MXPA01003036A - Regio-regular functionalized polymeric packaging material - Google Patents

Abstract

The present invention is directed to Packaging Materials and Packaging Articles having a structure composed of a substantially linear, regio-regular functionalized hydrocarbon polymer having C4-C12 hydrocarbon polymer repeating units wherein each unit has at least one functional group uniformly pendent therefrom.

Description

REGIO-REGULAR FUNCTIONALIZED POLYMERIC PACKING MATERIAL This invention was made with the support of the Government of the United States under contract No. 70NANB5H1136 granted by the Department of Commerce's National Institute of Standars and Technology. The United States has certain rights in the invention.

BACKGROUND OF THE INVENTION The present invention is directed to films, coatings and articles useful in packaging applications, especially in the packaging of oxygen sensitive materials, such as food material and medicines. The Packing Items, either in the form of a film (single or multi-layer) or a structural design that can be flexible, semi-rigid, rigid and that can be of a lid or collapsible design ("Packing Article") serves no merely to contain the substance that is packed, but, depending on the nature of the substance, to also prevent the entry of noxious matter from the environment or, alternatively, the discharge of volatiles within a Packing Article. Oxygen from the atmosphere has long been recognized as one of the most harmful substances for many packaged materials, especially food materials. Thus, the teaching herein will primarily address but is not limited to Packing Items which have high oxygen barrier properties because they have, as part of the structure of the article, a hydroxy functionalized hydroxy-regio hydrocarbon polymer. Packaging Articles that comprise subjecting a regular regio polymer having certain other functional groups, as described herein, provide articles with other desired properties, as fully described hereinafter. In the packaging of oxygen sensitive substances, such as food materials, beverages, and pharmaceuticals (collectively "products"), contamination with oxygen can be particularly uncomfortable. Care is generally taken to minimize the introduction or concentration of oxygen to reduce the harmful or undesirable effects of oxygen on food materials or beverages. Molecular oxygen (02) can be reduced to a variety of intermediary species by the addition of one to four electrons; These species are superoxide, hydroxyl radical, hydrogen peroxide and water. 02 and water are relatively non-reactive. However, the three intermediary species are very reactive. Also, 02 can be activated to the oxygen state of a single electron (which can undergo subsequent reduction to more reactive oxygen species) by irradiation, or by the presence of catalytic agents. These reactive oxygen species are free radicals in nature, and the oxidation reactions in which they participate are therefore autocatalytic. Carbon-carbon double bonds are particularly susceptible to reaction with intermediary species. Such carbon-carbon bonds are frequently found in foods and beverages, pharmaceuticals, dyes, photochemical adhesives and rubber and polymer precursors. Virtually any product that has complex organic constituents will contain such carbon-carbon double bonds or other oxygen-reactive components, and as a result are susceptible to oxidation reactions. Thus, if oxidation products adversely affect the quality of operation, smell or taste of the packaged product, then preventing the ingress of oxygen into a Packaging Item will greatly benefit the shelf life and utility of packaged products. There are a number of strategies to deal with the oxygen that is contained within a free empty space of the Packing Article. The most basic thing is to remove the oxygen by vacuum or by inert gas or both. More recently, treatment compositions have been added of oxygen to polymeric filler compositions used in certain Packing Items (eg, bottle tops and can closures) as well as in one or more layers of polymeric films used to form Packing Items. Such purifying compositions address the need to remove oxygen from the interior in a closed packing article by reacting or combining with entrapped oxygen or with oxygen that may enter the packing article during transportation or storage. Although the methods and compositions described above address the concerns with trapped oxygen, are not directed primarily to the problems associated with the entry of oxygen and other contaminants into a Packing Article from the outside environment. Glass and metals provide packaging materials that have extremely good barrier properties with respect to the ingress of substances from the outside environment. However, these packaging materials are expensive, they provide Packing Items that are heavy, rigid in construction and, in the case of glass, breakable. Polymers have also been used extensively in packaging applications where they have many advantages over the use of glass or metal. The advantages derive from the diversity of polymers themselves and their mechanical, thermal, chemical and optical properties and from the diversity and adaptability of manufacturing techniques that can be employed. Thus, flexible bags, semi-rigid and rigid containers as well as adhesive and shrink films can be made in Packing Products that have walls of homogeneous, laminated or coated structure. Additionally, packaging materials and articles may be formed of a single layer (a composition through its thickness) or as a multilayer structure, where different layers of the structure are present to provide a combination of desired properties. For example, one or both surface layers may be composed of the polymer or polymers having groups that provide sealing properties. Other layers of polymers having high tensile strength can be formed to impart tear resistance to the resulting film and article. Similarly, polymers or polymer blends can be used in different layers of a multi-sheet material to impart gas barrier properties, printing characteristics, strength, heat shrink properties, adhesion between other layers which are otherwise deficient. adhesion properties with each other, as well as other desired properties of the resulting Packing Article. It has now been found that improved packing materials can be formed by using certain polymers having functional groups capable of providing a particular property and wherein the structure of the polymers has a substantially linear hydrocarbon backbone chain (it is substantially devoid of secondary chains). ) and has a substantially uniform sequence of atoms along the polymer chains. It has further been found that improved packing materials of certain linear polymers having a uniform sequence of atoms can be formed along the polymer chain and have substantially uniform and uniformly functional functional groups thereof (regio-regular structure). Still further it has been found that improved packing materials can be formed from the regio-regular hydrocarbon polymers having pendant functional groups of neighboring carbons along the chain (i.e. the functional groups are present in an end-to-end configuration). Thus, it is the object of the present invention to provide packaging materials and Packing Articles formed therefrom comprising a regio-regular linear hydrocarbon polymer having a structure comprising pending functional groups uniformly distributed along the polymer chain. It is also an object of the present invention to provide packaging materials and Packing articles formed thereof comprising a regio-regular linear hydrocarbon polymer having a structure comprising neighboring pendant functional groups uniformly distributed along the polymer chain. It is a further object of the present invention to provide packaging materials and Packing articles formed thereof having a composite structure of at least one layer wherein at least one of the layers of the structure comprises a functionalized linear regioregular hydrocarbon polymer. It is still a further object of the present invention to provide packaging materials and Packing articles formed thereof having a composite structure of at least one layer wherein at least one of the layers of the structure comprises a regio-regular hydrocarbon polymer. functionalized linear hydroxyl and, preferably wherein the hydroxyl groups are pendent of carbon atoms neighboring the polymer chain. It is a further object of the present invention to provide packaging materials and Packing articles formed thereof which are capable of exhibiting very low gas permeability (ie, oxygen) and are capable of having low permeability without taking into account the content of environmental humidity.

FIGURES Figure 1 is a graphical representation of oxygen permeability versus environmental humidity (relative humidity) for monolayer packaging films formed of commercially known oxygen barrier polymers and for a neighboring dihydroxy regio-regular hydrocarbon polymer, as taught at the moment. The C-H polymers are commercial polymers used in the present for comparative purposes. The "C" polymer is a polyacrylonitrile copolymer (Barex 210 from British Petroleum); Polymer "D" is a nylon polymer of meta-xylenediamine-co-adipic acid (MXD6 from DuPont); Polymer "E" is a polyvinylidene chloride (Sarán® from Dow); Polymers "B", WF "and?, G" are ethylene-vinyl alcohol copolymers having 56, 68 and 73 mole percent vinyl alcohol, respectively, ((EVALCO Products E151A, Series F, and L Series) The polymers "B", WF "and" G "are each non-linear polymers that do not have a regio-regular structure.The polymer" 7"is a neighboring dihydroxyfunctional linear regio-regulating polymer formed by polymerization of metathesis of a 1,2-dihydroxycyclooct-5-ene ring (ROMP) followed by hydrogenation Figure 2 is a carbon-13 nuclear magnetic resonance spectrum of a polymer functionalized with a neighbor, regio-regular, substantially linear hydroxyl group, by ROMP of 1, 2-dihydroxycyclooct-5-ene followed by hydrogenation, which polymer has been found useful for forming materials and Packing Items of the present invention Figure 3 is a carbon-13 nuclear magnetic resonance spectrum of ethylene-alcohol copolymer vinyl merchant It is obtained that it has 56 mole percent vinyl alcohol units (polymer "B" above). This spectrum is for comparative purposes with respect to the spectrum of Figure 2 of a polymer having a comparable hydroxyl content.

SUMMARY OF THE INVENTION The present invention is directed to packaging materials and Packing articles having as part of their structure a functionalized linear regio-regular hydrocarbon polymer. The packaging material can be comprised of a layer or a plurality of layers with the proviso that at least one layer of the material and the resulting article comprises the functionalized linear regio-regular hydrocarbon polymer, preferably wherein the functional groups of the polymer are slopes of carbon atoms neighboring the spine of the hydrocarbon polymer.

DETAILED DESCRIPTION The packaging material and the Packing Items of the present invention will be described in terms of such materials and articles which have a thickness comprising a substantially uniform composition from one surface to the other surface forming the thickness limits (i.e. a single or monolayer sheet structure) as well as materials and articles having a thickness comprising a plurality of layers (i.e. a multi-layered or multilayer structure). Additionally, the present invention will be directed to the layer or layers of the structure using the currently described functionalized polymers which are substantially linear, have regio-regular structures with respect to the hydrocarbon backbone of the polymer and, preferably, have functional groups in a regular point-to-point relationship with one another (functional groups are dependent on adjacent carbon atoms of the hydrocarbon backbone of the polymer). The remaining layer or layers forming a multilayer material can be selected from any known composition used in packaging applications known to one reasonably skilled in the art to provide a multilayer packaging article material. The subject material and the structure formed thereof can be used to form part or substantially all of the object of the Packaging Article. The present invention is directed to packaging materials and articles which utilize a regular linear, substantially linear functionalized hydrocarbon polymer. Such polymers have repeating units that can be represented by the formula: wherein X and Y each independently represent hydrogen, a C 1 -C 5 alkyl, or a functional group selected from a hydroxyl group, a carboxylic acid group, a carboxylic acid ester group of a C 1 -C 5 alkyl, an acetate group , an amide group, a nitrile group or a carbonyl group; with the proviso that at least one of the groups X and Y of each unit of the polymer represents one of the functional groups and, preferably both groups X and Y of each unit of 1 polymer represent functional groups; each R independently represents a hydrogen atom or a C1-C5 alkyl, preferably hydrogen: "a" represents an integer from 1 to 9, preferably 1, 2 or 4-9- and more preferably 1, 2, 5, 7 or 9; and "n" represents an integer from 5 to 5000 and preferably from 10 to 3000. Thus, the subject polymer is substantially linear, has a spine chain of hydrocarbon polymer, has repeating units along the chain and comprises at least one functional group (preferably two groups on neighboring carbon atoms) regio-regularly placed along the polymer chain. The functionalized regio-regular hydrocarbon polymers having small repeating units can be formed by polymerization of acyclic diene metathesis, as described by Valentin and Wagner in Macromolecules (1998) 31, 2764-2773; by polymerization of ring-opening metathesis, as described by Hillmeyer, Laredo and Grubbs, in Macromolecules (1995) 28, 6311-6316; by hydroboration of unsaturated polymers to provide monohydroxy functional polymers, as described by Ramakrishnan in Macromolecules (1991) 24, 3753-3759 and by Ramakrishnan and Chung in Macromolecules (1990) 23, 4519-4524; and by polymerization of capped difunctional cyclobutene ring aperture metathesis 3,4 to provide an unsaturated polymer, as described by Perrot and Novak in Macromolecules (1995) 28, 3492-3494 which, after removal of the cap group protective, can be converted to the saturated polymer by hydrogenation. The teachings of each of the articles cited above are directed to synthesis processes for forming such polymers and, such teachings are hereby incorporated in their entirety for reference. In addition to the synthesis described above, certain functionalized regio-regulatory polymers prepared by ROMP of functionalized C7-C? 2 cyclic olefins have been described in the co-pending US patent application Serial No. 09 / 052,079, filed on 31 March 1998, the teachings of which are incorporated herein in their entirety for reference. The polymers of this co-pending application, in particular those having neighboring functional groups, are preferred polymers to be used to form the current Packing Items. Packaging materials and Articles of Packaging of the present invention comprises a structure of at least one layer (one or more than one layer) wherein at least one of the layer (s) is formed of a composition comprising a functionalized regio-regular hydrocarbon polymer or a mixture of the same. The regio-regular polymers used herein preferably have substantially all of the neighboring configuration of pendant functional groups of the polymer spine chain. The subject polymers can be formed by ring opening metathesis polymerization (ROMP) of a C5 or C-C2 cyclic olefin having at least one and more preferably, neighboring functional groups pendent of the ring carbon atoms. The polymer formed can then be hydrogenated to provide a resulting polymer of substantially linear alkylene chain having pendant functional groups (preferably configured end-to-end) periodically distributed along the polymer chain. Alternatively, the polymer formed by ROMP can be partially hydrogenated to provide a resulting polymer which also periodically has ethylenic unsaturation as part of the hydrocarbon backbone structure. These polymers have improved properties that make them useful for forming packaging materials and articles. The polymer used in the subject packaging material and article can be formed of a functionalized C5 or C7-C? 2 cyclohydrocarbon having an olefinic unsaturation group as part of the ring structure. The functionalized cyclohydrocarbon can, for example, selected from cyclopentene, cycloheptene, cyclooctene, cyclononene, cyclodecene, cyclo undecene, cyclohedecene and the like. Preferred functionalized cyclohydrocarbons are those having 5, -8, 10 or 12 carbon atoms that compensate for the ring. The resulting polymer I thus has repeating units where "a" is equal to 2, 5, 7, 9 respectively. The term C5 and C7-C12 refers to the number of carbon atoms that form the ring structure of the functionalized cyclic olefin. The functionalized polymer used herein may be formed from an unsaturated cyclohydrocarbon having at least one functional group pendent for a carbon atom of the initial ring material. Preferably, the starting material of cycloalkene and the resulting polymer must have neighboring functional groups pendent of carbon atoms of the ring and the backbone chain of the polymer respectively. The teachings made in reference to the co-pending application, North American Serial No. 09 / 052,079, with respect to the functionalized cycloolefin starting material, the resulting polymer, and the method for forming same are also applicable with respect to the initial material and the polymer having only one functional group per repeating unit (region) of the regio-regular polymer. Where the functional group can be either one or more than one group in a region, the teachings of the referenced co-pending application can be seen as having X of Formula II, IV and V hereinafter as they represent hydrogen or a functional group, and is preferably a functional group, as set forth in the co-pending co-pending US patent application. In any case, at least one carbon that is 14 a cyclic olefin of C5 or C7-C2 having at least one and more preferably, neighboring functional groups pendent of the ring carbon atoms. The polymer formed can then be hydrogenated to provide a resulting polymer of substantially linear alkylene chain having pendant functional groups (preferably configured end-to-end) periodically distributed along the polymer chain. Alternatively, the polymer formed by ROMP can be partially hydrogenated to provide a resultant polymer which also periodically has ethylenic unsaturation as part of the hydrocarbon backbone structure. These polymers have improved properties that make them useful for forming packaging materials and articles. The polymer used in the subject packaging material and article can be formed from a functionalized C5 or C7-C? 2 cyclohydrocarbon having an olefinic unsaturation group as part of the ring structure. The functionalized cyclohydrocarbide can, for example, be selected from cyclopentene, cycloheptene, cyclooctene, cyclononene, cyclodecene, cyclo undecene, cyclododecene and the like. Preferred functionalized cyclohydrocarbons are those having 5:, 8, 10 or 12 carbon atoms that compensate for the ring. The resulting polymer I thus has repeating units where "a" equals 2, 5, 7, 9 respectively. The term C5 and C7-C? 2 refers to the number of carbon atoms that form the ring structure of the functionalized cyclic olefin. The functionalized polymer used herein may be formed from an unsaturated cyclohydrocarbon having at least one functional group pendent for a carbon atom of the initial ring material. Preferably, the starting material of cycloalkene and the resulting polymer must have neighboring functional groups pendent of carbon atoms of the ring and the backbone chain of the polymer respectively. The teachings made in reference to the co-pending application, North American Serial No. 09 / 052,079, with respect to the functionalized cycloolefin starting material, the resulting polymer, and the method for forming same are also applicable with respect to the initial material and the polymer having only one functional group per repeating unit (region) of the regio-regular polymer. Where the functional group can be either one or more than one group in a region, the teachings of the referenced co-pending application can be seen as having X of Formula II, IV and V hereinafter as they represent hydrogen or a functional group, and is preferably a -functional group, as set forth in the co-pending co-pending US patent application. In any case, at least one carbon that is 16 adjacent to the olefinic group of the ring must be free of functional groups. This is when the ethylene carbons 1 and 2 are listed, the next carbon and, preferably, the carbon having the highest number defining the ring should not contain pendant groups except for hydrogen atoms. The hydrocarbon cycle, in addition to the functional groups set forth above, may contain pendant functional or hydrocarbon groups of other ring carbon atoms except for at least one ring carbon atom that is adjacent to the ethylene group, as described above. In general, the cyclic olefins useful to provide the regio-regular polymers used herein are a functionalized cycloalkene which may be represented as: wherein at least one carbon atom that is alpha with respect to the ethylenic group has only hydrogen atoms outstanding thereon. X represents hydrogen or a C1-C5 or Y alkyl; and Y represents a functional group 17 selected from a hydroxyl group, carboxylic acid, carboxylic acid esters of a C1-C5 alkyl, acetate, amide, nitrile or carbonyl. It is preferred that X and Y rsent functional groups and that they are the same functional group. The symbol "a" is a value from 0 to 6 and "b" has a value from 0 to 6 with the condition that the sum of a + b is a value of 0 or an integer between 2 and 7. Each R The ring carbon atoms of "a" and ttb "can independently rsent a hydrogen atom, a C1-C5 alkyl group (preferably one of C? ~ C2) or a functional group, as described above. Packaging material and the Packaging Article of the subject invention will be discussed herein in the following, primarily in terms of the use of hydroxylated polymers (wherein X or Y; or both X and Y represent a -OH group). These polymers can be seen as copolymers of vinyl alcohol and an alkylene, such as alkylene, linear propylene and the like. For example, 1,2-dihydroxycyclooct-5-ene ROMP has been found to provide a polymer which, after hydrogenation can be seen as a copolymer of ethylene and vinyl alcohol wherein the vinyl alcohol units are strictly arranged in a configuration tip to tip. Ethylene / vinyl alcohol copolymers (EVOH) are commonly aable and materials have been used. packaging items However, these known polymers are formed by copolymerization of free radicals of ethylene and vinyl acetate followed by hydrolysis of the acetate groups into hydroxyl groups. The conventional EVOH copolymer contains each vinyl alcohol monomer unit distributed randomly along the polymer chain, the hydroxyl groups (without considering the residual acetate groups) are generally configured tip-to-tail when part of the adjacent monomer units and the polymer contain considerable branched chains of long and short chain. In contrast, the preferred hydroxy-containing polymer provided by the present invention (a = 2; b = l; X and Y-OH, each R = H) can be seen as analogous to an ethylene / vinyl alcohol copolymer with the unique characteristic of having monomer units of vinyl alcohol pairs in a sequential arrangement of ethylene-vinyl alcohol / vinyl alcohol-ethylene along the polymer chain. Additionally, the adjacent vinyl alcohol units are only in an end-to-end configuration. Figure 2 is an NMR spectrum of the regio-regular polymer used herein while Figure 3 is a commercial EVOH copolymer NMR spectrum having substantially the same OH content. Another example of a polymer formation or ROMP 19 of 4-cycloocten-1-ol to provide a polymer which after hydrogenation can be viewed as a copolymer of ethylene and vinyl alcohol having 25 mole percent vinyl alcohol units. Again, EVOH copolymers having 25 mole percent vinyl alcohol are commercially available but differ from that currently used. The commercial materials have the vinyl alcohol units randomly distributed along the polymer chain and have a branched structure instead of a regio-regular, substantially linear configuration. Alternatively, linear, substantially regio-regular, hydroxy-functionalized polymers can be formed through hydroboration / oxidation of cis-1,4-polybutadiene according to the procedure of Ramakrishnan, supra. It is well known that the polymerization of 1,3-butadiene in cis-1,4-polybutadiene provides a linear hydrocarbon polymer having an olefinic unsaturation for every unit that is repeated every four carbon atoms of the polymeric spine chain. The olefinic units, evenly distributed throughout the polymer chain can be reacted by hydroboration / oxidation in the manner described by the Ramakrishnan references cited above for provide a single hydroxyl functional group for every four carbon atoms. Thus, the resulting polymer can be seen again as an ethylene / vinyl alcohol copolymer where the vinyl alcohol units are distributed substantially uniformly (regularly) along the polymer chain and the spinal hydrocarbon polymer is substantially linear compounds of regions of four repeating carbon units. Again, such polymers are distinct from the commercial counterpart formed of ethylene and vinyl acetate, as discussed above. Similar to its highest functional-hydroxyl unit-polymer polymer described in the co-pending North American application no. of Series 079, the use of this regio-regular polymer, linear to poly (hydroxybutylene), has been found to provide a high degree of gas barrier properties and other desired physical properties not obtainable by conventional materials of similar hydroxyl content. Other functionalized polymers that may be used herein may be prepared in the manner fully described in the referenced co-pending application, North American application no. of Series 09 / 052,079, and hereinafter. The initial monomeric compound, a functionalized C5 or C7-C? 2 cycloalkene, wherein C5 and C7 ~ C? 2 21 refers to the number of ring carbon atoms) represented by the formula wherein X represents hydrogen, a C1-C5 alkyl or Y; and Y represent functional groups, as described above and preferably X and Y represent the same functional group, "a" represents a numerical value from 0 to 6 and "b" represents a numerical value from 0 to 6, with the condition of that the sum of a + b is a value of 0 or an integer of 2 to 7. Each R of the ring carbon atoms of "a" and / or of?, b "may be unsubstituted (preferred) or additionally substituted as described above When X and Y are functional groups, the X and Y groups can be located sterically on the same or opposite sides of the plane that dissects the ring carbon atoms except in the case of X and / or And being a carbonyl group, in which case the group would be substantially within the plane of the ring In other words, X and Y can be either in a cis or trans configuration with respect to each other. 22 The formation of the preferred difunctional cycloalkenes (II) found useful herein can be achieved by known methods. For example, 5-cyclooctene-trans-1,2-diol can be prepared by reacting the 1,5-cyclooctadiene monoepoxide with a perchloric acid in an aqueous solution at elevated temperatures as taught in French Patent 1,294,313 whose teaching it is incorporated herein in its entirety for reference. Other methods for preparing the functionalized dihydroxy cycloalkene include reacting cycloalkadiene monoepoxide with acetic acid and potassium acetate 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. to the. Canadian Journal of Chemistry, Vol. 50. 1548 (1972)]; reacting a cycloalkadiene monoepoxide with an organic acid, such as formic or acetic acid to form the hydroxy compound / acetate followed by saponification [Mclntoch, Canadian Journal of Chemistry, Vol. 50, 2152 (1972)]: or reacting a cycloalkadiene with osmium tetraoxide in ether / pyridine solution at low temperatures followed by reflux with 'sodium sulfite in water / alcohol [Leitich Tetrahedron Letters. No. 38, 3589 (1978)]. A diol cycloalkene can be formed in the diol 23 neighbor according to the procedure described by Yates et al., Canadian J. of Chem. Vol. 50, 1548 (1972). The neighboring cycloalkene hydroxy ketone and the neighboring acetone / cycloalkene acetate are formed by oxidizing the hydroxy / acetate with chromic acid in acetone at low temperature (eg 0-10 ° C) to form the acetone / acetate. the acetone / cycloalkene acetate can be recovered by distillation. The acetone / acetate can be converted to the neighboring hydroxy ketone cycloalkene by hydrolysis with sodium hydroxide in methanol at slightly elevated temperatures (for example 40 ° C). The onoepoxy cycloalkene, which is the precursor of several of the synthetic routes described above, can be obtained by catalytic oxidation of a cycloalkadiene using a peroxide and sodium tungstate as a catalyst as described by Venturello, J., Org. Chem., ^ 8, 3831 (1983) and J. Org. Chem., 53, 1553 (1988). Other methods for forming ono-epoxycycloalkene are described by Grubbs.

Macromolecules, 28 ^, 6311 (1995); Camps. J. Org. Chem. 47, 5402 (1982); I uta J. Org. Chem. 44, 1351 (1979); Murray, Org. Syn. 74, 91 (1996); and Payne, Tetrahedron ,. 18, 763 (1962). The teachings of each of the references cited above is incorporated herein in its 24th Totality for reference. The functionalized cycloalkene can be subjected to ring opening metathesis polymerization using a well-defined ROMP catalyst. Such catalysts found useful herein are described by Schrock et al in JACS 1990, 112, 3875; and US Patent Nos. 4,681,956; 5,312,940; and 5,342.909. Preferred catalysts are those described in U.S. Patent No. 5,312,940. The teachings of each of the above references are incorporated herein in their entirety for reference. A class of ROMP catalyst found useful in providing the present polymers can be represented by the general formula: M (NRX) (OR 2) 2 (CHR 3) III (a) wherein: M is molybdenum or tungsten; R1 and R2 of Formula III (a) are independently selected from alkyl, aryl, aralkyl or halogen-substituted derivatives or silicon-containing analogs thereof. Examples of aryl groups are phenyl, 2,6-diisopropylphenyl and 2,4,6-trimethylphenyl. Examples of aralkyl groups are benzyl and triphenylmethyl. Examples of R 1 in the formula Illa are 2,6-disopropylphenyl, 2,4,6-trimethylphenyl, 2,6-di-t-butylphenyl, pentafluorophenyl, t-butyl, trimethylsilyl, triphenylmethyl, triphenylsilyl. tri-t-butylsilyl, and perfluoro-2-methyl-2-pentyl and the like. Examples of R2 in the Formula Illa are t-butyl, trifluoro-t-butyl [(CF3) (CH3) 2C], perfluoro-t-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 M = CHR3 complex and the olefin or olefins being metalated, alkyl having 1-20 carbons, aryl having 6-20 carbons and aralkyl having 7-20 carbons; R3 is preferably t-butyl or phenyl, but since the M-CHR3 portion of the compound of Formula Illa is intimately involved in the catalytic reaction, it is recognized that the CHR3 ligand is replaced by any other alkylidene fragment of the olefins which are being metatheized. Illa catalyst should not be used with monomer II which has a proton on the functional group, which is, for example, hydroxyl, carboxylic acid and the like. It can be used where the acetate, carbonyl groups and the like are present. 26 The preferred ROMP catalysts are those represented by the general formula: where: M is selected from Mo,, Os or Ru; and preferably Ru or Os, and more preferably Ru; R and R1 are independently selected from hydrogen; C2-C20 alkenyl, C2-C20 alkynyl, C1-C20 alkyl, aryl, C1-C20 carboxylate, C1-C20 alkoxy, C2-C20 alkenyloxy, C2-C20 alkenyloxy, aryloxy, C2- alkoxycarbonyl C20, C? -C20 alkylthio, C? -C2o alkylsulfonyl, or d.-C20 alkylsulfinyl; each optionally substituted with C 1 -C 5 alkyl, halogen, C 1 -C 5 alkoxy, or with phenyl group optionally substituted with halogen, C 1 -C 5 alkyl, or C 1 -C 5 alkoxy; preferably R and R1 are independently selected from hydrogen; vinyl, C 1 -C 10 alkyl, aryl, C 1 -C 10 carboxylate, C 2 -C 10 alkoxycarbonyl, C 1 -C 10 alkoxy or aryloxy; each optionally substituted with C 1 -C 5 alkyl, halogen, C 1 -C 5 alkoxy, or with a phenyl optionally substituted with halogen, C 1 -C 5 alkyl or C 1 -C 5 alkoxy; 27 X and X1 are independently selected from any anionic ligand; preferably X and X1 are independently selected from halogen, hydrogen, C? -C2alkyl, aryl, C? -C20 alkoxide, aryloxide, C3-C20alkyldicyketonate, aryldicyketonate, C? -C2oalkylate, aryl or alkyl sulfonyl C? ~ C2o, or C? -C20 alkylsulfinyl; each optionally substituted with C 1 -C 5 alkyl, halogen, C 1 -C 5 alkoxy, or with phenyl group optionally substituted with halogen, C 1 -C 5 alkyl, or Ci-C 5 alkoxy; L and L1 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, X1, L, L1 may optionally be linked together to form a multidentate chelating ligand. The ROMP of a functional C5 or C7-C? 2 cycloalkene (II) can be carried out neat or by providing a solution of (II) in a hydrocarbon solvent such as an aromatic hydrocarbon, such as, for example; benzene, toluene, tetrahydrofuran; dialkyl ethers, cyclic ethers; alcohol 28 sec-butyl, tert-butyl alcohol; and the like and halogenated solvents, such as halogenated aromatics as well as halogenated alkanes and the like. Preferred solvents are fluorinated alkanes, such as dichloromethane and the like, chlorinated aromatics such as monochlorobenzene and the like. The molar ratio of (II) to catalyst III (b) should be approximately 200 to 5,000, preferably from about 400 to 3000. The ROMP reaction can be carried out at temperatures of about 10 ° C, 75 ° C and preferably about 20 ° C to 50 ° C. The most preferred temperature will depend on the particular starting material, the ROMP catalyst and the solvent used can be determined by minor experimentation and is usually in the range of 35 to 50 ° C. The time spent to carry out the ROMP reaction can be in the range of only a few minutes to about 48 hours. The reaction time is usually 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 II to catalyst III (b) and / or (b) introducing a suitable acyclic olefin in small amounts to act as a chain transfer agent . Such agents must be soluble in the reaction medium of the polymerization or the monomer used and may be, for example, cis-3-buten-1-ol, cis-3-hexen-1-ol. and similar. When used, the chain transfer agent (CTA) must be present in a molar ratio of monomer II to CTA of about 50 to 2000 and preferably of about 200 to 1000. ROMP of the above functional cycloalkene (II) provides a polymer that has repeating units of the general formula: rCH-ZCH- - (CHR) -CHX CHY- (cHR-) t-CH: IV wherein X, Y, a and b are the same as defined for formula I above and each R independently represents hydrogen or a C 1 -C 5 alkyl or a Y group. It should be noted that the ROMP process of the preferred cycloalkene (II) provides a polymer IV having neighboring functional groups X and Y, the polymer chain is substantially linear, and the chain additionally contains an ethylenic unsaturation spaced (a) from carbon atoms of functional group X. In the polymer, groups X and Y may have the same or opposite stereo-configuration as that of the cyclic monomer used. Similarly, the polymeric product IV has double bonds which normally provides a mixture of both cis and trans geometric isomers (ie the hydrogen atom of the alkenyl can be cis or trans with respect to its neighboring hydrogen atom of 30). closest alkenyl). Additionally, the above structure IV is the repeating unit of the polymer formed and, thus, has no substantial degree of randomness of the X and Y groups and of the alkylene units along the polymer chain. The polymeric product IV can be recovered by introducing a non-solvent into the solution to cause the polymer to precipitate out of the solution. Such non-solvents include, for example, alkanes (e.g., pentane, hexane, heptane, etc.); ketones (for example acetone, methyl ethyl ketone, etc.) and the like. The particular non-solvent that is to be used can be easily determined by the artisan. The polymeric product IV can be easily recovered by introducing the polymerization reaction mixture into an excess of a non-solvent liquid. The preferred conditions and catalyst for carrying out a ROMP of 5-cyclooctene-trans-1,2-diol are: Catalyst: Compound III (b) wherein X = Xi = Cl L = L1 = tricycloalkylphosphine (ie tricyclohexylphosphine) R = phenyl or 1, 1-diphenylethenyl R 1 = hydrogen Solvent or solvents: chlorinated alkanes, (for example, methylene chloride) Temperature range: 40-50 ° C Time range: 6 to 24 hours The separated polymer IV can be subjected to conventional catalytic hydrogenation or, optionally, chemical hydrogenation (for example using chemical hydrogenation agents such as para-toluenesulfonyl hydrazine and the like) to provide a substantially saturated and fully saturated polymer V. The structure of the repeating units of polymer V can be represented by the formula: wherein R, X, Y, a and b are as defined for Formula IV above. Alternatively, partial hydrogenation can be achieved by controlling the hydrogenation reaction by known methods. Such methods are known to those skilled in the art and can include controlling the molar ratio of olefinic groups of the polymer of chemical hydrogenation agents, the hydrogenation time, etc. Where catalytic hydrogenation is employed, the degree of saturation can be controlled by the time or pressure of hydrogen used. Thus, the resulting polymer V may have residual ethylenic unsaturation for 32 provide sites for grafting, insertion of other functional groups or, for chemical crosslinking for desired reasons. Additionally, polymers with residual ethylenic unsaturation can be used to form Packing Items, such as films, which are subsequently subjected to irradiation such as electron beam irradiation to cause cross-linking of the polymer contained within the layer or layers of which it is a part. The amount of residual ethylenic unsaturation will depend on the degree of grafting, desired insertion or reticulation, the particular treatment that is used and the degree of such treatment. In the case of electron beam irradiation, it will depend on the dosage of the radiation and the position of the layer containing the target polymer within the structure of the Packaging Article. The exact degree of unsaturation which provides the desired property can be determined by simple experimentation by the artisan. The hydrogenation of polymer IV can be carried out using conventional hydrogenation, such as ilkinson catalyst and the use of hydrogen or the use of other conventional hydrogenation catalysts, such as Raney nickel, palladium on carbon, platinum on carbonate, ruthenium complex. alkylene or the like. The polymer IV is normally dissolved in a solvent or a mixture of solvents. such as those described above for the ROMP polymerization and are subjected to a hydrogen pressure of at least about 300 psi, preferably about 600 to 5000 psi. Hydrogenation is usually completed in less than 8 hours although shorter or longer times may be used. Normally the hydrogenation is carried out for a period of 2 to 8 hours, with 3 to 7 hours being preferred. When the ROMP reaction of the monomer II is carried out in solution, the resulting solution containing the polymer IV can be used directly to carry out the hydrogenation step. Thus, the step of separating polymer IV from the polymerization medium can be eliminated. Additionally, it is believed that any ROMP catalyst that may be present in the polymer IV solution may assist in the hydrogenation reaction. In a preferred embodiment, an amount of ROMP catalyst equivalent to that used to achieve the ring opening metathesis polymerization reaction is added, after the polymerization is complete, to catalyze the hydrogenation reaction. An alternative way to form regio-regular polymers found useful for forming packaging materials and Packing Items of the present invention is to submit a 34 cycloalkene monoepoxy of C5 or C7-C? 2 having at least one (and preferably both) ring carbon atoms adjacent to the ethylenic unsaturation as an unsubstituted carbon, for ROMP as described hereinbefore for the difunctional monomer II neighbour. The intermediate polymer product is isolated by precipitation with a non-solvent followed by further conversion of the epoxy groups to the desired neighboring functional groups according to the synthetic routes described above. The resulting polymer IV can be further hydrogenated to provide polymer V in the manner described above. Another alternative route to provide the regio-regular polymer V for use in the subject materials and packaging articles is to first epoxidize the ethylenic unsaturation units that are substantially and uniformly distributed along a linear unsaturated hydrocarbon polymer chain. The linear unsaturated hydrocarbon polymers having ethylenic units uniformly distributed within the polymeric spine chain can be formed by ROMP of a cycloalkene, such as a C7-C2-cycloalkene or a 1,5-cyclooctadiene. The resulting polymer is linear and contains units of ethylenic unsaturation which are substantially 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 to the desired neighboring functional groups using the synthesis methods described above, to provide the polymeric product V. Alternatively, ROMP polymers of non-functionalized cycloalkenes can be hydroborated / oxidized to provide useful polymers in films of the subject invention. In addition to forming polymers IV and V of a single monomer II, as described above, some can form ROMP copolymers of monomer II having X and Y groups as described above and ROMP of a bundle comonomer. Comonomer II (a) can be selected from a cycloalkene represented by the formula: where X1 and Y1 have the same definition as X and 36 And described above for monomer II or can be selected (one or both) of hydrogen, with the proviso that X1 and Y1 together provide pairs that are different from the X and Y pairs of monomer I; R1 has the same definition as R of monomer II and a and b are each independently an integer of 0-6 with the proviso that the sum of a + b is 0 or 2-7. The ROMP copolymerization of the monomers II and Ilia to provide a linear copolymer of the subject invention can be carried out with molar ratios of II to IA of from about 50:50 to about 100: 0 being preferred from 60:40 to 100: 0. Because the ROMP of the monomer present is substantially a support polymerization, some may introduce the monomer II and the monomer Ia sequentially into the polymerization reaction medium to provide the unit block (s) I defined above and the unit (s) block (s) where X and Y are as defined immediately below. previous to lia. Thus a regio-regular block copolymer product is formed which is linear and preferably has neighboring functional units uniformly spaced in an end-to-end configuration at least along a portion of the polymer chain (derived from monomer II and a second segment of the polymer chain that possibly has a second set of 37 neighbor functional units uniformly configured along a portion of the same polymer chain (derived from monomer lia). This block copolymer can be hydrogenated, as described above, for the homopolymer. The polymers referenced above have been compared to their copolymer counterpart formed by conventional free radical polymerization and hydrolysis and have been found to have superior elongation properties as well as improved toughness, lower melting temperature and lower density. Polymers have been found useful for forming films, coatings, laminates, molds and the like, for packaging applications. For example, regio-regular hydroxy-functional polymers (where the structure I, X = H, Y = OH and R = H, and where X and Y are each equal to OH and R = H) formed in accordance with the present invention have been found to have superior properties of toughness, flexibility and elongation, and very low and uniform properties of gas permeability not obtainable with conventional analog copolymers formed from free radicals having comparable hydroxyl content. Additionally, "when the functional group Y or the groups X and Y are ester groups of carboxylic acid, the resultant linear regio-regular polymer provides an packaging material that has good heat seal properties; when such a group or groups are free of carboxylic acid groups, the resulting regio-regular linear polymer provides bonding (bonding) properties to bond together distinctly different layers of a multi-sheet material; when such a group or groups are amide groups, the resulting polymer provides a packing material having good protein adhesion properties and good ink adhesion to allow printing thereon; and when such groups are carboxylic acid groups they can be treated with a base metal or alkaline or alkaline earth oxide or zinc oxide to provide ionomeric units, which provide a packing material having good antifogging properties, heat sealability and protein adhesion. As indicated above, the regio-regular polymer forms at least one layer of the packaging material and Packing Items of the subject invention. When the material and article are of a single layer structure, such materials and / or articles can be formed by extrusion, injection molding or extrusion / thermoforming processes. When the material and the article are of a multilayer structure, they are typically formed using coextrusion, coating, lamination, blow molding, 39 coextrusion / thermoforming, extrusion / coating or extrusion / lamination, as taught in U.S. Patents 5,350,622 and 5,529,833. The layers of the Packaging Item containing the regio-regular object polymer can be formed only of the regio-regular polymer having the desired functionality for a specific known use. It has been unexpectedly found that the material containing such a layer has improved physical properties, such as flexibility, toughness and elongation as well as functionality (ie end uses) when compared to a similar packaging material containing a conventional polymer layer of similar functional group content. Alternatively, the layer of the packaging material containing the regio-regular object polymer may be in the form of a composition comprising the regio-regular polymer uniformly distributed or dispersed in another polymer or polymers. It is preferred that the composition retain a high degree of transparency, since such property is highly desired in the packaging art and additionally, indicates the compatibility of the particular regio-regular polymer and the carrier polymer used. "Normally, the regio-regular polymer should be the main component of the composition, preferably being greater than 60% by weight and more than 40% by weight. preferably greater than 75% by weight. The carrier polymer can be selected from any thermoplastic polymer such as PVC, EVA, PET, PE, PP or copolymers thereof. For example, the functionalized regio-regularized hydroxyl V polymer described herein and in the referenced co-pending application can be mixed with a conventional EVOH copolymer for a particular end use. The exact nature of the carrier polymer and the amount to be mixed with the regio-regular polymer selected for use can be easily determined by the artisan depending on the end use, the desire to maintain transparency, and the degree of functionality that will be presented. for the material and packaging items. With respect to the preferred functionalized regio-regular hydrocarbon polymer wherein X or Y is a hydroxyl group or X and Y are neighboring hydroxyl groups, it has been found that the resulting packing material has extremely low values of gas permeability (oxygen) and keeps the values low regardless of the moisture content in the surrounding environments (exterior and interior to the resulting Packing Article). Comparative Results for the Regio-Regular Polymer Functionalised Dihydroxyl Neighbor Object versus Various Commercial Ethylene-Vinyl Alcohol Copolymers (which have diverse 41 vinyl alcohol content), as well as other known gas barrier polymers are illustrated in Figure 1. The material present shows to be almost 100 times more effective than a gas barrier material than its commercial counterpart EVOH having approximately 56% in moles of vinyl alcohol (Polymer B). The layer of the packing material containing the regio-regular object polymer can be of any thickness. The exact thickness will depend on its particular function as part of the packaging material as well as the structure of the packaging material (film or semi-rigid or rigid article). With respect to the films, the thickness can vary from 0.025 to 10 thousandths, preferably from 0.05 to 8 thousandths and more preferably 0.1 to 5 thousandths. Where the material is used as, or as part of, a semi-rigid or rigid article, the layer containing the functionalized regio-regular polymer defined herein may vary from about 0.025 mil to 10 mil, preferably 0.05 mil to 8 mil . The exact thickness can be determined by the artisan for the particular application. The composition of the layer comprising the regio-regular polymer defined herein may additionally contain other components, such as pigments, fillers, clays, exfoliated clays (for example nanocomposite utility), stabilizers, processing aids, plasticizers, flame retardants, antifog agents, staining material and the like. The total amount of the additives is generally less than 10%, commonly less than 5% by weight in relation to the total composition. The selection of such components depends mainly on the material and article that is going to be formed, its method of formation and its end use contemplated. Selection factors for such components are well known in the art. The packaging material and Packing article object of the present invention may be composed of a single-layer or multilayer structure wherein at least one layer comprises a functionalized linear regio-regular hydrocarbon polymer. The polymer can additionally be crosslinked and / or oriented by spreading (uni or biaxially) as desired by those skilled in the art. A packaging material and multilayer Packing Items can be constructed with a plurality of layers, each of which is selected to perform a particular function. When a layer of a functionalized polymer is formed, such a layer can be formed from the functionalized linear regio-regular hydrocarbon polymer contemplated herein wherein the polymer has the functionality of the polymer. appropriate Thus, for example, a multilayer packaging material and article may contain a gas barrier layer comprising a regio-regular hydroxy functionalized polymer (preferably the neighboring dihydroxy) and a sealant layer wherein the functionality is selected from carboxylate ester groups or simply linear polyethylene of the low density type. In many multilayer structures, at least one surface layer (and optionally, both surface layers) are structural and protective layers), such as those formed of olefinic thermoplastic material such as, for example, polypropylene, low density polyethylene, linear low density polyethylene. (LLDPE) and the like. An inner layer between the surface layers may include a gas barrier layer such as, for example, composed of the neighboring dihydroxy regio-regular polymer described hereinbefore and tie layers to provide interlaminate adhesion. Other examples of multi-layer structures useful for packaging materials and Packing Items include two-layer structures composed of a barrier layer (neighbor or monohydroxy dihydroxy regio-regular hydrocarbon polymer described above) and a heat sealable layer which may comprise a polyolefin such as, for example, ethylene / butene copolymers, copolymers of ethylene / hexene, ethylene / octene copolymers, ethylene / unsaturated ester copolymer (e.g., erylene / vinyl acetate or ethylene / alkyl acrylate copolymers) and the like. A three layer structure can comprise the two previous layers further having a wear resistant or abuse layer as the surface layer adjacent to the barrier layer to provide a multi-layer abuse resistant / barrier / sealer structure. The abuse resistant layer may comprise a polyolefin such as polyethylene, polypropylene and the like. Another multilayer structure may comprise a layer or more of a layer which is used to secure or improve the interlamellar bond strength between any or all of the other layers of a packaging material or article (a tie layer). The location of such a tie layer or layers will depend on the other layers used and their inherent adhesion to one another. The tie layer may comprise a copolymer of ethylene and (meth) acrylic acid, or an anhydride-grafted polyolefin, or the like or alternatively may be composed of a conventional adhesive or glue such as a polyurethane (more appropriate where the laminated construction). The tie layer can be formed of a regio-regular hydrocarbon polymer having pendant carboxylic acid groups thereon.

Four. Five The multilayer structure may also contain an oxygen scavenging layer. Such layers are normally an inner layer located towards the surface layer that is close to the cavity of the Packaging Article. Yes, a material or packaging of the present invention can, for example, have a structure comprising an abuse resistant structure / oxygen barrier / adhesive / oxygen scavenger / sealer. The purifying layer is usually composed of a carrier polymer that contains an agent capable of interacting with or absorbing and / or reacting with oxygen from the interior cavity of a Packaging Article. In any of the above multilayer structures or other structures suitable for providing a packing material and Packing article, the functionalized linear regio-regular hydrocarbon polymer contemplated herein and in co-pending application Serial No. 09 / 052,079 is used to provide at least one layer formed of polymer of the appropriate functional groups for the functions attempted with the article. It has unexpectedly been found that the current regio-regular functionalized hydrocarbon polymer provides improved functionality and a Packing Article with improved functional and tensile properties. The following examples are given for purposes 46 illustrative only and are not intended to be a limitation of the claims appended thereto. All parts and percentages are by weight unless otherwise indicated.

Examples The molecular weights of the polymers reported subsequently were determined by GPC at 50 ° C using a Waters Alliance System # 4 gel permeation chromatograph equipped with a Waters 41-RI detector. Phenogel 5 columns (linear 2x and lxlOOÁ) were used. The eluent was l-methyl-2-pyrrolidinone (50 mM lithium bromide) Polystyrene narrow molecular weight standards were used for calibration The melt flow rate of the polymers was reported as MFI (Melt Flow Index) in Grams for 10 minutes The MFI was determined at 190 ° C using 2.16 kg of weight according to ASTM D1238 using a melt flow indexer CSi MFI-2. The oxygen transmission rate (OTR) of the pressed film samples was determined using a Mocon Ox-Tran 2/20 ML module that follows ASTM D3985-81, the polymer powder was mixed with the stabilizers and compression molded into thin films (1-6 mils thick) to 47 190 ° C for 5 minutes. A compressive force of 15,000 pounds was applied and the sample was subsequently cooled to room temperature at about 15 ° per minute. The pressed films were dried in a vacuum oven at 80 ° C and conditioned in a desiccator for at least 24 hours before the test. Mechanical properties were measured using an Instron 4204 Tester. The Modulus, Stress Performance and Stress Performance were determined at an extension rate of 0.5 inch / minute and the Maximum Stress, Breaking Effort, Breaking Tension and Tenacity were measured. at a crosshead speed of 210 inches / minutes. The test samples were compression molded at 190 ° C for 5 minutes followed by cooling to 15 degrees / minute using 20 mil filler strips. The test films were allowed to condition for at least 24 hours in a desiccator at room temperature before the test. The dimensions of the Dumb-bell test specimens are 1 inch by 4.5 inches. EXAMPLE 1 Synthesis of Linear Homopolymer of 4-Cycloocten-1-ol and Saturated Derivative (Molar Ratio of Monomer / Catalyst = 400) The reaction was carried out in a resin pot 48 of 2 liters equipped with an upper stirrer, a thermocouple, an argon addition door, and 2 septum doors for the addition of catalyst and solvent. 450 Grams (3.5 moles) of l-hydroxycyclooct-4-ene was charged to the resin pot. The monomer was degassed in complete vacuum for a minimum of 30 minutes. 7.25 Grams (0.0088 moles) of phenylmethylene bis (tricyclohexylphosphine) ruthenium dichloride catalyst were weighed into a clean dry half pint bottle in a dry box and the bottle was capped with a septum before removing it from the dry box. The molecular weight of the polymer was controlled by the monomer / ruthenium molar ratio of 750. Methylene chloride (1.5 liters) was de-aerated with argon. 100 Grams of methylene chloride was added via syringe to the bottled catalyst with 1200 Grams of methylene chloride was loaded via cannula into the reaction resin pot. The mixture was vigorously stirred. Once the monomer was completely dissolved, the catalyst solution was added via syringe to the reaction resin pot. The color changed from purple to orange after several minutes. The reaction was carried out at 40 ° C for 24 hours under vigorous stirring under an argon atmosphere. As time passed, the solution became viscous. The reaction was completed after 24 hours. The progress of the reaction ROMP 49 was followed by NMR. The degree of conversion of the monomer into polymer was determined by proton NMR based on the integration of the vinyl protons of the monomer at 5.6 ppm and the vinyl protons of the polymer at 5.3 ppm. Ethylvinyl ether added, 70 grams (0.97 moles) to the reaction vessel through an attachment on top of the pot to terminate the ROMP reaction. After mixing the vinyl ether, the contents of the reaction pot were poured into a 4 L beaker. 791 grams of methanol and 0.45 grams of 2,6-di-t-butyl-4-methylphenol (BHT) were added. to the beaker and mixed with a stirring bar until a homogeneous solution was obtained. The unsaturated ethylenic polymer in the solution prepared above was hydrogenated using tris (triphenylphosphine) rhodium chloride as the catalyst at a hydrogen pressure of 640 psi and a temperature of 60 ° C for 6 hours. The molar ratio of double bonds in the unhydrogenated polymer to catalyst was 150 to 1. The final hydrogenated polymer (designated as Polymer 1) had the following molecular weights and melt flow rate: Mn = 80,300; Mw = 145,800; Mz = 246,000; PDI = 1.8; MFI = 2.3 g / 10 minutes (with 1% by weight of Irganox 1076, a commercial antioxidant available from Ciba Specialty Chemicals). The current polymer was compared with the random copolymer 50 conventional ethylene / vinyl alcohol having 25 mole percent vinyl alcohol (designated polymer A). Example 2 Synthesis of Linear Homopolymer 5-cycloocten-trans-1, 2-diol and its Saturated Derivative 5-cyclooctene-trans-1,2-diol (MW = 142.19.40 grams, 0.28 moles) to a pot of resin from 100 ml of three necks equipped with a mechanical agitator, argon inlet and a septum. The monomer was degassed under vacuum for 2 hours. The system was maintained under an argon atmosphere. In a dry box filled with argon, the ruthenium dichloride phenyl-methylene bis (tricyclohexylphosphine) catalyst (0.3087 grams, 0.375 mmol) was weighed into a glass ampoule capped with septum and dissolved in 10 ml of methylene chloride. . The deep purple catalyst solution was injected by syringe into the reaction vessel. Methylene chloride (30 ml) was purged with a vigorous stream of argon for 15 minutes and injected into the resin pot. The monomer / solvent solution was stirred vigorously. The reaction mixture was heated to 40 ° C with an oil bath under a slow atmosphere of argon for 24 hours under vigorous stirring. Subsequently, the resin pot is 51 removed from the oil bath and the reaction mixture was cooled to room temperature. Ethyl vinyl ether (0.754 grams, 1 ml, 10.5 mmol) was added to the reaction mixture together with 40 ml of tetrahydrofuran and 40 ml of methanol and stirred until complete dissolution. The homogeneous solution was subsequently poured into a solution of 700 ml of cold acetone and 0.4 g of 2,6-di-tert-butyl-4-methylphenol (BHT) to precipitate the polymer. The polymer was redissolved in 20 ml of tetrahydrofuran and 20 ml of methanol and 0.4 grams of BHT and reprecipitated in cold acetone as previously done. This process was repeated once again. The polymer was dried overnight in a vacuum oven at 60 ° C to produce 13.4 grams of a hard solid yellow polymer. 12 grams of the ethylenically unsaturated dry polymer were dissolved in 60 ml of tetrahydrofuran and 60 ml of methanol and 0.5205 grams (0.5625 mmoles) of tris (triphenylphosphine) rhodium chloride [RhCl (PPh3)] was added. The mixture was hydrogenated in a 600 ml Parr reactor at 600 psi / 54 ° C for 6 hours. The reactor was cooled to room temperature and the pressure discharged. The solution was filtered through a ceramic funnel and the polymer powder was washed with acetone. The polymer was redispersed in acetone overnight and filtered and washed with acetone once more. The slightly yellow polymer powder was dried 52 then in a vacuum oven for 7 hours to yield 11.2 grams of hydrogenated polymer (designated "Polymer 2"). The resulting polymer had the following molecular weights and melt flow rate: Mn = 23,900; Mw = 47,000; Mz = 78,900; PDI = 2; MFI = > 10 g / 10 min. with 0.1% by weight of Irganox 1076 as a stabilizer. This polymer was compared to the conventional ethylene / vinyl alcohol random copolymer having about 56 mole percent vinyl alcohol (designated "Polymer B"). EXAMPLE 3 Synthesis of Linear Homopolymer 5-cycloocten-trans-1, 2-diol and its Saturated Derivative 5-cycloocten-trans-1,2-diol (MW = 142.19, 30 grams, 0.21 moles) was transferred to a resin pot of 100 ml of three necks equipped with a mechanical agitator, argon inlet and a septum. The monomer was degassed under vacuum for 45 minutes and kept under an argon atmosphere. In a dry box filled with argon, the ruthenium catalyst, phenylmethylene bis (tricyclohexylphosphine) dichloride (MW = 822.96, 0.2319 grams, 0.2818 mmoles) was weighed in a glass vial capped with septum and dissolved in 30 ml of purged argon. with methylene chloride. The molar ratio of monomer to ruthenium was 750. The deep purple catalyst solution was injected by syringe 53 inside the reaction vessel. The reaction mixture was maintained at 40 ° C under an argon atmosphere for 24 hours under vigorous stirring. Subsequently, the resin pot was removed from the heat source and the reaction mixture was cooled to room temperature. Ethyl vinyl ether (0.528 grams, 0.7 ml, 7.3 mmol) was added to the reaction mixture together with 40 ml of tetrahydrofuran, 40 ml of methanol and 0.15 grams of 2,6-di-tert-butyl-4-methylphenol (BHT). The mixture was stirred until a homogeneous solution was obtained. The polymer was subsequently precipitated into a solution of 700 ml of methyl ethyl ketone (MEK) and 0.15 g of BHT. The polymer was redissolved in 30 ml of tetrahydrofuran and 30 ml of methanol and 0.15 grams of BHT and reprecipitated in a mixture of MEK / BHT as previously done. This process was repeated once again. The polymer was dried overnight in a vacuum oven at 60 ° C to produce 12.5 grams of a hard solid yellow polymer. The unhydrogenated polymer (12.5 grams) was redissolved in 36 grams of tetrahydrofuran and 36 grams of methanol and 0.0625 grams of BHT for hydrogenation. He Catalyst of tris chloride (triphenylphosphine) rhodium [RhCl (PPh3)] (MW = 925.27, 0.542 grams, 0.586 mmole) was added to the polymer solution. The mixture was hydrogenated in a 600 ml Parr reactor at 600 psi / 60 ° C for 6 hours. The 54 The reactor was cooled to room temperature and the pressure vented. The solution was filtered through a ceramic funnel and the polymer powder was washed with acetone. The polymer was redispersed in acetone overnight. The polymer was then filtered and washed with 400 ml of acetone. The slightly yellow polymer powder was then dried in a vacuum oven overnight. 12 grams of polymer was obtained (designated "Polymer 3"). The resulting polymer had the following molecular weights and melt flow rate: Mn = 19,200, Mw-43,600, Mz = 77,500, PDI = 2.3, MFI = 5.4 g / 10 min. with 1% by weight of Ultranox 2714A (from GE Specialty Chemical) as a stabilizer. EXAMPLE 4 Synthesis of Linear Homopolymer 5-cycloocten-trans-1,2-diol and its Saturated Derivative (Control of molecular weight using cis-3-hexen-1-ol as a chain transfer agent at a molar ratio of monomer / ruthenium of 2500 and a molar ratio of monomer / chain transfer agent of 260). 5-Cycloocten-trans-1,2-diol (50 grams, 0.35 mole) was transferred to a three-neck 200 ml resin pot equipped with a mechanical stirrer, argon inlet and a septum. The monomer was degassed under vacuum for one hour. The system was maintained under an argon atmosphere. Cis-3-hexen-l-ol (0.13 grams, 1352 mmol, 0.16 ml) was added distilled by syringe. Methylene chloride (40 ml) was purged with a vigorous stream of argon for 15 minutes and transferred by syringe into the resin pot. The monomer / solvent solution was stirred vigorously. In a dry box filled with argon, the ruthenium catalyst, phenylmethylenebis (tricyclohexylphosphine) dichloride (0.11 grams, 0.141 mmol) was weighed in a glass ampoule capped with septum and dissolved in 10 ml of methylene chloride. The deep purple catalyst solution was injected by syringe into the reaction vessel. The reaction mixture was maintained at 40 ° C under an argon atmosphere for 24 hours under vigorous stirring. Subsequently, the resin pot was removed from the heat source and the reaction mixture was cooled to room temperature. Ethyl vinyl ether (2.92 grams, 3.9 ml, 40.4 mmol) was added to the reaction mixture together with 100 ml of methanol, 100 ml of THF and 0.5 grams of 2,6-diter-butyl-4-methylphenol. The polymer solution was hydrogenated directly without precipitation and recovery of the non-hydrogenated polymer. The hydrogenation was carried out in a Parr 600 ml reactor. 2.17 Grams (2.34 mmol) of tris (triphenylphosphine) rhodium chloride was added to the above solution and the polymer was hydrogenated at 600 psi for 6 hours. The reactor 56 it was cooled to room temperature and vented. The resulting polymer solution was mixed with 600 ml of acetone and 0.5 grams of BHT. The solution was filtered and the polymer powder was washed three times with 200 ml of acetone. The filtered powder was resuspended in 600 ml of acetone, 0.5 grams of BHT and 0.25 ml of 2,4-pentadione and stirred overnight. The polymer dispersion was filtered and washed with 3 portions with 200 ml of acetone. The filtered polymer was dried in a vacuum oven at 60 ° C for 5 hours. The resulting polymer (designated "Polymer 4") had the following molecular weights and melt flow rate: Mn = 31,300, Mw = 145,000, Mz = 269,000, PDI = 4.6, MFI = 1.4 g / 10 min. with 0.5% by weight of sodium acetate and 0.5% by weight of Ultranox 626 (from GE Specialty Chemical) as a stabilizer. Example 5 Oxygen Transmission Velocity Measurements of Linear Copolymers of Ethylene-Vinyl Alcohol Table 1 describes the copolymers that were evaluated and compared.

Table 1. Description of polymers reported in Table 2. Polymer A A branched copolymer of ethylene-vinyl alcohol commercially obtained randomly 57 58 It can be seen from Table 2 that with 25 or 50 mole percent of vinyl alcohol content, the regular regio functionalized hydroxyl copolymers 59 linear ones have much better oxygen gas barrier property under dry and wet conditions than random branched copolymers having substantially the same molar content of vinyl alcohol. Table 3. Comparison of Mechanical Properties of Copolymers EVOH Polymer A Polymer 1 Polymer B Polymer 3 Percent in Moles of Alcohol 25 25 56 50 Vinyl: Chemical architecture Random regio-regular Random regio-regular Linear branching Linear branching Module ksi (sdp 113 (3) 188 (11) 337 (8.7) 180 (1.1) Limit Elastic psi (sd) 2,395 (82) 5,161 (182) 7737 (66) 4663 (159) Performance at Voltage% (sd) 6.7 (0.7) 4.3 (0.2) 4.3 (0.2) 5 (0.3) Maximum Effort psi (sd) 3,045 8,632 (835) 9093 (851) 6578 (1160) (110) Breaker Effort psi (sd) 2,402 8,580 (765) 7686 (1322) 6520 (1199) (151) Stress Effort% ( sd) 84 (26) 342 (11) 11.8 (8.8) 221 (34) Tenacity n.lb/in3 2,199 16,843 888 (743) 9226 (2089) (sd) (626) (1,368) (*) sd: standard deviation Regio-regular linear hydroxy functionalized polymers with 25 or 50 mole percent vinyl alcohol show significantly higher stress on breaking and tenacity than its branched counterparts. Improved tenacity and elongation can provide 60 improved orientability and thermoformability of the resulting film. Commercial branched random EVOH copolymers do not provide these properties. Example 6 Synthesis of Copolymer Ethylene Diblock - Vinyl Acetate A 200 mL resin pot was equipped with a mechanical stirrer, an inlet adaptation for argon or vacuum application, a thermocouple and a septum. The assembled reactor was evacuated and refilled with argon before the introduction of reagents and reactants. Distilled 1, 5-cyclooctadiene (30 grams, MW = 110.2, 0.27 mol) was transferred to the resin pot by syringe. Methylene chloride (40 mL) which had been sprayed with argon was injected into the resin pot. The mixture was stirred until homogeneous. In a dry box, a ruthenium phenylmethylene bis (tricyclohexylphosphine) dichloride catalyst (MW = 822.96, 0.249 grams, 0.3025 mol) was weighed into a glass ampoule capped with septum and dissolved in 10 mL of sprayed methylene chloride. with argon. The resulting deep purple solution of catalyst was injected by syringe into the reaction vessel. The reaction mixture was maintained under vigorous stirring under an argon atmosphere and heated to 34 ° C with an oil bath. After about 40 minutes, the reaction mixture became viscous. Additional methylene chloride (200 mL) was introduced into the reaction vessel. to reduce the viscosity of the mixture. After one hour, 5-acetoxycyclooct-l-ene (6.5 grams, 0.038 mol, MW = 168.2) was injected by syringe into the vessel in the reaction and allowed to proceed for an additional 24 hours. Toluene (200 mL) was added to dissolve the polymer and decrease the viscosity of the solution. The methylene chloride was then removed on a rotary evaporator and the toluene / copolymer solution was transferred to a Parr reactor lined with glass for hydrogenation. An additional 70 mL was added followed by grams (mol) of Wilkinson's catalyst. The reactor was pressurized to 600 psig of hydrogen and heated to 60 ° C. The hydrogenation reaction was carried out for 6 hours under these conditions. The resulting hydrogenated copolymer was precipitated and washed with acetone. The diblock copolymer was dried in a vacuum oven overnight at 60 ° C and gave a white powder with the following properties: MN = 59,400, Mw = 107,000, Mz = 175,000, PDI = 1.8, MFI = 0.7 grams / 10 minutes The ethylene-vinyl acetate diblock copolymer was found by 1 H NMR to contain 12.5 weight percent vinyl acetate. The copolymer had a glass transition temperature of 34 ° C and a melting point of 108 ° C. The block copolymer was pressed into a clear and transparent 6 mil film which exhibited a seal strength of 6.9 (± 1.3) lbs / in2 at 120 ° C. 62 EXAMPLE 7 Synthesis of Ethylene-Vinyl Alcohol Linear Copolymer by Hydroboration / Oxidation Medium Distillate 1, 5-cyclooctadiene (88.2 grams, 100 ml, 0.815 moles) was transferred to a 1 liter round bottom flask which was evacuated and filled again with argon. Methylene chloride (600 mL) which had been sprayed with argon was added into the reaction flask. A ruthenium phenylmethylene dichloride bis (tricyclohexylphosphine) catalyst (0.713 grams, 0.86 moles) was added followed by vigorous stirring under an argon atmosphere. The reaction was allowed to proceed for 4 hours. Then ethylvinyl ether (0.25 grams, 3.4 moles) was added to stop the reaction. The polymer was isolated by precipitation in methanol and dried to yield 70.7 grams of 1-polybutadiene. This polymer (59.4 grams) was placed in a 4 liter resin pot and the system was purged with argon. Drip 9-Borabicyclo [3.3. l) nonane (9-BBN, 0.5 M solution in tetrahydrofuran, 2.75 liters) was added to the pot and the reaction mixture was stirred at 55 ° C for 24 hours. The solution was then cooled to approximately 4 ° C with an ice bath. 6M sodium hydroxide solution (298 mL) was added dropwise to the reaction mixture. Subsequently, 609 L of a 30 percent hydrogen peroxide solution was added very slowly to the reaction. After the addition of peroxide 63 was completed hydrogen, the mixture was heated at 55 ° C for another 24 hours. The reaction mixture was cooled to room temperature, after which it was separated into two layers. The organic layer of THF was separated and reduced to a volume of about 1 liter using a rotary evaporator. Methanol (500 ml) was added to dissolve the polymer. The polymer solution was precipitated in 4 liters of water and washed again 3 times with water. The viscous solid mass was then suspended in acetone and mixed to break the polymer into smaller pieces for ease of processing. The polymer was recovered and redissolved in a 50/50 mixture of THF / methanol and reprecipitated in water. The solid mass was mixed and stirred in acetone overnight. The polymer was filtered, washed with water and dried in a vacuum oven overnight. A white solid mass of 30 grams (designated polymer 5) was obtained. Polymer 5 had the following properties: MN = 45,600, Mw = 132,000, PDI = 3 MFI = 2 grams / 10 minutes. The copolymer had a vitreous transition temperature of 45 ° C and a melting point of 108 ° C. The copolymer or block was pressed into clear and transparent films. The films showed oxygen permeability of 1 and 15 cc.mil/m2 day. atmosphere from 0 to 99% relative humidity, respectively.

Claims (34)

1. 64 CLAIMS 1. A packaging material comprising at least one layer wherein at least one of the layers comprises a substantially linear regio-regular functionalized hydrocarbon polymer having repeating units represented by the formula: X Y II | - '.: H3 (CR2) CHCH-] wherein X and Y each independently represents hydrogen, C1-C3 alkyl or a functional group selected from the group hydroxyl, carboxylic acid, carboxylic acid ester, acetate, amide , nitrile or carbonyl, with the proviso that at least one of the X and Y represents a group functions: each R independently represents hydrogen or a C1-C5 alkyl; and "a" represents an integer from 1 to 9. The packaging material of claim 1, wherein each R represents hydrogen. 3. The packaging material of claim 1, wherein "a" represents an integer of 1, 2 or 4 to 9. 4. The packaging material of claim 2, wherein "a" represents an integer of 1, 2 or 4 to 9. The packaging material of claim 1, wherein "a" represents an integer of 1, 2, 5, 7 or 9. 65 6. The packaging material of claim 1, wherein X and Y are each independently selected from a hydrogen atom, a hydroxyl group, a carboxylic acid group, an ester of the carboxylic acid of a C1-C5 alkyl, a group acetate, an amide group, a nitrile group or carbonyl group. The packaging material of claim 2, wherein X and Y are each independently selected from a hydrogen atom, a hydroxyl group, a carboxylic acid group, an ester of the carboxylic acid of a C1-C5 alkyl, an acetate group, an amide group, a nitrile group or a carbonyl group. The packaging material of claim 3, wherein X and Y are each independently selected from a hydrogen atom, a hydroxyl group, a carboxylic acid group, a carboxylic acid ester of a C1-C5 alkyl, an acetate group, an amide group, a nitrile group or a carbonyl group. 9. The packaging material of claim 4, wherein X and Y are each independently selected from a hydrogen atom, a hydroxyl group, a carboxylic acid group, an ester of the carboxylic acid of a C1-C5 alkyl, an acetate group, an amide group, a nitrile group or a carbonyl group. The packaging material of claim 6, wherein X and Y are independently selected from each of 66 a hydrogen atom or hydroxyl group, with the proviso that within each of the polymer units, one of each X and Y is a hydrogen atom and the other is a hydroxyl group. The packaging material of claim 7, wherein X and Y are each independently selected from a hydrogen atom or hydroxyl group, with the proviso that within each of the polymer units, one of each X and Y is a hydrogen atom and the other is a hydroxyl group. The packaging material of claim 8, wherein X and Y are each independently selected from a hydrogen atom or hydroxyl group, with the proviso that within each of the polymer units, one of each X and Y is a hydrogen atom and the other is a hydroxyl group. The packaging material of claim 9, wherein X and Y are each independently selected from a hydrogen atom or hydroxyl group, with the proviso that within each of the polymer units, one of each X and Y is a hydrogen atom and the other is a hydroxyl group. The packaging material of claim 6, wherein X and Y each represents a functional group selected from a hydroxyl group, a carboxylic acid group, an alkyl carboxylic acid ester of 67 C1-C5, an acetate group, an amide group, a nitrile group or a carbonyl group. The packaging material of claim 7, wherein X and Y each represents a functional group selected from a hydroxyl group, a carboxylic acid group, a carboxylic acid ester of a C? -C alkyl, an acetate group, an amide group, a nitrile group or a carbonyl group. 16. The packaging material of claim 8, wherein X and Y each represents a functional group selected from a hydroxyl group, a carboxylic acid group, a carboxylic acid ester of a C1-C5 alkyl, an acetate group , an amide group, a nitrile group or a carbonyl group. 17. The packaging material of claim 9, wherein X and Y each represents a functional group selected from a hydroxyl group, a carboxylic acid group, an ester of the carboxylic acid of a C1-C5 alkyl, an acetate group , an amide group, a nitrile group or a carbonyl group. 18. The packaging material of claim 6, wherein the material comprises a multilayer material. 19. The packaging material of claim 7, wherein the material comprises a multilayer material. 20. The packaging material of claim 8, wherein the material comprises a multilayer material. 68 tw-one. The packaging material of claim 9, wherein the material comprises a multilayer material. 22. The packaging material of claim 10, wherein the material comprises a multilayer material. 23. The packaging material of claim 11, wherein the material comprises a multilayer material. 24. The packaging material of claim 12, wherein the material comprises a multilayer material. 25. The packaging material of claim 13, wherein the material comprises a multilayer material. 26. The packaging material of claim 15, wherein the material comprises a multilayer material. 27. The packaging material of claims 18, 19, 20, 21, 22, 23, 24, 25 or 26 wherein the material is a film having a thickness of about 0.025 mils to about 10 mils. 28. A Packaging Item having a structure comprising the packaging material of claims 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16 , 17, 18, 19, 20, 21, 22, 23, 24, 25 or 26. 29. A Packing Article capable of retaining an oxygen sensitive material therein, the article having a structure comprising at least one layer wherein at least one of the layers comprises a regio-regular functionalized hydrocarbon polymer substantially 69 linear that includes repeating units represd by the formula: X Y I I | -Cl, (CR2 uCHCH-] wherein each X and Y independy represa hydrogen atom or a hydroxyl group with the proviso that at least one of the X and Y repres a hydroxyl group; R repres hydrogen or a C1-C5 alkyl; and "a" repres an integer of 1-9. 30. The Packaging Article of claim 29, wherein both of X and Y represhydroxyl groups. 31. The Packaging Article of claim 30, wherein "a" repres an integer of 1, 2, 5, 7 or 9; and each R repres hydrogen. 32. The Packaging Item of claim 31, wherein "a" repres 1 or 5. 33. The Packaging Article of claim 29, 30, 31 or 32 where the structure of the article is a movie. 34. The Packaging Article of claim 33, wherein the film is a multilayer film.