U.S. patent application number 10/041121 was filed with the patent office on 2003-09-18 for methods and compounds for making coatings, waveguides and other optical devices.
Invention is credited to Maaninen, Arto L.T., Maaninen, Tiina J., Pietikainen, Jarkko J., Rantala, Juha T..
Application Number | 20030176718 10/041121 |
Document ID | / |
Family ID | 28038624 |
Filed Date | 2003-09-18 |
United States Patent
Application |
20030176718 |
Kind Code |
A1 |
Rantala, Juha T. ; et
al. |
September 18, 2003 |
Methods and compounds for making coatings, waveguides and other
optical devices
Abstract
A compound of the general formula:
R.sup.1R.sup.2R.sup.4MR.sup.5, wherein R.sup.1, R.sup.2 and R.sup.4
are independently an aryl, alkyl, alkenyl or alkynyl group, wherein
at least one of R.sup.1, R.sup.2 and R.sup.4 is fully or partially
fluorinated, wherein M is selected from group 14 of the periodic
table, and wherein R.sup.5 is either an alkoxy group, OR.sup.3, or
a halogen group, X. This compound formed can be further reacted to
attach an additional organic R group, and/or hydrolyzed with one or
more similar compounds (preferably having one or two R groups bound
to M), to form a material having a molecular weight of from 500 to
10,000, which material can be deposited on various substrates as a
coating or deposited and patterned for a waveguide or other optical
device components. Methods for making and using compounds of the
general formula R.sup.1R.sup.2R.sup.4MR.sup.5 are also
disclosed.
Inventors: |
Rantala, Juha T.; (Oulu,
FI) ; Maaninen, Arto L.T.; (Oulu, FI) ;
Maaninen, Tiina J.; (Oulu, FI) ; Pietikainen, Jarkko
J.; (Oulu, FI) |
Correspondence
Address: |
GuideOptics, Inc.
Suite 250
2130 Gold St.
P.O. Box 1160
Alviso
CA
95002
US
|
Family ID: |
28038624 |
Appl. No.: |
10/041121 |
Filed: |
January 8, 2002 |
Current U.S.
Class: |
556/87 ; 556/482;
556/88 |
Current CPC
Class: |
C07F 7/12 20130101; C07F
7/0874 20130101; C07F 7/1804 20130101; C07F 7/1888 20130101; C07F
7/123 20130101 |
Class at
Publication: |
556/87 ; 556/88;
556/482 |
International
Class: |
C07F 007/22; C07F
007/24; C07F 007/02 |
Claims
In the claims:
1. A compound of the general formula:
R.sup.1R.sup.2R.sup.4MR.sup.5, wherein R.sup.1, R.sup.2 and R.sup.4
are independently an aryl, alkyl, alkenyl, epoxy or alkynyl group,
wherein at least one of R.sup.1, R.sup.2 and R.sup.4 is fully or
partially fluorinated, wherein M is selected from group 14 of the
periodic table, and wherein R.sup.5 is either an alkoxy group,
OR.sup.3, or a halogen group, X.
2. The compound of claim 1, wherein X is Br or Cl.
3. The compound of claim 1, wherein R1, R2 and/or R4 is fully
fluorinated.
4. The compound of claim 3, wherein R1, R2 and/or R4 is an alkenyl
or alkynyl group.
5. The compound of claim 1, wherein R1, R2 and/or R4 is an alkyl
group having from 1 to 14 carbons, vinyl or allyl group.
6. The compound of claim 1, wherein R1, R2 and/or R4 is an alkenyl
group.
7. The compound of claim 1, wherein R1, R2 and/or R4 is a fully
fluorinated alkenyl group.
8. The compound of claim 1, wherein R1, R2 and/or R4 is an aryl
group having one or more rings, or an alkyl group having from 1 to
14 carbons.
9. The compound of claim 1, wherein R1, R2 and/or R4 is an alkynyl
group.
10. The compound of claim 1, wherein R5 is an alkoxy groups.
11. The compound of claim 1, wherein R5 is a halogen group.
12. The compound of claim 1, wherein R1 is a fully or partially
fluorinated phenyl group substituted with fully or partially
fluorinated methyl, vinyl or ethyl groups.
13. The compound of claim 1, wherein OR3 is C1-C4 alkoxy.
14. The compound of claim 1, wherein M is Si, Ge, Al or Sn.
15. The compound of claim 1, wherein X is Cl.
16. The compound of claim 1, wherein X is Br.
17. The compound of claim 1, wherein R5 is methoxy.
18. The compound of claim 1, wherein R5 is an ethoxy or chlorine
group.
19. The compound of claim 1, wherein R1, R2 and/or R4 is a
C2+straight chain or C3+branched chain.
20. The compound of claim 1, wherein R1, R2 and/or R4 is a
perfluorinated organic group having an unsaturated double bond.
21. The compound of claim 1, wherein R1, R2 and/or R4 is an epoxy
group.
22. The compound of claim 1, wherein R1, R2 and/or R4 is an
acrylate group.
23. The compound of claim 22, wherein M is Si or Ge.
24. The compound of claim 1, wherein R1, R2 and/or R4 is vinyl.
25. The compound of claim 24, wherein R1, R2 and/or R4 is fully
fluorinated vinyl.
26. The compound of claim 1, wherein R5 is a methoxy, ethoxy or
propoxy, M is Si and R1 is perfluorinated phenyl or perfluorinated
vinyl.
27. The compound of claim 1, wherein R5 is bromine or chlorine, M
is Si, and R1 is perfluorinated phenyl.
28. The compound of claim 1, wherein R4 and R5 are ethoxy, M is Si,
and R1 is perfluorinated phenyl, or perfluorinated alkyl having
from 2 to 8 carbons.
29. The compound of claim 28, wherein R1, R2 and/or R4 is
perfluorinated ethyl or propyl.
30. The compound of claim 1, wherein OR3 is methoxy or ethoxy.
31. The compound of claim 1, wherein OR3 is ethoxy.
32. The compound of claim 1, wherein R1, R2 and/or R4 is a fully or
partially fluorinated single ring or polycyclic aromatic
substituent.
33. The compound of claim 32, wherein R1 and/or R4 has one or two
rings.
34. The compound of claim 1, wherein M is Si.
35. The compound of claim 1, wherein R1 is methyl.
36. The compound of claim 1, wherein R1 is ethyl.
37. The compound of claim 1, wherein R1 is propyl.
38. The compound of claim 1, wherein R1 is an alkenyl group and R4
is an aryl group.
39. The compound of claim 1, wherein R1 is an epoxy group and R4 is
an aryl group.
40. The compound of claim 1, wherein R1 is an alkynyl group and R4
is an aryl group.
41. The compound of claim 1, wherein R1 has an unsaturated double
bond, and R4 has a ring structure.
42. The compound of claim 1, wherein R1 is an alkenyl group and R4
is an alkyl group.
43. The compound of claim 42, wherein R1 is an alkenyl group and R4
is an alkyl group having 4 or more carbons.
44. The compound of claim 1, wherein R1 is an epoxy group and R4 is
an alkyl group.
45. The compound of claim 44, wherein R4 is an alkyl group having 4
or more carbons.
46. The compound of claim 1, wherein R1 is an alkynyl group and R4
is an alkyl group.
47. The compound of claim 1, wherein R1 is a vinyl group and R4 is
an aryl group.
48. The compound of claim 47, wherein R4 is a phenyl group.
49. The compound of claim 48, wherein the phenyl group is a
substituted phenyl group.
50. The compound of claim 1, wherein R1 is a methyl group and R4 is
a vinyl or epoxy group.
51. The compound of claim 1, wherein both R1, R2 and R4 are fully
fluorinated.
52. The compound of claim 1, wherein one of R1, R2 and R4 is fully
fluorinated and the other is partially fluorinated.
53. The compound of claim 52, wherein the partially fluorinated
group is an alkyl group having four or more carbon atoms, and
wherein the fully fluorinated group is an alkenyl or aryl
group.
54. The compound of claim 14, wherein M is Si or Ge.
55. The compound of claim 14, wherein M is Si.
56. The compound of claim 14, wherein M is Ge.
57. The compound of claim 1, wherein R1 and R2 are the same, but
different from R4.
58. The compound of claim 1, wherein R1, R2 and R4 are the
same.
59. The compound of claim 1, wherein R1, R2 and R4 are each
different from each other.
60. A method for making the compound R.sup.1R.sup.2R.sup.4MR.sup.5
of claim 1, comprising: providing a compound R1MOR3.sub.qX.sub.3-q
where M is an element selected from group 14 of the periodic table,
OR3 is an alkoxy group, X is a halogen and q is 2 or 3; reacting
the compound R1MOR3.sub.qX.sub.3-q with either a) Mg and R2X2 where
X2 is Cl, Br or I and R1 is an alkyl, alkenyl, aryl, epoxy or
alkynyl group, and q=3, or b) with R2M1 where R2 is an alkyl,
alkenyl, aryl, epoxy or alkynyl group and M1 is an element from
group 1 of the periodic table, and q=2 or 3; so as to form
R1R2MOR3.sub.2; reacting R1MOR3.sub.2 with a) Mg and R4X2 where X2
is Cl, Br or I and R4 is an alkyl, alkenyl, aryl, epoxy or alkynyl
group, or b) with R4M1 where R4 is an alkyl, alkenyl, aryl, epoxy
or alkynyl group and wherein R4 is fully or partially fluorinated
and M1 is an element from group 1 of the periodic table, or c) with
a halogen or halogen compound followed by reacting with R4M1 where
R2 is an alkyl, alkenyl, aryl, epoxy or alkynyl group, wherein M1
is an element from group 1 of the periodic table; so as to form
R.sup.1R.sup.2R.sup.4MOR.sup- .3.sub.q; and wherein if R.sup.5 is a
halogen, reacting R.sup.1R.sup.2R.sup.4MOR.sup.3.sub.q with a
halogen or halogen compound.
61. A method for using the compound of claim 1, comprising:
providing the compound of claim 1; hydrolyzing the compound of
claim 1 in the presence of H2O or D2O with another compound; so as
to form a compound with an -M-O-M-O- backbone with at least R1, R2
and R4 groups bound thereto and having a molecular weight of from
500 to 10,000.
62. The method of claim 61, wherein the compound has a molecular
weight of from 1500 to 5000.
Description
BACKGROUND OF THE INVENTION
[0001] Growing internet and data communications are resulting in
the need for greater numbers and types of optical components within
expanding optical networks. DWDM systems, or any system that
utilizes light to transmit information, utilize a variety of
components for creating, transmitting, manipulating and detecting
light. Such optical device components, also referred to as
optoelectronic or photonic components, often comprises at least a
portion that is transmissive to light at particular wavelengths.
Fibers and planar light guides are examples of passive light
transmissive optical components within an optical network. However,
light manipulators (components that modify, filter, amplify, etc.
light within the optical network) also often have portions that are
transmissive to light, as often do photodetectors and light
emittors.
[0002] Regardless of the type of optical device component, it is
usually desirable that a material is used that is highly
transmissive to the wavelengths used to transmit information
through the optical network. In addition to low optical absorbance,
the material should preferably have low polarization dependent loss
and have low birefringence and anisotropy, and low stress. It is
also desirable that the material be easy to deposit or form,
preferably at a high deposition rate and at a relatively low
temperature. Once deposited or formed, it is desirable that the
material can be easily patterned, preferably directly patterned
without the need for photoresist and etching steps, and preferably
patterned with small feature sizes if needed. Once patterned, the
material should preferably have low surface and/or sidewall
roughness. The material should also preferably be hydrophobic to
avoid uptake of moisture once installed and in use, and be stable
with a relatively high glass transition temperature (not degrade or
otherwise physically and/or chemically change upon further
processing or when in use).
[0003] Often, current materials used for making optical device
components have some, but not all, of these characteristics. For
example, inorganic materials such as silica are relatively stable,
have relatively high glass transition temperatures have relatively
low optical loss. However, silica materials often require higher
deposition temperatures (limiting substrates and components on the
substrates) and have lower deposition rates and cannot be directly
patterned. Organic materials such as polymers can be deposited at
lower temperatures and at higher deposition rates, but are
relatively unstable and have lower glass transition temperatures.
What are needed are materials for optical device components that
have a larger number of the preferred characteristics set forth
above.
SUMMARY OF THE INVENTION
[0004] A compound of the general formula
R.sup.1R.sup.2R.sup.4MR.sup.5 is disclosed, wherein R.sup.1,
R.sup.2 and R.sup.4 are independently an aryl, alkyl, alkenyl or
alkynyl group, wherein at least one of R.sup.1, R.sup.2 and R.sup.4
is fully or partially fluorinated, wherein M is selected from group
14 of the periodic table, and wherein R.sup.5 is either an alkoxy
group, OR.sup.3, or a halogen group, X. This compound formed can be
further reacted to attach an additional organic R group, or
hydrolyzed with one or more similar compounds (preferably having
one or two R groups bound to M), to form a material having a
molecular weight of from 500 to 10,000, which material can be
deposited on various substrates as a coating or deposited and
patterned for a waveguide or other optical device components.
Methods for making and using compounds of the general formula
R.sup.1R.sup.2R.sup.4MR.sup.5 are also provided.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
COMPOUNDS
[0005] In the present invention, compounds are made that can be
hydrolyzed and condensed (alone or with one or more other
compounds) into a material having a molecular weight of from 500 to
10,000 (preferably from 1,000 to 3,000), which material can be
deposited by spin-on, spray coating, dip coating, or the like. Such
compounds are preferably partially or fully fluorinated, though not
necessarily so in all embodiments. The compounds will preferably
have an element M selected from groups 3-6 or 13-16 of the periodic
table, which element is preferably tri-, tetra- or penta-valent,
and more preferably tetravalent, such as those elements selected
from group 14 of the periodic table. Connected to this element M
are from three to five substituents, wherein from one to three of
these substituents are organic groups to be discussed further
below, with the remainder being a halogen or an alkoxy group.
Compound Example I
[0006] In one embodiment of the invention, a compound is provided
of the general formula: R.sup.1MOR.sup.3.sub.3, where R.sup.1 is
any partially or fully fluorinated organic group (preferably a
partially or filly fluorinated aryl, alkenyl, alkynyl or alkyl
group), where M is an element selected from column 14 of the
periodic table, and where OR.sup.3 is an alkoxy group--except where
M is Si, R.sup.1 is perfluorinated phenyl or perfluorinated vinyl,
and OR.sup.3 is ethoxy, which, though not novel per se, can be part
of one of the novel methods of the invention as will be discussed
further below. R.sup.1 can have an inorganic component, though if
so, a portion should preferably be a partially or fully fluorinated
organic component, In a more preferred example of this embodiment,
R.sup.1 comprises a double bond that is capable of physical
alteration or degradation in the presence of an electron beam, or
electromagnetic radiation and a photoinitiator (or sensitizer,
photoacid or thermal initiator--to be discussed further below). In
this example, R.sup.1 could be an alkenyl group such as a vinyl
group, or could be an epoxy or acrylate group, that is preferably
partially or fully fluorinated. Such a group, as will be discussed
further herein, can allow for crosslinking upon application of an
electron beam or preferably electromagnetic radiation (e.g.
directing ultraviolet light through a mask with the material
comprising a photoinitiator). In the alternative, R.sup.1 could be
an organic group that is (or a hybrid organic-inorganic group that
comprises) a single or multi ring structure (an "aryl group") or an
alkyl group of any length, such as from 1 to 14 carbon atoms or
longer (preferably 4-10)--the alkyl group capable of being a
straight or branched chain. If R.sup.1 is a ring structure, or a
carbon chain of sufficient length (e.g. 4 (or 5) or more carbons),
then such an R.sup.1 group can provide bulk to the final material
once hydrolyzed, condensed and deposited on a substrate. If R.sup.1
is a ring structure, whether single ring or multi ring, it can have
substituents thereon, fluorinated, though not necessarily, such as
alkyl or alkenyl substituents (preferably from 1 to 5 carbons), and
where the substituents on the ring structure can be at from 1 to 3
locations around the ring. R.sup.1 can be a 4 to 8 sided ring
structure (preferably 5 or 6 sided) which ring structure could
comprise N or O. R1 could comprise nitrogen, or R.sup.1 can also
have an oxygen component, such as a carboxylate group (e.g.
acrylate, butenecarboxylate, propenecarboxylate, etc.).
[0007] In the example above, in R.sup.1MOR.sup.3.sub.3, M can be a
tetravalent element from column 14 of the periodic table (e.g. Si
or Ge), or a tetravalent element from column 16--e.g. Se (or a
tetravalent early transition metal--such as titanium or zirconium).
Also, OR.sup.3 is an alkoxy group, though preferably one having
from 1 to 4 carbon atoms (longer alkoxy groups can be used, but are
more expensive). Specific examples include: 12
Compound Example II
[0008] In yet another embodiment of the invention, a compound is
provided of the general formula: R.sup.1MOR.sup.3.sub.2X, where
R.sup.1 is any partially or filly fluorinated organic group
(preferably a partially or fully fluorinated aryl, alkenyl, alkynyl
or alkyl group) as set forth above, where M is an element selected
from group 14 of the periodic table as mentioned above, where X is
a halogen, and where OR.sup.3 is an alkoxy group as above. X in
this example is preferably F, Cl, Br or I, and more preferably Cl
or Br. Specific examples of compounds within this category include
34
Compound Example III
[0009] In another embodiment of the invention, a compound is
provided of the general formula: R.sup.1MX.sub.2OR.sup.3, where
R.sup.1 is any partially or fully fluorinated organic group
(preferably a partially or fully fluorinated aryl, alkenyl, alkynyl
or alkyl group) as set forth above, where M is an element selected
from group 14 of the periodic table as mentioned above, where
OR.sup.3 is an alkoxy group as above, and where X is a halogen as
above--Except where M is Si R.sup.1 is perfluorinated phenyl, X is
Cl, and OR.sup.3 is ethoxy, which, though not novel per se, is
novel when used as part of the methods of the invention as will be
discussed further below. Specific examples within this category
include 5
Compound Example IV
[0010] In a further embodiment of the invention, a compound is
provided of the general formula: R.sup.1MX.sub.3, where R.sup.1 is
any partially or fully fluorinated organic group (preferably a
partially or fuilly fluorinated aryl, alkenyl, alkynyl or alkyl
group) as set forth above, where M is an element selected from
group 14 of the periodic table as mentioned above, and where X is a
halogen as above--Except where M is Si, R.sup.1 is perfluorinated
phenyl, perfluorinated methyl or perfluorinated vinyl, and X is Cl,
which, though not novel per se, are novel when used as part of the
methods of the invention as will be discussed further below. (If M
is Si and X is Cl, some of these novel trichlorosilanes could be
used for forming self assembled monolayers for making a surface
hydrophobic, preferably by application in the vapor phase to a
surface made of silicon and having OH end groups and moisture.)
Specific examples within this category include 6
Compound Example V
[0011] In yet another embodiment of the invention, a compound is
provided of the general formula: R.sup.1R.sup.2MOR.sup.3.sub.2,
where R.sup.1 is any partially or fully fluorinated organic group
(preferably a partially or fully fluorinated aryl, alkenyl, alkynyl
or alkyl group) as set forth above with respect to R.sup.1, R.sup.2
is any partially or fully fluorinated organic group (preferably a
partially or fully fluorinated aryl, alkenyl, alkynyl or alkyl
group) as set forth above with respect to R.sup.1, or any such
organic groups nonfluorinated, and where R.sup.1 and R.sup.2 are
the same or different from each other, where M is an element
selected from group 14 of the periodic table as mentioned above,
and where OR.sup.3 is an alkoxy group as above--except where M is
Si, OR.sup.3 is ethoxy and R.sup.1 and R.sup.2 are perfluorinated
phenyl groups, which compound is not novel per se, but is novel
when used as part of the methods of the invention as set forth
below. Specific examples within this category include: 78
Compound Example VI
[0012] In another embodiment of the invention, a compound is
provided of the general formula: R.sup.1R.sup.2MXOR.sup.3, where
R.sup.1 is any partially or fully fluorinated organic group
preferably a partially or fully fluorinated aryl, alkenyl, alkynyl
or alkyl group) as set forth above with respect to R.sup.1, R.sup.2
is any partially or fully fluorinated organic group (preferably a
partially or fully fluorinated aryl, alkenyl, alkynyl or alkyl
group) as set forth above with respect to R.sup.1, or any such
organic groups nonfluorinated, and where R.sup.1 and R.sup.2 are
the same or different from each other, where M is an element
selected from group 14 of the periodic table as mentioned above,
where OR.sup.3 is an alkoxy group as above, and where X is a
halogen. R.sup.1 and R.sup.2 can be the same or different from each
other. Specific examples within this category include: 91011
Compound Example VIII
[0013] In a further embodiment of the invention, a compound is
provided of the general formula: R.sup.1R.sup.2MX.sub.2, where
R.sup.1 is any partially or fully fluorinated organic group
(preferably a partially or fully fluorinated aryl, alkenyl, alkynyl
or alkyl group) as set forth above with respect to R.sup.1, R.sup.2
is any partially or fully fluorinated organic group (preferably a
partially or fully fluorinated aryl, alkenyl, alkynyl or alkyl
group) as set forth above with respect to R.sup.1, or any such
organic groups nonfluorinated, and where R.sup.1 and R.sup.2 are
the same or different from each other, where M is an element
selected from group 14 of the periodic table as mentioned above,
and where X is a halogen as above--Except where M is Si, R.sup.1
and R.sup.2 are perfluorinated phenyl, and X is Cl, which, though
not novel per se, is novel when used as part of the methods of the
invention as will be discussed further below. Specific examples
within this category include: 1213
[0014] As Compounds V-VII have two organic groups, they can be
formed by various combinations of Methods A, B and/or C (described
in further detail below).
Compound VIII
[0015] In a further embodiment of the invention, a compound is
provided of the general formula: R.sup.1R.sup.2 R.sup.3MOR.sup.3,
where R.sup.1, R.sup.2 and R.sup.3 are independently an aryl,
alkenyl, alkynyl or alkyl group) as set forth above with respect to
R.sup.1 and R.sup.2, and where R.sup.1, R.sup.2 and R.sup.3 can
each be the same or different from each other (and preferably at
least one of where R.sup.1, R.sup.2 and R.sup.3 is partially or
fully fluorinated), where M is preferably an element selected from
group 14 of the periodic table as above, and where OR.sup.3 is an
alkoxy group as above. One example is 14
[0016] though the organic groups need not each be the same as in
this example, and need not each be fluorinated (though preferably
at least one of the organic groups is fluorinated).
Compound IX
[0017] In another embodiment of the invention, a compound is
provided of the general formula: R.sup.1R.sup.2 R.sup.3MX, where
R.sup.1, R.sup.2 and R.sup.3 are independently an aryl, alkenyl,
alkynyl or alkyl group) as set forth above with respect to R.sup.1
and R.sup.2, and where R.sup.1, R.sup.2 and R.sup.3 can each be the
same or different from each other (and preferably at least one of
where R.sup.1, R.sup.2 and R.sup.3 is partially or fully
fluorinated), where M is preferably an element selected from group
14 of the periodic table as above, and where X is a halogen as
above. One example is: 15
[0018] As Compounds VIII and IX have three organic groups, they can
be formed by various combinations of Methods A, B and/or C (which
methods are described in further detail below).
[0019] Other Compounds:
[0020] Additional compounds within the scope of the invention
include those having the general formula R.sup.1MHX.sub.2 where
R.sup.1, M and X are as above and H is hydrogen. One example is:
16
[0021] Other examples, where the fluorinated phenyl group is
replaced with a substituted phenyl, fluorinated alkyl vinyl, etc.
are possible.
[0022] It should be noted that M in the compound formula examples
above need not be tetravalent. M can also have other valencies,
though preferably tri- or penta-valent. Examples would include
early transition metals in group 3 or 5 of the periodic table (e.g.
Y, V or Ta), or elements in columns 13 (column headed by B) or 15
(column headed by N), such as B, Al or As. In such situations, the
compounds above would have one fewer or one additional alkoxy
(OR.sup.3), halogen (X) or an organic group (R.sup.1 or R.sup.2
independently from the other organic group(s)). Examples include
R.sup.1MOR.sup.3X, R.sup.1MOR.sup.3.sub.2, R.sup.1MX.sub.2,
R.sup.1R.sup.2MX, R.sup.1R.sup.2MOR.sup.3, where M is a trivalent
early transition metal (or similar examples with five substituents
selected from R.sup.1 and/or R.sup.2 groups, as well as alkoxy and
halogen groups for pentavalent elements (including metalloids or
transition metals). Such compounds could have the formula
R1.sub.3-mMOR3.sub.m, R1.sub.5-mMOR3.sub.m, R2R1.sub.4-mMOR3.sub.m
or R2R1.sub.4-mMOR3.sub.m. If such tri- or penta-valent elements
are used, such a compound would preferably be hydrolyzed and
condensed as a dopant, rather than as the main portion of the
material at the time of hydrolysis and condensation (likewise with
non-silicon tetravalent elements that form compounds in accordance
with the tetravalent examples above, such as germanium
compounds).
[0023] It should also be noted that the structures illustrated
above are exemplary only, as other ring structures (3 sided--e.g.
epoxy, or 4 to 8 sided--preferably 5 or 6 sided) are possible,
which structures can include nitrogen or oxygen in or bound the
ring. The aryl group can have from 1 to 3 substitutents, such as
one or more methyl, ethyl, ally, vinyl or other substituents--that
can be fluorinated or not. Also, carbon chain R groups can include
oxygen (e.g. carboxylate) or nitrogen, or sulpher. If an alkyl
group is bound to the silicon (or other M group), it can have from
1 to 4 carbons (e.g. a C2+ straight or C3+ branched chain), or up
to 14 carbons (or more)--if used as a bulk enhancing group for
later hydrolysis and deposition, 4 or more carbons are preferable.
These aryl groups can be fully or partially fluorinated, as can
alkenyl or alkynyl groups if used.
METHODS OF MAKING THE COMPOUNDS FOR LATER HYDROLYSIS AND
CONDENSATION
[0024] In a number of the following examples of methods within the
scope of the present invention, "M" is silicon, OR.sup.3 is ethoxy,
and X is Cl. However, as noted above, other alkoxy groups could
easily be used (methoxy, propoxy, etc.), and other group 3-5 or
13-16 elements could be used in place of silicon and other halogens
in place of chlorine. Starting materials can vary from tetraethoxy
silane, to ethoxy silanes having one or more organic groups bound
to the silicon, to chorosilanes having one or more chlorine groups
and/or one or more organic groups, as well as starting materials
having chlorine and alkoxy groups and with one or more organic
groups. Any compound examples within Compounds I-IX above could be
used as starting materials--or could be intermediate or final
compounds as will be seen below. For example,
trifluorovinyltriethoxysila- ne could be a final compound resulting
from reacting a particular trifluorovinyl compound with
tetraethoxysilane, or trifluorovinylsilane could be a starting
material that, when reacted with a particular pentafluorophenyl
compound, results in pentafluorophenyltrifluorovinyldie-
thoxysilane. As mentioned above, it is also preferred that any
organic groups that are part of the starting material or are
"added" by chemical reaction to become part of the compound as set
forth below, are partially or fully fluorinated (or fully or
partially deuterated), though such is not necessary as will also be
seen below.
[0025] One example of a method of the present invention comprises
providing a compound R.sup.1.sub.4-q MOR.sup.3q where M is selected
from group 14 of the periodic table, OR.sup.3 is an alkoxy group,
R.sup.1 is an alkyl, alkenyl, aryl or alkynyl, and q is from 2 to
4; reacting the compound R.sup.1.sub.4-q MOR.sup.3.sub.q with
either a) Mg and R.sup.2X.sup.2 where X.sup.2 is Cl, Br or I and
R.sup.2 is an alkyl alkenyl, aryl or alkynyl group, or b) reacting
with R.sup.2X.sup.1 where R.sup.2 is an alkyl, alkenyl, aryl or
alkynyl group and wherein R.sup.2 is fully or partially fluorinated
or deuterated and X.sup.1 is an element from group I of the
periodic table; so as to replace one of the OR.sup.3 groups in
R.sup.1.sub.4-q MOR.sup.3.sub.q so as to form R.sup.1.sub.4-q
R.sup.2MOR.sup.3.sub.q-1.
[0026] The starting material preferably has 1 or 2 (or no) organic
groups (R.sup.1) bound to the group 14 element "M", which organic
groups may or may not comprise fluorine, with the remaining groups
bound to M being alkoxy groups. An additional preferably
fluorinated (partially of fully) organic group becomes bound to the
group 14 element by one of a number of reactions. One method
(Method A) involves reacting the starting material with magnesium
and a compound having the desired organic group (2) bound to a
halogen X.sup.2 (preferably Cl, Br or I)--namely R.sup.2 X.sup.2,
which reaction replaces one of the alkoxy groups with the organic
group R.sup.2. In the above example, a single alkoxy group is
replaced, however, depending upon the molar ratios of starting
material to R.sup.2X.sup.2 and Mg, more than one alkoxy group can
be replaced with an R.sup.2 organic group. In one example of the
above, a tetraethoxysilane, MOR.sup.3.sub.4 is reacted with a
compound R.sup.2X.sup.2 where R.sup.2 is a preferably fluorinated
alkyl, aryl, alkenyl or alkynyl group and X.sup.2 is preferably Br
or I, so as to form R.sup.2MOR.sup.3.sub.3. In another example,
R.sup.1MOR.sup.3.sub.3 is reacted with R.sup.2X.sup.2 so as to form
R.sup.1R.sup.2MOR.sup.3.sub.2. This group of reactions can be
referred to as: reacting the starting material R.sup.1.sub.4-q
MOR.sup.3.sub.q with R.sup.2X.sup.2 where R.sup.2 is a preferably
fluorinated alkyl, aryl, alkenyl or alkynyl group and X.sup.2 is
preferably Br or I, so as to form R.sup.1.sub.4-q
R.sup.2MOR.sup.3.sub.q-- 1.
[0027] This method A can be described as a method comprising
reacting a compound of the general formula
R.sup.1.sub.4-mMOR.sup.3.sub.m, wherein m is an integer from 2 to
4, OR.sup.3 is an alkoxy, and M is an element selected from group
14 of the periodic table; with a compound of the general formula
R.sup.2X.sup.2+Mg, wherein X.sup.2 is Br or I, where R.sup.1 and
R.sup.2 are independently selected from alkyl, alkenyl, aryl or
alkynyl, and wherein at least one of R.sup.1 and R.sup.2 is
partially or fully fluorinated, so as to make a compound of the
general formula R2MR.sup.1.sub.3-nOR.sup.3.sub.n, wherein n is an
integer from 1 to 3.
[0028] An alternate to the above method (Method B) is to react the
same starting materials (R.sup.1.sub.4-q MOR.sup.3.sub.q) with a
compound R.sup.2X.sup.1 where, as above, R.sup.2 is an alkyl,
alkenyl, aryl or alkynyl group and wherein R.sup.2 is fully or
partially fluorinated or deuterated and X.sup.1 is an element from
group 1 of the periodic table; so as to replace an OR.sup.3 group
in R.sup.1.sub.4-q MOR.sup.3.sub.q to form R.sup.1.sub.4-q
R.sup.2MOR.sup.3.sub.q-1. In this example, X.sup.1 is an element
from group 1 of the periodic table, and is preferably Na, Li or K
(more preferably Na or Li). In one example of the above, a
tetraethoxysilane, MOR.sup.3.sub.4 is reacted with a compound
R.sup.2X.sup.1 where R.sup.2 is a preferably fluorinated alkyl,
aryl, alkenyl or alkynyl group and X.sup.1 is preferably an element
from group I of the periodic table, so as to form
R.sup.2MOR.sup.3.sub.3. In another example, R.sup.1MOR.sup.3.sub.3
is reacted with R.sup.2X.sup.1 so as to form
R.sup.1R.sup.2MOR.sup.3.sub.2.
[0029] This method B can be described as a method comprising
reacting a compound of the general formula R1.sub.4-mMOR3.sub.m
wherein m is an integer from 2 to 4, R1 is selected from alkyl
alkenyl, aryl, or alkyl, alkenyl or aryl, and wherein R1 is
nonfluorinated, or fully or partially fluorinated, OR3 is alkoxy,
and M is an element selected from group 14 of the periodic table;
with a compound of the general formula R2M1, wherein R2 is selected
from alkyl, alkenyl, aryl, alkynyl, and wherein R2 is at least
partially fluorinated; and M1 is an element from group I of the
periodic table; so as to make a compound of the general formula
R1.sub.4-mMOR.sub.3-m-1R2.
[0030] A modification (Method C) of the aforementioned (Method B),
is to react the starting material (R.sup.1.sub.4-q MOR.sup.3.sub.q)
with a halogen or halogen compound so as to replace one or more of
the OR.sup.3 groups with a halogen group due to reaction with the
halogen or halogen compound. The halogen or halogen compound can be
any suitable material such as hydrobromic acid, thionylbromide,
hydrochloric acid, chlorine, bromine, thionylchloride or
sulfurylchloride and the like. Depending upon the ratio of halogen
or halogen compound to starting material (and other parameters such
as reaction time and/or temperature), one or more alkoxy groups can
be replaced by a halogen group--though in most examples, a single
alkoxy group or all alkoxy groups will be replaced. If a single
alkoxy group is replaced, then the starting material
R.sup.1.sub.4-q MOR.sup.3.sub.q becomes R.sup.1.sub.4-q
MOR.sup.3.sub.q-1X.sup.3 where X.sup.3 is a halogen from the
halogen or halogen compound reacted with the starting material (or
simply begin with starting material R.sup.1.sub.4-q
MOR.sup.3.sub.q-1X.sup.3). If all alkoxy groups are replaced due to
the reaction with the halogen or halogen compound, then the
starting material R.sup.1.sub.4-q MOR.sup.3.sub.q becomes
R.sup.1.sub.4-q MX.sup.3.sub.q. Then, as mentioned for Method B
above, either starting material R.sup.1.sub.4-q
MOR.sup.3.sub.q-1X.sup.3 or R.sup.1.sub.4-q MX.sup.3.sub.q is
reacted with a compound R.sup.2X.sup.1 where R.sup.2 is a
preferably fluorinated alkyl, aryl, alkenyl or alkynyl group and
X.sup.1 is preferably an element from group I of the periodic
table, so as to form R.sup.1.sub.4-q R.sup.2MOR.sup.3.sub.q-1,
R.sup.1.sub.4-qR.sup.2MX.sup.3.sub.q-1 (or even
R.sup.1.sub.4-qR.sup.2.su- b.2 MX.sup.3.sub.q-2 depending upon
reaction conditions). A reaction with R.sup.1.sub.4-q
MOR.sup.3.sub.q-1X.sup.3 is preferred due to greater ease of
control of the reaction.
[0031] This Method C can be described as a method comprising
reacting a compound of the general formula X3MOR3.sub.3, where X3
is a halogen, M is an element selected from group 14 of the
periodic table, and OR3 is alkoxy; with a compound of the general
formula R1M1; where R1 is selected from alkyl, alkenyl, aryl and
alkynyl and wherein R1 is partially or fully fluorinated; and M1 is
an element from group I of the periodic table; so as to form a
compound of the general formula R1MOR3.sub.3.
[0032] Related Methods B and C can be described as a single method
comprising reacting a compound of the general formula
R1.sub.4-mMOR3.sub.m-nX.sub.n wherein m is an integer from 2 to 4,
and n is an integer from 0 to 2, R1 is selected from alkyl alkenyl,
aryl, or alkyl alkenyl or aryl, and wherein R1 is nonfluorinated,
or fully or partially fluorinated; OR3 is alkoxy, and M is an
element selected from group 14 of the periodic table; with a
compound of the general formula R2M1, wherein R2 is selected from
alkyl, alkenyl, aryl, alkynyl, and wherein R2 is at least partially
fluorinated, and M1 is an element from group I of the periodic
table; so as to make a compound of the general formula
R2MR1.sub.4-mOR3.sub.m-nX.sub.n-1.
[0033] Of course, as will be seen below, the above starting
materials in the method examples set forth above are only examples,
as many other starting materials could be used. For example, the
starting material could be a halide rather than an alkoxide (e.g. a
mono-, di- or trichlorosilanes) or another material having both
alkoxy and halogen groups on the group 14 element, along with 0, 1
or even 2 organic groups (alkyl, alkenyl aryl, alkynyl) also bound
to the group 14 element. Though the methods of the invention
preferably use starting materials having the group 14 element set
forth above, many different combinations of alkoxy groups, halogen
groups, and organic groups (alkyl, alkenyl, . . . etc.) can be
bound to the group 14 element. And, of course, such starting
materials can be commercially available starting materials or can
be made from other available starting materials (in which case such
materials are intermediate compounds in the methods of the
invention).
[0034] In addition, the methods of the invention include, it is
within the scope of the invention, that a method for forming a
final compound could include Methods A, B and/or C above. For
example, one organic group, preferably fluorinated, could become
bound to the group 14 element M by Method A followed by binding a
second organic group, preferably fluorinated, to the group 14
element M by Method B. Or, Method B could be performed first,
followed by Method A--or Method C could be performed in combination
with Methods A and/or B, etc. And, of course, any particular
reaction (binding of an organic group to M) could be performed only
once by a particular reaction, or multiple times (binding of
multiple organic groups, the same or different from each other) by
repeating the same reaction (a, b or c) multiple times. Many
combinations of these various reactions and starting materials are
possible. Furthermore, any of the methods or method combinations
could include any of a number of additional steps including
preparation of the starting material, replacing one or more alkoxy
groups of the final compound with halogens, purifying the final
compound, hydrolysis and condensation of the final compound (as
will be described further below), etc.
EXAMPLE 1
Making a Compound I via Method B
CF.sub.2.dbd.CF--Cl
+sec/tert-BuLi.fwdarw.CF.sub.2.dbd.CF-Li+BuCl
CF.sub.2.dbd.CF--Li+Si(OEt).sub.4.fwdarw.CF.sub.2.dbd.CF--Si(OEt).sub.3+Et-
OLi
[0035] 200 ml of freshly distilled dry Et.sub.2O is added to a 500
ml vessel (under an argon atmosphere). The vessel is cooled down to
-80.degree. C. and 15 g (0.129 mol) of CF.sub.2.dbd.CFCl gas is
bubbled to Et.sub.2O. 100 ml (0.13 mol) of sec-BuLi is added
dropwise during three hours. The temperature of the solution is
kept below -60.degree. C. all the time. The solution is stirred for
15 minutes and 29 ml (27.08 g, 0.130 mol) of Si(OEt).sub.4 is added
in small portions. The solution is stirred for over night allowing
it to warm up to room temperature. Formed red solution is filtered
and evaporated to dryness to result crude
trifluorovinyltriethoxysilane, CF.sub.2.dbd.CFSi(OEt).sub.3. 17
EXAMPLE 2
Making a Compound I via Method C
CF.sub.2.dbd.CF--Li+ClSi(OEt).sub.3.fwdarw.CF.sub.2.dbd.CF--Si(OEt).sub.3+-
LiCl
[0036] CF.sub.2.dbd.CFSi(OEt).sub.3 is also formed when 30.80 g
(0.155 mol) ClSi(OEt).sub.3 in Et.sub.2O is slowly added to
solution of CF2.dbd.CF--Li (0.155 mol, 13.633g, prepared in situ)
in Et.sub.2O at -78.degree. C. Reaction mixture is stirred
overnight allowing it slowly warm to room temperature. LiCl is
removed by filtration and solution evaporated to dryness to result
yellow liquid, crude trifluorovinyltriethoxysilane.
EXAMPLE 3
Making a Compound IV via Method B or C
[0037] Follow steps in Example 1 or 2 above, followed by
CF.sub.2.dbd.CF--Si(OEt).sub.3+excess
SOCl.sub.2+py.HCl.fwdarw.CF.sub.2.db- d.CF--SiCl.sub.3+3 SO.sub.2+3
EtCl
[0038] 24.4 g (0.100 mol) crude trifluorovinyltriethoxysilane, 44
mL (0.60 mol, 71.4 g) thionylcbloride and 1.1 g (0.0045 mol)
pyridinium hydrochloride are refluxed and stirred for 24 h. Excess
of SOCl.sub.2 is evaporated and trifluorovinyltrichlorosilane
18
[0039] is purified by distillation.
EXAMPLE 4
Making a Compound I via Method A
C.sub.7F.sub.7Br+Mg+excess
Si(OEt).sub.4.fwdarw.C.sub.7F.sub.7Si(OEt).sub.- 3
[0040] 250 g (0.8418 mol) heptafluorobromotoluene, 22.69 g (0.933
mol) magnesium powder, small amount of iodine (15 crystals) and 750
mL (3.3672 mol, 701.49 g) tetraethoxysilane are mixed together at
room temperature and diethylether is added dropwise to the
vigorously stirred solution until an exothermic reaction is
observed (.about.250 mL). After stirring at room temperature for 16
h diethylether is evaporated. An excess of n-heptane (.about.600
mL) is added to precipitate the magnesium salts. Solution is
filtrated and evaporated to dryness. The residue is fractionally
distilled under reduced pressure to yield
heptafluorotoluene-triethoxysilane. 19
EXAMPLE 5 Making a Compound IV via Method A
[0041] Follow the steps in Example 4, followed by
2. C.sub.7F.sub.7Si(OEt).sub.3+6
SOCl.sub.2+py.HCl.fwdarw.C.sub.7F.sub.7Si- Cl.sub.3
[0042] where 114.1 g (0.300 mol) heptafluorotoluenetriethoxysilane,
131 mL (1.800 mol. 214.1 g) thionylchloride and 4.51 g (0.039 mol)
pyridinium hydrochloride are refluxed and stirred for 16 h. Excess
of SOCl.sub.2 is evaporated and perfluorotoluenetrichlorosilane
20
[0043] isolated by vacuum-distillation.
EXAMPLE 6
Making a Compound m via Method A
[0044] Follow same steps as in Example 5, except isolate (by vacuum
distillation at the end), perfluorotoluenedichloroethoxysilane,
CF.sub.3--C.sub.6F.sub.4--Si(OEt)Cl.sub.2 21
EXAMPLE 7
Making a Compound V from a Compound I or II via Method C
C.sub.6F.sub.5Si(OEt).sub.3+SOCl.sub.2+py.HCl.fwdarw.C.sub.6F.sub.5Si(OEt)-
.sub.2Cl+EtCl 1.
C.sub.6F.sub.5Si(OEt).sub.2Cl+CF.sub.2.dbd.CFLi.fwdarw.C.sub.6F.sub.5(CF.s-
ub.2.dbd.CF)Si(OEt).sub.2 2.
C.sub.6F.sub.5(CF.sub.2.dbd.CF)Si(OEt).sub.2+excess
SOCl.sub.2+py.HCl.fwdarw.C.sub.6F.sub.5(CF.sub.2.dbd.CF)SiCl.sub.23.
[0045] 152.0 g (0.460 mol) pentafluorophenyltriethoxysilane, 34 mL
(0.460 mol, 54.724 g) thionylchloride and 6.910 g (0.0598 mol)
pyridinium hydrochloride are refluxed and stirred for 18 h.
Pyridinium hydrochloride is precipitated at -78.degree. C. and the
solution is filtrated. Pentafluorophenylchlorodiethoxysilane 22
[0046] is isolated by vacuum distillation.
[0047] Then 49.712 g (0.155 mol)
pentafluorophenylchlorodiethoxysilane,
C.sub.6F.sub.5SiCl(OEt).sub.2, in Et.sub.2O is slowly added to
solution of CF.sub.2.dbd.CF--Li (0,155 mol, 13.633g, prepared in
situ) in Et.sub.2O at -78.degree. C. Reaction mixture is stirred
overnight while it will slowly warm to room temperature. LiCl is
removed by filtration and the product,
pentafluorophenyltrifluorovinyldiethoxysilane, 23
[0048] purified by distillation.
EXAMPLE 8
Making a Compound VII from a Compound I or II via Method C
[0049] Follow the steps above for Example 7, and then
[0050] 12.1 g (0.0328 mol)
pentafluorophenyltrifluorovinyldiethoxysilane, 12 mL (0.1638 mol,
19.487 g) thionylchloride and 0.50 g (0.0043 mol) pyridinium
hydrochloride are refluxed and stirred for 24 h. Excess of
SOCl.sub.2 is evaporated and residue is fractionally distilled
under reduced pressure to yield a mixture of 80%
pentafluorophenyltrifluoroviny- ldichlorosilane. 24
EXAMPLE 9
Making a Compound I via Method A
C.sub.6F.sub.5Br+Mg+2
Ge(OEt).sub.4.fwdarw.C.sub.6F.sub.5Ge(OEt).sub.3
[0051] 61.5 mL (0.4944 mol. 122.095 g) pentafluorobromobenzene,
13.22 g (0.5438 mol) magnesium powder and 250.00 g (0.9888 mol)
tetraethoxygermane are mixed together at room temperature and
diethylether is added dropwise to the vigorously stirred solution
until an exothermic reaction is observed (.about.400 mL). After
stirring at 35.degree. C. for 16 h the mixture is cooled to room
temperature and diethylether evaporated. An excess of n-heptane
(.about.400 mL) is added to precipitate the magnesium salts.
Solution is filtrated and evaporated to dryness. The residue is
fractionally distilled under reduced pressure to yield
pentafluorophenyl-triethoxygermane. 25
EXAMPLE 10
Making a Compound IV via Method A
[0052] Follow the steps in Example 9, then:
[0053] 50 g (0.133 mol) pentafluorophenyltriethoxygermane, 58 mL
(0.80 mol, 95.2 g) thionylchloride and 1.97 g (0.0 17 mol)
pyridinium hydrochloride are refluxed and stirred for 24 h. Excess
of SOCl.sub.2 is evaporated and pentafluorophenyltrichlorogermane
isolated by vacuum distillation. 26
EXAMPLE 11
making a Compound I via Method A
C.sub.10F.sub.7Br+Mg+excess
Si(OEt).sub.4.fwdarw.C.sub.10F.sub.7Si(OEt).su- b.3
[0054] 166.5 g (0.50 mol) 2-bromoperfluoronaphthalene, 13.37 g
(0.55 mol) magnesium powder and 448.0 mL (2.00 mol, 416.659 g)
tetraethoxysilane are mixed together at room temperature and
diethylether is added dropwise to the vigorously stirred solution
until an exothermic reaction is observed (.about.200 mL). After
stirring at 35.degree. C. for 16 h the mixture is cooled to room
temperature and diethylether evaporated. An excess of n-heptane
(.about.400 mL) is added to precipitate the magnesium salts.
Solution is filtrated and evaporated to dryness. The residue is
fractionally distilled under reduced pressure to yield
perfluoronaphthalenetriethoxysilane. 27
EXAMPLE 12
Making a Compound IV via Method A
[0055] Follow the steps in Example 11, then
[0056] 100 g (0.240 mol) perfluoronaphthalenetriethoxysilane, 105.2
mL (1.442 mol, 171.55 g) thionylchloride and 3.54 g (0.0306 mol)
pyridiniumn hydrochloride are refluxed and stirred for 24 h. Excess
of SOCl.sub.2 is evaporated and perfluoronaphthalenetrichlorosilane
isolated by vacuum distillation. 28
EXAMPLE 13
Making Compound V via Method A
C.sub.6F.sub.5Br+Mg+4
MeSi(OMe).sub.3.fwdarw.C.sub.6F.sub.5(Me)Si(OMe).sub- .2
[0057] 57.9 mL (0.465 mol, 114.726 g) bromopentafluorobenzene,
12.42 g (0.511 mol) magnesium powder and 265 mL (1.858 mol. 253.128
g) methyltrimethoxysilane are mixed together at room temperature
and diethylether is added dropwise to the vigorously stirred
solution until an exothermic reaction is observed (.about.320 mL).
After stirring at 45.degree. C. for 16 h the mixture is cooled to
room temperature and diethylether evaporated. An excess of
n-heptane (.about.300 mL) is added to precipitate the magnesium
salts. Solution is filtrated and evaporated to dryness. The
residue, methyl(pentafluorophenyl)dimethoxysilane, is used without
further purification. 29
EXAMPLE 14
Making Compound VII via Method A
[0058] Follow steps in Example 13, then
[0059] 81.68 g (0.300 mol) methylpentafluorophenyl)dimethoxysilane,
109 mL (1.50 mol, 178.4 g) thionylchloride and 3.69 g (0.0319 mol)
pyridinium hydrochloride are refluxed and stirred for 16 h. Excess
of SOCl.sub.2 is evaporated and
methylpentafluorophenyldichlorosilane isolated by
vacuum-distillation. 30
EXAMPLE 15
Making a Compound V via Method A
[0060] 2 C.sub.6F.sub.5Br+2
Mg+Si(OEt).sub.4.fwdarw.(C.sub.6F.sub.5).sub.2- Si(OEt).sub.2
[0061] 265.2 mL (1.95 mol. 525.353 g) bromopentafluorobenzene,
52.11 g (2.144 mol) magnesium powder and 216 mnL (0.975 mol.
203.025 g) tetraethoxysilane are mixed together at room temperature
and diethylether is added dropwise to the vigorously stirred
solution until an exothermic reaction is observed (.about.240 mL).
The solution is stirred for 30 minutes after which additional 90 mL
of Et.sub.2O is carefully added. After stirring at 35.degree. C.
for 16 h the mixture is cooled to room temperature and diethylether
evaporated. An excess of n-heptane (.about.600 mL) is added to
precipitate the magnesium salts. Solution is filtrated and
evaporated to dryness. The residue is fractionally distilled under
reduced pressure to yield di(pentafluorophenyl)diethoxysi- lane.
31
EXAMPLE 16
Making a Compound V via Method C
C.sub.6F.sub.5Cl+sec-BuLi.fwdarw.C.sub.6F.sub.5Li+sec-BuCl
C.sub.6F.sub.5Li+C.sub.6F.sub.5Si(OEt).sub.2Cl.fwdarw.(C.sub.6F.sub.5).sub-
.2Si(OEt).sub.2+LiCl
[0062] 39.52 g (0.195 mol) chloropentafluorobenzene is weighed to a
1000 mL vessel and 250 mL Et.sub.2O is added. The vessel is cooled
down to -70.degree. C. and 150 mL (0.195 mol) of sec-BuLi (1.3 M)
is added dropwise during one hour. The temperature of the solution
is kept below -50.degree. C. all the time. The solution is stirred
for 30 minutes and 62.54 g (0.195 mol) of
diethoxychloropentafluorophenylsilane in Et.sub.2O (100 mL) is
added in small portions. The solution is stirred for over night
allowing it to warm up to room temperature. Formed clear solution
is filtered and evaporated to dryness to result
dipentafluorophenyl)dieth- oxysilane,
(C.sub.6F.sub.5).sub.2Si(OEt).sub.2.
EXAMPLE 17
Making a Compound VII via Method A or C
[0063] Follow the steps in Example 15 or Example 16, then:
(C.sub.6F.sub.5).sub.2Si(OEt).sub.2+SOCl.sub.2+py.HCl.fwdarw.(C.sub.6F.sub-
.5).sub.2SiCl.sub.2
[0064] 180.93 g (0.400 mol) di(pentafluorophenyl)diethoxysilane,
146 mL (2.00 mol, 237.9 g) thionylchloride and 4.92 g (0.0426 mol)
pyridinium hydrochloride are refluxed and stirred for 16 h. Excess
of SOCl.sub.2 is evaporated and di(pentafluorophenyl)dichlorosilane
isolated by vacuum-distillation. 32
EXAMPLE 18
Making an "Other Compound" via Method A
C.sub.6F.sub.5MgBr+HSiCl.sub.3.fwdarw.C.sub.6F.sub.5(H)SiCl.sub.2
[0065] 600.0 mL (0.300 mol) pentafluorophenyl magnesiumbromide (0.5
M sol. in Et.sub.2O) is added dropwise to a solution of 30.3 mL
(0.300 mol 40.635 g) HSiCl.sub.3 in Et.sub.2O at -70.degree. C.
Reaction mixture is allowed to warm slowly to room temperature by
stirring overnight. Diethylether is evaporated and an excess of
n-heptane (.about.200 mL) is added to precipitate the magnesium
salts. Solution is filtrated and evaporated to dryness. The
residue, pentafluorophenyldichlorosilane, is purified by fractional
distillation. 33
EXAMPLE 19
making a Compound I via Method C
CH.ident.C--Na+ClSi(OEt).sub.3.fwdarw.CH.ident.--Si(OEt).sub.3+NaCl
[0066] 79.49 g (0.400 mol) ClSi(OEt).sub.3 in Et.sub.2O is slowly
added to a slurry of CH.ident.C--Na (0.400 mol, 19.208 g) in
Xylene/light mineral oil at -78.degree. C. Reaction mixture is
stirred overnight allowing it slowly warm to room temperature. NaCl
is removed by filtration and solution evaporated to dryness to
result acetylenetriethoxysilane. 34
EXAMPLE 20
Making a Compound VII via Method A
C.sub.6F.sub.5Br+Mg+CHl.sub.2.dbd.CH--Si(OEt).sub.3.fwdarw.C.sub.6F.sub.5(-
CH.sub.2.dbd.CH)Si(OEt).sub.2 1.
C.sub.6F.sub.5(CH.sub.2.dbd.CH)Si(OEt).sub.2+SOCl.sub.2+py.HCl.fwdarw.C.su-
b.6F.sub.5(CH.sub.2.dbd.CH)SiCl.sub.2 2.
[0067] 100 mnL (0.8021 mol, 198.088 g) pentafluorobromobenzene,
24.90 g (1.024 mol) magnesium powder and 670 mL (3.2084 mol,
610.623 g) vinyltriethoxysilane are mixed together at room
temperature and Et.sub.2O is added dropwise to the vigorously
stirred solution until an exothermic reaction is observed
(.about.400 mL). After stirring at 35.degree. C. for 16 h the
mixture is cooled to room temperature and diethylether evaporated.
An excess of n-heptane (.about.500 mL) is added to precipitate the
magnesium salts. Solution is filtrated and evaporated to dryness.
The residue is fractionally distilled under reduced pressure to
yield pentafluorophenylvinyldiethoxysilane. 35
[0068] 120.275 g (0.3914 mol) pentafluorophenylvinyldiethoxysilane,
143 mL (1.9571 mol, 232.833 g) thionylchloride and 5.880 g (0.0509
mol) pyridinium hydrochloride are refluxed and stirred for 24 h
Excess of SOCl.sub.2 is evaporated and
pentafluorophenylvinyldichlorosilane 36
[0069] isolated by vacuum distillation.
EXAMPLE 21
Making a Compound I from Method B
CH.sub.2.dbd.CHC(--O)--O--Na+ClSi(OEt).sub.3.fwdarw.CH.sub.2.dbd.CH--C(.db-
d.O)--O--Si(OEt).sub.3+NaCl
[0070] 6.123 g (0.0651 mol) sodium acrylate is dissolved to 25 mL
TBIF and cooled to -70.degree. C. 12.8 mL (0.0651 mol, 12.938 g)
chlorotriethoxysilane in TBT (15 mL) is added dropwise to reaction
solution. The solution is stirred for over night allowing it to
warm up to room temperature. NaCl is removed by filtration and
solution evaporated to dryness to result clear liquid,
acryltriethoxysilane. 37
EXAMPLE 22
Making a Compound II
CF.sub.3--(CF.sub.2).sub.7--CH.sub.2--CH.sub.2--Si(OEt).sub.3+SOCl.sub.2+p-
y.HCl.fwdarw.CF.sub.3--(CF.sub.2).sub.7--CH.sub.2--CH.sub.2--Si(OEt).sub.2-
Cl
[0071] 183.11 g (0.300 mol)
1H,1H,2H,2H-Perfluorodecyltriethoxysilane, 22 mL (0.300 mol. 35.69
g) thionylchloride and 4.51 g (0.039 mol) pyridinium hydrochloride
are refluxed and stirred for 16 h. Excess of SOCl.sub.2 is
evaporated and 1H,1H,2H,2H-Perfluorodecylchlorodi(ethoxy)silane
isolated by vacuum-distillation. 38
[0072] Though this example is not using Methods A, B or C, method C
could be used to add a second organic group (replacing the Cl
group), or Methods A and B could be used replace an ethoxy group in
the starting material with an additional organic group. Also, the
starting material could be made by Methods A, B or C (starting
earlier with a tetraethoxysilane and reacting as in the other
examples herein).
EXAMPLE 23
Making a Compound I via Method A
C.sub.8F.sub.17Br+Mg+excess
Si(OEt).sub.4.fwdarw.C.sub.8F.sub.17Si(OEt).su- b.3
C.sub.8F.sub.17Si(OEt).sub.3+excess
SOCl.sub.2+py.HCl.fwdarw.C.sub.8F.sub.- 17SiCl.sub.3
[0073] 250 g (0.501 mol) 1-Bromoperfluorooctane (or 273.5 g, 0.501
mol 1-Iodoperfluorooctane), 13.39 g (0.551 mol) magnesium powder,
small amount of iodine (15 crystals) and 363 mL (2.004 mol, 339.00
g) tetraethoxysilane are mixed together at room temperature and
diethylether is added dropwise to the vigorously stirred solution
until an exothermic reaction is observed (.about.200 mL). After
stirring at room temperature for 16 h diethylether is evaporated.
An excess of n-heptane (.about.400 mL) is added to precipitate the
magnesium salts. Solution is filtrated and evaporated to dryness.
The residue is fractionally distilled under reduced pressure to
yield perfluorooctyltriethoxysilane. 39
EXAMPLE 24
Making a Compound IV via Method A
[0074] Follow the steps in Example 23, then
[0075] 174.7 g (0.300 mol) perfluorooctyltriethoxysilane, 131 mL
(1.800 mol, 214.1 g) thionylchloride and 4.51 g (0.039 mol)
pyridinium hydrochloride are refluxed and stirred for 16 h. Excess
of SOCl.sub.2 is evaporated and perfluorooctyltrichlorosilane
isolated by vacuum-distillation. 40
EXAMPLE 25
Making a Compound I via Method A
CF.sub.2.dbd.CF--O--CF.sub.2--CF.sub.2--Br+Mg+excess
Si(OEt).sub.4.fwdarw.CF.sub.2.dbd.CF--O--CF.sub.2--CF.sub.2--Si(OEt).sub.-
3
[0076] 138.47 g (0.500 mol) 2-Bromotetrafluoroethyl trifluorovinyl
ether, 13.37 g (0.550 mol) magnesium powder, small amount of iodine
(10 crystals) and 362 mL (2.000 mol, 338.33 g) tetraethoxysilane
are mixed together at room temperature and diethylether is added
dropwise to the vigorously stirred solution until an exothermic
reaction is observed (.about.200 mL). After stirring at room
temperature for 16 h diethylether is evaporated. An excess of
n-heptane (.about.400 mL) is added to precipitate the magnesium
salts. Solution is filtrated and evaporated to dryness. The residue
is fractionally distilled under reduced pressure to yield
tetrafluoroethyl trifluorovinyl ether triethoxysilane. 41
EXAMPLE 26
Making a Compound IV via Method A
[0077] Follow steps in Example 25, followed by
[0078] 108.1 g (0.300 mol) tetrafluoroethyl trifluorovinyl ether
triethoxysilane, 131 mL (1.800 mol. 214.1 g) thionylchloride and
4.51 g (0,039 mol) pyridinium hydrochloride are refluxed and
stirred for 16 h. Excess of SOCl.sub.2 is evaporated and
tetrafluoroethyl trifluorovinyl ether trichlorosilane is isolated
by vacuum-distillation. 42
EXAMPLE 27
Making a Compound I via Method B
CF.ident.C--Li+ClSi(OEt).sub.3.fwdarw.CF.ident.C--Si(OEt).sub.3+LiCl
[0079] 30.80 g (0.155 mol) ClSi(OEt).sub.3 in Et.sub.2O is slowly
added to solution of CF.ident.C--Li (0.155 mol, 7.744 g, prepared
in situ) in Et.sub.2() at -78.degree. C. Reaction mixture is
stirred overnight allowing it slowly warm to room temperature. LiCl
is removed by filtration and solution evaporated to dryness to
result fluoroacetylenetriethoxysilane. 43
EXAMPLE 28 Making a Compound VIII via Method C)
(C.sub.6F.sub.5).sub.2Si(OEt).sub.2+SOCl.sub.2.fwdarw.(C.sub.6F.sub.5).sub-
.2Si(OEt)Cl+EtCl+SO.sub.2
C.sub.6F.sub.5Li+(C.sub.6F.sub.5).sub.2Si(OEt)Cl.fwdarw.(C.sub.6F.sub.5).s-
ub.3SiOEt+LiCl
(C.sub.6F.sub.5).sub.3SiOEt+SOCl.sub.2.fwdarw.(C.sub.6F.sub.5).sub.3SiCl+E-
tCl+SO.sub.2
[0080] 180.93 g (0.400 mol) di(pentafluorophenyl)diethoxysilane, 29
mL (0.400 mol, 47.6 g) thionylchloride and 4.92 g (0.0426 mol)
pyridinium hydrochloride are refluxed and stirred for 16 h.
Unreacted SOCl.sub.2 is evaporated and
di(pentafluorophenyl)chloroethoxysilane isolated by vacuum
distillation. 44
[0081] 88.54 g (0.200 mol) of
di(pentafluorophenyl)chloroethoxysilane in Et.sub.2O is slowly
added to solution of C.sub.6F.sub.5--Li (0.200 mol, 34.80 g,
prepared in situ) in Et.sub.2O at -78.degree. C. The solution is
stirred for over night allowing it to warm up to room temperature.
Formed clear solution is filtered and evaporated to dryness to
result tri(pentafluorophenyl)ethoxysilane,
(C.sub.6F.sub.5).sub.3SiOEt. 45
EXAMPLE 29
Making a Compound IX via Method C
[0082] Follow steps in Example 28, followed by
[0083] 114.86 g (0.200 mol) tri(pentafluorophenyl)ethoxysilane,
14.6 mL (0.200 mol, 23.8 g) thionylchloride and 2.46 g (0.0213 mol)
pyridinium hydrochloride are refluxed and stirred for 16 h
Unreacted SOCl.sub.2 is evaporated and
tri(pentafluorophenyl)chlorosilane isolated by vacuum-distillation.
46
[0084] In addition to altering the organic groups in the above
examples, it is of course also possible to use other reagents in
the methods above. For example, in place of diethyl ether, other
solvents such as THF could be used. In place of n-heptane (in
Method A) other non polar solvents such as n-hexane could be used.
And in place of thionyl chloride (for replacing one or more alkoxy
groups with a halogen), chlorine, hydrochloric acid, hydrobromic
acid, thionylbromide, chlorine or sulfurylchloride could be used.
Also, the temperatures and times (and other process parameters) can
be varied as desired. In one embodiment, it is preferred that the
molar ratio of the starting material to R.sup.2X.sup.1 (Methods B
or C) is 0.5:1 to 2:1--preferably 1:1. Also, the starting material
and R.sup.2X.sup.1 are preferably mixed at a temperature less than
-40C. degrees, e.g. between -50C. and -100C. and warmed to a higher
temperature over a period of four hours or more (this higher
temperature can be room temperature or higher if desired)--or over
a longer period of time such as overnight.
[0085] As can be seen from the examples above, Methods B and C of
the invention involve reacting a first compound (having an M group
selected from group 14 of the periodic table, 0, 1 or 2 organic
groups bound to M) with a second compound (having an element from
group 1 of the periodic table and a "new" organic group). As can
also be seen from the above, such a reaction can take place if the
first compound has alkoxy groups bound to M or both alkoxy and
halogen groups (0, 1 or 2 halogen groups) bound to M. Method C, as
mentioned earlier, is a variation of Method B--and both methods can
be viewed as comprising: reacting a compound of the general formula
R.sup.1.sub.4-mMOR.sup.3.sub.m-nX.sub.n, where R.sup.1 is any
nonfluorinated (including deuterated) or partially or fully
fluorinated organic group (preferably a partially or filly
fluorinated aryl, alkenyl, alkynyl or alkyl group) as set forth
above, where M is selected from group 14 of the periodic table,
where X is a halogen, where OR.sup.3 is an alkoxy group, where m=2
to 4 and n=0 to 2. R.sup.1.sub.4-mMOR.sup.3.sub.m-nX.sub.n is
reacted with R.sup.2X.sup.1 where R.sup.2 is selected from alkyl,
alkenyl, aryl or alkynyl (and where R.sup.2 is fluorinated (fully
or partially), and where X.sup.1 is an element from group 1 of the
periodic table. X.sup.1 is preferably Na, Li or K, more preferably
Na or Li, and most preferably Li. M is preferably Si, Ge or Sn,
more preferably Si or Ge, and most preferably Si. X is preferably
Cl, Br or I, more preferably Cl or Br, and most preferably Cl.
OR.sup.3 is preferably an alkoxy group having from 1 to 4 carbon
atoms, more preferably from 1 to 3 carbons, and most preferably 2
carbons (ethoxy). Also, "m" is preferably 3 or 4, whereas "n" is
preferably 0 or 1.
[0086] R.sup.1 and R.sup.2 are independently preferably partially
or fully fluorinated (though not necessarily as can be seen in
prior examples) organic groups such as an aryl group (by aryl group
we mean any organic group having a ring structure) though
preferably a five or six carbon ring that is unsubstituted or
substituted. For a six carbon ring structure, 1, 2 or 3
substituents can be bound to the ring, which substituents can be
actively bound to the ring via a variation on the Method C set
forth above (to be described further below). The substituents can
be alkyl groups of any desired length, straight or branched chain,
preferably fluorinated, and preferably having from 1 to 4 carbon
atoms. Or the substituents on the ring structure can comprise a
C.dbd.C double bond and be an alkenyl group (by alkenyl group we
mean any organic group with a C.dbd.C double bond) such as an
acrylate, vinyl or allyl group. A fluorinated vinyl, methyl or
ethyl group on a fluorinated phenyl group are examples. Or, the
aryl group could be a multi ring structure (e.g.
perfluoronaphthalene or a biphenyl group). Or R.sup.1 and R.sup.2
could independently be an alkenyl group such as a vinyl or longer
chain group having a C.dbd.C double bond, or a group having other
types of double bonds (e.g C.dbd.O double bonds or both C.dbd.C and
C.dbd.O double bonds) such as acrylate and methacrylate groups.
R.sup.1 and R.sup.2 could also be an alkynyl group (by alkynyl
group we mean any organic group with a carbon-carbon triple bond)
as mentioned previously, as well as an alkyl group. If an alkyl
group (by alkyl group we mean a carbon chain of any length),
preferably the carbon chain is from 1 to 14, and more preferably
from 4 to 8. Perfluorinated alkyl groups from 1 to 8 carbons can be
used, as well as fluorinated (e.g. partially fluorinated) groups
longer than 8 carbons. All the organic groups above could be
deuterated in stead of fluorinated (or partially deuterated and
partially fluorinated), though fuilly or partially fluorinated
(particularly fully fluorinated) is preferred.
[0087] In Method C set forth above, an organic (or hybrid) group
"I" (e.g. R2) becomes bound to a group 3-6 or 13-16 element "M" by
replacing a halogen "X" bound to "M" via the specified reaction. In
an alternative to this method (Method D), an organic (or hybrid)
group "R" (e.g. R1) comprises the halogen "X"--preferably Cl or Br
(rather than "X" being bound to "M"). Thus when the reaction is
performed, R2 replaces X bound to R1, such that R2 becomes bound to
R1 (which is in turn bound to M). Preferably the other groups bound
to M are alkoxy groups (OR3) or other organic groups. More
particularly, such a method comprises providing a compound
X.sub.aR.sup.1MOR.sup.3.sub.2R.sup.4 where a is from 1 to 3, X is a
halogen(s) bound to R.sup.1, R1 is an organic group (preferably an
aryl, alkyl alkenyl or alkynyl--more preferably an alkyl or aryl
group), OR.sup.3 is an alkoxy, and R.sup.4 is either an additional
alkoxy group or an additional organic group (selected from aryl,
alkyl, alkenyl or alkynyl), and reacting this compound with
R.sup.2M.sup.1 where M.sup.1 is selected from group 1 of the
periodic table and R.sup.2 is an organic group preferably selected
from aryl, alkyl alkenyl and alkynyl, etc., so as to form
R.sup.2.sub.aR.sup.1MOR.sup.3.sub.2R.sup.4.
[0088] In one embodiment, R.sup.4 is an alkoxy group the same as
OR.sup.3, such that the method comprises reacting
X.sub.aR.sup.1MOR.sup.3.sub.3 with R.sup.2M.sup.1 to form
R.sup.2.sub.aR.sup.1MOR.sup.3.sub.3 (where R.sup.1 and OR.sup.3 are
bound to M and R.sup.2 is bound to R.sup.1. In another embodiment,
R.sup.4 is an organic group selected from aryl, alkyl, alkenyl and
alkynyl. Preferably OR.sup.3 is a methoxy, ethoxy or propoxy,
R.sup.1 is an aryl or alkyl (straight or branched chain) having
from 1 to 14 carbons, and R.sup.2 is an aryl, alkyl, alkenyl or
alkynyl, where a=1 or 2 if R.sup.1 is an alkyl and a=1, 2 or 3 if
R.sup.1 is an aryl group. R.sup.2 can be an epoxy, acrylate,
methacrylate, vinyl, allyl or other group capable of cross linking
when exposed to an electron beam or in the presence of a
photoinitiator and electromagnetic energy (e.g. UV light).
EXAMPLE A
Forming a Compound I or IV via Method D
[0089] 47
[0090] 250 g (0.812 mol) 1,4-dibromotetrafluorobenzene, 21.709 g
(0.8932 mol) magnesium powder, small amount of iodine (15 crystals)
and 181 mnL (0.812 mol. 169.164 g) tetraethoxysilane were mixed
together at room temperature and diethylether was added dropwise to
the vigorously stirred solution until an exothermic reaction was
observed (.about.250 mL). After stirring at room temperature for 16
h diethylether was evaporated. An excess of n-heptane (.about.600
mL) was added to precipitate the magnesium salts. Solution was
filtrated and evaporated to dryness. The residue was fractionally
distilled under reduced pressure to yield
4-bromotetrafluorophenyltriethoxysilane. 48
[0091] 78.246 g (0.200 mol) 4-bromotetrafluorophenyltriethoxysilane
in Et.sub.2O is slowly added to solution of CF.sub.2.dbd.CF--Li
(0.200 mol, 17.592 g, prepared in situ) in Et.sub.2O at -78.degree.
C. Reaction mixture is stirred overnight while it will slowly warm
to room temperature. LiBr is removed by filtration and the product,
4-triethoxysilylperfluorostyrene, purified by distillation. 49
[0092] 117,704 g (0.300 mol) 4-triethoxysilylperfluorostyene, 131
mL (1.800 mol, 214.1 g) thionylchloride and 4.51 g (0.039 mol)
pyridinium hydrochloride were refluxed and stirred for 16 h. Excess
of SOCl.sub.2 was evaporated and 4-trichlorosilyl-perfluorostyrene
isolated by vacuum-distillation. 50
[0093] The above example could be modified where 2 or 3 halogens
(in this case Br) are bound to the phenyl group so as to result in
multiple vinyl substituents. Also, the phenyl group could be
another organic group such as an straight or branched chain alkyl
group, a multi ring aryl group, etc., whereas the vinyl group could
be any suitable organic group capable of binding to a group I
element (in the above example Li) and replacing the halogen (in the
above example Br). Examples other than vinyl include methyl, ethyl,
propyl, phenyl, epoxy and acrylate.
EXAMPLE B
Forming a Compound I via Method D
CF.sub.2Cl--C(.dbd.O)--ONa+ClSi(OEt).sub.3.fwdarw.CF.sub.2Cl--C(.dbd.O)--O-
--Si(OEt).sub.3+NaCl
CF.sub.2.dbd.CF--Li+CF.sub.2Cl--C(.dbd.O)--O--Si(OEt).sub.3.fwdarw.CF.sub.-
2.dbd.CF--CF.sub.2--C(.dbd.O)--O--Si(OEt).sub.3+LiCl
[0094] 15.246 g (0.10 mol) sodium chlorodifluoroacetate, is
dissolved to 100 mL Et.sub.2O and cooled to -70.degree. C. 19.7 mL
(0.10 mol, 19.872 g) chlorotriethoxysilane in Et.sub.2O (50 mL) was
added dropwise to reaction solution. The solution was stirred for
over night allowing it to warm up to room temperature. NaCl is
removed by filtration and solution evaporated to dryness to result
clear colourless liquid, chlorodifluoroacetic acid, triethoxysilyl
ester. 51
[0095] 29.27 g (0.10 mol) chlorodifluoroacetic acid, triethoxysilyl
ester, is dissolved to 100 mL Et.sub.2O and slowly added to
solution of CF.sub.2.dbd.CF--Li (0.10 mol, 8.796 g, prepared in
situ) in Et.sub.2O at -78.degree. C. Reaction mixture is stirred
overnight allowing it slowly warm to room temperature. LiCl is
removed by filtration and solution evaporated to dryness to result
yellow liquid, crude perfluoro-3-butene acid, triethoxysilyl ester.
52
EXAMPLE C Forming a Compound I or IV via Method D
[0096] 53
[0097] 78.246 g (0.200 mol) 4-bromotetrafluorophenyltriethoxysilane
in Et.sub.2O is slowly added to solution of C.sub.6F.sub.5--Li
(0.200 mol, 34.80 g, prepared in situ) in Et.sub.2O at -78.degree.
C. Reaction mixture is stirred overnight while it will slowly warm
to room temperature. LiBr is removed by filtration and the product,
perfluorobiphenyltriethoxysilane, purified by distillation. 54
[0098] 143.516 g (0.300 mol) perfluorobiphenyltriethoxysilane, 131
mL (1.800 mol. 214.1 g) thionylchloride and 4.51 g (0.039 mol)
pyridinium hydrochloride were refluxed and stirred for 16 h. Excess
of SOCl.sub.2 was evaporated and perfluorobiphenyltrichlorosilane
isolated by vacuum-distillation. 55
EXAMPLE D
Forming a Compound I or IV via Method D
[0099] 56
[0100] 143.94 g (0.40 mol) 1,4-dibromooctafluorobutane, 10.69 g
(0.44 mol) magnesium powder, small amount of iodine (15 crystals)
and 88 mL (0.40 mol. 82.42 g) tetraethoxysilane were mixed together
at room temperature and diethylether was added dropwise to the
vigorously stirred solution until an exothermic reaction was
observed (.about.200 mL). After stirring at room temperature for 16
h diethylether was evaporated. An excess of n-heptane (.about.400
mL) was added to precipitate the magnesium salts. Solution was
filtrated and evaporated to dryness. The residue was fractionally
distilled under reduced pressure to yield
4-bromooctafluorobutanetriethoxysilane. 57
[0101] 88.641 g (0.200 mol) 4-bromooctafluorobutanetriethoxysilane
in Et.sub.2O is slowly added to solution of CF.sub.2.dbd.CF--Li
(0.200 mol, 17.592 g, prepared in situ) in Et.sub.2O at -78.degree.
C. Reaction mixture is stirred overnight while it will slowly warm
to room temperature. LiBr is removed by filtration and the product,
perfluoro-1-hexenetriethoxysilane, purified by distillation. 58
[0102] 133.295 g (0.300 mol) perfluoro-1-hexenetriethoxysilane, 131
mL (1.800 mol, 214.1 g) thionylchloride and 4.51 g (0.039 mol)
pyridinium hydrochloride were refluxed and stirred for 16 h. Excess
of SOCl.sub.2 was evaporated and perfluoro-1-hexenetrichlorosilane
isolated by vacuum-distillation. 59
[0103] In the above "Method D" examples, R.sup.1, R.sup.2, R.sup.3
and R.sup.4 are preferably partially or fully fluorinated.
[0104] Hydrolysis and Condensation of the Compound(s):
[0105] Compounds IV, VII and IX have organic (or hybrid) R group(s)
and halogen(s) (preferably Br or Cl) bound to M (selected from
groups 3-6 or 13-16--preferably group 14)). These compounds can be
hydrolyzed alone or in any combination to result in a material
having a -M-O-M-O- backbone with R groups bound to the backbone,
and that preferably has a molecular weight of from 500 to 10,000
(more preferably from 1000 to 5000). In one embodiment, a compound
selected from Compound IV is hydrolyzed with another compound
selected from Compound IV. In another embodiment, a single compound
from Compound VII is hydrolyzed. Many other combinations are
possible, including: a) Compound IV+Compound VII; b) Compound
IV+Compound IV+Compound IV; c) Compound VII+Compound VII; d)
Compound IV+Compound VII+Compound IX; e) Compound IV+Compound
IV+Compound IX; f) Compound VII+Compound IX, etc. Any other
combinations, in any desired ratio, can be used for the hydrolysis
and eventual deposition.
[0106] Hydrolysis Example 1--Compound IV+Compound IV:
[0107] If one of the compounds to be hydrolyzed and condensed is
pentafluorophenyltrichlorosilane, this can be prepared as in the
methods set forth above, by:
C.sub.6F.sub.5Br+Mg+excess
Si(OEt).sub.4.fwdarw.C.sub.6F.sub.5Si(OEt).sub.-
3+(C.sub.6F.sub.5).sub.2Si(OEt).sub.2
C.sub.6F.sub.5Si(OEt).sub.3+SOCl.sub.2+py.HCl.fwdarw.C.sub.6F.sub.5SiCl.su-
b.3
[0108] 100 mL (0.8021 mol, 198.088 g) pentafluorobromobenzene,
24.90 g (1.024 mol) magnesium powder and 716 mL (3.2084 mol,
668.403 g) tetraethoxysilane are mixed together at room temperature
and diethylether is added dropwise to the vigorously stirred
solution until an exothermic reaction is observed (.about.200 mL).
After stirring at 35.degree. C. for 16 h the mixture is cooled to
room temperature and diethylether evaporated. An excess of
n-heptane (.about.500 mL) is added to precipitate the magnesium
salts. Solution is filtrated and evaporated to dryness. The residue
is fractionally distilled under reduced pressure to yield
pentafluorophenyltriethoxysilane. 60
[0109] 100 mL (0.375 mol, 124.0 g)
pentafluorophenyltriethoxysilane, 167 mL (2.29 mol, 272.0 g)
thionylchloride and 5.63 g (0.0487 mol) pyridinium hydrochloride
are refluxed and stirred for 24 h. Excess of SOCl.sub.2 is
evaporated and pentafluorophenyltrichlorosilane 61
[0110] isolated by vacuum-distillation.
[0111] If a second of the compounds to be hydrolyzed and condensed
is trifluorovinyltrichlorosilane, this can be prepared by:
[0112] 119 mL (0.155 mol) sec-butyllithium (1.3 M solution in
cyclohexane) is added under argon with stirring to 18.053 g (0.155
mol) chlorotrifluoroethylene 62
[0113] dissolved in Et.sub.2O at -80.degree. C. After the addition
is complete the reaction mixture is stirred for 15 min to yield
lithiumtrifluoroethylene. 63
[0114] 30.80 g (0.155 mol) ClSi(OEt).sub.3 in Et.sub.2O is slowly
added to solution of CF.sub.2.dbd.CF--Li (0.155 mol. 13.633g,
prepared in situ) in Et.sub.2O at -78.degree. C. Reaction mixture
is stirred overnight while it will slowly warm to room temperature
LiCl is removed by filtration and the product,
trifluorovinyltriethoxysilane, 64
[0115] is isolated by distillation.
[0116] 24.4 g (0.100 mol) trifluorovinyltriethoxysilane, 44 mL
(0.60 mol, 71.4 g) thionylchloride and 0.497 g (0.0045 mol)
pyridinium hydrochloride are refluxed and stirred for 24 h. Excess
of SOCl.sub.2 is evaporated and trifluorovinyltrichlorosilane
65
[0117] is purified by distillation.
[0118] Then, to a solution of trifluorovinyltrichlorosilane and
pentafluorophenyltrichlorosilane at a molar ratio 1:1 in dehydrated
tetrahydrofuran, is added dropwise a stoichiometric amount of water
(e.g. H.sub.2O or D2O) in THF at 0.degree. C. (nonstoichiometric
amounts, higher or lower, can also be used). After stirring for 1
hour, the solution is neutralized with 3 equivalents of sodium
hydrogencarbonate. After confirming the completion of generation of
carbonic acid gas from the reaction solution, the solution is
filtered and volatile compounds are removed by vacuum evaporation
to obtain colorless, transparent viscous liquid,
poly(pentafluorophenyltrifluorovinylsiloxane), in a three
dimensional network of alternating silicon and oxygen atoms. 66
[0119] The above is but one example of a method comprising:
reacting a compound of the general formula R1MX3.sub.3 with a
compound of the general formula 1MX3.sub.3 where R1 is selected
from alkyl alkenyl, aryl and alkynyl, R2 is selected from alkenyl,
aryl or alkynyl, M is an element selected from groups 3-6 or 13-16
though preferably from group 14 of the periodic table, and X3 is a
halogen; with H2O or D20; so as to form a compound having a
molecular weight of from 500 to 10,000 with a -M-O-M-O- backbone
with R1 and R2 substituents on each M.
[0120] In the hydrolysis example above, silicon atoms of the
network are modified by pentafluorophenyl and trifluorovinyl groups
in an approximate ratio 1:1. Of course other ratios are possible
depending upon the ratio of starting materials, and, of course,
other three dimensional networks can be achieved by having other
(or additional) starting materials selected from Compound IV, VII
and IX, along with other hydrolyzable materials. An alternate
example is a method comprising: reacting a compound of the general
formula R1R2MX3.sub.2 where R1 is selected from alkyl, alkenyl,
aryl and alkynyl, R2 is selected from alkenyl, aryl or alkynyl, M
is an element selected from group 14 of the periodic table, and X3
is a halogen; with D2O; so as to form a compound having a molecular
weight of from 500 to 10,000 with a -M-O-M-O- backbone with R1 and
R2 substituents on each M.
[0121] Also, though "M" in the above hydrolysis example is silicon,
it is possible to have materials with other M groups, or "dope" one
or more silanes to be hydrolyzed with a lesser amount of a compound
having a different M group such as germanium (or boron, aluminum,
selenium, etc.).
[0122] Deposition of the Hydrolyzed and Condensed Material:
[0123] The material formed as above preferably has a molecular
weight between 500 and 10,000, more preferably between 1000 and
5000. Other molecular weights are possible within the scope of the
invention, however a weight between 1000 and 5000 provides the best
properties for depositing the material on a substrate. The
substrate can be any suitable substrate, such as any article of
manufacture that could benefit from a hydrophobic and/or
transparent layer or coating. In the fields of electronics and
optical communications, the material could be deposited as a final
passivation layer, as a glob top coating, as an underfill in a flip
chip process, as a hermetic packaging layer, etc. Because the
material can be patterned as will be discussed further below, the
material could be deposited on a substrate (e.g. a glass, quartz,
silicon or other wafer) as a buffer/cladding, waveguide/core or
other layer within a waveguide or other optoelectronic/photonic
device.
[0124] In general, the siloxane oligomer having the molecular
weight as set forth above is mixed with a suitable solvent and
deposited. If the material is to be patterned by exposure to
electromagnetic radiation (e.g. UV light) then a photoinitiator can
be mixed into the material along with the solvent. There are many
suitable types of photoinitiators that could be used, such as
Irgacure 184, Irgacure 500, Irgacure 784, Irgacure 819, Irgacure
1300, Irgacure 1800, Darocure 1173 or Darocure 4265. The initiator
could be highly fluorinated, such as 1
,4-bis(pentafluorobenzoyl)benzene or Rhodosil 2074 photoinitiator.
Also, thermal initiators can be applied for thermal crosslinking of
organic carbon double bond moieties, such as with Benzoyl peroxide,
2,2'-Azobisisobutyronitrile, or tert-Butyl hydroperoxide.
[0125] Deposition Example 1: Add 10 w-% of methyl isobutyl ketone
and 2 w-% of Irgacure 819 photoinitiator to result in the formation
of a spin-coatable and photo-sensitive material. The material is
deposited by spin coating, spray coating, dip coating, etc. onto a
substrate or other article of manufacture. As mentioned herein,
many other organic groups can be used in place of the above groups,
though preferably one of the groups in one of the compounds is
capable of cross linking when exposed to electromagnetic energy (or
an electron beam)--e.g. an organic group with a ring structure
(e.g. an epoxy) or a double bond (e.g. vinyl, allyl, acrylate,
etc.).
[0126] Forming a Waveguide:
[0127] One use of the material set forth above is as a layer within
a waveguide. Though the waveguide could be a fiber optic waveguide
(with substantially circular cross section) the example below is in
relation to a planar waveguide. On a substrate (PCB, IC, silicon,
glass or quartz wafer, etc.) is deposited a lower cladding layer.
(A buffer layer can first be deposited if desired.) The cladding
layer is made by forming Compounds IV, VII and/or IX and
hydrolyzing such compound(s), followed by mixing the hydrolyzed
material with a solvent and thermal initiator and then depositing
onto the substrate. After deposition, the cladding layer can be
fully or partially baked (or exposed to UV light if a
photoinitiator is used in place of the thermal initiator) to
solidify the cladding. On the cladding layer is deposited a core
layer that is made and deposited as above, except with a different
ratio of compounds or different compounds that are
hydrolyzed/condensed to form the material ready for deposition. By
modifying the hydrolysable compounds and/or ratios of compounds in
the core layer vs. those in the cladding layer, a different index
of refraction is achieved. A developer (e.g. e.g. methanol, ethanol
propanol, acetone, methyl isobutyl ketone, tetrahydrofran, Dow
Chemical DS2100, Dow Chemical DS3000, etc.) is then applied to
remove unexposed material. In this way, a core for the waveguide is
formed. Then an upper cladding layer is made and deposited in the
same way as the lower cladding layer. Though in this example the
mask is a binary mask (the material is either fully exposed or not
exposed to electromagnetic radiation), it is also possible to
provide partial exposure (e.g. in a continuum from full exposure to
a low or non-exposure level as in a gray scale mask). Such a gray
scale exposure can form a vertical taper in the waveguide when the
developer is applied.
[0128] This invention has been described in connection with the
preferred embodiments. Many variations of the above embodiments are
contemplated as being within the scope of the invention.
* * * * *