U.S. patent application number 13/046957 was filed with the patent office on 2011-10-13 for ultraviolet transmissive polyhedral silsesquioxane polymers.
This patent application is currently assigned to Panasonic Electric Works Co., Ltd.. Invention is credited to Richard M. Laine, Ken-ichi Shinotani, Norihiro Takamura, Lisa Viculis.
Application Number | 20110251357 13/046957 |
Document ID | / |
Family ID | 36097005 |
Filed Date | 2011-10-13 |
United States Patent
Application |
20110251357 |
Kind Code |
A1 |
Laine; Richard M. ; et
al. |
October 13, 2011 |
ULTRAVIOLET TRANSMISSIVE POLYHEDRAL SILSESQUIOXANE POLYMERS
Abstract
Inorganic/organic hybrid polymers containing silsesquioxane
cages are robust and exhibit desirable physical properties such as
strength, hardness, and optical transparency at infrared and
ultraviolet wavelengths. The polymers are prepared by polymerizing
functionalized polyhedral silsesquioxane monomers such as
polyhedral silsesquioxanes bearing two complementarily reactive
functional groups bonded to cage silicon atoms by means of spacer
moieties. The spacer moieties allow for steric mobility and more
complete cure than polyhedral silsesquioxanes bearing reactive
functional groups bound directly to cage silicon atoms.
Inventors: |
Laine; Richard M.; (Ann
Arbor, MI) ; Viculis; Lisa; (Pacentia, CA) ;
Takamura; Norihiro; (Osaka, JP) ; Shinotani;
Ken-ichi; (Osaka, JP) |
Assignee: |
Panasonic Electric Works Co.,
Ltd.
The Regents of the University of Michigan
|
Family ID: |
36097005 |
Appl. No.: |
13/046957 |
Filed: |
March 14, 2011 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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11075042 |
Mar 8, 2005 |
7915369 |
|
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13046957 |
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60633821 |
Dec 7, 2004 |
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Current U.S.
Class: |
525/478 ;
525/474; 525/477; 525/479 |
Current CPC
Class: |
C08G 77/045 20130101;
H01L 27/14625 20130101; H01L 27/14623 20130101; C08G 77/14
20130101; H01L 31/02164 20130101; C08G 77/06 20130101; H01L
2924/0002 20130101; H01L 23/296 20130101; H01L 2924/0002 20130101;
H01L 31/0216 20130101; C09D 183/04 20130101; H01L 2924/00
20130101 |
Class at
Publication: |
525/478 ;
525/474; 525/477; 525/479 |
International
Class: |
C08G 77/38 20060101
C08G077/38 |
Claims
1. (canceled)
2. (canceled)
3. (canceled)
4. (canceled)
5. (canceled)
6. (canceled)
7. (canceled)
8. (canceled)
9. (canceled)
10. (canceled)
11. (canceled)
12. (canceled)
13. (canceled)
14. (canceled)
15. (canceled)
16. (canceled)
17. (canceled)
18. (canceled)
19. A process for preparing an organic-inorganic hybrid polymer UV
transparent material, comprising: a) functionalizing a polyhedral
silsesquioxane with a first functionalizing group to form a first
reactive functionalized polyhedral silsesquioxane of the
approximate formula [R.sup.1Me.sub.2SiOSiO.sub.1.5].sub.n where n
is 6, 8, 10, or 12, or a mixture thereof, b) functionalizing a
polyhedral silsesquioxane with a second functionalizing group to
form a second reactive functionalized polyhedral silsesquioxane of
the approximate formula [R.sup.2Me.sub.2SiOSiO.sub.1.5].sub.n where
n is 6, 8, 10, or 12, or a mixture thereof, where R.sup.1 and
R.sup.2 are reactive functional groups which react with each other
to covalently bond said first reactive functional polyhedral
silsesquioxane with said second reactive silsesquioxane, and
wherein some of R.sup.1 and R.sup.2 may be replaced by R groups
which are non-reactive with R.sup.1 and R.sup.2, and c) curing said
first and second reactive functionalized silsesquioxanes.
20. The process of claim 19, wherein said first reactive
functionalized polyhedral silsesquioxane bears on average at least
2 R.sup.1 groups and said second reactive functionalized polyhedral
silsesquioxane bears on average at least 2 R.sup.2 groups.
21. The process of claim 19, wherein said first reactive
functionalized polyhedral silsesquioxane bears on average at least
4 R.sup.1 groups and said second reactive functionalized polyhedral
silsesquioxane bears on average at least 4 R.sup.2 groups.
22. The process of claim 19, wherein said first reactive
functionalized polyhedral silsesquioxane bears on average at least
6 R.sup.1 groups and said second reactive functionalized polyhedral
silsesquioxane bears on average at least 6 R.sup.2 groups.
23. The process of claim 19, wherein reactive functional groups
R.sup.1 comprise two different reactive functional groups R.sup.1'
and R.sup.2'' and wherein reactive functional groups R.sup.2
comprise two different reactive functional groups R.sup.2' and
R.sup.2'', R.sup.1' and R.sup.2' reactive with each other and
R.sup.1'' and R.sup.2'' reactive with each other.
24. The process of claim 19, wherein at least one reactive
functional group is selected from the group consisting of Si-bonded
hydrogen, alkenyl, alkynyl, and cycloalkenyl.
25. The process of claim 19, wherein non-reactive R group are
selected from the groups comprising of alkyl, cycloalkyl,
trialkylsilyl, and trialkylsilyl-terminated (poly)siloxy.
26. The process of claim 23, wherein at least one reactive
functional group is selected from the group consisting of Si-bonded
hydrogen, alkenyl, alkynyl, and cycloalkenyl.
27. The process of claim 19, wherein at least one reactive
functional group is derived from the reaction of a polyhedral
silsesquioxane moiety with a functionalizing reagent selected from
the group consisting of 4-vinyl-1-cyclohexene,
dimethylvinylchlorosilane, dimethylvinylmethoxysilane,
dimethylvinylethoxysilane, dicyclopentadiene,
bis[trimethylsilyl]acetylene, trimethylsilylacetylene and
cyclohexadiene, dimethylallylchlorosilane,
dimethylhexenylchlorosilane, and 5-vinyl-2-norbornene.
28. The process of claim 19, wherein the mol ratio of R.sup.1 to
R.sup.2 is 0.20:1 to 1:1.
29. The process of claim 23, wherein the mol ratio of R.sup.1'' to
R.sup.2'' is 0.20:1 to 1:1.
30. The process of claim 19, wherein in either or both steps of
functionalizing, a catalyst which accelerates the reaction of a
polyhedral silsesquioxane with a functionalizing reagent is
added.
31. The process of claim 30, wherein said catalyst comprises a
transition metal.
32. The process of claim 31, wherein said catalyst comprises at
least one of Pt(dvs), Pt(dcp), or PtO.sub.2.
33. The process of claim 30, wherein following reaching a targeted
average content of reactive functional groups, functionalization is
stopped without adding a deactivation agent. for the catalyst in
either or both steps of functionalizing.
34. The process of claim 30, wherein following reaching a targeted
average content of reactive functional groups, functionalization is
stopped by adding a catalyst deactivator in an amount less than
that required to totally deactivate said catalyst in either or both
steps of functionalizing.
35. The process of claim 34, wherein the catalyst comprises a
platinum compound and the catalyst deactivator comprises
triphenylphosphine in a deactivating amount greater than 0 mol %
and less than 0.09 mol % based on mols of functionalized polyhedral
silsesquioxane.
36. The process of claim 19, further comprising precipitating said
functionalized silsesquioxane following step b) from solution in a
solvent or solvent mixture, washing the precipitate with the same
or a different solvent or solvent mixture to provide a solid,
purified polyhedral silsesquioxane macromonomer, and optionally
redissolving, precipitating, and washing, more than two times, to
provide a further purified solid macromonomer in either or both
steps of functionalizing.
37. The process of claim 36, wherein at least one solvent is
selected from the group consisting of alcohols, nitriles, ethers,
sulfoxides, and amides.
38. The process of claim 19 or 23, wherein a curing catalyst
effective to accelerate the reaction of reactive functionalities is
added prior to or during curing.
39. The process of claim 19 or 23, wherein said curing is conducted
in a liquid phase.
40. The process of claim 39, wherein said liquid phase is a melt
phase.
41. The process of claim 39, wherein said liquid phase is a
solution phase.
42. The process of claim 19, wherein R.sup.1 and R.sup.2 are the
same.
43. The process of claim 42, wherein said first and said second
functionalized silsesquioxanes are prepared by reacting a
silsesquioxane of the approximate formula
[H--Si(Me).sub.2-O--SiO.sub.1.5].sub.n where n is 6, 8, 10, or 12,
or mixtures thereof, with at least one silane selected from the
group consisting of dimethylvinylmethoxysilane and
dimethylvinylethoxysilane.
44. A process for preparing an organic-inorganic hybrid polymer
encapsulating material, comprising: a) providing a polyhedral
silsesquioxane; b) functionalizing said polyhedral silsesquioxane
with one or more types of reactive functional groups R.sup.1 to
provide functional polyhedral silsesquioxane of the formula
[RMe.sub.2SiOSiO.sub.1.5].sub.n where n is 6, 8, 10, 12, or
mixtures thereof, and where R is a reactive or non-reactive organic
group, with the proviso that at least one R is a reactive
functional group R.sup.1, to form a macromonomer; c) adding a
crosslinking agent reactive with reactive functional group R.sup.1,
to form a curable mixture; and d) curing said curable mixture to
form a hybrid organic-inorganic encapsulant having a light
transmission at 215 nm of at least 60%.
45. The process of claim 44, wherein said polyhedral silsesquioxane
bears HMe.sub.2SiO-functionality, and said functionalizing
comprises hydrosilylating at least one functionalizing reagent
selected from the group consisting of 4-vinyl-1-cyclohexene,
dimethylvinylchlorosilane, dimethylvinylmethoxysilane,
dimethylvinylethoxysilane, dicyclopentadiene,
bis[trimethylsilyl]acetylene, trimethylsilylacetylene and
dimethylallylsilane, 1,1,3,3-tetramethyl-1-allyldisiloxane
1,1,3,3-tetramethyl-1-vinyldisiloxane, dimethyloctenylsilane,
dimethylsilane, 1,1,3,3-tetramethyl-1,3-disiloxane,
1,1,3,3,5,5-hexamethyltrisiloxane,
1,1,3,3,5,5,7,7-octamethyltetrasiloxane, 1,2-dimethylsilylethane,
divinyldimethylsilane, 1,3-diallyltetramethyldisiloxane,
1,3-diallyltetraphenyldisiloxane,
1,1,3,3-tetramethyl-1,3-divinyldisiloxane,
1,2-bis(dimethylsilyl)ethane, dimethylchlorosilane,
dimethylmethoxysilane, dimethylethoxysilane,
1,1,3,3-tetramethylvinylchlorosilane,
1,1,3,3-tetramethylvinylmethoxysilane,
1,1,3,3-tetramethylvinylethoxysilane,
[(bicycloheptenyl)ethyl]dimethylchlorosilane,
[(bicycloheptenyl)ethyl]dimethylmethoxysilane,
[(bicycloheptenyl)ethyl]dimethylethoxysilane,
allyldimethylchlorosilane, allyldimethylmethoxysilane,
allyldimethylethoxysilane, 6-hexenyldimethylchlorosilane,
6-hexenyldimethylmethoxysilane, 6-hexenyldimethylethoxysilane,
10-undecenyldimethylchlorosilane,
10-undecenyldimethylmethoxysilane,
10-undecenyldimethylethoxysilane,
[2-(3-cyclohexenyl)ethyl]dimethylchlorosilane,
[2-(3-cyclohexenyl)ethyl]dimethylmethoxysilane,
[2-(3-cyclohexenyl)ethyl]dimethylethoxysilane,
1,5-dichlorohexamethyltrisiloxane,
1,5-dimethoxyhexamethyltrisiloxane,
1,5-diethoxyhexamethyltrisiloxane,
1,3-dichlorotetramethyldisiloxane,
1,3-dimethoxytetramethyldisiloxane,
1,3-diethoxytetramethyldisiloxane,
1,3-dichlorotetraphenyldisiloxane,
1,3-dimethoxytetraphenyldisiloxane,
1,3-diethoxytetraphenyldisiloxane, diallyldiphenylsilane,
1,4-Bis(hydroxydimethylsilyl)benzene, diisopropylchlorosilane,
diisopropylmethoxysilane, diisopropylethoxysilane,
diisopropyldichlorosilane, diisopropyldimethoxysilane,
diisopropyldiethoxysilane, dimesityldichlorosilane,
diphenylchlorosilane, diphenylvinylchlorosilane,
diphenylvinylmethoxysilane, diphenylvinylethoxysilane,
diphenyldichlorosilane, diphenyldimethoxysilane,
diphenyldiethoxysilane, diphenylsilanediol, diphenylsilane,
di(p-tolyl)dichlorosilane, di(p-tolyl)dimethoxysilane,
di(p-tolyl)diethoxysilane,
1,5-divinyl-1,3-diphenyl-1,3-dimethyldisiloxane,
1,5-divinyl-3-phenylpentamethyltrisiloxane,
divinyltetraphenyldisiloxane, methyldichlorosilane,
methyldimethoxysilane, methyldiethoxysilane,
phenylethyldichlorosilane, phenylethyldimethoxysilane,
phenylethyldiethoxysilane, phenylmethyldichlorosilane,
phenylmethyldimethoxysilane, phenylmethyldiethoxysilane,
phenylmethylsilane, 3-phenyl-1,1,3,5,5-pentamethyltrisiloxane,
1,1,3,3-tetraisopropyl-1,3-dichlorodisiloxane,
1,1,3,3-tetraisopropyl-1,3-dimethoxydisiloxane,
1,1,3,3-tetraisopropyl-1,3-diethoxydisiloxane,
1,1,3,3-tetraisopropyldisiloxane, vinylphenylmethylchlorosilane,
vinylphenylmethylmethoxysilane, vinylphenylmethylethoxysilane, and
vinylphenylmethylsilane.
46. The process of claim 44 or 45, wherein a catalyst which
accelerates said step of functionalizing is present during said
step of functionalizing.
47. The process of claim 46, wherein a catalyst deactivator is
added when a targeted amount of functionalization has been reached,
said catalyst deactivator added in a quantity less than that
necessary to completely deactivate the catalyst.
48. The process of claim 44, further comprising purifying said
macromonomer at least twice by precipitating said macromonomer from
a solvent or solvent mixture and washing the precipitate with the
same or a different solvent or solvent mixture to obtain a purified
macromonomer.
49. The process of claim 44, wherein a curing catalyst which
accelerates the reaction between reactive groups R.sup.1 and the
crosslinker are added prior to or during curing.
50. The process of claim 44, wherein prior to curing said,
macromonomer is dissolved in one or more solvents.
51. A process for synthesizing a UV transparent organic-inorganic
hybrid macromonomer, comprising: a) providing a polyhedral
silsesquioxane having reactive sites thereon; b) reacting at least
a portion of said reactive sites with one or more functionalizing
reagents to provide a macromonomer of the formula
[RMe.sub.2SiOSiO.sub.1.5].sub.n wherein n is 6, 8, 10, 12, or
mixtures thereof, and R is a non-reactive or reactive group, with
the proviso that at least one R is an R.sup.1 reactive group and at
least one R is an R.sup.2 reactive group, where R.sup.1 and R.sup.2
are interreactive, and wherein all groups R are selected such that
said macromonomer has a light transmission of at least 60% at 215
nm.
52. The process of claim 51, wherein R.sup.1 and R.sup.2 are
individually selected from the group consisting of silicon-bonded
H, alkenyl, alkynyl, and cycloalkenyl.
53. The process of claim 51, wherein non-reactive R are
individually selected from the group consisting of alkyl,
cycloalkyl, trimethylsilyl, and
trimethylsilyl-terminated(poly)dimethylsiloxy.
54. The process of claim 51, wherein said polyhedral silsesquioxane
has the formula [HMe.sub.2SiOSiO.sub.1.5].sub.n and functionalizing
takes place with one or more functionalizing reagents selected from
the group consisting of 4-vinyl-1-cyclohexene,
dimethylvinylchlorosilane, dimethylvinylmethoxysilane,
dimethylvinylethoxysilane, dicyclopentadiene,
bis[trimethylsilyl]acetylene, trimethylsilylacetylene,
cyclohexadiene, dimethylallylchlorosilane,
dimethylhexenylchlorosilane, and 5-vinyl-2-norbornene.
55. The process of claim 51, wherein the mol ratio of R.sup.1 to
R.sup.2 is from 0.20:1 to 1:1.
56. The process of claim 51, wherein a catalyst which accelerates
functionalizing is present during said step of functionalizing.
57. The process of claim 56, wherein said catalyst is a transition
metal compound.
58. The process of claim 56, wherein said catalyst is a
platinum-containing catalyst.
59. The process of claim 56, wherein at least one catalyst
comprises Pt(dvs) or Pt(dcp), or PtO.sub.2.
60. The process of claim 56, wherein when a targeted degree of
functionalization with reactive groups has been attained,
functionalization is stopped without deactivating said
catalyst.
61. The process of claim 56, wherein when a targeted degree of
functionalization with reactive groups has been attained,
functionalization is stopped by adding a catalyst deactivator in an
amount less than that required to totally deactivate said
catalyst.
62. The process of claim 61, wherein the catalyst is a
platinum-containing catalyst and the catalyst deactivator is
triphenylphosphine added in an amount greater than 0 mol % and less
than 0.09 mol % relative to mols of macromonomer.
63. The process of claim 51, further comprising purifying said
macromonomer at least twice by each time precipitating from a
solution in a solvent or solvent mixture, washing the precipitate
with the same or a different solvent or solvent mixture, to obtain
a purified macromonomer.
64. The process of claim 63, wherein at least one solvent is
selected from the group consisting of alcohols, nitriles, ethers,
sulfoxides, and amides.
65. An organic-inorganic hybrid polymer material comprising a
plurality of identical or different covalently bonded polyhedral
silsesquioxane macromonomer-derived moieties of the formula
[A.sub.0.5Me.sub.2SiOSiO.sub.1.5].sub.n[RMe.sub.2SiOSiO.sub.1.5].sub.n'
where n is a positive whole number, n' is 0 or a positive whole
number and the sum n+n' is 6, 8, 10, or 12, R is a non-reactive
organic group or an unreacted reactive functional group R.sup.1 or
R.sup.2, and A is a divalent bridging group linking two polyhedral
silsesquioxane moieties and derived from the reaction of two
interreactive groups R.sup.1 and R.sup.2 which are different from
each other, each macromonomer possessing, on average, both R.sup.1
and R.sup.2 groups, wherein one of said reactive functional groups
is Si-bonded H, the other is derived from reaction of
silicon-bonded H with one or more functionalizing reagents selected
from the group consisting of dicyclopentadiene,
bis[trimethylsilyl]acetylene, trimethylsilylacetylene,
cyclohexadiene, and 5-vinyl-2-norbornene.
66. An organic-inorganic hybrid polymer material comprising a
plurality of identical or different covalently bonded polyhedral
silsesquioxane macromonomer-derived moieties, of the formula
[A.sub.0.5Me.sub.2SiOSiO.sub.1.5].sub.n[RMe.sub.2SiOSiO.sub.1.5].sub.n'
where n is a positive whole number, n' is 0 or a positive whole
number and the sum n+n' is 6, 8, 10, or 12, R is a non-reactive
organic group or an unreacted reactive functional group R.sup.1 or
R.sup.2, A is a divalent bridging group linking two polyhedral
silsesquioxane moieties and derived from the reaction of two
different interreactive groups R.sup.1 and R.sup.2, each
macromonomer bearing at least two R.sup.1 or R.sup.2 groups, and
not bearing both R.sup.1 and R.sup.2 groups, wherein the reactive
and non-reactive groups R and the bridging group A are selected
such that the polymer material has a light transmission of at least
60% at 215 nm.
67. An organic-inorganic hybrid polymer material comprising a
plurality of identical or different covalently bonded polyhedral
silsesquioxane macromonomer-derived moieties, of the formula
[A.sub.0.5Me.sub.2SiOSiO.sub.1.5].sub.n[B.sub.0.5Me.sub.2SiOSiO.sub.1.5].-
sub.n''[RMe.sub.2SiOSiO.sub.1.5].sub.n' where n' is 0 or a positive
whole number, and n and n'' are positive whole numbers, and the sum
of n, n', and n'' is 6, 8, 10, or 12, R is a non-reactive organic
group or an unreacted reactive functional group R.sup.1, R.sup.2,
R.sup.3, or R.sup.4, A is a divalent bridging group linking two
polyhedral silsesquioxane moieties and derived from the reaction of
two interreactive groups R.sup.1 and R.sup.2, B is a divalent
bridging group linking two polyhedral silsesquioxane moieties and
derived from the reaction of two interreactive groups R.sup.3 and
R.sup.4, wherein a first polyhedral silsesquioxane macromonomer
bears R.sup.1 and R.sup.3 groups and a second polyhedral
silsesquioxane macromonomer bears R.sup.2 and R.sup.4 groups, and
wherein non-reactive groups R, unreacted groups R, bridging groups
A, and bridging groups B are such that said polymer material has a
light transmission of at least 60% at 215 nm.
68. An organic-inorganic hybrid polymer material comprising a
plurality of identical or different covalently linked polyhedral
silsesquioxane macromonomers, of the formula
[A.sub.0.5Me.sub.2SiOSiO.sub.1.5].sub.n[RMe.sub.2SiOSiO.sub.1.5].sub.n'
wherein n is a positive whole number and n' is 0 or a positive
whole number and the sum n+n' is 6, 8, 10, or 12, R is a
non-reactive organic group or an unreacted reactive group R.sup.1,
R.sup.1 being the same or different; A is a bridging group linking
two polyhedral silsesquioxane moieties, formed from the reaction of
two R.sup.1, wherein R, R.sup.1, and A are such that the polymer
material has a light transmission of at least 60% at 215 nm.
69. An organic-inorganic polymer material comprising a plurality of
identical or different covalently bonded silsesquioxane
macromonomer-derived moieties, of the formula
[A.sub.0.5Me.sub.2SiOSiO.sub.1.5].sub.n[RMe.sub.2SiOSiO.sub.1.5].sub.n'
where n is a positive whole number and n' is 0 or a positive whole
number and the sum of n and n' is 6, 8, 10, or 12, R is a
non-reactive organic group or an unreacted reactive functional
group R.sup.1, R.sup.1 are the same or different reactive
functional groups which are interreactive with a reactive
functional group R.sup.5 borne on a crosslinker molecule having at
least two R.sup.5 groups, R.sup.5 being the same or different, A is
a divalent linking group derived from the reaction of a reactive
R.sup.1 group of a polyhedral silsesquioxane macromonomer and a
reactive R.sup.5 group of a crosslinker molecule, wherein R,
R.sup.1, R.sup.5, and A are such that the polymer has a light
transmission of at least 60% at 215 nm.
70. The polymer material of claims 65 to 69, wherein reactive
functional groups are selected from the group consisting of
silicon-bonded H, alkenyl, alkynyl, and cycloalkenyl groups, and
mixtures thereof.
71. The polymer material of claims 65 to 69, wherein said reactive
functional groups are derived from reaction of silicon-bonded H
with one or more functionalizing reagents selected from the group
consisting of 4-vinyl-1-cyclohexene, dimethylvinylchlorosilane,
dimethylvinylmethoxysilane, dimethylvinylethoxysilane,
dicyclopentadiene, bis[trimethylsilyl]acetylene,
trimethylsilylacetylene, cyclohexadiene, dimethylallylchlorosilane,
dimethylhexenylchlorosilane, and 5-vinyl-2-norbornene.
72. The polymer material of claims 65 to 69, wherein at least two
interreactive functional groups have reacted, these two
interreactive functional groups present, prior to forming bridging
moieties A or B, in a mol ratio of 0.25:1 to 1:1.
73. The polymer material of claim 68, wherein said reactive
functional groups R.sup.1 are the same.
74. The polymer material of claim 68, wherein said reactive
functional groups are derived from the reaction of polyhedral
silsesquioxane moiety with a functionalizing reagent selected from
the group consisting of dimethylvinylmethoxysilane and
dimethylvinylethoxysilane.
75. The polymer material of claim 69, wherein at least one
crosslinker is selected from the group consisting of
alkenyl-functional di- or polysiloxanes Si--H-functional di- or
polysiloxanes, and aliphatic di- and polyenes.
76. The polymer material of claim 69, wherein at least one
crosslinker is selected from the group consisting of
vinyl-functional di- or polysiloxanes containing minimally three
vinyl groups on average and Si--H-functional di- or polysiloxanes
containing minimally three Si-bonded H atoms on average.
77. A polymer exhibiting transmission below 380 nm, comprising the
polymerized product of a) a monomer mixture comprising one or more
polyhedral silsesquioxanes (A), the cage of which corresponds
approximately to the formula Si.sub.nO.sub.1.5n where n is from 6
to 12, wherein silicon atoms of polyhedral silsesquioxane (A) are
functionalized with complementarily reactive functional groups such
that from about 20 to 80 mol percent of a first complementarily
reactive group are present, and from about 80 to about 20 mol
percent of a second complementarily reactive group are present, and
not more than 80 mol percent of non-reactive groups are present, at
least one of said first or said second complementarily reactive
groups bonded to said silicon atoms of said polyhedral
silsesquioxane (A) through a spacer moiety; or b) a monomer mixture
comprising b)i) one or more polyhedral silsesquioxane (B), the cage
of which corresponds approximately to the formula
Si.sub.nO.sub.1.5n where n is from 6 to 12, wherein from 20 to 100
mol percent of silicon atoms of said polyhedral silsesquioxane (B)
are bonded to a first reactive group by means of a spacer moiety,
and the remaining silicon atoms of said cages silsesquioxane (b)
are bonded to non-functional groups; b)ii) optionally one or more
further polyhedral silsesquioxanes (C) of the approximate formula
Si.sub.nO.sub.1.5n wherein cage silicon atoms of said polyhedral
silsesquioxane (C) are bonded to reactive groups of the same
reactive type as said first reactive group of polyhedral
silsesquioxane (B), or to a complementarily reactive group with
respect to the first reactive groups of said polyhedral
silsesquioxane (B), wherein when said first reactive groups of said
polyhedral silsesquioxane (B) are not polymerizable without a
complementarily reactive group being present; then polyhedral
silsesquioxane (C) having a complementarily reactive group is
present, the reactive groups of polyhedral silsesquioxane (C)
optionally bonded to silicon atoms of polyhedral silsesquioxane (C)
by spacer moieties; or c) mixtures of a) and b).
78. The polymer of claim 77, comprising the polymerized product of
polyhedral silsesquioxane (A).
79. The polymer of claim 78, wherein said mixture further comprises
at least one of a hydrido-functional polyhedral silsesquioxane (D)
having hydrogen bonded to silicon atoms of said polyhedral
silsesquioxane (D) or a polyhedral silsesquioxane (E) having
hydridosiloxy or dihydridosiloxy groups bonded to silicon atoms of
said polyhedral silsesquioxane (D).
80. The polymer of claim 77, wherein for said polyhedral
silsesquioxane (A), a)i) said first reactive group comprises
hydrogen bonded directly to silicon atoms of said polyhedral
silsesquioxane (A) and said complementarily reactive groups
comprise alkenyl or alkynyl groups bonded to said silicon atoms of
said polyhedral silsesquioxane (A) through a spacer moiety; a)ii)
said first reactive group comprises silicon-bonded hydrogen bonded
to silicon atoms of said polyhedral silsesquioxane (A) through a
spacer moiety and said complementarily reactive groups comprise
alkenyl or alkynyl groups bonded directly to silicon atoms of said
polyhedral silsesquioxane (A) or bonded to silicon atoms of said
polyhedral silsesquioxane through spacer moieties; or a)iii) said
first reactive group and said complementarily reactive group are
both bonded to silicon atoms of said polyhedral silsesquioxane (A)
by spacer moieties.
81. A process for the preparation of the polyhedral silsesquioxane
(A) of claim 77, comprising one of a) reacting a polyhedral
silsesquioxane containing Si-bonded hydrogen with an amount of an
unsaturated compound having two sites of ethylenic or ethylynic
unsaturation in the presence of a hydrosilylation catalyst, the mol
ratio of unsaturated compound and time of reaction such that a
polyhedral silsesquioxane (A) containing spacer-linked unsaturated
moieties and retaining unreacted Si-bonded hydrogen is obtained; or
b) reacting a polyhedral silsesquioxane containing alkenyl groups
bonded to silicon atoms of said polyhedral silsesquioxane (A) with
an SiH.sub.2-functional compound in the presence of a
hydrosilylation catalyst in a mol ratio of SiH.sub.2-functional
compound to alkenyl groups and for a time such that a polyhedral
silsesquioxane (A) is obtained which contains SiH-functional groups
bonded to said polyhedral silsesquioxane (A) by alkylene spacer
moieties, and which also contains unreacted alkenyl groups bonded
to silicon atoms of said polyhedral silsesquioxane (A); or c)
reacting, in any order or simultaneously, an anion of the
approximate formula Si.sub.nO.sub.1.5n.sup.n+ with a chlorosilane
bearing a first reactive functional group and with a chlorosilane
bearing a complementarily reactive functional group.
82. The process of claim 81, wherein an Si--H functional polyhedral
silsesquioxane is reacted with an alkenyl- or alkynyl-functional
compound containing at least two alkenyl, alkynyl, or alkenyl and
alkynyl groups, wherein the hydrosilylation catalyst is a solid,
heterogenous hydrosilylation catalyst, further comprising
separating said solid, heterogenous catalyst from a hydrosilyated
reaction product.
83. The process of claim 82, wherein said hydrosilylation catalyst
comprises PtO.sub.2.
84. A process for the preparation of a transparent
inorganic/organic hybrid polymer, comprising selecting as a monomer
mixture one of the monomer mixtures a), b), or c) of claim 77 and
polymerizing said monomer mixture to form a rigid, non-elastomeric
transparent polymer, wherein at least one of polyhedral
silsesquioxanes (A), (B), or (C) have been purified following their
synthesis to remove oligomers and polymers produced during their
synthesis.
85. A process for the preparation of a transparent
inorganic/organic hybrid polymer, comprising polymerizing one or
more polyhedral silsesquioxane monomers prepared by the process of
claim 82.
86. An organic-inorganic hybrid polymer material comprising a
plurality of identical or different covalently bonded polyhedral
silsesquioxane macromonomer-derived moieties of the formula
[A.sub.0.5Me.sub.2SiOSiO.sub.1.5].sub.n[RMe.sub.2SiOSiO.sub.1.5].sub.n'
where n is a positive whole number, n' is 0 or a positive whole
number and the sum n+n' is 6, 8, 10, or 12, R is a non-reactive
organic group or an unreacted reactive functional group R.sup.1 or
R.sup.2, and A is a divalent bridging group linking two polyhedral
silsesquioxane moieties and derived from the reaction of two
interreactive groups R.sup.1 and R.sup.2 which are different from
each other, each macromonomer possessing, on average, both R.sup.1
and R.sup.2 groups, wherein one of said reactive functional groups
is Si-bonded H, the other is hexenyl.
87. An organic-inorganic hybrid polymer material comprising a
plurality of identical or different covalently bonded polyhedral
silsesquioxane macromonomer-derived moieties of the formula
[A.sub.0.5Me.sub.2SiOSiO.sub.1.5].sub.n[RMe.sub.2SiOSiO.sub.1.5].sub.n'
where n is a positive whole number, n' is 0 or a positive whole
number and the sum n+n' is 6, 8, 10, or 12, R is a non-reactive
organic group or an unreacted reactive functional group R.sup.1 or
R.sup.2, and A is a divalent bridging group linking two polyhedral
silsesquioxane moieties and derived from the reaction of two
interreactive groups R.sup.1 and R.sup.2 which are different from
each other, each macromonomer possessing, on average, both R.sup.1
and R.sup.2 groups, wherein both of said reactive functional groups
are alkoxy groups, each of said alkoxy groups is derived from
reaction of silicon-bonded H with one or more functionalizing
reagents selected from the group consisting of
dimethylvinylmethoxysilane and dimethylvinylethoxysilane.
Description
CROSS-REFERENCE TO RELATED APPLICATION
[0001] This application is a Continuation application of patent
application Ser. No. 11/075,042, filed Mar. 8, 2005, which claims
the benefit of U.S. provisional application Ser. No. 60/633,821
filed Dec. 7, 2004, the entire contents of which are hereby
incorporated by reference.
BACKGROUND OF THE INVENTION
[0002] 1. Field of the Invention
[0003] The present invention pertains to novel silsesquioxane
polymer precursors, to methods of preparing them, and to
ultraviolet transmissive polymers prepared therefrom.
[0004] 2. Background Art
[0005] Transparent polymers are widely used. Polymers exhibit
distinct processing advantages over other transparent media such as
glasses, including fused or vitreous silica, and crystalline
substances such as calcium fluorite. Polymers may be thermoplastic,
i.e. melt processable, or may be thermoset, i.e. curing to a
non-thermoplastic state by means of crosslinking. Hybrid polymers,
for example those which are initially thermoplastic but which
further crosslink upon heating, exposure to light, or over time,
are also available.
[0006] From a process standpoint, organic based materials are
desirable since they are compatible with low-temperature
processing. Accordingly, the development of transparent materials
that possess both advantages of organic and inorganic materials is
becoming important. In other words, materials that have high
transparency and durability to short wavelength light (advantages
of inorganic materials) and ease of processing at low temperatures
(advantages of organic materials) are needed.
[0007] Many applications require polymers which are robust, which
are abrasion resistant, which have low coefficients of thermal
expansion and refractive index, and which are transmissive over the
required portion of the spectrum. Ordinary glass, for example, is
transmissive over the visible region and partially into the
infrared (IR) and ultraviolet (UV) regions of the spectrum.
However, for emissive or responsive devices which operate further
in the IR or UV, quartz or fused silica must be used. These
materials are difficult to fabricate.
[0008] Polymers previously used for such applications, such as
transparent epoxy resins, polyesters, polyacrylates, and
organopolysiloxanes may have unwanted absorbtion peaks in the
spectral areas of interest due to their chemical linkages and the
presence of absorbing groups. Many of these materials do not
transmit appreciably in the IR and/or UV areas of the spectrum.
Importantly, these polymers also suffer from lack of abrasion
resistance, and have undesirably high coefficients of thermal
expansion and refractive index. Thus, while being quite
processable, their optical and physical properties are less than
desired.
[0009] Silsesquioxanes as polyhedral structures are generally
known. Silsesquioxanes may be prepared by hydrolysis of
trifunctional silanes such as A.sub.3SiB where A is an alkoxy group
or halogen and B is a functional or non-functional group, for
example an alkyl group, vinyl group, or hydrogen. While polyhedral
molecules can result from conventional synthetic methods, the
primary products are generally highly crosslinked resins which are
soluble in apolar solvents such as toluene. The resins may be cured
by reaction with interreactive functional monomers to produce a
wide variety of products. For example, Si--H functional resins may
be cured with divinyl compounds. However, the products are
generally high molecular weight elastomers or solids, and often
contain numerous unreacted functional groups, even when reacted in
solution.
[0010] Resinous silsesquioxanes are known from U.S. Pat. No.
5,047,492, and have been cited as of academic interest as well.
Some of these products may contain polyhedral silsesquioxanes.
However, when polyhedral silsesquioxanes are functionalized
directly at a cage silicon atom, i.e. when functional groups R in
FIG. 1 are vinyl or H, the spatial arrangement of functional groups
and their close proximity to the inflexible cage renders their
reaction incomplete. This is particularly the case since prior
functionalized silsesquioxanes have been completely functionalized,
i.e. in silsesquioxane cages containing eight silicon atoms, each
silicon bears the same reactive functional group. Unreacted groups
can later react, altering the properties of the product, or may
enter into a variety of degradation reactions, for example
oxidizing to produce colored species or hydrolyzing to produce
hydrolysis products as inclusions, which decreases
transparency.
[0011] It would be desirable to provide easily processable polymers
which do not have the above identified deficiencies, all or in
part.
SUMMARY OF THE INVENTION
[0012] It has now been surprisingly discovered that polymers based
on polyhedral silsesquioxanes which are functionalized via spacer
moieties at the cage silicon atoms are highly transmissive in the
UV region of the spectrum, and exhibit desirable properties such as
abrasion resistance and easy processability as well. The preferably
incompletely functionalized silsesquioxanes are easily prepared,
and when suitably purified, offer a long shelf life.
BRIEF DESCRIPTION OF THE DRAWINGS
[0013] FIG. 1 illustrates a preferred embodiment of incompletely
functionalized polyhedral silsesquioxane polymer precursor.
[0014] FIG. 2 illustrates schematically a polymer prepared from
incompletely functionalized precursors.
[0015] FIG. 3 illustrates the UV transmission spectrum of several
materials, including a preferred polymer of the subject
invention.
[0016] FIG. 4 illustrates cure employing various amounts of
catalyst deactivators, as measured by DSC.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT(S)
[0017] The subject invention is directed to polyhedral
silsesquioxanes which bear functional groups attached to cage
silicon atoms via spacer moieties which provide the functional
groups with steric mobility such that a higher portion of
functional groups can react. Preferably, the polyhedral
silsesquioxanes are incompletely functionalized such that on
average, each molecule bears from about 20 to 80 mol percent, more
preferably from 30 to 70 mol percent, and most preferably from 40
to 60 mol percent of functionalized cage silicon atoms, as more
fully detailed hereafter. For example, in Si.sub.8 silsesquioxanes
cages, it is preferable that on average 2 to 6, more preferably 3
to 5, and most preferably about 4 Si atoms are functionalized with
a given type of reactive functionality linked to the cage Si atoms
via spacer moieties.
[0018] The subject invention is also directed to novel UV
transmissive polymers which may be prepared from the inventive,
partially functionalized polyhedral silsesquioxanes, or from
completely functionalized silsesquioxanes where at least a portion
of the reactive functionalities are bonded to cage silicon atoms
via spacer molecules.
[0019] The polyhedral silsesquioxanes have the general formula
Si.sub.nO.sub.1.5n where n is from 6-12, and most preferably 8. The
actual Si/O stoichiometry can vary somewhat from the 1:3 ratio of
the formula given, either due to the presence of unavoidable
impurities, or the purposeful presence of SiO.sub.2/2 or
SiO.sub.4/2 units. In addition, cages may be incomplete (i.e. have
an open side) due to incomplete reaction, cleavage, or the presence
of unavoidable or purposefully introduced monofunctional groups
SiO.sub.1/2. In the SiO.sub.2/2, SiO.sub.4/2, and SiO.sub.1/2
moieties, the remaining valencies of the tetravalent silicon are
satisfied by organic groups, hydrogen, halogen, etc.
[0020] When SiO.sub.4/2 groups are purposefully added, for example
during preparation of the silsesquioxanes in the form of
tetrafunctional silanes such as SiCl.sub.4 and (MeO).sub.4Si, the
amounts should be less than 20 mol percent, more preferably less
than 10 mol percent, and most preferably less than 5 mol percent
relative to the content of trifunctional SiO.sub.3/2 moieties.
Preferably, no SiO.sub.4/2 moieties other than those introduced by
unavoidable impurities or side reactions are present.
[0021] A very minor portion of SiO.sub.2/2 moieties may also be
present, for example less than 5 mol percent, preferably less than
3 mol percent, and most preferably 2 mol percent or less, again
based on the content of SiO.sub.3/2 moieties. Preferably,
substantially no SiO.sub.2/2 groups are present. Such groups
derived from unavoidable impurities are acceptable. The presence of
SiO.sub.2/2 groups may have two different effects. In a first case,
these groups may extend the length of one or more "edges" of a
polyhedral silsesquioxanes structure. In such cases, a cage "side"
may be a pentagon or hexagon (with respect to Si) with the
SiO.sub.2/2 group at a non-three dimensionally bound apex of the
polygon. Such products are perfectly acceptable so long as the
amount of SiO.sub.2/2 groups is not inordinately large. Such
products can tolerate more than 5 mol percent of SiO.sub.2/2 units.
However, if the SiO.sub.2/2 groups react with themselves to form
oligomeric chains (SiO.sub.2/2).sub.m where m>3, or where they
serve to link two or more polyhedral silsesquioxanes together, the
polymerized product may lose its rigidity and hardness, and may
also generate regions within the polymer which will scatter light,
particularly of short wavelengths, reducing the transmission of
light under these conditions. Thus, if the mode of synthesis of the
silsesquioxanes cage can lead to such products, then the presence
of SiO.sub.2/2 units is desirably quite low, and preferably
substantially no such units are present.
[0022] The amounts of SiO.sub.4/2 groups discussed above are
relative to tetrafunctional monomers, i.e. tetrahalosilanes or
tetraalkoxysilanes introduced during the synthesis of
silsesquioxanes cage structures, and not to fully reacted, i.e.
SiO.sub.2 units which may be present when the silsesquioxanes are
prepared from silica sources such as precipitated or fumed silicas,
fly ash, rice hull ash, etc. In these sources, it is likely that
the SiO.sub.4/2 units (as SiO.sub.2) are already present in fully
or partially polyhedral structures.
[0023] The polyhedral silsesquioxanes used to prepare the inventive
polymers must be functionalized with reactive, i.e. polymerizable
groups, at least a portion of which must be bound to the Si atoms
of the polyhedral silsesquioxanes by spacer moieties. The reactive
functional groups may vary widely, and in principle include all
reactive groups which may be used to chain extend or crosslink
silicon-containing monomers or oligomers to produce
organopolysiloxane or organocarbosiloxane products. For example,
but not by limitation, such groups may be susceptible to reaction
by addition, hydrosilylation, or condensation. Non-limiting
examples include Si--H groups, unsaturated hydrocarbon groups,
groups capable of Michael addition to double bonds, hydrolyzable
groups such as Si--OH, SiX where X is halogen, preferably chlorine,
or Si--OR where R is a hydrocarbon group, preferably an alkyl
group.
[0024] The polyhedral silsesquioxanes may contain a single type of
reactive group or more than one type of reactive group. When more
than one type of reactive group is present, it is desirable that
the types of reactive groups are complementarily reactive, i.e.
interreactive. In such cases, one of the reactive groups may
optionally be directly bonded to a silicon atom of the polyhedral
silsesquioxanes molecule, i.e. with no spacer moiety.
[0025] Examples of reactive groups include ethylenically and
ethylynically unsaturated hydrocarbons such as vinyl, allyl,
2-propenyl, isopropenyl, 3-butenyl, 2-butenyl, 5-hexenyl,
cycloalkenyl, for example cyclopentenyl, cyclohexenyl, norbornenyl,
acetylenyl, 3-hexynyl, acryloyloxy, methacryloyloxy, etc. When
vinyl groups are present, these must not be directly linked to a
cage Si atom unless the polymerizable mixture also contains
complementarily reactive groups on the same or different molecule
linked to cage Si atoms via a spacer moiety.
[0026] Silicon-bonded hydrogen (Si--H) are also suitable reactive
groups when a complementarily reactive group such as an unsaturated
hydrocarbon group, Si-alkoxy group, silanol (Si--OH) group, oximino
group, acetoxy group, or the like group is present. When
complementarily reactive groups are present and all or in part are
bonded to cage Si atoms by a spacer moiety, the hydrogens of the
Si--H groups may be bonded directly to a cage Si atom.
Alternatively, and preferably, the hydrogen atoms of the Si--H
group may be bonded to a cage Si atom by means of a spacer group.
Examples of SiH groups and spacer moieties which may be bound to
cage Si atoms include, but are not limited, to --O--SiR.sub.2H,
--O--R.sup.1--SiR.sub.2H, --R.sup.1--(SiR.sub.2O).sub.2H, and the
like. When siloxane-linked SiH groups are present, it is preferable
that the spacer contain no more than 4 diorganosiloxy groups,
preferably on average less than 3 diorganosiloxy groups, and most
preferably, 1 or 2 diorganosiloxy groups. In the formulae above, R
is an organo group, preferably an alkyl, cycloalkyl, aryl, alkaryl,
or aralkyl group, preferably a methyl group, and R.sup.1 is a
divalent hydrocarbon group other than a vinyl group or phenyl
group, preferably an alkyl or cycloalkyl group.
[0027] The reactive functional group may be a condensable group
such as silanol, alkoxy, acetoxy, silazane, oximino-functional
silyl group, or other groups which react and generate a molecular
byproduct species. Condensable functional groups are not preferred
unless polymerization can be conducted in vacuo, or when the
byproduct molecules diffuse from the polymer or are present in such
small domains that light scattering at the wavelengths of interest
is minimal. Silanol, alkoxy, and acetoxy groups are all capable of
condensing with Si--H groups. During the condensation, the
byproducts, respectively, are molecular hydrogen, alkanol, and
acetic acid.
[0028] The spacer moieties may be any which allow for some steric
repositioning of the reactive functionalities such that a
relatively high degree of reaction is possible. The most preferred
spacer moieties include diorganosiloxy (OSiR.sub.2) and hydrocarbon
diradical spacers, although other spacer moieties such as alkoxy,
polyoxyalkylene, ester and the like may also be employed. Phenyl
groups and other aromatic groups are also useful spacer moieties,
especially when other more "flexible" moieties such as aliphatic
hydrocarbon diradicals or dialkylsiloxy diradicals are also
present, either on the same or on a different molecule.
[0029] Two or more different functionalized polyhedral
silsesquioxanes may be polymerized, or a single type of polyhedral
silsesquioxanes may be polymerized. It is particularly preferred
that a single type of polyhedral silsesquioxane be polymerized, for
example "incompletely functionalized" silsesquioxanes, or
complementarily reactive silsesquioxanes.
[0030] By "incompletely functionalized" is meant that a polyhedral
silsesquioxane is modified to contain a specific functional group
or type of functional group different from the group or groups
present in the initial polyhedral silsesquioxane, or is synthesized
from monomers, which synthesis results in having one type of
functional group present on between 20 mol percent and 80 mol
percent, on average, of the cage Si atoms. For example, a
convenient starting material for synthesis of the monomers of the
present invention is octakis[hydrido]silsesquioxane,
H.sub.8Si.sub.8O.sub.12 ("OHS"). By itself, even in admixture with
other polyhedral silsesquioxanes containing spacer-linked
complementarily reactive molecules such as alkenylsiloxy groups,
OHS is not a particularly good monomer. The ability of all eight of
the Si--H bound hydrogens to react is limited as reaction proceeds
due to the decreased mobility of the silsesquioxane cage and the
steric unavailability of Si--H/alkenyl reaction sites which
results. However, OHS may be reacted with from 2 to 6 mols of a
dialkenyl-functional silane such as allyldimethylcyclohexenylsilane
in a hydrosilylation reaction to prepare incompletely
functionalized polyhedral silsesquioxanes containing both SiH
groups and 1-propyl-(cyclohexenyl)dimethylsilyl groups. Preferably,
about 4 mols of hydrosilylating reactant is used, thus preparing
polyhedral silsesquioxanes having on average about 4 of each type
of complementarily reactive groups.
[0031] Preferred reactive polyhedral silsesquioxanes have all
reactive functional groups bonded to cage Si atoms via spacer
moieties, and most preferred polyhedral silsesquioxanes of this
type also contain at least two types of reactive functionality, or
a mixture of one or more reactive functionalities and also
non-reactive groups such as methyl groups or trimethylsiloxy
groups. Such preferred reactive polyhedral silsesquioxanes can be
readily prepared from the octaanion Si.sub.8O.sup.8-.sub.12 by
reaction with a suitably functionalized chlorodiorganosilane such
as chlorohydridodimethylsilane (to provide spacer-linked Si--H
functionality) or chlorocycloalkenyldimethylsilane (to provide
spacer-linked cycloalkenyl functionality). Actually, both of these
reactive moieties may be reacted simultaneously or sequentially to
provide polyhedral silsesquioxanes containing both SiH and
cycloalkenyl spacer-linked functionalities. The ratio of
functionalities may be easily adjusted, and polymers may be
prepared, in this case by hydrosilylation in the presence of a
hydrosilylation catalyst, from a single monomer, for example
tetrakis[hydridodimethylsiloxy]-tetrakis[(cycloalkenyl)dimethylsi-
loxy]silsesquioxane, or from mixtures of differently functionalized
silsesquioxanes, for example
hexakis[hydridodimethylsiloxy]-bis[(cyclohexenyl)dimethylsiloxy]silsesqui-
oxane and
bis[hydridodimethylsiloxy]-hexakis[(cyclohexenyl)dimethylsiloxy]-
silsesquioxane. While in general, equimolar ratios of
complementarily reactive functional groups is desired, with any
particular monomer system, ratios other than equimolar, for example
1:2 to 2:1, preferably 2:3 to 3:2 may be preferable. The optimal
ratio is easily determined by a series of polymerizations at
different ratios, and selecting the ratio which provides the best
property or combinations of properties under consideration, e.g.
ease of processability, color, transparency, hardness, tensile
strength, etc.
[0032] The length of the spacer moiety may be considered as the
number of intervening atoms of all types in a continuous chain
between the cage Si atom and the reactive functional group. In a
dimethylsiloxy group containing a 3-cyclohexenyl reactive
functional group, for example, the number of intervening atoms
between the cage Si atom and the site of ethylenic unsaturation is
7 atoms (1 O, 1 Si, 5 C). The spacer moiety is preferably less than
10 atoms in length, more preferably less than 8 atoms in length.
The spacer is too long on average when the polymer products begin
to become rubbery or elastomeric rather than rigid solids.
[0033] It is particularly surprising that spacer linked alkenyl or
cycloalkenyl functional groups may be prepared by reacting an SiH
functional polyhedral silsesquioxane (hydrogen bonded to cage Si)
or a hydridosiloxy-substituted polyhedral silsesquioxane such as
octakis[hydridodimethylsiloxy]silsesquioxane with a bis[alkenyl]
molecule such as allylcyclohexenyldimethylsilane, vinylcyclohexene,
cyclohexadiene, cyclopentadiene, norbornadiene, and the like. In
such cases, the principle product is the corresponding
alkylene-linked ethylenically unsaturated group. Dimer molecules
containing alkylene-linked silsesquioxane cages are present in only
small quantities, if at all, and can be removed readily. In
particular with conjugated systems such as cyclohexadiene,
cyclopentadiene, 1,3-hexadiene and the like, monoaddition products
still containing a reactive unsaturation site are the predominant
product.
[0034] Examples of multi-unsaturated molecules which can react with
Si--H functional polyhedral silsesquioxanes include the dienes
mentioned previously, as well a furan, pyrrole, thiophene,
thiophene-1,1-dioxide, dicyclopentadiene, vinylallyl ether,
5-hexenyallylether, divinylether, divinylbenzene, and the like.
Also suitable are unsaturated alkanol esters such as
hexanedioldiacrylate, glycerol diacrylate, and the like.
Multifunctional unsaturated molecules such as glycerol triacrylate
and trimethylolpropane triacrylate may be used when the total of
unsaturated functionality is desired to be higher than can be
obtained from compounds containing two sites of ethylenic
unsaturation.
[0035] In preparing polymers from the functionalized polyhedral
silsesquioxanes of the present invention, it is desirable, in
general, to prepare transparent products. It is also desirable to
provide monomers which have a long storage life prior to use, for
example one month at 25.degree. C. and preferably two months or
longer. It has been surprisingly and unexpectedly discovered that
both these goals are facilitated by purifying the sample by
precipitation in an incompatible solvent, and preferably by washing
the filtrate in further incompatible solvent. By "incompatible
solvent" is meant a solvent in which the product is insoluble or
sparingly soluble, e.g. a solvent, which when added to a solution
of the product in a first solvent, will cause the product to
precipitate. An example of a suitable "compatible" solvent is
toluene, while examples of suitable "incompatible" solvents include
methanol, ethanol, and acetonitrile when alkenylsiloxy- and
hydridosiloxy-functional polyhedral silsesquioxanes are involved.
Since the hydrosilylation catalyst used to prepare such products
has already been deactivated following hydrosilylation, further
purification would not be expected to have any effect. However, the
storage life is unexpectedly highly prolonged.
[0036] This step of precipitating from solvent or solvent
mixture(s) can be repeated two or more times, if desired. The same
solvent or solvent mixture may be used, or alternatively may be
changed. Furthermore, the wash solvent or solvent mixture may be
the same as the solvent or solvent mixture from which the product
is precipitated, or may be a different solvent or solvent mixture.
Preferred solvents and solvent mixtures are or include a solvent
selected from alcohols, nitriles such as acetonitrile, ethers such
as diethylether, sulfoxides such as dimethylsulfoxide, and amides
such as dimethylformamide and dimethylacetamide.
[0037] Even more surprising is that the purified monomers more
readily form transparent polymer products. Since unpurified monomer
solutions are clear and generally colorless also, indicating no
oligomeric or polymeric species capable of scattering light, the
polymers produced therefrom are sometimes cloudy or translucent
rather than transparent. It was highly surprising that purification
of the starting monomer would lead to more highly transparent
products in general.
[0038] It has also been surprisingly discovered that synthesis of
polyhedral silsesquioxane monomers via hydrosilylation reactions
can be facilitated by solid (heterogenous) hydrosilylation
catalysts to prepare monomers which in turn provide polymers with
superior properties. The heterogenous catalyst may be any solid
hydrosilylation catalyst which is substantially insoluble under the
reaction conditions, and include metals such as Pt, Pd, Rh, either
in particulate form or on supports such as alumina or silica. Other
insoluble metal compounds and complexes are suitable as well, for
example PtO.sub.2, which is preferred. PtO.sub.2 may be used in
particulate form or may be formed on a support. Following the
hydrosilylation, the solid catalyst is removed by conventional
methods such as distillation of the product monomer or by
decantation, centrifugation, or filtration of the solid catalyst
from the product, preferably filtration. The relatively expensive
catalyst is thus more susceptible to recycle and/or reuse. Most
surprisingly, monomers prepared by such techniques exhibit superior
properties as compared to monomers prepared using soluble
hydrosilylation catalysts, including lower coefficients of thermal
expansion and in some cases improved transparency.
[0039] Numerous synthetic techniques can be employed to produce the
monomers of the present invention, and other methods will be
apparent to the skilled organic chemist. The two preferred methods
are reaction of halosilanes with polyhedral silsesquioxane anions,
and hydrosilylation of Si--H functional polyhedral silsesquioxanes
as previously disclosed. The products of these reactions can be
used as intermediates in the synthesis of the other monomers as
well. For example, octakis[hydridodimethylsiloxy]silsesquioxane can
be easily synthesized by reacting chlorodimethylsilane with the
octaanion of Si.sub.8O.sub.12. The resulting product can be further
functionalized by reacting the Si--H functionality obtained in the
latter reaction with an unsaturated molecule such as
vinylcyclohexene. If less than an equimolar amount of unsaturated
compound is employed, a polyhedral silsesquioxane with both
hydridodimethylsiloxy and dimethy[ethylcyclohexenyl]siloxy
functionality will be obtained, both linked to the silsesquioxane
cage by spacers.
[0040] The Si.sub.8O.sub.12 octaanion and similar anions of other
polyhedral silsesquioxanes can also be reacted with reactive
halogens such as chlorosilanes and chloroorgano compounds in the
presence of base to generate other functionalities. Non-functional
groups such as methyl groups and phenyl groups can also be
introduced by these methods. The monomers of the subject invention
may contain such non-functional groups as well as functional
groups. Preferably, less than 70% of cage Si atoms are bonded
directly or indirectly to non-functional groups, more preferably
about 50% or less, and most preferably, 30% or less, on a mol/mol
basis.
[0041] It has also been discovered that the monomers of the present
invention are capable of sublimation. This is especially surprising
in view of the nature of these monomers, which can be considered as
having a high inorganic content due to their silsesquioxane cage.
The ability to sublime these monomers leads not only to additional
possibilities for monomer purification, but also to novel methods
of deposition of the monomers onto substrates to prepare
polymerization coatings, encapsulants, etc. In the case of
syntheses where oligomeric products are present, for example,
sublimation at low pressure may be used to separate the monomeric
molecules from dimers and oligomers.
[0042] In order to form polymers, the monomers or mixtures of
monomers are deposited, i.e. by sublimation, from solution, or from
the melt, onto a suitable substrate, which may, e.g., be a device
to be coated or encapsulated, a surface to be coated, a mold, etc.,
and where solvent is present, the solvent is evaporated at any
convenient pressure. The monomer(s) are then heated for a time
sufficient to provide the desired degree of reaction, i.e.
polymerization. The polymerizable mixture may contain catalysts to
accelerate cure, if desired. If the curing (polymerization)
reaction is a hydrosilylation, a hydrosilylation catalyst such as
the known platinum hydrosilylation catalysts, may be added. If the
reaction is a condensation reaction, condensation catalysts such as
tin catalysts, amine catalysts, or the like may be added. Many of
the monomers bearing unsaturated reactive functional groups can be
polymerized thermally without added catalyst, or only with catalyst
residues which may remain in the monomer product from its
preparation.
[0043] Suitable polymerization temperatures are easily determined
by polymerizing at various temperatures for various lengths of
time. The temperature and time will, in general, be dependent upon
the type of reaction, i.e. addition, hydrosilylation, condensation,
etc., as well as the reactivity of the specific monomers. The
determination of thermal polymerization parameters may be
simplified greatly by DSC and noting the temperature at which
polymerization begins by the reactive exotherm. Once a suitable
reaction temperature is established by DSC, a series of samples may
be polymerized at various lengths of time to determine the minimum
polymerization time necessary. In some cases, particularly when
active hydrosilylation catalysts are employed without inhibitors or
sulfur compounds, respectively, polymerization may take place at
room temperature.
[0044] Polymerization in the case of addition polymerization may
also take place photochemically. Exposure to UV light alone may in
some cases be sufficient, or the addition of photocuring catalysts
well known in the art, such as the Darocur.RTM. and Irgacure.RTM.
catalysts from Ciba Specialty Chemicals and Sartomer.RTM.
photoinitators from Sartomer Company can be used. Addition
polymerization may also be effected using free radical initiator
precursors, or from thermal sources such as organic peroxides,
hydroperoxides, peroxyesters, peroxyketones, and the like.
[0045] Thus, in one aspect, the subject invention pertains to
monomers and monomer systems containing a plurality of monomers,
these monomers containing as at least a portion of their reactive
or complementarily reactive groups, reactive functional species
linked to Si atoms of polyhedral silsesquioxanes by means of spacer
molecules. Preferably, the monomers contain two complementarily
reactive groups on the same molecule, at least one of which, or
portions of both of which are bonded to cage Si atoms by spacer
moieties. Preferred monomers contain Si-bound hydrogen bonded
directly to cage Si atoms and ethylenic or ethylynic sites bonded
to cage Si atoms via spacer moieties. When only ethylenic or
ethylynic sites are present, either of a single type or of a
plurality of types, at least a portion of these must be bonded to
cage Si atoms through spacer moieties.
Oktakis[hydrido]silsesquioxane and octakis[vinyl]silsesquioxane,
containing H and vinyl bound directly to each cage Si atom, are not
inventive monomers of the present invention, although these may be
used as comonomers in small amounts in the inventive polymers, i.e.
preferably less than 30 mol percent, most preferably less than 10
mol percent based on all monomers.
[0046] In another aspect, the invention pertains to a process for
preparing an organic-inorganic hybrid polymer UV protective
material by providing one or more polyhedral silsesquioxane
[SiO.sub.1.5].sub.n where n=6, 8, 10, or 12; functionalizing the
polyhedral silsesquioxane with a plurality of --SiMe.sub.2R groups
wherein at least some of R on average are R.sup.1 groups and at
least some of R are on average R.sup.2 groups where R.sup.1 and
R.sup.2 are R groups reactive with each other, and remaining R
groups are non-reactive groups to form polyhedral silsesquioxane
macromonomer(s); and curing the polyhedral silsesquioxane
macromonomer(s) to produce an organic-inorganic hybrid polymer by
reacting reactive R groups on different silsesquioxane
macromonomer(s), wherein the organic-inorganic hybrid polymer has
at least a 60% transmittance at 215 nm. In this embodiment, the
reactive R groups R.sup.1 and R.sup.2 may be individually selected
from silicon-bonded H, halo, OR.sup.3 where R.sup.3 is H or alkyl,
preferably C.sub.1-4 alkyl, alkenyl, preferably C.sub.2-18 alkenyl,
and more preferably C.sub.2-8 alkenyl, alkynyl, preferably
C.sub.2-8 alkynyl, and cycloalkenyl, preferably C.sub.4-18
cycloalkenyl, more preferably C.sub.4-12 cycloalkenyl, and most
preferably C.sub.6-10 cycloalkenyl, and non-reactive R are
preferably selected from the group consisting of alkyl, cycloalkyl,
trialkylsilyl, and .omega.-trialkylsilyl-terminated (poly)siloxy,
the allyl groups in non-reactive R groups preferably being methyl
groups. The ratio of reactive groups R.sup.1 to reactive groups
R.sup.2 is desirably from 0.25:1 to 1:1.
[0047] In yet another aspect, the invention pertains to a process
for preparing an organic-inorganic hybrid polymer UV transparent
material by functionalizing a polyhedral silsesquioxane with a
first functionalizing group to form a first reactive functionalized
polyhedral silsesquioxane of the approximate formula
[R.sup.1Me.sub.2SiOSiO.sub.1.5].sub.n where n is 6, 8, 10, or 12,
or a mixture thereof, and functionalizing a polyhedral
silsesquioxane with a second functionalizing group to form a second
reactive functionalized polyhedral silsesquioxane of the
approximate formula [R.sup.2Me.sub.2SiOSiO.sub.1.5].sub.n where n
is 6, 8, 10, or 12, or a mixture thereof, where R.sup.1 and R.sup.2
are reactive functional groups which react with each other to
covalently bond the first reactive functional polyhedral
silsesquioxane with the second reactive silsesquioxane, and wherein
some of R.sup.1 and R.sup.2 may be replaced by R groups which are
non-reactive with R.sup.1 and R.sup.2, and curing the reactive
functionalized silsesquioxanes. Preferably, the first reactive
functionalized polyhedral silsesquioxane bears on average at least
2 R.sup.1 groups, more preferably at least 4 W groups, and most
preferably at least 6 R.sup.1 groups and the second reactive
functionalized polyhedral silsesquioxane bears on average at least
2 R.sup.2 groups, more preferably at least 4 R.sup.2 groups, and
most preferably at least 6 R.sup.2 groups.
[0048] Reactive functional groups R.sup.1 may comprise two
different reactive functional groups R.sup.1' and R.sup.2'', and
reactive functional groups R.sup.2 may comprise two different
reactive functional groups R.sup.2' and R.sup.2'', R.sup.1' and
R.sup.2' reactive with each other and R.sup.1'' and R.sup.2''
reactive with each other. The reactive groups may be the same as
already disclosed in other embodiments, and need not be repeated.
The mol ratio of R.sup.1' to R.sup.2 is preferably 0.20:1: to 1:1,
more preferably 0.25:1 to 1:1, and the mol ratio of R.sup.1'' to
R.sup.2'' is preferably 0.20:1 to 1:1, more preferably 0.25:1 to
1:1.
[0049] Preferred first and said second functionalized
silsesquioxanes are prepared by reacting a silsesquioxane of the
approximate formula
[H--Si(Me).sub.2-O--SiO.sub.1.5].sub.n
where n is 6, 8, 10, or 12, or mixtures thereof, with at least one
of dimethylvinylmethoxysilane and dimethylvinylethoxysilane.
[0050] In yet another aspect, the invention pertains to a process
for preparing an organic-inorganic hybrid polymer encapsulating
material by providing a polyhedral silsesquioxane; functionalizing
the polyhedral silsesquioxane with one or more types of reactive
functional groups R.sup.1 to provide functional polyhedral
silsesquioxane of the formula
[RMe.sub.2SiOSiO.sub.1.5].sub.n
where n is 6, 8, 10, 12, or mixtures thereof, where R is a reactive
or non-reactive organic group, with the proviso that at least one R
is a reactive functional group R.sup.1, to form a macromonomer;
adding a crosslinking agent reactive with reactive functional group
R.sup.1, to form a curable mixture; and curing the curable mixture
to form a hybrid organic-inorganic encapsulant having a light
transmission at 215 nm of at least 60%, where R and R.sup.1 may be
as previously disclosed.
[0051] In a still further embodiment, the invention pertains to a
process for synthesizing a UV transparent organic-inorganic hybrid
macromonomer by providing a polyhedral silsesquioxane having
reactive sites thereon; reacting at least a portion of the reactive
sites with one or more functionalizing reagents to provide a
macromonomer of the formula
[RMe.sub.2SiOSiO.sub.1.5].sub.n
wherein n is 6, 8, 10, 12, or mixtures thereof, and R is a
non-reactive or reactive group, with the proviso that at least one
R is an R.sup.1 reactive group and at least one R is an R.sup.2
reactive group, where R.sup.1 and R.sup.2 are interreactive, and
wherein all groups R are selected such that said macromonomer has a
light transmission of at least 60% at 215 nm, where R, R.sup.1, and
R.sup.2 may be as previously disclosed. In one especially preferred
variant of this embodiment, the polyhedral silsesquioxane has the
formula
[HMe.sub.2SiOSiO.sub.1.5].sub.n
and functionalizing takes place with one or more functionalizing
reagents from among 4-vinyl-1-cyclohexene,
dimethylvinylchlorosilane, dimethylvinylmethoxysilane,
dimethylvinylethoxysilane, dicyclopentadiene,
bis[trimethylsilyl]acetylene, and trimethylsilylacetylene.
[0052] Other preferred functionalizing agents may be selected
independently from among the following compounds, although this
list is illustrative and not limiting: dimethylallylsilane,
1,1,3,3-tetramethyl-1-allyldisiloxane
1,1,3,3-tetramethyl-1-vinyldisiloxane, dimethyloctenylsilane,
dimethylsilane, 1,1,3,3-tetramethyl-1,3-disiloxane,
1,1,3,3,5,5-hexamethyltrisiloxane,
1,1,3,3,5,5,7,7-octamethyltetrasiloxane, 1,2-dimethylsilylethane,
divinyldimethylsilane, 1,3-diallyltetramethyldisiloxane,
1,3-diallyltetraphenyldisiloxane,
1,1,3,3-tetramethyl-1,3-divinyldisiloxane,
1,2-bis(dimethylsilyl)ethane, dimethylchlorosilane,
dimethylmethoxysilane, dimethylethoxysilane,
1,1,3,3-tetramethylvinylchlorosilane,
1,1,3,3-tetramethylvinylmethoxysilane,
1,1,3,3-tetramethylvinylethoxysilane,
[(bicycloheptenyl)ethyl]dimethylchlorosilane,
[(bicycloheptenyl)ethyl]dimethylmethoxysilane,
[(bicycloheptenyl)ethyl]dimethylethoxysilane,
allyldimethylchlorosilane, allyldimethylmethoxysilane,
allyldimethylethoxysilane, hexenyldimethylchlorosilane,
6-hexenyldimethylmethoxysilane, 6-hexenyldimethylethoxysilane,
10-undecenyldimethylchlorosilane,
10-undecenyldimethylmethoxysilane, 10-undecenyldimethylethoxy,
[2-(3-cyclohexenyl)ethyl]dimethylchlorosilane,
[2-(3-cyclohexenyl)ethyl]dimethylmethoxysilane,
[2-(3-cyclohexenyl)ethyl]dimethylethoxysilane,
1,5-dichlorohexamethyltrisiloxane,
1,5-dimethoxyhexamethyltrisiloxane,
1,5-diethoxyhexamethyltrisiloxane,
1,3-dichlorotetramethyldisiloxane,
1,3-dimethoxytetramethyldisiloxane,
1,3-diethoxytetramethyldisiloxane,
1,3-dichlorotetraphenyldisiloxane,
1,3-dimethoxytetraphenyldisiloxane,
1,3-diethoxytetraphenyldisiloxane, diallyldiphenylsilane,
1,4-bis(hydroxydimethylsilyl)benzene, diisopropylchlorosilane,
diisopropylmethoxysilane, diisopropylethoxysilane,
diisopropyldichlorosilane, diisopropyldimethoxysilane,
diisopropyldiethoxysilane, dimesityldichlorosilane,
diphenylchlorosilane, diphenylvinylchlorosilane,
diphenylvinylmethoxysilane, diphenylvinylethoxysilane,
diphenyldichlorosilane, diphenyldimethoxysilane,
diphenyldiethoxysilane, diphenylsilanediol, diphenylsilane,
di(p-tolyl)dichlorosilane, di(p-tolyl)dimethoxysilane,
di(p-tolyl)diethoxysilane,
1,5-divinyl-1,3-diphenyl-1,3-dimethyldisiloxane,
1,5-divinyl-3-phenylpentamethyltrisiloxane,
divinyltetraphenyldisiloxane, methyldichlorosilane,
methyldimethoxysilane, methyldiethoxysilane,
phenylethyldichlorosilane, phenylethyldimethoxysilane,
phenylethyldiethoxysilane, phenylmethyldichlorosilane,
phenylmethyldimethoxysilane, phenylmethyldiethoxysilane,
phenylmethylsilane, 3-phenyl-1,1,3,5,5-pentamethyltrisiloxane,
1,1,3,3-tetraisopropyl-1,3-dichlorodisiloxane,
1,1,3,3-tetraisopropyl-1,3-dimethoxydisiloxane,
1,1,3,3-tetraisopropyl-1,3-diethoxydisiloxane,
1,1,3,3-tetraisopropyldisiloxane, vinylphenylmethylchlorosilane,
vinylphenylmethylmethoxysilane, vinylphenylmethylethoxysilane,
vinylphenylmethylsilane, cyclohexadiene, dimethylallychlorosilane,
dimethylhexenylchlorosilane, and 5-vinyl-2-norbornene.
[0053] The subject invention also pertains to polymers produced by
the disclosed processes. In one such embodiment, an
organic-inorganic hybrid polymer material comprises a plurality of
identical or different covalently bonded polyhedral silsesquioxane
macromonomer-derived moieties, of the formula
[A.sub.0.5Me.sub.2SiOSiO.sub.1.5].sub.n[RMe.sub.2SiOSiO.sub.1.5].sub.n'
where n is a positive whole number, n' is 0 or a positive whole
number, and the sum n+n' is 6, 8, 10, or 12, R is a non-reactive
organic group or an unreacted reactive functional group R.sup.1 or
R.sup.2, and A is a divalent bridging group linking two polyhedral
silsesquioxane moieties and derived from the reaction of two
interreactive groups R.sup.1 and R.sup.2 which are different from
each other, each macromonomer possessing, on average, both R.sup.1
and R.sup.2 groups, wherein the reactive and non-reactive groups R
and the bridging group A are selected such that the polymer
material has a light transmission of at least 60% at 215 nm.
[0054] In a further embodiment, the invention pertains to an
organic-inorganic hybrid polymer material comprising a plurality of
identical or different covalently bonded polyhedral silsesquioxane
macromonomer-derived moieties, of the formula
[A.sub.0.5Me.sub.2SiOSiO.sub.1.5].sub.n[RMe.sub.2SiOSiO.sub.1.5].sub.n'
where n and n' are as described previously, R is a non-reactive
organic group or an unreacted reactive functional group R.sup.1 or
R.sup.2, A is a divalent bridging group linking two polyhedral
silsesquioxane moieties and derived from the reaction of two
different interreactive groups R.sup.1 and R.sup.2, each
macromonomer bearing at least two R.sup.1 or R.sup.2 groups, and
not bearing both R.sup.1 and R.sup.2 groups, wherein the reactive
and non-reactive groups R and the bridging group A are selected
such that the polymer material has a light transmission of at least
60% at 215 nm.
[0055] In a still further embodiment, the invention pertains to an
organic-inorganic hybrid polymer material comprising a plurality of
identical or different covalently bonded polyhedral silsesquioxane
macromonomer-derived moieties, of the formula
[A.sub.0.5Me.sub.2SiOSiO.sub.1.5].sub.n[B.sub.0.5Me.sub.2SiOSiO.sub.1.5]-
.sub.n''[RMe.sub.2SiOSiO.sub.1.5].sub.n'
where n, and n' are as previously disclosed, and n'' is 0 or a
positive whole number, and the sum of n, n', and n'' is 6, 8, 10,
or 12, R is a non-reactive organic group or an unreacted reactive
functional group R.sup.1, R.sup.2, R.sup.3, or R.sup.4, A is a
divalent bridging group linking two polyhedral silsesquioxane
moieties and derived from the reaction of two interreactive groups
R.sub.1 and R.sup.2, B is a divalent bridging group linking two
polyhedral silsesquioxane moieties and derived from the reaction of
two interreactive groups R.sup.3 and R.sup.4, wherein a first
polyhedral silsesquioxane macromonomer bears R.sup.1 and R.sup.3
groups and a second polyhedral silsesquioxane macromonomer bears
R.sup.2 and R.sup.4 groups, and wherein non-reactive groups R,
unreacted groups R, bridging groups A, and bridging groups B are
such that said polymer material has a light transmission of at
least 60% at 215 nm.
[0056] The invention still further pertains to an organic-inorganic
hybrid polymer material comprising a plurality of identical or
different covalently linked polyhedral silsesquioxane
macromonomers, of the formula
[A.sub.0.5Me.sub.2SiOSiO.sub.1.5].sub.n[RMe.sub.2SiOSiO.sub.1.5].sub.n'
wherein n and n are as disclosed previously; R is a non-reactive
organic group or an unreacted reactive group R.sup.1, R.sup.1 being
the same or different; A is a bridging group linking two polyhedral
silsesquioxane moieties, formed from the reaction of two R.sup.1,
wherein R, R.sup.1, and A are such that the polymer material has a
light transmission of at least 60% at 215 nm, and to an
organic-inorganic polymer material comprising a plurality of
identical or different covalently bonded silsesquioxane
macromonomer-derived moieties, of the formula
[A.sub.0.5Me.sub.2SiOSiO.sub.1.5].sub.n[RMe.sub.2SiOSiO.sub.1.5].sub.n'
where n and n are as described previously; R is a non-reactive
organic group or an unreacted reactive functional group R.sup.1;
R.sup.1 are the same or different reactive functional groups which
are interreactive with a reactive functional group R.sup.5 borne on
a crosslinker molecule having at least two R.sup.5 groups, R.sup.5
being the same or different; A is a divalent linking group derived
from the reaction of a reactive R.sup.1 group of a polyhedral
silsesquioxane macromonomer and a reactive R.sup.5 group of a
crosslinker molecule; wherein R, R.sup.1, R.sup.5, and A are such
that the polymer has a light transmission of at least 60% at 215
nm.
[0057] In addition to the monomers of the present invention, the
subject invention polymers may also contain up to 50 mol percent,
preferably less than 20 mol percent, and most preferably less than
10 mol percent of highly crosslinked, substantially non-cage-like
functionalized silicone resins, so long as the optical and physical
properties desired of the polymers can be maintained. The polymers
may also contain minor amounts of linear or branched
organopolysiloxanes which are at least trifunctional, and
preferably have a higher functionality. Examples include Si--H
functional poly(dimethylsiloxy)(methylhydridosiloxy) oligomers and
polymers. The latter are present in an amount such that the final
product is not elastomeric or rubbery, generally in amounts of less
than 20 mol percent, more preferably less than 10 mol percent. The
compositions are most preferably free of such species.
[0058] Difunctional organopolysiloxanes or oligomers such as
.alpha.,.omega.-Si(CH.sub.3).sub.2H-terminated siloxanes or
.alpha.,.omega.-divinyl-terminated siloxanes may be added in most
minor amount, for example less than 10 mol percent, more preferably
less than 5 mol percent, so long as hard, rigid polymers and not
rubbery elastomers are obtained. Likewise, polyalkenyl compounds
such as 1,5-hexadiene and isoprene may be used as well, with the
same limitations. Other higher functional monomers such as
trimethylolpropane triacrylates, glycerol triacrylates,
trivinylbenzene, trivinylcyclohexane, etc., can also be used. In
general, the higher the functionality of these non-subject
invention monomers, the higher the amount which can be tolerated.
Preferably, added monomers will not provide chemical groupings
which absorb light at the wavelengths of interest. Liquid and low
melting monomers can be employed to reduce the viscosity of the
polymerizable mixture, as well as, in some cases, to increase the
compatibility of oligomerization and polymerization products with
the non-polymerized or lesser polymerized portions of the matrix.
If the solubility of the polymerized products at the polymerization
temperature is low in the polymerizable mixture, a phase out of
polymer and/or oligomer particles may occur which will produce haze
or opaque materials as opposed to transparent materials.
[0059] The novel monomers of the subject invention are preferably
polyhedral silsesquioxanes with complementarily reactive functional
groups on each molecule. Preferred complementarily functional
groups are Si-bound hydrogen and ethylenic or ethylynic
unsaturation, and Si-bound hydrogen and silicon-bound alkoxy
groups. The novel monomers correspond to the general formula
[Si.sub.nO.sub.1.5n][R.sup.3].sub.a[R.sup.4].sub.b[R.sup.5].sub.c
where b and c are 1 or more and at least one of b or c is >2,
a+b+c=n, and n is an integer from 6 to 12, and most preferably, 8.
The [Si.sub.nO.sub.1.5n] unit is a polyhedral silsesquioxane.
R.sup.3 is a non-functional group, preferably a C.sub.1-18
hydrocarbon group, more preferably a C.sub.1-4 alkyl group or
C.sub.6-10 aryl group, most preferably a methyl group; R.sup.4 is
H, -L-SiR.sup.3.sub.2H, or -L-SiR.sup.3H.sub.2 where R.sup.3 is a
non-functional hydrocarbon such as R.sup.3 and L is a divalent,
non-reactive spacer moiety which may be a C.sub.2-C.sub.18
hydrocarbon, preferably C.sub.2-4 alkylene, C.sub.5-8
cycloalkylene, or C.sub.7-10 alkarylene, a siloxy group
--SiR.sup.3.sub.2--O-- or a polysiloxy group SiR.sup.3.sub.2O
.sub.m where m is an integer from 2-10, preferably 2-4; and R.sup.5
is an alkenyl-functional group other than a vinyl group, preferably
a C.sub.3-18 ethylenically or ethylynically unsaturated hydrocarbon
which is not connected to an Si atom of the polyhedral
silsesquioxane at an unsaturated carbon atom, preferably an alkenyl
or cycloalkenyl group, or a group SiR.sup.3.sub.2O .sub.o
SiR.sup.3.sub.2 .sub.pY where o is an integer from 0 to 4 and p is
0 or 1, wherein o and p may not both be 0, and wherein Y is an
ethylenically or ethylynically unsaturated group. R.sup.5 may also,
in lieu of an unsaturated group, bear an alkoxysilyl group such as
dimethylmethoxysiloxy, etc., in other words, groups which bear a
reactive silicon-bonded alkoxy group, preferably a C.sub.1-4 alkoxy
group. A plurality of alkoxy groups may also be present.
[0060] Preferred monomers are those where a is 0, 1, or 2,
preferably 0, and both b and c on average are between 2 and 6, more
preferably between 3 and 5, and the sum of b+c is on average 8. In
the preferred monomers, R.sup.4 is -L-SiR.sup.3.sub.2H or
-L-SiR.sup.3H.sub.2, and the preferred groups R.sup.5 are
ethylenically unsaturated aliphatic and cycloaliphatic hydrocarbons
having 4 to 10 carbon atoms. Cycloaliphatic in this sense includes
cycloaliphatic compounds attached to silicon via an alkylene group,
such as those derived from vinylcyclohexene. Further preferred
R.sup.5 are those of the formula --SiR.sup.3.sub.2--Y where Y is
alkenyl, alkynyl, or cycloalkenyl.
[0061] A preferred synthesis of the subject invention
complementarily reactive monomers is the partial hydrosilylation of
a polyhedral silsesquioxane bearing predominantly, and preferably
wholly, cage silicon-bonded --SiR.sup.3.sub.2H moieties.
Hydrosilylation is preferably conducted in a suitable, preferably
apolar organic solvent such as a paraffinic hydrocarbon such as
hexane, or preferably, an aromatic solvent such as toluene or
xylene (single isomer or mixture). Other solvents such as
tetrahydrofuran, diethyl ether, dimethylformamide,
dimethylacetamide, dimethylsulfoxide, etc., may also be used so
long as the starting materials are soluble or become solubilized
during the reaction.
[0062] As the hydrosilylation catalyst, compounds of Pt, Pd, Rh,
and other noble metals generally used as hydrosilylation catalysts
may be used, including platinum olefin complexes commonly known as
Karstedt catalysts. The noble metals themselves may be used as
well. Preferred hydrosilylation catalysts are those employed in the
examples, particularly Pt (divinylsiloxane) complexes, Pt
(dicyclopentadiene) complexes, and most preferably, metallic Pt and
PtO.sub.2.
[0063] Supported catalysts and solid catalysts are particularly
suitable, as these can be removed from the reaction mixture for
recycle or reuse, and catalyst deactivation need not occur. It has
been surprisingly and unexpectedly discovered, for example, that
TCHS prepared using the solid catalyst PtO.sub.2 which is
subsequently removed by filtration, can be polymerized to a
transparent polymer which has a lower coefficient of thermal
expansion than TCHS of similar composition prepared employing a
soluble catalyst which is subsequently deactivated.
[0064] The amount of hydrosilylation catalyst is typical for the
use of these catalysts, and may vary from 0.01 ppm based on the
weight of the starting polyhedral silsesquioxane with Si--H
functionality, to 1000 ppm, preferably 0.01 ppm to 200 ppm, more
preferably 0.01 to 50 ppm, and most preferably 0.02 to 2 pm. Where
heterogenous (solid or supported) catalysts are employed, somewhat
larger amounts are employed in order to keep the reaction time
reasonable. For 100 g octakis[hydridodimethylsiloxy]silsesquioxane,
from 0.05 to 0.2 g of PtO.sub.2 has been found to work
satisfactorily.
[0065] When soluble catalysts are employed, and the product is not
to be immediately used, the catalyst must generally be deactivated
to provide an adequate shelf life of the monomer product, since the
product itself contains both Si--H and ethylenic unsaturation which
can react with each other via hydrosilylation. Conventional means
of catalyst deactivation may be used, including addition of
phosphines such as triphenyl phosphine, addition of sulfur
compounds such as mercaptans, and any method generally known in the
art. Catalyst deactivation may not be necessary if the
hydrosilylation catalyst used is only effective at relatively high
temperatures. Also, alkynol inhibitors and other inhibitors known
to those skilled in the art of hydrosilylation can be used as well.
Such inhibitors are generally effective at relatively low
temperatures, e.g. room temperature and slightly elevated
temperatures, but are unable to inhibit the catalyst at higher
temperatures. When the platinum catalyst is to be deactivated,
triphenylphosphine is preferably used in an amount of less than
0.09 weight percent relative to the weight of the complementarily
reactive monomer. Other deactivators may be used as well, however,
including arsines, stibines, alkali cyanides, etc.
[0066] TCHS will cure above 80.degree. C. to a rigid body with less
than 0.09 mol % deactivation agent relative to TCHS, although the
hybrid does not fully cure even at 200.degree. C. overnight with
more than 0.2 mol % deactivation agent relative to TCHS. Less than
0.09 mol % of deactivating agent is preferred when
triphenylphosphine is added. Amounts used for other deactivators
will vary with the type and the curing conditions desired. Based on
these results, the amount of deactivation agent serves an important
role to prepare fully cured materials. In addition, the deactivator
also will control the temperature required or the time required to
fully cure these materials. Likewise, it will affect the rate of
cure in the presence or absence of oxygen.
[0067] Alternative methods which can be used to synthesize the
novel monomers of the subject invention are disclosed in U.S. Pat.
No. 5,047,492; herein incorporated by reference. However, the
reaction sequences and raw materials must be changed in order to
prepare polyhedral silsesquioxanes, and the polyhedral
silsesquioxanes must be synthesized to contain complementarily
reactive spacer-linked functional groups.
[0068] The novel polymers of the present invention comprise
polymers prepared from polyhedral silsesquioxane monomers bearing
spacer-linked unsaturated groups, optionally in conjunction with
silicone resins or silicone oligomers or polymers containing in
excess of three corresponding or complementarily reactive groups
and preferably no more than 5 mol percent of difunctional silicone
oligomers or polymers, preferably exclusively or substantially all
polyhedral silsesquioxanes containing spacer-linked ethylenically
unsaturated groups; or may contain the novel monomers of the
subject invention bearing complementarily reactive groups, at least
one of which is spacer-linked to the silicon atoms of the
polyhedral silsesquioxane, optionally with further silicone
oligomers or polymers or other molecules bearing at least two and
preferably three or more of a corresponding functional group (i.e.
of the same type as one of the complementarily reactive groups) or
a complementarily reactive group (i.e. of a different type, but
reactive with at least one type of reactive group on the polyhedral
silsesquioxane). Preferably, the polymers are prepared exclusively
from polyhedral silsesquioxanes of the same type, although the
proportion of complementarily reactive groups may differ. In either
case, the proportion of low functionality polymers, i.e. those with
a low "density" of functional groups per molecule, will be such
that the product is a solid, and not a rubbery elastomer.
[0069] The invention will now be described in terms of the
following examples, which are not to be interpreted as limiting the
invention in any way. Unless indicated otherwise, all synthesis are
performed at room temperature or a temperature reached following
mixing of the reactants, at the pressure of the surrounding
atmosphere.
EXAMPLES
Example 1
[0070] FIG. 3 compares the transparency of bulk synthetic quartz
(blue), fused quartz (pink), KE-106, Shinetsu silicone resin (light
blue, no aromatic components), low melting glass (red), transparent
epoxy resin (purple) and TCHS (green-blue curve).
[0071] From FIG. 3, the transparency of TCHS (green-blue) is much
better than the epoxy resin (purple) used as an organic transparent
encapsulate material for current infrared LEDs and offers almost
the same transparency as silicone resin (light blue) and low
melting glass (red). However, unlike silicone resins, this material
offers more robust mechanical properties. The FIG. 3 data indicate
that the TCHS hybrid nanocomposite has excellent potential for
transparent coatings and films, especially those which must be
transparent to UV light. Furthermore, TCHS cures at relatively low
temperatures (150-200.degree. C.), and is air stable to 400.degree.
C., a property often not found with silicone resins.
[0072] Transparency herein means.gtoreq.60% transmittance
at.gtoreq.215 nm, preferably>70% and most preferably>85%.
Preferably, the minimum wavelength of transmitted light is<380
nm and most preferably<300 nm. Cured TCHS materials satisfy all
of these requirements.
Example 2
Tetrakis(cyclohexenylethyldimethylsiloxy)tetrakis(dimethylsiloxy)silsesqui-
oxane, TCHS
##STR00001##
[0074] To a 250 ml Schlenk flask equipped with reflux condenser, is
added octakis[hydridodimethylsiloxy]silsesquioxane "OHSS" (20 g, 20
mmol). The flask is heated under vacuum to eliminate residual air
and moisture and then flushed with nitrogen. Toluene (50 ml),
5-vinyl-1-cyclohexene (8.7 g, 80 mmol), and 2 mM Pt(dcp)-toluene
solution (1 ml, Pt: 2 ppm) as a catalyst are then added to the
flask.
[0075] The mixture is stirred at 90.degree. C. for 5 h. Then
triphenylphosphine [5 mg 0.45 mol %)] is added to deactivate the
catalyst and solvent removed to provide a white powder product. The
yield is 27.5 g (0.019 mol) 94%. The powder is TCHS.
Analytical Data
[0076] DTA-TGA: Tg.sub.5: 367.degree. C. (in air), Ceramic yield:
66.9% (1000.degree. C. in air, Calcd.: 65.2%)
[0077] DSC: Mp: 76.3.degree. C., Curing temperature: 180.degree.
C.
[0078] .sup.1H NMR: Si--CH.sub.3, 0.15 ppm, 26H, s [0079]
H--SiCH.sub.3, 0.26 ppm, 23H, s [0080] Si--CH.sub.2, 0.65 ppm,
9.4H, d [0081] Cyclohexenyl, 1.1-2.1 ppm, 42H, m [0082] Si--H, 4.74
ppm, 4H, s [0083] C.dbd.C--H, 5.66 ppm, 8.8H, s
[0084] .sup.13C NMR: Si--CH.sub.3, 0.18 ppm, s [0085]
H--Si--CH.sub.3, 0.73 ppm, s [0086] Si--CH.sub.2, 15.3 ppm, s
Cyclohexenyl, 29.1, 30.2, 32.2, 37.0 ppm, s [0087] C.dbd.C, 127.5
ppm, d
[0088] FTIR: .nu. C--H, 3020 cm.sup.-1 [0089] .nu. Si--H, 2200
cm.sup.-1 [0090] .nu. Si--O--Si, 1095 cm.sup.-1
[0091] Based on the .sup.1H NMR spectrum and TGA-DTA data, the
average structure of TCHS is determined to be as shown below.
##STR00002##
Example 3
Synthesis of
Tetrakis(cyclohexenylethyldimethylsiloxy)tetrakis(dimethylsiloxy)octa-sil-
sesquioxane (TCHS) with Purification
##STR00003##
[0093] The synthesis procedure of Example 2 is followed except for
the addition of deactivation agent. Purification is accomplished on
a smaller scale (OHSS: 10 g, 10 mmol) by adding a TCHS toluene
solution dropwise to a solvent such as methanol and acetonitrile
(400 ml) to obtain white TCHS powder. This powder is filtered off
then washed with solvent (50 ml) in a beaker and filtered to give a
white powder. This procedure is repeated three times. The white
powder is dried in vacuum. The yield of purified TCHS is 3.5 g (2.4
mmol, 24.5%)
[0094] Note the shelf life of the sample is prolonged. Although the
shelf life of the unpurified sample without deactivation agent is 2
weeks, the shelf life of purified sample (no matter which
purification solvent) is 2 months.
Analytical Data
[0095] .sup.1H NMR: Si--CH.sub.3, 0.15 ppm, 28H, s [0096]
H--SiCH.sub.3, 0.26 ppm, 20H, s [0097] Si--CH.sub.2, 0.65 ppm, 10H,
d [0098] Cyclohexenyl, 1.1-2.1 ppm, 49H, m [0099] Si--H, 4.74 ppm,
3.2H, s [0100] C.dbd.C--H, 5.66 ppm, 9.4H, s
[0101] From the .sup.1H NMR spectrum, the integration ratio between
cyclohexene and Si--H is 4.7 to 3.3, representing the average
structure below. Compared with the .sup.1H NMR spectrum of the
unpurified sample described above, the ratio is changed from
4.2/3.8 (cyclohexene/Si--H). This suggests that the component with
lower degrees of substitution is removed from the system.
##STR00004##
[0102] OHSS and its Q.sub.6, Q.sub.10, and Q.sub.12 analogs can
also be synthesized by reaction of the corresponding anions with
organochlorosilanes such as dimethylchlorosilane, and unsaturated
compounds such as octakis[vinyl]silsesquioxane can be prepared by
reaction with dimethylvinylchlorosilane. The latter can be
hydrosilylated to produce spacer-linked silsesquioxanes, for
example by reaction with dimethylsilane or cyclohexeryl
dimethylchlorosilane.
Example 4
Synthesis of
Bis(cyclohexenylethyldimethylsiloxy)-hexakis(dimethylsiloxy)-silsesquioxa-
ne, BCHS
[0103] To a 100 ml Schlenk flask equipped with reflux condenser, is
added octahydridosilsesquioxane OHS (2.5 g, 2.5 mmol). The flask is
heated under vacuum to eliminate residual air and moisture, and
then flushed with nitrogen. Toluene (20 ml), 5-vinyl-1-cyclohexene
(0.26 g, 5 mmol), and 2 mM Pt(dcp)-toluene solution (0.1 ml, Pt:
0.2 ppm) as a catalyst are then added to the flask.
[0104] The mixture is stirred at 90.degree. C. for 5 h. After
reaction, solvent is removed to obtain white powder. The powder is
rinsed with methanol to purify and dry to provide a white powder.
The yield is 2.33 g (1.9 mmol) 76%.
Analytical Data
[0105] DTA-TGA: Tg.sub.5: 452.degree. C., Ceramic yield: 75.8%
(1000.degree. C. in air, Calcd.: 79.9%). Note that the TGA in
nitrogen also shows that some weight is also lost as some of the
complex sublimes.
[0106] DSC: Mp: 82.degree. C., Curing temperature: 102, 167.degree.
C.
[0107] .sup.1H NMR: Si--CH.sub.3, 0.15 ppm, 11H, s
[0108] H--SiCH.sub.3. 0.26 ppm, 37H, d [0109] Si--CH.sub.2, 0.65
ppm, 4H, d [0110] Cyclohexenyl, 1.1-2.1 ppm, 18H, m [0111] Si--H,
4.74 ppm, 6H, s C.dbd.C--H, 5.66 ppm, 3H, s
[0112] .sup.13C NMR: 0.15 ppm, s [0113] H--Si--CH, 0.70 ppm. s
[0114] Si--CH.sub.2, 15.2 ppm. s [0115] Cyclohexenyl, 29.1, 30.2,
32.2, 37.0 ppm. s [0116] C.dbd.C, 127.5 ppm, d
[0117] FTIR: .nu. C--H, 3020 cm.sup.-1 [0118] .nu. Si--H, 2200
cm.sup.-1 [0119] .nu. Si--O--Si, 1095 cm.sup.-1
[0120] Based on the .sup.1H NMR spectrum and TGA-DTA data, the
structure of BCHS is determined to be as shown below.
##STR00005##
Example 5
Synthesis of
Octakis(cyclohexenylethyldimethylsiloxy)silsesquioxane, OCHS
[0121] To a 250 ml Schlenk flask equipped with reflux condenser, is
added octahydridosilsesquioxane OHS (21.4 g, 21 mmol). The flask is
heated under vacuum to eliminate residual air and moisture and then
flushed with nitrogen. 5-vinyl-1-cyclohexene (18.2 g, 170 mmol),
and 2 mM Pt(dcp)-toluene solution (0.1 ml, Pt: 0.02 ppm) as a
catalyst are then added to the flask.
[0122] The mixture is stirred at 90.degree. C. for 4 h. After
reaction, solvent is removed to obtain a white powder. The powder
is rinsed with methanol to purify and then dried, providing a white
powder. The yield is 38.5 g (20 mmol) 97%.
Analytical Data
[0123] DTA-TGA: Tg.sub.5: 348.degree. C., Ceramic yield: 46.8%
(1000.degree. C. in air, Calcd.: 51.0%). Note that in nitrogen the
ceramic yield is only 36 st. % indicating that some material
sublimes at one atmosphere. It also indicates that this material
can be used for sublimation (CVD) coatings if desired.
[0124] DSC: Mp: 73.degree. C.
[0125] .sup.1H NMR: Si--CH.sub.3, 0.14 ppm, 48H, s [0126]
Si--CH.sub.2, 0.65 ppm, 17H, d [0127] Cyclohexenyl, 1.1-2.1 ppm,
77H, m [0128] C.dbd.C--H, 5.67 ppm, 16H, s
[0129] .sup.13C NMR: Si--CH.sub.3, -0.20 ppm, s [0130]
Si--CH.sub.2, 14.8 ppm, s [0131] Cyclohexenyl, 25.6, 28.7, 29.8,
31.8, 36.6 ppm, s C.dbd.C, 127.0 ppm, d
[0132] FTIR: .nu. C--H, 3020 cm.sup.-1 [0133] .nu. Si--O--Si, 1095
cm.sup.-1
[0134] Based on the .sup.1H NMR spectrum and TGA-DTA data, the
structure of OCHS is determined to be as shown above.
##STR00006##
Example 6
Curing TCHS
[0135] TCHS (.apprxeq.1 g) is added to a 10 ml Teflon
[23.3.times.18.3 mm ID] or aluminum cup (25.2.times.39.6 mm ID).
The cup is placed in a vacuum oven thermostatted at 85.degree. C.
Following degassing for 2 h at 85.degree. C., the oven is flushed
with nitrogen. The temperature is then raised at 30.degree. C./h to
200.degree. C. and kept there for 10 to 24 h overnight providing a
transparent disk with thickness of 2.0-4.0 mm.
[0136] When a deactivation agent is added as in Example 2, the
mixture cures only with difficultly, giving a rubbery material.
When the amount of deactivating agent is .gtoreq.0.09 mol % (molar
ratio of agent to TCHS), an incompletely cured, rubbery and hazy
disk is obtained. When less than 0.09 mol % agent is used a
completely cured product is obtained as a rigid and transparent
disk.
Analytical Data
[0137] DTA-TGA: Tg.sub.5: 317.degree. C.; Ceramic yield: 67.1%
(1000.degree. C. in air, calcd.: 65.2%)
[0138] FTIR: n Si--H, 2140 cm.sup.-1 [0139] .delta. .dbd.C--H, 1408
cm.sup.-1 [0140] .nu. Si--O--Si, 1088 cm.sup.-1
[0141] TMA:
[0142] 142 ppm (50-100.degree. C.): For a resin prepared from
unpurified TCHS
[0143] 160 ppm (50-100.degree. C.): For a resin prepared from TCHS
purified with methanol
[0144] 133 ppm (50-100.degree. C.): For a resin prepared from TCHS
purified with acetonitrile
[0145] Note that the TMA data shows the effect of the purification
procedure. The CTE (coefficient of thermal expansion) of resin
prepared from TCHS purified with acetonitrile is smaller than
unpurified TCHS or TCHS purified with methanol. This suggests
purification with acetonitrile is better to improve properties of
resin if low CTEs are desirable.
[0146] From the FT-IR, the intensity of the remaining Si--H peak is
affected by the addition of deactivation agent. For instance,
although the intensity ratio of Si--H (2140 cm.sup.-1) to Si--O--Si
(1088 cm.sup.-1) of resin from TCHS with 5 mg (0.45 mol %)
deactivation agent is 0.11 (intensity ratio of Si--H/Si--O--Si of
original TCHS is 0.32); the ratio of resin from TCHS without
deactivator is 0.06 when these resins are prepared under identical
conditions (air heating to 200.degree. C./24 h). This data suggests
that the curing TCHS without deactivator goes further to completion
than with deactivator.
Example 7
Curing BCHS
[0147] BCHS (.apprxeq.1 g) is added to a 10 ml Teflon
[23.3.times.18.3 mm ID] or aluminum cup (25.2.times.39.6 mm ID).
The cup is placed in a vacuum oven thermostatted at 85.degree. C.
Following degassing for 2 h at 85.degree. C., the oven is flushed
with nitrogen. The temperature is then raised at 30.degree. C./h to
200.degree. C. and kept there for 10 to 24 h overnight providing a
white powder. BCHS is not cured completely because of a lack of
functional groups to crosslink. Therefore, it does not provide a
homogeneous resin.
Example 8
Attempt to Cure OCHS
[0148] OCHS (.apprxeq.1 g) is added to a 10 ml Teflon
[23.3.times.18.3 mm ID] or aluminum cup (25.2.times.39.6 mm ID).
The cup is placed in a vacuum oven thermostatted at 85.degree. C.
Following degassing for 2 h at 85.degree. C., the oven is flushed
with nitrogen. The temperature is then raised at 30.degree. C./h to
200.degree. C. and there for 10 to 24 h overnight providing a white
powder. OCHS melts but does not cure by thermal polymerization of
vinyl groups.
Example 9
Curing OCHS/OHSS
[0149] OCHS (1 g, 0.5 mmol)/OHSS (0.5 g, 0.5 mmol) are added to a
10 ml Teflon [23.3.times.18.3 mm ID] or aluminum cup
(25.2.times.39.6 mm ID). The cup is placed in a vacuum oven
thermostatted at 85.degree. C. Following degassing for 2 h at
85.degree. C., the oven is flushed with nitrogen. The temperature
is then raised at 30.degree. C./h to 200.degree. C. and held there
for 10 to 24 h providing a white opaque disk.
Example 10
Curing OCHS/BCHS
[0150] OCHS (0.08 g, 0.04 mmol)/BCHS (0.1 g, 0.08 mmol) are added
to a 10 ml Teflon [23.3.times.18.3 mm ID] or aluminum cup
(25.2.times.39.6 mm ID). The cup is placed in a vacuum oven
thermostatted at 85.degree. C. Following degassing for 2 h at
85.degree. C., the oven is flushed with nitrogen. The temperature
is then raised at 30.degree. C./h to 200.degree. C. and left there
for 10 to 24 h providing a white opaque disk.
[0151] From examples 6-10, a 0.25 to 1 molar ratio of functional
moiety on functionalized polyhedral silsesquioxane to Si--H
functionality is preferred, most preferably 0.5 such as in TCHS
described above. Because the degree of substitution affects the
physical properties of the compound including solubility, melting
point, etc., mixtures of compounds with different numbers of
substituents like OCHS/BCHS are not always miscible, so that
homogeneous and transparent resins do not always form. In addition,
a large excess of one reactive group will lead to incomplete curing
and inhomogeneities that also will reduce transparencies.
Example 11
Octakis(dicyclopentadienyldimethylsiloxy)octasilsesquioxane
(ODCPDS)
##STR00007##
[0153] To a 100 ml Schlenk flask equipped with reflux condenser, is
added OHSS (5.1 g, 5 mmol). The apparatus is then gently heated in
vacuum to remove residual air and moisture and then flushed with
nitrogen. Then dicyclopentadiene [10.6 g or 13.2 g (80 mmol or 100
mmol, respectively)] and 2 mM Pt(dvs)-toluene solution (0.1 ml, Pt:
0.2 ppm) as a catalyst, are added to the flask.
[0154] The mixture is stirred at 90.degree. C. for 15 h under
nitrogen. Although initially opaque, the solution becomes
homogeneous after 10 min. The yield is quantitative.
Analytical Data
[0155] .sup.1H NMR: Si--CH.sub.3, 0.098 ppm, 32H, d [0156]
HSi--CH.sub.3, 0.27 ppm, 16H, s [0157] Si--H, 4.76 ppm, 2.6H, s
[0158] C.dbd.C--H, 5.5-5.6 ppm, 51H, hept
[0159] .sup.13C NMR: Si--CH.sub.3, -1.5, -1.3, -1.2 ppm, t [0160]
Si--H, 0.29 ppm, s [0161] C.dbd.C, 132.2 ppm, m
[0162] Based on the .sup.1H NMR spectrum, the structure of ODCPDS
is that shown below. Dicyclopentadiene does not react easily with
all Si--H group on OHS partly because of the potential steric
hindrance and also because it is a good ligand for the catalytic
species, thereby slowing the reaction down. Other catalysts such as
Pt or PtO.sub.2 may provide superior results.
##STR00008##
Example 12
Tetrakis(dicyclopentadienyldimethylsiloxy)tetrakis(hydridodimethylsiloxy)o-
ctasilsesquioxane, TDCPDS
##STR00009##
[0164] To a 100 ml Schlenk flask equipped with reflux condenser, is
added OHSS (19.0 g, 19 mmol). The apparatus is then gently heated
in vacuum to remove residual air and moisture and then flushed with
nitrogen. Toluene (100 ml), dicyclopentadiene (9.9 g, 75 mmol) and
2 mM Pt(dvs)-toluene solution (0:2 ml, Pt: 0:4 ppm) as a catalyst,
are added. The mixture is stirred at 90.degree. C. for 6 h. After
reaction, solvent is evaporated to yield a colorless viscous
liquid, TDCPS. The yield is 28.2 g (18 mmol), 98%.
Analytical Data:
[0165] DTA-TGA: Td.sub.5, 458.degree. C., Ceramic yield: 63.5%
(1000.degree. C. in air, Calcd.: 62.1%)
[0166] DSC: Curing temp.: 180.degree. C.
[0167] .sup.1H NMR: Si--CH.sub.3, 0.09 ppm, 22H, d [0168]
H--Si--CH.sub.3, 0.26 ppm, 23H, s [0169] Si--CH.sub.2, 0.67 ppm,
4H, d [0170] Dicyclopentadienyl, 1.2 ppm-3.2 ppm, 40H, m [0171]
Si--H, 4.75 ppm, 4H, s [0172] C.dbd.C--H, 5.4-5.8 ppm, 8H, q
[0173] .sup.13C NMR: Si--CH.sub.3, 0.28 ppm, d [0174]
Dicyclopentadienyl, 14.8, 25.6, 28.7, 29.8, 31.8, 36.6 ppm, m
[0175] C.dbd.C, 127.0 ppm, d
[0176] Based on .sup.1H NMR spectrum and TGA-DTA data, the
structure of DCPDS is that shown below.
##STR00010##
Example 13
Preparation of Resin from TDCPDS
[0177] TDCPDS (1 g) is added to a 10 ml Teflon (23.3.times.18.3 mm
ID) or aluminum cup (25.2.times.39.6 mm (ID)). The cup is placed in
a vacuum oven thermostatted at 85.degree. C. Following degassing
for a period of 2 h at 85.degree. C., the oven is flushed with
nitrogen. The temperature is then raised at 30.degree. C./h to
200.degree. C. and held there for 10 to 24 h providing a white
opaque (translucent) disk with thickness of 2-4 mm.
Analytical Data
[0178] DTA-TGA: Td.sub.5: 414.degree. C., Ceramic yield: 63.2%
(1000.degree. C. in air, Calcd.: 62.1%)
[0179] DMA: Tg: 170.degree. C.
[0180] TMA: 106 ppm (from 50.degree. to 100.degree. C.)
Example 14
Synthesis of
Octakis(bisdimethylsilylacetyldimethylsiloxy)-silsesquioxane,
OBTMSAS
##STR00011##
[0182] To a 100 ml Schlenk flask equipped with reflux condenser, is
added OHSS (1 g, 1 mmol). The apparatus is then gently heated in
vacuum to remove residual air and moisture and flushed with
nitrogen. THF or toluene (25 ml), bistrimethylsilylacetylene (1.7
g, 10 mmol) and 2 mM Pt(dvs)-toluene solution (0.1 ml, Pt: 0.2 ppm)
as a catalyst, are added.
[0183] The mixture is stirred at 60 or 90.degree. C. for 6 h to 2
D. After reaction, triphenylphosphine and charcoal are then added
to the solution to deactivate the catalyst and then filtered off
through celite. Solvent was evaporated from filtrate to yield white
opaque viscous liquid. The yield is 1.4 g (0.6 mmol), 58%.
Analytical Data
[0184] DTA-TGA: Td.sub.5: 113.degree. C., Ceramic yield: 76.0%
(1000.degree. C. in air, Calcd.: 85.6%). Some of the material
sublimes during the TGA run as determined by a TGA run in nitrogen.
This material offers potential for vapor deposition processes.
[0185] .sup.1H NMR: Si--CH.sub.3, 0.098 ppm, 61H, s [0186]
HSi--CH.sub.3, 0.27 ppm, 38H, s [0187] Si--H, 4.76 ppm, 5.8H, s
[0188] .sup.13C NMR: Si--CH.sub.3, 0.13 ppm, s [0189]
HSi--CH.sub.3, 0.24 ppm, s [0190] C.dbd.C, 114.0 ppm, s
[0191] FTIR: .nu. Si--H, 2148 cm.sup.-1 .nu. C--H, 1411 cm.sup.-1
.nu. Si--O--Si, 1141 cm.sup.-1
[0192] Based on the .sup.1H NMR spectrum and TGA-DTA data, the
structure of OBTMSAS is that shown below.
Bistrimethylsilylacetylene does not react stoichiometrically with
all of reaction sites (Si--H group) on OHS even when excess
bistrimethylsilylacetylene is added. This result is a combination
of steric hindrance and the fact that the catalytically active
species is bound with the vinyl groups which reduce its ability to
catalyze the reaction.
##STR00012##
Example 15
Synthesis of
Tetrakis(bisdimethylsilylacetynyldimethylsiloxy)-tetrakis(hydridodimethyl
siloxy)octasilsesquioxane, TBTMSAS
##STR00013##
[0194] To a 100 ml Schlenk flask equipped with reflux condenser, is
added OHSS (1 g, 1 mmol). The apparatus is then gently heated in
vacuum to remove residual air and moisture and flushed with
nitrogen. Then CH.sub.2Cl.sub.2, THF or toluene (25 ml),
bistrimethylsilylacetylene (0.68 g, 4 mmol) and 2 mM
Pt(dvs)-toluene solution (0.1 ml, Pt: 0.2 ppm) as a catalyst, are
then added.
[0195] The mixture is stirred at 60 or 90.degree. C. for 4 h to 5
d. After reaction, triphenylphosphine and charcoal are added and
filtered off through celite. Solvent is then evaporated from
filtrate at RT in vacuum to yield a white powder. The yields are
40, 68 and 68%, respectively.
Analytical Data
[0196] DTA-TGA: Td.sub.5: 233.degree. C., Ceramic yield: 74.1%
(1000.degree. C. in air, Calcd.: 81.1%). Some of the material
sublimes during the TGA run as determined by a TGA run in nitrogen.
This material offers potential for vapor deposition processes.
[0197] DSC: Curing temperature, 138.degree. C.
[0198] .sup.1H NMR: Si--CH.sub.3, 0.162 ppm, 58H, d [0199]
HSi--CH3, 0.225 ppm, 49H, m [0200] Si--H, 4.72 ppm, 5.2H, s [0201]
.dbd.--Si, 7.41 ppm, 3.1H, s
[0202] .sup.13C NMR: Si--CH.sub.3, 1.03 ppm, m [0203] .dbd.--Si,
164.7 ppm, s
[0204] FTIR: .nu. Si--H, 2140 cm.sup.-1 [0205] .nu. C--H, 1420
cm.sup.-1 [0206] .nu. Si--O--Si, 1100 cm.sup.-1
[0207] Based on the .sup.1H NMR spectrum and TGA-DTA data, the
structure of TBTMSAS is determined to be that shown below. From
this data less than four equivalents of bistrimethylsilylacetylene
react with the Si--H groups on OHS even though four equivalents are
added in the time allotted for the reaction to proceed.
##STR00014##
Example 16
Curing TBTMSAS
[0208] TBTMSAS (1 g) is added to a 10 ml Teflon (23.3.times.18.3 mm
ID) or aluminum cup, (25.2.times.39.6 mm ID). The cup is placed in
a vacuum oven thermostatted at 85.degree. C. Following degassing
for a period of 2 hr at 85.degree. C., the oven is flushed with
nitrogen. The temperature is then raised at 30.degree. C./h up to
200.degree. C. and held there for 10 to 24 h providing a white
opaque (translucent) disk with thickness of 2-4 mm.
Analytical Data
[0209] DTA-TGA: Td.sub.5: 238.degree. C., Ceramic yield: 65.3%
(1000.degree. C. in air, calcd: 81.1%). Some of the material
sublimes during the TGA run as determined by a TGA run in nitrogen.
This material offers potential for vapor deposition processes.
Example 17
Octakis(trimethylsilylacetynyldimethylsiloxy)octasilsesquioxane or
OTMSAS
##STR00015##
[0211] To a 100 ml Schlenk flask equipped with reflux condenser, is
added OHSS (1 g, 1 mmol). The apparatus is then gently heated in
vacuum to remove residual air and moisture and flushed with
nitrogen. Then THF (25 ml), trimethylsilylacetylene (0.98 g, 10
mmol) and 2 mM Pt(dvs)-toluene solution (0.1 ml, Pt: 0.2 ppm) as a
catalyst, are added.
[0212] The mixture is stirred at 60.degree. C. for 3 h. After
reaction, triphenylphosphine (5 mg) and charcoal (0.08 g) are then
added to the solution to deactivate the catalyst and thereafter
filtered off through celite. Solvent is evaporated to yield a white
powder. The yield is 1.67 g (0.93 mmol), 93%.
Analytical Data
[0213] DTA-TGA: Td.sub.5: 285.degree. C., Ceramic yield: 58.8%
(1000.degree. C. in air, Calcd: 79.8%). Some of the material
sublimes during the TGA run as determined by a TGA run in nitrogen.
This material offers potential for vapor deposition processes.
[0214] .sup.1H NMR: Si--CH.sub.3, 0.07, 0.21 ppm, 8H, d [0215]
H--C.dbd.C, 6.60 ppm, 1H, q
[0216] Based on the .sup.1H NMR and TGA-DTA data, the structure of
OTMSAS is determined to be that shown below.
##STR00016##
Example 18
Synthesis of
Tetrakis(trimethylsilylacetynyl-dimethylsiloxy)tetrakis(hydridodimethylsi-
loxy)octasilsesquioxane
##STR00017##
[0218] To a 100 ml Schlenk flask equipped with reflux condenser is
added OHSS (10 g, 10 mmol). The apparatus is then gently heated in
vacuum to remove residual air and moisture and flushed with
nitrogen. Then THF (50 ml), trimethylsilylacetylene (3.86 g, 40
mmol) and 2 mM Pt(dvs)-toluene solution (0.1 ml, Pt: 0.2 ppm) as a
catalyst, are added.
[0219] The mixture is stirred at 60.degree. C. for 2 h. After
reaction, solvent is evaporated at RT in vacuo to yield a white
powder. The yield is 12.5 g (89 mmol), 88%.
Analytical Data
[0220] DTA-TGA: Td.sub.5: 281.degree. C., Ceramic yield: 75.6%
(1000.degree. C. in air, Calcd.: 84.7%). Some of the material
sublimes during the TGA run as determined by a TGA run in nitrogen.
This material offers potential for vapor deposition processes.
[0221] DSC: Mp: 87.2.degree. C., Curing temperature: 130.1.degree.
C.
[0222] .sup.1H NMR: Si(CH.sub.3).sub.3, 0.073 ppm, 35H, d [0223]
Si(CH.sub.3).sub.2, 0.21 ppm, 26H, s [0224] HSi--CH.sub.3, 0.25
ppm, 23H, s [0225] Si--H, 4.75 ppm, 3.6H, s [0226] C.dbd.C--H, 6.53
ppm, 8.1H, q
[0227] .sup.13C NMR: Si(CH.sub.3).sub.3, -1.43 ppm, s [0228]
H--Si--CH.sub.3, 0.39 ppm, d [0229] C.dbd.C, 148.1, 152.7 ppm,
d
[0230] FTIR: .nu. Si--H, 2140 cm.sup.-1 [0231] .delta. .dbd.C--H,
1412 cm.sup.-1 [0232] .nu. Si--O--Si, 1095 cm.sup.-1
[0233] Based on the .sup.1H NMR and TGA-DTA data, the structure of
TTMSAS is determined to be as shown below.
##STR00018##
Example 19
Curing TTMSAS
[0234] TTMSAS (1 g) is added to a 10 ml teflon (23.3.times.18.3
mmID) or aluminum cup, (25.2.times.39.6 mm ID). The cup is placed
in a vacuum oven thermostatted at 85.degree. C. Following degassing
for a period of 2 h at 85.degree. C., the oven is flushed with
nitrogen. The temperature is then raised at 30.degree. C./h to
200.degree. C. and held there for 10 to 24 h providing a white
opaque (translucent) disk with thickness of 2-4 mm.
Analytical Data
[0235] TMA: CTE=212 ppm (between 50.degree. and 100.degree. C.)
Example 20
Synthesis of tetrakis(hydridodimethylsiloxy)octasilsesquioxane,
NorbTHS
##STR00019##
[0237] To a 100 ml Schlenk flask equipped with reflux condenser, is
added OHS (1 g, 1 mmol). The apparatus is then gently heated in
vacuum to remove residual air and moisture and flushed with
nitrogen. Then THF (10 ml), 5-vinyl-2-norbornene (0.47 g, 3.9 mmol)
and 2 mM Pt(dcp)-toluene solution (0.1 ml, Pt: 0.2 ppm) as a
catalyst, are added.
[0238] The mixture is stirred at 60.degree. C. for 5 h. After
reaction, solvent is evaporated at RT in vacuo to yield white
powder. The yield is 1.6 g (1 mmol), which is quantitative.
Analytical Data
[0239] DTA-TGA: Td.sub.5: 302.degree. C., Ceramic yield: 55.7%
(1000.degree. C., in air, Calcd.: 64.1%). Some of the material
sublimes during the TGA run as determined by a TGA run in nitrogen.
This material offers potential for vapor deposition processes.
[0240] .sup.1H NMR: Difficult to assign
[0241] .sup.13C NMR: N/A
[0242] FTIR: .nu. .dbd.C--H: 3060 cm.sup.-1 [0243] .nu. Si--H: 2140
cm.sup.-1 [0244] .delta. .dbd.C--H: 1450 cm.sup.-1 [0245] .nu.
Si--O--Si: 1080 cm.sup.-1
Example 21
Curing norbTHS
[0246] NorbTHS (1 g) is added to a 10 ml Teflon (23.3.times.18.3 m
(ID) or aluminum cup (25.2.times.39.6 mm ID). The cup is placed in
a vacuum oven thermostatted at 85.degree. C. Following degassing
for a period of 2 h at 85.degree. C., the oven is flushed with
nitrogen. The temperature is then raised at 30.degree. C./h to
200.degree. C. and held there for 10 to 24 h providing a white
solid.
Example 22
Synthesis of Octakis(cyclohexenyldimethylsiloxy)octasilsesquioxane,
OCHDS
##STR00020##
[0248] To a 100 ml Schlenk flask equipped with reflux condenser, is
added OHSS (1 g, 1 mmol). The apparatus is then gently heated in
vacuum to remove residual air and moisture and flushed with
nitrogen. Then THF (10 ml), 1,3-cyclohexadiene (0.79 g, 10 mmol)
and 2 mM Pt(dcp)-toluene solution (0.1 ml, Pt: 0.2 ppm) as a
catalyst, are added.
[0249] The mixture is stirred at 60.degree. C. for 3 h. After
reaction, solvent is removed at RT in vacuo to yield white opaque
viscous liquid. The yield is 1.80 g (1.13 mmol), quantitative.
Analytical Data
[0250] DTA-TGA: Td.sub.5: 270.degree. C., Ceramic yield: 52.7%
(1000.degree. C., in air, Calcd.: 57.9%). Some of the material
sublimes during the TGA run as determined by a TGA run in nitrogen.
This material offers potential for vapor deposition processes.
[0251] .sup.1H NMR: Si--CH.sub.3, 0.141 ppm, 48H, s [0252]
Cyclohexane: 1.3-1.9 ppm 51H, m [0253] H--C.dbd.C, 5.67 ppm, 16H,
s
[0254] .sup.13C NMR: Si--CH.sub.3, -1.4 ppm, s [0255] Cyclohexane:
23.0, 23.4, 25.6, 27.9 ppm, s [0256] C.dbd.C, 126.6, 127.2 ppm,
d
[0257] FTIR: .nu. C.dbd.C--H, 3016 cm.sup.-1 [0258] .nu.
C.dbd.C--H, 1442 cm.sup.-1 [0259] .nu. Si--O--Si, 1145
cm.sup.-1
[0260] Based on .sup.1H NMR and FTIR, the structure of OCHDS is
that described below.
##STR00021##
Example 23
Synthesis of
Tetrakis(cyclohexenyldimethylsiloxy)tetrakis(hydridodimethylsiloxy)octasi-
lsesquioxane, TCHDS
##STR00022##
[0262] To a 100 ml Schlenk flask equipped with reflux condenser, is
added OHSS (1 g, 1 mmol). The apparatus is then gently heated in
vacuum to remove residual air and moisture and flushed with
nitrogen. Then THF (10 ml), 1,3-cyclohexadiene (0.32 g, 4 mmol) and
2 mM Pt(dcp)-toluene solution (0.1 ml, Pt: 0.2 ppm) as a catalyst,
are added.
[0263] The mixture is stirred at 60.degree. C. for 3 h. After
reaction, solvent is removed at RT in vacuo to yield white opaque
viscous liquid. The yield is 1.40 g (1 mmol), essentially
quantitative.
Analytical Data
[0264] DTA-TGA: Td.sub.5: 238.degree. C., Ceramic yield: 63.4%
(1000.degree. C., in air, Calcd.: 65.8%)
[0265] .sup.1H NMR: Si--CH.sub.3, 0.141 ppm, 32H, s [0266]
HSi--CH.sub.3, 0.252 ppm, 14H, s [0267] Cyclohexane: 1.3-1.9 ppm,
57H, m [0268] Si--H, 4.74 ppm, 2.6H, s [0269] H--C.dbd.C, 5.67 ppm,
11H, s
[0270] .sup.13C NMR: Si--CH.sub.3, -1.4 ppm, s [0271]
HSi--CH.sub.3, 0.73 ppm, s [0272] Cyclohexane: 23.0, 23.4, 25.6,
27.9 ppm, s [0273] C.dbd.C, 126.6, 127.2 ppm, d
[0274] FTIR: .nu. C.dbd.C--H, 3016 cm.sup.-1 [0275] .nu. Si--H2152
cm.sup.-1 [0276] .nu. C.dbd.C--H, 1438 cm.sup.-1 [0277] .nu.
Si--O--Si, 1146 cm.sup.-1
[0278] Based on .sup.1H NMR spectrum, the structure of TCHDS is
determined to be as shown below.
##STR00023##
Example 24
Curing TCHDS
[0279] TCHDS (1 g) is added to a 10 ml Teflon (23.3.times.18.3 m
(ID) or aluminum cup (25.2.times.39.6 mm ID). The cup is placed in
a vacuum oven thermostatted at 85.degree. C. Following degassing
for a period of 2 h at 85.degree. C., the oven is flushed with
nitrogen. The temperature is then raised at 30.degree. C./h to
200.degree. C. and held there for 10 to 24 h providing a white
opaque (translucent) disk with thickness of 2-4 mm.
Analytical Data
[0280] DTA-TGA: Td.sub.5: 349.degree. C., Ceramic yield: 66.7%
(1000.degree. C. in air, calcd: 65.8%)
[0281] TMA: CTE=180 ppm
Example 25
Synthesis of
Tetrakis(vinyldimethylsiloxy)tetrakis(hydridodimethylsiloxy)silsesquioxan-
e, TViTHS
##STR00024##
[0283] To a 500 ml Schlenk flask equipped with additional funnel,
is added hexane (130 ml), dimethylchlorosilane (3.74 g, 31 mmol)
and dimethylvinylchlorosilane (2.93 g, 31 mmol).
[0284] The mixture is cooled to 0.degree. C. An octaanion/methanol
solution (50 ml, 6.2 mmol) is then added dropwise over a period of
40 min. After the addition was complete, the mixture is stirred at
0.degree. C. for another 30 min and then at RT for 5 h.
[0285] The hexane layer is separated and dried over
Na.sub.2SO.sub.4 and then removed via rotary evaporator to produce
white TViTHS powder. The yield is 4.46 g (3.8 mmol) 64%.
[0286] Interestingly, the molar ratio of dimethylchlorosilane and
dimethylvinylchlorosilane directly affects the ratio of
substitution ratio on synthesized compound. For example, when the
ratio of dimethylchlorosilane/dimethylvinylchlorosilane/octaanion
silsesquioxane=5/5/1 described above, the ratio of dimethylsilyl
group/dimethylvinylsilyl group on obtained compound is 4.02/3.98
based on .sup.1H NMR spectrum. The determined structure is shown
below. On the other hand, if the ratio is changed to the ratio
dimethylchlorosilane/dimethylchlorosilane/octaanion=4/5/1, the
ratio of dimethylvinylsilyl group to dimethylsilyl group is
3.26/4.74. This means that the composition of the groups on the
cube is very easily modified.
Analytical Data
[0287] DTA-TGA: Td.sub.5: 132.degree. C., Ceramic yield: 79.2%
(1000.degree. C. in air, Calcd.: 85.6%). Some of the material
sublimes during the TGA run as determined by a TGA run in nitrogen.
This material offers potential for vapor deposition processes.
[0288] DSC: Curing temperature: 207.degree. C.
[0289] .sup.1H NMR: .dbd.Si--CH.sub.3, 0.16 ppm, 25H, s [0290]
H--Si--CH.sub.3, 0.20 ppm, 23H, s [0291] Si--H, 4.75 ppm, 4H, s
[0292] C.dbd.C--H, 5.7-6.2 ppm, 11H, m
[0293] .sup.13C NMR: SiCH.sub.3, -0.07 ppm, 0.28 ppm, d [0294]
C.dbd.C, 132.7 ppm, 138.1 ppm, d
[0295] FTIR: .nu. .dbd.C--H, 3050 cm.sup.-1 [0296] .nu. Si--H, 2140
cm.sup.-1 [0297] .delta. .dbd.C--H, 1412 cm.sup.-1 [0298] .nu.
Si--O--Si, 1191 cm.sup.-1
[0299] Based on the .sup.1H NMR spectrum and TGA-DTA data, the
structure of TViTHS was determined to be as shown below.
##STR00025##
Example 26
Curing TViTHS
[0300] TViTHS (1 g) is added to a 10 ml Teflon (23.3.times.18.3 mm
ID) or aluminum cup (25.2.times.39.6 mm ID). The cup is placed in a
vacuum oven thermostatted at 60.degree. C. Following degassing for
a period of 2 h at 85.degree. C., the oven is flushed with
nitrogen. The temperature is then raised at 30.degree. C./h to
200.degree. C. and held there for 10 to 24 h providing a white
opaque (translucent) disk with thickness of 2-4 mm.
Analytical Data
[0301] DTA-TGA: Td.sub.5: 395.degree. C., Ceramic yield: 71.8%
(1000.degree. C. in air, Calcd: 85.6%). Some of the material
sublimes during the TGA run as determined by a TGA run in nitrogen.
This material offers potential for vapor deposition processes.
Example 27
Synthesis of
Tetrakis(allyldimethylsiloxy)tetrakis-(hydridodimethylsiloxy)silsesquioxa-
ne, TallylTHS
##STR00026##
[0303] To a 250 ml Schlenk flask equipped with additional funnel,
is added hexane (65 ml), dimethylchlorosilane (1.47 g, 16 mmol) and
dimethylallylchlorosilane (2.09 g, 16 mmol). The mixture is cooled
at 0.degree. C. and an octaanion/methanol solution (25 ml, 3.1
mmol) is then added dropwise over a period of 20 min. After the
addition is complete, the mixture is stirred at 0.degree. C. for
another 30 min and then at RT for 24 h.
[0304] The hexane layer is separated and dried over
Na.sub.2SO.sub.4 and then removed via rotary evaporator to produce
transparent TallylTHS liquid. The yield is 2.84 g (2.4 mmol),
78%.
Analytical Data
[0305] DTA-TGA: Td.sub.5: 174.degree. C., Ceramic yield: 78.0%
(1000.degree. C. in air, Calcd.: 80.4%). Some of the material
sublimes during the TGA run as determined by a TGA run in nitrogen.
This material offers potential for vapor deposition processes.
[0306] DSC: Curing temperature: 208.degree. C.
[0307] .sup.1H NMR: --Si--CH.sub.3, 0.085, 0.17 ppm, 28H, d [0308]
H--Si--CH.sub.3, 0.26 ppm, 20H, s [0309] --CH.sub.2--SiCH.sub.3,
1.65 ppm, 8H, dd [0310] Si--H, 4.76 ppm, 4H, s [0311]
.dbd.CH.sub.2, 4.85 ppm, 8H, m [0312] .dbd.CH, 5.80 ppm, 4H, m
[0313] .sup.13C NMR: SiCH.sub.3, -0.35 ppm, 0.62 ppm, d [0314]
Si--CH.sub.2--, 26.1 ppm, d [0315] C.dbd.C, 114.1 ppm, 134.5 ppm,
dd
[0316] FTIR: .nu. O--H, 3700 cm.sup.-1 [0317] .nu. .dbd.C--H, 3075
cm.sup.-1 [0318] .nu. Si--H, 2145 cm.sup.-1 [0319] .delta.
.dbd.C--H, 1412 cm.sup.-1 [0320] .nu. Si--O--Si, 1150 cm.sup.-1
[0321] When the ratio of
dimethylallylchlorosilane/dimethylchlorosilane/octaanion is 5/5/1,
the ratio of dimethylallylsilyl to dimethylsilyl groups substituted
on octaanion is 3.7/3.7 as described above and remaining positions
may be OH groups from unreacted sites on octaanion based on .sup.1H
NMR and FTIR data. The determined structure is shown below. On the
other hand, when the ratio is changed to 6/5/1
(dimethylallylchlorosilane/dimethylchlorosilane/octaanion), the
ratio of dimethylallylsilyl to dimethylsilyl groups is 4.2/3.1 with
some residual OH groups as suggested by the .sup.1H NMR and FTIR
data. In this system, it is as easy to modify the ratio and type of
reactant organic groups. No efforts have been made to optimize this
synthesis.
[0322] Based on the .sup.1H NMR spectrum and TGA-DTA data, the
structure of AllylTHS is determined to be as shown below. Under the
conditions chosen here, all of organic group do not react with all
possible reaction sites on octaanion.
##STR00027##
Example 28
Curing TAllylTHS
[0323] TAllylTHS (1 g) is added to a 10 ml Teflon (23.3.times.18.3
mm ID) or aluminum cup (25.2.times.39.6 mm ID). The cup is placed
in a vacuum oven thermostatted at 85.degree. C. Following degassing
for a period of 2 h at 85.degree. C., the oven was flushed with
nitrogen. The temperature is then raised at 30.degree. C./h to
200.degree. C. and held there for 10-24 h providing a brown opaque
disk with thickness of 2-4 mm.
Analytical Data
[0324] DTA-TGA: Td.sub.5: 345.degree. C., Ceramic yield: 82.5%
(1000.degree. C. in air, Calcd: 81.5%)
[0325] TMA: CTE=227 ppm (at the range between 50 and 100.degree.
C.)
Example 29
Synthesis of
Tetrakis(hexenyldimethylsiloxy)tetrakis(hydridodimethylsiloxy)silsesquiox-
ane, THexenylTHS
##STR00028##
[0327] To a 250 ml Schlenk flask equipped with additional funnel,
Is added hexane (65 ml), dimethylchlorosilane (1.84 g, 0.019 mol)
and dimethylhexenylchlorosilane (3.42 g, 0.019 mol). The mixture Is
cooled at 0.degree. C. and an octaanion/methanol solution (25 ml,
0.0031 mol) Is added dropwise over a period of 20 min. After the
addition was complete, the mixture is stirred at 0.degree. C. for
another 30 min and then at RT for 24 h.
[0328] The hexane layer is separated and dried over
Na.sub.2SO.sub.4 and then removed via rotary evaporator to produce
transparent ThexenylTHS liquid. The liquid is purified by washing
with methanol/acetonitrile (1:1 by volume) giving a yield of 4.68 g
(3.5 mmol) 90%.
Analytical Data
[0329] DTA-TGA: Td.sub.5: 95.degree. C., Ceramic yield: 51.9%
(1000.degree. C. in air, Calcd.: 71.3%). Some of the material
sublimes during the TGA run as determined by a TGA run in nitrogen.
This material offers potential for vapor deposition processes.
[0330] DSC: Curing temperature, 224.degree. C.
[0331] .sup.1H NMR: --Si--CH.sub.3, 0.085, 0.11, 0.14, 0.18 ppm,
32H, dd [0332] H--Si--CH.sub.3, 0.26 ppm, 16H, s [0333]
--CH.sub.2--SiCH.sub.3, 0.55 ppm, 8H, m [0334]
--CH.sub.2--CH.sub.2, 1.40 ppm, 17H, broad [0335]
--CH.sub.2--CH.dbd.CH.sub.2, 2.06 ppm, 8H, broad [0336] --Si--H,
4.75 ppm, 3.4H, d [0337] .dbd.CH.sub.2--, 4.96 ppm, 7H, m [0338]
.dbd.CH--, 5.82 ppm, 3.6H, m
[0339] .sup.13C NMR: Si--CH.sub.3, -0.47 ppm, -0.02 ppm, d [0340]
--CH.sub.2--, 17.4 ppm, 22.4 ppm, 32.5 ppm, 33.4 ppm, d [0341]
.dbd.CH.sub.2--, 114.1 ppm, s [0342] .dbd.CH--, 138.9 ppm, s
[0343] FTIR: .nu. .dbd.C--H, 3074 cm.sup.-1 [0344] .nu. Si--H, 2140
cm.sup.-1 [0345] .delta. .dbd.C--H, 1412 cm.sup.-1 [0346] .nu.
Si--O--Si, 1150 cm.sup.-1
##STR00029##
[0347] Based on the .sup.1H NMR spectrum, the structure of
ThexenylTHS is determined to be as shown above.
[0348] When the ratio of
dimethylhexenylchlorosilane/dimethylchlorosilane/octaanion is
5/5/1, the ratio of dimethylhexenylsilyl to dimethylsilyl groups on
the obtained product is 3.6/3.4. Residual OH groups make up the
remaining reactive sites based on .sup.1H NMR and FTIR data. The
determined structure is shown above. When the ratio of
dimethylbexenylchlorosilane/dimethylchlorosilane/octaanion is
6/5/1, the ratio of dimethylhexenylsilyl to dimethylsilyl groups on
the product is 4.1/2.9. The remaining groups are SiOH. Thus, the
initial ratio affects the substitution ratio of the final product.
In this system it is easy to modify the substitution ratio in
TViTHS like the TallylTHS system described above.
Example 30
Curing ThexenylTHS
[0349] ThexenylTHS (1 g) is added to a 10 ml Teflon
(23.3.times.18.3 mm ID) or aluminum (25.2.times.39.6 min ID). The
cup is placed in a vacuum oven thermostatted at 60.degree. C.
Following degassing for a period of 2 h at 85.degree. C., the oven
is flushed with nitrogen. The temperature is then raised at
30.degree. C./h up to 200.degree. C. and held there for 10 to 24 h
providing a colorless transparent disk with thickness around 2-4
mm.
Analytical Data
[0350] DTA-TGA: Td.sub.5: 468.degree. C., Ceramic yield: 76.5%
(1000.degree. C. in air, Calcd: 71.3%).
[0351] TMA: CTE=277 ppm (between 50.degree. and 100.degree. C.)
Example 31
Melt Curing OVS/OHS Mixtures
[0352] Octakis(vinyldimethylsiloxy)silsesquioxane (OVS, 1.5 g, 1.2
mmol) and Octakis(hydridodimethylsiloxy)ostasilsesquioxane (OHS,
1.25 g, 1.2 mol) are mixed with mortar and pestle. The mixture is
placed in a 10 ml Aluminum cup (25.2.times.39.6 mm ID). The cup is
placed in a vacuum oven at room temperature. Then the oven is
flushed with nitrogen and the temperature raised at 30.degree. C./h
up to 360.degree. C. and held there for 10 to 24 h providing a
colorless transparent disk 2-4 mm thickness.
Analytical Data
[0353] DTA-TGA: Td.sub.5: 450.degree. C., Ceramic yield: 78.3%
(1000.degree. C. in air, Calcd: 85.6%)
[0354] TMA: CTE=180 ppm (between 50.degree. and 100.degree. C.)
Example 32
Synthesis of
Tris(dimethylethoxysilylethyldimethylsiloxy)pentakis(hydridodimethylsilox-
y)-silsesquioxane, TrisViMe.sub.2SiOEtS
##STR00030##
[0356] To a 250 ml Schlenk flask equipped with reflux condenser, is
added OHSS (10 g, 10 mmol). The apparatus is then gently heated in
vacuum to remove residual air and moisture and then flushed with
nitrogen. Then toluene (50 ml), dimethylvinylethoxysilane (3.91 g,
mmol) and 2 mM Pt(dvs)-toluene solution (0.1 ml, Pt: 0.2 ppm) as a
catalyst, are added. The mixture is stirred at 90.degree. C. for 2
h. After reaction, solvent is evaporated at RT in vacuo to yield a
transparent viscous liquid, 11.2 g (74 mmol), 72%.
Analytical Data
[0357] DTA-TGA: Td.sub.5: 268.degree. C., Ceramic yield: 67.5%
(1000.degree. C. in air, Calcd.: 74.1%). Some of the material
sublimes during the TGA run as determined by a TGA run in nitrogen.
This material offers potential for vapor deposition processes.
[0358] DSC: Endothermic peaks, 55.degree. C., 92.degree. C.,
127.degree. C.
[0359] .sup.1H NMR: EtOSiCH.sub.3, 0.10 ppm, 21H, s [0360]
--SiCH.sub.5, 0.4 ppm, 21H, s [0361] H--Si--CH.sub.3, 0.25 ppm,
24H, s [0362] Si--CH.sub.2--CH.sub.2--Si, 0.53 ppm, 14H, s [0363]
OCH.sub.2--CH.sub.3, 1.19 ppm, 10H, t [0364] O--CH.sub.2--, 3.66
ppm, 7H, q [0365] Si--H, 4.74 ppm, 4H, s
[0366] .sup.13C NMR: --Si--CH.sub.3, -1.33 ppm, -0.87 ppm, 0.26
ppm, t [0367] --CH.sub.2--, 9.14 ppm, d [0368]
CH.sub.3--CH.sub.2--, 18.5 ppm, s [0369] --OCH.sub.2--, 58.3 ppm,
s
##STR00031##
[0370] Based on the .sup.1H NMR spectrum, the structure of
TrisViMe.sub.2SiOEtS is determined to be as shown above.
Example 33
Tris(dimethylethoxysilylethyldimethylsiloxy)pentakis(hydridodimethylsiloxy-
)-silsesquioxane, (partially hydrolyzed TrisViMe.sub.2SiOEtS)
##STR00032##
[0372] To a 100 ml flask equipped with reflux condenser, are added
TrisViMe.sub.2SiOEtS (5.6 g, 3.6 mmol) and THF (20 ml). The mixture
is then cooled at 0.degree. C. for 30 min. 0.1 N HCl acq (0.43 ml)
is added into the flask and the solution stirred at 0.degree. C.
for 30 min and at RT for 30 min. The mixture is stirred at
60.degree. C. for 1 d to complete the hydrolysis.
Analytical Data
[0373] DTA-TOA: Td.sub.5: 273.degree. C., Ceramic yield: 78.2%
(1000.degree. C. in air, Calcd.: 77.0%)
[0374] .sup.1H NMR: --OSiCH.sub.3, 0.10 ppm, 30H, s [0375]
--SiCH.sub.3, 0.14 ppm, 20H, s [0376] H--Si--CH.sub.3, 0.25 ppm,
17H, s [0377] Si--CH.sub.2--CH.sub.2--Si, 0.53 ppm, 14H, s [0378]
OCH.sub.2--CH.sub.3, 1.19 ppm, 10H, t [0379] O--CH.sub.2--, 3.66
ppm, 7H, q [0380] Si--H, 4.74 ppm, 3H, s
[0381] .sup.13C NMR: N/A
[0382] FTIR: .nu. --OH, 3340 cm.sup.-1 [0383] .nu. Si--O--Si, 1145
cm.sup.-1
##STR00033##
[0384] Based on the .sup.1H NMR spectrum, the structure of partial
hydrolyzed TrisViMe.sub.2SiOEtS is determined to be that shown
above.
Example 34
Curing Partially Hydrolyzed TrisViMe.sub.2SiOEtS
[0385] TrisViMe.sub.2SiOEtS (Ig) is added to a 10 ml teflon cup
(23.3.times.18.3 mm ID). The cup is placed in a vacuum oven
thermostatted at 30.degree. C. to evaporate solvent over 2 h. Then
the oven ambient pressure was restored. The temperature is raised
at 30.degree. C./h to 150.degree. C. and held therefor 10 to 24 h
providing a colorless transparent disk 2-4 mm thick.
Analytical Data
[0386] DTA-TGA: Td.sub.5: 297.degree. C., Ceramic yield: 80.0%
(1000.degree. C. in air, Calcd.: 74.1%)
[0387] FTIR: .nu. --OH, 3640, 3380 cm.sup.-1 [0388] .nu. Si--H,
2140 cm.sup.-1 [0389] .nu. Si--O--Si, 1072 cm.sup.-1
[0390] TMA: 215 ppm (at the range between 50 and 100.degree.
C.)
Example 35
Tris(dimethylethoxysilylethyldimethylsiloxy)pentakis(trimethylsilylethyldi-
methylsiloxy)silsesquioxane, (TrisSiOEtPentakisSiMe.sub.3S)
##STR00034##
[0392] To a 100 ml flask equipped with reflux condenser, is added
TrisViMe.sub.2SiOEtS (2.2 g, 0.0015 mol). The apparatus is then
gently heated in vacuum to remove residual air and moisture and
then flushed with nitrogen. Then toluene (10 ml),
trimethylvinylsilane (0.87 g, 0.0087 mol) and 2 mM Pt(dvs)-toluene
solution (0.1 ml, Pt: 0.2 ppm) as a catalyst, are added. The
mixture is stirred at 90.degree. C. for 3 h. After reaction,
solvent was evaporated at RT in vacuo to yield a transparent
liquid. The yield is 3.5 g (1.9 mmol).
Analytical Data
[0393] .sup.1H NMR: Si(CH.sub.3).sub.3, -0.02 ppm, 38H, s [0394]
--SiOEt, 0.10 ppm, 21H, s [0395] --Si(CH.sub.3).sub.2--, 0.13 ppm,
47H, s [0396] --CH.sub.2--CH.sub.2--, 0.52 ppm, 32H, s [0397]
OCH.sub.2--CH.sub.3, 1.19 ppm, 9H, t [0398] O--CH.sub.2--, 3.66
ppm, 6H, q
[0399] FTIR: .nu. CH: 2960, 2900 cm.sup.-1 [0400] .nu. Si--O--Si:
1145 cm.sup.-1
##STR00035##
[0401] Based on the .sup.1H NMR spectrum, the structure of partial
hydrolyzed TrisViMe.sub.2SiOEtS is determined to be as shown
above.
Example 36
Tris(dimethylethoxysilylethyldimethylsiloxy)pentakis-(trimethylsilylethyld-
imethylsiloxy)silsesquioxane, (Partially Hydrolyzed
TrisSiOEtPentakisSiMe.sub.3S)
##STR00036##
[0403] To a 100 ml flask equipped with reflux condenser, are added
TrisSiOEtPentakisSIMe.sub.3S (5 g, 0.0025 mol) and THF (15 ml). The
mixture is then cooled at 0.degree. C. for 30 min. 1 N HCl.sub.aq
(0.025 ml) and H.sub.2O (0.11 g) were added to the flask and
stirred at 0.degree. C. for 30 min and at RT for 30 min. Then the
mixture was further hydrolyzed by stirring at 60.degree. C. for 1
d.
Analytical Data
[0404] DTA-TGA: Td.sub.5: 334.degree. C., Ceramic yield: 61.0%
(1000.degree. C. in air, Calcd: 78.9%). Some of the material
sublimes during the TGA run as determined by a TGA run in nitrogen.
This material offers potential for vapor deposition processes.
[0405] .sup.1H NMR: --Si--(CH.sub.3).sub.3, -0.02 ppm, 38H, s
[0406] EtOSi--CH.sub.3, 0.05 ppm, 19H, s [0407]
CH.sub.2Si--CH.sub.3, 0.13 ppm, 51H, s [0408]
CH.sub.2--Si(CH.sub.3), 1.20 ppm, 1H, broad
##STR00037##
[0409] Based on the .sup.1H NMR spectrum, the structure of partial
hydrolyzed TrisViMe.sub.2SiOEtS is determined to be as shown
above.
Example 37
Curing TrisSiOEtPentakisSiMe.sub.3S
[0410] TrisSiOEtPentaldsSiMe.sub.3S solution and 1 wt. % dibutyl
tin dilaurate as a curing catalyst are added to 10 ml Teflon
(23.3.times.18.3 mm ID). The cup is placed in a vacuum oven
thermostatted at 30.degree. C. to evaporate solvent. Then the oven
pressure is returned to ambient. The temperature is raised at
30.degree. C./h up to 150.degree. C. and held there for 10 to 24 h
providing an opaque disk 2.0-4.0 mm thick.
Analytical Data
[0411] DTA-TGA: Td.sub.5: 334.degree. C., Ceramic yield: 61.0%
(1000.degree. C. in air, Calcd.: 80.2%). Some of the material
sublimes during the TGA run as determined by a TGA run in nitrogen.
This material offers potential for vapor deposition processes.
[0412] FTIR: .nu. --OH, 3710 cm.sup.-1 [0413] .nu. Si--O--Si, 1084
cm.sup.-1
[0414] TMA: 483 ppm (between 50 and 100.degree. C.)
Example 38
Synthesis of TCHS with PtO.sub.2
[0415] To a 250 ml Schlenk flask equipped with reflux condenser,
are added octahydridosilsesquioxane OHS (10 g, 10 mg) and PtO.sub.2
(0.02, 0.01, 0.005 g, Pt content: 0.08, 0.04, 0.02 mol,
respectively) as a catalyst. The apparatus is degassed and heated
under vacuum to eliminate residual air and moisture and then
flushed with nitrogen. Toluene (50 ml), 5-vinyl-1-cyclohexene (4.3
g, 40 mg) are then added to the flask.
[0416] The mixture is stirred at 100.degree. C. for 5 h. Then
solution is filtered on celite to remove catalyst and filtrate is
evaporated for 30 min in vacuum and then precipitated into
acetonitrile to receive white powder. The yield is 47%. The powder
is TCHS.
Analytical Data
[0417] DTA-TGA: Tg.sub.5: 454.degree. C. (in N.sub.2) [0418]
367.degree. C. (in air)
[0419] Ceramic yield: 66.9% (1000.degree. C. in air, Calcd.:
67%)
[0420] DSC: Mp: 76.3.degree. C.
[0421] Curing temperature: 180.degree. C.
[0422] .sup.1H NMR spectrum: Si--CH.sub.3, 0.15 ppm, 24H [0423]
H--SiCH.sub.3, 0.26 ppm, 23H [0424] Si--CH.sub.2, 0.65 ppm, 9.5H
[0425] Cyclohexenyl, 1.2-2.1 ppm, 48H [0426] Si--H, 4.74 ppm, 4H
[0427] Vinyl in cyclohexenyl, 5.66 ppm, 8H
[0428] .sup.13C NMR spectrum: Si--CH.sub.3, 0.18 ppm [0429]
H--Si-Ch.sub.3, 0.73 ppm [0430] Si--CH.sub.2, 15.3 ppm [0431]
Cyclohexenyl 29.1, 30.2, 32.2, 37.0 ppm [0432] Vinyl in
cyclohexenyl, 127.5 ppm
[0433] IR spectroscopy: .dbd.C--H, 3020 cm.sup.-1 [0434] SiH, 2200
cm.sup.-1 [0435] Si--O--Si, 1095 cm.sup.-1
##STR00038##
[0435] Example 39
Preparation of Resin from PtO.sub.2-Prepared TCHS
[0436] TCHS (.apprxeq.1 g) as prepared in Example 28 is added to a
10 ml Teflon [23.3.times.18.3 mm ID] or aluminum cup
(25.2.times.39.6 mm ID). The cup is placed in vacuum oven
thermostatted at 85.degree. C. Following degassing for 2 h at
85.degree. C., the oven is flushed with nitrogen. The temperature
is then raised at 30.degree. C./h to 200.degree. C. and held there
for 10 to 24 h overnight providing a transparent disk with
thickness of 2.0-4.0 mm.
[0437] CTE (50.degree. C.-100.degree. C.): 126 ppm
Example 40
[0438] A catalyst deactivating agent may be added to lower the room
temperature reactivity. However, the reactivity can also be
controlled by storing at lower temperatures, or the catalyst can be
removed by passing through a column designed to capture the
catalyst. Alternatively, the amount of deactivating agent can be
minimal such that at higher temperatures, reaction will proceed. In
some instances exposure to air or water can oxidize or decompose
the deactivating agent. Furthermore, while triphenylphosphine is
used above, it is meant only to be representative of a large group
of hydrosilylation catalyst deactivators that those practiced in
the art will recognize. For instance, other possible deactivators
include other phosphines, arsines, stibnines, alkali cyanides, etc
that will not also react with the cube macromonomers but can
deactivate the transition metal complex by exchange reaction of
ligands.
[0439] FIG. 4, shows how the amount of deactivating agent
(triphenylphosphine provides an example) controls reaction at
150.degree. C. From FIG. 4, the endotherm at.apprxeq.70 C indicates
melting. Depending on the amount of deactivator added, an exotherm
corresponding to curing appears between 120.degree. and 180.degree.
C. The intensity of the exotherm correlates with the inverse amount
of deactivator used. From this data, less than 1 mg of deactivating
agent is preferred when triphenylphosphine is added. Amounts used
for other deactivators will vary with the type and the curing
conditions desired.
[0440] TCHS will cure above 80.degree. C. to a rigid body with less
than 1 mg (0.09 mol % to the TCHS) deactivation agent, although the
hybrid does not fully cure even at 200.degree. C., overnight with
more than 2.5 mg (0.2 mol % to TCHS) deactivation agent. Based on
these results, the amount of deactivation agent serves an important
role to prepare fully cured materials. In addition, the deactivator
also will control the temperature required or the time required to
fully cure these materials. Likewise, it will affect the rate of
cure in the presence or absence of oxygen.
[0441] While embodiments of the invention have been illustrated and
described, it is not intended that these embodiments illustrate and
describe all possible forms of the invention. Rather, the words
used in the specification are words of description rather than
limitation, and it is understood that various changes may be made
without departing from the spirit and scope of the invention.
* * * * *