FI63428C - REFRIGERATION FOR ALUMINUM POLYAMINERS MODIFIED UREAFORMALDEHYDHARTS - Google Patents

Description

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Patent- och ragisterstyralswt '' amttkan utii «d och utUkrtfun puMtcmd ^ 0. . 01 (32) (33) (31) P) rr4 «** y · * οΛ ·« μ- »· | · Η prloriMt (71) Nizhnetagilsky Zavod Plastmass, Nizhny Tagil Sverdlovskoi oblasti, USSR (SU) (72) Anatoly Abramovich Kruglikov, Nizhny Tagil Sverdlovskoi oblast,

Lia Ilinichna Aronova, Nizhny Tagil Sverdlovsk Oblast, "Vladimir Vasilievich Kuftarev, Nizhny Tagil Sverdlovsk Oblast,

Zoya Sergeevna Sevrjugina, Nizhny Tagil Sverdlovskoi oblast,

Vera Konstantinovna Eletskaya, Moskovskaya oblast, USSR (SU) (7 * 0 Oy Kolster Ab (5 * 0 Method for the preparation of water-soluble urea-formaldehyde resins modified with aliphatic polyamines

The invention relates to a process for the preparation of water-soluble urea-formaldehyde resins modified with aliphatic polyamines by reacting urea, formaldehyde and aliphatic polyamines with each other at a temperature of 80-100 ° C with a urea / formaldehyde molar ratio between 1: 1.5 and 1: 3-, 0 and varying the range during the reaction.

The invention is characterized in that branched aliphatic polyamines having a molecular weight of 200 to 440 and containing 10 to 16% by weight of tertiary nitrogen are used as aliphatic polyamines, and that the reaction of urea with formaldehyde and branched aliphatic polyamines is initially carried out in an alkaline medium. 9.5, which is adjusted by adding a certain amount of branched aliphatic polyamine, then in an acidic medium at a pH of 4.8 to 6.0, which is adjusted by adding sulfosalicylic acid or an aromatic or aliphatic sulfonic acid of the general formula R - SO 2 H, wherein R is an aryl or alkyl group, and then again in an alkaline medium at a pH of 7.2 to 9.5, which is adjusted by adding sodium hydroxide to form an oligomer which is reacted at 100 to 105 ° C for 0.2 to 2.0 with 100 parts by weight of urea per 100 parts by weight of isooctylphenol polyoxyethylene ether containing 7 to 11 oxyethylene units.

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The production of aliphatic polyamine-modified urea-formaldehyde resins that can replace rosin in offset paper production, increase paper surface strength, and also reduce dusting and surface fiber detachment is a technological problem.

Today's offset paper is obtained by adding rosin to the pulp, which is a scarce substance due to limited sources. In addition, rosin is insoluble in water, making it difficult for it to be evenly distributed in the paper pulp. Offset paper obtained using rosin is characterized by dusting and detachment of surface fibers.

Methods for preparing aliphatic polyamine-modified urea formaldehyde resins are known in the art.

DE patent 1 445 264 discloses a process for the preparation of water-soluble urea formaldehyde resins modified with polyamines. This process uses straight-chain, low molecular weight polyamines: ethylenediamine, propylenediamine, diethylenetriamine and triethylenetriamine, with anionic compounds in addition to polyamine being used as modifiers. The resins thus obtained are easily soluble in water and, when used in the paper industry, increase the wet strength of the paper. However, these resins cannot be used to replace rosin in offset paper production, they do not increase the surface strength of the paper, and they do not reduce dusting and fluffing of the paper web during printing.

Also known in the art is a process for preparing water-soluble urea-formaldehyde resins by modifying urea-formaldehyde polycondensation products with polyamines of the general formula H (N (-CH. -NH-) H, where x is 2 or 3.2, n 2 x for example diethylenetriamine or triethylenetetramine, 80- At 100 ° C. The resins thus obtained increase the wet strength of the paper. However, they cannot be used to make offset paper instead of rosin. In addition, they do not increase surface strength or reduce dusting and loosening of surface fibers.

Also known in the art is a process for preparing water-soluble urea formaldehyde resins modified with polyamines. According to the process, the urea-formaldehyde condensation products are modified with an alkylenediamine, for example ethylenediamine, at a pH of 5.0 to 6.5. The resulting resins are used to make paper with increased wet strength. However, they cannot be used to make offset paper, resins do not increase surface strength, and do not reduce dusting and peeling of surface fibers.

Furthermore, there is a process known in the art for which it is essential that the urea-formaldehyde oligomer be modified with straight-chain polyalkylene polyamines, for example diethylenetriamine, triethylenetetramine or tetraethylene-pentamine at 63-100 ° C, by doping and then separating to a large molecule. Precipitation is performed by cooling the resulting oligomer to 10 ° C.

The resins obtained by the known method increase the wet strength of the paper, but they cannot be used for the production of offset paper. They do not improve the surface strength and also do not reduce dusting and detachment of surface fibers.

Known methods for preparing water-soluble polyamine-modified urea-formaldehyde resins are, disadvantageously, due to the limited use of the resulting resins. Their use in the paper industry is limited to the production of wet-strength paper. They cannot be used instead of rosin in the production of offset paper. The resins do not increase the surface strength, nor do they reduce dusting and loosening of the surface fibers.

The object of the invention is to eliminate the above-mentioned disadvantages. The main object of the invention is to change the production conditions of water-soluble urea formaldehyde resins modified with aliphatic polyamines, so that the obtained resins have properties which make it possible to replace rosin in offset papermaking, to improve the surface strength of paper and to reduce dust and surface fibers.

The modifiers used according to the invention have the following properties: 1. nitrogen content tir with acid - at least 16.7% by weight; 2. total nitrogen content by the Kjeldahl method - at least 28% by weight; 3. chlorine content - at least 0.2% by weight; 4. fractions of vacuum distillation at 10 mm Hg: (a) fraction boiling below 75 ° C - not more than 1% by weight; b) a fraction boiling in the range of 75 to 210 ° C - not more than 15% by weight; (c) bottom product boiling above 210 ° C - not more than 85% by weight; 5. tertiary nitrogen content - 10-16% by weight; 6. molecular weight - 200-440.

The series of process steps according to the invention described above, in particular the performance of polycondensation under varying pH conditions of the medium (alkaline-acid-alkaline) in a selected range, as well as the use of branched aliphatic polyamines and isooctylphenol oxyethylene ethers, give the desired product.

It is preferred to carry out the condensation first with a urea / formaldehyde molar ratio of between 1: 2.2 and 1: 2.4 at pH 7.5-9.0 and 96-100 ° C.

In an acidic medium, it is desirable to cause condensation to occur in the pH range of 5.0 to 5.5, which is achieved by the addition of aromatic or aliphatic sulfonic acids of the general formula R-SO 2 H, wherein R is an aryl or alkyl group, and 96-100 ° C.

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It is desirable to neutralize the reaction product after condensation in an acidic medium with sodium hydroxide to a pH of 8.8 to 9.3.

After condensation in an acidic medium, it is more preferable to use hensenesulfonic acid as the aromatic sulfonic acid, which promotes the process and is the best available and most widespread compound in this class. However, other sulfonic acids such as toluenesulfonic acid, xylenesulfonic acid, naphthalenesulfonic acid and salicylsulfonic acid can also be used successfully.

As the aliphatic sulfonic acid, it is preferable to use butylsulfonic acid or a sulfonic acid obtained by sulfonating paraffin hydrocarbons.

Polyoxyethylene ethers of isooctylphenol having 9-10 oxyethylene units are most preferred for further condensation of the oligomer with polyoxyethylene ethers of isooctylphenol.

In order to obtain the most suitable product for the production of offset paper, it is recommended to concentrate the latter in a vacuum of 550-650 mm Hg to a refractive index of 1,456-1 * 458 before adding the polyoxyethylene ethers of iso-oxyphenol to the oligomer.

The resins obtained according to the proposed invention have the following properties:

In appearance they are a homogeneous transparent liquid * Resins are indefinitely soluble in water. After a river of water has been added to the resin, a homogeneous transparent solution is formed. No coagulation of the resin or turbidity of the solution, indicating separation of the solid phase from the solution, is observed.

The resins obtained according to the invention have a dry matter content exceeding 40% by weight. The pH of the resins is between 7 and 5-9 * 0 $, the free formaldehyde content varies from 3.0 to 4.0% by weight.

The viscosity of the resin, determined by the flow time of the viscometer with a nozzle diameter of 5 * 4 mm at 20 ° C, is between 10 and 40 seconds. The time for the resin solution to become cloudy after the addition of alumina is less than 3 minutes.

The resins obtained according to the proposed invention are stable for more than 3 months, which is sufficient for long-distance transport, storage and also for use.

Offset paper made by a known method based on bleached sulphate pulp by adding the proposed resin to a pulp of 30 kg / t, provided that the rosin is completely omitted, fully meets the modern requirements imposed on this type of paper. It is characterized by the fact that the surface fibers do not come off, dusting is considerably less compared to ordinary offset paper. The general and printing characteristics of this paper are as follows: 5 63428

General properties: 2 + 1. 1 m in mass - 120-4 g} 2. volumetric weight - 0.75-0.80 g / cm ^ j 3 · average breaking length in two directions - 2,500-2,700 m) 4 · fracture number) in the transverse direction - 9-12j 5 · whiteness - 83-88 6. ash content - 10-14 $> \ 7. gloss - 30-80 s; 8. Transverse deformation after 30 minutes of dissolution in water - 1.7 - 2.0

Printing characteristics 1. detachment of surface fibers - not at all 2. dusting - negligible 3. satisfactory printing (visually) - better than in group 4.

Thus, the proposed method provides resins which, in contrast to the known methods, allow the use of rosin in the production of offset paper completely, increase the surface strength of the paper and reduce dusting and peeling of the fibrous fibers.

The method is also advantageous in that it can be carried out as a batch or continuous process, the latter being more advantageous.

The method is simple in technology and is implemented as follows. The preparation of the modified urea formaldehyde resins as a batch process is carried out according to the following formula.

Formalin is placed in a standard type reaction vessel equipped with a reflux condenser, stirrer and steam jacket. The pH is adjusted to the required value by adding polyamines, after which urea is added. The resulting mixture is heated to 80-100 ° C, unchanged! stirring for the required time. Condensation is effected under these conditions, first in an onset and then in an acidic medium, which is effected by placing aromatic or aliphatic sulfonic acids in a reaction vessel. Further condensation is carried out in the presence of an alkaline substance which guarantees the pH of the required medium. The result is an oligomer to which polyoxyethylene ethers of isooctylphenol are added and the condensation process is continued at the required temperature until the final product is formed. It is convenient to concentrate the oligomer in vacuo before condensing with polyoxyethylene ethers of isooctylphenol.

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The continuous process is carried out as follows. Reaction mixtures having the required ratio of urea, formaldehyde and branched aliphatic polyamines are continuously fed at a constant rate to a first reaction vessel equipped with a reflux condenser, stirrer and steam jacket. In this reaction vessel, condensation takes place in an age-old medium under constant stirring and heating. The product obtained is continuously passed through a water seal to a second reaction vessel equipped in the same way as the first. In the second reactor, to which aromatic or aliphatic sulfonic acid is also continuously fed, condensation takes place in an acidic medium under constant stirring and heating. After the second reactor, the product is passed through a water seal to a continuous evaporator. The required amount of alkali is also added to the evaporator and at the same time the oligomer is concentrated and the concentrate is continuously removed through a barometer tube. The concentrated oligomer is continuously fed to a third reaction vessel equipped in the same manner as the first and second. In the third reactor, further condensation of the oligomer is carried out, whereby the polyoxyethylene ether of isooctylphenol is fed continuously. The final product is continuously passed through a water seal to a tubular heat exchanger where it is cooled and then pre-packaged for storage.

The manufacturing process of the resins according to the proposed invention can be easily automated.

For a better understanding of the invention, specific examples are provided below to illustrate the invention.

In the examples given, an alkaline substance and aromatic or aliphatic eulonic acids have been used in the form of aqueous solutions.

Example 1 324 parts by weight of 37 to # formalin and 2 parts by weight of branched aliphatic polyamines are placed in a metal reactor equipped with a reflux condenser, a stirrer, a steam-water jacket and a vacuum collector. Polyamines are known for their following parameters! 1. acid-titrated nitrogen content - 20.9% by weight * #) 2. total nitrogen content by the Kjeldahl method - 34, β by weight #) 3. chlorine content - 0.12% by weight #) 4 * vacuum distillate in 10 mm Hg fractions: a) boiling fraction below 75 ° C - 0.3 by weight h) boiling fraction between 75 and 210 ° C - 11.2 weight - # * c) bottom fraction boiling above 210oC - 88.3 by weight #) 3. tertiary nitrogen content - 13.9 wt.%) 6. average molecular weight - 398.

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After the addition of the polyamines, the pH is 8.8. 100 parts by weight of urea are then introduced into the reactor. After the urea has dissolved after stirring, steam is introduced into the jacket and the mixture is heated to boiling for 40 minutes. At 96-97 ° C, the mixture is stirred for 45 minutes.

At the end of the alkali condensation, the pH of the medium is 7 »5 · Hensenesulfonic acid in the form of a 0.25 N solution is then added to the reactor until a pH of 5.5 is reached. Condensation in an acidic medium is continued at 96-97 ° C for 50 minutes. Next, a solution of sodium hydroxide from 4 to 4 is added to the reaction mixture until the pH is 8.8. The reaction mixture is cooled to 65 ° C and the oligomer is concentrated at 65-70 ° C under a vacuum of 550-650 mm Hg. Concentration is stopped when the refractive index reaches 1.456} 0.5 part by weight of polyoxyethylene ether of isooctylphenol having an average number of oxyethylene units of 10 is added to the reactor. the resin is cooled to 40 ° C and emptied into packaging containers.

The resin obtained has the following characteristics: 1. dry matter content - 63.2 2. miscibility with water - unlimited} 3. condition-dependent viscosity - 17 seconds} at 20 ± 1 ° C 4. pH - 9.0} 5 · time, when the resin solution becomes cloudy after the addition of alumina - 2.6 minutes

Offset paper made on the basis of bleached sulphite distillate in a known manner, adding this resin to the pulp in amounts of 30 kg / t, provided that the rosin is completely omitted, is characterized by the following parameters: 2 1. 1 m pulp - 120 g} 2. volumetric weight - 0.85 g / cnr *) 3 · average breaking length in two directions - 2,500 m} 4 · fracture (number of double folds) in the transverse direction - 12} 5 · whiteness - 85} 6. ash content - 14 7 · gloss - 80 s.} 8. deformation in the transverse direction after 30 minutes of dissolution in water - 1.9 i »\ 9« detachment of surface fibers - absent} 10. dusting - absent) 11. print satisfaction - better than in group 4 · 8

Example 2 63428 406 parts by weight of 37 to # formalin and 2 parts by weight of branched polyamines are placed in a metal reactor equipped with a reflux condenser, a stirrer, a steam-water jacket and a vacuum collector. Polyamines are characterized by the following parameters: 1. acid titrated nitrogen content - 16.8 wt%; 2. total nitrogen content by the Kjeldahl method - 26.1 wt.%; 3. chlorine content - 0 (14 wt.%; 4 · vacuum distillation, at 10 mm Hg, fractions: a) boiling fraction below 75 ° C - 0.4 wt. # B) boiling fraction between 75-210 ° C - 11.5 weight #; c) bottom fraction boiling above 210 ° C - 88 wt.%; 5 · tertiary nitrogen content - 11.7 weight · #; 6. average molecular weight - 224 ·

After the addition of the polyamines, the pH is 8.7 · 100 parts by weight of urea are then introduced into the reactor. After the urea has dissolved after stirring, steam is introduced into the jacket and the mixture is heated to boiling for 40 minutes. At 96-97 ° C, the mixture is stirred for 45 minutes. At the end of the alkali condensation, the pH of the medium is 7.4 · Benzenesulfonic acid in the form of a 0.25 N solution is then added to the reactor until a pH of 5.0 is reached. Condensation in an acidic medium is continued at 96-97 ° C for 30 minutes. Next, a 4 - # solution of sodium hydroxide is added until the pH is 8.9. · The reaction mixture is cooled to 65 ° C and the oligomer is concentrated at 65-70 ° C under a vacuum of 55Ο-65Ο mm Hg. Concentration is stopped when the refractive index of 1.456 is reached; 0.2 parts by weight of isooctylphenol polyoxyethylene ether having an average of 7 oceethylene units is introduced into the reactor. · Further condensation of the oligomer with isooctylphenol polyoxyethylene ether is carried out at 100-105 ° C for 15 minutes, after which the resin is cooled to 40 ° C and emptied.

The obtained shoulders have the following characteristics: 1. dry matter content - 63.2 #; 2. miscibility with water - unlimited; 3 · condition-dependent viscosity at 20+ l ° C - 18 s .; mm 4 · pH - 8.3; 5 · free formaldehyde content - 3.1 wt. 6. time at which the resin solution becomes cloudy after the addition of alumina - 2.5 minutes.

Offset paper made on the basis of bleached sulphite pulp by a known method, adding this resin to the pulp in quantities of 35 kg / t, provided that rosin is completely omitted, is characterized by the following parameters: 9 63428 2 1. 1 m tn pulp - 122 g} 2. volumetric weight - Ο, ΘΟ g / cm ^} 3. average breaking length in two directions - 2300 m; 4 · fracture (number of double folds) in the transverse direction - 11} 5. whiteness - 84 6. ash content - 10 7. gloss - 30 sj 8. Transverse deformation after 30 minutes of dissolution in water - 1.8 9 «detachment of surface fibers - absent} 10. dusting - missing} 11th print satisfaction - better than in group 4 *

Example 3 203 parts by weight of 37% formalin and 1.9 parts by weight of branched polyamines are placed in a metal reactor equipped with a reflux condenser, a stirrer, a steam-water jacket and a vacuum collector. Polyamines are known from the following parameters: 1. acid-titrated nitrogen content - 17 »7 wt.-96} 2. total nitrogen content by the Kjeldahl method - 24.8 wt-f ^} 3. chlorine content - 0.19 wt- $} 4. vacuum distillation, at 10 mm Hg, fractions: oa) boiling fraction below 75 ° C - 0.6 wt- $} b) boiling fraction between 75-210 ° C - 11.6 wt-f6} c) 210 ° Bottom fraction boiling above C - 87.4 wt. #} 5. tertiary en nitrogen content - 12.6 wt. · #} 6. average molecular weight - 301 «

After the addition of the polyamines, the pH is 9.0. 100 parts by weight of urea are then introduced into the reactor. After the urea has dissolved after stirring, steam is introduced into the jacket and the mixture is heated to 80 ° C for 40 minutes. 80-61 ° C: the mixture is stirred for 45 minutes. Upon completion of the alkali condensation, the pH of the medium is 7.8. Benzenesulfonic acid in the form of a 0.23 N solution is then added to the reactor until a pH of 5.3 is reached. In an acidic medium, the condensate is continued at 80-81 ° C for 30 minutes. Next, a 4 to 3 * solution of sodium hydroxide is added until the pH is 7.2. 2.0 parts by weight of polyoxyethylene ether of isooctylphenol with an average of 11 oxyethylene units are introduced into the reactor. Further condensation of the oligomer with polyoxyethylene ether of iso-octylphenol is carried out at 100-105 ° C for 15 minutes, after which the resin is cooled to 40 ° C and emptied into packaging containers.

The resin obtained has the following characteristics: 1. dry matter content - 40.0 weights 2. miscibility with water - unlimited} 5 * condition-dependent viscosity at 20-1V - 10 s; 4. pH - 8.1} 5 «free formaldehyde content - 4.0 wt. ^ 6. 6. time when the resin solution becomes cloudy after the addition of aluminum coke - 2.6 minutes.

Offset paper made on the basis of bleached sulphite pulp by a known method, adding this resin to the pulp in quantities of 30 kg / t, provided that the rosin is completely omitted, is characterized by the following parameters: 2 1. 1 m pulp - 119 g} 2. volumetric weight - 0.84 g / cm ^} 3 * average breaking length in two directions - 2500 m} 4 «fracture (number of folds) in the transverse direction - 12; 5 · whiteness - 83} 6. ash length - li #} 7. gloss - 50 s} 8. transverse deformation after 30 minutes of solution in water - 1.7 #} 9 · detachment of surface fibers - absent} 10. dusting - slight} 11. print satisfaction - better than in group 4 *

Example 4 298 parts by weight of 37 to # formalin and 2 parts by weight of branched aliphatic polyamines are placed in a metal reactor equipped with a reflux condenser, a stirrer, a steam-water jacket and a vacuum collector. Polyamines have the following parameters: 1. nitrogen content titrated with acid - 18.2 wt. #} 2. total nitrogen content by the Kjeldahl method - 31 * 7 wt. #} 3 · chlorine content - 0.17 wt.} 4 * vacuum distillation, 10 mm In Hgt, fractions of fractions: a) boiling fraction below 75 ° C - 0.8 wt. # B) boiling fraction between 75 and 210 ° C - 12.4 wt. ^} 63428 π c) 210 ° C boiling bottom fraction above - 85.1 wt. 5. tertiary nitrogen content - 10.0 wt.%; 6 average molecular weight - 200.

After the addition of the polyamines, the pH is 8.3 · 100 parts by weight of urea are then introduced into the reactor. After the urea has dissolved after stirring, »steam is fed into the jacket and the mixture is heated to boiling for 35 minutes. The mixture is stirred at 99-100 ° C for 45 minutes. At the end of the alkali condensation, the pH of the medium is 7 * 2. Hensenesulfonic acid in the form of a 0.23 N solution is then added to the reactor until a pH of 5 * 1 is reached. Condensation in an acidic medium is continued at 99-10 ° C for 30 minutes. Next, a 4 to 8 solution of sodium hydroxide is added to pH 8.8. The reaction mass is cooled to 63 ° C and the oligomer is concentrated at 65-7 ° C at 55Ο-65Ο mm Hg vacuum. The process is controlled by the refractive index. When it is 1.436, the concentration is stopped and 0.3 part by weight of isooctylphenol polyoxyethylene ether having 10 oxyethylene units is added to the reactor. Additional condensation of the oligomer with polyoxyethylene ether of isooctylphenol is performed at 100-103 ° C for 13 minutes, after which the shoulders are cooled to room temperature and emptied into packaging containers.

The obtained resin has the following characteristics: 1. dry matter content - 64.1% by weight; 2. miscibility with water - unlimited; 3. condition-dependent viscosity at 20 ± 1 ° C - 15 s; 4. Ph - 7.5; 5 · free formaldehyde content - 3.5 wt. 6. time for the resin solution to become cloudy after the addition of alumina - 2.9 minutes;

Offset paper made on the basis of bleached eulphite pulp by a known method is added to this pulp in an amount of 30 kg / t, provided that no rosin is used at all, is characterized by the following parameters: 2 1. 1 m pulp - 121 g; 2. bulk density - 0.75 g / cm 2; 3 · average concealment length in two directions - 2600 m; 4. fracture (number of double folds) in the transverse direction - 9; 5. whiteness - 88 #; 6. ash content - 10 #; 7. gloss - 40 s; 8. Transverse deformation after 30 minutes of dissolution in water - 1.7, #; 63428 12 10 * dusting - low! 11. Satisfaction of printing - better than in group 4.

Example S

324 parts by weight of 37% of formalin and 2.1 parts by weight of branched aliphatic polyamines are placed in a metal reactor equipped with a reflux condenser, a stirrer, a steam-water jacket and a vacuum collector. Polyamines have the following parameters: 1. acid titrated nitrogen content - 18.4 weights; 2. total nitrogen content by the Kjeldahl method - 30.4 weights; 3 · chlorine content - 0.16 weights; 4 »vacuum! Sines, 10 mm Hgt, fractions: a) fraction boiling below 75 ° C - 0.9 weight * ^; h) a boiling fraction between 75 and 210 ° C - 14 * 9 wt. c) fractions boiling above 210 ° C -88.1 wt-f (; 3 «tertiary nitrogen content - 16.0 wt. 6. average molecular weight - 440.

After the addition of the polyamines, the pH is 9 * 3 · Then 100 parts by weight of urea are introduced into the reactor. After the urea has dissolved after stirring, vigorous steam is fed and the mixture is heated to boiling in 33 minutes. The mixture is stirred at 99-100 ° C for 43 minutes. At the end of the alkali condensation, the pH is 7 * 9. «Hensene sulfonic acid in the form of a 0.23 H solution is added to the reactor until a pH of 3.2 is reached. Condensation is continued in an acidic medium at 99-100 ° C for 30 minutes. A 4 to 4 solution of sodium hydroxide is then added to the reactor to pH 9. The reaction mixture is cooled to 63 ° C and the oligomer is concentrated at 63-70 ° C under a vacuum of 330-630 mm Hg. Concentration is stopped when the refractive index is 1.430, followed by the addition of 0.3 parts by weight of polyoxyethylene ether of isooctylphenol having an average number of oxyethylene units of 10. Further condensation of the oligomer with isooctylphenol polyoxyethylene ether is carried out at 100-105 ° C for 13 minutes.

The resin obtained is known from the following parameters: 1. dry matter content - 63.7 by weight 2. miscibility with water - unlimited; 3. condition-dependent viscosity at 20 + - 1 ° C - 14 s; 4- pH - 7.9; 5. free formaldehyde content - 3.6 weights; 6. time when the resin solution becomes cloudy After the addition of alumina - 2.8 minutes.

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Offset paper made on the basis of bleached sulphite pulp by a known method, adding this resin to the pulp in amounts of 30 kg / tsn, provided that the addition of rosin is completely omitted, is characterized by the following parameters: 2 1. 1 m in mass - 121 g) 2. volumetric weight - 0, 79 g / cm ^) 3 · average breaking length in two directions - 2600 mj 4 · fracture (number of double folds) in the transverse direction - 12; 5 · whiteness - Θ7 #) 6. ash content - 12 #) 7. gloss - 89 s; 8. transverse deformation after 30 minutes of dissolution in water - 2.0 io \ 9 · detachment of surface fibers - absent) 10. dusting - slight) 11 · print satisfaction - better than in group 4

Example 6

The process is carried out according to the process described in Example 1, but instead of using polyoxyethylene of isooctylphenol having an average of 10 oxyethylene units, an ether of 9 oxyethylene units is used.

The resulting resin is characterized by the following parameters: 1. dry matter content - 62.1 wt% ^) 2. miscibility with water - unlimited) 3. condition-dependent viscosity at 2θί l ° C - 10 sec) 4. pH - 7t7i 3 * free formaldehyde content - 3 »S weight- $ j 6. time when the resin solution becomes cloudy after the addition of alumina - 2.9 minutes.

Offset paper made from a bleached sulphite pulp base by this known method by adding 30 g / t of this resin to the pulp, provided that rosin is completely omitted, is characterized by the following parameters:} 2 63428 u 1. 1 m pulp - 124 g; 2. voluuepai.no - 0.83 g / cm 2; 3 * average breaking length in two directions - 2600 m; 4 · fracture (number of double folds) in the transverse direction - 11; 5 · whiteness - $ 86; 6. ash content - 11 #; 7. gloss - 30 s; 8. deformation in the transverse direction after 30 minutes of dissolution in water - 1,9 9 * release of fiber - no; 10. dusting - low; 11. Satisfaction of printing - better than in group 4 *

Example 7

The process is carried out following the steps set out in Example 1, but using butylsulfonic acid instead of hensenesulfonic acid until a pH of 6.0 is reached.

The resin obtained has the following characteristics: 1. dry matter content - 63.8 weights; 2. miscibility with water - unlimited; 3 · condition-dependent viscosity at 20-1 ° C - 17 s; 4. pH - 8.2; 3 · free formaldehyde content - 3.9 wt%; 6. time for the resin solution to become cloudy after the addition of aluminum coke - 26 minutes.

Offset paper made on the basis of bleached eulphite pulp by a known method, adding this resin to the pulp in amounts of 30 kg / t, provided that the rosin is completely omitted, is characterized by the following parameters: 2 1. 1 m pulp - 116 g; 2. bulk density - 0.81 g / cm 2; 3 · average breaking length in two directions _ 2600 m; 4 · fracture (number of double folds) in the transverse direction - 11; 3 · whiteness - 85 <&; 6. Ash holding area - li 7 · gloss - 40 s; 8. Transverse deformation after 30 minutes of dissolution in water - 1.8%; 63428 15 9. detachment of surface fibers - missing) 10. dusting - missing) 11. print satisfaction - better than in group 4 *

Example 8

The process is carried out according to the process of Example 1, but instead of benzene-sulfonic acid, salicylsulfonic acid is added until a pH of 4 * 8 is reached.

The resin obtained has the following characteristics: 1. dry matter content - 60.0 weight · ^} 2. miscibility with water - unlimited) 3 * condition-dependent viscosity at 20+ l ° C - 18) 4. pH - 8.3) 5 · free formaldehyde content - 3.7 weights) 6. time when the resin solution becomes cloudy after the addition of alumina - 2.4 minutes.

Offset paper prepared by a known method was bleached on the basis of sulphite pulp by adding this resin to the pulp in amounts of 30 kg / t, provided that no rosin is used at all, is characterized by the following parameters: 2 1. 1 m pulp - 117 g) 2. volumetric weight - 0.82 g / cm ^) 3. average breaking length in two directions - 2600 m) 4. "fracture (number of double folds) in the transverse direction - 10 5. whiteness - 83 #) 6. ash content -12 i» \ 7. gloss - 60 s) 6. deformation in the transverse direction after 30 minutes of dissolution in water - 1.7 i »\ 9. detachment of surface fibers - absent) 10. dusting - absent) 11. print satisfaction - better than in group 4.

Example 9

The process is carried out following the procedure described in Example 3, but instead of bentenesulphonic acid, a mixture of sulphonic acids obtained by sulphonating a mixture of paraffinic hydrocarbons with an average molecular weight of 230 is used.

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The obtained shoulders have the following characteristic values: k. Dry matter content - 61.2% by weight; 2. miscibility with water - unlimited; 3 · condition-dependent viscosity at 20 ± 1 ° C - 40 s; 4. pH - 8,4 | 3 · free formaldehyde content - 3 * 0 weight #; 6. time when the resin solution becomes cloudy after the addition of alumina * -2.3 minutes

Offset paper prepared by a known method based on bleached sulphite pulp by adding this resin to the pulp in amounts of 30 kg / t, provided that no rosin is used at all, is characterized by the following parameters: 2 l. 1 m tn pulp - 119 g; 2. bulk density - 0) 83 kg / cm 2; 3 * average breaking length in two directions - 2700 m; 4 · fracture (number of kake folds) in the transverse direction - 11; 3 · whiteness - 84; 6. ash content - 10 #; 7. gloss - 50 s; 8. Transverse deformation after 30 minutes of dissolution in water - 1.7 #; 9 «detachment of surface fibers - missing; 10. dusting - low; 11. Satisfaction of painting - better than in group 4 *

Example 10

The following example is provided to illustrate a continuous process for preparing water-soluble urea-formaldehyde resins modified with aliphatic polyamines.

The reaction mixture containing 325 parts by weight of 37 .mu.l of formalin and 100 parts by weight of drug urea at pH 8.8, initially obtained using 2 parts by weight of branched aliphatic polyamines as described in Example 1, is fed continuously to the first reactor, which is with a reflux condenser, a stirrer and a steam jacket, at a rate which ensures that the pulp remains in the reactor for 45 minutes. The temperature in the first reactor is maintained in the range of 96-97 ° C. The condensation product obtained in the first reactor passes through a water seal to a second reactor which is equipped in the same way as the first. Benzenesulfonic acid 0.25 K

17 63428 solution is added to the second reactor in an amount that ensures a pH of the product of 5-2. The temperature in the second reactor is 96-97 ° C. The residence time of the product in the second reactor is 30 minutes. The product from the second reactor is continuously fed to an evaporator which operates continuously and in which the oligomer is concentrated under a vacuum of 350 mm Hg until a refractive index of 1.457 is reached. The pH of the product in the evaporator is maintained at 8.8 by continuous feeding of a 40% solution of sodium hydroxide. The condensate is continuously removed from the evaporator through a barometer tube, while the concentrated oligomer is continuously fed to a third reactor equipped in the same way as the first and second. In the third reactor, further condensation of the oligomer is carried out with a polyoxyethylene ether of isooctylphenol having an average number of oxyethylene units of 10, this ether being fed continuously. The residence time of the product in the third reactor is 13 minutes. From the third reactor, the resin continuously passes through a water seal to a tubular heat exchanger where it is cooled to 40 ° C and then emptied into packaging tanks for storage.

The resulting resin is characterized by the following parameters: 1. dry matter content - 63.7 by weight 2. miscibility with water - unlimited} 3. condition-dependent viscosity at 20 ± 1 ° C - 20 s; 4. pH - 7 # 5l 5. free formaldehyde content - 3 »6 weight #; 6. time for the resin solution to become cloudy after the addition of alumina - 2.7 minutes

Offset paper prepared by a known method on the basis of bleached sulphite pulp and adding this resin to the pulp in quantities of 30 kg / t, provided that no rosin is used at all, is characterized as follows: 2 1. 1 m pulp - 120 g; 2. bulk density - 0 ^ 84 g / cm 2; 3. average breaking length in two directions - 2700 m; 4. fracture (number of double folds) in the transverse direction - 12; 3. whiteness - 88 56; 6. ash content - $ 10; 7. gloss - 40 s; 8. Transverse deformation after 30 minutes of dissolution in water - $ 1.8 6; 9. detachment of surface fibers - missing; 10. dusting - missing; 11. Satisfaction of printing - better than in group 4.

Claims (2)

18 63428 A process for preparing water-soluble urea-formaldehyde resins modified with aliphatic polyamines by reacting urea, formaldehyde and aliphatic polyamines at a temperature of 80-100 ° C with a urea / formaldehyde molar ratio between 1: 1.5 and 1: 3.0 and changing the pH of the medium during the reaction, characterized in that branched aliphatic polyamines having a molecular weight of 200 to 440 and containing 10 to 16% by weight of tertiary nitrogen are used as aliphatic polyamines and that the reaction of urea with formaldehyde and branched aliphatic polyamines is initially carried out in an alkaline medium 7.2 to 9.5, which is adjusted by adding a certain amount of branched aliphatic polyamine, followed by the addition of an acidic medium at a pH of 4.8 to 6.0, which is adjusted by adding sulfosalicylic acid or an aromatic or aliphatic sulfonic acid of the general formula R- SO 2 H, where R is an aryl or alkyl group, and then again in an alkaline v in a medium at a pH of 7.2-9.5, which is adjusted by adding sodium hydroxide to form an oligomer which is reacted at 100-105 ° C with 0.2-2.0 parts by weight of urea per 100 parts by weight of urea , iso-octylphenol polyoxyethylene ether containing 7-11 oxyethylene units. Process according to Claim 1, characterized in that before the addition of isooctylphenol polyoxyethylene ether to the oligomer, the latter is concentrated in a vacuum of 550 to 650 mm Hg until a refractive index of 1.456 to 1.458 is reached.