COMPOSES QUATERNAIRES TENSIOACTIFS ET METHODE DE TRAITEMENT DES FIBRES DE CELLULOSE A L'AIDE DE CES COMPOSES

QUATERNARY SURFACE ACTIVE COMPOUNDS AND PROCESS OF TREATING CELLULOSE FIBERS THEREWITH

Abrégé anglais

ABSTRACT OF THE DISCLOSURE
Quaternary surface active compounds provided, useful
for preparing cellulose fibers such as paper of low mechanical
strength and good softness, having the structure:
<IMG>
wherein:
R1 and R3 are selected from the group consisting of mono-,
di-, and tri- alkyl phenyl groups having from about fourteen to
about forty-six, suitably about twenty to about thirty-eight,
preferably about twenty-three to about thirty-two carbon atoms,
of the form
<IMG>
wherein R is alkyl having from one to about twenty-two carbon atoms,
and n, is 1, 2 or 3; R can be in any position on the ring, ortho,
para, or meta to the phenolic hydroxyl.
R3 and R4 are selected from the group consisting of methyl,
ethyl, and hydroxyethyl groups;
n1 and n2 are numbers within the range from about 4 to about
40, suitably from about 6 to about 30, preferably from about 11 to
about 25, representing the average number of oxyethylene units
present; and
X is an anion.

Revendications

Having regard to the foregoing disclosure, the following
is claimed as the inventive and patentable embodiments thereof:
1. A process for treating a substrate comprising
cellulose fibers to impart improved wettability, softness and low
mechanical strength thereto, which comprises applying to the substrate a
quaternary ammonium compound having the general formula:
<IMG>
wherein:
R1 and R2 are alkyl phenyl groups totalling from about
fourteen to about forty-six carbon atoms in from one to three alkyl groups
and the phenyl group;
R3 and R4 are selected from the group consisting of
methyl, ethyl and hydroxyethyl;
n1 and n2 are numbers within the range from about 4 to
about 40, representing the average number of oxyethylene groups present
in each substituent; and
X is an anion.
2. A process according to claim 1, in which n1 and
n2 are numbers within the range from about 6 to about 30.
3. A process according to claim 1, in which R1 and
R2 have from about twenty to about thirty-eight carbon atoms.
4. A process according to claim 1, in which the
quaternary ammonium compound is in aqueous solution in a concentration
17

within the range from about 1% to about 15% by weight.
5. A process according to claim 1, in which the amount
of quaternary ammonium compound applied to the substrate is within the
range from about 0. 02% to about 3% by weight of the substrate.
6. A process according to claim 1, in which the
quaternary ammonium compound is applied to cellulose pulp after screening
the pulp.
7. A process according to claim 1, in which the
quaternary ammonium compound is applied to cellulose pulp after bleaching
the pulp.
8. A process according to claim 1, in which the
quaternary ammonium is applied to cellulose pulp prior to drying the pulp.
9. A process according to claim 1, in which the
substrate to which the quaternary ammonium compound is applied is
cellulose pulp.
10. A process according to claim 1, in which the
substrate to which the quaternary ammonium compound is applied is
paper.
11. A process according to claim 1, in which the
substrate to which the quaternary ammonium compound is applied is a
sheet material including cellulose fiber s in admixture with other fibers
of natural or synthetic fibrous material.
18

12. Quaternary ammonium compounds capable of
imparting improved wettability, softness and low mechanical strength
to a substrate comprising cellulose fibers, and having the general
formula:
<IMG>
wherein:
R1 and R2 are alkyl phenyl groups totalling from about
fourteen to about forty-six carbon atoms in from one to three alkyl
groups and the phenyl group;
R3 and R4 are selected from the group consisting of
methyl, ethyl and hydroxyethyl;
n1 and n2 are numbers within the range from about 4 to
about 40, representing the average number of oxyethylene groups
present in each substituent; and
X is an anion.
13. Quaternary ammonium compounds in accordance
with claim 12, in which n1 and n2 are numbers within the range from 6
to 30.
14. Quaternary ammonium compounds in accordance
with claim 12, in which R1 and R2 have from about twenty to about
thirty-eight carbon atoms.
19

15. A stable aqueous solution comprising a quaternary
ammonium compound in accordance with claim 12, in a concentration
from about 1% to about 15% by weight.
16. Quaternary ammonium compounds in accordance
with claim 12, in which R3 and R4 are methyl groups.
17. Quaternary ammonium compounds in accordance
with claim 12, in which R1 and R2 are nonyl.
18. Quaternary ammonium compounds in accordance
with claim 12, in which R1 and R2 are dodecyl.
19. A process for the preparation of alkyl phenoxy
ethylene oxy (2-hydroxy) propylene quaternary ammonium compounds
having the formula:
<IMG>
wherein:
R1 and R2 are alkyl phenyl groups, totalling from about
fourteen to about forty-six carbon atoms in from one to three alkyl groups
and the phenyl group;
R3 and R4 are selected from the group consisting of
methyl, ethyl and hydroxyethyl;
n1 and n2 are numbers within the range from about 4 to
about 40, representing the average number of oxyethylene groups

present in each substituent; and
X is an anion;
which comprises reacting from four to about forty mols of ethylene oxide
with one mol of an alkyl phenol having from about fourteen to about
forty-six carbon atoms, in the presence of an alkaline catalyst at an
elevated temperature within the range from about 30° to about 150°C;
reacting the resulting alkyl phenoxy ethylene glycol ether with
epichlorohydrin, producing the corresponding chloroglyceryl or
chlorohydroxypropylene ether, and then reacting this ether with a
secondary amine having the formula R3R4NH, where R3 and R4, are
selected from the group consisting of methyl, ethyl and hydroxy-
ethyl in the presence of alkali and in the presence of an organic solvent
with a boiling point of at least 60°C at an elevated temperature within the
range from about 30° to about 150°C, to obtain the quaternary ammonium
compound of the above formula in the form of its chloride salt.
20. A process according to claim 19, which comprises
exchanging the chloride anion by another anion.
21. A process according to claim 19, in which the re-
action between the ethylene oxide adduct and the epichlorhydrin is
carried out in the presence of a catalyst selected from the group
consisting of stannic chloride, boron trifluoride, perchloric acid HClO4,
toluene sulfonic acid and sulfuric acid.
22. A process according to claim 19, in which the
solvent during quaternization is selected from the group consisting of
methanol, ethanol, and the monoethylether of diethylene glycol.
21

Description

SPECIFICATION
Treatment of wet cellul~se pulp with a surface active agent
reduces the interfibre bonds oE the c.ellulose. Thus, cellulose pulp
or paper with improved softness ancl low mechanical strength is ob-
tained, which are desirable properties for example if the cellulose
fibers are to be disintegrated int~ fluff, for liquid-absorbing sani-
tary products. Surface-active agents useful for this purpose and as
textile softeners include the qlaternary ammonium compounfls hav-
ing tw~ R-O-(CH2CH20)n -CH2CH-CH2- groups, where n is rom 1 to
lo bH :~
10 and :R is an ~lkoxy group having from twelve to twenty-two carbon
atoms.
; , . .
Extensive investigations have shown that when the number of ~.
carbon atoms in the alkoxy group exceeds eighteen in such surface
15 active quaterna.ry ammonium compounds, the effectiveness of the
compounds as cellulose fiber softeners is re~uced, and.has mainly
disappeared when the num~er of carbon atoms reaches twenty-twoO It
is also known that softening agents which contain aliphatic groups have
better softening properties than softenin~ agents containing alkyl
~0 aryl groups..
- Unexpectedly,. it ha~ now been found that to cellulose fibers
such as pulp or paper, surface-active quate.rnary ammonium com- -~
pounds of this class having in place of the Pc al~oxy group an a~yl~
substituted phenolic .group having from about Pourteen to about
25 forty-six, preferably from about twen~ to about thirty-eight, and
still ~lore prefer~ly from about twenty-three t~ about thirty-tw~,
,
;~,,,, , , . . . : , .

~ 0~ 6~
carbon atoms,are capable of imparting an improved c~mbinatioll o
s~ftness ancl lo~v mech~nical streng~h, in acldition to good hydrophilic
properties. The surEace-active quaternary ammonium compounds
according to the inv~3ntion have the general formula:
CATION ANION
.. , I _
lRl O-(C2E~O)n-C~I2-C~r-CH2
E~`2~~(C2Hg~)n -CH2-.~H-C~I2 \
C)H
wherein:
Rl and ~?2 are selected from the group consisting of mon~-,
di-~ a~ld tri- a~kyl phenyl gr~ups having from about four~een t~ ab~ut :~
- forty-six, suitably about twenty to about thirty-eight, preEerably
a~out twenty-three to about thir~two,carbon~ a~oms,o~ the fvrm ~ ~:
Rn 0
where Pc is alkyl having from ~ne to ab~ut twenty-two carb~n a~oms,
and n3 is l~ 2 or 3;
R3 and R~L are selected from the group consisting o~ methyl,
ethyl, and hydroxyethyl gr~ups; - . :
nl and n2 are numbers within the range from about 4 to ab~ut
40, suitably îrom about 6 ~ about 307 preferably from 11 to about
25, representing the average mlmber of o~Tethylene units present; and
X i~ an anion.
- 2
. . .. . . . , .. .. . ~ .

~)4Z4~i~
The compounds of the invention give a very sati~factory com-
bination of wettabilit~, good sof~ness and low mechanical strength.
Generally, the wettability impro~es as the number of o}~ëthylene
units increases. The reduction in strength increases and the wetta-
bility diminishes as the number of carbon atoms in the alkyl phenyl
substituents Rl and R2 increases. Thus, by varying the numher of
carbon atoms in Rl and R2 and the number o~ oxyethylene units it is
passible to obtain the combination of wettability and interfibre bond-
reducing properties desired for each special purpose. Particularly
good properties from both these points of view are found in com- ~`
pounds where Rl and R2 are a~yl phenyl groups having from twenty-
three to thirty-two carbon atoms, and nl and n2 are within the range ~;
from 11 to 25.
- The alk~rl groups R of Rl and R2 either have7 or are ~aken irl ~
; su~icient number to aggregate, the number ~f carbon atvms includ- ~ -
ing the six carbon atoms of the phenyl ring within the above-stal:ed
.
ranges. - -
The a~71 groups can for e2~Lmple be methyl, ethyl, pr~pyl,
isopropyl, butyl, isobutyl7 ter~-butyl, amyl, isoamyl, tert-amyl,
hexyl, 2-ethyl hexyl, heptyl, octyl, isooctyl, nonyl, isononyl~ decyl,
undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, palmit~rl, stearyl7
behenyl, eicosyl, heptadecyl, myricyl, lacceryl, and heptacosyl.
The compounds according to the in~rention can be added to the
cellulos~ fibers at any stage after screening and/or bleach~g of the
- ~5 pulp. (~enerally the addition is done before or during dehydratian or
drying of the cellulose pulp, for example, during processing int~
c~ntinuous webs on a cellulose drying machine, or on a paper
.
- .
. .. . . . : .. . . ~ ' .. . : '

machine, or into flakes in a fla~e dryer.
~ ny kind of cellulose pulp can be tr~ated, such as
mech~nical pulp, s~mi-chemical pulp and chemical pulp, bleacln-
ed or unbleached. Thus, the compounds in qucstion have been
found useful for .reating mechanical or semi-cllemical pul~s
as well as che~ical pulps, such as sulphite or sulpnate pulps,
commonly used in manufacturing of soft products with good
water-a~sorption properties.
The compounds of the invention will improve softness
of substratPs o~ all kinds including both woven and non~oven
sheet materials, especially substrates made of cellulose fibers,
either entirely or in admixtures with other natural or synthetic
fi~ers. Examples of such substrates are regenerated callulose
or rayon, acetate rayon, cellulose acetate-propionate, cellulose
acetate-butyrate, polyvinyl chloride, polyamide, polypropylene,
polyethylene, polyacrylonitrile, polyesters sucn as ethylene
glyco`l-terepht~alic acid polymers, cotton, linen, jute, ramie,
.
sisal, wool, mohair, alginate fi~ers, zein fibPrs, glass,
potassium titanate, bast, ~agasse, polyvinylidene chloride,
and fur fibers of various kinds such as beaver, rabbit, seal,
mus'-rat, otter, mink, caracul, lamb and squirrel.
The substrate materials can ta~e any form, including
non~woven materials such as felts, bats, ~nd mats; wovan mater
ials such as fabrics, cloth, carpets, rugs and upholstery;
synthetic fur materials; curtains, and covering materials of
all kinds.
The co~pounds are preferably added as aqueous solutions
in a concentration of from 1 to 15~ by weiglit o~ active substance.
Viscosity reducing additives may be included in the solution, for
example t~e monoetilyl ether of diethylene glycol~ r7onionic
cb/
. .

~1~4~
surfactants such as a~lclucts of ethylene oxicle or propylene oxide to
aliphatic alcohols or alkyl phenols may be aclded for an additional
improvemerlt of the rewettability of the cellulose fibers in pulp s~r
paper.
While the usual solvent is water, if rapid volatilizati~n of the
solvent is desirad, the quaternary amm~nium compounds of the
invention can be applied frs)m a sohltivn in a rapidly volatllizable
organic solvent, such as acetnne~ methanol, ethanol, isopropanol,
or mixtures thereoI. In this case, the concentrations are the s~me
as aque~us solutions.
The solutis)ns of the quaternary ammonium compounds ~E the
inventi~n call be applied by dlpping, spraying3 or coating, using c~n-
ventional techniques.
The amount s~f the quaternary ammonium comp~urlds accord-
15 - ing to the invention va~ies accorcling to the desired effect but is
normally within the range from about 0. 02.~to abou~ 3~ by weight,
preferably from 0.1 to l. 5% by weight, calculated on the dry weight
of the cellulose fibers.
The cellulose fibers, pulp or pape~ treated with compounds
according to the i~vention can be used for many differen~ purposes.
Cellulose pulp ~ibers can be disintegrated into so-called fluff fibers
used for differen~ sanitary products, The compounds can also b~
used in manufacturin~ pa.per when softness îs of grea~ importance,
such as sanitary paper, tissue paper,and paper included in different
te}:tile substitutes for bed linen, towels, table-cloths, clothes, etc.
.- .. :

6~
The SyntileSiS of the alkyl pheno~cy ethyleneoxy-2-hydroxy-
propylene quatern~l~y ~mmoni~lm cc)mpounds in accordance with the ~-
invention includes the following reaction steps:
1) Rl(C2~I4)n OH + CH2-- /C:EICHzCl > Rl(C2H~.)n OCH2CHCHaCl
OH
R~ R3
2) 2Rl(C2H40)n OCH2CHC~2Cl ~ NH~R1(C2H~O)n OC~2CHCHZ~ N\ C
OH R~ OH R~
In the above reaction formulae7 R~ 3, R4, and nl have the
meaning earlier mentioned.
The aLkylphenoxyethylene oxy-(2-hydroxy)propylene quaternary
ammonium ~ompounds in accordance with the invention can be pre-
pared by reaction of from about four to about forty mols of ethylene
oxide with one mol of an aLkyl phenol having from about fourteen to
1~ about forty-six carbon atoms. The reaction of ethylene oxide with ~ -
the phenol is carried out in the presence of an a~ali catalyst,
preferably po~assium hydroxide~ at an elevated temperature within the
range from about 30 to about 150Co
The resulting alkyl phenoxyethylene glycol ether is reacted
with epichlorhydrin, producing the corresponding chloroglyceryl or
chlorohydroxypropylene ether, which is then preferably reacted with
a secondary amine having the formular :R3R~NH, where R3 and P~ are
methyl, ethyl, or hydroxyethyl.
Suitable secondary amines for the process according to the
invention are dimethyl amine and diethyl amine, which are commer-
cially available O
. ~:
1 . ' ' '' " ' : ' '

i6
The procluct i9 a quaternary amm~nium compo~md of the
invention, in the form of its chloride salt. The chlnride ion can
then be exchanged by another anion, using known techniques, for
example, by a~dltion of a sodium salt with a higher solubility
constant than s~dium chloride, or ~T ion exchange in an anion ex-
changer. Amon~ anions ~her than chloride ion which can serve as
X in the quaternary ammonium compounds of the inventi~ are
hydroxyl, nitrate, carbonate, hydro~rl, phosphate, iodide, bromide,
methyl sulfate, acetate, carbonate, farmate, citrate, propionate,
and tartrate. The mono~ralent anions are preferred.
The reaction between the all{ylphenoxyethyleneoxide adduct
and the epichlorhydrin proceeds at an elevated temperature within
the range from about 30 to about 159C in the presence of a catalyst,
such as stannic chloride, boron trifluoride, and perchloric acid,
HCl~. These give a rapid easily controllable reactis)n, but ~her
acid catalysts such as toluene sulfonic acid and sulfuric acid can also
be used.
In order to ensure complete reaction of the ethylene oxide
adduct~ an excess nf epichlorhydrin is generally added.
The quaterni2a$ion of the secondary amine with the chloro~ly-
- ceryl ether is carried out in the presence of alkali, generally sodium
hydroxide, at an elevated temperature within the range from abo~lt
40 to about 150C, in the presence of water or a water-miscible
organic solvent.
- It is not necessary that the organic solvent be miscible wi~h
wat@r in all proportions, but it should be miscible with water in the
proportions use~ so as to form a h~mogeneous solvent mixture, if
wate.r is also present.
- -- - - - -- - - .
.' . ~ .

a6~
Any ~ater-lni,sci~Te organic solvent wllicll is inert under the
re~ction conditions c~n be used. The organic salvent accordi~Lg;ly can
be select~cl from the clas~es consisting of lower aliphatic alcohols
having from one to about six carbon atoms, lower aliphatic polyhydric
alcohols having from two to about si:c carbon a~oms and ~rvm two to
six hydrs:~xyl groups, and monoa~kyl ethers of such lower aliphatic
polyhydric alcohols having~ from two to about six carbon atoms in the
aLkyl group; polyoxyalkylene glycols and polyoxyalkylene glycol
monoethers ha~ing at least one oxyether linkage anA two alkylene
groups, the alkylene gr~ups having from two to four carbon atoms i~
a straight or branched chain, and having not more than one hydroxyl
group etherified with a lower alkyl group having from one t~ about six
carbon at~ms; and heterocyclic ethers having ilp to six ring atoms oE
which one or two may be ether o}ygen, and four or five carbo~} atoms.
16 Exemplary lower aliphatic alcohol9 include methànol, ethanol~
propanol, isopropanol, butanol~ isobutan~l, tertiarybutanol9 secondary ~ :
butanol, pentan~l, isopentanol~ hexanol, isohex~nol~ and tertiaryhex-
anol.
Exemplary polyoxya~kylene glycols and glycol ethers include
the monoethyl ethers of diethylene glycol, diethylene glycDI~ tri-
ethylene glycol~ tetraethylene glycoI, the monomethyl ether of
triethylene glycol, dipropylene glycol, dibutylene glycol, tributylene
glycol, tetrabut~lene glycol, tetrapropylene glycol~ the monomethyl : .
ether of dipropylene glycol, and the monomethyl ether of dibu~Tlene
2~ glycs~l.
Exemplary polyhydric alcohols include ethylene glycol,
propylene glycal, butylene glycol, the monomethyl ethers ~f
ethylene glycol, propylene glycol and butylene glycol, and the m~no-
ethyl ethers of ethylene glyco~ propylene glycol and butylene glycol~
3~ glycer~l, sorbitol, pentaerythritol~ and neopentyl glycol.
. ~, . .
.; . . . . . . . .
., .. , . ~ : .
.. , , ~ . .

61~
It i~ also possible to react the chl~roglyceryl ether wil:h
arnmonia or with a primary ~mine having a methyl, ethyl, or hydroxy- ~ :
ethyl group, ancl the resulting product may then be q.uaternized with :~
methyl or ethyl chloride or dimethyl or diethyl suLfate. However,
this procedure is more complicated than the previously described
- procedure, and it involves more reaction steps, and results in larger
amounts of byproducts and lower total yields of the desired quatern-
ary amm~nium compounds.
Phenols which can be used as the source of Rl and R2 in the
compounds according to the inventl~n are for example octyl phenol,
nonyl phenol, decyl phenol, dodecyl phenol, tetradecyl phenol,
hexadecyl phenol~ octadecyl phenol, eicosyl phenol, dioctyl phenol,
dinonyl phenol, didecyl phenol, didodecyl phen~l, ditetradecyl phen~l,
dihexadecyl phen~l, dioctadecyl phenol, tributyl phenol, trihe~yl
phenol, trioctyl phenol, tridecyl phenol~ and tridodecyl phen~l.
- Among these octadecyl phen~lg dioctyl phenol, dinonyl phenolg
didecyl phenol, didodecyl phen31 and ditetradecyl phenol should be
~mphasized.
The dialkyl phenols preferably have the alkyl groups in the
~9 4- p~sition but 2, 3-; ~, 6- and 2, 6-dialkyl phenols can be used. The
- triaLkyl phenols have th~ a~yl groups preferably in the 29 4, 6- posi- : ;
tions, but 2, 3, 6-; 2, 3, 5- and 2, 3, 4- can also be used. `~
Among the compounds according to the invention based on the
above-mentioned alkyl phenols~ the f~llowing have been found to have
go~d properties:
' "
'
.. . ..

~ 42~
C~I37--O~O (c2H4o)~2-c~lcHcET2 ~ C~I3
OH N C1
C ~1~,O_O--(C2H~O),Z.-c~I2c~Ic~-I2 \ C~I3
- OH
C8Erl7 ~O_(C2~I40)~ H2lCHC~2 /CH3
C8 H 17 ~ ~N~ . C 1
C 8E~17--O--o~CzH40) 8-CH~ 2 CE3~3
.C8 H l7 OH
C8 ~17--O--O--~C2H40) l2~CEI2CHCH2 CE3
`C8 E lq lH N/ Cl
C8~l7--O--O--(C2EI~O)~-~H2l ~ICF2/ \C~I3
C8 H 17 ~ -
C~4Hz9--l--~ 2~ 8~ ~2\ ~jC~I3
89 0~ N Cl
15C~4 Ea~,{>~ (C2H~0)~2-C~ICEI2 \C~I3 ~;
C ~H29 H
C~4 H~'29--~ (C2:EI40)22-CH~2l HCII2 (~I3 -
29 . OH N . C l
C4~12f~OI--~)~C2~0)22-CH2j~ECH2 \C1~13
. iC 14 H;!~ O~I ~ `::
: , ' , ' ~,
''

L6
The ollowing coxnpoun(ls sllow particularly go~d properties:
C9Hl9 `^~S>~o (c2~I~,o),~-cH2lcHcH~ /C~I3
C 9 ~ 9 O~E N C l
Cg Hl9--q--O--(C2H40),2-CH2lC~:C~I2 Cl:I3
Cg Hlg OH
Mlg~ (C2H,I0)l6-C~2lcHc~I2 /CH3
Cg Hl9 OH N Cl
Cg Hlg - - O O~C2H,~O)l,J-C~12~HCF~ CH3
Cg Hlg OH
Cg Hlg I----(C2H4O~z4-CEI2l~CH2 /CH3
CgHlg N Cl
Cg Hlg--O--~--(C2H~O)2g-CH2l HCH2/ \ CH3
C9 Hlg OH ~ .
CloH2~ - I----(C2H4(3)l6-~2l HCH2 /~H3 Q ~ :
CloH2l OH N Cl :
clo~)--(C2H4O),~-CH2lHC~I2 \CH3
C~ lo H2 l H ~ ~;
C1O E2~OI~--(C2H4O)24-CH2l HCH2\ 0~CH3
CloH2l OH N Cl
Cl0E2~ --~c2EI4o)2~l-cH2~c~2 - \CH3
cloH2l . ~ .
'.''' ~''

66
Cl2~I2~ 0--O----(C2H~0)l6-C~I2l ~IC~2 /CH3
C l2H2s OH /N C 1
C,?H2s-- I :)~C2H,EO)l~,-CH2l HCH~ I3
C l2H25 OH
C~H2s~ (C2F[~O)2~-CHzl HCH2 /CH3
C 12~25 OE N C 1
Cl2H25--<~>~O~C2EI40)2~-CH2CHCH2 \CH
C ,2H25 IOH
The in~enti~n is further illustrated by the following Examples,
10 whîch in the opini~n of the inventor represent pra~erred e~nb~diments
of the invention.
E~AMPL 1
In a r~action vessel pr~vided with devices for heating,s~irring,
and a reflux condenser, 2 m~les of 2, 4- dinonyl phenol were intro~
15 duc~d. The dinonyl phenol was reacted with 16 moles ethylene o~ide
together with 0.1% ~odium hydroxid~ catalyst.
The ethylene 1~xide adduct ~hus obtained was wor~ed up, and
reacted with 2~2 moles epichlorhydrin at a temperature of about 100C
during 100 miIlutes. As catalyst during this reaction 6 g SnCl~ wa~
20 - used. ~esidues of epichl~rhydrin were rem~ved by vacuum treatment
~ .
12
.
-
- .
.

4~i6
and a reaction product in the state oP a yellowish viscous liquid was
obtainecl.
~ n ~ autoclave with a stirrer and a heating device 1.8 mol~s
of this reaction product was introduced together with ~50 grams
5 ethanol in which were ~issolved 0. 9 mole dimethyl amine, 50 grams
sodium hydrox~de, and 30 grams of water. The mixture was kept in
the autoclave for three hours at 125C. Traces of residual dimethyl
amine were removed by bubbling nitrogen gas through the reaction
mixture.
10The reaction product was a yellowish substance, 90% quater~
nar~r amine and 6q~o tertiary amine, calculated on the the~re~ical yield
of amine. The quaternary amm~nitlm compound thus ~btained had the --
fs~rmula:
,
Cg H~ ~ (C8H~0)8 -CH2fHCH8 ~CEI3 .
1~ CgH~ O~I N Cl `
CH
Cg Hlg--q--O-(C2H~0)8 -CH2CHGH~
CglIlg OH
EXAMPLES 2 to 6
.
- In the same way as the compound ~, of Ex~mple 1, the fol~
. ~
aDlowing comp~unds were synthesized: ;
,.~ .
Example 2. Reaction product of 2 moles dinonyl phenol, 24
moles ethylene oxide, 2 m~les epichl~rhydrin and 1 mole of dimethyi-
amine:
`
13
.. . . .
.. ,.~.,. .. , . ; ... . - . . .
" ; ! ~ ,.. . ..

C~ Hl9--0~ (c2EI~o),2c}I2c~lc~2 CEI9
/ \C~I3
C9Hl9--C~o--(C2H,I0)12CI-IaC~ HCH2
~9 Hl9 OH
Example 3. Reaction product aE. 2 moles dinonyl phenol7 32
moles ethylene oxide, 2 moles epichlorhydrin and 1 m~le dimethyl
amine:
Cg H~> O-(C2H4Q~1~CH2,~C~ 9/CH
C H3
0 C9H~l9 ~ O--(C2HgO)16!: H2CEICE~
9 ~19 ~)H ;
~: Example 4. Reaction product of 2 moles dinonyl phen~l,., 60
moles ethylene oxide, ~ m~les epi~hlorhydrin and 1 mole dimethyl
amine~
CgHl~o--(C2H40)3~CH2CHcE~ ~,CH
Cg Hlg--0--0--(C2HgO)30CH2CHClI2/ CH3
Cg H39 ~H ~ .
Example 5. ~eacti~ product o~ 2 moles didodecyl phenol7
20 ~2 moles ethylene oxid~,2 moles epichlorhydrin alld 1 m~le dimethyl
amine: .
C~2HZ5 0--O--~C2H~LO)l.6 ~H2CbHcH2\ ~)~CE~3 ~3 .
C~ZH25 ~ ~ H~
C~[2D--O--O--(C2H0~ 16 C H2~E3CH2
~;L3 bl2H25 bH
14
., . ,. ~ . . . -- . . . .

~04~66
~ . Rcaction product of 2 mol~s dioctyl phenol,
2~ mol~s etl~ylen~ oxide, 2 moles eplchlorhydrin and 1 mole dim~thyl
amine.
C8ll17 - I ( 2 4 )12 21 2 \ ~? / C~
C8H17 N Cl
/ CE13
C8E~17 C~- (C2~l }) 1~C~ CHCH2
C8~17 ~ '
0.5~ each of the products of Examples 1 to 6 were
added to samples of an aqueous ~leached pine sulphate cellulose
pulp slurry of 2% consistency.
In a control, for comparison, 0.5% of di(C16-C20-fatty-
alkoxy (ethyleneoxy)6-2-hydroxy propylene) dimetnyl ammonium
chloride was added.
-- ~and sheets were form~d ~rom the pulp slurries in tha
usual way, and tes,ed after dr~ing for mec~anical strength
~burs~ factor according to SC~I) and water absorption according
to Klemm. The results are shown in Table I:
,;
TABLE I
20Additive; __ Burst Factor Water Absorption, mm
No additive 21.1 100
Example 1 10.6 91
Example 2 11.5 92
Exa~lple 3 12.7 95
Example 4 16.8 98
Example 5 12.2 93
Example 6 12.9 92
Control 12.9 90
' ' ' ~'
, ':
cb/ ~ 15 _
,~.. ... . ..

4L6~
From the results it is evident that a~dition of the compounds
oE Examples 1 to 6 according to the inventi~n in a very noticeable way
reduces the mechanical strength (burst factor) of the cellulose pulp
fibers, while preserving a high wettability. Comparison of the re-
sults with those of the cellulose treated with the control makes evident
that only the Example 4 gives cellulose pulp fibers with a higher burst
factor, while on the other hand all the compounds according to the in-
vention give cellulose pulp fibers with better wettability.
.
' ` -
.
16
.. ,~ . .
. .~