Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
CA 02232915 1998-03-23
1
Hydrolysable and uolymerizable vinylcyclopropane silanes
The invention relates to hydrolysable and polymerizable vinylcy-
clopropane silanes, processes for the preparation thereof,
silicic acid condensates, polymers and compositions prepared
therefrom and the use of all these materials inter alia for the
preparation of macromolecular compositions and for the prepara-
tion of composite materials, adhesives, coatings and in particu-
lar dental materials.
Hydrolysable silanes, which contain polymerizable organic
rad_'Lcals, are used in the preparation of coatings, particulate
fillers, adhesive compositions and monolithic moulded articles
and in the surface modification of reinforcing substances. The
silanes are hydrolytically condensed and polymerized thermally,
phoi~ochemically or by redox initiation, i . a . cured, alone, mixed
with other silanes or in the presence of other metal alkoxides.
Of particular interest in connection with the preparation of
organic-inorganic composite materials are above all organically
modified silanes with polymerizable organic groups, such as
vinyl, (meth)acrylic, allyl or styryl groups, since they permit
the simultaneous or consecutive formation both of an inorganic
and of an organic network and therefore of composite materials
with customized properties (cf H. Schmidt, Mat. Res. Soc. Symp.
Proc . Vol . 32 ( 1984 ) , 327-335; H. Schmidt, H. Wolter, J. Non-
Cryst . Solids 121 ( 1990 ) 428-435 ) . The polymerizable silanes are
as a rule initially hydrolytically condensed in solution. After
the addition of thermal initiator or photoinitiator and removal
of the solvent, nanoparticulate resins then form which are shaped
and then polymerized and thus cured.
A major disadvantage of these materials, however, is that the
development of the organic network which takes place on polymeri-
zation is mostly accompanied by a considerable volume contraction
which may result in deformation of the moulded articles,.
reduction in substrate adhesion, layer separation, development
CA 02232915 1998-03-23
- 2 -
of 'voids or development of material stresses. A reduced volume
contraction takes place with silanes which bear ring-opening
groups. In this connection, EP-B-0 358 011 describes scratch-
res.istant materials inter alia based on 3-glycidyloxypropyl
silanes, EP-B-0 486 469 describes organic-inorganic hybrid
polymers of 3-glycidyloxypropyl silanes and DE-C-41 33 494
des~~ribes dental resin compositions in which e.g. silanes with
ring-opening spiroorthoester groups are used. It proves to be
disadvantageous, however, that a ring opening is only possible
cat:ionically in the case of silanes having epoxide or
spi_roorthoester groups and these silanes thus polymerize only in
the absence of moisture, furthermore the polymerization of the
epo:!~ide silanes proceeds sufficiently quickly at elevated
temperatures only and the spiroorthoester silanes exhibit only
a low stability.
Furthermore, only trimethylsiloxy-substituted vinylcyclopropanes
(cf J. Amer. Chem. Soc. 116 (1994), 6453-6454) and 1-
trialkylsilyl-2-vinylcyclopropanes (M. Katsukiyo et al.
Tetrahedron Lett. 30 (1989), 4413-4416) have become known up to
now as silicon-containing vinylcyclopropane derivatives, i.e.
compounds of the following formula:
1 - R~~ = OSi(CH3)3, R2 = R3 = H
~ ~ - R1 =OSi(CH;)3,R2 = H,R3= Ph
R
- R1 = H, R2 =OSi(CH3)H R3 = COOC?H5
P?
It _'Ls the object of the invention to provide hydrolysable and
polymerizable vinylcyclopropane silanes from which, alone or
together with other hydrolytically condensable and polymerizable
components, compositions can be prepared which polymerize with
only low shrinkage and which are suitable as composite or coating
material, adhesive, adhesion promoter or for the preparation of
fillers or materials for medical or dental purposes. These
sila.nes are to be able to be covalently incorporated into
CA 02232915 1998-03-23
- 3 -
organic-inorganic composite materials and be synthetically
obtainable so that the distance between silicon and the
pol.ymerizable groups can be varied.
This object is achieved according to the invention by the
hydrolysable and polymerizable vinylcyclopropane silanes
according to Claims 1 to 3. The invention further relates to the
silicic acid condensates according to Claim 4, the polymers
according to Claim 5, the compositions according to Claims 6 and
7 and the use according to Claim 8.
The hydrolysable and polymerizable vinylcyclopropane silanes
according to the invention and the stereoisomers thereof
correspond to the general formula (I}:
R7
8R
(I)
R-~1/-R,. R? R~ R=t SiXXR34-a.x
c a b
in which the variables R, Rl, R2, R3, R4, R5, R6, R', Rg, R9, W, X,
Y, a, b, c, x, unless otherwise stated, independently of one
another have the following meanings:
R - hydrogen, substituted or unsubstituted C1 to Clz
alkyl, C~ to C15 alkylaryl or C6 to C14 aryl, or
R3g-xXzS.7--R4-R1-RZ- i
R1 - missing or represents substituted or
unsubstituted C1 to C18 alkylene, C6 to C1g
arylene, C~ to C18 alkylenearylene or
arylenealkylene, these radicals being able to be
interrupted by at least one group selected from
CA 02232915 1998-03-23
- 4 -
ether, thioether, ester, carbonyl, amide and
urethane groups or being able to bear these in
the terminal position;
R2 - missing or represents substituted or
unsubstituted C1 to C18 alkylene, C6 to C1g
arylene, C~ to C18 alkylenearylene or C~ to C1$
arylenealkylene, these radicals being able to be
interrupted by at least one group selected from
ether, thioether, ester, thioester, carbonyl,
amide and urethane groups or being able to bear
these in the terminal position;
R3 - missing or represents substituted or
unsubstituted C1 to C18 alkyl, CZ to C18 alkenyl,
C6
to C18 aryl, C~ to Ci$ alkylaryl or C~ to C1$
arylalkyl, these radicals being able to be
interrupted by at least one group selected from
ether, thioether, ester, carbonyl, amide and
urethane groups;
R4 - missing or represents substituted or un-
substituted -CHR6-CHR6-, -CHR6-CHR6-S-R5
-S-RS-
-
,
,
5
S
Y-CO-NH-R
- or -CO-0-R
-;
RS - substituted or unsubstituted C1 to C18 alkylene,
C6 to C18 arylene, C6 to C18 alkylenearylene or C6
to C18 arylenealkylene, these radicals being able
to be interrupted by at least one group selected
from ether, thioether, ester, carbonyl, amide and
urethane groups;
R6 - hydrogen or substituted or unsubstituted C1 to Ci8
alkyl or C6 to Cio aryl;
R' - hydrogen or substituted or unsubstituted C1 to Clo
alkyl, or halogen or hydroxy;
R8 - hydrogen or substituted or unsubstituted C1 to Clo
alkyl;
R9 - missing or represents substituted or
unsubstituted C1 to Cio alkylene;
CA 02232915 1998-03-23
- 5 -
W - missing or represents carbonyl, ester, ether,
thioether, amide or urethane groups;
X - a hydrolysable group, namely halogen, hydroxy,
alkoxy or acyloxy;
Y - 0 or S;
a - 1, 2 or 3;
b - 1, 2 or 3;
c - 1 to 6; and
x - 1, 2 or 3;
and with the proviso that
(i) a+x = 2, 3 or 4
and
(ii) a and/or b = 1.
However, the above formula covers only those compounds which are
compatible with the valency theory.
The silanes according to the invention are usually present as
stereoisomer mixtures and in particular as racemates.
The ether, thioether, ester, thioester, carbonyl, amide and
urethane groups which are possibly present in the radicals are
defined by the following formulae: -O-, -S-, -CO-O-, -O-CO-,
CO-;i-, -S-CO-, -CS-0-, -0-CS-, -CO-, -CO-NH-, -NH-CO-, -0-CO-NH
and -NH-CO-0-.
The non-aromatic radicals or non-aromatic parts of the radicals
possible in formula (I) can be straight-chained, branched or
cyclic.
Alkyl radicals have preferably 1 to 8 and particularly preferably
1 to 4 carbon atoms. Particular examples of possible alkyl
radicals are methyl, ethyl, n- and iso-propyl, sec- and tert-
butyl, n-pentyl, cyclohexyl, 2-ethylhexyl and octadecyl.
CA 02232915 1998-03-23
- 6 -
Alkenyl radicals have preferably 2 to 10 and particularly
preferably 2 to 6 carbon atoms. Particular examples of possible
alkenyl radicals are vinyl, allyl and iso-butenyl.
Preferred examples of possible aryl radicals are phenyl, biphenyl
and naphthyl.
Alkoxy radicals preferably have 1 to 6 carbon atoms. Particular
examples of possible alkoxy radicals are methoxy, ethoxy, n-
propoxy, iso-propoxy and tert-butoxy.
Acy:loxy radicals preferably have 2 to 5 carbon atoms . Particular
examples are acetyloxy and propionyloxy.
Preferred alkylene radicals are derived from the above preferred
alkyl radicals and preferred arylene radicals are derived from
the above preferred aryl radicals.
Preferred radicals consisting of a combination of non-aromatic
and aromatic parts, such as alkylaryl, arylalkyl, alkylenearylene
and arylenealkylene radicals, are derived from the above
preferred alkyl and aryl radicals. Particular examples thereof
are benzyl, 2-phenylethyl and tolyl.
The stated substituted R radicals bear one or more simple
substituents. Examples of these substituents are methyl, ethyl,
phenyl, benzyl, hydroxymethyl, hydroxyethyl, methoxy, ethoxy,
chlaro, bromo, hydroxy, mercapto, isocyanato, vinyloxy, acryloxy,
methacryloxy, allyl, styryl, epoxy, carboxy, S03H, P03H2 or P04H2.
For a, b, c or x _> 2, the radicals X and W and the individual R
radicals can in each case have the same or a different meaning.
Moreover, preferred definitions exist for the above-stated
variables of formula (I) which, unless otherwise stated, can be
chosen independently of one another and are as follows:
CA 02232915 1998-03-23
-
R - C1 to C5 alkyl, benzyl or phenyl or R33_,~X.~Si-R4-R1-
R2_:
R1 - C1 to C8 alkylene, these radicals being able to
be interrupted by at least one group selected
from ether, thioether, ester and urethane groups;
R2 - missing or represents C1 to C$ alkylene, these
radicals being able to be interrupted by at least
one group selected from ether, thioether, ester,
thioester, carbonyl, amide and urethane groups or
being able to bear these in the terminal
position;
R3 - missing or represents methyl, ethyl or phenyl;
R4 - missing or represents -CHR6-CHR6-, -S-RS-, -Y-CO-
NH-R5- or -CO-0-RS-;
RS - C1 to C8 alkylene, these radicals being able to be
interrupted by at least one group selected from
ether, thioether, ester, carbonyl, amide and
urethane groups;
R6 - hydrogen or C1 to CS alkyl; _
R' - hydrogen or C1 to C5 alkyl;
R8 - hydrogen or C1 to C5 alkyl;
R9 - missing or represents C1 to C3 alkylene;
W - ester, amide or urethane group;
X - methoxy, ethoxy or chloro;
Y - 0 or S;
a - 1;
b - 1;
c - 1 to 6;
x - 2 or 3; and/or
a+x - 3.
The individual R radicals can in turn bear simple substituents.
Preferred compounds are accordingly those in which at least one
of the variables of formula ( I ) has the above-described preferred
def i.nition .
CA 02232915 1998-03-23
Furthermore, those vinylcyclopropane silanes of formula (I) are
preferred in which the indices a, b and/or c have the value 1,
and examples thereof are the silanes according to the general
formulae (II), (III), (IV) and (V) below.
R~
8
R_W-R \ R2 ~ R ; R~ SiXXR33_x ( II )
c
R~
~ (III)
8R
R_W-R ~ R2 P,~ R4----SiXXP,33_x
R~
8R (IV)
P-W-R R? R ~ Rs SiXXR~d_~_x
a
CA 02232915 1998-03-23
_ g _
~R%
R-W-R9 ~ R2 R~ Ra SiXXR~3_X
(v)
Particular examples of preferred vinylcyclopropane silanes
according to the invention of formula (I) are given below:
15
CH;O-OC CO-S-(CHZ)3-Si(OCH,;);
CH;O-OC CO-S-(CH~)3-Si(OC~HS)3
CH30-OC CO-S-(CH~3-Si(OCH3)2CH3
35
CA 02232915 1998-03-23
- 10 -
CH30-OC CO-S-CH2-Si(OC2H5)2CH3
CH30-OC CO-NH-(CH2)4-Si(OC2H5)3
CH30-OC CO-NH-(CH2)3-Si(OC2H5)s
CH30-OC CO-NH-(CH~3-Si(OC2H5)2CH3
CH30-OC CO-NH-(CH~3-Si(CH3)20CZH5
CH;O-OC CO-NH ~ Si(OCH,;);
CH30-OC CO-O-(CHI),;-O-CO-NH-(CH~3-Si(OC2H~)3 -
CH30-OC CO-O-(CH~)4-O-CO-NH-(CH2)3-Si(OCZH~)3
--,
CH30-OC CO-(O-CH2-CH~3-O-CQ-NH-(CH2)3-Si(OC2H~)3
CA 02232915 1998-03-23
- 11 -
CH30-OC CO-O-CH2-CHZ-O-CG--fVH-(CH2)3-Si(OC2H5)s
CH30-OC CO- ~ O-CO-NH-(CH2)3-Si(OCZH$)3
CH30-OC CO-O-CHZ O CH2-O-CO-NH-(CH2)3-Si(OCZHS)3
CH30-OC CO-O O CO-NH-(CHz)3-Si(OCZH$)3
OH
CHs~C CO-O CO-O-CHZCHCH2-O-(CH2)s-SI(OCZHS)3
OH
I
CH30-OC CO-O-CH2-CH-CH2-O-(CH~)3-Si(OCH3)3
OH
I
CH30-OC CO-O-CH2-CH-CH2-O-(CH2)3-Si(OCH3)ZCH3
OH
I
CH30-OC CO-O-CHI-CH-CH2-O-(CH2)3-Si(OC2H~)2CH3
OH
CH30-OC CO-O-CH2-CH-CHZ-O-(CH~3-SI(CH3)20C2H5
CA 02232915 1998-03-23
- 12 -
(CH30)3Si-(CH~3-NH-OC CO-NH-(CH2)3-Si(OCH3)s
(C2H50)3Si-(CH~3-NH-OC CO-NH-(CH~3-Si(OC2H5)3
(C2H~0)3Si-(CH~4-NH-OC CO-NH-(CH2)4-Si(OC2H~)3
CH3O-OC CO-
(C z H50)3 S i-(C HZ)3-NH-C O-O
CO-NH-(CH~3-S i (OC2H5)3
O
CH30-OC CO-O-CH2-CH-CH,;
CH3(C2H50)2Si-(CH~3-NH-OC CO-NH-(CH~3-Si(OCZH~)3CH3
C2H5O(CH3)2Si-(CH~3-NH-OC CO-NH-(CH~3-Si(CH3)20C2H5
(CH~O~-JSI ~ NH-OC CO-NH ~ Si(OCH3)s
CA 02232915 1998-03-23
- 13 -
(CH30)3Si-(CH~3-S-OC CO-S-(CH~3-Si(OCH3)3
(C2H50)3Si-(CH~J3-S-OC CO-S-(CH~3-SI(OC2H~)3
CH3(CH30)2Si-(CHZ)3-S-OC CO-S
-(C H~}3-S i (OC H~)3CH3
CH3(C~H~O)2Si-(CH2)3-S-OC CO-S-(CH~3-SI(OC2H~)3CH3
CH30-OC CO-O-CH2-C
O
(CZ H50)3S i-(CH2)3-NH-CO
OH OH
(CH30)3Sr-(CHZ)30-CHZCHCHZ-OC CO-CHZCHCH2--O(CHZ)3-Si(OCH3)3
O O
OH OH
CH3(CH30)2Si--(CH2)30-CH2CHCH2-OC CO-CH2CHCH2-O(CHz)3-Si(OCH~)3CH3
O O
OH OH
CH3;C~H~O)~Si-(CH~)30-CH~CHCH~-OC CO-CHZCHCHz--O(CH2)3-SI(OC2H5)2CH3
II II
O O
OH OH
(CH3)2CZHSOSi--(CH2)30-CH2CHCH2-OC CO-CH2CHCH2-O(CH2)3-SiOCZHs(CH3)2
O O
CA 02232915 1998-03-23
- 14 -
O O
II II
(C2H50)3Si-(CH2)3-NH-C-O-CHZ CH2-O-C-NH-(CH2}3-Si(OCZH$)3
CH3-OOC COO ~ O-CH2-O-CO-NH-(CHZ)3-Si(OC2H5)s
CH3-OOC CO OOC COO-CH3
C H2-O-C O-NH-(C H~}3-S i (OC 2H5)3
2 0 C H3-OOC C -C H3
O-C H2-O-CO-NH-(CHI;,-S i (OC2H5)3
\ \
CH3-OOC COO-CH2- i H-CH2-OOC COO-CH3
O-C O-NH-(C H~3-S I (OC2H5)a
CH3O-OC CO-O-CH2-CH ~ CH-CHZ-O-OC CO-CH3
O O
I I
3 5 (C2H~0)-~S i-(C H~);,-NH-CO C O- (~H-(C H~)~-S i (OC2H~)3
CA 02232915 1998-03-23
- 15 -
10
CH30-OC CO-O-CH2-CH-CH-CHI-O-OC CO-CH3
O O
I I
(C2H~0)3Si-(CH~3-NH-CO CO-NH-(CH2)3-Si(OC2H5)3
20
The preparation of the vinylcyclopropane silanes (I) according
to the invention is possible in particular via a large number of
conventional addition or condensation reactions which are carried
out according to the methods customary for these reactions.
Processes which can be used for preparing the silanes according
to the invention are described e.g. in W. Noll, Chemie and
Technologie der Silicone, 2nd edition, Verlag Chemie, Weinheim,
19 6 8 , in particular p . 22 et seq . , and in the review by R . C .
Mehrotra in J. Non-Crystalline Solids 100, (1988) 1-15 and the
literature quoted in this article.
In a first variant, e.g. 1-methoxycarbonyl-2-vinylcyclopropane-1-
carboxylic acid (1) or the acid chloride or potassium salt
thereof can be reacted with amino- or mercapto-functionalized
silanes by means of a nucleophilic substitution.
CA 02232915 1998-03-23
- 16 -
~ H-V-RS-SiXXR33_x
Nucleophilic substitution:
(-H~)
- ' CH30-OC CO-V-RS--SiXxR33-x
CH30-OC CO-Z
(Z = OH, C1, 0 K+; V = NH, S)
I Concrete example:
CCH30)3 S ~-(G H2)3-N~'2
(-HCI)
--
CH3O-OC CO-NH-(CH2)3-Si(OCH3)3
CH;O-OC CO-CI
Analogously thereto, the acid (1) can also be added to an
isocyanate group-containing silane:
Isocyanate addition:
OCN-R~-SiXXR33..x
f
(-CO~)
CH30-OC CO-NH-R~-SiXXR33-x
CH30-OC CO-OH
CA 02232915 1998-03-23
- 17 -
Concrete example:
{CzHsO)3Si--(CH~)3-NCO
(-C02)
CH30-OC CO-OH
CH~O-OC CO-NH-(CHz)3-Si{OC~~-is)3
15 Furthermore, the addition of the acid (1) to an epoxide silane
is possible:
Epoxide addition:
~O' 5-SiXxR3
CH2-CH-CHZ-C-F 3-x t
n
CH~o-oC co-off
f ~-
j OH
CH~,O-OC CO-O-Ci-i2-CH-CH2-O-RS S~XXR33-x
~ Concrete example:
O
CHI NCH-CH2-O-(CH2);-Si(OCH~;)3 +
CH~O-OC CO-OH
v
OH
CH30-OC CO-O-CHI-CH-CHI-O-(CHz;;-Si(OCH3)3
. CA 02232915 1998-03-23
- 18 -
Silanes with R - R33_,~XxSi-R4-Rl-RZ- can also be prepared in a
corresponding manner, in place of the acid (1) the 2-
vinylcyclopropane-1,1-dicarboxylic acid (2) or the acid chloride
or potassium salt thereof being reacted with e.g. amino- or
mercapto-functionalized silanes by means of a nucleophilic
substitution.
Nucleophilic substitution:
H-~/-F5-- SiXx°33.x
(-2H~~ Z-OC CO-Z
R3g_xXxSi---KS-V-OC CO-V-R~---SiXxF,33.x _
(Z - GH, C1, 0 K~; V = NH, Si
Concrete example:
2 (CH30)3Si-(CH2)3-NH2
(-2HC1) CI-OC CO-CI
(CH30)~Si-(CH2)~-NH-OC CO-NH-(CH~)3-Si(OCH3)3
CA 02232915 1998-03-23
- 19 -
Epoxide addition:
i ~ ~--SiXxR3
2 CHz-CH-CN,~-O-P 3-x /
HG~-OC CCr-OH
I
1
OH OH
r~,33_xXXSi R$O-CHZCHCH~ O-:7v~, CO-O-CH~CHCH~-ORS--S~XxR33_x
~ Concrete example:
O
i
2 CHI-CH-CHZ-O-;CHI);-Si(O~:,H;,)3 +
HO-OC CG-GH
f
~~'~ ~ OH
(CH;C);Si(CH~}3-O-CHZGHCH~O-OC CO-G-CH~CHCH2-O-(CH~)~Si(OCH3)3
Finally, 1,1-bis(hydroxymethyl)-2-vinylcyclopropane (3) can also
be added to isocyanate-containing silanes:
Isocyanate addition:
2 ocN-P~---sxx~~3-x .
HO-CHI CH2-OH
RJ3-xXXSi-RICO-O-CHI CHI-O-CO-NH-RS SiXxR33_x
CA 02232915 1998-03-23
- 20 -
Concrete example:
2 (L2H5~~3~~-(Cf"~~3-NCO t
Ho-~cH2 cHz-oh
(~-~HsO!;Si'yCHj;3-MH-CG-O-CHI ..Hz-O-CC-NH-(CH~~3-Si(OC H
2 5)3
IO
The individual synthesis methods can also be combined. For
example, multifunctional silanes can be obtained by combining the
epoxide addition with the isocyanate addition, such as
I5
CHZ-C H-CHZ-O-(CHZ);-S i (OC H~)3
CH;O-OC CO-OH
OH
CH30-OC CO-O-CHI-CH-CHI-O-{CH~);-Si(OCH3)s
v (C~HsO)3S1-(CH2)3-NCO
i O-NH-(CHz)~-Si{OC_H~)~
O
CHJO-OC CO-~O-CH2-CH-CHI-O-(CH2)3-Si(OCH;)~
The silanes (I) according to the invention are polymerizable via
the C=C double bonds of the 2-vinylcyclopropane radicals and
hydrolysable via the radicals X. The polymerization of the 2-
vinylcyclopropane groups leads to the formation of an organic
network, whereas the hydrolysable groups produce an inorganic
polysiloxane network through polycondensation.
CA 02232915 1998-03-23
- 21 -
The vinylcyclopropane silanes according to the invention are
substances of high reactivity which on hydrolysis form
polymerizable silicic acid condensates which can be polymerized
in the presence of radical initiators thermally or by irradiation
with light of the visible or W range to form mechanically stable
layers, moulded articles or fillers.
The number of hydrolysable groups, polymerizable groups and
further functional groups can be varied by suitable selection of
the starting materials used in the preparation of the
vinylcyclopropane silanes. Depending on the type and number of
the hydrolysable groups and on the number of vinylcyclopropane
groups, the condensation of the vinylcyclopropane silanes and the
polymerization of the obtained condensates results in materials
with properties which range from silicone rubber-like to glass-
like.
The development of a three-dimensional, organic network is
possible when at least two vinylcyclopropane radicals are
present, the mechanical properties, such as e.g. strength and
flexibility, and the physico-chemical properties, e.g.
adhesiveness, water absorption and refractive index, of the
obtained silicic acid condensates being variable and optimally
adaptable to the requirements of the respective case of
application via the distance between the Si atom and the
vinylcyclopropane radical, i.e. via the length of the spacer
group, and by incorporation of further functional groups.
Aliphatic groups result in products which are rather flexible,
and aromatic groups result in products which are rather rigid.
Furthermore, the crosslinking density, which then likewise
influences the properties and possible applications of the
corresponding silicic acid condensates formed, can be set by
means of the number of polymerizable vinylcyclopropane groups.
Moreover, if the vinylcyclopropane silanes according to the
invention also contain ionically crosslinkable groups as
CA 02232915 1998-03-23
- 22 -
substituents, such as epoxy groups, then a further increase in
crossi:inking density can be achieved simultaneously or
consecutively, i.e. as a 2-stage process, by their ionic
polymerization.
The vinylcyclopropane silanes according to the invention and
their silicic acid condensates possess only a low volatility,
with the result that they can be processed in an easy and largely
harmless manner. In view of the above-stated variation
possibilities of the condensable and polymerizable radicals of
the vinylcyclopropane silanes according to the invention, silicic
acid condensates which can be prepared therefrom can be provided
as resins or fillers for very different areas of application.
The silanes (I) are stable compounds which can be processed
either alone or together with other hydrolysable, condensable
and/or polymerizable components to form the silicic acid
condensates according to the invention.
In addition to the silanes of formula (I), other hydrolytically
condensable compounds of silicon, aluminium, titanium, zirconium
or phosphorus can be used in the preparation of the silicic acid
condensates according to the invention, which are then also
referred to as silicic acid ( hetero ) condensates . These compounds
can be used either as such or in already precondensed form. It
is preferred that at least 20 mol.~, particularly preferably at
least 80 mol.~, based on monomeric compounds, of hydrolysable
silicon compounds are used for the preparation of the silicic
acid (hetero)condensates according to the invention. It is also
preferred that at least 10 mol.$, in particular 40 to 100 mol.~,
in each case based on monomeric compounds, of vinylcyclopropane
silanes according to the invention are used for the preparation
of the silicic acid (hetero)condensates.
Preferably at least one silane of the general.formula (VI) is
used as other hydrolytically condensable compounds:
CA 02232915 1998-03-23
- 23 -
io , m ,
R k( z R )mSiX 4_tk+m) (VI )
in which R1°, Z' , Rll, X' , k and m, unless otherwise stated,-
independently of one another have the following meanings:
R1° - C1 to Cg alkyl, C2 to C12 alkenyl or C6 to C14 aryl;
Rll - C1 to C8 alkylene, CZ to C12 alkenylene or C6 to Cia
arylene;
X' - hydrogen, halogen or C1 to C$ alkoxy;
Z' - mercapto, glycidyl, acrylic, methacrylic, vinyl, allyl
or vinyl ether group;
k - 0, 1, 2 or 3;
m - 0, 1, 2 or 3; and
k+m - 1, 2 or 3.
Such silanes are described e.g. in DE-C-34 07 087, and particular
examples of hydrolytically condensable silanes of general formula
(VI) are:
CH3-Si-C13, CH3-Si- ( OCZHS ) 3, C2H5-Si-C13, C2H5-Si- ( OCZHS ) 3, CHZ=CH-Si-
( OCZHS ) 3, CHZ=CH-Si- ( ~CH3 ) 3, CH2=CH-Si- ( OC2H4OCH3 ) 3, ( CH3 ) 2-Si-
C12,
( CH3 ) 2-Sl- ( OCyHS ) 2 r ( C2H5 ) 3-Sl-C1 , ( C2H5 ) 2-S1.- ( OCZHS ) 2 r (
CH3 ) 3-Sl.-Cl ,
( CIi30 ) 3-Si-C3H6-NHZ r ( CH30 ) s-Si-C3H6-SH, ( CH3~ ) 3-Si-C3H6-NH2.
O
(CH~)z-Si(OCH~)~ CHI NCH-CH~-O-(CH~3-Si(OCH3)3
--/
Furthermore, at least one zirconium, titanium or aluminium
compound of the formulae
MeX"R12Z A1R13~
can be used as other preferred hydrolytically condensable
compounds, in which Me, R12, R13, X", y and z independently of one
another have the following meanings:
CA 02232915 1998-03-23
- 24 -
Me - Zr or Ti;
R12 - hydrogen, substituted or unsubstituted C1 to C12 alkyl,
C~ to C15 alkylaryl or C6 to C14 aryl;
R13 - halogen, OH, C1 to CB alkoxy;
X" - halogen, OH, C1 to C8 alkoxy;
y - 1 to 4, in particular 2 to 4;
z - 1 to 3, in particular 0 to 2.
Preferred examples of zirconium and titanium compounds which can
be used are ZrCl4, Zr ( OCZHS ) 4, Zr ( OC3H~ ) 4, Zr ( OC4H9 ) 4, ZrOClz,
TiCl4,
Ti ( OCZHS ) 4 , Ti ( OC3H~ ) 4 and Ti ( OC4H9 ) 4 . Pref erred examples of
aluminium compounds which can be used are A1 ( OCH3 ) 3, A1 ( OCZHS ) s.
A1 ( OC3H~ ) 3, A1 ( OC4H9 ) 3 and A1C13 .
Complexed Zr, Ti and A1 compounds can also be used, in which
inter alia acids or j3-dicarbonyl compounds can act as complexing
agents.
Other hydrolysable compounds which can be used for preparing the
silicic acid (hetero)condensates are e.g. boron trihalides, tin
tetrahalides, tin tetraalkoxides and vanadyl compounds.
The silicic acid condensates according to the invention of the
silanes ( I ) are obtained by hydrolysis of the hydrolysable groups
X present, e.g. alkoxy groups, and by subsequent condensation,
which results in the formation of an inorganic network of Si-O-Si
units. The hydrolysis and condensation usually take place in
basic or acidic medium, a linking of C=C double bonds which are
contained in the silanes used being generally undesired.
The silicic acid condensates according to the invention can also
be present in incompletely hydrolysed and condensed form. In
such cases, they are referred to as so-called precondensates.
The customary procedure in the preparation of the silicic acid
(hetero)condensates according to the invention is that the
CA 02232915 1998-03-23
- 25 -
silanes (I), optionally dissolved in a solvent, are reacted at
room temperature or with slight cooling and in the presence of
a hydrolysis and condensation catalyst with the necessary
quantity of water, and the resulting mixture is stirred for one
to several hours. Coming into consideration as solvents are
above all aliphatic alcohols, such as ethanol or i-propanol,
dialkyl ketones, such as acetone or methyl isobutyl ketone,
ethers, such as diethyl ether or tetrahydrofuran (THF), esters,
such as ethyl or butyl acetate, and mixtures thereof.
If the hydrolytic condensation is carried out in the presence of
reactive Zr, Ti or A1 compounds, the addition of water should
take place in stages at ca. 0 to 30°C. It is usually favourable
not to add water as such, but to introduce it in the form of
water-containing solvents, such as aqueous ethanol, or by release
via a chemical reaction, such as via an esterification.
The hydrolysis and condensation preferably takes place in the
presence of a condensation catalyst, preference being given to
proton- or hydroxyl ion-releasing compounds, such as organic or
inorganic acids or bases. Particularly preferred are volatile
acids or bases, in particular hydrochloric acid or ammonia. It
has proved to be worthwhile for the hydrolysis and condensation
to adopt procedures of sol-gel technology, as are described e.g.
in C.J. Brinker et al., "Sol-Gel Science", Academic Press,
Boston, 1990. The "sol-gel process" is also disclosed in DE-A-27
58 414, DE-A-27 58 415, DE-A-30 11 761, DE-A-38 26 715 and DE-A-
38 35 968.
The obtained silicic acid (hetero)condensates of the silanes (I)
and optionally of other hydrolytically condensable compounds can
be used either as such or after partial or complete removal of
the solvent used. In some cases, it can also prove to be
advantageous to replace the solvent used for the hydrolytic
condensation with another solvent.
CA 02232915 1998-03-23
- 26 -
The polymerizable silicic acid (hetero)condensates according to
the invention and the silanes (I) and compositions containing
these condensates or silanes can be cured by thermal,
photochemical or redox-induced polymerization, the polymerization
usually taking place after suitable initiators and other
polymerizable components have been added. If different
polymerizable groups, e.g. vinylcyclopropane and epoxide groups,
are present, several curing mechanisms, e.g. radical and cationic
polymerization, can also be used simultaneously or in successive
stages.
Thermal initiators and/or photoinitiators are preferably used to
initiate the radical polymerization. Preferred examples of
thermal initiators are the known peroxides, such as dibenzoyl
peroxide, dilauryl peroxide, tert-butyl peroctoate or tert-butyl
perbenzoate, and also azobisisobutyroethyl ester, benzpinacol or
2,2-dimethylbenzpinacol.
Examples of suitable photoinitiators are benzophenone, benzoin
and derivatives thereof or oc-diketones or derivatives thereof,
such as 9,10-phenanthrenequinone, diacetyl or 4,4-dichlorobenzil.
Camphor quinone and 2,2-methoxy-2-phenyl-acetophenone are
preferably used, and ~-diketones in combination with amines as
reducing agents, such as N-cyanoethyl-N-methylaniline, 4-(N,N-
dimethylamino)benzoic acid ester, N,N-dimethylaminoethyl
methacrylate, N,N-dimethyl-sym-xylidine or triethanolamine are
particularly preferably used. Particularly suitable are also acyl
phosphines, such as 2,4,6-trimethylbenzoyldiphenyl- or bis(2,6-
dichlorobenzoyl)-4-N-propylphenylphosphine oxide.
Particularly suitable for the dual curing of radically and
cationically polymerizable compounds are diaryliodonium or
triarylsulphonium salts, such as triphenylsulphonium
hexafluorophosphate or hexafluoroantimonate.
CA 02232915 1998-03-23
- 27 -
Redox-initiator combinations, such as combinations of benzoyl or
lauryl peroxide with N,N-dimethyl-sym-x~rlidine or N,N-dimethyl-p-
toluidine, are used as initiators for a polymerization carried
out at room temperature.
In the compositions according to the invention, suitable
polymerizable mono- or multifunctional monomers which can also
be referred to as diluent monomers can also be present in
addition to the silanes (I) or the corresponding silicic acid
(hetero)condensates. Particularly preferred diluent monomers are
above all mono- and multifunctional vinylcyclopropane
derivatives, such as 1,1-bis(alkoxycarbonyl)- or 1,1-
bis(aryloxycarbonyl)-2-vinylcyclopropanes, e.g. 1,1-bis-
(methoxycarbonyl)-, 1,1-bis(ethoxycarbonyl)- or 1,1-bis-
(phenoxycarbonyl)-2-vinylcyclopropane, or bis(2-
vinylcyclopropane-1-alkoxycarbonyl-1-carbonyloxy) derivatives,
e.g. bis(2-vinylcyclopropane-1-methoxycarbonyl-1-
carbonyloxy)ethane or bis(2-vinylcyclopropane-1-methoxycarbonyl-
1-carbonyloxy)benzene. Moreover, other radically polymerizable
diluent monomers such as monofunctional (meth)acrylates, e.g.
methyl (meth)acrylate, ethyl (meth)acrylate, butyl
(meth)acrylate, benzyl (meth)acrylate, furfuryl (meth)acrylate
or phenyl (meth)acrylate, and polyfunctional (meth)acrylates,
e.g. bisphenyl-A-di(meth)acrylate, bis-GMA (an addition product
of methacrylic acid and bisphenol-A-diglycidyl ether), UDMA (an
addition product of 2-hydroxyethyl methacrylate and 2,2,4-
hexamethylene diisocyanate), di-, tri- or tetraethylene glycol
di(meth)acrylate, decanediol di(meth)acrylate, trimethylolpropane
tri{meth)acrylate, pentaerythritol tetra(meth)acrylate,
butanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate or
1,12-dodecanediol di(meth)acrylate, can also be used.
The silanes according to the invention, the silicic acid
condensates or silicic acid heterocondensates thereof and
compositions containing them can be used as such or in at least
partially polymerized form e.g. as varnishes for coating
CA 02232915 1998-03-23
- 28 -
plastics, glass or other substrates, as fillers or bulk material
for composites and in particular for medical materials , e'. g . for
the production of contact lenses. They are, however,
particularly preferably used as dental material or a constituent
thereof .
The compositions according to the invention can also optionally
contain other additives, such as coloring agents (pigments or
dyes), stabilizers, flavorants, microbiocidal active ingredients,
flameproofing agents, plasticizers or UV absorbers.
Other possible additives are fillers. Examples of preferred
fillers are quartz, glass ceramic or glass powders, in particular
barium or strontium silicate glass powder, lithium-aluminium
silicate glass powder, silicon, zirconium or aluminium oxides,
or mixtures thereof, finely divided silicas, in particular
pyrogenic or precipitated silicas, and X-ray-opaque fillers, such
as e.g. ytterbium trifluoride.
A particularly preferred composition according to the invention
contains:
(a) 5 to 90, in particular 10 to 70 wt.$, relative to the
composition, of silicic acid(hetero)condensate of silane
a
(I),
(b) 0 to 80, in particular 0 to 50 wt.$, relative to the
composition, of diluent monomer,
( c ) 0 . 1 to 5, particular 0 to 2 . 0 wt relative to the
in . 2 . ~,
composition, of polymerization initiator,and/or
(d) 0 to 90, in particular 0 to 80 wt.$, relative to the
composition, of fillers.
The compositions according to the invention are particularly
preferably used as dental cement, dental filling material or
dental bonding for filling materials. The compositions are used.
CA 02232915 1998-03-23
- 29 -
in particular by applying them to the area of a false or natural
tooth to be treated and curing by roiymerization.
It proves to be a particular advantage of the compositions
according to the invention that on the one hand they exhibit a
low polymerization shrinkage and on the other hand they result
in composite materials with high mechanical strength. Such a
combination of properties is of particular significance
especially in the case of dental materials.
The invention is explained below with reference to examples.
Example 1:
Synthesisof 1-methoxycarbonyl-1-f(3-triethoxvsilvl)propvlamino-
carbonyl Ll-2-vinylcyclopropane (4)
O
NH~Si(OEt)3
~COOMe ( 4 ~
14.5 g (58.8 mmol) of isocyanatopropyltriethoxysilane were added
dropwise to an ice-cooled solution of 10 g (58.8 mmol) of 2-
vinylcyclopropane-1,I-dicarboxylic acid monomethyl ester and 20
mg of dibutyl tin dilaurate in 20 ml of methylene chloride.
After 2 days stirring at room temperature, no more isocyanate was
detectable using IR spectroscopy. After distilling off, 22 g of
a faintly coloured liquid remained.
1H-NMR ( CDC1, ), : 0 . 6 ( t, 2H, CHZSi ) , 1 . 25 (m, 11H, CH2, CH3 ) ,
1.62 (m, 2H, CH2), 2.6 (m, 1H, CH), 3.16 (t,
2H, CH2 ) , 3 . 8 ( q, 9H, OCH2, OCH3 ) , 4 . 80-5 . 00
(br, 1H, NH), 5.1-5.8 (m, 3H, CH=CHZ) ppm.
IR rFilm): 3355, 2979, 1718, 1081 cm-1.
CA 02232915 1998-03-23
- 30 -
Example 2:
Synthesisof 1,1-fbis-ftriethoxysilylpropylaminocarboxymethvl
2-vinvlcyclopropane (51
~ O
O NH Si(OEt)3 ( 5 )
~O
~NH~SV(OEt)3
//O
8 g (32 mmol) of 3-isocyanatopropyltriethoxysilane were added
carefully to a solution of 2 g ( 16 mmol ) of bis ( hydroxymethyl ) -2-
vinylcyclopropane and 20 mg of dibutyl tin dilaurate in 50 ml of
dry methylene chloride. After 48 hours stirring under reflux,
no more isocyanate was detectable using IR spectroscopy. After
the solvent had been distilled off, 10 g (100 yield) of a clear
liquid remained.
1H-NMR (CDClz): 5.00-5.65 (m, 3H, CH=CH2), 4.99 (br, 2H,
NH), 3.99 (m, 4H, CH20), 3.83 (q, 12H, CH20),
3.18 (t, 4H, CH2N), 1.76 (m, 3H, CH-
cyclopropyl), 1.22 (m, 22H, CH2, CH3), 0.61
(t, 4H, CH2Si) ppm.
I~ Filmy,: 3444, 2976, 1718, 1517, 1266, 1077 cm 1.
Example 3:
Synthesis of the adduct (6, of isocyanatopropyltriethoxysilane
to 1-methoxycarbonyl-2-vinylcyclopropane-1-carboxylic acid-(2-
hydroxy-3-phenoxy~prop-1-yl ester
(Et0)3Si~NH
O iy P~t 20 O ~ ( )
6
/ O~O
i
\ ! O
CA 02232915 1998-03-23
- 31 -
6.1 g (19 mmol) of 1-methoxycarbonyl-2-vinylcyclopropane-1-
carboxylic acid-(2-hydroxy-3-phenoxy)prop-1-yl ester, which was
obtained by adding 1-methoxycarbonyl-2-vinylcyclopropane-1-
carboxylic acid to phenylglycidyl ether, 4.7 g (19 mmol) of
isocyanatopropyltriethoxysilane and 20 mg of dibutyl tin
dilaurate were stirred under argon and under reflux for 4 days
until no more isocyanate was detectable using IR spectroscopy.
After the solvent had been distilled off, 10.5 g (97~ yield) of
a yellow viscous liquid remained.
1H-NMR ( CDC1.~) : 0 . 5-0 . 6 ( t, 2H, CHZSi ) , 1. 2 (m, 11H, CHZ,
CH3), 1.5-1.8 (m, 2H, CHZ), 2.6 (m, 1H, CH),
3.1-3.4 (t, 2H, CH2), 3.6-3.9 (m, 11H, OCH2,
OCH3), 4.1 (m, 1H, CHO), 5.1-5.4 (br, 1H,
NH ) , 6 . 8-7 . 3 ( 5 Hark ) ppm .
IR ~Filml: 3385, 2974, 2928, 1729, 1600 ciril.
Example 4:
Di-adduct (7) of 3-isocyanatopropyltriethoxysilane to bisf((~1,4-
12-vinyl-1-methoxycarbonyl)-cyclopropan-1-yl)-carbonyloxy)-2-
hvdroxypropoxy)-methyll-cyclohexane
(Et0)~Si~NN
0
O 0 Me0
0~0
0~0 O
O OMe O~0
(7)
NH~Si(OEt)3
8 g (13.4 mmol) of bis[(((1,4-(2-vinyl-1-methoxycarbonyl)-
cyclopropan-1-yl)-carbonyloxy)-2-hydroxypropoxy)-methyl]-
cyclohexane (di-adduct of 1-methoxycarbonyl-2-vinylcyclopropane-
CA 02232915 1998-03-23
- 32 -
1-carboxylic acid to 1,4-cyclohexanedimethanoldiglycidyl ether)
and 6.6 g (26.8 mmol) of 3-isocyanatopropyltriethoxysilane and
20 mg of dibutyl tin dilaurate were heated under reflux for 4
days in 20 ml of dry methylene chloride, until no more isocyanate
was detectable using IR spectroscopy. After the solvent had been
distilled off, 13.2 g (90$ yield) of a yellow, viscous liquid
remained.
1H-NMR ( CDC1~ ~ 0 . 55-0 . 66 ( t, 4H, CH2Si ) , 1.15-1. 25 (m, 22H,
CH3, -CHZ-CHz-CHZ-), 1.3-1.8 (br. m, 14H,
cyclohexyl, cyclopropyl-CH2), 2.55-2.65 (m,
2H, CH), 3.1-3.3 (m, 4H, CHZN), 3.4-3.7 (m,
12H, CHZO), 3.75 (s, 6H, OCH3), 3.85 (t, 4H,
CHz), 4.1-4.4 (m, 2H, CHO), 5.01 (br, 2H,
NH), 5.25-5.55 (m, 6H, CH=CHZ), ppm.
IR (Filml: 3354, 2975, 1728, 1527, 1078 coil.
Example 5:
Hvdrolvtic condensation of 1-methoxvcarbonvl-1-ff3-
triethoxysilyllpropylaminocarbon~rl)1-2-vinylcyclopropane f4~
100 mmol of the silane (4) were dissolved in 15 ml of anhydrous
ethanol or THF. Hydrolysis took place by adding 150 mmol of
water in the form of 0.1 N aqueous HC1. After 72 hours stirring
at room temperature, the volatile components were removed in
vacuo and there formed a viscous resin which could be used as
monomer component for a radical polymerization, e.g. as component
for a radically curable dental material.
CA 02232915 1998-03-23
- 33 -
Example 6:
Hydrolvtic condensation of 1,1-fbis-ftriethoxvsilvlprowlami-
nocarboxymethyl)1-2-vinylcyclopropane (5Z
100 mmol of the silane (5) were dissolved in 25 ml of anhydrous
ethanol or THF. Hydrolysis took place by adding 150 mmol of
water in the form of 0.1 N aqueous HCl. After 2 to 4 hrs
stirring at room temperature, the volatile components were
removed in vacuo and there formed a viscous resin which, after
radical initiator had been added, could be used as component for
a light-curing coating or a light-curing dental material.
CA 02232915 1998-03-23
- 34 -
Example 7:
Product of addition of 3-aminoprogvltriethoxysilane to 1-(2
acrvlocvloxvethyloxycarbonyl)-1-methoxycarbonyl-2-vinvlcxclopro
pane
C02Me O
~O~N~Si(OEt)3
0
to
0~0 O
O
A mixture of 6.2 g (28 mmol) 3-aminopropyltriethoxysilane and
15.0 g (56 mmol) 1-(2-acryloyloxyethyloxycarbonyl)-1-methoxy-
carbonyl)-1-methoxycarbonyl-2-vinylcyclopropane in 20 ml
dichloromethane was stirred at room temperature. After 14 days
the solvent was distilled off in vacuo. 19.2 g (91 ~ yield) of
a clear, viscous liquid remained.
1H-NMR ( CDC13~ 0 . 56 ( t, 2H, SiCHz) , 1 . 22 ( t, 9H, CH3 ) , 1 . 50
(m, 2H, CHZ), 1.58-1.76 (m, 4H, cyclopropyl-
CHZ), 2.48 (m, 6H, NCHz), 2.61 (m, 2H, cyclo-
propyl-CH), 2.78 (t, 4H, OCCHZ), 3.74 (s, 6H,
OCH31, 3.82 (q, 6H, OCHZ), 4.28 (m, 8H, OCHz)
and 5.14-5.77 (m, 6H, CH=CHz) ppm.
IR (film): 2974, 1737 and 1645 cm-1.
CA 02232915 1998-03-23
- 35 -
Exan~le 8:
Product of addition of 3-mercaptopropyltriethoxysilane to 1-(2
acrYloyloxyethyloxycarbonyl)-1-methoxycarbonyl-2-vinylcyclopro
ane
C~Me O
°~O~s~s<<oE~~3
0
la
A mixture of 29.0 g (0.1 mol) 1-(2-acryloyloxyethyloxycarbonyl)-
1-methoxycarbonyl-2-vinylcyclopropane, 24.5 g (0.1 mol) 3-mer-
captopropyltriethoxysilane and 70 mg 1.8-diazabicyclo[5.4.0]un-
dec-7-en (DBU) in 60 ml acetonitrile was stirred at room tempe-
rature for 3 days. After removal of solvent in vacuo, 50 g (93
$ yield) of a clear, viscous liquid remained.
1H-NMR (CDCI.~~~ : 0.73 (t, 2H, SiCH2), 1.24 (s, 12H, CH3),
1.58-1.74 (m, 2H, cyclopropyl-CH2 and 2H,
CHZ), 2.52-2.79 (m, 6H, SCHZ, OCH and cyclo-
propyl-CH), 3.74 (s, 3H, OCH3), 3.82 (q, 6H,
OCH2 ) , 4 . 3 2 ( m, 4H, OCHZ ) and 5 .13-5 . 84 ( m,
3H, CH=CH2 ) ppm .
IR film: 2974, 1738 and 1652 cm-1.
Example 9:
Synthesis of 1-methoxycarbonyl-2-vinylcyclopropane-1-carboxylic
acid-f2-hydroxy-3-l3-trimethoxysilylpropoxy~propyllester
COZMe H
3 5 ~' Si (OMe~
O
CA 02232915 1998-03-23
- 36 -
A mixture of 10.0 g (58 mmol) 1-methoxycarbonyl-2-vinylcyclo-
propane carboxylic acid, 14.0 g trimethoxysilylpropylglycidyl-
ether and 100 mg lithium perchlorate in 20 ml dichloromethane
were stirred at room temperature for 15 days. After removal of
solvent in vacuo, 20 g (83 $ yield) of a clear, yellow viscous
liquid remained.
1H-NMR ( CDC I, L 0 . 6 8 ( br, 2H, SiCH2 ) , 1. 7 3 ( br, 2H, CH2 ) ,
1.98-2.15 (m, 2H, cyclopropyl-CH2), 2.6I (m,
1H, cyclopropyl-CH), 3.40-3.54 (m, 5H, OH-CH-
CHZOCHZ ) , 3 . 57 ( s, 9H, OCH3 ) , 3 . 75 ( d, 2H,
OCH2 ) , 3 . 8 3 ( s , 3H, OCH3 ) and 5 . 24-5 . 6 3 ( m,
3H, CH=CHZ) ppm.
IR (film L 3626, 2972, 1736 and 1645 cm-1.
Example 10:
Synthesis of 2-vinylcyclopropane-1,1-dicarboxylic acid-fN,N'-
bis 3-triethoxysilylpropyl)1-amide
(C~H50~S' H NH i(OC2H5};,
O O
A mixture of 10.0 g (65 mmol) 2-vinylcyclopropane-1,1-dicarbox-
ylic acid, 31.7 g (130 mmol) 3-isocyanatopropyltriethoxysilane
and 40 mg dibutyltindilaurate in 100 ml anhydrous acetone were
stirred at room temperature for 4 days . After no more isocyanate
was detectable using IR-spectroscopy, the mixture was filtered
and volatile components were removed in vacuo. 26.5 g (72 $
CA 02232915 2001-04-06
, _ 37 _
yield) of a dark oil remained.
iH-Nl~t ~(CDC1.,L 0.62 (br, 4H, SiCH2), 1.24 (t, 18H, CH3),.
1.60 (br, 4H, CH2), 2.05-2.19 (m, 2H, cyclo-
propyl-CH2), 2.77 (m, 1H, cyclopropyl-CH),
3 . I 4 ( t, 4H, NCH) , 3 . 7 6 ( s , 12H, OCHZ ) . and
5.22-5.89 (m, 3H, CH=CHZ) PPm.
I~film,~ : 3346, 2977, 1716 and 1362 c~ 1.
Example I1:
Hydrolytic condensation of 1-methoxycarbonyl-1-rr3-triethoxysi=
I5 lvllpropylaminocarbonylll-2-vinylcvclo~ropane (4 1
100 mmol of si.lane (4) were dissolved in 35 ml anhydrous tetra-
hydrofuran (THF). The hydrolysis of the silane was accomplished
by addition of 300 mmol water in form of an aqueous 0.1 N NH4F
solution. After stirring at room temperature for 22 hours, the
volatile components were removed in vacuo. The obtained viscous
resin was dissolved in 30 ml THF and 100 mmol collidine as base
and 100 mmol trimethylchl,orosilane (TMCS) were added under coo-
ling to silylate remaining Si-OH groups. To complete the reac-
tion the mixture was stirred at room temperature for about 12
hours and then the formed precipitate was separated by filtra-
tion. Before removing volatile components in vacuo, 20 mmol
urethanedimethacrylate
UDMA (from Ivocolar AG, product of addition of 2 mol 2-
hydroxyethylmethacrylate
3 ~ to 1 mol 2,2,4=trimethylhexame thylenediisocyanate) were added as a
diluent to
the mixture. After removal of volatile components in vacuo, a viscous resin
(r) = 45
Pas (23 °C) ) was obtained. After addition of LUCIRIN ~ photoinitiator
(0.8 wt.%),
(LUCIRIN ~ is a trade-mark of BASF AG), test specimens were formed according
to
ISO-standard 4049 (1988) in order to examine the properties and the test
specimens
were cured by irradiating with light of a wave length from 400 to 500 nm (2 x3
minutes)
CA 02232915 2001-04-06
- 38 _
using the SPECTR.AMAT ~ dental light source (SPECTRAMAT ~ is a trade-mark of
Etablissement Vivadent of Liechtenstein). It was found that the shrinkage upon
polymerization was only 4.5 vol. %. Subsequently, the bending strength was
determined to be 29 MPa. By means of differential scanning calorimetry (DSC)
a glass transition temperature Tg of 90 ° was determined. In view of
these properties
the material was useful as a light-curing coating or a light-curing dental
material.
Examine 12:
Hydrolytic condensation of 1-methoxycarbonYl-1-f(3-triethoxysi-
lvllpropylaminocarbonyl)1-2-vinylcvclopropane (4~ and co-conden-
sation with Zr ,OPr,~,
100 mmol of the silane ( 4 ) were dissolved in 15 ml anhydrous
ethanol. The pre-hydrolysis of the silane was accomplished by
additon of 150 mmol water in form of an aqueous 0.1 N NH~F solu-
tion. After stirring at room temperature for 2 hours, 10 mmol of
a prepared Zr(OR)-complex was added. For producing the Zr(OR)-
complex 100 mmol Zr(OPr)4 (80 ~ in propanol) were mixed with 100
mmol 2-vinylcyclopropane-1,1-dicarboxylic acid monoethylester
under cooling with ice, and the mixture was subsequently stirred
at room temperature for 2 hours. Then, the mixture of pre-hydro-
lysate and Zr(OR)-complex was stirred at room temperature for
further 6 hours. Before removing volatile components in vacuo,
20 mmol I,1,1-tris-[(2-vinylcyclopropane-1-carboxylic acid me-
thylester-1-carbonyloxy)methyl]propane and 30 mmol 2-vinylcyclo-
propane-L,1-cticarboxylic acid methylester as cross-linker and
diluent were~added to the mixture. After removing volatile com-
ponents iii-.~wacuo, a viscous resin (r~ - 46 Pas (23 °C) ) was ob-
tained which, after addition of a radical photoinitiator in
accordance with Example 11, could be used as component for a
light-curing coating or a light-curing dental material.
CA 02232915 1998-03-23
- 39 -
Examt~le 13:
Hydroxytic condensation of 1-methoxycarbonyl-1-f(3-triethoxvsi
lyl)propylaminocarbonyl)1-2-vinyl-cyclopropane (4) and co con
densation with tetraethoxysilane
100 mmol tetraethoxysilane (TEOS) were dissolved in 30 ml anhy-
drous ethanol. The pre-hydrolysis of the TEOS was effected by
addition of 150 mmol water in form of aqueous 0.1 N hydrochloric
acid. After stirring at room temperature for 15 minutes, 25 mmol
of the silane ( 4 ) were added to the pre-hydrolysate, and 37 . 5
mmol water were then added in form of 0.1 N hydrochloric acid to
effect hydrolysis. After stirring at room temperature for 72
hours, volatile components were removed in vacuo and a viscous
resin formed which, after addition of a radical photoinitiator
in accordance with Example 11, could be used as component for a
light-curing coating or a light-curing dental material.
Example 14:
Hydrolytic condensation of the adduct (6) of Example 3
100 mmol of silane ( 6 ) were dissolved in 55 ml anhydrous THF .
The hydrolysis of the silane was effected by addition of 300
mmol water in form of aqueous 0.1 N hydrochloric acid. After
stirring at room temperature for 25 hours, the volatile compo-
nents were removed in vacuo. The formed visous resin was dis-
solved in 50 ml THF and 100 mmol collidine as a base and 100
mmol TMCS were added under cooling to silylate remaining Si-OH-
groups. To complete the reaction, the mixture was stirred at
room temperature for about 12 hours and then the formed precipi-
tate of collidine hydrochloride was separated by filtration.
Before removing volatile components in vacuo, 30 mmol urethane-
dimethacrylate UDMA were added to the mixture as diluent. After
removing volatile components in vacuo, a viscous resin was ob-
CA 02232915 2001-04-06
- 40 -
tamed (r) = 65 Pas (23 °C) ). After addition of the LUCIRIN ~
photoinitiator (0.8 wt. %) the
resin was cured in an analogous manner as in Example 11 and the shrinkage upon
polymerization was only 3.7 vol. % and the Tg was 68 °C.
Example 15:
Hvdrolytic condensation of the adduct ~ 6) of Example 3 and co-
condensation with Zr(OPr)h
I00 mmol of the silane (6) were dissolved in 25 ml anhydrous
ethanol. The pre-hydroxlysis of the silane was effected by ad-
dition of 150 mmol water in form of an aqueous 0.1 N NH4F solu-
tion. After stirring at room temperature for 2 hours, 10 mmol of
the prepared Zr(OR)-complex were added: In order to prepare the
Zr(OR)-complex, 100 mmol Zr(OPr)4 (80 $ in propanol) were mixed
with 100 mmol 2-vinylcyclopropane-1,1-dicarboxylic acid mono-
ethylester under cooling with ice and subsequently the mixture
was stirred at room temperature for 2 hours. The mixture of pre-
hydrolysate and Zr-complex was then stirred at room temperature
for additional 15 hours. Before removing volatile components in
vacuo, 20 mmol 1,1,1-tris-[(2-vinylcyclopropane-I,1-dicarboxylic
acid methylester-1-carbonyloxy)methyl]propane and 30 mmol 2-
vinylcyclopropane-1,1-dicarboxylic acid methylester as cross
linker and diluent were added to the mixture. After removing
volatile components in vacuo, a viscous resin (~ - 120 Pas (23
°C)) was obtained which, after addition of a radical photoini
tiator ana~.ot~ous to Example 11, was useful as component for a
' N
light-curing coating or a light-curing dental material.
CA 02232915 1998-03-23
- 41 -
Example 16:
Hydrolytic condensation of adduct (61 of Example 3 and co-con-
densation with tetraethoxysilane
100 mmol TEOS were dissolved in 35 mol anhydrous ethanol. The
pre-hydrolysis of the TEOS was accomplished by addition of 150
mmol water in form of 0.1 N hydrochloric acid. After stirring at
room temperature for 15 minutes, 25 mmol of silane (6) were
added to the pre-hydrolysate. Then, 37.5 mmol water in form of
0.1 N hydrochloric acid were added to effect hydrolysis. After
stirring at room temperature for 72 hours, volatile components
were removed in vacuo and a viscous resin formed which, after
addition of photoinitiator, gave a light-curing resin useful as
component of a dental material.
Example 17:
Hydrolytic condensation of the di-adduct (7) of Example 4 and
co-condensation with diphenyldimethoxysilane
100 mmol of silane (7) and 100 mmol diphenyldimethoxysilane
(DPhDMS) were dissolved in 30 ml anhydrous THF. The hydrolysis
of the silanes was accomplished by addition of 500 mmol water in
form of 0.1 N hydrochloric acid. After stirring at room tempera-
ture for 36 hours, volatile components were removed in vacuo and
a viscous resin formed which, after addition of radial initia-
tor, was useful as component for a light-curing dental material.
Example 18:
Hydrolytic condensation of the silane of Example 7
100 mmol of silane according to Example 7 were dissolved in 75
CA 02232915 1998-03-23
- 42 -
ml anhydrous THF. The hydrolysis of the silane was accomplished
by addition of 300~mmo1 water in form of an aqueous 0.1 N NH4F
solution. After stirring at room temperature for 22 hours, vola-
tile components were removed in vacuo. The so-produced viscous
resin was dissolved in 60 ml THF and 100 mmol collidine as base
and 100 mmol TMCS were added under cooling in order to silylate
still present Si-OH groups. The mixture was stirred at room
temperature for about 12 hours in order to complete the reaction
and then the formed precipitate of collidine hydrochloride was
separated by filtration. Before removing volatile components in
vacuo, 30 mmol urethane dimethacrylate UDMA were added as dilu-
ent to the mixture. After removing volatile components in vacuo,
a viscous resin (r~ - 80 Pas (23 °C)) was obtained. After addi-
tion of photoinitiator lucirin TPO (0.8 wt.~), the resin was
cured in a manner analogous to Example 11 and the bending
strength of the obtained material was 40.5 MPa, the shrinkage
upon polymerization was only 3.9 vol.~ and the Tg was 76 °C.
2 0 Example 19
Hydrolytic condensation of silane of Example 7 and co-condensa-
tion with tetraethoxysilane
25 mmol TEOS were dissolved in 45 ml anhydrous ethanol. The pre-
hydrolysis of the TEOS was accomplished by addition of 37.5 mmol
water in form of 0.1 N hydrochloric acid. After stirring at room
temperature for 15 minutes, 100 mmol of the silane of Example 7
were added to the pre-hydrolysate, and then 150 mmol water in
form of 0.1 N hydrochloric acid were added to effect hydrolysis.
After stirring at room temperature for 72 hours, the volatile
components were removed in vacuo, whereupon a viscous resin
formed which, after addition of radical initiator, was useful as
component for a light-curing coating or a light-curing dental
material.
CA 02232915 1998-03-23
- 43 -
Examt~le 20:
Hydrolytic condensation of silane of Example 8
100 mmol of the silane of Example 8 were dissolved in 30 ml
anhydrous THF. The hydrolysis of the silane was accomplished by
addition of 300 mmol water in form of an aqueous 0.1 N NH4F solu-
tion. After stirring at room temperature for 36 hours, the vola-
tile components were removed in vacuo and a viscous resin formed
which, after addition of radical initiator, was useful as compo-
nent for a light-curing dental material.
Example 21:
Hydrolytic condensation of silane of Example 8 and co-condensa-
tion with AlfOBu),
100 mmol of silane of Example 8 were dissolved in 25 ml anhy-
drous THF. The pre-hydrolysis of the silane was accomplished by
addition of 150 mmol water in form of an aqueous 0.1 N NH4F
solution. After stirring at room temperature for 20 hours, 10
mmol of prepared A1(OR) complex were added. In order to prepare
the A1(OR) complex, 100 mmol A1(OBu)3 were dissolved in 55 ml THF
and mixed with 200 mmol 2-vinylcyclopropane-1,1-dicarboxylic
acid monoethylester under cooling with ice, and subsequently the
mixture was stirred at room temperature for 2 hours. After stir-
ring at room temperature for 72 hours, the volatile components
were removed in vacuo and a viscous resin formed which, after
addition of a radical initiator, was useful as component for a
light-curing dental material.
