WO2001049628A1 - Composites renforces par fibres et polymerises par catalyseur - Google Patents

Composites renforces par fibres et polymerises par catalyseur Download PDF

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Publication number
WO2001049628A1
WO2001049628A1 PCT/US2001/000476 US0100476W WO0149628A1 WO 2001049628 A1 WO2001049628 A1 WO 2001049628A1 US 0100476 W US0100476 W US 0100476W WO 0149628 A1 WO0149628 A1 WO 0149628A1
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WO
WIPO (PCT)
Prior art keywords
sizing composition
reinforcing fiber
fiber material
lubricant
coupling agent
Prior art date
Application number
PCT/US2001/000476
Other languages
English (en)
Inventor
Donald B. Sage, Jr.
Andrew B. Woodside
Luann E. Barsotti
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Owens Corning
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Owens Corning filed Critical Owens Corning
Priority to AU27687/01A priority Critical patent/AU2768701A/en
Publication of WO2001049628A1 publication Critical patent/WO2001049628A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
    • C08J5/06—Reinforcing macromolecular compounds with loose or coherent fibrous material using pretreated fibrous materials
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C25/00—Surface treatment of fibres or filaments made from glass, minerals or slags
    • C03C25/10—Coating
    • C03C25/24—Coatings containing organic materials
    • C03C25/26—Macromolecular compounds or prepolymers
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C25/00—Surface treatment of fibres or filaments made from glass, minerals or slags
    • C03C25/10—Coating
    • C03C25/24—Coatings containing organic materials
    • C03C25/26—Macromolecular compounds or prepolymers
    • C03C25/32—Macromolecular compounds or prepolymers obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
    • C03C25/326—Polyureas; Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G61/02—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes
    • C08G61/04—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms
    • C08G61/06—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms prepared by ring-opening of carbocyclic compounds
    • C08G61/08—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms prepared by ring-opening of carbocyclic compounds of carbocyclic compounds containing one or more carbon-to-carbon double bonds in the ring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2365/00—Characterised by the use of macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Derivatives of such polymers

Definitions

  • the present invention relates to a sizing composition for coating glass or other fibers that are used to manufacture fiber-reinforced composites using a cycloolefm resin.
  • the composition is advantageously compatible with the catalyst, in that chemical interactions between the catalyst and the components of the sizing are eliminated.
  • fiber-reinforced composites Due to their corrosion resistance, light weight, design flexibility and efficiency, and cost effectiveness, fiber-reinforced composites are finding ever increasing use in industries such as the aerospace, automotive, chemical and oil, electronic, infrastructure, and military industries.
  • the reinforcements for these composites may initially be formed as fabrics, mats, pellets, chopped strands, or unidirectional fiber products such as rovings or strands.
  • These intermediate products may be further processed and combined with various matrices to form useful articles such as engine cowlings, grill opening panels, pipes, circuit boards, structural beams, missile launch tubes, and other molded products.
  • the molded products typically comprise a fiber-reinforcement component and a molding resin, and may further include fillers, pigments, catalysts and other processing aids.
  • the fiber reinforcements are typically coated with a protective sizing that provides resilience to the fibers and aids in the processing and wettability of the fibers in the molding resin.
  • the sizings themselves may comprise thermoplastic or thermosetting resins, and may include components known to enhance coating ability and reduce abrasion between fibers and contact points. It is desirable that the sizing used to coat the glass be highly compatible with the molding resin that forms the rest of the composite product.
  • hnpregnating or molding resins for producing composites include, for example, polyesters, vinylesters, epoxies, phenolics, polyurethanes, polyimides, bismaleimides, polycarbonates, nylons, polyether-etherketones, polyphenylene sulfides, polyetherimides, polyvinylchlorides, polystyrenes, polyethylenes, polypropylenes, or other polyolefins.
  • cycloolef ⁇ ns which can be polymerized by a ring opening metathesis polymerization reaction (ROMP).
  • the cycloolefms usually must be polymerized in the presence of a ROMP catalyst to solidify the composite.
  • Such ROMP catalysts include tungsten and molybdenum compounds, such as those disclosed in U.S. Patent Nos. 4,427,595, 4,681, 956, 4,727,215, 4,882,401 and 5,082,909.
  • these ROMP catalysts have been used in combination with aluminum alkoxy compounds or alkylaluminum compounds as co-catalysts.
  • the use of the aluminum co-catalysts is often detrimental to the polymerization process, because the presence of even slight amounts of water inhibits their activity. Since small amounts of water are normally present on the surfaces of glass fibers after forming, the effectiveness of the polymerization process is often compromised, and the resulting product, instead of being a tough, hard composite material, has an undesirable, soft, rubbery consistency.
  • these ruthenium and osmium catalysts do not require the additional use of the above discussed aluminum co-catalyst compounds, and thus these catalysts do not suffer from the same intolerance to moisture.
  • a significant drawback of using these ruthenium and osmium carbene catalysts in the polymerization of typical composite formulations containing cycloolefin resins such as dicyclopentadiene (DCPD) is that the ingredients typically used to prepare the fiber reinforcement material poison these carbene catalysts, thereby reducing or eliminating their effectiveness.
  • the term "poison", as it is used herein with respect to the ingredients used to prepare fiber reinforcement materials, is intended to mean that these ingredients inhibit, slow, prevent or terminate the desired polymerization reaction.
  • the components of conventional sizing formulations such as polymers, lubricants and other additives are poisonous to the osmium and ruthenium carbene catalysts and therefore hinder the catalytic reaction needed to cure the resin.
  • the result is that the end product is soft and rubbery, instead of being a hardened and resilient composite. This incompatibility between the sizing and the catalyst is a significant problem in the art, which, heretofore, has not been addressed.
  • the present invention relates to an improved sizing composition for reinforcing fiber materials that is compatible with catalysts used to initiate a ring opening metathesis (ROMP) polymerization of a cycloolefin resin, this sizing composition comprising: one or more film forming polymers; a silane coupling agent; and a lubricant; wherein the film forming polymer, the silane coupling agent and the lubricant are compatible with one or more ROMP catalysts used to initiate ring opening metathesis polymerization of the cycloolefin resins.
  • ROMP ring opening metathesis
  • the invention also relates to a method of making a sized reinforcing fiber material comprising the steps of: i) preparing a sizing composition comprising: one or more film forming polymers; a silane coupling agent; and a lubricant; wherein the film forming polymer, the silane coupling agent and the lubricant are compatible with one or more ROMP catalysts used to initiate ring opening metathesis polymerization of the cycloolefin resins ; ii) contacting the surfaces of a plurality of filaments of a reinforcing fiber material with the sizing composition; and iii) allowing the sizing composition to solidify onto the surfaces of the filaments of the reinforcing fiber material.
  • the invention also relates to a sized reinforcing fiber material coated with the sizing composition of the present invention.
  • the present invention further relates to a molded composite article comprising (i) a reinforcing fiber material sized with the sizing composition of the present invention, and (ii) a cycloolefin resin polymerized using a ROMP catalyst.
  • the present invention additionally includes a method of making a fiber reinforced composite, comprising the steps of:
  • a sizing composition on the surfaces of a reinforcing fiber material, the sizing composition comprising: one or more film forming polymers a silane coupling agent; and a lubricant; to form a coated reinforcing fiber material; and (ii) molding the coated reinforcing fiber material with a cycloolefin resin in the presence of a ROMP catalyst to form a fiber reinforced composite; wherein the film forming polymer, the silane coupling agent and the lubricant in the sizing composition are compatible with one or more ROMP catalysts used to initiate ring opening metathesis polymerization of the cycloolefin resins.
  • the invention additionally comprises a composite article comprising a sized reinforcing fiber material coated with the sizing composition comprising a film forming polymer, a silane coupling agent and a lubricant; wherein the film forming polymer, silane coupling agent lubricant are compatible ROMP catalysts used to initiate ring opening metathesis polymerization of cycloolefin resins.
  • the present invention relates to a sizing composition that is highly compatible with ROMP catalysts used in the ring opening metathesis polymerization of cycloolefins.
  • the term "compatible”, as used herein, is intended to mean that the sizing does not poison the catalyst or interact, in any other way, so as to diminish the effectiveness of the catalyst when it is added to the cycloolefin resin.
  • the sizing composition when applied to reinforcing fiber materials used in composite winding, molding or casting, provides desirable properties such as good compatibility with a molding resin, reduced fuzz and good shear strength.
  • the effectiveness of the sizing compositions of this invention may also be attributed to the absence of certain reactive functional groups on the molecules of the various ingredients of the sizing composition. As a result of the absence of these reactive functional groups, it is believed that the molecules of the various ingredients of the sizing composition cannot react with the catalyst and therefore cannot cause a poisoning effect.
  • the conventional sizings of the prior art contain ionic species, such as salt or certain nucleophilic impurities, which appear to interact adversely with the ROMP catalyst.
  • the sizing composition of the present invention may include one or more film forming polymers selected from the group consisting of film forming polymers compatible with the ROMP catalyst used to initiate ring opening metathesis polymerization of cycloolefin resins.
  • the film forming polymer improves the wettability of the sizing and protects the individual fibers and fiber bundles within the reinforcing fiber material during processing by providing a controlled level of strand integrity, which is the ability of the fibers to adhere together during processing.
  • Suitable film forming polymers may be selected from the group consisting of bis- A epichlorohydrin epoxies, modified epoxies, epoxy-polyesters, epoxy-polyurethanes, epoxy novolac resins, polyvinyl acetates, vinylacrylics, styrenated acrylics, polybutylacrylates, saturated or unsaturated polyesters, polyurethanes, polyamides, paraffin waxes, carnauba waxes, micro-crystalline waxes, polyethylenes, polypropylenes, polycarboxylic acids, polyvinyl alcohols and mixtures thereof.
  • Examples of preferred film forming polymers are: a polyurethane such as "Witcobond 320", which is available commercially as a liquid emulsion from Witco Inc; an acrylic resin such as “NS-7170”, which is commercially available from National Starch Inc.; and a styrenated acrylic resin such as "Product No. 3661", which is commercially available from H.B. Fuller Inc.
  • the amount of the film former in the aqueous size mixture ranges from about 0.5% by weight to about 10.0% by weight.
  • the amount used is from about 3% by weight to about 5% by weight.
  • the sizing composition of the present invention also includes a silane coupling agent, which is compatible with ROMP catalysts.
  • the silane coupling agent improves the adhesion between the sized fiber surface and the composite matrix resin, by providing functional groups for reaction with the surface molecules of the fiber and the matrix resin, in effect acting as a "bridge” between the inorganic fiber surface and the organic composite matrix resin.
  • Suitable silane coupling agents include ROMP-compatible silanes, such as those commercially available from OSi, Inc., a division of Witco, and Dow Corning, Inc. Examples of these include: vinyltrimethoxysilane, commercially available under the tradename "A-171" from OSi, Inc., or as "Q 96300" from Dow
  • One preferred ROMP compatible silane is vinyltrimethoxysilane.
  • the silane coupling agent is used in an amount of from about 0.3% to about 1.0% by weight based upon the total weight of the sizing composition. At concentrations above 1.0%, the resulting product is of undesirable quality because the silane increases fuzz development. Therefore, it is necessary to balance the amount of the silane sufficiently to provide the desired, coupling effect, but without promoting high levels of fuzz in the sized product.
  • the sizing composition also includes a cationic lubricant that is compatible with the ROMP catalysts.
  • the cationic lubricant is added to the sizing to reduce the development of fuzz and to improve the coating ability of the sizing composition.
  • the cationic lubricant may be selected from the group consisting of functionalized polyalkyleneimines. Examples of suitable cationic lubricants include water-soluble, partially amidated polyethyleneimines (PEIs) substituted with a varying number of ethylene residues, for example PEI-12.
  • PEIs water-soluble, partially amidated polyethyleneimines
  • a cationic lubricant based on PEI-12 is a cationic lubricant, "Henkel 6760T", which is commercially available from Henkel, Inc.
  • exemplary cationic lubricants include fatty acid amine cationic lubricants such as a cocoamine acetate, available as "PF-710" from Henkel Inc.; or the reaction products of tetraethylene pentamine with stearic acid, pelargonic, or caprylic acid.
  • the cationic lubricant is used in an amount of from about 0.04% to about 0.25% by weight based upon the total weight of the sizing composition. At an amount over 0.2%) by weight, however, some discoloration of the fiber package formed from the sized reinforcing fiber material may occur. Such discoloration is an aesthetically undesirable result. More preferably, therefore, the cationic lubricant is used in an amount of from about 0.05% to about 0.1% by weight based upon the total weight of the sizing composition.
  • a second lubricant which is preferably a nonionic lubricant, may be added to the sizing composition.
  • this second lubricant may be substituted for the cationic lubricant.
  • a second lubricant is a polyethyleneglycol monoester, for example, a polyethyleneglycol monopelargonate having the tradename "Emerstat 2658", which is a nonionic lubricant that is commercially available from Henkel, Inc.
  • the second lubricant when used in combination with the cationic lubricant, may be used in an amount from about 0 to about 1.5% by weight based upon the total weight of the sizing composition, and more preferably at from 0 to about 0.5% weight.
  • a suitable emulsified wax may be added to the sizing composition.
  • emulsified wax is intended to encompass olefinic wax compounds, including polyethylenes and polypropylenes, or mixtures thereof, that have been emulsified by combination with a surfactant, which is preferably a nonionic surfactant.
  • a surfactant which is preferably a nonionic surfactant.
  • the addition of a surfactant to emulsify the wax serves to improve the solubility or dispersibility of the emulsified wax in the sizing composition.
  • Suitable emulsified waxes include paraffins, carnauba and polyolefins.
  • the emulsified wax is an emulsified paraffin wax.
  • the emulsified paraffin wax acts as a modifier for the one or more film forming polymers in the sizing composition, and also acts as a lubricant within the sizing composition.
  • An example of a suitable emulsified paraffin wax is "FIBERGLASS X-12", an emulsion that is commercially available from Michelman Inc. or "Velvetrol 77-70", available commercially from Rhone Poulenc.
  • the amount of emulsified paraffin wax in the sizing composition may range from 0 to about 5% by weight, preferably from about 1% by weight to about 4% by weight, and more preferably about 2.3% by weight, based on the total weight of the sizing composition.
  • a hydrolyzing agent for hydrolyzing the silane coupling agent may also be included in the sizing composition.
  • Any suitable hydrolyzing agent that promotes the hydrolysis of the alkoxy groups on the silane-coupling agent to hydroxyl groups may be used.
  • suitable hydrolyzing agents include hydrochloric, acetic, formic, citric, oxalic and phosphorous acids.
  • an effective amount of glacial acetic acid is used as the hydrolyzing agent.
  • an effective amount of glacial acetic acid may be from about 0.25% to about 0.5% by weight based upon the total weight of the sizing composition. More preferably, about 0.25% by weight of glacial acid, based upon the total weight of the sizing composition, is used.
  • the sizing composition may generally be of a pH in the range of from about 2 to about 10, it is recognized that the glacial acetic acid, or any of the other suitable hydrolyzing agents, also performs the additional function of maintaining the pH of the sizing composition in a preferred range of from about pH 3 to about pH 5.
  • the sizing composition may also include one or more additives useful to improve wetting, processing and the reduction of fuzz.
  • additives useful to improve wetting, processing and the reduction of fuzz.
  • Such agents may be selected from the group consisting of processing aids, wetting agents and other additives.
  • Suitable processing aids may include one or more compounds selected from the group consisting of salt-free polyethylene glycol (hereinafter "PEG") compounds such as PEG monopelargonate and other PEG fatty acid esters, polyvinylpyrrolidones and pentaerythritols.
  • PEG polyethylene glycol
  • Polyvinylpyrrolidones for example, enhance pick-up of the sizing composition by the reinforcing fiber material by up to about 20%.
  • the processing aid is added to facilitate contact between the sizing and the fiber surface.
  • a particularly useful processing aid is a salt-free PEG 400 monopelargonate ester, which is highly compatible with, and which does not inhibit the cure of DCPD resin.
  • salt-free is intended to mean the absence of substantially any ionic species, residues or functional groups in a preparation containing the pelargonate ester.
  • the inventors have unexpectedly discovered that this salt-free PEG 400 monopelargonate does not poison the ROMP catalysts, unlike other PEG compounds, which are traditionally used in sizing formulations.
  • a salt-free PEG 400 monopelargonate is commercially available, for example, as "Emery 2658", from Henkel, Inc.
  • the sizing composition comprises a film forming polymer, a silane coupling agent, a cationic lubricant and a hydrolyzing agent.
  • the sizing composition further comprises an emulsified paraffin wax that is compatible with the ROMP catalyst.
  • the sizing composition of the present invention may be made by any method known to one of ordinary skill in the art.
  • the sizing composition may be made by blending the individual components of the sizing composition with a diluent to form a solution or suspension.
  • the diluent is water.
  • the components such as the film-forming polymer, the coupling agent, the hydrolyzing agent, the lubricants and processing aids are preferably used in amounts effective to formulate a stable dispersion having a storage stability of up to about 72 hours at temperatures from about 50°F to about 120°F, and a pH of from about 3 to about 5.
  • the sizing composition of the present invention may be applied to the reinforcing fiber material by any suitable method, to form a coated fiber reinforcing material.
  • the sizing composition may be applied to filaments of a reinforcing fiber material immediately after they are formed in an on-line operation, or the sizing composition may be applied, off-line, to unwound strands of reinforcing fiber material that were previously formed and packaged.
  • the invention may also be applied to the reinforcing fiber material after it has been woven or knitted into a fabric.
  • Means for applying the sizing composition include, but are not limited to, pads, sprayers, rollers or immersion baths.
  • the reinforcing fibers are wetted with the sizing composition as soon as they are formed.
  • the sizing composition may be sprayed onto continuous glass fibers as they are formed from a bushing or like device.
  • the bushing is equipped with small apertures to allow passage of thin streams of the molten material.
  • each stream is attenuated and pulled downward to form a long, continuous fiber.
  • the continuously forming fibers may be gathered into strands for winding.
  • the forming packages or doffs formed by the above- described winding operation are then dried for about 13 to 25 hours at 265°F, after which they are ready for use in composite-making operations such as filament winding.
  • the amount of sizing composition that is applied to the surfaces of the reinforcing fiber material may be selected to provide an effective thickness of the sizing composition on the surfaces of the reinforcing fiber material. If an insufficient coating of the sizing composition is applied, the fibers of the reinforcing fiber material are not protected during the processing operation, which results in unnecessary fuzz development caused by broken fiber filaments in the sized reinforcing fiber material. Another effect of insufficient coating is that the ability of the fibers of the reinforcing fiber material to wet out in a molding resin, such as the cycloolefin resin, during the composite forming process is reduced.
  • the effective amount of sizing composition that should be applied to the reinforcing fiber material is determined by monitoring the loss on ignition (LOI) value, which is a measure of the amount of sizing present on the surfaces of the sized reinforcing fiber material.
  • LOI loss on ignition
  • the amount of sizing composition deposited on the surfaces of the reinforcing fiber material may then be adjusted by conventional means, depending on the nature of the reinforcing fiber material being sized and the type of applicator being used.
  • Such means for adjusting the amount of size pickup include varying the applicator speed, increasing or decreasing the concentration of the sizing composition, increasing or decreasing the viscosity of the sizing by adding viscosity modifiers, or by changing the temperature of the sizing.
  • the sizing composition may be applied by contacting the fiber strand with a roller applicator containing the sizing composition.
  • the speed of the roller applicator can be varied to change the amount of sizing composition that is applied to the surface of the continuous fiber strand. Accordingly, it is possible to increase or decrease the level of impregnation of the continuous fiber strand with the sizing composition, and, accordingly, the amount of sizing composition present on the surface of the continuous fiber strand, by decreasing or increasing the speed of the roller applicator.
  • the roller applicator speeds that may be used in the process of sizing according to the invention may vary from about 15 rpm to about 120 rpm. Preferably, roller applicator speeds from about 30 rpm to about 75 rpm may be used.
  • the sized reinforcing fiber material may then be used in continuous form, for example, in the formation of filament wound composites, or as input for a weaving or knitting process to make a fabric.
  • the fabric may subsequently be used in a centrifugal casting process or as input for an RTM or SCRIMP molding process.
  • the sizing composition is applied to reinforcing fibers used to manufacture filament wound composite articles, such as pipes.
  • the sized reinforcing fibers are impregnated with a catalytically activated cycloolefin resin, and a polymerization reaction allowed to progress until a hardened composite is formed.
  • the sized reinforcing fibers may be laid down as a mat, which is then impregnated with the activated cycloolefin resin to be polymerized.
  • the sized reinforcing fibers are woven or knitted into a fabric that is then impregnated and molded with the activated cycloolefin resin.
  • the cycloolefin resin used to form the composite of the present invention includes any suitable cycloolefin that can be polymerized by a ring opening methathesis polymerization reaction.
  • the term "cycloolefin resin" as it is used herein, is intended to include monomers, dimers, tetramers, pentamers, or oligomers of conventionally known cycloolefin resins.
  • the cycloolefin resin is a liquid resin which is cured or hardened by the ROMP polymerization process.
  • a suitable cycloolefin maybe selected from the group consisting of cyclobutene, cyclopentene, cycloheptene, cyclooctene, cyclooctadiene, cyclopentadiene, dicyclopentadiene, 7-oxanorbornene, 7- oxanorbornadiene, tetracyclododecadiene, cyclododecene, cyclononadiene, cyclopentadiene trimers or tetramers, dicyclopentadiene trimers or tetramers, and mixtures thereof.
  • the cycloolefin resin may be a dicyclopentadiene (DCPD) resin, such as DCPD resins having the tradenames "Ulfrene 99" and “Ultrene 97", which may be obtained commercially from B.F. Goodrich Inc.
  • DCPD dicyclopentadiene
  • the cycloolefin resin may preferably be used in combination with an effective amount of a gel modification agent, which slows the hardening of the cycloolefin resin during the polymerization or curing process and thus allows sufficient time to form and shape the combination of the cycloolefin resin and the reinforcing fiber material.
  • a gel modification agent which slows the hardening of the cycloolefin resin during the polymerization or curing process and thus allows sufficient time to form and shape the combination of the cycloolefin resin and the reinforcing fiber material.
  • An exemplary composite molding process that describes using a combination of a cycloolefin resin and a gel modification agent is disclosed in U.S. Patent No. 5,266,370. Any suitable gel modification agent may be used in the composite molding process of the present invention.
  • An example of a suitable gel modification agent is triphenyl phosphine (TPP), which is commercially available, for example, as Product No. T8,440-9, from
  • Suitable ROMP catalysts that may be used to form the molded composite articles of this invention may be selected from the group consisting of ruthenium and osmium catalysts.
  • a ROMP catalyst useful in this invention may be selected from the group consisting of ROMP catalysts described, for example, in U.S. Patent Nos. 5,312,940, 5,342,909, 5,831,108, 5,840,238, 5,849,851 and 5,939,504.
  • An anionic ligand is defined as any ligand which, when removed from a metal center in its closed shell electron configuration, has a negative charge.
  • a neutral electron donor is any ligand which, when removed from a metal center in its closed shell electron configuration, has a neutral charge, such as a
  • ROMP catalyst is phenylmethylenebis(tricyclohexylphosphine)ruthenium dichloride, which is commercially available from Advanced Polymer Technologies, Inc.
  • the ROMP catalyst is used in amount effective to initiate the polymerization of the cycloolefin resin. This effective amount is proportionate to the batch weight of resin being molded. Accordingly, the weight/weight ratio of cycloolefin resin in relation to the ROMP catalyst in the sizing composition may range from about 600:1 to about 1700:1. Preferably, the weight ratio of cycloolefin resin to the ROMP catalyst is approximately 1250:1.
  • the ROMP catalyst may be dissolved in a solvent before it is combined with the cycloolefin resin for molding. Any suitable solvent may be used to dissolve the ROMP catalyst. Suitable solvents are those that are non-reactive during the polymerization of the activated cycloolefin resin.
  • solvents examples include hydrocarbons, toluene, xylene, trichloroethane, methylene chloride and water.
  • a preferred solvent is methylene chloride.
  • the ROMP catalyst may be used without first dissolving it in a solvent.
  • a molded composite article is prepared according to the invention can be accomplished by first dissolving a gel modification agent such as triphenyl phosphine (TPP), in a cycloolefin resin such as DCPD, the cycloolefin resin having been melted by warming to a temperature of from about 90°F to 120 °F. Subsequently, the catalyst, dissolved in a solvent such as methylene chloride, may be added to the combination of the cycloolefin resin and the gel modification agent, and the mixture stirred for approximately two minutes.
  • a gel modification agent such as triphenyl phosphine (TPP)
  • TPP triphenyl phosphine
  • DCPD cycloolefin resin
  • the catalyst dissolved in a solvent such as methylene chloride, may be added to the combination of the cycloolefin resin and the gel modification agent, and the mixture stirred for approximately two minutes.
  • the resulting resin mixture may then be combined, by any molding means conventionally known in the art, with a reinforcing fiber material sized according to the present invention.
  • molding means include, but are not limited to, resin injection molding, centrifugal casting, and filament winding.
  • strands of the reinforcing fiber material may be pulled through a bath containing the resin mixture, to provide strands impregnated with resin mixture.
  • the impregnated strands may then be wound, for example, on a mandrel, to form a raw composite in the form of a filament wound pipe or ring.
  • This raw composite may be cured by a process including gelling and post-curing according to any method conventionally known in the art.
  • the raw composite may be allowed to gel, preferably at a temperature between 90°F and 140 °F.
  • the gelling is caused by the initiation of polymerization of the cycloolefin resin.
  • the gelled composite may then be fully cured by heating in an oven, for example, at about 300 °F for from 1 to 16 hours. After the cure is completed, the composite may be allowed to cool, and then removed from the mandrel.
  • an effective ROMP polymerization process using the sized reinforcing fiber material and the combination of a ROMP catalyst and cycloolefin resin according to the present invention can provide a tough, resilient composite.
  • the sized reinforcing fiber material may also be successfully molded by any other conventional molding means known in the manufacture of fiber-reinforced composites.
  • the sized reinforcing fiber materials of the present invention include strands, ravings, yarns or threads, in continuous or chopped form, fibrous fabrics, mats and surfacing veils.
  • the term "strand" as used herein, is intended to include a collection of a plurality of individual filaments, typically from about 20-8000 filaments, and preferably from about 2000-4000 filaments.
  • Any suitable reinforcing fiber material may be used in the molded composite article of the present invention.
  • the reinforcing fiber material may be made from any suitable molten fiberizable material, or from any fibrous material.
  • the reinforcing fiber material is selected from the group consisting of glass, carbon, graphite, aramid (such as Kevlar®) or other polymer fibers, such as Spectra®, natural fibers, or blends thereof, as well as any other fibrous reinforcing materials that may conventionally be used in the manufacture of reinforced composites.
  • aramid such as Kevlar®
  • other polymer fibers such as Spectra®, natural fibers, or blends thereof, as well as any other fibrous reinforcing materials that may conventionally be used in the manufacture of reinforced composites.
  • These reinforcing fiber materials when coated with the sizing composition of the present invention and combined with a catalyzed cycloolefin resin, may be molded into composite articles by any molding procedure conventionally known in the art.
  • the composite articles of the present invention may include filament wound composites such as pipes, fittings, shafts or waterfront or ocean pilings; or composite articles formed by resin injection molding (RIM), such as automobile parts, recreational vehicle parts, or chemical process equipment.
  • RIM resin injection molding
  • Other composite articles within the scope of the present invention may be formed by centrifugally casting the cycloolefin resin, catalyst and a woven or knitted fabric or mat made according to the invention described in U.S. Patent No. 5,266,370.
  • An exemplary sizing composition was prepared according to the following composition:
  • the vinyltrimethoxysilane was first dissolved in water and glacial acetic acid added as a hydrolyzing agent to facilitate dissolution and hydrolysis.
  • the cationic lubricant which is water-soluble, and the polyurethane dispersion, in water, were then added to the silane solution to form an aqueous solution or dispersion.
  • the resulting solution that is, the sizing composition, was then applied to glass roving ends using a rotating applicator and dried in an oven for 13 to 25 hours at 265°F.
  • compositions according to the present invention were prepared. The percentage weight or the amount by weight of each component necessary to make a 50,000 gram batch is indicated, the balance being comprised of water as the solvent.
  • Fiber reinforcing materials in the form of continuous glass fiber strands were treated with each of the sizing compositions of Examples 12-19, at applicator rotation speeds that were varied to change the amount of sizing composition deposited on the surfaces of the glass fiber strands.
  • Eight samples of glass fiber strand that had been sized with the sizing composition of each of Examples 12-19 were prepared and tested at each applicator speed.
  • the glass fiber strand samples were sized at applicator rotation speeds of 45 rpm and 75 ⁇ m, respectively.
  • the resulting sized glass fiber strands were evaluated for the development of fuzz, package growth measured as delta L, and loss on ignition rate. The average test values for each group of eight samples is reported in Table 2.
  • a preferred composition of the present invention which included a film forming polymer, a silane coupling agent, a cationic lubricant, a nonionic lubricant and an emulsified paraffin wax, as taught in Example 18, exhibited very low fuzz, about 0.0059 at an application rate of 45 ⁇ m (0.0080 at 75 ⁇ m), and low LOI (0.59 at 45 ⁇ m and 0.70 at 75 ⁇ m, respectively).
  • a continuous strand of glass fiber roving that had been sized according to the invention were used to prepare a filament wound composite by molding the sized roving with a DCPD resin.
  • 1000 grams of a DCPD monomer were liquefied by warming to a temperature of about 94°F.
  • 0.83 grams of triphenyl phosphine (TPP, Product No. T8,440-9, Aldrich Chemicals) were dissolved in the liquefied DCPD resin.

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Abstract

Composition d'encollage extrêmement compatible avec les catalyseurs utilisés dans la polymérisation par métathèse à ouverture de noyau de cyclooléfines. Cette composition d'encollage contient une combinaison spécifique d'ingrédients qui, quand on l'applique aux fibres de renforcement utilisées dans la fabrication de composites, permettent de mouler les fibres avec une résine de cyclooléfine catalysée sans empoisonnement du catalyseur. L'invention concerne également un procédé de fabrication de composites renforcés par fibres au moyen de produits fibreux comprenant cette composition d'encollage.
PCT/US2001/000476 2000-01-05 2001-01-05 Composites renforces par fibres et polymerises par catalyseur WO2001049628A1 (fr)

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US60/174,557 2000-01-05

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Publication number Priority date Publication date Assignee Title
US6890650B2 (en) 2002-07-23 2005-05-10 Ppg Industries Ohio, Inc. Glass fiber sizing compositions, sized glass fibers, and polyolefin composites
EP2982709A1 (fr) * 2014-08-07 2016-02-10 Telene SAS Composition durcissable et article moulé comprenant la composition
US9856352B2 (en) 2014-08-07 2018-01-02 Ppg Industries Ohio, Inc. Glass fiber sizing compositions, sized glass fibers, and polyolefin composites
EP3024856B1 (fr) 2013-07-23 2018-08-29 Bostik Sa Polymères hydrocarbonés à groupement terminal alcoxysilane

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WO1986001811A1 (fr) * 1984-09-24 1986-03-27 Owens-Corning Fiberglas Corporation Parage sans chrome pour roving de fibres de verre a injection
EP0347819A2 (fr) * 1988-06-21 1989-12-27 Nippon Zeon Co., Ltd. Matrice polymère renforcée
EP0424833A2 (fr) * 1989-10-24 1991-05-02 The B.F. Goodrich Company Fibres d'reenforcement couverts avec catalysateur d'methathesis
US5428098A (en) * 1993-01-29 1995-06-27 Hoechst Aktiengesellschaft Fiber-reinforced cycloolefin copolymer material, process for its preparation and shaped articles from the material
US5712036A (en) * 1996-05-08 1998-01-27 N.V. Owens-Corning S.A. High solubility size compositon for fibers
WO1999011454A1 (fr) * 1997-09-05 1999-03-11 A. O. Smith Corporation Composites d'olefine polymerises par metathese comprenant une matiere de renforcement encollee

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US4271229A (en) * 1979-09-04 1981-06-02 Ppg Industries, Inc. Sizing composition to yield sized glass fibers with improved UV stability
WO1986001811A1 (fr) * 1984-09-24 1986-03-27 Owens-Corning Fiberglas Corporation Parage sans chrome pour roving de fibres de verre a injection
EP0347819A2 (fr) * 1988-06-21 1989-12-27 Nippon Zeon Co., Ltd. Matrice polymère renforcée
EP0424833A2 (fr) * 1989-10-24 1991-05-02 The B.F. Goodrich Company Fibres d'reenforcement couverts avec catalysateur d'methathesis
US5428098A (en) * 1993-01-29 1995-06-27 Hoechst Aktiengesellschaft Fiber-reinforced cycloolefin copolymer material, process for its preparation and shaped articles from the material
US5712036A (en) * 1996-05-08 1998-01-27 N.V. Owens-Corning S.A. High solubility size compositon for fibers
WO1999011454A1 (fr) * 1997-09-05 1999-03-11 A. O. Smith Corporation Composites d'olefine polymerises par metathese comprenant une matiere de renforcement encollee

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6890650B2 (en) 2002-07-23 2005-05-10 Ppg Industries Ohio, Inc. Glass fiber sizing compositions, sized glass fibers, and polyolefin composites
US10662265B2 (en) 2013-07-23 2020-05-26 Bostik Sa Hydrocarbon-based polymers bearing an alkoxysilane end group
EP3024856B1 (fr) 2013-07-23 2018-08-29 Bostik Sa Polymères hydrocarbonés à groupement terminal alcoxysilane
WO2016020261A1 (fr) * 2014-08-07 2016-02-11 Telene Sas Composition durcissable et article moulé comprenant la composition
CN107075143A (zh) * 2014-08-07 2017-08-18 特伦尼有限公司 玻璃纤维上浆组合物、上浆的玻璃纤维及聚烯烃复合材料
CN107109034A (zh) * 2014-08-07 2017-08-29 特伦尼有限公司 可固化组合物和包含所述组合物的模制品
US9856352B2 (en) 2014-08-07 2018-01-02 Ppg Industries Ohio, Inc. Glass fiber sizing compositions, sized glass fibers, and polyolefin composites
EP3177675A4 (fr) * 2014-08-07 2018-03-14 Telene SAS Compositions d'ensimage de fibres de verre, fibres de verre ensimées et composites polyoléfiniques
US10017615B2 (en) 2014-08-07 2018-07-10 Telene Sas Curable composition and molded article comprising the composition
WO2016022751A1 (fr) * 2014-08-07 2016-02-11 Ppg Industries Ohio, Inc. Compositions d'ensimage de fibres de verre, fibres de verre ensimées et composites polyoléfiniques
CN107109034B (zh) * 2014-08-07 2019-02-19 特伦尼有限公司 可固化组合物和包含所述组合物的模制品
US10336870B2 (en) 2014-08-07 2019-07-02 Telene Sas Glass fiber sizing compositions, sized glass fibers, and polyolefin composites
EP2982709A1 (fr) * 2014-08-07 2016-02-10 Telene SAS Composition durcissable et article moulé comprenant la composition

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