DE19525365A1 - Paper supplies with recurring succinyl units - Google Patents

Abstract

The invention concerns an auxiliary producing-paper aid containing polymers with recurring succinyl units.

Description

The invention relates to paper auxiliaries based on polymers that contain recurring succinyl units as building blocks, and a process for the preparation of the auxiliaries by using maleic anhydride as Raw material.

A number of tools are needed in the pulp and paper industry which are used as additives in the manufacturing process and also the Properties of the product, d. H. of paper, cardboard and cardboard products influence. For the purposes of the invention, aids are understood to mean: as a grinding aid, as a complexing agent in the bleaching of cellulose, Wood pulp or waste paper, in the deinking process as a complexing agent or Dispersant for dispersing the detached ink components continue to be used in cleaning products for the anionic products Sieve and felt cleaning of the paper machine.

Polyacrylic acid and its derivatives are due to the good availability and low price level widely used raw materials of the paper industry. Problematic however, is poor biodegradability. As a grinding aid usually Na salts of carboxymethyl cellulose, galactomannans or poly- Acrylic acid derivatives used. The disadvantage of these products is often that Decrease in the rate of drainage of the fabric when the leaves form. At the material is mechanically opened during the grinding, with fibrils of the Cell wall can be detached. As a result, new fiber Fiber bonds are knotted resulting in improved strength. With however, increasing grinding time is observed after an initial one Increase again a drastic decrease in tear work.

The object of the invention is therefore to provide grinding aids that in addition a reduction in grinding energy also an increase in dry strength and tear resistance.

Furthermore, improved agents for the preparation or production of aqueous Pigment and filler dispersions in the production of graphic papers and special papers as well as cardboard, aids in deinking processes and in the pulp and pulp bleaching are made available.

The invention relates to the use of recurring polymers Contain succinyl units as aids in papermaking. Prefers contains the remedy

• A) 5 to 90 wt .-%, based on the agent, of a polymer with at least one recurring structural unit of the formula in which
  R¹ to R² independently of one another represent H, a hydrocarbon radical having 1 to 60 C atoms, which can be substituted by hydroxyl, carboxy or amino groups and / or interrupted by ether, ester, amide or urethane groups,
  M⁺ denotes a counter ion from the group of the alkali metals, NH₄⁺ or a primary, secondary or tertiary ammonium radical or H containing C₁-C₄-hydroxyalkyl or alkyl groups (so that a COOH function results),
• B) 0 to 10 wt .-%, based on the agent, of an external anionic or cationic emulsifier, preferably from the group of fatty acids, fatty alcohol ethoxylates, fatty alcohol sulfates, phosphates and fatty alkyl ammonium salts
  and
• C) 10 to 95 wt .-% water, based on the agent.

In a preferred embodiment, the proportion of the residues A and / or B is 0 to 70 mol%, the proportion of the radicals C and / or D 99.9 to 30 mol%, the proportion the radicals E and / or F 0 to 10 mol% and the proportion of the radical G 0 to 10 mol%, based on the sum of units A to G.

Iminodissucinate units, preferably at least one of the following structures, can also be contained in the polymer:

where R is -OH, O⁻NH₄⁺ or -NR¹R² and where R¹ and R² independently of one another one of the indicated under R¹ and R² Have meanings.  

The iminodisuccinate units can be randomly distributed or preferred in the polymer available as end group. Based on the sum of all recurring units the iminodisuccinate unit is generally at least 0.1 mol%. The molar ratio of the iminodisuccinate units (H) to the polymer to the sum of all monomer units incorporated in the polymer is preferred example, 0.1 mol% to 99 mol%, preferably 1 mol% to 50 mol%, particularly preferably 2 mol% to 25 mol%.

The agents according to the invention are preferably prepared by

• 1. in a first stage maleic anhydride, optionally a mixture from 80 to 100 mol% maleic anhydride and 0 to 20 mol% Succinic anhydride, with ammonia optionally in the presence of a Solvent, condensed,
• 2. the product of the first stage 1 with at least one amine of the formula I R¹ and / or R² - NH₂ (I) in which
  R¹ and R² have the meaning given above, and
• 3. Water or an aqueous solution, an emulsifier and / or a base added

or by

• 1. maleic anhydride, optionally a mixture of 80 to 100 mol% Maleic anhydride and 0 to 20 mol% succinic anhydride, with Ammonia, optionally condensed in a solvent,
• 2. the product of the 1st stage in the presence of a solvent with at least one amine I of the formula R¹ NH₂ and / or R² NH₂ (I) in which
  R¹ and R² have the meaning given above,
• 3. the product mixture is isolated by adding a precipitant and
• 4. the solvent freed from the polymer in water or an aqueous Solution, an emulsifier and / or a base, dispersed.

In the event that the radicals R¹ and / or R² an ester group or Urethane group is preferred

• 1. in a first stage maleic anhydride, optionally a mixture from 80 to 100 mol% of MA and 0 to 20 mol% of succinic anhydride, condensed with ammonia,
• 2. the product of the first stage with an amine or amine mixture, the one Hydroxyalkylamine contains, implemented,
• 3. the reaction product from the second stage with a (di) carboxylic acid or their derivative or a monoisocyanate or a polyisocyanate, the latter having NCO groups of different reactivity, implemented, and
• 4. Water or an aqueous solution of an emulsifier and / or a base added.

Examples of radicals R¹ and R² which may be mentioned are: octadecyl, oleyl, butyl, Hexyl, cyclohexyl, octyl, octenyl, decyl, undecyl, undecenyl, dodecyl, Tetradecyl, hexadecyl, hydroxyethyl, hydroxypropyl, stearoyloxyethyl, Stearylcarbamoyloxy-ethyl; Residues that differ from amino acids such as glycine, alanine, β-alanine, valine, leucine, isoleucine, methionine, N-methylglycine, tyrosine, serine, Hydroxyproline, tryptophan, arginine, lysine, histidine, asparagine, aspartic acid, Derive glutamine, glutamic acid by abstraction of the amino group, as well Remains of the formulas

in which independently
R⁵ and R⁶ are C₁ to C₃₀ alkyl,
R⁷ to R⁹ is C₁ to C₁₈ alkyl, -OSi (R¹⁰) ₆ or -O-Si (R¹¹) (R¹⁰) ₂,
where R¹⁰ is C₁-C₄ alkyl and
R¹¹ represents C₁-C₁₈ alkyl,
M⁺ has the meaning given above.

Suitable (di) carboxylic acid (derivatives) are, for example, succinic anhydride, Maleic anhydride, phthalic anhydride, butyrolactone, acetic anhydride, Tetrahydro-phthalic anhydride, methacrylic acid chloride, methacrylic anhydride, Acrylic acid chloride.  

Suitable (poly) isocyanates are, for example, methyl isocyanate, ethyl isocyanate, Butyl isocyanate, hexyl isocyanate, dodecyl isocyanate, stearyl isocyanate, dehydro abietyl isocyanate, cyclohexyl isocyanate, phenyl isocyanate, 4-isocyanato-4-methyl-1- isocyanatomethyl-cyclohexane, 1- (4-isocyanatobenzoyl) oxy-2,2-dimethyl-2-isocya natoethan.

In the event that the radicals R¹ and / or R² one or more ether groups or contain one or more amide groups, a corresponding one is used Amine (I) containing ether groups or amide groups for the reaction with the polysuccinimide. Suitable amine-containing amines are, for example monofunctional polyethers with ethylene oxide and / or propylene oxide units a primary or secondary amino end group which are commercially available and prepared by amination of the corresponding monofunctional polyethers can be. The amines containing amide groups are, for example, by partial condensation of polyamines with monocarboxylic acids in the Easily accessible manner known to those skilled in the art.

Polysuccinimide is a suitable precursor for the reaction with the amines I. or imide groups, amide or carboxyl groups containing condensates Maleic acid and ammonia, condensates from aspartic acid, condensates from Maleic acid halamide, condensates from maleic acid ammonium, bisammonium Salts and maleic acid halamide ammonium salts and co-condensates from them mentioned raw materials with asparagine, glutamine, glutamic acid or others Amino acids. Suitable raw materials are also the derivatives of the above Polycondensates based on aspartic acid, the carboxyl groups in contain neutralized form, especially as a neutralizing agent Ammonia and amines are mentioned.

The production and use of polyaspartic acid (PAS) and their Derivatives are the subject of numerous publications and patents.

So the production by thermal polymerization of aspartic acid take place (J. Org. Chem. 26, 1084 (1961)). According to FR 70 24831 and P. Neri, Journal of Medicinai Chemistry 16, 893 (1973) may contain aspartic acid in the presence be dehydrated by phosphoric acid in vacuo at 170-200 ° C, whereby Molar masses up to 10⁵ g / mol can be achieved. Instead of phosphoric acid  are also acidic ion exchangers and the use of diphenyl ether have been recommended (US 4,363,797, L'Oreal).

Other processes are based on maleic anhydride and ammonia. The U.S. 4th 839 461 (= EP-A 0 256 366) describes the preparation of polyaspartic acid from maleic anhydride, water and ammonia. Maleic anhydride is used in aqueous medium with the addition of concentrated ammonia solution in the Monoammonium salt converted, which is condensed to the polysuccimide. According to DE-A 43 05 368, the polyaspartic acid is prepared by Maleic acid monoammonium salt, preferably at 150 to 180 ° C in one Reactor with a residence time of 5 to 300 minutes of a thermal, optionally subjected to continuous polymerization and the obtained Polysuccinimide by hydrolysis to polyaspartic acid or in the presence of Bases converted into a salt of it. As bases are alkali or Carbonates or ammonia or amines are particularly suitable.

The condensation can also be carried out in the presence of solubilizers be described in DE-A 43 10 503. DE-A 43 06 412 describes a process that is used as a continuous or batch process in the presence of Solvents can be carried out. Polar solvents are special such as pyrrolidone, N-methylpyrrolidone, DMF or diethylene glycol, ethylene glycol, Caprolactam suitable.

The reaction of polysuccinimide with amines is known from EP-A 0 519 119, the US-A 3 846 380, US-A 4 363 797 and US-A 3 927 204. A general working procedure is given in the literature: P.Neri, G.Antoni, Macromolecular Syntheses 8, 25.

That as a starting compound for the preparation of the invention used polycondensate is advantageously by Reaction of maleic anhydride, optionally mixtures of 80 to 100 mol% maleic anhydride and 0 to 20 mol% succinic anhydride as Chain terminators and ammonia are obtained with removal of the water of reaction, e.g. B. among those in US-A 4,839,461, DE-A 43 06 412, DE-A 43 10 503 or the conditions described in DE-A 43 05 368. When condensation occurs usually polycondensates made up of different monomer building blocks are built up. The polycondensate predominantly contains succinimide units that  after dissolving the condensate in water in the presence of bases such as Alkali hydroxide or carbonate, ammonia or amines have the following structure elements contain: succinimide units, aspartic acid units, asparagine units, aspartic acid units that act as alkali or ammonium salt lie, and optionally malic acid, maleic acid and fumaric acid units and their salts.

If polymers with substituted amide groups are to be obtained, that is Structural units of the formulas (A) to (B) contain the predominant Polycondensates containing succinimide units are reacted with the amines I. and then in water with the addition of bases, preferably Alkali hydroxides, ammonia or amines, optionally with the addition of external ones Emulsifiers dissolved or emulsified. In the case of short-chain alkyl residues, the Rule solutions are obtained while increasing the chain length of the alkyl radical the substituents R¹ to R² emulsions are obtained.

Preferred polymers contain 0 to 50 mol% of the units A / B, 99.9 to 50 mol% of the units C / D and 0 to 10 mol% of the units E / F and 0 to 5 mol% of units G.

Preferred polymers containing polyaspartic acid units have a medium one Molecular weight (weight average) between approx. 500 and 50,000 g / mol, preferably 500 up to 20,000 g / mol, particularly preferably 500 to 10,000 g / mol. The determination of Molecular weights refer to those by gel permeation chromatography with polyacrylic acid as standard, values obtained (calculated inclusive of the substituents). The polyaspartic acid condensates themselves preferably have Molar masses in the range from 200 to 10,000 g / mol, in particular from 200 to 6000 g / mol.

In a particularly preferred embodiment, these polymers have 0 to 50 mol% of units A and / or B, 99.9 to 50 mol% of units C and / or D, 0 to 10 mol% of the units E and / or F and 0 to 5 mol% of the Units G based on all recurring units.

Examples of amines I are: monofunctional polyethers with a primary or secondary amino group such as α-methyl-ω-amino-polyoxyethylene,  α-methyl-ω-amino-polyoxypropylene, N, N-dimethylethylene diamine, butylamine, Stearylamine, tallow fatty amine, oleylamine, undecylamine, dodecylamine, octylamine, Hexylamine, eicosanylamine, hexadecylamine, 2-ethylhexylamine, morpholine, Ethanolamine, diethanolamine, bis-2-hydroxypropylamine, bis-3-hydroxypropyl amine, 2- or 3-hydroxypropylamine, ethoxy-ethylamine, ethoxy-ethoxy-ethylamine, Butoxy-ethoxy-ethoxy-ethylamine, 2-methoxy-ethyl-amine, tetrahydrofurfurylamine, 5-aminopentanol, benzylamine, 4-dimethylaminocyclohexylamine, taurine Na salt, Glycine methyl ester, N-methylaminoethyl sulfonic acid Na salt, sodium salts of natural amino acids or their racemates, amino acids,

Suitable anionic emulsifier components B) are, for example, oleic acid, Ricinoleic acid, stearic acid, fatty acid partial esters of polyalcohols such as tri methylolpropane, glycerol or pentaerythritol or their acylation and Alkoxylation products with ethylene oxide and / or propylene oxide, e.g. B. Glycerol monostearate or glycerol monooleate and their reaction product with Maleic anhydride, succinic anhydride, phthalic anhydride or tetra hydrophthalic anhydride, reaction products of bis-hydroxymethyl-tricyclo decane and maleic anhydride or succinic anhydride and their derivatives, preferably in the form of their alkali and ammonium salts.

Suitable bases are alkali carbonate, alkali hydroxides, NH₃ or amines with C₁₄- Hydroxyalkyl or C₁-C₄ alkyl groups. These bases serve for neutralization the carboxyl groups present in the polymer.

Suitable residues M⁺ are, for example, hydroxyethylammonium, dihydroxy ethylammonium, trishydroxyethylammonium, triethylammonium, ammonium, Butylammonium, sodium, potassium, lithium.

The preparation of the polymers to be used according to the invention is carried out preferably in a solvent such as dimethylformamide, dimethyl sulfoxide, Caprolactam, ethylene glycol, diethylene glycol, propylene glycol, N-methylcaprolactam, N-methylpyrrolidone or mixtures thereof. The reaction mixture can also preferably contain water. The implementation is preferably carried out in a temperature range from 20 to 180 ° C. the reaction times are preferably between 2 to 72 hours. The Product can be removed by distillation or by distillation Precipitation of the product in a non-solvent such as acetone, methanol, ethanol, Water, isopropanol can be isolated. The implementation under is also preferred solvent-free conditions, provided the polymer has a share of contains unsubstituted amide groups.  

It is also advantageous to use only a portion of the carboxyl groups that are present during hydrolysis of the succinimide units form in the neutralized form convict. It is usually sufficient to add 5 to 50% of the COOH To convert groups into the neutralized form.

For the application according to the invention, the polymer, preferably a poly aspartic acid derivative into a solution or a stable aqueous dispersion leads. The polymer is dependent on the amine used or Amine mixture I soluble in water or self-emulsifying or with the addition of external emulsifiers dispersible in water. Especially with polyaspartamide Derivatives with a proportion of structural elements A and B of more than 50 mol %, based on all structural elements, is a dispersion using External emulsifiers are only required if long-chain amines I are used hydrophobic properties are used. For this, the polymer is in a solution as an emulsifier, preferably an in situ salt formed from a contains long-chain fatty acid and an amine, preferably with heating, dispersed. The preferred temperature range for emulsification is the range between 40 and 100 ° C. The amine used for this can also be from the group of the amines I originate or with the for the preparation of the structural units (A) and / or (B) amine I used are identical. Particularly preferred amines are amino acids, alkanolamines and ammonia, as feedstocks that are used for Neutralization of the COOH groups are suitable.

The solution of the polymer can also be directly, i.e. H. without intermediate insulation, too an aqueous dispersion. In a preferred out An aqueous solution, which is an emulsifier which is formed in situ, is the embodiment Salt from a long-chain fatty acid, preferably oleic acid, and an amine preferably hydroxyethylamine, bishydroxyethylamine or trishydroxyethylamine contains, at a temperature between 70 and 150 ° C to the reaction mixture Stir metered in, the desired emulsion forms. The share of Solvent that was used for the implementation should have a share of Do not exceed 30% by weight based on the solution. In one too preferred embodiment, the amine already described above is preferred a hydroxyalkylamine, added to the solution of the polyaspartic acid amide and then water at a temperature between 70 and 150 ° C with stirring metered into the reaction mixture, the desired emulsion being formed.  

Solutions or a finely divided dispersion of the polymer are obtained, preferably a polyaspartic acid derivative, in water. The particle size determined as mean by laser correlation spectroscopy (LKS) or by Ultracentrifuge of the dispersed polymer is less than 1000 nm, preferably less than 700 nm, particularly preferably less than 400 nm (each Values from LKS).

The application technology effects can be greater with dispersions mean particle diameter adapted to the intended use be that they are in dispersions with a particle size below 400 nm converts. For this purpose, the pre-emulsion already obtained can be used at high Shear traps in known dispersing machines such as in a jet disperser or mixers with the rotor-stator principle. The disperser duration can be between a few minutes and up to 4 hours. The Disper Alloy is preferably in a temperature range between 20 and 90 ° C. carried out.

The polymers according to the invention, in particular polyaspartic acid derivatives hydrophobic substituents, form solutions or dispersions in water. Concentrations of up to 70% by weight are preferred for use, preferably up to 50% by weight, particularly preferably up to 40% by weight, which in Water finely divided dispersions with medium particle diameters (ultracentri joint) <500 nm. The agents can be used in particular with solids contents above 30% by weight in the form of pastes, but which can be mixed with water let dilute slightly. The agents with a solids content below 30% by weight is in the form of emulsions or microemulsions. The pH The value of the emulsions or pastes is between 4.5 and 12, preferably in the pH Range between 6 and 10.

Products that do not contain long-chain residues form solutions in water.  

Applications

The invention relates in particular to the use of the agents mentioned for the treatment of cellulosic material. Cellulosic materials in According to the invention, the fibrous materials used in the paper industry are like Wood pulp, TMP, CTMP, sulfite and sulfate pulp from needle and Hardwoods and waste paper and scrap from paper production as well as the Products paper, cardboard and cardboard.

The invention relates in particular to the use of the invention appropriate agents as grinding aids in the manufacture and preparation of Fibers for papermaking.

The advantage of the grinding aids according to the invention is the good biodegradation availability. In addition, when using the agents according to the invention Savings in grinding energy of up to 30% possible. The increase in the degree of grinding allows the papermaker to increase the strength of the paper or at same strength economically cheaper pulp like secondary fibers / short fibers or more fillers.

The amounts used are advantageously 0.001 to 5.0%, preferably 0.01- 3%, particularly preferably 0.01 to 1%, based on absolutely dry (atro) Fiber. The grinding units used are those customary in the prior art Devices used like Jokro-Mill, Cone Refiner etc. The tools are used usually added to the substance in dissolved or emulsified form. The The temperature during grinding is usually between 10 and 70 ° C, preferably 20 to 60 ° C. The pH in the stock suspension is usually 5 to 8. The grinding is measured by measuring the Schopper-Riegler values.

The invention also relates to the use of the agents according to the invention for Preparation or production of aqueous pigment and filler dispersions in the production of graphic papers and special papers (e.g. Decorative papers) and cardboard. Such dispersants are preferably suitable for the dispersion of kaolin, china clay, various forms of CaCO₃, Talc, zeolites, bentonites, colloidal silicas, titanium dioxide, silicates, Iron oxides, carbon blacks, organic color pigments and their mixtures. Compared to the polyaspartic acids known from WO 94/19 409  advantages with regard to the dispersion of the fillers and the opacity of the papers made from it. The opacity of the coating colors for graphic Papers are improved due to the surprisingly good dispersing effect.

The amounts of the agents according to the invention are generally from 0.01 to 0.5% preferably 0.1 to 0.44% based on the filler or the pigment. The Viscosity of the pigment or filler dispersions is increased by the addition of agents according to the invention drastically reduced. The dispersions are also at Solids contents pumpable up to 70% by weight and stable over a longer period.

It is also possible to improve the filler by reloading the filler. To achieve retention in combination with cellulose fibers by adding cationic polymers were previously cationized. This is particularly the case with CaCO₃ a great advantage that is generally poorly paid.

The invention also relates to the use of the agents according to the invention as Complexing agents in pulp and pulp bleaching and as auxiliaries, especially as a complexing agent in deinking processes. To prevent a premature decomposition of peroxides in the bleaching of wood and cellulose complexing agents are usually added. Beyond that Metal ions containing the lignin residues modified by the cooking process color-intensive complexes result in being trapped. State of the art Nitrilotriacetic acid (NTA), ethylenediamine tetraacetic acid (EDTA), Dipropylenetriamine-pentaacetic acid (DPTA) and diethylenetriaminepentaacetic acid (DTPA). Without complexing agents, a much higher use is required Oxidizing agents required.

Complexing agents are also important components of the deinking process Aid formulations. Your job is to eliminate more value Metal ions, support for ink separation, prevention of Back adsorption of detached ink particles by stabilizing the particles, avoiding the precipitation of insoluble salts even with substoichio metric amounts of complexing agents. In addition, due to the increased use of chalk as a filler for paper high calcium Ion concentrations, which generally have a negative effect on the complexing effect of the known polyanions. Those to be used according to the invention Polymers have good complexing properties in the neutral and alkaline pH range  properties, are inexpensive and prevent deposits of Ca salts in the Paper machine cycle. The quantities used for this application are in the Range between 0.01 and 2.0%, advantageously between 0.05 and 1.0% based on fiber.

Another advantage of the complexing agents according to the invention is their dispersion effect of harmful resin, so that dirt spots in the paper are reduced can be.

The invention also relates to the use of the agents according to the invention as a component in detergents and cleaning agents for the paper industry, especially the removal of resin deposits on rollers and Screen cleaning.

Manufacturing examples Polymer 1

50 g of polysuccinimide prepared according to EP-A 612 784, Example 2 with a average molecular weight of 3000 g / mol are dissolved in 200 g of dimethylformamide and heated to 140 ° C with 43 g of stearylamine. The approach is at this Temperature stirred for 6 hours. Then it is cooled to room temperature. The Reaction mixture is poured into excess (1000 ml) methanol, whereby the reaction product is fine. The product is over a nutsche suction filtered and washed with methanol and dried. You get a bright one Powder.

typical IR spectrum [cm ^-1 ]

3600-3150 (br, max. At 3370),
2940, 2860 (CH)
1720 (sh, Imid)
1670, 1550 (amide I and II)
1475, 1390 (m),
several bands <1300.

Preparation of the dispersion

20 grams of the above product are placed in a heated to 70-75 ° C Given solution consisting of 2 grams of oleic acid, 0.86 grams of monoethanolamine and There is 91.4 grams of water. The dispersion first becomes 30 at 70 to 75 ° C Minutes homogenized. The dispersion obtained can, if it is still coarse Contains particles, adjusted in their particle size by a jet disperser will. The emulsion has a particle size even without this dispersion technique <700 nm. The dispersion is adjusted to a solids content of 20% by weight.

Polymer 2

146 g of polysuccinimide prepared according to EP-A 612 784, Example 2 with a average molecular weight of 3000 g / mol are suspended in 90 g of NMP and with 201.7 g of stearylamine heated to 140 ° C. The batch becomes 6 at this temperature Hours stirred. The reaction mixture obtained is processed directly.  

Preparation of the dispersion

50 grams of the above product (equivalent to 39.7 grams of active ingredient) are presented at 110 ° C. At this temperature a solution of 7.74 Grams of oleic acid, 1.67 grams of monoethanolamine added dropwise in 186 grams of water. After adding the entire amount of water, the dispersion is initially at Homogenized 80-90 ° C within 180 minutes. The dispersion obtained can, if it still contains coarse particles, through a jet disperser in its Particle size can be adjusted. The emulsion also has without this Dispersion technology a particle size <700 nm. The dispersion is on a Fixed content of 20 wt .-% set.

Polymer 3 Production of poly (aspartic acid) Na salt

245 g of maleic anhydride in 89 g of water are placed in an autoclave and heated to 60 ° C. Now 44.5 g of NH₃ are pumped in liquid. It will then heated to 200 ° C within 30 minutes and at 30 minutes this temperature stirred. After cooling to 60 ° C, 167 g (1.25 mol) 30% NaOH added. After cooling to room temperature, one obtains a red solution. The solution is used for complete conversion into the Na salt 60 ° C with a further 140 g (1.05 mol) of 30% NaOH solution. That after the poly-aspartic acid sodium salt obtained by spray drying has one Aspartic acid content of 72% (HPLC after total hydrolysis).

Polymer 4 Production of poly (aspartic acid) Na salt

245 g of maleic anhydride in 72 g of water are placed in an autoclave and heated to 80 ° C. Now 63.5 g of NH₃ are pumped in liquid. It will then heated to 170 ° C within 30 minutes and at 30 minutes this temperature stirred. After cooling, the solution remains up to approx. 60 ° C liquid, but solidifies on further cooling to room temperature. Therefore a further 100 g of water are added at 80 ° C. The obtained at room temperature  Solution of poly (succinimide-co-aspartic acid) by adding 30% NaOH converted into the sodium salt.

Instructions for the preparation of polymers 5 and 6

The following examples were carried out in a reactor system which from a jet mixer of the type smooth jet nozzle and a subsequent one Tube reactor or multi-phase spiral tube reactor existed. The thermal Polymerization was optionally ended in a downstream, continuously operated, self-cleaning and equipped with hollow shafts Constant twist screw machine. In the examples, molten malein acid anhydride using a smooth jet nozzle together with aqueous ammonia solution injected and quickly into the tubular reactor or multiphase spiral tube reactor mixed into it.

Polymer 5

It was melted maleic anhydride at 100 ° C through a smooth jet mixed with 7 ° C cold 45 wt .-% aqueous ammonia solution and in the Multi-phase spiral tube reactor dosed. An indwelling tube led from Multi-phase spiral tube reactor to a downstream stirred tank in which 20 kg of water were submitted. The maleic anhydride melt was with a mass flow of 29.8 kg / h at 46 bar through the smooth jet nozzle in the Reaction space pressed. The aqueous ammonia solution was at 30 bar 14.65 kg / h metered into the reaction space. The molar ratio of Maleic anhydride to ammonia was 1: 1.7. The temperature in Reaction space was 174-187 ° C. When relaxing behind the valve it happened due to the evaporation of water only to a temperature decrease about 167 ° C. The hot mixture was heated to 60.degree Feed boiler passed and 45 wt .-% sodium hydroxide solution was metered in the pH was kept at about 10.3 by regulation. The hydrolysis was until the residual content of the hydrolyzable nitrogen is less than 5% of theory was. An orange-red aqueous polyaspartic acid was obtained. Copolymer sodium salt solution. The isolated solid had a GPC measurement average molecular weight Mw of 1300 g / mol. The product showed very good Heavy metal masking behavior.  

Polymer 6

It was melted maleic anhydride at 100 ° C through a smooth jet mixed with 7 ° C cold 40 wt .-% aqueous ammonia solution and in the Multi-phase spiral tube reactor dosed. An indwelling tube led from Multi-phase spiral tube reactor to a downstream stirred tank in which 20 kg of water were submitted. The maleic anhydride melt was with a mass flow of 18.7 kg / h at 40 bar through the smooth jet nozzle in the Reaction space pressed. The aqueous ammonia solution was at 25 bar 19.5 kg / h metered into the reaction space. The molar ratio of Maleic anhydride to ammonia was 1: 2.4. The temperature in Reaction space was 163-172 ° C. When relaxing behind the valve it happened due to the evaporation of water only to a temperature decrease about 154 ° C. The hot mixture was heated to 60.degree Feed boiler passed and 45 wt .-% sodium hydroxide solution was metered in the pH was kept at about 10.3 by regulation. The hydrolysis was until the residual content of the hydrolyzable nitrogen is less than 5% of theory was. An orange-red aqueous polyaspartic acid was obtained. Copolymer sodium salt solution. The isolated solid had a GPC measurement average molecular weight Mw of 850 g / mol. The product showed very good Heavy metal masking behavior.  

Application example example 1 Testing of poly-aspartic acid sodium salt as grinding aid

16 g of dry spruce sulfite pulp (bleached) was made up with distilled water Replenished 267 ml. The pulp is swollen at room temperature for 18 hours. Polymer 3 (charge density = 5.266 mmol / g, titration with Poly-DADMAC [1g / l]) added. The mixture is then poured into a Mill convicted. The grinding time was 15 or 40 minutes at one speed of 150 revolutions per minute. Then the material so ground equalized for 2 minutes at 3000 revolutions per minute in the disintegrator. Out of it were on a Rapid-Köthen sheet former paper sheets with a surface area weight of 80 g / m².

The test results are summarized in the following table:

It can be seen that even a small addition of 0.1% is a considerable one Increasing the degree of grinding can be achieved.  

Example 2 Regulation for determining the calcium carbonate dispersing capacity (CCDK)

To determine the CCDK value, 1.5 g of the substance to be examined are used dissolved in 90 ml of distilled water and with hydrochloric acid or sodium hydroxide solution neutralized. The solution is thermostatted to 25.0 ° C and with 10.00 mL a sodium carbonate solution with a mass fraction w (Na₂CO₃) = 0.10. The pH of the solution is increased by adding 1 N hydrochloric acid or 1 N sodium hydroxide solution set to 11. During the titration, the pH is adjusted to mean pH stat. constant held.

With an addition rate of 0.5 mL / min the measuring solution becomes 0.1 molar Calcium acetate standard solution added. The extent of the turbidity that arises as a loss of light transmission using an optical fiber photometer at λ = 650 nm measured and recorded with an X / t recorder whose paper feed Should be 2 cm / min. The measurement of the titration is from 100% Transmission carried out up to approx. 30%.

The end point of the titration is linearized through the intersection of the Extension of the course before and after the onset of turbidity shown. The volume of calcium acetate consumed is determined solution to the end point.

The calculated mass of the result up to the end point is used as the CCDK value Calcium carbonates per gram of co-builder used.  

Table II

Example 3 Determination of heavy metal masking using the example of H₂O₂ stabilization

4 mL copper sulfate solution (100 mg / L) and 40 mg of active ingredient are introduced, then made up to 200 mL. Then in Water bath heated to 70 ° C and with 0.8 g of 35% hydrogen peroxide solution transferred. After a minute, 30 minutes, 1, 3, 5, 10 and 22 hours will be 20 mL aliquot titrated iodometrically.

One can clearly see the excellent complexing effect of the polymers Examples 5 and 6: No decrease in the H₂O₂ content is observed.

Claims (10)

1. A process for paper manufacture in the presence of a polymer, characterized in that the polymer contains recurring succinyl units. 2. The method according to claim 1, characterized in that the agent contains

• A) 5 to 90 wt .-%, based on the agent, of a polymer with at least one structural unit of the formula in which
  R¹ to R² independently of one another represent H, a hydrocarbon radical having 1 to 60 C atoms, which can be substituted by hydroxyl, carbonyl or amino groups and / or interrupted by ether, ester, amide or urethane groups,
  M⁺ is a counter ion from the group of alkali metals, NH₄⁺ or a primary, secondary or tertiary ammonium radical or H containing C1-C4-hydroxyalkyl or alkyl groups, and
• B) 0 to 10 wt .-%, based on the agent, of an external anionic or cationic emulsifier, preferably from the group of fatty acids, fatty alcohol ethoxylates, fatty alcohol sulfates, phosphates and fatty alkyl ammonium salts and
• C) 10 to 95 wt .-%, based on the agent, water using conventional additives.

3. The method according to at least one of the preceding claims, characterized in that the polymer additionally iminodisuccinate Contains units. 4. The method according to at least one of the preceding claims, characterized in that the polymer by condensation of Maleic anhydride and ammonia and optionally further order Settlement was obtained with an amine. 5. The method according to at least one of the preceding claims, characterized in that the polymer as an aqueous solution or Dispersion is used. 6. The method according to at least one of the preceding claims, characterized characterized in that the polymer is in the form of particles with a particle size of substantially less than 1000 nm is used. 7. The method according to at least one of the preceding claims, characterized characterized in that the polymer as an aid in the grinding of cellulosic material to reduce the necessary grinding energy and increasing the strength of the paper obtained. 8. The method according to claim 1, characterized in that the polymer for dispersing aqueous pigment and / or filler dispersions is used.   9. The method according to claim 1, characterized in that the polymer as an aid in pulp and / or pulp bleaching to prevent premature decomposition of peroxy compounds becomes. 10. Paper auxiliaries containing a polymer with recurring succinyl units, optionally an emulsifier, and water.