Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
104Z133
The present invention relates to cationic poly-
urethanes, to a proces~ for their production and to their use
as sizing agents for paper.
- Cationic polyurethanes have long been known.
Cationic polyurethanes are polyurethanes containing one
or more atoms with a positive charge in the polymeric
molecule. Compounds of this kind can be obtained for
example from polyurethanes containing groups capable of
onium formation.
The production of polyurethanes of this kind is ~ -~
described for example, in German Patent Specification No.
880,485. The compounds mentioned in that Patent
Specification are prepared as follows. The starting
compound used is, for example, a glycol containing a
group capable of onium formation, such as tertiary
nitrogen or ether oxygen. This glycol is reacted with an
equivalent quantity of a diisocyanate and the products
obtained in this way treated with polyfunctional and,
~ optionally, even with monofunctional alkylating agents.
¦ 20 It is also known that a prepolymer containing NCO-
groups can initially be prepared from polyesters (German
! Patent No. 891,742) containing terminal hydroxyl groups,
} and subsequently further reacted with dihydroxy compounds
containing groups capable of onium formation.
Other cationic polyurethanes are described, for
¦ example, in Germany Offenlegungsschrift No. 1,595,602 and
in the article by D. Dieterich et al in "Angewandte Chemie",
vol 82 (1970), No. 2, pages 53 to 63. It i~ known that
compounds of thi~ kind can be used as textile auxiliaries,
dyeing auxiliaries, for producing thickeners, rubber-like
. .
- 2 -
~" , . . J . .
'' . ~ .
104,;~13,;~
.,
plasticg~ d:imoll,;ionally Stal)le pla9ti¢8 coatings,~ SOIt
tacky compositioll.s, 1;hermoplastic products or even glas,s-
hard duroplasts. They are ~ ~,o_s~id to be suitable for
coating and for impregnating woven and nonwovcn textiles,
~ 5 leather, paper, wood, metals, ceramics, stone, concrete~
t~' bitumen, hard fibres, straw, glass~ porcelain~ various
kinds of plastics, for antistatic and noncrease finishing,
as binders for nonwovens, adhesives~ adhesion promoters,
laminating agents~, hydrophobising agents, plasti.cisers~
10 binders, for example for powdcred eork or sawdust~ glass
fibers, asbestos, paper-like materials, plastics or
. rubber wastc~ ceramic materials, as auxi].iaries in cloth
- - - : -
"J printing and in the paper industry, as additives to polymer - ~ :. .. - .
.~¦ dispersions, as sizes and ior finishing leather and also
as sizing agents for paper.
~lthough a large number of cationic polyurethanes
have already been described in the literature~ there is
still a demand for compounds.of this kind because~ on the
;~. one hand~ the processes by which they are conventionally
.',7 20 produced involves eertain difficulties and because~ on the
other hand~ the properties of conventional cationic .-
polyurethanes are unsatisfactory and in need of improvement :
. ~or eertain applieation.
It has now surprisingly been found that eationic
j~ 25 polyurethanes with outstanding properties ean be obtained by ~ -
reaeting a monomeric aliphatic dihydroxy compound, eontaining
an aliphatic substituent with at least 10 earbon atoms~
with a polyisocyanatc to form a preadduct eontaining terminal ~ .
i NC0-groups and cha.in-e~tending the prcaclduct thus obtained
¦ 30 either with an aliphatic monomeric diol containi.ng tertiary
ls ' ~. - ' ' : .
? j JSf 3
1042~3~
`~ nitrogcn followc~ by conver6lon of tl1e chain-oxtended
-
product into ~n amll1onium co~,nl-ound~ or wlth a eorrespondlng
I monomcric alipllatic diol alre~ i~ the form of an
ammonium compound. In the context of the invention, -- -
ammonium compounds are compounds containing positively
x charged nitrogen, as is the case for example with salts
of tertial~ amines or with quaternary ammonium salts.
Monomeric aliphatic dihydroxy eompounds eontaining an
aliphatie substituent with at least 16 carbon atoms are
particularly suitable. In the context of the invention~
monomeric aliphatic dihydroxy compounds nre non-polymerie
j aliphatic glycols~ i.e. organic compounds with two hydroxyl
groups in the l,2- or l,3-position or in any other
position, for example the ~,W-position. It is preferred
to use monomerie substituted aliphatic dihydroxy compounds
wherein the two hydroxy groups are attached to one another
by at most 7 atoms in the aliphatic ehain.
The aliphatic substituent, which the aliphatie
dihydroxy compound must contain, may be situated on a
carbon atom attached to one of the two hydroxy groups,
although it may also be situ~ted on a carbon atom lying
¦ between those carbon atoms attached to the two hydroxy
funetions. Preferably~ the aliphatie substituent eontains
from lO to 22 carbon atomsO
In addition, it is not absolutely essential ior the
aliphatie ehain of the glycol, through which the two hydroxy
groups are attaehed to one another~ to eontain only earbon
atoms. Thus~ one earbon atom may be replaeed by a hetero
atom sueh as ox~gen or nitrogen. If the hetero atom present
in the aliphatic chain is nitrogen, the aliphatic
i '' ':
Il jf 4
d ~-~
~,.... . .. . ... ... .. .. ~.. ~ . .. .... ... .. .
~,. .. .. ; . . .. ... . . ; . . . .. . . .. . . - . . . ... . . . . . .. ..... . .
~'''`" ` ''' " ~'` ` ' ` ` ' . .'
iO4Z~3;~
substituent and may in f~ct ~o attnched to the hetero atom
If a hctoro atom i 9 Si tuatod in the aliphatic chaln, lt
is essential for the purp sos of the process according to
the invention that no radical capable of reacting with
isocyanate groups should be present on the hetero atom
during the reaction of the dihydroxy compound with the
polyisocyanatesO Thus when, for example~ nitrogen is
present in the chain, the third valence must be satisiied
by a radical without any active hydrogen atoms.
- 10 The aliphatic substituent on the dihydroxy compound
must contain at ieast 10 carbon atoms and preferably at
least 16 carbon atoms. It is not absolutely essential
for the substituent to be merely a corresponding hydro-
carbon radical. Aliphatic substituents in the context oi
the invention also include the group RC00-, where ~ is an
aliphatic radical with at least 9 carbon atoms and preierably
with at least 15 carbon atoms. Glycerin fatty acid
monoesters, for example glycerin monostearate or glycerin
behenic acid monoester~ are particularly suitable.
,
N-Substituted dialkanolamines~ especially N-stearyl
diethanolamine~ are mentioned as examples o~ compounds in -~
~ ich one carbon atom in the aliphatic chain is replaced -~
by a hetero atom. -
1,2-Dihydroxy octadecane and 1,4-dihydroxy octadecane
have also proved to be very suitable dihydroxy compounds ;~
containing a substituent with the corresponding number of
carbon atoms for the purposes oi the invention. ;
~he reaction of the substituted monomeric aliphatic
dihydroxy compo~nd with a polyisocyanate is best carried
out in an anhydrous solvent~ preferably in acetone.
jf 5
1 . , . ~ . . ,. . - , - -
, : , : ~, , . ~, :
.' ~ -, .' ., : ~ ' , . . .
104Z~33
JTowcver~ th~ rcaotion may also be carrled out ln other
solvents whlch are inert wlth respect to isocyanate groups
or whlch s~ow only limited reactivit~ by comparison with
the reaction components. Solvents o~ this kind are
tetrahydrofuran, dimethyl formamide, chloroiorm, per- - --
chlorethylene, methylene chloride~ methyl ethyl ketone~ -
ethyl acetate, dimethyl sulphoxide.
However, reaction oi the aliphatic substituted
dihydroxy compound with the polyisocyanate may also be
carried out in the melt~ i.e. in the absence of a solvent.
Catalysts may be used ior the reaction oi the
dihydroxy compound with the polyisocyanate. Diacetoxy
dibutyl tin has proved to be a particularly suitable catalyst~
although it is also possible to use other catalysts such as -~
dibutyl tin laurate~ cobalt naphthenate~ zinc octoate
and tertiary amines~ ior example triethyl amine or 1~4-
diaza-t2~2,2]-bi¢yclooctane. The diols containing tertiary
nitrogen used ior chain extension may also be used as -
oatalysts.
,~ .
The polyisocyanates used ior preparing the preadduct
may be both aliphatic and aromatic polyisocyanates. ~ -
Mixed aliphatic/aromatic ¢ompounds may also be used. It is
prefèrred to use diiso¢yanates. Tolylene diiso¢yanate~
- diphenyl methane-4,4~-diiso¢yanate and hexamethylene ~ -
diisocyanate have proved to be particularly suitable. p
It is also possible to use so-¢alled masked diiso¢yanates~ b ~- '
su¢h as~ ior examplo~ the rea¢tion product of diphenyl
methane-~,4~-diso¢yanate with 2 mols oi phenol.
Among the triiso¢yanates whi¢h may be used in the
present invention~ the addition product of ~lycerin ~nd
~ ~ ~i 6
~ - ~
104Zl;~
3 mols of tolylone dlisocynnate and also tri~ isocyanato-
phellyl)-mollo-tlljophosphatc~ have proved to be particularly
suita~leO In cases where polyisocyanates~ with more than
two isocyanate groups in the molecule ~ also used, it is
preferred to use a larger proportion of diisocyanates, because
uncontrollable crosslinking can occur very easily in cases
where only, or alternatively a large proportion of~
polyisocyanates with three or more isocyanate functions
in the molecule are used, and in fact generally~ it is
pre~erred to use aromatic diisocyanates in the praotioe
of the invention.
The ratio between the reactants~ i.e~ the molar
ratio of dihydrox~ compound to polyisocyanate~ may be
varied within a relatively wide range. Thus, it is
possible $or example to use a molar ratio oi dihydroxy
compound to diisooyanate in the range from 1:1.1 to 1:3.
The molar range from 1:1.5 to 1:2.5 is particularly
suitable~ a ratio of exactly 1:2 being preferred.
~he preadduct obtained may then be reacted with
substantially equivalent quantities of an aliphatic diol
containing tertiary nitrogen. In the context of the
invention~ equivalent quantities mean that it is possible
to use the same number of hydroxyl groups of the diol ~ -
relative to the number of isocyanate groups present~ -
N-Methyl diethanolamine and 1~2-propane diol-3-dimethyl
amine have proved to be partioularly suitable aliphatic
diols containing tertiary nitrogen. It is of course also
possible to use other compounds containing tertiary
~itrogen, such as for ex~nple N-n-butyl diethanolamineJ N-t-
butyl diethanolamine, N-methyl dipropanolamine, N-N-bi~-
:
jf 7
: - :: . - ,, 1 -:' ' ' .
:. . . :
: .: .. ., - : .. . .. .
133
2-hydroxy etll~l-p-tolidine and 1~4-bis-hydroxy ethyl
piperazine. ~he diol preferably contains only one or two
tertiary nitrogen ato~s and ge~erally has a molecular weight
oi less than 300,`prefera ~ ess than 200. The reaction
o~ the preadduct with thè diol is generally a chain-
extending reaction.
The reaction of the preadduct with the chain
extender is preierably carried out in an anhydrous
solvent, acetone ha~ing proved to be parti¢ularly ~uitable~
and is best carried out at boiling temperature. The
course of the reaction may be rollowcd by an appropriate
isocyanate determination method. Towards the end of the ~ -
reaction the NC0 content should be less than 1%. The
chain-extended product is then converted into an ammonium
compound. The pair of electrons still free in the tertiary
nitrogen are bonded~ so that the nitrogen receives a
positive charge. In this operation~ hydrogen from a
suitable acid or an alkyl group may be bonded to the
tertiary nitrogen. This operation~ which follows chain
,
extension, may be circumvented by using~ for chain extension~ -
. ...
a corresponding glycol which is already present in the form
o~ an ammonium compound, ~or example a salt which has been
obtained by reacting an acid with a glycol having tertiary - -
nitrogen~ ~or example the hydrochloride o~ N-methyl
diethanolamine.
onversion of the chain-extended product obtained -
into an ammonium compound is pre~erably carried out with
hydrogen chlorideD It may be carried out with aqucous
HCl, although HCl gas may also be introduced into a
solution. A solution o~ ~Cl in acetone may also be used
.. ' ' . ' -:-j~ 8
.:
104Z133
Wit]l good cf~ect. Conversion into an ammonium compound
may also be cnrried out t~ith a conventional alkylating
agent It is proferred to use dimethyl sulphate.
Extremely favourable results are~ obtained by replacing
some of the HCl with dimèthyl ~ulphate during the reaction
with hydrogen ch]oride. It is possible in this way to
bond the methyl group, rather than hydrogen, to some of
the tertiary nitrogen atoms.
For conversion into an ammonium compound, it iB 0~
particular advantage to use acid or alkylating agent in only
such a quantity that from 45 to 200 milliequivalents per
100 g of polymer o~ the tertiary nitrogen atoms are ~ ~-
converted into the ammonium form. The quantity of acid or
alkylating agent required for adjusting a value in this
; . ~, . .~ , ;
range may readily be calculated rrom the quantities Or
starting materials used.
It is particularly favourable to convert the chain~
extended product into an ammonium compound be~ore drying. -~ -~
In the context o~ the invention, by intermediate drying is
meant a suitable method o~ treatment by which the solvents - -
used, i~ any, or residues of other liquids may be removed. ~ -
Spray drying or treatment in a rotary evaporator~are
particularly suitable for this purposeO
- The product which has been subjected to intermediate
drying may then be suspended, for example in water~ ~nd
- converted into an ammonium compound by the addition o~
hydrochloric acid. In cases where acids~ such as hydro-
chloric acid, are used, it is best not to add the chain-
extended product to them, but instead to add the acid
slow]y to the chain-extended product.
.
jf
.: - ~ . : - : ..
1042~;~3
Thc invention also relate~ to oationio polyurethane~
obtaina~lc by reacting a monomeric al.iphatlo dihydroxy
compound, containing an aliphatic substituent with at
least 10 carbon atoms and preferably with 16 carbon atoms,
with a polyisocyanate to form al~readduct containing
terminal NCO-groups, and chain-ex ~ n ~ g the preadduct
with an aliphatic diol containing tertiary nitrogen, and
converting the chain-e~tended product into an ammonium
compound by treatment with an acid or an alkylating agent.
The polyurethanes according to the invention may be
obtained from the starting compounds re~erred to previously
in the description of the process according to the invention.
The cationic polyurethanes according to the invention :
may be built up irom structural units corresponding to the
~eneral formula ABAD~ the members by which the structure is
~uilt up hnving the ~ollowing meaning:
O O ~ ' ' ~:-.
n "
~ A a -C-NE-R-NH-C~ where R = a divalent aliphatic~ aromatic
or araliphatic radical
2~ CH20R'
; B - -OCE2-CEOR~-CH20- or -0-CE-CH2-0- where
R = -C-R"~ R" = CnH2n + 1 n = 9 to 21
D a ~O ~ CH2 ~ NHR"~ ~ CH2-)S O ~ X or
t
_ - CE2- CHO ~ X
~3 ~ ; -
CH2 N
~A~CH
- ~ 3
104Z~33
n~ 2n~ + 1, -
r = 2 to ~, s = 2 to 6 and x is an acid radical,
preferably Cl .
Member B may also be of the following types
- OCH - Cl-I 0 -
CmI~2m+1 .
_
where m = 10 to 22 preferably 16 to 22
or
.
- 0 -fH - CH2 - CH2 ~ CH2 0
Cm~H2ml + 1
. - X'
where m' = 10 to 22 preferably 16 to 22
or
CH2 CH2 1 CH2-- CH2 0-- ~:
where m = 10 to 22 preferably 16 to 22
- 20
Member A is formally derived from a diisocyanate and ~ `~
is explained by the formula which reproduces the structure
as it exists within the polymer chain. It is obvious to
the expert that member A, where it is terminal, contains
a terminal isocyanate function, i.e. the -N=C=0- group.
~- The same applies as regards member D which is formally
derived from a diol and which, once again, is also shown in
the formulae as a member within the polymer chain which,
where it is terminal, contains a terminal hydroxyl group.
The terminal groups may also be modified by secondary
,
. .
jf 11 ~ ~
104~
reactions.
The proc~ss according to the invention gives cationic
polyuretllanes with outstanding properties in a very simple,
advantageous manner. The reactions are substantially
quantitative. No secondary products are fo ~ neither
do any undesirable crosslinking reactions take place.
The solvent used, if any, is very easy to recover. The
individual reactions ta~e place quickly, with the result
that a high conversion may be obtained in the process
according to the invention. The successive reactions
leading to the cationic polyurethane may be carried out
one after the other in difierent vessels. However, the
individual reactions may also be carried out in a single
vessel. It is also possible to simultaneously react the
starting compounds required ior iorming the cationic
polyurethane according to the invention. In particular, -
the chain-extended product may be prepared by a so-called
one-pot process. However, the preadduct is preierably
iormed to begin with, iollowed by chain extension.
The properties oi the cationic polyurethanes may be
varied within a wide range by selecting suitable starting
eompounds. Thus, the use oi aromatic diisocyanates
generally leads to cationic polyurethanes with even bettersj2;~
- properties. The particle size oi the polyurethanes may be
iniluenced by varying the proportion oi nitrogen atoms
eonverted into the ammonium iorm, and it is possible to
obtain coarse-particle, iine-particle and even eolloidal
systems.
~ The basicity oi the polyurethanes according to the
invention is generally higher when chain extenders in which
ji 12
104'~3;)
the tertiary nitrogen or ammoniUnl ni1rogon is not directly
sit1lated in thc chain botween the two hydroxyl groups, are
used. l,2-1'r~pane diol-3-dimethyl amine iB one example of
such a compound.
The cationic polyurethanes obtained ar ~ xtremely
stable in storage. They may be processed ln the form of --
solutions or dispersions. They may readily be admixed with
other additives, and may be processed into shaped articles?
for example films. They are also suitable for coating
various kinds of plastics.
It is particularly surprising that the cationic
polyurethanes produced in accordance with the invention
should represent very valuable sizing agents for paper.
The invention further relates to a sizing agent for paper
containing the cationic polyurethanes according to the --
invention. The sizing agents according to the invention
may be used for sizing paper by methods known per se.
Thus, the polyurethanes have proved to be effective
sizing agents both for the bulk sizing and also for the
surface sizing of paper. It is also possible to carry out
¦ both processes at the same time with the sizing agents
according to the invention. It is also possible to carry
out bulk sizing with conventional sizing agents, for
example resin sizes, followed by surface sizing with the
1 25 cationic polyurethanes according to the invention.
¦ More details on the sizing o~ paper may be found, for
example, in the book by Engelhard, Granich and Ritter
entitled "DAS Leimen von Papier" VEB, Fachbuch-Verlag
Leipzig, 1972.
By using the cationic polyurethanes according to the
jf 13 ~ -
-- - - - .... - ... ~ .- . ,. .: , .
-.. - -: .. - , .. .. . ~ .. : . : . . . .
:' ~ ' , '' ' , " ' ' '. - . " ~.':~` . ' -
- ~04Z~3;~
inventioll, sizing mny be carlied out at pll-values withln a
re]ative]y 1~ide rMnge, so th~1; chalk n~ay also be u~ed AS
filler. Tlle compati1~ility oi the polyurethanes with alum
is excellent. They may be processed very effectively
together Iqith products of the type normall ~ for the
surface treatment of paper, such as starch, which may be
degraded either by oxidation or by fermentation or
chemica]ly modified, cellulose derivatives, for example
carboxy methyl cellulose, cellulose ethers, polyvinyl
alcohol and alginates.
In cases where the cationic polyurethanes produced
in accordance with the invention are used for sizing
¦ paper, the sized paper exhibits extremely favourable
sliding friction so that no difficulties which can be -
atrributed to a dccrease in sliding friction are encountered -
during processing, for example during stacking of the
paper. In addition, papers which have been sized with the
sizing agent according to the invention show outstanding
processing properties when it comes to rolling and cutting,
and so on.
A very good degree of liming is obtainable with the
cationic polyurethanes. One particular advantage is that
the sizing effect is instantaneous and, once applied, the
size remains effective over prolonged storage periods.
This is of considerable importance, above all in the case
~ of raw paper for coating~ because uniform ink uptake is
! required during further processing.
j Hardly any effluent problems occur either in the
production of the polyurethanes or where they are used for
SiZillg paper. It is particu]arly emphasised that, where
jf 1~
104Z~3;~
the po]yuretllarles are u~ed as sizing agent~, foaming is
largely avoided both in bulk sizing and also in surface
sizing.
The favourable sizing properti ~ f the product are
also emphasised insofar as they enableJsizing to be - -
carried out with far less material than is the case with
conventional products. The starting compounds are
readily obtainable, so that no dif:Eiculties are involved
in large-scale production.
The cationic polyurethane~ according to the invention
may be used ~or full si~ing, three quarter sizing, half
sizing and quarter sizing. ~-
The invention is illustrated by the following
Examples. The test methods referred to in the Examples
are described below:
1.. Degree of sizing against ink with the Hercules Sizing
Tester, in accordance with the operating instructions
of the manuf~acturers, ~ercules Incorporated, Wilmington,
Delaware, USA. The quantity measured is the tlme in
seconds elapsing until an 80 ~ decrease in the
remission value of paper is obtained when the test
ink is applied to the paper and breaks through the
paper.
Test ink: Papier-Pruitinte, Blau, as defined in DIN~ ~-
53126
2. Cobb Test: (DIN standard 53/32 - 1 minute)
a) Absorbency with respect to water, expressed in ~ --
g/m2 of water taken up after 1 minute~s contact
. . with water.
b) Absorbency with respect to 10 ~ Na2C03 solution,
,. ~ ' '
jf 15
' . ~ .' '.
104Z~33
expressed in g/m2 after 1 mlnute's conta~t, as
in 2a),
~rther particulars oi the test methods may be iound
in the book by Engelhardt et al re~ rred to previously,
. J
EXAMPLE 1
The apparatus used is a heatable, 500 ml capacity
three-necked spherical ilask equipped with a stirrer,
reilux condenser with drying tube and a dropping funnel,
19,5 g of standnrd commercial-grade glycerin mono-
stearate (0.0545 mol) are introduced into the flask, 15 mg
! oi dibutyl tin diacetate, 24 ml o* anhydrous acetone and
16,0 ml(l9,5 g) oi an 80 : 20 mixture oi 2,4- and 2,6-
tolylene diisocyanate (0,112 mol), are then successively
added, -
The reaction vessel is then heated for 30 minutes
with stirring until the solvent begins to reilux gently,
~ In the meantime the reaction temperature i8 approximately
65C,
A solution o~ 6.5 g oi N-methyl diethanolamine
(0,0546 mol) in 20 ml o~ anhydrous acetone is added dropwise
over a period oi 10 minutes, followed by heating in such a
way that a moderate re~lux is again maintained,
; After a reaction time oi 60 minutes, the NC0-content
has iallen to below 1,5 ~, and a moderately viscous,
crystal-clear solution oi the polyurethane has iormed, being
diluted by the addition oi 160 ml of commercial-grade
acetone,
For salt formation, 27.3 ml of 2N hydrochloric acid
are added over a period oi approximately 5 minutes, There-
_ if 16
.. . . .
alter the salt i8 present partly in colloidal ~orm and
partly in the iorm oi a white precipitate which i~ di~solved
by runnin~ in 140 ml oi water over a period oi 15 minutes
during which the contents of the flask are k~ept at a
temperature of approximately 50C. ~
The clear solution formed i8 freed irom the acetone
by vacuum distillation.
- A 20 % by weight, slightly opalescent, pale yellow
coloured solution o* the polyurethane ionomer i~ obtained.
The concent~ation can be increased by distilling oif
more wate~. A~ 32 % by weight the polymer solution i8
still ~ree-ilowing.
. .'
EXAMPLE 2
The procedure is as in Example 1, except that 6.5 g
; instead o~ 6.o g of N-methyl diethanolamine are used and
salt iormation is carried out with 25.2 mol oi 2-normal
~ hydrochloric acid. The polyuretbane solution is not iurther
diluted with acetone before addition of the hydrochloric
~ 20 acld.-
! A shimmering blue emulsion with an average particle -~
size of 0.5 to 1 um is formed. ~ -
~ , . ' .j~.' ''
~ EXAMPLE 3
¦ 25 The procedure is as in Example 2, except that the
chain-extended product is subjected to intermediate drying
by spray drying. The product thus dried has a melting point ~ --
of approximatbly 93 C. s~ ~
- For conversion into an ammonium compound, the dried- -
product is suspended in water, iollowed by the gradual
:~ ' . ':, " ' :'
ji ` 17~ -
' . .
104Z133
addition o~ hydrochloric acid.
F~fP]J~
The procedure i9 as in Example 1, excep~ that the
reaction between glycerin monostearate~s~/tolylene
diiosy~ate is catalysed by 3 ~ of the total quantity of
N-methyl dicthanolamine which is deducted for chain
extension. A product of the same kind as in Example 1
is formed.
EXAMPLE 5
,
The procedure is as in Example 1, except that the
solution of the N-methyl diethanolanline in acetone i9
added dropwise immediately after dissolution of the glycerin
monostearate and tolylene diisocyanate, i.e. without a
preliminary reaction of these components catalysed by the
addition of organo tin compounds, tertiary amines or
compounds with a similar effect. The reaction time is 2
hours. The dispersion of the ionomer is slightly clouded.
EXAMPLE 6
19.5 g of clyerin monostearate are initially introduced
and heated to melting point. 16 ml of tolylene diisocyanate ~-
are then added dropwise in such a way that the temperature
does not exceed 75C. On completion of the exothermic
- reaction, the reaction mixture is stirred for another 20
minutes at 75C. The melt is then dissolved by the addition -
oi 50 ml of anhydrous acetone.
Further reaction with N-methyl diethanolamine, salt
.
formation and dispersion is as jn Example 1.
ji 18
-
. . . . .. . ..
, . - . . . : , .
: .: . . ~
; ' . ' , -, ~ ~ ' , -
1042
.
The proccdure 1~ aY i~_ ~ ~ple 1, except that 8.0 g
of ~-butyl diethanolamine are used instead of 6.5 g of
N-methyl diethanolamine. A fine-particle opalescent
dispersion is formed.
EXA~LE 8
The procedure is as in Example 1, except that 29.4 g
of bis-(4-isocyanatocyclohexyl)-methane are used instead of
19.5 g of tolylene dii*ocyanate. A slightly opaleeoent
solution is obtai~ed.
EXAMPLE 9
- ~he procedure is as in Example 1, except that only
80 % of the tertiary nitrogen is neutralised by reducing
the quantity of hydrochloric acid to 21.9 ml. ~ -
A stable, fine-particle emulsion is ~ormed.
EXAMPLE 10 . _
- 20 The procedure is as in Example.l, except that the
glycerin monostearate is replaced by 19.5 g o~ N,N-di--
hydroxyethyl stearylamine.
', ..
EXAMPLE 11
.The procedure JS as in Example 1, except that the
glycerin monostearate is replaced by 15.6 g of 1,2-
. .
dihydroxy octadecane.
A slightly opalescent, pale yellow dispersion is ~ -
obtained. - . ~ -
- -
, ' ' . - ~
j~ 19 . , `-,: .
, , ~
' ' ' ' ' ' ' . ' ,' . ~ . . ~ , ! : ~ .
~ 04;~
F~ MPI.E 12
The procedure i8 as in Examp~ 1 up to and including
the reaction with N-metl~yl diethanolamine.
25 % of the tertiary nitrogen is quaternised by the
addition of 0.86 g of dimethyl sulphate, followed by
reaction under reflux for another 30 minutes.
After dilution with 160 ml of commercial-grade
acetone, 20,4 ml of 2N-hydroohloric acid are added dropwise,
followed by dispersion as in Example 1.
A stable, fine-particle emulsion with strongly
cationic centrcs is obtalned as the end product
EXAMPLE 13
A cellulose pulp for producing paper is bulk-sized
in a Hollander in known manner. Of the total pulp input,
70 % consists of bleached pinewood pulp and 30 % of bleached
- beechwood pulp. In addition, 1 ~ Or sizing agent produced
in accordance wi~h Example 2 iæ added. Bulk sizing is carried
out once without the addition of a retention agent and then
in the presence oi 0.3 ~ of a standard commercial-grade
¦ retention agent (polyamide amine).
- The papers produced have a weight per unit area of
70 g/m2~ For comparison, bulk sizing was carried out with
a standard commercial-grade cationic size based on modified ~ ~
2~ maleic acid anhydride-styrene copolymers under otherwise -
I the same conditions.
l'he degree of sizing, the Cobb water value and the Cobb
value of 10 f soda solution were measured on the papers
produced in this way. The results are set out in the
following Table.
.
jf 20
.
- . ~ . .
."
,. . -
,
, ~ - : -
104213;~
.
Tal)le 1
Polyurethane produced Standard
in accordance with commerclal-
Example 2 J grade product
degree oI sizing (seconds) ~
without retentioR agent 458 ` 140
with 0.3 % of retention
agent 833 l90
Cobb (water)
without retention agent 27 28
with 0.3 % of retention
agent 23 27
Cobb (lO ~ soda solution)
without retention agent ' 20 22
with 0.3 ~ of retention
agent 19 20
EXAMPLE 14
.,
An unsized raw paper weighing 80 g/m2 is treated in a ~,
sizing press with a size containing 10 % of potato starch
degraded by oxidation and 0.25. % of a.d. sizing agent
produced in accordance with E~ample 2. The papor takes
- up 1.85 ~ o~ dry substance, based on its own weight, in
~ . . . .
the sizing press.
Sur~ace sizing is carried out using a standard
commercial-grade cationic sizing agent based on modified ~ -
maleic acid anhydride-styrene copolymers under otherwise ~ ~ ;
the same oonditions. The values measured on the paper -~
are set out in Table 2.
- ' ' `: :`,.' :.~ ~,
- ~' ', ' ~
. ~ .
~.
21
... . . , . . ... , .. ,.. -. . ,. ~ , ..... -
--.: ,. - . . . ...... . ,. ..... . :.................. - : ,
. 104Z13;~
.
Tablo 2
Standard Polyurethane
com~ercia]- \dispersion according
grade product `t-o_Example 2
Degrec of sizing.
(Herculcs seconds) 310 1590
Cobb value (water)
1 minute 26 19
'
EXA~I.E 15
Sur~ace sizing is carried out under the same conditions
as in Example 14, except that the siæe contains only 5 % of
starch and 0.3 ~ of a.d. sizing agent. The paper takes up
1.8 ~ of dry dusbstance in the 8i7.ing press. The properties
measured on the paper are set out in Table 3.
Table ~ .
Commercial Polyurethane
' product dispersion~Qccor~ 9 ~ .
to Example~2
Degree of sizing (seconds) 120 4920
Cobb value (water)
1 minute 37 19
Cobb value
(10 ~ soda solution) 27 ~ 15
1 minute
1 25 EXAMPLE IG 0
¦ Surface sizing is carried out under the same
I conditions as in Example 15, except that 0.2 and 0.3 ~ -
of a.d. sizing agent accord~ng to Example 1 are used. The
properties measured on the paper are set out in Table 4.
.
~ . . .
;~ 22 ~
,- . -',
104Z133
.
Table 4
0.2 % o~ a.d. 0.2 % o~ a.d.
standard polyurethane
commereial ~ dispersion accordin6
product ~-t~o Example 1
Degree of sizing-(secs) 218 2136
Cobb value (water)
1 minute 47 21
Cobb value
(10 ~ soda solution)
1 minute 40 17
0 3 % of a.d. .3 % o~ a.d.
standard polyurethane
eommercial- dispers lon laee 8
Degree of sizing (sees) 312 2602
Cobb value (water) ~ ~ -
1 minute 33 19
Cobb value (10
soda solution)
I minute 30 - 16
- ': ~: ' , . .:
~ EXAMPLE 17
- .-
~ A eellulose pulp for produeing paper is bulk-limed in a
: - , . - :
Hollander in known manner. 0~ the total pulp input, 75 %
eonsiæts of bleaehed pinewood sulphite cellulose, 15 % of
. ~ .. .
bleaehed birchwood sulphate pulp and 10 % o~ bleached - - -
Seotch pine sulphate pulp ground to a ~ineness of 40 SR.
In addition, 1 ~ o~ a.d. sizing agent produeed in aeoordance -
with Example 1 is added.
The papers produeed in this way weight 45 g/m .
The test results are set out in Table 5.
: , ' ' ~ ' '
~' ' .
, . '
~ jf 23
, :.
lO~Z133
Tab]e 5
Co~b va]ue (water 14
1 mi.nute.
Cobb value (10 %
soda solution) J
1 minute 13 ~ "
.
EXI~IPLE 18
An unsized raw paper weighing 80 g/m is treated in a
sizing press with a size containing only 0.50 ~ of a.d.
sizing agent produced in accordance with Example 1.
The properties measured on the paper are set out
~ in Table 6.
¦ Table 6
. , .
~ ., ' '
0.5 % of a.d. 0.5 % of a.d. ~-
standard - polyurethane
- , commercial grade dispersion ~cco~ing
product to Example 1 -
- Cobb value (water)
1 minute - 21 15
- Cobb value
(10 % soda solution)
20 1 minute , 21 16 ~ ~
- : -' '
EXAMPLE 19
An unsized raw paper weigh~ing 80 g/m2 is treated in a
sizing press with a size containing 5 % of starch and 0.3 %
, 25 o~ a.d. sizlng agent produced in accordance with Example 11.
The properties measured on the paper are set out in
Table 7.
.
,
j~ 24
.. ,. . : ,., - , : :::
- . : . . :. . . -
. . . . . . . - . - .
:, . ~ . .
104Z133
. Table 7
standard Polyurethane
commlercial grade dispersion-u4r~g
product to Fxample 11
Degree Or sizing (seconds) 300 1250
Cobb value (water)
1 minute 24 17
~' , '.
Surrace sizing is carried out under the same conditions
; as in Example 15, except that 0.1, 0.2 and 0.3 % of a.d.
sizing agent according to Example 12 ar,e used.
¦ The properties measured on the paper are set out in
¦ Table 8. -; ~ ~ -
, . ' ' .~
Table 8
0.1 % oi a.d. 0.1 ~ of a.d. -
standard polyurethane ~ ~.
- commercial grade dispersion
product according to
Example 12
Degree Or sizing (seconds) 55 420 `-
Cobb value (water)
1 minute 92 90
0.2 ~ of a.d. 0.2 ~ of a.d.`
~ standard polyurethane
l commercial grade dispersion - -
j product according to - - :
Example 12
1~ 25 Degree of sizing (seconds) . 260 1840
3~ Cobb value (water)
I 1 minute 35 2
1, . . .
.
1 , .
I _ jf 25
., -.. . .. . .... ~, .. .
: . - .: :.: ~ ;: .:: - .:- - - - : . . : .. . .
0.3 ~ Or a.d. .3 ~ of a.d,
standald polyurethane
cononercial ~rade disperYion
product accordin~ to
Example lZ
Degree of sizin~ (seconds) 305 3250
Cobb value (water~
1 minute ^ 30 21
EXA~PLE 21
~~
Surface sizing is carried out under the same conditions
as in Example 14, except that the size contains 5 ~ of starch.
and 0,3 ~ of sizing agent. The polyurethane dispersion
described in Example 1 is compared with a product obtained in
accordance with DOS 1,595,602. -
The results are set out in Table 9.
Table 9
product according polyurethane
to DOS 1,595,602, dispersion
Example 8 according to
Example 1
Degree,of sizing (seconds) 229 1850
Cobb value (water) ~ -
1 minute 7 19
.. . . .
'~
- .
- jf 26
-
. : ,- - .- " . , . - : ~
;: .. , ,, ,,, . ,, . . -. .,.. ,. - - : : :
