Disclosed are novel, cross-linked or cross-linkable linear poly(organohydrosiloxanes) wherein the cross-linking units are derived from polycyclic polyenes. These polymers or prepolymers are prepared by reacting or partially reacting the poly(organohydrosiloxanes) with the polycyclic polyene in the presence of a catalyst.

This invention relates to cross-linked or cross-linkable 
poly(organosiloxanes). 
It has been known for quite some time that compounds containing the 
hydrosilane (i.e., .tbd.Si--H) functional group can be reacted with 
alkenes containing vinyl (terminal) unsaturation to form alkyl silanes. 
The simplest example of this reaction is the addition of ethylene to 
trichlorosilane to form ethyl trichlorosilane. This exothermic reaction is 
catalyzed by platinum halide compounds and proceeds readily to virtually 
100% conversion. 
This reaction, known.as the hydrosilation reaction, has been effective with 
a large number of vinyl compounds. Likewise, other silanes, such as 
dialkyl silanes, halo-alkyl silanes and alkoxy silanes, have been found to 
undergo this reaction so long as they possess the requisite .tbd.Si--H 
group. 
The hydrosilation reaction has been used with difunctional linear siloxanes 
to build up long chain siloxanes. For example, U.S. Pat. No 3,410,886 
teaches reacting a hydroterminated trisiloxane with a vinyl-terminated 
trisiloxane to form a linear compound containing six silicon atoms. U.S. 
Pat. Nos.3,220,972 and 3,271,362 teach that a compound containing both 
hydrogen-silicon linkages and aliphatic unsaturation can react with 
itself. 
A few instances have been reported in which polymerization takes place via 
reaction between compounds containing a vinyl silane 
(.tbd.Si--CH.dbd.CH.sub.2) group and a hydrosilane (.tbd.Si--H) group to 
form cross-linked polymers. Examples of this type of polymer are found in 
U.S. Pat. Nos. 3,197,432; 3,197,433; and 3,438,936. Each of these patents 
teaches the preparation of polymers from vinyl alkyl cyclotetrasiloxanes 
and alkyl cyclotetrasiloxanes containing 2 to 4 silanic hydrogen atoms. 
A number of organosilicon polymers have been disclosed in the prior art, 
which are actually vinyl addition polymers modified with 
silicon-containing moieties. Polymerization takes place in some cases via 
conventional olefin polymerization routes without making use of the 
hydrosilation reaction. The silicon-containing moiety is then present as a 
polymer modifier. Examples of such polymerizations can be found in, e.g., 
U.S. Pat. Nos. 3,125,554; 3,375,236; 3,838,115; 3,920,714; and 3,929,850. 
There is a need for high molecular weight organosilicon polymers that have 
outstanding physical, thermal and electrical properties and improved 
resistance to water. There is also a need for a method of preparing the 
aforesaid high molecular weight organosilicon polymers and of preparing 
shaped items therefrom. 
According to the invention, a cross-linked or cross-linkable 
organohydrosiloxane polymer is characterized in that the 
organohydrosiloxane is a linear poly(organohydrosiloxane) having at least 
30% of its .tbd.SiH groups reacted with hydrocarbon residues derived from 
polycyclic polyenes. 
Preferably, poly(organohydrosiloxane) has the general formula: 
##STR1## 
wherein R is a substituted or unsubstituted, saturated alkyl radical or a 
substituted or unsubstituted phenyl radical, and about 1% to about 50%, 
preferably 5 to about 50%, of the R's are hydrogen and m is an integer 
from about 5 to 1000, preferably 5 to 100, and the maximum value of m is 
desirably 40. 
Preferably, according to the invention, the poly(organohydrosiloxane) 
defined by the above general formula is trimethylsiloxy-terminated 
methylhydropolysiloxane. Other exemplary poly(organohydrosiloxanes) 
include: 
trimethylsiloxy-terminated dimethylsiloxane-methylhydro 
siloxane copolymer, 
dimethylsiloxy-terminated dimethylsiloxane 
methylhydrosiloxane copolymer, 
dimethylsiloxy-terminated polydimethylsiloxane, 
trimethylsiloxy-terminated methyloctylsiloxane 
methylhydrosiloxane copolymer, 
dimethylsiloxy-terminated phenylmethylsiloxane 
methylhydrosiloxane copolymer, 
trimethylsiloxy-terminated methylcyanopropylsiloxane 
methylhydrosiloxane copolymer, 
trimethylsiloxy-terminated 3,3,3-trifluoropropylmethyl 
siloxane methylhydrosiloxane copolymer, 
trimethylsiloxy-terminated 3-aminopropylmethylsiloxane 
methylhydrosiloxane copolymer, 
trimethylsiloxy-terminated 2-phenylethylmethylsiloxane 
methylhydrosiloxane copolymer, and 
trimethylsiloxy-terminated 2-(4-methylphenyl) 
ethylmethylsiloxane-methylhydrosiloxane copolymer. 
Cross-linking of the poly(organohydrosiloxane) takes place via the 
hydrosilation reaction with a polycyclic polyene. Two or more 
carbon-to-carbon double bonds react with a like number of silicon-hydrogen 
linkages to form the cross-linked product. 
Cyclic polyenes that can be employed are polycyclic hydrocarbon compounds 
having at least two non-aromatic, non-conjugated carbon-to-carbon double 
bonds. Exemplary compounds include cyclopentadiene oligomers such as 
dicyclopentadiene and cyclopentadiene trimer, methyl dicyclopentadiene, 
dimethanohexahydronaphthalene, norbornadiene, norbornadiene dimer, and 
substituted derivatives of any of these. Preferred compounds are 
dicyclopentadiene and cyclopentadiene trimer, the most preferred of which 
is dicyclopentadiene. Mixtures of polycyclic polyenes, particularly the 
cyclopentadiene oligomers, are useful. 
Polymerization can be promoted thermally or by using well known 
hydrosilation catalysts, e.g., metal salts and Group VIII elements. 
Radical generators such as peroxides and azo compounds may also be used, 
either by themselves or in combination with other catalysts. 
The hydrosilation reaction proceeds readily in the presence of a 
platinum-containing catalyst. The preferred catalyst, in terms of both 
reactivity and cost, is chloroplatinic acid (H.sub.2 PtCl.sub.6 
.cndot.nH.sub.2 O). Catalyst concentrations of 0.001 to about 0.4%, 
preferably 0.0025 to 0.1%, by weight, based on weight of the polyene 
monomer, will effect smooth and substantially complete reaction. Other 
platinum compounds can also be used to advantage in some instances, such 
as PtCl.sub.2. Platinum metal on carbon is also effective for carrying out 
the reaction at high temperatures. Other useful platinum catalysts are 
disclosed in, e.g., U.S. Pat. Nos. 3,220,971; 3,715,334; 3,159,662; and 
4,600,484. An exhaustive discussion of the catalysis of hydrosilation can 
be found in Advances in Organometallic Chemistry, Vol. 17, beginning on 
page 407. 
In one embodiment, to form the cross-linked polymers of this invention, the 
platinum-containing catalyst and polycyclic polyene are mixed and heated 
to form a complex, and, then, the complex and the 
poly(organohydrosiloxane) are combined, and the mixture is heated for a 
time sufficient for substantially all of the polycyclic polyene to react 
with silanic hydrogen. It is often preferred to slowly add the two reagent 
streams to the reactor in order to control the heat of reaction. In some 
cases a single heating temperature can be used and maintained until the 
reaction is driven to substantial completion. This is suitable for lower 
levels of cross-linking. However, for higher levels of cross-linking, 
heating is usually carried out in stages. Thus, periodic increases in 
temperature are effected over time to drive the reaction as the molecular 
weight increases. 
To prepare shaped objects, the reaction can be carried out in a mold, at 
least up to the point at which sufficient cross-linking has taken place to 
fix the polymer in the desired shape. Heat treatment can then be continued 
after removal from the mold in order to drive the reaction to completion. 
It is possible to prepare polymers of a wide range of cross-link density 
within the scope of this invention. Cross-link density is a function of 
the number of .tbd.Si--H linkages and the ratio of silane hydrogens to 
carbon-carbon double bonds in the reaction mix. This ratio can be from 
about 5 to 1 up to about 1 to 2. 
Properties and physical form of the cross-linked polymers vary with 
cross-link density. Thus, it has been found possible to prepare tacky 
solids, elastomeric materials and tough glassy polymers. The tacky solids 
and elastomeric materials, while they have utility on their own merits, 
are usually intermediate products that are further polymerized to the 
tough glassy polymer state by heat treatment to effect further 
cross-linking. 
By selecting appropriate cyclic polyenes, the initial product of the 
reaction at lower temperatures can be recovered as a flowable, 
heat-curable polymer, even though the ratio of 
##STR2## 
to .tbd.Si--H is otherwise suitable for cross-linking. Such cyclic 
polyenes musr have chemically distinguishable carbon-carbon double bonds, 
i.e., one being more reactive during hyrosilation than the other (more 
"electron-rich" and/or less hindered), and therefore include, for example, 
cyclopentadiene oligomers such as dicyclopentadiene and cyclopentadiene 
trimer, and methyl dicyclopentadiene. 
Such flowable, heat-curable polymers, analogous to the so-called B-stage 
resins encountered in other thermoset preparations, can be recovered and 
stored if desired for curing at a later time. They are stable at room 
temperature for varying periods of time, but upon reheating to an 
appropriate temperature they cure to the same types of polymers as are 
prepared when complete polymerization is carried out substantially 
immediately. 
The B-stage type polymers can be prepared by heating the reaction mass to 
about 40.degree. to 65.degree. C. and maintaining it at that point for 
several hours, and then interrupting the reaction by removing the heat 
until such time as it is desired to complete the transition to a 
cross-linked elastomeric or glassy polymer. The flowable polymers will 
have 5 to 90%, preferably 30 to 60% of the .tbd.Si--H groups reacted. 
These B-stage type polymers are generally viscous, flowable liquids at 
room temperature. The viscosity of such liquids varies with the degree of 
.tbd.Si--H groups reacted. The practitioner can select, for his own 
purposes, the point at which the polymerization is to be interrupted by 
monitoring the viscosity build-up. 
The unique silicon-containing polymers of this invention have a range of 
utilities, depending upon their physical form. Tacky solids or the B-stage 
type liquid materials are useful as tackifiers in pressure sensitive 
adhesives and as contact adhesives. They are also useful as structural 
adhesives, curable in situ, to form strong bonds due to a high affinity of 
the silicones for polar metal or glass surfaces. The elastomeric 
embodiments make excellent potting compounds for electronic applications, 
since they can be cured in situ and are insensitive to water. 
Thermal properties of these polymers are also outstanding. The cross-link 
density can be controlled to give a wide range of glass transition 
temperatures. Thermal stability in air or nitrogen is excellent with 
usually less than 10% weight loss at 500.degree. C. during 
thermogravimetric analysis. At 1100.degree. C. in air or nitrogen, they 
leave residue ranging from about 50% weight to about 75 weight % residue. 
The residues maintain some structural integrity. 
The polymers are fire resistant. They burn very slowly when subjected to a 
flame and self-extinguish when the flame is removed. 
A particularly striking property of these polymers is their virtually total 
insensitivity to water. They have been found to be unaffected by boiling 
water after extended periods, e.g., 5 days or more. Glass laminates 
exposed to boiling water exhibit minimal weight gain and insignificant or 
no change in rheometric properties (e.g., glass transition temperature). 
Further cross-linking may be achieved by platinum catalyzed reaction of 
.tbd.Si--H with .tbd.Si--OH. The .tbd.Si--OH groups are generated by the 
reaction of .tbd.Si--H with water so properties can actually improve upon 
exposure to water. 
The polymers also exhibit high temperature resistance, which makes them 
useful as refractory materials and also as ablative materials for, e.g., 
rocket reentry cones. 
A number of options exist for incorporating additives into the polymer. 
Additives such as fillers and pigments are readily incorporated. Carbon 
black, vermiculite, mica, wollastonite, calcium carbonate, sand, glass 
spheres, and glass beads or ground glass are examples of fillers that can 
be incorporated. Fillers can serve either as reinforcement or as fillers 
and extenders to reduce the cost of the molded product. When used, fillers 
can be present in amounts up to about 80%. 
Glass or carbon, e.g., graphite fibers are wetted very well by the liuid 
prepolymer embodiment making the polymers excellent matrix materials for 
high strength composite structures. Thus a mold containing the requisite 
staple or continuous filament can be charged with the B-stage type 
prepolymer and the prepolymer cured to form the desired composite 
structure. Fiber in fabric form (e.g., a woven glass mat) can also be 
employed. Fiber reinforced composites of the polymers of this invention 
can contain as much as 80% of fibrous reinforcement, and, when fully 
cured, typically exhibit extremely high tensile and flexural properties 
and also excellent impact strength. Other types of fibers, e.g., metal, 
ceramic or synthetic polymer fibers, can also be used. 
Stabilizers and antioxidants are useful to maintain the storage stabilty of 
the prepolymers and the thermal oxidative stability of the final product.

In the examples that follow, a series of poly(methylhydrosiloxanes) were 
cross-linked with polycyclic polyenes under the influence of 
chloroplatinic acid catalyst. The poly(methylhydrosiloxanes) have the 
general formula: 
##STR3## 
The following polymers were cross-linked: 
______________________________________ 
Formula.sup.(b) 
Designation x.sup.(a) 
y.sup.(a) Weight 
______________________________________ 
PS-1 22 0 1,500 
PS-2 35 0 2,270 
PS-3 6 6 950 
PS-4 9 17 2,000 
PS-5 5 25 2,250 
______________________________________ 
.sup.(a) x and y estimated based on data from supplier. 
.sup.(b) Approximate formula weight as reported by supplier. 
EXAMPLE 1 
A dry, N.sub.2, sparged vessel was charged with a stir bar and 0.0113 g of 
chloroplatinic acid. The vessel was sealed and charged with 13.69 g of 
norbornadiene. The mixture was stirred for 30 minutes at 50.degree. C. 
PS-3 (43.46 g) was added and the reaction mixture stirred 16 hours at 
50.degree. C. A sample of the viscous, flowable reactinn mixture was 
poured into an aluminum pan and the sample was heated in a nitrogen 
sparged oven at 150.degree. C. for 16 hours, 225.degree. C. for 2 hours, 
250.degree. C. for 2 hours and 280.degree. C. for 16 hours. The product 
was a clear elastomer. 
EXAMPLE 2 
Following the general procedure in Example 1, PS-3 (68.63 g) was added to a 
heated (73.degree. C.) mixture of norbornadiene (21.63 g) and 
chloroplatinic acid (0.0183 g) and the resulting mixture was stirred for 2 
hours at 73.degree. C. The reaction mixture was injected into a 
teflon-coated mold and the mold was placed in a nitrogen sparged oven at 
150.degree. C. for 16 hours. The clear cross-linked sample was removed 
from the mold and postcured at 200.degree. C. for 2 hours and 280.degree. 
C. for 4 hours to give a clear elastomer. 
EXAMPLE 3 
Following the general procedure in Example 1, PS-3 (76.03 g) was added to a 
heated (70.degree. C.) mixture of dicyclopentadiene (34.40 g) and 
chloroplatinic acid (0.0221 g). The reaction mixture exothermed to 
115.degree. C. 20 seconds after the PS-3 addition. The mixture was stirred 
for 5 hours at 100.degree. C. and then injected into a teflon-coated mold. 
The mold was placed in a nitrogen sparged oven and heated 11 hours at 
175.degree. C. and 24 hours at 200.degree. C. The cross-linked sample was 
a clear elastomer. 
EXAMPLE 4 
Following the general procedure in Example 1, PS-3 (8.71 g) was added to a 
heated (50.degree. C.) mixture of dimethanohexahydronaphthalene (4.71 g) 
and chloroplatinic acid (0.0027 g). The reaction mixture exothermed to 
159.degree. C. and set up into a clear elastomer 3 minutes after the PS-3 
addition. The elastomer was removed from the reaction vessel and postcured 
in a nitrogen sparged oven 2 hours at 225.degree. C., 2 hours at 
250.degree. C. and 16 hours at 280.degree. C. The postcured sample was a 
clear elastomer. 
EXAMPLE 5 
Following the general procedure in Example 1, a solution of PS-3 (19.72 g) 
in methylene chloride (2 ml) was added to a heated (70.degree. C.) mixture 
of dimethanohexahydronaphthalene (10.66 g) and chloroplatinic acid (0.0061 
g). The reaction mixture exothermed to 153.degree. C. and set up into a 
flexible foam 60 seconds after addition of the PS-3/CH.sub.2 Cl.sub.2 
addition. The foam was heated for 2 hours at 75.degree. C. and removed 
from the reaction vessel. The foam was then postcured 2 hours at 
150.degree. C., 4 hours at 200.degree. C. and 4 hours at 280.degree. C. to 
give a white elastomeric foam. 
EXAMPLE 6 
Following the general procedure in Example 1, PS-4 (17.5 g) was added to a 
heated mixture (50.degree. C.) of norbornadiene (3.82 g) and 
chloroplatinic acid (0.0042 g). The reaction mixture was stirred for 16 
hours at 50.degree. C. A sample of the reaction mixture was poured into an 
aluminum pan and cured 16 hours at 150.degree. C., 2 hours at 225.degree. 
C., 2 hours at 250.degree. C. and 16 hours at 280.degree. C. The 
cross-linked sample was a clear elastomer. 
EXAMPLE 7 
Following the general procedure in Example 1, PS-4 (14.23 g) was added to a 
heated mixture (50.degree. C.) of dicyclopentadiene (4.45 g) and 
chloroplatinic acid (0.0037 g). The reaction mixture was stirred for 16 
hours at 50.degree. C. The reaction mixture was poured into an aluminum 
pan and cured 16 hours at 150.degree. C., 2 hours at 225.degree. C., 2 
hours at 250.degree. C. and 16 hours at 280.degree. C. to give a clear 
elastomer. 
EXAMPLE 8 
Following the general procedure in Example 1, PS-5 (56.8 g) was added to a 
heated (60.degree. C.) mixture of norbornadiene (6.42 g) and 
chloroplatinic acid (0.0125 g). The reaction mixture was stirred for 16 
hours at 60.degree. C. The reaction mixture was poured into an aluminum 
pan and cured 16 hours at 150.degree. C., 2 hours at 225.degree. C., 2 
hours at 250.degree. C. and 16 hours at 280.degree. C. to give a clear 
elastomer. 
EXAMPLE 9 
Following the general procedure in Example 1, PS-5 (78.09 g) was added to a 
heated (75.degree. C.) mixture of norbornadiene (8.80 g) and 
chloroplatinic acid (0.0177 g). The reaction mixture was stirred for 2 
hours at 75.degree. C. and injected into a teflon-coated mold. The mold 
was placed in a nitrogen sparged oven and heated for 16 hours at 
150.degree. C. The clear elastomer was removed from the mold and post 
cured 4 hours at 200.degree. C. to give a clear elastomer. 
EXAMPLE 10 
Following the general procedure in Example 1, PS-1 (10.0 g) was added to a 
heated (60.degree. C.) mixture of dicyclopentadiene (9.83 g) and 
chloroplatinic acid (0.0040 g). The reaction mixture exothermed to 
180.degree. C. 15 seconds after the PS-1 addition. The mixture was stirred 
for 2 hours at 60.degree. C., then poured into an aluminum pan. The sample 
was cured for 40 hours at 150.degree. C., 2 hours at 225.degree. C., 2 
hours at 250.degree. C. and 16 hours at 280.degree. C. to give a hard, 
glassy clear solid. 
EXAMPLE 11 
Following the general procedure in Example 1, PS-1 (48.75 g) was added to a 
heated (68.degree. C.) mixture of dicyclopentadiene (47.91 g) and 
chloroplatinic acid (0.0196 g). The reaction mixture exothermed to 
133.degree. C. 20 seconds after the PS-1 addition. The reaction mixture 
was stirred for 16 hours at 130.degree. C., then injected into a 
teflon-coated mold and cured for 16 hours at 150.degree. C. to give a 
hard, glassy clear solid. 
EXAMPLE 12 
Following the general procedure in Example 1, PS-1 (5.68 g) was added to a 
heated (75.degree. C.) mixture of dimethanohexahydronaphthalene (6.67 g) 
and chloroplatinic acid (0.0025 g). The reaction mixture exothermed to 
200.degree. C. and the mixture polymerized to a white elastomer. The 
sample was removed from the reaction vessel and postcured for 2 hours at 
225.degree. C., 2 hours at 250.degree. C. and 16 hours at 280.degree. C. 
to give a hard, glassy clear solid. 
EXAMPLE 13 
Following the general procedure in Example 1, a solution of PS-1 (7.50 g) 
in methylene chloride (2 ml) was added to a heated (70.degree. C.) mixture 
of dimethanohexahydronaphthalene (8.80 g) and chloroplatinic acid (0.0033 
g). The reaction mixture exothermed to 181.degree. C. and set into a white 
foam 120 seconds after addition of the PS-1/CH.sub.2 Cl.sub.2 solution. 
The foam was removed from the reaction vessel and cured for 16 hours at 
200.degree. C. and 24 hours at 280.degree. C. to give a glassy white foam. 
EXAMPLE 14 
Following the general procedure in Example 2, PS-2 (9.71 g) was added to a 
heated (65.degree. C.) mixture of norbornadiene (6.91 g) and 
chloroplatinic acid (0.0033 g). The reaction mixture was stirred for 16 
hours at 65.degree. C. to give a clear elastomer. The sample was removed 
from the reaction vessel and cured for 16 hours at 200.degree. C., 2 hours 
at 225.degree. C., 2 hours at 250.degree. C. and 16 hours at 280.degree. 
C. to give a clear glassy solid. 
EXAMPLE 15 
Following the general procedure in Example 1, PS-2 (9.71 g) was added to a 
heated (65.degree. C.) mixture of norbornadiene (6.91 g) and 
chloroplatinic acid (0.0033 g). The reaction mixture was stirred for 2 
hours at 65.degree. C. and poured into an aluminum pan. The sample was 
cured for 16 hours at 150.degree. C. and 7 hours at 200.degree. C. to give 
a hard, clear, glassy solid. 
EXAMPLE 16 
Following the general procedure in Example 1, PS-2 (16.0 g) was addd to a 
heated (65.degree. C.) mixture of dicyclopentadiene (16.53 g) and 
chloroplatinic acid (0.0064 g). The reaction mixture exothermed to 
182.degree. C. 15 seconds after the PS-2 addition. The reaction mixture 
was stirred for 16 hours at 55.degree. C. and 48 hours at 75.degree. C. 
The mixture was poured into an aluminum pan and cured for 16 hours at 
200.degree. C., 2 hours at 225.degree. C., 2 hours at 250.degree. C. and 
16 hours at 280.degree. C. to give a hard, clear, glassy solid. 
EXAMPLE 17 
Following the general procedure in Example 1, PS-2 (76.21 g) was added to a 
heated (75.degree. C.) mixture of pentadiene (77.90 g) and chloroplatinic 
acid (0.0317 g). The reaction mixture exothermed to 153.degree. C. 70 
seconds after the PS-2 addition. The reaction mixture was stirred for 16 
hours at 136.degree. C. and injected into a teflon-coated mold. The sample 
was cured for 16 hours at 280.degree. C. to give a hard, clear, glassy 
solid. The cross-linked polymers prepared in Examples 1 through 17 were 
subjected to thermogravimetric analysis in air or nitrogen to determine 
the temperature at which their thermal weight loss reached 10% and the 
residue remaining after increasing the temperature to 1100.degree. C. at 
the rate of 20.degree. per minute. Results are recorded in the following 
Table 1. 
TABLE 1 
______________________________________ 
Example TGA 10% Wt. Loss 
% 
No. Atmosphere (.degree.C.) 
Residue 
______________________________________ 
1 N.sub.2 510 68 
2 Air 480 66 
3 Air 490 58 
4 N.sub.2 500 64 
5 Air 430 58 
6 N.sub.2 540 63 
7 N.sub.2 500 62 
8 N.sub.2 500 52 
9 Air 400 56 
10 N.sub.2 525 72 
11 Air 520 50 
12 N.sub.2 510 68 
13 Air 400 54 
14 N.sub.2 550 75 
15 Air 525 76 
16 N.sub.2 510 67 
17 Air 525 49 
______________________________________ 
EXAMPLE 18 
A complex of 0.0190 g of chloroplatinic acid and 48.54 g of 
dicyclopentadiene was prepared by heating at 170.degree. C. under a 
nitrogen blanket for one hour. PS-2 (47.50 g) was added to the complex at 
74.degree. C. The reaction exothermed to 182.degree. C. in 12 seconds. The 
opaque, milky white mixture that resulted was cooled to 30.degree. C. and 
injected into a glass filled plaque mold and cured at 150.degree. C. for 
17 hours and 200.degree. C. for 6 hours. The glass filled plaques were 
removed from the molds and post cured at 100.degree. C. for 0.5 hours, 
150.degree. C. for 0.5 hours, 200.degree. C. for 2 hours, 225.degree. C. 
for 2 hours, 250.degree. C. for 2 hours and 280.degree. C. for 16 hours. 
EXAMPLE 19 
A complex of 0.0379 g of chloroplatinic acid and 94.75 g of 
dicyclopentadiene was prepared as described in Example 18. PS-2 (72.62 g) 
was added to the complex at 74.degree. C. The reaction immediately 
exothermed to 144.degree. C. The opaque, milky white mixture was cooled to 
30.degree. C. and injected into glass filled molds. The resin was cured as 
described in Example 18. 
EXAMPLE 20 
A complex of 0.0360 g of chloroplatinic acid and 45.99 g of 
dicyclopentadiene was prepared as described in Example 18. PS-2 (90.00 g) 
was slowly added to the complex at 72.degree. C. The reaction immediately 
exothermed to 135.degree. C. The resultant opaque, creamed colored mixture 
was cooled to 30.degree. C. and injected into glass filled molds and cured 
at 150.degree. C. for 15 hours and 200.degree. C. for 8 hours. The glass 
filled plaques were removed from the mold and post cured as described in 
Example 18. 
Physical properties of these glass filled resins are recorded in Table 2. 
TABLE 2 
______________________________________ 
Physical Data 
Rheometrics 
Example Wt. G' (GPa) at T (C) 
No. Glass Tg (C) 25 100 140 180 200 
______________________________________ 
18 55 150 1.6 1.0 0.58 0.38 0.37 
19 57 124 1.4 0.84 0.56 0.52 0.54 
20 50.6 60 0.80 0.46 0.44 0.45 0.46 
______________________________________ 
Mechanical 
Flexural Tensile 
Example Wt. Strength Modulus 
Strength 
Modulus 
No. Glass Ksi Msi Ksi Msi 
______________________________________ 
18 55 24.5 1.69 18.7 1.31 
19 57 22.8 1.70 17.0 1.09 
20 50.6 11.5 1.25 10.6 0.819 
______________________________________ 
EXAMPLE 21 
A dry, nitrogen sparged vessel was charged with dicyclopentadiene (17.14 g) 
and chloroplatinic acid (0.7369 g). The mixture was stirred for one hour 
at 70.degree. C. and filtered through a 0.45 micron filter under a 
nitrogen atmosphere to give a greenish-brown solution. The platinum 
concentration was 3500 ppm. 
A dry, nitrogen sparged three neck round bottom flask equipped with a 
mechanical stirrer, condenser, and a septum inlet was charged with hexane 
(500 g), dicyclopentadiene (245.20 g), and PS-1 (250.00 g). Catalyst 
concentrate (3.times.0.26 g) was added to the stirred solution every 2.5 
hours. The reaction mixture was stirred for 15 hours (ambient temperature) 
after the final catalyst addition. Tetramethylethylene diamine (0.13 g) 
was added to 250 g of the reaction mixture. The resulting solution was 
stirred for one hour at room temperature. The hexane was removed under 
reduced pressure at 50.degree. C. A sample of the resulting viscous liquid 
was heated in a nitrogen sparged oven at 150.degree. C. for 2 hours and 
250.degree. C. for two hours to give a slightly turbid, hard, glassy 
solid. 
EXAMPLE 22 
A sample of the B-stage resin prepared in Example 21 (10 g) was mixed with 
Di-Cup R (dicumyl peroxide; available from Hercules Incorporated, 
Wilmington, Del.) (0.10 g). The resulting mixture was heated in a vacuum 
oven for one hour at 50.degree. C. to give a clear viscous resin. The 
resin was heated in a nitrogen sparged oven at 150.degree. C. for two 
hours and 275.degree. C. for two hours to give a slightly yellow flexible 
elastomer. 
While this invention has been described with respect to specific 
embodiments, it should be understood that these embodiments are not 
intended to be limiting and that many variations and modifications are 
possible without departing from the scope of this inventinn.