MXPA00008948A - Novel regio-regular copolymer and methods of forming same - Google Patents

Abstract

A new and novel linear, regio-regular vicinal functionalized polymer methods of forming thesame are described. The polymer has a linear hydrocarbon polymer backbone with vicinal functional groups having oxygen and/or nitrogen atom containing groups, such as hydroxy, carboxylic acid or ester, carbonyl acetate, amide, nitrile and the like, pendent from the polymer backbone chain in a regio-regular manner.

Description

"NEW REGIO-REGULAR COPOLYMER AND METHODS TO FORM THE SAME" BACKGROUND OF THE INVENTION The present invention is directed to regio-regular, novel and novel functionalized hydrocarbon polymers (ie, polymers that carry an oxygen and / or nitrogen atom in the suspended functional groups) and methods for forming them. Specifically, the present invention is directed to regio-regular polymers that have essentially all of the neighborhood (ie, head-to-head) configuration of the functional groups suspended from the polymer backing chain. The polymers are formed by ring opening metathesis polymerization of a cycloalkene of 7 to 12 carbon atoms having a vicinal pair of functional groups suspended from the ring carbon atoms. The resulting polymer can then be hydrogenated to provide an essentially straight chain polymer-alkylene having suspended head-to-head functional groups distributed periodically along the polymer chain. These polymers exhibit improved gas and / or voltage barrier properties and have other properties that make them useful for forming films and other articles. High-pressure free radical polymerization has been an important industrial technique for providing a wide variety of polymer products. The technique requires an initiator such as a peroxide, to initiate the growth of the chain. A variety of homopolymers and copolymers have been formed by this technique. However, the monomer units forming the copolymers are normally randomly distributed along the length of the polymer chain and the polymer has a high degree of short and long chain branching due to side reactions. Even when homopolymers containing a functional group are formed, there is a high degree of head-to-tail arrangement of the functional groups with respect to the polymer chain. The head-to-tail orientation of the consecutive polymers of a vinyl polymer can be simply represented as: -CH2-C? X-CH2-CHX-, while the head-to-head orientation is represented as: -CH2-CHX -CHX-CH2-, where X represents the functional groups. Normally, only small amounts of head-to-head arrangement of the functional group containing monomer units can be found in the - polymers formed by the free radical polymerization. More recently, polymerizations with a Ziegler-Natta or metallocene catalyst have been carried out. However, polymerization by this technique is generally limited to non-functionalized tnonomers, such as the appropriate olefins to form polyethylene, polypropylene and the like. Ring opening metathesis polymerization (ROMP) has been studied for the last two decades using initial transition metal complexes. These studies were carried out on deformed cyclic olefins to provide weight polymers and controlled molecular structure. For example, cyclobutenes have been subjected to ROMP to provide poly (butadiene) or polybutenomer. It has been well proven with documents that this polymerization is driven by the high deformation energy of the cyclobutene ring (29.4 kcal / ol). In Makromol. Chem. 1962, 56, 224. Dall'Asta and others first disclosed the ROMP of cyclobutene using TiCl 4 / Et 3 I to provide a polybutadiene having high cis configuration. Other two component ROMP catalyst systems have been used to polymerize cyclobutene and its derivatives. In addition, one-component catalysts, such as Ph (MeO) C = (CO) 5, PhC = WC05 and RUCI3 - - they were used successfully in similar polymerizations. However, none of the previously mentioned cases was observed to be living polymerization. The polymerization reactions are considered to be living when the reaction is able to proceed essentially in the absence of termination steps and chain transfer reactions. When the polymer chain initiation regime occurs more rapidly than the chain propagation, the living system provides polymers of controllable molecular weight and critical polydispersity. Living polymerization systems are also capable of synthesizing block copolymers (see Noshay et al., Block Copolymers, Academic Press, NY 1977). ~ The area of functionalized polyolefins has recently received great attention. and the number of functional groups, as well as the site of the functional groups in the polymer support to optimize the properties that can be achieved by a specific polymer has been of great interest.The functionalized alkylene polymers have been -prepared conventionally by polymerization However, these polymerization techniques of the functionalized vinyl unsaturated monomers have provided polymers with a preponderance of head-to-tail configuration of the monomeric units, with a high degree of branching and , where the copolymerization is carried out, the Monomeric ades are usually randomly distributed along the fundamental chain of the polymer. Due to the electrophillic nature of the transition metal catalysts, such as their conventional metallocene or "Ziegler-Natta" catalysts, towards a wide variety of functional groups, the synthesis of polyolefins with the polar functional groups has obtained only limited success Recently, ROMP has been achieved for certain substituted cyclic and bicyclic olefins, 3-methylcyclobutene and 3, 3-dimethylcyclobutene as well as norbornene have been subjected to ring opening and polymerized. They are substituted only with acid or alcohol functional groups only indirectly, for example, highly deformed 3,4-disubstituted cyclobutenes bearing benzyl-protected methylene ether or ether or ester suspended groups have been subjected to ROMP followed by removal by post-polymerization of the protection group to provide an alcohol homopolymer product of polyallyl - With the development of other metathesis initiators, such as those described by Nguyen et al. In JACS 1992, 114, 3974 and JACS 1993, 115 9858; by Schwab et al. in JACS 1996, 118, 100; Schrock et al., In JACS 1990, 112, 3875; Fox and others in Inorg. Chem. 1992, 31., 2287; and by Grubbs et al., in U.S. Patent No. 5,312,940, metathesis polymerization of certain cyclic olefin compounds containing functional groups has been achieved. However, these polymerizations were not living polymerizations and, therefore, non-linear high dispersion polymer products were achieved. In addition, the monomers were highly deformed compounds, such as norbornene derivatives that provide a cyclic residue within the polymer chain or alternatively, were monofunctional acyclic olefins that provided polymers having the functional groups placed finitely along the pdel chain. polymer. It has been highly desirable to provide linear polyolefin polymer having suspended functional groups uniformly distributed in a controlled manner along the polymer backing. These polymers are believed to be capable of providing polymer films and articles having a uniform structure and highly desired properties.

- COMPENDIUM OF THE INVENTION It has now been unexpectedly found that functionalized polymers can be produced which are essentially linear, have low polydispersity and whose functionality is regio-regular with respect to the support polymer chain. The polymers present have. functional groups that are head-to-head in orientation with respect to one another (suspended from adjacent carbon atoms of the polymer backing) and placed in an essentially uniform sequence with respect to the carbon atoms of the polymer backbone. These novel and novel functionalized, regio-regular polymers are suitable for providing improved packaging film products.

DETAILED DESCRIPTION The present polymers are capable of being "formed by ring opening metathesis polymerization of certain cyclic monoolefinic compounds having vicinal functional groups directly suspended from atoms of the ring carbon, as fully described below.

The cyclic olefin can be selected from cyclohydrocarbon of 7 to 12 carbon atoms having an ethylenic unsaturation group as part of the ring structure. The cyclohydrocarbon, for example, can be selected from cycloheptene, cyclooctene, cyclononene, cyclodecene, cyclohexane, cyclododecene-like. Preferred idrocarbon rings are those that have an even number of carbon atoms that make up the ring. The term of 7 to 12 carbon atoms refers to the number of carbon atoms that form the ring structure of the cyclic olefin. The unsaturated cyclohydrocarbon used to form the present polymer must have vicinal functional groups suspended from ring carbon atoms. At least one carbon atom that remains adjacent to the ethylenic group of the ring must be free of functional groups. That is, when the ethylenic atoms 1 and 2 are listed, the next carbon atom and, preferably, the carbon atom having the highest number defining the ring should not contain suspended groups except for the atoms of hydrogen. The cyclohydrocarbon in addition to the functio-na-1-side groups contains hydrocarbon or functional groups suspended from other carbon atoms except at least one ring carbon atom that remains adjacent to the ethylenic group, as described in the foregoing. In general, the cyclic olefin found useful in providing the regio-regulating polymer is a cycloalkene which can be represented as: wherein at least one carbon atom that is alpha with respect to the ethylenic group has only hydrogen atoms suspended at the same time, X and Y together represent the functional groups that are suspended from the vicinal carbon atoms of the cycloalkene and wherein X and Y each, independently, is selected from hydroxyl, carboxylic acid, carboxylic acid esters of an alkyl of 1 to 5 carbon atoms, acetate, amide, a nitrile or carbonyl group. It is preferred that X and Y represent the same functional group. The symbol "a" is a value from Q to 6 and "b" has a value from 0 to 6 as long as the sum of a + b is of a value between 2.and 7. Each of the carbon atoms of the ring of and of "b" may be unsubstituted (contains only hydrogen atoms) or may be substituted with an alkyl group of 1 to 5 carbon atoms (preferably 1 to 2 carbon atoms) or with a group functional, as described above. The present invention will be discussed below in terms of hydroxylated polymers (wherein X and Y each represents an -OH group). These polymers can be seen as copolymers of vinyl alcohol and an alkylene, such as ethylene, linear propylene and the like. For example, it has been found that the ROMP of 5,6-dihydroxycyclooctene provides a polymer that can be viewed as a copolymer of ethylene and vinyl alcohol. Ethylene / vinyl alcohol copolymers (EVOH) can be commonly obtained. However, these polymers are currently formed by free radical copolymerization of ethylene and vinyl acetate followed by hydrolysis of the acetate groups into hydroxyl groups. The conventional EVOH copolymer contains each monomer unit randomly distributed along the polymer chain, the hydroxyl groups (not taking into account the residual acetate groups) are usually configured head-to-tail when part of the the adjacent monomeric units and the polymer contain considerable branching. In contrast, a hydroxy-containing polymer provided by the present invention (a = 2); b = l; and Y = OH) can be seen as analogous to an ethyl ene / vinyl alcohol copolymer with the unique feature of having pairs of ethylene and vinyl alcohol of monomeric units in a sequence arrangement of ethylene-vmyl alcohol / vinyl-ethylene alcohol along the polymer chain. In addition, the adjacent alcohol units are only in a head-to-head configuration. _ ___ Other functional polymers can be obtained from the manner described fully below. The present invention can be seen as using, as the starting material, a cycloalkene of 7 to 12 disubstituted vicinal carbon atoms (wherein from 7 to 12 carbon atoms refers to the number of carbon atoms of the ring) between groups same group 0 to 6 and "b" and when the - sum of a + b is from 2 to 7. Each of the carbon atoms of the "a" and / or "b" ring may be unsubstituted or substituted further, as described above. The groups X and Y can be placed sterically on the same side or on opposite sides of the plane that bisects the ring carbon atoms except in the case of X and / or Y when it is an icarbonyl group, in which case the group would remain within the plane of the ring. In other words, X and Y can either be of a cis or trans configuration with respect to each other. The formation of difunctional cycloalkenes (I) found useful herein can be achieved by known methods. For example, trans-5-cycloocten-1,2-diol can be prepared by reacting the 1,5-cyclooctadiene monoepoxide with perchloric acid in an aqueous solution at elevated temperature, as disclosed in French Patent Number 1,294,313. whose teaching is incorporated in the present in its entirety by reference. Other methods for preparing the functionalized cycloalkene of vicinal dihydroxy include reacting the cycloalkane monoepoxide with acetic acid and potassium acetate in order to initially form the hydroxy / acetate compound followed by saponification; Oxidation of cycloalkadiene with peroxide and formic acid, followed by basic hydrolysis [Yates et al. Canadian Journal of - Chemistry, Volume 50, 1548 (1972)]; reacting a cycloalkadiene monoepoxide with an organic acid, such as formic or acetic acid in order to form the hydroxy / acetate compound followed by saponification [Mclntosch, Canadian Journal of Chemistry, Volume 50, 2152 (1972)]; or reacting a cycloalkadiene with osmium tetroxide in an ether / pyridine solution at low temperatures followed by reflux with sodium sulfite in water / alcohol [Leitich, Tetrahedron Letters, Number 38, 3589 (1978)]. The vicinal dione cycloalkene can be formed from the vicinal diol according to the procedure described by Yates et al., Canadian J. of Chem., Volume 50, 1548 (1972). The vicinal hydroxy ketone cycloalkene and the vicinal ketone / acetate cycloalkene are formed by oxidizing the hydroxy / acetate with chromic acid in acetone at low temperatures (e.g., from 0 ° to 10 ° C) to form the ketone / acetate. The ketone / acetate cycloalkene can be recovered by distillation. The ketone / acetate can be converted to vicinal hydroxy ketone cycloalkene by hydrolysis with sodium hydroxide - in methanol at slightly elevated temperatures (e.g., 40 ° C). The monoepoxy cycloalkene, which is the precursor of several of the synthetic routes described above can be obtained by catalytic oxidation of - a cycloalkadiene using sodium peroxide and tungstate as the catalyst as described by Venturello, in J. Org. Chem., 4_8, 3831 _ (1983) and J. Org. Chem., __ 53, 1553 (1988). Other methods for forming the epoxy cycloalkadiene are disclosed by Grubbs. Macromolecules, 28, 6311 (1995); Camps. J. Org. Chem. 47, 5402 __ (1982J, Imutax J. Org. Chem. 44, 1351 (1979), Murray, Org. Syn., 7_4, 91 (1996), and Payne, Tetrahedron, 18_, 763 (19621. ~ Z teachings of each of the references cited above is hereby incorporated in its entirety by reference.The vicinal functionalized cycloalkene is subjected to ring opening metathesis polymerization using a well-defined ROMP catalyst.These catalysts are found to be useful herein are disclosed by Shrock et al. in JACS 1990. 112, 3875, and U.S. Patent Nos. 4,681,956, 5,312,940, and 5 / 342,909. Preferred labels are those described in the U.S. Patent. Number 5,312,940 The teachings of each of the aforementioned references are hereby incorporated by reference in their entirety.A class of ROMP catalyst found useful in providing the present polymers can be represented by the general formula: - MIN1) (OR2) 2 (CHR3) II (a) wherein M is molybdenum or tungsten; R1 and R2 of Formula II (a) are independently selected from alkyl, aryl, aralkyl or the halogen-substituted derivatives or analogs containing silicon thereof. Examples of the aryl groups are phenyl, 2,6-diisopropylphenyl and 2,4-trimethylphenyl. Examples of aralkyl groups are benzyl and triphenylmethyl. Examples of R ^ in Formula 1 are 2,6-diisopropylphenyl, 2,4,6-trimethylphenyl, 2,6-di-t-butylphenyl, pentafluorophenyl, butyl-tertiary, trimethylsilyl, triphenylmethyl, triphenylsilyl, tri-t. -butylsilyl, and perfluoro-2-methyl-2-pentyl and the like. Examples of R2 in Formula Ia are tertiary butyl, trifluoro-t-butyl [(CF3) (CH3) 2C], tertiary perfluoro-butyl, perfluoro-2-methyl-2-pentyl, 2,6-diisopropylphenyl, pentafluorophenyl, trimethylsilyl, triphenylsilyl, tri-t-butylsilyl, and hexafluoro-t-butyl [(CF3) 2 (CH3) C] and the like. R3 of Formula III (a) is selected from an alkyl, aryl, aralkyl, or any substituent that results from the initial reaction between the complex of M = CHR3 and the olefin (s) which are (are) being subjected to metathesis, the alkyl has from 1 to 20 carbon atoms, aryl has from 6 to 20 carbon atoms and the - Aralkyl has from 7 to 20 carbon atoms; R3 is preferably tertiary butyl or phenyl, "but since the M-CHR3 residue of the compound of Formula Ia is intimately involved in the catalytic reaction, it is recognized that the coordinating group CHR3 is replaced by another alkylidene fragment of the olefins The catalyst Ia should not be used with the monomer I having a proton in the functional group, ie, for example hydroxyl, carboxylic acid and the like It can be used when the ester, acetate, carbonyl and the like The preferred ROMP catalysts are those represented by the general formula: X R \ M C IIb / X R 1 where: M is selected from Mo, W, Os or Ru; and preferably Ru or OS; and most preferably Ru; R and R1 are independently selected from hydrogen; alkenyl of 2 to 20 carbon atoms, alkynyl of 2 to 20 carbon atoms, alkyl of 1 to 20 carbon atoms carbon, aryl, carboxylate of 1 to 20 carbon atoms, alkoxy of 1 to 20 carbon atoms, alkenyloxy of 2 to 20 carbon atoms, alkynyloxy of 2 to 20 carbon atoms, aryloxy, alkoxycarbonyl of 2 to 20 carbon atoms carbon, alkylthio of 1 to 20 carbon atoms, alkylsulfonyl of 1 to 20 carbon atoms or alkylsulfinyl of 1 to 20 carbon atoms; each optionally substituted with alkyl of 1 to 5 carbon atoms, halogen, alkoxy of 1 to 5 carbon atoms or with a phenyl group optionally substituted with halogen, alkyl of 1 to 5 carbon atoms or alkoxy of 1 to 5 5 carbon atoms; preferably R and R ^ are independently selected from hydrogen; vinyl, alkyl of 1 to 10 carbon atoms, aryl, carboxylate of 1 to 10 carbon atoms, alkoxycarbonyl of 2 to 10 carbon atoms, alkoxy or aryloxy of 1 to 10 carbon atoms; each optionally substituted with alkyl of 1 to 5 carbon atoms, halogen, alkoxy of 1 to 5 carbon atoms or with tm phenyl optionally substituted with halogen, alkyl of 1 to 5 carbon atoms or alkoxy of 1 to 5 carbon atoms; X and? they are independently selected from any anionic coordinating group; preferably X and X ^ - are independently selected from halogen, hydrogen; alkyl of 1 to 20 carbon atoms, aryl, alkoxide of 1 to 20 carbon atoms, aryloxide, alkyldicketonate of 3 to 20 - carbon atoms, aryldicyketonate, carboxylate of 1 to 20 carbon atoms, aryl or alkylsulfonyl of 1 to 20 carbon atoms or alkylsulfinyl of 1 to 20 carbon atoms; each optionally substituted with alkyl of 1 to 5 carbon atoms, halogen, alkoxy of 1 to 5 carbon atoms or with a phenyl group optionally substituted with halogen, alkyl of 1 to 5 carbon atoms or alkoxy of 1 to 5 atoms carbon; L and Ll are independently selected from any neutral electron donor preferably L and L1 are independently selected from phosphine, sulfonated phosphine, phosphite, phosphinite, phosphonite, arsine, stilbene, ether, amine, amide, sulfoxide, carbonyl, nitrosyl, pyridine or thioether; and wherein any 2 or 3 of X, X ^, L, L ^ can optionally be linked together to form a multidentate chelation coordinating group. The ROMP of the cycloalkene of 7 to 12 atoms difunctional difunctional carbon (I) can be carried out neat or by providing a solution of (I) in a hydrocarbon solvent-U-ro such as, for example, aromatic hydrocarbons, such as, toluene, tetrahydrofuran, dialkyl ethers, cyclic ethers and the like and their halogenated derivatives, such as halogenated aromatics as well as halogenated alkanes and the like. The preferred solvents - are chlorinated alkanes such as dichloromethane and the like, chlorinated aromatic compounds such as monochlorobenzene and the like. The molar ratio of (I) to catalyst II should be from about 200 to 5,000, preferably from about 400 to 3000. The ROMP reaction can be carried out at temperatures of about 10 ° C to 75 ° C and preferably from about 20 ° C to 50 ° C. The especially preferred temperature will depend on the specific starting material, the ROMP catalyst and the solvent used and can be determined by small experiments and usually falls within the range of 35 ° C to 50 ° C. The time spent to carry out the ROMP reaction can vary from only a few minutes to several hours, such as up to about 48 hours. The reaction time is usually from 2 to 30 hours, with 10 to 20 hours being preferred. The molecular weight of the polymer product formed can be regulated by (a) altering the ratio of monomer I to catalyst II, and / or by (b) introducing an acyclic olefin - appropriate in small amounts to act as a transfer agent chain. These agents must be soluble in the polymerization reaction medium or monomer used and, for example, they can be cis-3-buten-l-ol, cis-3-hexen-l-ol and the like. When used, the XCTAJ chain transfer agent must be present in a molar ratio of monomer I to CTA of about 50 to 2000 and ae pr '-. rf-no i or .jpro? i mad.iment.e 200 to 1000. The ROMF ael e 'el < > to 1 difunctional neighborly (I) cited above provides a polymer having the repeating units of the general formula: wherein X, Y a and b are as defined above and each R independently represents hydrogen or an alkyl of 1 to 5 carbon atoms or a group X. It should be noted that the ROMP process of. Cycloalkene (I) provides a polymer III which has functional vicinal X and Y, the polymer chain, essentially linear, and the chain also contains carbon atom separated from non-saturation Functional group _X In the polymer, groups X and Y can have the same or opposite stereo-configuration of that of the cyclic monomer used.Similarly, the polymer product TTT has double bonds, which provide Normally, a mixture of cis- and trans-cis-rich Lauto atoms (ie, the alkenyl hydrogen atom can be either cis or trans with respect to its neighbor the closest hydrogen atom and ulquenyl. - III "above is the repeating unit of the polymer formed and, therefore, does not have any considerable degree of alloy of the X and Y groups and, as appropriate, the alkylene units along the chain of the The polymer product III can be recovered by introducing a non-solvent compound into the solution to cause the polymer to precipitate from the solutions.These non-solvents include, for example, alkanes (eg, pentane, hexane, heptane, etc.). ketones (eg, acetone, methylethyl ketone, etc.) and the like The specific non-solvent to be used can be easily determined by the artisan.The polymer product III can be easily recovered by introducing the polymerization reaction mixture into a Excess of a non-solvent liquid The preferred conditions and the catalyst for carrying out a ROMP of trans-5-cycloocten-1,2-diol are: Catalyst: Compound II (b) wherein X =? l = CL L = Ll = tr cycloalkylphosphine (eg, exophosphine tricyclic) - - R = phenyl or 1, 1-diphenylethenyl Rl = hydrogen Solvent (s) chlorinated alkanes (eg, methylene chloride) Temporal Scale: | n ° rr) 0nO T Tempo Scale : from 0 or 2] hours The separated ITT polymer can be subjected to conventional catalytic hydrogenation or, optionally, to chemical hydrogenation (e.g., using chemical hydrogenation agents, such as para-toluene sulfonyl hydrazide and the like) to provide an almost fully saturated polymer IV. The structure of the repetition unit of the TV series can be represented by the formula: IV Alternatively, partial hydrogenation can be achieved by controlling the hydrogenation reaction by known methods. All methods can include controlling the molar ratio d < what, group ... olot polymer nuclides with i < , | o, -i (,, i | 111 (>? 11 i ¡) 11 i < ii < i μ n? < io 11 i] i rn io, the I mpf > of hideogenac Finally, when using catalytic hydrogenation, the degree of saturation can be controlled by the time and / or the hydrogen pressure used.This way, the resulting IV polymer can have - residual ethylenic unsaturation to provide sites for grafting, insertion of other functional groups or due to other desired reasons. ™ The hydrogenation of the polymer can be carried out using conventional hydrogenation, such as the Wiikinson catalyst and the use of hydrogen or the use of other conventional hydrogenation catalysts, such as Raney nickel, palladium on carbon, platinum on carbonate, complex of ruthenium alkylidene or the like. The polymer is normally dissolved in a solvent or a mixture of solvents such as those described above for the polymerization of ROMP and is subjected to a hydrogen pressure of at least approximately 21.09 g / cm2, preferably of 42.18 g / cm2. to 351.50 kilograms per "square centimeter. Hydrogenation is usually completed in less than 8 hours even when shorter or longer periods of time may be used. Normally the hydrogenation is carried out for a period of 2 to 8 hours with one of 3 to 7 hours being preferred. When the ROMP-reaction of the monomer I is carried out in solution, the resulting solution containing the polymer III can be used directly to carry out the hydrogenation step. In this way, the separation step of the -polymer III from the medium of - Polymerization can be eliminated. In addition, it is believed that any ROMP catalyst that may be present in the polymer III solution can aid the hydrogenation reaction. An alternative way of forming the regio-regular polymer subject matter of the present invention is to subject a cycloalkene of 7 to 12 carbon atoms of monoepoxy having at least one (and preferably both) ring carbon atom adjacent to the no ethylenic saturation as an unsubstituted carbon atom, up to ROMP as hereinabove described for the difunctional vicinal monomer I. The intermediate polymer product is precipitated by precipitation with a non-solvent composition followed by further conversion of the epoxy groups to the desired vicinal functional groups in accordance with the synthetic routes described above. The resulting polymer III can also be hydrogenated to provide polymer IV in the manner described above. Another alternative route for the novel and novel regio-regular polymer IV present is to first epoxidize the ethylenic non-saturation units which are distributed almost uniformly along a linear unsaturated hydrocarbon polymer chain. Conventional polymers having non-saturation groups, such as conventional polybutadiene, isoprene and the like, are not linear polymers due to the presence of suspended 1,2- or 3,4-double bonds. However, linear unsaturated hydrocarbon polymers having ethylenic units evenly distributed within the polymer backbone can be formed by ROMP_of a cycloalkene, such as cycloalkene of J to 12 carbon atoms. The resulting polymer is linear and contains ethylenically unsaturated units uniformly distributed along the chain. These ethylenic units can then be epoxidized by standard techniques such as catalytic oxidation using a peroxide and a tungstate catalyst. The epoxy groups can then be converted into the desired vicinal functional groups, using the synthesis methods described above, to provide the polymer product IV. In addition to forming the polymers III and IV of a single monomer I, as described above, copolymers can be formed by ROMP of the monomer I having functional groups X and Y and the ROMP of a la comonomer. The comonomer I (a) can be selected from the cycloalkene represented by the formula: where X ^ and Y ^ have the same definition as X and Y that are described above for monomer I or can be selected (one or both) of hydrogen, provided that they together provide pairs that are other than the X and Y pairs of monomer I; R - "- has the same definition as R of monomer I and a and b each is independently an integer from 0 to 6 as long as the sum a + b is 0 or 2 * 7. The copolymerization by ROMP of the monomers I and that to provide a linear copolymer of the present invention can be carried out at molar ratios of I to that of about 50:50 to about 100: 0 with 60:40 a, 100: 0 being preferred. of the present monomer is essentially a living polymerization, the monomer I and the monomer can be introduced in sequence into the polymerization reaction means to provide a block (s) of unit III defined above and a block ( s) of units II.I where X and Y are as defined immediately above, in this way, a polymer product is formed. of regio-regular block that is linear and that has neighborhood functional units evenly spaced in a head-to-head configuration for at least the length of a portion of the polymer chain (derived from monomer I) and a second segment of the polymer chain that possibly has a second set of vicinal functional units uniformly configured along a portion of the same polymer chain (derived from monomer la). This copolymer can be hydrogenated, as described above for the homopolymer. The polymers produced by the present invention have been compared to their duplicate copolymer formed by conventional free radical polymerization and have been found to have superior elongation properties as well as improved toughness, lower melting temperature and lower density. The polymers are useful for forming films or coatings and the like, for packaging applications. For example, functional regio-regular hydroxy-vicinal functional polymers formed in accordance with the. present invention has been found to have superior tenacity and elongation properties, and gas permeability properties lower than the conventional analogous free radical formed from copolymers having a comparable hydroxyl content. Similarly, the copolymers of the present invention can provide films or coatings having a high degree of function resistance, toughness and print adhesion properties. The following examples are provided for illustrative purposes only and are not intended to be a limitation for the claimed invention appended to. the present. All parts and percentages are by weight unless otherwise stated. _ Example 1 Polymerization of Ring Opening Metathesis (ROMP) of 5-cycloocten-tr-ans-l, 2-diol A three-necked resin container of 300 milliliter capacity equipped with a mechanical stirrer, an argon inlet and a septum was charged with 5-cycloocten-trans-1,2-diol (40 grams, 0.28 mol). The monomer was degassed in vacuo for 2 hours. The contents of the reaction vessel were kept under an atmosphere of inert argon. Methylene chloride (30 milliliters) was sprayed with a vigorous stream of argon for 30 minutes and transferred through a cannula to the resin container. The monomer / solvent solution is - He waved vigorously. In a separate glass vessel equipped with a septum, the ruthenium catalyst, phenylmethylenebis (tricyclohexylphosphine) dichloride (0.31 gram, 0.27 millimole) was dissolved under dry box conditions in 10 milliliters of methylene chloride purged with argon. The catalyst solution was supplied by syringe to a reaction vessel. The reaction mixture was heated to 40 ° C with an oil bath and kept under a stream of slow argon for 24 hours with vigorous stirring. Subsequently, the resin vessel was removed from the oil bath and the reaction mixture was cooled to room temperature. Ethylvinyl ether (0.75 gram, 10.5 mmol) was added to the reaction mixture and stirred for 1 hour. - The polymer solution was then dissolved in a mixture of 40 milliliters of tetrahydrofuran, 40 milliliters of methanol and 0.4 gram of 2,6-di-tert-butyl-4-methylphenol. After the polymer had completely dissolved to form a homogeneous solution, it was precipitated in cold acetone (cooled with an ice bath). The polymer was redissolved in a mixture of 20 milliliters of tetrahydrofuran, 20 milliliters of methanol and 0.4 gram of 2,6-di-tert-butyl-4-methylphenol and re-precipitated in cold acetone. This process was repeated again. The polymer was collected and dried overnight in a vacuum oven at 60 ° C. HE - - obtained 13.4 grams of a hard solid yellow polymer (Polymer 1-U). The molecular weights of the polymer were determined by GPC at 50 ° C using a Waters Alliance System number 4 gel permeation chromatograph equipped with a Waters 41ORI detector. The columns of phenolgel 5 (2 x linear and 1 x 100 angstrom units) were used. The eluent was l-methyl-2-pyrrolidinone / 50 mM lithium bromide. The polystyrene standards were used for calibration. The number average molecular weight (Mn), the weight average molecular weight (Mw) and the polydispersity (PDI) were determined. For the specific polymer prepared in this example (Polymer l.U), the Mn, Mw and PDI were 9,500, 27,800 and 2.9, respectively.

Example 2 Hydrogenation of the Polymer Prepared in Example 1 with respect to the Regio-Regular Linear Polymer A Parr reactor of 600 milliliter capacity equipped with a glass liner was used for the hydrogenation reaction. The polymer 1-U (12.0 grams, 0.0844 mol of double bonds) was dissolved in a mixture of 60 milliliters of tetrahydrofuran and 60 milliliters of methanol. He - Wilkinson's catalyst [tris (triphenylphosphine) rhodium (I) chloride] (0.52 gram, 0.56 millimole) (prepared triphenylphosphine and rhodium (III) chloride in ethanol) was added to the polymer solution. The reactor head plate assembly was secured to the reactor body and the reactor inlet and vent valves were closed. The reactor was placed in a heating mantle and connected with a pneumatic agitator. A thermoelectric pair was connected to the reactor. The hydrogenation process was carried out at a temperature of about 54 ° C under a hydrogen pressure of 42.18 kilograms per square centimeter for 6 hours. After completion of the reaction, the reactor was slowly discharged and the reaction mixture was filtered through a thick glass frit funnel. The solid polymer was washed with acetone and resuspended in acetone and stirred overnight. The dispersion of the polymer was then filtered and rinsed with 2 portions of acetone. The final polymer (Polymer 1-S) was dried in a vacuum oven at 60 ° C overnight. The resulting polymer was a fine powder with a light beige color and can be seen as an ethylene / straight-line regio-regular vinyl copolymer having 50 percent -molar units of vinyl alcohol in the head-to-head configuration -head. The molecular weights of the 'polymer - The resulting results were: Mn = 23,900, Mw = 47,000 and PDI = 2, which are also disclosed in Table II, which is presented below. The polymer melt flow index was determined at 190 ° C with a mass of 2.16 kilograms _ according to the D1238 method of the American Society for the Testing of Materials using a CSI MFT-2 fusion flow index apparatus. this value was also disclosed in Table III, which will be presented below. The polymer was stabilized with 1 weight percent --- Ult-ranox 2714A (GE) weight for melt flow index measurements. The 1-S polymer had a melt flow rate greater than 10 grams / 10 minutes. The copolymer had a glass transition temperature (Tg) of 45 ° C and a melting temperature, as determined by the Differential Scanning Calorimeter (DSC), of 148 ° C.

Example 3 Comparison of the Mechanical Properties of the Functionalized Polymer of Regio-Regular Linear Hydroxy Vecinal Versus The Conventional Branched Ethylene Copolymer-Random Vinyl Alcohol Copolymer _ _ __ _ - The polymer produced in Example 2 above (the hydroxy content equivalent to that of the ethylene / vinyl alcohol copolymer having 50 mole percent of vinyl alcohol units) was compared to a commercially available vinyl alcohol-ethylene copolymer which has 56 mole percent of vinyl alcohol units, predominantly in a head-to-tail configuration. The commercial copolymer was formed from the copolymerization of ethylene and vinyl acetate followed by conversion of the acetate groups into hydroxyl groups. All tests were carried out by conventional methods and the same conditions were used for the d-test both polymer samples. Table I below shows the properties of the conventional branched polymer that has 56 mole percent vinyl alcohol (EVAL, a product of EVALCA Co. ) and the polymer of Example 2.

- TABLE I EVOH Commercial 56% molar polymer of Example "2 of VOH 50% Molar of VOH Branched _ Linear THERMAL PROPERTIES Melting Temperature (DSC / ° C) 165 148 Crystallization Temperature (DSC / ° C) 142 118 Vitreous State Transition Temperature (DMTA / ° C) 55 45 Crystal clarity (DSC,% by weight) 27 2.3 PHYSICAL PROPERTIES Module (kilo kg / cm2 (sd) 337.2 (8.7) 180.3 (1.1) Deformation during Yield / kg / cm2 (sd) 7737 (66) 4663 (159) Deformation During Performance /% (sd) 4.3 (0.2) 5 (0.3 Maximum Deformation / kg / cm2 (sd) 9093 (851) 6578 (1160) Deformation at Break / kg / cm2 (sd) 7686 (1322) B520 (1199) Deformation at Break /% (sd) 11.8 (8.8) 221 (34) Tenacity in pound / cm3 (sd) 888 (743) 9226 (2089) Density grams / cm ^) 1,144 1,098 sd = standard deviation DMTA = dynamic mechanical thermal analysis - The foregoing shows that Polymer 2 has improved flexibility (lower modulus), tenacity, elongation properties and has a lower melting temperature. These properties show that Polymer 2 present may be able to be extruded more easily as film products having improved toughness.

Example 4 Ring Opening Metathesis Polymerization (ROMP) of 5-cycloocten-trans-1, 2-diol The 5-cycloocten-trans-1,2-diol (50 grams, 0.35 mol) was transferred to a resin container of 300 milliliters of three necks equipped with a mechanical agitator, an argon inlet and a septum. The monomer was degassed under vacuum for one hour. The content of the reaction vessel was maintained under an argon atmosphere. Methylene chloride (40 milliliters) was sprayed for 15 minutes using a stream of argon and then a cannula was transferred to the resin container. The monomer / solvent solution was stirred vigorously. In a dry box filled with argon, the ruthenium catalyst, phenylmethylene-bis (tricycloxyphosphine) dichloride (0.72 - gram, 0.879 millimole) was weighed into a glass container capped with a septum and dissolved in -10 milliliters of methylene chloride. The intense purple color catalyst solution was injected by syringe into the reaction vessel. The reaction mixture was heated and maintained at 40 ° C under an argon atmosphere with vigorous stirring for 24 hours. Subsequently, the resin container was removed from the heat and the reaction mixture was cooled to room temperature. Ethylvinyl ether (2.92 grams, 3.9 milliliters, 40.4 mmol) was added to the reaction mixture and stirred for 1.5 hours. A mixture of 100 milliliters of methanol, 50 milliliters of methylene chloride and 0.5 gram of 2,6-di-tert-butyl-4-methylphenol was added to the reaction mixture to dissolve the polymer. The homogeneous solution was subsequently emptied into a solution of 1200 milliliters of cold acetone and 0.5 gram of butylated hydroxytoluene (BHT) to precipitate the polymer. The polymer was redissolved in a mixture of 100 milliliters of methylene chloride. 100 milliliters of methanol and 0.5 gram of BHT. 2,4-pentanedione added (0.25 milliliter) and the solution was stirred for 15 minutes. the polymer was re-precipitated in cold acetone as above. The dissolution and reprecipitation were repeated one more time. The polymer was collected by filtration and dried overnight in. a vacuum oven at 60 ° C to yield 22.6 grams of a solid hard yellow polymer having ethylenic unsaturation in the polymer chain (designated Polymer 2-U). The molecular weights of the polymer are disclosed in Table II, which will be presented below.

Example 5 Ring Opening Metathesis Polymerization (ROMP) of 5-cycloocten-trans-1, 2-diol using a Chain Transfer Agent.

The 5-cycloocten-trans-1,2-diol (50 grams, 0.35 mol) was transferred to a ream container with a capacity of 250 milliliters of three neck-s equipped with an agitator-mechanical, an entrance of argon and a septum. The monomer was degassed under vacuum for one hour. The content of the reaction vessel was then maintained under an argon atmosphere. Distilled cis-3-hexen-1-ol (0.13 gram, 1.35 millimole, 0.16 milliliter) was added via syringe. The methylene chloride (40 milliliters) was sprayed for 15 minutes with a vigorous argon stream and then the cannula was transferred to the resin container. The monomer / solvent solution was stirred vigorously. In a dry box filled with argon, - the ruthenium catalyst, the bis (tricyclohexylphosphine) phenylmethylene dichloride (0.11 gram, 0.141 millimole), was weighed into a glass vessel capped with a septum and dissolved in 10 milliliters-methylene chloride. The catalyst solution was injected through a syringe into the reaction vessel. The reaction mixture was heated and maintained at 40 ° C while stirring vigorously under an argon atmosphere for 24 hours. The reaction mixture was then cooled to room temperature. To the reaction mixture was added a mixture of ethylvinyl ether (2.92 grams, 3.9 milliliters, 40.4 millimoles) together with 50 milliliters of methanol and 0.5 gram of 2,6-di-tert-butyl-4-methylphenol. After two hours, the "homogeneous polymer solution was precipitated in 2 portions of the non-solvent compound, each containing 500 milliliters of cold acetone and 0.5 gram of butylated hydroxytoluene (BHT) .The polymer was redissolved in a mixture of 50 milliliters of methylene chloride, 50 milliliters of methanol and 0.5 gram of BHT 2,4-pentanedione was added (0.25 milliliters) and the solution was stirred for 15 minutes. The polymer was again precipitated using cold acetone, as was done previously. This process was repeated once again. The polymer was collected by filtration and dried overnight in a vacuum oven at 60 ° C to yield 18.9 grams of a hard solid colorless polymer (designated as Polymer 3-U). The molecular weights of the polymer are shown in Table II. - Example 6 _ Hydrogenation of poly (5-cycloocten-trans-1, 2-diol) prepared in Example 4 A Parr reactor of 600 milliliter capacity was used for hydrogenation and a glass liner that fits within the reactor body was used as the reaction vessel. The polymer 2-U (20 grams, 0.14 mol of olefins) was dissolved in a mixture of 82 milliliters of tetrahydrofuran, 82 milliliters of methanol, 20 milliliters of methylene chloride and 0.2 gram of BHT. The Wiikinson catalyst, [tris (tp-phenylphosphine) rhodium (I)] chloride prepared from triphenylphosphine and rhodium chloride (III) in ethanol), (0.869 gram, 0.939 millimole) was added to the polymer solution. The whole of the reactor head plate was secured to the reactor body and the reactor inlet and vent valves were closed. The reactor was placed in a heating mantle and connected with a pneumatic agitator. A thermoelectric pair was connected to the reactor. The hydrogenation process is - carried out at 60 ° C under a hydrogen pressure of about 42.18 kilograms per square centimeter for 6 hours. After completion of the reaction, the reactor was slowly discharged and the reaction mixture was mixed with 600 milliliters of acetone and 0.2 gram of BHT. The solid polymer was recovered by filtration and rinsed with acetone. The polymer powder was resuspended in 600 milliliters of acetone and 0.2 gram of BHT and stirred overnight. The dispersion of the polymer was then filtered and rinsed with acetone. The final polymer was collected by filtration and dried in a vacuum oven at 60 ° C. The resulting polymer (designated as Polymer 2-S) was a fine powder with a light beige color. The yield of the polymer after hydrogenation was greater than 90 weight percent. The molecular weights and the melt flow property of Polymer 2-S are shown in Tables II and III.

Example 7 Hydrogenation of poly (5-cycloocten-trans-1, 2-diol) prepared in Example 5 The polymerase 3-U as prepared-er Example 5 (17 grams, 0.1195 mol of olefins) was dissolved in a - mixture of 70 milliliters of methanol, 70 milliliters of THF, 17 milliliters of methylene chloride and 0.17 grams of BHT. The Wiikinson catalyst (0.739 gram, 0.798 millimole) was added to the polymer solution. The hydrogenation was carried out following the procedure as described in Example 6 at a temperature of about 60 ° C for 6 hours and under hydrogen pressure of about 42.18 kilograms per square centimeter. The process of treating the polymer after hydrogenation was carried out as described in Example 6. A powder of the white polymer (designated as 3-S polymer) was obtained. See Tables 2 and 3 for molecular weight data and melt flow properties.

Example 8 Direct Hydrogenation of poly (5-cycloocten-trans-1,2-diol) Another ROMP reaction was repeated having been carried out as described in Example 5. At the end of the ROMP reaction, 3.9 milliliters were added. (2.92 grams, 40.4 millimoles) of ethylvinyl ether to the reaction mixture together with a mixture of 100 milliliters of methanol, 100 milliliters of tetrahydrofuran and 0.5 gram - of 2,6-di-tert-butyl-4-methylphenol. Hydrogenation of the polymer in solution was carried out after the procedure of Example 6 using 2.17 grams (2.34 millimoles) of the Wiikinson catalyst. A white polymer powder product (25.4 grams) was obtained (designated as Polymer 4-S). The data of the molecular weight and the melt flow index of the polymer are shown in Tables 2 and 3.

Example 9 A permeation chromatography of the Waters Alliance System number 4 equipped with a Waters 410RI detector was used to determine the molecular weight of the polymer. Phenogel 5 columns (2xlineal and 1x100 angstrom units) were used. The eluent was l-methyl-2-pyrrolidinone / 50 mM lithium bromide and GPC was carried out at 50 ° C. The polystyrene standards were used for calibration.

TABLE II Molecular Weight of Polymers Mn Mw Mz PDI Polymer 1-U 9,500 27, 800 50, 000 2.9 Polymer 1-S 23,900 47,000 78,900 2.0 Polymer 2-U 15,900 56,100 112,000 3.5 Polymer 2-S 24, 800 75,100 149,000 Polymer 3-U 41,700 110,000 201,000 2.6 Polymer 3-S 66,200 146,000 252,000 2.2 Polymer 4-S 31,300 145,000 269.00X1 4.6 The melt flow index of the polymers was determined at 190 ° C with 2.16 kilograms according to Method D1238 of the American Society for the Testing of Materials using a melt flow index device CSI MFI-2.

- Table III Property of Polymer Fusion Flow Fusion Flow Index (grams / 10 minutes) Stabilizer Polymer 1-S Polymer 2-S Polymer 3-S Polymer 4-S 0.5% by weight of sodium acetate 3.3 3.4 0.5% by weight of sodium acetate + 0.5% 10 2.3 1.4 by weight of Ultranox 626

Claims (33)

REIVI.?D ATIONS

1. A polymer product comprising a regulatory local-regulatory functionalized polymer represented by the formula: wherein each X and Y independently represents a functional group, each R independently represents a hydrogen, alkyl of 1 to 5 carbon atoms or a group X, a and b each independently represents an integer from 0 to 6 as long as the sum of a -ib is from 2 to 7 yn It has a value of at least 10.

2. The polymer product of the claim 1, wherein each R represents hydrogen.

3. The polymer product of the claim 1, wherein at least one R represents an alkyl of 1 to 2 carbon atoms.

4. The polymer product of the claim 3, wherein at least one R represents methyl.

5. The polymer product of the claim 1, 2, 3 or 4 wherein the functional groups are selected from hydroxyl, carboxylic acid, acid ester - carboxylic, acetate, carbonyl, amide or a nitrile group.

6. The polymer product of claim 5, wherein X and Y are each hydroxyl groups.

7. The polymer product of claim 5 wherein X and Y are selected from the carboxylic acid or ester groups.

8. The polymer product of claim 5, wherein X is a carbonyl group.

9. The polymer product of the claim 5, where X is an acetate group.

10. The polymer product of the claim 6, wherein each R is hydrogen, a is 2 and b is 1.

11. The polymer product of claim 5, wherein the regulatory, regulatory, neighborhood-functionalized polymer wherein the polymer further comprises units represented by the formula: wherein each X1 and Y1 independently represents a functional group selected from hydroxyl, carboxylic acid, carboxylic acid ester, acetate, carbom, amide or nitrile, or hydrogen; each R ^ independently represents hydrogen, alkyl of 1 to 5 carbon atoms, or '/', aybra one represents an integer from 0 to 6 as long as the sum of a and b is 0 or 2 to 7 and m has a value so less than about 5.

The polymer product of claim 107 wherein the regio-regular polymer further comprises units represented by the formula: wherein each YX and Y ^ independently represents a functional group selected from hiaroxyl, carboxylic acid, carboxylic acid ester, acetate, carbonyl, amide or nitrile, or hydrogen; each R1 independently represents hydrogen, alkyl of 1 to 5 carbon atoms, or X ^ -, avb each represents an integer from 0 to 6 as long as the sum a and b is 0 or 2 to 7 and m has a value so less than about 5.-

13. The polymer product comprising a regio-regular neighbor functionalized polymer represented by the formula -CH2 CH2- (CHR) -CHX CHY (cHF) r -CH2- 3 D rv where each X or Y icpr., independently of a functional group, each R independently represents a - - hydrogen, alkyl of 1 to 5 carbon atoms, or a group X, a and b each independently represents an integer from 0 to 6 as long as the sum of a + b is from 2 to 7 and n has a value of at least 10.

14. The polymer product of the claim 13, wherein each R represents hydrogen.

15. The polymer product of claim 13, wherein at least one R represents an alkyl of 1 to 3 carbon atoms.

16. The polymer product of the claim 15, wherein at least one R represents methyl.

17. The polymer product of claim 13, 14, 15 or 16, wherein the functional groups are selected from hydroxyl, carboxylic acid, carboxylic acid ester, acetate, carbonyl, amide or a nitrile group.

18. The polymer product of claim 17 wherein X and Y are each hydroxyl groups.

19. The polymer product of claim 17, wherein X and Y are selected from the carboxylic acid or ester groups.

20. The polymer product of claim 17, wherein X is carbonyl.

21. The polymer product of claim 17 wherein X is an acetate group.

22. The polymer product of claim 18, wherein each R is hydrogen, a is 2 and b is 1.

23. The polymer product of claim 17, wherein the regio-regular neighbor functionalized polymer further comprises units represented by the formula : wherein each x "'or Y" 1 independently represents a functional group selected from hydroxyl, carboxylic acid, carboxylic acid ester, acetate, C-alkyl, amide or ni Ir ilo, or hydrogen; each R ^ - independently represents hydrogen, alkyl of 1 to 5_ carbon atoms, oxayb each represents an integer from 0 to 6 as long as the sum of a and b is from 0 or 2 to 7 and m has a value at least Approximately 5.

The polymer product of claim 22, wherein the regio-regular neighbor functional polymer also comprises units represented by the formula iv - wherein each? and Y - * - independently represents a functional group selected from hydroxy, carboxylic acid, carboxylic acid ester, acetate, carbonyl, amide or nitrile, or hydrogen; each R1 independently represents hydrogen, alkyl of 1 to 5 atoms. of carbon, or X - * -, a and b each represent an integer from 0 to 6, as long as the sum a and b is 0 or 2 to 7 and m has a value of at least about 5. __

25. A method To form a regio-regular polymer having functional groups suspended from the vicinal carbon atoms of the polymer support and placed in a regular sequence arrangement along the polymer chain, which comprises polymerizing a cycloalkene of 7 to 12 carbon atoms. neighborhood functionalized carbon that has the general formula wherein X and Y, each independently, is selected from a functional group; a and b each independently represents an integer from 0 to 6 as long as a + b has a value of 2 to 7; each R independently represents hydrogen, an alkyl of 1 to 5 carbon atoms or X; putting I heard < nrn ac to the cotylic alky of 7 to 12 functionally neighboring carbon atoms with a ROMP catalyst agent to form a first linear polymer having alternative vicinal functional groups and ethylenic saturation groups; Separate the regio-regular polymer formed.

26. A method for forming a regio-regular polymer having functional groups suspended from the vicinal carbon atoms of the polymer support and placed in a regular sequence position along the polymer chain comprising a cycloalkene polymer. 7 to 12 localized carbon atoms that have the general formula wherein X and Y, each independently, is selected from a functional rupin; a and b each represent tndo í,? h < Do not monlr a IÍ IO from 0 to 6 as long as a + b has a value of? to 7; each R independently represents hydrogen, an alkyl of 1 to 5 carbon atoms or X; putting in contact the cycloalkene of 7 to 12 atoms of --urbon? fune 1a with a ROMP catalyst agent to form a first linear polymer having alternative vicinal functional groups and cytylenic unsaturation groups; hydrogenate the polimeric primer to reduce at least a portion of the ethylenic unsaturation groups therein.

27. The method of claim 25 or 26, wherein the polymerization is carried out by further contacting a second cycloalkene of the general formula: wherein X ^ and Y-- each independently is selected from a functional group or hydrogen as long as the pair of? l and Y ^ are different from the pair of X and Y; a and b each represents an integer from 0 to you as long as the sum of at-b has a value of ae 0 or 2 to 7; and each R1 independently represents hydrogen, an alkyl of 1 to 5 carbon atoms or X.

28. The method of claim 27 wherein the cycloalkene of 7 to 12 functionalized vicinal carbon atoms and the second cycloalkene are contacted in sequence with the ROMP catalyst.

29. The process of claims 25 or 26 wherein the ROMP catalyst is selected from the compound represented by the formula: L X R \ / M C IIb / XJ RJ where: M is selected from Mo, W, Os or Ru; and preferably Ru or OS; and most preferably Ru; R and R! they are independently selected from hydrogen; alkenyl of 2 to 20 carbon atoms, alchemy of 2 to 20 carbon atoms, alkyl of 1 to 20 carbon atoms, aryl, carboxylate of 1 to 20 carbon atoms, alkoxy of 1 to 20 carbon atoms, alkenyloxy of 2 at 20 carbon atoms, alkynyloxy of 2 to 20 carbon atoms, aryloxy, alkoxycarbonyl of 2 to 20 carbon atoms, alkylthio of 1 to 20 carbon atoms, alkylsulfonyl of 1 to 20 carbon atoms or alkylsulfinyl of 1 to 20 atoms of carbon; each is optionally substituted with alkyl of 1 to 5 carbon atoms, halogen, alkoxy of 1 to 5 carbon atoms or with a phenyl group optionally substituted with halogen, alkyl of 1 to 5 carbon atoms or alkoxy of 1 to 5 carbon atoms; preferably R and R - * - are independently selected from hydrogen; vinyl, alkyl of 1 to 10 carbon atoms, aryl, carboxylate of 1 to 10 carbon atoms, alkoxycarbonyl of 2 to 10 carbon atoms, alkoxy or aryloxy of 1 to 10 carbon atoms; each optionally substituted with alkyl of 1 to 5 carbon atoms, halogen, alkoxy of 1 to 5 carbon atoms or with a phenyl optionally substituted with halogen, alkyl of 1 to 5 carbon atoms or alkoxy of 1 to 5 carbon atoms; X and X-L are independently selected from any anionic coordinating group; preferably X and X ^ are independently selected from halogen, hydrogen; alkyl of 1 to 20 carbon atoms, aryl, alkoxide of 1 to 20 carbon atoms, aryloxide, alkyldicketonate of 3 to 20 carbon atoms, aryldicketonate, carboxylate of 1 to 20 carbon atoms, aryl or alkylsulfonyl of 1 to 20 atoms of carbon or alkylsulfinyl of 1 to 20 carbon atoms; each optionally substituted with alkyl of 1 to 5 carbon atoms, halogen, alkoxy of 1 to 5 carbon atoms or with a phenyl group optionally substituted with halogen, alkyl of 1 to 5 carbon atoms or alkoxy of 1 to 5 carbon atoms; L and iX are independently selected from any neutral electron donor, preferably L and L1 are independently selected from phosphine, sulfonated phosphine, phosphite, phosphinite, phosphonite, arsine, stilbene, ether, amine, amide, sulfoxide, carbonyl, nitrosyl, pyridine or thioether; and wherein any of 2 or 3 of X, I, L, X can optionally be ligated to form a multidentate chelation coordinating group.

30. The process of claims 25 or 26 wherein the molar ratio of I to II is from 2000 to 5000.

The process of claims 25 or 26 wherein the cycloalkene has from 7 to 12 functionalized carbon atoms and the ROMP catalyst is contacted in solution.

32. The process of claims 25 or 26 wherein the cyclolaquene of 7 to 12 functionalized vicinal carbon atoms, the second cycloalkene and the ROMP catalyst are contacted in solution at a temperature of about 10 ° C to 65 ° C. for a period of time of approximately 2 to 48 hours. The process of claims 25 or 26 wherein the cycloalkene of 7 to 12 carbon atoms - functionalized, the second cycloalkene and the ROMP catalyst are contacted in sequence in solution.