CA1058794A - Crosslinked polyamidoamine condensation products for papermaking - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE

Crosslinked water-soluble reaction products for the papermaking industry obtained by reacting (a) 1 part by weight of an ethyleneimine-grafted polyamidoamine obtained by condensing 1 mole of a dicarboxylic acid having from 4 to 10 carbon atoms with from 0.8 to 1.4 moles of a polyalkylene polyamine having from 3 to 10 alkyleneimine units, followed by grafting of from 2 to 8 ethyleneimine units per basic nitrogen atom onto the resulting polyamidoamine, with (b) from 0.3 to 2 parts by weight of a reaction product obtained by reacting a polyalkylene oxide having from 8 to 100 alkylene oxide units with epichlorohydrin in the presence of a Lewis acid, so that from 1.0 to 1.5 moles of epichlorohydrin are present per equivalent of hydroxyl groups in the polyalkylene oxide, at a temperature of from 20° to 100°C in aqueous solution or in a solution in water and a water-soluble organic solvent, the solution having a solids content of from 5 to 50% by weight, the reaction being carried to a point at which the viscosity of an aqueous solution containing 20% of the auxiliary is from 300 to 2,500 centipoises at 20°C.

Description

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10~ 7~ ~

f `' : O.Z. 30,668/31,262 ` -~
CROSSLINKED POLYAMIDOAMINE CONDENSA~ION PRODUC~S FOR PAPERMAKING
~¦~ This invention relates to novel reaction products of po-ly-amidoamines with higher molecular weight difunctional crosslinkers, which are valuable for use in the papermaking industry~ The i! ' invention also relates to the manufacture and use of such ` reaction products, particularly as retention and drainage aids .'~ in the papermaking industryO
;1 It is well known that polyethyleneimine and9 to a lesaer ~ extent, polypropyleneimine are useful in the papermaking industry ';1 as retention aids for ~illers and ~ibers, as aids for improving the drainage rate during sheet formation and as flocculants in pulp recoveryO Such products have been known for more than 30 yearsO New progress was achieved by the use of epichlorohydrin , ~ :

.~ - .

,:, 0 ZO 30,668/31,262 as crosslinker giving crosslinked polyethyleneimines such as are described, for example, in German Patent 1,670,296~ ~inally, it .~ ...
is also known that crosslinking, for example with epichlorohydrin, of polyamidoamines, iOe~ reaction products o~ such polyamines with dicarboxylic acids, gives paper auxiliaries which also constitute good ~iber retention aidsO However, in use, these . :
groups of products suffer from the drawback that each shows its optimum e~fect only within a~limited pH rangeO For example, cross- j linked polyamines obtained according to German Patent 1,670,296 show best results only at neutral pH~ whilst crosslinked poly~
amidoamines such as are discIosed in US Patent 3,250,664 exhibit optimum properties only at acid pH~
In papermaking, more or les~ rapid changes in manufacturing conditions from acid to neutral and vice versa are usually ~ .
necessary when different types of paper are made, and this gave rise, at an early ~tage, to the desire to develop an auxiliary which is capable o~ producing optimum results both at neutral and at acid pHo `. .
i, .
The next stage of development in this field satis~ied this . :~
.
requirement and is de~cribed in US Patent 3,642,572, where the problem is solved by grafting ethyleneimine onto a polyamido- :
amine and then crossIinking with epichlorohydrinO These aids have hitherto given completel~ satis~actory results. However, one drawback thereof, which does not relate to the quality of the paper obtained9 consists in the danger involved in using the monomeric ethyleneimine necessary for the manufacture o~
such agents, this substanoe being well known as one requiring increased care when used in synthesis techniques on account o~ :

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its toxicity. Furthermore, this compound is not universally available, as it is not e~erywhere possible to carry out the ;
process described in the cited patent without restrictions.
Thus economical considerations have led to the problem forming the basis of the present invention, i.e. the problem of providing a paper auxiliary in the manufacture of which monomeric ethyleneimine is used not at all or only in small amoun~s and which nevertheless show the same or even better results when used in the papermaking industry.
It is becoming increasingly important to the paper manufacturer to improve the efficiency of the papermaking processes, this including, in particular, thelr acceleration.
This consideration has led to a further problem forming the basis of the present invention i.e. the problem of providing novel auxiliaries which accelerate drainage to a greater extent than the agents described in the last-mentioned reference and which increase the retention of fibers and fillers on the wire screen and further improve the flocculating action for pulp recovery without a return of the already solved problem relating to the use of such agents in both acid and neutral pH ranges.
Thus, the present invention not only aims at avoiding the use of monomeric ethyleneimine but also at improvements designed to accelerate and thus cheapen the various papermaking processes.
The present invention relates to a process for the manufacture of nitrogen-containing condensation products, which compr~ses reacting (a) 1 part by`weight of an ethyleneimine-grafted polyamido-~amine obtained by condensing 1 mole of a dicarboxylic acid having from 4 to 10 carbon atoms with from 0.8 to ~ -1.4 moles of a polyalkylene polyamine having from 3 to 10 alkyleneimine units, followed by grafting of from 2 to 8 ethyleneimine units per basic nitrogen - atom onto the resulting polyamidoamine, with ~`

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- 10~8~94 (b~ ~rom 0.3 to 2 parts by weight of a product obtained by reacting a polyalkylene oxide having from a to 100 alkylene ,~
oxide units with epichlorohydrin in the presence of a Lewis acid, such that from 1.0 to 1.5 moles of epichloro- ~
hydrin are present per equivalent of the hydroxyl groups -in the polyalkylene oxide, , . .
at a temperature of from 20 to 100C in aqueous solution or in a solution in water and a water-soluble organic solvent, the solution having a solids content of from 5 to 50% by weight, the reaction being carried to a point at which the ; , ..
viscosity of an aqueous solution containing 20~ by weight -' ;`~
of auxiliary is from 300 to 2,500 centipoises at 20C. ~ i`
The principle of reacting such epichlorohydrin-treated polyalkylene oxide derivatives with nitrogen-containing compounds is known, per se, from German Published Application 1,932,394 and US Patents 3,691,110 and 3,215,654. More complicated reac- ~
tions, in which such difunctional crosslinkers are involved, `
are revealed in German Published Application 2,162,567, in which the end products are described as being suitable for us~e in~the papermak1ng~industry, includlng for use as retention aids. However, the;basic idea of these three references relates to the treatment o the condensation products thus obtained for the purpose of rendering them fully effective, which treatment consists either in post-crosslinking with epichlorohydrin or conversion to a water-soluble form using sodium bisulfite. Th~
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OOZo 30,668/31 3 262 latter measure is described in US Patent 3,691,1100 Another teaching which reveals the principle o~ this reac-tion is German Published Application 1,546,2900 In this case how-ever the aforementioned difunctional polyalkylene oxide deriv-atives are reacted not with polyamido amines but only with poly-alkylene polyamines, pre~erably low molecular weight polyalkylene polyaminesO The only application mentioned in this re~erence is the use o~ such products as auxiliaries in the recovery of` fibers :~
and ~illers from the effluents leaving paper machinesO However, such agents are less suitable as fiber retention aids or drainage aids, sinoe they are use~ul for these latter applications only within narrow pH rangesO Thus the process o~ the invention having the basic concept o~ using polyamido amines, maintaining speci~ic proportions by weight and molar ratios and, above all, achieving specific final viscosities and, therefore, o~ obtaining novel product~ o~ optimum efficiency constitutes an unexpected advance in the artO
The polyalkylene polyamines to be used as starting materials in the manufaoture o~ the products o~ the invention are well-known compounds which are commercially available and which aregenerally obtainable by condensing corresponding alkenyl diamines.
They are also obtained as byproducts in the synthesis o~ ethylene diamine and are readily obtained by hydrogenation of acrylo-nitrile adductsO
Pre~erred suitable polyalkylene polyamines are those which contain ~rom 2 to 6 alkylene bridges between the amino groupsO
Advantageously, use is made o~ those having from 3 to lO basic ;~:
nitrogen atoms in the molecule, Examples of suitable polyalkylene ~ - 5 -, ''~ ~; '.
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''', ' ' ' ~ 58794 oO~O 30,668/31,262 polyamines are diethylene triam;ne, triethylene tetramine, tetra-ethylene pentamine9 dipropylene triamine, tripropylene tetramine and dihexamethylene triamineO The polyalkylene polyamines may be used as crude products or mixtures, if desired in the presence of small amounts of diaminesO The amount of such diamines9 prefer~
ably ethylene diamine, which may be present is pre~erably up to ; .
10% by weightO -j Suitable d;carboxylic acids ~or reaction with the said :::
polyalkylene polyamines are those having from 4 to 10 carbon atoms such as succinic acid, maleic acid9 adipic acid, glutaric acidg suberic acid~ sebacic acid and terephthalic acidO In general, ~ use is made of ~rom 008 to 104 moles of polyamine per mole of - dicarboxylic acid~ If desired, up to 8 moles o~ ethyleneimine per basic nitrogen grouping may be grafted onto the reaction products according to US Patent 3,642~5720 In this case, prefer-ably from 2 to 8 ethyleneimine units are selectedO
: ~he other reactant is the polyalkylene oxide derivative whose terminal hydroxyl groups have been reacted with epichloro- ` :
, hydrinO Su;table compounds o~ this kind are generally those :~
~20 containing ~rom 8 to 100 alkylen:e oxide un;ts in the polyalkylene oxide prior to reaction with epichlorohydrinO Suitable poly-alkylene oxides are mainly homopolymers and copolymers of ethylene oxide and/or propylene oxide, the proportion of propylene oxide groups advantageously being not more than 50% of the total alkylene oxide groupsO We prefer to use block copolymers of the formula :
Ar ~ORl)mtOR2)n(0Rl)pHJ2 ;
in which R1 is an ethylene radical~ R2 is a 1,2-propylene radical7 " . .' . .

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OOZo 303668/31,262 m and p denote values of from 4 to 50, n denotes values of from O to 50 and A denotes the radical of a dihydric alcohol of from 2 to 6 carbon atoms or a polypropylene glycol radical having ~.
~rom 1 to 50 propylene oxide units, in which case n is equal to 00 Individual representatives o~ such substances are ethoxylated or ethoxylated-oxypropylated dihydric alcohols such as glycol, propylene glycol, hexanediol and simple polypropylene glycol which may contaln up to 50 propylene oxide units in the moleculeD
The latter substanceg when ethoxylated on both sides, provides mixed block copolymers of ethylene oxide and propylene oxideO
Thus the polyethoxylated or polyoxypropylated products are com-pounds hav;ng two terminal free hydroxyl groupsO These terminal hydroxyl groups are the sites for subsequent reaction with epichlorohydrinD To this end, at least equivalent amounts and preferably from lol to 105 moles of epichlorohydrin are used per OH groupO There are produced ~-hydroxy-7-chloropropyl ether ¢ompounds which are converted to glycidyl ethers by the elimination of HCl, these being the compounds which have the crossl;nking action on the aforementioned polyam;doamines 3 These compounds . :
are referred to below as ''crosslinkers''O
The rea¢tion of epichlorohydrin with the polyalkylene oxide .
derivatives proceeds according to well-known reaction mechaniRms and i8 initiated by means of Lewis acidsO Suitable Lewis acids ;
are, for example9 borofluoride etherate, phosphoric acid, sulfuric acid, perchlorio aoid, chloroacetic acid, aromatic sulfonic acids3 zinc chloride and aluminum chlorideO However, it is generally advantageous to use borofluoride etherate as catalyst (Lewis acid) for this reaction - 7 ~

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oO~, 30,668/31,262 This high molecular we;ght di~unct;onal crosslinkers are then reacted with the polyamidoamines~ the amount o~ crosslinker used being ~rom 003 to 2 parts by weight per part by weight of polyamidoamineO It will be appreciated that the amount of said : .
difunctional compounds necessary for crosslinking depends on the constitution of the polyamidoamine used and that of the cross-linker itsel~O On the other hand) when crosslinking a given starting polyamidoamine with sald high moleaular weight cross~
linkers in order to obtain a solut;on hav;ng a specific viscosity it will be necessary9 on account o~ possible hydrolysis of the crosslinker, to use increasing amounts of crossl;nker ~or increasing reaction temperatures and increasing contents o~ ~.
water in the solutionO
Use is made of the aforementioned amounts o~ crosslinker, pre~erably from 0035 to 108 parts by weight 3 per part by weight o~ polyamidoamineO The crosslinking reaction is advantageously carried out in a 5 to 50% and pre~erably 10 to 30% wtw aqueous -.
: solution9 based on the total weight o~ the reactantsO The amount o~ crosslinker necessary to achieve the desired degree of cross- :
. 20 linking may be added ~o the reaction solution either all at once or in portion~O The course o~ the reaction is ~ollowed by ~
observing the increase in viscosity of the aqueous solutionO
The portion-wise procedure i9 alway~ pre~erable, since the reaction can be better controlled in this manner and the risk . :
of the reaction mixture gelling îs muah lessO Furthermore, the portion-wise addition o~ the high molecular weight crosslinker obviates the addition o~ an excessive quantity and makes it -.
easy to obtain a specific viscosityO The reaation is carried ~..-. .

~$~79~ oOz~ 30,668/3~,262 to the point where the high molecular weight resins formed are 8till just water~soluble and have a viscosity of more than or equal to 300 mPasec when measured at 20C on a 20% aqueous solutionO It is preferred to aim at obtaining resins having viscosities of ~rom 400 to 2,500 mPa~secO The reaction is gen-erally carried out at temperatures of rrom 20C to 100C and preferably from 40 to 80C ov0r from 1 to 15 hours~ The conden~
sation reaction is advantageously carried out at a pH above 8 and preferably at from pH 9 to llo The condensates o~ the invention are ba~ic on account of the amino groups contained thereinO However, the effeotiveness of the producks o~ the invention as drainage aids, flocculants and retention aids is not af~ected by neutralization of the resinous solution with acidsO In the maiority of cases, they have the same advantages as the products described in US
Patent 3,642,572~ that is to say they can be used in both the .~
acid and the alkaline pH rangeO Compared with products consisting .
o~ basically crosslinked polyamidoamines or crosslinked 1,2-polyalkylene polyamines using epichlorohydrin alone, the present ~; .
20 products show improved properties as regarde the retention of illers9 the drainage rate and the flocculation or floatation .;
in pulp recovery processes involved in papermakingO There is : , also frequently an unexpeated improvement in said properties ~: :
over the products of US Patent 3,642,5720 Particular mention ` :
r may be made of the greatly improved whiteness Or the papers ::~
obtained, which show far less tendency to yellow eVen when ~tored ~or relatively long periodsO The present products may be used in any pH range encountered in papermaking. Like the : :
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' 1051~794 O~Z~ 30,668/31,262 products of US Patent 3,642,572, they are more universally appli~
cable than the products of German Published Application 1,546,290, which are merely useful to a limited extent as floatation agents in waste waters coming from papermaking machinesO
The products of the invention may be successfully used in the manufacture Or papers of all kinds, in an amount of from about OoOl to about 003% by weight of the weight of dry pulp, and of sized and un~ized cardboard material~, in the presence or absence o~ aluminum sulfateO
In the following Examples the parts and percentages are by weight O
EXAMPLES
(A) Manufacture of Pol~eth~lene ~1YCO1 ether-bi~-R~hvdro~v~
chloroProP~l ether I parts o~ a polyethylene glycol ether having an average molecular . ~ .
size of II ethylene oxide units thydroxyl number III), (water content IV as measured according to Ko Fischer in % w/w) are ~ -mixed with V parts of epichlorohydrin and VI parts o~ borofluoride diethyl etherate are added and then, at a temperature of from 60 ~:i to 75C, a further VII parts of epichlorohydrin are added over from .
about 005 to 105 hoursO Condensation is continued at from 60 to 70C until the epoxide titer of the solution has dropped to 0 (VIII hour~)c The resulting product has a chlorohydrin oontent o~ IX in equivalents per gram (boiling for 30 minutes with O.lN
caustic soda followed by back-titration) and an acid content of X milliequivalent~ per gram.

` 10~87~ oOzO 30,668/31,262 ~ -Designation ~ V 1 V 2 V 3 V 4 V 5 moles of epichlorohydrin :
per mole of polyethylene glycol 1 : 300 202 3.0 206 3.0 III 266 136 145 83.5 29 IV OolO 0.22 00017 0.03 o.o4 V 222 102 139 72 33 . :
VI 606 8,1 801 901 1700 VII 1998 916 1148 650 300 ~.:
VIII 302 400 507 5 4 .:
IX 3052 2.00 2024 1033 0054 ..
X 000097 0.0085 o.oo6 0~008 0.013 ;.`~ ;
: (B) Manu~acture of ~olyamid a n s V 6 (reaction product of '.
~` glutaric acid and diethylene triamine) ,.
660 parts of glutaric acid are added to 566.6 parts (molar ratio 1 : 1~1) o~ diethylene triamine in an atmosphere o~
nitrogen over 20~minutes with thorough stirring. The temperàture ; ~:
of the reaction mixture ri~es to about 130C. The temperature of ...:.
1~ i . i ~,. ...
j the reaction melt is then raised to from 158 to 160C over about '~
I 2 hours and then to 170C over a further hour, the water ~ormed ~ :
..
being distilled of~ during condensation (172 parts o~ diQtillate).
A~ter the bottom~ temperature'ha~ been maintained at 170C ~or ~;
2.5 houræ ? the acld number o~ the resin has dropped to 505. It is `
cooled and 1,040 parts o~ water are slowly added after the temper- ~ .
;
ature has reached 150C. The pale-colored aqueous resin solution has the following properties~
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OOZo 30,668~31,262 water content (Ko Fischer) 49 D 7%
acid number 3O54 amine num~er in glacial acetic acid titrated with perchloric acid: 4Oo5 milliequivalents per gram , viscosity o~ 45~ solution at 20C (Hoeppler ~alling ball method): 196 centipoisesO
Manufacture o~ V 7 (reaction product o~ adipic acid and diethylene triamine) 1,044 parts o~ water and 2,150 parts of diethylene triamine ~.
are mixed together under nitrogen at room temperature, and 2,800 parts of adipic acid are then added below 80C with cooling. .
The bottomæ temperature is raised to 170C over 5 hours3 during ~I which period the water added and the water ~ormed during con-.. densation is distilled off, and this temperature is maintained l until the resin has an acid number of less than 10 ~908) (after i about 10 hours at 170C)o The mixture is then cooled and 3,100 ;~
,¦ parts o~ water are added to the viscous resin after the tem- :
! perature has reached about 130 to 140C o The aqueous resin 1 solution has the following properties:
'I , ~ater content (Ko Fischer): 3806% (solids content: 6104%) acid numbero lOo ~ based on 100% product Z 20 amine content (in glacial acetic acid titrated with perchloric acid): 503 milliequivalents per gram based on 100% product ~ .
.' viscosity (45% solution at 20C, Hoeppler falling ball method): .
202 centipoises O ~ ' .. " ' Z

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~5879~ -.
O~Zo 30~568/31~262 -Manufacture of V 8 (reaction product o~ adipic acid and dipropylene triamine) 585 parts o~ dipropylene triamine dissolved in 300 parts .
of water are mixed with 584 parts of adipic acid under a blanket of nitrogenO The temperature of the aqueous solution rises to about 120Co The condensation temperature is then raised to 150C over 5 hours and then to 165-170C over 2 hours and is maintained at this value for a further 9 hoursO Evaporated bases are replaced during the final 9 hours of oondensation by the ' dropwise addition of 67 parts of dipropylene triamineO Following condensation, the resin has an acid number of 90 20 It is cooled and 440 parts of water are added when the temperature has reached ~::
1~0Co ~ `
Solids content (Heidbrinktsee "Fette und Seifen" 5~ ~5), 1951~ '!`. ''"
page 291 0~3 g~ 60 minO 80C)o 6904%
amine number- 3094 milliequivalents per gram . :~
acid number: 806 viscosity of 45% a~ueou~ solution at 20C (Hoeppler falling ball method)- 300 cp ; :~.
nD 104259 (45% solution)O . j .
Manuracture of V 9 (methyl adipate ~ dipropylene triamine) 585 parts o~ dipropylene triamine are mixed with 696 parts ;.. :;
of dimethyl adipate under nitrogen at from 80 to 85C. Amidization iB e~ected by raising the bottoms temperature to rrom 168 to 170C over 5 hours and distilling off the methanol formed, After a further two hours at 168-170C, the total amount of di~tillate ~ ;
is 252 partsO The visoou~ resin is cooled and about 1,000 parts of water are added when the temperature has reached 140C. The .~;
- 13 - . :

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10~8794 OOZo 30,668/31,262 ..
properties o~ the product are as ~ollows:
water content (Ko Fischer)o 4806%
solids content (Heidbrink, see V 8 above): 5009%
amine content (in glacial acetic acid titrated with HCl04)o 20 96 milliequivalent/g viscosity of 45% aqueous solution at 20C (Hoeppler falling ball method): 151 cp nD of 45% solution~ lo 425gO
M2nufacture of V 10/11 (adipic acid ~ tetraethylene pentamine ,:
I (~ ethylenediamine)) i 692 parts of tstraethylene pentamine (529 parts of tetra- :
ethylene pentamine and 113 parts of ethylene diamine) are dissolved in 300 (400) parts of water and mixed with 438 (584?
parts Or adipic acidO The temperature of the reaction solution rises to more than 100Co The bottoms temperature is raised to from 160 to 170C over 6 hours with~distillation of the water and is maintained at th;s value for about a further 7 hoursO
. .
~he amount of distillate produced during condensation is 383 parts (540 parts)~ the amine content o~ the distillate being oO78 (1034) milliequivalents per gO Condensation of the resin is stop~
¦ ped at an acid number of lOoO (1007), after which the resin is : 20 cooled and, when the temperature has reached 140C, 1,000 parts ;:
(1,050 parts) o~ water are added thereto. ~he properties of the products are as follows:
.1 ' , : .

~794 O~Z~ 30,668~31,262 ,~:
V 10 V 11 '',,:'.' .
water content (Ko Fischer) 490g% 5004% ~
;., solids content (Heidbrink) 5002% 4909%
amine content 5.65 meq~g 4010 meq/g ;
acid content OoO88 ~ oOog6 1t viscosity (45% solution/20C, 721 cp 882 cp .
Hoeppler ~alling ball method) .
Manufacture of V 12 (adipic acid ~ diethylene triamine - hexa~
methylene d;amine ad;phate ("AH salt") 584 parts of adipic acid and 204 parts of AH salt are added to 458 parts o~ diethylene triamine and 458 parts of water under ;
nitrogen, durin~ which process the temperature rises to about : .
: 120C. This bottoms temperature is then raised to 165-175C over 5 to 6 hoursO Condensation is continued ~or a further 8 hours at `
about 170C until the aci.d number of the resin has fallen to 9~90 ~`
The distillate formed (642 parts) contains 0.103 equivalent of : baseO The pale-colored viscous resin is cooled and, when the tem- :
~ perature haæ reaohed 140C, is diluted with lS100 parts o~ water ! The product has the ~ollowing properties: ~.
~;~ water content (Ko Fischer)~ 510 2% :
solids content (Heidbrink): 4806%
;;,, amine content: 204 milliequivalents per g acid content: oOo68 " " " /:

20 viscosity (20C, aqueous solution, Hoeppler ~alling ball method)o 422 cp ..

nD (45% solution)o ~ 104234 ~. :

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oOz. 30,668/31,262 Manufacture of V 13t(14) (according to German Published Application 1,802,435) .
326 parts of the 6104 % resin V 7 are mixed with 405 parts of concentrated sulfuric acid in 50 (70) parts o~ water and the `.
mixture is heated to 80Co The mixture is stirred well and 800 ``
(200) parts of 50% aqueous ethylene imine are added over from 4 to 5 hours, the temperature of the resin solution then being maintained at from 80 to 90C for a further 2 to 3 hours (until no ~urther aziridine ring can be detected with p~nitrobenzyl pyridine)0 The products have the following propertieso V 1~ V 14 water content (Ko Fischer)~ 4804% 4902%
(solids content): (5106% 50.8%) amine content (in glacial acetic ~. .
acid titrated with perchloric acid): 701 meq/g 502 meq/g '~
nD (45% solution): 1~4389 103229 ~ .
vi~cosity (20C, 45% solution, ~`
Hoeppler falling ball method) 822 cp 393 cp (C) Manufacture Of condensation product_ :
EXAMPLES 1 to 14 a parts Of the b% aqueous solution of polyamidoamine V c are 1: diluted with d parts o~ water and the now e% solution is heated ¦ to fCo i parts o~ a 20g aqueous solution of crosslinker V k are then added to the resin at hC over ~ hours, during which addition "~
~ the pN of the reaction solution is maintained at m by the addition

3 of 1 parts of a 50% wlw caustic soda solutionO The crosslinker ¦~
¦ 20 solution is added in portion~ Or reducing magnitude as the resin i formation progressesO The rate of addition of the crosslinker ~ - 16 ~5~79~ OOZ~ 30,668~31,262 :`
depends on the ~inal viscosity desiredO Since these resins show ;
no "Newton flow'l, the viscosity is measured at two different shear .~
gradients (the value given is that obtained after rotation for .: :
3 minutes)0 At a shear gradient of 2405 sec 1 the viscosity of ~!'`.~"
the resin at the end of crosslinking is n cP (20C) and at a shear gradient of 6905 sec 1 it is p cP (20C) using a rotary viscometer by Haake, Berlin)O The pH of the resin is q. The resin solution is neutralized with r parts of 85% formic acid to pH 800 and is then diluted with s parts of water to a an active content .;
(WS)~ of 18%. The final product shows a viscosity of t cP at 20C
at a shear gradient of 2405 sec 1 or of u cP at 20C at a shear gradient of 69.5 sec lo v parts o~ crosslinker (100%) are introduced per part of `;
polyamidoamide resin (100%) to effect crosslinking ~ Caustic soda, formic acid and water are not regarded as active ... .
ingredientsO i ~

TABLE .
Exo 1 2 3 4 5 6 7 8 g a 800 390 326 326 228 252 356 350 350 b 20 6104 6Io4 6104 61.4 6904 51 50~1 4906 c 6 7 7 7 7 8 9 10 11 :
: d 0 810 674 674 472 623 552 525 518 .~:
e (20) 20 20 20 20 20 20 20 20 ` .
.
f 70 70 55 70 60 60 40 60 50 ,.. .
~ 14 8 5~6 608 905 902 2~8 501 605 h 50-70 67-70 55-70 66-74 60-74 60-67 67-70 66-70 68-72 1 652 428 475 785 1280 689 618 795 270 r . .
k 4 1 3 4 5 4 2 4 4 .

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'` '-~ ~' : '' O D Z o 30 ~ 668/ 31 ~ 262 Exo 1 2 3 4 5 6 7 8 9 l 16~7 2000 1805 1700 1500 lOoO 20~0 17~5 6~0 m 1006~ 1002- 1007- 1005- 1005- 1005- 1099- 10~5- 1005-9ol 9~2 903 9ol 903 906 908 9~2 9~2 n 1363 1055 883 1635 1280 1180 1290 1291 1035 p 903 806 683 1144 926 877 901 921 745 `~
g 10~2 lOol 1007 1003 10~1 9u9 10~8 1005 10 ~. .
r 20 D 3 20 26 28 14 2503 41 42 33 s 144 150 146 183 191 139 111 122 87 `
t 1055 700 622 1371 1153 819 691 963 818 .

.
v 0081 0035 0~47 oO78 1083 0079 o~68 Oo91 0031 ;
Exo 10 11 lZ 13 14 a 300 400 400 400 400 b 48 5106 5106 50D8 5008 c 12 13 13 14 14 d 430 630 630 620 620 e 20 20 20 20 20 --f 70 70 65 65 65 302 10 ~ 6 1005 908 8~ 5 ~1 h 68-73 60~70 60-66 60-68 62-70 1 : _ ¦ k 4 4 5 4 5 805 aOO O 600 0 m 10 D 2 9 ~ 6 1006 9 D 6 1007 9 D 2 10 ~ 5 9 ~ 1 10 ~ 5 9 ~ 4 n 1164 1525 1220 1400 1218 908 9 D 2 9 ~ 6 9 ~ 4 ~ 18 ~

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:' 58794 `:
OOZo 30,668/31,262 Ex. 10 11 12 13 14 r 1405 84 7~ 49 45 ",: .
s 112 60 105 113 179 ' , .
t 689 1000 764 910 855 u 514 738 572 652 642 ''~, oO65 00~2 oO60 0050 1,0 (D) ~plication ,~
The following Tables present a comparison of the papermaking properties of our products compared with those of a modified ':-polyethyleneimine (PEI) prepared according to Examples of ~erman :
Published Application 1~8Q2~435. ~ ;
Measuring methods-Acceleration of drain~e : This is characterized by the reduction in freene~s in $R. ., ~.
The freeness in SR is determined according to the Leaflet 107 of ~ ' the Verein der Zellsto~f- und Papierchemiker und IngenieureO
Filler retention This is characterized by the ash content of sheets of paper produced on a Koebhen apparatus according to Leaflet 108 of the ;
Verein der Zellstoff und Papierchemiker und IngenieureO
Composition o~ pulp of paper ko be tested: 80% o~ bleached , sulfite cellu- . , 'l' lose 35SR '` `
, 20% of China clay ,l pulp density: 0024 g/l .,`
,, In~luence on paper whiteness and effect on optical brîghteners', Thi~ î~ characterized by the whiteness of ash-free sheets 'll of paper: `~

., ;: '':' ' .'. ~.

' ' ~

il~S8794 O.Z. 30,668~31,262 `
composition o~ pulp: 100~ o~ bleached sul~ite cellulose (35SR) 0015% of optical brightener ~ :
005% o~ alum ` . -ooO6% o~ resin additi~e Measuremento percentage re~lectance measured in known manner with ~ :
a Zeiss-Elrepho instrument, ~ilter R46T with and without W excitation.
TABLE la:
Drainage acceleration (measured as redu~tion in ~reeness in SR) Material: newspapers (beaten in an Ultraturrax unit to a smooth composition) pH 7.3 pH 5 105 % o~ alum Additive (100~ resin, based on absolutely dry cellulose) 0.05 0.1% 0005 001%
Control v~lue (no resin added) ;.
~ SR) 7905 72.3 Modified PEI (according to Example 6 o~ German Published Application 15802,435) 4806 38.4 39.8 36.0 :-Resin o~ Example 1 40.6 31.1 3609 3100 TABLE lb: :
Filler retention: ash content Or paper in %, addition of resin (100%~: 00015% and 0~03%, based on cellulose and ~iller pH of ~iber suspension: 6 408 Alum added, based on cellulose and ~iller: 0.5% 1.5%
Control value: 3.5 3.o ) Modified PEI (of Ex. 6 of German % o~
Published Application 1,802,435): ash 0~015% addition 5.5 6.3 ) in 0003% addition 7~6 7.0 ) paper Resin o~ Example 1:
00015% addition 5.5 6.3 ) 0~03% addition 6.9 7.0 ) . .
'`

10S87g4 '. :
OOZ~ 30j,668~31,262 TABLE lc:
Influence on paper whiteness and ef~ect on optical brighteners Control value resin of Exo 6 of Resin of German Published Application 1,802,435 Example 1 ~
. .: -with UV 9302% 8007 88.3%
without W 8700% 7806% 84.o%
TABLE 2a:
Drainage acceleration (measured as reduction in freeness in SR) Material- newspapers (beaten in an Ultraturrax unit to a ~mooth composition) pH 7~2pH 5 1.5% of alum Additive ~100% resin, based on ; :~
absolutely dry cellulose)0005 001% 0005 0.1%
Control vaOlue (no resin added) ( SR) 79 77 Modified PEI (according to Example 1 of German Published Application 1,802,435) 5107 3507 3908 36.1 Resin o~ Example 2 46~5 3105 3805 3500 TABLE 2b~ ~-,.. .. :
Filler retention. ash content of paper in %, addition of resin ~ :
~100%): 00015% and 0003%;, based on cellulose and ~iller pH o~ ~iber suspensiono 6 408 . . .
Alum added, based on cellulose and filler: 005% 1.5%
Control value. 307 305 ) Modified PEI (of Exo 1 o~ ~erman % Or Published Application 1,802,435): ash 00015% addition 504 9.6 ) in 0003~ addition 709 lloO ) paper ~
., ~,.',:
.
Resin o~ Example 2: ; -00015% addition 5.2 10.6 ) ~
0003S addibion 7~6 lloO ) ~ ~.
- 21 - ;

.:

, , ~ .

-~ 3LOS879~
O.Z. 30,668/319262 ~ABLE 2co Influence on paper whiteness and effect on optical brighteners Control value Resin of Exo l o~ Resin of German Published Application ~`
1,802,435 Example 2 with UV 91.2~ 8007% 88.7%
without W 8604% 77.9% 8510%
TABLE 3a~
Drainage acceleration (measured as reduction in freeness in SR) Material: newspapers (beaten in an Ultraturrax unit to a smooth composition3 pH 700pH 5 lo5% of alum Additive (100% resin, based on .:
absolutely dry ce11ulose)0005 001%0.05 00l%
Control v~lue (no resin added) ( SR) 60 62 .
Modi~ied PEI (according to : Example 6 of German Published Application 1J802,435) 47 41 54 50 Resin o~ Example 3 45 39 51 47 ..
TABLE 3bo .
Filler retention: ash content o~ paper in %, addition o~ resin :: ;
(100%)o 00015% and 000}%, based on cellulose and ~iller pH o~ fiber suspension: 6 408 Alum added, based on cellulose and filler: 005% 105%
Control value: 30~ 209 ) ~:
Modiried PEI (according to Example 6 of ~erman Published Application .
19802,435 .
00015% addition 3.9 5.6 ) %
0003% addition 504 606 ) ash in Re~in o~ Example 3: ..
00015% addition 501 7.2 ) paper 0003% addition 702 8.8 ) . , ~ .
.- .'~:

,, S8794 :
OOZo 30J668/31,262 '`
TABLE 3c:
In~luence on paper whiteness and ef~ect on optical brighteners Control value Resin o~ Exo 6 o~ Resin of .~:
~erman Published Applo , . .
1,802,435 Example 3 ,?~
with W 92~7% 79.5% 87~8% : .
without W8608% 7703% 8306%
TABLE 4a: ~ :
Drainage acceleration (measured as reduction in freeness in SR) Material- newspapers (beaten in an Ultraturrax uni~ to a smooth composit;on) ~ pH 703 p~ 5 1~5% of alum Additive (100% resin, based on absolutely dry eellulose)0005 0014%0005 0.1% -~
Control vaOlue (no resin added) i ( SR) 67 68 .;:-Miodified PEI (according to ;: .
Example 6 of German Published Application 19802,435) 58 46 50 44 :.
Resin of Example 4 57 46 49 42 :
TABLE 4b: ~
Filler retention. a3h content of paper in %, addition o~ re~in :
(100%)o~ 00015% and 0003%, based on cellulose and ~iller pH o~ ~iber su~pension: 6 408 c;
Alum added, ba~ed on cellulose :
: and ~iller: 005% 1 0 5% i' Control valueO lo9 302 ) Modified PEI ~o~ Ex. 6 of Cerman % of Published Application 1,802,435): ash :::
00015% addition 2.6 5.7 ) in 0003% addition 5.0 602 ) paper Resin o~ Example 40 00015~ addition 5.7 508 ) .
0003% addition 706 609 ) , ., 7 ~ ~
OOZo ~0~668/31,262 TAB~E 4c~
Influence on paper whiteness and e~fect on optical brighteners Control value Resin of Exo 6 o~ Resin o~ ~ -German Published Appl~
1,8023435 Example 4 with UV 9302% 8007% 88.1%
without W 8700% 7806% 83.1%
TABLE 5a:
Drainage acceleration (measured as reduction in ~reeness in SR) Material~ newspapers (beaten in an Ultraturrax unit to a smooth composition) pH 7O3pH 5 1O5% o~ alum Additive (100% resin~ based on absolutely dry cellulose) 005 001%0005 001%
Control vOalue (no resin added) ( SR) 62 60 Modified PEI (according to Example 3B o~ German Publi~hed Application 1~802~4}5) 47 41 54 50 Re~in of Example 5 46 40 55 53 TABLE 5b~
Filler retention. ash content of paper in %, addition of resin (100%)o 00015% and 0003%, based on cellulose and filler pH of ~iber su~pensionO 6 408 Alum added3 based on cellulose and filler. 005% 105g Control valueO 3O1 209 ) Modified PEI (according to Example 3B of German % of ash Publi~hed Application 1~8029435 in paper 00015% addition 3O9 5O6 ) 0O03% addition 504 606 ) Resin of Example 5.
00015% addition 4O2 6O7 ) 0O03% addition 507 7O6 ) '' :'~
~.
:' ' , . . .
. . - . . . .. . . .. ... .. . . ... . . . ..

~OS87~4 OOZO 30,668/31,262 :
TABLE 5c.
, : ' - : .
In~luence on paper whiteness and effect on optical brighteners Control value Resin of Ex~ 3B ofResin of German Published Appl.
1,802,435 Example 5 with UV 9302~ 8303% 8808% .
without UV 8700% 8OD1% 83,7%
TABLE 6aO
Drainage acceleration (measured as reduction in freeness in SR) .
Material: newspapers (beaten in an Ultraturrax unit to a smooth composition) . :
pH 703 pH 5105% o~ alum Additive (100% resin, based on absolutely dry cellulose~ 0005 001% 0O050.1% .~
Control v~lue (no resin added) .. . ( SR) 62 61 .,............................................. .................... ... ......... ~
Modi~ied PEI (according to . :
Example 6 of German Published , Application 1,802~435) 49 44 54 50 Resin o~ Example 6 48 42 44 38 TABLE 6bo Filler retention- a h content of paper in %~ addition of resin :
100%)~ 00015% and~ 0003%~ based on cellulose and ~lller pH of fiber suspension~: 6 4a8 ` ~.
Alum added, based on cellulose and filler~ 005% 105%
Control value: 305 3.1 ) Modified PEI (according to Example 6 Or ~erman % of ash Published Application 19802,435 in paper 00015% addition 4 a 2 6O2 ) ,.
0003% addition 606 7~1 ) ; .
Resin o~ Example 6a 00015% addition 409 6 aQ ) ;
0003% addition 604 6.9 ) . .

, -`;`1 ~ S ~7 9 4 oOz. 30,668/31,262 TABLE 6c:
Influence on paper whiteness and effect on optical brighteners Control value Resin of Ex. 6 o~ Resin o~
German Published Appl.
1,802,435 Example 6 with W 9302% 80.7% 8898%
without UV 87.0% 7806% 83.6%
TABLE 7a:
Drainage acceleration (measured as reduction in ~reeness in SR) Material: newspapers (beaten in an Ultraturrax unit to a smooth ; composition) pH 703 pH 5105% of alum Additive (100% resin, based on absolutely dry cellulose) 0005 001% 0.05 0.1%
Control vOalue (no resin:added) ( SR) 63 59 Modified PEI (according to , Example 6 of German Published Application 1,802,435) 51 4 52 51 Resin of Example 7 54 46 52 51 j~ TABLE 7bo i ~: Filler retention: ash content of paper in %, addition of resin (100%): 00015% and 0003%, based on cellulose and filler pH of fiber suspe~sion: 6 408 Alum added, based on cellulose and filler: o.5% 105%
I Control value: 3.0 207 ) ! Modified PEI (according to ! Example 6 of German Published ~ % o~ ash Application 1,802,435 in paper 00015% addition 500 5.2 ) 0003% addition 6.7 603 ) Resin o~.Example 7:
0.015% addition 5.8 5.0 ) .:.
; 0~03% addition 6.9 607 ) ~ :
: - 26 ~

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

`~ ~L0~879~1L `
OoZo 30~668/31~262 TABLE 7c~
In~luence on paper whiteness and ef~ect on optical brighteners Control value Resin of Exo 6 of Resin of German Publ;shed Applo 1,802,435 Example 7 with UV 9302% 8007% 88.0%
without W 8700% 7806% 83~0% ~:~
TABLE 8a: ~ .
Drainage acceleration (measured as reduction in freeness in SR) Material~ newspapers (beaten in an Ultraturrax unit to a smooth :~
composition) . .
pH 703 pH 5 1~5% o~ alum .. :
Additive (100% resin, based on absolutely dry cellulose) 0005 001% 0005 0 Control vOalue (no resin added~ :
( SR) 58 56 ;
Modifled PEI (according to Example 1 o~ ~erman:Published Application 19802,435) 46 37 42 40 Res;n:of Example 8 45 38 42 39 TABLE 8b~ :
. .
Filler retention: ash content of paper in %, addition of resin lOOS)- 00015% and 0003%,~based on cellulose and ~iller pH of ~iber ~uspension: ~ 6 408 Alum added, based on cellulose and filler: 005% lo 5%
Control valueo ~ 30o 300 ) Modified PEI (according to Example 1 o~ ~erman Published Application 1,802,435 ) % o~ ash OoO15% addition 401 50 4 ) in paper ~ :
:~ 0003% additi:on 602 6~7 ) -:
Resin of Example 8. . ..
00015% addition 501 506 ) 0003% addition 700 701 ) _ ~:
.- . :.
' '' ~"
'`

.

S~794 O~Z0 30,668~31,262 TABLE 8co Influence on paper whiteness and e~fect on optical brighteners Control value Resin of Exo 1 of Resin of German Published Appl~
1,802,435 Example 8 with UV 96% 8405% 8872%
without UV 8705% 8000% 8203%
TABLE 9a:
Drainage acceleration ~measured as reduction in freeness in SR) Material. newspapers (beaten in an Ultraturrax unit to a smooth composition) pH 703 pH 5 1.5% of alum Additive (100% resin, based on :
absolutely dry cellulose)0005 001%0.05 001%

Control value tno resin addied) (SR) 65 63 Modi~ied PEI (according to I Example 3 of German Published t Application 19802,435) 59 53 56 50 ¦ Re~in of Example 9 60 54 54 50 ¦ TABLE 9b-~ Filler retention- ash content of paper in %, addition of resin ¦ (100%)o 00015% and 0003%, based on cellulose and filler j pH of fiber suspension: 6 4~8 ¦ Alum added, based on cellulose : :.
j and filler: 005% 105%
¦ Control valueO 302 302 ) I Modified PEI (a¢¢ording to i Example 3 of ~erman Published :~
I Application 19802,435 i 00015% addition 307 6.o ) % of ash j 0~03% addition 603 608 ) in I Resin of Example 9:
¦ 0~015% addition 404 701 ) paper 0003~ addition 6.3 706 ) :

' '' ' ' :'. ' : .

. . ~La~s~3794 00~ 30,668/31,262 TABLE 9co Influence on paper whiteness and effect on optical brighteners :

Control value Resin of Exo 3 of Resin of German Published Applo - -1,802g435 Example 9 ~.
with W 9600% 8508% 88~2% ` ~ .
without W 8705% 8000% 8203%
TABLE lOao Drainage acceleration (measured as reduction in ~reeness in SR) Material- newspapers (beaten in an Ultraturrax unit to a smooth composition) pH 703pH 5 lo 5% of alum Additive-tlOO% resin, based on ~ `
absolutely dry cellulose)0005 001% 0005 001%

Control value (no resin added) (SR) 65 63 Modi~ied PEI (according to Example 6 of German Published Application 19802,435) 59 53 56 53 Resin o~ Example 10 53 47 52 49 TABLE 10b:
Filler retention~ ash content of paper:in %, addition of resin (lGO%)o 00015% and 0003%, based on cellulose and filler ~ :.
pH o~ ~iber suspensionO 6 4.8 Alum added, based on cellulose ..
and filler: 005% 105%
Control value: 302 302 Modi~ied PEI (according to Example 6 of German Published Application 1~802~435 00015% addition 307 600 ) % o~ ash .:
0003% addition 603 608 ) in paper :.

Resin o~ Example lOo 00015% addition 502 704 0003% addition 608 803 - 2g -~ 0 S~ 7 ~ 4 00~, 30,668~31,262 TABLE lOco Influence on paper whiteness and e~fect on optical brighteners Control value Res;n of Exo 6 o~ Resin of German Published Applo 1,802,435 Example 10 .
with UV 9302% 8007% 88.1%
without W 8700% 7806% 8304%
TABLE lla~
Drainage acceleration (measured asi reduction in freenesis in SR) Ma~erial o newspapers (beaten in an Ultraturrax unit to a smooth :
composition) ~.
pH 703 pH 5 105% of alum Additive (100% resin, based on . :: :
absolutely dry cellulose) 0~05 001% 0005 001% ; `
Control vOalue (no resin added) .:
( SR) 61 56 Modified PEI (according to .:
Example 3B o~ German Published Application 19802,435) 59 56 55 53 Resin o~ Example 11 57 52 54 51 - -:
TABLE llbo Filler retentionOo ash content of paper in %, addition of resin (lOO~)o 00015% and 0003%, based on cellulose and ~iller ~ ... . .
pH of ~iber suspensionO 6 408 ~.
Alum added9 based on cellulose : :
and filler~ oO5% 105%
Control value. 9 o l 805 Modified PEI (according to :~:
Example 3B Or German Published :
Application 1,8029435~ .i 00015% addition 1002 llol ) % of ash ::~
00~03% addition 1107 11.8 ) in paper Resin of Example 11: :
00015% addition lOol lloO ~ ~.
0003% addition 1200 1203 ) :
- 30 - ~ ;

, ,.:
'~
-, :
", ~- ~1)58~94 0OZ~ 3Q,668/31,252 TABLE llco Influence on paper whiteness and ef~ect on optical brighteners Control value Resin of Ex~ 3B of Resin of German Published Applo 1,802,435 Example 11 with W 88~7% 78O8% 81O8%
without W 8402% 7607% 78~8%
TABLE 12a:
Drainage acceleration (measured as reduction in freeness in SR) Materialo newspaper~ (beaten in an Ultraturrax unit to a smooth composition) ;
pH 7O3pH 5 1O5% of alum Additive (100% resin, based on absolutely dry cellulose)0O05 001%0O05 001% , Control v~lue (no resin added) ~::
; ( SR) 67 66 Modified PEI (according to Example 6 o~ German Published Application 1,8029435) 59 56 57 54 .:
Resin oP Example 12 60 50 57 53 ~ :
TABLE 12b:
Filler retentiono. ash content o~ paper in %, addition of resin (100%)o 00015% and 0O03%J based on cellulose and ~iller :pH o~ fiber suspension: 6 4O8 : Alum addedg based on cellulose and ~illerOo 0O5% 1O5%
Control value: 903 8O6 Modified PEI (aocordin~ to Example 6 Or German Publîshed : Application 1,802,435 :~.
0~015% additlon 9.4 llo0 ) % of ash 0~03% addition 1003 1108 ) in paper :.:
Resin o~ Example 12 :~
00015% addition llo 4 13.0 0O03~ addition 1201 1404 0~8794 O,ZO 30,668/3~,262 TABLE 12c:
Influence on paper whiteness and effect on optical brighteners Control value Resin of Exo 6 of Resin of German Published Appl.
1,802,435 Example 12 with UV 9508% 79~7% 8400%
without W 88~9% 7707% 80.7% -.
TABLE 13a o ~ ~ .
Drainage acceleration (measured as reduction in ~reeness in SR) Materialo newspapers (beaten in an Ultraturrax unit to a smooth : .
omposi.tion~ -pH 703 pH 5 105% of alum Add;tive tlOO% resin, based on ~;
absolutely dry cellulose)0005 001% 0005 001%

Control vOlue (no resin added) ( SR) 65 62 ::

Modified PEI (according to :~
Example 1 o~ German Publ;shed ....
Appl;cation 1,802,435) 59 l~8 52 49 Resin o~ Example 13 57 47 50 50 .:
TABLE 1 3b o Flller retentionOo ash content o~ paper in %, addition o~ resin (100%~ 00015% and 0003%, based on cellulose and ~iller - :
pH of fiber suspensiono 6 408 Alum added, based on cellulose and ~iller: 0~5% 105%
Control value: 20 1 204 Modified PEI (according to Example 1 of German Published Application 1,802~435 00015% addition 301 505 ) % of ash ::.
0003% addition 503 6.5 ) in paper Resin of Example 13 00015% addition 406 506 0003~ addition 605 605 _ 32 -~ .'.

.

OOZo 30,~68/31,262 TABLE 13c~
Influence on paper whiteness and e~fect on optical brighteners Control value Resin of Exo 1 o~ Resin of German Published APP10 13802,435 Example 13 with W 9508% 8206% 84,o%
without W 8809% 7808% 8007%
TABLE 14a. ~ :
Drainage acceleration tmeasured as reduction in freeness in SR) Mater;al, newspapers (beaten in an Ultraturrax unit to a smooth composition) pH 70 3 pH 5 10 5% o~ alum :
Additive (100% resin, based on absolutely dry cellulose)0005 001~ 0005 OD1%
Control vOlue (no resin added) ( SR) 66 65 Modified PEI (according to Example 6 o~ German Published .
Application 1~802,435) 58 50 56 53 ~.
Resin o~ Example 14 57 51 54 51 TABLE 14bo Filler retentiono ash content of paper in %~ addition o~ resin , (100%)0 00015% and 0003%, based on cellulose and filler :; :
pH o~ ~iber suspensionO 6 408 Alum added, based on cellulo~e ,.
and filler: 005% 105%
Control valueo 20 2 204 Modified PEI (according to Example 6 0~ German Published Application 1~802,435 00015% addition 409 500 ) % Of ash 0003~ addition 700 603 ) in paper Resin of Example 14 0,015% addition 503 501 O ~ 03% addition 607 509 ~ 33 ~

,: , 7 ~ 4 OOZ. 30,668/31,262 TABLE 14c~
In~luence on paper whiteness and effect on optical brighteners Control value Reæin of Ex. 6 of Resin of .. :
German Published Appl. ~
1,802,435 Example 14 : -with UV 8807% 77.6% 81.8%
without W 8402% 75~9% 78.8%
EXAMPLE 15 :~ ;
As under (B), V 7, above, a condensation product o~ adipic ~ .
acid and diethylene triamine is preparedO This condensate is then ~
: .-; ~::
gra~ted with ethyleneimine in a ratio o~ 1 : 1, by weight, as in the case of V 13/14 aboveO The resulting reaction product has . .
a viscosity of 400 centipoises at a temperature of 20C in 45% -~
aqueous solution~ This condensation product is referred to below as component (a)O
Component (b) is prepared as under (A) o~ the above Examples by reacting a polyglycol ether ha~ting a molecular weight of 1,500 with epichlorohydrin in a ratio o~ 608 : 1 by weight. -:
Condensation of components (a) and (b):
500 parts of a 2305% aqueous solution o~ components (a) are placed in a reaction vessel provided with a stirrer and heated to :~.
65Co 130 parts of a 20.5% aqueous solution of component ~b) are added and khe mixture i9 condensed at a temperature ranging from 60 to 65C until the viscosity is 50 centipoises. When this viscosity ha9 been reached, 12 parts o~ a mixture previously ~ ~
prepared by combinine equal parts by weight of the above described ~ .
2305% aqueous solution of component (a) and the 20.5% aqueous solution o~ component (b) are added to the mixture every ten ;
minutes.
- 34 - ~-`

O~Z0 30,668/31,262 After a total of 290 parts of that mixture have been added, the viscosity of the condensate has risen to 200 centipoises.
There is then added to the reaction mixture, every ten minutes, ~ a mixture consisting of 6 parts of the above component (a) and ~:
1 3 parts of the above component tb)~ After 5LI parts of that mix- ~ :
ture have been added and condensation has been continued at a :
temperature o~ from 60 to 65C, the viscosity of the condensate has r;sen to 900 centipoisesO The reaction product is adjusted to pH 8 with 85% ~ormic acid and then diluted with water to a solids content of 20%o There is obtained a clear aqueous res;n solution containing virtually no insoluble particles which have been condensed too farO This resin solut;on is used in the paper industry as drainage aidO . .
~ EXAMPLE 16 ;' Example 15 is repeated except that the component (a) used ..
.. . .
i is a condensation product obtained by reactin~ the reaction product of adipic acid and diethylene triamine with ethylene-imine in a ratio of 1 . 2 b~ weightO :i I~ Here again9 there is obtained a resin solution containing I virtually no insoluble particlesO The resin solution is used in the paper industry as flocculantO
; EXAMPLE 17 .~ The components (a) and (b) given in Example 15 are conden~ed I with each other in the following manner: 500 parts of component ¦ (a) in the form of a 2305% aqueous solution are placed in a vessel provided with ~tirrer and heated to a temperature of 70Co 130 parts of component (b) are added in the form o~ a ., , : - 35 ~

.. . . . . .. . . .. . .. . . .. . . .

A
~51~7~
` OOZ. 30,668/31,262 2005% aqueous solution. The two components are first condensed batchwise until a viscosity of 50 centipoises is obtained.
Further quantities of components (a) and (b) are then added through computer-controlled mekering orifices. Before ; components (a) and (b) reach the condensation vessel, they -~
are mixed in a small mixer~
The ratio of component (a) to component (b) is 1 : 1 up ~
to the point where the viscosity of the condensate is 120 centi- ~ ;
poises and is then continuously reduced to a rakio of 1 : o.6 until the viscosity of the condensate is 250 centipoises and is thereafter continuously reduced to 1 : 0.3 until the viscos-ity is 700 centipoises. A total of 250 parts of component (a) and 200 parts of component (b), based on solid, is required.
The condensate is then adjusted to pH 8 with 85% formic acid and diluted with water to a solids content of 20%. The conden-sation product is used in the paper industry as retaining agent.
It contains AO insolub`e parlioles. ~ ;

' ~

.

... . . . .. . . . . . . . .. . . . .. . ..

Claims (5)

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

1. A process for the manufacture of nitrogen-containing condensation products, which comprises reacting (a) 1 part by weight of an ethyleneimine-grafted polyamidoamine obtained by condensing 1 mole of a dicarboxylic acid having from 4 to 10 carbon atoms with from 0.8 to 1.4 moles of a polyalkylene polyamine having from 3 to 10 alkyleneimine units, followed by grafting of from 2 to 8 ethyleneimine units per basic nitrogen atom onto the resulting polyamido-amine, with (b) from 0.3 to 2 parts by weight of a product obtained by reacting a polyalkylene oxide having from 8 to 100 alkylene oxide units with epichlorohydrin in the presence of a Lewis acid, such that from 1.0 to 1.5 moles of epichloro-hydrin are present per equivalent of the hydroxyl groups in the polyalkylene oxide, at a temperature of from 20° to 100°C in aqueous solution or in a solution in water and a water-soluble organic solvent, the solution having a solids content of from 5 to 50% by weight, the reaction being carried to a point at which the viscosity of an aqueous solution containing 20% by weight of auxiliary is from 300 to 2,500 centipoises at 20°C.

2. A process as claimed in claim 1, wherein a portion of components (a) and (b) are initially condensed batchwise, a mixture of components (a) and (b) is added to the resulting condensation product continuously or batchwise and the relative proportions of components (a) and (b) is so adjusted that the concentration of component (b) in the mixture of (a) and (b) is lowered as condensation proceeds.

3. A process as claimed in claim 1, wherein the polyamidoamine is obtained by condensing 1 mole of adipic acid with from 0.8 to 1.4 moles of diethylene triamine.

4. A process for the manufacture of paper, which comprises adding, to an aqueous suspension of cellulosic fiber for making paper sheet, from about 0.01 to 0.3% by weight, based on the weight of dry pulp, of a water-soluble crosslinked reaction product obtained by reacting (a) 1 part by weight of an ethyleneimine-grafted polyamido-amine obtained by condensing 1 mole of dicarboxylic acid having from 4 to 10 carbon atoms with from 0.8 to 1.4 moles of a polyalkylene polyamine having from 3 to 10 alkyleneimine units, followed by grafting of from 2 to 8 ethyleneimine units per basic nitrogen atom onto the resulting polyamidoamine, with (b) from 0.3 to 2 parts by weight of a reaction product obtained by reacting a polyalkylene oxide having from 8 to 100 alkylene oxide units with epichlorohydrin in the presence of a Lewis acid, so that from 1.0 to 1.5 moles of epichlorohydrin are present per equivalent of hydroxyl groups in the polyalkylene oxide, at a temperature of from 20° to 100°C in aqueous solution or in a solution in water and a water-soluble organic solvent, the solution having a solids content of from 5 to 50% by weight, the reaction being carried to a point at which the viscosity of an aqueous solution containing 20% of the auxiliary is from 300 to 2,500 centipoises at 20°C.

5. Nitrogen-containing condensation products when obtained by the process as claimed in claim 1.