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WO1994016129A1 - Fibres d'oxyde inorganique a traitement chimique et a stabilite thermique, convenant a des polymeres resistants aux temperatures elevees - Google Patents

Fibres d'oxyde inorganique a traitement chimique et a stabilite thermique, convenant a des polymeres resistants aux temperatures elevees Download PDF

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Publication number
WO1994016129A1
WO1994016129A1 PCT/US1994/000574 US9400574W WO9416129A1 WO 1994016129 A1 WO1994016129 A1 WO 1994016129A1 US 9400574 W US9400574 W US 9400574W WO 9416129 A1 WO9416129 A1 WO 9416129A1
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around
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group
film forming
present
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Johnson C. Watkins
Robert G. Swisher
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PPG Industries Inc
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PPG Industries Inc
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
    • 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
    • C08J5/08—Reinforcing macromolecular compounds with loose or coherent fibrous material using pretreated fibrous materials glass fibres
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes

Definitions

  • the present invention is directed to chemically treated or "sized" fibers of organic oxides such as silica, alumina, calcium oxide, magnesium oxide and the like, for instance, those present in glass fibers and ceramic fibers.
  • organic oxides such as silica, alumina, calcium oxide, magnesium oxide and the like, for instance, those present in glass fibers and ceramic fibers.
  • These sized fibers can display good thermal properties for use as reinforcement and fillers for numerous matrix polymer and especially for the high temperature stable or high temperature processable matrix polymers.
  • Fiber reinforced plastics have utilized inorganic oxide fibers like glass fibers to reinforce thermosetting and thermoplastic polymers for the ultimate production of various molded products.
  • the production of glass fiber reinforcement involves chemically treating the glass fibers with a sizing composition to increase the oleophilic character of the glass fibers and to protect the glass fibers from external abrasion and intrafilament abrasion during formation and processing.
  • Developments in the area of matrix polymers for the FRP industry resulted in polymers designed for use at higher temperatures to expand the
  • matrix polymers such as polyethersulfone (PES), polyphenylene sulfide (PPS), polyaromatic ketones like polyetheretherketone (PEEK) and polyetherketone (PEK) and polyetherketone-ketone (PEKK) and polyketone (PAEK) and amorphous, aromatic polyesters
  • PES polyethersulfone
  • PPS polyphenylene sulfide
  • PEEK polyaromatic ketones like polyetheretherketone
  • PEK polyetherketone
  • PEKK polyetherketone-ketone
  • PAEK polyketone
  • polyarylates are just a few examples of matrix polymers developed or in the development stage having good heat or temperature resistance.
  • the glass and ceramic fibers by themselves have good heat or temperature resistance so that in a composite of FRP a weak link in the armor of thermal resistance may be the chemical treatment or sizing on the fibers.
  • the sizing composition typically includes one or more film forming polymers, a coupling agent like an organo- functional silane coupling agent, a fiber lubricant, possibly emulsifiers for the film forming polymer, and perhaps wetting agents, all of which are usually present in an aqueous solution for application to the fibers.
  • a coupling agent like an organo- functional silane coupling agent
  • a fiber lubricant possibly emulsifiers for the film forming polymer, and perhaps wetting agents, all of which are usually present in an aqueous solution for application to the fibers.
  • This composition has an alkoxide or hydroxide of a titanium and/or zirconium metal where the compound has organic functionality.
  • This organoalkoxide or organohydroxide titanium or zirconium is present along with polyurethane and epoxy film forming polymers and/or an organo functional silane coupling agent as an additional coupling agent or in a blend, mixture, reaction product with the silane coupling agent.
  • the amount of the organofunctional silane coupling agent as a separate coupling agent can range up to around and including an effective coupling agent amount.
  • the amount of the organoalkoxide or organohydroxide titanium or zirconium is generally an amount greater than 10 parts per 100 parts of any film forming polymer and an amount to give a ratio of an amount with the organosilane, when present, in the range of about 2:1 to about 1:2. Also there can be present at least one film forming polymer that can be essentially free of polyvinylacetate homopolymer and
  • polyacrylic homopolymers and copolymers where the amount is an effective film forming amount. Also present can be at least one fiber lubricant in an effective lubricating amount. Also present is a carrier for application of the size to the substrate, and the carrier is present in an effective
  • Another aspect of the present invention is where the chemically treated inorganic oxide substrates are fibers having a volatile reduced residue of an aqueous size
  • At least one film forming polymer is present that is a polyurethane film forming polymer, and also present are: the fiber lubricant that is essentially free of large amounts of propylene oxide moieties.
  • the ratio of the organofunctional silane coupling agent, when present, to the organo alkoxide of titanium and/or zirconium is in the range of around 6:1 to around 1:6, and the carrier is water.
  • additional film forming polymer can be present such as an epoxy film forming polymer generally to give a ratio of the amounts of the epoxy to polyurethane film forming polymers of around 10:1 to around 1:10.
  • the organofunctional silane coupling agent need not be present, and the amount of the organo alkoxide or hydroxide of titanium and/or zirconium is present in an effective coupling agent amount. Otherwise than with this combination of film forming polymers, the organo- functional silane is generally present.
  • the chemically treated (sized) inorganic oxide fibers and especially glass fibers of the present invention find suitability in reinforcing polymeric matrices and especially the higher melting polymers or more thermally resistant polymers.
  • Nonexclusive examples of these include: (PPS), (PPS), (PEI), polyarylates, (PES), (PEEK), (PAEK), (PEK), (PEKK) and the like.
  • Other matrix polymers like poly (butylene terephthalate) polyamides may be reinforced with the sized fibers of the present invention.
  • the film forming polymer that can be utilized in the chemical treating composition in the present invention is any film forming polymer that forms a film upon evaporation of volatiles or upon curing by the addition of a curing agent. Those that are especially useful are essentially free of unmodified polyvinylacetate homopolymer and polyacrylates. For instance, the removal of the volatiles or the curing can occur when the treated fibers or substrates are heated.
  • the film that is formed need not be a vertically self-supported film, but it should at least be a discontinuous coating of a perceivable thickness.
  • the film forming polymer can be a liquid or an emulsion, suspension or dispersion of the polymer in a carrier compatible liquid.
  • the emulsion can be an oil-in-water type emulsion where, when the water and any other volatiles are removed, the film of the polymer is formed.
  • Nonexclusive examples of the film forming polymer include: polyurethane polymers, epoxy polymers, epoxy- polyurethane copolymers, polyester polymers, bisphenol A thermoplastic polyesters, polyvinylpyrrolidone, and the like.
  • emulsion examples include those discussed in U.S. Patent No. 4,615,946 (Temple), which is incorporated herein by reference.
  • One such epoxy polymer emulsion is that available from Interez, Inc., under the trade designation "EPI-REZ CMD 35201" material.
  • This epoxy resin has an epoxy resin dispersion which has 60 percent nonvolatiles and the only volatile material is water and the dispersion has a weight per epoxide of approximately 530, a pH of 8.3, and an average particle size between 1 and 4 microns.
  • the most suitable epoxy resin is the epoxy resin dispersion available from Interez, Inc., under the trade designation CMD-W-60 5520 which has a percent solids of 60 ⁇ 2 and a viscosity LVT No. 4 at 30 rpm of 10,000 ⁇ 2,000.
  • polyurethane polymers Another suitable film forming polymer that can be used is one or more polyurethane polymers.
  • polyurethane it is meant to include reaction products of organic compounds having at least two active hydrogens and di and/or polyisocyanates, wherein the resulting polymer is a curable polyurethane or polyurethane urea type polymer through removal of volatiles or curing by a curing agent.
  • the organic compounds with at least two active hydrogens is a polyol such as a polyester polyol or polyether polyol and most preferably, a polyol which is linear.
  • polyester-based polyurethane elastomers include those where the polyester is prepared from carboxylic acid such as adipic and the glycol portion can be selected from such materials as ethylene glycol, 1,3-propylene glycol, 1,3- butylene glycol and 1,4-butylene glycol.
  • polyfunctional polyesters which can be used are those based on phthalic anhydride, adipic acid, ethylene glycol, trimethylol propane, and the like.
  • a slight amount of branching of the polyol can be tolerated but the degree of functionality or branching of the polyol should be kept to a minimum since increased branching results in films that are tougher, harder and less flexible.
  • the di or polyisocyanates generally used to form the polyurethane are selected from aromatic, aliphatic and mixtures thereof, isocyanates but the aliphatic
  • isocyanates are preferred.
  • the polyisocyanates that can be used include: the aromatic isocyanate of toluene diisocyanate and the aliphatic isocyanates such as hexa- methylene diisocyanate, methylcyclohexylene diisocyanate, dicyclohexyl methane diisocyanate, lysine diisocyanate where the aromatic group is methyl or ethyl, bis (2-isocyanato ethyl)fumaric, bis (2-isocyanato ethyl) carbonate and dimeryl diisocyanate, where the organic group is essentially a C 36 hydrocarbon radical.
  • the polyurethane polymer can be made as an uncurable or as a curable material by any method known to those skilled in the art, for instance, additional monomers like diisocyanate, polyols or epoxies can be added to the polymer and/or a curable moiety can be introduced into the polymer.
  • the polyurethane polymers can be produced by any one-shot or single step method known to those skilled in the art or by the two step chain extension process utilizing linear or lightly branched polyols with the
  • polyurethane polymers in an oil-in-water emulsion that can be used include a blend of polyester based
  • polyurethane dispersions such as Witcobond W-290-H, available from Witco Chemical Corporation and XW-110 dispersion
  • the XW-110 material is a fully reacted polyurethane dispersed in water/N- methyl-2-pyrrolidone and contains little or no free
  • the dispersion has a hazy off-white appearance with a 35 percent solids level and a density of 8.7 lb/gal.
  • the viscosity at 25°C (77°F) in cps is 130, and the surface tension in dynes/cm is 41.
  • the film properties include:
  • the Witcobond W-290-H polyurethane has a milky white appearance, is aliphatic in type with a 65 percent solids level with an anionic charge and with a particle size of around 2 micrometers and with a pH at 25°C (77°F) of 7.5 and with a viscosity as measured by Brookfield LVF in cps of 200 and with a surface tension of 42 dynes/cm.
  • the film properties of the 290H material are: 4500 psi tensile strength, 720 percent elongation and moduli of 250 psi at 100%, 540 psi at 300% and 1550 psi at 500%.
  • a combination of film forming polymers may be used in the form of a combination of two distinct emulsions, suspensions or dispersions or solutions or as a mixture of these or as copolymers of the functional moieties such as epoxy polyurethane copolymers.
  • the polyurethane polymer can be the sole film forming polymer in the size composition.
  • film forming polymers may be present to give further enhanced properties, but the polyurethane is
  • a suitable combination of the film forming polymers is a polyester urethane polymer used in conjunction with an epoxy- containing film forming polymer or their emulsions,
  • a suitable ratio of the two to yield an effective film forming amount of total film forming polymer is around 4:1 to around 1:1 of the epoxy containing polymer to the polyurethane polymer. Additional amounts of the epoxy polymer may reduce some handling characteristics of chopped sized glass fibers. Specifically the filamentation resistance may be decreased, while additional amounts of polyurethane polymer may result in less thermal resistance of a reinforced
  • the amount of the film forming polymer is an effective film forming amount. This amount results in the film residue upon evaporation of the volatiles or curing of the curing agent with film forming polymer.
  • the effective film forming amount generally ranges from around 1 to around 25 weight percent of the total size including the carrier, although higher amounts are possible for higher solids applications. For instance, when an oil-in-water emulsion with a film forming polymer is present in an aqueous size, the amount of the emulsion on a solids basis is around 5 to around 90 weight percent of the solids of the aqueous chemical treating composition.
  • the percent solids of the oil-in-water film forming emulsion is in the range of about 10 to about 80 weight percent of the emulsion.
  • the chemical treating composition has at least one lubricant selected from cationic fiber
  • Nonexclusive examples of cationic lubricants include: oxyalkylated amines, alkyl- trialkyl quaternary ammonium salts, alkyl imidazoline
  • nonionic lubricants include fatty acids, esters such as fatty esters, wax esters, glycerol esters, glycol esters, fatty alcohol esters and those described as complex esters, fatty alcohols, paraffinic and micro- crystalline waxes, polyethylenes, oxidized polyethylenes, and the like.
  • the amount of the lubricant employed in the chemical treating composition in the present invention is an effective lubricating amount which is generally in the range of around 0.1 to 5 weight percent of the total size or around 1 to around 20 weight percent of the nonaqueous components of the size.
  • the most suitable lubricant is a polyoxyalkylene copolymer which is a block copolymer with a majority of ethylene oxide moiety to the propylene oxide moiety.
  • Nonexclusive examples of these lubricants are those having viscosities ranging from around 400 to around 100,000
  • centistokes for instance, the polyoxyalkylene copolymer available from Union Carbide Chemical Corporation under the trade designation UCON 75-H-90,000, having a viscosity of 90,000 measured in centistokes is a suitable lubricant.
  • a reactable organosilane coupling agent having at least one hydrolyzed or hydrolyzable group and having the general formula of R"-Si-(OR')3 where: R' is hydrogen and/or alkoxy groups having 1 to 5 carbon atoms; and R" is an aminoalkyl, polyaminoalkyl where the alkyl group is from 1 to 6 carbon atoms, alkyl or aryl ester, glycidoxyalkyl, glycidoxyaryl or glycidoxyaraalkyl group or an isocyanato alkyl, isocyanato aryl or isocyanato araalkyl group or ureido, ureidoalkyl and ureidoaraalkyl.
  • the amount of the organofunctional silane coupling agent present in the treating composition is an effective coupling agent amount. This amount, when the organosilane is present, generally ranges from about 1 to about 10 weight percent of the solids of the size composition and from about 0.1 to about 5 weight percent of the aqueous size composition. Use of additional amounts result in further incremental improvements that are insufficient to justify the additional cost.
  • an organo functional alkoxide or hydroxide of titanium and/or zirconium where the alkoxide preferably is compatible and active in water.
  • the alkoxide titanate and/or zirconate can have the general formula:
  • X is titanium (Ti) or zirconium (Zr)
  • R is hydrogen and/or a lower alkyl group with 1 to 5 carbon atoms
  • A is an alkylate, carboxyl, sulfonyl, phenolic, phosphate pyrophosphate or phosphite group
  • R' is a short or long chain carbon group having amine or methacrylate functionality.
  • the letters "y” and "z” represent integers, where y can range from 1 to 4 and z can range from 1 to 3 and (y + z) ranges from 2 to 6.
  • the titanate and/or zirconate are preferably soluble in water without the use of surfactants and the titanate or zirconate is still active in water.
  • active it is meant that the titanate and zirconate are not fully reacted or do not have too rapid a rate of reaction with water to produce substantial amounts of titanium or zirconium dioxide.
  • the titanate and/or zirconate can react with water but at a slow rate of reaction so as not to produce a lot of dioxides and to be still reactive with the inorganic substrate.
  • the amount of the organotitanate and/or organozirconate is generally an amount greater than 10, but more particularly 12 or greater, parts per 100 parts of the film forming polymer.
  • the amount is an effective coupling agent amount.
  • the ratio amounts of the titanate salt to the organosilane on a solids basis is in the range, of 6:1 to 1:6. This ratio of amounts is useful when the film forming polymer is a polyurethane and/or epoxy polymer. A particularly useful ratio of the amounts is in the range of around 2:1 to around 1:2.
  • the organotitanate includes alkyl amino alkoxide titanates and zirconates, and lactic acid ammonium salt derivatives of titanate and/or zirconates and organo salts of oxyacids of titanium and/or zirconium.
  • the alkyl and alkoxide groups can have from 1 to 5 carbon atoms, and the titanate and zirconate can be of the monoalkoxy type, the coordinate type, the chelate type and/or the quat type.
  • titanates and/or zirconates have y equal to at least 1 and the .alkoxide includes partially or fully hydrolyzed derivatives thereof, and z is an integer up to 3 and A and R' are part of one group such as an alkanol where O in formula I is from the alcoholic or acidic oxygen and A is hydrogen or part of the carboxyl and R' is a lower alkyl group having 1 to 5 carbon atoms. Also included are the titanates and zirconates like acetyl acetonate titanate and zirconate.
  • organotitanate and/or organozirconate in the amounts greater than those amounts typically used as antistatic agents, these compounds function to enhance promotion of adhesion when used in conjunction with organofunctional silanes. This enhancement is measured by improvement in mechanical properties of fiber reinforced plastic composite like tensile strength notched and unnotched Izods.
  • reaction product of the titanate and/or zirconate with the silane coupling agent can also occur with the use of the reaction product of the titanate and/or zirconate with the silane coupling agent.
  • a reaction product is formed by reaction of the coupling agents in a liquid medium under mild conditions to limit the formation of high molecular weight species and preferably to favor the lower molecular weight oligomers.
  • the liquid medium can be a solvent such as water or organic solvents like alcohols which may influence the reaction conditions of temperature and time.
  • the reaction product in an organic solvent can be used directly if added to an aqueous treating composition or can be added to water after most of the organic solvent is removed.
  • the reaction conditions preferably are ambient conditions to slightly elevated temperatures; for example, up to around 40 to 60 degrees Centigrade.
  • the time for the reaction can be on the order of minutes to hours whereas at ambient conditions the time is generally longer. Preferably at ambient conditions in water, the time of reaction is around two to four hours. It is believed without limiting the scope of the present invention that the reaction is similar to a sol-gel type of reaction.
  • the molar ratio of the titanate and/or zirconate to the silane is generally around 2:1 to around 1:2 but preferably around 1:1.
  • the titanates and zirconates generally are those that do not strongly or quickly react with water to produce metal oxides but are more stabile in water although they may hydrolyze in water.
  • the amount of the reaction product used in the size can range from a trace amount as for a lower yield product to an effective coupling agent amount.
  • a suitable polyoxyethylene (POE) polymer to improve the wet state strand integrity.
  • a polyoxyethylene is available under the trade designation WSR-301 having a molecular weight of around 4 million or more.
  • WSR-301 having a molecular weight of around 4 million or more.
  • This POE is present in an amount in the range of about 0.05 to about 0.6 weight percent of the total solids of the size. Use of higher amounts leads to more viscous treating compositions.
  • the POE can be dispersed or emulsified in water by any method known to those skilled in the art.
  • reaction product obtained by reacting an alkoxylated nitrogen containing compound such as an alkoxylated fatty amine or amide with a polycarboxylic acid and then reacting the resultant product with an epoxide compound, as further described in U.S. Patent 3,459,585 (Killmeyer, et al.), which is hereby incorporated by reference.
  • the amount of this material can range generally from around 1 to about 10 and particularly from around 1 to around 5 weight percent of the solids of the aqueous treating composition.
  • Other additional film forming polymers, coupling agents and lubricants known to those skilled in the art can be incorporated, but their contribution to performance properties may not be substantial enough to justify the cost of their addition.
  • a carrier for application or disposition of the size composition onto inorganic oxide surfaces is present in the size.
  • the carrier is water although other carriers for compositions of different
  • viscosity such as foams and gels may also be employed.
  • the carrier can be organic solvents wherein most of the size components would be soluble. These organic solvent based sizes would be applied to the inorganic oxide substrate in an environment to minimize the risk of fires.
  • the preferred carrier is water in an amount to produce an aqueous size composition having a proper viscosity and solids level for application of the composition to the inorganic oxide
  • the total solids (nonaqueous components) of the aqueous chemical treating composition is about 1 to about 30 weight percent and preferably about 5 to 15 weight percent.
  • the amounts of the solids in the aqueous size composition for application to fibers should not exceed that amount which will cause the viscosity of the aqueous solution to be greater than about 100 centipoise at 20°C. Solutions having viscosities greater than this are difficult to apply to the glass fibers during their formation without breaking the fibers.
  • the total solids level may be varied to accommodate different processing speeds and application efficiency. It is preferred that the viscosity of the size be between about 1 and 20 centipoise at 20°C for best results.
  • Preparation of the size involves adding any of the components either simultaneously or sequentially to each other with a medium degree of agitation.
  • the method of preparing the size can be any method known to those skilled in the art.
  • the size is applied to inorganic oxide surfaces such as ceramic and glass fibers where the major inorganic oxide component is silica.
  • Inorganic oxide fibers like ceramic fibers may have a substantial amount of aluminum oxide, and/or alkali metal and alkaline earth metal oxides with small amounts of ferric oxide, titanium dioxide and the like.
  • the glass substrates can be any of the glass
  • the application of size to fibers is in such a manner to result in a moisture or volatile-reduced residue of the size in the range of around 0.5 to 5 weight percent based on the total weight of the fibers with the sizing composition.
  • the aqueous sizing is applied to the glass fibers during conventional forming processes to produce sized glass fibers at attenuation speeds to accommodate the addition of the proper amount of the size.
  • the size is applied to the glass fibers before they are gathered together to form one or more strands by means of an applicator known in the art to permit contact of the liquid size with the solid fiber such as a roller or belt applicator, partially submerged in the size contained in a reservoir such as the applicator shown in U.S. Patent 2,728,972, which is hereby incorporated by reference.
  • the fibers are gathered into one or more strands by a
  • Attenuation of the fibers is from the orifices in the bushing of the glass fiber direct melting furnace or marble melting furnace for the addition of the proper amount of the size to the fibers.
  • Other methods of applying the size to the fibers such as pad applicators may be employed.
  • the amount of the volatile reduced residue on the fibers is based on the measurement by the loss on ignition (LOI) method.
  • Continuous glass fiber strands wound on forming packages in annular layers or wet chop glass fiber strands are typically heated to reduce the volatiles including the moisture content of the size on fibers in the strands by air drying or in any conventional drying ovens known to those skilled in the art.
  • the temperatures are around 110°C to around 150°C, preferably around 115°C to around 130°C for a time of around 11 hours.
  • Other equivalent temperatures and times may be used to give equivalent heating or drying to remove a substantial amount of the volatiles including moisture from the strands.
  • the moisture content of the heated strands is usually less than around 0.06 weight percent and constitutes the glass fibers with the residue of the size.
  • a plurality of the strands with the size residue can be chopped in a dry chop operation or can be gathered in parallel to form a rope or a roving.
  • the chopped strands or continuous strands or rovings or even woven rovings or mats of chopped strands and continuous strands are useful in preparing polymeric molding compounds. Particularly, these sized strands are useful in reinforcing the high performance polymers having higher processing temperatures and/or melt temperatures to produce RP products capable of use in a wider temperature range including elevated temperatures.
  • a few nonexclusive examples of these high performance polymers were previously listed.
  • the size is an aqueous size having two film formers, a nonionic lubricant, amino organo-functional silane coupling agent and triethanolamine zirconate.
  • One film former is an epoxy polymer in an oil-in-water dispersion where the epoxy is a bisphenol A type epoxy with approximately a 500 to 600 equivalent weight.
  • the second film forming polymer is a poly (esterurethane) in an oil-in-water emulsion.
  • the ratio of amounts of the solids of the film formers is in the range of around 4 to around 1 of the epoxy to the polyurethane.
  • the nonionic fiber lubricant is poly(ethyleneoxide)-propylene oxide copolymer (PEO-PPO) with a low molecular weight and a viscosity of around 90,000 centistokes.
  • the aminosilane is gamma-aminopropyltriethoxy-silane or 3-triethoxysilyl- propylamine available from Union Carbide Corporation under the trade designation A-1100 silane.
  • the organoalkoxide titanate or zirconate is a triethanolamine zirconate available under the trade designation MPD-6212 Tyzor from DuPont de Nemours and Company that is an alkanolamine chelate now available as Tyzor 212 crosslinking zirconium alkoxide.
  • This zirconate results in a sized fiber having good color.
  • a triethanolamine titanate is used in an alternative embodiment where the color of the sized fibrous strand is less important.
  • the amounts of the components in the size on a solids basis are listed below for the preferred embodiment and in Table 1 at Example 2 for the use of the triethanolamine titanate.
  • This aqueous size was prepared by adding 25 gallons of water (deionized) to a main mix tank.
  • the epoxy dispersion was added to this main tank with stirring in a manner not to induce very much air.
  • the PEO-PPO lubricant was added to a premix tank, and five gallons of water (deionized) at 150°F were added with stirring to dissolve the lubricant. An additional five gallons of water were added to the dissolved lubricant for cooling, and the dissolved lubricant was added to the main mix tank.
  • Fifteen gallons of deionized water were added to a premix tank and the A-1100 was added with stirring not to induce too much air.
  • Ten gallons of deionized water were added to a premix tank, and the triethanol amine
  • zirconate was added with stirring so as not to induce too much water. This diluted material was stirred for 5 minutes and transferred to the diluted A-1100 mixture. The combined premix was stirred for 10 minutes and added to the main mix tank. Fifteen gallons of deionized water were added to a premix tank, and the polyurethane dispersion was added. The diluted mixture was stirred for 5 minutes and transferred to the main mix tank. The mixture in the main mix tank was diluted to 100 gallons with water and stirred for 30 minutes. The solids of the size is 8.3 ⁇ 0.2 weight percent, and the pH is around 10.3 ⁇ 0.5. The viscosity is around 2 ⁇ 1 as measured by Brookfield LVT #1 spindle at 30 rpm at 75 °F.
  • the size to the fibers involves forming the glass fibers in a direct melt forming operation to have fiber diameters of G or K 9-13 microns.
  • the fibers are cooled by pre-size-application sprays of water, and the size is applied to the plurality of fibers by the fibers contacting a roller-type applicator.
  • a plurality of fibers are gathered into one or more strands and fed into a chopping device from the attenuation rollers to produce wet chopped strands.
  • the chopped strands are collected and dried.
  • the conditions of drying include a temperature in the range of 115°C to 130°C and a time of around 11 hours.
  • a plurality of the dried, chopped strands having the volatile and moisture-reduced residue of the size have lengths ranging from around 1/16 to 1/4 of an inch but most preferably around 1/8 of an inch.
  • Fiber reinforced polyetherimide such as the Ultem polymers available from General Electric Company, Plastics Group, Pittsfield, Massachusetts.
  • the fibers are combined with the PEI and formed into a ribbon by an extruder and are pelletized.
  • the pellets are useful in injection molding of FRP parts.
  • Table 1 presents 20 formulations of the size utilized in the present invention including the sizes of the alternative embodiment. All of the sizes were prepared in a similar manner as those of the preferred and alternative
  • Table 2 presents three illustrative size
  • the FRP test specimens were tested for tensile strength, percent elongation, flexural strength and modulus, Izods (notched and unnotched) by standard tests known to those skilled in the art. These tests are from the American Society of Testing Materials and respectively are identified as D-638, D-790 and D-256. The Izod impact tests are more fully discussed in the book "Reinforced Plastics Theory and
  • Table 3 The results of these tests for molded FRP involving most of the sizes of Table 1 are presented in Table 3. Also shown in Table 3 are control samples that were molded samples prepared from pellets made with commercially available glass fibers. Control 1 utilized commercially available glass fibers having diameters of 13 microns and prepared by a dry chop operation in accordance with U.S. Patent 4,271,229.
  • Control 2 utilized commercially available glass fibers having a diameter of 13 microns by a wet chop (direct chop) operation in accordance with U.S. Patent 4,615,716.
  • Control 3 utilized commercially available glass fibers having diameters of 10 microns sold for reinforcement of PES and polyamide polymers.
  • Examples 1 through 16 and 18 was 13 microns. In Example 17 the diameter was 10 microns.
  • the molded samples of Examples 1 and 3-11 were made with controls 1 and 3 as one set of experiments. These involved preparation of pellets at 60 1b/hour with a number 4 screw at 4,240 rpm.
  • the molded samples of Examples 2 and 12-16 were made along with molded samples with control 2 glass fibers at 50
  • Table 4 presents data on molded samples utilizing glass fiber strands with sizes of the illustrative examples of Table 2, controls and one example similar to example 17 of Table 1.
  • pellets and molded specimens for testing from the pellets for the illustrative examples control and 17B were prepared in a manner similar to the preparations used for the pellets and molded specimens of Table 3. In comparing Tables 3 and 4, it is evident that the formulations and sized glass fibers of illustrative examples 1 and 2 are less than
  • Example 3 is not acceptable in mechanical properties when compared to the control.
  • the formulation 17B, number 2 from Table 3, number 14 from Table 3 and number 20 from Table 3 and glass fibers sized with these formulations gave good thermal performance as shown by the increased value for bulk density, especially over those of illustrative
  • Example 1 and 2 show good mechanical properties compared to the control. Also, formulation 14 using the organo zirconate as opposed to the organo titanate . of Example 2 from Table 3 gave a slight increase in the Izod impact strength while maintaining the 20 percent improvement in tensile strength over formulation of illustrative Example 3 without either the titanate or zirconate. Also, the color of the molded test bar was not as dark as the molded test bar made with the chopped, sized glass fibers of formulation 2 having the titanate.
  • formulation 20 of Table 3 shows improved fiber forming performance while maintaining the improvements of thermal resistance in the bulk density and the tensile strength previously observed for glass fibers sized with formulations having the organotitanate or zirconate along with the aminosilane coupling agent.
  • a long-term heat aging test was conducted on two samples of PEI matrix polymer reinforced with 30 weight percent glass fibers.
  • One sample was PEI reinforced with sized glass fibers of the preferred embodiment, where the fiber diameter was 13 microns.
  • the second sample was control 3, where the fiber diameter was 9 microns.
  • the long term heat aging test was conducted by testing specimens before heat aging and by placing numerous specimens of both samples of reinforced PEI in an oven at 220°C. Specimens of both samples were withdrawn after 1,000 hours, 2,000 hours and 3,000 hours for tensile strength testing.
  • 1 % COV is percent coefficient of variation.
  • Table 5 shows the PEI reinforced with the glass fibers of the preferred embodiment have good retention of tensile strength after long term heat aging and especially after 3,000 hours.
  • Table 6 shows the performance of the reaction product of the silane coupling agent with the titanate vs. the silane coupling agent alone for two types of silane coupling agents.
  • the results are obtained from studies of glass slides that were coated with the indicated coupling agent or reaction product.
  • the reaction product of the gamma-aminopropyltriethoxysilane and triethanolamine titanate and the reaction product of the gamma-glycidoxypropyltrimethoxysilane and the triethanolamine titanate for the studies were produced in the following manner.
  • the particular silane and titanate were combined in an aqueous mixture in an amount of five grams of the titanate and 5 grams of the silane per 100 grams of water at conditions of 23 degrees Centigrade and for four hours.
  • reaction products as well as the individual silanes depicted in Table 6 were wiped onto separate glass slides with cotton swabs.
  • the slides were air dried, and the treated slides were heated on a hot plate to the softening temperature of the particular resin of Table 6 to be added to that particular slide.
  • the particular resin was pressed onto the slide with an untreated glass slide, and the resin was cooled for a period of 30 minutes.
  • HIPS high impact polystyrene
  • A gamma-aminopropyltriethoxysilane (A-1100)
  • TEAT tetraethanolamine titanate

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Abstract

Substrats d'oxyde inorganique traités avec une composition de traitement chimique aqueuse comprenant au moins un organo-alcoxyde ou hydroxyde d'un métal choisi entre titane et zirconium, ainsi qu'une combinaison choisie de polymères filmogènes et/ou d'un ou plusieurs agents de couplage à base de silane organo-fonctionnels. L'agent de couplage à base de titane ou de zirconium et l'agent de couplage à base de silane peuvent être combinés sous forme de deux composés distincts.
PCT/US1994/000574 1993-01-13 1994-01-13 Fibres d'oxyde inorganique a traitement chimique et a stabilite thermique, convenant a des polymeres resistants aux temperatures elevees Ceased WO1994016129A1 (fr)

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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000069392A1 (fr) * 1999-05-19 2000-11-23 Southwest Research Institute Materiaux composites transparents ou translucides a grande resistance mecanique, fabriques a partir de nanoparticules d'oxyde de zirconium
US6646027B2 (en) 2001-02-16 2003-11-11 General Electric Company High modulus polyether sulfone compositions with improved impact
EP1371686A1 (fr) * 2002-06-10 2003-12-17 General Electric Company Compositions de polyéthersulfones à module élevé et à resistance aux chocs améliorée
US7041234B2 (en) 2001-01-23 2006-05-09 Southwest Research Institute Methods for synthesis of liquid crystals
US7094358B2 (en) 2001-03-07 2006-08-22 The University Of Texas System Ultra-low shrinkage composite resins based on blended nematic liquid crystal monomers
US7147800B2 (en) 2001-01-23 2006-12-12 Southwest Research Institute Selective ether cleavage synthesis of liquid crystals
US11001525B2 (en) 2016-06-17 2021-05-11 Owens Corning Intellectual Capital, Llc Sizing composition for wet use chopped strand glass fibers
CN115028376A (zh) * 2022-05-30 2022-09-09 西安交通大学 一种聚乙烯亚胺热交联抑制玻璃纤维浸润剂迁移的方法

Citations (2)

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US3920596A (en) * 1973-06-27 1975-11-18 Kao Corp Sizing agent for glass fibers
US4615946A (en) * 1985-03-29 1986-10-07 Ppg Industries, Inc. Chemically treated glass fibers for reinforcing polymeric matrices

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3920596A (en) * 1973-06-27 1975-11-18 Kao Corp Sizing agent for glass fibers
US4615946A (en) * 1985-03-29 1986-10-07 Ppg Industries, Inc. Chemically treated glass fibers for reinforcing polymeric matrices

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6194481B1 (en) 1999-05-19 2001-02-27 Board Of Regents Of The University Of Texas System Mechanically strong and transparent or translucent composites made using zirconium oxide nanoparticles
US7037583B2 (en) 1999-05-19 2006-05-02 Southwest Research Institute Functionalized zirconium oxide particles
WO2000069392A1 (fr) * 1999-05-19 2000-11-23 Southwest Research Institute Materiaux composites transparents ou translucides a grande resistance mecanique, fabriques a partir de nanoparticules d'oxyde de zirconium
US7147800B2 (en) 2001-01-23 2006-12-12 Southwest Research Institute Selective ether cleavage synthesis of liquid crystals
US7238831B2 (en) 2001-01-23 2007-07-03 Southwest Research Institute Mesogens
US7041234B2 (en) 2001-01-23 2006-05-09 Southwest Research Institute Methods for synthesis of liquid crystals
US7108801B2 (en) 2001-01-23 2006-09-19 Southwest Reasearch Institute Methods and blends for controlling rheology and transition temperature of liquid crystals
US6646027B2 (en) 2001-02-16 2003-11-11 General Electric Company High modulus polyether sulfone compositions with improved impact
US7094358B2 (en) 2001-03-07 2006-08-22 The University Of Texas System Ultra-low shrinkage composite resins based on blended nematic liquid crystal monomers
US7135589B2 (en) 2001-03-07 2006-11-14 Board Of Regents, The University Of Texas System Bridged monomers
EP1371686A1 (fr) * 2002-06-10 2003-12-17 General Electric Company Compositions de polyéthersulfones à module élevé et à resistance aux chocs améliorée
US11001525B2 (en) 2016-06-17 2021-05-11 Owens Corning Intellectual Capital, Llc Sizing composition for wet use chopped strand glass fibers
CN115028376A (zh) * 2022-05-30 2022-09-09 西安交通大学 一种聚乙烯亚胺热交联抑制玻璃纤维浸润剂迁移的方法
CN115028376B (zh) * 2022-05-30 2023-03-28 西安交通大学 一种聚乙烯亚胺热交联抑制玻璃纤维浸润剂迁移的方法

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