U.S. patent application number 12/515511 was filed with the patent office on 2010-03-25 for supramolecular polymers from low-melting, easily processable building blocks.
This patent application is currently assigned to SUPRAPOLIX B.V.. Invention is credited to Anton Willem Bosman, Gaby Maria Leonarda Hoorne-Van Gemert, Henricus Marie Janssen, Egbert Willem Meijer.
Application Number | 20100076147 12/515511 |
Document ID | / |
Family ID | 39365704 |
Filed Date | 2010-03-25 |
United States Patent
Application |
20100076147 |
Kind Code |
A1 |
Hoorne-Van Gemert; Gaby Maria
Leonarda ; et al. |
March 25, 2010 |
SUPRAMOLECULAR POLYMERS FROM LOW-MELTING, EASILY PROCESSABLE
BUILDING BLOCKS
Abstract
PCT The present invention relates to a supramolecular polymer
comprising 1-50 4H-units, said supramolecular polymer being
obtainable by reacting at least one monomeric building block with a
prepolymer. The present invention further relates to articles or
compositions comprising the supramolecular polymer, in particular
articles or compositions selected from the group consisting of
decorative, thermo-reversible, or self-healing coatings, adhesive
compositions, sealing compositions, thickeners, gelators and
binders.
Inventors: |
Hoorne-Van Gemert; Gaby Maria
Leonarda; (Landgraaf, NL) ; Janssen; Henricus
Marie; (Eindhoven, NL) ; Meijer; Egbert Willem;
(Waalre, NL) ; Bosman; Anton Willem; (Eindhoven,
NL) |
Correspondence
Address: |
FOLEY AND LARDNER LLP;SUITE 500
3000 K STREET NW
WASHINGTON
DC
20007
US
|
Assignee: |
SUPRAPOLIX B.V.
AX Eindhoven
NL
|
Family ID: |
39365704 |
Appl. No.: |
12/515511 |
Filed: |
November 14, 2007 |
PCT Filed: |
November 14, 2007 |
PCT NO: |
PCT/NL2007/050562 |
371 Date: |
May 19, 2009 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
60866509 |
Nov 20, 2006 |
|
|
|
Current U.S.
Class: |
524/548 ;
526/258; 526/261 |
Current CPC
Class: |
C08G 18/3212 20130101;
C08G 77/388 20130101; C08G 18/3848 20130101; C08G 18/4277 20130101;
C08G 18/73 20130101; C08G 83/008 20130101; C08G 64/42 20130101;
C08G 18/4238 20130101; C08G 18/8108 20130101; C08G 18/7887
20130101; C08G 18/10 20130101; C08G 18/3848 20130101; C08G 18/10
20130101 |
Class at
Publication: |
524/548 ;
526/258; 526/261 |
International
Class: |
C09D 139/04 20060101
C09D139/04; C08F 226/06 20060101 C08F226/06 |
Claims
1. A supramolecular polymer comprising 1-50 4H-units, said
supramolecular polymer being obtainable by reacting at least one
monomeric building block selected from the group consisting of
monomeric building blocks (I)-(VI) with a prepolymer
P--(F.sub.i).sub.n, ##STR00021## wherein R.sub.1 is selected from
the group consisting of hydrogen, cyclic, linear or branched
C.sub.2-C.sub.20 alkyl groups, C.sub.6-C.sub.20 aryl groups,
C.sub.7-C.sub.20 alkaryl groups and C.sub.7-C.sub.20 arylalkyl
groups, wherein the alkyl groups, aryl groups, alkaryl groups and
arylalkyl groups optionally comprise 1-5 heteroatoms selected from
the group consisting of oxygen, nitrogen and sulphur; R.sub.2 and
R.sub.3 are independently selected from the group consisting of
hydrogen, cyclic, linear or branched C.sub.1-C.sub.20 alkyl groups,
C.sub.6-C.sub.20 aryl groups, C.sub.7-C.sub.20 alkaryl groups and
C.sub.7-C.sub.20 arylalkyl groups, wherein the alkyl groups, aryl
groups, alkaryl groups and arylalkyl groups optionally comprise 1-5
heteroatoms selected from the group consisting of oxygen, nitrogen
and sulphur; with the proviso that R.sub.1 and R.sub.2 are not both
hydrogen; A is a linking moiety that is selected from the group
consisting of linear, cyclic or branched C.sub.1-C.sub.20 alkylene
and C.sub.6-C.sub.20 arylene groups, wherein the alkylene and
arylene groups optionally comprise 1-5 heteroatoms selected from
the group consisting of oxygen, nitrogen and sulphur, and wherein
the arylene groups are optionally substituted with one or more
linear or branched C.sub.1-C.sub.20 alkyl, alkylene groups, or
both; B.sub.1 is a linking moiety that is independently selected
from the group consisting of linear, cyclic or branched
C.sub.1-C.sub.20 alkylene and C.sub.6-C.sub.20 arylene groups,
wherein the alkylene and arylene groups optionally comprise 1-5
heteroatoms selected from the group consisting of oxygen, nitrogen
and sulphur, and wherein the arylene groups are optionally
substituted with one or more linear or branched C.sub.1-C.sub.20
alkyl, alkylene groups, or both; D is --OH, --SH, --NH.sub.2 or
--NHR.sub.4, wherein R.sub.4 is selected from the group consisting
of cyclic, linear or branched C.sub.1-C.sub.6 alkyl,
C.sub.6-C.sub.20 aryl groups, C.sub.7-C.sub.20 alkaryl groups and
C.sub.7-C.sub.20 arylalkyl groups; X is independently selected from
the group consisting of --NCO, --OH, --SH, --NHR.sub.5, oxiranyl,
--C(Z)ZR.sub.6 and --C(Z)NHR.sub.6, wherein R.sub.5 and R.sub.6 are
independently selected from the group consisting of hydrogen,
cyclic, linear or branched C.sub.1-C.sub.6 alkyl, C.sub.6-C.sub.20
aryl groups, C.sub.7-C.sub.20 alkaryl groups and C.sub.7-C.sub.20
arylalkyl groups and wherein Z is independently O or S; and P
represents a polymeric or oligomeric chain, F.sub.i represents a
group that is complementary reactive with X, and n represents the
average number of the groups F.sub.i in P and is in the range of 1
to 10,000.
2. The supramolecular polymer according to claim 1, wherein the
monomeric building block is selected from the group consisting of
monomeric building blocks (I), (III), (IV) and (VI).
3. The supramolecular polymer according to claim 1, wherein the
monomeric building block is monomeric building block (I).
4. The supramolecular polymer according to claim 1, wherein n is 2
to 50.
5. The supramolecular polymer according to claim 1, wherein the
prepolymer P--(F.sub.i).sub.n has an average molecular weight of
100-10,000.
6. A process for the preparation of a supramolecular polymer, said
process comprising reacting at least one monomeric building block
selected from the group consisting of monomeric building blocks
(I)-(VI) with a prepolymer P--(F.sub.i).sub.n, ##STR00022## wherein
R.sub.1 is selected from the group consisting of hydrogen, cyclic,
linear or branched C.sub.2-C.sub.20 alkyl groups, C.sub.6-C.sub.20
aryl groups, C.sub.7-C.sub.20 alkaryl groups and C.sub.7-C.sub.20
arylalkyl groups, wherein the alkyl groups, aryl groups, alkaryl
groups and arylalkyl groups optionally comprise 1-5 heteroatoms
selected from the group consisting of oxygen, nitrogen and sulphur;
R.sub.2 and R.sub.3 are independently selected from the group
consisting of hydrogen, cyclic, linear or branched C.sub.1-C.sub.20
alkyl groups, C.sub.6-C.sub.20 aryl groups, C.sub.7-C.sub.20
alkaryl groups and C.sub.7-C.sub.20 arylalkyl groups, wherein the
alkyl groups, aryl groups, alkaryl groups and arylalkyl groups
optionally comprise 1-5 heteroatoms selected from the group
consisting of oxygen, nitrogen and sulphur; with the proviso that
R.sub.1 and R.sub.2 are not both hydrogen; A is a linking moiety
that is selected from the group consisting of linear, cyclic or
branched C.sub.1-C.sub.20 alkylene and C.sub.6-C.sub.20 arylene
groups, wherein the alkylene and arylene groups optionally comprise
1-5 heteroatoms selected from the group consisting of oxygen,
nitrogen and sulphur, and wherein the arylene groups are optionally
substituted with one or more linear or branched C.sub.1-C.sub.20
alkyl, alkylene groups, or both; B.sub.1 is a linking moiety that
is independently selected from the group consisting of linear,
cyclic or branched C.sub.1-C.sub.20 alkylene and C.sub.6-C.sub.20
arylene groups, wherein the alkylene and arylene groups optionally
comprise 1-5 heteroatoms selected from the group consisting of
oxygen, nitrogen and sulphur, and wherein the arylene groups are
optionally substituted with one or more linear or branched
C.sub.1-C.sub.20 alkyl, alkylene groups, or both; D is --OH, --SH,
--NH.sub.2 or --NHR.sub.4, wherein R.sub.4 is selected from the
group consisting of cyclic, linear or branched C.sub.1-C.sub.6
alkyl, C.sub.6-C.sub.20 aryl groups, C.sub.7-C.sub.20 alkaryl
groups and C.sub.7-C.sub.20 arylalkyl groups; X is independently
selected from the group consisting of --NCO, --OH, --SH,
--NHR.sub.5, oxiranyl, --C(Z)ZR.sub.6 and --C(Z)NHR.sub.6, wherein
R.sub.5 and R.sub.6 are independently selected from the group
consisting of hydrogen, cyclic, linear or branched C.sub.1-C.sub.6
alkyl, C.sub.6-C.sub.20 aryl groups, C.sub.7-C.sub.20 alkaryl
groups and C.sub.7-C.sub.20 arylalkyl groups, and wherein Z is
independently O or S; and P represents a polymeric or oligomeric
chain, F.sub.i represents a group that is complementary reactive
with X, and n represents the average number of the groups F.sub.i
in P and is in the range of 1 to 10,000.
7. The process according to claim 6, wherein the reacting is
performed in the melt.
8. The process according to claim 6, wherein the reacting is
performed at a temperature below 150.degree. C.
9. The process according to claim 6, wherein the monomeric building
block is selected from the group consisting of monomeric building
blocks (I), (III), (IV) and (VI).
10. The process according to claim 6, wherein the monomeric
building block is monomeric building block (I).
11. The process according to claim 6, wherein n is 2 to 50.
12. The process according to claim 6, wherein the prepolymer
P--(F.sub.i).sub.n has an average molecular weight of
100-10,000.
13. A composition comprising the supramolecular polymer according
to claim 1.
14. A composition according to claim 13, wherein the composition is
selected from the group consisting of coatings, adhesive
compositions, sealing compositions, thickeners, gelators and
binders.
15. A composition according to claim 14, wherein the coating is a
decorative coating, thermo-reversible coating, or self-healing
coating.
16. (canceled)
17. A monomeric building block according to formulae (I)-(VI),
enantiomers, diastereomers and tautomers thereof: ##STR00023##
wherein R.sub.1 is selected from the group consisting of hydrogen,
cyclic, linear or branched C.sub.7-C.sub.20 alkyl groups,
C.sub.6-C.sub.70 aryl groups, C.sub.7-C.sub.70 alkaryl groups and
C.sub.7-C.sub.20 arylalkyl groups, wherein the alkyl groups, aryl
groups, alkaryl groups and arylalkyl groups optionally comprise 1-5
heteroatoms selected from the group consisting of oxygen, nitrogen
and sulphur, R.sub.2 and R.sub.3 are independently selected from
the group consisting of hydrogen, cyclic, linear or branched
C.sub.1-C.sub.20 alkyl groups, C.sub.6-C.sub.20 aryl groups,
C.sub.7-C.sub.20 alkaryl groups and C.sub.7-C.sub.20 arylalkyl
groups, wherein the alkyl groups, aryl groups, alkaryl groups and
arylalkyl groups optionally comprise 1-5 heteroatoms selected from
the group consisting of oxygen, nitrogen and sulphur; with the
proviso that R.sub.1 and R.sub.2 are not both hydrogen; A is a
linking moiety that is selected from the group consisting of
linear, cyclic or branched C.sub.1-C.sub.20 alkylene and
C.sub.6-C.sub.20 arylene groups, wherein the alkylene and arylene
groups optionally comprise 1-5 heteroatoms selected from the group
consisting of oxygen, nitrogen and sulphur, and wherein the arylene
groups are optionally substituted with one or more linear or
branched C.sub.1-C.sub.20 alkyl, alkylene groups, or both; B.sub.1
is a linking moiety that is independently selected from the group
consisting of linear, cyclic or branched C.sub.1-C.sub.20 alkylene
and C.sub.6-C.sub.20 arylene groups, wherein the alkylene and
arylene groups optionally comprise 1-5 heteroatoms selected from
the group consisting of oxygen, nitrogen and sulphur, and wherein
the arylene groups are optionally substituted with one or more
linear or branched C.sub.1-C.sub.20 alkyl, alkylene groups, or
both; D is --OH, --SH, --NH, or --NHR.sub.4, wherein R.sub.4 is
selected from the group consisting of cyclic, linear or branched
C.sub.1-C.sub.6 alkyl, C.sub.6-C.sub.20 aryl groups,
C.sub.7-C.sub.10 alkaryl groups and C.sub.7-C.sub.10 arylalkyl
groups; and X is independently selected from the group consisting
of --NCO, --OH, --SH, oxiranyl, --C(Z)ZR.sub.6 and --C(Z)NHR.sub.6,
wherein R.sub.5 and R.sub.6 are independently selected from the
group consisting of hydrogen, cyclic, linear or branched
C.sub.1-C.sub.6 alkyl, C.sub.6-C.sub.20 aryl groups,
C.sub.7-C.sub.20 alkaryl groups and C.sub.7-C.sub.20 arylalkyl
groups, and wherein Z is independently O or S.
Description
FIELD OF THE INVENTION
[0001] The invention relates to supramolecular polymers comprising
quadruple hydrogen bonding units that are preferably obtained via
reaction in the melt. In this reaction, building blocks containing
(precursors of) quadruple hydrogen bonding groups are reacted with
prepolymers of choice at temperatures below 150.degree. C. The
resulting supramolecular polymers show unique new characteristics
due to the presence of additional physical interactions between the
polymer chains that are based on multiple hydrogen bonding
interactions (supramolecular interactions) and benefit from easier
and faster preparation using known reactive-processing
techniques.
BACKGROUND OF THE INVENTION
[0002] This invention relates to supramolecular polymers comprising
quadruple hydrogen bonding units that are capable of forming at
least four H-bridges with each other in a row leading to physical
interactions between different polymer chains. The physical
interactions originate from multiple hydrogen bonding interactions
(supramolecular interactions) between self-complementary units
comprising at least four hydrogen bonds in a row. Units capable of
forming at least four hydrogen bonds in a row, i.e. quadruple
hydrogen bonding units, are in this patent application abbreviated
as 4H-units. Sijbesma et al. (U.S. Pat. No. 6,320,018; Science 278,
1601, 1997; incorporated by reference herein) discloses 4H-units
that are based on 2-ureido-4-pyrimidones. These
2-ureido-4-pyrimidones in their turn are derived from
isocytosines.
[0003] Telechelic polymers or trifunctional polymers have been
modified with 4H-units (Folmer, B. J. B. et al., Adv. Mater. 2000,
Vol. 12, 874; Hirschberg et al., Macromolecules 1999, Vol. 32,
2696; Lange, R. F. M. et al, J. Polym. Sci. Part A, 1999, 37,
3657-3670). However, these polymers are obtained by reaction in
chloroform or toluene, both toxic organic solvents, and need
prolonged reaction times of several hours in order to reach
completion.
[0004] Polymers with 4H-units grafted on the main chain have been
obtained by copolymerizing an olefin bearing a 4H-unit with a
common olefin (Coates, G. W. et al., Angew. Chem. Int. Ed., 2001,
Vol. 40, 2153). However, complex chemistry has to be used to
prepare the monomer. Additionally, the monomer must be polymerized
by a Ziegler-Natta catalyst which is known as being sensitive for
oxygen and moisture. Moreover, the reaction has to be performed in
dilute toluene solution, thereby worsening the reaction economy
because of the need of removal of large amounts of organic solvent.
Hence, such a synthesis process is commercially less
attractive.
[0005] WO 02/46260 discloses polyurethane based polymers with
4H-units as end-cappers that can be used as hot melt adhesive.
Example 4 in this patent discloses the preparation of
supramolecular polyurethane polymers which are obtained by the bulk
reaction of 6-methyl-isocytosine with 4,4'-methylene bis(phenyl
isocyanate) (MDI) end-capped polyesters in the melt at 180.degree.
C., said reaction being performed in a Brabender mixer with a
residence time of not more than 3 minutes. In this process it is
preferred that the 6-methyl-isocytosine is finely milled to a
particular particle size to facilitate rapid and efficient
conversion.
[0006] JP A2 2004250623, incorporated by reference, discloses
polyester diols derived from poly(butanediol terephthalate) or
polylactide that are reacted in the melt with an isocyanato
functional 4H-unit obtained by the reaction of diisocyanatohexane
with 6-methyl-isocytosine. The reaction proceeds by kneading at
150.degree. C. to 300.degree. C., preferably at 160.degree. C. to
250.degree. C. and more preferably at 180.degree. C. to 230.degree.
C. JP 2004250623 further discloses that it is desirable to perform
the reaction above the melting point of the polymer. However, in
order to control decomposition of the reactants and final products,
the reaction is desirably performed at a temperature as low as
possible, provided that the reactants are prevented to solidify as
much as possible during the reaction. According to the examples,
the reaction requires temperatures of 200.degree. C. or higher and
an excess of the isocyanato functional 4H-unit. Comparable
functionalisation of poly(butanediol terephthalate) and
poly(butanediol isophthalate) with this isocyanato functional
4H-unit at temperatures above 180.degree. C. are also disclosed by
Yamauchi et al. (Macromolecules 2004, Vol. 37, 3519). In both cases
the excess of the 4H-unit in the synthesis has been removed using
organic solvents (Soxhlet-extraction with methanol or precipitation
from HFIP), thereby re-introducing the need of (toxic) organic
solvents into the process. Moreover, the occurrence of side
reactions with the isocyanate functional compound, like
allophonate, biuret or isocyanurate formation, is eminent at the
temperatures applied (High Polymers Vol. XVI, Polyurethanes:
chemistry and technology, Part 1, Ed.: J. B. Saunders and K. C.
Frisch; J. Wiley & Sons 1962).
[0007] US 2004/0087755 and US 2007/0149751, both incorporated by
reference, disclose a process for the manufacture of a
supramolecular polymer wherein a mixture of a polyol, a chain
extender, a diisocyanate, an amino-functional organic powder and
optionally a catalyst are heated to a temperature of about
100.degree. to about 250.degree. C., preferably in a twin-screw
extruder. The amino-functional organic powder has an average
particle size of less than about 100 .mu.m and is preferably
selected from particular pyrimidine, isocytosine, pyridine,
pyrimidone, uracil and pyridine compounds. However, Examples 7 and
8 disclose that the minimum temperature for manufacturing is
150.degree. C. or higher, because of the high melting point of the
used 6-methyl isocytosine.
[0008] Clearly, there is a need for a general production process
for supramolecular polymers containing 4H-units that does not
require organic solvents because of toxicological, ecological and
economical reasons. Moreover, there is a need for a process in the
melt that can be performed at temperatures below 150.degree. C. in
order to prevent thermal degradation or the occurrence of side
reactions and to reduce the amount of energy necessary in the
production process. There is also a need for a broad range of
monomers comprising 4H-units or precursors of these 4H-units that
can be used comfortably in reactive processing due to their low
melting point and easy processing.
[0009] The present invention discloses novel 4H-unit building
blocks that have melting points below 230.degree. C. and building
blocks, which are usually isocytosines, that are precursors of
4H-units, having melting points below 295.degree. C. It was
unexpectedly found that small changes on the isocytosine ring or on
the ureido-position result in lowering of the melting points and,
more importantly, in a large lowering of the temperature required
to perform reactive processing. This makes it possible to prepare
new supramolecular polymers using reactive processing techniques at
temperatures below 150.degree. C. without the occurrence of
isocyanate side-reactions, resulting in supramolecular polymers
containing one or more 4H-units with excellent mechanical
properties.
SUMMARY OF THE INVENTION
[0010] The invention relates to 4H-unit containing building blocks
with lower melting points than 4H-unit building blocks presently
known in the art that dramatically improve the process of making
polymeric materials that comprise 4H-units and thereby form
supramolecular polymers. Furthermore, the novel supramolecular
polymers can also be prepared from the precursors of the 4H-unit
building blocks. As the introduced building blocks allow synthetic
procedures in the melt at temperatures below 150.degree. C., no
(toxic) organic solvents are needed and the relatively low
processing temperature makes it possible to perform the chemical
functionalisation without the occurrence of side-reactions that
would negatively influence the chemical and material properties of
the desired material. Especially side reactions of isocyanates that
are known to occur at elevated temperatures can be avoided.
[0011] The present invention therefore relates to new
supramolecular polymers comprising 1-50 4H-units, said
supramolecular polymer being obtainable by reacting at least one
monomeric building block selected from the group consisting of
monomeric building blocks (I) (VI) or their precursors
(I-p)-(VI-p), and enantiomers, diastereomers or tautomers thereof,
with a suitable prepolymer P--(F.sub.i).sub.n. The precursors are
isocytosine derivatives (I-p) to (V-p), or triazine derivatives
(VI-p).
##STR00001## ##STR00002##
[0012] For building blocks (I)-(VI), thio-ureas in stead of regular
ureas are also possible, although they are not preferred.
[0013] In the formulas (I)-(VI) and (I-p)-(VI-p), R.sub.1 is
selected from the group consisting of hydrogen, cyclic, linear or
branched C.sub.2-C.sub.20 alkyl groups, C.sub.6-C.sub.20 aryl
groups, C.sub.7-C.sub.20 alkaryl groups and C.sub.7-C.sub.20
arylalkyl groups, wherein the alkyl groups, aryl groups, alkaryl
groups and arylalkyl groups optionally comprise 1-5 heteroatoms
selected from the group consisting of oxygen, nitrogen and sulphur,
preferably nitrogen or sulphur;
[0014] R.sub.2 and R.sub.3 are independently selected from the
group consisting of hydrogen, cyclic, linear or branched
C.sub.1-C.sub.20 alkyl groups, C.sub.6-C.sub.20 aryl groups,
C.sub.7-C.sub.20 alkaryl groups and C.sub.7-C.sub.20 arylalkyl
groups, wherein the alkyl groups, aryl groups, alkaryl groups and
arylalkyl groups optionally comprise 1-5 heteroatoms selected from
the group consisting of oxygen, nitrogen and sulphur; with the
proviso that R.sub.1 and R.sub.2 are not both hydrogen;
[0015] In structure (I) and (I-p), R.sub.1 and R.sub.2 are
preferably not connected to form a fused cyclic structure, as such
fused structures generally lead to less-processable building
blocks;
[0016] A is a linking moiety that is selected from the group
consisting of cyclic, linear or branched C.sub.1-C.sub.20 alkylene
or C.sub.6-C.sub.20 arylene groups, wherein the alkylene and
arylene groups optionally comprise 1-5 heteroatoms selected from
the group consisting of oxygen, nitrogen and sulphur, and wherein
the arylene groups are optionally substituted with one or more
linear, cyclic or branched C.sub.1-C.sub.20 alkyl and/or alkylene
groups;
[0017] B.sub.1 and B.sub.2 are linking moieties that are
independently selected from the group consisting of cyclic, linear
or branched C.sub.1-C.sub.20 alkylene or C.sub.6-C.sub.20 arylene
groups, wherein the alkylene and arylene groups optionally comprise
1-5 heteroatoms selected from the group consisting of oxygen,
nitrogen and sulphur, wherein the arylene groups are optionally
substituted with one or more cyclic, linear or branched
C.sub.1-C.sub.20 alkyl and/or alkylene groups, and wherein B.sub.1
optionally comprises a functional group such as a (thio)urethane,
ester, amide or (thio)urea;
[0018] D is an --OH, --SH, --NH.sub.2 or --NHR.sub.4, wherein
R.sub.4 is selected from the group consisting of cyclic, linear or
branched C.sub.1-C.sub.6 alkyl, C.sub.6-C.sub.20 aryl groups,
C.sub.7-C.sub.20 alkaryl and C.sub.7-C.sub.20 arylalkyl groups;
[0019] X is independently selected from the group consisting of
--NCO, --OH, --SH, --NHR.sub.5, oxiranyl, --C(Z)ZR.sub.6 and
--C(Z)NHR.sub.6 wherein R.sub.5 and R.sub.6 are independently
selected from the group consisting of hydrogen, linear, cyclic or
branched C.sub.1-C.sub.6 alkyl, C.sub.6-C.sub.20 aryl groups,
C.sub.7-C.sub.20 alkaryl groups and C.sub.7-C.sub.20 arylalkyl
groups and wherein Z is independently O or S;
[0020] Y is selected from the group consisting of --OH, --SH,
--NHR.sub.5, oxiranyl, --C(Z)ZR.sub.6 and --C(Z)NHR.sub.6, wherein
Z, R.sub.5 and R.sub.6 are as defined above;
[0021] In the prepolymer P--(F.sub.i).sub.n, P represents a
polymeric or oligomeric chain, F.sub.i represents a reactive group
that is complementary reactive with groups X in building blocks (I)
(VI), groups Y in building blocks (I-p)-(VI-p) and/or the exocyclic
amine groups in building blocks (I-p)-(VI-p), and n represents the
average number of the groups F.sub.i in the prepolymer and is in
the range of 1 to 10000.
[0022] In particular, the novel supramolecular polymer is
preferably prepared by melt processing or reactive processing.
[0023] The supramolecular polymer according to the present
invention is very useful in coating applications such as
decorative, protective, thermo-reversible and self-healing
coatings, adhesive compositions, sealing compositions, as
thickener, gelator or binder, and in imaging or biomedical
applications. The present invention therefore also relates to an
article or a composition comprising the supramolecular polymer
according to the invention, wherein the article or composition is
preferably selected from the group consisting of decorative,
protective, thermo-reversible and self-healing coatings, adhesive
compositions, sealing compositions, thickeners, gelators and
binders.
DETAILED DESCRIPTION OF THE INVENTION
[0024] In this description and in its claims, the verb "to
comprise" and its conjugations is used in its non-limiting sense to
mean that items following the word are included, but items not
specifically mentioned are not excluded. In addition, reference to
an element by the indefinite article "a" or "an" does not exclude
the possibility that more than one of the element is present,
unless the context clearly requires that there is one and only one
of the elements. The indefinite article "a" or "an" thus usually
means "at least one".
[0025] In this description, "melt processing" and "reactive
processing" involve polymerisation process without the use of any
solvent.
Description and Synthesis of the 4H Unit
DEFINITIONS
[0026] In this document a functional group is indicated by the
terms "ester", "ether", "urea" or "ureido", "urethane", "amide",
"imide", etc. These functional groups are known in the art and have
the following structures: ester: --C(O)O--; ether: --O--; urea or
ureido: --NHC(O)NH--; urethane: --NHC(O)O--; amide: --NHC(O)--;
imide: --C(O)NC(O)--, etc. Similar functional groups based on (at
least in part) sulphur in stead of oxygen are also possible, giving
sulfides (--S--), thio-ureas (--NHC(S)NH--), thio-urethanes
(--NHC(S)O--, --NHC(O)S-- or --NHC(S)S--), thio-esters (--C(S)O--,
--C(O)S-- or --C(S)S--), thio-amide (--NHC(S)--), etc.
[0027] As indicated in this document, alkyl groups may be cyclic,
linear or branched which implies that e.g. a C.sub.8 alkyl group
may be n-octyl, 2,3-dimethylhexyl or cyclohexylethyl. Likewise, an
alkaryl group may be an aryl group substituted with a linear,
branched or cyclic alkyl group, whereas an arylalkyl group may be a
cyclic, linear or branched alkyl group substituted with an aryl
group. Similarly, arylene groups substituted with alkyl groups
include structures such as 2,3-dimethylphenylene and arylene groups
substituted with alkylene groups include structures such as
1,4-dimethylenephenyl as well as diphenylmethylene.
[0028] In general, the structural element that forms the 4H-unit is
capable of forming at least four hydrogen bridges (4H) and has the
general form (1') or (2') as is disclosed in U.S. Pat. No.
6,320,018, incorporated by reference herein:
##STR00003##
[0029] If the structural element (4H) is capable of forming four
hydrogen bridges which is preferred according to the invention, the
structural element (4H) has preferably the general form (1) or
(2):
##STR00004##
[0030] In all general forms shown above the C--X.sub.i and
C--Y.sub.i linkages each represent a single or double bond, n is 4
or more and X.sub.1 . . . X.sub.n represent donors or acceptors
that form hydrogen bridges with the H-bridge-forming unit
containing a corresponding structural element (2) linked to them,
with X.sub.i representing a donor and Y.sub.i an acceptor or vice
versa. Properties of the structural element having general forms
(1'), (2'), (1) or (2) are disclosed in U.S. Pat. No. 6,320,018
which is expressly incorporated herein by reference.
[0031] The structural elements (4H) or 4H-units have at least four
donors or acceptors, preferably four donors or acceptors, so that
they can in pairs form at least four hydrogen bridges with one
another. Preferably the structural elements (4H) have at least two
successive donors, followed by at least two acceptors, preferably
two successive donors followed by two successive acceptors,
preferably structural elements according to general form (1') or
more preferably (1) with n=4, in which X.sub.i and X.sub.2 both
represent a donor and an acceptor, respectively, and X.sub.3 and
X.sub.4 both an acceptor and a donor, respectively. According to
the invention, the donors and acceptors are preferably O, S, and N
atoms.
[0032] Molecules that can be used to construct the structural
element (4H) or 4H-units are precursors of the 4H-unit and are
chosen from nitrogen containing compounds that are reacted with
isocyanates, thioisocyanates or activated amines, or that are
activated and reacted with primary amines, to obtain a urea or
thiourea moiety that is part of the quadruple hydrogen bonding site
as is well known in the art. The nitrogen containing compound is
usually an isocytosine derivative (i.e. a
2-amino-4-hydroxy-pyrimidine derivative) or a triazine derivative,
or a tautomer, enantiomer or diastereomer of these derivatives. The
isocytosine or triazine derivatives are preferably represented by
formulas (I-p) to (VI-p), as described above. More preferably, the
nitrogen containing compound is an isocytosine derivative,
according to formulas (I-p) to (V-p).
[0033] According to one embodiment of this invention, the building
blocks (I-p)-(VI-p) are considered precursors of the building
blocks (I)-(VI). Therefore, building blocks (I)-(VI) can be
prepared from building blocks (I-p)-(VI-p) by direct reaction with
bifunctional molecules, preferably diisocyanates, dithioisocyanates
or bifunctional molecules having two activated primary amine
groups. Therefore, these bifunctional molecules preferably have the
schematic form:
X-A-X
wherein A is defined as above and wherein X is --NCO, --NCS,
--NHC(O)L or --NHC(S)L, wherein L is a leaving group such as an
imidazole group, a succidimyl group, a caprolactam group or a
(substituted) phenol group. Preferably, X is --NCO. In this
embodiment, X-A-X is more preferably, an alkylene diisocyanate
wherein the alkylene group comprises 1-20 carbon atoms and wherein
the alkylene group may be linear, cyclic or branched, preferably
linear, or an arylene diisocyanate, wherein the arylene group
comprises 6-20 carbon atoms and may be substituted with alkyl or
alkylene groups comprising 1-6 carbon atoms. The bifunctional
molecule is even more preferably n-hexyldiisocyanate (HDI) or
4,4'-methylene bis(phenyl isocyanate) (MDI), most preferably
HDI.
[0034] Alternatively, to produce building blocks (I)-(VI),
(I-p)-(VI-p) are first activated with activating reagents such as
carbonyl diimidazole, disuccidimidyl carbonate or other phosgene
derivatives, and then reacted with primary amines bearing other
reactive group(s), such as diamines, amino alcohols, amino thiols,
amino acids, amino esters, more preferably diamines such as
branched, cyclic or linear alkylene diamines or arylene diamines
wherein the arylene may be substituted with alkyl or alkylene
groups comprising 1-6 carbon atoms, most preferably linear alkylene
diamines such as preferably n-hexylene diamine or n-butylene
diamine.
[0035] Apart from the 4H-unit building blocks (I)-(VI), other
triazine derived building blocks that are useful according to the
invention are those described in formulas (VII) and (VIII), wherein
A, B.sub.1, D and X are defined as under "Summary of the
invention":
##STR00005##
[0036] These triazine derived building blocks can be prepared in a
similar fashion as building blocks (I)-(VI), by reaction of the
triazine precursors with the bifunctional molecules X-A-X, that are
described above. These building blocks are less preferred than
(I)-(VI).
The 4H-Unit Building Blocks (I) to (VI) and Their Precursors (I-p)
to (VI-p)
[0037] A preferred class of the building blocks according to
formulas (I)-(VI) and (I-p)-(VI-p) are those wherein R.sub.1 is a
linear, cyclic or branched C.sub.2-C.sub.12 alkyl group, a
C.sub.6-C.sub.12 aryl group, a C.sub.7-C.sub.12 alkaryl group or a
C.sub.7-C.sub.12 alkylaryl group, wherein the alkyl, aryl, alkaryl
and alkylaryl groups optionally comprise 1-3 heteroatoms, more
preferably comprising 1 nitrogen atom, wherein the nitrogen atom is
preferably directly connected to the ring structure. More
preferably, R.sub.1 is a linear, cyclic or branched C.sub.2-C.sub.6
alkyl group. Even more preferably, R.sub.1 is selected from the
group consisting of ethyl, n-propyl, i-propyl, n-butyl, s-butyl,
t-butyl, n-pentyl, s-pentyl, 2,2-dimethyl propyl, 3-methyl butyl,
cyclohexyl and n-hexyl. Most preferably, R.sub.1 is selected from
the group consisting of ethyl, n-propyl and i-propyl.
[0038] Yet another preferred class of the building blocks according
to formulas (I)-(VI) and (I-p)-(VI-p) are those wherein R.sub.2 is
a hydrogen, or a linear, cyclic or branched C.sub.1-C.sub.12 alkyl
group, optionally comprising 1-3 heteroatoms, wherein the
heteroatoms are selected from nitrogen, oxygen and sulphur. More
preferably, R.sub.2 is a hydrogen or a linear or branched
C.sub.1-C.sub.6 alkyl group or a C.sub.1-C.sub.6 alkylene group
that comprises an ester end group (for example, R.sub.2 is a
(CH.sub.2).sub.nCOOR.sub.7 group, wherein n=1 or 2 and R.sub.7 is a
methyl or ethyl group). More preferably R.sub.2 is a hydrogen or a
linear or branched C.sub.1-C.sub.6 alkyl group. Most preferably,
R.sub.2 is a hydrogen.
[0039] Yet another preferred class of building blocks according to
formulas (I)-(VI) and (I-p)-(VI-p) are those wherein A is a linear,
cyclic or branched C.sub.2-C.sub.13 alkylene or a C.sub.6-C.sub.13
arylene group, wherein the arylene group is optionally substituted
with linear or branched C.sub.1-C.sub.6 alkyl or alkylene groups.
More preferably, A is a linear or branched C.sub.4-C.sub.13
alkylene or C.sub.6-C.sub.13 arylene group, wherein the arylene
group is optionally substituted with linear or branched
C.sub.1-C.sub.6 alkyl or alkylene groups. Even more preferably, A
is a linear hexamethylene or diphenylmethylene group. Most
preferably, A is a linear hexamethylene group.
[0040] Yet another preferred class of building block structures
according to formulas (I)-(VI) and (I-p)-(VI-p) are those wherein
B.sub.1 and B.sub.2 are independently linear or branched
C.sub.1-C.sub.6 alkylene groups, wherein B.sub.1 optionally
comprises an amide, urea, ester or urethane functional group that
connects th is C.sub.1-C.sub.6 alkylene group with linking group A.
More preferably, B.sub.1 and B.sub.2 are linear or branched
C.sub.1-C.sub.6 alkylene groups, wherein B.sub.1 optionally
comprises a urethane functional group. Most preferably, B.sub.1 is
an ethylene urethane (i.e. CH.sub.2CH.sub.2OC(O)NH) and B.sub.2 is
an ethylene group.
[0041] Another preferred class of building blocks according to
formulas (VI) and (VI-p) are those wherein D is a NH.sub.2 or OH
functionality. More preferably, D is a NH.sub.2 functionality.
[0042] Another preferred class of building blocks according to
formulas (I) (VI) are those wherein X is --NCO, --SH, oxiranyl or
--NHR.sub.5. More preferably, X is --NCO or --NHR.sub.5, wherein
R.sub.5 is a hydrogen atom or a linear or branched C.sub.1-C.sub.6
alkyl group, more preferably a hydrogen atom. Most preferably, X is
--NCO.
[0043] Yet another preferred class of building blocks according to
formulas (I-p)-(VI-p) are those wherein Y is --OH or --NHR.sub.5,
wherein R.sub.5 is a hydrogen atom or a linear or branched
C.sub.1-C.sub.6 alkyl group, more preferably a hydrogen atom. Most
preferably, Y is OH.
[0044] More preferably, in formulas (I) and (I-p), R.sub.1 is a
linear, cyclic or branched C.sub.2-C.sub.6 alkyl group, R.sub.2 is
hydrogen, X is --NCO and A is a C.sub.4-C.sub.13 alkylene or a
C.sub.6-C.sub.13 arylene group, wherein the arylene group is
optionally substituted with linear or branched C.sub.1-C.sub.6
alkyl or alkylene groups. In another embodiment of this invention,
R.sub.1 in formula (I-p) is an alkyl amine R.sub.8NH group or a
dialkyl amine R.sub.8R.sub.9N group, wherein R.sub.8 and R.sub.9
are independently linear or branched C.sub.1-C.sub.10 alkyl groups,
preferably linear or branched C.sub.1-C.sub.6 alkyl groups, and
R.sub.2 is a hydrogen.
[0045] More preferably, in formulas (II), (III), (II-p) and
(III-p), R.sub.2 is a hydrogen, or a linear or branched
C.sub.1-C.sub.6 alkyl group, X is --NCO and A is a C.sub.4-C.sub.13
alkylene or a C.sub.6-C.sub.1-3 arylene group, wherein the arylene
group is optionally substituted with linear or branched
C.sub.1-C.sub.6 alkyl or alkylene groups.
[0046] More preferably, in formulas (IV) and (IV-p), R.sub.1 is a
linear, cyclic or branched C.sub.2-C.sub.6 alkyl group, X is --NCO,
A is a C.sub.4-C.sub.13 alkylene or a C.sub.6-C.sub.13 arylene
group, wherein the arylene group is optionally substituted with
linear or branched C.sub.1-C.sub.6 alkyl or alkylene groups,
B.sub.1 is a C.sub.1-C.sub.6 alkylene group containing a urethane
group that bridges this C.sub.1-C.sub.6 alkylene group with linking
group A, B.sub.2 is a C.sub.1-C.sub.6 alkylene group, and Y is
--OH.
[0047] More preferably, in formulas (V) and (V-p), R.sub.2 is a
hydrogen atom or a linear or branched C.sub.1-C.sub.6 alkyl group,
preferably a hydrogen atom, R.sub.3 is a hydrogen or a linear or
branched C.sub.1-C.sub.6 alkyl group, X is --NCO, A is a
C.sub.4-C.sub.13 alkylene or a C.sub.6-C.sub.13 arylene group,
wherein the arylene group is optionally substituted with linear or
branched C.sub.1-C.sub.6 alkyl or alkylene groups, B.sub.1 is a
C.sub.1-C.sub.6 alkyl ene group containing a urea or urethane group
that bridges this C.sub.1-C.sub.6 alkylene group with linking group
A, B.sub.2 is a C.sub.1-C.sub.6 alkylene group, and Y is --OH or
--NHR.sub.5, wherein R.sub.5 is a hydrogen atom or a linear or
branched C.sub.1-C.sub.6 alkyl group, more preferably a linear or
branched C.sub.1-C.sub.6 alkyl group. Y is most preferably
--OH.
[0048] More preferably, in formulas (VI) and (VI-p), R.sub.1 is a
linear or branched C.sub.2-C.sub.6 alkyl group, X is --NCO, A is a
C.sub.4-C.sub.13 alkylene or a C.sub.6-C.sub.13 arylene group,
wherein the arylene group is optionally substituted with linear or
branched C.sub.1-C.sub.6 alkyl or alkylene groups. In another
embodiment of this invention, R.sub.1 in formula (VI-p) is a linear
or branched C.sub.2-C.sub.12 alkylene group, where this alkylene
group bears a reactive endgroup, preferably an --OH reactive group.
Alternatively, in this embodiment, R.sub.1 is an alkylamine
--NHR.sub.8 group, a dialkyl amine --NR.sub.8R.sub.9 group, a --NH
amino alkylene group or a --NR.sub.8 aminoalkyl alkylene group,
wherein the C.sub.2-C.sub.10 alkylenes bear a reactive endgroup,
preferably a --NH.sub.2 or a --OH reactive group, most preferably a
--OH reactive group, and wherein R.sub.8 and R.sub.9 are
independently linear or branched C.sub.1-C.sub.10 alkyl groups,
preferably linear or branched C.sub.1-C.sub.6 alkyl groups.
[0049] Building blocks (I)-(VI) are preferred over building blocks
(I-p)-(VI-p). The building blocks according to formulas (I), (III),
(IV) and (VI) are preferred over those of (II) and (V). More
preferred are structures (I), (III) and (IV), most preferred is
structure (I). The building blocks according to formulas
(I-p)-(V-p) are preferred over that of (VI-p). More preferred are
structures (I-p), (IV-p) and (V-p), and most preferred is structure
(I-p).
Description of the Prepolymer
[0050] The prepolymer can be any functional polymer or oligomer and
can be represented in the following simple schematic form:
P--(F.sub.i).sub.n
[0051] wherein P represents the polymeric or oligomeric chain,
F.sub.i represents the complementary reactive groups and n
represents the average number of these groups in the prepolymer.
The complementary reactive groups (F.sub.i) are groups that can
react with the reactive groups in the building blocks (I)-(VI) or
(I-p)-(VI-p), and can be any reactive functionality known in the
art. The function (F.sub.i) can be alcohol groups (--OH groups),
preferably primary alcohols, thiols, amines, preferably primary
amines, activated primary amines, isocyanates, thioisocyanates,
blocked (thio)isocyanates, (activated) carboxylic acid derivatives
such as (activated) esters, such as anhydrides, maleimides,
oxiranyls (or epoxides) or the like. More preferably, (F.sub.i) are
alcohols, amines, oxiranyls, anhydrides or isocyanates, most
preferably (F.sub.i) are amines (--NH.sub.2), alcohols (--OH) or
isocyanates (--NCO). The reactive groups (F.sub.i) can be of the
same chemical nature, of a different chemical nature, preferably of
the same chemical nature. For example, n=2 and F.sub.1 and F.sub.2
are both alcohols. The average number of reactive or groups n in
the prepolymer is 1 to 10000, preferably 2 to 50, most preferably 3
to 25.
[0052] P represents any polymer backbone, such as polyether,
polyester, polyamide, polyacrylate, polymethacrylate, polyolefin,
polysiloxane, hydrogenated polyolefin, polycarbonate, or copolymers
of any kind. According to a preferred embodiment of the invention,
the prepolymer is selected from the group consisting of polyether,
polyester, polycarbonate, polysiloxane, hydrogenated polyolefin, or
low molecular weight precursors derived from dimerized fatty acids,
such as Pripol and Priplast, both marketed by Uniqema BV, the
Netherlands. The number average molecular weight of the prepolymer
is preferably in the range from 100 to 100000, more preferably from
200 to 20000, even more preferably 300 to 10000, most preferably
from 500 to 4600.
[0053] Preferably, the prepolymer is a polymer with about two
hydroxyl end-groups. Examples are polyetherdiols having a
polyoxyalkylene structure and hydroxyl end-groups, such as
polyethylene glycol, polypropylene glycol,
poly(ethylene-co-propylene)glycol, polytetramethylene glycol, or
polyesterdiols, such as polycaprolactonediol, diol end-capped
poly(1,4-butylene adipate), diol end-capped poly(1,4-butylene
glutarate), or polyolefindiols, such as hydroxyl functionalized
polybutadiene, hydroxyl functionalized poly(ethylene-butylene), or
polycarbonates such as poly(1,3-propanediol carbonate)glycol,
trimethylenecarbonate, or poly(1,6-hexanediol carbonate) glycol, or
polyamide diols, or low molecular weight diols based such as Pripol
2033 and Priplast 3190 or 3192 (marketed by Uniqema BV, the
Netherlands).
[0054] Another preferred prepolymer is a polymer with about two
primary amine end-groups. Examples are Jeffamines.RTM.
(polyoxyalkylene amines produced and marketed by Huntsman),
aliphatic polyamides and polysiloxanes with amine end groups.
[0055] Another preferred prepolymer is a polymer with about two
isocyanate end groups. These functionalized prepolymers can for
example and preferably be prepared by reacting prepolymers with
hydroxyl end groups (see above for examples of such prepolymers)
with appropriate equivalents of a diisocyanate or dithioisocyanate,
more preferably a diisocyanate, more preferably a linear, branched
or cyclic C.sub.1-C.sub.12 alkylene diisocyanate or a
C.sub.6-C.sub.13 aryl ene diisocyanate, most preferably isophorone
diisocyanate (IPDI) or methylene bis(phenyl isocyanate) (MDI).
Preferably, the prepolymer has two hydroxyl end groups and
therefore (approximately) two equivalents of diisocyanate are
used.
[0056] Alternatively, the prepolymer is a maleated polyolefin,
which can be modified with 4H-unit building blocks in the melt.
Description and Synthesis of the Supramolecular Polymer
[0057] The present invention further relates to the synthesis of a
novel supramolecular polymers and copolymers, wherein a building
block according to formulas (I)-(VI) or (I-p)-(VI-p) is reacted
with a suitable prepolymer P--(F.sub.i).sub.n. The supramolecular
polymer of this invention has a number average molecular weight of
500 to 500000, preferably 1100 to 200000, more preferably 1500 to
100000, more preferably 2000 to 50000, and most preferably 2500 to
19000 Dalton, and has 1 to 50, preferably 2 to 20, more preferably
2 to 15, and most preferably 3 to 10 4H-units.
[0058] Suitable prepolymers are prepolymers with reactive groups
(F.sub.i) that are complementary reactive with groups X in
structures (I)-(VI) or with groups Y or with the exocyclic amine
groups in structures (I-p)-(VI-p) or with optional reactive groups
in the R.sub.1-group of (VI-p). In this patent application,
complementary reactive groups are to be understood as reactive
groups that form, preferably covalent, bonds under conventional
reaction conditions as will be apparent to a person skilled in the
art. Examples of complementary reactive groups are isocyanate and
hydroxyl groups that can form a urethane functional group,
isocyanate and amine groups that can form a urea group, carboxyl
acid or ester and hydroxyl groups that can form an ester group,
carboxyl acid or ester and amino groups that can form an amide
group, oxiranyl (or epoxide) and amino groups that can form a
secondary amine group, acid-anhydride and amino groups that can
form an amide or imide group, hydroxyl groups that can form an
ether group etc. Preferably, (thio)urethane, (thio)urea, ester,
amide or secondary amine functional groups are formed between the
complementary reactive groups. More preferably, the formed
functional group is a urethane or a urea, most preferably a
urethane.
[0059] More specifically, in the embodiment of this invention where
the functional prepolymer P--(F.sub.i).sub.n is reacted with one of
the building blocks (I)-(VI), and X is an electrophilic reactive
group, such as for example X.dbd.NCO, the complementary reactive
groups (F.sub.i) are preferably alcohols or amines, more preferably
alcohols. If X is a nucleophilic group, such as for example for
X.dbd.OH or NH.sub.2, the complementary reactive groups (F.sub.i)
are preferably isocyanates, blocked isocyanates, epoxides,
activated amines or (activated) carboxylic acid derivatives, more
preferably isocyanates, epoxides or (activated) carboxylic acid
derivatives, most preferably isocyanates.
[0060] In the embodiment of this invention where the functional
prepolymer P--(F.sub.i).sub.n is reacted with one of the building
blocks (I-p)-(VI-p), the complementary reactive groups (F.sub.i)
are preferably isocyanates, thioisocyanates or (activated) primary
amines, most preferably isocyanates.
[0061] Hence, the supramolecular polymer according to the present
invention can be structurally characterised by a supramolecular
polymer comprising 1-50 4H-units and at least one monomeric
building block selected from the group consisting of monomeric
building blocks (I)-(VI) and (I-p)-(VI-p), wherein R.sub.1,
R.sub.2, R.sub.3, R.sub.4, R.sub.5, R.sub.6, Z, P and n are as
defined above, D=D', X.dbd.X' and Y.dbd.Y'; D' is --O--, --S--,
--NH-- or --NR.sub.4--; X' is --N--C(O)--, --O--, --S--,
--NR.sub.5--, --C(Z)-Z- or --C(Z)-NR.sub.6--; Y' is --O--, --S--,
--NR.sub.5--, --C(Z)-Z- or --C(Z)-NR.sub.6--; and F.sub.i' is
derived from a group that is complementary reactive with X, Y
and/or exocyclic amines in building blocks (I-p)-(VI-p).
[0062] The molar ratio of the number of reactive groups in the
building blocks (I)-(VI) or (I-p)-(VI-p) to the number of reactive
groups in the prepolymer is between 1:20 and 2:1, preferably
between 1:5 and 1.2:1, more preferably between 1:1.2 and 1.2:1 and
most preferably between 1:1.1 and 1.1:1.
[0063] Apart from prepolymers, co-monomers can additionally be
added during the reactive processing to produce the supramolecular
polymers of this invention. Co-monomers are small or relatively
small molecules bearing reactive groups. Examples of co-monomers
are diols, such as linear or branched C.sub.1-C.sub.20 alkylene
diols, diamines, such as linear or branched C.sub.1-C.sub.20
alkylene diamines, diisocyanates, such as linear, branched or
cyclic C.sub.1-C.sub.20 alkylene diisocyanates (linear is
preferred), isophorone diisocyanate (IPDI), methylene diphenyl
diisocyanate (MDI), methylene bis(cyclohexylisocyanate) (HMDI; the
hydrogenated version of MDI), C.sub.1-C.sub.20 amino alcohols,
C.sub.1-C.sub.20 triols, C.sub.1-C.sub.20 triamines,
C.sub.1-C.sub.20 tri-isocyanates, C.sub.1-C.sub.20 polyalcohols,
C.sub.1-C.sub.20 poly amines or C.sub.1-C.sub.20 poly isocyanates.
Specific examples of C.sub.1-C.sub.20 tri-isocyanates are
Vestanats.RTM. of different grades that are produced by Degussa;
these are isocyanurates with approximately three pendant isocyanate
moieties.
[0064] According to the invention, it is possible to use a
combination of prepolymers, wherein the used prepolymers have a
different chemical composition (backbone P) and/or different
reactive groups (F.sub.i). Likewise, it is also possible to use a
combination of building blocks (I)-(VI) and (I-p)-(VI-p) in order
to produce the supramolecular polymer.
[0065] According to the described building blocks (I)-(VI) and
I-p)-(VI-p), the described prepolymers, and the described ways in
which to combine and react these components, the supramolecular
polymer of this invention is a polymer that contains 4H-units that
are preferably flanked by linkers that are derived from
bifunctional molecules selected from the group consisting of
C.sub.1-C.sub.20 alkylene diisocyanates, C.sub.6-C.sub.20 arylene
diisocyanates, C.sub.1-C.sub.20 alkylene dithioisocyanates,
C.sub.6-C.sub.20 arylene dithioisocyanates, C.sub.2-C.sub.20
alkylene diamines or C.sub.2-C.sub.20 alkylene amino alcohols, more
preferably C.sub.1-C.sub.20 alkylene diisocyanates or
C.sub.2-C.sub.20 alkylene diamines, most preferably
C.sub.1-C.sub.20 alkylene diisocyanates. At the other flank, the
linker is connected to the prepolymeric chain P via a functional
group such as for example a (thio)urethane, a (thio)urea, an ester,
an amide or a secondary amine. More preferably, the functional
group is a urethane or a urea, most preferably a urethane.
Process for the Preparation of the Supramolecular Polymer by Melt
Processing or Reactive Processing
[0066] The present invention further relates to a process for the
synthesis of the supramolecular polymer. Said process may involve
any process known in the art including especially and preferably
reactive processing or melt processing in the bulk.
[0067] The improved processing method according to this invention
is possible because of the relatively low melting point and higher
solubility (in a suitable solvent, or preferably in the melt) of
the 4H-unit building blocks according to formulas (I)-(VI), that
have melting points preferably below 230.degree. C., or that of
their corresponding precursor building blocks according to formulas
(I-p)-(VI-p), that have melting points preferably below 295.degree.
C. Surprisingly, reactive processing of these building blocks
appears to be much easier, when (a) the methyl group in the
6-position of known isocytosine or triazine derived building blocks
is replaced with organic residues containing two to twenty carbon
atoms, (b) organic residues containing one to twenty carbon atoms
at the 5-position of the isocytosine ring are present, or when (c)
an organic residue containing two to twenty carbon atoms at the
ureido position of the 4H-unit building block is present, or by a
combination of these changes.
[0068] The reactive processing of the building blocks presented in
this invention with suitable prepolymers can be done by any method
known in the art, for example by simply mixing in a cup, by using a
Banbury-type mixer, by using a Brabender mixer, by using a single
screw extruder, or by using a twin screw extruder. The reactive
processing is performed between 70.degree. C. and 150.degree. C.,
more preferably between 70.degree. C. and 145.degree. C., more
preferably between 90.degree. C. and 140.degree. C., and most
preferably between 110.degree. C. and 135.degree. C.
[0069] In one embodiment of the invention no catalyst is added to
the reaction mixture, for example, when isocyanates are reacted
with amines or in some cases where no stoichiometric amounts of
reactants are used. This is preferred when complete absence of
residual catalyst is required for the use of the material, for
example in biomedical applications. In another embodiment of this
invention a catalyst is added to the reaction mixture that promotes
the reactions between the complementary groups. Examples are
catalysts known in the art that promote the reaction between
isocyanates and hydroxyl groups that are derived from tertiary
amines such as 1,4-diazabicyclo[2.2.2]octane (DABCO) or
1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), or derived from
transition metals, such as tin(II) octanoate, dibutyltin(IV)
laurate or zirconium acetoacetate. Preferably, these catalyst are
tin(II) or tin(IV) compounds. The amount of catalyst is generally
below 1% by weight, preferably below 0.5% by weight and most
preferably below 0.2% by weight of the total amount of
reactants.
[0070] The supramolecular polymer is obtained as a melt, that can
be isolated as such, or can be chopped in pellets, spun in fibers,
directly dissolved in a medium of choice, or transformed or
formulated into whatever form that is desired.
Applications of the Supramolecular Polymer
[0071] The supramolecular polymers (and copolymers) according to
the invention are in particular suitable for applications benefit
from a low viscosity in the melt or solution with good mechanical
properties at room temperature. Such as applications related to
coatings (leather, textile, wood, optical fibers, paper and paint
formulations), imaging technologies (printing, stereolithography,
photography and lithography), biomedical applications (materials
for controlled release of drugs and materials for
tissue-engineering, tablet formulation), thermo-reversible or
self-healing coatings, adhesive and sealing compositions,
thickening agents, gelling agents and binders.
EXAMPLES
[0072] The following non-limiting examples further illustrate the
preferred embodiments of the invention. When not specifically
mentioned, chemicals are obtained from Aldrich.
Precursors of 4H-Units: Examples of Building Blocks (I-p) to
(VI-p)
Example 1
##STR00006##
[0074] Methyl-4-methyl-3-oxo-valerate (83.0 g) and guanidine
carbonate (103.8 g) are heated overnight under a nitrogen
atmosphere in ethanol (500 mL) at an oil bath temperature of
80.degree. C. The yellow reaction mixture is evaporated down, ice
water is added and the pH is brought to 6 by addition of acetic
acid. The white precipitate is filtered, washed with ice water and
dried in vacuo. Yield of isocytosine: 61.5 g (70%). .sup.1H NMR
(400 MHz, DMSO-d.sub.6): .delta. 10.6 (1H), 6.4 (2H), 5.4 (1H), 2.5
(1H), 1.1 (6H).
Example 2
##STR00007##
[0076] Methyl-4,4-dimethyl-3-oxo-pentanoate (50.0 g) and guanidine
carbonate (56.9 g) are heated overnight under a nitrogen atmosphere
in ethanol (400 mL) at an oil bath temperature of 80.degree. C. The
reaction mixture is filtered, the filtrate is evaporated down,
water (50 mL) is added and the pH is brought to 6 by addition of
acetic acid. The white precipitate is filtered, washed with several
portions of water and dried in vacuo to give a quantitative yield
of isocytosine product. .sup.1H NMR (400 MHz, DMSO-d.sub.6):
.delta. 10.6 (1H), 6.4 (2H), 5.45 (1H), 1.1 (9H).
Example 3
##STR00008##
[0078] Methyl-propionyl acetate (102.6 g) and guanidine carbonate
(142 g) are heated overnight under a nitrogen atmosphere in ethanol
(600 mL) at an oil bath temperature of 80.degree. C. The reaction
mixture is evaporated down, water is added and the pH is brought to
6 by addition of acetic acid. The white precipitate is filtered,
washed with several portions of water and dried in vacuo to give a
90% yield of product. .sup.1H NMR (400 MHz, DMSO-d.sub.6): .delta.
10.6 (1H), 6.4 (2H), 5.4 (1H), 2.3 (2H), 1.1 (3H).
Example 4
##STR00009##
[0080] Triethylamine (94 mL) is added dropwise to an ice-cooled
mixture of potassium ethyl malonate (106.3 g) and dry acetonitrile
(1 L) that is kept under an inert argon atmosphere. MgCl.sub.2
(72.2 g) is added in portions and the mixture is stirred for 2
hours at room temperature. After cooling the reaction mixture down
to 0.degree. C., 2-ethyl hexanoyl chloride (53 mL) is added drop
wise. Overnight stirring at room temperature is followed by
evaporation of acetonitrile and co-evaporation with toluene. The
crude product is dissolved in diethyl ether and acidic water (3M
HCl), the aqueous layer is extracted with several portions of
ether, and the collected organic layers and subsequently washed
with 3M HCl, a saturated sodium bicarbonate solution and a
saturated sodium chloride solution. The ether solution is dried
over Na.sub.2SO.sub.4, filtered and evaporated down to give the
crude beta-keto ester oil (47%), that is used in the next step
without further purification. The beta-keto ester (55.7 g),
guanidine carbonate (47.0 g) and ethanol (600 mL) are stirred for
two days under a nitrogen atmosphere at an oil bath temperature of
80.degree. C. The reaction mixture is evaporated down, the
remaining residue is dissolved in chloroform, and the resulting
solution is washed with a saturated bicarbonate solution. The
organic solution is then dried using MgSO.sub.4, concentrated and
precipitated by dropwise addition to heptane. Finally, the solid is
washed with pentane and dried in vacuo to give 1-ethyl-pentyl
substituted isocytosine product in a 59% yield.
Example 5
##STR00010##
[0082] 2-Amino-4-hydroxy-6-chloro pyrimidine (2.0 g),
2-(ethylamino)-ethanol (3.7 g) and methoxyethanol (10 mL) are
stirred overnight under an argon atmosphere at an oil bath
temperature of 115.degree. C. The solvent is removed by evaporation
at reduced pressure and co-evaporation with toluene. Addition of
chloroform (50 mL) gives a clear solution that in time develops
into a suspension. Filtration and washing of the residue with
chloroform gives a white powder (1.6 g; 66%). .sup.1H NMR (400 MHz,
DMSO-d.sub.6): .delta. 9.8 (1H), 6.2 (2H), 4.7 (1H), 4.5 (1H), 3.5
(2H), 3.4 (4H), 1.0 (3H).
Example 6
##STR00011##
[0084] 2-Acetylbutyrolactone (2 mL) and guanidine carbonate (3.3 g)
were put to reflux in absolute ethanol (20 mL) in the presence of
triethylamine (5.2 mL). The solution became yellow and turbid.
After overnight heating at reflux, the solid was filtered, washed
with ethanol, and suspended in water. The pH was adjusted to a
value of 6-7 with an HCl-solution, and the mixture was stirred for
a while. Filtration, rinsing of the residue with water and ethanol
and subsequent drying of the solid gave the pure product. .sup.1H
NMR (400 MHz, DMSO-d.sub.6): .delta. 11.2 (1H), 6.6 (2H), 4.5 (1H),
3.4 (2H), 2.5 (2H), 2.1 (3H). FT-IR (neat): .nu. (cm.sup.-1) 3333,
3073, 2871, 1639, 1609, 1541, 1487, 1393, 1233, 1051, 915, 853,
789, 716.
[0085] In comparison with other 5-(2-hydroxyethyl) substituted
isocytosines, this 6-methyl substituted isocytosine has the highest
melting point or traject. See the examples below for the
corresponding 6-isopropyl and 6-cyclohexyl substituted
isocytosines.
Example 7
##STR00012##
[0087] Sodium ethoxide (35.7 g) is added to a stirred solution of
gamma-butyrolactone (26.7 g) and methyl-2-methyl-propanoate (21.3
g) in dry dioxane (100 mL) and DMSO (15 mL). The mixture is kept
under an inert atmosphere, and is heated overnight at 100.degree.
C. The brown mixture is cooled down, ice water (400 mL) is added,
the pH is adjusted to 6, and the solution is extracted with three
portions (100 mL) of chloroform. The collected organic layers are
washed with water, a saturated bicarbonate solution and brine, and
are dried using Na.sub.2SO.sub.4. Evaporation of the volatiles
gives the beta keto ester in a crude yield of 73% (23.8 g), and its
high purity is assessed using GC-MS. The crude product and
guanidinium carbonate (27.5 g, 2 moleq. of guanidine) are stirred
in ethanol (50 mL) and are heated to 50.degree. C., while the
solution is kept under an argon atmosphere. After dropwise addition
of a ca. 30 (w/w) % sodium methoxide solution in methanol (54 mL,
ca. 2 moleq of NaOMe), the reaction mixture is heated overnight at
an oil bath temperature of 90.degree. C. The volatiles are removed
by evaporation, ice water (200 mL) is added to the residue and the
mixture is carefully (CO.sub.2-formation) brought to pH=6 by
addition of an HCl-solution. The precipitate is filtered, washed
with water and dried in vacuo to yield a white powder. .sup.1H NMR
(300 MHz, DMSO-d.sub.6): .delta. 10.8 (1H), 6.3 (2H), 4.6 (1H), 3.3
(2H), 3.0 (1H), 2.5 (2H), 1.0 (6H).
Example 8
##STR00013##
[0089] In a similar method as for example 7, the beta keto ester of
alpha-cyclohexylcarbonyl-gamma-butyrolactone is prepared (see also
compound IVa in Chem.Pharm.Bull. 37(4), 958-961, 1989 by Uchida et
al.): methyl cyclohexanecarboxylate (30 g) and gamma-butyrolactone
(26.7 g, 1.5 moleq.) are dissolved in 120 mL of dry dioxane and 20
mL of dry dimethyl sulfoxide. Sodium ethoxide (35.4 g, 2.5 moleq.)
is added and the mixture is stirred overnight under N.sub.2 at a
temperature of 100.degree. C. The mixture is then cooled to
.about.50-60.degree. C. and ca. 400 mL H.sub.2O is added. The
aqueous layer is brought to pH=6 with acetic acid, and is extracted
with three 100 mL portions of chloroform (careful; CO.sub.2
formation). The organic layer is washed with H.sub.2O, thereafter
with a NaHCO.sub.3-solution and finally with brine (a saturated
NaCl solution), and is then dried with Na.sub.2SO.sub.4.
Evaporation of the volatiles gives a ca. 85% yield of an oil. This
crude beta-keto-ester (34 g) and guanidinium carbonate (31.2 g; 2
moleq. of guanidine) are stirred in ethanol (200 mL). To this
mixture, that is heated to 50.degree. C. and that is kept under an
argon atmosphere, a 30 (w/w) % sodium methoxide solution in
methanol (18.7 g of NaOMe in 65 mL of solution; 2 moleq. of NaOMe)
is added drop wise. The mixture is heated overnight at an oil bath
temperature of 90.degree. C., is then evaporated down and water is
added to the residue. The pH of the mixture is adjusted to 6 by
addition of an HCl solution (careful; CO.sub.2 formation), and the
resulting suspension is filtered. The residue is washed with
several portions of water and dried in vacuo to give a white powder
in a 70% yield. .sup.1H NMR (200 MHz, DMSO-d.sub.6): .delta. 10.6
(1H), 6.2 (2H), 4.6 (1H), 3.3 (2H), 2.5 (3H), 2.0-1.0 (10H).
TABLE-US-00001 TABLE 1 Melting points of prepared and commercially
available isocytosines Isocytosine precursor of 4H-unit Melting
point (.degree. C.) Example 1 248 Example 2 288-290 Example 3
251-254 Example 4 158-160 Example 5 236-238 Example 6 275 Example 7
248-249 Example 8 253 6-Methyl-isocytosine >299
6-Amino-isocytosine 285 5,6-Dimethyl-isocytosine 333-337
4H-Unit Building Blocks: Examples of (I)-(VI)
Example 9
##STR00014##
[0091] 1,6-Hexyldiisocyanate (650 g) and methylisocytosine (or
2-amino-4-hydroxy-6-methyl-pyrimidine, 65.1 g) were suspended in a
2-liter flask. The mixture was stirred overnight at 100.degree. C.
under an argon atmosphere. After cooling to room temperature, a
litre of pentane was added to the suspension, while stirring was
continued. The product was filtered, washed with several portions
of pentane and dried in vacuum. 6-isocyanato-hexyl modified
6-methylureidopyrimidinone was obtained as a white powder. .sup.1H
NMR (400 MHz, CDCl.sub.3): .delta. 13.1 (1H), 11.8 (1H), 10.1 (1H),
5.8 (1H), 3.3 (4H), 2.1 (3H), 1.6 (4H), 1.4 (4H). FT-IR (neat):
.nu. (cm.sup.-1) 2935, 2281, 1698, 1668, 1582, 1524, 1256.
##STR00015##
Example 9A
[0092] 4,4'-Methylenebis(cyclohexyl isocyanate) (371 g) and
methylisocytosine (or 2-amino-4-hydroxy-6-methyl-pyrimidine, 29.5
g) were suspended in a 2-liter flask. To the mixture was added NMP
(35 mL) and subsequently stirred for 16 h at 100.degree. C. under
an argon atmosphere. After cooling to room temperature, a liter of
diethylether was added to the suspension, while stirring was
continued. The product was filtered, washed with several portions
of diethylether and dried in vacuum.
4-Methylene-(4'-isocyanato-cyclohexyl)-cyclohexyl modified
6-methylureidopyrimidinone was obtained as a white powder. .sup.1H
NMR (400 MHz, CDCl.sub.3): .delta. 13.2 (1H), 11.8 (1H), 9.9 (1H),
5.8 (1H), 3.8-3.1 (2H), 2.2-0.6 (23H). FT-IR (neat): .nu.
(cm.sup.-1) 2935, 2281, 1698, 1668, 1582, 1524, 1256.
Example 10
##STR00016##
[0094] The isocytosine from example 1 (10.4 g) and
hexyldiisocyanate (68 g) are stirred and kept under an argon
atmosphere. The mixture is heated overnight at an oil bath
temperature of 100.degree. C. After cooling to room temperature,
the clear solution becomes turbid. Hexane (300 mL) is added, and
the mixture is stirred to obtain a suspension of fine particles.
The solid is filtered, washed with several portions of hexane and
dried. Yield: 86%. .sup.1H NMR (400 MHz, CDCl.sub.3): .delta. 13.2
(1H), 11.9 (1H), 10.1 (1H), 5.8 (1H), 3.2 (4H), 2.7 (1H), 1.6 (4H),
1.4 (4H), 1.2 (6H). FT-IR: .nu. (cm.sup.-1) 2270 (NCO-band).
Example 11
##STR00017##
[0096] The isocytosine from example 8 (2 g) is suspended in HDI (14
mL). A drop of dibutyltin dilaurate is added, and the mixture is
stirred for about three hours at 90.degree. C. under an argon
atmosphere until a clear solution has developed. The solution is
cooled to room temperature, some dry chloroform is added to
redissolve the product and this organic solution is added dropwise
to heptane (450 mL). The precipitate is filtered, rinsed with
several portions of heptane and dried, yielding the diisocyanate
product. Yield: ca. 98%. .sup.1H NMR (400 MHz, CDCl.sub.3): .delta.
13.1 (1H), 11.9 (1H), 10.2 (1H), 4.6 (1H), 4.2 (2H), 3.3-3.0 (9H),
2.8 (2H), 1.9-1.2 (26H). FT-IR (neat): .nu. (cm.sup.-1). 220
(NCO-band).
Example 12
##STR00018##
[0098] The isocytosine from example 7 (2.0 g) is suspended in
hexyldiisocyanate (17.1 g). The reaction mixture is kept under an
argon atmosphere and stirred for 3 hours at an oil bath temperature
of 90.degree. C. The solution, that is now clear, is cooled down,
and ca. 50 mL of dry chloroform is added. Dropwise addition to
pentane (500 mL) gives a white powder that is isolated by
filtration, subsequent washing with several portions of heptane and
in vacuo drying of the solid. Yield: 5.0 g (94%). .sup.1H NMR (200
MHz, CDCl.sub.3): .delta. 13.2 (1H), 12.0 (1H), 10.2 (1H), 4.7
(1H), 4.2 (2H), 3.4-3.0 (9H), 2.8 (2H), 1.6-1.0 (22H). FT-IR: .nu.
(cm.sup.-1) 2262 (NCO-band).
Example 13
##STR00019##
[0100] The isocytosine from example 4 (0.86 g) and diphenylmethane
diisocyanate (4.9 g) are heated to 100.degree. C., and this thick
reaction mixture is stirred overnight in an argon atmosphere.
Chloroform (8 mL) is added, and the resulting milky, heterogenous
mixture is precipitated into ether. The solid is filtered and
washed with ether. Drying gives a cream colored product.
[0101] .sup.1H NMR (200 MHz, CDCl.sub.3): .delta. 13.2 (2H), 12.3
(2H), 12.2 (2H), 7.6 (2H), 7.1 (4H), 7.0 (2H), 5.9 (1H), 3.9 (2H),
2.3 (1H), 1.5-18 (4H), 1.4-1.2 (4H), 0.9 (6H). FT-IR: .nu.
(cm.sup.-1) 2258 (NCO-band).
Example 14
##STR00020##
[0103] The isocytosine from example 1 (17 g) and
carbonyldiimidazole (CDI, 22.5 g) are stirred in chloroform (150
mL) under an argon atmosphere. The mixture is heated overnight at
an oil bath temperature of 60.degree. C. Ether (150 mL) is added to
the cooled down reaction mixture, the resulting suspension is
stirred for a short time and the precipitate is then isolated by
filtration, washing of the residue with several portions of
chloroform/ether 1:1 and drying of the powder. The yield of the
CDI-activated product is 96%. This CDI-activated product (15.0 g)
is added in powder form and in small portions to a well-stirred
solution of 1,6-hexyldiamine (72 g) in chloroform (150 mL). The
solution is stirred overnight at room temperature and under an
argon atmosphere, and is then filtered over a glass filter to
remove traces of undissolved by-products. The filtrate is treated
with ether (150 mL), inducing precipitation of the product. The
solids are filtered and once more suspended and stirred in
chloroform (150 mL), to which ether (150 mL) is added in portions.
The precipitate is filtered, washed with chloroform/ether 1/1 and
dried in vacuo to give the product as a white powder. .sup.1H NMR
(200 MHz, DMSO-d.sub.6): .delta. 9.7 (1H), 5.6 (1H), 3.2 (2H), 2.6
(3H), 1.6-1.2 (8H), 1.1 (6H).
TABLE-US-00002 TABLE 2 Melting transitions of 4H-unit building
blocks Melting point 4H-unit building block (.degree. C.) Example 9
235-237 Example 10 98 Example 11 121 Example 12 110-112 Example 13
148-153 Example 14 216-218
General Procedure for Reactive Processing Used in Examples 15-18
and Comparative Examples 1-2
[0104] The reactive processing was performed in a Haake MiniLab
extruder with co-rotating screws, as sold by the Thermo Electron
corporation with a total filling volume of 7 mL. For reactive
processing the following general procedure was followed: the
prepolymer was dried at 120.degree. C. in vacuo for 2 hours
followed by cooling to 100.degree. C. Subsequently the desired
amount of 4H-unit building block or isocytosine building block was
added to the polymer melt and mixed until a homogeneous mixture was
obtained, 5-6 grams of this mixture was feeded to the MiniLab
extruder at 120.degree. C. with screws rotating at 40 rpm followed
by the addition of 1 drop DBDTL when desired. The MiniLab extruder
was heated to the desired reaction temperature in a closed loop
configuration and the mixture was cycled for 10 minutes at the
desired temperature followed by extrusion into a cup at room
temperature.
Example 15
[0105] A prepolymer mix consisting of 5.45 g Pripol 2033
(.alpha.,.omega.-bis-hydroxyfunctional C36 compound obtained from
Uniqema BV) and 6.47 g of the 4H-unit building block from example
10 was partly fed into the Minilab together with 1 drop of DBDTL
and extruded at 130.degree. C. This resulted in a clear glassy
rubber. .sup.1H NMR confirmed complete functionalization of the
Pripol-prepolymer as the signal at 3.6 ppm (belonging to unreacted
hydroxyl-functional Pripol) had completely disappeared and
re-emerged at 4.1 ppm belonging to the polymer product. FT-IR
confirmed complete reaction of the isocyanate by complete
disappearance of the NCO-band at 2270 cm.sup.-1.
Example 16
[0106] A prepolymer mix consisting of 11.03 g
bis-hydroxy-functional polycaprolactone (PCL, M.sub.n=2 k) and 3.54
g of the 4H-unit building block from example 10 was partly fed into
the Minilab together with 1 drop of DBDTL and extruded at
130.degree. C. This resulted in a clear glas that crystallized into
a white brittle polymer upon standing. .sup.1H NMR confirmed
complete functionalization of the PCL-prepolymer as the signal at
3.6 ppm (belonging to unreacted hydroxyl-functional PCL) had
completely disappeared and re-emerged at 4.2 ppm belonging to the
polymer product. FT-IR confirmed complete reaction of the
isocyanate by complete disappearance of the NCO-band at 2270
cm.sup.-1. GPC-analysis using RI-detection: Mn=4.6 kDa, PD=2.0,
relative to polystyrene standards.
Example 17
[0107] A prepolymer mix consisting of 5.47 g
poly-(2-methyl-1,3-propylene)adipate with hydroxy end groups and a
molecular weight M.sub.n of 2000 and 3.54 g of the 4H-unit building
block from example 12 was partly fed into the Minilab together with
1 drop of DBDTL and extruded at 140.degree. C. This resulted in a
clear elastic material. .sup.1H NMR confirmed complete
functionalization of the prepolymer as the signal at 3.5 ppm
(belonging to unreacted hydroxyl-functional prepolymer) had
completely disappeared. FT-IR confirmed complete reaction of the
isocyanate by complete disappearance of the NCO-band at 2260-2270
cm.sup.-1.
Example 18
[0108] A mixture consisting of 19.0 g bis-hydroxy-functional
polycaprolactone (PCL, M.sub.n=2 k) dissolved in chloroform (50 mL)
was slowly added to IPDI (4.23 g) at room temperature in the
presence of 1 drop DBDTL. The mixture was stirred for 16 h under an
argon atmosphere, followed by drying in vacuo. This
isocyanato-functional prepolymer (4.57 g) was heated to 90.degree.
C. and mixed with the isocytosine of example 1 (0.57 g). This
mixture was fed into the Minilab and extruded at 130.degree. C.
This resulted in a clear glas that crystallized into a white
brittle polymer upon standing. .sup.1H NMR confirmed complete
functionalization of the PCL-prepolymer as the signal at 3.6 ppm
(belonging to unreacted hydroxyl-functional PCL) had completely
disappeared and re-emerged at 4.2 ppm belonging to the polymer
product. FT-IR confirmed complete reaction of the isocyanate by
complete disappearance of the NCO-band at 2270 cm.sup.-1.
GPC-analysis using RI-detection: Mn=4.5 kDa, PD=1.9, relative to
polystyrene standards.
Example 19
[0109] A mixture of the isocytosine of example 1 (7.96 g) and
carbodiimidazole (CDI, 10.1 g) in chloroform (50 mL) was heated at
60.degree. C. under an argon atmosphere for 16 hours. After cooling
down diethylether (50 mL) was added to the reaction mixture
resulting in the precipitation of the carbonylimidazole activated
isocytosine which was isolated by filtration and drying in vacuo.
The carbonylimidzaole activated derivatives of the isocytosines of
examples 2 and 3 were prepared in the same manner using
respectively 7.17 g isocytosine and 8.35 g CDI, and 11.0 g
isocytosine and 15.2 g CDI. In the following step the CDI-activated
isocytosine of example 1 (1.57 g), the CDI-activated isocytosine of
example 2 (1.62 g), and the CDI-activated isocytosine of example 3
(1.66 g) were mixed and dissolved in chloroform (100 mL) together
with 8.23 g of bis(aminopropyl) endblocked polydimethylsiloxane DMS
A11 (having a viscosity of 10-15 cSt, obtained from ABCR, Germany).
This mixture was stirred for 4 h at 60.degree. C. under an argon
atmosphere, followed by washings with, subsequently, 1N aqueous
HCl-solution, water, and saturated aqueous NaCl solution. The
organic fraction was dried over Na.sub.2SO.sub.4, followed by
filtration and drying in vacuo, resulting in a clear yellowish
rubberlike material consisting of low molecular weight PDMS
comprising the new 4H-units. .sup.1H NMR (400 MHz, CDCl.sub.3):
.delta. 13.5, 13.2, 11.9, 10.2, 5.9, 5.8, 3.2, 2.7, 2.5, 1.6, 1.2,
1.1, 0.6, 0.2-0.1. FT-IR (neat): .nu. (cm.sup.-1) 2961, 1698, 1659,
1587, 1527, 1258, 1010, 780.
Comparative Example 1
[0110] A prepolymer mix consisting of 2.68 g Pripol 2033
(.alpha.,.omega.-bis-hydroxyfunctional C36 compound obtained from
Uniqema BV) and 2.89 g of the 4H-unit building block from example 9
was partly fed into the Minilab together with 1 drop of DBDTL and
extruded at 130.degree. C. This resulted in an opaque white
product, indicating the presence of unreacted 4H-unit building
block. Indeed, .sup.1H NMR showed incomplete functionalization of
the Pripol-prepolymer as the signal at 3.6 ppm (belonging to
unreacted hydroxyl-functional Pripol) was still present and had
only partly re-emerged at 4.1 ppm. Also FT-IR confirmed incomplete
reaction of the isocyanate, as the NCO-band at 2270 cm.sup.-1 was
still present. Clearly, the higher melting point of the 4H-unit
building block of example 9 compared to the 4H-unit building block
of example 10, prevented complete functionalization at this
processing temperature in contrast to the results of example
15.
Comparative Example 2
[0111] A prepolymer mix consisting of 11.03 g
bis-hydroxy-functional polycaprolactone (PCL, M.sub.n=2 k) and 3.54
g of the 4H-unit building block from example 10 was partly fed into
the Minilab together with 1 drop of DBDTL and extruded at
180.degree. C. This resulted in a brownish glass that crystallized
into a brown brittle polymer upon standing. Although .sup.1H NMR
confirmed complete functionalization of the PCL-prepolymer as the
signal at 3.6 ppm had completely disappeared and re-emerged at 4.2
ppm, also a new signal appeared at 5.7 ppm belonging to an
unidentified product. FT-IR confirmed complete reaction of the
isocyanate by complete disappearance of the NCO-band at 2270
cm.sup.-1. GPC-analysis using RI-detection: Mn=5.4 kDa, PD=2.6,
relative to polystyrene standards. When compared to example 16, the
higher processing temperature of 180.degree. C. clearly results in
the occurrence of side products and/or polymer degradation as
indicated by the brown color, the .sup.1H NMR signal at 5.7 ppm and
the higher molecular weight and broader polydispersity of the
obtained polymer.
Comparative Example 3
[0112] A prepolymer mix consisting of 14.10 g
bis-hydroxy-functional polycaprolactone (PCL, M.sub.n=2 k) and 5.46
g of the 4H-unit building block from example 9A was partly fed into
the Minilab together with 1 drop of DBDTL and extruded at
160.degree. C. This resulted in an elastic material that
crystallized into a white brittle polymer upon standing. .sup.1H
NMR confirmed complete functionalization of the PCL-prepolymer as
the signal at 3.6 ppm (belonging to unreacted hydroxyl-functional
PCL) had completely disappeared. FT-IR confirmed complete reaction
of the isocyanate by complete disappearance of the NCO-band at 2270
cm.sup.-1. GPC-analysis using RI-detection: Mn=4.6 kDa, PD=1.9,
relative to polystyrene standards.
Comparative Example 4
[0113] Poly-(2-methyl-1,3-propylene)adipate with hydroxy end groups
(9.5 g, M.sub.n=2 k) was slowly added to
4,4'-methylenebis(cyclohexyl isocyanate) (2.49 g) at 20.degree. C.
in the presence of 1 drop DBDTL. After complete addition of the
polymer, the mixture was subsequently stirred for 8 h under an
argon atmosphere. The resulting isocyanato-functional prepolymer
was heated to 90.degree. C. and mixed with the isocytosine of
example 1 (1.2 g). This mixture was fed into the Minilab and
extruded at 160.degree. C. This resulted in a polymer melt that
became an elastic material upon cooling. FT-IR confirmed complete
reaction of the isocyanate by complete disappearance of the
NCO-band at 2270 cm.sup.-1 as well as the formation of the
ureido-pyrimidone moiety (absorptions at 1698, 1659, 1587, 1527
cm.sup.-1) GPC-analysis using RI-detection: Mn=4.5 kDa, PD=1.9,
relative to polystyrene standards.
* * * * *