U.S. patent application number 15/304028 was filed with the patent office on 2017-08-24 for composition for rheology control.
The applicant listed for this patent is BYK-Chemie, GmbH. Invention is credited to Sylvia BUHNE, Marc EBERHARDT, Daniela LEUTFELD, Rene NAGELSDIEK, Jurgen OMEIS, Jasmin RUDNER.
Application Number | 20170240748 15/304028 |
Document ID | / |
Family ID | 50486707 |
Filed Date | 2017-08-24 |
United States Patent
Application |
20170240748 |
Kind Code |
A9 |
LEUTFELD; Daniela ; et
al. |
August 24, 2017 |
COMPOSITION FOR RHEOLOGY CONTROL
Abstract
The invention relates to a rheology control agent containing i)
15-95% by weight of an amide compound (A), ii) 5-75% by weight of a
urea compound (B), iii) 0-50% by weight of an ionogenic compound
(C) and iv) 0-35% weight of an organic solvent (D).
Inventors: |
LEUTFELD; Daniela; (Wesel,
DE) ; EBERHARDT; Marc; (Wesel, DE) ;
NAGELSDIEK; Rene; (Hamminkeln, DE) ; BUHNE;
Sylvia; (Duisburg, DE) ; OMEIS; Jurgen;
(Dorsten-Lembeck, DE) ; RUDNER; Jasmin;
(Dinslaken, DE) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
BYK-Chemie, GmbH |
Wesel |
|
DE |
|
|
Prior
Publication: |
|
Document Identifier |
Publication Date |
|
US 20170044378 A1 |
February 16, 2017 |
|
|
Family ID: |
50486707 |
Appl. No.: |
15/304028 |
Filed: |
February 11, 2015 |
PCT Filed: |
February 11, 2015 |
PCT NO: |
PCT/EP2015/000300 PCKC 00 |
371 Date: |
October 13, 2016 |
Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C09D 5/04 20130101; C08K
5/20 20130101; C08K 5/21 20130101; C09D 7/43 20180101 |
International
Class: |
C09D 5/04 20060101
C09D005/04; C09D 7/12 20060101 C09D007/12 |
Foreign Application Data
Date |
Code |
Application Number |
Apr 15, 2014 |
EP |
14001367.3 |
Claims
1. A composition comprising i) 15-95 wt % of an amide compound (A),
ii) 5-75 wt % of a urea compound (B), iii) 0-50 wt % of an
ionogenic compound (C), and iv) 0-35 wt % of an organic solvent
(D), where the amide compound (A) has a molar mass of 70 to 600
g/mol, the amide compound (A) contains not more than one amide
group with hydrogen bonded to its nitrogen atom, the amide compound
(A) has no urea group, no phosphorus, no silicon, and no halogen,
and the amide compound (A) is present in accordance with the
general formula (I), ##STR00013## where Xx is identical or
different and is represented by an amide group C(.dbd.O)--N which
is linked to Rz, Ra, and Rb in accordance with one of the general
formulae RzC(.dbd.O)--NRaRb (Xx1), RaC(.dbd.O)--NRzRb (Xx2), and
RbC(.dbd.O)--NRzRc (X.times.3) Xy is identical or different and is
represented by an amide group C(.dbd.O)--N which is linked to Rz,
Rc, and Rd in accordance with one of the general formulae
RzC(.dbd.O)--NRcRd (Xy1), RcC(.dbd.O)--NRzRd (Xy2), and
RdC(.dbd.O)--NRzRc (Xy3) Rz in each case is identical or different
and is represented by a branched or unbranched, saturated or
unsaturated hydrocarbon radical which has 1 to 32 carbon atoms and
which as heteroatom-containing groups may contain exclusively amino
and/or amide groups, Ra, Rb, Rc, and Rd, in each case identically
or differently and in each case independently of one another, are
represented by hydrogen and/or a branched or unbranched, saturated
or unsaturated organic radical containing 1 to 16 carbon atoms,
with the proviso that Ra, Rb, Rc, and Rd in their entirety have at
least four carbon atoms, not more than one of the radicals from the
group of Ra, Rb, Rc, and Rd is present in the form of hydrogen, Ra
and Rb and/or Rc with Rd, together with the CO--N moiety joining Ra
to Rb and/or Rc to Rd, may together, in accordance with the general
formula (.alpha.-1), form a cyclic structure having 4 to 10 ring
atoms, and/or ##STR00014## Ra and Rb and/or Rc with Rd, together
with the N atom joining Ra to Rb and/or Rc to Rd, may together, in
accordance with the general formula (.beta.-1), form a cyclic
structure having 4 to 7 ring atoms, or ##STR00015## Rb and Rc
together with the N atom bonded to each of Rb and Rc, and also with
the radical Rz, may, in accordance with the general formula
(.gamma.-1), form a cyclic structure having 5 to 7 ring atoms
##STR00016## Ra, Rb, Rc, Rd, and Rz in their entirety have not more
than 36 carbon atoms and also not more than 8 heteroatoms from the
group of N and O, the urea compound (B) has a molecular weight of
at least 350 g/mol and at least one urea group, the ionogenic
compound (C) contains a cationic component and an anionic component
and is different from the amide compound (A) and from the urea
compound (B), and the organic solvent (D) contains no urea group
and no ionic group and also has not more than two heteroatoms
selected from the group consisting of nitrogen and oxygen.
2. The composition as claimed in claim 1, comprising i) 30-90 wt %
of the amide compound (A), ii) 8-55 wt % of the urea compound (B),
iii) 0-15 wt % of the ionogenic compound (C), and iv) 2-25 wt % of
the organic solvent (D).
3. The composition as claimed in claim 1, characterized in that on
the one hand 50-100 wt % of the amide compound (A) has no amide
group with hydrogen bonded to its nitrogen atom, and on the other
hand this 50-100 wt % of the amide compound (A) is also present in
accordance with a general formula (I) in which none of the radicals
from the group of Ra, Rb, Rc, and Rd is represented by
hydrogen.
4. The composition as claimed in claim 1, characterized in that
50-100 wt % of the amide compound (A) is present in accordance with
the general formula (Ia) ##STR00017##
5. The composition as claimed in claim 1, characterized in that
50-100 wt % of the amide compound (A) is present in accordance with
the general formula (Ia), where Ra and Rb and/or Rc with Rd,
together with the N atom joining Ra to Rb and/or Rc to Rd, in
accordance with the general formula (.beta.-1), together form a
branched or unbranched, saturated or unsaturated cyclic structure
having 4 to 7 ring atoms which has not more than two heteroatoms
from the group consisting of O and N.
6. The composition as claimed in claim 1, characterized in that
50-100 wt % of the amide compound (A) is present in accordance with
the general formula (Ia), where Ra, Rb, Rc and/or Rd in each case
are not present in cyclic structures.
7. The composition as claimed in claim 1, characterized in that the
general formula (I) for 50-100 wt % of the amide compound (A) is
present in accordance with the general formula (Ib)
##STR00018##
8. The composition as claimed in claim 1, characterized in that the
general formula (I) for 50-100 wt % of the amide compound (A) is
present in accordance with the general formula (Ib), where Rb and
Rc together with the N atom bonded to each of Rb and Rc, and also
with the radical Rz, in accordance with the general formula
(.gamma.-1), form a branched or unbranched, saturated or
unsaturated cyclic structure having 5 to 7 ring atoms which has not
more than two heteroatoms from the group consisting of O and N.
9. The composition as claimed in claim 1, characterized in that the
general formula (I) for 50-100 wt % of the amide compound (A) is
present in accordance with the general formula (Ib), where Ra and
Rb and/or Rc with Rd, together with the CO--N moiety joining Ra to
Rb and/or Re to Rd, in accordance with the general formula
(.alpha.-1), together form a branched or unbranched, saturated or
unsaturated cyclic structure having 4 to 10 ring atoms which has
not more than two heteroatoms from the group consisting of O and
N.
10. The composition as claimed in claim 1, characterized in that
70-100 wt % of the urea compound (B) either has at least two urea
groups or has at least one urea group and at least one urethane
group.
11. The composition as claimed in claim 1, characterized in that
50-100 wt % of the urea compound (B) is present in accordance with
the general formula (II)
R.sup.31--[R.sup.33--Z--R.sup.34--W-].sub.nR.sup.32 (II) where
R.sup.31 and R.sup.32 each identically or differently and also each
independently of one another are represented by a branched or
unbranched, saturated or unsaturated organic radical which contains
1-100 carbon atoms and which has not more than one urea group each
and not more than one urethane group each, R.sup.33 and R.sup.34
each identically or differently and also each independently of one
another are represented by branched or unbranched polyester
radicals containing 1-300 carbon atoms and optionally containing
ether groups, branched or unbranched polyether radicals containing
2-300 carbon atoms, branched or unbranched polyamide radicals
containing 1-300 carbon atoms, polysiloxane radicals containing 3
to 100 silicon atoms, branched or unbranched C2-C22 alkylene
radicals, branched or unbranched C3-C18 alkenylene radicals, C5-C12
arylene radicals and/or branched or unbranched C7-C22 arylalkylene
radicals, Z and W each identically or differently and also each
independently of one another are represented by NH--CO--O and/or
NH--CO--NH, n is in each case identical or different and is
represented by an integer from 1 to 150.
12. The composition as claimed in claim 1, characterized in that
50-100 wt % of the urea compound (B) has in each case a molecular
weight of 2000 to 55000 and also 4-150 urea groups.
13. The composition as claimed in claim 1, characterized in that
50-100 wt % of the urea compound (B) is present in each case in
accordance with one of the general formulae selected from the group
consisting of (IIIa), (IIIb), (IIIc), and (IIId) ##STR00019## where
AM is identical or different and is represented by a linear or
branched, saturated or unsaturated, aliphatic, aromatic or
aliphatic-aromatic organic radical having 2 to 50 C atoms, AM1 and
AM2 in each case are identical or different and in each case
independently of one another represented by a linear or branched,
saturated or unsaturated, aliphatic, aromatic or aliphatic-aromatic
organic radical having 1 to 50 C atoms, IC1 and IC2 are in each
case identical or different and in each case independently of one
another represented by a linear or branched, saturated or
unsaturated, aliphatic, aromatic or aliphatic-aromatic hydrocarbon
radical having 2 to 40 C atoms, IC3 is identical or different and
is represented by a linear or branched, saturated or unsaturated,
aliphatic, aromatic or aliphatic-aromatic hydrocarbon radical
having 2 to 24 carbon atoms, RP1 and RP2 are in each case identical
or different and in each case independently of one another
represented by a linear or branched, saturated or unsaturated,
aliphatic, aromatic or aliphatic-aromatic organic radical having 1
to 24 C atoms and/or by a polyether radical having 1 to 120 ether
oxygen atoms and/or by a polyester radical having 1 to 100 ester
groups and optionally containing ether groups, and/or by a
polyamide radical having 1 to 100 amide groups, and/or by a
polysiloxane radical having 3 to 100 silicon atoms, RP3 is
identical or different and is represented by a linear or branched,
saturated or unsaturated, aliphatic, aromatic or aliphatic-aromatic
hydrocarbon radical having 2 to 24 C atoms and/or by a (poly)ether
radical having 1 to 120 ether oxygen atoms and/or by a polyamide
radical having 1 to 100 amide groups and/or by a polysiloxane
radical having 3 to 100 silicon atoms and/or by a polyester radical
having 1 to 100 ester groups and optionally containing ether
groups, and p is identical or different and is represented by 0
and/or 1.
14. The composition as claimed in claim 13, characterized in that
70-100 wt % of the urea compound (B) is present in each case in
accordance with one of the general formulae selected from the group
consisting of (IIIa), (IIIb), (IIIb), and (IIId), where AM is
identical or different and is selected from the group consisting of
##STR00020## where R.sub.x and Ry are identical or different and
are in each case independently represented by CH.sub.3 and/or
hydrogen, (CH.sub.2).sub.q where q is identical or different and is
represented by an integer from 2 to 12, AM1 and AM2 are each
identical or different and are selected from the group consisting
of n-propyl, isopropyl, butyl, isobutyl, tert-butyl, lauryl, oleyl,
stearyl, polyisobutylene, and polyethers having 2 to 40 ether
oxygen atoms, benzyl, methylbenzyl, cyclohexyl, carboxyalkyl,
hydroxyalkyl, and alkylalkoxysilane, IC1 and IC2 are each identical
or different and are selected from the group consisting of
##STR00021## IC3 is identical or different and is selected from the
group consisting of methyl, ethyl, phenyl, benzyl, cyclohexyl, and
stearyl, RP1 and RP2 are each identical or different and are
selected from the group consisting of branched or unbranched C1 to
C18 alkyl, oleyl, benzyl, allyl, polyether radical optionally
containing structural units of ethylene oxide, propylene oxide
and/or butylene oxide, and polyester radical containing structural
units of epsilon-caprolactone and/or delta-valerolactone, RP3 is
identical or different and is selected from the group consisting of
linear or branched C1 to C18 alkylene, linear or branched C2 to C18
alkenylene, polyether optionally containing structural units of
ethylene oxide, propylene oxide and/or butylene oxide and having 1
to 25 ether oxygen atoms.
15. The composition as claimed in claim 1, characterized in that
70-100 wt % of the urea compound (B) in each case is prepared by
reaction of monofunctional amines with isocyanates oligomerized by
isocyanurate formation and/or uretdione formation.
16. The composition as claimed in claim 1, characterized in that
95-100 wt % of the urea compound (B) contains in each case at least
one molecule segment of the general formula (IVa)
--O--CO--NH--Y.sub.1--NH--CO--NH-- (IVa) where Y.sub.1 is identical
or different and is represented by a saturated or unsaturated,
branched or unbranched hydrocarbon radical containing 6 to 20
carbon atoms, and in each case contains no molecule segment of the
general formula (IVb) --O--CO--NH--Y.sub.2--NH--CO--O-- (IVb) where
Y2 is identical or different and is represented by a saturated or
unsaturated, branched or unbranched hydrocarbon radical containing
6 to 20 carbon atoms.
17. The composition as claimed in claim 1, comprising 0.5-4.0 wt %
of the ionogenic compound (C), where 50-100 wt % of the ionogenic
compound (C) is present in the form of lithium salt or calcium
salt, optionally in the form of a chloride, acetate and/or nitrate
thereof.
18. The composition as claimed in claim 1, which is suitable for
rheology control or for thixotroping of liquid systems.
19. (canceled)
20. A method comprising adding the composition of claim 1 to a
liquid mixture for theology control or thixotroping, characterized
in that the liquid mixture is present in the form of a coating, a
paint or varnish, a plastics formulation, a pigment paste, a
sealant formulation, cosmetics, a ceramic formulation, an adhesive
formulation, an encapsulating composition, a drilling mud solution,
a building material formulation, a lubricant, a filling compound, a
printing ink or a liquid ink.
21. A preparation which is present in the form of a paint or
varnish, a plastics formulation, a pigment paste, a sealant
formulation, cosmetics, a ceramic formulation, an adhesive
formulation, an encapsulating composition, a building material
formulation, a lubricant, a drilling mud solution, a filling
compound, a printing ink or a liquid ink and to which 0.1 to 7.5 wt
% of a composition as claimed in claim 1 has been added.
Description
[0001] The present invention relates to a composition and also to
the use thereof and to a preparation comprising the
composition.
[0002] To control the rheology of liquid systems, especially liquid
coating systems, rheological aids used are, primarily, organically
modified bentonites, silicas, hydrogenated castor oil, and
polyamide waxes.
[0003] A disadvantage of using these rheological aids is that they
are usually present in the form of dry solids. Consequently, said
rheological aids before being used are therefore destructurized to
form an intermediate product, using solvents and shearing forces.
Alternatively, before being destructurized, the rheological aids
may also be used by being introduced into the liquid coating system
by targeted temperature control. Where this temperature control
does not take place in accordance with the specified targets,
crystallites typically appear in the finished coating system, and
can lead to defects in the coating.
[0004] A general disadvantage of using these rheological aids is
that they give rise to clouding and haze in clear, transparent
coatings. Moreover, handling dry, pulverulent products which may
give rise to dusts during processing is undesirable.
[0005] A liquid application alternative to these solid rheology
control agents is represented by solutions of specific urea
compounds. Solutions of this kind are frequently used in practice
and are described for example in EP-A-1 188 779. Serving as solvent
and/or carrier medium typically are polar/aprotic solvents and/or
ionic liquids, which are de facto salt melts which are liquid under
moderate temperature conditions (usually below 80.degree. C.,
ideally at room temperature). The rheology control properties of
dissolved urea compounds are usually fairly good, but in many cases
a desire exists for even further optimized rheology control
characteristics. Optimized characteristics are manifested
frequently not only in improved rheological activity, but also,
optionally, in broad compatibility in application-relevant
formulations as well (e.g., binders).
[0006] WO2011/091812 relates to the use of urea compounds and amide
compounds as rheologically active components in baking varnishes. A
disadvantage is that the mutual incompatibility of said urea
compounds and amide compounds means that they must be metered
separately from one another into the baking varnish and are
therefore unavailable as an additive mixture to the varnish
manufacturer.
[0007] The problem addressed by the present invention is therefore
that of providing a high-quality rheology control agent which can
be used universally and practically.
[0008] The solution to this problem is a composition comprising
[0009] i) 15-95 wt % of an amide compound (A), [0010] ii) 5-75 wt %
of a urea compound (B), [0011] iii) 0-50 wt % of an ionogenic
compound (C), and [0012] iv) 0-35 wt % of an organic solvent (D),
where the amide compound (A) has a molar mass of 70 to 600 g/mol,
the amide compound (A) contains not more than one amide group with
hydrogen bonded to its nitrogen atom, the amide compound (A) has no
urea group, no phosphorus, no silicon, and no halogen, and the
amide compound (A) is present in accordance with the general
formula (I),
##STR00001##
[0012] where Xx is identical or different and is represented by an
amide group C(.dbd.O)--N which is linked to Rz, Ra, and Rb in
accordance with one of the general formulae RzC(.dbd.O)--NRaRb
(Xx1), RaC(.dbd.O)--NRzRb (Xx2), and RbC(.dbd.O)--NRzRa (Xx3) Xy is
identical or different and is represented by an amide group
C(.dbd.O)--N which is linked to Rz, Rc, and Rd in accordance with
one of the general formulae RzC(.dbd.O)--NRcRd (Xy1),
RcC(.dbd.O)--NRzRd (Xy2), and RdC(.dbd.O)--NRzRc (Xy3) Rz in each
case is identical or different and is represented by a branched or
unbranched, saturated or unsaturated hydrocarbon radical which has
1 to 32 carbon atoms and which as heteroatom-containing groups may
contain exclusively amino and/or amide groups, Ra, Rb, Rc, and Rd,
in each case identically or differently and in each case
independently of one another, are represented by hydrogen and/or a
branched or unbranched, saturated or unsaturated organic radical
containing 1 to 16 carbon atoms, with the proviso that Ra, Rb, Rc,
and Rd in their entirety have at least four carbon atoms, not more
than one of the radicals from the group of Ra, Rb, Rc, and Rd is
present in the form of hydrogen,
[0013] Ra and Rb and/or Rc with Rd, together with the CO--N moiety
joining Ra to Rb and/or Rc to Rd, may together, in accordance with
the general formula (.alpha.-1), form a cyclic structure having 4
to 10 ring atoms, and/or
##STR00002##
Ra and Rb and/or Rc with Rd, together with the N atom joining Ra to
Rb and/or Rc to Rd, may together, in accordance with the general
formula (.beta.-1), form a cyclic structure having 4 to 7 ring
atoms, or
##STR00003##
Rb and Rc together with the N atom bonded to each of Rb and Rc, and
also with the radical Rz, may, in accordance with the general
formula (.gamma.-1), form a cyclic structure having 5 to 7 ring
atoms
##STR00004##
Ra, Rb, Rc, Rd, and Rz in their entirety have not more than 36
carbon atoms and also not more than 8 heteroatoms from the group of
N and O, the urea compound (B) has a molecular weight of at least
350 g/mol and at least one urea group, the ionogenic compound (C)
contains a cationic component and an anionic component and is
different from the amide compound (A) and from the urea compound
(B), and the organic solvent (D) contains no urea group and no
ionic group and also has not more than two heteroatoms selected
from the group consisting of nitrogen and oxygen.
[0014] The components (A), (B), (C) and/or (D) may each be present
in the form of different kinds of species, i.e., as mixtures. In
addition to the components (A), (B), (C), and (D), the composition
of the invention may optionally also comprise further
constituents.
[0015] The molecular weight of the urea compounds (B) that are
relevant in accordance with the invention is limited in the
low-molecular range by the fact that urea compounds (B) having
molar masses of less than 350 g/mol are generally less active
rheologically or completely inactive rheologically. Substances of
this kind with little or no activity, having molecular weights
below 350 g/mol, are customarily specific monomeric or
low-molecular oligomeric compounds of defined molecular weight, and
so the statement of a weight-average or number-average molecular
weight is unnecessary, given that these compounds generally lack
any molecular nonuniformity. The lower limit of 350 g/mol selected
according to the claim therefore represents the actual molecular
weight of the species and can be determined for example by means of
NMR.
[0016] The upper limit to the molecular weight of the urea
compounds (B), on the other hand, is not critical, provided there
is still compatibility between the urea compounds (B) and the other
constituents of the rheology control agent and of the subsequent
preparation in which the urea compounds (B) are used. The typical
compatibility limits are customarily attained by polymeric urea
compounds (B) for which only averaged molecular weights can be
specified. Customarily suitable as urea compounds (B) are those
which possess a weight-average molecular weight of less than 60000
g/mol, although in certain cases it is possible also to use urea
compounds which have a higher molecular weight, such as 80000 or
100000 g/mol, for example, provided that compatibility is ensured
in the systems in question. If compatibility is lacking, a person
of ordinary skill in the art is easily able to employ urea
compounds (B) which have a lower weight-average molecular weight.
The synthesis of urea compounds (B) with weight-average molecular
weights, even of far more than 100000 g/mol, is therefore not a
general problem to a person of ordinary skill in the art.
[0017] The person of ordinary skill in the art is aware that for
higher molecular weight ranges, there are other methods to be
preferred for determining the molecular weights, instead of NMR
spectroscopy. Determining the weight-average molecular weight of
the urea compounds (B) which have a molar mass of more than 1000
g/mol is accomplished, in accordance with the description below, as
the weight average of the molar mass distribution determined by gel
permeation chromatography (GPC). The GPC molar mass distribution is
determined according to DIN 55672 Part 2 of January 2008. The
eluent used is a solution of lithium bromide (5 g/l concentration)
in dimethylacetamide. Calibration takes place using narrowly
distributed, linearly constructed polymethyl methacrylate standards
having molecular weights of between 1000000 and 102 g/mol. The
temperature of the GPC system as a whole (injector, sample plate,
detectors, and columns) is 80.degree. C. The weight-average molar
masses of the urea compounds (B) with 350 g/mol up to about 1000
g/mol can be determined for example by NMR, (B) by forming ratios
of the integrals of relevant NMR resonance signals. The choice of
the method of determination in this range is not critical, however,
since all that should be ensured in accordance with the invention
is that the urea compounds (B)--as explained above--have a
molecular weight of at least 350 g/mol.
[0018] In one particularly preferred embodiment of the invention,
therefore, 70 to 100 wt % of the urea compound (B) has a molecular
weight of at least 350 g/mol up to a maximum of 60000 g/mol.
[0019] The composition of the invention is an application-friendly
presentation form which can be provided in liquid form. The end
user (e.g., user or formulator of paints, varnishes, plastics or
adhesives) can employ the additive simply and with little risk of
application errors. The fact that the rheologically active additive
components (A) and (B) are present in a mixture reduces the cost
and complexity of storage for the paint or varnish user (now only
one storage container for (A) and (B)) and allows paint or varnish
production to be accelerated, since there are fewer components to
be metered. Features deserving of emphasis are the high storage
stability of the composition of the invention, and the universal
applicability in a variety of systems (e.g., in different kinds of
binders).
[0020] The composition of the invention exhibits particularly good
rheological activity. For example, the rheological activity of the
composition can be determined on the basis of the sag resistance
(sagging limit) or the gel strength of a corresponding paint or
varnish formulation. Furthermore, the composition of the invention
exhibits broad compatibility (criterion: e.g., bittiness, hazing
and/or clouding in the formulation) in application-relevant
formulations (e.g. binders).
[0021] Critical to the rheological performance and/or suitability
as rheology control agent is the interaction of two rheologically
active ingredients, namely the amide compound (A) and the urea
compound (B).
[0022] Besides the above-described components (A), (B), (C), and
(D), the composition of the invention may also comprise components
which are different from each of these. What is essential is that
these different (from A, B, C and D in each case) components do not
impair the quality of the composition of the invention. Said
impairments relate in particular to the suitability as
(rheological) additive. If the composition of the invention has too
high a fraction of compounds which are not very inert (e.g.,
functional groups which may give rise to crosslinking reactions),
the quality may be impaired (for example, because the storage
stability is lowered). In terms of application, moreover, the
composition of the invention ought to be readily manageable and to
contain as few components as possible which bring no benefit to the
use as additive. For the reasons above, it is possible to state the
following initially concerning the components that are different
from each of A, B, C, and D: [0023] The components that are
different from each of A, B, C, and D are present in the
composition of the invention in total preferably at not more than
50 wt %, but more preferably at not more than 30 wt %, but very
preferably at not more than 20 wt %, but especially preferably at
not more than 10 wt %. In further specific embodiments, they are
present at not more than 5 wt % and at not more than 3 wt %. In
another particularly preferred embodiment, the composition is
substantially free from components that are different from each of
A, B, C, and D. [0024] The components that are different from each
of A, B, C, and D have in their entirety preferably a hydroxyl
number of less than 15 mg KOH/g (becomes relevant if corresponding
hydroxyl-containing species are present). [0025] The components
different from each of A, B, C, and D are preferably not in the
form of crosslinking agents. Crosslinking agents in this sense are,
for example, polyisocyanates, amino resins, such as melamine
resins, urea-formaldehyde resins, and benzoguanamine resins,
polyamines, and polyepoxides. [0026] The composition of the
invention preferably contains no pigments and no solid fillers.
[0027] The composition of the invention preferably contains less
than 5 wt %, more preferably less than 3 wt %, and very preferably
less than 1 wt % of water. [0028] Organic components of the
composition of the invention, which in each case are not assigned
to components A, B, C, and D and which have a molecular weight of
more than 800 g/mol (preferably more than 500 g/mol), have in total
preferably at most a weight fraction in the composition of the
invention of 35 wt %, more preferably of at most 8 wt %.
Higher-molecular components customarily increase the viscosity and
hence the ease of handling. The molar masses of the components
having a molecular weight of up 800 g/mol (or up to 500 g/mol) can
be determined customarily by NMR, by forming ratios of the
integrals of relevant NMR resonance signals. In one particularly
preferred embodiment, the composition is substantially free from
such additional components having a molecular weight of more than
800 g/mol (preferably of more than 500 g/mol).
[0029] In one embodiment of the invention, the composition of the
invention comprises [0030] i) 30-90 wt % of the amide compound (A),
[0031] ii) 8-55 wt % of the urea compound (B), [0032] iii) 0-15 wt
% of the ionogenic compound (C), and [0033] iv) 2-25 wt % of the
organic solvent (D).
[0034] The presence of the solvent (D) may be practicable; in many
cases, alternatively, the solvent is omitted as well. In that case
it is generally useful for the mixture of the amide compound (A)
and urea compound (B) (optionally in the presence of the ionogenic
compound (C)) to be provided in liquid or single-phase form (in the
absence of D).
[0035] A high solvent fraction means that in the end application,
an undesirably high quantity of the composition in question has to
be introduced into the application system in order to achieve a
sufficiently high concentration of the active ingredient components
(A) and (B) that are active rheologically.
[0036] The organic solvent is selected by the skilled person with a
view in particular to the later use as (theological) additive (in
particular, to be sufficiently inert and fluid). Corresponding
solvents customarily have a molecular weight of not more than 250
g/mol. If solvents are used at all, it is preferred for not more
than three, more preferably not more than two solvents different
from one another to be used. Very preferably no solvent at all is
used or only one solvent at most is used.
[0037] In one preferred embodiment of the invention, the
composition of the invention comprises
i) 40-85 wt % of the amide compound (A), ii) 15-60 wt % of the urea
compound (B), iii) 0-5 wt % of an ionogenic compound (C), and iv)
0-25 wt % of the organic solvent (D).
[0038] The components that are different from each of A, B, C, and
D are then present preferably in the composition of the invention
in total with a fraction of 0-30 wt %, more preferably with a
fraction of 0-20 wt %, very preferably with a fraction of 0-10 wt
%, especially preferably with a fraction of 0-5 wt % or with a
fraction of 0-3 wt %.
[0039] In one particularly preferred embodiment of the invention,
the composition of the invention comprises
i) 45-82 wt % of the amide compound (A), ii) 18-55 wt % of the urea
compound (B), iii) 0-4 wt % of an ionogenic compound (C), and iv)
0-10 wt % of the organic solvent (D).
[0040] In one decidedly typical embodiment of the invention, the
composition of the invention comprises
i) 50-75 wt % of the amide compound (A), ii) 25-50 wt % of the urea
compound (B), iii) 0-3 wt % of an ionogenic compound (C), and iv)
0-5 wt % of the organic solvent (D).
[0041] The components that are different from each of A, B, C, and
D are then present preferably in the composition of the invention
in total with a fraction of 0-20 wt %, more preferably with a
fraction of 0-10 wt %, very preferably with a fraction of 0-5 wt %,
especially preferably with a fraction of 0-3 wt %.
[0042] In one preferred embodiment of the invention, on the one
hand 50-100 wt % of the amide compound (A) has no amide group with
hydrogen bonded to its nitrogen atom, and on the other hand this
50-100 wt % of the amide compound (A) is also present in accordance
with a general formula (I) in which none of the radicals from the
group of Ra, Rb, Rc, and Rd is represented by hydrogen.
[0043] Frequently 50-100 wt % of the amide compound (A) is present
in accordance with the general formula (Ia)
##STR00005##
[0044] Not unusually 50-100 wt % of the amide compound (A) is
present in accordance with the general formula (Ia), where Ra and
Rb and/or Rc with Rd, together with the N atom joining Ra to Rb
and/or Rc to Rd, in accordance with the general formula (.beta.-1),
together form a branched or unbranched, saturated or unsaturated
cyclic structure having 4 to 7 ring atoms which has not more than
two heteroatoms from the group consisting of O and N.
[0045] Viewed schematically, such a structure may then be present
as follows:
##STR00006##
[0046] R-Ring1 and R-Ring2 are then typically present in the form
of a bridging aliphatic radical having 4 to 6 C atoms, which
optionally includes an ether group as substituent.
[0047] Depending on the type of structure, the respective amide
compounds (A) are prepared using known methods of organic
chemistry. The above types of structure are usefully prepared
starting from dicarboxylic acids or corresponding carboxylic acids
of higher functionality, by reaction of suitable amines.
Alternatively to the corresponding carboxylic acids it is also
possible to react their reactive derivatives (e.g., anhydrides,
halides or esters) with a corresponding amine for the amidation.
One possible synthesis route lies in the reaction of a
corresponding carboxylic acid with thionyl chloride to form the
acyl chloride (typical conditions: 5 h at 60.degree. C., thionyl
chloride used optionally in excess and removed by distillation
after reaction), dissolution in an anhydrous organic solvent (e.g.,
toluene), and the reaction therein of the acyl chloride with a
suitable amine (typical conditions: start reaction at 0.degree. C.
and allow warming to room temperature over 6 h). The subsequent
purification may be accomplished for example by distillation.
[0048] Compounds of type (Ib) (see below) are prepared preferably
using corresponding cyclic amines, as for example piperidine,
pyrrolidine or morpholine. Accordingly, the preparation of
corresponding amides is described for example in U.S. Pat. No.
3,417,114. Furthermore, the preparation processes which can be used
for preparing acid amides from monocarboxylic acids can be
transposed analogously to the preparation of acid amides from
dicarboxylic acids and carboxylic acids of higher functionality:
corresponding preparation processes are for example described in
U.S. Pat. No. 2,667,511, U.S. Pat. No. 3,288,794, U.S. Pat. No.
3,751,465 or in U.S. Pat. No. 3,674,851.
[0049] In another embodiment, 50-100 wt % of the amide compound (A)
is present in accordance with the general formula (Ia), where Ra,
Rb, Rc and/or Rd in each case are not present in cyclic
structures.
[0050] According to another variant of the invention, the general
formula (I) for 50-100 wt % of the amide compound (A) is present in
accordance with the general formula (Ib)
##STR00007##
[0051] In one specific embodiment the general formula (I) for
50-100 wt % of the amide compound (A) is present in accordance with
the general formula (Ib), where Rb and Rc together with the N atom
bonded to each of Rb and Rc, and also with the radical Rz, in
accordance with the general formula (.gamma.-1), form a branched or
unbranched, saturated or unsaturated cyclic structure having 5 to 7
ring atoms which has not more than two heteroatoms from the group
consisting of O and N.
[0052] Preferred in this case is a cyclic structure having six ring
atoms, which is obtainable with particular preference by reaction
of piperazine with a corresponding carboxylic acid (or reactive
derivative thereof):
##STR00008##
[0053] In another embodiment the general formula (I) for 50-100 wt
% of the amide compound (A) is present in accordance with the
general formula (Ib), where Ra and Rb and/or Rc with Rd, together
with the CO--N moiety joining Ra to Rb and/or Rc to Rd, in
accordance with the general formula (.alpha.-1), together form a
branched or unbranched, saturated or unsaturated cyclic structure
having 4 to 10 ring atoms which has not more than two heteroatoms
from the group consisting of O and N.
[0054] This may be illustrated by way of example by the two
following structures:
##STR00009##
[0055] The radical Rz often comprises C2 to C6 alkylene radicals,
or a cyclohexylene radical or xylylene radical
(--CH.sub.2--C.sub.6H.sub.4--CH.sub.2--).
[0056] R-Ring3 and R-Ring4 are frequently present in the form of
--(CH.sub.2).sub.3-- and/or of --(CH.sub.2).sub.4--.
[0057] Particularly typically, R-Ring3 and R-Ring4 are each present
in the form of --(CH.sub.2).sub.3--.
[0058] Depending on the type of structure, the respective amide
compounds (A) are prepared using known methods of organic
chemistry. For example, by reaction of alkylenediamines,
arylenediamines, and alkylarylenediamines or (poly)etherdiamines
(where R possesses no further amino or amide groups) or of
corresponding polyamines of higher functionality (where R does
possess further amino or amide groups) with corresponding,
optionally substituted carboxylic acids or derivatives thereof
(e.g., halides, anhydrides, esters, and--as a special case of
esters--lactones as well). Other types of structure are prepared
preferably by reaction of corresponding diamines or polyamines with
corresponding lactones. The preparation of further types is
described for example in U.S. Pat. No. 5,326,880, U.S. Pat. No.
3,989,815, and in U.S. Pat. No. 6,497,886.
[0059] The rheological activity of the amide compound (A) is
boosted significantly by the presence of the urea compound (B).
[0060] Frequently 70-100 wt % of the urea compound (B) either has
at least two urea groups or has at least one urea group and at
least one urethane group.
[0061] In one embodiment 50-100 wt % of the urea compound (B) is
present in accordance with the general formula (II)
R.sup.31--[R.sup.33--Z--R.sup.34--W-].sub.nR.sup.32 (II) [0062]
where [0063] R.sup.31 and R.sup.32 each identically or differently
and also each independently of one another are represented by a
branched or unbranched, saturated or unsaturated organic radical
which contains 1-100 carbon atoms and which has not more than one
urea group each and not more than one urethane group each, [0064]
R.sup.33 and R.sup.34 each identically or differently and also each
independently of one another are represented by branched or
unbranched polyester radicals containing 1-300 carbon atoms and
optionally containing ether groups, branched or unbranched
polyether radicals containing 2-300 carbon atoms, branched or
unbranched polyamide radicals containing 1-300 carbon atoms,
polysiloxane radicals containing 3 to 100 silicon atoms, branched
or unbranched C2-C22 alkylene radicals, branched or unbranched
C3-C18 alkenylene radicals, C5-C12 arylene radicals and/or branched
or unbranched C7-C22 arylalkylene radicals, [0065] Z and W each
identically or differently and also each independently of one
another are represented by NH--CO--O and/or NH--CO--NH, [0066] n is
in each case identical or different and is represented by an
integer from 1 to 150, preferably from 2 to 120.
[0067] Not unusually 50-100 wt % of the urea compound (B) has in
each case a molecular weight of 2000 to 55000 and also 4-150 urea
groups.
[0068] In one specific embodiment 50-100 wt % of the urea compound
(B) is present in each case in accordance with one of the general
formulae selected from the group consisting of (IIIa), (IIIb),
(IIIc), and (IIId)
##STR00010##
where AM is identical or different and is represented by a linear
or branched, saturated or unsaturated, aliphatic, aromatic or
aliphatic-aromatic organic radical having 2 to 50 C atoms, AM1 and
AM2 in each case are identical or different and in each case
independently of one another represented by a linear or branched,
saturated or unsaturated, aliphatic, aromatic or aliphatic-aromatic
organic radical having 1 to 50 C atoms, IC1 and IC2 are in each
case identical or different and in each case independently of one
another represented by a linear or branched, saturated or
unsaturated, aliphatic, aromatic or aliphatic-aromatic hydrocarbon
radical having 2 to 40 C atoms, IC3 is identical or different and
is represented by a linear or branched, saturated or unsaturated,
aliphatic, aromatic or aliphatic-aromatic hydrocarbon radical
having 2 to 24 carbon atoms, RP1 and RP2 are in each case identical
or different and in each case independently of one another
represented by a linear or branched, saturated or unsaturated,
aliphatic, aromatic or aliphatic-aromatic organic radical having 1
to 24 C atoms and/or by a polyether radical having 1 to 120 ether
oxygen atoms and/or by a polyester radical having 1 to 100 ester
groups and optionally containing ether groups, and/or by a
polyamide radical having 1 to 100 amide groups, and/or by a
polysiloxane radical having 3 to 100 silicon atoms, RP3 is
identical or different and is represented by a linear or branched,
saturated or unsaturated, aliphatic, aromatic or aliphatic-aromatic
hydrocarbon radical having 2 to 24 C atoms and/or by a (poly)ether
radical having 1 to 120 ether oxygen atoms and/or by a polyamide
radical having 1 to 100 amide groups and/or by a polysiloxane
radical having 3 to 100 silicon atoms and/or by a polyester radical
having 1 to 100 ester groups and optionally containing ether
groups, and p is identical or different and is represented by 0
and/or 1.
[0069] Frequently 70-100 wt % of the urea compound (B) is present
in each case in accordance with one of the general formulae
selected from the group consisting of (IIIa), (IIIb), (IIIb), and
(IIId), where
[0070] AM is identical or different and is selected from the group
consisting of
##STR00011##
where R.sub.x and R.sub.y are identical or different and are in
each case independently represented by CH.sub.3 and/or
hydrogen,
(CH.sub.2).sub.q
where q is identical or different and is represented by an integer
from 2 to 12, AM1 and AM2 are each identical or different and are
selected from the group consisting of n-propyl, isopropyl, butyl,
isobutyl, tert-butyl, lauryl, oleyl, stearyl, polyisobutylene, and
polyethers having 2 to 40 ether oxygen atoms, benzyl, methylbenzyl,
cyclohexyl, carboxyalkyl, hydroxyalkyl, and alkylalkoxysilane, IC1
and IC2 are each identical or different and are selected from the
group consisting of
##STR00012##
IC3 is identical or different and is selected from the group
consisting of methyl, ethyl, phenyl, benzyl, cyclohexyl, and
stearyl, RP1 and RP2 are each identical or different and are
selected from the group consisting of branched or unbranched C1 to
C18 alkyl, oleyl, benzyl, allyl, polyether radical preferably
containing structural units of ethylene oxide, propylene oxide
and/or butylene oxide, and polyester radical containing structural
units of epsilon-caprolactone and/or delta-valerolactone, RP3 is
identical or different and is selected from the group consisting of
linear or branched C1 to C18 alkylene, linear or branched C2 to C18
alkenylene, polyether preferably containing structural units of
ethylene oxide, propylene oxide and/or butylene oxide and having 1
to 25 ether oxygen atoms.
[0071] In one specific embodiment 70-100 wt % of the urea compound
(B) in each case is preparable by reaction of monofunctional amines
with isocyanates oligomerized by isocyanurate formation and/or
uretdione formation.
[0072] In one typical embodiment 95-100 wt %, preferably 98-100 wt
%, of the urea compound (B) contains in each case at least
one molecule segment of the general formula (IVa)
--O--CO--NH--Y.sub.1--NH--CO--NH-- (IVa)
where Y.sub.1 is identical or different and is represented by a
saturated or unsaturated, branched or unbranched hydrocarbon
radical containing 6 to 20 carbon atoms, and in each case contains
no molecule segment of the general formula (IVb)
--O--CO--NH--Y.sub.2--NH--CO--O-- (IVb)
where Y.sub.2 is identical or different and is represented by a
saturated or unsaturated, branched or unbranched hydrocarbon
radical containing 6 to 20 carbon atoms.
[0073] The urea compounds (B) may be prepared in a known way by
reaction of corresponding isocyanates with amines. Preparation
processes for urea compounds of this kind are described in more
detail for example in EP 0006252, DE 2822908, DE 10241853, DE
19919482, EP 1188779, and in DE 102008059702.
[0074] The preparation in particular of higher-molecular polyurea
compounds is described for example in EP 2292675.
[0075] In one embodiment of the invention, the composition of the
invention comprises the ionogenic compound (C). This compound is
usually present in the form of a salt, preferably a lithium,
calcium or magnesium salt, more preferably a lithium or calcium
salt. Preferred as anion (counterion) is halide, pseudohalide,
formate, acetate and/or nitrate, more preferably chloride, acetate
and/or nitrate. The ionogenic compounds (C) also include ionic
liquids, which are not organic solvents in the sense of the
invention.
[0076] In one embodiment of the invention, the composition of the
invention comprises 0.5-4.0 wt % of the ionogenic compound (C),
where 50-100 wt % of the ionogenic compound (C) is present in the
form of lithium salt or calcium salt, preferably in the form of the
chloride, acetate and/or nitrate thereof.
[0077] The composition of the invention is suitable preferably for
rheology control, more particularly for thixotroping, of liquid
systems or liquid mixtures.
[0078] These liquid mixtures are present preferably in the form of
a coating, more particularly a paint or varnish, a plastics
formulation, a pigment paste, a sealant formulation, cosmetics, a
ceramic formulation, an adhesive formulation, an encapsulating
composition, a building material formulation, a lubricant, a
filling compound, a printing ink or a liquid ink (e.g., an inkjet
ink). A further use as auxiliaries for drift reduction or drift
avoidance in the context of spraying operations ("drift
reduction/deposition aids") is possible.
[0079] The composition of the invention is suitable for rheology
control, more particularly for thixotroping, of liquid systems.
[0080] The invention also relates to the use of the composition of
the invention for rheology control, more particularly for
thixotroping, of a liquid mixture.
[0081] The liquid mixture may be present in the form of a coating,
more particularly a paint or varnish, a plastics formulation, a
pigment paste, a sealant formulation, cosmetics, a ceramic
formulation, an adhesive formulation, an encapsulating composition,
a drilling mud solution, a building material formulation, a
lubricant, a filling compound, a printing ink or a liquid ink.
[0082] Lastly the present invention relates to a preparation which
is present in the form of a paint or varnish, a plastics
formulation, a pigment paste, a sealant formulation, cosmetics, a
ceramic formulation, an adhesive formulation, an encapsulating
composition, a building material formulation, a lubricant, a
drilling mud solution, a filling compound, a printing ink or a
liquid ink and to which 0.1 to 7.5 wt % of the composition of the
invention has been added.
[0083] Particularly preferred is the use of the composition of the
invention as rheology control agent, preferably as thixotropic
agent, for the rheology control of paints and varnishes, printing
inks, liquid inks (such as inkjet inks, for example), plastics
formulations, cosmetic preparations, building material
formulations, formulations for use in petroleum and natural gas
extraction, lubricants and/or adhesives.
[0084] The paints and varnishes, printing inks and liquid (inkjet)
inks may be alternatively solvent-containing or else solvent-free
or water-based paints and varnishes, printing inks, and liquid
inkjet inks. Paints and varnishes can be used in a very wide
variety of fields of application, in sectors including automobile
finishes, architectural coatings, protective coatings (painting of
ships and bridges, among others), can coatings and coil coatings,
wood coatings and furniture coatings, industrial coatings, coating
systems for plastics, wire enamels, coatings on foods and seed, and
also as what are called color resists, which are used for color
filters in LC displays, for example. The sector of application of
paints and varnishes also includes paste-like materials, which
generally have a very high fraction of solid material and a low
fraction of liquid components, examples being pigment pastes or
else pastes based on finely divided metal particles or metal
powders (based for example on silver, copper, zinc, aluminum,
bronze, brass).
[0085] The plastics formulations may comprise the (liquid) starting
materials for the production of plastics materials, which are
reacted preferably by a chemical crosslinking process ("curing" to
give a thermoset). Preferred plastics preparations are therefore
unsaturated polyester resins, vinyl ester resins, acrylate resins,
epoxy resins, polyurethane resins, formaldehyde resins (such as
melamine-formaldehyde or urea-formaldehyde). They may be cured
under a wide variety of different conditions, as for example at
room temperature (cold-curing systems) or at elevated temperature
(hot-curing systems), where appropriate also with application of
pressure ("closed mold" application, sheet molding compound or bulk
molding compound). The preferred plastics formulations also include
PVC plastisols.
[0086] The cosmetic preparations may comprise diverse liquid
compositions which are used in the personal care or else health
care sectors, as for example lotions, creams, pastes (e.g.,
toothpaste), foams (e.g., shaving foam), gels (e.g., shaving gel,
shower gel, active pharmaceutical ingredients formulated as gels),
hair shampoo, liquid soaps, nail varnishes, lipsticks, hair
colorants.
[0087] The building material formulations may comprise materials
which are liquid or pastelike on processing and which are employed
in the construction sector and become solid after hardening, as for
example hydraulic binders such as concrete, cement, mortar, tile
adhesive, plaster.
[0088] The lubricants are agents which are used for lubrication, in
other words which serve to reduce friction and wear, and also for
force transmission, cooling, vibration damping, sealing, and
corrosion control, with preference here being given to liquid
lubricants and lubricating greases. Additionally, slip agents and
drilling fluids (the latter as used in petroleum extraction) are
included in terms of definition among the lubricants.
[0089] The adhesives may be all processing materials which are
liquid under processing conditions and which are able to join
adherends by surface adhesion and internal strength. Adhesives may
be solvent-containing, solvent-free or water-based.
[0090] The invention will be elucidated in more detail below, using
examples.
[0091] In the examples which follow, the amine number was
determined according to DIN 16945. In analogy, the OH number was
determined according to DIN/ISO 4629.
[0092] Commercial raw materials employed were as follows:
TABLE-US-00001 Name Description Manufacturer Borchi Nox M 2
Synthetic OMG Borchers GmbH antiskinning agent (methyl ethyl
ketoxime) BYK-066 Silicone- BYK-Chemie GmbH containing defoamer
Dowanol PM Methoxypropanol Dow Chemical Company Dowanol PMA
1,2-Propanediol Dow Chemical monoacetate Company monomethyl ether
Epikote 1001-X 75 Bisphenol A Hexion Specialty resin, in Chemicals
solution in xylene Isopar H Hydrocarbon ExxonMobil solvent with low
Chemical odor and low aromatic fraction (primarily consisting of
isoalkanes) Kraton 1118 AS Styrene-butadiene Kraton block copolymer
Performance Polymers Nuodex Combi APB Lead-free and Elementis
barium-free Specialties B.V. combination drier Palapreg P 17-02
Unsaturated DSM Composite polyester resin Resins for producing
fiber-reinforced plastics or unreinforced filled products Palapreg
H814-01 Solution of DSM Composite polystyrene in Resins styrene
Setalux D A 870 Polyisocyanate- Nuplex Resins BA crosslinking GmbH
acrylate resin, 70% in butyl acetate Synthalat W48 Water-thinnable,
Synthopol Chemie specially modified alkyd resin, approx- imately
35% in BG/ammonia/ water (8:2.3:54.7) Worleekyd S 366 Long-oil
alkyd Worlee Chemie resin, 60% in GmbH Isopar H Worleekyd S 351
Medium-fatty, Worlee Chemie air-drying alkyd GmbH resin modified
with soybean oil
Example 1b
[0093] A reaction vessel (round-bottom flask with stirrer, reflux
condenser, water separator, and dropping funnel) was charged under
a nitrogen atmosphere at 60.degree. C. with 412.5 g (2.48 mol) of
hexamethylenediamine in the form of a 70% strength aqueous
solution. Over the course of minutes, with stirring, 430.0 g (5.0
mol) of butyrolactone were added dropwise. The exothermic reaction
raised the temperature to 90.degree. C. Then 0.4 g of
p-toluenesulfonic acid was added.
[0094] The temperature was raised via 20-minute temperature ramps,
by 10.degree. C. in each case, to 170.degree. C. This was followed
by heating to a final temperature of 250.degree. C., which was
maintained for 18.5 hours. Throughout the reaction time, the water
of reaction was removed from the reaction mixture by distillation.
The reaction product is a yellow, slightly viscous liquid having an
amine number of 15.4 mg KOH/g.
[0095] For the removal of residual reactants, the reaction product
was purified by distillation with a thin-film evaporator at
120.degree. C. and <1 mbar. The amine number thereafter was
<1 mg KOH/g.
Example 2b
[0096] A reaction vessel (round-bottom flask with stirrer, reflux
condenser, water separator, and dropping funnel) was charged under
a nitrogen atmosphere at 60.degree. C. with 42.0 g (0.7 mol) of
ethylenediamine. Over the course of 45 minutes, with stirring,
132.6 g (1.54 mol) of butyrolactone were added dropwise. The
exothermic reaction raised the temperature to 140.degree. C.
[0097] The temperature was thereafter raised via 45-minute
temperature ramps, by 10.degree. C. in each case, to 250.degree. C.
This final temperature was maintained for 9 hours. Throughout the
reaction time, the water of reaction was removed from the reaction
mixture by distillation. The end product is crystalline.
Example 3b
[0098] A reaction vessel (round-bottom flask with stirrer, reflux
condenser, water separator, and dropping funnel) was charged under
a nitrogen atmosphere at 60.degree. C. with 74.1 g (1.0 mol) of
1,3-propanediamine. Over the course of 75 minutes, with stirring,
189.4 g (2.2 mol) of butyrolactone were added dropwise. The
exothermic reaction raised the temperature to 120.degree. C. Then
0.4 g of p-toluenesulfonic acid was added.
[0099] The temperature was thereafter raised via 45-minute
temperature ramps, by 10.degree. C. in each case, to 250.degree. C.
This final temperature was maintained for 9 hours. Throughout the
reaction time, the water of reaction was removed from the reaction
mixture by distillation. The reaction product had a hydroxyl number
of 4.0.
Example 4b
[0100] A reaction vessel (round-bottom flask with stirrer, reflux
condenser, water separator, and dropping funnel) was charged under
a nitrogen atmosphere at 60.degree. C. with 37.1 g (0.5 mol) of
1,2-propanediamine. Over the course of 40 minutes, with stirring,
94.7 g (1.1 mol) of butyrolactone were added dropwise. The
exothermic reaction raised the temperature to 110.degree. C.
[0101] The temperature was thereafter raised via 45-minute
temperature ramps, by 10.degree. C. in each case, to 250.degree. C.
This final temperature was maintained for 9 hours. Throughout the
reaction time, the water of reaction was removed from the reaction
mixture by distillation. The end product is crystalline.
Example 5b
[0102] A reaction vessel (round-bottom flask with stirrer, reflux
condenser, water separator, and dropping funnel) was charged under
a nitrogen atmosphere at 60.degree. C. with 64.9 g (0.73 mol) of
1,4-diaminobutane. Over the course of 30 minutes, with stirring,
69.7 g (0.81 mol) of butyrolactone were added dropwise. The
exothermic reaction raised the temperature to 100.degree. C.
[0103] The temperature was thereafter raised via 45-minute
temperature ramps, by 10.degree. C. in each case, to 250.degree. C.
This final temperature was maintained for 9 hours. Throughout the
reaction time, the water of reaction was removed from the reaction
mixture by distillation. The end product is crystalline.
Example 6b
[0104] A reaction vessel (round-bottom flask with stirrer, reflux
condenser, water separator, and dropping funnel) was charged under
a nitrogen atmosphere at 100.degree. C. with 72.1 g (0.5 mol) of
melted 1,8-octamethylenediamine. Over the course of 20 minutes,
with stirring, 94.7 g (1.1 mol) of butyrolactone were added
dropwise. The exothermic reaction raised the temperature to
160.degree. C.
[0105] The temperature was thereafter raised via 45-minute
temperature ramps, by 10.degree. C. in each case, to 250.degree. C.
This final temperature was maintained for 12 hours. Throughout the
reaction time, the water of reaction was removed from the reaction
mixture by distillation. The end product is liquid.
Example 7b
[0106] A reaction vessel (round-bottom flask with stirrer, reflux
condenser, water separator, and dropping funnel) was charged under
a nitrogen atmosphere at 80.degree. C. with 84.1 g (0.42 mol) of
melted dodecanediamine. Over the course of 20 minutes, with
stirring, 79.5 g (0.92 mol) of butyrolactone were added dropwise.
The exothermic reaction raised the temperature to 135.degree.
C.
[0107] The temperature was thereafter raised via 20-minute
temperature ramps, by 10.degree. C. in each case, to 250.degree. C.
This final temperature was maintained for 11 hours. 0.4 g of
p-toluenesulfonic acid was added. Throughout the reaction time, the
water of reaction was removed from the reaction mixture by
distillation. The end product is solid and bright red in color.
Example 8b
[0108] A reaction vessel (round-bottom flask with stirrer, reflux
condenser, water separator, and dropping funnel) was charged under
a nitrogen atmosphere at 30.degree. C. with 68.1 g (0.5 mol) of
m-xylylenediamine. Over the course of 10 minutes, with stirring,
94.1 g (1.1 mol) of butyrolactone were added dropwise. The batch
was heated initially to 100.degree. C., then the temperature was
raised via 20-minute temperature ramps by 10.degree. C. in each
case. At 120.degree. C., an exothermic reaction was ascertainable.
The temperature rose to 170.degree. C. Thereafter the temperature
was raised further via 20-minute temperature ramps by 10.degree. C.
in each case up to 250.degree. C., and was maintained for 7 hours.
0.4 g of p-toluenesulfonic acid was added, and stirring was
continued at 250.degree. C. for 6 hours more. Throughout the
reaction time, the water of reaction was removed from the reaction
mixture by distillation. The reaction product is an orange-colored
liquid of high viscosity with an amine number of 0.6 mg KOH/g.
Example 9b
[0109] A reaction vessel (round-bottom flask with stirrer, reflux
condenser, water separator, and dropping funnel) was charged under
a nitrogen atmosphere at 30.degree. C. with 57.1 g (0.5 mol) of
1,2-diaminocyclohexane. Over the course of 10 minutes, with
stirring, 94.1 g (1.1 mol) of butyrolactone were added dropwise.
The temperature was raised via 20-minute temperature ramps by
10.degree. C. in each case. At 90.degree. C., an exothermic
reaction was ascertainable. The temperature rose to 104.degree. C.
Thereafter the temperature was raised further via 20-minute
temperature ramps, by 10.degree. C. in each case, to 250.degree.
C., and was maintained for 6 hours. 0.4 g of p-toluenesulfonic acid
was added, and stirring was continued at 250.degree. C. for 6 hours
more. Throughout the reaction time, the water of reaction was
removed from the reaction mixture by distillation. The end product
is solid.
Example 10b
[0110] A reaction vessel (round-bottom flask with stirrer, reflux
condenser, water separator, and dropping funnel) was charged under
a nitrogen atmosphere at 30.degree. C. with 68.1 g (0.4 mol) of
isophoronediamine. Over the course of 10 minutes, with stirring,
75.8 g (0.88 mol) of butyrolactone were added dropwise. The batch
was heated initially to 100.degree. C., then the temperature was
raised via 20-minute temperature ramps by 10.degree. C. in each
case. At 120.degree. C., an exothermic reaction was ascertainable.
The temperature rose to 160.degree. C. Thereafter the temperature
was raised further via 20-minute temperature ramps, by 10.degree.
C. in each case, to 250.degree. C., and was maintained for 6 hours.
0.4 g of p-toluenesulfonic acid was added, and stirring was
continued at 250.degree. C. for 6 hours more. Throughout the
reaction time, the water of reaction was removed from the reaction
mixture by distillation. The reaction product is a liquid having an
amine number of 15.6 mg KOH/g.
Example 11b
[0111] A reaction vessel (round-bottom flask with stirrer, reflux
condenser, water separator, and dropping funnel) was charged under
a nitrogen atmosphere at 30.degree. C. with 92.0 g (0.4 mol) of
polyetherdiamine (Jeffamine D230 from Huntsman). Over the course of
10 minutes, with stirring, 75.8 g (0.88 mol) of butyrolactone were
added dropwise. The temperature was via 20-minute temperature
ramps, by 10.degree. C. in each case, to 250.degree. C. maintained
at this temperature for 6 hours. 0.4 g of p-toluenesulfonic acid
was added and stirring continued at 250.degree. C. for 6 hours
more. Throughout the reaction time, the water of reaction was
removed from the reaction mixture by distillation. The end product
is a slightly viscous liquid having an amine number of 6 mg
KOH/g.
Example 12b
[0112] A reaction vessel (round-bottom flask with stirrer, reflux
condenser, water separator, and dropping funnel) was charged under
a nitrogen atmosphere at 30.degree. C. with 120.0 g (0.3 mol) of
polyetherdiamine (Jeffamine D400 from Huntsman). Over the course of
10 minutes, with stirring, 56.8 g (0.66 mol) of butyrolactone were
added dropwise. The temperature was via 20-minute temperature
ramps, by 10.degree. C. in each case, to 250.degree. C. maintained
at this temperature for 6 hours. 0.4 g of p-toluenesulfonic acid
was added and stirring continued at 250.degree. C. for 6 hours
more. Throughout the reaction time, the water of reaction was
removed from the reaction mixture by distillation. The end product
is a slightly viscous liquid having an amine number of 7.7 mg
KOH/g.
Example 13b
[0113] A reaction vessel (round-bottom flask with stirrer, reflux
condenser, water separator, and dropping funnel) was charged under
a nitrogen atmosphere at 80.degree. C. with 200.0 g (0.1 mol) of
polyetherdiamine (Jeffamine D2000 from Huntsman). Over the course
of 10 minutes, with stirring, 18.9 g (0.22 mol) of butyrolactone
were added dropwise. The temperature was via 20-minute temperature
ramps, by 10.degree. C. in each case, to 200.degree. C. maintained
at this temperature for 6 hours. 0.4 g of p-toluenesulfonic acid
was added and stirring continued at 250.degree. C. for 6 hours
more. Throughout the reaction time, the water of reaction was
removed from the reaction mixture by distillation. The end product
is a viscous liquid having an amine number of 6.5 mg KOH/g.
Example 14b
[0114] A reaction vessel (round-bottom flask with stirrer, reflux
condenser, water separator, and dropping funnel) was charged under
a nitrogen atmosphere at 80.degree. C. with 81.7 g (0.39 mol) of
4,9-dioxadecane-1,2-diamine. Over the course of 10 minutes, with
stirring, 75.7 g (0.87 mol) of butyrolactone were added dropwise.
The temperature was via 20-minute temperature ramps, by 10.degree.
C. in each case, to 200.degree. C. maintained at this temperature
for 6 hours. 0.4 g of p-toluenesulfonic acid was added and stirring
continued at 250.degree. C. for 6 hours more. Throughout the
reaction time, the water of reaction was removed from the reaction
mixture by distillation. The end product is a slightly viscous
liquid having an amine number of 3.5 mg KOH/g.
Example 15b
[0115] A reaction vessel (round-bottom flask with stirrer, dropping
funnel, and reflux condenser) was charged under a nitrogen
atmosphere with 315.0 g (1.9 mol) of dimethyl glutarate and 508.0 g
(3.8 mol) of dibutylamine. The reaction mixture was stirred at
100.degree. C. for 2 hours. Then a water separator was connected to
the apparatus and the temperature was raised to 170.degree. C. In
this procedure, 200 g of methanol were separated off. After the end
of the reaction time, the reaction mixture had an amine number of
73 mg KOH/g.
[0116] For the removal of residual reactants, the reaction product
was purified by distillation using a thin-film evaporator at
120.degree. C. and <1 mbar. The amine number thereafter was
<4.5 mg KOH/g.
Example 16b
[0117] In a four-neck flask with stirrer, thermometer and water
separator, 84.0 g of 5-(dimethylamino)-2-methyl-5-oxomethyl
pentanoate (0.449 mol) and 116.0 g of dibutylamine (0.898 mol) are
heated at 150.degree. C. with stirring. The methanol produced is
separated off on a water separator. The mixture is heated at this
temperature for 16 hours. It is then heated to 170.degree. C. and a
vacuum of 0.8 mbar is applied for 2 hours to remove volatile
constituents. The clear, liquid product obtained is checked by IR
spectroscopy for the absence of the ester band at 1711 cm.sup.-1:
no ester band was detected. Yield: 119 g of clear liquid (=93% of
the theoretical yield).
Example 17b
[0118] In a four-neck flask with stirrer, thermometer and water
separator, 90.8 g of 5-(dimethylamino)-2-methyl-5-oxomethyl
pentanoate (0.485 mol) and 130.0 g of oleylamine (0.482 mol) are
heated at 150.degree. C. with stirring. The methanol produced is
separated off on a water separator. The mixture is heated at this
temperature for 10 hours. It is then cooled to 80.degree. C. and at
this temperature a vacuum of 0.8 mbar is applied for 2 hours to
remove the residual volatile constituents. The clear, liquid
product obtained is checked by IR spectroscopy for the absence of
the ester band at 1711 cm.sup.-1: no ester band was detected.
Yield: 198 g of clear paste-like fluid (=97% of the theoretical
yield).
Example 18t
[0119] In a four-neck flask with stirrer, dropping funnel,
thermometer and water separator, 140.8 g of
5-(dimethylamino)-2-methyl-5-oxomethyl pentanoate (0.752 mol) and
43.7 g of 1,6-hexamethylenediamine (0.376 mol) are heated at
180.degree. C. with stirring. The methanol produced is separated
off on a water separator. The mixture is heated at this temperature
for 10 hours. It is then cooled to 150.degree. C. and at this
temperature a vacuum of 0.8 mbar is applied for 2 hours to remove
the residual volatile constituents.
[0120] The clear, liquid product obtained is checked by IR
spectroscopy for the absence of the ester band at 1711 cm.sup.-1:
no ester band was detected. Yield: 150 g of viscous clear liquid
(=94% of the theoretical yield).
Example 19t
[0121] In a four-neck flask with stirrer, dropping funnel,
thermometer and water separator, 150.3 g of
5-(dimethylamino)-2-methyl-5-oxomethyl pentanoate (0.803 mol) and
54.6 g of meta-xylylenediamine (0.402 mol) are heated at
150.degree. C. with stirring. The methanol produced is separated
off on a water separator. The mixture is heated at this temperature
for 11 hours. Subsequently at 150.degree. C. a vacuum of 0.8 mbar
is applied for 2 hours in order to remove the residual volatile
constituents. The clear, liquid product obtained is checked by IR
spectroscopy for the absence of the ester band at 1711 cm.sup.-1:
no ester band was detected.
Example 20p
[0122] In a four-neck flask with stirrer, dropping funnel,
thermometer and water separator, 160.2 g of
5-(dimethylamino)-2-methyl-5-oxomethyl pentanoate (0.856 mol) and
44.2 g of diethylenetriamine (0.428 mol) are heated at 180.degree.
C. with stirring. The methanol produced is separated off on a water
separator. The mixture is heated at this temperature for 15 hours.
It is then cooled to 150.degree. C. and at this temperature a
vacuum of 0.8 mbar is applied for 2 hours to remove the residual
volatile constituents. The clear, liquid product obtained is
checked by IR spectroscopy for the absence of the ester band at
1711 cm.sup.-1: no ester band was detected. Yield: 168 g of solid
product (=95% of the theoretical yield).
[0123] After the end of the reaction, the water of reaction formed
was removed by distillation on a rotary evaporator. Pale yellow
liquid with an amine number of 4 mg KOH/g was obtained.
Composition K1:
Stage 1
[0124] First of all 64.4 g of a diisocyanate monoadduct are
prepared in accordance with patent specification EP 1188779 from a
polyethylene glycol monobutyl ether having a hydroxyl number of 220
mg KOH/g (determined according to DIN/ISO 4629) and a mixture of
35% 2,4-tolylene diisocyanate and 65% 2,6-tolylene
diisocyanate.
Stage 2
[0125] A four-neck flask is provided with stirrer, dropping funnel,
thermometer, and reflux condenser. It is charged with 118.2 g of
the reaction product from example 1b, which is heated under a
nitrogen atmosphere with stirring to 120.degree. C. 4.2 g of
lithium chloride are added and at this temperature are dissolved
with stirring in one hour. Temperature is then lowered to
80.degree. C. 10.2 g of m-xylylenediamine are added and the mixture
is homogenized.
[0126] The isocyanate adduct prepared beforehand (stage 1) is added
dropwise with stirring over the course of 1 hour to the amine
solution at a slow rate such that the temperature does not exceed
85.degree. C. To complete the reaction, the reaction mixture is
stirred at 80.degree. C. for a further three hours. The amine
number is 3.6 mg KOH/g (determined according to DIN 16945). The
product is a liquid of high viscosity and contains 38 wt % of the
urea compound.
Composition K2:
Stage 1
[0127] First of all 64.4 g of a diisocyanate monoadduct are
prepared in accordance with patent specification EP 1188779 from a
polyethylene glycol monobutyl ether having a hydroxyl number of 220
mg KOH/g (determined according to DIN/ISO 4629) and a mixture of
35% 2,4-tolylene diisocyanate and 65% 2,6-tolylene
diisocyanate.
Stage 2
[0128] A four-neck flask is provided with stirrer, dropping funnel,
thermometer, and reflux condenser. It is charged with 188 g of the
reaction product from example 8b, which is heated under a nitrogen
atmosphere with stirring to 120.degree. C. 5.1 g of lithium
chloride are added and at this temperature are dissolved with
stirring in one hour. Temperature is then lowered to 80.degree. C.
10.2 g of m-xylylenediamine are added and the mixture is
homogenized.
[0129] The isocyanate adduct prepared beforehand (stage 1) is added
dropwise with stirring over the course of 1 hour to the amine
solution at a slow rate such that the temperature does not exceed
85.degree. C. To complete the reaction, the reaction mixture is
stirred at 80.degree. C. for a further three hours. A cloudy,
colorless, and slightly viscous product is obtained. The amine
number is 3 mg KOH/g (determined according to DIN 16945). The
product contains 28 wt % of the urea compound.
Composition K3:
Stage 1
[0130] First of all 64.4 g of a monoadduct are prepared in
accordance with patent specification EP 1188779 from a polyethylene
glycol monomethyl ether having a molar mass of 450 g/mol and a
mixture of 35% 2,4-tolylene diisocyanate and 65% 2,6-tolylene
diisocyanate.
Stage 2
[0131] In a four-neck flask with stirrer, dropping funnel,
thermometer, and reflux condenser, 187.8 g of the reaction product
from example 7b are heated to 100.degree. C. and, when the
temperature is reached, 5.9 g of lithium chloride are added. The
lithium chloride is thereafter dissolved with stirring at
100.degree. C. within one hour. The temperature is then lowered to
80.degree. C.
[0132] 10.2 g of m-xylylenediamine are added and the mixture is
homogenized.
[0133] The isocyanate adduct prepared beforehand (stage 1) is added
dropwise with stirring over the course of 1 hour to the amine
solution at a slow rate such that the temperature does not exceed
85.degree. C. To complete the reaction, the reaction mixture is
stirred at 80.degree. C. for three hours. A brownish and waxlike
product is obtained which is liquid at 80.degree. C. The product
contains 28 wt % of the urea compound.
Composition K4:
Stage 1
[0134] First of all 64.4 g of a monoadduct are prepared in
accordance with patent specification EP 1188779 from a polyethylene
glycol monomethyl ether having a molar mass of 450 g/mol and a
mixture of 35% 2,4-tolylene diisocyanate and 65% 2,6-tolylene
diisocyanate.
Stage 2
[0135] In a four-neck flask with stirrer, dropping funnel,
thermometer, and reflux condenser, 187.8 g of the reaction product
from example 11b are heated to 100.degree. C. and, when the
temperature is reached, 4.2 g of lithium chloride are added. The
lithium chloride is thereafter dissolved with stirring at
100.degree. C. within one hour. The temperature is then lowered to
80.degree. C.
[0136] 10.2 g of m-xylylenediamine are added and the mixture is
homogenized.
[0137] The isocyanate adduct prepared beforehand (stage 1) is added
dropwise with stirring over the course of 1 hour to the amine
solution at a slow rate such that the temperature does not exceed
85.degree. C. To complete the reaction, the reaction mixture is
stirred at 80.degree. C. for three hours. A cloudy and viscous
product is obtained. The product contains 28 wt % of the urea
compound.
Composition K5:
Stage 1
[0138] First of all 64.4 g of a diisocyanate monoadduct are
prepared in accordance with patent specification
[0139] EP 1188779 from a polyethylene glycol monobutyl ether having
a hydroxyl number of 220 mg KOH/g (determined according to DIN/ISO
4629) and a mixture of 35% 2,4-tolylene diisocyanate and 65%
2,6-tolylene diisocyanate.
Stage 2
[0140] A four-neck flask is provided with stirrer, dropping funnel,
thermometer, and reflux condenser. It is charged with 239.1 g of a
mixture of the reaction product from example 15b, which is heated
under a nitrogen atmosphere with stirring to 120.degree. C. 5.1 g
of lithium chloride are added and at this temperature are dissolved
with stirring in one hour. Temperature is then lowered to
80.degree. C. 10.2 g of m-xylylenediamine are added and the mixture
is homogenized.
[0141] The isocyanate adduct prepared beforehand (stage 1) is added
dropwise with stirring over the course of 1 hour to the amine
solution at a slow rate such that the temperature does not exceed
85.degree. C. To complete the reaction, the reaction mixture is
stirred at 80.degree. C. for a further three hours. A cloudy and
viscous product is obtained. The product contains 23 wt % of the
urea compound.
Composition K6:
Stage 1
[0142] First of all 64.4 g of a diisocyanate monoadduct are
prepared in accordance with patent specification EP 1188779 from a
polyethylene glycol monobutyl ether having a hydroxyl number of 220
mg KOH/g (determined according to DIN/ISO 4629) and a mixture of
35% 2,4-tolylene diisocyanate and 65% 2,6-tolylene
diisocyanate.
Stage 2
[0143] A four-neck flask is provided with stirrer, dropping funnel,
thermometer, and reflux condenser. It is charged with 31.2 g of the
reaction product from example 14b, which is heated under a nitrogen
atmosphere with stirring to 120.degree. C. 0.7 g of lithium
chloride is added and at this temperature is dissolved with
stirring in one hour. Temperature is then lowered to 80.degree. C.
3.0 g of m-xylylenediamine are added and the mixture is
homogenized.
[0144] 17.1 g of the isocyanate adduct prepared in stage 1 are
added dropwise with stirring over the course of 1 hour to the amine
solution at a slow rate such that the temperature does not exceed
85.degree. C. To complete the reaction, the reaction mixture is
stirred at 80.degree. C. for a further three hours. The product
contains 39 wt % of the urea compound.
Composition K7:
Stage 1
[0145] First of all a monoadduct is prepared in accordance with
patent specification EP 1188779 from 2,4-tolylene diisocyanate
(Desmodur T100, Bayer) and 1-dodecanol.
Stage 2
[0146] In a reaction vessel (round-bottom flask with stirrer,
reflux condenser, and dropping funnel), under a nitrogen atmosphere
and with stirring, 12.6 g (0.3 mol) of LiCl are dissolved in 280 g
of the reaction product from example 1b. Then 13.6 g (0.125 mol) of
meta-xylylenediamine are added and the clear mixture is heated to
80.degree. C. Subsequently 72.0 g (0.20 mol) of the isocyanate
adduct described (stage 1) are added dropwise with stirring over
the course of 1 hour at a rate such that the temperature does not
exceed 85.degree. C. To complete the reaction, the reaction mixture
is stirred at 80.degree. C. for 3 hours. A clear and viscous
product is obtained. The fraction of the urea compound in the
resulting product is 23 wt %.
Composition K8:
Stage 1
[0147] First of all 93.6 g of a monoadduct are prepared in
accordance with patent specification EP 1188779 from a polyethylene
glycol monomethyl ether having a molar mass of 450 g/mol and a
mixture of 35% 2,4-tolylene diisocyanate and 65% 2,6-tolylene
diisocyanate.
Stage 2
[0148] In a four-neck flask with stirrer, dropping funnel,
thermometer, and reflux condenser, 162.0 g of the reaction product
from example 1b are heated to 100.degree. C. and, when the
temperature is reached, 4.2 g of lithium chloride are added. The
lithium chloride is thereafter dissolved with stirring at
100.degree. C. within one hour. The temperature is then lowered to
80.degree. C.
[0149] 10.2 g of m-xylylenediamine are added and the mixture is
homogenized.
[0150] The isocyanate adduct prepared beforehand (stage 1) is added
dropwise with stirring over the course of 1 hour to the amine
solution at a slow rate such that the temperature does not exceed
85.degree. C. To complete the reaction, the reaction mixture is
stirred at 80.degree. C. for three hours. A viscous, brownish
product is obtained. The product contains 38 wt % of urea
compound.
Composition K9:
Stage 1
[0151] First of all 93.6 g of a monoadduct are prepared in
accordance with patent specification EP 1188779 from a polyethylene
glycol monomethyl ether having a molar mass of 450 g/mol and a
mixture of 35% 2,4-tolylene diisocyanate and 65% 2,6-tolylene
diisocyanate.
Stage 2
[0152] In a four-neck flask with stirrer, dropping funnel,
thermometer, and reflux condenser, 252.0 g of the reaction product
from example 14b are heated to 100.degree. C. and, when the
temperature is reached, 4.2 g of lithium chloride are added. The
lithium chloride is thereafter dissolved with stirring at
100.degree. C. within one hour. The temperature is then lowered to
80.degree. C.
[0153] 10.2 g of m-xylylenediamine are added and the mixture is
homogenized.
[0154] The isocyanate adduct prepared beforehand (stage 1) is added
dropwise with stirring over the course of 1 hour to the amine
solution at a slow rate such that the temperature does not exceed
85.degree. C. To complete the reaction, the reaction mixture is
stirred at 80.degree. C. for three hours. A cloudy, brownish
product is obtained. The amine number is 3 mg KOH/g (determined
according to DIN 16945). The product contains 29 wt % of urea
compound.
Composition K10:
Stage 1
[0155] First of all 93.6 g of a monoadduct are prepared in
accordance with patent specification EP 1188779 from a polyethylene
glycol monomethyl ether having a molar mass of 450 g/mol and a
mixture of 35% 2,4-tolylene diisocyanate and 65% 2,6-tolylene
diisocyanate.
Stage 2
[0156] In a four-neck flask with stirrer, dropping funnel,
thermometer, and reflux condenser, 324.0 g of the reaction product
from example 16b are heated to 100.degree. C. and, when the
temperature is reached, 4.2 g of lithium chloride are added. The
lithium chloride is thereafter dissolved with stirring at
100.degree. C. within one hour. The temperature is then lowered to
80.degree. C.
[0157] 10.2 g of m-xylylenediamine are added and the mixture is
homogenized.
[0158] The isocyanate adduct prepared beforehand (stage 1) is added
dropwise with stirring over the course of 1 hour to the amine
solution at a slow rate such that the temperature does not exceed
85.degree. C. To complete the reaction, the reaction mixture is
stirred at 80.degree. C. for three hours. A brownish product is
obtained. The product contains 24 wt % of urea compound.
COMPARATIVE EXAMPLES
Not Inventive
Comparative Example C1
Stage 1
[0159] First of all 64.4 g of a diisocyanate monoadduct are
prepared in accordance with patent specification EP 1188779 from a
polyethylene glycol monobutyl ether having a hydroxyl number of 220
mg KOH/g (determined according to DIN/ISO 4629) and a mixture of
35% 2,4-tolylene diisocyanate and 65% 2,6-tolylene
diisocyanate.
Stage 2
[0160] A four-neck flask is provided with stirrer, dropping funnel,
thermometer, and reflux condenser. It is charged with 72.7 g of
1-ethylpyrrolidin-2-one, which is heated under a nitrogen
atmosphere with stirring to 120.degree. C. 4.2 g of lithium
chloride are added and at this temperature are dissolved with
stirring in one hour.
[0161] Temperature is then lowered to 80.degree. C. 10.2 g of
m-xylylenediamine are added and the mixture is homogenized.
[0162] The isocyanate adduct prepared beforehand (stage 1) is added
dropwise with stirring over the course of 1 hour to the amine
solution at a slow rate such that the temperature does not exceed
85.degree. C. To complete the reaction, the reaction mixture is
stirred at 80.degree. C. for a further three hours. A clear, yellow
product is obtained. The amine number is 1 mg KOH/g (determined
according to DIN 16945). The product contains 49 wt % of the urea
compound.
Comparative Example C2
Stage 1
[0163] First of all 64.4 g of a diisocyanate monoadduct are
prepared in accordance with patent specification EP 1188779 from a
polyethylene glycol monobutyl ether having a hydroxyl number of 220
mg KOH/g (determined according to DIN/ISO 4629) and a mixture of
35% 2,4-tolylene diisocyanate and 65% 2,6-tolylene
diisocyanate.
Stage 2
[0164] A four-neck flask is provided with stirrer, dropping funnel,
thermometer, and reflux condenser. It is charged with 72.7 g of
dimethyl sulfoxide, which is heated under a nitrogen atmosphere
with stirring to 120.degree. C. 4.2 g of lithium chloride are added
and at this temperature are dissolved with stirring in one hour.
Temperature is then lowered to 80.degree. C. 10.2 g of
m-xylylenediamine are added and the mixture is homogenized.
[0165] The isocyanate adduct prepared beforehand (stage 1) is added
dropwise with stirring over the course of 1 hour to the amine
solution at a slow rate such that the temperature does not exceed
85.degree. C. To complete the reaction, the reaction mixture is
stirred at 80.degree. C. for a further three hours. A clear, yellow
product is obtained. The amine number is 1 mg KOH/g (determined
according to DIN 16945). The product contains 49 wt % of the urea
compound.
Comparative Example C3
Stage 1
[0166] First of all 64.4 g of a diisocyanate monoadduct are
prepared in accordance with patent specification EP 1188779 from a
polyethylene glycol monobutyl ether having a hydroxyl number of 220
mg KOH/g (determined according to DIN/ISO 4629) and a mixture of
35% 2,4-tolylene diisocyanate and 65% 2,6-tolylene
diisocyanate.
Stage 2
[0167] A four-neck flask is provided with stirrer, dropping funnel,
thermometer, and reflux condenser. It is charged with 72.7 g of
N-methylpyrrolidone, which is heated under a nitrogen atmosphere
with stirring to 120.degree. C. 4.2 g of lithium chloride are added
and at this temperature are dissolved with stirring in one hour.
Temperature is then lowered to 80.degree. C. 10.2 g of
m-xylylenediamine are added and the mixture is homogenized.
[0168] The isocyanate adduct prepared beforehand (stage 1) is added
dropwise with stirring over the course of 1 hour to the amine
solution at a slow rate such that the temperature does not exceed
85.degree. C. To complete the reaction, the reaction mixture is
stirred at 80.degree. C. for a further three hours. A clear, yellow
product is obtained. The product contains 49 wt % of the urea
compound.
Comparative Example C4
[0169] First of all a monoadduct is prepared in accordance with
patent specification EP 1188779 from 2,4-tolylene diisocyanate
(Desmodur T100, Bayer) and lauryl alcohol. In a reaction vessel
(round-bottom flask with stirrer, reflux condenser, and dropping
funnel), under a nitrogen atmosphere and with stirring, 1.7 (0.039
mol) of LiCl are dissolved in 75 g of N-methylpyrrolidone
(commercial product). Then 3.6 g (0.026 mol) of
meta-xylylenediamine are added and the clear mixture is heated to
80.degree. C. Subsequently 19.8 g (0.052 mol) of the monoadduct of
Desmodur T100 and lauryl alcohol are added dropwise with stirring
over the course of 1 hour at a rate such that the temperature does
not exceed 85.degree. C. To complete the reaction, the reaction
mixture is stirred at 80.degree. C. for 3 hours. A clear and liquid
product is obtained. The fraction of the urea compound in the
resulting product is 23 wt %.
Comparative Example C5
[0170] First of all a monoadduct is prepared in accordance with
patent specification EP 1188779 from 2,4-tolylene diisocyanate
(Desmodur T100, Bayer) and lauryl alcohol. In a reaction vessel
(round-bottom flask with stirrer, reflux condenser, and dropping
funnel), under a nitrogen atmosphere and with stirring, 1.7 g
(0.039 mol) of LiCl are dissolved in 75 g of 1-N-ethylpyrrolidone
(commercial product). Then 3.6 g (0.026 mol) of
meta-xylylenediamine are added and the clear mixture is heated to
80.degree. C. Subsequently 19.8 g (0.052 mol) of the monoadduct of
Desmodur T100 and lauryl alcohol are added dropwise with stirring
over the course of 1 hour at a rate such that the temperature does
not exceed 85.degree. C. To complete the reaction, the reaction
mixture is stirred at 80.degree. C. for 3 hours. A clear and
low-viscosity product is obtained. The fraction of the urea
compound in the resulting product is 23 wt %.
Comparative Example C6
Stage 1
[0171] First of all 93.6 g of a monoadduct are prepared in
accordance with patent specification EP 1188779 from a polyethylene
glycol monomethyl ether having a molar mass of 450 g/mol and a
mixture of 35% 2,4-tolylene diisocyanate and 65% 2,6-tolylene
diisocyanate.
Stage 2
[0172] In a four-neck flask with stirrer, dropping funnel,
thermometer, and reflux condenser, 99.7 g of N-methylpyrrolidone
(commercial product, BASF) are heated to 100.degree. C. and, when
the temperature is reached, 4.2 g of lithium chloride are added.
The lithium chloride is thereafter dissolved with stirring at
100.degree. C. within one hour. The temperature is then lowered to
80.degree. C.
[0173] 10.2 g of m-xylylenediamine are added and the mixture is
homogenized.
[0174] The isocyanate adduct prepared beforehand (stage 1) is added
dropwise with stirring over the course of 1 hour to the amine
solution at a slow rate such that the temperature does not exceed
85.degree. C. To complete the reaction, the reaction mixture is
stirred at 80.degree. C. for three hours. A clear, yellowish
product is obtained. The product contains 48 wt % of urea
compound.
Comparative Example C7
Stage 1
[0175] First of all 93.6 g of a monoadduct are prepared in
accordance with patent specification EP 1188779 from a polyethylene
glycol monomethyl ether having a molar mass of 450 g/mol and a
mixture of 35% 2,4-tolylene diisocyanate and 65% 2,6-tolylene
diisocyanate.
Stage 2
[0176] In a four-neck flask with stirrer, dropping funnel,
thermometer, and reflux condenser, 132.0 g of dimethyl sulfoxide
(commercial product from Sigma Aldrich) are heated to 100.degree.
C. and, when the temperature is reached, 4.2 g of lithium chloride
are added. The lithium chloride is thereafter dissolved with
stirring at 100.degree. C. within one hour. The temperature is then
lowered to 80.degree. C.
[0177] 10.2 g of m-xylylenediamine are added and the mixture is
homogenized.
[0178] The isocyanate adduct prepared beforehand (stage 1) is added
dropwise with stirring over the course of 1 hour to the amine
solution at a slow rate such that the temperature does not exceed
85.degree. C. To complete the reaction, the reaction mixture is
stirred at 80.degree. C. for three hours. A clear, yellowish
product is obtained. The product contains 43 wt % of urea
compound.
Comparative Example C8
Stage 1
[0179] First of all 93.6 g of a monoadduct are prepared in
accordance with patent specification EP 1188779 from a polyethylene
glycol monomethyl ether having a molar mass of 450 g/mol and a
mixture of 35% 2,4-tolylene diisocyanate and 65% 2,6-tolylene
diisocyanate.
Stage 2
[0180] In a four-neck flask with stirrer, dropping funnel,
thermometer, and reflux condenser, 99.7 g of N-ethylpyrrolidone
(commercial product, BASF) are heated to 100.degree. C. and, when
the temperature is reached, 4.2 g of lithium chloride are added.
The lithium chloride is thereafter dissolved with stirring at
100.degree. C. within one hour. The temperature is then lowered to
80.degree. C.
[0181] 10.2 g of m-xylylenediamine are added and the mixture is
homogenized.
[0182] The isocyanate adduct prepared beforehand (stage 1) is added
dropwise with stirring over the course of 1 hour to the amine
solution at a slow rate such that the temperature does not exceed
85.degree. C. To complete the reaction, the reaction mixture is
stirred at 80.degree. C. for three hours. A clear, yellowish
product is obtained. The product contains 50 wt % of urea
compound.
Comparative Example C11
Stage 1
[0183] First of all 64.4 g of a diisocyanate monoadduct are
prepared in accordance with patent specification EP 1188779 from a
polyethylene glycol monobutyl ether having a hydroxyl number of 220
mg KOH/g (determined according to DIN/ISO 4629) and a mixture of
35% 2,4-tolylene diisocyanate and 65% 2,6-tolylene
diisocyanate.
Stage 2
[0184] A four-neck flask is provided with stirrer, dropping funnel,
thermometer, and reflux condenser. It is charged with 118.2 g of
methyl 5-(dimethylamino)-2-methyl-5-oxopentanoate, which is heated
under a nitrogen atmosphere with stirring to 120.degree. C. 4.2 g
of lithium chloride are added and at this temperature are dissolved
with stirring in one hour. Temperature is then lowered to
80.degree. C. 10.2 g of m-xylylenediamine are added and the mixture
is homogenized.
[0185] The isocyanate adduct prepared beforehand (stage 1) is added
dropwise with stirring over the course of 1 hour to the amine
solution at a slow rate such that the temperature does not exceed
85.degree. C. To complete the reaction, the reaction mixture is
stirred at 80.degree. C. for a further three hours. A clear, yellow
product is obtained. The amine number is 1 mg KOH/g (determined
according to DIN 16945). The product contains 38 wt % of the urea
compound.
Comparative Example C12
Stage 1
[0186] First of all 64.4 g of a diisocyanate monoadduct are
prepared in accordance with patent specification EP 1188779 from a
polyethylene glycol monobutyl ether having a hydroxyl number of 220
mg KOH/g (determined according to DIN/ISO 4629) and a mixture of
35% 2,4-tolylene diisocyanate and 65% 2,6-tolylene
diisocyanate.
Stage 2
[0187] A four-neck flask is provided with stirrer, dropping funnel,
thermometer, and reflux condenser. It is charged with 118.2 g of
1-(morpholine-4-yl)ethanone, which is heated under a nitrogen
atmosphere with stirring to 120.degree. C. 4.2 g of lithium
chloride are added and at this temperature are dissolved with
stirring in one hour.
[0188] Temperature is then lowered to 80.degree. C. 10.2 g of
m-xylylenediamine are added and the mixture is homogenized.
[0189] The isocyanate adduct prepared beforehand (stage 1) is added
dropwise with stirring over the course of 1 hour to the amine
solution at a slow rate such that the temperature does not exceed
85.degree. C. To complete the reaction, the reaction mixture is
stirred at 80.degree. C. for a further three hours. A clear, yellow
product is obtained. The amine number is 1 mg KOH/g (determined
according to DIN 16945). The product contains 38 wt % of the urea
compound.
Comparative Example C13
Combination of Noninventive Amide Compounds with Urea Compounds
[0190] For the following combination experiments, in analogy to WO
2011/091812, BYK-430 (30% strength solution of a high-molecular
modified polyamide, from BYK-Chemie GmbH) is used as noninventive
amide compound. This amide component was combined with various urea
compounds in accordance with comparative examples above (i.e.,
dissolved urea compounds containing no inventive amide component as
a mixing constituent). Mixing was carried out with continuous
stirring.
TABLE-US-00002 Weight ratio of Appearance urea solution to of the
Ex. Urea solution BYK-430 combination C13-1 C3 (410) 7:3 slightly
cloudy, gelled C13-2 C3 (410) 5:5 slightly cloudy, gelled C13-3 C3
(410) 3:7 very cloudy, gelled C13-4 C6 (420) 7:3 slightly cloudy,
gelled C13-5 C6 (420) 5:5 cloudy, gelled C13-6 C6 (420) 3:7 cloudy,
gelled
[0191] The example shows that the compositions of the invention
ensure high compatibility of the relevant urea and amide
components, leading to ease of preparation combined with good
storage stability of the rheologically active compositions
comprising amide and urea, whereas the noninventive amide compounds
do not enable a storage-stable combination and therefore also do
not enable easy handling as a whole composition. In the case of the
noninventive combinations, therefore, incorporation into the system
must always take place separately, meaning that more worksteps and
therefore extra production effort and complexity are required.
Performance Testing of the Compositions Suitable as Rheology
Additives
[0192] Test System 1: Solvent Mixture of n-Butyl Acetate and
Methoxypropanol
[0193] For this series of tests an amount of the urea compound of
28 wt % in the additive composition is set for all of the products
tested, by the addition to the composition--where necessary--of a
further quantity of the respective amide compound. In a 100 ml
glass bottle, 50 g of the solvent mixture n-butyl acetate/Dowanol
PM 75:25 (w/w) are introduced, and then the respective additive
composition is added in an amount corresponding to 0.5 wt % of the
urea compound. This incorporation takes place with stirring with
the Dispermat CV (toothed disk d=2.5 cm at 1000 rpm). The addition
is followed by a further minute of stirring. The samples are then
left to stand at RT for one hour, after which a visual appraisal is
made of the gel strength, as a measure of the rheological activity,
and of the clouding, for the compatibility of the additive.
Evaluation Scale:
TABLE-US-00003 [0194] Gel strength: 1 very strong 2 strong 3
moderate 4 very weak 5 no gel Cloudiness 1 clear (compatibility): 2
slightly cloudy 3 cloudy 4 very cloudy 5 extremely cloudy
Results:
TABLE-US-00004 [0195] Composition (each containing Gel 28 wt % of
urea) strength Cloudiness Control 5 1 Comparative Ex. C1 4 2 K1 3 1
K2 3 1 K4 4 1 K3 4 1 K6 3 2
[0196] From the results it is evident that the inventive
compositions in comparison to comparative example C1 permit either
better compatibility (i.e., less cloudiness in the system) or the
development of a greater gel strength (i.e., better rheological
activity) or exhibit both advantageous effects in combination.
Test System 2: Setalux D A 870 BA Clear Coat
[0197] For this series of tests an amount of the urea compound of
28 wt % in the additive composition is set for all of the products
tested, by the addition to the composition--where necessary--of a
further quantity of the respective amide compound. In a 100 ml
glass bottle, 50 g of Setalux D A 870 BA clear coat are introduced
and then the respective additive is incorporated with stirring
using the Dispermat CV (toothed disk d=2.5 cm at 1000 rpm). The
amount of the additive composition is selected in each case to
correspond to 0.4 wt %, relative to the urea compound. The addition
is followed by stirring for a further minute.
[0198] The samples are then left to stand at RT for one day, after
which they are first appraised visually for the gel strength, as a
measure of the rheological activity, and for cloudiness, for the
compatibility of the additive. This is followed by testing of the
sag resistance, as a measure of the rheological activity under
application conditions.
[0199] For this purpose, the sample is stirred evenly with a
spatula and then applied to contrast charts using the 30-300 .mu.m
stepped doctor and an automatic applicator from BYK Gardner, at a
speed of 5 cm/s. Following application, the contrast charts are
hung up directly, in horizontal position, for drying. After drying
has taken place, a determination is made of the wet film thickness,
in .mu.m, at which the coating does not run, meaning that no runs
or fat edging are apparent. The higher the figure for the sag
resistance for a given active substance employed, the better the
rheological activity.
Coating Formulation (Parts by Weight):
TABLE-US-00005 [0200] Setalux D A 870 BA 80.0 Butyl acetate 9.9
Dowanol PMA 9.9 BYK-066 0.2
Results:
TABLE-US-00006 [0201] Composition Sag (each containing Gel
resistance 28 wt % of urea) strength Cloudiness .mu.m wet Control 5
1 30 Comparative Ex. C3 2 2 90 K1 1 1 150 K2 1 2 450 K4 2 1 200 K3
1-2 2 400
[0202] From the results it is apparent that the inventive
compositions in comparison to comparative example C3 allow either
better compatibility (i.e., less cloudiness in the system) or the
development of a greater gel strength and also an improved sag
resistance (i.e., maximum possible film thickness) or exhibit the
advantageous effects in combination.
Test System 3: Epikote 1001-X75--Clear Coat
[0203] For this series of tests an amount of the urea compound of
38 wt % in the additive composition is set for all of the products
tested, by the addition to the composition--where necessary--of a
further quantity of the respective amide compound. In a 100 ml
glass bottle, 50 g of Epikote 1001-X75 clear coat are introduced
and then the respective additive is incorporated with stirring
using the Dispermat CV (toothed disk d=2.5 cm at 1000 rpm). The
amount selected in each case corresponds to 0.8 wt % of the urea
compound. The addition is followed by stirring for a further
minute.
[0204] The samples are then left to stand at RT for one day, after
which they are first appraised visually for the gel strength, as a
measure of the rheological activity, and for cloudiness, for the
compatibility of the additive. This is followed by testing of the
sag resistance, as a measure of the rheological activity under
application conditions.
[0205] For this purpose, the sample is stirred evenly with a
spatula and then applied to contrast charts using the 30-300 .mu.m
stepped doctor and an automatic applicator from BYK Gardner, at a
speed of 5 cm/s. Following application, the contrast charts are
hung up directly, in horizontal position, for drying. After drying
has taken place, a determination is made of the wet film thickness,
in .mu.m, at which the coating does not run, meaning that no runs
or fat edging are apparent. The higher the figure for the sag
resistance for a given active substance employed, the better the
rheological activity.
Coating Formulation (Parts by Weight):
TABLE-US-00007 [0206] Epikote 1001-X75 75.3 Methyl isobutyl ketone
17.3 Isobutanol 7.4
Results:
TABLE-US-00008 [0207] Composition Sag (each containing Gel
resistance 38 wt % of urea) strength Cloudiness .mu.m wet Control 5
1 <50 Comparative Ex. C3 3 1 200 K1 2 1 300
[0208] From the results it is apparent that the inventive
composition in comparison to comparative example C3, while having
equally good compatibility, permits a greater gel strength and also
an improved sag resistance (i.e., maximum possible film
thickness).
Test System 4: Worleekyd S 351 Binder
[0209] In a 100 ml glass bottle, 50 g of Worleekyd S 351 binder are
introduced and then the respective additive is incorporated with
stirring using the Dispermat CV (toothed disk d=2.5 cm at 1000
rpm). The amount selected in each case corresponds to 0.7 wt % of
the urea compound. The addition is followed by stirring for a
further minute.
[0210] The samples are then left to stand at RT for one day, after
which an assessment is made of the sag resistance, as a measure of
the rheological activity under application conditions. For this
purpose, the sample is stirred evenly with a spatula and then
applied to contrast charts using the 50-500 .mu.m stepped doctor
and an automatic applicator from BYK Gardner, at a speed of 5 cm/s.
Following application, the contrast charts are hung up directly, in
horizontal position, for drying. After drying has taken place, a
determination is made of the wet film thickness, in .mu.m, at which
the coating does not run, meaning that no runs or fat edging are
apparent. The higher the figure for the sag resistance for an
identical active substance employed, the better the rheological
activity.
Results:
TABLE-US-00009 [0211] Composition Sag (each containing Gel
resistance 23 wt % of urea) strength Cloudiness .mu.m wet Control 5
1 <50 Comparative Ex. C4 3 3 300 Comparative Ex. C5 3-4 3 350 K7
1 2 450
[0212] From the results it is apparent that the inventive
composition in comparison to comparative examples C4 and C5, while
having equally improved compatibility, permits a greater gel
strength and also an improved sag resistance (i.e., maximum
possible film thickness).
Test System 5: Worleekyd S 366 Clear Coat
[0213] In a 100 ml glass bottle, 50 g of Worleekyd S 366 clear coat
are introduced and then the respective additive is incorporated
with stirring using the Dispermat CV (toothed disk d=2.5 cm at 1000
rpm). The amount selected in each case corresponds to 0.5 wt % of
the urea compound. The addition is followed by stirring for a
further minute. The samples are then left to stand at RT for one
day, after which an assessment is made of the sag resistance, as a
measure of the rheological activity under application
conditions.
[0214] For this purpose, the sample is stirred evenly with a
spatula and then applied to contrast charts using the 50-500 .mu.m
stepped doctor and an automatic applicator from BYK Gardner, at a
speed of 5 cm/s. Following application, the contrast charts are
hung up directly, in horizontal position, for drying. After drying
has taken place, a determination is made of the wet film thickness,
in .mu.m, at which the coating does not run, meaning that no runs
or fat edging are apparent. The higher the figure for the sag
resistance for a given active substance employed, the better the
rheological activity.
Coating Formulation (Parts by Weight):
TABLE-US-00010 [0215] Worleekyd S 366 60% in Isopar H 80.9 Isopar H
16.0 Nuodex Combi APB 2.6 Borchi Nox M 2 0.3 BYK-066 0.2
Results:
TABLE-US-00011 [0216] Composition Sag (each containing Gel
resistance 23 wt % of urea) strength .mu.m wet Control 5 50
Comparative Ex. C4 3-4 150 K7 1 300
[0217] From the results it is apparent that the inventive
composition in comparison to comparative example C4, permits a
significantly increased gel strength and also improved sag
resistance (i.e., maximum possible film thickness).
Test System 6: Polystyrene Palapreg P17-02/Palapreg H 814-01
[0218] In a 175 ml PE beaker, first of all the two resin components
Palapreg P17-02 and Palapreg H 814-01 are homogenized with the
Dispermat CV, with a 4 cm toothed disk, at 1200 rpm for one minute.
50 g of this mixture are then placed in a 175 ml PE beaker, and the
respective additive is incorporated with stirring using the
Dispermat CV (toothed disk d=2.5 cm at 1000 rpm). The amount
selected in each case is that corresponding to 0.8 wt % of the urea
compound. Following addition, stirring is continued for two minutes
more.
[0219] The samples are then introduced directly into 50 ml snap-on
lid bottles, and left to stand at RT. After three days, the
separation of the samples is assessed, in percent relative to the
total amount introduced, and there is also visual evaluation of the
gel strength, as a measure of the rheological activity. The lower
the separation of the samples, the better the rheological activity
of the samples. Besides the rheological activity, color influence
by the additive on the formulation also plays a part, and must be
as small as possible. At the same time, a high boiling point of the
amide compound is relevant for application in the sheet molding
compounds sector, since otherwise the ambient air will be polluted
when the compounds are subjected to hot pressing, and gas bubbles
which form cause unwanted air inclusions in the pressed
compound.
Resin Formulation (Parts by Weight):
TABLE-US-00012 [0220] Palapreg P 17-02 70 Palapreg H 814-01 30
Results:
TABLE-US-00013 [0221] Separation after Composition Gel three days
at (each containing strength room temperature 38 wt % of urea)
visual % Control 38 Comparative Ex. C11 5 37 Comparative Ex. C12 5
38 K1 1 0
[0222] From the results it is apparent that the inventive
composition in comparison to comparative examples C11 and C12 has a
marked influence on the unwanted phase separation and, by
increasing the gel strength, effectively and completely prevents
separation.
* * * * *