CA1315912C

CA1315912C - Metathesis polymerized terpolymers

Info

Publication number: CA1315912C
Application number: CA000586288A
Authority: CA
Inventors: Douglas R. Leach
Original assignee: Hercules LLC
Current assignee: Hercules LLC
Priority date: 1987-12-24
Filing date: 1988-12-19
Publication date: 1993-04-06
Anticipated expiration: 2010-04-06
Also published as: KR890010006A; BR8806866A; AU608398B2; EP0324965A3; EP0324965A2; AU2755588A; JPH01203425A

Abstract

0765p(FF) Leach Case 5 Metathesis Polymerized Terpolymers Abstract of Disclosure This invention teaches the preparation of crosslinked terpolymers of dicyclopentadiene, tricyclopentadiene and tetracyclododecene or alkyl/alkylene derivatives of tetra-cyclododecene, which have significantly higher glass transi-tion temperatures than that of dicyclopentadiene homopoly-mers, and which concomitantly exhibit significantly improved values of impact resistance over that known for copolymers of dicyclopentadiene.

Description

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It is known that a high modulus, high impact resistant thermoset homopolymer of poly(dicyclopentadiene) ~PDCPD) can be prepared from ring-opening polymerization of dicyclopenta-diene in the presence of a metathesis catalyst. Such a pro-cess is described, for example, in U.SO Patent No. 4,400,340(Klosiewicz). The polymer has limited use in many applica-tions, however, due to its relatively low glass transition temperature (Tg) of approximately 120C. ~hus, the maximum use temperature of the polymer is limited to about 80 to 90C, since the polymer begins to soften at temperatures above this range.
It has been proposed to overcome such a shortcoming by copolymerizing dicyclopen~adiene (DCPD) with other strained-ring cycloolefins in the presence of a metathesis catalyst.
For example, U.S. Patent No. 4,689,380 (Nahm) teaches that copolymers:can be prepared from ring-opening metathesis cata-lyst copolymerization of DCPD with norbornene-type comonomers such as tetracyclododecene (1,4,5,8-dimethano-1,4,4a,5,8,8a-octahydronaphthalene (DM0~)). Copolymers prepared in such a process are reported to have significantly higher values of Tg and heat distortion temperature (HDT) relative to PDCPD, : therein providing polymers with a higher maximum use tempera-ture and greatly increased scope of products manufactured therefrom. It is also taught in U.S. Patent ~o. 4,703,098 : 25 (Matlack) ~hat copolymers prepared from ring-opening metathe-:sis catalyst copolymerization of DCPD with dicyclopentadiene , ' ~
-, . , .
. .

- 2 _ oligomers, for example, tricyclopentadiene and higher oligo-mers, result in products with significantly higher Tg and HDT
values relative to PDCP~.
It is believed that by copolymerizing dicyclopentadiene with such comonomers an increase in Tg and ~DT i5 caused by decreased mobility of the polymer chains due to the presence of longer, more rigid norbornene-type monomer and oligomer molecules relative to dicyclopentadiene. ~t is for this same reason, however, that the impact resistance of polymers pre-pared by s~ch processes is significantly reduced compared tothat of dicyclopentadiene homopolymer. Thus, a major short-coming of polymers prepared as such is that a gain in Tg and ~DT values is typically accompanied by correspondingly re-duced values of impact resistance resulting in brittle poly-mers of limited utility.
It is, therefore, an object of this invention to providepolymers comprising dicyclopentadiene which exhibit signifi-cantly improved values of Tg and HDT over that heretofore known in the art for dicyclopentadiene homopolymer, and which concomitantly exhibit significantly improved values of impact resistance over that known for copolymers of dicyclopenta-diene.
In accordance with the instant invention, it has now been found that crosslinked terpolymers of dicyclopentadiene with tricyclopentadiene and tetracyclododecene or derivatives thereof can be prepared which have the above-mentioned desir-able properties of significantly increased Tg and HDT, relative to dicyclopentadiene homopolymer, an* significantly improved values of impact resistance, relative to that ex-hibited by copolymers comprising dicyclopentadiene. Theterpolymers, according to this invention, comprise from about 20 to about 80% by weight, based on total terpolymer weight~
o~ repeating units derived from dicyclopentadiene, from about lO to about 50% by weight of repeating units derived from :
: .

~ 3 ~ 59 ~

tricyclopentadiene, and from about 10 to about 50~ by weight of repeating units derived from tetracyclododecene or deriva-tives of tetracyclododecene, having the general formula:

wherein Rl-R2 denote the same or different hydrogen atoms or lower alXyl and alkylene groups having from 1 to 10 carbon atoms. Preferred terpolymers aré those having from about 20 to about 80~ by weight dicyclopentadiene, from about 10 to about 40~ by weight tricyclopentadiene, and from about 10 to about 40% by weight tetracyclododecene or tetracyclododecene derivative. Most preferred are those terpolymers having from about 45 to abou~ 70% by weight dicyclopentadiene, from about 20 to about 35% by weight tricyclopentadiene, and from about 10 to about 30% by weight tetracyclododecene. The terpoly-mers, according to this invention, can be prepared by sub-stantially any technique known in the art for the preparation of dicyclopentadiene homopolymers. Thus, the reaction is carried out under the influence of a tungsten or molybdenum catalyst compound activated via an alkyl aluminum compound~
A preferred method for carrying out the terpolymeriza-tion is taught, for example, in U.S. Patent ~o. 4,400,340 (Klosiewicz). In such a process, known as reaction injection molding (RIM), a plurality of reactive liquid streams, usual-ly two or three streams, comprising a metathe~is catalyst 25~ system are mixed together, the combined streams then being ~injected into a mold where they quickly set up into a solid polymerized mass. One of these streams contains a metathesis catalyst component, preferably a tungsten halide or tungsten oxyhalide complex dissolved in a non-poIymerized three-part comonomer mixture of dicyclopentadiene-tricyclopentadiene-` .
.

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-.' : , ' ~ - :' ' ' ~ ,', :

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tetracyclododecene/tetracyClododecene derivative. Another stream contains the alkylaluminum activator compound, pre-ferably comprising an alkylaluminum iodide, and a reaction rate moderator to delay catalyst activation clissolved in the three part comonomer mixture. The streams are mixed and immediately injected into a mold of the desired shape where the terpolymerization reaction takes place. The reaction rate moderator delays the onset of the reaction for the time required to transfer the entire mix into the mold, following which reaction is substantially completed with about one-half minute or less.
Dicyclopentadiene comonomer useful in this invention can be obtained commercially from any convenient source. If desired, such commercially obtained dicyclopentadiene can be further purified to prevent impurities from inhibiting the terpolymerization reaction. Such a purification method is described, for example, in U.S. Patent No. 4,568,660 (Klosiewicz~.
~ mixture of dicyclopentadiene and tricyclopentadiene (sometimes referred to as cyclopentadiene trimer) can be conveniently and inexpensively prepared in situ. In such a process, described, for example, in U.S. Patent ~o. 4,703,098 (Matlack), a mixture comprising the desired proportions of dicyclopentadiene and tricyclopentadiene and higher oligomers of dicyclopentadiene, for example, tetra-oligomers, can be prepared by heating dicyclopentadiene under proper condi-tions. For purposes of this invention, it is not necessary to effect any separation of higher oligomers from the mix-ture, however, it is preferred that tricyclopentadiene comprise the predominant portion of the higher oligomers present in the mixture. Thu~, an oligomeric mixture com-prising at least 85~ tricyclopentadiene with a small amount of the tetra-oligomer and negligible amounts of higher oligomers is preferred, with 90% tricyclopentadiene most preferred.
Tricyclopentadiene prepared as described above usually exists in both symmetrical and unsymmetrical isomeric forms having the following respective structural formulas 2~ and 3):

2) 3) ( ~ 3 As can be seen from the above formulas, a major differ-ence between the two isomers is that the symmetrical version contains two terminal norbornene-type unsaturated moieties, whereas the unsymmetrical version contains one terminal norbornene-type unsaturated moiety and a cyclopentene-type unsaturated moiety. For purposes of this invention, however, it is not necessary to effect separation of the two isomers, as both are equally useful in the preparation of the cross-linked terpolymers of this invention. Thus, both the - terminal norbornene-type and cyclopentene-type unsaturated moieties present in the unsymmetrical comonomer isomer of formula 3) can undergo ring-opening metathesis catalyst co-polymerization with the norbornene-type unsaturated moieties present in both the dicyclopentadiene and tetracyclododecene comonomers as well as with the cyclopentene-type unsaturated moiety also present in the dicyclopentadien~ comonomer to form the crosslinked terpolymers of the present invention.

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- 6 - 1~ 2 Further, it is not critical in any way to the instant invention that tricyclopentadiene be provided via a dicyclo-pentadiene-tricyclopentadiene oligomeric mixture prepared by heat treatment in situ as described above. Should a source of isolated tricyclopentadiene comonomer, symmetrical or un-symmetrical isomers or a mixture of both, be available, such comonomer can be blended into a mixture with dicyclopenta-diene, or with dicyclopentadiene and tetracyclododecene (or tetracyclododecene derivative) to -form the three-part comono-mer mixture; the order of addition of comonomers to the mix-ture is not critical in any way to the preparation of the terpolymers of this invention.
Tetracyclododecene comonomer (or 1,4,5,8-dimethano-1,4,4a,5,8,8a-octahydronaphthalene, sometimes referred to as DMOM) useful in this invention can be prepared by any suit-able method known in the art, for example, such as described in U.S. Patent ~os. 4,568,660 (Klosiewicz) and 4,320,239 (Schneider). In such processes norbornene is reacted with cyclopentadiene to produce tetracyclododecene which can be further purified by distillatlon. Tetracyclododecene derivatives useful in this invention can be prepared, as further described in U.S. Patent No. 4,320,239, by reacting a cyclopentadiene with a norbornene derivative, for example, a monoalkyl, monoalkylene, dialkyl, dialkylene, or monoalkyl-monoalkylene norbornene derivative. As previously stated,the preparation of all such tetracyclododecene comonomers is well known and will be readily apparent to those skilled in the artO
The significant improvement in the terpolymers of this invention is the improved glass transltion temperature (Tg) and heat distortion temperature (HDT) of such terpolymers compared to that of cyclopentadiene homopolymer, while concomitantly maintaining significantly improved values of ^ :~
_ 7 _ ~3~5~

impact resistance relative to that of copolymers of dicyclo-pentadiene heretofore known in the art. Dicyclopentadiene homopolymer exhibits a Tg value on the order of about 120C, and HDT of about 90C, and a notched izod impact strength of about 9 ft./lbs/in.. Copolymers prepared from dicyclo-pentadiene with either tetracyclododecene or tricyclopenta-diene, as taught, for example, in U.S. Patent Nos. 4,68g,380 (Nahm) and 4,703,098 (Matlack), respectively, exhibit in-creased Tg values of from about 130C to about 165C and HDT's of from about 90C to 140C. However, the impact strength of such copolymers correspondingly decreases, relative to the homopolymer, to the order of from about 1-8 ft./lbs./in. to about 2-4 ft./lb./in. In comparison, cross-linked terpolymers of this invention exhibit Tg values of from about 1~5C to about 170C and HDT values of from about 115C to 13~C while simultaneously maintaining notched izod impact strength within the range of from about 2-4 ft./lb/in.
to about 3-5 ft/lb/in.
Other compounds known in the art to improve impact strength of polymers comprising dicyclopentadiene repeating units can, of course, be incorporated into the terpolymers of the present invention. For example, a hydrocarbon elastomer such as butyl rubber, polyisoprene, polybutadiene, polyiso-butylene, styrene-butadiene block and random rubbers, ethylene-propylene copolymers, ethylene-propylene-diene terpolymers, styrene-butadiene-random copolymer rubber and the like can be formulated with the three-part comonomer mixture prior to terpolymerization. Such elastomers can comprise from about 3% to about 10% by weight, based on the total terpolymer weight. The amount of elastomer used is determined by its molecular weight and is limited by the maximum viscosity tolerable in the resultant reactive streams. The viscosity must not be so high as to interfere with rapi~ mi~ing of the reactive streams. The elastomer can 8 1 ~ 2 be added to one or all of the reactive streams, but is preferably dissolved in all streams since mixing of the streams takes place most readily when all have essentially the same viscosity.
~einforcement of the instant terpolymers to increase their impact resistance relative to dicyclopentadiene homopolymer can also be accomplished by addition of fibrous reinforcing materials. Preferred reinforcement materials include organic or inorganic fibrous materials, in particular glass. ~he fiber can be either chopped as a staple fiber or in a continuous mat form. It is sometimes preferred to use a low viscosity reaction stream which can readily flow around and in among the ~i~ers. For this reason, elastomer is fr~-quently not included in the reactant streams in the fiber-filled embodiment.
The following examples more fully illustrate preferred embodim~nts of the instant invention. It is not intended, however, that this invention be limited in any way thereto.

Example 1 Pre aration of Catalvst and Activator P ~
~ 0.5 molar solution of tungsten catalyst is prepared by weighing, under nitrogen, 19.80 g (0.05 moles~ of WCl~ into a 200 ml pop bottle containing a stirring bar. The tungsten is then slurried in 90 ml toluene that has been previously distilled from a sodium/potassium alloy under nitrogen.
Tert-butanol (0.925 g, 0.0125 moles) dissoIved in 5 ml toluene is added, and the mixture stirred for one hour while sparging with nitrogen. Nonylphenol (11.05 g, 0~05 moles) dissolved in 5 ml toluene is next added, and the mixture stirred for one hour while again sparging with nitrogen.
Acetylacetone (10.0 g, 0.100 moles) is then added by syringe and the mixture stirred overnight while further sparging with nitrogen to remove HCl gas. Toluene is then added to restore 9 ~ 2 the volume of the solution to its original level resulting in a 0.05 molar solution.
A 1.97 molar alkylaluminum activator solution is pre-pared by mixing tri-n-octylaluminum (155.8 g, 0.425 moles) and dic,ctylaluminum iodide (28.5 g, 0.0250 moles) in a capped and sparged pop bottle under nitrogen. Dimethoxyethyl ether (diglyme) (67.1 g, 0.500 moles~ is then added slowly by syringe to the alkyl mixture.

Examples 2 to 6 Terpolymerization Terpolymers of dicyclopentadiene, tricyclopentadiene and tetracyclododecene are prepared in accordance with the follow-ing procedure. Mixtures of comonomers are prepared according to the proportions indicated in Table 1 below in capped bottles that have been previously sparged with nitrogen.
Alkylaluminum activator (0.385 ml, 0.681 mm) is then added to 60 ml monomer mixture by syringe. After mixing the solution, 0.454 ml (0.227 mm) tungsten catalyst solution is added by syringe and the contents of the bottle shaken several times.
The contents of the bottle are then syringed into a flat, upright mold (5" x 5" x 1/8" thick) and the mold placed in an oven for 10 minutes at 60C to accelerate the terpolymeriza-tion reaction. The mold is then removed from the oven and a flat, hard plaque is removed therefrom for testing. Results ar~ reco~deo 1~ Table 1 below.

, - lo - 13~9~ ~

Examples I II III IV V ~JI
a) Terpolymer co~position Dicyclopentadiene (wt %)63 59 56 67 65 63 Tricyclopentadiene (wt ~) 27 26 24 25 23 21 Tetracyclododecene (wt ~) 10 15 20 8 12 16 b) Terpolymer properties HDT, C* 123 117 115 126 124 120 c) Mechanical properties Flex modulus (kpsi)344 364 325 338 350 355 Flex strength (kpsi) 14.0 15.415.8 14.2 14.8 15.1-Tensile modulus (kpsi) 275 272 280 252 25g 264 Tensile strength (kpsi) 7.9 8.1 8.1 7.7 7.8 8.2 *ASTM D-648.

1 3 1 ~

Examples 7 to 12 T r ol merization Via Reaction In ection Moldinq e ~ y The following examples describe preparation of preferred terpolymers of this invention by Reaction Injection Molding (RIM). Samples of such terpolymers are maae using a standard RIM machine supplied by the Accuratio Co., Jeffersonville, Indiana. The procedure for molding samples is as follows:
First, two monomer storage tanks attached to the machine (tanks A and B) are sparged with nitrogen. A mixture of comonomers and elastomer in proportions as indicated below in Table 2 is next added to each tank. If desired, solid fillers such as glass fiber or wollastonite can be added to each tank at this point. Alkylaluminum activator solution, as prepared in Example 1 above, is then added in sufficient amount to tank A such that the resulting concentration of activator is 0.0213 molar. ~ext, sufficient tungsten catalyst solution, as prepared in Example 1, is added to tank B such that the resulting concentration of catalyst is 0.0071 molar. All transfers of chemical reagents, catalyst, etc.
are done and all materials handlPd in a way to insure against oxygen or moisture contam nation of the system. The mixtures in tanks A and B are then thoroughly blended.
The mixing of streams from tanks A ahd B, respectively, is accomplished using a standard inpingement type RIM mixhead and by passing both streams through orifices 0.032 inches in diameter at a flow rate of approximately 80 ml/second at a pumping pressure of approximately 1,000 psi. The ratio of activator/comonomer solution mixed with the catalyst/comonomer solution is l:l. The resulting mixture of streams from tanks A and B flows directly into a mold heated to between 50 to 60C. Approximately lO to 30 seconds after the mold is filled, the terpolymerization reaction is completed. The mold is then opened and a plaque sample (10" x lO" x l/8") is removed ~or testing. Results are recorded in ~able 2 below.

,.,, ,,., ~, -, - 12 - ~31 Examples VII VIII IX X XI XII
a) Terpolymer composition Dicyclopentadiene (wt %) 65 5250.7 49 50.8 67 Tricyclopentadiene (wt %)20 25 25 28 20 30 Tetracyclododecene (wt %)12 20 20 20 25 EDPM (wt %)* 3 3 4-4 3 4~33 b) Terpolymer properties Tg, C 147 157 167172 158175 HDT, C** 119 124 120133 115133 c) Mechanical properties Flex modulus (kpsi)357 367 326330 341348 Flex strength (kpsi) 15.3 15.613.0 12 13.2 14 Tensile modulus (kpsi) 263 272260 245300 265 Tensile strength (kpsi)8.0 8.17.6 7.2 7.4 7.9 Tensile elongation (kpsi)26 24 29 52 60 22 Notched Izod Impact2.7 2~g 3.22.4 3.1 1.8 (ft.-lb./in.) Plate impact (ft.-lb.) - 16.112.8 11 8.3 *Ethylene-propylene-diene rubber.
**ASTM D-648.

.. . ..

Claims

1. A metathesis catalyst ring-opening copolymerizable composition comprising from about 20% to about 80% by weight, based on total terpolymer weight, or repeating units derived from dicyclopentadiene, from about 10% to about 50% by weight of repeating units derived from tricyclopentadiene, and from about 10% to about 50% by weight of repeating units derived from tetracyclododecens or derivatives of tetracyclododecene, having the general formula:

wherein R1-R2 denote the same or different hydrogen atoms or lower alkyl and alkylene groups having from 1 to 10 carbon atoms.

2. A crosslinked terpolymer comprising from about 20%
to about 80% by weight, based on total terpolymer weight, of repeating units derived from dicyclopentadiene, from about 10% to about 50% by weight of repeating units derived from tricyclopentadiene, and from about 10% to about 50% by weight of repeating units derived from tetracyclododecene or deriva-tives of tetracyclododecene, having the general formula:

wherein R1-R2 denote the same or different hydrogen atoms or lower alkyl and alkylene groups having from 1 to 10 carbon atoms.

3. A crosslinked terpolymer as claimed in claim 2 which comprises from about 20% to about 80% by weight of repeating units derived from dicyclopentadiene, from about 10% to about 40% by weight of repeating units derived from tricyclopentadiene, and from about 10% to about 40% by weight of repeating units derived from tetracyclododecene or deriva-tives of tetracyclododecene.

4. A crosslinked terpolymer as claimed in claim 2 which also comprises a hydrocarbon elastomer in an amount of from about 3% to about 10% by weight, based on the total terpolymer weight.

5. A crosslinked terpolymer as claimed in claim 3 which also comprises a hydrocarbon elastomer in an amount of from about 3% to about 10% by weight, based on the total terpolymer weight.

6. A process for producing a crosslinked terpolymer comprising reacting in the presence of a metathesis catalyst from about 20% to about 80% by weight, based on total ter-polymer weight, or repeating units derived from dicyclopenta-diene, from about 10% to about 50% by weight of repeating units derived from tricyclopentadiene, and from about 10% to about 50% by weight of repeating units derived from tetra-cyclododecene or derivatives of tetracyclododecene, having the general formula:

, wherein R1-R2 denote the same or different hydrogen atoms or lower alkyl and alkylene groups having from 1 to 10 carbon atoms.