MXPA00002284A - Pipe made from metathesis polymerized olefins - Google Patents

Abstract

Thermosetting resin pipes and pipe fittings are provided which are prepared by polymerizing a cyclic olefin monomer in the presence of a ruthenium or osmium metathesis polymerization catalyst. These articles may be prepared by various methods, such as centrifugal casting. Reinforced articles may also be prepared by filament winding.

Description

TUBE MADE OF POLY OLEFINS POLISHED BY METTESIS DESCRIPTIVE MEMORY The present invention relates to tubes and fittings for thermosetting resin tubes made from olefins polymerized by metathesis, and methods for producing them. Particularly, the invention relates to tube and fittings for thermosetting resin tube made of polycycloolefin wherein the cycloolefins are polymerized through ring opening metathesis polymerization reactions (ROMP). Many olefin polymers produced through metathesis polymerization reactions, especially cycloolefin polymers produced through ROMP reactions, are strong and rigid, and have good chemical resistance. It is desirable to produce tubes and tube fittings from said material for use in various applications. In general, a method for producing articles from thermosetting resins is to create a reaction mixture by mixing a liquid monomer and a polymerization catalyst. The mixture is then processed or worked through an appropriate polymer process technique to shape the desired article, and the polymerization reaction (the article "cures") continues to form the desired polymer article. The time during which the liquid monomer / catalyst mixture can be worked or processed after the monomer and the catalyst are mixed is known as "crucible life" of the polymerization reaction. Several important problems have arisen with respect to the production of tube from olefins polymerized by metathesis using these techniques. In general, these problems are due to the metathesis catalytic systems that are used. The original catalytic systems used for metathesis reactions are those of the Ziegler type. Another great variety of systems, based on tungsten and molybdenum, has also been developed. All these catalyst systems have significant disadvantages for use in the manufacture of thermosetting resin tube. With these catalyst systems, the polymerization reaction has a very short crucible life, and there are no efficient methods to control the polymerization rate once the reaction mixture is formed. Due to the short life in the crucible of these reactions by metathesis, many traditional methods for making pipe and fittings for thermosetting resin pipe are generally unsuitable, because to produce a pipe successfully, the reaction mixture should not gel before to completely form the tube. In many production methods, life in the short crucible adds significant complexity to the methods and requires the use of special procedures to produce pipe or tube fittings. For example, in the methods of spin casting and centrifugation, pressure is normally required in the casting environment to ensure that the gas bubbles formed using traditional catalysts are removed from the monomer before the gelling of the monomer due to the rapid polymerization. Additionally, the monomer must be immediately moved to the emptying position within the casting mold so that the monomer is in the correct tube emptying position prior to gelation of the monomer. In addition, uncontrolled entanglement occurs during these rapid metathesis polymerization reactions, which consequently does not allow the maximum chain growth and molecular weight of the polymer. As a consequence, these catalyst systems produce polymers with less desirable properties. This uncontrolled entanglement prevents the easy production of random and block copolymers or thermopolymers having unique properties. Additionally, these metathesis catalyst systems are easily contaminated by impurities, air, humidity, and various pigments, fillers and additives. Therefore, the production of tube and tube fittings using these catalysts should occur under highly controlled conditions and with exceptionally high purity degrees of monomer. Methods such as filament winding, stretch extrusion, centrifugal casting and spin casting are difficult to practice in the inert environment necessary for traditional catalysts. In addition, this increases the cost to produce tubes and accessories ^ ¡^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^^^^^^ for reinforced and non-reinforced thermosetting resin tubing made from olefins polymerized by metathesis. Thanks to these disadvantages and difficulties, it has been very difficult to produce tubes made of olefins polymerized by metathesis. Although it has been possible to produce such tubes, production costs are high, and sometimes economically unattainable. As a result, said tubes and pipe fittings, which have excellent chemical resistance and improved physical properties, are not widely available. It is desirable to provide reinforced and unreinforced thermosetting resin tube made from metathesis-polymerized olefins, especially a cycloolefin polymer polymerized by ROMP reaction, and a method for producing it, wherein these disadvantages and difficulties can be substantially avoided. The present invention focuses on those needs by providing tubes and fittings for tubes made of metallized polymerized olefins, and a method for making them, using an osmium-carbene or ruthenium complex catalyst to polemicize the olefin. In the present invention, many of the disadvantages and difficulties discussed above are minimized or avoided. The use of osmium-carbene or ruthenium complex catalyst allows the metathesis reaction to become slower and more easily controlled, thus providing longer lives in the crucible as desired for tube production. As a result, it is possible to use methods such as centrifugal casting and spin casting without the need to pressurize the pouring tube, or perform other operations necessary to counteract the life in the short crucible of the traditional catalysts. The use of ruthenium or osmium catalysts also provides improved chain growth and molecular weight before interlacing, thus providing polymers with better properties. In addition, the use of these catalysts provides controlled entanglement, and easy production of random and block copolymers, and random and block terpolymers, thus allowing the production of tubes made of polyolefins polymerized by metathesis that present unique and improved physical characteristics in comparison with those that occurred previously. For example, it is possible to produce tubes and tube fittings with better ductility and impact resistance through these methods. Additionally, the ruthenium and osmium catalysts are not easily contaminated by impurities, air, moisture, and many pigments, fillers and additives. Therefore, the production of tube and pipe fittings from polyolefins polymerized by metathesis is simplified using this method. Other features and advantages of the invention will be apparent to those skilled in the art upon reading the following detailed description and claims. Before explaining in detail the embodiments of the invention, it should be understood that the invention is not limited in its application to the details of the composition and concentration of components established in the following description. The invention is capable of containing other modalities and practiced or carried out in different ways. In addition, it should be understood that the phrases and terminology used herein are for the purpose of description and should not be viewed as limiting. The invention provides tube and fittings for thermosetting resin tubes made from olefins polymerized by metathesis, and methods for producing them. The reactions by olefin metathesis are catalyzed by ruthenium and osmium-carbene complex catalysts to produce tubes and fittings for polyolefin pipe. The life in the crucible of the olefin polymerization reaction can be extended using the ruthenium or osmium-carbene metathesis catalysts and known methods to extend the life in the crucible of the reactions using these catalysts. The extension of life in the crucible allows the tube and tube fittings to be made through procedures not available or difficult to use before the present invention. Additionally, the ruthenium or osmium-carbene metathesis catalysts tolerate more impurities than the traditional metathesis catalysts, and therefore, the presence of additives, binding agents, impurities and some lower-grade monomers do not substantially affect the catalysts. According to the invention, an olefin monomer is polymerized through metathesis catalysis with a osmium-carbene or ruthenium metathesis catalyst, and the monomer is polymerized using a polymer process technique to form a thermosetting olefin resin tube. . Suitable ruthenium and osmium carbene catalysts, methods for synthesizing said catalysts, and suitable olefin monomers as well as other methods for carrying out and controlling the polymerization reaction are described in the following patents and patent application: US Patents. 5,312,940 and 5,342,909 and WO 97/20865.

Catalysts The generally suitable catalysts are ruthenium and osmium-carbene complex catalysts described in the references cited above. Preferred catalysts of the ruthenium and osmium carbene complex include those which are stable in the presence of a variety of functional groups including hydroxyl, thiol, thioether, ketone, aldehyde, ester, ether, amine, imine, amide, nitro, carboxylic acid, disulfide, carbonate, isocyanate, carbodiimide, carboalkoxy, peroxo, anhydride, carbamate and halogen. When the catalysts are stable in the presence of these groups, the starting monomers, impurities in the monomer, coupling agents, any substituent group on the catalyst, and other additives may include one or more of the groups listed above without deactivating the catalysts.

The catalyst preferably includes a metal center of osmium or ruthenium which is in an oxidation state +2, has an electron count of 16, and is pentacoordinated. These complex catalysts of ruthenium or osmium-carbene can be represented by the formula: where: M is Os or Ru; R and R1 may be the same or different and may be hydrogen or a substituent group which may be C2-C20 alkenyl, C2-C20 alkynyl, C1-C20 alkyl, aryl, C1-C20 carboxylate. C1-C20 alkoxy, C2-C20 alkenyloxy, C2-C2o alkynyloxy, aryloxy, C2-C20 alkoxycarbonyl, d-C20 alkylthio, C1-C20 alkylsulfonyl, and C2-C2 alkylsulfinyl- Optionally, the group Substituent can be substituted with one or more groups selected from C 1 -C 5 alkyl, halide, C 1 -C 5 alkoxy and phenyl. The phenyl group may be optionally substituted with one or more groups selected from halide, C1-C5 alkyl and C1-C5 alkoxy. Optionally, the substituent group can be substituted with one or more functional groups selected from hydroxyl, thiol, thioether, ketone, aldehyde, ester, ether, amine, imine, amide, nitro, carboxylic acid, disulfide, carbonate, isocyanate, carbodiimide, carboalkoxy , peroxo, anhydride, carbamate and halogen. In a preferred embodiment, R and R1 * MMj - ^ - t * feji are the same or different and can be hydrogen, substituted aryl, unsubstituted aryl, substituted vinyl and unsubstituted vinyl; wherein the substituted aryl and the substituted vinyl are each substituted with one or more groups selected from hydroxyl, thiol, thioether, ketone, aldehyde, ester, ether, amine, imine, amide, nitro, carboxylic acid, disulfide, carbonate, isocyanate , carbodiimide, carboalkoxy, peroxy, anhydride, carbamate and halogen, CrC5 alkyl. C 1 -C 5 alkoxy, unsubstituted phenyl, and phenyl substituted with halide, C 1 -C 5 alkyl. or C1-C5 alkoxy; X and X1 may be the same or different and are generally hydrogen or any anionic ligand. In general, an anionic ligand is any ligand that when removed from a metal center has a negative charge in its closed-layer electron configuration. In a preferred embodiment, X and X1 are the same or different and may be halogen, hydrogen or a substituent group selected from CrC2o alkyl, aryl, C1-C20 alkoxide, aryloxide, C3-C20 alkyldicyketonate, aryldicketonate, C1- carboxylate. C20, aryl or C 1 -C 2 alkylsulfonate, C 1 -C 20 alkylthio, C 1 -C 20 alkylsulfonyl, and C 1 -C 2 alkylsulfinyl Substituent groups can optionally be substituted with C 1 -C 5 alkyl, halogen, alkoxy or C1-C5 phenyl. The phenyl may be optionally substituted with halogen, C 1 -C 5 alkyl, or C 1 -C 5 alkoxy. In a highly preferred embodiment, X and X1 are the same or different and may be Cl, Br, I, H or a substituent group selected from benzoate, C1-C5 carboxylate, C1-C5 alkyl, phenoxy, C1-C5 alkoxy , C 1 -C 5 alkylthio, aryl and C 1 -C 5 alkylsulfonate. The substituent groups can be optionally substituted with C 1 -C 5 alkyl or a phenyl group. The phenyl group can be optionally substituted with halogen, C 1 -C 5 alkyl or C 1 -C 5 alkoxy. In a particularly preferred embodiment, X and X1 are the same or different and are selected from Cl, CF3CO2, CH3CO2, CFH2CO2, (CH3) 3CO, (CF3) 2 (CH3) CO, (CF3) (CH3) 2CO, PhO , MeO, EtO, tosylate, mesylate, and trifluoromethanesulfonate. In the modality with greater preference, X and X1 are Cl; and L and L1 may be the same or different and are generally an electron-neutral donor. In general, a neutral electron donor is any ligand that, when removed from a metal center in its closed-capped electron configuration, has a neutral charge. In a preferred embodiment, L and L1 can be the same or different and can be phosphines, sulfonated phosphines, phosphites, phosphinites, phosphonites, arsines, stibines, ethers, amines, amides, sulfoxides, carboxyls, nitrosyls, pyridines and thioethers. In a most preferred embodiment, L and L1 are the same or different and are phosphines of the formula PR3R4R5 wherein R3 is a secondary alkyl or cycloalkyl and R4 and R5 are the same and different and are aryl, C1-C10 primary alkyl, secondary alkyl or cycloalkyl. In the embodiment of the invention which is especially preferred, L and L1 are the same or different and are -P (cyclohexyl) 3, - P (cyclopentyl) 3, or -P (isopropyl) 3. L and L1 can also be -P (phenyl) 3. A preferred group of catalysts are those wherein M is Ru; R1 and R are independently hydrogen or substituted or unsubstituted aryl or substituted or unsubstituted vinyl; X and X1 are Cl; and L and L1 are triphenylphosphine or trialkylphosphine such as tricyclopentylphosphine, trichiohexylphosphine and triisopropylphosphine. The substituted aryl and the substituted vinyl, each may be substituted with one or more groups including C1-C5 alkyl, halide, C1-C5 alkoxy and a phenyl group which may be optionally substituted with one or more halide, C1 alkyl groups -C5 or C1-C5 alkoxy. The substituted aryl and the substituted vinyl can also be substituted with one or more functional groups including hydroxyl, thiol, thioether, ketone, aldehyde, ester, ether, amine, imine, amide, nitro, carboxylic acid, disulfide, carbonate, isocyanate, carbodiimide , carboalkoxy, peroxy, anhydride, carbamate and halogen. Particularly preferred catalysts can be represented by the formulas: wherein Cy is cyclopentyl or cyclohexyl, and Ph is phenyl. The most preferred catalysts can be represented by the formula: wherein Cy is cyclopentyl or cyclohexyl, and Ph is phenyl. The catalysts described above are useful in the polymerization of a large variety of olefin monomers through polymerization by metathesis, particularly ROMP of cycloolefins.

Monomers: Suitable monomers include olefins that can be polymerized by any of the osmium or ruthenium metathesis polymerization catalysts described above. The olefin monomers may be functionalized or non-functionalized to contain one or more functional groups selected from hydroxyl, thiol, thioether, ketone, aldehyde, ester, ether, amine, mine, amide, nitro, carboxylic acid, disulfide, carbonate, isocyanate. , carbodiimide, carboalkoxy, peroxy, anhydride, carbamate and halogen. The olefin may be a cyclic taut olefin or an unstressed cyclic olefin; any of these can be functionalized or not functionalized.

Preferred monomers include functionalized or non-functionalized cyclic olefins that are polymerized through ROMP reactions. This polymerization process includes contacting a functionalized or non-functionalized cyclic olefin with a ruthenium or osmium metathesis catalyst discussed above. The cyclic olefins can be taut or non-taut and can be monocyclic, bicyclic or multicyclic olefins. If the cyclic olefin is functionalized, it may comprise one or more functional groups including hydroxyl, thiol, thioether, ketone, aldehyde, ester, ether, amine, imine, amide, nitro, carboxylic acid, disulfide, carbonate, isocyanate, carbodiimide, carboalkoxy, peroxy, anhydride, carbamate and halogen. Suitable cyclic olefin monomers include monomers described in the U.S.A. No. 4,943,621 to Janda, et al, patent of E.U.A. No. 4 324 717 of Layer, and patent of E.U.A. No. 4 301 306 of Layer. Suitable cyclic olefin monomers include norbornene type monomers, which are characterized by their presence of at least one norbornene group which can be substituted or unsubstituted. Suitable norbornene monomers include substituted norbornenes and unsubstituted norbornenes, diclopentadiene, di (methyl) dicyclopentadiene, dihydrodicyclopentadiene, cyclopentadiene trimers, cyclopentadiene tetramers, tetracyclododecene and substituted tetracyclododecenes. The & The Mg ^ "common norbornene monomers can be represented by the following formulas: Wherein R and R 1 may be the same or different and may be hydrogen or a substituent group which may be halogen, C 1 -C 12 alkyl groups, C 2 -C 2 alkylene groups, 2) C 6 -C 2 cycloalkyl groups, cycloalkylene groups of C6-C-? 2 and aryl groups of C6-C1 or R and R1 together form saturated or unsaturated cyclic groups having from 4 to 12 carbon atoms with the two carbon atoms in the ring connected thereto, said carbon atoms in the ring form part of and contribute to the 4 to 12 carbon atoms in the cyclic group. The less common norbornene type monomers of the following formulas are also suitable. wherein R and R1 have the same meaning as indicated above and n is greater than 1. For example, cyclopentadiene tetramers (n = 2), a ^^? fl | j? & amp; p-cyclic pentamers (n = 3) and hexacyclopentadecene (n = 2) are monomers suitable for use in the invention. Other specific examples of monomers suitable for use in the invention include: ethylidenebornene, methyltetracyclododecene, methylnormen, ethylnormen, dimethylnorbornene and similar derivatives, norbomadiene, cyclopentene, cycloheptene, cyclooctene, 7-oxanormeno, derivatives of 7-oxanormeno, derivatives of 7-oxabicyclo [ 2.2.1] hept-5eno, 7-oxanorbornadiene, cyclododecene, 2-norbornene, also called bicyclo [2.2.1] -2-heptene and substituted bicyclic norbornenes, 5-methyl-2-norbornene, 5,6-dimethyl-2 -norbornene, 5-ethyl-2-norbomene, 5-butyl-2-norbornene, 5-hexyl-2-norbornene, 5-octyl-2-norbomene, 5-dodecyl-2-norbornene, 5 -sobutyl-2- norbornene, 5-octadecyl-2-norbomene, 5-isopropyl-2-norbomene, 5-phenyl-2-norbornene, 5-p-toluyl-2-norbornene, 5-a-naphthyl-2-norbornene, 5-cyclohexyl- 2-norbomeno, 5,5-dimetil-2-norbomeno, diciclopentadieno (or dimer of ciclopentadieno), dihidrodiciclopentadieno (or codimer of ciclopentenciclopentadieno), dimer of metil-ci clopentadiene, ethyl cyclopentadiene tetracyclododecene dimer, also called 1, 2, 3, 4, 4a, 5, 8, 8a- octahydro-1,4: 5,8-dimethianonaphthalene 9-methyl-tetracycle [6.2.1.13,6. O2,7] -4-dodecene, also called 1, 2, 3, 4, 4a, 5, 8, 8a- octahydro-2-methyl-4,4: 5,8-dimethanonaphthalene 9-ethyl-tetracycle [6.2.1.13'6.02] -4-dodecene, 9-propyl-tetracycle [6.2.1.13'6.02 7] -4-dodecene, 9-hexyl-tetracycle [6.2.1.13 6.02'7] -4-dodecene, 9-decyl-tetracycle [6.2.1.13'6.02'7] -4-dodecene, 9,10-dimethyl-tetracycle [6.2.1.13'6.027 ] -4-dodecene, 9-ethyl, 10-methyl-tetracycle [6.2.1.13'6.02'7] -4-dodecene, 9-cyclohexyl-tetracycle [6.2.1.13'6.02] -4-dodecene, 9-chloro- tetracycle [6.2.1.13,6.0 '7] -4-dodecene, 9-bromo-tetracycle [6.2.1.13'6.02] -4-dodecene, cyclopentadiene trimer, methylcyclopentadiene trimer and the like. In a preferred embodiment, the cyclic olefin is cyclobutene, dimethyldiopentadiene, cyclopentene, cycloheptene, cyclooctene, cyclononene, cyclodecene, cyclooctadiene, cyclononadiene, cyclododecene, norbornene, norbornadiene, 7-oxanormeno, 7-oxanorbornadiene and dicyclopentadiene; each of these can be functionalized or not functionalized. In a most preferred embodiment, the cyclic olefin is diclopentadiene. Suitable dicyclopentadiene can be obtained commercially, for example, from Lyondell under the trade names of Lyondell 108 and Lyondell 103.

Preferably the olefin monomer has a purity greater than about 95 weight percent. This invention contemplates the preparation of homopolymers, as well as random and block copolymers and terpolymers of the suitable monomers discussed above.

Reinforcement materials Tubes or tube fittings can be reinforced or non-reinforced. Suitable reinforcing materials include those that are added to the strength or stiffness of the tube and tube fittings when incorporated with the polymer. The reinforcing material may be in the form of filaments, fibers, wicks, grids, fabrics, fabrics or other known structures. Preferably, the reinforcing material is in the form of a filament or fiber or fibers that are woven into a fabric. Suitable representative reinforcing materials include barium sulfate, minerals, such as glass, carbon, graphite, ceramics, boron and the like; metallic materials; organic polymers, such as aromatic polyamides including aramid fibers, such as Kevlar®, and polybenzimide, polybenzoxazole, polybenzothiazole, polyesters and the like; polyolefins; fluoropolymer, such as Halar®; cellulosic materials; and any other material known to be useful as reinforcement material for polymer systems. Examples of other commercially available reinforcing materials include the following products: Fiberfrax® from Unifrax Corporation, Akzo Nobel Interfil®, and Nyco wollastonite. Preferred is glass fiber or glass fiber woven into a fabric. The reinforcing materials may be "sizing", that is, they are treated or coated with a coupling agent, often referred to as a sizing or bonding agent, to give it more compatibility to adhere to the olefin polymer matrix. As used herein, "coupling agent" refers to ^^ te | ij »^^^ B | WWM & ^^^^^^^ ™ ^^^^^^^^^^^ g ^^ any material that can be applied to a reinforcement material that improves adhesion / removal of moisture between the reinforcement materials and the polyolefin. The coupling agents must be capable of being used in the presence of the metathesis polymerization reactions, preferably ring opening metathesis polymerization reactions (ROMP), catalyzed with a ruthenium or osmium catalyst, without adversely affecting the catalyst or the reaction of polymerization. Suitable sizing agents include conventional sizing agents that do not include functional groups that contaminate or affect the polymerization reaction by metathesis or catalyst. Suitable coupling agents include a variety of conventional agents, including: chromium; silane; titanate; zirconate, zircon-aluminate and amphiphilic hydroxyl terminated. Preferably, those that do not contain the following functionalities: vinyl ethers; active oxygen functionalities such as hydroperoxides or activated epoxides; acetylenes; and other Lewis bases that can contaminate or affect the ruthenium or osmium catalyst.

Methods for manufacturing pipe Suitable methods for making pipe and fittings for polyolefin resin pipe include those that are generally known in the art for producing thermosetting pipe. Methods Suitable feeds can include a variety of polymer process techniques, such as: pouring, spin casting, molding, spin molding, open molding, reaction injection molding (RIM), resin transfer molding (RTM), casting, surface coating, stretch extrusion, filament winding and other known methods useful for producing pipe and fittings for polyolefin resin pipe. Preferably, the tube is manufactured by spin molding, centrifugal casting, RTM, stretch extrusion, or filament winding methods. These methods are preferred due to their character to control the life in the crucible of the reactions by metathesis catalyzed by the ruthenium or osmium catalysts, and the stability of these catalysts in the presence of impurities, which provides a different advantage over methods that use traditional catalysts. Normally, pressures greater than ambient are not required to form quality tube using the methods of the present invention. The centrifugal casting can be used to prepare reinforced or non-reinforced plastic articles. As is known in the art, centrifugal emptying generally consists in feeding a reaction mixture into a rotating mold and allowing the reaction mixture to polymerize. Centrifugation may be performed, for example, as described in the US patent. No. 5,266,370 to Woodson. Filament winding is a preferred method for manufacturing reinforced polyolefin pipe. As is known in the art, filament winding is performed Generally, at least a portion of a reinforcing material with the reaction mixture is coated; winding the coated reinforcing material around a mandrel; and allowing the olefin monomer to polymerize while the coated reinforcing material is wound around the mandrel. Alternatively, the reinforced polyolefin tube can be prepared by extrusion by stretching. Stretch extrusion is a process where the reinforcements are carried through a bath of the reaction mixture in a heated die where the coated reinforcement is formed in a tube profile and cured as the tube passes through the die; or, alternatively, the dry reinforcement can be carried to the die, and then the reaction mixture can be injected into the die to form the tube. Stretch extrusion can be carried out as a continuous process.

Reaction and processing conditions: The parameters for the metathesis polymerization reactions used in the present invention, such as atmosphere, catalyst to olefin ratio, reaction temperatures, solvents that can be used, additives and other agents that may occur during the reaction of polymerization, and the methods for performing the polymerization by metathesis are discussed in the references identified above. In general, the polymerization of the olefin is performed by adding the catalyst by osmium-carbene or ruthenium metathesis to the monomer starting material that has been heated to a starting resin temperature.

Alternatively, the catalyst can be added to the monomer starting material and the mixture heated to the required temperature. The starting resin temperature is not critical; but, as is known, this temperature does affect the speed of the polymerization reaction. In general, the reaction temperature will be in the range from 0 ° C to 100 ° C, and preferably from 25 ° C to 45 ° C. The ratio of catalyst to starting material is not critical and may be in the range of 1: 5 to 1: 200,000 per mole. The catalyst to raw material ratios of between 1: 2,000 and 1: 15,000 per mole are preferred. The invention can be practiced using ratios of catalyst / starting material other than the above scales. Optionally, the monomer starting material can be refluxed, operated through absorption purification and degassed before the catalyst is added; however, none of these procedures is necessary to carry out the invention. If a gel modification additive, crosslinking agent or other additive is used it is preferred that the additives be added before the catalyst; however, in some modalities this is not essential. Although it is preferred that the reaction be carried out in the absence of a solvent, this is also not relevant. Solvents that can be used include organic, protic or aqueous solvents that are inert under reaction conditions. Examples of suitable solvents include aromatic hydrocarbons, chlorinated hydrocarbons, ethers, aliphatic hydrocarbons, alcohols, water or mixtures thereof. After completing the polymerization (ie, after the article has been "cured") the polyolefin article must be post-cured to initiate increased entanglement. As is known, additional entanglement can be achieved by post-cure at an elevated temperature. Also as is known in the art, it is possible to use other methods to post-cure the polyolefin material. Unlike previous catalyst systems, the catalyst / monomer starting material mixture of the present invention can remain liquid for a considerable period of time, even in air, depending on the temperature and amount of gel modification additive present. This feature of the catalyst system herein allows the pipe and fittings for polyolefin pipe to be made using a variety of polymer process techniques discussed above. The monomer starting material may optionally include one or more gel modification additives that are added to control the life in the crucible of the reaction mixture. The monomer starting material may also optionally include one or more crosslinking agents to initiate the further post-cure entanglement of the polyolefin.

The monomer starting material may optionally include additives such as fillers, binders, plasticizers, pigments or dyes, as is known in the art. However, due to the tolerance of the functional group of the catalysts, the additives that can not be used with other catalyst systems, in the preparation of tube and tube fittings can be used. The monomer starting material may also include a flame retardant agent to reduce the flammability of the polyolefin tube. The flame retardant agent should be capable of being used in the presence of metathesis polymerization reactions catalyzed by a ruthenium or osmium catalyst, without adversely affecting the catalyst or the polymerization reaction. Suitable flame retardants include flame retardants that do not include functional groups that contaminate or adversely affect the polymerization reaction by metathesis or catalyst.

EXAMPLE 1 A reinforced five-inch diameter polydicyclopentadiene (PolyDCPD) tube was produced using a centrifugation casting method. A standard fiberglass cloth was used as the reinforcement material. The fiberglass was sizing it with a methacrylatechrome chloride complex sizing agent purchased from Du Pont under the trade name "Volan". The following components, including an exudate flame retardant agent purchased from Clariant under the trade name Exolit IFR-11, were mixed to make the resin mixture DCPD / catalyst: Resin Inquired (Parts per hundred) Monomer of DCPD 100 Catalyst * 0.083 Trifenilfosfina 0.0938 Exolit IFR-11 or 10 11.11 Ciba-Geigy Tinuvin 123 0.10 Albemarle Ethanox 702 4.0 TOTAL 115.387 * Di- (tricyclohexylphosphine) -benzylidine-ruthenium dichloride The following steps of the process were then used to produce the tube: 1. The Volan sizing fiber cloth was wound around a tube (mandrel) smaller than the inner diameter of the desired finished tube. The number of layers and weight of the fabric can vary with the diameter and pressure velocity of the finished tube. 2. The cloth and tube were inserted into the mold tube, and the tube was rotated at revolutions per minute (RPM) high enough to "unwind" the mandrel fabric. 3.- After removing the mandrel, plugs were inserted in each end of the mold tube. One of the plugs included a port that could be sealed after injecting the resin / catalyst mixture into the tube through the port. 4. A pre-measured amount of the above resin / catalyst mixture was injected into the tube through the port in the end plug. The amount of resin depends on the desired wall thickness and diameter of the finished tube. 5. The tube was rotated at a speed that would result in approximately 75 G's of force on the outside of the mold tube. A temperature of 29.4-32.2 ° C was maintained, maintaining the temperature of the room where the tube was produced at this temperature.

This ensures that the mold, glass and resin are at the same temperature. 6.- The tube was allowed to rotate for approximately 30 minutes (the resin was subjected to an exothermic reaction and gelled during this time). 7. The mold tube and tube were removed from the rotating machine and placed in a post-cure oven for 30 minutes at 148.8 ° C. 8. The tube was removed from the mold tube, the ends of the tube were cut, and the mold tube was recycled. After removing the tube, no odor of DCPD was perceived, indicating that there was no significant amount of monomer residue after curing.

The end caps were adhesively bonded to each end of the sizing tube so that the hydrostatic pressure test could be performed according to the procedure of ASTM D1599. The sizing tube was pressurized to 105.45 kilograms per square centimeter before being damaged by pulling the fiberglass cloth. There was no runoff to this point, which indicates that the tube is substantially impermeable, and that there was no path for runoff along the unreacted monomer.

EXAMPLE 2 A reinforced DCPD tube 5 cm in diameter was prepared as in example 1. The tube was tested under various ASTM D test conditions. The results are shown below: The impact resistance test was performed on fewer samples than the traditional ones for the ASTM D 2444 test. The impact resistance data of the DCPD tube indicated that, on average, the DCPD tube samples were not damaged when subjected to test as big as 80.62 meter-kilograms.

Claims (22)

NOVELTY OF THE INVENTION CLAIMS

1. - A polyolefin article comprising: a polyolefin prepared by polymerizing a cyclic olefin monomer in the presence of a metathesis polymerization catalyst comprising a ruthenium complex catalyst or an osmium complex catalyst, wherein the article is a tube or accessory for tube.

2. A method for making a polyolefin article, the method comprising the steps of: a) adding a catalyst by Ru u Os metathesis to a cyclic olefin monomer to form a reaction mixture; b) forming the reaction mixture in a figure for the article, wherein the article is a tube or a tube fitting; and c) allowing the reaction mixture formed to polymerize under polymerization conditions.

3. The method according to claim 2, further characterized in that the cyclic olefin monomer comprises a monomer of the norbornene type.

4. The method according to claim 2, further characterized in that the cyclic olefin monomer comprises dicyclopentadiene.

5. The method according to claim 2, further characterized in that the reaction mixture is formed in a figure by feeding the reaction mixture into a rotating mold before allowing the reaction mixture to polymerize.

6. The method according to claim 2, further characterized in that it comprises the step of incorporating a reinforcing material with the reaction mixture before allowing the reaction mixture to polymerize.

7. The method according to claim 6, further characterized in that the reinforcing material comprises glass fiber.

8. The method according to claim 2, further characterized in that the polymerization is carried out in ambient air.

9. The method according to claim 2, further characterized in that the polymerization is carried out at ambient pressure.

10. A centrifuged cast plastic article formed by a process comprising the steps of: a) mixing a Ru u Os metathesis polymerization catalyst with a cyclic olefin monomer to form a reaction mixture; b) feeding the reaction mixture in a rotating mold; and c) allowing the reaction mixture to polymerize.

11. The article according to claim 10, further characterized in that the cyclic olefin monomer comprises a monomer of the norbornene type.

12. - The article according to claim 10, further characterized in that the cyclic olefin monomer comprises dicyclopentadiene.

13. The article according to claim 10, further characterized in that the article is a tube or a tube accessory.

14. The article according to claim 10, further characterized in that the article includes a reinforcing material placed therein.

15. The article according to claim 14, further characterized in that the reinforcing material comprises glass fiber.

16. A method for manufacturing tubing or accessories for polyolefin tubing by filament winding, the method comprising the steps of: a) mixing a catalyst by Ru u Os metathesis with a cyclic olefin monomer to form a reaction mixture; b) coating at least a portion of a reinforcing material with the reaction mixture; c) winding the coated reinforcing material around a mandrel; and d) allowing the olefin monomer to polymerize while the coated reinforcing material is wound around the mandrel to form a polyolefin tube or pipe fitting.

17. The method according to claim 16, further characterized in that the method is performed in ambient air.

18. - A tube or accessory for polyolefin tube wound with filament comprising a polymerized olefin monomer and a reinforcing material, the tube is formed by: a) adding a catalyst by metathesis of Ru or Os to a cyclic olefin monomer to form a reaction mixture; b) coating at least a portion of the reinforcing material with the reaction mixture; c) winding the coated reinforcing material around a mandrel; and d) allowing the olefin monomer to polymerize while the coated reinforcing material is wound around the mandrel to form a tube or fixture for polyolefin tubing

19. The tube or fixture for filament-wound polyolefin tubing in accordance with claim 18, further characterized in that the olefin monomer comprises dicyclopentadiene.

20. The tube or accessory for polyolefin tube wound by filament according to claim 18, further characterized in that the catalyst has the formula: where: M is Os u Ru; R and R1 are independently selected from hydrogen, or a substituent group selected from C2-C2o alkenyl > C2-C20 alkynyl. C 1 -C 20 alkyl, aryl, C 1 -C 20 carboxylate, Ci-C 2 alkoxy, C 2 -C 20 alkenyloxy, C 2 -C 20 alkynyloxy, aryloxy, C 2 -C 20 alkoxycarbonyl, C 1 -C 20 alkylthio, C 1 -C 20 alkylsulfonyl C20 or C1-C20 alkylsulfinyl. each substituent group is optionally substituted with one or more groups selected from C 1 -C 5 alkyl, halide, C 1 -C 5 alkoxy or a phenyl group optionally substituted with halide, C 1 -C 5 alkyl or C 1 alkoxy -C5; X and X1 are independently selected from hydrogen or an anionic ligand; and L and L1 are any electron-neutral donor.

21. A method for manufacturing a polyolefin tube by extrusion by stretching, the method comprising the steps of: a) mixing a catalyst by Ru u Os metathesis with a cyclic olefin monomer to form a reaction mixture; b) carrying a reinforcement material to a die where the reinforcing material is formed in a tube profile; c) before or after step b), at least partially coating the reinforcing material with the reaction mixture; and d) curing the reaction mixture to form the polyolefin tube.

22. A tube of polyolefin subjected to extrusion by stretching comprising a polymerized olefin monomer and a reinforcing material, the tube is formed by: a) mixing a catalyst by metathesis of Ru or Os with a cyclic olefin monomer to form a reaction mixture; b) carrying a reinforcement material to a die where the reinforcement is formed in a tube profile; c) before or after step b), at least partially coating the reinforcing material with the reaction mixture; and d) curing the reaction mixture to form the tube.