EP0651732A1 - Compositions emulsifiees de liaison de fibres de verre, a base de resine furannique, et procede de liaison de fibres de verre - Google Patents

Compositions emulsifiees de liaison de fibres de verre, a base de resine furannique, et procede de liaison de fibres de verre

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Publication number
EP0651732A1
EP0651732A1 EP94919186A EP94919186A EP0651732A1 EP 0651732 A1 EP0651732 A1 EP 0651732A1 EP 94919186 A EP94919186 A EP 94919186A EP 94919186 A EP94919186 A EP 94919186A EP 0651732 A1 EP0651732 A1 EP 0651732A1
Authority
EP
European Patent Office
Prior art keywords
glass fiber
composition
binding composition
furan
binding
Prior art date
Legal status (The legal status 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 status listed.)
Withdrawn
Application number
EP94919186A
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German (de)
English (en)
Inventor
Thomas John Taylor
William Henry Kielmeyer
Carlo Martin Golino
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Johns Manville
Original Assignee
Schuller International Inc
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Filing date
Publication date
Application filed by Schuller International Inc filed Critical Schuller International Inc
Publication of EP0651732A1 publication Critical patent/EP0651732A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • 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
    • C08G16/00—Condensation polymers of aldehydes or ketones with monomers not provided for in the groups C08G4/00 - C08G14/00
    • C08G16/02—Condensation polymers of aldehydes or ketones with monomers not provided for in the groups C08G4/00 - C08G14/00 of aldehydes
    • C08G16/025—Condensation polymers of aldehydes or ketones with monomers not provided for in the groups C08G4/00 - C08G14/00 of aldehydes with heterocyclic organic compounds
    • 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
    • C03C25/28—Macromolecular compounds or prepolymers obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C03C25/30—Polyolefins
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B26/00—Compositions of mortars, concrete or artificial stone, containing only organic binders, e.g. polymer or resin concrete
    • C04B26/02—Macromolecular compounds
    • C04B26/10—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C04B26/105—Furfuryl alcohol polymers, e.g. furan-polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives

Definitions

  • This application relates to emulsified furan resin based binding compositions for glass fibers, a process for binding glass fibers using the disclosed binding compositions, and also two glass fiber compositions made with the disclosed binding compositions.
  • Fiber glass comes in many shapes and sizes and can be used for a variety of applications. A general discussion of fiber glass technology is provided in "Fiber Glass” by J. Gilbert Mohr and
  • glass fibers are generally mass produced in two types: bulk or blown fiber for insulation and allied applications, and continuous-filament, or reinforcing fibers.
  • raw fiber glass In either form raw fiber glass is abrasive and easily fragmentized. Damage to the individual glass fibers can occur as a result of the self-abrasive motion of one fiber passing over or interacting with another fiber. The resulting surface defects cause reductions in overall mechanical strength. Consequently, binders have been developed to prevent these problems.
  • a typical binder may prevent the destructive effects of self-abrasion without inhibiting the overall flexibility of the finished glass fiber product. Extremely good resistance and resilience to conditions of elevated humidity and heat are beneficial in view of the wide variety of end use applications for glass fiber/binder compositions.
  • Cured glass fiber/binder compositions are normally very bulky and voluminous. Batts and rolls used as insulation in buildings have densities ranging from 0.5 to 1.0 pound per cubic foot (pcf) and generally require binder contents of 3 to 7% by weight. Since it is prohibitively expensive to ship such materials in an uncompressed state, the batts and rolls are bundled and compressed in packages to 8 to 25% of their manufactured thickness. During the shipping process these packages are normally subjected to conditions of elevated temperature and humidity. Once the compressed batt or roll reaches the consumer and is removed from its packaging, it should recover between 40% to 100% of its original volume. Insulation materials not achieving such recovery values normally have difficulty meeting advertised thermal resistivity (R) values. In general, the better the recovery value of the glass fiber/binder composition, the better insulating properties the composition will possess.
  • R thermal resistivity
  • Fiber glass products denser than 0.7 pcf generally have load bearing requirements, either in the form of compressive or flexural strength, as well as thermal and sound attenuation restrictions.
  • binder content is determined by the loss on ignition test, described below, and is given as % L.O.I. In general, binder contents may range from 1 to 25% L.O.I. , depending on the specific end use application. Applications include sound control batts with low binder content; industrial-grade thermal insulation for driers, ovens, boilers, furnaces, and other heat generators; low-to- intermediate L.O.I, duct liners and fiber glass flexible ducts and high-L.O.I. rigid ducts; and pipe insulation with intermediate to high binder levels.
  • Molded fiber glass parts are generally thin pieces of high density (15-22 pounds per cubic foot at 1/8 to 3/8 inches thick, for example) and require binders to provide excellent flexural strength. Fiber glass products used for filtration have wide ranges of fiber diameter and binder levels.
  • phenolic binders contain large amounts of low molecular weight species including phenol, formaldehyde and volatile 1:1 and 1:2 phenol formaldehyde adducts such as 2-methylolphenol and 4-methylolphenol.
  • VOC volatile organic compounds
  • the process of manufacturing fiber glass typically involves spraying large volumes of phenol formalde ⁇ hyde binders into high volume air streams, and then curing the product in convection ovens that involve high volumes of air, fiber glass manufacturers have an urgent need to reduce their VOC emissions, particularly with regard to formaldehyde. Such reduction must occur without an increase in the emissions of compounds such as furfuryl alcohol, bis-hydroxy ethyl- furan, and the like.
  • Phenol formaldehyde resins also require careful handling procedures. Since the cooked resin must be refrigerated until use, refrigerated trucks and holding tanks are required. Even with refrigeration, the storage life of a phenolic resin is typically 15 days. Adding to these problems is the fact that phenol formaldehyde resins have a short life span. Finished binders based on such resins must be used within 2 to 12 hours of their initial formulation.
  • phenol formaldehyde resins are petroleum based, they are particularly vulnerable to fluctuations in price and availability.
  • the present invention solves the problems caused by the use of phenol formaldehyde resins in binders for fiber glass by providing binders based on aqueous compatible furan resins.
  • the furan binders of the instant invention provide many of the ad ⁇ vantages of phenolic binders while resulting in substantially reduced VOC emissions. What is particularly desirable about the furan binders disclosed herein is the use of water as a significant component.
  • the furan binders of the present invention have several advantages. Formaldehyde is not a significant curing or decomposition product and the furan resins form very rigid thermosets. Since furan resins are derived from vegetable cellulose, a renewable resource, they are relatively inexpensive and readily available.
  • the present invention further provides for glass fiber binding compositions utilizing emulsified furan resins.
  • Such compositions will allow for the incorporation of furan resins which normally might be incompatible with water at a particular solids level and prone towards the formation of two-phase solutions.
  • finished glass fiber compositions made with such binding compositions often exhibit good performance properties, high viscosity and insoluble participates can cause processing difficulties.
  • the emulsified furan resin based glass fiber binding compositions are advantageous since they allow for the use of furan resins having high molecular weights and/or the addition of other materials which would give rise to the formation of two-phase systems.
  • an object of the instant invention is to provide emulsified furan resin based glass fiber binding compositions as well as a process of binding glass fibers using the emulsified binding compositions as well as glass fiber compositions made with the same.
  • Another object of the present invention is to provide methods of applying the novel furan binder to raw or bare glass fibers so as to provide the required performance characteristics.
  • An additional object of the invention is to provide glass fiber compositions employing the novel binders which are suitable for incorporation into a variety of end use applications.
  • This invention particularly relates to glass fiber binding compositions utilizing an effective binding amount of a furan resin, an effective emulsifying amount of an emulsifier agent, and sufficient water to produce a binding composition having from 0.5 to 80% nonvolatile.
  • the invention further relates to a method of binding glass fibers using a binding composition incorporating an emulsified furan resin.
  • the invention also provides for glass fiber composition made with the disclosed emulsified binding compositions.
  • Figure 1 illustrates a desired distribution of a 66% N.V. bis(hydroxmethyl)furan resin based binder applied to glass fibers;
  • Figure 2 illustrates a desired distribution of a 40% N.V. bis(hydroxmethyl)furan resin based binder applied to glass fibers.
  • the present invention broadly provides glass fiber binding compositions comprised of aqueous compatible furan resins which provide finished products with properties similar to that achieved with traditional phenol formaldehyde binders.
  • aqueous compatible furan resin Compatible as used herein is defined as an aqueous mixture comprised of water and a resinous or polymeric component forming either a solution, an emulsion, or a sol.
  • a furan resin will be deemed aqueous compatible if, at some ratio of resin to water, a mixture will form which is either a solution, an emulsion or a sol.
  • the use of furan resins greatly reduces the emissions of particular VOC's such as formaldehyde and furfuryl alcohol during the curing cycle.
  • the emissions of other VOC's such as bis hydroxymethyl furan (BHMF) , and 5- methylfurfural (5mF) with the use of the furan resin based binders disclosed herein.
  • the present invention also provides a process of making the claimed glass fiber binding compositions, a process of binding glass fibers and further provides for glass fiber compositions having applicability for use in a wide variety of end products.
  • the invention further pertains to glass fiber binding compositions comprised of furan resins which may not be aqueous compatible.
  • These binding compositions utilize an effective emulsifying amount of an emulsifier agent to provide aqueous binding compositions which are stable, one phase, compositions when applied to glass fibers.
  • These binders have the advantage of producing low VOC levels during the manufacture of glass fiber compositions.
  • Furan is traditionally defined as a heterocyclic ring compound with two carbon-carbon double bonds linking an oxygen atom on one side with a single carbon-carbon bond on the other.
  • furan resin is defined to include resinous products which are comprised of polymer molecules which contain the traditional furan ring structure as described above as well as the saturated analogs thereof. Such analogs will consist of five membered rings having four carbons and one oxygen and 0 to 1 carbon-carbon double bonds. The structures encompassed by this definition are illustrated below:
  • R may be methylene; methylidyne; methylcarbonyl ; methylester; methylene ether; methylene dioxy; ethylene; heterocyclic; polymeric methylene ether wherein R is (-CH 2 -(OCH 2 ) n and n may be from 1 to 10; ethylene methyl carbonyl; ethylene methyl ester; methylene oxy; ethyl oxy; and hydroxy methyl. Of these, it is most preferred that R be methylene, methylene ether, or polymeric methylene ether wherein n is 1 to 5.
  • R may also be characterized as the residue resulting from the polymerization of at least one reactant selected from the group consisting of: furan, furfural, furfuryl alcohol,
  • 2,5-furan diacid dichloride 2,5-furan dicarboxylic acid dimethyl ester, 2,5-furan methylamine, 5-carboxy-2-furan amine, 5-methylester-2-furan amine, bis-(2, 5-methylene isocyanate) furan, bis(2, 5-isocyante) furan, 2-isocyanatefuryl, and 2-methylene isocyanate furyl.
  • composition of R will vary greatly as it is dependent upon the identity of the starting reactants and the mechanism of polymerization; "n" may be any value greater than 1 but will most preferably be no greater than 25.
  • furan-based binders stems from the fact that they are derived from vegetable cellulose. Suitable sources of vegetable cellulose are corn cobs, sugar cane bagasse, oat hulls, paper mill byproducts, biomass refinery eluents, cotton seed hulls, rice hulls, and food stuffs such as saccharides and starch. These materials undergo acid digestion to produce furfural. Furfural is the chief reagent used to produce materials such as furfuryl alcohol, 5-hydroxymethyl-2- furancarboxyaldehyde (HMF) , 2, 5-dicarboxyaldehyde-furan, and bis(hydroxymethyl) furan (BHMF) . These furan containing monomers in turn can undergo reactions to produce various furan containing monomers with a wide variety of substituents at the C 2 and C 5 positions.
  • HMF 5-hydroxymethyl-2- furancarboxyaldehyde
  • BHMF bis(hydroxymethyl) furan
  • furan resins may be identified via the names of the starting reactants (i.e., furfural-phenol resin or furfuryl alcohol resin)
  • furan resin as used herein is intended to describe resins derived from a variety of starting reactants. Typically at least one of these reactants will contain the basic furan ring structure or the saturated analogs thereof.
  • furan resin is further defined as a resinous mixture comprised of either monomers, oligomers, polymers and/or mixtures thereof, resulting from the polymerization reaction wherein at least one of the reactants is selected from the group consisting of the furan containing molecule having the general formula:
  • Suitable X and Y groups are those comprised of molecular species comprising one or more functional moieties selected from the group consisting of: hydrogen; C,-C 10 alkyl groups; mono, di- or tri- substituted vinyl radicals; di- or tri- substituted aromatic rings; ketones; anhydrides; polysubstituted furfuryl; hydroxyls; aldehydes; carboxylic acids; esters; ethers; amines; amides; imines;- imides; alkynes; alkyl halides; aromatic halides; olefinic halides; ethers; thiols; sulfides; nitriles; nitro groups; sulfones; carbofunctional siloxanes; and sulfonic acids. It will be appreciated that combinations of these various functional groups can be employed to form either X or Y.
  • Examples of specific compounds containing suitable X and Y groups include: furan, furfural, furfuryl alcohol,
  • X and Y be comprised of molecular species containing one or more functional moieties selected from the group consisting of hydrogen; C1-C6 alkyl groups; mono, di-, or tri- substituted vinyl radicals; ketones; hydroxyIs; aldehydes; carboxylic acids; esters; ethers; amines; amides; imines, imide; and polysubstituted furfuryls. It is furthermore particularly desired that at least one of X and Y be comprised of a molecular species comprising an oxygen containing functional moiety such as a ketone, hydroxy1, aldehyde, carboxylic acid, ester or ether.
  • X and Y be comprised of methylol (-CH 2 OH) terminated groups.
  • a suitable furan resin for use in the glass fiber binding compositions described herein are those resins resulting from the polymerization of 2,5- bis(hydroxymethyl) furan. Such resins may be further defined as 'BHMF' resins.
  • furan containing monomers can polymerize through two well known mechanisms.
  • a comprehensive discussion of such reactions is provided by Agricultural and Synthetic Polymers, Biodegradability and utilization ; edited by J. E. Glass and G. Swift, Symposium sponsored by Divisions of Cellulose, Paper and Textile Chemistry; and Polymeric Materials: Science and Engineering at the 197th National Meeting of the American Chemical Society, Dallas, Texas, April 9-14, 1989, herein incorporated by reference.
  • the second method is typically known as condensation polymerization.
  • Polymers and copoly ers resulting from acid catalyzed condensation reactions result in macromolecules with furan rings in the main chain.
  • the furan resins formed by polycondensation reactions have stiffer chains and higher glass transition temperatures. These reactions may involve self condensation of the furan monomers described above, as well as condensation reactions of such monomers with aminoplast resins, organic anhydrides, aldehydes such as formaldehyde, ketones, urea, phenol and other suitable reagents.
  • the binder compositions described herein will contain furan resins produced by acid catalyzed condensation reactions.
  • furan resin for use herein is Farez 1 " M, a commercially available composition from QO" 1 Chemicals, a division of Great Lakes Chemical Corporation, located in West Lafayette, Indiana.
  • the material safety data sheet (MSDS) for FarezTM M indicates that it is a furfuryl alcohol-urea formaldehyde resin containing about 6% free furfuryl alcohol and 0.4 to 1.1% by weight free formaldehyde.
  • This resin is believed to be based on the most preferred furan monomer wherein X and Y are terminal methylol groups; i.e. bis(hydroxymethyl) furan (“BHMF").
  • Quacorr 1300 is a commercially available resin believed to result from the acid catalyzed self condensation of furfuryl alcohol. Quacorr* 1300 is received with a viscosity of about 2000 to 17,000 cPs at 25'C. It contains between 2 to 18% free furfuryl alcohol and is believed to have a substantial fraction of higher molecular weight oligomers. It has a percent nonvolatile between 72 to 98%.
  • FarezTM M as received from QOTM Chemicals, Inc., has a pH of between 4.0 to 7.0, 13 to 17% by weight water and 4-7% by weight unreacted furfuryl alcohol. Because furfuryl alcohols is relatively volatile, it is most preferred that its presence be minimized to decrease overall VOC. FarezTM M normally has a percent nonvolatile (% N.V.) of approximately 75%-90% and is received at a viscosity of between 250 cPs to 2,000 cPs at 25°C. A hydroxyl number of 17 to 21% has been measured for different patches of this material.
  • % N.V. percent nonvolatile
  • furan resins having low levels of monomeric or volatile species such as formaldehyde and furfuryl alcohol.
  • the most preferred resin for use herein is FarezTM XP type 'M' , as supplied by Q.O. Chemicals.
  • the MSDS sheet for this resin indicates that it is a furfural alcohol-formaldehyde resin with 9% by weight formaldehyde. This resin generally has less than 2% furfuryl alcohol.
  • An identifying parameter of the furan resins suitable for use herein is the cloud point. This refers to the maximum percentage of water which the resin can absorb while maintaining a single phase solution. The most preferred furan resins for use herein will have a cloud point above 60.
  • the hydroxyl number or percent hydroxyl was determined using the following testing procedure. Approximately 1.2 grams of binder was dissolved in 25 milliliters of pyridine in a volumetric flask. Sufficient 3A molecular sieve was added to cover the bottom of the flask. The flask was shaken and left to stand overnight in order to remove any water present in the binder sample. Residual water was determined by the presence of a shoulder at 3560cm "1 and corrected by the addition of more 3A molecular sieve. A Perkin- Elmer 621 Grating Spectrophotometer, equipped with an infrared absorbance mode, was used to determine the hydroxyl number.
  • the sample and reference cell were a pair of matching NaCl liquid cells with 0.05 to 0.10 mm path lengths and were scanned from 4000 cm '1 to 3200 cm "1 . Absorbance was read at a peak maximum of 3240 cm ' 1 . Standard curves for each sample cell were generated by analyzing solutions containing 1.25, 0.625, 0.313, and 0.156 grams of furfuryl alcohol or bis(hydroxymethyl) furan per 25 ml dry pyridine. Solutions were scanned in NaCl liquid cells of path lengths 0.075 mm. A standard curve absorbance versus concentration was plotted and the percent hydroxyl calculated by extrapolating grams of hydroxyl per 25 ml sample and then dividing this value by the sample weight in grams and multiplying by 100.
  • Additional water is added to the material as received from QO'" Chemicals, Inc to make the glass fiber binders of the invention. Addition of water between 10% to 70% by weight produces acceptable viscosities of between 1.1 cPs to 600 cPs. Generally, between 15 to 99% water by weight of the binder composition may be added to obtain binding compositions with a % nonvolatile (%N.V.) from 0.5 to 80%. However, it has been found that adding more than 15 to 17% by weight water to some furan resins may produce nonhomogeneous mixtures. Although two-phase binders can provide desired properties, one phase systems are most preferred. Thus in the absence of the co-solvents discussed below, it is preferable that 13 to 17% by weight of water be added to the furan resins such as Farez M and QuaCorrTM 1300. Such an addition results in approximately 30% total water by weight.
  • sufficient water will be added to the most preferred furan resin so as to achieve a binder having between 0.5 to 80% N.V.
  • these furan resins will initially be combined with sufficient water so as to achieve binder compositions having from 40-60% N.V.
  • subsequent dilutions with water may occur in response to processing considerations. As indicated above, these dilutions may result in solutions having a % N.V. as low as 0.5%.
  • % N.V. as used herein refers to the theoretical amount of non-volatile materials in the binder.
  • this will consist of the resin solids (also known as active binder solids) and the solid portions of any catalysts, additives, fillers, etc. used in the binder.
  • Active binder solids may be defined to include all materials which are believed to participate in the binder forming reaction. Those skilled in the art will appreciate that this will include the nonvolatile portions of materials such as the furan resins, urea and melamine. Viscosities from 1.1 to 600 cPs are acceptable for the binding compositions disclosed herein. Lower viscosities from 1.1 to 400 cPs are normally preferred and viscosities in the range of 2 to 200 cPs at 25C are most preferred.
  • co-solvent is defined herein as any material which upon addition to the composition allows for the addition of greater amounts of water. These co-solvents are generally added in an amount equal to 2 to 10% by weight.
  • suitable organic mono-, di-, and polyacids are methacrylic acid, propionic acid, levulinic acid, maleic _acid, citric acid and succinic acid. Of these maleic acid is most preferred in an amount from 1 to 8% by weight and most preferred in 2 to 6%.
  • an effective amount of one or more materials traditionally known as acid catalysts may be added to the furan resin as received from QO'" Chemicals.
  • Acid catalysts for curing furan resins are well known in the art. Selection of a particular catalyst ultimately depends upon the desired rate of cure and desired end properties.
  • a feature of the present invention is the choice of particular combinations of catalysts to minimize the release, of VOC's originating from different resin components.
  • this element of the preferred binder compositions will be defined as a catalyst system.
  • catalyst system is intended to encompass combinations of catalysts as well as the use of single catalysts.
  • Suitable organic acids which may be defined as active catalysts include aliphatic saturated monocarboxylic acids, aliphatic unsaturated monocarboxylic acids, saturated and unsaturated dicarboxcylic acids, hydroxy acids, aromatic acids and diacids, and alicyclic acids.
  • Suitable organic and inorganic acids include hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, benzene sulfonic acid, toluene sulfonic acid, xylene sulfonic acid, naphthalene sulfonic acid, oleic acid, benzoic acid, salicylic acid, acetic acid, propionic acid, maleic acid, fumaric acid, oxalic acid, malonic acid, phthalic acid, lactic acid, succinic acid, glutaric acid, adipic acid, citric acid, tartaric acid and levuline acid. Of these tartaric acid and maleic acid are preferred and maleic acid most preferred.
  • Friedel-Crafts type catalysts such as aluminum chloride, zinc chloride, aluminum bromide, and boron fluoride are also suitable.
  • Salts of both inorganic and organic acids may also be used.
  • suitable inorganic acid salts are ammonium chloride, ammonium sulfate, ammonium hydrogen sulfate, ammonium nitrate, aluminum chloride, aluminum nitrate, aluminum sulfate, copper chloride, copper nitrate, copper sulfate. Of these, ammonium sulfate is most preferred. Ammonium sulfate in particular may be defined as a latent catalyst which may become active at approximately 110-15 ⁇ Celsius.
  • Suitable organic salts are the urea salt of toluene sulfonic acid, the polyammoniu salts of polycarboxylic acids such as the diammonium salts of citric acid and the ammonium salts of maleic acid.
  • Acid anhydrides are also suitable for use as catalysts in the present invention.
  • cyclic anhydrides resulting from the dehydration of dicarboxylic acids are suitable for use in the present invention.
  • Suitable acid anhydrides include acetic anhy ⁇ dride, maleic anhydride, succinic anhydride and phthalic anhydride. Of these maleic anhydride is most preferred.
  • polyether co-polymers are formed between the anhydride and the free hydroxylated species present in the resin.
  • maleic acid in addition to functioning as a co- solvent where necessary, also promotes the polymerization reaction. Furthermore, it is believed that maleic acid may preferentially reduce the emission of BHMF monomer during the curing process. Since it is desirable to maximize the reduction of VOC's, the most preferred catalyst system will be comprised of maleic acid and ammonium sulfate.
  • maleic acid may modify the molecular structure of the most desirable BHMF resin via the following reaction:
  • X may be either (-CH 2 OH) or a polymer chain.
  • the remaining free acid groups may act to 'catalyze' the reaction at conditions of elevated temperatures.
  • a catalyst has been traditionally defined as a substance whose presence changes the rate of a chem ⁇ ical reaction without undergoing permanent change in its composition, catalyst as used herein is further defined to include materials such as maleic acid and maleic anhydride whose molecular structure may be altered via reaction with the macromolecules of the furan resin.
  • the catalyst system should be generally present in an amount equal to 1-20% by weight of resin solids or active binder solids. Preferably, the amount will be from 5-12% and most preferably, 6-10% by weight of active binder solids.
  • the ratio of maleic acid to ammonium sulfate will be from 10:1 to 1:10. Most preferably, the ratio of maleic acid to ammonium sulfate will be from 5:4 to 3.2.
  • the aqueous compatible furan binder composition may further comprise compounds such as ammonia or urea in an amount equal to 0 to 30% by weight. It has been found that the incorporation of urea in the disclosed binder compositions causes further reductions in the emission of free formaldehyde. It will be appreciated by those skilled in the art that other formaldehyde scavengers may be utilized.
  • urea-is used as a traditional formaldehyde scavenger it may be incorporated with the furan resin just prior to application to the glass fibers, along with sufficient water to produce a binder having solids between 0.5-80%.
  • the urea and furan may be allowed to pre-react.
  • the urea and furan will be allowed to pre-react for a period from 1-24 hours prior to application and most preferably from 12-24 hours before use.
  • silanes may be incorporated to improve the overall characteristics of the cured glass fiber/binder composition. Silanes appear to have the ability to improve recovery properties by facilitating an adhesive bond between the glass fiber surface and the furan resin.
  • Suitable silane coupling agents are Union Carbide A1100'" , Union CarbideTM A1160, Union CarbideTM A-187, Alpha" 1 4IB, Dow- CorningTM Z6026 and WackerTM B.S.-20. WackerTM B.S.-20 -is siloxane based. Experimental data showed a general trend in which all of the tested silanes narrowed the variability of recovery results from 40-70% to 60-70%. Reactive silanes are preferred for use in the present invention. In particular those silanes with reactive groups such as primary amines and -uriedo are most preferred.
  • the aqueous compatible furan binder compositions of the invention contain reactive silanes in an amount from 0.05 - 0.50% by weight and most preferably approximately 0.2% by weight of the total binder solids.
  • the most preferred reactive silane is gamma-aminopropyltriethoxy-silane, supplied by Union Carbide as A1100.
  • the actual amount incorporated will be dependent upon the reactivity of the silane and can be determined by one skilled in the art.
  • coupling agents such an organotitanates and organozirconates are suitable for use in the present invention.
  • the amounts of such coupling agents to be incorporated will depend upon the agent's particular chemistry.
  • extenders to reduce cost and coloring agents may also be incorporated without departing from the spirit of the invention.
  • suitable extenders are silica, alumina, and calcium carbonate.
  • suitable coloring agents are red dye 42 and similar such materials.
  • Surfactants may also be added to the furan binder compositions of the instant invention. It has been found that sodium dodecyl benzene sulfonate is a preferred surfactant. It may be added in an amount equal to 0.05 to 1.0% by weight.
  • the emulsified furan resin glass fiber binding compositions of the invention are comprised of an effective binding amount of a furan resin, an effective emulsifying amount of an emulsifying agent and sufficient water to produce a binding composition having a percent nonvolatile from 0.5 to 80% nonvolatile.
  • Furan resins as defined above are suitable for incorporation into the emulsified binding compositions. While it is preferred to use furan resins which have low levels of volatile organic compounds, it is possible to incorporate furan resins such as Farez "M" and Quacor 1300 as discussed above. Furan resins having BHMF functionally are preferred. The most preferred resin is Farez M.
  • suitable furan resins need not be aqueous compatible.
  • materials such as furfuryl alcohol are known to break emulsions
  • Examples 6 and 7 indicate that the present invention provides for the emulsification of furan resins having furfuryl alcohol concentrations of up to 7.1% by weight.
  • Emulsifier agents suitable for use in the instant invention may be generally classified as emulsifier agents such as those in the cellulose ether family are particularly suitable. Suitable types of cellulose ethers are those of the type sold by Dow Chemical under the tradename "Methocel”TM 1 Methyl cellulose and substituted methyl cellulose are particularly suitable. Substituted methyl celluloses are preferred.
  • the emulsifier agent is most preferably, however, hydroxypropylmethyl cellulose. Most
  • the agent will be a MethocelTM F4M which is a hydroxypropylmethyl cellulose which in a 2% concentration in water produces a viscosity of 4000 cPs.
  • pph parts per 100 parts active binder solids
  • pph parts per 100 parts active binder solids
  • a methyl cellulose material will be added to the furan resin.
  • 1 to 2 ppH of MethocelTM F4M will be utilized.
  • the composition will further contain sufficient water so as to produce a binding composition having from 0.5 to 80% nonvolatile.
  • the emulsified glass fiber binding composition of the instant invention will have a percent nonvolatile of between 15-25% and most preferably 20% nonvolatile.
  • the emulsified furan resin based binding compositions may also incorporate catalysts to cure the furan resin. Suitable catalysts are as discussed above. The most preferred catalyst will be the combination of ammonium sulfate and maleic acid in amounts as discussed above.
  • step number (3) Continue to mix the cold water of step number (2) with the emulsifying paste of step number (1) under continuous mechanical agitation for at least 20 minutes after the temperature of the resulting mixture has reached 30°C or less until a uniform viscous liquid forms.
  • the cold water of step number (2) may further comprise all or part of a catalyst and additives desired to be incorporated with the furan resin.
  • Such additives may consist of catalysts, additives such as silanes or coupling agents, as well as formaldehyde scavengers such as urea and melamine. These materials are as described above.
  • the hot water of step number (1) will most preferably comprise less than 50% of the total water required. Most preferably, the following procedure will be followed in preparing the emulsified binders:
  • hydroxpropyl methyl cellulose F4 is added to 100 parts of furan resin and mixed continuously with a stirrer until a uniform mixture forms, with well dispersed hydroxy propyl methyl cellulose. This could take around 30 minutes.
  • the resin should contain as little water as possible, preferably less than 8 to 10% and most preferably less than 3 to
  • Examples 6 and 7 further disclose the particular parameters of the emulsified binder compositions.
  • the invention further comprises glass fiber compositions made according to the present invention.
  • the amount of binder present in a glass fiber composition depends in large part on the performance requirements of the finished product.
  • the amount of resin on a cured glass fiber mat is typically determined by the loss on ignition test (L.O.I.) . After ignition of a weighed, cured glass fiber/binder sample at 950°F, the total percent weight loss is determined. This value represents the amount of thermoset binder originally present.
  • the compositions of this invention should contain 1 to 25% by weight cured resin or % L.O.I. Preferably, such systems will contain 2 to 18% L.O.I. It is most preferred that L.O.I, values for the compositions of the instant invention range from 4 to 12%.
  • glass fiber/binder compositions of the instant invention may be darker in color than glass fiber batts produced with traditional phenol formaldehyde binders.
  • the dark color and thermal resistance of furan based binders are favored for many OEM and industrial fiber glass markets, such as duct and furnace liners and automotive hoodliners.
  • glass fiber/binder compositions One of the most desirable properties required of glass fiber/binder compositions is a high compressibility ratio of between 4-12:1 and recovery values of between 40 to 100%. This is especially true of glass fiber products with densities of approximately 1/2 pound to 1 pound per cubic foot. As previously discussed, such materials have great applicability for use in insulation.
  • the recovery of a glass fiber/binder composition is generally tested via the following method known as the "Recovery test".
  • Cured glass fiber/binder compositions having densities of between 0.5 to 1.0 pound per cubic foot are compressed to densities of approximately 2.0 to 4.0 pounds per cubic foot.
  • the compressed materials are inserted into humidity cabinets and are subjected to temperatures of between 25 to 70C at 95% R.H. After 2 to 500 hours, the samples are uncompressed and left to recover for a period of 1.0 hour. Their resultant "recovered" thicknesses are measured and the percent recovery calculated as a percentage of the initial thickness.
  • the glass fiber compositions disclosed herein will recover between 60 to 100% of their initial thickness and most preferably between 70-100%.
  • the ability of the glass fiber compositions to recover is substantially influenced by the modulus of the glass fibers themselves.
  • the distribution of the binder on the glass fibers affects not only the movement of the individual glass fibers but also the collective overall movement and hence the recovery characteristics.
  • the aqueous compatible furan resins of the instant invention be present mainly at a portion of the glass fibers junctions.
  • the number and size of the binder-junction furan resin particles appears to have a direct effect on recovery proper ⁇ ties. It is also believed that some sheathing of the glass fibers by the binder may contribute to the recovery properties of the fiber glass batt. However, it will be appreciated that in the glass fiber/binder compositions of the instant invention, the binder does not completely fill the interstitial space surrounding the individual glass fibers.
  • Figures 1 and 2 illustrate acceptable distributions of binder on glass fibers.
  • Figures 1 and 2 illustrate acceptable distributions of bis(hydroxy ethyl) furan resin-based binders.
  • the binder of Figure 1 has ammonium sulfate as catalyst.
  • the binder of Figure 2 contains a combination of maleic acid and ammonium sulfate. Compositions of the binders used to produce the illustrated distributions are given in Table 2.
  • Figures 1 and 2 also represent different methods of binder application.
  • Figure 1 illustrates binder distribution derived from applying the binder through a fiberglass column expander whereas
  • Figure 2 shows distribution resulting from application through an air assisted spray nozzle.
  • both binder systems and application methods produced fiberglass product with acceptable recoveries. There is a sufficient proportion of bonded junction points to non-bonded junction points in both figures to provide adequate product recovery. It is believed that the average size of such binder- junction particles should most preferably be no larger than 1 to 20 times the average fiber diameter.
  • the invention further comprises a process for binding glass fiber compositions with the aqueous compatible furan resin compositions described herein. Glass fiber compositions made ac ⁇ cording to this process have recovery properties sufficient to allow them to be used in a wide variety of end use applications including insulation and or filtration and or separation applications. In addition, the high acid resistance of furan based binders makes them suitable for filtration applications.
  • the furan binder compositions disclosed herein and intended to be used in the process of the invention have a viscosity from 1-
  • compositions 400 cPs at a % N.V. from 0.5 to 80%. While it is desirable that such compositions be homogeneous one phase mixtures, two phase mixtures can provide the desired performance properties.
  • the most preferred binding compositions disclosed herein be applied as two-component systems.
  • the first component will preferably be comprised of a homogeneous one phase mixture of the furan resin and additives such as urea, ammonium, silanes etc. if used, and sufficient water to achieve a % N.V. from 40-80%.
  • the second component is comprised of the catalyst system and sufficient water to achieve a % N.V. of about 4-8% and most preferably 6% N.V.
  • the two components are mixed to form a binding composition as disclosed herein. Such mixing will occur before application.
  • furan binder compositions will be to glass fibers using known prior art fiber manufacturing methods. Most preferably, the binder will be applied to the newly formed glass fibers in mid air prior to their collection as described below. Suitable manufacturing processes are the well known rotary process or pot and marble process. The rotary process is described on pages 12-14 of "Fiber Glass" by Mohr & Rowe previously referenced above.
  • the glass fibers with a binder sprayed thereon are collected on a moving chain as a loose blanket.
  • the glass fibers will most preferably be newly formed.
  • This chain is pulled into an oven wherein the blanket is partially compressed as it is going through the oven to achieve desired blanket thickness. As the blanket is squeezed between the oven flights, hot air is pumped through the blanket via a series of internal plenums or air ducts.
  • cure may be a variable effecting reduced V.O.C. emissions.
  • a desirable cure for VOC purposes is a cure cycle wherein the temperature is increased from ambient of a rate of between 10-20°C per minute up to as low as a final a temperature as possible, preferably 200°C.
  • This type of cure cycle is defined herein as a 'ramp cure'. Given appropriate oven conditions this should result in an optimum cure cycle of 10 minutes or less at 200°C. However, oven temperatures between 75°C - 250°C may be used as long as the residence time in the oven is adjusted accordingly.
  • the most preferred cure cycle for the compositions illustrated in Table 1 is 8 minutes at an oven temperature of 200°C.
  • the desired cure cycle is affected by the strength of the chosen acid catalyst.
  • a relatively strong acid catalyst such as para-toluene sulfonic acid (PTSA) may be chosen.
  • PTSA para-toluene sulfonic acid
  • a pK a of approximately .5 to 1.0, it may cause the furan resin to cure almost instantly on the glass fiber.
  • a cure rate is acceptable because the glass fiber/binder composition does not need to undergo any forming process in the oven. In many cases this type of fiber glass will be reduced in size, normally by a hammer mill, prior to its end use application.
  • the fiber glass and binder will be collected and packaged prior to cure.
  • This material is known as uncured wool and is cured via a molding process. It may be molded in-house or packaged and transported to an outside molding facility.
  • Suitable catalysts for this application are the catalysts discussed above. Most preferably the catalyst will be a 5:3 wt:wt, maleic acid and ammonium sulfate mixture, present in an amount equal to 7% by weight.
  • Such molded glass fiber compositions normally have 5 to 25% by weight cured resin or % L.O.I. It is preferred that they have 5 to 20% by weight catalyst.
  • This uncured wool is typically molded in a 300-500°F flat press at 45 second or less intervals.
  • the resulting materials may be utilized in various automotive applications such as headliners. Although compressed, it should be noted that the resulting glass fiber compositions are air permeable. Although, the individual glass fibers may be coated, the furan binder does not fill the interstitial space in the finished article.
  • compositions of the various samples tested are illustrated below in Table 4.
  • “Farez MTM” denotes the resin- previously described and supplied by QO Chemicals, while '1300' denotes the use of QuacorrTM 1300 as received from QO Chemicals. Any catalysts used or other materials added are identified to the right of the resin. Preparation of the samples consisted of mixing the various components together under a typical laboratory mixing apparatus.
  • the tube furnace is used to heat samples in a controlled envi ⁇ ronment designed to simulate a fiber glass binder curing._process. It consists of a glass tube, about one foot long and with a one inch inside diameter, wrapped with a nickel-chromium wire heater and surrounded with a vacuum jacket. The temperature inside the furnace can be monitored by a thermocouple in the thermocouple well placed between the heater wire and the wall of the inside tube.
  • Sample support consisted of a glass microfiber filter (Whatman 5.5 cm GF/B) inside a carrier consisting of a 1.5 inc long piece of 0.75 inch diameter PyrexTM glass tubing. Between 0.15 and 0.90 gram of the final binder solution was placed and weighed to the nearest 0.1 mg on the filter. The sample support and sample were placed near the outlet end of the tube furnace and the cap replaced. Dry air or an inert gas was used to sweep the inside of the tube.
  • a trapping solution comprised of 2.50 gm of 2,4-dinitrophenylhydrazine in 1000 ml of acetonitrile solvent that also contained 5 ml of glacial acetic acid (to facilitate the reaction between the 2,4-dinitrophenylhydrazine and formaldehyde), and a small, accurately known quantity, of diethyl phthalate as an internal standard.
  • the reaction between 2,4-dinitrophenylhydrazine and formaldehyde to form a stable 2,4-dinitrophenyl-hydrazone derivative is well known to those skilled in the art of analytical organic chemistry and need not be discussed further here.
  • the purpose of this experiment was to establish the ability of silanes to improve moisture resistance in the bonded fibers.
  • Binderless fiber glass batts were prepared by subjecting com ⁇ flashal insulation batts from Schuller International, Inc., type "R-19", to 950"F to burn out the binder. The "burned out” batts were sliced horizontally into strips approximately 3/8 inch in thickness. Furan binders consisting of 100 grams FarezTM M resin, 6 grams ammonium sulfate, 20 grams water, and a quantity of silane based on its individual activity was sprayed onto both sides of each strip. The three strips were combined and cured at 425°F for 10 minutes to make up one sample.
  • the brand and quantity of silane used were as follows: Union Carbide A1100, 0.2 parts; Union Carbide A1160, 0.4 parts; Union Carbide A-187 2 , 0.2 parts; Alfa 41B 3 , 0.2 parts; Dow-Corning Z-6026 4 , 0.1 part; and acker BS-20 5 , 0.5 parts.
  • test specimens Four 6" x 6" test specimens were cut from each prepared sample, weighed, and measured for thickness. Then the specimens were compressed to one quarter of their original thickness and placed in a humidity cabinet at 155°F and 95% R.H. for two hours. After removal, the specimens were left to cool undisturbed for 30 minutes and then allowed to expand. Following an hour of specimen equilibration, their thicknesses were again measured. The samples were then reheated to 950°F for binder determination. (% L.O.I.)
  • A1100 and A1160 are tradenames of Union Carbide.
  • 3 4IB is a tradename of Alfa.
  • 5 BS-20 is a tradename of Wacker Silicones. Sample recovery, density and binder values are summarized below.
  • the binder based on resin A and using Methocel F4M as the emulsifier agent was stable but did not disburse well on the glass. However, this was believed to be due to the higher than expected viscosity of the binder and a low atomizing air pressure. Interestingly enough, however, the uncured wool showed approximately a two-inch increase in loft. A second run using resin B and Methocel A4M failed to exhibit the loft increase. A third run using resin B and Methocel AM4 but at 40% resin solids showed no differences with respect to the second run.
  • Emulsified furan resin based binding compositions were tested on a pot and marble unit manufacturing pipe insulation.
  • the furan resin which was emulsified was a standard Farez M-type resin, the characteristics of which are given below.
  • Resin C was incorporated with an emulsifier agent according to the above-discussed procedure.
  • the formulation is set forth below in Table 13.
  • the resulting binding composition produced a very yellow fiber web with excellent tact. Wrap-up was good. Stack opacities were very low. At a 425°F oven temperature, the pipe insulation came out dark brown to black in color. The binder content of the cured tubes was high, 11.8% L.O.I.

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Abstract

La présente invention se rapporte à une composition de liaison de fibres de verre comprenant une quantité de liaison efficace de résine furannique, une quantité émulsifiante efficace d'un agent émulsifiant, et une quantité suffisante d'eau pour obtenir une composition de liaison contenant de 0,5 à 80 % d'éléments non volatils. L'invention se rapporte en outre à un procédé de liaison de fibres de verre au niveau des points de jonction des fibres, consistant à prendre les fibres de verre, à appliquer, aux points de jonction, une quantité de liaison efficace d'une composition émulsifiée de liaison de fibres de verre, et à faire durcir l'agent de liaison au niveau de ces points de jonction. Enfin, l'invention se rapporte à une composition de fibres de verre comprenant une pluralité de fibres de verre présentant une pluralité de points de jonction entre au moins deux fibres, ainsi qu'une quantité de liaison efficace d'une composition émulsifiée de liaison de fibres de verre appliquée à une partie des points de jonction desdites fibres.
EP94919186A 1993-05-19 1994-05-17 Compositions emulsifiees de liaison de fibres de verre, a base de resine furannique, et procede de liaison de fibres de verre Withdrawn EP0651732A1 (fr)

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GB201103291D0 (en) * 2011-02-25 2011-04-13 Tuffbau Ltd Improved binder blends
FR3064009B1 (fr) 2017-03-15 2021-06-18 Saint Gobain Isover Solution concentree de poly(alcool furfurylique) pour encollage de fibres organiques ou minerales
FR3090671B1 (fr) 2018-12-20 2022-05-27 Saint Gobain Isover Composition d’encollage a base de resine furanique, de sucre reducteur et/ou de sucre non reducteur
CN117665173B (zh) * 2024-02-01 2024-04-30 深圳天祥质量技术服务有限公司 一种生活消费品中四氢糠醇的测定方法

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US3409582A (en) * 1964-04-22 1968-11-05 Quaker Oats Co Alkaline refractory mixtures containing formaldehyde-furylethylenealdehyde resins and gunning therewith
US3742101A (en) * 1969-10-02 1973-06-26 Agency Ind Science Techn Carbon-glass composite and manufacturing method therefor
US3681287A (en) * 1971-03-03 1972-08-01 Quaker Oats Co Siliceous materials bound with resin containing organosilane coupling agent
NZ197438A (en) * 1980-09-22 1984-05-31 Quaker Oats Co Making composite articles using furanformaldehyde condensation products
DE3148326C2 (de) * 1981-12-07 1984-09-13 Keramchemie GmbH, 5433 Siershahn Teigige Formmasse
DE3616454C3 (de) * 1986-05-15 1997-04-17 Gruenzweig & Hartmann Verwendung einer stabilen wäßrigen Emulsion eines wasserunlöslichen Zusatzstoffes zum Imprägnieren (Schmälzen) von künstlichen Mineralfasern von Dämmstoffen
US5364904A (en) * 1990-06-29 1994-11-15 Unilever Patent Holdings B.V. Emulsion polymerization

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