United States Patent (19) 11) 4,080,491 Kobayashi et al. 45) Mar. 21, 1978 54) PROCESS OF PRODUCING RING-OPENING 56 References Cited POLYMERIZATION PRODUCTS U.S. PATENT DOCUMENTS (75) Inventors: Yukio Kobayashi; Takashi Ueshima; 3,798,175 3/1974 Streck .................................. 526/136 Shoichi Kobayashi, all of Yokohama, 3,856,758 - 12/1974 Ueshima ............................... 526/169 Japan 3,859,265 1/1975 Hepworth ............................ 526/281 3,959,234 5/1976 Kurosawa ............................ 526/281 Assignee: Showa Denko K.K., Tokyo, Japan (73) Primary Examiner-Paul R. Michl 21 Appl. No.: 714,833 Attorney, Agent, or Firm-Fitzpatrick, Cella, Harper & 22) Filed: Aug. 16, 1976 Scinto Foreign Application Priority Data 57 ABSTRACT (30) A process of producing a ring-opening polymerization Aug. 27, 1975 Japan ................................ 50-103060 product of a norbornene derivative containing at least Mar. 26, 1976 Japan .................................. 51-32464 one polar group or aromatic group, a norbornadiene Mar. 26, 1976 Japan .................................. 51-32465 derivative containing at least one of said groups or a Apr. 5, 1976 Japan .................................. 51-37274 cycloolefin using a catalyst system prepared from an Apr. 27, 1976 Japan .................................. 51-47268 organometallic compound and the reaction product of May 25, 1976 Japan .................................. 51-59642 tungsten oxide or molybdenum oxide and a phosphorus 51 Int. C.’................................................ C08F 4/78 pentahalide or phosphorus oxytrihalide or these com (52) U.S. C. ..... o e s p s 8 v 8 526/137; 526/113; pounds and other third components. The catalyst sys 526/127; 526/136; 526/169; 526/281; 526/308 temi possesses a high polymerization activity. (58) Field of Search ..................... 526/96, 97,98, 100, 526/102, 104, 105, 114, 169,281, 136, 137, 113 37 Claims, No Drawings 4,080,491 1. 2 and a Lewis acid such as aluminum chloride, titanium PROCESS OF PRODUCING RING-OPENING tetrachloride, tintetrachloride, vanadium tetrachloride, POLYMERIZATION PRODUCTS etc., or these components and an organometallic com pound of a metal belonging to Groups I to IV of the BACKGROUND OF THE INVENTION periodic table, in particular an organoaluminum com The present invention relates to a process of produc pound as described in the specifications of Japanese ing ring-opening polymerization products and more Patent Application Laid Open Nos. 17,389/72; particularly it relates to a process of producing a ring 39,388/72; and 39,599/73. The polymerization products opening polymerization product at a high polymeriza obtained by these processes are suitable as rubber-like tion activity by subjecting a norbornene derivative con 10 materials owing to their excellent elastic property. taining at least one polar group or aromatic group, a Furthermore, it has been discovered that the same norbornadiene derivative containing at least one of said ring-opening polymerization products of the norbor groups or a cycloolefin to a ring-opening polymeriza nene derivatives as mentioned above can be obtained by tion in the presence of, if desired, an unsaturated poly using the catalyst system described in the above-men mer, using a catalyst system prepared from an organo 15 tioned specifications (Japanese Patent Application No. metallic compound and the reaction product of tung 18470/74). However, even if a cycloolefin or norbor sten oxide or molybdenum oxide and a phosphorus nene derivative is polymerized in the presence of a pentahalide or phosphorus oxytrihalide or these com catalyst system comprising tungsten trioxide and alumi pounds and other third components. It has been discov num chloride or these compounds and an organoalumi ered that a novel and useful ring-opening polymeriza 20 num compound which is described as having the high tion product is obtained by polymerizing a norbornene est polymerization activity in the above-mentioned derivative containing at least one cyano group, ester specifications, the polymerization activity is yet unsatis group, acid anhydride group, ether group, imide group, factory. halogen atom or aromatic group, norbornadiene deriva Since the polar group present in the monomeras used tives containing at least one of said groups, a cycloolefin 25 in the present invention is known to inactivate the cata or a mixture of at least one of the aforesaid derivatives lyst system thereby markedly decreasing the catalytic using a catalyst system prepared from a tungsten com activity, attempts to obtain catalyst systems possessing pound or a molybdenum compound and an organome excellent catalytic activity for the ring-opening poly tallic compound or these compounds and other third merization of norbornene derivatives containing a polar components such as, an organic peroxide, an acetalic 30 group have not succeeded. compound, and an alcoholic compound as described in the specifications of our U.S. Pat. No. 3,856,758; Japa SUMMARY OF THE INVENTION nese Patent Application Laid Open Nos. 77,999/74; It is, therefore, a primary objective of the present 58,200/75; 61,500/75; 71,800/75; 75,300/75; 103,600/75; invention to provide a process of producing ring-open 110,000/75 and 153,100/75. 35 ing polymerization products of a norbornene derivative Some of the ring-opening polymerization products containing at least one polar group or aromatic group, a obtained by the aforesaid processes are superior to poly norbornadiene derivative containing at least one of said vinyl chloride resin and polypropylene resin which groups or a cycloolefin using a catalyst system possess have now been manufactured on an industrial scale and ing excellent catalytic activity. widely used in various industrial fields in not only the 40 Other objects, features and advantages will be appar mechanical properties such as impact strength, low ent from the following detailed discussion. temperature impact strength and tensile strength but The above and other objects are achieved in a process also heat resistance and transparency. Furthermore, of producing a ring-opening polymerization product these polymerization products can be fabricated or which comprises ring-opening polymerizing the nor molded into various forms by applying to a fabrication 45 bornene derivative, norbornadiene derivative or cyclo or molding method which has widely been employed in olefin in the presence of, if desired, an unsaturated poly the field of thermoplastic resins, such as injection mold mer having a carbon-carbon double bond (the polymer ing, extrusion molding, blow molding, compression is referred to hereafter as "unsaturated polymer') using molding and can be used for various purposes as con the catalyst system prepared from an organometallic tainers, films, sheets, pipers and the like. Moreover, the 50 compound and the reaction product of at least one of properties of these polymerization products can be im tungsten oxide and molybdenum oxide and at least one proved for fitting desired purposes by blending together of phosphorus pentahalide and phosphorus oxytriha with a thermoplastic resin such as a polyvinyl chloride lide, or these compounds and other third components. riesin, a polymethyl-methacrylate resin, etc.; said ther That is, according to the present invention, there is moplastic resin also including an impact resistant resin 55 provided a process of producing a ring-opening poly such as an ABS resin and an ACS resin; a heat resistant merization product which comprises ring-opening poly resin such as a polyacetal resin, a polyamide resin, etc.; merizing in the presence or absence of an unsaturated and/or a rubber-like material such as a polybutadiene polymer having a carbon-carbon double bond at least rubber, a chlorinated polyethylene rubber, etc., or fur one of the norbornene derivatives each containing at ther by adding thereto various additives. f 60 least a polar group selected from the group consisting of Still further, some other ring-opening polymerization a nitrile group, an ester group, an ether group, an amide products prepared by the aforesaid processes can be group, a halogen atom, an acid anhydride group, an used, as is or following the polymer reaction, as ion-ex imide group and an aromatic nitrogen-containing heter change resins, adhesives, and flocculants. ocyclic group or an aromatic group, a norbornadiene Also, it has been proposed to produce a ring-opening 65 derivative containing at least one said groups or a cy polymerization product by polymerizing a cycloolefinic cloolefin using the catalyst system prepared from (A) an compound such as cyclopentene using a catalyst system organometallic compound of a metal belonging to comprising tungsten oxide and/or molybdenum oxide Groups IA, IIA, IIB, IIIB, IVA, or IVB of the periodic 4,080,491 3. 4. table and (B) the reaction product of at least one of hydrocarbon group having or not having a nitrile tungsten oxide and molybdenum oxide and at least one group, at least one of W, X, Y and Z being, however, of phosphorus pentahalide and phosphorus oxytriha a nitrile group or the hydrocarbon residue substituted lide. with a nitrile group. Since the catalyst system used in this invention pos 5 Examples of the hydrocarbon groups represented by sesses quite a high polymerization activity (or catalytic W, X, Y and Z of general formula (I) are methyl, activity) and hence can give a high production yield of ethyl, n-propyl, isobutyl, n-butyl, hexyl, octyl, dodecyl, the ring-opening polymerization product per unit tetradecyl, hexadecyl, eicosyl, phenyl, naphthyl, tolyl, amount of catalyst or in other words, a small amount of cyclohexyl, 1-methylcyclohexyl and 2-octenyl. the catalyst is sufficient for producing a definite amount 10 Typical cyano type norbornene derivatives are 5 of the ring-opening polymerization product, not only cyano-bicylo-2,2,1)-heptene-2; 5,5-dicyano the amount of catalyst used can be reduced but also the bicylo2,2,1)-heptene-2; 5,6-dicyano-bicyclo2,2,1)-hep production efficiency of the polymerization apparatus tene-2; 5-cyano-5-methyl-bicyclo[2.2, 1-heptene-2; 5 can be increased in the case of using the catalyst.