Cycloolefin copolymerization method, feed composition and product

Abstract

A cycloolefin copolymerization method, feed composition and product made from the feed which includes: a nonpolar cycloolefin, a polar cycloolefin and a catalyst. Preferably, the nonpolar cycloolefin is dicyclopentadiene, the catalyst comprises WCl₆, the polar cycloolefin is an ester, and the composition also includes an activator.

Description

This copolymer product composition may have a glass transition temperature of at least 153°C, at least 160°C, at least 165°C or at least 175°C

Preparation of Comonomers

1,4,5,8-Dimethano-1,4,4a,5,8,8a-hexahydronaphthalene (DMHN)

DMHN is prepared by reaction bicyclo [2.2.1]-2,5-heptadiene (norbornadiene) with cyclopentadiene according to reaction I as follows: ##STR6##

EXAMPLE 35

Norbornadiene (5.0 kg) was charged to a five gallon autoclave while maintaining an inert nitrogen atmosphere in the autoclave. DCPD (1.35 kg) was then charged to the reactor.

The reactor was then heated to 180°C over five hours while stirring, and then maintained at 180°C for sixteen hours. The reactor was then cooled to room temperature, after which the reactor was vented and opened and the contents of the reactor removed. The DMHN was purified by distillation in a packed column. Excess norbornadiene (BP₇0 =38°C) is removed first by distilling at a pressure of 70 torr. DMHN (BP₁0 =90°C) is then purified by distilling at 10 torr to obtain 1.84 kg of product.

Tricyclo [8.2.1.0]trideca-5,11-diene (TTD)

TTD is prepared by reaction ,5-cyclooctadiene with cyclopentadiene according to reaction II as follows: ##STR7##

EXAMPLE 36

Dicyclopentadiene Cyclopentadiene (50 grams) and 150 grams of 1,5-cyclooctadiene were added by cannula to a sparged pop bottle. The mixture was then heated to 190°C over 2 hours and then maintained at that temperature for 4 hours and then allowed to cool. TTD was purified by first distilling our out excess 1,5-cyclooctadiene at a pressure of 5 torr and then distilling the TTD (BP₀5 =80°C) at 0.03 torr to give 63 grams of product.

Trimethylolpropane-tris-(5-norbornene-2-carboxylate) (TPNC)

TPNC is prepared by reacting trimethylolpropane triacrylate with cyclopentadiene according to reaction III as follows: ##STR8##

EXAMPLE 37

A solution of 14.8 grams of trimethylolpropane triacrylate in 150 ml of methylene chloride was sparged with nitrogen for 15 minutes. Cyclopentadiene (42.8 ml, 0.52 moles) was added in one portion by syringe, after which the mixture was heated to 40°C for 3 hours. After cooling, the methylene chloride and excess cyclopentadiene were removed by rotary evaporator and high vacuum to provide the product.

Ethylene-bis-(5-norbornene-2-carboxylate) (ENC)

ENC is prepared by reacting ethylene glycol diacrylate with cyclopentadiene according to reaction IV as follows ##STR9##

EXAMPLE 38

A solution of 17.0 g (.100 moles) of distilled ethylene glycol diacrylate in 200 ml of methylene chloride was sparged with nitrogen in a 0.5 l reactor. Cyclopentadiene (46 g, 0.70 moles) was added in one portion by syringe, after which the mixture was heated to 40°C for 4 hours under a nitrogen atmosphere. The mixture was then cooled, after which the methylene chloride and excess cyclopentadiene were removed with a rotary evaporator. The crude product was purified by chromatography on a column of 100 g of neutral alumina, eluting first with 1.5 l of hexane and then with 4 l of a 1:1 mixture of hexane and methylene chloride. The haxane/methylene chloride was then stripped to provide the pure ENC.

Ethylene-bis-(2-methyl-5-norbornene-2-carboxylate Ethylene-bis-(2-methyl-5-norbornene-2-carboxylate) (EMNC)

PAC EXAMPLE 39

EMNC is prepared by first adding a solution of 21.0 g (0.200 moles) of methacryloyl chloride in 50 ml of ether to a solution of 26 g (0.39 moles) of cyclopentadiene in 50 ml of ether over one hour at 0°C The mixture was then warmed to room temperature and stirred overnight. This solution was then transferred by cannula to a 0°C solution of 6.10 g (0.983 moles) (0.0983 moles) of ethylene glycol and 25 g (0.32 moles) of pyridine in 150 ml of methylene chloride. This mixture was then stirred overnight while warming to room temperature. The solution was then decanted away from precipitated salts which were washed with two 50 ml portions of hexane. The organic layer was washed with 200 ml of 5% KOH in saturated aqueous NaCl, dried over magnesium sulfate and concentrated on a rotary evaporator. The crude product was purified by chromatography on alumina by eluting first with 200 ml of hexane followed by one liter of methylene chloride. Evaporation of the methylene chloride provided 12.5 grams of EMNC.

1,4-Butane-bis-(2-methyl-5-norbornene-2-carboxylate) (BMNC)

PAC EXAMPLE 40

BMNC is prepared by first adding a solution of 15.5 g (0.148 moles) of methacryloyl chloride in 25 ml of ether to a solution of 15 g (0.23 moles) of cyclopentadiene in 25 ml of ether over one hour at 0°C The mixture is then warmed to room temperature and stirred overnight. This solution is then transferred by cannula to a 0°C solution of 6.66 g (0.107 moles) of ethylene glycol and 20 g (0.253 moles) of pyridine in 180 ml of methylene chloride. This mixture is then stirred overnight while warming to room temperature. The solution is then decanted away from precipitated salts which are washed with two 50 ml portions of hexane. The organic layer is washed with 200 ml of 5% KOH in saturated aqueous NaCl, dried over magnesium sulfate and concentrated on a rotary evaporator. The crude product is purified by chromatography on alumina by eluting first with 100 ml of hexane followed by 600 ml of methylene chloride. Evaporation of the methylene chloride provided 12.5 grams of BMNC.

Bis-(202-Hydroxymethyl-5-norbornene)Adi pate

PAC EXAMPLE 41

A solution of 227.5 grams of adipoyl chloride in 1 liter of ether was cooled to 0°C in a 3 liter reactor. A solution of 31.7 317 grams of 5-hydroxy-methyl-2-norbornene in 227.5 ml of pyridine was added slowly over a period of two hours. The mixture was stirred overnight and filtered. The solids were then washed with hexane which was combined with the filtrate and washed with 1 liter of dilute HCl solution, 250 ml of saturated NaCl solution and dried over magnesium sulfate. After removal of solvent and other volatiles, the crude product is purified by chromatography on alumina to give 271 grams of HMNA.

The adduct of cyclopentadiene and norbornene contains only one double bond and thus will not increase the cross-link density of the resulting copolymer. However, the comonomer is a tetracyclic monomer so that in the ring-opened copolymer the repeat unit in the polymer chain will contain three fused rings. These tricyclic units have considerably less free rotation, and therefore less flexibility, than DCPD so that their presence results in a stiffer polymer chain and a correspondingly higher Tg. Similar results should be obtained with the cyclopentadiene adducts of alkylnorbornenes such as 5-methylnorbornene.

1,4,5,8-Dimethano-1,4,4a,5,8,8a-octahydronaphthalene (DMON)

DMON is prepared by reacting norbornene with cyclopentadiene according to reaction V as follows: ##STR10##

EXAMPLE 42

Norbornene (76 g, 0.807 moles) is weighted into a 10 oz. bottle which is then capped and sparged. DCPD Cyclopentadiene (54 ml, 0.439 moles) was added by syringe. The mixture was heated to 180° C. for 16 hours, after which the bottle was cooled to room temperature and opened. Excess norbornene was removed by distillation after which the product was distilled under nitrogen in a pop bottle to give 41.7 g of DMON.

Preparation of Copolymers Copolymers of DCPD

PAC EXAMPLE 43

A 0.1 M solution of a tungsten catalyst is prepared by weighing 3.96 grams of WCl₆ under nitrogen into a 200 ml bottle. Nonyl phenol (2.21 grams, 0.01 moles) dissolved in 100 ml of toluene, that had been distilled from Na/K alloy under nitrogen, is added, and the mixture is stirred for one hour while sparging with nitrogen. Acetylacetone (2.00 grams, 0.02 moles) is then added by syringe and the mixture was stirred overnight while sparging with nitrogen to remove HCl gas.

An aluminum alkyl activator solution is prepared by diluting 2.00 ml (0.00376 moles) of a 1.88 M solution of diethylaluminum chloride (DEAC) with 8.00 ml of distilled toluene and 0.64 ml (0.0038 moles) of di-butyl ether.

Solutions are prepared containing measured mixtures of DCPD and DMHN. Into a 15 mm×125 mm test tube that had been capped with a rubber septum and sparged with nitrogen is syringed 5 grams of one of the solutions of the comonomers. The aluminum alkyl activator (0.15 ml, 0.054 mmoles) is added to the monomers by syringe. Next, 0.15 ml of di-butyl ether was added. After a thermocouple probe has been inserted to measure the exotherm of the reaction, 0.19 ml (0.019 mmoles) of 0.1 M tungsten catalyst is added and the tube is quickly shaken to mix the reactants. After a short period of time the mixture polymerized into a solid infusible polymer mass. Table 12 gives values for the % insoluble gel, % swell in toluene, and Tg, as determined by differential scanning calorimetry, of the copolymers.

TABLE 12
______________________________________
wt. % DMHN % Gel        % Swell  Tg
______________________________________
0          97           110      140
5          94           67       175
10         93           52       187
20         93           40       196
______________________________________

EXAMPLES 44 and 45

These examples describe the preparation of a copolymer of 10 wt % DMHN and 90 wt % DCPD by reaction injection molding (RIM). Samples of DCPD copolymers made by RIM processing were made using a standard RIM machine supplied by Accuratio Co. of Jeffersonville, Ind. The following description illustrates the standard procedure for molding samples. First the two monomer storage tanks on the machine were closed off and inerted with nitrogen. The tanks are located on different sides of the RIM machine: the tank on the A side is the one to which the activator was later added and the tank on the B side is the one to which the catalyst was later added.

A mixture of 90% DCPD and 10% DMHN, containing 6% by weight of Stereon 720 styrene-butadiene rubber, was added to both tanks. If desired, solid fillers such as milled glass fiber or Wollastonite can be added. Sufficient diethylaluminum chloride was transferred into the A tank so that the concentration was 0.048 M and sufficient di-n-butyl ether was added so that the ether to aluminum ratio was 1.5:1. Next, sufficient tungsten catalyst solution was added to the B side tank to bring the concentration of catalyst to 0.0071 M. All transfers were done and all materials were handled in a way to preclude the entrance of oxygen or moisture into the system. The materials were then thoroughly blended in their respective tanks.

The mixing of the A stream and the B stream was accomplished using a standard impingement type RIM mixhead. The ratio of the activator/monomer solution mixed with the catalyst/monomer solution was 1:1. The impingement mixing was accomplished by passing both the solutions through orifices 0.032" in diameter at a flow rate approximately 80 ml/sec. This required pumping pressures of approximately 1000 psi.

The resulting mixture flows directly into a mold heated to between 50° and 60°C The mold has a flat cavity that forms a plaque sample 10"×10"×1/8" thick. The mold was opened and the finished plaque was removed approximately 10 to 30 seconds after the mold was filled. In Example 10, the procedure outlined above was followed to give plaques that could be removed from the mold in 15 seconds. In Example 11, 1/16" milled glass fiber was added to the monomer solutions so that the samples contained 20% glass. These samples were made by initially slurrying the glass into both the catalyst/monomer and the activator/monomer solutions. The physical properties for these samples are shown in Table 13.

TABLE 13
______________________________________
Example 10
Example 11
______________________________________
% Glass Filler     0         20
Flex Modulus (kpsi)
23°C      224       421
100°C     66        187
Flex Strength (kpsi)
23°C      9.6       10.7
100°C     1.4       2.0
Plate Impact Energy (ft-lb)
23°C      8.4       9.1
-29°C     3.8       9.0
______________________________________

Copolymers of DCPD and TTD

PAC EXAMPLE 46

The procedure of Example 9 is followed except that TTD is used as the comonomer with DCPD. A solid infusible polymer mass was obtained. The % insoluble gel, % swell in toluene and Tg, as determined by dynamic mechanical analysis, for these copolymer samples are shown Table 14.

TABLE 14
______________________________________
wt % [DMHN] TTD
% Gel       % Swell  Tg
______________________________________
5             99          108
10            99          103
20            98          94       145
______________________________________

Copolymers of DCPD with Ester-Containing Monomers

PAC EXAMPLES 47-51

An aluminum alkyl activator solution is prepared by diluting 2.00 ml (0.00376 moles) of a 1.88 M solution of diethylaluminum chloride (DEAC) with 8.00 ml of distilled toluene. The procedure of Example 9 is followed except that the above aluminum alkyl activator solution is used and no di-n-butyl ether is added to the monomers. In addition, the solution of monomers is heated to 60°C immediately upon addition of the tungsten catalyst solution by placing the tube in a 60°C heating bath. The comonomer, % comonomer, % insoluble gel, % swell in toluene and Tg, as determined by dynamic mechanical analysis, for the copolymers are given in Table 15.

TABLE 15
______________________________________
%
Example
Comonomer  Comonomer  % Gel % Swell
Tg
______________________________________
47     TPNC       5          95    93     158
10         94    63
20         94    58     165
48     ENC        5          95    95
10         94    85
20         92    71     153
49     EMNC       5          93    107
10         94    89
20         94    79
50     BMNC       5          97    94
10         97    90
20         95    81     138
51     HMNA       5          98    100
10         98    87
20         94    76     122
______________________________________

Copolymers of DCPD with DMON

PAC EXAMPLE 52

The procedure of Example 43 is followed except that DMON is used as the comonomer with DCPD in place of DMHN. A solid infusible polymer mass is obtained in all cases. Table 16 gives the % insoluble gel, % swell in toluene, and Tg, as determined by differential scanning calorimetry for these copolymer samples.

TABLE 16
______________________________________
% Comonomer
% Gel        % Swell  Tg
______________________________________
5          97           110
10         100          105      160
20         98           120      167
100        94           102      195
______________________________________

Other features, advantages and specific embodiments of this invention will become readily apparent to those exercising ordinary skill in the art after reading the foregoing disclosures. In this regard, while specific embodiments of this invention have been described in considerable detail, variations and modifications of these embodiments can be effected without departing from the spirit and scope of the invention as disclosed and claimed.

EXAMPLES 53-59

In Examples 53-59, substantially crosslinked dicyclopentadiene polymer and copolymer products are formed. The products are formed by mixing a catalyst solution and an activator solution to form a polymerization solution which polymerizes to form the polymer products as described in Table 17. The catalyst solution on a molar basis is tungsten catalyst in monomer. The tungsten catalyst is made as follows: t-butanol is stirred with 20 grams of WCl₆ in 70 ml of dry toluene under N₂ atmosphere in a t-butanol to WCl₆ molar ratio of 0.50 to form a 0.841 M catalyst solution of WCl₆ and WOCl₄. The molar ratio of WCl₆ to WOCl₄ formed is about 3 to 1. 11.1 grams of nonyl phenol in 30 ml of toluene is then added. 10.1 grams of 2,4-pentanedione is then added by syringe. This solution is then sparged 18 hours with N₂ to remove HCl. 10 ml of monomer is then added to 0.30 ml of the catalyst solution. The monomer and catalyst soluiton is then warmed at 35° C. for 24 hours while sparging with nitrogen to evaporate the toluene and phenol to form a substantially solvent free monomer solution of catalyst. The activator solution is prepared by combining under N₂ 8.6 ml of monomer and 0.39 ml of 1.0 M tri-n-octylaluminum in monomer.

In Examples 53-59, the activator solution also includes 0.1 ml of bis-(2-methoxyethyl) ether. The exotherm of polymerization occurs in about 15 to 25 seconds after mixing 5.0 ml the catalyst in monomer solution to 5.0 ml of the activator in monomer solution. Both solutions are initially at 25°C They are intimately mixed in the mixed and the mixture injected into a mold.

In Examples 53 and 56 flame retardant is added to the catalyst solution prior to mixing with the activator solution. In Examples 55, 58 and 59 milled glass is added to the activator solution prior to mixing with the catalyst solution. In Examples 56-59 elastomer is added equally to both the catalyst solution and the activator solution prior to mixing.

TABLE 17
__________________________________________________________________________
Example              53   54   55   56   57   58   59
__________________________________________________________________________
Activator to Catalyst ration
3.0  3.0  3.0  3.0  3.0  3.0  3.0
Monomer weight %
DCPD                 100  80   80   95   95   95   95
DMHN                 --   20   20   5    5    5    5
Additive             32   --   --   32   --   --   --
parts flame
retardant
N,N'-ethylene-bis-tetrabromophthalimide/Sb2 O3 /
NH4 BH4) per 100 parts
monomer (by weight)
Weight % residual monomer
0.1  0.3  0.04 0.4  0.4  0.05 0.05
Tg °C.        140  196  198  175  175  175  175
Weight % swell       100  40   38   60   60   60   60
Weight % gell        98   93   99.9 89.5 89.5 89.9 89.9
Flexural modulus (psi)
380,000
300,000
576,000
385,000
245,000
526,000
546,000
Notched Izod         2.1  2.0  2.3  10.5 8.8  10.2 8.9
impact strength
(ft-lb/inch notch)
Filler               --   --   33   --   --   33   33
weight % 1/8inch
milled glass
Elastomer styrene-butadiene
weight % butyl rubber
--   --   --   6    --   6    --
weight %             --   --   --   --   10   --   10
weight % saturated styrene
weight % butadiene-styrene
weight % triblock rubber
__________________________________________________________________________

Rate Moderation By Use of Polar Monomer

PAC EXAMPLE 60

Synthesis of 2-Hydroxymethyl-5-Norbornene Acetate

Into a solution of 99.2 g of 2-hydroxymethyl-5-norbornene and 50 ml of chloroform is added dropwise a solution of 84.0 g of acetic anhydride in 100 ml of chloroform. This mixture is allowed to stir overnight at room temperature, followed by heating at reflux for three hours. The cooled reaction mixture is poured into water and stirred to hydrolyze unreacted acetic anhydride. The layers are separated, the organic phase is diluted with an equal volume of hexane, and the mixture repeatedly washed with water to remove most of the pyridine. A final wash with dilute HCl solution, saturated sodium bicarbonate solution and saturated sodium chloride solution removes pyridine, acetic acid and water from the organic phase. Drying over anhydrous magnesium sulfate and removal of the solvent on a rotory evaporator affords 137 g of crude product as a faintly yellow, pleasant smelling oil. This is diluted with 2 volumes of hexane and passed through a 300 g column of neutral alumina, followed by continued hexane elution (1) until "no more" material was found in the effluent. Distillation of the hexane and vacuum distillation of the residue (55°C, 0.8 mm) provides 103.1g (84%) of the acetate as a clear, colorless oil of characteristic fruity odor; ir: 3139, 3061, 2965, 2868, 1741, 1361, 1235, 1028, 714 cm-1 ; 60 MHZ NMR (CDCl₃) 2.02 (H₃ CCO₂ --),

EXAMPLE 61

PAC Synthesis of 2-Hydroxymethyl-5-Norbornene Adipate

Into a solution consisting of 62.0 g of the 5-hydroxymethyl-2-norbornene and 100 ml of pyridine under N₂ cooled to 0°C is added dropwise a solution of 45.7 g (36.4 ml) of distilled adipoyl chloride (107°C/2 mm) in 200 ml of chloroform. The ice bath is removed after addition was completed, and the mixture stirred overnight at room temperature. The reaction mixture is diluted with 2 volumes of hexane and repeatedly washed with dilute aq. HCl solution to remove the pyridine. This is followed by saturated sodium bicarbonate washes, saturated NaCl solution, and drying over anhydrous magnesium sulfate. Removal of the solvent gives 95.53 g (104%) of crude product as a pleasant smelling yellow oil. The crude product is distilled under vacuum (206°/0.4 mm) to give 93.82 g (82%) of product as a nearly colorless and odorless oil. Dilution of this material with 2 volumes of hexane and elution through 250 g of neutral alumina, continued elution with hexane and solvent stripping at reduced pressure finally gave a water white product in 75% yield; ir: 3120, 3061, 2965, 2870, 1735, 1170, 714 cm-1.

EXAMPLE 62

PAC Synthesis of Methyl 5-Norbornene-2-Carboxylate

In 100 ml of anhydrous ether at 0°C is mixed 30 ml of cyclopentadiene and 32 ml of methyl acrylate. The ice bath is removed and the mixture allowed to stir overnight. The solvent, unreacted methyl acrylate, and cyclopentadiene are removed at ambient temperature at reduced pressure; as less material distilled out of the mixture the pressure is gradually reduced to 0.5 mm. The desired epimeric mixture of methyl carboxylates is distilled at 42°-43° and 0.5 mm; ir: 3118, 3060, 2965, 2941, 2862, 1734, 1428, 1329, 1264, 1190, 1024, 704, cm-1 ; 60 MHz NMR: endo/exo=80/20.

The rate of cycloolefin polymerization can be adjusted by use of polar monomers such as norbornene esters. Copolymers of DCPD and norbornene esters are polymerized in from about one to two and one fourth minutes without the addition of a noncycloolefin rate moderator as shown in Examples 63-65 and Table 18. The copolymers have percent by weight gel of from about 88.7 to 99.2 as shown in Table 19.

EXAMPLES 63-65

PAC Catalyst Preparation

In an Argon-filled glove box, 3.96 g of WCl₆ is weighed into one 10 oz pop bottle and 19.80 g into another for preparation of 0.1M and 0.5M solutions, respectively. These bottles are then removed from the box and placed in a N₂ filled glove bag. Into one centrifuge bottle is weighed 2.00 g of nonylphenol (C₉ PhOH) and 10.00 g into another. The bottles are then filled with 100.0 ml of toluene (from Na/K), capped and sparged with N₂ for 30 minutes. The contents of the bottles are transferred via cannula under positive N₂ pressure into their respective WCl₆ bottles to form the 1:1 complexes followed by N₂ sparging overnight to remove evolved HCl. The contents of the 0.1M WCl₆ /C₉ PhOH bottle are distributed in 9 4" poly tubes (previously N₂ sparged) in a glove bag. The DEAC (Et₂ AlCl) solution is used as received (25% wt in toluene), or a known volume is transferred to a 4" poly tube (previously capped and sparged) and the calculated amount of n-Butyl ether added to form the 1:1.1 Al/Bu₂ O complex.

Copolymerization of DCPD and Functional Monomers

A typical procedure for copolymerization of DCPD and an ester comonomer is as follows: Six 1×13 cm test tubes are loaded with the indicated weight % of functional comonomer, a rubber septum was wired on, and the assembly sparged with N₂ for 10 minutes. Enough dicyclopentadiene is then added to bring the contents of the tubes to 5.0 g and sparging continued for 10 minutes. To each tube immediately prior to polymerization is added 0.03 ml of 1.84M DEAC in toluene, and the contents thoroughly mixed. A solution of 0.5M WCl₆ /C₉ PhOH in toluene (0.04 ml) is then added, the contents are mixed by multiple inversions (15 sec), a thermocouple probe (soldered into a 14 ga syringe needle) inserted through the top, and the tube placed in a 60°C oil bath to initiate polymerization. The times reported in the table are for reaching the oxotherm maximum from time of immersion in the oil bath; precision is within the ±10 sec envelope. A sample without catalyst will take 2 minutes to reach bath temperature from time of immersion.

Gel Swell Determinations on Comonomers

The general procedure used is as follows: A 5 g sample of copolymer is removed from its test tube (by breaking the glass) and carefully sliced into 1-2 mm thick sections across the cylindrical axis with a band saw. The burrs are removed, each slice weighed to the nearest milligram, and strung onto a stainless steel wire taking care to keep them in known sequence. This is done for each sample at a given comonomer feed. The wire is made into a closed loop and placed in 50 ml of toluene for each gram of copolymer. Whereas, in some cases, several loops of copolymer are placed in a single flask of toluene, only those of common functional monomer are ever placed together. These flasks are then heated to reflux for 16 hours (overnight) and cooled. Each loop is successively removed from the flask and placed in a small crystallizing dish of fresh tolune. The slices are removed, patted dry, and weighed individually, again taking care not to not to disturb their sequence or to tear the swollen samples. After weighing, they are restrung and placed in a forced draft (N₂) oven at 135°C for 16 hours (overnight). The samples are reweighed and their gel and swell values calculated.

Two samples are reacted under each set of comonomer composition. Each sample is then sliced into thin sections for gel/swell determinations.

TABLE 18
______________________________________
Copolymerization of Dicyclopentadiene
and Functional Monomer(a)
DCPD/        Time
CM      Tmax
tp Tmax
Example
Comonomer (CM)     (wt %)  (°C.)
(min)
______________________________________
63
##STR11##         95/5 95/5 90/10 90/10 80/20 80/20
201 190 206 202 198 198
1 3/4  1 1/4  1 1/2  1 1/2  1 1/2
1/2
64
##STR12##         95/5 95/5 90/10 90/10 80/20 80/20
203 204 205 206 197 205
1 1 1 1/2  1 1/2  2 1/4  2
65
##STR13##         95/5 95/5 90/10 90/10 80/20 80/20
199 199 204 201 203 206
1 1 1 1 1 1/4  1 1/4
Homopolymerization 100/0   194  3/4
of DCPD (Room Temper-
ature Initiation)
______________________________________
All polymerizations are run with the same concentration of catalysts,
calculated as 2000:1:2.75 Monomer:W:Al based on 5 g of DCPD. All reaction
are run in a 60°C oil bath except homopolymerization of DCPD
(last entry). Times recorded are from immersion of sample tube in the bat
to the maximum temperature of the exotherm. A tube with no catalyst
requires 2 minutes to reach bath temperature.

TABLE 19
______________________________________
Gel-Swell Values for Copolymers of DCPD
and Functional Monomers
DCPD/   Swell Gel
CM      (Weight
(Weight
Example
Comonomer (CM)     (wt %)  %)    %)
______________________________________
63
##STR14##         95/5 95/5 90/10 90/10 80/20 80/20
153 152 184 144 213 190
95.3 92.8 95.0 93.8 89.1 88.7
64
##STR15##         95/5 95/5 90/10 90/10 80/20 80/20
95 105 86 88 77 75
98.2 98.6 97.9 97.6 94.8 93.8
65
##STR16##         95/5 95/5 90/10 90/10 80/20 80/20
122 113 200 127 186 245
96.0 94.7 97.3 98.9 97.0 99.2
______________________________________

In Examples 66, 67, 71 and 73, the fluorinated alkyl methacrylate copolymer surfactant used is FC-740, manufactured by Minnesota Mining and Manufacturing Company.

EXAMPLE 66

The catalyst used is a 1:1 molar mixture of WCl₆ to WCl₄ O as prepared herein above. An aluminum alkyl activator solution that is 1.06 M in trioctylaluminum (TNOA), 0.19 M in diethylaluminum iodide (DEAI) and 1.25 M in methoxyethyl ether is prepared by dissolving 85.0 grams of methoxyethyl ether, 196.1 grams of TNOA, and 20.00 grams of diethylaluminum iodide (DEAI) in 157.3 ml of dicyclopentadiene. The molar ratio of TNOA to DEAI to methoxyethyl ether is then 0.85:0.15:1.00.

Examples 67 through 70 illustrate small scale examples where a cellular polymer of dicyclopentadiene monomer is formed using a mixture of diethylaluminum iodide and trioctylaluminum as catalyst activators where the dicyclopentadiene monomer also contains 6 weight percent styrene-butadiene rubber.

EXAMPLE 67

A catalyst and monomer solution is prepared by mixing under nitrogen 50 grams of DCPD that had previously had 3.0 grams of styrene-butadiene rubber dissolved in it with 3.8 ml of the 0.1 M catalyst solution, 2.5 grams of trichlorofluoromethane, and 0.50 grams of fluorinated alkyl methacrylate copolymer.

An activator and monomer solution is prepared by mixing under nitrogen 50.0 grams of DCPD that has 3.0 grams of styrene-butadiene rubber dissolved in it with 1.45 ml of 1.25 M aluminum alkyl activator solution, 2.5 grams of trichlorofluoromethane, and 0.50 grams of fluorinated alkyl methacrylate copolymer.

The catalyst and monomer and activator and monomer were then combined and mixed rapidly under nitrogen. The mixture was then poured rapidly into a vented mold and allowed to polymerize into a cellular polymer.

EXAMPLE 68

The procedure of Example 2 is followed except that ten per cent trichlorofluoromethane was used as the blowing agent, 0.5 percent fluorinated alkyl methacrylate copolymer surfactant was used and 1.16 ml of the aluminum alkyl activator is used to make up the activator and monomer solution.

EXAMPLE 69

The procedure of Example 2 was followed except that seven per cent trichlorofluoromethane was used as the blowing agent and 1.40 ml of aluminum alkyl activator solution is used to make up the activator and monomer solution.

EXAMPLE 70

The procedure of Example 2 was followed except that 1.51 ml of aluminum alkyl activator solution is used to make up the activator and monomer solution.

EXAMPLE 71

The procedure of Example 3 is used except that fifteen percent methylene chloride was used as the blowing agent and 1.06 ml of aluminum alkyl activator solution is used to make up the activator and monomer solution.

Table 20 shows the polymerization mixtures from which foam products are formed in Examples 66-71.

TABLE 20
__________________________________________________________________________
FOAM EXAMPLES
Examle 67
Example 68
Example 69
Example 70
Example 71
__________________________________________________________________________
DCPD (grams)    100   100   100   100   100
Tungsten catalyst mmol
.756  .756  .756  .756  .756
Diethylaluminum diodide (mmol)
.272  .218  .262  .280  .198
Trioctyl aluminum (mmol)
1.54  1.234 1.49  1.61  1.12
Methoxyethyl ether (mmol)
1.81  1.452 1.75  1.89  1.32
Blowing Agent   CFC13 CFC13 CFC13 CFC13 CH2Cl2
Weight per cent 5     10    7     5     15
Rubber (elastomer)
SBR   SBR   SBR   SBR   SBR
Weight per cent 6     6     6     6     6
Surfactant      FC-740
FC-740
FC-740
FC-740
FC-740
Weight per cent 1.0   0.5   1.0   1.0   0.5
Density (g/cc)  0.30  0.13  0.21  0.39  0.18
__________________________________________________________________________

EXAMPLE 72

This example illustrates a preferred embodiment of the synthesis of a cellular cross-linked polymerized dicyclopentadiene via reaction injection molding where the catalyst system is activated by a mixture of trioctylaluminum (TNOA) and diethylaluminum iodide (DEAI).

Into two tanks, which have previously been closed and inerted with nitrogen, having a capacity of two gallons each is charged DCPD containing 6% by weight of a random styrene-butadiene rubber. Sufficient WCl₆ /nonylphenol/acetylacetone catalyst, having a ratio of 1:1:2, in xylene is added to one of the tanks to provide a DCPD:tungsten catalyst ratio of 1000:1. Next, to the other tank is added sufficient trioctylaluminum:diethylaluminum iodide:methoxyethyl ether solution, having a molar ratio of 0.85:0.15:1.0 to provide a DCPD: aluminum ratio of 1000:2.4. Fluorinated alkyl methacrylate copolymer surfactant is added to each tank to achieve a concentration of 0.5 parts per hundred, based on the weight of DCPD. Methylene chloride is then added to each tank to achieve a concentration of 5.0 parts per hundred, based on the weight of DCPD. All transfers are done in a way to preclude the entrance of oxygen or moisture into the system. The materials are then thoroughly blended in their respective tanks.

The components of the two tanks are combined in a standard impingement type RIM mixhead. The ratio of the activator/monomer solution mixed with the catalyst and monomer solution is 1:1. The impingement mixing is accomplished by passing both of the solutions through orifices 0.032 inch in diameter at a flow rate of approximately 80 ml/sec. This requires pumping pressure of approximately 500 psi to 1000 psi.

The resulting mixture flows directly into a mold heated to between 35°C and 70°C The mold is made out of chrome plated aluminum. The mold has a flat cavity which forms a plaque sample 8 inch×8 inch×3/8 inch thick. The reactants polymerize rapidly in the closed mold, reaction being substantially complete in about one minute or less. The mold is opened and a cellular cross-linked poly DCPD is recovered having a density of 0.55 grams/cc.

EXAMPLE 73

A catalyst and monomer solution is prepared by mixing under nitrogen 400 grams of DCPD, 30.7 ml of 0.1 M tungsten catalyst solution, 2 grams of silica, and 57 grams of trichlorofluoromethane.

An activator and monomer solution is prepared by mixing under nitrogen 390 grams of DCPD, 39 grams of styrene-butadiene rubber, 5.49 ml of a 0.825 M solution of DEAC in DCPD, 15.5 ml of a 0.450 M solution of DEAI in DCPD, and 56 grams of trichlorofluoromethane.

171.4 grams of catalyst and monomer solution and 188.6 grams of activator and monomer solution were then combined and mixed under nitrogen and poured into a mold. After about one minute the mixture starts to polymerize and expand into a cellular cross-linked polymer. The final density of the foam is 0.034 grams/cc.

The silica used in Example 8 above is Cab-o-sil EH-5, manufactured by Cabot Corp.

EXAMPLE 74

A catalyst and monomer mixture is prepared by mixing under nitrogen 100 grams of DCPD, 10 grams of SDP-760 polyethylene powder (SDP-760 from Arco Chemical, 10 grams of methylene chloride, 0.50 grams of fluorinated alkyl methacrylate copolymer surfactant, and 7.56 ml of 0.1 M tungsten catalyst solution.

An activator and monomer solution is prepared by mixing under nitrogen 100 grams of DCPD, 10 grams of styrene-butadiene rubber, 10 grams of methylene chloride, 0.50 grams of fluorinated alkyl methacrylate copolymer surfactant, 2.8 ml of a 0.825 M solution of DEAC in DCPD, 0.53 ml of a 0.450 M solution of DEAI in DCPD, and 0.70 grams of butyl ether.

The activator and monomer solution and the catalyst and monomer mixture are mixed at 40°C and poured rapidly into a 3 inch×4 inch×9 inch mold at 45°C where the mixture polymerizes into a cellular polymer having a density of 0.13 grams/cc.

Examples 75 and 76 show preexotherm gelation of the monomer.

EXAMPLE 75

A 0.1 M solution of the tungsten catalyst having a 1:1 molar ratio of WCl₆ to WCl₄ O is used. Nonyl phenol (2.21 grams, 0.01 moles) dissolved in 100 ml of toluene, that has been distilled from Na/K alloy under nitrogen, is added, and the mixture is stirred for one hour while sparging with nitrogen. Acetylacetone (2.00 grams; 0.02 moles) is then added by syringe and the mixture is stirred overnite while sparging with nitrogen to remove HCl gas.

Polymerizations are conducted in a capped 10 ml vial that has been previously sparged with nitrogen. The vial cap has five small holes in it to accommodate a gas line for flushing with nitrogen, a tube for introducing the monomer mixture, thermocouple leads to measure the exotherm of the sample during the polymerization and the spindle of a digital Brookfield viscometer to measure the viscosity of the sample during the polymerization.

A catalyst/monomer solution is prepared by mixing under nitrogen 10.0 grams of DCPD and 0.76 ml of the 0.1 M catalyst solution. An activator/monomer solution is prepared by mixing under nitrogen 10.0 grams of DCPD, 0.63 M solution of diethylaluminum chloride in toluene, and 0.15 grams of butyl ether.

Polymerization of DCPD is accomplished by simultaneously syringing 4.0 ml each of catalyst/monomer solution and activator/monomer solution through a T-shaped tube which is connected to the sample vial. Mixing of the two solution is accomplished by impingement of the two streams upon each other in the T-shaped tube. After a brief induction period the viscosity of the monomer increased rapidly to greater than 100,000 centipoise. After an additional period of time a sharp exotherm is observed and a solid insoluble polymer was formed. The time that elapsed until gellation, the time until the exotherm, and the total exotherm are shown in Table II.

EXAMPLE 76

In this example the procedure of Example 75 is followed except that 0.20 ml of a 1.12 M solution of trioctylaluminum and methoxyethyl ether in DCPD was added in place of the diethylaluminum chloride and butyl ether to prepare the activator/monomer solution. A solid insoluble polymer is formed. The results are shown in Table 21.

Using the procedure of Examples 77-79 on intricate molds to form solid products.

EXAMPLE 77

This example illustrates delaying the gellation of the monomer by using a mixture of diethylaluminum chloride and diethylaluminum iodide.

The procedure of Example 75 is followed except that 0.57 ml of a 0.36 M solution of diethylaluminum chloride in toluene and 0.054 ml of a 0.42 M solution of diethylaluminum iodide in toluene are used in place of 0.63 ml of diethylaluminum chloride to prepare the activator/monomer solution. A solid insoluble polymer is obtained. The time until gellation, the time until oxotherm, and the exotherm of the sample are given in Table II.

EXAMPLE 78

This example illustrates delaying the gellation of the monomer by using a mixture of trioctylaluminum and diethylaluminum iodide.

The procedure of Example 75 is followed except that 0.47 ml of a solution that was 0.34 M is trioctylaluminum, 0.06 M in diethylaluminum iodide, and 0.40 M in methoxyethyl ether in DCPD was used in place of the diethylaluminum chloride and butyl ether to make up the activator/monomer solution. A solid insoluble polymer was obtained. The time until gellation, the time until exotherm, and the exotherm of the sample are given in Table 21.

TABLE 21
______________________________________
Example 75        76        77      78
______________________________________
DCPD    60.5 mmol 60.5 mmol 60.5 mmol
60.5 mmol
Tungsten
.0303 mmol
.0303 mmol
.0303 mmol
.0303 mmol
catalyst
Et2 AlCl
.0908 mmol          .0818 mmol
Octyl3 Al    .0908 mmol
Et2 AlI                .00909 mmol
.0113 mmol
Octyl2 AlI
Butyl   0.454 mmol          0.454 mmol
Ether
Methoxy-          .0908 mmol        .0756 mmol
ethyl ether
Gellation
10 sec    20 sec    29 sec  24 sec
time
Time until
48 sec    38 sec    30 sec  25 sec
exotherm
Exotherm
162°C
163°C
165°C
164°C
______________________________________

In Example 79, sufficient methoxyethyl ether is added so that the final methoxyethyl ether/aluminum ratio was 3/1. In each case, a solid insoluble cross-linked polymer is obtained. The times until gellation, the times until exotherm, and the exotherms of the samples are given in Table 22. In each case, a solid insoluble cross-linked polymer is obtained. The times until gellation, the times until exotherm, and the exotherms of the samples are given in Table 22.

EXAMPLE 79

In Example 79 the procedure of Example 75 is followed except that 0.54 ml of a solution that is 0.36 M in trioctylaluminum, 0.063 M in dioctylaluminum iodide, and 0.42 M in methoxyethyl ether in toluene is used in place of the diethylaluminum chloride and the butyl ether to make up the activator/monomer solution. A solid insoluble polymer is obtained. The time until gellation, the time until exotherm, and the exotherm of the sample are given in Table 22.

TABLE 22
______________________________________
Example 79
______________________________________
DCPD                  60.5 mmol
Tungsten catalyst     .0303 mmol
Et2 AlCl
Octyl3 Al        .0773 mmol
Et2 AlI
Octyl2 AlI       .0136 mmol
Butyl Ether
Methoxyethyl ether    .0909 mmol
Gellation time        24 sec
Time until exotherm   26 sec
Exotherm              156°C
______________________________________

The solid insoluble polymers formed in Examples 75-79 are substantially cross-linked having notched Izod impact strengths of at least 1.5 ft-lb/in notch; a flexural moduli of at least 150,000 psi at ambient temperature (about 70° F.); and a percent gel swell determined after the polymer is immersed in toluene for two hours at 100°C of less than about 200%.

Polymerization by the present invention may be carried out in any mold. For example, cyclic olefin monomer may be polymerized in accordance with the present invention by reaction injection molding, pour molding or spray molding.

The substantially cross-linked polymerized dicyclopentadiene of the present invention provides the beneficial flex creep properties. The weight percentage swelled in toluene is the amount of absorbed toluene as a percent by weight of the original substantially cross-linked polymerized dicyclopentadiene. The percent of flexural creep strain is the change in length of the substantially cross-linked polymerized dicyclopentadiene as a percentage of the original length of the sample tested.

The polymeric product of Example 77 has a percent gel swell of 110%. The number of monomer units between crosslinks in the polymeric product of Example 77 is about 10.

The polymeric composition of the present invention comprising substantially cross-linked polymerized units of dicyclopentadiene is preferably characterized as having a percent gel swell, determined after the polymer is immersed in toluene for two hours at 100°C, of from about 15 to about 200. More preferably, the polymeric composition of the invention is characterized as having a percent gel swell of from about 30 to about 180. Most preferably, the polymeric composition of the invention is characterized as having a percent gel swell of from about 50 to about 150.

The polymeric composition of the present invention comprising substantially cross-linked polymerized units of dicyclopentadiene is preferably characterized as having from about 1 to about 30 monomeric units between crosslinks. More preferably, the polymeric composition of the invention is characterized as having from about 2 to about 24 monomeric units between crosslinks. Most preferably, the polymeric composition of the invention is characterized as having from about 3 to about 16 monomeric units between crosslinks.

The product density may vary from about 1.2 g/ml with some filler to about 0.04 g/ml. The ultra low density foam product of the invention is novel at densities below 0.2 g/ml, for example, 0.18 g/ml and lower.

Preferably, in the substantially crosslinked polymer composition of the invention the average distance between cross-linking is preferably from about one to about 65 monomer units and more preferably from one monomer unit to about 20 monomer units. This range of crosslinking in the crosslinked polymer is characterized as having a gel swell determined after the crosslinked polymer is immersed in toluene for two hours at 100°C of from about 15% to about 200%. Also, this range of crosslinking in the crosslinked polymer is characterized as having a flexural creep strain of from about 0.3% to about 4.5% after 100 hours of exposure to a 2000 psi stress load at 150° F.

Other features, advantages and specific embodiments of this invention will become readily apparent to those exercising ordinary skill in the art after reading the foregoing disclosures. In this regard, while specific embodiments of this invention have been described in considerable detail, variations and modifications of these embodiments can be effected without departing from the spirit and scope of the invention as disclosed and claimed.

Claims

1. A substantially cross-linked copolymer product comprising polymerized units of dicyclopentadiene and a comonomer selected from the group consisting of

bis(2-hydroxymethyl-5-norbornene) adipate;

methyl-5-norbornene-2-carboxylate;

ethylene-bis-(5-norbornene-2-carboxylate);

2-hydroxymethyl-5-norbornene acetate; and

ethylene-bis-(2-methyl-5-norbornene-2-carboxylat e); and, said copolymer product having a glass transition temperature of at least 145°C, and a swell of less than about 245% in toluene after for 16 hours.

2. A method of rate moderated dicyclopentadiene polymerization comprising:

contacting dicyclopentadiene, cycloolefin comonomer, an aluminum containing alkylaluminum activator and a tungsten containing catalyst, to form a polymerization mixture, said mixture being 50% by weight or less of said cycloolefin, said cycloolefin being

bis(2-hydroxymethyl-5-norbornene) adipate;

methyl-5-norbornene-2-carboxylate;

ethylene-bis-(5-norbornene-2-carboxylate);

2-hydroxymethyl-5-norbornene acetate; or

ethylene-bis-(2-methyl-5-norbornene-2-carboxylate); and

polymerizing said polymerization mixture, said cycloolefin being present in a concentration effective to increase the time from said contacting to the maximum temperature of the exotherm of polymerization.

3. The composition of claim 1 wherein said glass transition temperature is at least 153°C4. The composition of claim 1 wherein said glass transition temperature is at least 160°C5. The composition of claim 1 wherein said glass transition temperature is at least 165°C6. The composition of claim 1 wherein said glass transition temperature is at least 175°C7. A substantially cross-linked copolymer product comprising polymerized units of dicyclopentadiene and a polar cycloolefin monomer, said cycloolefin being;

2-hydroxymethyl-5-norbornene adipate;

methy-5-norbornene-2-carboxylate;

2-hydroxymethyl-5-norbornene acetate;

ethylene-bis-(5-norbornene-2-carboxylate); or ethylene-bis-(2-methyl-5-norbornene-2-carboxylate) said copolymer product having a glass transition temperature of at least 145°C, and a swell of less than about 245% in toluene after reflex for 16 hours.8. The composition of claim 7 wherein said copolymer product composition has a glass transition temperature of at least 153° C.9. A solid, infusible, crosslinked copolymer, prepared by metathesis-catalyzed, ring-opening polymerization of a cycloolefin monomer having a norbornene group, in admixture with a comonomer selected from the group consisting of ethylene-bis-(5-norbornene-2-carboxylate), ethylene-bis-(2-methyl-5-norbornene-2-carboxylate), 1,4-butane-bis-(2-methyl-5-norbornene-2-carboxylate), bis-(2-hydroxymethyl-5-norbornene) adipate, trimethylolpropane-tris-(5-norbornene-2-carboxylate), and 1,4,5,8-dimethano-1,4,4a,5,8,8a-hexahydronaphthalene.10. The copolymer of claim 9, wherein the cycloolefin monomer is dicyclopentadiene and the amount of the comonomer is up to about 30% by weight.11. The copolymer of claim 9, wherein the cycloolefin monomer is dicyclopentadiene and the amount of the comonomer

is from about 1% to 30% by weight.12. The copolymer of claim 9, wherein the cycloolefin monomer is dicyclopentadiene and the amount of the comonomer is up to about 20% by weight.13. The copolymer of claim 9, wherein the cycloolefin monomer is dicyclopentadiene and the amount of the comonomer is from 5% to 20% by weight.14. The copolymer of claim 9, wherein the cycloolefin monomer is dicyclopentadiene and the amount of the comonomer is from about 10% to 20% by weight.15. The copolymer of claim 9, wherein the comonomer comprises

1,4,5,8-dimethano-1,4,4a,5,8,8a-hexahydronaphthalene.16. A solid, infusible, crosslinked copolymer, prepared by metathesis-catalyzed, ring-opening polymerization of a cycloolefin monomer having a norbornene group in admixture with a comonomer selected from the group consisting of ethylene-bis-(5-norbornene-2-carboxylate), ethylene-bis-(2-methyl-5-norbornene-2-carboxylate), 1,4-butane-bis-(2-methyl-5-norbornene-2-carboxylate), and

bis-(2-hydroxymethyl-5-norbornene) adipate.17. The copolymer of claim 16, wherein the cycloolefin monomer is dicyclopentadiene and the amount of the comonomer is up to about 30% by weight.18. The copolymer of claim 16, wherein the cycloolefin monomer is dicyclopentadiene and the amount of the metathesis polymerizable comonomer is from about 1% to 30% by weight.19. The copolymer of claim 16, wherein the cycloolefin monomer is dicyclopentadiene and the amount of the metathesis polymerizable comonomer is up to about 20% by weight.20. The copolymer of claim 16, wherein the cycloolefin monomer is dicyclopentadiene and the amount of the metathesis polymerizable comonomer is from about 5% to 20% by weight.21. The copolymer of claim 16, wherein the cyclolefin monomer is dicyclopentadiene and the amount of the metathesis polymerizable comonomer is from about 10% to 20% by weight.22. A process for preparing a solid, infusible crosslinked copolymer, the process comprising the step of polymerizing a cycloolefin monomer having a norbornene group, in the presence of a metathesis catalyst system and a comonomer selected from the group consisting of ethylene-bis-(5-norbornene-2-carboxylate), ethyelene-bis-(2-methyl-5-norbornene-2-carboxylate), 1,4-butane-bis-(2-methyl-5-norbornene-2-carboxylate), bis-(2-hydroxymethyl-5-norbornene adipate), trimethylolpropane-tris-(5-norbornene-2-carboxylate), and 1,4,5,8-dimethano-1,4,4a,5,8,8a-hexahydronaphthalene.23. The process of claim 22, wherein the cycloolefin monomer is dicyclopentadiene and the amount of the comonomer is up to about 30% by weight.24. The process of claim 22, wherein the cycloolefin monomer is dicyclopentadiene and the amount of the metathesis polymerizable comonomer is from about 1% to 30% by weight.25. The process of claim 22, wherein the cycloolefin monomer is dicyclopentadiene and the amount of the comonomer is up to about 20% by weight.26. The process of claim 22, wherein the cycloolefin monomer is dicyclopentadiene and the amount of the

comonomer is from about 5% to 20% by weight.27. The process of claim 22, wherein the cycloolefin monomer is dicyclopentadiene and the amount of the comonomer is from about 10% to 20% by weight.28. The process of claim 22, wherein the comonomer is 1,4,5,8-dimethano-1,4,4a,5,8,8a-hexahydronaphthalene.29. The process of claim 22, wherein the metathesis catalyst system comprises an activator selected from the group consisting of tetraalkyl tin compounds and trialkylaluminum compounds.30. A process for preparing a solid, infusible crosslinked copolymer, the process comprising the step of polymerizing a cycloolefin monomer having a norbornene group, in the presence of a metathesis catalyst system and a comonomer comprising a 1:1 Diels-Alder adduct of cyclopentadiene with 1,5-cyclooctadiene.31. A process for preparing a solid, infusible crosslinked copolymer, the process comprising the step of polymerizing a cycloolefin monomer having a norbornene group, in the presence of a metathesis catalyst system and a comonomer selected from the group consisting of ethylene-bis-(5-norbornene-2-carboxylate), ethylene-bis-(2-methyl-5-norbornene-2-carboxylate), 1,4-butane-bis-(2-methyl-5-norbornene-2-carboxylate), and bis-(2-hydroxymethyl-5-norbornene) adipate.32. The process of claim 31, wherein the cycloolefin monomer is dicyclopentadiene and the amount of the comonomer is up to about 30% by weight.33. The process of claim 31, wherein the cycloolefin monomer is dicyclopentadiene and the amount of the metathesis polymerizable comonomer is from about 1% to 30% by weight.34. The process of claim 31, wherein the cycloolefin monomer is dicyclopentadiene and the amount of the comonomer is up to about 20% by weight.35. The process of claim 31, wherein the cycloolefin monomer is dicyclopentadiene and the amount of the comonomer is from about 5% to 20% by weight.36. The process of claim 31, wherein the cycloolefin monomer is dicyclopentadiene and the amount of the comonomer is from about 10% to 20% by weight.37. A process for preparing a solid, infusible crosslinked copolymer comprising the step of polymerizing a cycloolefin monomer selected from the group consisting of: ##STR17## where R and R¹ are independently selected from hydrogen, alkyl groups of 1 to 20 carbon atoms, and saturated and unsaturated cyclic groups formed by R and R¹ together with the two ring carbon atoms connected thereto, and where R² and R³ are independently selected from hydrogen and alkyl groups containing 1 to 20 carbon atoms, in the presence of a metathesis catalyst system and a comonomer selected from the group consisting of ethylene-bis-(5-norbornene-2-carboxylate), ethylene-bis-(2-methyl-5-norbornene-2-carboxylate), 1,4-butane-bis-(2-methyl-5-norbornene-2-carboxylate), and

bis-(2-hydroxymethyl-5-norbornene) adipate.38. A process for preparing a solid, infusible, crosslinked copolymer comprising the step of polymerizing a cycloolefin monomer selected from the group consisting of: ##STR18## where R and R¹ are independently selected from hydrogen, alkyl groups of 1 to 20 carbon atoms, and saturated and unsaturated cyclic groups formed by R and R¹ together with the two ring carbon atoms connected thereto, and where R² and R³ are independently selected from hydrogen and alkyl groups containing 1 to 20 carbon atoms, in the presence of a metathesis catalyst system and a comonomer selected from the group consisting of 1,4,5,8-dimethano-1,4,4a,5,8,8a-hexahydronaphthalene, ethylene-bis-(5-norbornene-2-carboxylate), ethylene-bis-(2-methyl-5-norbornene-2-carboxylate), 1,4-butane-bis-(2-methyl-5-norbornene-2-carboxylate), and

bis-(2-hydroxymethyl-5-norbornene adipate).39. The process of claim 38, wherein the cycloolefin monomer is dicyclopentadiene.40. The process of claim 38, wherein the amount of comonomer is between about 1 and 25 weight percent, based on total weight of monomers.41. A solid, infusible, crosslinked copolymer, prepared by metathesis-catalyzed, ring-opening polymerization of a cycloolefin monomer selected from the group consisting of: ##STR19## where R and R¹ are independently selected from hydrogen, alkyl groups of 1 to 20 carbon atoms, and saturated and unsaturated cyclic groups formed by R and R¹ together with the two ring carbon atoms, and where R² and R³ are independently selected from hydrogen and alkyl groups containing 1 to 20 carbon atoms, in admixture with a comonomer selected from the group consisting of ethylene-bis-(5-norbornene-2-carboxylate), ethylene-bis-(2-methyl-5-norbornene-2-carboxylate), 1,4-butane-bis-(2-methyl-5-norbornene-2-carboxylate), bis-(2-hydroxymethyl-5-norbornene adipate), trimethylolpropane-tris-(5-norbornene-2-carboxylate), and

1,4,5,8-dimethano-1,4,4a,5,8,8a-hexahydronaphthalene.42. A solid, infusible, crosslinked copolymer, prepared by metathesis-catalyzed, ring-opening polymerization of a cycloolefin monomer selected from the group consisting of: ##STR20## where R and R¹ are independently selected from hydrogen, alkyl groups of 1 to 20 carbon atoms, and saturated and unsaturated cyclic groups formed by R and R¹ together with the two ring carbon atoms, and where R² and R³ are independently selected from hydrogen and alkyl groups containing 1 to 20 carbon atoms, in admixture with a comonomer selected from the group consisting of 1,4,5,8-dimethano-1,4,4a,5,8,8a-hexahydronaphthalene, ethylene-bis-(5-norbornene-2-carboxylate), ethylene-bis-(2-methyl-5-norbornene-2-carboxylate), 1,4-butane-bis-(2-methyl-5-norbornene-2-carboxylate), and

bis-(2-hydroxymethyl-5-norbornene) adipate.43. The copolymer of claim 42, wherein the cycloolefin monomer is dicyclopentadiene and the amount of comonomer is up to about 50 weight percent, based on the total weight of monomers.44. The copolymer of claim 42, wherein the cycloolefin monomer is dicyclopentadiene.45. The copolymer of claim 42, wherein the cycloolefin monomer is dicyclopentadiene and the amount of comonomer is from about 1 to 25 weight percent, based on total weight of

monomers.46. A process for increasing the glass transition temperature of polymerized dicyclopentadiene by producing a crosslinked copolymer, comprising polymerizing a monomer charge comprising dicyclopentadiene in the presence of a metathesis catalyst system and metathesis polymerizable comonomer selected from the group consisting of ethylene-bis-(5-norbornene-2-carboxylate), ethylene-bis-(2-methyl-5-norbornene-2-carboxylate), trimethylolpropane-tris-(5-norbornene-2-carboxylate), and 1,4,5,8-dimethano-1,4,4a,5,8,8a-hexahydronaphthalene.47. A process for preparing a crosslinked polymer, the process comprising polymerizing dicyclopentadiene in the presence of a metathesis catalyst system and a comonomer selected from the group consisting of ethylene-bis-(5-norbornene-2-carboxylate), ethylene-bis-(2-methyl-5-norbornene-2-carboxylate), 1,4-butane-bis-(2-methyl-5-norbornen-2-carboxylate), bis-(2-hydroxymethyl-5-norbornene adipate), trimethylolpropane-tris-(5-norbornene-2-carboxylate), and 1,4,5,8-dimethano-1,4,4a,5,8,8a-hexahydronaphthalene.48. The process of claim 47, wherein the crosslinked polymer has a percent swell, determined after the polymer is immersed in toluene for two hours at 100°C, of less than about 200.49. The process of claim 48, wherein the crosslinked polymer has a percent swell of less than 150.50. The process of claim 49, wherein the crosslinked polymer has a percent swell of less than

100. The process of claim 47, wherein the comonomer is present in an amount of from about 1 to 25 percent, based on total weight of monomers.52. The process of claim 47, wherein the comonomer comprises etheylene-bis-(5-norbornene-2-carboxylate).53. The process of claim 47, wherein the comonomer comprises ethylene-bis-(2-methyl-5-norbornene-2-carboxylate).54. The process of claim 47, wherein the comonomer comprises 1,4-butane-bis-(2-methyl-5-norbornene-2-carboxyalte).55. The process of claim 47, wherein the comonomer comprises bis-(2-hydroxymethyl-5-norbornene adipate).56. The process of claim 47, wherein the comonomer comprises trimethylolpropane-tris-(5-norbornene-2-carboxylate).57. The process of claim 47, wherein the comonomer comprises

dimethanohexahydronaphthalene.58. The copolymer of claim 9, wherein said polymerization is in the presence of (a) a catalyst that is a tungsten compound and (b) an activator selected from the group consisting of tetraalkyl tin compounds and alkylaluminum compounds; and wherein said cycloolefin monomer is selected from the following monomers: ##STR21## where R and R¹ are independently selected from hydrogen, alkyl groups of 1 to 20 carbon atoms, and saturated and unsaturated cyclic groups formed by R and R¹ and the two ring carbon atoms connected thereto, and where R² and R³ are independently selected from hydrogen and

alkyl groups containing 1 to 20 carbon atoms.59. The copolymer of claim 58, wherein the activator comprises at least one member selected from the group consisting of a tetraalkyl tin compound and a

trialkylaluminum compound.60. A solid, infusible, crosslinked copolymer, prepared by metathesis-catalyzed, ring-opening polymerization of a cyclolefin monomer having a norbornene group in admixture with a comonomer comprising a 1:1 Diels-Alder adduct of cyclopentadiene with 1,5-cyclooctadiene.61. The process of claim 22, wherein said metathesis catalyst system includes a catalyst and an activator, said catalyst being a tungsten compound and said activator being selected from the group consisting of tetraalkyl tin compounds and alkylaluminum compounds; wherein said cycloolefin monomer is selected from the following monomers: ##STR22## where R and R¹ are independently selected from hydrogen, alkyl groups of 1 to 20 carbon atoms, and saturated and unsaturated cyclic groups formed by R and R¹ and the two ring carbon atoms, and R² and R³ are independently selected from hydrogen and alkyl groups

containing 1 to 20 carbon atoms.62. A solid, infusible, crosslinked copolymer, prepared by metathesis-catalyzed, ring-opening polymerization of a monomer charge comprising a cycloolefin monomer having a norbornene group in admixture with a comonomer selected from the group consisting of ethylene-bis-(5-norbornene-2-carboxylate), ethylene-bis-(2-methyl-5-norbornene-2-carboxylate), 1,4-butane-bis-(2-methyl-5-norbornene-2-carboxylate), bis-(2-hydroxymethyl-5-norbornene adipate), trimethylolpropane-tris-(5-norbornene-2-carboxylate), and 1,4,5,8-dimethano-1,4,4a,5,8,8a-hexahydronaphthalene; wherein said polymerization is in the presence of (a) a catalyst that is a tungsten compound and (b) an activator comprising at least one member selected from the group consisting of tetraalkltin compounds and trialkylaluminum compounds.63. The copolymer of claim 62, wherein the cyclolefin monomer is dicyclopentadiene and the amount of the comonomer is up to about 30% by weight.64. The copolymer of claim 62, wherein the cycloolefin monomer is dicyclopentadiene and the amount of the comonomer is from about 1% to 30% by weight.65. The copolymer of claim 62, wherein the cycloolefin monomer is dicyclopentadiene and the amount of the comonomer is up to about 20% by weight.66. The copolymer of claim 62, wherein the cycloolefin monomer is dicyclopentadiene and the amount of the comonomer

is from about 5% to 20% by weight.67. The copolymer of claim 62, wherein the cycloolefin monomer is dicyclopentadiene and the amount of the comonomer is from about 10% to 20% by weight.