3,830,877 United States Patent Office Patented Aug. 20, 1974 2 a quantity not higher than 10% of the copolymer's total 3,830,877 sequences, may have - in some cases-a number 2. COPOLYALKENAMERS HAVING A SEQUENTIAL lower than 5 or higher than 1000. STRUCTURE, AND METHOD FOR PREPARENG The polymeric chains constituting our sequential co SAME polyalkenamers are therefore characterized-when only Gino Dall Asta, San Giuliano Milanese, and Giuseppe Motroni, Milan, Italy, assignors to Montecatini Edison homosequences are present in said chains-by the fol S.p.A. Milan, Italy lowing general formula (3): No Drawing. Filed Aug. 1, 1972, Ser. No. 277,120 Claims priority, application Italy, Aug. 2, 1971, (3) -CH=CH(-CH2)-2-CH=CH(-CH2)mize 27,061/71 O -CH=CH(-CH) , , int, C, C08f 7/00 wherein ni', m', and z', z', have the values indicated U.S. C. 260-875 7 Claims hereinbefore respectively for m and z. The ratio between the various types of alkenameric ABSTRACT OF THE DISCLOSURE units is generally comprised between 5 and 90% of a 5 type of alkenameric units with respect to the polymer There are disclosed new high molecular weight copoly total. alkenamers the chains of which are made up of two or Besides the structures indicated in formula (3), the se more more alternating types of monomeric units arranged quential copolyalkenamers according to the present in according to either homo-sequences or both homo-Se vention may contain also small amounts, not higher than quences and hetero-sequences (which is to Say Sequences 20 15% of the total copolymer, of other monomeric units, made up of statistically distributed monomeric units). such as those deriving from the copolymerization with Also disclosed is a method of preparing the new copoly alkyl-substituted cycloolefins (for instance 3-methylcyclo alkenamers by reacting a homopolyalkenamer, prefer pentene) or with bicycloolefins (for instance norbornene). ably dissolved in a suitable solvent, with one or more cy Chain end groups not derived from cycloolefins may be cloolefins (other than the one making up the starting 25 present too, such as those which form when the molecu homopolyaikenamer) in contact with a particular cata lar weight of the copolymer is regulated by preparing it in lytic system prepared from a transition metal salt such as the presence of acyclic olefins or acyclic dienes. a tungsten salt; preferably but not necessarily an oxygen We have found, and this is another object of our inven ated compound such as molecular oxygen; and a derivative tion, that it is possible to prepare sequential copoly of a metal belonging to Groups I, II, III or IV of the 30 alkenamers corresponding, when formed only by homo Mendelyeev Periodic Table, such as, for instance, a hy sequences, to general formula (3). Like the copolyalkena dride or organometallic compound of aluminum. mers having a random distribution, also the sequential co polyalkenamers are generally crystalline, particularly when THE PRIOR ART the double bonds contained therein are essentially of one single type, for example cis-type or trans-type. Owing to Homopolymers having the structure of polyalkenamers the particular distribution of the monomeric units, the and obtained by homopolymerization of cycloolefins have sequential copolyalkenamers according to this invention been described in, for instance, Italian Pats. Nos. 701,182, exhibit-the compositions being equal-degrees of crys 733,857; and 778,370 assigned to the present assignee, tallinity and melting temperatures higher than those of Montecatini Edison, S.p.A. Another Italian patent, No. 40 the corresponding copolyalkenamers having a random dis 773,657, to the same assignee, also describes copolymers tribution. exhibiting a copolyalkenameric structure, having a ran A further surprising aspect of the copolyalkenamers ac dom (statistical) and nonsequential distribution of the cording to this invention consists in that they have more units deriving from the monomers, and obtained by the than one melting point, as the various types of sequences copolymerization of two or more cycloolefins. 45 melt at different temperatures. THE PRESENT INVENTION Such features result in improved utility of the sequential copolymers for certain purposes, in particular when the An object of this invention was to provide a new class production of elastic fibers or elastomers for special uses of copolyalkenamers consisting of high molecular weight is desired. polymeric chains along which two or more types of mono Sequential copolyalkenamers according to the present meric units alternate and which are arranged in either 50 long homo-sequences or in both homo-sequences and invention are, for example, those containing sequences of hereto sequences, i.e., sequences made up of statistically monomeric units selected from distributed monomeric units. butenamer (m=2), pentenamer (n=3), heptenamer This and other objects are achieved by the method re (m=5), octenamer (m=6), nonenamer (m=7), de ferred to in the Abstract Of Disclosure, supra. 55 cenamer (m=8), undecenamer (n=9) and dodecena The alkenameric monomeric units in our new copoly mer (m=10), alkenamers correspond to the following general formula: having double bonds prevailingly of the cis-type or trans type. Preferred examples are those containing sequences (1) -CH=CH(CH2) 60 of monomeric units selected from butenamer, pentenamer, heptenamer, octenamer, decenamer and dodecenamer. wherein m is a whole number selected from 2, 3, 5, 6, 7, 8, The preferred copolymers are those which contem 9 and 10. poraneously contain sequences of butenamer and pentena In the sequential copolyaikenamers, which are the ob mer, of pentenamer and octenamer, of pentenamer and ject of the present invention, said monomeric units form dodecenamer, of heptenamer and dodecenamer or of oc homosequences corresponding to the general formula (2): 65 tenamer and dodecenamer. Moreover, the preferred co polyalkenamers of the above said types are those in which (2) -CH=CH(-CH2)] the double bonds are prevailingly of the trans-type. wherein z is the mean length of the homosequences ex These new sequential polyalkenamers can be prepared pressed as monomeric units and being a whole number from the homopolyalkenamer, by reacting it, preferably generally comprised between 5 and 1000, preferably be 70 dissolved in a suitable solvent, with one or more cyclo tween 10 and 300. Small amounts of homosequences, in olefins other than the one making up the homopoly 3,830,877 3 4 alkenamer, in the presence of a catalyst as disclosed here Preparation of the catalytic mixture and the successive in. Analogously, it is also possible to use, instead of the copolymerization reaction are preferably conducted in an homopolyalkenamer, a statistical copolyalkenamer and inert gas atmosphere, such as, for instance, nitrogen or to react it with cycloolefin. It is also possible to start argOn. from a sequential copolyalkenamer according to this in Preparation of the catalyic mixture and the subsequent vention and to react it with a cycloolefin other than those copolymerization reaction are preferably carried out in a forming the starting copolyalkenamer. solvent capable of dissolving the polyalkenamer. Suitable The catalysts employed to bring about said reaction are solvents are hydrocarbons or halogenated hydrocarbons. those which have been described in, for instance, Italian Preferred examples thereof are benzene, toluene, cyclo Patent No. 778,370. Said catalysts are obtained by O hexane, n-heptane and chlorobenzene. The amount of mixing: solvent to be employed can be selected from polyalkena mer/solvent weight ratios ranging from 1:1 to 1:100, (A) a salt of a transition metal selected from tungsten, preferably from 1:10 to 1:50. molybdenum, rhenium, tantalum, niobium, titanium For the reaction with the cycloolefin, instead of using and zirconium; 5 any of the solvents specified hereinabove, it is possible (B) preferably, but not necessarily, an oxygenated com also to employ as a solvent the cycloolefin itself. In this pound containing at least one O-O, O-H, C=O, case the starting polyalkenamer is dissolved in the cyclo C-O-C or N=O bond; and olefin selected for the reaction, the catalytic components (C) a metal hydride, an organometallic compound, a being then added to the solution. a halide or amide of metal belonging to any of the 1st, 20 The reaction is usually conducted at temperatures com 2nd, 3rd or 4th groups of the Periodic Table according prised between -50 and --80 C., preferably between to Mendelyeev. -30 and --50° C. The reaction may be illustrated as follows (A repre Examples of useful transition metals salts (catalytic senting the monomeric units of the starting homopoly component A) are WCls, WCls, WBrs, WF, WOBra, 25 alkenamer, B representing the cycloolefin molecules): WCls (OR), WCl(OR)2, WOCIA (wherein R is an alkyl or haloalkyl group), WCl4, WCl2, W(allyl), W(acetyl acetonate), MoCls, MoCCl3, MoBrs, MoC)=(acetylace A-A-A-A-A-A-A-A-A-A-A-A-A-A (starting homopolyaikenamer) tonate), TaCl, NbCls, ReCls, ReCls, TiCl4, ZrCl4. Presently preferred transition metal salts are WCls, 30 WOCl, WF and MoCls. B Useful oxygenated compounds (catalytic component B (B)) which may be used are, for instance, molecular B B B B B B (cycycoolefin ) oxygen, water, alcohols, halogenated alcohols, epoxides, B ethers, acetals, carbon dioxide, hydroperoxides, organic 35 and inorganic peroxides, nitrobenzene derivatives. Pres A-A-AA-A-A-B-B-B-B-B-B-A-A-A-A-A-A-A-A (sequential ently preferred examples of these compounds are molecu copolyakenamer resulting therefrom) lar oxygen, water, ethanol, betachloroethanol, ethylene oxide, propylene oxide, epichlorhydrin, cumyl hydro peroxide, cyclopentene hydroperoxide, benzoyl peroxide, 40 In a presently preferred embodiment of the invention, cumyl peroxide, tert, butyl peroxide and carbon dioxide. the starting homopolyalkenamer is 1,4-polybutadiene Examples of metal compounds useful as catalyst com (polybutenamer), polypentenamer, polyoctenamer, poly ponent (C) are, in particular, organometallic compounds, decenamer, or polydodecenamer.