CA1056097A - Method of producing water-soluble urea-formaldehyde resins modified with aliphatic polyamines - Google Patents

Abstract

Abstract of the Disclosure METHOD OF PRODUCTING WATER-SOLUBLE UREA-FORMALDEHYDE
RESINS MODIFIED WITH ALIPHATIC POLYAMINES
A method of producing water-soluble urea-formaldehyde resins modified with aliphatic polyamines, residing in that 1 mole of urea, 1.5-3.0 moles of formaldehyde, and branched aliphatic polyamines with a molecular weight of 200-440, containing 10-16 wt.% of tertiary nitrogen, are interacted at 80-100°C and pH of an alkaline medium 7.2-9.5 attained by a proper amount polyamines. Aromatic or aliphatic sulphonic of the general formula R-SO3H, where R is aryl or alkyl, are introduced into the obtained mixture until pH of an acid me-dium 4.8-6.0 is attained. Then an alkaline agent is added up to pH 7.2-9.5. As a result an oligomer is formed which is interacted with polyoxyethylene ether of isoctylphenol with 7-11 oxyethylene units at 100-105°C. The ethers are taken in an amount 0.2-2.0 wt.
parts per 100 wt. parts of the initial urea.
The proposed method of producing urea-formaldehyde resins modified with aliphatic polyamines ensures the production of resins which, being used in paper industry, completely replace colophony in manufacturing offset paper. They increase the sur-face strength of the paper and decrease dusting and picking.
The method is simple in technology and can be performed both as a continuous and batch process.

Description

METHOD 0~ ~RODUCING WA~ER-SOLUBIE UREA-FOEM~IDEH~DE
R~SINS ~O~IFIED WITH A~IPHA~IC POI~MIN~$

~ he present i~vention relate~ to producing of water-solu-ble urea-iormalde~yde re~ins modified with aliphatic polyamines~
These resi~s are used in paper iDdustry for improving the qua-lity of paper, in particular, for manufacturing paper with in-creased strength in the ~et state.
An important technological problem is producing the re-sin~ oi this type able to replace colophony in manufacturi~g offset paper, to increase the ~urface strength of the paper, a~ well as to decrease dusting and picking.
Ofrseb paper manufactured at present i8 obtained by intro-ducing ¢olophony into the paper mass which is a scarce material because of limited resources. Besides, colophony does not di~-801ve in water, which complicates its uni~orm distribution i~
a paper mass. Offset paper obtained with the use of colophony is ¢haracterized by dusting and picking.
~ no~n in the art are methods of producing urea-~ormaldeh~-de re~ins modified uith aliphatic po bamines, residing in that the products of urea- formaldehyde condensation are modi~ied I with low-mole¢ular aliphatic polyamines of linear structure.
~he resins find appli¢ation in paper industr~ for increa~ing i paper wet-stre~th.
~ now~ in the art is a method o~ producing ~ater-~oluble uroa-~ormaldeh~de resins by modifying the products of urea-1056~197 : ~

-f~rmaldehyde polycond~nsation with polyamines of the general formula E ~(-CnH2n-N~ , where 2 i~ 2 or 3, for example, diethylenetriamine or triethylenetetramine~ at 80-100C.
The resins thus obtained increaRe the wet-stre~gth of the pape~
But they cannot be used for manufacturing offset paper instead of colopho~y. In addition~ they neither increase the ~urface strength, nor decrease dusting and picking.
Likewise know~ in the art is a method of producing water--~oluble urea-iormaldehyde resins modified with polyamines.
According to the method, the products of urea-formaldehyde conden~ation are modified with alkylenedia~ine, for instance, ethylenediamine at p~ 5.0-6.5. The resins obtained are applied ~or producing paper with increased strength in a wet state.
However, they cannot be used for manufacturing offset papert the resin~ neither increase the surface stren~th, nor decrease du~ting and picking.
~ lso known in the art is a method residing in that urea--formaldehyde oligomer is modified with polyalkylenepolyamines oi linear ~tructureJ for example, diethylenetriamine, triethy-lentetramine, or tetraethylenepentamine at 85-100C with ~ub~e~uent precipitation and separation of the high-molecular part of the resin. Precipitation i8 performed by cooling the oligomer obtained down to 10C.
~ he resin~ obtained b~ the kno~ method increa~e the strength oi the paper in a wet state but cannot be u~ed ior

- 2 -. . . . . . .. . . . . . - .. .. . -. - ............. . . -. ~ - . .
.. .. . . . . - . .. . ..... - . - - -1(~56097 manu~acturing o~fset paper. ~he~ neither enhance the surface ætrength~ nor decrea~e dusting and picking.
The known methods of producing water-soluble urea-formal-dehyde resins modi~ied with aliphatic polyamines are disadvan-tageous in that the re~ins obtained have limited application.
Thus, their application in paper indust~y is confined to manu-facturing wet-strong paper. ~hey cannot be used instead of colophony in production of oifset paper. The resins neither i~crease the sur~ace qtrength nor reduce dusting and picking.
It is an ob~ect oi the invention to provide a method of producing water-soluble urea-formaldehyde resins modified with aliphatic polyamine~ which ~ill yield resins with propertieæ
ensuring the replacement of colophony in of~set paper produc-tion, an increa~e o~ the surface strength of the paper, a re-duction of dusting and picking.
In aecordance ~ith this and other objects, the invention consists in that a ~ethod is proposed involving an interaction of urea~ formaldehyde~ and aliphatic polyamines at 80-100C and p~ varylng in the proces~ of said interaction. ~ccording to the invention~ a~ aliphatic polyPm~ne~ use is made o~ branched aliphatic polyamines with molecular weight 200-440 and with a aontent o~ tertiary nitrogen 10-16 wt.%. The process of inter-acting urea with formaldehyde in a mole ratio 1s1.5-3.0, res-pecti~ely, and branched aliphatic polyamine~ is run first in an alkaline medium at p~ 7.2-9.5 which is provided by the amour~

~ 3 --., . . . . ~ . . .. . . , -1056~97 of polyamine~, then in an acid medium at pH 4.8-6.0 which is en~ured by the introduction of aromatic or aliphatic sul-phonic acids o~ the general ~ormula R-S03H, where R is aryl or alkyl) and th~n again in an alkaline medium at pH 7.2-9.5 attained by the introduction of an alkaline agent, with the formation of oligomer which is interacted at 100-105C with pol~oxyethylene ether of isooctylphenol~ having 7-11 oxyethyle-- ne units~ bg adding the latter to oligomer in an amount 0.2--~.0 wt. parts per 100 wt. parts of the initial urea.
~odifiers used according to the invention are character-ized by the following parameter~:
1. Content o~ nitrogen titrated with an acid - no less than 16.7 wt.%~
2. ~otal content of nitrogen by ~eldahl's method - no les~ than 28 wt.%l i 3. Clorine content - no more than .2 ~t.%~
4. Fractional composition of vacuum di~tillation at 10 mm $gs a) ~raction boiling belo~ 75C - no more than ~ ~t.%~
b) fraction boiliDg in the range o~ 75-210C - no more thqn 15 ~t.%~
c) bottome boillng above 210C - no less than 85 wt.%~
' :' ~., ~ .. , , . , . .. , .. - .. . , . .. . -. ~ . . ~ , . , , .. , , . : - , , - . . . .

1056~97 5~ Content of tertiary nitrogen - 10-16 wt~%;
6. Molecular weight - 200 'l40.
Urea, formaldehyde, and aliphatic polyamines are inte-racted at a mole ratio of urea to formaldehyde equal to 1:1.5--3Ø Aliphatic polyamines are introduced in amou~ts ensuring the interaction conducted in an alkaline medium at pH 7.2-9.5.
The chosen temperature range allows for the process of co~de~-sation of the reacting components. The further condsnsation ifi condu¢ted in an acid medium at p~ 4.8-6.0 which i8 attained due to the introduction of aromatic or aliphatic sulphonic acid~ of the general formula R-S03H, where R i~ aryl or alkyl.
The obtained product i8 neutralized with an alkaline agent to pH 7.2-9.5. Any known al~aline agent can be used as an alkaline agent~ sodium hydroxide being the mo~t suitable one. ~8 the re~ult of the above-cited operations, oli~omer is obtained which is ~urther treated with polyoxyethylene ethers of iso-octylphenol at 100-~05 & . ~8 the ether, in the pre~ent inven-tion u~e i9 made of polyoxyethylene ethers of isooctylphenol with 7-11 oxyeth~lene unit~. Polyox~ethylene ether8 o~ i800-ctylphenol are introduced in amounts of 0.2-2.0 ~t parts per 100 ~t. part~ of the urea.
~ he ~et of the above operations, in particular~ the perfor mance of po bco~densation under the condition~ of varyin~ p~
o~ the medium (alkali~e-acid-alkaline) within the~cho8en range, a8 ~ell a8 the use oi branched aliphatic polyami~e~ and poly-: . . ~ - :. ~ , . - -, . , . - . : :,. . ; , . - , . , ,:, ., :,, . - , -lC~S60~7 oxyethglene ethers of isooctylphenol, ensure~ the end product with the desired properties.
It i~ preferable to carry out condensation fir~t with a more ratio of urea to formaldehyde equal to 2.2-2.4 at pH
7.5-9.0 and 96-100C.
In an acid medium it i~ de~irable to run condensation over the pH range 5.0-5.5, which is attained by introduction of aromatic or aliphatic sulphonic acids of the general ~or-; mula R-$03H, where ~ i~ aryl or alkyl, and 96-100C.
It is de~irable to neutralize the reaction product a~ter conden~ation in an acid medium with sodium hydroxide to p~
8.8-9.3.
Upo~ condensation in an acid medium, it is more preferable to u~e~ a~ an aromatic ~ulphoacid, benzenesulphonic acid which faVours the process and is the most available and wide-spread compound of this clas~. However, other ~ulpho~ic acid~, such as toluenesulphonic ac~d, x~lenesulphonic acid, naphtalene-~ulphonic acid~ and salic~l3ulphonic acid can also be ~ucces~-~ully used.
As aliphatic sulphonic acid, it i8 preferable to use bu-tylsulpho~ic acid or ~ulphonic obtained b~ ~ulphonation of paraffinic h~drocarbons.
Polyo~yethyle~e ethers of isooctylphe~ol with 9-10 oxyethylene units are the most preferable for additio~al conden-~ation of oligomer with polyoxyethylene ethers o~ i~ooctylphe-~ol.

.
.

.
. . . ~: : . - . . .
. . . .
.,, ' ` .
",' '' ,'' ,' ~, , ~' . ' ' ' .' ' ' ' ~L056~7 In order to obtain the most suitable product ~or the of~-set paper production, it is recommendable, before polyoxyet-hylene ether~ of isooctylphenol are added to oligomer, to con-centrate the latter in vacuum at 550-650 mm Hg till the re-fractive inde~ 1.456-1.458.
The resins obtained in accordance with the proposed in-vention have the following properties.
In appearance, the~ are a homogeneous transparent liquid.
The resins are unlimitedly soluble in water. Upon addition of any amount oi water to the resin, a homogeneous transparent solution iB formed. Neither resin coagulation, nor turbidity Or the solution indicative of the ~eparation of a solid phase from the solution, is obqerved.
~ he content oi dry substance in the resins obtained in accordance with the proposed invention exceeds 40 wt.%. pH
of the resin~ is within the range of 7.C _9.0~ the content oi free formaldehyde ~aries from 3.0 to 4.0 wt.%.
The viscosity of the re3ins determined by the flow time from viscometer with the nozzle diameter 5.4 mm at 20C is within the range 10-40 ~ec. ~he time during which the solution o~ re8in becomes turbid upon the addition of alumina is les~
than 3 m~nutes.
~ hs resins obtained according to the proposed in~ention are ~table ~or more than three months which is ~uf~icient for lon~ dl~tanoe tra~sporti~, ~tor~ge, o~d nlrther application.

_ 7 _ ,~ . . ~. . .
.. ; .. .. . - .~ , . , ~ : .

~o56097 Offset paper manufactured by known method on the basis of sulphite bleached pulp with introduction of the proposed resin into the paper mass in amounts 30 kg/t, under the con-ditions of complete e~imination of colophony, fully meets the modern requirements imposed upon the paper of this type. It is characterized by the absence of picking and considerably lower dusting as compared to common offset paper. General and printing properties of this paper are as follows:

General Properties 1. Mass of 1 m - 120+4 g;
2. Volume mass - 0.75-0.80 glcm

3. Breakage length on an average in 2 directions - 2.500-2.700m;

4. Fracture (number of double folds) in transverse di-rection - 9-12;

5. Whiteness - 83-88%;

6. Ash content - 10-14%;

7. Smoothness - 30-80 sec.;

8. Deformation in transverse dlrection after wetting in water for 30 minutes - 1.7-2.0%;

Printlng Properties 1. Picking` - none 2. Dusting - negligible ~56097 3. Saturation of impression (visually) - higher than in group 4, ~ hus, the proposed method provides resins which, in contrast to the known ones, allow complete obviation o~ the use of colophony in manufacturing offset paper, increase the surface strength o~ the paper, decrease dusting and pickiLg.
~ he method is also advantageous in that it can be perfore med both as a batch and conti~uou~ process, the latter bei~g more pre*erable.
The method is ~imple in technology and i~ accomplished as follow~. Batch process o* producing modi*ied urea-*ormaldehyde re~in~ i~ carried out by the ~ollowing scheme.
~ ormalin i~ put into a reactor of conventional type *itted~
with a re*lux condenser, a stirrer, and a ~team ~ackeb. pH i~
adjusted to the required value by addition o* polyamine~, a~ter which urea is introduced. The mixture obtained i8 heated up to 80-100C at con8tant stirring over a required period o~
time. Condensation i8 conducted under these condition8 fir8t in a ~ lkaline and then in an acid medium which i~ attained by putting aromatic or aliphatic sulphonic acid8 into the reactor.
~urther conden8atlon i8 run in the presence o~ an alkaline agent ~hich en~ure~ the required p~ of the medium. A8 a result, oligomer i~ formed to which polyo~yethylene ethers of isooctyl-phenol are added~ and the condensation process i8 continued at _ g _ I

: ,. . : ~ ~ - - .
; . . .,, ... ~ . . .. .

~os~

the required temperature until the end product is formed. It is expedient to concentrate oligomer in vacuum prior to con-densation with pol~oxyethylene ethers of isooctylphenol.
Continuous process is acco~plished in the iollo~ing way.
The reaction mixture with the required ratio between urea, for-maldehyde, and branched aliphatic polyamine~ is ied continuou~
ly at a constant rate to a first reactor equipped with a re-flux condenser, a ~tirrer, and a steam jac~et. In this reactor condensation takes place in an alkaline medium under constant stirring and heating. The obtained product is delivered ~nti-nuou~l~ through a hydroseal to a second reactor equipped in the same way as the first one. In the second reactor, where an aromatic or aliphatic sulphonic acid i8 ~ed also continu-ously~ condensation takes place in an acid medium under con~tant stirring and heating. ~fter the second reactor the product i8 delivered through a hydroseal to an evaporator operating continuously. Into the evaporator the required amount of an alkali is also added and at the same time oligomer is concentrated, the conden~ate being removed continuously through a barometric tube. ~he concentrated oligomer is fed continuously to a bhird reactor equipped in the same way a~
the iirst and the second ones. In the third reactor an ad-ditional condensation oi oligomer is performed, polyoxyethylene sther o~ isooctylphenol being ~upplied continuously. ~he end .. . . .
.

.. .. ~, ~ .
.: .. . ~ .. . - : , ' .

.. . ... . . .

1056~97 product goes continuously into a tubular heat exchanger through a hydroseal, where it is cooled down and then prepacked for storage.
~ he pxoce~s of producing resins by the proposed i~vention can ea~ily be automated.
For a better understanding of the present invention specific examples are given hereinbelow by wa~ of illustration.
In the given example~ an alkaline agent and aromatic or aliphatic sulphonic acid~ are used in the for~ of aqueous 80-lution~.
Exam~le 1 324 wt. parts of 37% for~alin and 2 wt. part~ of branched aliphatic pol~amine~ are put i~to a metal reac$or equipped with a conden~er, stirrer, steam-water jacket, and vacuum col-lector. ~he polyamines are characterized b~ the following pa-rameterss 1. Content of nitrogen titrated with an acid 20.9 wt.%~
2. ~otal content of nitrogen by K~eldahl~ method - 34.8 wt.%~
3. Chlorine content - 0.12 wt.%
4. ~ractio~alcomposition of vacuum di~tillation at 10 mm Hg:
a) ~raction boiling below 75& - 0.3 wt.%~
b) fraction boliling in the raDge of 75-210C - 11.2 wt.%~
c) bottoms boiling above 210C - 88.5 ut.%~

5. Content of tertiary nitrogen - 13.9 wt.~/o;
6. Average molecular weight - 398.
Ater introduction of polyamines pH is 8.8. Then 100 wt.
parts of urea are put into the reactor. When urea is dis-solved upon stirring, steam is fed into the jacket and the mixture is heated up to boiling for 40 minutes. At 96-97C the mixture is stirred for 45 minutes.
A~ the end of alkaline condensation pH of the medium is 7.5. After that benzenesulphonic acid in the form of a 0.25 N
solution is added to the reactor until pH 5.5 is attained. ?~ In an acid medium condensation is run at 96-97C for 30 minutes.
Next, 4% solution of sodium hydroxide is introduced to pH 8.8.
The reaction mixture is cooled down to 65C and oligomer is concentrated at 65-70C in vacuum at 550-650 mm Hg. The concentration is stopped when the refractive index becomes 1.456; 0.5 wt.
parts of polyoxyethylene ether of isooctylphenol with an ave-rage number of oxyethylene units equal to 10 is put into the reactor~ An additional condensation of oligomer with polyoxyet-hylene ether of isooctylphenol is performed at 100-105C for 15 minute~, after which the resin is cooled down to 40C and discharged into containers.
The resin obtained has the following characteristics:
1. Content of dry residue - 63.2%;
2. Miscibility with water - unlimited;
3. Conditional vlscosity at 20+1C - 17 sec.;
4. pH - 9.0;

, .

1056~97 5. Content of free formaldeh~de - 3.7 ~t~o;
6. Time duri~g whi~h the re~in solution becomes turbid after addition of alumina - 2.6 minute~.
O~et paper manufactured on the basis of the sulphite bleached cellulose by known method with introduction of said resin into a paper mas~ in amounts o~ 30 ~g/t under con-ditions of complete elimination of colopho~y i8 characterized by the following parameters:
1. Ma~s of 1 m - 120 g~
2. Volume masQ - 0.85 g/cm3 3. Breakage length on an average in ; 2 directions - 2.500 m~
4. Fracture (the ~umber of double folds) in transver~e direc-tion - 12;
5. Whitene~s _ 85;
6. Ash content - 14%~
?. ~mooth~ess - 80 sec.
8. De~ormation in tra~sver~e directio~ a~ter wettiDg in water ~or 30 minutes - 1.9%~

9. Picking - absent;

10. Dusting - absent;

11. 6aturatio~ of impres~ion - more than in group 4.

.

Exam~le 2 406 wt. parts of 37~ formalin and 2 wt. parts of branched polyami~es are put into a metal reactor ~itted with a condenser, a ~tirrer, a steam-water iacket, and a vacuum collector. The polyamines are characterized by the following parameter~:
1. Content of nitrogen titrated with an acid - 16.8 wt.%~
2. ~otal content of nitroge~ by ~jeldahl's method - 28.1 wt.%S ~1 3. Chlorine content - 0.14 wt.%;
4. ~ractional composition of vacuum distillation at 10 mm Hg:
a) fraction boilin~ below 755 - 0.4 JJt.~o;
b) fraction boiling in the range of 75-210C - 11.5%~
c) bottoms boiling above 210C - 88 wt.%~
5. Content of tertiary ~itrogen - 11.7 wt.%~
6. ~vera~e molecular weight - 224.
After introduction of polyamines pH is 8.7. Then 100 wt.
parts of urea are put into the reactor. A~ter urea is dis-sol~ed upo~ stirring~ steam i8 fed into the jacket and the mixture is heated up to boiling for 40 minutes. At 96-97C
the mixture i~ stirred for 45 minutes. At the end of alkaline condensation pH o~ the medium is 7.4. After that benzenesul-phonic acid in the form o$ a 0.25 N solution is added to the .
'. . .. . . .

. , ~, . , . -- :

reactor until ph 5.0 is attained. In an acid medium condensa-tion is run at 96-97C for 30 minutes. Next, 4% solution of sodium hydroxide is introduced up to pH 8.9. The reaction mixture is cooled down to 65C and oligomer is concentrated at 65-~0 C in vacuum at 550-650 mm H8. The concentrating is stopped when the refractive index is 1.456; 0.2 wt. parts of polyoxy-ethylene ether of isooctylphenol with an average number of oxyethylene units equal to 7 is put into the reactor. An additional condensation of oligomer with polyoxyethylene ether of isooctylphenol is performed at 100-105C for 15 mi-nutes~ after which the resin is cooled down to 40C and discharged i~to containers.
The resin obtained has the following characteristics:
1. Content of dry residue - 63.2%;
2. Miscibility with water - unlimited;
3. Conditional viscosity at 20~1C - 18 sec.;
4. pH - 8.3;
5. Content of free formaldehyde - 3.1 wt.%
6. Time during which the resin so-lution becomes turbid after ad-dition of alumina - 2.5 minutes.
Offset paper manufactured on the basis of sulphite bleach-ed cellulose by the known method with introduction of said re-sin into a paper mass in amounts of 30 kg/t under conditions of complete elimination of colophony is characterized by the following parameters;

_15-.... .... .... . . .. .. ..... . . .

1~56t~97 1. Ma~s of 1 m - 122 g 2. Volume mass - 0.80 g/cm3 3. Breakage length on an average in 2 directions - 2500 m~
4. ~racture (number of double folds) in tran~verse direction 5. Whitenes~ - 84%~
6. Ash content - 10~;
7. Smoothnes~ - 30 sec.;
8. De~ormation i~ trans~erse direc-tion a~ter wetting in water ; for 30 minutes - 1.8%~
9. Pic~ing - absent~
10. Du~ting - absent~
11. ~aturation of impression - more than in group 4.
~xamle ~
203 wt. parts o~ 37% ~ormalin and 1.9 wt. parts of branched polyamines are put into a metal reactor fitted with a condenser, a stirrer~ a steam-water jacket, and a vacuum collector. ~he polyami~ are characterized by the ~ollowing parameter~
1. Content of nitrogen titrated with an acid - 17.7 wt.%~
2. Total content o~ nitrogen ~y E~eldahl' 9 method - 24.8 wt.%~

.. . . .
- . . '..... ': - . - ' -, . " . ~ . .. ., .. . ~ : .
.. .. . .. . . . .
. .

1056~97 3. Chlorine content - 0.19 wt.yo3 4. Fractio~al composition of vacuum distillation at 10 mm Hg:
a)fraction boiling below 75C - 0~6 wt~o b)raction boiling in the ra~ge of 75-210C - 11.6 wt.%;
c)bottoms boiling above 210C - 87.4 wt.%~
5. Content o~ tertiar~ nitrogen - 12.6 wt.%;
6. A~erage molecular weight - 301.
A~ter introduction of polyamine~ pH i3 9Ø Then 100 wt.
part~ of urea are put into the reactor. After urea is dis-solved upo~ ~tirring, steam i8 fed into the jacket and the mixture is heated up to 8~C for 40 minutes. At 80-81C
bhe mixture i8 ~tirred for 45 minutes. At the end of alkaline conden~ation p~ of the medium i8 7.8. After that benzene-sulphonic acid in the form oi a 0.25 N solution is added into the reactor until pH 5.3 is attained. In an acid medium con-densation is ¢arried out at 80-81C for 30 minutes. Next, 4%
solution of sodium hydroxide i8 introduced up to pH 7.2.
2.0 wt. parts of polyoxyethylene ether of isoo¢tylphenol with an average number o~ oxyethylene units equal to 11 are put into tbe reactor. An additional condensation of oligomer with polyoxyebhylene ether o~ isooctylphenol i9 performed at 100-105C ~or 15 minute~, after which the resin i~ cooled down to 40C and di~charged into container~.
.
- 17 - :

1~356r~97 ~he obtained resin has the followîng characteristics:
1. Content of dr~ residue - 40.0 wt.%;
2. Miscibility with water - unlimited 3. Conditional viscosity at 20+1C - 10 sec.;
~ _ 8.1 5~ Content of free formaldehyde - 4.0 wt~%;
6~ ~ime during which the resin solution become~ turbid a~ter addition of alumina - 2.6 minutes.
O~fset paper manufactured on the basis of sulphite bleach-ed cellulose by the ~now~ method with introduction o~ said resin into a paper mass in a~ounts o~ 30 kg/t under condi-tions of complete elimi~ation of colophony i~ characterized by the following parameters:
1. ~ass of 1 m - 119 g~
2. Volume mass - 0.84 g/cm3;
3. Brea~age length on an aVerage in 2 directions - 2500 m~
4~ Fracture (number o~ double fo,lds) in transverse direction - 12 5- Whitene~s _ 83%~
6. Ash content - 11%
7. Smoothness _ 50 sec.
8. Deformation in transverse direction a~ter wetting in water for 30 mi-nutes - 1.7%J

~ 18 -,, , . , . - . ~ ~

::

9. Picking - absent;
10. Dusting - small;
11. Saturation of impression - more than in group 4.

298 ~eight parts of 37~ formalin and 2 wt. part~ of branched aliphatic polyamines are put into a metal reactor fitted with a condenser, a stirrer, a steam-water jacket, and a vacuum collector. The polyamines ha~e the following parameterss 1~ Content of ~itrogen titrated with an a¢id - 18.2 wt.%~
2. Total co~te~t of nitrogen by K~eldahl~s method - 31.7 wt.%~
3. Chlorine content - 0.17 wt.%~
4. Fractional composition of vacuum distillation at 10 mm Hgs a) fraction boiling below 75C - 0.8 wt.%~ ~;
b) fractio~ boiling in the range of 75-210C - 12.4 wt.%~
c) bottoms boiling above 210C - 85.1 wt.%~
5. Content of tertiar~ nitrogen - 10.0 wt.%~
6. Average molecular ~eight - 200.
After introduction of po b ~mines pH i8 8.5. Then 100 wt.
pa~ts of urea are put into the reactor. After urea is dissolved upon stirring, steam is fed into the ~acket and the mixture ~ - : . ~ , . . .
.. , , : ~ ".

is heated up to boiling for 35 minutes. At 99-lOO~C the mixture is stirred for 45 minutes. At the end of alkaline condensation pH of the medium is 7.2. After that benzenesulphonic acid in the form of a 0.25 N solution is added into the reactor until pH 5.1 is attained. In an acid medium condensation is carried out at 99-100 C for 30 minutes. Next, 4% solution of sodium hydroxide is introduced up to pH 8.8. The reaction mass is cooled down to 65C and oligomer is concentrated at 65-70C in vacuum at 550-650 mm Hg. The process is controlled by the refract-ive index. When it equals 1.456 concen~ration is stopped and 0.5 wt. parts of polyoxyethylene ether of isooctylphenol with an average number of oxyethylene units equal to 10 is intro-duced into the reactor. An additional condensation of oligomer with polyoxyethylene ether of isooctylphenol is perfor~ed at 100-105C for 15 minutes, after which the resin is cooled down and discharged into containers.
The obtained resin has the following characteristics:
1. Content of dry residue - 64.1 wt.Z;
2. Miscibility with w8ter - unlimited 3. Conditional viscosity at 20t1C - 15 sec;
4. pH - 7.5;
5. Content of free formaldehyde - 3.5 wt.%;
6. Tlme during which the resin solution becomes turbid 8fter addition of alumina - 2.9 minutes -20_ , .

lOS6~97 Offset paper manufactured by the kno~m method on the basis of sulphite bleached cellulose with introduction of said resin lnto the paper mass in amounts of 30 kg/t under conditions of complete elimination of colophony is characterized by the fol-lowing parameters:
1. Mass of 1 m2 - 121 g;
2. Volume mass - 0.75 g/cm ;
3. Breakage length on an average in 2 directions - 2600 m; -4. Fracture (the number of double folds) in transverse direction - 9;
5. Whiteness - 88%;
6. Ash content - 10%;
7~ Smoothness - 40 sec.;
8. Deformation in transverse direction after wetting in water for 30 minutes - 1.7/~;
9. Picking - absent;
10. Dusting - small;
11. Saturation of impression - more than in group 4.
Example 5 324 wt. parts of 37% formalin and 2.1 wt. parts of branded aliphatlc polyamines are put into a metal reactor fitted with a condenser~ a stirrer~ a steam-water ~acket, and a vacuum collector. The polyamines have the following parameters:

,.. . ..

_21-l. Content of nitrogen titrated with an acid 18.4 wt%;
2. Total content of nitrogen by Kjeldahl's method - 30.4 wt.~;
3. Chlorine content - 0.16 wt.%;
. Fractional composition of vacuum distillation at lO mm Hg;
a) fraction boiling below 75C - O.9wt.%;
b) fraction boiling in the range of 75 -210 C - 14.9wt.%;
c) bottoms boiling above 210C 88.1 wt%;
5. Content of tertiary nitrogen - 16.0 wt.%;
6. Average molecular weight - 440.
After introduction of polyamines pH is 9.5. Then, 100 wt. parts of urea are introduced into the reactor.
After urea is dissolved upon sitrring, steam is fed into the jacket and the mixture is heated up to boiling for 35 minutes. At 99-100C the mixture is stirred for 45 minutes.
At the end of alkaline condensation pH is 7.9. After that benzenesulphonic acid is introduced into the reactor in the form of a 0.25 N solution until pH 5.2 is attained. In an acid medium condensation is run at 99-100C for 30 minutes.
Then 4% solution of sodium hydroxide is put into the reac-tor up to pH 9.5. The reaction mixture is cooled down to 65C and oligomer is concentrated at 65-70C in vacuum at 550-650 mm Hg. Concentrating is stopped when the refrac-tive index is 1.458, after which 0.5 wt. parts of 1~3~6~D9 7 polyoxyethylene ether of isooctylphenol with an average number of oxyet~ylene units equal to 10 i~ added. An additio-nal condensation of oligomer with polyoxyethylene ether o~
i~ooctylphenol is performed at 100-105C for 15 minutes.
~he re~in obtained is characterized by the following parameters:
1. Content of dry re~idue - 63.7 wt.%;
2. ~iscibility with water - unlimited;
3~ Conditional ~isco~ity at 20~1C - 14 sec.;
4. pE - 7.9~
5. Content of free formalde~de -- 3.6 wt.%s 6. Time during which the resin solution becomes turbid after addition of alumina - 2.8 minutes.
Offset paper manufactured by the known method on the basis of sulphite bleached cellulose with introduction of said resin into the paper mass in amounts of 30 kg/t under the conditions of complete elimination of colophony i~ charac-terized by the following parameterss 1. ~ass of 1m - 121 g~
2. Volume mass - 0.79 g/cm3~ -3. Breakage length on an average in 2 directions - 2600 m~
4. Fracture (number of double folds) ln transverse direction - 12 5. Whiteness - 87%~

- , - , . .

~L056097 6. Ash content - 12%~
7. Smoothness - 80 sec.;
8. Deformation in transverse direc-tion after wetting in water for 30 minutes - 2~~o~
9. Picking - absent;
100 Dusting - small~
11. Saturation of impression - more than in group 4.
~xample 6 ~he process i8 run by following the procedure described in Example 1, but instead of polyog~ethylene ether of isooctyl-phe~ol with an a~erage number of oxyethylene u~its equal to 10, a similar ether with 9 o~yethylene units is used.
~he re~in obtained is characterized by the following parameber~s 1. Content oi dry residue - 62.1 wt.%~
2. ~i~cibilit~ ~ith water - unlimited;
3. Conditional ~i~cosity at 20~1C - 10 sec.;
4. p~ - 7.7 5. Content Qi ~ree iormaldehyde - 3.8 ~t.
6. ~ime during which the resin ~olution becomes turbid aiter addition of alumina - 2.9 minute3.

.~..... , . : ~ .. , .. . . - . . . . .

1056~97 -~:
Offset paper manufactured b~ the kno~n method on the basis o~ sulphite bleached cellulose with introduction o~
said resin into a paper mass in amount~ of 30 kg/t under condition~ of complete elimination of colophony is charac-terized by the following parameters:
1. Mass of 1 m2 _ 12~5 2. Volume mass - 0.83 g/cm3;
3. Breakage length on an average in 2 direction~ - 2600 m;
4. Fracture (number of double folds) in transver~e di-rection - 11 5. Whitenes~ - 86%;
6. A~h content - 11%~
7. ~moothness - ~0 sec.J
8. Deformation i~ tran~erse directio~
aiter wetting in water for 30 mi-nutes _ ~.9%~
9. Pic~ing - absent~
10. Du~ting - small~
aturation oi impre~sio~ - more than in group 4.
Exam,~le 7 ~he ~roce~ i8 run b~ following the procedure de~cribed ~Example 1, but instead of benzenesulphonic acid~ butylsul-iphonic acid is used which is introduced u~til ph 6.0 i~ reached.
!

_ ~ , .. , , . . . - - . ' . , : ' . -:

1~56097 The resin obtained has the following characteristic~: -1. Co~tent of d~ residu~ - 63.8 wt.%;
2. ~iscibility with water - unlimited;
3. Conditio~al viscosity at 20+1C - 17 sec.;
4. pH - 8.2S
5. Content of ~ree ~ormalde~de - 3.9 wt.%;
60 Time during which the re~in solution becomes turbid after addition o~
alumina - 2.6 minutes ~ffset paper manufactured by the known method on the basis of sulphite bleached cellulo~e with introduction of said resin into a paper ma~s in amou~ts 30 kg/t under conditions o$ com-plete elimination of colophon~ i~ characterized by the follow-ing parameters 1. Ma~s of 1m - 116 gS
2, Volume mass - 0.81 g/cm3 3. Breakage length on an average in 2 directions - 2600 m3 4. Fracture (number of double folds) in tran~vers direction - 11S
5. Whitene~ - 85%S
6. Ash content - 11%~
7- æmoothne~ _ 40 ~ec~s 8. De~ormat~on in transverse direction after wetting i~ water for 30 mi-nutes - 1.8%~

:. : - , - ,-10~6~97 9. Picking - absent;
10. Dusting - absent;

11. Saturation of impression - more than in group 4.
Example 8 The process is run by following the procedure desc-ribed in Example 1, but instead of benzenesulphonic acid, salicylsulphonic acid is used which is introduced until pH --4.8 is reached .
The resin obtained has the following parameters:
1. Content of dry residue - 6Ø0 wt.%
2. Miscibility with water - unlimited;
3. Conditional viscosity at 20+1C - 18 sec.;
4. pH - 8.3;
5. Content of free formaldehyde - 3.7 wt.%

6. Time during which the resin solution becomes turbid after addition of alumina - 2.4 minutes.
Offset paper manufacture by the known method on the basis of sulphite bleached cellulose with introduction of said resin into a paper mass in amounts of 30 kg/t under conditions of complete elimination of colophony is charac-terized with the following parameters:
1. Mass of 1 m2 - 3 2. Volume mass - 0.82 g/cm ;

3. Breakage length on an average in 2 directions - 2600 m;

., .

1~ 5 6~9 7 4. ~racture (number of double folds) in transverse direction - -~10;
5. Whiteness - 83~o;
6. Ash content - 12%;
7. Smoothness _ 60 sec.3 8. De~ormation in transverse direction after wetting in water for 30 minutes - 1.7%~
9~ Picking - ab~ent~
10. Dusting - ~mall~
11. Saturation of impression - more than in group 4.
Exampl~
~he proce~s is run by ~ollowing the procedure described in E~ample 1, but in~tead of benzenesulphonic acid, a mixture of ~ulphonio acids i8 used obtained by ~ulphonating a mixture Or paraffinic hydrocarbons with an average molecular weight of 250.
~he resin obtained has the following characteristic~:
1. Content of dr~ re~idue - 61.2 wt.%~
2. Miscibility with water - unlimited~
3. Conditional vi~co~ity at 20~1 & - 40 sec.
4. p~ - 8.4 5. Content of free formaldehyde - 3.8 wt.%~
6. ~ime durlng which the resin solution becomeo turbid after addition of alumina - 2.5 minutes.

.
.. , , , . , ., . . : .

.~. . -~0560~7 Offset paper manufactured by known method on the basi~ o~
~ulphite bleached cellulose with introduction o~ said resin into a paper mass in amounts of 30 kg~t under conditions o~ -complete elimination of colopho~y is characterized by the fol-lowing parameter~:
1. Mas~ of 1 m2 - 119 g~
2. Volume ma~ - 0.83 ~g/cm3 3. Breakage length on an average in 2 directionQ - 2700 m3 4~ Fracture (number of double .~old~) in transverse di-rection - 11~
5. ~hitene~s - 84%;
6. Ash content - 10%~
7~ Smoothness _ 50 sec.
8. De~o~mation in tranqverse direc-tion after wettin~ in water for 30 minutes - 1.7~
9. Picki~g - ab~entJ
10. Du~ting - small~
11. Saturation o~ impression - more than in group 4.
EsamPle 10 ~he present eYample i5 gi~en for illustrating ~ continuous process o~ producinB water-~oluble urea-formalde~de resin~ mo-di~ied with aliphatic polyami~es.

.

`, ! . ' "' " ' ' ';.' '. ' . ~' " ~ .' ' . ' ~

-lOS6097 A reaction mixture containing 324 wt. parts of 37%
formalin per 100 wt. parts of urea pH 8.8, preliminary reached by using 2 wt. parts of branched aliphatic polya~
mines described in Example 1, is fed continuously into a first reactor, equipped with a reflux condenser, a stirrer, and a steam jacket, at a rate which ensures the residence time of the mass in the reactor equal to 45 minutes. The temperature in the first reactor is maintained within the range of 96-97 C. The condensation product obtained in the first reactor goes through a hydroseal into a second reactor equipped in the same way as the first one. 0.25 N solution of benzenesulphonic acid in an amount ensuring Ph of the product equal to 5.2 is added into the second reactor. The temperature in the second reactor is 96-97C.
The residence time of the product in the second reactor is 30 minutes. The product from the second reactor is fed continuously to an evaporator operating continuously where concentrating of oligomer takes place in vacuum at 550mm Hg until the refractive index 1.457 is reached. pH of the product in the evaporator is kept equal to 8.8 by contin-uous feeding of 40% solution of sodium hydroxide. The condensate is discharged continuously from the evaporator through a barometric tube while the concentrated oligomer is delivered continuously to a third reactor equipped as the first and the second ones. In the third reactor an additional condensation of oligomer with a polyoxyethylene ether of isooctylphenol, with an average ,, .
;

~ -30-number of oxyethylene units equal to 10, is performed, said ether being fed continuously. The residence time of the product in the third reactor is 15 minutes. From the third reactor the resin goes continuously through a hydroseal into a tubeular heat exchanger where it is cooled down to 40C and then discharged into containers for storing.
The resin obtained is characterized by the following parameters:
1. Content of dry residue - 63.7 wt.%;
2. Miscibilitywith water - unlimited 3. Conditional viscosity at 20+1C - 20 sec.;
4. pH ~ 7.5;
5. Content of ~ree formaldehyde - 3.6 wt.%;

6. Time during which the resin solution becomes turbid after addition of alu-mina - 2.7 minutes.
Offset paper manufactured by the known method on the basis of sulphite bleached cellulose with introduction of said resin into a paper mass in amounts 30 kg/t under condi-tions of complete elimination of colophony has the following properties:
1. Mass of lm2 - 120 g;
2. Volume mass - 0.84 g/cm3;

3. Breakage length on an average in 2 directions - 2700 m;

.

1C~56~97 4. ~racture (number of double f`olds) in transverse direction - 12;
5. Whiteness - 88%~
6. Ash content - 10%;
7. Smoothness - 40 sec.;
8. Deformation in transverse direction after wetting in water for 30 minutes - 1.8%;
9. Picking - ~one 10. Dusting - none;
11. Saturation of impres~ion - ~ore tha~ i~
group 4.

., . ~ .

- - ~ :

Claims (10)

The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:

1. A method of producing water-soluble urea-formaldehyde resins modified with aliphatic polyamines, residing in that interaction is performed of 1 mole of urea, 1.5-3.0 moles of formaldehyde, and branched aliphatic polyamines, with molecular weight of 200-440 and the con-tent of tertiary nitrogen 10-16 wt.%, at 80-100°C and pH
of the alkaline medium 7.2-9.5, which is attained by proper amounts of polyamines; a sulphonic acid selected from the group consisting of aromatic and aliphatic sul-phonic acids of the general formula R-SO3H, where R is a radical selected from the group consisting of aryls and alkyls is introduced into the obtained mixture until pH

of an acid medium equal to 4.8-6.0 is attained; an alka-line agent is added up to pH of an alkaline medium 7.2-9.5 with the formation of oligomer; said oligomer is inter-acted with polyoxyethylene ether of isooctylphenol, which has 7-11 oxyethylene units, at 100-105°C and is introduced in amounts of 0.2-2.0 wt. parts per 100 wt. parts of the initial urea.

2. A method as claimed in Claim 1, wherein urea and formaldehyde are used in the mole ratio 1:2.2-2.4 respectively.

3. A method as claimed in Claim 1, wherein branched aliphatic polyamines are introduced in amounts ensuring pH of the alkaline medium equal to 7.5-9Ø

4. A method as claimed in Claim 1, wherein sulphonic acids selected from the group consisting of aromatic and aliphatic sulphonic acids are introduced in amounts ensuring pH of an acid medium 5-5.5.

5. A method as claimed in Claim 1, wherein an alkaline agent is added in amounts ensuring pH of the medium 8.8-9.3.

6. A method as claimed in Claim 1, wherein as aromatic sulphonic acids use is made of sulphonic acids selected from the group consisting of benzenesulphonic acid, toluenesulpho-nic acid, xylenesulphonic acid, naphtalenesulphonic acid, and salicylsulphonic acid.

7. A method as claimed in Claim 1, wherein as aliphatic sulphonic acids use is made of sulphonic acids selected from the group consisting of butylsulphonic acid and sulphonic acids obtained by sulphonating hydrocarbons of paraffinic series.

8. A method as claimed in Claim 1, wherein as polyoxyethy-lene ethers of isooctylphenol use is made of polyoxyethylene ethers isooctylphenol with 9-10 oxyethylene units.

9. A method as claimed in Claim 1, wherein, prior to add-ing polyoxyethylene ether of isooctylphenol to oligomer, the latter is concentrated in vacuum at 550-650 mm Hg.

10. A method as claimed in Claim 9, wherein oligomer is concentrated until the refractive index 1.456-1.458 is attained.