 invention are predominantly prepared and transported in the form of the 10 - 35% strength aqueous formulation, which for use on the paper-stuff can be diluted to concen-trations below 1%. On the other hand, it is also possible to add the pure basic amides to the paper-stuff, in which case the aqueous dispersion of the auxiliary can then form and act in the paper vat.
The advantage of the porositizing agents according to the invention is, inter alia, that additional measures for changing the porosity of the paper can be avoided and that the porositizing agents, which are compatible with sizing agents, can be used in very small amounts of 0.05 to about 5, preferably 0.2 to 0.8, % by weight, relative to solid content and paper-stuff.
The long-chain fatty acids and fatty acid mix-tures used can in principle be any fatty acid having more than 9, preferably more than 15, C atoms and a melting point below 30C (under standard conditions). Their usually natural fatty acids such as oleic acid, elaidic acid, linseed oil fatty acids and soya oil fatty acids and other vegetable fatty acids, for example tall oil fatty acid, but also fatty acids obtainable from mineral depo-sits or petroleum or train oil or fish oil fatty acids having 9 to above 28 C atoms, in particular 15 - 25 C
atoms, but even synthetic, preferably monofunctional long-chain fatty acids obtainable by oxo synthesis or Fischer-Tropsch processes or oxidation processes or dimerization or oligomerization processes are possible. Preference is given to the use of oleic acid or preferably of (technical) fatty acid mixtures containing oleic acid.
The reaction of the fatty acids with the poly-alkylenepolyamines is effected by processes of the art, preferably by heating the components while separating off water, where appropriate in the absence of air or under a protective gas (N2). Although other mixing ratios in the amide synthesis lead to products having a certain Le A 23 776 ~.~764~5 degree of activity, the best results are obtained by com-bining in the amide synthesis such amounts of fatty acids and polyalkylenepolyamines as will enable 40 - 100% of the primary amino groups present in the amine of amine mixture to be converted by carboxyl groups into amide groups.
Preferably 55 - 100% of the primary amino groups should be converted into amide groups. The use cf superstoichio-metric amounts of fatty acid is possible.
The polyalkylenepolyamines used to prepare the amide are for reasons of availability not so much poly-butylenepolyamines or polypropylenepolyamines but prefer-ably polyethylenepolyamines. In general, such amines are prepared by reacting ~,~-dihalogenoethane with ammonia.
In general, all the polyamines obtained in this synthesis, provided about S0 and more % of the primary amino groups can be converted into the amide, can be considered as star-ting amines according to the invention. Since, however, ethylenediamine and diethylenetriamine are much sought-after industrial intermediates, it is preferable according to the invention to use polyethylenepolyamines having more than 3 amino groups, since these are inexpensively avai-lable as by-products of diamine and triamine synthesis.
Such amines are triethylenetetramine fractions, tetraethylenepentamine and pentaethylenehexamine fractions.
Of particular interest and, surprisingly, of excel-lent activity in the porositizing agent according to the invention are the residual mixtures which remain behind when the diamines and triamines are distilled out of the reaction mixture and which are referred to as the tetra-mine bottom product.
What is surprising is not only that such a non-specific mixture of a very wide range of linear~ branched and cyclic amines of different basicities and different molecular weights can be used with excellent results for the porositizing action in place of an amine fraction defined by a certain boiling range.
Le A 23 776 It is especially surprising that it has been found that such wide-ranging polyamine mixtures can be used to obtain porositizing agents of improved activity over for example a pure tetramine fraction, which in turn is not only by itself but also in conjunction with the obviated need for fractionating the polyalkylenepolyamines a significant advance in the art.
It has been found, surprisingly, that the process described here for obtaining porositizing agents can be significantly improved still further by using as the poly-amines to be used not for example a technical fraction of for example triethylenetetramine which additionally con-tains its isomers and trace substances having the same boiling range but by using the whole of the reaction pro-ducts obtained in the polyethylenepolyamine synthesis from~J~-dihalogenoalkane and ammonia which has merely been stripped by distillation of alkylenediamine (ethylene-diamine) and where appropriate dialkylenetriamine (di-ethylenetriamine) as starting amine for reaction with the fatty acids. This technical amine mixture which contains a plurality of different amine components having predomi-nantly 4 and more nitrogen atoms in the molecule is ob-tained as the tetramine bottom product in the synthesis of dipropylenetriamine or in particular diethylenetri-amine and is particularly readily available. This tet-ramine bottom product has the advantage that its use necessitates no expensive further distillation and other purification steps although for example coarse purifica-tiOn by means of activated carbon, silica, exchangers, or similar purification aids is perfectly feasible. For ex-ample, it can also be possible because of the self-colour to subject the tetramine bottom product to a non-fractional distillation in order to separate off any higher molecular usually deeply coloured resin constituents which may be present. However, this operation is basically not necessary.
Suitable technical amine mixtures for preparing Le A 23 776 ~7~4~
g the bas;c fatty acid amides are preferably technicaL poly-ethylenepolyamines, i.e. tetramine bottom product from the synthesis of technical diethylenetriamine.
Also suitable are in general the corresponding technical polypropylenepolyamine fractions. Of particular interest is technical triethylenetetramine bottom product, i.e. the bottom product material which is left behind after the diethylenetriamine fraction has been distilled off and which contains triethylenetriamine and also the amines.
Examples of components which can be present in the technica~ tetramine bottom product are: aminoethyLp;pe-razine, trisaminoethylamine, N,N'-bisaminoethylpiperazine, aminoethylated N-aminoethylpiperazines in the form of various isomers, and a numher of unidentified other impuri-ties. And also for example tetraethylenepentamine, penta-ethylenehexamine, hexaethyleneheptamine and their branched and cyclic isomers as well as oligomeric and polymeric amino resins of unknown structure.
while the "technical" triethylenetetramine as the tetramine fraction consists in addition to ill-defined low amounts as trace substances essentially of 4 tetramine isomers, namely a linear (main fraction), a branched and two isomers containing piperazine rings, the tetramine bottom product contains in addition to these trace sub-stances and isomers in amounts above 1 - 3% pentamines (about 30%) having about 5 isomers and hexamines (about 14%) having about 9 types of isomer which are linear, branched, cyclic, and also of course higher types of amine and other trace substances. The tetramines, pentamines and hexamines account for about 91 - 97% of the tetramine bottom product.
The linear compounds should be present in at least 20% by weight and preferably above 40% by weight. It is also possible to include mixtures of technical polyalky-lenepolyamines having lower boiling ranges and amine con-tents in the process.
Le A 23 776 ~:764~5 Relative to the amount of amine fraction or tet-ramine bottom product used, the fatty acids for preparing the amide precursor for the porositizing agents according to the invention are used in such amounts as to make it possible to convert 50 - 100% of the primary amino groups present into the amide. This means that the resulting basic amide preferably still contains per molecule on average at least two basic amino groups.
This is the case for example when 150 parts by 1û weight of technical tetramine bottom product are reacted with about 1.5 moles of oleic acid or Fisch fatty acid or ricinoleic acid, and the acetylation of the basic amides by the OH number method gives OH numbers of from 150 to 210, while the acid numbers should be below 10.
The preparation of the basic amides can be effec-ted by various methods familiar to the person skilled in the art, for example very simply by heating caLculated amounts of tall oil fatty acid and amine, ahere approp-riate under nitrogen, to 180C to 220C, and distilling off the water formed in the course of the amidation. The acid numbers of the amidation product should be below 15, preferably below 8.
Subsequently the melt of the basic amides formed, after cooling down to a suitable temperature range, for example in the vicinity of the melting points of the amides, which are between 30 and 70C, can be dispersed in water, being reacted with thorough stirring where appropriate with a dispersing auxiliary. The melt is then converted after 0.5 - 10 h formulation time, preferably while still warm, where appropriate with further water and cooling and further stirring at 10 - 80C in the course of 0.1 -10 h into a 5 - 40% by weight strength, preferably 10 -25% by weight strength, solution, suspension or emulsion.
This is generally effected by simple stirring, including where appropriate the use of mechanical emulsifying apparatus.
Le A 23 776 ~. ~7~ 5 It is also possible to react the amide melt before the dispersing in water with minor amounts of an inorganic or organic acid as a dispersing auxiliary (preferably below 20%, in particular 0 - 10%, of the amount necessary for neutralization) in order to facilitate the dispersing step.
It has been found to be advantageous for the amount of water present in the dispersing step to be smaller than the amount of water contained later in the aqueous preparation, since then the standardization of the desired porositizing agent concentration can be optimally combined with a viscosity-reducing addition of electrolyte (for example NaCl solution) which is in accordance with the invention and which should be contemplated where appropriate.
In the preparation of the aqueous preparations according to the invention of the basic fatty amide, "dis-persing auxiliaries" is to be understood as meaning not only customary dispersing auxiliaries present to be used in amounts of 0 - about 15% by weight such as protective colloids and/or emulsifiers on anionic, cationic or non-ionic bases but also additions of quaternizing agents such as esters and amides of halogenoacetic acid, for example chloracetamide, propanesultone, dimethyl sulphate, benzyl chloride, alkyl chloride, methyl chloride and other ~-halogenoalkanes, ethylene oxide, preferably epichloro-hydrin, in amounts of 0.05 ~ 5 equivalents, preferably 0 1 - 1 equivalents, relative to the amino groups contained in the basic amide. However, preferred dispersing auxi-liaries which have no adverse effect on the porositizing and bulking actions of the additives according to the invention are in particular inorganic, but above all organic, acids such as halohydric acids, phosphoric, sul-phuric or nitric acid and fumaric, maleic, citric, malic, succinic acid or toluenesulphonic acids, in particular however because of the relatively low corrosiveness, com-bined with high volatility, formic acid and/or acetic acid.
Le A 23 776 ~ ~7~4~5 These acids, which are preferably used ;n such amounts that the result is a neutral reaction (pH about 7) of the aqueous formulation, combine with the basic amide in question itself to form an emulsifying or dispersing salt which guarantees the stabilization of the aqueous formulation of the basic fatty amines according to the invention which are active porositizing agents. It is also possible to add less or more acid when for example the reaction of the paper-stuff is to be left within the 10 weakly basic or the acid range.
When the solids content is above 10% by weight, the aqueous formulations described according to the inven-tion have in some instances a pasty consistency which can lead to handling problems. The formulations then can have added to them 0.05 - 5, preferably 0.1 - 1% by weight (relative to solids) of electrolytes, thereby effecting liquefaction. This is most advantageously done in the final dilution stage of preparation of the porositizing agent by dissolving the desired amount of electrolyte, for example NaCl, in the water intended for the final dilution and incorporating the electrolyte in that way.
Although it is also possible to add the eLectro-lyte from the start or as early as the first or second addition of water, it has been found to be most effective to incorporate the electrolyte ideally at the conclusion of the dilution process. This gives formulations which are highly mobile while having solids contents above 10%
by weight and do not subsequently thicken.
Suitable electrolytes are in addition to organic salts such as ammonium or alkali metal formates, acetates, benzoates, phosphonates or sulphonates preferably inorganic salts such as ammonium chloride, potassium chloride, cal-cium chloride, zinc chloride, magnesium chloride, aluminium chloride or in particular sodium chloride, although soluble chlorides, nitrates, sulphates, phosphates, carbonates of other elements and even acids or bases themselves are Le A 23 776 likewise suitable in principle.
The ready-to-use aqueous porositizing agent formu-lations obtained have sol;ds concentrations of 5 - 40, preferably lO to 35, % by weight. These formulations are diluted further when used to the then required concen-trations, for example down to concentrations below 5~ by weight, which are likewise customary in the sizing of paper.
The auxiliaries according to the l~nvention have the advantage of having virtually unlimited storability in the form of their aqueous formulations while being very highly active and also of not requiring additions of alum (sizing agent) or cationic or anionic auxiliaries, although addition of fillers or such auxiliaries for ex-ample based on cationic starch, quaternized polyamines,quaternized polyamideamines, quaternized basic formalde-hyde resins, methylcellulose, carboxymethylcellulose, ligninsulphonic acid, starches and polysaccharides of different origins, xanthan, pullulan, chitosan, polymers or copolymers of (meth)acrylic acid, maleic, fumaric, itaconic acid or other polymers and copolymers having carboxyl or sulpho groups which may be present in salt form, collagen, gelatin, alginates or karaginates or even substantive or reactive dyestuffs is perfectly feasible ~5 and possible.
Their activity is not impaired by whiteners. The aqueous formulations can be prepared without additional emulsifying agents.
The porositizing agents are highly suitable alone or in combination with sizing agents for increasing the opalescence, porosity and volume of paper, but can of course also be used in other paper-modifiers. They can be used not only in the case of wood-, chalk-containing or kaolin-containing, screenings, or recycling papers but also in the case of those which contain no or a dif-ferent filler, such as for example talc or gypsum. They Le A 23 776 ~ ~7~15 are also suitable for modifying cellulosic and other mate-rials such as board, textile material, leather, cardboard or woodchip boards or insulating boards or gypsum or gypsum cardboard sheets.
A significant advantage of the new porositizing agents is that additional measures for modifying the porosity of paper can be avoided and that the porositizing agents, which are compatible with sizing agents, can be used in very low amounts of 0.05 to about 5, preferably 0.2 to 0.8, % by weight, relative to solids and paper-stuff.
Following, the invention will be illustrated by examples; the parts and percentages are by weight, unless otherwise stated.
Examples 1 and 2 (comparative examples) A sizing agent conforming to German Offenlegungs-schrift 2,838,270 is prepared (auxiliary A).
Preparation of dibasic amide A
170 parts of stearic acid are meltecl and 43.8 parts of technical triethylenetetramine are added with stirring (molar ratio about 2 : 1). The temperature is then raised to 190C under N2~ and all volatile mat-ter is distilled off. 6 h later an acid number of 1.9 is reached. The melting range of the amide is 87 - 107C.
Auxiliary A
201.6 parts of basic amide are stirred at 120C
together with 3.7 parts of epichlorohydrin for 30 minutes.
7U parts of water are then added, followed by 32.3 parts sf epichlorohydrin, which is followed by stirring at 100 -120C for 1 h. Subsequently 1,182 parts of preheatedwater at about 95C are add ed, and the emuLsion formed is stirred under gentle reflux for about 1 h. This is followed by cooling down to about 40C and addition to the pasty emulsion of a solution of 1.2 parts of NaCl in 92 parts of water, producing a highly mobile, approximately 15% strength sizing agent formulation.
Le A 23 776 The following comparative exampLe, auxiliary 9 is now carried out using oLeic acid in place of stearic acid.
The tabulated test values show that in the case of auxiliary A the porositizing action is relatively low while sizing is good, while in the case of auxiliary B
no sizing but a moderate porositization action is present.
Example 3 This illustrates the higher activity of the poro-sitizing agents according to the invention compared withauxiliaries A and B:
The method used for preparing amide A is repeated, except that the stearic acid is replaced by oleic acid.
The basic amide, which has a melting point of about 64C, is used as in the case of auxiliary A, but in place of a total of 36 parts of epichlorohydrin 16 parts of formic acid are added. The result is a neutral porosi-tizing agent dispersion having a solids content of about 13%.
Example 4 Example 3 is repeated, except for the following points:
Pure oteic acid is replaced by soya oil acid;
triethylenetetramine is replaced by a technical tetramine bottom product of the approximate composition: less than 1% by weight of triamines, 52% by weight of tetramines, 30% by weight of pentamines, 13% by weight of hexamines and 4% by weight of other constituents; 16 parts of formic acid are replaced by 24 parts of acetic acid.
This gives an approximately 13% strength disper-sion of the porositizing agent. The table of the test values shows the particularly good action of the tetramine bottom product used for preparing the amide.
Example 5 Using the method for preparing amides A and E~, an amide is prepared from 5,100 parts of tall oil fatty acid Le A 23 77_ .7641 and 1,314 parts of tetramine bottom product of the approxi-mate composition specified in Example 4. The resulting amide has a melting point of around 41C and an acid number of 6.3. 202 parts of the amide are melted together with 29 parts of acetic acid at a temperature not above 80C. The salt formed has a melting point of around 63C. This salt can be added to the paper mixture in the vat as a powder which may have been stabilized by powdering with clay, silica or talc or be dissolved before-hand as such to give an aqueous auxiliary formulationhaving a solids content of about 15% by dispersing the optionally comminuted melt (150 parts) in 85 parts of warm water at 80C with thorough stirring and stirring until cold.
The 15% strength dispersion thus obtained can be used directly as a porositizing agent.
Example 6 Example 5 is repeated, except that tall oil fatty acid is replaced by Fisch oil fatty acid which contains about 60 - 70% of C22 fatty acids.
The table below features a comparison of Examples 1 - 6 in the following tests:
Sizing:
The sizing is assessed by means of the so-called ink flotation test in which a strip of paper finished with the agent to be tested is placed on the surface of a dish filled with standard ink in accordance with DIN 53 126 and the time which elapses until the ink penetrates through to the side of the emplaced paper facing the observer is measured. This test, if carried out in a standardized manner, provides a very good way of assessing different sizing agents~
Opacity:
The opacity is assessed by the method of DIN 53 146, which quotes the opacity in %, so that high % values correspond to high non-transparency.
Le A 23 776 ~7~ 5 The thickness of the paper in the comparison and the examples is 0.11 mm.
Porositization:
The porosity is assessed by the method of DIN 53120 and the permeability is determined in ml of air/min.
The thickness of the paper in the comparison and in the examples is 0.11 mm.
Change in volume:
The weight per unit volume is determined for a given thickness of paper of 0.11 mm from the weight/unit area and is expressed in kg/dm, i.e. the weight per unit volume is used as a measure of any change in volume for a given use of substance.
The porositizing agents according to the invention are tested illustratively on alum-free, chalk-containing paper:
5 9 of a mixture of 50 9 of spruce sulphite pulp and 25 9 of chalk are suspended in 200 ml of tap water. x% of the porositizing agent (solids based on pulp plus filler) are then stirred in. Water is then added without addition of a thickening agent to make the volume up to about 1 litre, and a sheet of paper is prepared on a sheet-former.
This sheet of paper is sucked off, pressed off and dried at 90 and 110C on a drying cylinder for 5 min. The sheet is cut into pieces for the tests, for example into 2 cm x 6 cm strips for the ink flotation test, which are then tested.
The following tabulated assessments were found.
The comparison is against the products of Examples 1 and 2 and as Example No. 0 a paper which has not been sized and not been treated with porositizing agents.
The assessments of ppacity and porosity were also carried out on papers prepared on an experimental paper-machine.
Le A 23 776 ~;~7~4L~5 Example No A B C D E F G
_ Product of Example No. 1 2 3 4 5 6 0 Sizing sec. 900 12 810 9 11 2 Opacity about %72 77 80 82 81 82 71 5 Porosity about ml/min 380 410 620 790 800768 300 Volume +15 +15 +35 +49 +51~50 + O
Amount used % 0.6 0.6 0.6 0.6 0.60.6 --Tabulation of the assessment of different poro-sitizing agent formulations.
The tabulated values show the superiority of thefatty acids which are non-crystalline at 30C and the adverse effect of the quaternization and the especially favourable effect of the amine mixture present n the tetramine bottom product.
Examp(e 7 (according to the invention) The method used for preparing dibasic amide A is used to prepare an amide from 5,500 parts of technical oleic acid and 1,500 parts of reactor base of the approxi-mate composition (in % by weight):17% of water, 7% of ethylenediamine, 0.2% of piperazine, 0.1% of tricyclic diamine, 0.1% of ethanolamine, 14% of triamine, 1% of aminoethylpiperazine, 19% of tetramine, 16% of pentamine, 7% of hexamine, 5~6% of heptamine, 9% of higher-boiling resinous constituents and 4% of salt and ash. The numbers have been rounded off and can fluctuate about the value by about + 10%.
The resulting amide has a melting point of around 45C, an ûH number of 128 and an acid number of 5Ø
200 parts of the amide are melted together with 35 parts of acetic acid while the temperature is not above 80C.
The salt formed has a melting point of around 63C. This salt can be added to the paper mixture in the vat as a pouder which may have been stabilized by powdering with clay, starch, silica or talc, or can be dissolved before-Le A 23 776 ~ ~64L~5 hand as such to give an aqueous auxiliary formulation containing about 15% of solids by dispersing the melt (80C) in 1,000 parts of warm water at 80C with thorough stirring and cooling down to 50C. A solution of 1.15 parts of sodium chloride in 100 parts of water is then added, which is followed by stirring with cooling down to 20 - 25C.
The test values lis~ed in the table clearly show the improvement in the porositizing action which is obtainable according to the invention.
Example 8 (according to the invention) Example 7 is repeated, except that oLeic acid is replaced by tall oil acid.
The table below shows Examples 1, 7 and 8 in com-parison in the following properties:Sizing:
The sizing is assessed by means of the so-ca~led ink flotation test in which a strip of paper finished with the agent to be tested is placed on the surface of a dish filled with standard ink in accordance with DIN 53 126 and the time which elapses until the ink penetrates through to the side of the emplaced paper facing the observer is measured. This test, if carried out in a standardized manner, provides a very good way of assessing different sizing agents.
Opacity:
The opacity is assessed by the method of DIN 53 146, which quotes the opacity in %, so that high % values correspond to high non-transparency.
The thickness of the paper in the comparison and the examples is 0.11 mm.
Porositization:
The porosity is assessed by the method of DIN 53 120 and the permeability is determined in ml of air/min.
The thickness of the paper in the comparison and in the examples is 0.11 mm.
Le A 23 776 ~i~76~5 Change in volume:
The weight per unit volume is determined for a given thickness of paper of 0.11 mm from the weight/unit area and is expressed in kg/dm, i.e. the weight per unit volume is used as a measure of any change in volume for a given use of substance.
The porositizing agents according to the invention are tested illustratively on alum-free, chalk-containing paper:
10 5 g of a mixture of 50 y of birch sulphate pulp and pine sulphate pulp (degree of beating 35C SR) are suspended in 200 ~l of tap water. x% of the porositizing agent (solids based on pulp plus filler) are then stirred in. ~ater is then added without addition of a thickening agent to make the volume up to about 1 litre, and a sheet of paper is prepared on a sheet-former (Rapid-K8then).
This sheet of paper is sucked off, pressed off and dried at 90C on a vacuum dryer for 5 min. The sheet is cut into pieces for the tests, for example into 2 cm x 6 cm strips for the ink flotation test, which are then tested.
The weight per unit area is about 100 g/m2.
The following tabulated assessments were found.
The comparison was against the products of Example 1 (auxiliary A), and Example O is paper which has not been sized and not been treated with porositizing agents.
The c,pacity and porosity were also assessed on papers prepared on an experimental paper-machine.
Example No A B C D
Product from Example No. 1 7 8 0 30 Sizing sec. 900 5 6 2 Opacity about ~ 83 88 88 83 Porosity about ml/min145 225218 140 Volume (relative)+2.9 +8.0 +7.1 +0 Amount used %0.7 0.7 0.7 0.7 Tabulation of the assessment of different porositizing agent formulations; the values Le A 23 776 ~27~4~5 shown are averages of 5 experiments in each case.
The tabulated values reveal the superiority of fatty acids which are non-crystalline at 30C and the considerable improving effect of the amine mixture referred to as a reactor base.
Example 4 A paper-machine is used to prepare a paper having a weight per unit area of about 100 9/m2 on the basis of a paper-stuff prepared from mixed waste paper using 0.075%
of a retention aid based on polyam;deamine.
If the paper-stuff has now added to it an amount of 0.3% of porositizing agent of Example 7 (relative to solids) ahead of the forward end of the machine, the volume of the paper leaving the machine in the dried state increases by 7.5%.
Le A 23 776
The invention relates to a process for preparing papers of paperlike materials.
Papers which, cornpared with the papers prepared by conventional processes, have increased opacity, porosity or even increased volume from the same starting material are frequently desired in industry.
Hitherto attempts have been made to meet these demands by changing the degree of beating, which was successful at least with regard to the opacity, but necessitated additional beatings and stockholdings. Even the addition of fillers or of plastics latexes which act as special fillers has been tried at times, but, if at all, was successful only with respect to the opacity or the volume alone but not with respect to all three paper properties:
opacity, porosity, volume.
According to the present invention there is provided in the making of paper from an aqueous pulp slurry, the improve-ment which comprises incorporating into such slurry an agent consisting essentially of a basic amide of a long-chain fatty acid haying a melting point below 30C, whereby the resulting paper exhibits increased porosity. As mentioned, the improvea process leads to papers or paperlike materi~ls which compared with papers or paperlike materials prepared in the absence of amides, have higher porosity, higher nontransparency (opacity) and higher volume.
It is admittedly known to add the salts and quater-nization products o basic amides of long-chain fatty acids having melting points above 30C as sizing agents to the paper-stuff, but compared with the auxiliaries according to the invention any ~Z~7~i415 -la- 23189-6244 obseryable effect with such sizing agents is insignificant and requires significantly more costly amounts. By contrast, the porosity auxiliaries according to the invention have only a small, negligible sizing agent action. Furthermore, the state of the art sizing agent preparations obtain their activity only 7~
through a quaternization reaction~ As a consequence, it was impossible to infer from the fact that there are sizing agents based on quaternized or non-quaternized long-chain fatty acid amides that basic amides of long-chain fatty acids or fatty acid mixtures which have melting points be-low 30C can be used as porositization agents for paper.
The basic amides used according to the invention are preferably added to the paper-stuff in the course of papermaking in the form of an aqueous preparation.
Preference is given to the use of such amides as are preparable by reacting the fatty acids with polyalky-lenepolyamines by converting 50-100% of the primary amino groups into amide groups. Use is made here in particular of polyethylenepolyamines having more than three amino groups in the molecule, such as triethylenetetramine, tetraethylenepentamine and pentaethylenehexamine, which can be used in the form of technical fractions.
Preference is also given to the use of such amine mixtures as are formed in the polyamine synthesis from dihalogenoalkanes and ammonia.
These amine mixtures preferably have the follow-ing composition:
A. about 3 to about 27% by weight of diamines B. about 10 to about 22% by weight of triamines 25 C. about 15 to about 25% by weight of tetramines D. about 10 to about 20% by weight of pentamines 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 constituents, where the sum of cDmponents A. - G. is 100% by weight.
Depending on the starting alkane, diamine compo-nent A. can contain monoalkylenediamines such as 1,3-propylenediamine, butylenediamines or diaminohexanes such as 1,6-diaminohexane and in particular ethylenediamine~
Preference is given to the use of such amine mix-tures as are obtained in the industrial dipropylenetriamine Le A 23 776 ~i~7~15 and propylenediamine synthesis from dichloropropane and ammonia as so-called reactor base mixtures.
Particular preference is given to the use of such amine mixtures as are obtained in the industrial diethy-lenetriamine and ethylenediamine synthesis from 1,2-di-chloroethane and ammonia as so-called reactor base mixtures.
These mixtures have the advantage that they can be used without expensive further distillation and other purification steps, although for exampLe coarse purifica-tion by means of activated carbon, siLica, exchangers, drying processes or similar purification aids is perfectly feasible. For example, because of the self-colour it may also be necessary to subject the reactor base to a non-fractional distillation so as to separa~e said base fromany higher-molecular, usually deeoly coloured resin con-stituents which may be present. However, this operation is basically not necessary.
The base mixture formed in the industrial poly-ethylenepolyamine synthesis based on dichloroethane con-tains for example the following constituents:
ethylenediamine, diethylenetriamine, triethylene-tetramine, aminoethylenepiperazine, trisaminoethylamine, N,N'-bisaminoethylpiperazine, aminoethyla~ed N-aminoethyl-piperazines in the form of various isomers and a number of unidentified other impurities. Plus, for example, tetra-ethyleneepentamine, pentaethylenehexamine, hexaethylene-heptamine and their branched and cyclic isomers and oligo-meric and polymeric amino resins of unknown structure.
While in addition to ethylenediamine in the reac-tor base the "technical" triamine content consists largely of diethylenetriamine, the tetramine content contains in addition to ill-defined small amounts of trace sub-stances essentially four tetramine isomers, namely one linear (main fraction), one branched and two isomers which contain piperazine rings; also present are (in addition Le A 23 776 ~7~ 5 to undefined trace substances and isomers in amounts below 3%) pentamines in the form of about S isomers and hexamines (about 14%) in the form of about 9 types of isomer which are linear, branched, or cyclic. And also of course higher amines and other trace substances. The diamines, tri-amines, tetramines, pentamines and hexamines account for about 95 to 99% of the water-free reactor base The linear unbranched water-free compounds should be present in an amount of at least 40% by weight and preferably above 60% by weightO It is also possible to include mixtures of technical alkylenepolyamines having different boiling ranges and amine contents in the process.
A reactor base from ethylenepolyamine production has in the state it is obtained in industry and in which it is particularly highly suitable for preparing porosi-tizing agents in accordance with the invention the follow-ing composition, determined by fractional distillation and gas chromatography:
(The compositions describe the customary produc-tion variations) 15 - 25 % by weight of water ( 17 ) 3 - 20 " ethylenediamine ( 7 ) 0.1 - 0.5 " piperazine ( 0.2) 0.0 - 0.8 " tricyclic diamine ( 0.1) 25 0.0 - 0.3 " ethanolamine ( 0.1) 10 - 20 " triamine ( 14 ) 0.5 - 2 " aminoethylpiperazine ( 1 ) 15 - 25 " tetramine ( 19 ) 10 - 20 " pentamine ( 16 ) 5 - 10 " hexamine ( 7 ) 3 - 9 " heptamine ( 5.6) 5 - 15 " higher-boiling, resinous constituents ( 9) 1 - 6 " salt, ash ( 4) 101.4 The numbers in brackets are those of a typical Le A 23 776 ~76415 reactor base as also used in the later illustrative section;
the numerical values have been rounded off and can fluc-tuate by about + 10% of their value.
Preference is also given to the use of surh amine mixtures as are obtained as the tetramine bottom product in the industrial synthesis of dialkylenetriamines, in particular dipropylenetriamine and especially diethylene-triamine, from dihalogenoalkanes and ammonia after the triamine fraction has been distilled off.
This gives amine mixtures which contain for example A) less than 10% by weight, preferably less than 1%
by weight, of triamines, B) about 50 to about 60% by weight, preferably about 52 to about 55% by weight, of tetramines, 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 20 E) about 1 to about 15% by weight, preferably about 2 to about 10% by weight, of other constituents, the sum of components A) + B) + C) + D) + E) being 100% by weight. Particular preference is given to the use in the process according to the inven-tion of basic amides of oleic acid or of fatty acid mixtures containing oleic acid and the amine mixture obtained as tetramine bottom product.
The aqueous preparations of the basic amides are preferably basic amides which are partly or wholly conver-ted at the amine groups in the salt form and are dispersed or dissolved in an aqueous medium; preference is given to the use of the acetates and/or formates of the basic amides.
The invention further relates to the papers and paperlike materials prepared using the process according 5 to the invention, such as, in particular, cardboards.
The porositizing auxiliaries according to the Le A 23 776 -~.~76~15 invention are predominantly prepared and transported in the form of the 10 - 35% strength aqueous formulation, which for use on the paper-stuff can be diluted to concen-trations below 1%. On the other hand, it is also possible to add the pure basic amides to the paper-stuff, in which case the aqueous dispersion of the auxiliary can then form and act in the paper vat.
The advantage of the porositizing agents according to the invention is, inter alia, that additional measures for changing the porosity of the paper can be avoided and that the porositizing agents, which are compatible with sizing agents, can be used in very small amounts of 0.05 to about 5, preferably 0.2 to 0.8, % by weight, relative to solid content and paper-stuff.
The long-chain fatty acids and fatty acid mix-tures used can in principle be any fatty acid having more than 9, preferably more than 15, C atoms and a melting point below 30C (under standard conditions). Their usually natural fatty acids such as oleic acid, elaidic acid, linseed oil fatty acids and soya oil fatty acids and other vegetable fatty acids, for example tall oil fatty acid, but also fatty acids obtainable from mineral depo-sits or petroleum or train oil or fish oil fatty acids having 9 to above 28 C atoms, in particular 15 - 25 C
atoms, but even synthetic, preferably monofunctional long-chain fatty acids obtainable by oxo synthesis or Fischer-Tropsch processes or oxidation processes or dimerization or oligomerization processes are possible. Preference is given to the use of oleic acid or preferably of (technical) fatty acid mixtures containing oleic acid.
The reaction of the fatty acids with the poly-alkylenepolyamines is effected by processes of the art, preferably by heating the components while separating off water, where appropriate in the absence of air or under a protective gas (N2). Although other mixing ratios in the amide synthesis lead to products having a certain Le A 23 776 ~.~764~5 degree of activity, the best results are obtained by com-bining in the amide synthesis such amounts of fatty acids and polyalkylenepolyamines as will enable 40 - 100% of the primary amino groups present in the amine of amine mixture to be converted by carboxyl groups into amide groups.
Preferably 55 - 100% of the primary amino groups should be converted into amide groups. The use cf superstoichio-metric amounts of fatty acid is possible.
The polyalkylenepolyamines used to prepare the amide are for reasons of availability not so much poly-butylenepolyamines or polypropylenepolyamines but prefer-ably polyethylenepolyamines. In general, such amines are prepared by reacting ~,~-dihalogenoethane with ammonia.
In general, all the polyamines obtained in this synthesis, provided about S0 and more % of the primary amino groups can be converted into the amide, can be considered as star-ting amines according to the invention. Since, however, ethylenediamine and diethylenetriamine are much sought-after industrial intermediates, it is preferable according to the invention to use polyethylenepolyamines having more than 3 amino groups, since these are inexpensively avai-lable as by-products of diamine and triamine synthesis.
Such amines are triethylenetetramine fractions, tetraethylenepentamine and pentaethylenehexamine fractions.
Of particular interest and, surprisingly, of excel-lent activity in the porositizing agent according to the invention are the residual mixtures which remain behind when the diamines and triamines are distilled out of the reaction mixture and which are referred to as the tetra-mine bottom product.
What is surprising is not only that such a non-specific mixture of a very wide range of linear~ branched and cyclic amines of different basicities and different molecular weights can be used with excellent results for the porositizing action in place of an amine fraction defined by a certain boiling range.
Le A 23 776 It is especially surprising that it has been found that such wide-ranging polyamine mixtures can be used to obtain porositizing agents of improved activity over for example a pure tetramine fraction, which in turn is not only by itself but also in conjunction with the obviated need for fractionating the polyalkylenepolyamines a significant advance in the art.
It has been found, surprisingly, that the process described here for obtaining porositizing agents can be significantly improved still further by using as the poly-amines to be used not for example a technical fraction of for example triethylenetetramine which additionally con-tains its isomers and trace substances having the same boiling range but by using the whole of the reaction pro-ducts obtained in the polyethylenepolyamine synthesis from~J~-dihalogenoalkane and ammonia which has merely been stripped by distillation of alkylenediamine (ethylene-diamine) and where appropriate dialkylenetriamine (di-ethylenetriamine) as starting amine for reaction with the fatty acids. This technical amine mixture which contains a plurality of different amine components having predomi-nantly 4 and more nitrogen atoms in the molecule is ob-tained as the tetramine bottom product in the synthesis of dipropylenetriamine or in particular diethylenetri-amine and is particularly readily available. This tet-ramine bottom product has the advantage that its use necessitates no expensive further distillation and other purification steps although for example coarse purifica-tiOn by means of activated carbon, silica, exchangers, or similar purification aids is perfectly feasible. For ex-ample, it can also be possible because of the self-colour to subject the tetramine bottom product to a non-fractional distillation in order to separate off any higher molecular usually deeply coloured resin constituents which may be present. However, this operation is basically not necessary.
Suitable technical amine mixtures for preparing Le A 23 776 ~7~4~
g the bas;c fatty acid amides are preferably technicaL poly-ethylenepolyamines, i.e. tetramine bottom product from the synthesis of technical diethylenetriamine.
Also suitable are in general the corresponding technical polypropylenepolyamine fractions. Of particular interest is technical triethylenetetramine bottom product, i.e. the bottom product material which is left behind after the diethylenetriamine fraction has been distilled off and which contains triethylenetriamine and also the amines.
Examples of components which can be present in the technica~ tetramine bottom product are: aminoethyLp;pe-razine, trisaminoethylamine, N,N'-bisaminoethylpiperazine, aminoethylated N-aminoethylpiperazines in the form of various isomers, and a numher of unidentified other impuri-ties. And also for example tetraethylenepentamine, penta-ethylenehexamine, hexaethyleneheptamine and their branched and cyclic isomers as well as oligomeric and polymeric amino resins of unknown structure.
while the "technical" triethylenetetramine as the tetramine fraction consists in addition to ill-defined low amounts as trace substances essentially of 4 tetramine isomers, namely a linear (main fraction), a branched and two isomers containing piperazine rings, the tetramine bottom product contains in addition to these trace sub-stances and isomers in amounts above 1 - 3% pentamines (about 30%) having about 5 isomers and hexamines (about 14%) having about 9 types of isomer which are linear, branched, cyclic, and also of course higher types of amine and other trace substances. The tetramines, pentamines and hexamines account for about 91 - 97% of the tetramine bottom product.
The linear compounds should be present in at least 20% by weight and preferably above 40% by weight. It is also possible to include mixtures of technical polyalky-lenepolyamines having lower boiling ranges and amine con-tents in the process.
Le A 23 776 ~:764~5 Relative to the amount of amine fraction or tet-ramine bottom product used, the fatty acids for preparing the amide precursor for the porositizing agents according to the invention are used in such amounts as to make it possible to convert 50 - 100% of the primary amino groups present into the amide. This means that the resulting basic amide preferably still contains per molecule on average at least two basic amino groups.
This is the case for example when 150 parts by 1û weight of technical tetramine bottom product are reacted with about 1.5 moles of oleic acid or Fisch fatty acid or ricinoleic acid, and the acetylation of the basic amides by the OH number method gives OH numbers of from 150 to 210, while the acid numbers should be below 10.
The preparation of the basic amides can be effec-ted by various methods familiar to the person skilled in the art, for example very simply by heating caLculated amounts of tall oil fatty acid and amine, ahere approp-riate under nitrogen, to 180C to 220C, and distilling off the water formed in the course of the amidation. The acid numbers of the amidation product should be below 15, preferably below 8.
Subsequently the melt of the basic amides formed, after cooling down to a suitable temperature range, for example in the vicinity of the melting points of the amides, which are between 30 and 70C, can be dispersed in water, being reacted with thorough stirring where appropriate with a dispersing auxiliary. The melt is then converted after 0.5 - 10 h formulation time, preferably while still warm, where appropriate with further water and cooling and further stirring at 10 - 80C in the course of 0.1 -10 h into a 5 - 40% by weight strength, preferably 10 -25% by weight strength, solution, suspension or emulsion.
This is generally effected by simple stirring, including where appropriate the use of mechanical emulsifying apparatus.
Le A 23 776 ~. ~7~ 5 It is also possible to react the amide melt before the dispersing in water with minor amounts of an inorganic or organic acid as a dispersing auxiliary (preferably below 20%, in particular 0 - 10%, of the amount necessary for neutralization) in order to facilitate the dispersing step.
It has been found to be advantageous for the amount of water present in the dispersing step to be smaller than the amount of water contained later in the aqueous preparation, since then the standardization of the desired porositizing agent concentration can be optimally combined with a viscosity-reducing addition of electrolyte (for example NaCl solution) which is in accordance with the invention and which should be contemplated where appropriate.
In the preparation of the aqueous preparations according to the invention of the basic fatty amide, "dis-persing auxiliaries" is to be understood as meaning not only customary dispersing auxiliaries present to be used in amounts of 0 - about 15% by weight such as protective colloids and/or emulsifiers on anionic, cationic or non-ionic bases but also additions of quaternizing agents such as esters and amides of halogenoacetic acid, for example chloracetamide, propanesultone, dimethyl sulphate, benzyl chloride, alkyl chloride, methyl chloride and other ~-halogenoalkanes, ethylene oxide, preferably epichloro-hydrin, in amounts of 0.05 ~ 5 equivalents, preferably 0 1 - 1 equivalents, relative to the amino groups contained in the basic amide. However, preferred dispersing auxi-liaries which have no adverse effect on the porositizing and bulking actions of the additives according to the invention are in particular inorganic, but above all organic, acids such as halohydric acids, phosphoric, sul-phuric or nitric acid and fumaric, maleic, citric, malic, succinic acid or toluenesulphonic acids, in particular however because of the relatively low corrosiveness, com-bined with high volatility, formic acid and/or acetic acid.
Le A 23 776 ~ ~7~4~5 These acids, which are preferably used ;n such amounts that the result is a neutral reaction (pH about 7) of the aqueous formulation, combine with the basic amide in question itself to form an emulsifying or dispersing salt which guarantees the stabilization of the aqueous formulation of the basic fatty amines according to the invention which are active porositizing agents. It is also possible to add less or more acid when for example the reaction of the paper-stuff is to be left within the 10 weakly basic or the acid range.
When the solids content is above 10% by weight, the aqueous formulations described according to the inven-tion have in some instances a pasty consistency which can lead to handling problems. The formulations then can have added to them 0.05 - 5, preferably 0.1 - 1% by weight (relative to solids) of electrolytes, thereby effecting liquefaction. This is most advantageously done in the final dilution stage of preparation of the porositizing agent by dissolving the desired amount of electrolyte, for example NaCl, in the water intended for the final dilution and incorporating the electrolyte in that way.
Although it is also possible to add the eLectro-lyte from the start or as early as the first or second addition of water, it has been found to be most effective to incorporate the electrolyte ideally at the conclusion of the dilution process. This gives formulations which are highly mobile while having solids contents above 10%
by weight and do not subsequently thicken.
Suitable electrolytes are in addition to organic salts such as ammonium or alkali metal formates, acetates, benzoates, phosphonates or sulphonates preferably inorganic salts such as ammonium chloride, potassium chloride, cal-cium chloride, zinc chloride, magnesium chloride, aluminium chloride or in particular sodium chloride, although soluble chlorides, nitrates, sulphates, phosphates, carbonates of other elements and even acids or bases themselves are Le A 23 776 likewise suitable in principle.
The ready-to-use aqueous porositizing agent formu-lations obtained have sol;ds concentrations of 5 - 40, preferably lO to 35, % by weight. These formulations are diluted further when used to the then required concen-trations, for example down to concentrations below 5~ by weight, which are likewise customary in the sizing of paper.
The auxiliaries according to the l~nvention have the advantage of having virtually unlimited storability in the form of their aqueous formulations while being very highly active and also of not requiring additions of alum (sizing agent) or cationic or anionic auxiliaries, although addition of fillers or such auxiliaries for ex-ample based on cationic starch, quaternized polyamines,quaternized polyamideamines, quaternized basic formalde-hyde resins, methylcellulose, carboxymethylcellulose, ligninsulphonic acid, starches and polysaccharides of different origins, xanthan, pullulan, chitosan, polymers or copolymers of (meth)acrylic acid, maleic, fumaric, itaconic acid or other polymers and copolymers having carboxyl or sulpho groups which may be present in salt form, collagen, gelatin, alginates or karaginates or even substantive or reactive dyestuffs is perfectly feasible ~5 and possible.
Their activity is not impaired by whiteners. The aqueous formulations can be prepared without additional emulsifying agents.
The porositizing agents are highly suitable alone or in combination with sizing agents for increasing the opalescence, porosity and volume of paper, but can of course also be used in other paper-modifiers. They can be used not only in the case of wood-, chalk-containing or kaolin-containing, screenings, or recycling papers but also in the case of those which contain no or a dif-ferent filler, such as for example talc or gypsum. They Le A 23 776 ~ ~7~15 are also suitable for modifying cellulosic and other mate-rials such as board, textile material, leather, cardboard or woodchip boards or insulating boards or gypsum or gypsum cardboard sheets.
A significant advantage of the new porositizing agents is that additional measures for modifying the porosity of paper can be avoided and that the porositizing agents, which are compatible with sizing agents, can be used in very low amounts of 0.05 to about 5, preferably 0.2 to 0.8, % by weight, relative to solids and paper-stuff.
Following, the invention will be illustrated by examples; the parts and percentages are by weight, unless otherwise stated.
Examples 1 and 2 (comparative examples) A sizing agent conforming to German Offenlegungs-schrift 2,838,270 is prepared (auxiliary A).
Preparation of dibasic amide A
170 parts of stearic acid are meltecl and 43.8 parts of technical triethylenetetramine are added with stirring (molar ratio about 2 : 1). The temperature is then raised to 190C under N2~ and all volatile mat-ter is distilled off. 6 h later an acid number of 1.9 is reached. The melting range of the amide is 87 - 107C.
Auxiliary A
201.6 parts of basic amide are stirred at 120C
together with 3.7 parts of epichlorohydrin for 30 minutes.
7U parts of water are then added, followed by 32.3 parts sf epichlorohydrin, which is followed by stirring at 100 -120C for 1 h. Subsequently 1,182 parts of preheatedwater at about 95C are add ed, and the emuLsion formed is stirred under gentle reflux for about 1 h. This is followed by cooling down to about 40C and addition to the pasty emulsion of a solution of 1.2 parts of NaCl in 92 parts of water, producing a highly mobile, approximately 15% strength sizing agent formulation.
Le A 23 776 The following comparative exampLe, auxiliary 9 is now carried out using oLeic acid in place of stearic acid.
The tabulated test values show that in the case of auxiliary A the porositizing action is relatively low while sizing is good, while in the case of auxiliary B
no sizing but a moderate porositization action is present.
Example 3 This illustrates the higher activity of the poro-sitizing agents according to the invention compared withauxiliaries A and B:
The method used for preparing amide A is repeated, except that the stearic acid is replaced by oleic acid.
The basic amide, which has a melting point of about 64C, is used as in the case of auxiliary A, but in place of a total of 36 parts of epichlorohydrin 16 parts of formic acid are added. The result is a neutral porosi-tizing agent dispersion having a solids content of about 13%.
Example 4 Example 3 is repeated, except for the following points:
Pure oteic acid is replaced by soya oil acid;
triethylenetetramine is replaced by a technical tetramine bottom product of the approximate composition: less than 1% by weight of triamines, 52% by weight of tetramines, 30% by weight of pentamines, 13% by weight of hexamines and 4% by weight of other constituents; 16 parts of formic acid are replaced by 24 parts of acetic acid.
This gives an approximately 13% strength disper-sion of the porositizing agent. The table of the test values shows the particularly good action of the tetramine bottom product used for preparing the amide.
Example 5 Using the method for preparing amides A and E~, an amide is prepared from 5,100 parts of tall oil fatty acid Le A 23 77_ .7641 and 1,314 parts of tetramine bottom product of the approxi-mate composition specified in Example 4. The resulting amide has a melting point of around 41C and an acid number of 6.3. 202 parts of the amide are melted together with 29 parts of acetic acid at a temperature not above 80C. The salt formed has a melting point of around 63C. This salt can be added to the paper mixture in the vat as a powder which may have been stabilized by powdering with clay, silica or talc or be dissolved before-hand as such to give an aqueous auxiliary formulationhaving a solids content of about 15% by dispersing the optionally comminuted melt (150 parts) in 85 parts of warm water at 80C with thorough stirring and stirring until cold.
The 15% strength dispersion thus obtained can be used directly as a porositizing agent.
Example 6 Example 5 is repeated, except that tall oil fatty acid is replaced by Fisch oil fatty acid which contains about 60 - 70% of C22 fatty acids.
The table below features a comparison of Examples 1 - 6 in the following tests:
Sizing:
The sizing is assessed by means of the so-called ink flotation test in which a strip of paper finished with the agent to be tested is placed on the surface of a dish filled with standard ink in accordance with DIN 53 126 and the time which elapses until the ink penetrates through to the side of the emplaced paper facing the observer is measured. This test, if carried out in a standardized manner, provides a very good way of assessing different sizing agents~
Opacity:
The opacity is assessed by the method of DIN 53 146, which quotes the opacity in %, so that high % values correspond to high non-transparency.
Le A 23 776 ~7~ 5 The thickness of the paper in the comparison and the examples is 0.11 mm.
Porositization:
The porosity is assessed by the method of DIN 53120 and the permeability is determined in ml of air/min.
The thickness of the paper in the comparison and in the examples is 0.11 mm.
Change in volume:
The weight per unit volume is determined for a given thickness of paper of 0.11 mm from the weight/unit area and is expressed in kg/dm, i.e. the weight per unit volume is used as a measure of any change in volume for a given use of substance.
The porositizing agents according to the invention are tested illustratively on alum-free, chalk-containing paper:
5 9 of a mixture of 50 9 of spruce sulphite pulp and 25 9 of chalk are suspended in 200 ml of tap water. x% of the porositizing agent (solids based on pulp plus filler) are then stirred in. Water is then added without addition of a thickening agent to make the volume up to about 1 litre, and a sheet of paper is prepared on a sheet-former.
This sheet of paper is sucked off, pressed off and dried at 90 and 110C on a drying cylinder for 5 min. The sheet is cut into pieces for the tests, for example into 2 cm x 6 cm strips for the ink flotation test, which are then tested.
The following tabulated assessments were found.
The comparison is against the products of Examples 1 and 2 and as Example No. 0 a paper which has not been sized and not been treated with porositizing agents.
The assessments of ppacity and porosity were also carried out on papers prepared on an experimental paper-machine.
Le A 23 776 ~;~7~4L~5 Example No A B C D E F G
_ Product of Example No. 1 2 3 4 5 6 0 Sizing sec. 900 12 810 9 11 2 Opacity about %72 77 80 82 81 82 71 5 Porosity about ml/min 380 410 620 790 800768 300 Volume +15 +15 +35 +49 +51~50 + O
Amount used % 0.6 0.6 0.6 0.6 0.60.6 --Tabulation of the assessment of different poro-sitizing agent formulations.
The tabulated values show the superiority of thefatty acids which are non-crystalline at 30C and the adverse effect of the quaternization and the especially favourable effect of the amine mixture present n the tetramine bottom product.
Examp(e 7 (according to the invention) The method used for preparing dibasic amide A is used to prepare an amide from 5,500 parts of technical oleic acid and 1,500 parts of reactor base of the approxi-mate composition (in % by weight):17% of water, 7% of ethylenediamine, 0.2% of piperazine, 0.1% of tricyclic diamine, 0.1% of ethanolamine, 14% of triamine, 1% of aminoethylpiperazine, 19% of tetramine, 16% of pentamine, 7% of hexamine, 5~6% of heptamine, 9% of higher-boiling resinous constituents and 4% of salt and ash. The numbers have been rounded off and can fluctuate about the value by about + 10%.
The resulting amide has a melting point of around 45C, an ûH number of 128 and an acid number of 5Ø
200 parts of the amide are melted together with 35 parts of acetic acid while the temperature is not above 80C.
The salt formed has a melting point of around 63C. This salt can be added to the paper mixture in the vat as a pouder which may have been stabilized by powdering with clay, starch, silica or talc, or can be dissolved before-Le A 23 776 ~ ~64L~5 hand as such to give an aqueous auxiliary formulation containing about 15% of solids by dispersing the melt (80C) in 1,000 parts of warm water at 80C with thorough stirring and cooling down to 50C. A solution of 1.15 parts of sodium chloride in 100 parts of water is then added, which is followed by stirring with cooling down to 20 - 25C.
The test values lis~ed in the table clearly show the improvement in the porositizing action which is obtainable according to the invention.
Example 8 (according to the invention) Example 7 is repeated, except that oLeic acid is replaced by tall oil acid.
The table below shows Examples 1, 7 and 8 in com-parison in the following properties:Sizing:
The sizing is assessed by means of the so-ca~led ink flotation test in which a strip of paper finished with the agent to be tested is placed on the surface of a dish filled with standard ink in accordance with DIN 53 126 and the time which elapses until the ink penetrates through to the side of the emplaced paper facing the observer is measured. This test, if carried out in a standardized manner, provides a very good way of assessing different sizing agents.
Opacity:
The opacity is assessed by the method of DIN 53 146, which quotes the opacity in %, so that high % values correspond to high non-transparency.
The thickness of the paper in the comparison and the examples is 0.11 mm.
Porositization:
The porosity is assessed by the method of DIN 53 120 and the permeability is determined in ml of air/min.
The thickness of the paper in the comparison and in the examples is 0.11 mm.
Le A 23 776 ~i~76~5 Change in volume:
The weight per unit volume is determined for a given thickness of paper of 0.11 mm from the weight/unit area and is expressed in kg/dm, i.e. the weight per unit volume is used as a measure of any change in volume for a given use of substance.
The porositizing agents according to the invention are tested illustratively on alum-free, chalk-containing paper:
10 5 g of a mixture of 50 y of birch sulphate pulp and pine sulphate pulp (degree of beating 35C SR) are suspended in 200 ~l of tap water. x% of the porositizing agent (solids based on pulp plus filler) are then stirred in. ~ater is then added without addition of a thickening agent to make the volume up to about 1 litre, and a sheet of paper is prepared on a sheet-former (Rapid-K8then).
This sheet of paper is sucked off, pressed off and dried at 90C on a vacuum dryer for 5 min. The sheet is cut into pieces for the tests, for example into 2 cm x 6 cm strips for the ink flotation test, which are then tested.
The weight per unit area is about 100 g/m2.
The following tabulated assessments were found.
The comparison was against the products of Example 1 (auxiliary A), and Example O is paper which has not been sized and not been treated with porositizing agents.
The c,pacity and porosity were also assessed on papers prepared on an experimental paper-machine.
Example No A B C D
Product from Example No. 1 7 8 0 30 Sizing sec. 900 5 6 2 Opacity about ~ 83 88 88 83 Porosity about ml/min145 225218 140 Volume (relative)+2.9 +8.0 +7.1 +0 Amount used %0.7 0.7 0.7 0.7 Tabulation of the assessment of different porositizing agent formulations; the values Le A 23 776 ~27~4~5 shown are averages of 5 experiments in each case.
The tabulated values reveal the superiority of fatty acids which are non-crystalline at 30C and the considerable improving effect of the amine mixture referred to as a reactor base.
Example 4 A paper-machine is used to prepare a paper having a weight per unit area of about 100 9/m2 on the basis of a paper-stuff prepared from mixed waste paper using 0.075%
of a retention aid based on polyam;deamine.
If the paper-stuff has now added to it an amount of 0.3% of porositizing agent of Example 7 (relative to solids) ahead of the forward end of the machine, the volume of the paper leaving the machine in the dried state increases by 7.5%.
Le A 23 776
Claims (14)
1. In the making of paper from an aqueous pulp slurry, the improvement which comprises incorporating into such slurry an agent consisting essentially of a basic amide of a long chain fatty acid having a melting point below 30°C, whereby the resulting paper exhibits increased porosity.
2. Process according to Claim 1 wherein the basic amide is in aqueous formulation.
3. Process according to Claim 1 wherein the amide is preparable by reacting a long-chain fatty acid or fatty acid mix-ture which has a melting point below 30°C with a polyalkylene-polyamine to convert 50 - 100% of the primary amino groups.
4. Process according to Claim 1 wherein the amidation is carried out with a polyethylenepolyamine having more than three amino groups in the molecule.
5. Process according to Claim 1 wherein the amidation is carried out with triethylenetetramine, tetraethylenepentamine or pentaethylenehexamine.
6. Process according to Claim 5 wherein said triethyl-netetramine, tetraethylenepentamine or pentaethylenehexamine is in the form of a technical fraction.
7. Process according to Claim 1 wherein the amidation is carried out with an amine mixture obtained as tetramine bottom product in industrial synthesis of a dialkylenetriamines from a dihalogenoalkane and ammonia, after distilling off the triamine fraction.
8. Process according to Claim 7 wherein said dialkyl-enetriamine is dipropylenetriamine.
9. Process according to Claim 7 wherein said dialkylene-tramine is diethylenetramine.
10. Process according to Claim 1 wherein the amidation is carried out with an amine mixture obtained in industrial prepar-ation of diethylenetriamine and ethylenediamine from 1,2-dichloro-ethane and ammonia.
11. Process according to Claim 3 wherein the fatty acid or fatty acid mixture comprises oleic acid.
12. Process according to Claim 1 wherein the basic amide is dispersed or dissolved in an aqueous medium in the form of an acetate or a formate.
13. Paper or paperlike material prepared according to the process according to Claim 1.
14. Board prepared according to the process according to Claim 1.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP3515479.9 | 1985-04-30 | ||
| DE19853515479 DE3515479A1 (en) | 1985-04-30 | 1985-04-30 | Process for making paper or paper-like materials |
| DE19853527976 DE3527976A1 (en) | 1985-08-03 | 1985-08-03 | Process for producing paper or paper-like materials |
| DEP3527976.1 | 1985-08-03 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1276415C true CA1276415C (en) | 1990-11-20 |
Family
ID=25831833
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000507692A Expired - Lifetime CA1276415C (en) | 1985-04-30 | 1986-04-28 | Process for preparing paper or paperlike materials |
Country Status (5)
| Country | Link |
|---|---|
| EP (1) | EP0201761B1 (en) |
| AT (1) | ATE43662T1 (en) |
| CA (1) | CA1276415C (en) |
| DE (1) | DE3663701D1 (en) |
| FI (1) | FI84196C (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5101015A (en) * | 1989-04-10 | 1992-03-31 | Abbott Laboratories | Reagents for an amphetamine-class fluorescence polarization immunoassay |
| JP3011788B2 (en) * | 1991-05-16 | 2000-02-21 | 日石三菱株式会社 | Papermaking sizing agent |
| US5399241A (en) * | 1993-10-01 | 1995-03-21 | James River Corporation Of Virginia | Soft strong towel and tissue paper |
| US10135737B2 (en) | 2014-09-30 | 2018-11-20 | Nicira, Inc. | Distributed load balancing systems |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BE446575A (en) * | 1939-05-27 | |||
| GB711404A (en) * | 1951-04-18 | 1954-06-30 | American Cyanamid Co | Improvements relating to the production of sized paper |
| GB1030396A (en) * | 1963-04-26 | 1966-05-25 | I C I Organics Inc | Bis-acyl-dialkylene triamines |
| DE2819039A1 (en) * | 1978-04-29 | 1979-11-08 | Bayer Ag | SIZING AGENT FOR PAPER |
| NO792679L (en) * | 1978-09-01 | 1980-03-04 | Bayer Ag | LIM FOR PAPER. |
| DE3208139A1 (en) * | 1982-03-06 | 1983-09-08 | Bayer Ag, 5090 Leverkusen | SIZE |
-
1986
- 1986-04-21 DE DE8686105464T patent/DE3663701D1/en not_active Expired
- 1986-04-21 EP EP86105464A patent/EP0201761B1/en not_active Expired
- 1986-04-21 AT AT86105464T patent/ATE43662T1/en not_active IP Right Cessation
- 1986-04-28 CA CA000507692A patent/CA1276415C/en not_active Expired - Lifetime
- 1986-04-28 FI FI861780A patent/FI84196C/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| FI84196C (en) | 1991-10-25 |
| ATE43662T1 (en) | 1989-06-15 |
| FI84196B (en) | 1991-07-15 |
| FI861780A0 (en) | 1986-04-28 |
| EP0201761A1 (en) | 1986-11-20 |
| DE3663701D1 (en) | 1989-07-06 |
| FI861780A (en) | 1986-10-31 |
| EP0201761B1 (en) | 1989-05-31 |
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