ANTISTATIC POLYAMIDE COMPOSITIONS, THEIR USE AND PROCESSES FOR THEIR PRODUCTION

COMPOSES ANTISTATIQUES DE POLYAMIDE, LEUR USAGE ET LA METHODE DE PRODUCTION CONNEXE

English Abstract

ABSTRACT OF THE DISCLOSURE
The invention relates to antistatic polyamide compositions compris-
ing a polyamide and as an antistatic agent from 0.1 to 20%, preferably from
1.5 to 15%, by weight based on the total weight of the composition of ure-
thanes with ether groups, which do not contain free hydroxyl groups and which
do not have any hydrogen atoms on the nitrogen atom. These urethanes with
ether groups are stable in melts of aliphatic polyamides for prolonged periods
at temperatures of up to about 300°C and filaments and fibers of such poly-
amides or woven fabrics, knitted fabrics, non-woven or pile fabrics produced
from these filaments or fibers show outstanding antistatic properties.

Claims

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. An antistatic polyamide composition comprising a polyamide and, as
an antistatic agent, from 0.5 to 20% by weight based on the total weight of
the composition, of a polyalkylene glycol ether with secondary terminal urethane
groups corresponding to the general formula:
(IV)
<IMG>
in which m is a number from 1 to 6; n is a number of at least 3; R represents
an m-functional, straight-chain, cyclic or branched, saturated or unsaturated
alkyl radical optionally comtaining at least one hetero atom selected from
oxygen and nitrogen, in which case at least one hetero atom with more than two
bonds may also be the starting point for one or more branches, an m-functional
aralkyl radical, an optionally alkyl-substituted m-functional aromatic radical
or, where m = 1, the radical Y; R' represents a hydrogen atom, an alkyl group
with 1 to 5 carbon atoms, a cycloalkyl, aryl, alkaryl or aralkyl group; Y
represents a group of the formula:
<IMG> (V)
or a hydrogen atom, at least 70% of the radicals Y representing the group of
formula (V); and R" and R"', independently of each other each represent an
alkyl group with 1 to 30 carbon atoms, a cycloalkyl, aryl, aralkyl or alkaryl
group or, together with the nitrogen atom, form a heterocyclic ring, in which
case at least one further hetero atom selected from oxygen and nitrogen may be
introduced into an alkyl group R" or R"' and/or into the heterocycle formed from
R", R"' and the N-atom, of which hetero atoms a nitrogen atom may in turn be
part of a secondary terminal urethane group of a polyalkylene ether.
38

2. A composition as claimed in claim 1, wherein more than 90% of the
radicals Y represent the group of formula (V).
3. Antistatic polyamide compositions as claimed in claim 1, wherein the
antistatic agent corresponds to the formula:
<IMG>
in which n is a number of at least 3, R is a monofunctional straight-chain
or branched, saturated or unsaturated alkyl radical with 1 to 30 carbon atoms
or an optionally alkyl-substituted aryl radical, R' is a hydrogen atom or an
alkyl radical with 1 to 5 carbon atoms, and R" and R"', independently of one
another, represent an alkyl radical with 1 to 20 carbon atoms or R", R"' and
the nitrogen atom together form a heterocycle which may contain one or more
further hetero atoms selected from oxygen and nitrogen.
4. Antistatic polyamide compositions as claimed in claim 1, wherein the
antistatic agent corresponds to the formula:
<IMG>
in which n is a number of at least 3.
5. Antistatic polyamide compositions as claimed in claim 1, wherein the
antistatic agent corresponds to the general formula:
<IMG>
in which n and n' are each a number of at least 3; b is a number from 2 to 10;
R represents a monofunctional, straight-chain or branched, saturated or unsatur-
ated alkyl radical with from 1 to 30 carbon atoms or is an optionally alkyl-
substituted aryl radical; R' represents a hydrogen atom or an alkyl radical
with 1 to 5 carbon atoms; and R" and R"', independently of one another, may
39

represent an alkyl radical with 1 to 20 carbon atoms and R" and R"' together
may form an alkylene bridge.
6. Antistatic polyamide compositions as claimed in claim 1, wherein
the antistatic agent corresponds to the general formula:
Y-O-(CH2-CH2-O)p-Y
in which p is a number of at least 8; Y represents the group of formula (V);
<IMG> (V)
or a hydrogen atom, at least 70% of the radicals Y having to be the group of
formula (V); and R" and R"' independently of one another may be alkyl groups
with 1 to 30 carbon atoms, cycloalkyl, aryl, aralkyl or alkaryl groups or,
together with the nitrogen atom, may form a heterocycle.
7. Antistatic polyamide compositions as claimed in claim 1, wherein the
antistatic agent corresponds to the general formula:
<IMG>
in which n, n' and n", independently of one another, may be numbers from 3 to
50 and, together, should total at least 10; R' is a hydrogen atom or an alkyl
group with 1 to 5 carbon atoms; RIV is a hydrogen atom, an alkyl group with 1
to 18 carbon atoms or an aryl group; Y represents the group of formula (V):
<IMG> (V)
or a hydrogen atom, at least 70% of the radicals Y having to be the group of
formula (V); and R" and R"' independently of one another, may be alkyl groups
with 1 to 30 carbon atoms, cycloalkyl, aryl, aralkyl or alkaryl groups or,
together with the nitrogen atom, form a heterocycle.

8. Antistatic polyamide compositions as claimed in claim 1, wherein the
antistatic agent corresponds to the general formula:
<IMG>
in which a, b, c, d, e and f, independently of one another, may be numbers from
3 to 45 and, together, should total at least 18; Y represents the group of for-
mula (V):
<IMG> (V)
or a hydrogen atom, at least 70% of the radicals Y having to be the group of
formula (V); and R" and R"', independently of one another, may be alkyl groups
with 1 to 30 carbon atoms, cycloalkyl, aryl, aralkyl or alkaryl groups or,
together with the nitrogen atom, form a heterocycle.
9. Antistatic polyamide compositions as claimed in claim 1, wherein the
antistatic agent corresponds to the general formula:
<IMG>
in which c is a number from 2 to 6; n, n', n" and n"', independently of one
another, may be numbers from 3 to 50 and, together, should total at least 15;
R' represents a hydrogen atom or an alkyl group with 1 to 5 carbon atoms; B is
an alkylene group with 2 to 10 carbon atoms whose carbon chain may be interrupt-
ed by one or more hetero atoms selected from oxygen and nitrogen or an arylene
group; Y represents the group of formula (V):
<IMG>
41

or a hydrogen atom, at least 70% of the radicals Y having to be the group of
formula (V); and R" and R"', independently of one another, may be alkyl groups
with 1 to 30 carbon atoms, cycloalkyl aryl, aralkyl or alkaryl groups or, to-
gether with the nitrogen atom, form a heterocycle.
10. Antistatic polyamide composition as claimed in claim 6 or 7, wherein
at least 90% of the radicals Y are groups of formula (V).
11. Antistatic polyamide composition as claimed in claim 8 or 9, wherein
at least 90% of the radicals Y are groups of formula (V).
12. Antistatic polyamide compositions as claimed in claim 1, wherein n
is a number from 7 to 60.
13. Antistatic polyamide compositions as claimed in claim 3, 4 or 5, where-
in n is a number from 7 to 45.
14. Antistatic polyamide compositions as claimed in claim 6, wherein p
is a number from 12 to 50.
15. Antistatic polyamide compositions as claimed in claim 1, wherein they
contain from 1.5 to 15% by weight of the antistatic agent.
16. A process for the production of antistatic polyamide compositions of
the kind claimed in claim 1, wherein from 0.5 to 20% by weight of polyalkylene
glycol ethers with secondary terminal urethane groups corresponding to the
general formula (IV) as defined in claim 1, are applied to granulated polyamide
in uniform distribution, the polyamide is melted and, the mass intensively
mixed.
17. A process for the production of antistatic polyamide compositions of
the type claimed in claim 1, wherein from 0.5 to 20% by weight of polyalkylene
glycol ethers with secondary terminal urethane groups corresponding to the
general formula (IV) as defined in claim 1, are introduced into a polyamide
melt and the mass intensively mixed.
18. A process for the production of antistatic polyamide compositions of
42

the kind claimed in claim 1, wherein from 0.5 to 20% by weight of polyalkylene
glycol ethers with secondary terminal urethane groups corresponding to the
general formula (IV) as defined in claim 1, are introduced into a polymerisation
or polycondensation melt before, during or after production of a polyamide,
and uniformly distributed in the melt.
19. A process for the production of antistatic polyamide compositions of
the kind claimed in claim 1, wherein from 0.5 to 20% by weight of a melt freed
from monomers is added from a VK-pipe to a polyalkylene glycol ether with secon-
dary terminal urethane groups corresponding to the general formula (IV) as de-
fined in claim 1.
20. A process for incorporating polyalkylene glycol ethers with secondary
terminal urethane groups corresponding to the general formula (IV) as defined
in claim 1, into polyamide compositions, wherein from 0.5 to 20% by weight of
the antistatic agent are added to the granulate during spinning.
21. Fibres, filaments, woven fabrics, knitted fabrics, nonwovens and pile
fabrics formed of antistatic polyamide compositions as claimed in claim 2 or 3.
43

Description

~6~53827
This inven-tion relates to permanently antistatic
polyamide compositions which may be processed into per
manently antistatic filaments, fibres, films, and other
shaped articles, and to processes for producing polyamide
- 5 compositions of this kind.
It is known that fibres, woven fabrics, knitted fabrics
and ~ilms of polyamides can be antistatically finished by
treating their surfaces with polyethers containing urethane
groups corresponding to formula (I) or (II) below (cf.~T-OS
1,768, 058 and US-PS 3,658,882).
R-O-(CH2-CH -O)n-C-N ~ 2 m (I)
wherein
R = an alkyl or alkaryl radical, x = H, CH3 or C2H5,
n = 1-10, m=1-6; and
~4 ~ -0)m(CN2-C~l-O)n-O~N~-c}l2-c}lz-c~z-N (II)
wherein
R4, R5 = alkyl radicals,
Rl, R2 = alkyl or hydroxy alkyl radicals,
x = H, CH3 or C2H5,
n = 1-10,
m = 0-1.
One disadvantage of this process, however, is that the
antistatic finish i~ not washproof. Tests have shown that a
single wash is sufficient to eliminate the antistatic effect
Le A 15 5~2 - 1 -

1~531~Z7
almost completely.
It is also known from DT~AS 1,27~,124 that polyalkylene
glycol ethers with a molecular weight o~ at lenst 600, cont-
aining at least one alkyl, aryl or aralkyl ether group at
their ends, give polyamides fav~urable antistatic properties
when they are uniformly incorporated into the polyamide
as a separate phase.
One disadvantage of products of this kind is that the
polyalkylene glycol ethers with only partly etherified terminal
hydroxyl groups can be partly incorporated into the polymer
by reaction with the polyamides, for example with free termina]
carboxyl groups, and are then redundant so far as producing
an antistatic effect is concerned, because it has been sho~ln
that it is only additives ol the type which are not incorporated
into the polymer that a~e antistatica11y active. On tlle other
hand, polyalkylene glycol ethers ~ith only partly etherieied
terminal hydroxyl groups can be removed relatively easily from
the polymers during washing, with the result that the anti-
static activity is gradually lost. It should be possible
to eliminate these by using polyalkylene glycol ethers with
very few, if any, free terminal hydroxyl groups. However,
polyalkylene glycol ethers in which all the terminal hydroxyl
groups are etherified can only be obtained relatively
complicated processes.
It is also known that polyethers containing urethane
groups and corresponding to the formula (III):
O O
~-o-(cH2-cH2-o)x-c~ Rl-NH-c-(o-cII2-cH2)x-o-R (III)
wherein
R = an alkyl, aryl, aralkyl or alkaryl radical
Rl = an alkylene, arylene, aralkylene, alkarylene
Le A 15 522 - 2 -

~ S~Z7
or cycloalkylene radical, and
_ = 5-50
give polymers excellent antista~ic pr~perties when incor-
porated in them in quantities of from 0.5 to 15 % by wei~ht (cfo
German OLS 23 06 920). One disadvantage of these compounds,
however, is that they can only be incorporated into polymers
of the kind which are processed from solutions, because when
the products are incorporated into a polymer melt, or example
of a polyamide polyester, at the high melting temperatures
necessary the urethane group with a free hydrogen atom on the
nitrogen atom is not stable and the compounds of formula ~III)
are destroyed through the reformation of isocyanates and
hydroxyl compounds. The same applies to the compounds of
formula (II).
Although, in compounds of formula (I), the urethane
group should be more stable at the melting temperature
of the aliphatic polyamides, because there is no longer
a free hydrogen atom present on the nitrogen atom, the ter-
minal hydroxyl groups of the compounds can in this case, too,
enter into secondary reactions with the polymer, as a result
of which the compound is used up and the antistatic effect r~
is weakened accordingly.
However, it should be possible to avoid these disadvan-
tages by usin~ polyether urethanes which do not contain any
free hydroxyl groups and which do not have any hydrogen atoms
on the nitrogen atom. At all events urethanes could be ex-
pected to undergo transesterification or aminolysis reactions
on the 0 -bond in polymer melts, resulting in chain termination
--O--C--
and, hence, in reduced molecular weightsO
It has now surprisingly been found that polyalkylene
ethers with secondary urethane groups corresponding to the
.. ~ . . . . .. . . . .

~L0538Z~
general formula:
R~0-CH2-CH~_G_y (IV)
R'
_ _ m
wherein m is a number from 1 to 6; n i5 a number of at least 3, preferably a
number from 7 to 60; R represents an m-functional, straight;chain, cyclic or
branched, saturated or unsaturated alkyl radical optionally containing at least
one hetero atom selected from oxygen and nitrogen atoms, in which case hetero
atoms with more than two bonds may also be the starting points for branches,
an aralkyl radical, an optionally alkyl-substituted m-functional aromatic radi-
cal or, where _ = 1, even the radical Y; R' represents a hydrogen atom, an
alkyl group with 1 to 5 carbon atoms, a cycloalkyl, aryl9 alkaryl or aralkyl
group; and Y represents the group:
/ R" . -
-C-N (V~
\ R ~
or a hydrogen atom, at least 70% and preferably more than 90~ by weight of the
radicals Y having to represent the group:
/ R"
-C-N ~ ~V) :
R" '
wherein R" and R " ', independently of each other may represent alkyl groups :
with 1 to 30 carbon atoms, cycloalkyl, aryl, aralkyl or alkaryl groups or, to- :
gether with the nitrogen atom, form a heterocyclic ring, in which case at least
one further-hetero atom selected from oxygen and nitrogen, may be introduced
20 into the alkyl group R" or R " ' and/or into the heterocycle formed from R", ~ .
R " ' and the N-atom, of which hetero atoms the nitrogen atoms may in turn be -
: .
part of a secondary terminal ~rethane group of a polyalkylene ether, are stable
in melts of aliphatic polyamides for prolonged periods at temperatures of up
to about 300C. Polyamides containing urethanes of this kind, more especially
-4~
,. _ , :~
...~

105~8Z~
filaments and fibres of such polyamides or woven fabrics, knitted ~abrics, .
nonwovens or pile fabrics produced from these filaments or fibres, show out- `
standing antistatic properties and polycondensation or polymerisation is not
adversely affected by the addition of the above urethanes.
The particular advantage of the new antistatic polyamide compositions
over conventional antistatic polyamide compos:itions containing products with- .
out these terminal urethane groups, is that for about the same or slightly ~ -
improved initial antistatic values ~he antistatic properties are much more re- -
sistant to washing following an aftertreatment, more especially after fixing
10 in hot air or saturated steam at temperatures of around or above 100C. . .
Accordingly, the invention relates to antistatic polyamide composi-
tions comprising a polyamide and, as an antistatic agent, from 0.5 to 20%,
preferably from 1.5 to 15%, by weight based on the total weight of composition,
of urethanes with ether groups corresponding to the general formula:
R ~ (O-CH2-CH)n-O-Y ] (IV)
R'
_ _ m
in which R, R`, Y, m and _ are as defined above.
Preferred antistatic agents are polyalkylene glycol ethers with
terminal urethane groups corresponding to the general formulae:
, / R"
~ a) R-(0-CH2-CH)nO-C-N \
I _ R ~ l :
20 in which n is a number of at least 3, preferably a number of from 7 to 45; R . ::
represents a monofunctional straight-chain or branched, saturated or unsaturated
alkyl radical with from 1 to 30 carbon atoms or an optionally alkyl-substituted : :
aryl radical; R' represents a hydrogen atom or an alkyl radical with from 1 to
5 carbon atoms; and R" and Rl " , independently of each other, represent an
alkyl radical with from 1 to 20 carbon atoms, or R", R " ' and the nitrogen atom ~ .
together form a heterocycle which may contain oxygen or nitrogen as a further
~ ~ -5-
... . . .

11 (~5~827
hetero atom;
0 R" R"' 0
(b) R-(0-CH2-C~)-0-C-N-(CH2)b-N -C-0-( CH-CH2-O)n,-R
R' R'
in which n and n' each represents a number of at least 3, preferably a number
of from 7 to 45; b is a number of from 2 to 10; R represents a monofunctional9
straight-chain or branched, saturated or unsaturated alkyl radical with from
1 to 30 carbon atoms or an optionally alkyl-substituted aryl radical; R' re-
presents a hydrogen atom or an alkyl radical with from 1 to 5 carbon a~oms; and
R" and R"', independently of each other represent an alkyl radical with from 1
to 20 carbon atoms, or R" and R"' together may also form an alkylene bridge;
(c) Y-O- tCH2-CH2-0)~-Y ,.`
in which p is a number of at least 8, preferably a number of from 12 to 50; and
Y represents the group: :
R1~ '
-C-N \
R " '
or represents a hydrogen atom, at least 70% and preferably at least 90% of the
radicals Y representing the group;
,, / R" : .
-C-N \ ~:
R " '
and R" and R" ', independently of each other, may be alkyl groups with from 1
to 30 carbon atoms, cycloalkyl, aryl, aralkyl or alkaryl groups or, together
20 with the nitrogen a~om, may form a heterocycle; :
CH2-(0-CH2-CH)n-0-Y ~ :
¦ R'
RIV -C-(0-CH2-CH)n'-0-Y ~
¦ R' : . .
CH2~(0-CH2-CH)n~-o Y :
R' . -:
ln whlch n, n' and n'l, independently of one another, can be numbers of from
~ -6_
,

-- 10~i3~3~7
3 to 50 and, together, should total at least 10; R' rapresents a hydrogen atom
or an alkyl group with from 1 to 5 carbon atoms; RIV represents a hydrogen atom,
an alkyl ~roup with from 1 to 18 carbon atoms or an aryl group; and Y repre-
sents the group:
R"
-C-N ~V)
0 \ R"'
or represents a hydrogen atom, at least 70% and preferably at least 90% of the
radicals Y representing the group:
/ R"
-C-N \ (V)
" R"'
O '
and R" and R"l, independently of each other, may be alkyl groups with from 1
to 30 carbon atoms, cycloalkyl, aryl aralkyl or alkaryl groups or, together
with the nitrogen atom, fDrm a heterocycle;
Y-o-(Hc-H2c-o)n~-(H2c)c ~ ~ tCH2)c-(0-cH2-cH)n-o-y
~d) R' N-B-N R'
y_o-(HC-H2C-O)n (H2C)c \ (CH2)C-tO-cH2-cH)n~-o-y
_ ,.
R' Rl
in which c is a number of from 2 to 6; _, n', n" and n"', independently of one
another, may be numbers from 3 to 50 and, together, should total at least 15;
R' represents a hydrogen atom or an alkyl group with 1 to 5 carbon atoms; B -
represents an alkylene group with from 2 to 10 carbon atoms, whose C-chain may -
even be interrupted by one or more hetero atoms selected from oxygen and nitro- -: .
gen, or an arylene group; and Y represents the group: :~
/ R"
-C-N \ ~V)
0 R"'
or a hydrogen atom, at least 70% and preferably at least 90% of the radicals Y
representing the group:
/ R"
-C-N (V)
ll \
0 R"~
_~ -7-
.
,, . , - ,. , ~ . ~

~0~3~3Z7
and R" and R"', independently of each other, may be alkyl groups with from 1
to 30 carbon atoms, cycloalkyl, aryl, aralkyl OT alkaryl groups, or together
with the nitrogen atom form a heterocycle.
The invention also relates to shaped articles produced from antistat- -
ic polyamide compositions of the above type, more especially antistatic fibres,
filaments and films, and also to woven fabrics, knitted fabrics, nonwovens,
pile fabrics or similar sheet-form materials produced from these antistatic
fibres or filaments.
The invention also relates to processes for producing the antistatic
polyamide compositions in which the urethanes with ether groups used in accord-
ance with the invention are introduced into and intensively mixed with the poly-
amide melt before the polyamides are spun or extruded; the urethanes ~.
~ '., .
._ -. 8

1~538~7
are applied to solid granulated polyamide which is then melted, intensively
mixed and spun or extruded; or in which the urethanes with ether groups
used in accordance with the invention are introduced into the polymerisa-
tion or polycondensation mixtures before or after production of the poly-
amides, after which the antistatic polyamide may either be directly spun
or may initially be processed into a granulate which may then be further
processed in known manner.
The following compounds are mentioned as examples of urethanes
containing ether groups which are particularly sui~able for use in the
production of the antistatic polyamide compositions according to the in-
vention, although the process is by no means confined to these particular
compounds: ~ .
,, ~ 3 .
H21Clo~lO~CH2~CH2)n~0~C~N
~ CH3
21 10 ~ 2 2)n ~
18H37
" ~ CH3
H 7C 8-(0-CH2-CH2) -0-C-N
O
3 ( 2)7 CH CH-(CH2)g-(O-GH2-CH2) -0-C-N
_ CH3
0 ~ C4Hg
H C -~0-CH -CH ) -0-C-N C4Hg
~ ~ 3 ~ :
H C -(0-CH -CH ) -0-C-N l8H37
o / CH2-CH2 \
H37C18- (0-CH2-CH2)n-0-C-N ~0 ,
2 2
/ CH2 CH2
37 18 ( 2 2)n 1 2
\ CH2-CH2--CH2
_ g _
.', ' ' . ' ' , ~, ,, :

~)5~8~7
, o
2 2)n = CII3
isononyl
0-CH2-CH2) -0-C-N C 3
isononyl
0 CH CH3 0
" , 3 , "
37C18-(o-cH2-cH2)n-o-c-N CH2-CH2-N C~~(CH2~CH2~)n~C18H37
O O
H37C18-(0-CH2-CH2 3 n-0-C-N ~' 2,,N_C_o-(cH2-cH2-o)n-c 18~I37
n is at least 3, preferably 7-45
O O
3 ~ 3
~I C ~ N C (CH2 CH2 )p C N 3
O O
II C " " CH
3 / N-C-O-(cH2-cH2-o)~-C-N C18H37
p is at least 8, preferably 12-50
O O
3 N C o-(CH -CH2-O)n-CH2-CH2-CH2-CH2-~0 C~2 2)n ~ C~3
n + n' = 6-90
~H2-0-(CElz~cEl2~o) -C-E C CH~ :
CH-O- ( CH2-CH2-0 ) n ' -C-l~ 3
~H2-0- ( CH2~CH2 ~ ) n ~ ~0 ~ C~I3
~_ .'IJe A 15 522

~S38Z7
o
" CH3
CH2-o-(cH2-cH2-o)n-c-N 3
" C~3
5 2 f-o- (C~12-CH2-0, -C-N ~ 3
Il CH
CH2-0-(CH2-CH2-0)n"-C-N-''' 3
n, n', n" = 3-45, n+n'+n" = 9-135
~ CH3
fH2-o-(cH2-c~l2-o)a-co-N 3
fH-o - (CH2-CH2-)b-C0-N 3
CH-0-(CH2-CH2-0)c-CO_N CH3
CH3
H 0 (CH2 CH2 )d C0 N ~ 3
¦EI-O-(CHZ-CEI2-O)e-CO-N ~ 3
CE12--0--(CHe--CE12--O)f~--CO--N = cCH3
a, b, c, d, e, and f, independently of one another = 3-45,
a+b+c+d+e+f = 18-270
Le A 15 522 _
. : - .: - .

~os~7
/ CH2~CH2~~~CH2~CH2~)n~C~N = CH3
H3C-N 0 GH
~ CH -CH -0-(CH2-CH -0) '-C-N 3
n and _' independently of one cmother = 7-45
~N-C-(0-H2C-H2C)n"-0-H2C-H2C /CH22CH2-0-~CH2-CH2-0) -C-N
H C N-CH-CH-N ~ 3 ~
3 ~N-C-~~H2C~H2c)n'''~~H2c~H2c CH2-cH2-o-~cH2-cH2-o)n ,C, N \CH :` :
O
n ~ n' + n" + n"' = 12-180
CH3 C,H3 / CH : `
CH2-CH O- ~CH2-CH O) a- ~CH2-CH2-0) C-C-N ~
_ 2 \ / CH3
CH2-CH O-(CH2-CH O)b-(CH2-CH2-O)d-C-N
CH3 CH3 CH3 ~ 2 : :
a + b = 10-60; c + d = 10-80
' ' - ~
Polyalkylene ethers of this kind containing ter-
minal urethane groups may be prepared by converting the
corresponding polyalkylene ethers with one or more terminal . -
hydroxyl groups into the chlorocarbonic acid esters with phos-
gene by conventional methods and subsequently reacting ~he
chlorocarbonic acid esters with secondary amines, again by
. ~: ',
- 12 -

~3~
conventional methods, or by reacting the polyalkylene
ethers with free terminal hydr~xyl groups ~-ith the
corresponding carbamic acid chlorides in the presence of basic
compounds~
In oases where the reaction is carried out with a
deficit of phosgene or carbamic acid chloride, compounds
are obtained ~hose terminal hydroxyl groups have only besn
partly convertecl into the urethane groups. Compounds of
this kind may also be used with advantage as antistatic agents
in polyamides. However, it is better to select the quantities
of the reacting components and also the reaction conditions
in such a way that the terminal hydroxyl groups are converted
substantially completely into urethane groups.
The polyalkylene ethers with one or more hydroxyl groups
used as starting compounds can ~)e obtained, for example,
by polymerising epoxides, for exam~le ethylene oxide or
propylene oxide or by subjecting epoxides of this kind to
polyaddition with low molecular weight monohydric or poly-
hydric alcohols or monoamides or polyamides (cf. Houben Weyl,
Methoden der organischen Chemie Vol. XIV/2, pages 426 to
462).
The described polyalkylene ethers with secondary urethane
groups may also be used as antistatic agents in combination
with other antistatic agents, for example with polyethoxy- -
lated stearyl alcohol, polyethoxylated nonyl phenol, poly-
ethoxylated ethylene diamine or tertiary amides.
In addition to the antistatic agents, the antistatic
polyamide compositions may also contain the usual additives,
such as light stabilisers, heat stabilisers, fillers and/or
pigments.
The polyalkylene glycol ethers oontaining terminal
urethane groupæ are suitable for use as additives in any
'~'`
Le A 15 522 - ~A~-
- ;

538~7
fusible, aliphatic polyamides, but especially in poly-~-cap-
roic amide.
The antistatic properties of the polyamide compositions
according to the invention are reflected in a distinct reduc-
tion in electrical surface resistance. Electrical surface
resistance is measured in accordance with DIN 54 345 on fibres~
filaments or sheet-form materials.
The following Examples illustrate the production of
the antistatic polyamide compositions and describe their
properties, although neither the processes used nor the pro-
perties of the polyamide compositions thus obtained are
intended to be limited in any way by the Examples. The
relative viscosity (nrel) quoted in the Examples was measured
on a 1% solution in _-cresol. To this end, 1 g of polyamide
was dissolved in 100 ml of m-cresol and the run-through time
~te) of the solution was measured in an Ubbelohde viscosimeter
at 25C. The relative viscosity nrel was then calculated from
the equation: -
~rel
tem
in which tem is the run-through time of the pure solvent.
: :, .
EXAMPLE 1
(a) Preparation of the bis-dimethyl urethane of poly-
ethylene glycol 1000
51205 g (1/2 mol) of polyethylene glycol with a mole-
cular weight of 1025 are dissolved in 4 litres of toluene
at 30C. 105 g of phosgene are introduced at 30C. After
stirring for 2 hours, nitrogen is blown through the solution
for 3 hours at room temperature in order to remove the
excess phosgene. 100 g of dimethylamine are then introduced
into the solution at room temperature, followed by stirring
for a few hoursO The dimethylamine hydrochloride precip- `
- 14 -

:~538Z7
itated is filtered off under suction and the filtrate con-
centrated in vacuo. Accordin~ to I~- and ~-analysis,
the residue which solidifies on cooling is the required
bis-dimethyl urethane of the polyethylene glycol used.
(~) Production of the antistatic polyamide compositions
130 g of ~-caprolactam, 15 g of ~-aminocaproic acid
and 3 g of the diurethane prepared in accordance with
l(a) are heated under nitrogen to 270C and condensed with
intensive stirring for 3 hours at that temperature. The
polyamide obtained is spun into filaments on which the
following electrical surface resistances were measured
in accordance with DIN 54 345:
~fter production: 5.109~ .cm2
~fter the first wash~ 0ll~ cm2
After $he fifth ~ash: 3.10 ~.cm
Polycaprolactam without any antistatic additives has a
surface resistance of approximately 5.1012~a .cm2 after only
the first wash.
Poly caprolactam filaments which, instead of the diure-
thane, contain the same quantity of polyethylene glycol
1000 without any terminal urethane groups, have an electrical
surface resistance of 7.10111~ .cm2 after the wash and an
electrical surface resistance of 2.1012~ .cm2 after the
fifth wash.
EXAMPI.E 2
The procedure is as in Example l(b) except that 7.5 g
of diurethane are used instead of 3 g of diurethane. Filaments
obtained from the resulting polyamide, which has a ~ rel f
2.85 (as measured on a 1 ~ solution in cresol), have the
following electrical surface resistance:
After production: 4-18~ .cm2
After the first wash: 3 lolO~ cm2
; ~ e A 15 $22 ~ _
. ~. .. ;~

~()538Z7
After the fifth wash: 6.1ol~ cm2
EX~ LE 3
130 g of -caprolactam l'j g of -aminocaproic~ acid
and 3 g of a diurethane, obtained from polyethylene glycol
of molecular weight 2050, phosgene and dimethyl amine in
accordance with Example l(a) are heated under nitrogen
to 270C and condensed with intensive stirring fDr 4
hours at that temperature. Filaments obtained from this
polyamide, which has a relative viscosity of 2.95 have the
following electrical surface resistances:
After production: 1.109 ~.cm2
After the first wash: 5-101~.cm2
After the fifth wash: g.lolO~.cm2
Polycaprolactam without any antistatic additives has an
electrical surface resistance of 5.1012~ .cm2 after only -
one wash.
EXAMPLE 4
Example 3 is repeated with 7.5 g of the diurethane of the
polyethylene glycol 2050. Filaments obtained from this
polyamide composition were found by measurement to have the
following electrical surface resistance:
After production: 6 . 1 o8 ~L.cm2
After the first wash: 3 lolOn cm2
After the fifth wash: 6.1ol~ cm2
Polycaprolactam filaments which, instead of the diure-
thane, contain the same quantity of polyethylene glycol
2000 without any urethane groups, have an electrical surface
resistance of 3.10 ~L ~cm after the first wash and an
electrical surface resistance of l.lOllSL .cm2 after the
fifth wash.
EXAMPLE 5
130 g of -caprolactam 15 g of -aminocaproic acid t
Le A 15 522 ~6
.

~os3827
and 3 g of a dimethyl urethane, obtained from 10-fold
ethoxylated isononyl phenol in accordancc with Example
l(a), were heated under nitrogen to 270C and condensed
with intensive stirring for 4 hours at that temperature.
The polyamide composition obtained is processed into
filaments on which the following electrical surface
resistance were measured:
After production: 6.109~ .cm2
After the first wash: 1 10~ cm2
After the fifth wash: 3~loll~ m2
After the tenth wash: 5.10 5~.cm
Polycaprola¢tam without any antistatic additives has
an electrical surface resistance of about 5.1012~ .cm2
after only one wash. Polycaprolactam filaments which, instead
f the urethane contain the same quantity of 10-fold etho-
xylated nonyl phenol without any urethane groups, have a
surface resistance of 2.1011~fL .cm2 after one wash and a
surface resistance of as high as 2.1012 5h .cm2 after only
five washes.
EXA~lPLE 6
Example 5 is repeated with 7.5 g of dimethyl urethane
of the 10-fold ethoxylated isononyl phenol. Filaments
were found by measurement to have the following electrical
surface resistance:
After production: 9.108~ .cm2
After the first wash: 3 101 ~ cm2
After the fifth wash: 7 1olO3 cm2
~fter the tenth wash: 7 1011~ cm2
EXAMPIE ?
130 g of ~ -caprolactam 15, g of ~-aminocaproi~ acid
and 3 g of a dimethyl urethane, obtained from 18-fold
ethoxylated isononyl phenol in accordance with F~ample 1(~)
Le A 15 522
/7
,,
. .. . . ,.-, . .

~ `
- ~53~ 7
were condensed under the conditions described in Example 5.
Filaments obtained from the resulting polyamide composition
were found to have the following electrical surface res-
istance:
After production: 6.109~L .cm2
After the first wash: 6 lolOn cm2
After the fifth wash: 6,10 ~b.cm
After the tenth wash: 8 lolOn cm2
Polycaprolactam filaments which, instead of the
urethane, contain the same quantity of 18-fold ethoxyla$ed
isononyl phenol, have an electrical surface resistance
of 6.101SL .cm2 after the first wash and an electrical
surface resistance of as high as 4.1011~1 .cm2 after five
washes.
EXA~IPLE 8
Example 7 is repeated with 7.5 g of the dimethyl urethane
of the 18-fold ethoxylated isononyl phenol. The foll-
owing electrical surface resistance were measured on
filaments obtained from the resulting polyamide compos-
ition:
After production: 4.109SL .cm2
After the first wash: 9.109SL .cm2
After the fifth wash: l~lol0~cm2
After the tenth wash: 2 1010~1 cm2
25 EXAMPLES 9 to 11
The electrical surface resistance of filaments obtained
from polyamide compositions prepared in accordance with
Example 7, which contain similar urethanes of ethoxylated
isononyl phenols, are shown in Table. 1.
.i Le A 15 522 -~y~-
- .

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- 19 -

EXAMPLE 12 lQS3~7
130 g of ~-caprolactam, 15 g of s-aminocaproic acid and
3 g of dimethyl urethane, obtained from 20-fold ethoxylated
stearyl alcohol, phosgene and dimethyl amine in accordance with
Example l(a), were heated under nitrogen to 270C and condensed
with intensive stirring for 3.5 hours at that temperature.
The polyamide composition obtained was processed into filaments
on which the following electrical surface resistances were
measured:
After production: 4.109Q .cm
After the first wash: 4.10 Q .cm
After the fifth wash: 4.10 Q .cm -
After the tenth wash: 6.10 Q .cm -
EXAMPLE 13
Example 12 is repeated with 7.5 g of the dimethyl urethane
of 20-fold ethoxylated stearyl alcohol. The following electrical
surface resistances were measured on filaments of this polyamide -
composition:
After production: 9.108Q .cm
After the first wash: 4.109Q .cm
After the fifth wash: 4.109Q .cm
After the tenth wash: 8.10 ~ .cm
Polycaprolactam filaments which, instead of urethane,
contain the same quantity of 20-fold ethoxylated stearyl `
alcohol without any urethane groups, have an electrical surface ~ `
resistance of 2.10 Q .cm after the first wash, a surface
resistance of 3.10 Q .cm after the fifth wash and a surface
resistance of 8.10 Q .cm after the tenth wash.
When the dimethyl urethane of 20-fold ethoxylated stearyl
alcohol is applied in the form of a 5~ preparation to finished
polycaprolactam fibres without any antistatic additives, the
electrical surface resistance rises to as high as 5.10 Q .cm
- 20 -
.:

'1~53~27
after only one wash.
EXAMPLES 1~ to 25
The electrical surface resistances of polyamide
compositions which were prepared in accorda~ce with Example 12
and which contain different polyaIkylene ether urethanes, are
shown in Table 2.
- 21 -

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53827
EXAMPLE 26
A mixture of 180 g of caprolactam, 10 g of f-aminocaproic
acid, 0.2 g of benzoic acid, o.6 g of t;itanium dioxide and lO g
of stearyl 32-fold ethoxylated N,N-dimethyl urethane are
heated under nitrogen for 2 hours to 260C, followed by
stirring for another 6 hours at that temperature. The
resulting polycaprolactam, which has a relative viscosity of
2.55 in the form of a 1% solution in m-cresol, is processed
into filaments which have the following surface resistances:
After production: 10 2
After the fifth wash: 7.109Q .cm
After the tenth wash: 4.10 Q .cm
EXAMPLE 27
A polycaprolactam granulate containing 0.33% by weight ~ ;
of titanium dioxide and having a relative viscosity (1%
solution in _-cresol) of 2~66, is mixed with 5% by weight
of stearyl 32-fold ethoxylated N,N-dibutyl urethane, and the
resulting mixture is melted at 260C, stirred homogeneously
and processed into filaments which have a surface resistance
of 2.10 Q .cm , a surface resistance of 7.109Q .cm after
the fifth wash and a surface resistance of 3.10 Q .cm after `
the tenth wash.
EXAMPIE 28
130 g of e-caprolactam, 15 g of ~-aminocaproic acid
and 7.5 g of a dimethyl urethane, obtained in accordance
with Example l(a) from l9-fold ethoxylated oleyl alcohol,
phosgene and dimethylamine, were heated under nitrogen to
270 C and condensed with stirring for 3.5 hours at that tempera- -
ture. The polyamide composition obtained was spun into filaments
on which the following electrical surface resistances were
measured:
- 24 -

`
~O~ 'Z7
After production: l.lO9Q .cm
After the first wash: 2.10 Q .cm
After the fifth wash: 5.10 Q .cm
After the tenth wash: 4.10 Q .cm
Examples 29 to 36 below describe the production of anti-
static polyamide compositions according to the invention on a
commercial scale.
EXAMPLES 29 to 31
In a closed autoclave, caprolactam, water and the anti-
static agent mentioned in Example 12, together with benzoic
acid as a chain regulator and titanium dioxide concentrate, in
the quantities specified in Table 3 are heated with stirring
for 2 hours to 260 C under the pressure developin~. Over the
next 30 minutes the temperature is increased to 265 C, and,
at the same time, the autoclave is vented. Polycondensation is
then completed by passing dry nitrogen over and stirring the
reaction mixture for 2.5 hours. The melt is degassed for 30
minutes after which five 2 to 3 mm thick polyamide strands are
spun into water o~er a period of 80 minutes, the strands thus
spun subsequently being chopped into cylindrical granules
3 mm long.
The granulate is extracted with fully desalted water for
24 hours at 80 C and subsequently dried for 24 hours at 95 C/O.l
Torr. After drying, the granulate has a moisture content of
less than 0.07%.
Further details of the individual tests are set out in -~
Table 3 below: ~
.. "' :'. :
.,' ~ .
- 25 - ~
,. :
` '

~1~3538Z~7
Table 3
Example Capro- Water Chain reg- TiO2 Anti- Solution Anti-
No. lactam kg ulator mol ~ static viscosity static
ke . ~ addi- ~ % rel cDntent
29 98.5 3.o 2.25 o.30 1.5 2.73 1.51
97.o 3.0 2.25 0.30 3.o 2.68 2.88
31 95-5 3.0 2.00 0.30 4.5 2.64 4.
(a) = analytically aetermined
The granulates are melted at 283 C in a 2~ D extruder with
a screw diameter of 30 mm, and are spun through a spinneret with
126 bores, each 0.30 mm in diameter. The spinning rate is
160 g per minute. The filaments are run off at a rate of
200 metres per minute and are wound into packages. After
stretching in a ratio of 1:3.72, the surface resistance of
the filaments can be determined in the same way as described
above. The values quoted in Table 4 were measured:
Table
.
Filaments of Electrical surface resistance CQ cm
polyamide according after the after the after the
to Example No. first wash fifth wash tenth wash
. . .. .. . . _
29 2.1011 1.1011 2.10
7.lolo 6.lolo 1.10
31 4.1ol 3. lolo 6.1ol
The filaments of Examples 29 to 31 were fixed in hot ;
air and their electrical surface resistances were re-measured.
The results are set out in Table 5.
. ~"
.,
- 26- ~
.. . . : , . : . : - . .

~0538Z7
Table 5
Filaments of Electrical surface resistance ~Q cm ~
polyamide according after fixing after the after the after the
to Example No. first wash fifth wash tenth wash
. _ .
29 2.1011 2~loll 2~loll l.
8.1011 9~lolo 8~lolo 5~lolo
31 4.1o1 5.lolo 5.lolo 3 1010 1 ;
The filaments of Examples 29 to 31 were fixed with satu-
rated steam and were found to have the surface resistances quoted in
Table 6.
Table 6
Filaments of Electrical surface resistance ~Q cm ~
polyamide according after fixing after the after the after the
to Example No. first wash fifth wash tenth wash
.
29 2.1011 5~loll 4~loll 4
6.lolo 2.loll l.loll l.loll
31 4 101 7~lolo 5~lolo 5.10 _
After fixing with saturated steam, filaments which, instead
of the diurethane, contain 4.5% of 20-fold ethoxylated stearyl - -
alcohol as antistatic agent, have an electrical surface resistance j ~
of 3.10 Q .cm which, after only one wash, rises to 2.10 Q .cm . -~-
Following removal of the preparation from the filaments,
the antistatic agent was isolated from the granules of Example
31 and from the filaments treated with saturated steam, and it --
was found by IR- and NMR-spectroscopy that the polyalkylene
ether urethane originally used had remained unchanged.
~ he outstanding antistatic properties of fibres obtained
from polyamide compositions according to Example 31 were also
': '

`` ~o~3~'~7
tested on tufted carpets and knitted fabrics.
A. Tufted carpet test
~ ibres with an individual denier of 20 dtex and a staple
length of 150 mm were processed into a yarn with a count of 3.5/1,
from which a tufted velour carpet on a polyester backing was
produced on a tufting machine with a division of 5/32, and
subsequently piece-dyed. The backing was then consolidated
first with a standard commercial-grade latex and then with a
latex made conductive by the addition of carbon black. These
carpets were then stored for 72 hours under conditions of -
20 C/30 ~ relative atmospheric humidity. The antistatic
properties of the carpets were tested by measuring the charge
picked up by a person walking over the carpets with rubber-
soled and leather-soled shoes. The test person walking over
the carpet was connected to a fully insulated metal plate by
means of a conductive cable. The electrical charge developed
by the test person walking over the carpet and transmitted to
the metal plate was measured by means of a modulation measuring
head, for example of Professor Schwenkhagen's design.
During measurement, the test carpet rested on a
heavily insulated rubber mat (volume resistance according to
DI~ 54 345 > 10 2
A person walking over the carpet with a standard ;
backing developed a maximum charge of 2000 volt .cm when
wearing leather-soled shoes, and a maximum charge of 1700 volt
.cm when wearing rubber-soled shoes. The maximum charge
developed from the carpet with a conductive backing amounted to
1000 volt .cm in the case of leather-soled shoes and to 800
volt .cm in the case of rubber-soled shoes. Charges in excess
of 10,000 volt .cm were measured on a carpet produced for -
comparison from unmodified polyamide fibres and backed in the
usual way both when it was walked on with leather-soled shoes
- 28 -

1~538Z~
and when it was walked on with rubber-soled shoes.
When the standard backing was replaced by a conductive
backing, the charge was reduced to 800o volt .cm . However,
these values are still distinctly above the so-called percep-
tibility limit of 3000 volt .cm at which people generally
sense shock-like discharges on coming into contact with
articles of high capacity, such as door handles, typewriters,
etc. These critical values are never reached in the case
of carpets produced from fibres according to the invention.
B. Knitted fabr_c test
A warp knit fabric was produced from a dtex 44 f 10
filament yarn. A 15 cm wide strip of this fabric was fixed
on one side to a metal clamp and, on its other sida, was
placed at an interval of 30 cm over a metal roller and loaded `
at an angle of 90 with a 1 kg weight. A rotating friction
arm whose friction surface was covered with Dralon Fabric was
moved over the taught, horizontal surface. After lO strokes~
the charge developed in the knitted fabric was measured as `
field strength by means of the modulation measuring head
described above arranged at a distance of 3 cm. A charge of
600 volt .cm was measured on the knitted fabric produced
from fibres according to the invention at 23 C/50 ~ relative
humidity. Half the charge produced had dissipated after less
than 2 seconds. By contrast, the charge developed in a knitted
fabric produced from unmodified polyamide filament yarn of
the same denier amounted to 8000 volt .cm and had a half-life
of 15 seconds. When a preparation-free woven polyester fabric
was rubbed over the knitted fabric of filament yarn produced ~`
in accordance with the invention under conditions of 20 C/30 %
relative humidity, it did not adhere to the knitted fabric,
whereas when the same fabric was rubbed over the comparison
knitted fabric of unmodified polyamide filament yarn, the two
*Trademark - 29 - .

~0~3~'~7
pieces were still adhering to one another after as long as
60 seconds.
EXAMPLES 32 to 35
Using the extruder described in the preceding Examples,
chips with a relative solution viscosity of 2.9 are melted and
spun under the same conditions. Some of the properties ~ the
filament yarn obtained are shown in Table 7 for Example 32.
In Examples 33 to 35, the same antistatic agent as in
the preceding Examples 29 to 31 in molten form is directly intro-
duced into the chip inlet of the screw in the quantities specified
in Table 7 by means of a piston metering pump ~Lewa pump). The
properties of these filament yarns are shown in Table 7 below.
Table 7
.
Test Antistatic additive Surface
No. resistance
quantity analytically after the tensile elongation `added determined first wash strength at break
% % Q.cm2 P/dtex %
32 0 0 5.1ol2 4.6 36 :~
33 1.5 1.45 1.1011 4.7 38
34 3.0 2.87 7.10 4.5 40
4.5 4.23 4.lolo 4.5 36
EXAMPLE 36
3% of the antistatic additive used in Example 12 are
mixed into the monomer-free melt from a VK* tube ~cf. Hermann
Klare, Synthetische Fasern aus Polyamiden, Akademie-Verlag,
Berlin 1973) both by means of a piston metering pump ~cf.
Examples 33-35) and by means of a dynamic mixer of the type ~`
described in DT-AS 1,557,064 ~laid open on the 16.11.1972).
.,: .
*Trademark
- 30 -
., ~ , .
~: . . . .

~)5~ 7
The melt is further processed under the same conditions
as in Examples 29 to 31.
The measurement results are set out in Table 8.
Table 8
.:
Surface
Test Antistatic additive resistance
No. quantity analytically after the tensile elongation
added determined first wash strength at break
% % ~.cm2 p/dtex %
36 3.0 2.95 6.lolo 4.6 38 `
EXAMPLE 37 ;~
(a) Preparation of a diurethane from 20-fold ethoxylated
stearyl alcohol and N,N'-dimethyl ethylene diamine
585 g of 20-fold ethoxylated stearyl alcohol were dis- ; :
solved in 1.5 litres of toluene, 60 g of phosgene were introduced
at 50C, followed by rinsing with nitrogen. A slight haze
was removed by filtration under suction. The solution was
concentrated, a temperature of 130C and a vacuum of 15 Torr
ultimately being applied. The chlorocarbonic acid ester of
the 20-fold ethoxylated stearyl alcohol was left as residue in a
su~stantially quantitative yield. 246 g of this chlorocarbonic
acid ester were dissolved in 400 ml of benzene. The resulting
solution was then added dropwise to a solution, cooled to
5-10C, of 9 g of N,N'-dimethyl ethylene diamine and 35 g of
triethylamine in 200 ml of benzene. The mixture was then -`
stirred for 2 hours at 50C. The triethylamine hydrochloride
was filtered off under suction. The filtrate was concentrated. i
IR-examination and analysis showed that the desired compound -
had been obtained. -~
(b) Production of the antistatic polyamide composition
130 g of -caprolactam, 15 g of -aminocaproic acid and
..~ .
- 31 - `
. .
.. . .

~C~5;~8'~ 7
7.5 g of the diurethane prepared in accordance with(a) were
heated under nitrogen to 270C and condensed with intensive
stirring for 4 hours at that temperature. The polyamide
com~)osition obtained ( ~ rel = 2,66) was processed into filaments
on which the following electrical surface resistances were
deterinined:
After production: 2.109 S~ .cm
After the first wash: 3.101~ .cm
After the fifth wash: 6.101~.cm
After the tenth wash: 5.10 ~.cm
~XA~IPL~ 38
(a) Preparation of a diurethane from 20~fold ethoxylated
stearyl alcohol and piperazine
20-fold ethoxylated stearyl alcohol was converted into
the chlorocarbonic acid ester in the same way as described in
Example 37a), 123 g of this chlorocarbonic acid ester were
dissolved in 600 ml of water. The resulting solution and
a 30 ~ NaO~-solution were simultaneously added dropwise to
a solution of 9.7 g of piperazine hexahydrate in 3VO ml of
water, the dropwise addition being made in such a way that the
p~-value of the solution was always between 10 and 10.5.
On completion of the addition, the reaction mixture was stirred
for 1 hour, after which a p~l-value of 7 was adjusted with
concentrated hydrochloric acid. The water was distilled off,
the residue was taken up in 600 ml of dioxan, the sodium
chloride was filtered off and the filtrate was concentrated~
120 g of residue were obtained. According to analysis and
IR-examination, the residue was the de3ired diureLhaneO
(b) Production of the antistatic polyamide comFosition
130 g of -caprolactam, 15 g of -aminocaproic acid and
7.5 g of the diurethane produced in accordance~with 38(a) were
heated under nitrogen to 270C and condensed with intensive
Le A 15 522 _33~
32
. .
.
. ~ . .

stirring for 4 hours at that temperature. The polyamide
composition obtained (~rel = 2-41) was processed into filaments
on which the following electrical surface resistances were
measured:
After production 3.109Q .cm
After the first wash: 3.10 Q .cm
After the fifth wash: 7.10 Q .cm
After the tenth wash: 6.10 Q .cm
EXAMPLE 39
2 5 C LCH2 (OCH2-CH2)11-0-C-N(CH3)2~ 3
14.2 kg of 33-fold ethoxylated trimethylol propane of
molecular weight 1586 are dissolved with stirring in 30 litres
of toluene. 3.12 kg of phosgene are introduced at 0 to 10 C -
and the temperature allowed to rise slowly to 20 C, followed
by stirring for another 3 hours. The excess phosgene and the
hydrogen chloride formed are then blown off with nitrogen at
a temperature of approximately 80 C. 2.3 kg of dimethylamine
are then introduced at 20 to 30C and 2 kg of a 50%
aqueous sodium hydroxide solution added dropwise, followed by
stirring for 3 hours. For working up, the water is separated
off azeotropically through a water separator. After filtration ~-
to isolate the sodium chloride precipitated, the toluene is
removed by distillation, ultimately in vacuo.
Analysis C H N
Calculated 54.1 8.9 2.3
found 54.3 9.3 2.2
5% of the urethane formed are worked into polycapronamide
as in Example 26 and the melt is spun into filaments. The filaments
thus obtained have the following surface resistances:
After production: 2.109Q .cm ;~
After the first wash: 3.10 Q .cm
After the fifth wash: 5.10 Q .cm
- 33 -
.

5;~7
After the tenth wash: 5.101Q .cm
Polycapronamide fibres containing 5% of the starting
product without any urethane groups have a surface resistance
of 2.10 Q .cm after ten washes.
EXAMPLE 40 r O
5 2 ~H2-(OCH2-CH2)16-0-C-N(CH3)
The triurethane is prepared as in Example 1 from 48-
fold ethoxylated trimethylol propane, phosgene and dimethylamine.
The IR-spectrum of the product does not show an OH-band.
Polycapronamide filaments containing 5% of this substance
have the following surface resistances:
After the first wash: 4.10 Q .cm
After the third wash: 8.10 Q .cm
After the fifth wash: 8.10 Q .cm
After the tenth wash: 5.10 Q .cm
Polycapronamide fibres containing 5% of the starting -
product without any urethane groups have a surface resistance
of 2 . lOllQ .cm2 after ten washes --
EXAMPLE 41 r O 1 ~
5 2 C ~H2-(0CH2-CH2)s s-0-C-~-(CH3)2¦
The triurethane is prepared as in Example 1 from 16.5-
fold ethoxylated trimethylol propane, phosgene and dimethylamine.
The IR-spectrum of the product does not show an OH-band.
Polycapronamide filaments containing 5% of this substance
show the following surface resistances.
After the first T~ash: 6.10 Q .cm
After the third wash: 7.10 ~ .cm
After the fifth wash: 9.10 Q .cm
After the tenth wash: 7.10 Q .cm
- 34 - -

- ~05;~27
EXAMPLE 42
CH3 "
H5C2-C 2 ( CH2 CH )7-(OCH2-CH2)10-0-C-N(CH3)2
2500 g (1.0 mol) of trimethylol propane, to which a
total of 21 equivalents of propylene oxide to begin with and then
30 equivalents of ethylene oxide were added, are dissolved in
5 litres of benzene. 372 g (3.75 mol) of phosgene are introduced
at 20 to 30 C, followed by stirring for 4 hours at 20 C.
The rest of the phosgene and the hydrogen chloride formed are
removed by a vigorous stream of nitrogen. 205 g (4.5 mols)
of dimethylamine are then introduced and the hydrochloride
is precipitated. 240 g of a 50% sodium hydroxide solution
(corresponding to 3.0 mols of NaOH) are then added dropwise,
followed by stirring for 5 hours at 50 C. The salt is
filtered off and the aqueous phase is separated. The benzene
is then distilled off under normal pressure, ultimately in vacuo.
Polycapronamide filaments containing 5% of this sub-
stance have the following surface resistances:
After the first wash: 5.10 Q .cm
After the third wash: 6.10 Q .cm
After the fifth wash: 6.10 Q .cm
After the tenth wash: 5.10 Q .cm
EXAMPLE 43
- O CH3 ~
(X3C)2-N-C(OCH2-CH2)15(0CH-CH2)17 2 2 i -
- O CH3 - ¦
(H3C)2-~-C(OCX2-CH2)15(0CH CH2)17 2~ CH2
1700 g (0.25 mol) of an ethylene diamine, to which a total
of 68 equivalents of propylene oxide to begin with and then 60
equivalents of ethylene oxide were added, are dissolved in
approximately 1.5 litres of benzene. 200 g (2.0 mols) of
.' :
.

10~3~Z7
phosgene are introduced at 20 C and, after stirring for 3 hours
at 30 C, the excess phosgene and some of the hydrogen chloride
formed are removed with a vigorous stream of nitrogen. 250 g
of dimethylamine are then introduced, after which the solution
should show an alkaline reaction. After stirring for 5 hours
at 50C, the solution is filtered off under suction from the
hydrochloride precipitated, diluted with another 3 litres of
benzene and washed once with approximately 300 ml of a 5%
sodium carbonate solution. The solution is then washed until
neutral with saturated sodium chloride solution, after which
the benzene is distilled off. The residue is taken up in
ethanol, filtered off from the sodium chloride and re- -
concentrated.
Polycapronamide filaments containing 5% of this
tetraurethane have the following surface resistances:
After production: 5.109Q
After the first wash: 2.10 Q
After the fifth wash: 9.10 Q
After the tenth wash: 8.10 Q
EXAMPLE 44
(a) Preparation of a dimethyl urethane corresponding to
the formula
0 / CH3
3 \ " f 2 2 2 )a
/ N-C-(0-CH2-CH2)b-o-cH
3 \ " ¦
/ N-C-(0-CH -CH ) -0-CH 0 / CH3
H3C f ( 2 2 )d \ -
0 ~ H3
CH-0-(CH2-CH2-O)e-c-N \
CH3
0 / CH3
CH2-0-(CH2-CH2-O)f-C-N \
- 36 - CH3
: ~ .,.

~"` lns3s~7
a + b + c + d + e + f = 84
18.2 g of mannitol were treated with ethylene oxide at
170 C in the presence of 0.1 g of solid NaOH until about 370 g of
ethylene oxide have been taken up, so that an average of about 14
-O-CH2-CH2 groups were present per hydroxyl group of the mannitol.
The residue was taken up in 2 litres of toluene, and 75 g of phosgene
were then introduced into the resulting solution at 50 C. The excess
phosgene and the hydrochloric acid formed were then blown out with
nitrogen. 90 g of dimethylamine were then introduced into the solu-
tion at 30 C. The solution was then filtered off from the dimethyl-
amine hydrochloride precipitated and the toluene was subsequently -
distilled off, a water jet vacuum being applied towards the end of
distillation. According to IR-measurements, the residue left is free
from OH-groups.
Analysis N
calculated 1.87%
found 1.90%
(_) 130 g of ~-caprolactam 15 g of e-aminocaproic acid and
7.5 g of the dimethyl urethane prepared in accordance with (a)
were condensed under the conditions of Example 5. Filaments ;~
obtained from the resulting polyamide composition were found to
have the following electrical surface resistances:
After production: 2.109Q .cm
After the first wash: ~.101Q .cm2
After the second wash: 6.10 Q .cm
After the third wash: 7.10 Q .cm
Polycaprolactam filaments which, instead of the urethane,
contain the same quantity of the thoxylated mannitol produced in
accordance with (a) which had not yet been further reacted to
the dimethyl urethane, have an electrical surface resistance
of 7.10 Q .cm after the first wash, and an electrical surface
resistance of as high as 2.10 Q .cm after only the third wash.
- 37 -
~,
- ~ : ; ~ , . .; , ," ;,