U.S. patent application number 11/360073 was filed with the patent office on 2006-11-02 for polymers with urea groups and silyl groups and production and use thereof.
This patent application is currently assigned to Henkel Kommanditgesellschaft Auf Aktien (Henkel KGAA). Invention is credited to Thomas Bachon, Wilfried Huebner, Wolfgang Klauck, Johann Klein, Hermann Kluth.
Application Number | 20060247407 11/360073 |
Document ID | / |
Family ID | 7661415 |
Filed Date | 2006-11-02 |
United States Patent
Application |
20060247407 |
Kind Code |
A1 |
Bachon; Thomas ; et
al. |
November 2, 2006 |
Polymers with urea groups and silyl groups and production and use
thereof
Abstract
A process for the production of compounds which contain at least
one urea group and at least one silyl goup. The process involves
reacting a compound containing at least one amino group and a
carbamate compound. The compounds produced by this process are
useful as surface coating compositions, foams, and adhesives.
Inventors: |
Bachon; Thomas;
(Duesseldorf, DE) ; Huebner; Wilfried;
(Langenfeld, DE) ; Kluth; Hermann; (Duesseldorf,
DE) ; Klauck; Wolfgang; (Meerbusch, DE) ;
Klein; Johann; (Duesseldorf, DE) |
Correspondence
Address: |
WOODCOCK WASHBURN LLP
ONE LIBERTY PLACE, 46TH FLOOR
PHILADELPHIA
PA
19103
US
|
Assignee: |
Henkel Kommanditgesellschaft Auf
Aktien (Henkel KGAA)
|
Family ID: |
7661415 |
Appl. No.: |
11/360073 |
Filed: |
February 23, 2006 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
10415185 |
Apr 25, 2003 |
7057001 |
|
|
PCT/EP01/12291 |
Oct 24, 2001 |
|
|
|
11360073 |
Feb 23, 2006 |
|
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|
Current U.S.
Class: |
528/29 |
Current CPC
Class: |
Y10T 428/249985
20150401; C08G 71/02 20130101; C08G 71/04 20130101 |
Class at
Publication: |
528/029 |
International
Class: |
C08G 77/04 20060101
C08G077/04; C08G 18/77 20060101 C08G018/77 |
Foreign Application Data
Date |
Code |
Application Number |
Oct 27, 2000 |
DE |
100 53 545.3 |
Claims
1. A process for the production of compounds containing at least
one urea group and at least one silyl group in which a compound
containing at least one amino group and a carbamate are reacted
together as reactants, at least one of the reactants carrying a
silyl group.
2. A process as claimed in claim 1, characterized in that the
reaction is carried out in the presence of a catalyst.
3. A process as claimed in claim 1 or 2, characterized in that a
methyl carbamate or ethyl carbamate is used as the carbamate.
4. A process as claimed in any of claims 1 to 3, characterized in
that a catalyst selected from the group consisting of organic bases
and organometallic compounds is used as the catalyst.
5. A process as claimed in any of claims 1 to 4, characterized in
that at least one polymer is used as at least one reactant.
6. A process as claimed in any of claims 1 to 5, characterized in
that the polymer used is a polymer selected from the group
consisting of polyacrylates, polymethacrylates, polystyrenes,
polyesters, polyethers, polyamides, polyurethanes, polycarbonates,
polylactones, polyethylene imine, polyureas, polyolefins and
polyoxazolidones.
7. A process as claimed in any of claims 1 to 6, characterized in
that at least one reactant containing at least two carbamate groups
is used.
8. A process as claimed in claim 7, characterized in that the
reactant containing at least two carbamate groups is a polymer.
9. A process as claimed in claim 7 or 8, characterized in that it
is carried out in the presence of a trimerization catalyst.
10. A process as claimed in any of claims 1 to 9, characterized in
that the reaction of the reactants is not continued to the complete
reaction of all the carbamate groups.
11. A process as claimed in any of claims 1 to 10, characterized in
that at least one compound containing a silyl group, a urea group
and a carbamate group is present after the reaction.
12. A polymer obtainable by the process claimed in any of claims 1
to 11.
13. A polymer which contains at least one isocyanurate structural
element, at least one urea group and at least one alkoxysilyl
group; if the polymer contains more than one isocyanurate
structural element, no structural element obtainable by reaction of
an isocyanate group with an isocyanate-reactive functional group is
present between at least two isocyanurate structural elements in
the polymer or the structure lying between two isocyanurate groups
has a molecular weight of at least 300.
14. A polymer which contains at least one urea group, at least one
alkoxysilyl group and at least one carbamate group.
15. A polymer as claimed in claim 14, characterized in that it
contains at least one isocyanurate group.
16. A polymer obtainable by reaction of a prepolymer containing at
least two carbamate groups or a mixture of two or more such
prepolymers with an alkoxysilane containing at least one amino
group, the molar ratio of carbamate groups to amino groups being
less than 1.
17. A polymer as claimed in claim 16, characterized in that the
reaction is not continued to the complete reaction of all the
carbamate groups.
18. The use of the compound produced by the process claimed in any
of claims 1 to 11 or of the polymer claimed in any of claims 12 to
17 for the production of surface coating compositions, sealants,
adhesives, assembly or insulating foams.
19. A surface coating composition, sealant, adhesive, assembly or
insulating foam containing at least one polymer produced by the
process claimed in any of claims 1 to 11 or the polymer claimed in
any of claims 12 to 17.
20. A surface coating composition, sealant, adhesive, assembly or
insulating foam as claimed in claim 19, characterized in that it
contains at least one crosslinking catalyst.
Description
CROSS REFERENCE TO RELATED APPLICATIONS
[0001] This application is a divisional of U.S. application Ser.
No. 10/415,185, filed on Apr. 25, 2003, which is the National Stage
of International Application No. PCT/EP01/12291 filed on Oct. 24,
2001, which claims the benefit of German Application No.
10053545.3, filed on Oct. 27, 2000, each of which is hereby
incorporated herein by reference in its entirety.
FIELD OF THE INVENTION
[0002] This invention relates to a process for the production of
compounds containing at least one urea group and at least one silyl
group, in which a compound containing at least one amino group is
reacted with a carbamate, either the compound with at least one
amino group or the carbamate bearing a silyl group, to compounds
produced by this process, to their use and to surface coating
compositions, foams and adhesives containing these compounds.
BACKGROUND
[0003] Organic compounds, especially polymers, which contain both a
silyl group and a urea group are used in many branches of industry,
for example in the coating or adhesives field. The advantages of
such compounds, especially the polymers, lie in particular in their
ability both to hydrophobicize and to impart a binding effect to
hydrophilic substrates and also to crosslink with one another under
the effect of moisture.
[0004] Surface coating compositions containing the above-mentioned
compounds show improved adhesion both on hydrophobic and on
hydrophilic surfaces. Adhesives containing such polymers are
capable, for example, of permanently bonding both hydrophilic and
hydrophobic substrates and substrates of different polarity to one
another.
[0005] Hitherto, the simultaneous introduction of urea groups and
silyl groups into polymers has been difficult for a variety of
reasons. In many cases, isocyanatosilanes have been used to
introduce such groups even though they were unpopular among
manufacturers of such products because of their toxicity and their
sensitivity to water. In addition, residues of isocyanatosilanes
often could not be removed to a satisfactory level from the
compounds thus produced so that a residual content of isocyanates
often resulted in an obligation to declare the compounds themselves
or products produced from them. However, the declaration of such
ingredients reduces consumer acceptance of the products produced
from them.
[0006] However, the problem illustrated here with reference by way
of example to the interplay between urea groups and silyl groups
also applies in principle to many other methods of introducing
structural elements obtainable using isocyanate groups into
polymers. The presence of isocyanates in reaction mixtures often
leads to the formation of unwanted products or to
isocyanate-containing material remaining in the end product so that
the problems mentioned above arise.
[0007] A process for the production of polyethers containing both a
urea group and an alkoxysilyl group is described, for example, in
Chemical Abstracts 123:171406 (abstract of JP 93-185 595). To
produce these compounds, an aminofunctional polyether is reacted
with a silyl compound containing as isocyanate group.
[0008] U.S. Pat. No. 5,886,205 relates to a process for the
production of isocyanate compounds containing silyl groups which
comprises the thermal decomposition of carbamic acid esters
containing silyl groups in the presence of a catalyst. The reaction
of a carbamate with a compound containing at least one amino group
is not mentioned in this document.
[0009] U.S. Pat. No. 5,218,133 relates to a process for the
production of silyl carbamates or silyl isocyanurates, in which an
aminosilane is reacted with a dialkyl carbonate, diaryl carbonates
or a mixture thereof in the presence of a basic catalyst to give a
silyl organocarbamate. The basic catalyst is then optionally
neutralized and residual aminosilane is neutralized. After addition
of a decomposition catalyst and heating under reduced pressure, a
silyl isocyanurate is obtained. However, the cited document does
not describe how silyl compounds containing urea structural
elements can be obtained by reaction of carbamates with amino
compounds, either the amino compound or the carbamate or both
containing a silyl group.
[0010] U.S. Pat. No. 6,008,396 describes a process for the
production of an isocyanato-organsosilane, in which a
carbamato-organosilane is converted into an isocyanato-organosilane
in an inert liquid medium. The production of compounds containing
both a urea group and a silyl group is not mentioned in the cited
document.
[0011] U.S. Pat. No. 5,886,205 describes a process for the
production of an isocyanate containing silyl groups in which a
carbamic acid ester containing silyl groups is decomposed in the
presence of a catalyst at a pH value of at most 8. A process for
the production of compounds containing both urea groups and silyl
groups is not described in the cited document.
[0012] In addition, many combinations of structural elements
obtainable using isocyanate groups and silyl groups have hitherto
only been obtainable by multistage and hence expensive processes.
This applies in particular to the production of polymers containing
both isocyanurate groups and urea and silyl groups. Such polymers
are of considerable interest with regard in particular to their
crosslinking and hence to the resulting material properties of
surface coating compositions and adhesives.
[0013] EP-A 1 006 132 relates to alkoxysilane-containing lacquer
preparations produced using 4,4'-diisocyanatodicyclohexyl methane
polyisocyanates. The cited document describes, for example, the
reaction of polyisocyanates obtainable by trimerization of
4,4'-diisocyanatodicyclohexyl methane with aminofunctional
alkoxysilanes. Unfortunately, the described reaction has the
disadvantage that isocyanurates generally containing low molecular
weight diisocyanates are used. Low molecular weight isocyanates
such as these have a considerable toxic potential. In addition, the
crosslinking of a polymer produced using such isocyanurates is
difficult to control because the isocyanurates described in the
cited document always represent a complex mixture of compounds
differing in their functionality in which isocyanurates having a
functionality of more than three are always present. The use of
such mixtures involves the disadvantage for the user that the
properties of a polymer produced using these
triisocyanatotriisocyanurate mixtures are difficult to adjust in
view of slight crosslinking. Another disadvantage of the compounds
described in the cited document is that a urea group or a urethane
group is always present in the immediate vicinity of the
isocyanurate group because of the structure of the isocyanurates
used. This constellation complicates or prevents the production of
highly flexible binders because this direct proximity of the
functional groups mentioned generally leads to hard brittle
binders.
[0014] In addition, the presence of urethane groups reduces the
thermal stability of these compounds because urethane groups split
at ca. 140-160.degree. C. Unfortunately, such behavior prevents the
use of such compounds in heat-resistant applications.
[0015] Another disadvantage of the described compounds is that
isocyanurates containing isocyanate groups are difficult to
produce. On account of the danger of crosslinking, which increases
with increasing conversion, the trimerization of isocyanates to
isocyanurates can only be carried out to a certain degree below a
corresponding crosslinking point. The isocyanate originally used
for crosslinking and the isocyanurate containing isocyanate groups
obtained as product then have to be separated in complicated
distillation processes. After distillation, the isocyanate
distilled off is returned to the trimerization process. The
volume/time yields of such a process are poor on account of the
complex separation steps.
SUMMARY
[0016] Accordingly, there was a need for a process that would lead
to polymers containing both at least one urea group and a silyl
group in which the disadvantages mentioned above would be avoided.
In addition, there was a need for polymers containing isocyanurate
groups, urea groups and silyl groups which would not attended by
any of the disadvantages mentioned above.
[0017] The problem addressed by the present invention is solved by
a process for the production of compounds containing at least one
urea group and at least one silyl group, by compounds produced by
this process, by polymers containing at least one isocyanurate
group and at least one silyl group, by processes for the production
of such polymers and by the use of the compounds produced by the
process according to the invention and the compounds according to
the invention in surface coating compositions, foams or
adhesives.
DETAILED DESCRIPTION
[0018] Accordingly, the present invention relates firstly to a
process for the production of compounds containing at least one
urea group and at least one silyl group, in which a compound
containing at least one amino group and a carbamate are reacted as
reactants, at least one of the reactants carrying a silyl
group.
[0019] A "urea group" in the context of the present invention is
understood to be a structural element corresponding to general
formula I: ##STR1## in which R.sup.8 is hydrogen and R.sup.9 is
hydrogen, a linear or branched alkyl group containing 1 to 24
carbon atoms, an optionally substituted aryl group containing 6 to
24 carbon atoms, an alkyl or arylsilyl group. The substituent
R.sup.9 may also contain one or more substituents, such as ester
groups, keto groups, amino groups or hydroxyl groups. The
substituent R.sup.9 is preferably hydrogen or a linear or branched
alkyl group containing 1 to 12 carbon atoms, more particularly
hydrogen.
[0020] A "silyl group" in the context of the present invention is
understood to be a compound corresponding to general formula II:
##STR2## in which R.sup.1 to R.sup.6 independently of one another
represent a linear or branched, saturated or unsaturated
hydrocarbon radical containing 1 to about 24 carbon atoms, a
saturated or unsaturated cycloalkyl group containing 4 to about 24
carbon atoms or an aryl group containing 6 to about 24 carbon
atoms, n, m and j are each integers of 0 to 3 (m+n+j=3), a is an
integer of 0 to 3, b is an integer of 0 to 2 and c is a number of 0
to 8.
[0021] In a first embodiment of the present invention, a compound
containing a silyl group corresponding to general formula II is
used as at least one reactant. Suitable compounds are in particular
compounds corresponding to general formula III: ##STR3## in which
R.sup.1 to R.sup.6, a, b, c, n, m and j are as defined above,
R.sup.7 is an optionally substituted alkylene group containing 1 to
about 44 carbon atoms, an optionally substituted cycloalkylene
group containing 6 to about 24 carbon atoms or an optionally
substituted arylene group containing 6 to about 24 carbon atoms and
Z is an amino group or a carbamate group. Suitable substituents
are, for example, functional groups, such as thioether, mercapto,
amino, ester, amido, nitro or ether groups or mixtures of two or
more thereof.
[0022] A "carbamate group" in the context of the present invention
is understood to be a structural element corresponding to general
formula IV: ##STR4## in which the substituent R.sup.10 is a linear
or branched, saturated or unsaturated alkyl group containing 1 to
about 10 carbon atoms, a saturated or unsaturated cycloalkyl group
containing about 6 to about 24 carbon atoms or an aryl group
containing 6 to about 24 carbon atoms.
[0023] In a preferred embodiment of the present invention,
compounds corresponding to general formula II, in which Z is an
amino group, are used as at least one reactant. Compounds such as
these are also referred in the present specification as
aminosilanes.
[0024] Suitable aminosilanes are, for example,
N-.alpha.-methyldimethoxysilylmethyl)-amine,
N-(.alpha.-trimethoxysilylmethyl)-amine,
N-(.alpha.-diethylmethoxysilylmethyl)-amine,
N-.alpha.-ethyldimethoxysilylmethyl)-amine,
N-(.alpha.-methyldiethoxysilylmethyl)-amine,
N-.alpha.-triethoxysilylmethyl)-amine,
N-(.alpha.-ethyldiethoxysilylmethyl)-amine,
N-(.beta.-methyldimethoxysilylethyl)-amine,
N-(.beta.-trimethoxysilylethyl)-amine,
N-(.beta.-ethyldimethoxysilylethyl)-amine,
N-(.beta.-methyldiethoxysilylethyl)-amine,
N-(.gamma.-triethoxysilylethyl)-amine,
N-(.beta.-ethyldiethoxysilylethyl)-amine,
N-(.gamma.-methyldimethoxysilylpropyl)-amine,
N-(.gamma.-trimethoxysilylpropyl)-amine,
N-(.gamma.-ethyldimethoxysilylpropyl)-amine,
N-(.gamma.-methyldiethoxysilylpropyl)-amine,
N-(.gamma.-triethoxysilylpropyl)-amine,
N-(.gamma.-ethyldiethoxysilylpropyl)-amine,
N-(4-methyldimethoxysilylbutyl)-amine,
N-(4-trimethoxysilylbutyl)-amine, N-(4-triethylsilylbutyl)-amine,
N-(4-diethylmethoxysilylbutyl)-amine,
N-(4-ethyldimethoxysilylbutyl)-amine,
N-(4-methyldiethoxysilylbutyl)-amine,
N-(4-triethoxysilylbutyl)-amine,
N-(4-diethylethoxysilylbutyl)-amine,
N-(4-ethyldiethoxysilylbutyl)-amine,
N-(5-methyldimethoxysilylpentyl)-amine,
N-(5-trimethoxysilylpentyl)-amine, N-(5-triethylsilylpentyl)-amine,
N-(5-ethyldimethoxysilylpentyl)-amine,
N-(5-methyldiethoxysilylpentyl)-amine,
N-(5-triethoxysilylpentyl)-amine,
N-(5-diethylethoxysilylpentyl)-amine,
N-(5-ethyldiethoxysilylpentyl)-amine,
N-(6-methyldimethoxysilylhexyl)-amine,
N-(6-trimethoxysilylhexyl)-amine,
N-(6-ethyldimethoxysilylhexyl)-amine,
N-(6-methyldiethoxysilylhexyl)-amine,
N-(6-triethoxysilylhexyl)-amine,
N-(6-ethyldiethoxysilylhexyl)-amine,
N-[.gamma.-tris-(trimethoxysiloxy)silylpropyl]-amine,
N-[.gamma.-tris(trimethoxysiloxy)silylpropyl]amine,
N-(.gamma.-trimethoxysiloxydimethylsilylpropyl)-amine,
N-(.gamma.-trimethylsiloxydimethoxysilylpropyl)-amine,
N-(.gamma.-triethoxysiloxydiethylpropyl)-amine,
N-(.gamma.-triethoxysiloxydiethoxysilylpropyl)-amine,
N,N-butyl-(.gamma.-trimethoxysilylpropyl)-amine,
N,N-butyl-(.gamma.-triethoxysilylpropyl)-amine,
N,N-phenyl-(.gamma.-trimethoxysilylpropyl)-amine,
N,N-phenyl-(.gamma.-triethoxysilylpropyl)-amine,
N,N-cyclohexyl-(.gamma.-trimethoxysilylpropyl)-amine,
N,N-ethyl-(.gamma.-trimethoxysilylpropyl)-amine,
diethyl-N-(trimethoxysilylpropyl)-aspartate,
diethyl-N-(triethoxysilylpropyl)-aspartate
N,N-ethyl-(.gamma.-dimethoxymethylsilylpropyl)-amine,
N,N-ethyl-(.gamma.-trimethoxysilylisobutyl)-amine,
N,N-Bis-(trimethoxypropyl)-amine,
N,N-ethyl-(.gamma.-trimethoxysilylisobutyl)-amine,
N,N-ethyl-(.alpha.-trimethoxysilylmethyl)-amine,
dibutyl-N-(trimethoxysilylpropyl)-aspartate,
dibutyl-N-(triethoxysilylpropyl)-aspartat,
N,N-(.beta.-aminopropyl)-(.gamma.-trimethoxysilylpropyl)-amine,
N,N'-di-(trimethoxysilylpropyl)-ethylenediamine,
tetra-(trimethoxysilylpropyl)-ethylendiamine and
N,N-ethyl-(.beta.-trimethoxysilylethyl)-amine or
N-[.gamma.-tris(trimethylsiloxy)silylpropyl]-amine or mixtures of
two or more thereof.
[0025] In addition, aminosilanes corresponding to general formula
III in which the recurring unit characterized by the parameter c is
a recurring unit corresponding to general formula V: ##STR5## where
c has a value of 1 to about 6, may also be used in accordance with
the invention.
[0026] Carbamatosilanes corresponding to general formula III in
which Z is a carbamate group corresponding to general formula IV
are also suitable for use as reactants in accordance with the
invention.
[0027] Carbamatosilanes corresponding to general formula III can be
obtained, for example, by reaction of an aminosilane with a dialkyl
or diaryl carbonate or pyrocarbonate or a mixture of two or more
thereof. Such a reaction is normally carried out in the presence of
a basic catalyst. Basically, however, any other known processes for
the production of carbamates may also be used providing they are
suitable for the production of carbamatosilanes, for example the
reaction of aminosilanes with chloroformic acid esters or the
reaction of isocyanatosilanes with alcohols.
[0028] Suitable carbonates are, for example, dimethyl carbonate,
diethyl carbonate, dipropyl carbonate, dibutyl carbonate,
diisobutyl carbonate, di-tert.butyl carbonate, diisopentyl
carbonate, diisopropyl carbonate, ethylmethyl carbonate,
ethyl-2-butoxyethyl carbonate, bis-(2-chloroethyl)-carbonate,
diphenyl carbonate, bis-(o,m-chlorophenyl)-carbonate,
bis-(o,p-chlorophenyl)-carbonate, bis-(dichlorophenyl)-carbonate,
bis-(trichlorophenyl)-carbonate or bis-(o-,m-,p-tolyl)-carbonate or
mixtures of two or more thereof.
[0029] Carbamatosilanes produced using dimethyl carbonate, diethyl
carbonate or dipropyl carbonate or pyrocarbonate or mixtures of two
or more thereof are preferably used in accordance with the
invention.
[0030] Suitable dialkyl pyrocarbonates are, for example, dimethyl
pyrocarbonate, diethyl pyrocarbonate or di-tert.butyl
pyrocarbonate. The reaction between the aminosilane and the organic
carbonate may be carried out, for example, using stoichiometric
quantities of the reactants. However, it is also possible, and
often preferable, to use an excess of organic carbonate of about
0.05 to about 1 mol per mol aminosilane. Good results can be
obtained, for example with a carbonate excess of about 0.1 to about
0.4 mol per mol aminosilane. In the case of relatively high
molecular weight silanes, for example with a molecular weight of
more than about 200 or more than about 500, or in the case of
aminosilanes with a sterically hindered amino group, it may be
necessary to use an even larger excess of carbonate.
[0031] The reaction between aminosilane and carbonate is normally
catalyzed by a basic catalyst. A strongly basic catalyst is
preferably used. Suitable basic catalysts are, for example, the
alkali metal alkoxides obtainable by reaction of monohydric
alcohols with alkali metals. Suitable alkali metals are, for
example, lithium, sodium or potassium; suitable monohydric alcohols
are, for example, methanol, ethanol, propanol or butanol. Suitable
strongly basic catalysts are, in particular, sodium methanolate,
sodium ethanolate, sodium propanolate, sodium tert.butanolate,
potassium methanolate, potassium ethanolate, potassium propanolate
or potassium tert.butanolate and the like.
[0032] The quantity of catalyst during the reaction is about 0.01
to about 2% by weight, based on carbonate and aminosilane used.
[0033] The reaction between aminosilane and organic carbonate is
slightly exothermic. Normally, the aminosilane and organic
carbonate are reacted with one another in the presence of the basic
catalyst in such a way that the reaction temperature remains in the
range from about 10 to about 120.degree. C., for example in the
range from about 20 to about 80.degree. C. or in the range from
about 25 to about 60.degree. C. The stability of the temperature
within these ranges may be achieved, for example, by typical
cooling processes, such as cold water, ice bath, dry ice bath or by
controlling the rate at which the reactants are added. The reaction
is normally carried out at ambient pressure in an inert gas
atmosphere.
[0034] On completion of the reaction, catalyst remaining in the
reaction mixture and excess aminosilane are neutralized by addition
of a neutralizing agent. Suitable neutralizing agents are, for
example, inorganic acids, such as water-free hydrochloric acid,
water-free phosphoric acid, or organic acids, such as glacial
acetic acid, propionic acid, butyric acid, hexanoic acid, oleic
acid, maleic acid, fumaric acid, succinic acid and the like. Weak
organic acids, such as glacial acetic acid, or inorganic acids,
such as water-free phosphoric acids, for example superphosphoric
acid or polyphosphoric acid, or--where they exist--anhydrides
thereof are preferably used for neutralization. It is particularly
suitable to use anhydrides of the corresponding acids because both
the catalyst and excess amine are bound. The reaction product may
be separated off by typical known methods. The separation of
precipitated salts by filtration, for example through silica gel or
a suitable filter paper, and subsequent removal of volatile
components by reduced pressure or an increase in temperature or
both is particularly suitable.
[0035] Particularly suitable carbamatosilanes corresponding to
general formula III are, for example,
methyl-N-(.alpha.-methyldimethoxysilylmethyl)-carbamate,
methyl-N-(.alpha.-trimethoxysilylmethyl)-carbamate,
methyl-N-(.alpha.-ethyldimethoxysilylmethyl)-carbamate,
methyl-N-.alpha.-methyldiethoxysilylmethyl)-carbamate,
methyl-N-(.alpha.-triethoxysilylmethyl)-carbamate,
methyl-N-(.beta.-methyldimethoxysilylethyl)-carbamate,
methyl-N-(.beta.-trimethoxysilylethyl)-carbamate,
methyl-N-(.beta.-diethylmethoxysilylethyl)-carbamate,
methyl-N-(.beta.-ethyldimethoxysilylethyl)-carbamate,
methyl-N-(.beta.-methyldiethoxysilylethyl)-carbamate,
methyl-N-(.beta.-triethoxysilylethyl)-carbamate,
methyl-N-(.beta.-ethyldiethoxysilylethyl)-carbamate,
methyl-N-(.gamma.-methyldimethoxysilylpropyl)-carbamate,
methyl-N-(.gamma.-trimethoxysilylpropyl)-carbamate,
methyl-N-(.gamma.-ethyldimethoxysilylpropyl)-carbamate,
methyl-N-(.gamma.-methyldiethoxysilylpropyl)-carbamate,
methyl-N-(.gamma.-triethoxysilylpropyl)-carbamate,
methyl-N-(.gamma.-ethyldiethoxysilylpropyl)-carbamate,
methyl-N-(4-trimethoxysilylbutyl)-carbamate,
methyl-N-(4-ethyldimethoxysilylbutyl)-carbamate,
methyl-N-(4-methyldiethoxysilylbutyl)-carbamate,
methyl-N-(4-triethoxysilylbutyl)-carbamate,
methyl-N-(4-ethyldiethoxysilylbutyl)-carbamate,
methyl-N-(5-methyldimethoxysilylpentyl)-carbamate,
methyl-N-(5-trimethoxysilylpentyl)-carbamate,
methyl-N-(5-ethyldimethoxysilylpentyl)-carbamate,
methyl-N-(5-methyldiethoxysilylpentyl)-carbamate,
methyl-N-(5-triethoxysilylpentyl)-carbamate,
methyl-N-(5-ethyldiethoxysilylpentyl)-carbamate,
methyl-N-(6-trimethoxysilylhexyl)-carbamate,
methyl-N-(6-ethyldimethoxysilylhexyl)-carbamate,
methyl-N-(6-triethoxysilylhexyl)-carbamate,
methyl-N-(6-ethyldiethoxysilylhexyl)-carbamate,
methyl-N-[.gamma.-tris-(trimethoxysiloxy)-silylpropyl]-carbamate,
ethyl-N-.alpha.-methyldimethoxysilylmethyl)-carbamate,
ethyl-N-.alpha.-trimethoxysilylmethyl)-carbamate,
ethyl-N-.alpha.-methyldiethoxysilylmethyl)-carbamate,
ethyl-N-.alpha.-triethoxysilylmethyl)-carbamate,
ethyl-N-.alpha.-ethyldiethoxysilylmethyl)-carbamate,
ethyl-N-(.beta.-methyldimethoxysilylethyl)-carbamate,
ethyl-N-(.beta.-trimethoxysilylethyl)-carbamate,
ethyl-N-(.beta.-ethyldimethoxysilylethyl)-carbamate,
ethyl-N-(.beta.-dimethylethoxysilylethyl)-carbamate,
ethyl-N-(.beta.-methyldiethoxysilylethyl)-carbamate,
ethyl-N-(.beta.-triethoxysilylethyl)-carbamate,
ethyl-N-(.gamma.-trimethoxysilylpropyl)-carbamate,
ethyl-N-(.gamma.-ethyldimethoxysilylpropyl)-carbamate,
ethyl-N-(.gamma.-methyldiethoxysilylpropyl)-carbamate,
ethyl-N-(.gamma.-triethoxysilylpropyl)-carbamate,
ethyl-N-(.gamma.-ethyldiethoxysilylpropyl)-carbamate,
ethyl-N-(4-methyldimethoxysilylbutyl)-carbamate,
ethyl-N-(4-trimethoxysilylbutyl)-carbamate,
ethyl-N-(4-ethyldimethoxysilylbutyl)-carbamate,
ethyl-N-(4-methyldiethoxysilylbutyl)-carbamate,
ethyl-N-(4-triethoxysilylbutyl)-carbamate,
ethyl-N-(4-ethyldiethoxysilylbutyl)-carbamate,
ethyl-N-(5-methyldimethoxysilylpentyl)-carbamate,
ethyl-N-(5-trimethoxysilylpentyl)-carbamate,
ethyl-N-(5-ethyldimethoxysilylpentyl)-carbamate,
ethyl-N-(5-triethoxysilylpentyl)-carbamate,
ethyl-N-(5-ethyldiethoxysilylpentyl)-carbamate,
ethyl-N-(6-methyldimethoxysilylhexyl)-carbamate,
ethyl-N-(6-trimethoxysilylhexyl)-carbamate,
ethyl-N-(6-ethyldimethoxysilylhexyl)-carbamate,
ethyl-N-(6-methyldiethoxysilylhexyl)-carbamate,
ethyl-N-(6-triethoxysilylhexyl)-carbamate,
ethyl-N-[.gamma.-tris-(trimethoxysiloxy)silylpropyl]-carbamate,
methyl-N-[.gamma.-tris(trimethoxysiloxy)silylpropyl]-carbamate,
methyl-N-(.gamma.-trimethoxysiloxydimethylsilylpropyl)-carbamate,
methyl-N-(.gamma.-trimethylsiloxydimethoxysilylpropyl)-carbamate,
methyl-N-[.gamma.-tris(triethoxysiloxy)silylpropyl]-carbamate,
methyl-N-(.gamma.-triethoxysiloxydiethylpropyl)-carbamate,
methyl-N-(.gamma.-triethoxysiloxydiethoxysilylpropyl)-carbamate,
methyl-N-[.gamma.-tris(trimethylsiloxy)silylpropyl]carbamate and
methyl-N-[6-tris(triethoxysiloxy)silylhexyl]-carbamate.
Ethyl-N-[.gamma.-tris(trimethoxysiloxy)silyl-propyl]-carbamate,
ethyl-N-(.gamma.-trimethoxysiloxydimethylsilylpropyl) carbamate,
ethyl-N-(.gamma.-trimethylsiloxydimethoxysilylpropyl)-carbamate,
ethyl-N-[.gamma.-tris(triethoxysiloxy)silylpropyl]-carbamate,
ethyl-N-(.gamma.-triethoxysiloxydiethylpropyl)-carbamate,
ethyl-N-(.gamma.-triethoxysiloxydiethoxysilylpropyl)-carbamate,
ethyl-N-[.gamma.-tris(trimethylsiloxy)silylpropyl]-carbamate and
ethyl-N-[6-tris-(triethoxysiloxy)silylhexyl]-carbamate.
[0036] In the process according to the invention, a compound
containing at least one amino group and a compound containing at
least one carbamate group, at least one of the compounds carrying a
silyl group, are reacted with one another. In the illustrated
variants, i.e. where Z is an amino group or Z is a carbamate group,
the above-mentioned compounds of general formula III satisfy the
corresponding requirements. Accordingly, it is possible by the
process according to the invention to produce compounds which
contain one urea group and two silyl groups by reacting two
compounds corresponding to general formula III with one another,
one of the compounds mentioned containing an amino group and one a
carbamate group. However, it is also possible in accordance with
the invention for one of the reactants not to contain a silyl
group.
[0037] Suitable reactants have, for example, a structure
corresponding to general formula VI: R.sup.11-(Z).sub.p (VI) where
Z is as already defined, p is a rational number of 1 to about 1,000
and R.sup.11 is a linear or branched, saturated or unsaturated,
optionally substituted alkyl group containing 2 to about 44 carbon
atoms, a saturated or unsaturated, optionally substituted
cycloalkyl group containing 6 to about 44 carbon atoms, an
optionally substituted aryl group containing 6 to about 44 carbon
atoms, an isocyanurate ring or a polymer with a molecular weight of
at least about 150.
[0038] In another embodiment of the present invention, a compound
corresponding to general formula VI, in which Z is an amino group,
is used as at least one reactant in the process according to the
invention. If, in a compound corresponding to general formula VI, Z
is an amino group, at least one other reactant corresponding to
general formula III, in which Z is a carbamate group, must be
present in the reaction mixture.
[0039] If a compound corresponding to general formula VI, in which
Z is an amino group, is used in the process according to the
invention, the substituent R.sup.11 may be, for example, a linear
or branched, saturated or unsaturated, optionally substituted alkyl
group containing 1 to about 44 carbon atoms. Suitable alkyl groups
have a length of, for example, 3 to about 20 carbon atoms. If the
alkyl group is unsubstituted, the compounds corresponding to
general formula VI are monoalkylamines. Suitable monoalkylamines
are, for example, ethylamine, propylamine, butylamine, pentylamine,
hexylamine and linear or branched higher homologs thereof
containing up to about 100 carbon atoms, the amino group being
positioned either terminally or anywhere within the alkyl
group.
[0040] According to the invention, the substituent R.sup.11 may
also be a substituted alkyl group. Suitable substituents are, for
example, hydroxyl groups, ester groups, carboxylic acid groups,
sulfonic acid groups, phosphonic acid groups and the corresponding
esters of the acid groups mentioned.
[0041] In another embodiment of the present invention, the
substituent R.sup.11 has two or more groups Z, i.e. p is a number
of 2 or more.
[0042] Accordingly, in another embodiment of the present invention,
the reaction mixture may contain, for example, a compound VI with
two or more amino groups as a reactant. Suitable such compounds
are, for example, ethylenediamine, propylenediamine,
butylenediamine, hexamethylenediamine, 2,4,4-trimethyl
hexamethylenediamine, diethylenetriamine, 1,12-diaminododecane,
diamines derived from dimer fatty acids or triamines derived from
trimer fatty acids or a mixture of two or more of the compounds
mentioned.
[0043] In another embodiment of the present invention, R.sup.11 may
be a saturated or unsaturated, optionally substituted cycloalkyl
group containing 6 to about 24 carbon atoms. A corresponding
cycloalkyl group may carry the substituents already mentioned above
as substituents. In particular, the cycloalkyl group may contain
one or more other amino groups. Suitable cycloalkyl compounds are,
for example, cyclohexylamine, dicyclohexylamine,
1,4-cyclohexyldiamine, 4,4'-dicyclohexylmethanediamine,
isophoronediamine, 1,3-bis-(aminomethyl)-cyclohexane,
1,4-bis(aminomethyl)-cyclohexane and hydrogenated toluenediamines,
such as 1-methyl-2,4,-diaminocyclohexane,
1-methyl-2,6-diaminocyclohexane and the like.
[0044] In another embodiment of the present invention, the
compounds of general formula VI used may be amines in which the
substituent R.sup.11 represents optionally substituted aryl groups
containing 6 to about 24 carbon atoms. Suitable substituents are in
particular the substituents already mentioned in the foregoing.
Particularly suitable aryl compounds corresponding to general
formula VI are, for example, aniline, 1,4-diaminobenzene,
aminotoluene, m- or p-phenylenediamine, diaminobiphenyl,
p-methoxyaniline, p-chloroaniline, o-, m- or p-toluidine,
2,4-xylidine, 2,4- and 2,6-toluenediamine and corresponding
mixtures, 4,4'-diphenylenediamine, methylene-bis-(anilines)
including 4,4'-methylenebis-(aniline),
2,4'-methylene-bis-(aniline), 4,4'-oxy-bis-(aniline),
4,4'-carbonylbis-(aniline), 4,4'-sulfonyl-bis-(aniline) or
naphthyidiamines or mixtures of two or more of the compounds
mentioned.
[0045] In another embodiment of the present invention, the
compounds of general formula VI used may be amines in which the
substituent R.sup.11 represents optionally substituted
isocyanurates. Particularly suitable compounds are
1,3,5-trisaminoalkyl, cycloalkyl and aryl isocyanurates. The
following are mentioned as examples:
1,3,5-tris-(6-aminohexyl)-isocyanurate,
1,3,5-tris(6-aminopropy)-isocyanurate,
1,3,5-tris(6-aminoethyl)-isocyanurate,
1,3,5-tris-(3-aminophenyl)-isocyanurate and
1,3,5-tris-(4-methyl-3-aminophenyl)-isocyanurate. Mixtures of two
or more of the compounds mentioned may also be used.
[0046] Another embodiment of the present invention is characterized
by the use of compounds corresponding to general formula VI in
which R.sup.11 stands for one of the groups mentioned above which
contains at least one carbamate group as the functional group Z.
Compounds such as these may be obtained by reaction of the
above-mentioned amino compounds with organic carbonates or
pyrocarbonates as already described in the present specification.
Suitable compounds are, for example, compounds which contain only
one carbamate group. However, compounds containing two or more
carbamate groups may also be used in the process according to the
invention. If a compound containing one or more carbamate groups is
used as the compound of general formula VI in accordance with the
invention, at least one compound of general formula III where Z is
an amino group must be used as a further reactant in the process
according to the invention.
[0047] In addition, compounds of general formula VI containing both
an amino group and a carbamate group may also be used in accordance
with the invention. Such compounds may be obtained, for example, by
reaction of compounds of the type described above containing more
than one amino compound with organic carbonates in a corresponding
stoichiometric ratio, for example in a molar ratio of 1:1 or
less.
[0048] In another embodiment of the present invention, the
substituent R.sup.11 in formula VI is a polymer.
[0049] In a preferred embodiment of the present invention, the
polymer used is a polymer selected from the group consisting of
polyacrylates, polymethacrylates, polystyrenes, polyesters,
polyethers, polyamides, polyurethanes, polycarbonates,
polylactones, polyethylenimine, polyureas, polyolefins and
polyoxazolidones.
[0050] A "polymer" in the context of the present invention is
understood to be a compound with a molecular weight of at least
about 150 but preferably higher, for example at least about 500,
800 or at least about 1,000.
[0051] The polymers suitable for use as compounds of general
formula VI in accordance with the invention may contain, for
example, only one functional group Z. However, it is equally
possible, and preferred in accordance with the invention, for the
number of functional groups Z to be more than 1, for example at
least about 2, 3, 4, 5 or more.
[0052] According to the invention, the number p in general formula
VI is a rational number of 1 to about 1,000. The number p of
functional groups Z in a polymer corresponding to general formula
VI may then assume a value differing from an integer if the number
of functional groups Z is taken as an average value in a mixture of
molecules of general formula VI, the number of functional groups
per molecule varying, as frequently encountered in polymer
chemistry. Such variations can arise, for example, due to the
functionalization of a polymer in a polymer-analog reaction.
[0053] In a preferred embodiment of the present invention, the
number p has a value of about 1.5 to about 10, more particularly a
value of about 1.8 to about 5 and most particularly a value of
about 1.9 to about 3.
[0054] In the context of the process according to the invention, a
functional group Z may be positioned terminally or laterally of the
polymer chain R.sup.11. If the number of functional groups Z is
more than 1, two or more functional groups may be positioned both
exclusively terminally and also exclusively laterally or terminally
and laterally of a polymer chain.
[0055] According to the invention, suitable polymers R.sup.11 are,
for example, polymers obtainable by polymerization of compounds
containing at least one olefinically unsaturated double bond.
Suitable polymers are, for example, polyacrylates,
polymethacrylates, polyvinyl esters, polyvinyl ethers, polyolefins
or polystyrenes.
[0056] The molecular weight (M.sub.n) of polymers suitable as
R.sup.11 is preferably in the range from about 300 to about
1,000,000, more preferably in the range from about 500 to about
300,000 and most preferably in the range from about 1,000 to about
30,000.
[0057] The molecular weight distribution of the polymers, which can
be determined, for example, by gel permeation chromatography, based
on polystyrene as standard, under measuring conditions typically
applied for polymers, need not be monomodal. A suitable polymer may
also have a bimodal or higher distribution.
[0058] The terms "polyacrylate" or "polyacrylates" used in the
present specification apply in the following both to polymers or
copolymers of acrylic acid and/or derivatives thereof and to
polymers or copolymers of methacrylic acid and/or derivatives
thereof, unless otherwise indicated in the text.
[0059] Polyacrylates can be produced by subjecting acrylic acid
and/or methacrylic acid and/or derivatives of acrylic acid and/or
methacrylic acid, for example esters thereof with mono- or
polyhydric alcohols, either individually or in the form of mixtures
of two or more thereof, to polymerization in known manner, for
example to radical, ionic or metal-catalyzed polymerization.
[0060] According to the invention, both homo- and copolymers may be
used as polyacrylates. Besides the corresponding acrylates or
methacrylates, suitable copolymers may also contain, for example,
styrene, acrylonitrile, vinyl acetate, vinyl propionate, vinyl
chloride, vinylidene chloride and/or butadiene.
[0061] Suitable monomers for the production of the polyacrylates
are, in particular, methyl acrylate, ethyl acrylate, n-butyl
acrylate, isobutyl acrylate, tert.butyl acrylate, hexyl acrylate,
2-ethylhexyl acrylate or lauryl acrylate and the corresponding
esters of methacrylic acid. Acrylic acid, methacrylic acid,
acrylamide or methacrylamide may also be added in small quantities
as further monomers during the polymerization.
[0062] Other acrylates and/or methacrylates containing one or more
functional groups may optionally be present during the
polymerization. These are, for example, maleic acid, itaconic acid,
butanediol diacrylate, hexanediol diacrylate, triethylene glycol
diacrylate, tetraethylene glycol diacrylate, neopentyl glycol
diacrylate, trimethylol propane triacrylate, 2-hydroxyethyl
methacrylate, hydroxypropyl acrylate or propylene glycol
methacrylate.
[0063] The corresponding functional groups Z may be introduced into
the polymer, for example, using correspondingly functionalized
monomers containing amino groups which are incorporated in the
monomers forming R.sup.11 in a copolymerization reaction. However,
the polymers may also be provided with functional groups Z after
polymerization in a suitable polymer-analog reaction. Corresponding
reactions are known to the expert.
[0064] Monomers suitable for introducing amino groups into the
polymers are, for example, 2-aminoethyl acrylamide, 2-aminoethyl
methacrylamide, 3-aminopropylacrylamide, 3-aminopropyl
methacrylamide and allylamine.
[0065] The polymers containing amino groups as functional groups Z
may then be converted in a polymer-analog reaction into compounds
corresponding to general formula VI which contain a carbamate group
as the functional group Z. A corresponding polymer-analog reaction,
for example with organic carbonates, may be carried out by the
scheme already described in the foregoing.
[0066] If the corresponding polymer contains more than one amino
group, the conversion of amino groups into carbamate groups may be
carried out completely or only partly.
[0067] In addition, polyesters may be used as the polymers R.sup.11
in accordance with the invention. Suitable polyesters may be
obtained in known manner by polycondensation of acid and alcohol
components, more particularly by polycondensation of a
polycarboxylic acid or a mixture of two or more polycarboxylic
acids and a polyol or a mixture of two or more polyols.
[0068] Polycarboxylic acids suitable in accordance with the present
invention for the production of the polyester usable as R.sup.11
may be based on an aliphatic, cycloaliphatic, araliphatic, aromatic
or heterocyclic parent compound and, besides the at least two
carboxylic acid groups, may optionally contain one or more
substituents which do not react in a polycondensation reaction, for
example halogen atoms or olefinically unsaturated double bonds. The
free carboxylic acids may even be replaced by their anhydrides
(where they exist) or esters with C.sub.1-5 monoalcohols or
mixtures of two or more thereof for the polycondensation
reaction.
[0069] Suitable polycarboxylic acids are, for example, succinic
acid, adipic acid, suberic acid, azelaic acid, sebacic acid,
glutaric acid, glutaric anhydride, phthalic acid, isophthalic acid,
terephthalic acid, trimellitic acid, phthalic anhydride,
tetrahydrophthalic anhydride, hexahydrophthalic anhydride,
tetrachlorophthalic anhydride, endomethylene tetrahydrophthalic
anhydride, glutaric anhydride, maleic acid, maleic anhydride,
fumaric acid, dimer fatty acids or trimer fatty acids or mixtures
of two or more of the polycarboxylic acids mentioned. Small
quantities of monofunctional fatty acids may optionally be present
in the reaction mixture.
[0070] Various polyols may be used as the diols for producing a
polyester or polycarbonate usable as R.sup.11 in a compound
corresponding to general formula VI. Examples of such polyols are
aliphatic polyols containing 2 to 4 OH groups per molecule. These
OH groups may be both primary and secondary OH groups. Suitable
aliphatic polyols include, for example, ethylene glycol,
propane-1,2-diol, propane-1,3-diol, butane-1,4-diol,
butane-1,3-diol, butane-2,3-diol, butene-1,4-diol, butine-1,4-diol,
pentane-1,5-diol, and the isomeric pentanediols, pentenediols or
pentinediols or mixtures of two or more thereof, hexane-1,6-diol
and the isomeric hexanediols, hexenediols or hexinediols or
mixtures of two or more thereof, heptane-1,7-diol and the isomeric
heptane, heptene or heptinediols, octane-1,8-diol and the isomeric
octane, octene or octinediols and higher homologs or isomers of the
compounds mentioned, which are obtained in known manner from a
step-by-step extension of the hydrocarbon chain by one CH.sub.2
group at a time or by introducing branches into the carbon chain,
or mixtures of two or more thereof.
[0071] Other suitable polyols are alcohols of relatively high
functionality, such as glycerol, trimethylol propane,
pentaerythritol or sugar alcohols, such as sorbitol or glucose, and
oligomeric ethers of the substances mentioned either as such or in
the form of a mixture of two or more of the compounds mentioned
with one another, for example polyglycerol with a degree of
polymerization of about 2 to about 4. In the alcohols of relatively
high functionality, one or more OH groups may be esterified with
monobasic carboxylic acids containing 1 to about 20 carbon atoms,
with the proviso that, on average, at least two OH groups remain
intact. The alcohols mentioned with a functionality of more than 2
may be used in pure form or, where possible, in the form of the
technical mixtures obtainable in the course of their synthesis.
[0072] The reaction products of low molecular weight polyfunctional
alcohols with alkylene oxides, so-called polyether polyols, may
also be used as polyol component for the production of the
polyesters. Polyether polyols, which are to be used for the
production of polyesters suitable as R.sup.11, are preferably
obtained by reaction of polyols with alkylene oxides. The alkylene
oxides preferably contain 2 to about 4 carbon atoms. Suitable
polyether polyols are, for example, the reaction products of
ethylene glycol, propylene glycol, the isomeric butanediols or
hexanediols, as mentioned above, or mixtures of two or more thereof
with ethylene oxide, propylene oxide or butylene oxide or mixtures
of two or more thereof. Other suitable polyether polyols are
products of the reaction of polyhydric alcohols, such as glycerol,
trimethylol ethane or trimethylol propane, pentaerythritol or sugar
alcohols or mixtures of two or more thereof with the alkylene oxide
mentioned to form polyether polyols. Polyether polyols with a
molecular weight (M.sub.n) of about 100 to about 3,000 and
preferably in the range from about 200 to about 2,000 obtainable
from the reactions mentioned are particularly suitable. The
polyether polyols mentioned may be reacted with the polycarboxylic
acids mentioned above in a polycondensation reaction to form the
polyesters suitable for use as the polymers R.sup.11.
[0073] The functionalization of the polymers R.sup.11 with
corresponding functional groups Z may be carried out in known
manner. Polyesters containing a carboxylic acid group as terminal
group are particularly suitable for functionalization. Polyesters
such as these may be reacted with polyamines, for example, in a
polymer-analog reaction so that the polyester contains terminal
amino groups. If the polyester is provided with amino groups in a
polymer-analog reaction, it would also be possible, for example, to
use polyesters containing terminal carboxylic acid groups or
lateral and terminal amino groups which are subsequently
functionalized with polyamines to form aminofunctional
polyesters.
[0074] The polyesters containing amino groups as functional groups
Z may then be converted in a polymer-analog reaction into compounds
corresponding to general formula VI which contain a carbamate group
as the functional group Z. A corresponding polymer-analog reaction,
for example with organic carbonates, may be carried out to the
scheme already described in the foregoing.
[0075] Polyether polyols are also suitable for as the polymers
R.sup.11. Suitable polyether polyols are normally obtained by
reacting a starting compound containing at least two reactive
hydrogen atoms with alkylene or arylene oxides, for example
ethylene oxide, propylene oxide, butylene oxide, styrene oxide,
tetrahydrofuran or epichlorohydrin or mixtures of two or more
thereof.
[0076] Suitable starting compounds are, for example, water,
ethylene glycol, 1,2- or 1,3-propylene glycol, 1,4- or 1,3-butylene
glycol, 1,6-hexanediol, 1,8-octanediol, neopentyl glycol,
1,4-hydroxymethyl cyclohexane, 2-methylpropane-1,3-diol, glycerol,
trimethylol propane, hexane-1,2,6-triol, butane-1,2,4-triol,
trimethylol ethane, pentaerythritol, mannitol, sorbitol, methyl
glycosides, sugars, phenol, isononyl phenol, resorcinol,
hydroquinone, 1,2,2- or 1,1,2-tris-(hydroxyphenyl)-ethane, ammonia,
methyl amine, ethylenediamine, tetra- or hexamethylenediamine,
triethanolamine, aniline, phenylenediamine, 2,4- and
2,6-diaminotoluene and polyphenyl polymethylene polyamines which
can be obtained by condensing aniline with formaldehyde.
[0077] Polyether polyols modified by vinyl polymers are also
suitable for use as the polymers R.sup.11. Products such as these
can be obtained, for example, by polymerizing styrene or
acrylonitrile or a mixture thereof in the presence of
polyethers.
[0078] The polyether polyols are functionalized in known manner.
For example, conventional polyether polyols may be converted into
the corresponding polyetheramines by reacting the terminal OH
groups with ammonia or primary amines using methods known from the
literature.
[0079] Corresponding polyether polyols are commercially obtainable
in various compositions, for example under the name of
JEFFAMIN.RTM.. Examples include the Jeffamin types D 230, D 400 and
D 2000 based on difunctional polypropylene glycols, the types T
403, T 3000 and T 5000 based on trifunctional polypropylene
glycols, the types ED 600, ED 900, ED 2001 and ED 6000 based on
difunctional polyethylene glycols and the types M 300, M 600, M
1000 and M 2070 based on monofunctional polypropylene glycols.
[0080] Suitable aminofunctional polyethers may be converted by
polymer-analog functionalization into polymers which contain a
carbamate group as the functional group Z.
[0081] Polyacetals are also suitable for use as the polymers
R.sup.11. Polyacetals are understood to be compounds obtainable by
reacting glycols, for example diethylene glycol or hexanediol, with
formaldehyde. Polyacetals suitable for the purposes of the
invention may also be obtained by polymerizing cyclic acetals. The
foregoing observations in the description of the polyesters apply
to the functionalization of the polyacetals with functional groups
Z.
[0082] Polycarbonates are also suitable for use as the polymers
R.sup.11. Polycarbonates may be obtained, for example, by reacting
the polyols mentioned above, more particularly diols, such as
propylene glycol, butane-1,4-diol or hexane-1,6-diol, diethylene
glycol, triethylene glycol or tetraethylene glycol or mixtures of
two or more thereof, with diaryl carbonates, for example diphenyl
carbonate or phosgene. The foregoing observations in the
description of the polyesters apply to the functionalization of the
polycarbonates with functional groups Z.
[0083] Polylactones are also suitable for use as the polymers
R.sup.11. Preferred polylactones are derived from compounds with
the general formula HO--(CH.sub.2).sub.z--COOH, where z is a number
of 1 to about 20. Examples are .epsilon.-caprolactone,
.beta.-propiolactone, .gamma.-butyrolactone or
methyl-.epsilon.-caprolactone or mixtures of two or more thereof.
The foregoing observations in the description of the polyesters
apply to the functionalization of the polylactones with functional
groups Z.
[0084] Polyethyleneimines are also suitable for use as the polymers
R.sup.11. Suitable polyethyleneimines can be obtained by
polymerizing reaction of ethyleneimine and have a molecular weight
of about 300 to about 100,000.
[0085] Polyamides are also suitable for use as the polymers
R.sup.11 in accordance with the invention. Suitable polyamides can
be obtained, for example, by reaction of the above-mentioned
dicarboxylic acids with corresponding diamines. Suitable diamines
are, for example, those which have a molecular weight of about 32
to about 200 g/mol and which contain at least two primary, two
secondary or one primary and one secondary amino group. Examples of
such diamines are diaminoethane, diaminopropanes, diaminobutanes,
diaminohexanes, piperazine, 2,5-dimethylpiperazine,
amino-3-aminomethyl-3,5,5-trimethyl cyclohexane (isophorone
diamine, IPDA), 4,4'-diaminodicyclohexylmethane,
1,4-diaminocyclohexane, aminoethyl ethanolamine, hydrazine,
hydrazine hydrate or--optionally in small quantities--diamines,
such as diethylenetriamine or 1,8-diamino-4-aminomethyl octane.
Synthesis from lactams, such as .epsilon.-caprolactam, or
aminocarboxylic acids, such as 11-aminoundecanoic acid, is also
possible.
[0086] The molecular weights of the compounds of general formula VI
usable in the process according to the invention is preferably in
the range from about 300 to about 1,000,000. If a polymer is to be
used as the compound of general formula VI, a polymer with a
molecular weight of about 500 to about 300,000 and more
particularly in the range from about 1,000 to about 30,000 is
preferably used.
[0087] If a polyester to used as the compound corresponding to
general formula VI, it preferably has a molecular weight of about
300 to about 100,000, for example in the range from about 500 to
about 50,000 or in the range from about 1,000 to about 30,000.
[0088] If a polyether to used as the compound corresponding to
general formula VI, it preferably has a molecular weight of about
300 to about 100,000, for example in the range from about 500 to
about 50,000 or in the range from about 1,000 to about 30,000, for
example in the range from about 3,000 to about 20,000 or in the
range from about 4,000 to about 8,000 or about 12,000.
[0089] Suitable molecular weights for polycarbonates, polylactones,
polyethyleneimines or polyamides usable as polymers corresponding
to general formula VI in accordance with the invention are
preferably in the range from about 300 to about 50,000 and more
particularly in the range from about 1,000 to about 30,000.
[0090] In another embodiment of the present invention, the
compounds corresponding to general formula VI may contain one or
more silyl groups corresponding to general formula II besides the
functional groups Z as functional groups.
[0091] According to the invention, the process according to the
invention is carried out by reacting a compound containing at least
one amino group with a carbamate, at least one of the reactants
carrying a silyl group. Accordingly, another possible embodiment of
the present invention is characterized, for example, by the
reaction of two compounds corresponding to general formula III, of
which one compound carries an amino group and the other a carbamate
group, with one another. In another embodiment of the invention for
example, one compound corresponding to general formula III is
reacted with one compound corresponding to general formula VI or
two compounds corresponding to general formula VI are reacted with
one another, with the proviso that one of the reactants bears an
amino group and the other reactant a carbamate group. Besides
reacting two of the compounds mentioned, it is also possible in
accordance with the invention to react three or more different
compounds corresponding to general formula III or to general
formula VI or mixtures of two or more different compounds
corresponding to general formula III with one or more compounds
corresponding to general formula VI or mixtures of two or more
compounds corresponding to general formula VI with a compound
corresponding to general formula III.
[0092] In a preferred embodiment of the invention, the reaction on
which the process according to the invention is based takes place
in the presence of a catalyst. Suitable catalysts are, for example,
compounds corresponding to general formula VII: M(OR.sup.12).sub.x
(VII) in which M is a metal selected from the group consisting of
aluminium, titanium, magnesium or zirconium and R.sup.12 stands for
the same or different, linear or branched hydrocarbon radicals
containing 1 to 8 carbon atoms and x has a value of 2, 3 or 4.
Suitable catalysts are, for example, aluminium alkoxides, titanium
alkoxides, magnesium alkoxides and zirconium alkoxides.
Particularly suitable catalysts are, for example, aluminium
trimethoxide, aluminium triethoxide, aluminium triisopropoxide,
aluminium trisec.butoxide, aluminium tritert.butoxide, titanium(IV)
methoxide, titanium(IV)ethoxide, titanium(IV)isopropoxide,
titanium(IV) butoxide, titanium(IV)2-ethylhexoxide,
zirconium(IV)ethoxide, zirconium(IV)propoxide,
zirconium(IV)butoxide, zirconium(IV) isopropoxide, zirconium(IV)
tert.butoxide, magnesium methoxide, magnesium ethoxide, magnesium
butoxide, magnesium propoxide or magnesium phenoxide.
[0093] Other suitable catalysts for the process according to the
invention are tin compounds, more particularly organotin
carboxylates, such as dibutyltin dilaurate, dibutyltin diacetate,
dibutyltin bis-(2-ethylhexanoate) or other organotin compounds,
such as dibutyltin oxide, dibutyltin dimethoxide, dibutyltin
dibromide, dibutyltin dichloride, ditert.butyltin dichloride,
dimethyltin dibromide, dimethyltin dichloride, diphenyltin
dichloride or tin octoate. Of the catalysts mentioned, dibutyltin
dilaurate, dibutyltin oxide and dibutyltin diacetate are
preferred.
[0094] Other suitable catalysts are compounds which contain at
least one metal selected from the group consisting of antimony,
iron, cobalt, nickel, copper, chromium, maganese, molybdenum,
tungsten or lead. The oxides, halides, carboxylates, phosphates or
organometallic compounds of the metals mentioned are particularly
suitable. Examples of particularly suitable catalysts include iron
acetate, iron benzoate, iron naphthenates; iron acetyl acetonates,
manganese acetate, manganese naphthenate and manganese acetyl
acetonate.
[0095] The quantity of catalyst used in the process according to
the invention is in the range from about 0.01 to about 0.5% by
weight and more particularly in the range from about 0.05 to about
0.2% by weight.
[0096] The process according to the invention is preferably carried
out at a pH of about 2 to about 12 and more particularly at a pH of
about 5 to about 9, for example at a pH of about 5.5 to about
8.5.
[0097] The process according to the invention may be carried out in
the absence of solvents or in an organic solvent. Suitable organic
solvents have a boiling point of at least about 100.degree. C. and
preferably higher. Suitable solvents are, for example, dioctyl
phthalate, didecyl phthalate, didoceyl phthalate and other
homologous esters of polybasic carboxylic acids. Other suitable
organic solvents are phosphoric acid esters, for example
chlorinated phosphoric acid esters, and also dibenzyltoluene,
triphenylmethane, phenylnaphthalene, biphenyl, diethylbiphenyl or
triethylbiphenyl. Basically, any solvents with a sufficiently high
boiling point may be used providing they are inert to the
reactants.
[0098] In a preferred embodiment of the invention, the solvent is a
solvent which is used in a subsequent formulation involving the
compounds according to the invention, for example as plasticizers,
and which may therefore remain in the prepolymer.
[0099] The reaction is preferably carried out at a temperature of
about 50 to about 300.degree. C. and more particularly as a
temperature of about 50 to about 250.degree. C. Suitable reaction
temperatures are, in particular, in the range from about 80 to
about 220.degree. C. or up to about 190.degree. C.
[0100] The reaction time is between about 0.1 and about 10 hours,
depending on the temperature and the catalyst(s) used. In a
preferred embodiment of the invention, the reaction conditions are
selected so that the reaction time is between about 0.5 and about
1.5 hours. The progress of the reaction may be followed, for
example, by monitoring the amine value in the reaction mixture. The
reaction is preferably continued until the amine value has fallen
to a value of about 5 or less, for example to a value of 1 or less,
more particularly to a value of 0.5 or less.
[0101] On completion of the reaction, i.e. after the required amine
value has been reached, the reaction mixture is cooled. Depending
on the required conduct of the reaction, the pressure may be
reduced during cooling, for example, so that any readily volatile
constituents, such as low molecular weight alcohols or any solvent
used, are removed in vacuo.
[0102] The above-mentioned reactants may be used in various molar
ratios in the process according to the invention. Basically, any
ratios of amino groups to carbamate groups may be used. In a
preferred embodiment, however, the ratio of amino groups to
carbamate groups is selected so that it is at most about 1:1. This
ensures that substantially every amino group reacts with a
carbamate group.
[0103] Another embodiment of the present invention is characterized
by a conduct of the reaction in which the reactant carrying the
carbamate groups has at least two carbamate groups. In this case,
another embodiment of the invention is characterized in that the
ratio of carbamate groups to amino groups is 1 or less than 1, for
example about 0.1 to about 0.99 or about 0.3 to about 0.9 or about
0.4 to about 0.8.
[0104] Basically, suitable reactants containing at least two
carbamate groups are any reactants carrying at least two carbamate
groups which correspond to general formula VI. Suitable compounds
may be produced, for example, from the above-described compounds
carrying at least two amino groups in the manner already
described.
[0105] In a preferred embodiment of the present invention, however,
a polymer is used as the reactant containing at least two carbamate
groups.
[0106] Suitable polymers containing at least two carbamate groups
can be produced from the polymers containing at least two amino
groups already described in the foregoing in the manner already
described.
[0107] In a preferred embodiment of the present invention, a
polymer containing at least one ether group is used as the polymer
containing at least two carbamate groups. In another preferred
embodiment of the present invention, a polyether or a polyamide or
a polyurea or a mixture of two or more thereof is used as the
polymer containing at least two carbamate groups.
[0108] According to the invention, a compound containing an amino
group or a compound containing two or more amino groups is used as
reactant for the compound containing at least two carbamate groups
or the mixture of two or more such compounds. In a preferred
embodiment, however, a compound containing only one amino group is
used.
[0109] According to the invention, at least the reactant containing
the amino group(s) preferably contains one or more silyl groups. In
a preferred embodiment of the invention, a polymer containing at
least two carbamate groups or a mixture of two or more such
polymers and an aminosilane or a mixture of two or more
aminosilanes are used as reactants.
[0110] If the reaction according to the invention between a
compound containing at least two carbamate groups or a mixture of
two or more thereof and a compound containing one or more amino
groups is carried out in such a way that the ratio of amino groups
to carbamate groups is <1, the process according to the
invention is preferably carried out in the presence of a
trimerization catalyst. In the reaction on which the process
according to the invention is based, isocyanurate groups are formed
in the presence of a trimerization catalyst.
[0111] According to the invention, the reaction according to the
invention (cracking/trimerization reaction) may be carried out, for
example, until the reaction mixture no longer contains carbamate
groups. In another embodiment of the present invention, however,
the reaction is incomplete. In the context of the invention, an
"incomplete reaction" is understood to be a reaction in which not
all the carbamate groups present in the reaction mixture are
reacted, i.e. in which carbamate groups remain in the reaction
product. Basically, this variant of the process according to the
invention is suitable for any combinations of reactants where at
least one reactant carries at least one carbamate group. However,
this variant is particularly advantageous when one of the reactants
contains at least two carbamate groups.
[0112] Accordingly, the present invention also relates to a polymer
which contains at least one urea group, at least one alkoxysilyl
group and at least one carbamate group. In another embodiment of
the present invention, this polymer may additionally contain, for
example, one or more isocyanurate groups.
[0113] The reaction may readily be terminated by methods known to
the expert, for example by the addition of a catalyst poison or by
lowering the temperature.
[0114] The effect of the remaining carbamate groups is that the
reaction product has a lower viscosity than the fully reacted
product and hence simplifies use as a binder for adhesives and
sealants. In addition, the remaining carbamate groups may
additionally be used for formulating heat-activatable adhesives and
sealants because the carbamate groups split at temperatures above
150.degree. C. to give the isocyanate and can be further
crosslinked by trimerization or allophanatization.
[0115] Trimerization catalysts are known to the expert from the
relevant literature (see, for example, Laas et al., J. prakt. Chem.
336 (1994), pages 192 to 196 and various patent publications, such
as U.S. Pat. No. 5,218,133 (Union Carbide), U.S. Pat. No. 4,412,073
(Rhone-Poulenc), U.S. Pat. No. 5,260,436 (Iowa), U.S. Pat. No.
5,837,796 (Bayer) and U.S. Pat. No. 4,124,545 (Bayer)). Suitable
trimerization catalysts are, for example, the catalysts already
described in the foregoing in connection with the reaction of
carbamate groups and amino groups. Other suitable trimerization
catalysts are the alkali metal salts of organic acids or alkali
metal salts of phosphoric acid and also amines which do not react
with the carbamate groups. Examples of alkali metal salts of
organic acids include the sodium, potassium, lithium or caesium
salts of acetic acid, propionic acid, butyric acid, hexanoic acid,
oleic acid, maleic acid, fumaric acid, succinic acid and the like.
Examples of alkali metal salts of phosphoric acid include, for
example, alkali metal orthophosphates, such as trisodium
orthophosphate, tripotassium orthophosphate or dipotassium
orthophosphates, such as disodium orthophosphate or dipotassium
orthophosphate. Amines suitable as trimerization catalysts are, for
example, tertiary amines, such as N,N-dimethyl dodecylamine,
1,4-diazabicyclo-[2.2.2]-octane (DABCO). Mixtures of two or more of
the compounds mentioned are also suitable.
[0116] In a preferred embodiment of the present invention, either
an organotin compound, more particularly dibutyltin dilaurate,
aluminium triisopropylate, iron(II)acetyl acetonate or a mixture of
the catalysts mentioned is used as the trimerization catalyst.
Catalysts which simultaneously catalyze cracking and trimerization,
for example aluminium triisopropylate, are particularly
preferred.
[0117] It is possible by the process according to the invention to
produce polymers which, in contrast to polymers containing
isocyanurate structures, contain only one isocyanurate group and
three urea groups and three silyl groups or, if the ratio of
carbamate groups to amino groups is selected accordingly, several
triisocyanurate groups and a corresponding number of urea groups
and silyl groups. However, in the case of those polymers which
contain more than one isocyanurate group, no other structural
element obtainable by reaction of isocyanate groups with an
isocyanate-reactive compound is present between two isocyanurate
groups.
[0118] Accordingly, the present invention also relates to a polymer
which contains at least one isocyanurate structural element and at
least one alkoxysilyl group. If the polymer contains more than one
isocyanurate structural element, no structural element which can be
formed by reaction of an isocyanate group with an
isocyanate-reactive functional group is present between at least
two isocyanurate structural elements in the polymer or the
structure lying between two isocyanurate groups has a molecular
weight of at least 300.
[0119] In the context of the present invention, a "structure lying
between two isocyanurate groups" is understood to be a chain of
covalently bonded atoms. The polymers according to the invention
contain either only one isocyanurate structural element, at least
one urea group and at least one alkoxysilyl group or more than one
isocyanurate structural element, at least one urea group and at
least one alkoxysilyl group. If a polymer according to the
invention contains more than one isocyanurate structural element,
it has to satisfy various requirements. Either no structural
element obtainable by reaction of an isocyanate group with an
isocyanate-reactive functional group is present between at least
two isocyanaurate structural elements in the polymer, i.e. no
urethane group, urea group or oxazolidone group is present between
at least two isocyanurate groups.
[0120] Corresponding polymers according to the invention can be
obtained, for example, when compounds containing at least two
carbamate groups which have no structural elements obtainable by
the reaction of an isocyanate group with an isocyanate-reactive
compound in the substituent R.sup.11 are used as the compounds
corresponding to general formula VI. Substantially all the polymers
already mentioned in the foregoing are suitable.
[0121] The term "molecular weight" as used in the present
specification applies to the molecular weight determined by GPC
under conditions typical of the particular polymer, based on
polystyrene as standard.
[0122] The polymers according to the invention may be produced by
reaction of a prepolymer containing at least two carbamate groups
or a mixture of two or more such prepolymers with an alkoxysilane
containing at least one amino group, the molar ratio of carbamate
group to amino groups being less than 1.
[0123] Accordingly, the present invention also relates to a polymer
obtainable by reaction of a prepolymer containing at least two
carbamate groups or a mixture of two or more such prepolymers with
an alkoxysilane containing at least one amino group, the molar
ratio of carbamate groups to amino groups being less than 1.
[0124] A "prepolymer" in the context of the invention is understood
to be a compound corresponding to general formula VI which contains
at least two functional groups Z, at least two of the functional
groups Z being a carbamate group. A prepolymer according to the
invention has a molecular weight of at least about 150 and at most
about 1,000,000 and preferably in the range from at least about 500
to about 50,000, for example in the range from about 1,000 to
50,000.
[0125] The compounds produced by the process according to the
invention and the polymers according to the invention are suitable,
for example, for use in surface coating compositions, such as
paints or similar coating systems, and for use in adhesives,
sealants and foams.
[0126] Accordingly, the present invention also relates to the use
of a compound produced by the process according to the invention or
of a polymer according to the invention for the production of
surface coating compositions, sealants, adhesives, for example
pressure-sensitive adhesives or hotmelt adhesives, assembly or
insulating foams.
[0127] The present invention also relates to a surface coating
composition or an adhesive at least containing a polymer produced
by a process according to the invention or a polymer according to
the invention.
[0128] In a preferred embodiment of the invention, surface coating
compositions or adhesives contain a crosslinking catalyst which
catalyzes the crosslinking of the silyl groups or a mixture of two
or more such catalysts.
[0129] Suitable crosslinking catalysts are, for example, amino
compounds, such as triethylenediamine, trimethylaminoethyl
piperazine, pentamethyl diethylenetriamine, tetramethyl
iminoisopropylamine or bis-(dimethylaminopropyl)-N-isopropanolamine
or dimorpholinodiethyl ether. Other suitable catalysts are those
based on organic or inorganic heavy metal compounds, such as cobalt
naphthenate, dibutyl tin dilaurate, tin mercaptides, tin
dichloride, zirconium tetraoctoate, antimony dioctoate, lead
dioctoate, metal--more particularly iron--acetyl acetonate. Any of
the known catalysts for accelerating the condensation of silanols
are particularly suitable. Examples of such catalysts include
organotin, organotitanium, organozirconium- or organoaluminium
compounds. Examples of such compounds are dibutyltin dilaurate,
dibutyltin dimaleate, tin octoate, isopropyl triisostearoyl
titanate, isopropyltris-(dioctylpyrophosphate)-titanate,
bis-(dioctylpyrophosphate)-oxyacetate titanate, tetrabutyl
zirconate, tetrakis-(acetylacetonato)-zirconium, tetraisobutyl
zirconate, butoxytris-(acetylacetonato)-zirconium,
tris-(ethylacetoacetato)-aluminium. Dibutyltin alkylesters, such as
dibutyltin alkylmaleates or dialkyltin laurates, are particularly
suitable, more particularly dibutyltin bis-ethylmaleate, dibutyltin
bis-butylmaleate, dibutyltin bis-octylmaleate, dibutyltin
bis-oleylmaleate, dibutyltin bis-acetylacetate, dibutyltin
diacetate, dibutyltin dioctoate, dibutyltin oxide, dibutyltin
bis-triethoxy silicate and catalytically active derivatives
thereof. The catalysts mentioned may be used individually or in the
form of a mixture of two or more.
[0130] A crosslinking catalyst may be used, for example, in a
quantity of 0.01% to about 2% and preferably in a quantity of 0.05%
to about 0.5%, based on the weight of the silyl groups.
[0131] In another embodiment of the present invention, a surface
coating composition according to the invention or an adhesive
according to the invention may contain further additives. Suitable
additives are, for example, tackifiers, plasticizers, rheological
additives, antioxidants, UV stabilizers, dyes, pigments, adhesion
promoters, drying agents, flame retardants, cell regulators,
propellent gases or fillers.
[0132] The storage stability of the compounds according to the
invention or the compositions produced from them can be increased,
for example, by reactive silanes. Suitable reactive silanes are,
for example, tetramethoxysilane, trimethoxy methyl silane or
trimethoxy vinyl silane which are suitable for trapping water. The
content of such compounds should not exceed 3% by weight, based on
the mixture as a whole containing the reactive silane or the
mixture of two or more reactive silanes.
[0133] Suitable flame retardants are, for example, any of the usual
phosphorus-containing compounds, more particularly elemental
phosphorus, phosphates or phosphonates, for example triethyl
phosphate or trichloropropyl phosphate. Compounds such as these can
have both plasticizing and viscosity-adjusting properties. Other
suitable flame retardants are, for example, diphenylcresyl
phosphates, triphenyl phosphate, dimethylmethane phosphonate and
the like. In addition, chloroparaffins may also be used as flame
retardants. Also suitable are halogenated polyester or polyether
polyols, for example commercially available brominated polyether
poylol. Halogenated polyester or polyether polyols may be
incorporated, for example, in the polymers according to the
invention.
[0134] If the compounds according to the invention, particularly
the polymers according to the invention, are present in
compositions suitable for the production of foams, these
compositions may contain, for example, cell regulators or
propellents or both. The cell regulators used are normally
silicone-based compounds. In a preferred embodiment of the present
invention, liquid, crosslinkable polybutadiene, silicone oils or
paraffin oils are used as the cell regulator. In a preferred
embodiment of the invention, commercially available silicone
stabilizers are used as the stabilizers.
[0135] If the compounds according to the invention are to be used
for the production of foams, they are preferably supplied to the
user in pressurized containers (aerosol cans). A composition
containing a compound according to the invention additionally
contains at least one propellent for dispensing the binders or
binder compositions according to the invention from the aerosol
cans. Suitable propellents are, for example, low-boiling
fluorocarbons, hydrocarbons or ethers or mixtures of two or more
thereof. The fluorocarbons R124, R125, R134a, R142b, R143 and
R152a, R227, the pure hydrocarbons propane, butane and isobutane
and dimethyl ether either individually or in the form of mixture of
two or more thereof are particularly preferred. In addition,
CO.sub.2, N.sub.2O or N.sub.2 may be present as propellents. Any
combinations of these gases are possible. For aerosol can
formulations, propellent gas contents of 5 to 40% by weight and
more particularly 5 to 20% by weight, based on the composition as a
whole, are preferred. The content of gases non-condensible under
the prevailing pressure conditions should be gauged so that the
volume based on the empty space of the pressurized container gives
a pressure of about 8 to 10 bar, depending on the relevant national
regulations for aerosol cans and pressurized containers (where such
regulations exist). Since no CO.sub.2 is given off during the
crosslinking of the compounds according to the invention,
sufficient propellent gas must be present both for dispensing and
for foaming.
[0136] The tackifiers used are, for example, hydrocarbon resins,
more particularly C5 or C9 resins or C5-resin-modified C9 resins.
Other suitable tackifiers are resins based on pure hydrocarbon
monomers, for example resins obtainable from the polymerization of
mixtures of styrene, .alpha.-methyl styrene and vinyl toluene. The
hydrocarbon resins mentioned may be partly hydrogenated or fully
hydrogenated.
[0137] Also suitable for use as tackifiers are natural resins, such
as gum rosin obtainable, for example, from trees and liquid rosin
which is obtained, for example, in papermaking. The natural resins
may be used in the above-mentioned form as tackifiers although they
may also be used after esterification with corresponding polyhydric
alcohols as pentaerythritol esters, glycerol esters, diethylene
glycol esters, triethylene glycol esters or methyl esters.
[0138] Polyterpene resins are also suitable tackifiers. Terpenes
are obtained in the separation of oleoresin acids from their
natural solvents and can be polymerized to polyterpene resins. Also
suitable for use as tackifiers are the terpene/phenol resins
obtainable from polyterpene resins by phenol modification.
[0139] In addition, the adhesive according to the invention may
contain stabilizers or antioxidants as additives. These generally
include the phenols, the sterically hindered high molecular weight
phenols, polyhydric phenols, sulfur- and phosphorus-containing
phenols or amines. Suitable stabilizers are, for example,
hydroquinone, hydroquinone methylether,
2,3-(ditert.butyl)-hydroquinone,
1,3,5-trimethyl-2,4,6-tris(3,5-ditert.butyl-4-hydroxybenzyl)-benzene;
pentaerythritol
tetrakis-3-(3,5-ditert-butyl-4-hydroxyphenyl)-propionate;
n-octadecyl-3,5-ditert-butyl-4-hydroxyphenyl)-propionate;
4,4-methylene-bis-(2,6-ditert.butylphenol);
4,4-thiobis-(6-tert.butyl-o-cresol); 2,6-ditert.butylphenol;
6-(4-hydroxyphenoxy)-2,4-bis-(n-octylthio)-1,3,5-triazine;
di-n-octadecyl-3,5-ditert.butyl-4-hydroxybenzyl phosphonates;
2-(n-octylthio)-ethyl-3,5-ditert.butyl-4-hydroxybenzoate; and
sorbitol hexa-[3-(3,5-ditert.butyl-4-hydroxyphenyl)-propionate];
and p-hydroxydiphenylamine or N,N'-diphenylenediamine or
phenothiazine.
[0140] The surface coating composition according to the invention
or the adhesive according to the invention may additionally contain
plasticizers, such as benzoate plasticizers, phosphate
plasticizers, liquid resin derivatives or vegetable and animal
oils. Suitable plasticizers are, for example, sucrose benzoate,
diethylene glycol dibenzoate and/or diethylene glycol benzoate
where about 50 to about 95% of all hydroxyl groups have been
esterified, phosphate plasticizers, for example t-butylphenyl
diphenyl phosphate, polyethylene glycols and derivatives thereof,
for example diphenyl ethers of poly(ethylene glycol), liquid resin
derivatives, for example the methyl ester of hydrogenated resin,
vegetable and animal oils, for example glycerol esters of fatty
acids and polymerization products thereof.
[0141] Plasticizers based on phthalic acid, particularly the alkyl
phthalates, are also suitable.
[0142] The surface coating composition according to the invention
or the adhesive according to the invention may additionally contain
dyes, such as titanium dioxide, fillers, such as gypsum, talcum,
clay and the like, and pigments.
[0143] The additives may be present individually or in the form of
a mixture of two or more of the substances mentioned. The quantity
in which the additives are present should not exceed about 20% by
weight (based on the surface coating composition as a whole or the
adhesive as a whole). Suitable quantities are, for example, about
0.1 to about 15% by weight or about 1 to about 10% by weight, In a
preferred embodiment of the invention, the additives are used in
quantities of, for example, about 2, 3, 4, 5, 7 or 9% by
weight.
[0144] Suitable surface coating compositions or adhesives have, for
example, the following approximate composition:
Basic formulations:
Foams:
[0145] 40-80% by weight prepolymer
[0146] 10-25% by weight plasticizer or flame retardant
[0147] 0-5% by weight foam stabilizer
[0148] 0-2% by weight catalyst(s)
[0149] 0-5% by weight other additives
[0150] 10-25% by weight propellent gas
1. Sealant and assembly adhesive
[0151] 25-50% by weight prepolymer
[0152] 25-50% by weight filler(s)
[0153] 0-25% by weight additives
[0154] >1% by weight catalyst(s)
[0155] The invention is illustrated by the following Examples.
EXAMPLES
Example 1
[0156] 51.7 g octylamine, 94.8 g
methyl-N-(trimethoxysilylpropyl)-methyl carbamate and 0.1 g
dibutyltin dilaurate were heated under nitrogen to 180.degree. C.
After 3 h, the amine value had fallen from 153 to <10. After
cooling to room temperature, a white solid was obtained.
Example 2
Silylation of Jeffamin T5000 with
methyl-N-(trimethoxysilylpropyl)-carbamate
[0157] 385.0 g Jeffamin T5000 (propoxylated glycerol with terminal
amino groups, molecular weight ca. 5,000, amine value: 27.5) were
weighed into a 1-liter three-necked flask and dried at ca.
100.degree. C. under a pressure of 20 mbar. After purging with
nitrogen, 57.1 g N-(trimethoxysilylpropyl)-methylcarbamate and 0.1
g dibutyltin dilaurate were added and the whole was heated under
nitrogen to 190.degree. C. Within an hour, the amine value had
fallen to 2.5. After cooling to room temperature, a clear liquid
with a viscosity of ca. 100 Pas (Brookfield RVT, spindle 6, 5
r.p.m.) was obtained.
[0158] 0.2% dibutyl tin diacetonate was added to the liquid which
was then introduced into a rectangular mold in a layer thickness of
2 mm and stored for 1 week at 50% relative humidity/23.degree. C.
for complete hardening.
[0159] A colorless, flexible and elastic polymer film was obtained
after full curing.
Comparison Example 1
Silylation of Jeffamin D4000 with 3-isocyanatopropyl
trimethoxysilane
[0160] 106 g 3-isocyanatopropyl trimethoxysilane were added
dropwise over a period of 20 mins. to 1,000 g Jeffamin. D4000
(.alpha.,.omega.-aminopolypropylene glycol, molecular weight ca.
4,000, amine value: 28); increase in temperature ca. 15.degree. C.
1 hour after the end of the addition of the isocyanatosilane, no
more isocyanate could be detected. A clear colorless liquid with a
viscosity of 5,000 mPas was obtained.
[0161] 0.2% dibutyl tin dilaurate was added to the liquid which was
then introduced into a rectangular mold in a layer thickness of 2
mm and stored for 1 week at 50% relative humidity/23.degree. C. for
complete hardening.
[0162] 24 hours after application, the surface of the cured film
(catalyst 0.1% by weight dibutyltin bis-(2,4-pentanedionate)) was
slightly tacky.
Example 3
Silylation of Jeffamin D4000 with
methyl-N-(trimethoxysilylpropyl)-carbamate
[0163] 200.0 g Jeffamin D4000 were weighed into a 0.5 liter
three-necked flask and dried at ca. 100.degree. C./20 mbar. After
purging with nitrogen, 25.6 g
N-(trimethoxysilylpropyl)-methylcarbamate and 0.1 g dibutyltin
dilaurate were added and the whole was heated under nitrogen to
180.degree. C. Within an hour, the amine value had fallen to 0.5.
After cooling to <150.degree. C., the mixture was slowly cooled
in vacuo (ca. 20 mbar) to room temperature. A clear yellow liquid
with a viscosity of 9,000 mPas (Brookfield RVT, spindle 6, 20
r.p.m.) was obtained.
[0164] 24 hours after application, the cured film (catalyst 0.1% by
weight dibutyltin-bis-(2,4-pentanedionate)) was flexible, elastic
and tack-free.
Example 4
Silylation of a polyamide with
methyl-N-(trimethoxysilylpropyl)-carbamate
[0165] 150.0 g Macromelt TPX 22-405 (polyamide with terminal amino
groups) were melted under nitrogen and 0.15 g dibutyltin dilaurate
and 4.4 g N-(trimethoxysilylpropyl)-methylcarbamate were stirred
into the melt. The mixture was then heated for ca. 2 h to
180-190.degree. C. After cooling to <150.degree. C., the mixture
was slowly cooled in vacuo (ca. 20 mbar) to room temperature.
[0166] A transparent yellow solid was obtained.
Comparison Example 2
Silylation of a polyamide of dimer fatty acid and ethylenediamine
with 3-isocyanatopropyl trimethoxysilane
[0167] 24.5 g 3-isocyanatopropyl trimethoxysilane were added
dropwise with stirring to 100 g of the polyamide at 80.degree. C.
(temperature increase ca. 20.degree. C.). One hour after the end of
the addition of the isocyanatosilane, no more isocyanate could be
detected. A yellow-brown, slightly cloudy wax-like substance which
melted at 70.+-.5.degree. C. was obtained. The cured, clear yellow
film (catalyst 0.15% by weight dibutyltin-bis-(2,4-pentanedionate))
is hard and inelastic.
Example 5
Silylation of a polyamide of dimer fatty acid and ethylenediamine
with methyl-N-(trimethoxysilylpropyl)-carbamate
[0168] 21.0 g methyl-N-(trimethoxysilylpropyl)-carbamate and 0.15 g
dibutyltin dilaurate were stirred into 100 g of the polyamide at
100.degree. C. and the resulting mixture was stirred for 1 h at
180.degree. C. It was then slowly cooled in vacuo (ca. 20 mbar) to
room temperature. A yellow-brown, slightly cloudy wax-like
substance which melted at 70.+-.5.degree. C. was obtained. The
cured, clear yellow film (catalyst 0.15% by weight
dibutyltin-bis-(2,4-pentanedionate)) had the same properties as in
Comparison Example 2.
Example 6
Reaction of Jeffamin D 2000 to polyoxypropylene dicarbamate and
subsequent pyrolysis in the presence of 3-aminopropyl
trimethoxysilane
[0169] 2 g of a 30% methanolic sodium methylate solution were
stirred dropwise into 100 g water-free dimethyl carbonate, after
which 250 g Jeffamin D 2000 were added dropwise with stirring over
a period of 30 minutes. The reaction to the carbamate took place
over a period of 5 hours at 75.degree. C. and produced a yield of
>90%. The sodium methylate was then neutralized with 0.6 g
acetic acid, the salt was filtered off and the solvent distilled
off.
[0170] The purified dicarbamate was then mixed with 44.8 g
3-aminopropyl trimethoxysilane and 0.3 g dibutyltin dilaurate and
the resulting mixture was reacted at 180-190.degree. C. as in
Example 3 to form a silylated prepolymer.
Example 7
Pyrolysis of 1,6-(di-N-methylcarbamato)-hexane in the presence of
bis-(trimethoxysilylpropyl)-amine
[0171] 100 g 1,6-(di-N-methylcarbamato)-hexane, 73.2 g
bis-(trimethoxysilylpropyl)-amine and 0.17 g dibutyltin dilaurate
were weighed into a 0.25 liter three-necked flask and the mixture
was heated with vigorous stirring under nitrogen to 190.degree. C.
After 30 mins., a vacuum (300 mbar) was applied. After another 30
mins., the vacuum was reduced to about 20 mbar and the mixture was
slowly cooled to room temperature.
[0172] A yellow-brown, soft resin was obtained.
* * * * *