WO1988003090A1 - Composites en polyurethane comprenant un agregat grossier et certains liants au polyurethane - Google Patents

Composites en polyurethane comprenant un agregat grossier et certains liants au polyurethane Download PDF

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Publication number
WO1988003090A1
WO1988003090A1 PCT/US1987/002737 US8702737W WO8803090A1 WO 1988003090 A1 WO1988003090 A1 WO 1988003090A1 US 8702737 W US8702737 W US 8702737W WO 8803090 A1 WO8803090 A1 WO 8803090A1
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WIPO (PCT)
Prior art keywords
void
binder
composite
premix
filling
Prior art date
Application number
PCT/US1987/002737
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English (en)
Inventor
William Graham Carpenter
A. Leonard Haugse
Colleen M. Henry
Tai-Ming Liang
Gary A. Tolhurst
Original Assignee
Ashland Oil, Inc.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Ashland Oil, Inc. filed Critical Ashland Oil, Inc.
Publication of WO1988003090A1 publication Critical patent/WO1988003090A1/fr

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Classifications

    • E—FIXED CONSTRUCTIONS
    • E01—CONSTRUCTION OF ROADS, RAILWAYS, OR BRIDGES
    • E01C—CONSTRUCTION OF, OR SURFACES FOR, ROADS, SPORTS GROUNDS, OR THE LIKE; MACHINES OR AUXILIARY TOOLS FOR CONSTRUCTION OR REPAIR
    • E01C11/00—Details of pavings
    • E01C11/005—Methods or materials for repairing pavings
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/16—Catalysts
    • C08G18/18—Catalysts containing secondary or tertiary amines or salts thereof
    • C08G18/20—Heterocyclic amines; Salts thereof
    • C08G18/2009—Heterocyclic amines; Salts thereof containing one heterocyclic ring
    • C08G18/2018—Heterocyclic amines; Salts thereof containing one heterocyclic ring having one nitrogen atom in the ring
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/54—Polycondensates of aldehydes
    • C08G18/542—Polycondensates of aldehydes with phenols

Definitions

  • the invention relates to polyurethane composites comprising a coarse aggregate and certain polyurethane binders.
  • the composites are useful for filling voids in roads, runways and other structures made of asphalt, concrete, cement and other such building materials.
  • Certain embodiments of the invention are effective in aqueous conditions.
  • Composites for repairing roads, runways and other structures made from asphalt, concrete, cement and similar building materials are well known. Generally they consist of an aggregate and a polymeric binder. The physical characteristics of such composites must be sufficient to support the load to which the composite will be subjected. For instance, an adequate compression strength of at least 2,000 psi and an adequate flexural strength of at least 400 psi is required. The composite must also be resistant to shrinkage and be compatible with materials such as asphalt, concrete, cement, and the like.
  • the materials used in the composite must be acceptable from a safety and toxicilogical viewpoint. In particular they must not have dangerously low flashpoints.
  • the materials must also be easy to handle and mix and have an adequate shelf life.
  • the worktime of such composites can be varied depending upon the use, but that the composites cure rapidly (within 60 seconds) after the worktime has elapsed.
  • the composites preferably should also be effective at both lower temperatures (such as -6°C) and higher temperatures (such as 35°C) , and should work effectively in aqueous conditions.
  • a polyurethane binder comprising the reaction product of i) a phenolic resin component comprising 1. a resole phenolic resin, and 2.- a hydrophobic solvent system; ii) an isocyanate component comprising
  • aromatic polyisocyanate selected from the group consisting of diphenylmethane diisocyanates, oligomeric derivatives of diphenylmethane diisocyanates, and mixtures thereof, and
  • the weight ratio of the binder to the aggregate is from about 8:92 to about 50:50;
  • the ratio of hydroxyl groups in the phenolic resin to isocyanate groups of the isocyanate component is from about 0.8:1 to about 1.2:1 and
  • the urethane catalyst is used in an amount effective to result in a sufficient worktime under use conditions.
  • the composites are useful for filling voids in roads, runways and other structures made of asphalt, concrete, cement, and other such building materials.
  • the composites can be used as a premix or the polyurethane binder can be percolated through the aggregate which has been added to a void in a road, runway, or other structure made of asphalt, concrete, cement, or other such building materials.
  • Such composites have satisfactory physical characteristics, are resistant to excessive shrinkage, satisfy reasonable safety specifications, are easy to mix, and have adequate shelf lives. In addition to this they work effectively at rather varying temperatures (such as -6 °C and
  • the binder is preferably allowed to percolate into the aggregate which occupies a void in a road, runway, or other structure made of asphalt, concrete, cement, or other such building materials.
  • the polyurethane composites comprise a coarse aggregate and a polyurethane binder.
  • the coarse aggregates used in the subject composites are such as those defined in ASTM D448-80 (1983) . This standard specifies various ' standard sizes of coarse aggregate used as paving materials. Other commonly known coarse aggretates such as pea gravel and TUFCHEM® grout made by Pennwalt 0 Corporation may be used.
  • the coarse aggregate may also contain some fine aggregate such as sand, quartz, zircon, olivine, aluminosilicate, chromite, and the like. The total volume of the aggregate, however, is predominately (more than
  • the polyurethane binder system used to make the polyurethane binder that is used with the aggregate is comprised of three components: (a) the phenolic resin component, (b) the isocyanate component, and (c) the catalyst.
  • the phenolic resin component is comprised-- of (a) a resole phenolic resin, and (b) a hydrophobic solvent system which preferably is one in which water is not soluble in any significant amounts.
  • Resole phenolic resins are well known and are generally 5 prepared by reacting a phenolic material with a molar excess of formaldehyde in the presence of an alkaline catalyst or a metal ion catalyst.
  • These resins are the reaction products of an aldehyde with a phenol. They contain a preponderance of bridges joining the phenolic nuclei of the polymer which are ortho-ortho benzylic ether bridges. They are prepared by reacting an aldehyde and a phenol in a mole ratio of aldehyde to phenol of at least 1:1 in the presence of a metal ion catalyst, preferably a divalent metal ion such as zinc, lead, manganese, copper, tin, magnesium, cobalt, calcium, and barium.
  • a metal ion catalyst preferably a divalent metal ion such as zinc, lead, manganese, copper, tin, magnesium, cobalt, calcium, and barium.
  • the phenols may be represented by the following structural formula: •
  • A, B, and C are hydrogen atoms, or hydroxyl radicals, or hydrocarbon radicals or oxyhydrocarbon radicals, or halogen atoms, or combinations of these.
  • the phenol may be a multiple ring phenol such as bisphenol A.
  • the phenolic resin is preferably non-aqueous.
  • non-aqueous is meant a phenolic resin which contains water in amounts of no more than about 10%, preferably no more than about 1% based on the weight of the resin.
  • the phenolic resin component preferably includes benzylic ether resins.
  • the aldehyde has the formula R'CHO wherein R* is a hydrogen or hydrocarbon radical of 1 to 8 carbon atoms.
  • phenolic resin is meant the reaction product of a phenol with an aldehyde in which the final mixture of molecules in the reaction products is dependent upon the specific reactants selected, the starting ratio of these reactants, and the conditions of the reaction (for example, the type of catalyst, the time and temperature of the reaction, the solvents, and/or other ingredients present, and so forth).
  • the reaction products, that is the phenolic resin will be a mixture of different molecules and may contain in widely varying ratios addition products, condensation products, and unreacted reactants such as unreacted phenol and/or unreacted aldehyde.
  • addition product is meant reaction products in which an organic group has been substituted for at least one hydrogen of a previously unreacted phenol or of a condensation product.
  • condensation product is meant reaction products that link two or more aromatic rings.
  • the phenolic resins are substantially free of water and are organic solvent soluble.
  • the phenolic component includes any one or more of the phenols which have heretofore been employed in the formation of phenolic resins and which are not substituted at either the two ortho-positions or at one ortho-position and the para-position, such unsubstituted positions being necessary for the polymerization reaction. Any one, all, or none of the remaining carbon atoms of the phenol ring can be substituted.
  • the nature of the substituent can vary widely and it is only necessary that the substituent not interfere in the polymerization of the aldehyde with the phenol at the ortho-position and/or para-position.
  • Substituted phenols employed in the formation of the phenolic resins include alkyl-substituted phenols, aryl-substituted phenols, cyclo-alkyl-substituted phenols, aryloxy-substituted phenols, and halogen-substituted phenols, the foregoing substituents containing from 1 to 26 carbon atoms and preferably from 1 to 12 carbon atoms.
  • Suitable phenols include phenol, 2,6-xylenol, o-cresol, p-cresol, 3,5-xylenol, 3,4-xylenol, 2,3,4-trimethyl phenol, 3-ethyl phenol, 3,5-diethyl phenol, p-butyl phenol, 3,5-dibutyl phenol, p-amyl phenol, p-cyclohexyl phenol, p-octyl phenol, 3,5-dicyclohexyl phenol, p-phenyl phenol, p-crotyl phenol, 3,5-dimethoxy phenol, 53,4,5-trimethoxy phenol, p-ethoxy phenol, p-butoxy phenol, 3-methyl-4-methoxy phenol, and p-phenoxy phenol.
  • Multiple ring phenols such as bisphenol A are also suitable.
  • the phenol reactant is preferably reacted with an aldehyde to form phenolic resins and more preferably benzylic
  • the aldehydes reacted with the phenol can include any of the aldehydes heretofore employed in the formation of phenolic resins such as formaldehyde, acetaldehyde, pro ionaldehyde, furfuraldehyde, and benzaldehyde.
  • the aldehydes employed have the
  • R'CHO wherein R' is a hydrogen or a hydrocarbon radical of 1 to 8 carbon atoms.
  • the most preferred aldehyde is formaldehyde.
  • Alkoxy-modified phenolic resins may also be used as the phenolic resin. These phenolic resins are prepared in
  • the phenolic resin used must be liquid or organic solvent soluble. Solubility in an organic solvent is desirable to achieve uniform distribution of the binder on the aggregate.
  • the solvent system for the phenolic resin component is
  • a hydrophobic solvent preferably in which water is not significantly soluble.
  • solvents with high flashpoints such as at least 50°C. Suitable solvents can be determined by looking at physical data sheets on various solvents.
  • the 5 solvent will be from 40 to 60 weight percent of the phenolic resin component.
  • the viscosity of the phenolic resin component is generally less than 500 cps and preferably less than 100 cps, which allows for easy mixing with the isocyanate component.
  • the viscosity of the resin component 0 can be adjusted by varying the amount of solvent.
  • the solvent component can include liquid dialkyl esters such as dialkyl phthalate of the type disclosed in U.S. Patent 3,905,934.
  • liquid dialkyl esters such as dialkyl phthalate of the type disclosed in U.S. Patent 3,905,934.
  • R 1 and R2 are alkyl radicals of 1 to 12 carbon atoms 0 and the total number of carbon atoms in the R groups does not ⁇ ⁇ exceed 16. More usually R ⁇ and R ' are alkyl radicals of 3 to
  • R group can be methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl, isopentyl, hexyl, isohexyl, heptyl, isoheptyl, octyl, isooctyl, and other isomers of the foregoing.
  • dialkyl esters include dimethyl glutarate such as available from Du Pont under the trade designation DBE-5; dimethyl adipate, available from Du Pont under the trade designation DBE-6; dimethyl succinate; and mixtures of such esters which are available from Du Pont under the trade designation DBE, and dialkyl adipates and succinates with alcohols up to 12 carbon atoms.
  • a chain extender or crosslinking compound is also added to the phenolic resin component.
  • Such compounds are low molecular weight diols or triols having a molecular weight of approximately 40-200. These compounds should be soluble in the solvent system. Examples of such compounds are propylene glycol, ethylene glycol, diethylene glycol, glycerine and the like. These compounds are useful in formulating a phenolic resin component which is approximately equal in volume to the isocyanate component which makes field use easier.
  • the chain extenders and crosslinking compounds also have been found to improve the compression strength of the finished composite.
  • the isocyanate component of the polyurethane binder comprises certain aromatic polyisocyanates and a hydrophobic solvent system, preferably in which water is not signifi ⁇ cantly soluble.
  • Aromatic polyisocyanates which are used are those selected from the group consisting of diphenylmethane diisocyanates, oligomers of diphenylmethane diisocyanates, and mixtures thereof. Specific examples of such aromatic polyisocyanates are 2,2 r -, 2,4'- or 4,4'-diphenylmethane diisocyanate; 3,3'-dimethyl-2,2 r -, 2,4'- or
  • Aromatic polyisocyanates particularly preferred are the mixture of diphenylmethane diisocyanate isomers with polyphenyl polymethylene polyisocyanates ("crude MDI") .
  • Such polyisocyanates are sold under the trademarks PAPI (Dow Chemical Company) and MONDUR MR (Mobay Chemical Company) .
  • the polyisocyanates are used in sufficient concentrations to cause the curing of the phenolic resin when reacted with the curing catalyst. In general the ratio of hydroxyl groups of the phenolic resin to the isocyanato groups of the polyisocyanate is from 0.8:1 to 1.2:1, preferably about 1:1.
  • the polyisocyanate is used in a liquid form. Solid or viscous polyisocyanate must be used in the form of organic solvent solutions, the solvent generally being present in a range of up to 80% by weight of the solution.
  • the solvents used with the isocyanate component must satisfy the requirements of those used with the phenolic resin component. They must be hydrophobic and preferably are solvents in which water is not soluble in any significant amount. They also should preferably have flashpoints of at least 50°C.
  • the solvent systems used in the phenolic resin component and the isocyanate must be compatible with each other. Such compatibility is necessary to achieve complete reaction and curing of the binder compositions of the present invention.
  • Polar solvents of either the protic or aproti ⁇ type are good solvents for the phenolic resin, but have limited compatibility with the polyisocyanates.
  • Aromatic solvents, although compatible with the polyisocyanates, are less compatible with the phenolic resins. It is therefore preferred to employ combinations of solvents and particularly combinations of aromatic and polar solvents. Suitable aromatic solvents are benzene, toluene, xylene, ethylbenzene, and mixtures thereof.
  • Preferred aromatic solvents are mixed solvents that have an aromatic content of at least 90% and a boiling point range within a range of 138°C to 232°C.
  • the polar solvents should not be extremely polar such as to become incompatible with the aromatic solvent.
  • Suitable polar solvents are generally those which have been classified in the art as coupling solvents and include furfural, furfuryl alcohol, Cellosolve acetate, butyl Cellosolve, butyl Carbitol, diacetone alcohol and "Texanol.”
  • a preferred embodiment of the invention also requires that the phenolic resin component and isocyanate component be formulated such that their density is greater than water. This is important where the composites are to be formed in aqueous conditions.
  • a particular solvent system which satisifies the requirements of this invention consists of a combination of an aromatic solvent such as HI-SOL 10 or HI-SOL 15 sold by Ashland Chemical Company with butyl cellosolve acetate, a polar solvent.
  • the catalysts used in the polyurethane-forming binder system are liquid urethane promoting catalysts such as tertiary amines, metal salts, or mixtures thereof.
  • catalyli ⁇ compounds examples include triethylamine, dimethylaminoethanol, , ,N' ,N'-tetraethylethylenediamine, , ,N' , r -tetramethyl-1,3-butanediamine, bis (dim thylaminoethyl)ether, N,N-dimethyl-3-dimethylaminopropionamide,
  • 1,4-diazo(2.2.2)bicyclooctane N-methyl- or ethylraorpholine, stannous oleate, stannous 2-ethylhexanoate, dibutyltin dilaurate, dibutyltin dilauryl mercaptide, dibutyltin diacetate, lead naphthenate, zinc stearate, or mixtures thereof.
  • the urethane promoting catalyst is a base having a pK, value in the range of about 7 to about 11.
  • the pK value is the negative logarithm of the dissociation constant of the base and is a well-known measure of the basicity of a basic material. The higher this number is, the weaker the base.
  • the bases falling within this range are generally organic compounds containing one or more nitrogen atoms. Preferred materials are heterocyclic compounds containing at least one nitrogen atom in the ring structure.
  • bases which have pK values within the necessary range include 4-alkyl pyridines wherein the alkyl group has from one to four carbon atoms, isoquinoline, arylpyridines such as phenyl pyridine, pyridine, acridine, 2-methoxypyridine, pyridazine, 3-chloro pyridine, quinoline, N-methyl imidazole, 4,4-dipyridine, phenyl-propyl pyridine, 1-methylbenzimidazole, and 1,4-thiazine.
  • the urethane catalyst is used in an amount effective to result in a sufficient worktime under use conditions.
  • Worktime is defined under ASTM C 308-77 (Definition 2.2) as the time interval in minutes after initial mixing of the aggregate and binder at which the composite can be applied to a surface without curling behind the trowel.
  • ASTM C 308-77 Determination 2.2
  • An important feature of the subject invention is that worktime can be varied depending upon the application and use conditions. For instance, a premix will require less catalyst to provide a greater worktime while a binder, which will be percolated through an aggregate, will generally require more catalyst. Under colder work conditions, more catalyst will have to be used than under warmer work conditions. The presence of water at the work site will also require that more catalyst be used in order to prevent foaming.
  • catalyst concentrations will vary widely. In general the lower the pK value is, the shorter will be the worktime of the composition and the faster, more complete will be the cure. Solvents and any acidity present in added ingredients such as the aggregate may alter the catalytic activity. In general, however, catalyst concentrations will range from approximately 0.5 to 15 percent by weight of the phenolic resin.
  • Silanes which are useful include those having the general formula:
  • R' is a hydrocarbon radical and preferably an alkyl radical of 1 to 6 carbon atoms and R is an alkyl radical, an alkoxy-substituted alkyl radical, or an alkyl-amine-substi- tuted alkyl radical in which the alkyl groups have from 1 to 6 carbon atoms.
  • the aforesaid silane when employed in concentrations of 0.1% to 2%, based on the phenolic binder and hardener, improves the humidity resistance of the system.
  • silanes examples include Dow Corning Z6040 and Union Carbide A-187 (gamma glycidoxy propyltrimethoxy silane) ; Union Carbide A-1100 (gamma aminopropyltriethoxy silane) ; Union Carbide A-1120 (N-beta(aminoethyl)-gamma-amino-propyltrimethoxy silane); and Union Carbide A-1160 (Ureido-silane) .
  • the polyurethane binder materials are prepared by adding the catalyst to the phenolic resin component. If a premix is formed the isocyanate component is then mixed with the phenolic resin component. This mixture is then added to the aggregate to form a workable composite which is used for filling voids in roadways, runways, and other structures made with asphalt, concrete, cement, and other such building materials.
  • BR-1 a phenolic resole benzylic ether prepared by reacting paraformaldehyde with phenol in a mole ratio of paraformaldehyde to phenol of approximately 1.6 to 1 in the presence of 0.24 weight percent (based upon the weight of the total charge) of Lead CemAll (24% ' active) sold by Mooney Chemicals, Inc.
  • BR-2 an alkoxy modified phenolic resole benzylic ether prepared by reacting paraformaldehyde with phenol in a mole ratio of paraformaldehyde to phenol of approximately 1.3 to 1 in the presence of approximately 2.0 weight percent of methanol and 0.06 weight percent of 2n (C H 0 ) ,2H 0, said weight percent being based upon the weight of the total charge.
  • BR-1 and BR-2 five phenolic resin components were prepared by mixing the specified base resins with the specified solvents:
  • PRC-1 phenolic resin components
  • the viscosity of PRC-1 is 130 cps and the flashpoint is 52°C.
  • PRC-2 The viscosity of PRC-1 is 130 cps and the flashpoint is 52°C.
  • the viscosity of PRC-2 is 70 cps and the flashpoint is 69°C.
  • the viscosity of PRC-3 is 80 cps and the flashpoint is 69°C.
  • BCA is butyl cellulose acetate 2 HISOL 10 and 15 are hydrophobic aromatic solvents sold by
  • the viscosity of PRC-5 was 58 cps and the flashpoint was 68°C.
  • DBE dibasic ester which functions as a hydrophobic solvent.
  • 4 PG is propylene glycol which functions as a chain extender,
  • the two catalysts components used in the examples are as follows:
  • TCGF TUFCHEM Grout Filler
  • PGA pea gravel
  • pp-2010 PLURACOL R Polyol 2010 sold by BASF Corporation
  • Examples 1-6 several premix polyurethane composites were prepared by mixing a polyurethane-forming binder system with a coarse aggregate.
  • the catalyst was first mixed with the phenolic resin component. Thereafter, the isocyanate component was mixed with the phenolic resin component. This binder systems was then added to the aggregate and mixed.
  • the amount of catalyst used was sufficient to provide a worktime of the composite of about 20 to 40 minutes. This enables the user to have ample time to move to the place where the void exists and fill the void in the structure to be patched before the composite cures.
  • Examples 7-14 disclose systems which are particularly useful for applications wherein it is beneficial to percolate the binder into the aggregate which is filling the void to be repaired.
  • the examples show that considerably higher levels of catalyst are used than when forming premixes. They also show systems which cured in aqueous conditions.
  • Example 13 discloses a system wherein the volume of the phenolic resin component and isocyanate component are equal. This embodiment is significant because it makes the system easier to use in the field.
  • the binder system was poured into water, It gelled in 3 min, 8 sec. and had a good appearance.
  • the binder cured effectively in water. It also cured in wet pe gravel and made a composite in 2" cubes having an average compressive strength of 3044 psi.
  • the binder was poured into 2" cube molds containing dry pea gravel.
  • the compressive strength was 3882 after one day and 4097 psi after thirty-five days.
  • the binder was poured into wet pea gravel in 2" cubes.
  • the average compression strength was 3,578 psi.
  • the volume of the phenolic resin component and isocyanate component used in this experiment were equal.
  • Example 13 was repeated except the binder system was poured into dry pea gravel in 2" cube molds.
  • the compression strength was 4448 psi.
  • a premix was prepared with 52.9 pbw of PRC-1, 56.1 pbw of IC-1, 803 pbw of TCGF, and various amounts of C-l as indicated in Table which follows.
  • the premix was formed as previously disclosed, i.e., by adding the catalyst to the phenolic resin, mixing the catalyst and resin with the isocyanate component, and then mixing with the aggregate.
  • the temperature of the environment and worktime are also given in the Table.
  • Example 1 The composite formed in Example 1 was tested to determine its adhesion with respect to concrete.
  • a 3/8" overlay to a concrete block was made with the composite.
  • a cap was glued to the overlay with Dural 5-minute epoxy resin.
  • An Elcometer was then used to determine the strength of adhesion between the composite and concrete. The cap was pulled off from the overlay. The overlay was not separated from the concrete block.

Abstract

Des composites en polyuréthane comprenant un agrégat grossier et certains liants en polyuréthane sont particuièrement utiles pour remplir des cavités de routes, pistes d'atterrissage et autres structures en asphalte, en béton ou en matériaux de construction similaires. On peut ajouter ces composés à ces surfaces ouvertes après un mélange préalable ou en laissant le liant s'infiltrer dans un agrégat déjà en place. Certains modes de réalisation de l'invention sont efficaces dans des conditions aqueuses.
PCT/US1987/002737 1986-10-28 1987-10-22 Composites en polyurethane comprenant un agregat grossier et certains liants au polyurethane WO1988003090A1 (fr)

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US923,920 1986-10-28

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Cited By (9)

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US4960620A (en) * 1988-06-17 1990-10-02 Uop Coating method for room-temperature-cured polyurethanes and polyureas
US5173222A (en) * 1990-06-07 1992-12-22 Mckay Australia Limited Repairing rail ties
GB2353993A (en) * 1999-09-09 2001-03-14 Sterling Technology Ltd Binders for aggregates
US6214265B1 (en) 1998-12-17 2001-04-10 Bayer Corporation Mixed PMDI/resole resin binders for the production of wood composite products
US6224800B1 (en) 1998-12-17 2001-05-01 Bayer Corporation Extended polymethylene poly(phenylisocyanate) resin binders for the production of wood composite products
US6294117B1 (en) 1998-12-17 2001-09-25 Bayer Corporation Mixed PMDI/solid novolac resin binders for the production of wood composite products
US6416696B1 (en) 1999-12-16 2002-07-09 Bayer Corporation Aqueous mixed pMDI/phenolic resin binders for the production of wood composite products
US6822042B2 (en) 2001-10-24 2004-11-23 Temple-Inland Forest Products Corporation Saccharide-based resin for the preparation of composite products
US6846849B2 (en) 2001-10-24 2005-01-25 Temple-Inland Forest Products Corporation Saccharide-based resin for the preparation of foam

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US3432457A (en) * 1967-07-12 1969-03-11 Ashland Oil Inc Resinous composition comprising benzylic ether resin,polyisocyanate,and tertiary amine
US3676392A (en) * 1971-01-26 1972-07-11 Ashland Oil Inc Resin compositions
US4021401A (en) * 1974-12-09 1977-05-03 Jeppsen Harvey I Building material and method for making same
US4139676A (en) * 1974-02-12 1979-02-13 Minnesota Mining And Manufacturing Company Consolidation of aggregate material

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US2934452A (en) * 1956-12-14 1960-04-26 Steelcote Mfg Company Resurfaced concrete structure
US3409579A (en) * 1966-08-01 1968-11-05 Ashland Oil Inc Foundry binder composition comprising benzylic ether resin, polyisocyanate, and tertiary amine
US3429848A (en) * 1966-08-01 1969-02-25 Ashland Oil Inc Foundry binder composition comprising benzylic ether resin,polyisocyanate,and tertiary amine
US3432457A (en) * 1967-07-12 1969-03-11 Ashland Oil Inc Resinous composition comprising benzylic ether resin,polyisocyanate,and tertiary amine
US3676392A (en) * 1971-01-26 1972-07-11 Ashland Oil Inc Resin compositions
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Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4960620A (en) * 1988-06-17 1990-10-02 Uop Coating method for room-temperature-cured polyurethanes and polyureas
US5173222A (en) * 1990-06-07 1992-12-22 Mckay Australia Limited Repairing rail ties
US6214265B1 (en) 1998-12-17 2001-04-10 Bayer Corporation Mixed PMDI/resole resin binders for the production of wood composite products
US6224800B1 (en) 1998-12-17 2001-05-01 Bayer Corporation Extended polymethylene poly(phenylisocyanate) resin binders for the production of wood composite products
US6294117B1 (en) 1998-12-17 2001-09-25 Bayer Corporation Mixed PMDI/solid novolac resin binders for the production of wood composite products
US6641761B2 (en) 1998-12-17 2003-11-04 Bayer Corporation Mixed PMDI/resole resin binders for the production of wood composite products
US6641762B2 (en) 1998-12-17 2003-11-04 Bayer Corporation Mixed PMDI/solid novolac resin binders for the production of wood composite products
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