US20030186035A1 - Infusion of cyclic olefin resins into porous materials - Google Patents

Infusion of cyclic olefin resins into porous materials Download PDF

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US20030186035A1
US20030186035A1 US10/233,066 US23306602A US2003186035A1 US 20030186035 A1 US20030186035 A1 US 20030186035A1 US 23306602 A US23306602 A US 23306602A US 2003186035 A1 US2003186035 A1 US 2003186035A1
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wood
resin
metathesis
group
infused
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Christopher Cruce
Gary Filice
Michael Giardello
Anthony Stephen
Mark Trimmer
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Materia Inc
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Materia Inc
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Assigned to MATERIA, INC. reassignment MATERIA, INC. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: TRIMMER, MARK S., CRUCE, CHRISTOPHER J., FILICE, GARY W., GIARDELLO, MICHAEL A., STEPHEN, ANTHONY R.
Publication of US20030186035A1 publication Critical patent/US20030186035A1/en
Priority to US11/260,754 priority patent/US20060052487A1/en
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L65/00—Compositions of macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Compositions of derivatives of such polymers
    • 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
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/009—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone characterised by the material treated
    • 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
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
    • C04B41/46—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with organic materials
    • C04B41/48—Macromolecular compounds
    • C04B41/4857—Other macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • 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
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/60—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only artificial stone
    • C04B41/61—Coating or impregnation
    • C04B41/62—Coating or impregnation with organic materials
    • C04B41/63—Macromolecular 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
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/36—After-treatment
    • C08J9/40—Impregnation
    • C08J9/42—Impregnation with macromolecular compounds
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/02—Polyamines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L97/00—Compositions of lignin-containing materials
    • C08L97/02—Lignocellulosic material, e.g. wood, straw or bagasse
    • 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
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/20—Resistance against chemical, physical or biological attack
    • C04B2111/27—Water resistance, i.e. waterproof or water-repellent materials
    • 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
    • C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C08K5/098—Metal salts of carboxylic acids
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/54—Silicon-containing compounds
    • C08K5/541—Silicon-containing compounds containing oxygen
    • C08K5/5425—Silicon-containing compounds containing oxygen containing at least one C=C bond
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/249921—Web or sheet containing structurally defined element or component
    • Y10T428/249924—Noninterengaged fiber-containing paper-free web or sheet which is not of specified porosity
    • Y10T428/249925—Fiber-containing wood product [e.g., hardboard, lumber, or wood board, etc.]

Definitions

  • the invention is directed generally to methods and systems for the infusion of cyclic olefin resins into free standing porous materials, together with ring opening metathesis polymerization (ROMP) catalysts to effect the polymerization of such olefins within the porous materials to yield specific composite structures and novel derivatives.
  • REP ring opening metathesis polymerization
  • a wide variety of both natural and synthetic structural materials have a porous nature. Common examples include wood, cement and concrete, open-cell foams and sponges, paper and cardboard, and various sintered materials.
  • the porosity of these materials may be an unintended consequence of their mode of origin or may be a deliberate design feature. Depending upon the intended use of a given material, such porosity may offer advantages such as decreased weight, absorbency, breathability, or unique conductivity or insulative characteristics. However, for many applications, porosity can also lead to problems such as decreased mechanical performance and durability. As a common example, water or moisture routinely enters and exits the pores of porous materials. Aside from affecting the resulting mechanical properties of the material, this moisture often also accelerates degradation by chemical and/or mechanical action.
  • thermoset resins which would be easier to infuse, typically form brittle polymers upon cure.
  • thermoset resin chemistries may be incompatible with moieties present in the interstices or surfaces of porous materials (porous materials have very high surface areas) and are quite often susceptible to hydrolysis, thereby limiting their long-term durability.
  • thermoset resins yielding tough, moisture-resistant polymers would seem to be ideal candidates for infusion into porous materials as protectants and mechanical performance enhancers.
  • Such polymers may be obtained by the ring-opening metathesis polymerization (ROMP) of cyclic olefin monomers.
  • ROMP ring-opening metathesis polymerization
  • the resulting ROMP polymers possess non-hydrolyzable hydrocarbon backbones and are generally very tough.
  • ROMP typically depends upon transition metal catalysts that are extremely sensitive to air, moisture, and functional groups that may be present in the monomers or the porous materials. Thus, ROMP polymers are not commonly considered as candidate impregnants for porous materials.
  • FIG. 1 shows a preferred method of infusing baseball bats with DCPD resin.
  • the present invention encompasses novel compositions comprising porous materials infused with polymers obtained from metathesis reactions, for example ROMP derived polymers and ADMET derived polymers.
  • Another embodiment of the invention is cyclic olefin monomer formulations, including ruthenium or osmium carbene metathesis catalysts, useful for the infusion of porous materials.
  • a further embodiment of the invention includes methods for preparing the porous materials infused with cyclic olefin resin formulations.
  • Other embodiments of the present invention are specific composite structures and articles fabricated from porous materials infused with cyclic olefin polymers.
  • a number of catalysts have been developed recently for initiating olefin metathesis reactions, including ring-opening metathesis polymerization (ROMP) of cyclic olefins, ring-closing metathesis (RCM) of dienes to form ring-closed products, acyclic diene metathesis polymerization (ADMET), depolymerization of unsaturated polymers to form the depolymerized products, synthesis of telechelic polymers by reaction of a cyclic olefin with a functionalized olefin, and synthesis of cyclic olefins by self-metathesis of an acyclic olefin or cross-metathesis of two acyclic oletins.
  • ROMP ring-opening metathesis polymerization
  • RCM ring-closing metathesis
  • ADMET acyclic diene metathesis polymerization
  • depolymerization of unsaturated polymers to form the depolymerized products
  • metathesis catalysts include, but are not limited to, neutral ruthenium or osmium metal carbene complexes that possess metal centers that are formally in the +2 oxidation state, have an electron count of 16, are penta-coordinated, and are of the general formula I.
  • Other preferred metathesis catalysts include, but are not limited to, cationic ruthenium or osmium metal carbene complexes that possess metal centers that are formally in the +2 oxidation state, have an electron count of 14, are tetra-coordinated, and are of the general formula II.
  • Still other preferred metathesis catalysts include, but are not limited to, neutral ruthenium or osmium metal carbene comlexes that possess metal centers that are formally in the +2 oxidation state, have an electron count of 18, are hexa-coordinated, and are of the general formula III.
  • M is ruthenium or osmium
  • n is an integer between 0-5;
  • L, L 1 and L 2 are each independently any neutral electron donor ligand
  • R, and R 1 are each independently hydrogen or any hydrocarbyl or silyl moiety
  • X and X 1 are each independently any anionic ligand
  • Y is any noncoordinating anion
  • Z and Z 1 are each independently any linker selected from the group nil, —O—, —S—, —NR 2 —, —PR 2 —, —P( ⁇ O)R 2 —, —P(OR 2 )—, —P( ⁇ O)(OR 2 )—, —C( ⁇ O)—, —C( ⁇ O)O—, —OC( ⁇ O)—, —OC( ⁇ O)O—, —S( ⁇ O)—, or —S( ⁇ O) 2 —; and
  • any two or more of X, X 1 , L, L 1 , L 2 , Z, Z 1 , R, R 1 , and R 2 may be optionally joined together to form a multidentate ligand and wherein any one or more of X, X 1 , L, L 1 , L 2 , Z, Z 1 , R, and R 1 may be optionally linked chemically to a solid or glassy support.
  • L, L 1 and L 2 are each independently selected from the group consisting of phosphine, sulfonated phosphine, phosphite, phosphinite, phosphonite, arsine, stibine, ether, amine, amide, imine, sulfoxide, carbonyl, carboxyl, isocyanide, nitrosyl, pyridine, quinoline, thioether, and nucleophilic carbenes of the general formula IV or V:
  • A is either carbon or nitrogen
  • R 3 , R 4 , R 5 , and R 6 are each independently hydrogen or any hydrocarbyl moiety, except that in the case where A is nitrogen R 5 is nil;
  • Z 2 and Z 3 are each independently any linker selected from the group nil, —O—, —S—, —NR 2 —, —PR 2 —, —P( ⁇ O)R 2 —, —P(OR 2 )—, —P( ⁇ O)(OR 2 )—, —C( ⁇ O)—, —C( ⁇ O)O—, —OC( ⁇ O)—, —OC( ⁇ O)O—, —S( ⁇ O)—, or —S( ⁇ O) 2 —, except that in the case where A is nitrogen Z 3 is nil; and
  • Z 2 , Z 3 , R 4 , and R 5 together may optionally form a cyclic optionally substituted with one or more moieties selected from the group consisting of C 1 -C 10 alkyl, C 1 -C 10 alkoxy, aryl, and a functional group selected from the group consisting of hydroxyl, thiol, thioether, ketone, aldehyde, ester, ether, amine, imine, amide, nitro, carboxylic acid, disulfide, carbonate, isocyanate, carbodiimide, carboalkoxy, carbamate, and halogen.
  • moieties selected from the group consisting of C 1 -C 10 alkyl, C 1 -C 10 alkoxy, aryl, and a functional group selected from the group consisting of hydroxyl, thiol, thioether, ketone, aldehyde, ester, ether, amine, imine, amide, nitro, carboxylic acid
  • L and L 1 are each a phosphine of the formula PR 7 R 8 R 9 , where R 7 , R 8 , and R 9 are each independently any hydrocarbyl moiety, particularly aryl, primary C 1 -C 10 alkyl, secondary alkyl or cycloalkyl.
  • L and L 1 are selected from the group consisting of —P(cyclohexyl) 3 , —P(cyclopentyl) 3 , —P(isopropyl) 3 , —P(butyl) 3 , and —P(phenyl) 3 .
  • These phosphines are commonly referred to by their abbreviated designations: PCy 3 , PCp 3 , P(i-Pr) 3 , PBu 3 , and PPh 3 , respectively.
  • L is a phosphine and L 1 is a nucleophilic carbene of the general formula III.
  • L is selected from the group consisting of —P(cyclohexyl) 3 , —P(cyclopentyl)3, —P(isopropyl) 3 , —P(butyl) 3 , and —P(phenyl) 3 and L 1 is selected from the group consisting of structures VI, VII, or VIII (wherein m is an integer between 0 and 5):
  • L is a phosphine or a nucleophilic carbene of the general formula IV and L 1 and L 2 are each independently a pyridine or substituted pyridine ligand or L 1 and L 2 together form a chelating bispyridine or phenanthroline ligand, either of which may be substituted or unsubstituted.
  • hydrocarbyl moieties include, but are not limited to, the group consisting of C 1 -C 20 alkyl, C 3 -C 20 cycloalkyl, C 2 -C 20 alkenyl, C 2 -C 20 alkynyl, aryl, heteroaryl, aralkyl, or arylalkyl.
  • silyl moieties include, but are not limited to, the group consisting of tri(hydrocarbyl)silyl, tri(hydrocarbyloxy)silyl, or mixed (hydrocarbyl)(hydrocarbyloxy)silyl.
  • each of the R, R 1 or R 2 substituent groups may be substituted with one or more hydrocarbyl or silyl moieties, which, in turn, may each be further substituted with one or more groups selected from a halogen, a C 1 -C 5 alkyl, C 1 -C 5 alkoxy, and phenyl.
  • any of the catalyst ligands may further include one or more functional groups.
  • Suitable functional groups include but are not limited to: hydroxyl, thiol, thioether, ketone, aldehyde, ester, ether, amine, imine, amide, nitro, carboxylic acid, disulfide, carbonate, isocyanate, carbodiimide, carboalkoxy, carbamate, and halogen.
  • any or all of R, R 1 and R 2 may be joined together to form a bridging or cyclic structure.
  • the R substituent is hydrogen and the R 1 substituent is selected from the group consisting C 1 -C 20 alkyl, C 2 -C 20 alkenyl, aryl, alkaryl, aralkyl, trialkylsilyl, and trialkoxysilyl.
  • n equals 0, 1 or 2 and the R 1 substituent is phenyl, t-butyl or vinyl, optionally substituted with one or more moieties selected from the group consisting of C 1 -C 5 alkyl, C 1 -C 5 alkoxy, phenyl, and a functional group.
  • n 0 or 1 and R 1 is phenyl, t-butyl, or vinyl substituted with one or more moieties selected from the group consisting of chloride, bromide, iodide, fluoride, —NO 2 , —NMe 2 , methyl, methoxy and phenyl.
  • X and X 1 are each independently hydrogen, halide, or one of the following groups: C 1 -C 20 alkyl, aryl, C 1 -C 20 alkoxide, aryloxide, C 3 -C 20 alkyldiketonate, aryldiketonate, C 1 -C 20 carboxylate, arylsulfonate, C 1 -C 20 alkylsulfonate, C 1 -C 20 alkylthiol, aryl thiol, C 1 -C 20 alkylsulfonyl, or C 1 -C 20 alkylsulfinyl.
  • X and X 1 may be substituted with one or more moieties selected from the group consisting of C 1 -C 10 alkyl, C 1 -C 10 alkoxy, and aryl which in turn may each be further substituted with one or more groups selected from halogen, C 1 -C 5 alkyl, C 1 -C 5 alkoxy, and phenyl.
  • X and X 1 are halide, benzoate, C 1 -C 5 carboxylate, C 1 -C 5 alkyl, phenoxy, C 1 -C 5 alkoxy, C 1 -C 5 alkylthiol, aryl thiol, aryl, and C 1 -C 5 alkyl sulfonate.
  • X and X 1 are each halide, CF 3 CO 2 , CH 3 CO 2 , CFH 2 CO 2 , (CH 3 ) 3 CO, (CF 3 ) 2 (CH 3 )CO, (CF 3 )(CH 3 ) 2 CO, PhO, MeO, EtO, tosylate, mesylate, or trifluoromethanesulfonate.
  • X and X 1 are each chloride, bromide, or iodide.
  • the X and X 1 together may comprise a bidentate ligand.
  • Y may be derived from any tetracoordinated boron compound or any hexacoordinated phosphorus compound.
  • Preferred boron compounds include BF 4 ⁇ , BPh 4 ⁇ , and fluorinated derivatives of BPh 4 ⁇ .
  • Preferred phosphorous compounds include PF 6 ⁇ and PO 4 ⁇ .
  • the noncoordinating anion may be also any one of the following: ClO 4 ⁇ , SO 4 ⁇ , NO 3 ⁇ , OTeF 5 ⁇ , F 3 CSO 3 ⁇ , H 3 CSO 3 ⁇ , CF 3 COO ⁇ , PhSO 3 ⁇ , or (CH 3 )C 6 H 5 SO 3 ⁇ .
  • Y may be also derived from carboranes, fullerides, and aluminoxanes.
  • the catalyst:olefin monomer ratio in the invention is preferably between about 1:5 and about 1:1,000,000. More preferably, the catalyst:olefin ratio is between about 1:100 and about 1:100,000 and, most preferably, is between about 1:1,000 and about 1:30,000.
  • Particularly preferred metal catalysts include, but are not limited to: (PCy 3 ) 2 Cl 2 Ru ⁇ CHPh, (PCy 3 ) 2 Cl 2 Ru ⁇ CH—CH ⁇ CMe 2 , (PCy 3 ) 2 Cl 2 Ru ⁇ C ⁇ CHCMe 3 , (PCy 3 ) 2 Cl 2 Ru ⁇ C ⁇ CHSiMe 3 , (PCy 3 )(s-IMES)Cl 2 Ru ⁇ CH—CH ⁇ CMe 2 , (PCp 3 ) 2 Cl 2 Ru ⁇ CH—CH ⁇ CMe 2 , (PCp 3 ) 2 Cl 2 Ru ⁇ C ⁇ CHPh, (PCp 3 )(s-IMES)Cl 2 Ru ⁇ CH—CH ⁇ CMe 2 , (PPh 3 )(s-IMES)Cl 2 Ru ⁇ C ⁇ CHCMe 3 , (PPh 3 ) 2 Cl 2 Ru ⁇ C ⁇ CHSiMe 3 , (P(i-Pr) 3 ) 2 Cl 2 Ru ⁇ C ⁇ CHPh, (PPh 3 )(s
  • the inventive formulation resins include any olefin monomer and metathesis catalyst.
  • the olefin monomers may be used alone or mixed with each other in various combinations to adjust the properties of the olefin monomer composition.
  • mixtures of cyclopentadiene oligomers offer a reduced melting point and yield cured olefin copolymers with increased mechanical strength and stiffness relative to pure poly-DCPD.
  • incorporation of COD, norbornene, or alkyl norbornene comonomers tend to yield cured olefin copolymers that are relatively soft and rubbery.
  • the polyolefin resins of the invention are amenable to thermosetting and are tolerant of various additives, stabilizers, rate modifiers, hardness and/or toughness modifiers, viscosity modifiers, adhesion or coupling agents, and fillers.
  • olefin monomers for infusion include at least one of all “tight” cycloolefins as described in U.S. Pat. No. 6,001,909; and at least one of all cycloolefins as described in U.S. Pat. No. 5,840,238 and U.S. Pat. No. 5,922,802; and at least one of all Diels-Alder adducts as described in U.S. Pat. No. 6,100,323.
  • the most preferred olefin monomer for use in the invention is dicyclopentadiene (DCPD).
  • DCPD resin may optionally contain other cyclopentadiene oligomers, including trimers, tetramers, pentamers, and the like. Such oligomers may be introduced into DCPD by heat treatment of DCPD as described in U.S. Pat. No. 4,899,005 to Lane (et al.) and U.S. Pat. No.
  • the oligomer content may be controlled by varying the heat treatment conditions or by blending oligomer mixtures of known composition with DCPD until the desired oligomer concentration is obtained.
  • Advantages of using such oligomer mixtures include decreased melting point of the monomer mixture and increased mechanical properties and glass transition temperature of the cured resin.
  • olefin monomers include cyclooctadiene (COD; DuPont); cyclooctene (COE); cyclohexenylnorbornene; norbornene; norbornene dicarboxylic anhydride (nadic anhydride); norbornadiene (Elf Atochem); and substituted norbornenes including ethylidene norbornene (ENB), butyl norbornene, hexyl norbornene, octyl norbornene, decyl norbornene, and the like.
  • COD cyclooctadiene
  • COE cyclooctene
  • COE cyclohexenylnorbornene
  • norbornene norbornene dicarboxylic anhydride
  • norbornadiene Elf Atochem
  • substituted norbornenes including ethylidene norbornene (ENB), butyl norbornene,
  • the olefinic moieties include mono-or disubstituted olefins and cycloolefins containing between 3 and 200 carbons.
  • metathesis-active olefinic moieties include cyclic or multicyclic olefins, for example, cyclopropenes, cyclobutenes, cycloheptenes, cyclooctenes, [2.2.1]bicycloheptenes, [2.2.2]bicyclooctenes, benzocyclobutenes, cyclopentenes, cyclopentadiene oligomers including trimers, tetramers, pentamers, and the like; cyclohexenes.
  • compositions include frameworks in which one or more of the carbon atoms carry substituents derived from radical fragments including halogens, pseudohalogens, alkyl, aryl, acyl, carboxyl, alkoxy, alkyl- and arylthiolate, amino, aminoalkyl, and the like, or in which one or more carbon atoms have been replaced by, for example, silicon, oxygen, sulfur, nitrogen, phosphorus, antimony, or boron.
  • radical fragments including halogens, pseudohalogens, alkyl, aryl, acyl, carboxyl, alkoxy, alkyl- and arylthiolate, amino, aminoalkyl, and the like, or in which one or more carbon atoms have been replaced by, for example, silicon, oxygen, sulfur, nitrogen, phosphorus, antimony, or boron.
  • the olefin may be substituted with one or more groups such as thiol, thioether, ketone, aldehyde, ester, ether, amine, amide, nitro, carboxylic acid, disulfide, carbonate, isocyanate, phosphate, phosphite, sulfate, sulfite, sulfonyl, carbodiimide, carboalkoxy, carbamate, halogen, or pseudohalogen.
  • groups such as thiol, thioether, ketone, aldehyde, ester, ether, amine, amide, nitro, carboxylic acid, disulfide, carbonate, isocyanate, phosphate, phosphite, sulfate, sulfite, sulfonyl, carbodiimide, carboalkoxy, carbamate, halogen, or pseudohalogen.
  • the olefin may be substituted with one or more groups such as C 1 -C 20 alkyl, aryl, acyl, C 1 -C 20 alkoxide, aryloxide, C 3 -C 20 alkyldiketonate, aryldiketonate, C 1 -C 20 carboxylate, arylsulfonate, C 1 -C 20 alkylsulfonate, C 1 -C 20 alkylthio, arylthio, C 1 -C 20 alkylsulfonyl, and C 1 -C 20 alkylsulfinyl, C 1 -C 20 alkylphosphate, arylphosphate, wherein the moiety may be substituted or unsubstituted.
  • groups such as C 1 -C 20 alkyl, aryl, acyl, C 1 -C 20 alkoxide, aryloxide, C 3 -C 20 alkyldiketonate, aryl
  • the viscosity of the formulated olefin monomers is typically less than about 500 centipoise at temperatures near room temperature (e.g., from about 25-35° C.).
  • the viscosity of the formulated olefin monomers is less than about 200 centipoise, more preferably is less than about 75 centipoise, and most preferably, is less than about 50 centipoise. In many circumstances, the viscosity is less than 25 centipoise to promote facile infusion.
  • the viscosity of the formulated olefin monomers can be controlled by selection of the combination of monomers and additives, stabilizers, and modifiers used.
  • the viscosity of the formulated resin may be increased or decreased by varying the temperature or by the use of additives such as thixotropes, thickeners, or dilutents.
  • Preferred hardness modulators include, for example, elastomeric additives such as polybutadienes, polyisoprenes, and the like.
  • Polybutadienes and polyisoprenes of various sources, as well as various number-average molecular weights (M n ) or weight-average molecular weights (M w ), may be utilized in the invention as rubber-like hardness modulators.
  • M n number-average molecular weights
  • M w weight-average molecular weights
  • the poly-DCPD resins of the invention allow compositions containing polybutadiene to be clear rather than opaque.
  • the hardness modulators of the invention when added to a polyolefin resin composition, alter the hardness, toughness and/or surface “feel” of the composition compared to the unmodified or native polyolefin.
  • hardness modulators include plasticizers such as dioctyl phthalate and various molecular weight hydrocarbon and the like jellies, greases and waxes, carboxylic acids and salts thereof, and co-monomers such as norbornene, cyclooctadiene, cyclooctene, cyclohexenylnorbornene, norbornadiene, cyclopentene and/or methylcyclopentene.
  • the amount of hardness modulator included in the polyolefin compositions of the invention is preferably about 0.1%-20% by weight of the olefin monomer to which it is added. More preferably, the amount of hardness modulator is about 1%-10% by weight of the olefin monomer and, most preferably, is about 2.5%-7.5%.
  • Especially preferred toughness modulators are rubber triblock copolymers such as styrene-butadiene-styrene, styrene-isoprene-styrene, styrene-ethylene/butylenes-styrene, styrene-ethylene/propylene-styrene, and the like.
  • An example of such toughness modulators is the commercially available KratonTM polymers.
  • Other preferred toughness modulators include polysiloxanes, because the resulting polyolefin compositions possess significantly increased toughness properties without significant concomitant losses in heat distortion temperature (HDT).
  • the amount of toughness modulator included in the polyolefin compositions of the invention is preferably about 0.1%-10% by weight of the olefin monomer to which it is added. More preferably, the amount of toughness modulator is about 0.5%-6% by weight of the olefin monomer and, most preferably, is about 2%-4%.
  • poly-DCPD resins containing 3 parts per hundred low molecular weight (MW) poly(dimethylsiloxane) (Shin Etsu DMF-50) possess notched Izod impact values in excess of 4 ft.-lb./in. and HDT values above 130° C. Hardness and toughness modulators are further described in PCT Publication No. WO 99/60030, the contents of which are incorporated herein by reference.
  • the UV and oxidative resistance of the polyolefin compositions of the invention may be enhanced by the addition of various stabilizing additives such as primary antioxidants (e.g., sterically hindered phenols and the like), secondary antioxidants (e.g., organophosphites, thioesters, and the like), light stabilizers (e.g., hindered amine light stabilizers or HALS), and UV light absorbers (e.g., hydroxy benzophenone absorbers, hydroxyphenylbenzotriazole absorbers, and the like).
  • one or more stabilizing additives are included in the polyolefin resin composition at a level from about 0.01-15 phr.
  • the antioxidant(s) are present at a level of about 0.05-10 phr and, most preferably, 0.1-8 phr.
  • Exemplary primary antioxidants include, for example, 4,4′-methylenebis (2,6-di-tertiary-butylphenol) (Ethanox 702®; Albemarle Corporation), 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene (Ethanox 330®; Albemarle Corporation), octadecyl-3-(3′,5′-di-tert-butyl-4′-hydroxyphenyl) propionate (Irganox 1076®; Ciba-Geigy), and pentaerythritol tetrakis(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate)(Irganox® 1010; Ciba-G
  • Exemplary secondary antioxidants include tris(2,4-ditert-butylphenyl)phosphite (Irgafos® 168; Ciba-Geigy), 1:11 (3,6,9-trioxaudecyl)bis(dodecylthio)propionate (Wingstay® SN-1; Goodyear), and the like.
  • Exemplary light stabilizers and absorbers include bis(1,2,2,6,6-pentamethyl-4-piperidinyl)-[[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl]butylmalonate (Tinuvin® 144 HALS; Ciba-Geigy), 2-(2H-benzotriazol-2-yl)-4,6-ditertpentylphenol (Tinuvin® 328 absorber; Ciba-Geigy), 2,4-di-tert-butyl-6-(5-chlorobenzotriazol-2-yl)phenyl (Tinuvin® 327 absorber; Ciba-Geigy), 2-hydroxy-4-(octyloxy)benzophenone (Chimassorb® 81 absorber; Ciba-Geigy), and the like.
  • the UV and oxidative resistance of polyolefin compositions are further discussed in PCT Publication No
  • a suitable rate modifier such as, for example, triphenylphosphine (TPP), tricyclopentylphosphine, tricyclohexylphosphine, triisopropylphosphine, trialkylphosphites, triarylphosphites, mixed phosphites, pyridine, or other Lewis base, may be added to the olefin monomer to retard or accelerate the rate of polymerization as required.
  • TPP rate modifier it is preferably included in an amount of about 10-200 mg per 64 g olefin monomer.
  • the amount of TPP is about 20-100 mg per 64 g olefin monomer and, most preferably, is about 30-80 mg per 64 g olefin monomer.
  • the amount of rate modifier is preferably about 0.1-50 mg per 64 g olefin monomer, more preferably about 1-40 mg per 64 g olefin monomer, and most preferably is about 1-30 mg per 64 g olefin monomer.
  • rate modifiers can be seen in U.S. Pat. No. 5,939,504 and U.S. application Ser. No. 09/130,586, the contents of each of which are incorporated herein by reference.
  • various pigments or dyes may be included in the polyolefin resin compositions of the invention for applications where color is desired.
  • Preferred pigments include Ferro and Dayglo products, in an amount of about 0.05-2 parts per hundred of polyolefin resin.
  • the cyclic olefin resin formulation may also contain coupling agents or adhesion agents that promote bonding between the walls of the substrate and the infused resin.
  • U.S. Pat. Nos. 6,040,363 and 6,001,909 disclose various preferred sizing or coupling agents useful with cyclic olefin resin formulations.
  • Especially preferred coupling agents are metathesis active adhesion agents as disclosed in WO 00/46257, the contents of which are incorporated herein by reference, and organotitanates and organozirconates such as the Ken-React® products available from Kenrich Petrochemicals, Inc.
  • organotitanates and organozirconates are those containing olefinic groups that may react during polymerization to form carbon-carbon chemical bonds with the resulting polycycloolefin polymer.
  • Examples of such compounds include tetra(2,2-diallyloxymethyl)butyl di(ditridecyl)phosphito titanate (Ken-React® KR 55), tetra(2,2-diallyloxymethyl)butyl di(ditridecyl)phosphito zirconate (Ken-React® KZ 55), and cyclo[dineopentyl(diallyl)]pyrophosphato dineopentyl(diallyl) zirconate (Ken-React® KZ TPP).
  • Especially preferred metathesis active adhesion agents are olefin-containing silanes such as allyltrimethoxysilane, butenyltriethoxysilane, hexenyltriethoxysilane, octenyltriethoxysilane, norbornenyltriethoxysilane, norbornenylethyltriethoxysilane, and the like.
  • porous materials may be used in the present invention so long as such materials are pervious to the unpolymerized cyclic olefin resin formulation and do not contain chemical groups that are incompatible with the olefin metathesis catalyst.
  • Such porous materials include but are not limited to wood, cement, concrete, open-cell and reticulated foams and sponges, papers, cardboards, felts, ropes or braids of natural or synthetic fibers, and various sintered materials.
  • Preferred non-organic materials include unglazed porous ceramics, compacted free standing metal powder objects, and porous concrete aggregates such as cinder blocks.
  • Preferred organic materials include wood, wood products and related cellulosic materials in various forms. These include but are not limited to monolithic wood objects as well as laminated wood, plywood, particleboard and chipboard objects and products. The most preferred porous materials are various types of wood.
  • Portland cement or concrete has an open pore structure that is interwoven and interconnected.
  • One particular form of cement called Enhanced Porosity Cement (EPC) uses little or no sand and has a 20-25% void volume.
  • EPC Enhanced Porosity Cement
  • the markedly porous structure of all cements and related materials allows for the ready diffusion of air, other gases and water vapor. This porous structure also facilitates moisture migration and the wicking of water.
  • Such processes are capable of incorporating destructive pollutants such as nitrate, sulfate and chloride salts into the concrete. At various rates, these salts weaken the concrete structure, promote rusting of embedded steel reinforcing materials, which expand on oxidation and promote the formation of hairline cracks and fissures.
  • infused composites of the present invention Catalyzed cyclic olefin monomer formulations effectively infuse into the pore structure, cracks and fissures of concrete, and related materials, to provide chemically stable ROMP polymers that provide a barrier to water, water vapor and dissolved salts as well as a reduced permeability to corrosive gases such as NO x and SO 2 .
  • the infused concrete can also exhibit up to a three to four times increase in compressive strength, flexural strength and durability along with a 50-100% increase in the modulus of elasticity.
  • the high reactivity and functional group tolerance of the preferred metathesis catalysts allow for polymerization within the porous structures of a wide variety of porous materials. These catalysts are effective at relatively low loading in resins, they operate at relatively low temperature, and are tolerant of reactive molecules surface absorbed in the porous structure and reactive functional groups on such surfaces, as well as such reactive functional groups in the resin materials.
  • the initiation and polymerization rates of the cyclic olefin monomers may be controlled over a wide range by judicious choice of the chemical structure of the preferred metathesis catalyst and/or the use of rate-modifying additives as is well known in the art.
  • the low viscosity of the preferred cyclic olefin resin formulations facilitates the infusion of the porous materials.
  • DCPD has a much lower resin viscosity than other polymeric starting materials such as epoxy resins.
  • the low viscosity of DCPD resins allows for a greater degree of infusion into porous and microporous structures characteristic of porous materials such as wood.
  • ROMP catalysts together with the low viscosity of the DCPD resin allows the resins to cure without the extreme temperatures and pressures required for other polymers derived from phenols, polyesters, epoxies, resorcinols or ureas that can cause breakdown of the porous material structure, especially for sensitive organic substrates such as wood.
  • polymers derived from metathesis polymerization of cyclic olefin monomers are stable to hydrolysis and are insoluble in polar organic solvents and therefore yield infused products that are stable to leaching and polymer decomposition.
  • the preferred resins are also compatible with and will accommodate a variety of additional additives and fillers to impart additional properties to the infused composites.
  • the resulting infused composites are generally tougher, harder, more dense, and more rigid than the starting porous substrate alone.
  • less expensive softer woods are, therefore, able to replace more expensive harder woods in various applications such as sporting equipment, tool handles, furniture, flooring, railings, window frames, stairs, decking, etc; and marine applications such as boats, piers and pilings.
  • Such infused and treated wood will be resistant to the uptake of water and resistant to rot and insect damage. The surface wear characteristics will be greatly improved for such applications.
  • compositions exhibit unique properties of the composite for the portion of the material that is infused, while the shape of the final product is determined by that of the starting free-standing object.
  • the invention allows for a wide variety of infused products to be manufactured without the use of complex molds.
  • the polyolefin-infused compositions of the invention are useful in the production of a variety of products in the areas of sports and recreation equipment, marine infrastructure, and construction and consumer goods where enhanced mechanical performance, durability, and/or moisture-resistance are required.
  • sports and recreation products and applications include, but are not limited to, the following: golf tees, clubs (including weighted club heads), shafts, and gradient shafts (where the formulation or density varies along the length of the club shaft); basketball backboards; tennis rackets, squash rackets, racquetball rackets, and badminton racquets; snow boards, surfboards, boogie boards, skis, backboards, sleds, toboggans; baseball and cricket bats; hockey sticks; pool cues; archery bows and arrows; rifle butts; polo and croquet mallets; and tent stakes.
  • Examples of marine infrastructure applications include, but are not limited to, the following: piers, docks, posts, decking, hulls, oars, propellers, rudders, keels, masts, boat fascia, kayaks, canoes, and ferro-cement boats.
  • Examples of construction and consumer goods applications include, but are not limited to, the following: hand-tool handles, knife handles, ladders, wood flooring panels, deck lumber, treated concrete or cinder blocks, door and window frames, office furniture, concrete bridge decks, parking structure ramps, post-tensional beams and slabs, treated concrete pipes and channel liners for aggressive and acidic fluids, sewer pipes, containment structures, pavers, stone consolidation (e.g., James R. Clifton, National Bureau of Standards, Technical Note 1118, May 1980, Government Documents C 13.46:1118), plaster or concrete ornamental objects, and other pre-cast concrete objects.
  • stone consolidation e.g., James R. Clifton, National Bureau of Standards, Technical Note 1118, May 1980
  • porous materials infused with ROMP polymers to provide new composites with improved physical properties include unglazed sintered ceramics of all types including but not limited to ceramic magnets, superconducting ceramic materials, ceramic capacitors, and capacitors from reconstituted mica paper.
  • Various open cell plastic foams including but not limited to those derived from polyurethane, provide new compositions with a wide variety of applications.
  • Graphite foams with continuous porous structures have a variety of novel applications as heat sinks and in thermal management technology. This material has the thermal conductivity of aluminum with approximately 20% of its weight.
  • applications of graphite foam are limited by the inherently brittle and friable nature of this material and corresponding incidental damage in use. Infusing ROMP polymers into graphite foam provide an effective means to ruggedize the structures and objects as formed and to yield new composites.
  • a variety of processing techniques may be utilized to prepare the resin-infused composites of the present invention.
  • highly porous materials it may be sufficient to place the porous substrate in a container and simply pour in the formulated resin.
  • medium-porosity materials a simple dipping or soaking process may be feasible.
  • pressure or a combination of vacuum and pressure may be required to get the formulated resin to completely permeate the porous substrate. This may be accomplished by variations of standard processing techniques such as resin-transfer molding (RTM) or vacuum-assisted RTM (VARTM or SCRIMP@, Seemann Composite Resin Infusion Molding Process).
  • a mold or container such mold may be constructed of various materials including, for example, aluminum, teflon, delrin, high- and low-density polyethylenes (HDPE and LDPE, respectively), silicone, epoxy, aluminum-filled epoxy, polyurethane and aluminum-filled polyurethane, plaster, polyvinylchloride (PVC), and various alloys of stainless steel.
  • the mold temperature is preferably about 20-150° C., more preferably about 30-100° C., and most preferably about 40-60° C.
  • the infused part or article of the invention may also be subjected to a post-cure heating step.
  • the post-cure involves heating to about 60-200° C. for about 10 minutes-3 hours. More preferably, the post-cure involves heating to about 80-160° C. for about 30 minutes-2 hours and, and most preferably, heating to about 140° C. for about 1 hour.
  • the progress of the infusion may be determined and/or controlled by monitoring the weight of the substrate.
  • Pressure alone may be effective in the infusion of microporous substrates if their internal structure and/or the infusion methodology is such that any gas displaced by the infused resin can escape rather than becoming pressurized. If pressurization occurs, then the typically low-viscosity (at least before they are cured) cyclic olefin resin formulations may be at least partially expelled from the pores of the substrate upon the release of the externally applied pressure due to the backpressure exerted by the compressed gasses trapped within the pores.
  • porous substrates may require chemical or mechanical pretreatment prior to the resin infusion process.
  • the pores of pre-shaped (e.g., machined) wood billets tend to be at least partially clogged by sawdust and other particulate impurities that hinder the ingress of resin during infusion.
  • Careful mechanical cleaning of the surface of such wood billets with a wire brush has been found to be an effective, albeit labor intensive, pretreatment process.
  • a high-pressure water spray treatment which may clean and wet an object, followed by careful drying serves as an excellent pretreatment method for wood substrates.
  • this methodology more deeply opens the pores of water-swellable substrates such as wood due to both the mechanical cleaning action of the impinging water droplets at the surface of the substrate as well as the bulk expansion and contraction of the substrate during the overall wetting and drying process.
  • This methodology also has the advantages that it is amenable to automation and that adhesion or coupling agents, that will facilitate chemical bonding between the resin and substrate, can be easily incorporated into the water treatment rather than as a separate step.
  • a mixture comprising 100 grams of Ultrene®-99 dicyclopentadiene (BF Goodrich), 3.0 grams of Ethanox®-702 (Albemarle) primary antioxidant, 0.10 grams of triphenylphosphine inhibitor, 1.0 grams of Ferro PDI® Type 34 blue colorant (to enable improved visualization of the extent of infusion of the resin into the wood grain), and 0.11 grams of (PCp 3 ) 2 Cl 2 Ru ⁇ CH—CH ⁇ CMe 2 metathesis catalyst was prepared and poured into a cylindrical mold. The temperature of the resin and mold was 21° C. A low-grade white ash dowel (1A), as described in Example 1 was placed into the mold. The mold was sealed and pressurized to 60 psi for one hour.
  • the pressure was released and the dowel removed from the mold and heated in an oven at 60° C. for eight hours to cure the resin. After curing, the surface of the dowel was lightly sanded to remove excess resin. The sanded dowel was then post-cured in an oven for one hour at 140° C. The density of the dowel increased from 40.77 pcf to 45.95 pcf due to the infused resin.
  • a mixture comprising 500 grams of Ultrene®-99 dicyclopentadiene (BF Goodrich), 15 grams of Ethanox®-702 (Albemarle) primary antioxidant, 0.5 grams of triphenylphosphine inhibitor, 5.0 grams of Ferro PDI® Type 34 blue colorant (to enable improved visualization of the extent of infusion of the resin into the wood grain), and 0.55 grams of (PCp 3 ) 2 Cl 2 Ru ⁇ CH—CH ⁇ CMe 2 metathesis catalyst was prepared and poured into a cylindrical mold. The temperature of the resin and mold was 20° C. A low-grade white ash dowel (IC), as described in Example 1 was placed into the mold.
  • IC white ash dowel
  • the mold was sealed, evacuated to degas the resin and the pores of the dowel, and then pressurized to 60 psi for one hour.
  • the pressure was released and the dowel removed from the mold and heated in an oven at 60° C. for 6.5 hours to cure the resin.
  • the dowel was then post-cured in an oven for one hour at 140° C.
  • the density of the dowel increased from 40.96 pcf to 49.72 pcf due to the infused resin.
  • the stiffness of the treated wood also increased as evidenced by the decrease in the measured deflection from 0.013 inches before treatment to 0.011 inches after treatment.
  • a mixture comprising 100 grams of Ultrene®-99 dicyclopentadiene (BF Goodrich), 3 grams of Ethanox®-702 (Albemarle) primary antioxidant, 0.1 grams of triphenylphosphine inhibitor, 1 gram of Ferro PDI® Type 34 blue colorant (to enable improved visualization of the extent of infusion of the resin into the wood grain), and 0.11 grams of (PCp 3 ) 2 Cl 2 Ru ⁇ CH—CH ⁇ CMe 2 metathesis catalyst was prepared and poured into a cylindrical mold. The temperature of the resin and mold was 22° C. A low-grade white ash dowel (40A), as described in Example 1 was placed into the mold.
  • the mold was sealed, evacuated to degas the resin and the pores of the dowel, and then pressurized to 60 psi for seven hours.
  • the pressure was released and the dowel removed from the mold and heated in an oven at 60° C. for eight hours to cure the resin.
  • the dowel was then post-cured in an oven for one hour at 140° C.
  • the density of the dowel increased from 37.55 pcf to 45.90 pcf due to the infused resin.
  • the stiffness of the treated wood also increased as evidenced by the decrease in the measured deflection from 0.026 inches before treatment to 0.013 inches after treatment.
  • a DCPD resin formulation comprising approximately 3.5% of trimeric CPD isomers along with smaller amounts of higher oligomers was prepared by blending 44 grams of Ultrene®-99 DCPD with 6 grams of CM15T (heat-treated DCPD containing approximately 29% trimeric CPD and smaller amounts of higher oligomers obtained from BF Goodrich), 1.5 grams of Ethanox®-702 (Albemarle) primary antioxidant, 0.05 grams of triphenylphosphine inhibitor, 0.518 grams of Ferro PDI® Type 34 blue colorant (to enable improved visualization of the extent of infusion of the resin into the wood grain), and 0.062 grams of (PCp 3 ) 2 Cl 2 Ru ⁇ CH—CH ⁇ CMe 2 metathesis catalyst.
  • Example 3 The stiffness and impact resistance of the DCPD-infused white ash dowels of Example 3-Example 6 were measured as described in Example 1. The data are summarized in Table 3, compared with untreated samples 1B and 40B from Example 1, and demonstrate the increased impact performance of the infused wood. TABLE 3 Sample Example Max. Impact Total Impact Number Number Level (ft ⁇ lb) Energy (ft ⁇ lb) 1A Example 3 36 249 1B Example 1 32 114 1C Example 4 40 406 40A Example 5 36 429 40B Example 1 14 42 40C Example 6 42 513
  • the adhesion between resin and wood can be measured using a 1′′ long wood dowel (1.125′′ diameter) with a 1 ⁇ 2′′ diameter hole drilled down through its center.
  • the specimen can be optionally conditioned before the desired resin formulation is poured into the bore and cured into place.
  • the adhesion between the wood and the resin is then evaluated by determining the force required to push the cast resin plug out of the bore.
  • a baseline DCPD resin formulation comprising approximately 3.5% of trimeric CPD isomers along with smaller amounts of higher oligomers was prepared by blending 1,759 grams of Ultrene®-99 DCPD with 241 grams of CM15T (heat-treated DCPD containing approximately 29% trimeric CPD and smaller amounts of higher oligomers obtained from BF Goodrich).
  • Example 8 Five white ash wood specimens as described in Example 8 were soaked in a solution of 2 phr allyltriethoxysilane (Gelest) in 0.6 millimolar aqueous acetic acid for 20 minutes. The specimens were then dried for 3 hours at 60° C. in an oven. The resin mixture of Example 8 was poured into the bore and cured for 1 hour at 40° C. to form a solid plug within the wood dowel. After 5 hours, the specimens were post-cured at 140° C. for 1 hour. Results for these specimens averaged 2,721 ⁇ 176 psi.
  • Gelst 2 phr allyltriethoxysilane
  • Example 8 Two white ash wood specimens as described in Example 8 were soaked in a solution of 0.6 millimolar aqueous acetic acid for 20 minutes. The specimens were then dried for 3 hours at 60° C. in an oven. The resin mixture of Example 8 was poured into the bore and cured for 1 hour at 40° C. to form a solid plug within the wood dowel. After 5 hours, the specimens were post-cured at 140° C. for 1 hour. Results for these specimens averaged 2,593 ⁇ 11 psi.
  • Example 8 Five white ash wood specimens described in Example 8 were soaked in deionized water for 20 minutes. The specimens were then dried for 3 hours at 60° C. in an oven. The resin mixture of Example 8 was poured into the bore and cured for 1 hour at 40° C. to form a solid plug within the wood dowel. Results for these specimens averaged 2,606 ⁇ 193 psi.
  • Example 8 Two white ash wood specimens as described in Example 8 were soaked in 50% isopropanol for 20 minutes. The specimens were then dried for 3 hours at 60° C. in an oven. The resin mixture of Example 8 was poured into the bore and cured for 1 hour at 40° C. to form a solid plug within the wood dowel. Results for these specimens averaged 2,526 ⁇ 44 psi.
  • Example 8 Two white ash wood specimens as described in Example 8 were soaked in a solution of 0.2 grams of mono-methyl-cis-5-norbornene-endo-2,3-dicarboxylate (Sigma-Aldrich) in 10 grams of 50% isopropanol for 20 minutes. The specimens were then dried for 3 hours at 60° C. in an oven. The resin mixture of Example 8 was poured into the bore and cured for 1 hour at 40° C. to form a solid plug within the wood dowel. Results for these specimens averaged 2,308 ⁇ 184 psi.
  • Example 8 Specimens as described in Example 8 were prepared using low-grade white ash wood dowels, within the density range indicated in Example 14, wherein the resin mixture was modified by the addition of 1 phr of various titanate and zirconate coupling agents available from Kenrich Petrochemicals, Inc.
  • Chart 3 summarizes the results obtained for variations in infusion time. All of these experiments were performed using net-shape bats with 60-psi infusion pressure. Data for high-density (e.g., over 800 grams) and low-density (e.g., under 800 grams) bats were analyzed separately. The data suggest that infusion occurs fairly quickly, likely aided by the very low viscosity of the DCPD resins, although somewhat higher resin loadings might be attained with extended infusion times.
  • Pre-shaped wood baseball bat blanks, with a cupped end, of minor grade white ash were weighed and then subjected to a high-pressure water spray treatment with ordinary municipal tap water under pressure of approximately 50 PSI across the bat from the knob to the handle to the barrel of the bat, as the bat was manually turned in order to completely cover the long axis and along the grain of the bat for approximately 30 seconds.
  • the cupped end of the bat barrel and the knob end of the bat and across the grain of the wood were given particular attention with approximately 15 seconds of wash.
  • This water spray treatment appeared to mechanically remove loose material, sand or saw dust and to open the end grain of the wood.
  • the weight of the bat blanks before the water treatment varied from approximately 700 to 800 grams and from approximately 725 to 825 grams after the water wash.
  • each bat was then allowed to air dry for approximately 24 hours at ambient temperature and humidity during which the weight of the bat dropped to a range of approximately 710 to 810 grams.
  • the bats were then placed into an oven at 60° C. for 30 minutes. The oven temperature was then increased over a five-minute period to 100° C. and maintained there for an additional 60 minutes. After cooling, the bats then weighed near or slightly below the original range of 700-800 grams.
  • a goal of the infusion process is to bring each wood bat up to a weight of 900 grams regardless of the starting weight of the bat.
  • the stepwise process utilizing the equipment as shown in FIG. 1 achieves this goal using a system of two separate metal chambers that are connected by high-pressure flexible tubing.
  • One chamber is used to perform the infusion process (the “Mold”) and the other is used to store the DCPD resin formulation (the “Resin Chamber”).
  • the process allows a variety of DCPD resin formulations to be introduced to the free standing porous wooden bat under vacuum in order to completely coat or cover the bat, followed by raising the pressure of the liquid resin to facilitate its infusion into voids of the wood.
  • wood bat blanks of low-medium grade ash and with a cupped end are weighed and then subjected to a high-pressure water spray treatment as described in Example 18. After complete drying, each bat is then placed into the Mold of cylindrical dimensions sufficient to closely and completely enclose the bat and with a removable end to allow the bat to be placed in the vessel.
  • the Mold is mounted vertically to allow the bat to be completely submerged in resin with the removable end at the top of the cylinder.
  • the removable end of the Mold is equipped with two valves (V 3 and V 4 ) with removable tubing fittings with one to allow the chamber to be placed under vacuum and the other to allow the introduction of a gas under pressure to flush the resin from the chamber.
  • a third pressure fitting and valve (V 2 ) on the bottom of the Mold allows the introduction of DCPD resin formulations from the separate Resin Chamber.
  • the Resin Chamber has a removable top equipped with a dip tube (V 1 ) to allow resin from the bottom of the chamber to be introduced into the bottom of the infusion chamber through a flexible pressure tube. Additional valves (V 5 and V 6 ) are used for applying or venting pressure to the resin chamber.
  • the Resin Chamber may be periodically refilled with freshly mixed DCPD resin formulation through valve V 7 .
  • the mold, containing a bat, and the resin transfer tube are evacuated through valve V 3 , with valve V 2 open and valves V 1 and V 4 closed, with a mechanical pump to approximately 10 ⁇ 3 atmospheres, which results in removal of air from the pores of the wood.
  • the vacuum valve V 3 is then closed, and the weighing mechanism is tared.
  • the Mold is then completely backfilled with resin from the Resin Chamber by opening valves V 1 and V 5 .
  • the infusion pressure is controlled by the pressure of the inlet gas at valve V 5 and is usually 55 psi or more to promote the infusion of the formulated DCPD resin into the porous structure of the wood.
  • the total weight of the mold is continuously monitored until the uptake of resin is sufficient to bring the total weight of each bat up to a weight of 900 grams. This can be easily calculated for each bat if the Mold volume and the bat volume and weight are known. The time that this can take typically varies from as short as 10 seconds to as long as 7 minutes.
  • valves V 2 and V 5 are closed and the pressure is released from the Resin Chamber by opening pressure release valve V 6 .
  • the excess DCPD resin in the mold is then flushed back into the resin chamber by opening valves V 2 and V 4 .
  • Valves V 1 and V 4 and then Valves V 2 and V 6 are closed.
  • the Mold is then opened, the infused bat is removed to a curing oven, and the next bat is placed into the Mold so that the cycle can be repeated. If required, additional DCPD resin formulation can also be added to the Resin Chamber at this time.
  • the resin curing process is promoted by placing the infused bat in an oven at 60° C. for 30 minutes, followed by 2 hours at room temperature, and then a final post-cure at 140° C. for 1 hour. After cooling back to room temperature, the bat is then ready for finishing to a commercial product by a final sanding, painting and/or the addition of graphics, and application of a polyurethane top-coat for UV protection and improved appearance.
  • untreated high-grade baseball bats would typically be expected to exhibit approximately 200-250 hits to failure while low-grade or medium-grade bats would typically fail after fewer hits.
  • the infused bats typically exhibit greater durability (usually greater than 300 hits-to-failure) than comparable untreated bats and allow a much lower grade of wood to perform as well or better than untreated bats made of high-grade wood.
  • One of the unexpected features of the DCPD-infused wood is its greater surface “toughness” or its ability to resist denting, compared to untreated wood. Since surface denting is a significant contributor to the failure of wooden bats, increased surface hardness is desirable feature.
  • Chart 5 shows the depth of dents measured in both untreated and DCPD-infused baseball bats relative to the number of hits sustained. These measurements were done with a baseball impinging at 136 miles per hour, 5 inches from the barrel end and with the wood grain parallel to the point of impact. The data demonstrate the significant resistance to denting by the infused wood.
  • the mold was sealed and then pressurized to 55 psi. The pressure was released and the infused pieces removed from the mold and allowed to cure overnight at room temperature. The next day, they were post-cured in an oven at 140° C. for one hour. Weight measurements indicated about 10% resin pickup by the concrete block pieces and there was no odor of unpolymerized DCPD. The infused pieces were normal in appearance but exhibited increased hydrophobicity.
  • a dowel was placed into a 1.25′′ ⁇ 1.25′′ ⁇ 18′′ chamber, which was then evacuated to a vacuum of between 25-29 mm Hg (usually about 1 minute). Resin was then backfilled into the chamber and then pressurized to 40-45 psi for 2-3 minutes to fully infuse the specimens. At the end of this cycle, the pressure was released and the resin drained out of the chamber. The specimen was then moved into a oven and cured at 60° C. for 1 hour and then post-cured at 160° C. for an additional hour.
  • the final resin uptake for each specimen is summarized in Table 6.
  • the flexural properties were tested using a specimen of each of the woods by a 3-point bending method and are summarized in Table 7.
  • the compression properties were tested for each piece parallel to the direction of the grain and are summarized in Table 8.
  • the Shore D hardness was measured for a specimen of each wood and is summarized in Table 9.
  • a resin formulation comprising DCPD with 10% trimeric CPD content, 3 phr Ethanox®-702 antioxidant, 0.2 phr triphenylphosophine inhibitor, 1 phr Ken-React® KR 55 organotitanate, and 0.104 phr of (PCp 3 ) 2 Cl 2 Ru ⁇ CH—CH ⁇ CMe 2 metathesis catalyst was applied to pieces of 0.010′′ thick predried cardstock cut into a dogbone shape suitable for tensile testing. The resin appeared to quickly wet into the porous web. The sheet was then cured for 1 hour at 40° C., 2 hours at room temperature, and then post-cured for 1 hour at 140° C.

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  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Ceramic Engineering (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
  • Infusion, Injection, And Reservoir Apparatuses (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
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US20060229374A1 (en) * 2005-04-07 2006-10-12 Je Kyun Lee Microporous polydicyclopendiene-based aerogels
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US20080057288A1 (en) * 2006-08-31 2008-03-06 Sironko Philip T Vacuum-infused fiberglass-reinforced fenestration framing member and method of manufacture
US20080141908A1 (en) * 2006-12-13 2008-06-19 James Hardie International Finance B.V. Engineered composite building materials and methods of making same
US20090048459A1 (en) * 2006-01-10 2009-02-19 Michael John Tupy Method of making hydrogenated metathesis products
US20090054588A1 (en) * 2006-03-10 2009-02-26 Alois Maier Fluoride-modified additive for cementitious products, process for its preparation and use thereof
US20090264672A1 (en) * 2006-10-13 2009-10-22 Elevance Renewable Sciences, Inc. Methods of making organic compounds by metathesis
US20090297711A1 (en) * 2008-05-28 2009-12-03 Air Products And Chemicals, Inc. Process Stability of NBDE Using Substituted Phenol Stabilizers
US20100145086A1 (en) * 2006-10-13 2010-06-10 Elevance Renewable Sciences, Inc. Synthesis of Terminal Alkenes From Internal Alkenes Via Olefin Metathesis
US7780875B2 (en) 2005-01-13 2010-08-24 Cinvention Ag Composite materials containing carbon nanoparticles
US20100261538A1 (en) * 2009-04-10 2010-10-14 Nike, Inc. Golf Club Having Hydrophobic And Hydrophilic Portions
US8067623B2 (en) 2006-07-12 2011-11-29 Elevance Renewable Sciences, Inc. Ring opening cross-metathesis reaction of cyclic olefins with seed oils and the like
US8067610B2 (en) 2006-07-13 2011-11-29 Yann Schrodi Synthesis of terminal alkenes from internal alkenes and ethylene via olefin metathesis
US20110293954A1 (en) * 2010-04-29 2011-12-01 The Regents Of The University Of California Application of high toughness, low viscosity nano-molecular resin for reinforcing pothole patching materials in asphalt and concrete base pavement
US8895771B2 (en) 2006-10-13 2014-11-25 Elevance Renewable Sciences, Inc. Methods of making organic compounds by metathesis and hydrocyanation
US8979679B2 (en) 2011-12-27 2015-03-17 Nike, Inc. Golf ball having hydrophilic and hydrophobic portions
US9156185B2 (en) 2009-04-09 2015-10-13 Kebony Asa Apparatus and operating systems for manufacturing impregnated wood
US9469739B2 (en) 2005-04-07 2016-10-18 Aspen Aerogels, Inc. Microporous polyolefin-based aerogels
US9498830B1 (en) * 2012-08-07 2016-11-22 Rawlings Sporting Goods Company, Inc. Automated boning machine for wooden bats
US9975605B2 (en) 2009-04-23 2018-05-22 Kebony Asa Decking
US10633484B2 (en) * 2014-01-10 2020-04-28 Materia, Inc. Method and composition for improving adhesion of metathesis compositions to substrates
US11135790B2 (en) * 2016-11-21 2021-10-05 Carbon, Inc. Method of making three-dimensional object by delivering reactive component for subsequent cure
WO2021236161A1 (fr) * 2020-05-22 2021-11-25 Halliburton Energy Services, Inc. Composition et procédés d'étanchéité de puits
WO2021242636A1 (fr) 2020-05-29 2021-12-02 Exxonmobil Chemical Patents Inc. Procédés de production d'oléfines cycliques à partir de polymères et leur re-polymérisation
CN113786589A (zh) * 2021-07-05 2021-12-14 厦门理工学院 一种体育用篮球自动清洁消毒装置
US11384324B2 (en) 2015-02-24 2022-07-12 Albrecht Holdings Llc Reconditioned or infused fluid containers and related methods
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US9139605B2 (en) 2006-07-13 2015-09-22 Elevance Renewable Sciences, Inc. Synthesis of terminal alkenes from internal alkenes and ethylene via olefin metathesis
US9255117B2 (en) 2006-07-13 2016-02-09 Materia, Inc. Synthesis of terminal alkenes from internal alkenes and ethylene via olefin metathesis
US8067610B2 (en) 2006-07-13 2011-11-29 Yann Schrodi Synthesis of terminal alkenes from internal alkenes and ethylene via olefin metathesis
US20080023884A1 (en) * 2006-07-18 2008-01-31 Dow Global Technologies Inc. Method for preparing poly(dicyclopentadiene)
US20080053011A1 (en) * 2006-08-31 2008-03-06 Sironko Philip T Vacuum-infused fiberglass-reinforced fenestration framing member and method of manufacture
US7897097B2 (en) 2006-08-31 2011-03-01 Milgard Manufacturing Incorporated Vacuum-infused fiberglass-reinforced fenestration framing member and method of manufacture
US7749424B2 (en) 2006-08-31 2010-07-06 Milgard Manufacturing, Inc. Vacuum-infused fiberglass-reinforced fenestration framing member and method of manufacture
US20080057288A1 (en) * 2006-08-31 2008-03-06 Sironko Philip T Vacuum-infused fiberglass-reinforced fenestration framing member and method of manufacture
US20100145086A1 (en) * 2006-10-13 2010-06-10 Elevance Renewable Sciences, Inc. Synthesis of Terminal Alkenes From Internal Alkenes Via Olefin Metathesis
US9120742B2 (en) 2006-10-13 2015-09-01 Elevance Renewable Sciences, Inc. Methods of making organic compounds by metathesis
US20090264672A1 (en) * 2006-10-13 2009-10-22 Elevance Renewable Sciences, Inc. Methods of making organic compounds by metathesis
US10906861B2 (en) 2006-10-13 2021-02-02 Wilmar Trading Pte Ltd Methods of making organic compounds by metathesis
US8895771B2 (en) 2006-10-13 2014-11-25 Elevance Renewable Sciences, Inc. Methods of making organic compounds by metathesis and hydrocyanation
US8569560B2 (en) 2006-10-13 2013-10-29 Elevance Renewable Sciences, Inc. Synthesis of terminal alkenes from internal alkenes via olefin metathesis
US8501973B2 (en) 2006-10-13 2013-08-06 Elevance Renewable Sciences, Inc. Synthesis of terminal alkenes from internal alkenes via olefin metathesis
US8415009B2 (en) 2006-12-13 2013-04-09 James Hardie Technology Limited Engineered composite building materials and methods of making same
US20080141908A1 (en) * 2006-12-13 2008-06-19 James Hardie International Finance B.V. Engineered composite building materials and methods of making same
US8906500B2 (en) * 2006-12-13 2014-12-09 James Hardie Technology Limited Engineered composite building materials and methods of making same
US8173213B2 (en) * 2008-05-28 2012-05-08 Air Products And Chemicals, Inc. Process stability of NBDE using substituted phenol stabilizers
US20090297711A1 (en) * 2008-05-28 2009-12-03 Air Products And Chemicals, Inc. Process Stability of NBDE Using Substituted Phenol Stabilizers
US9156185B2 (en) 2009-04-09 2015-10-13 Kebony Asa Apparatus and operating systems for manufacturing impregnated wood
US8147352B2 (en) * 2009-04-10 2012-04-03 Nike, Inc. Golf club having hydrophobic and hydrophilic portions
US20100261538A1 (en) * 2009-04-10 2010-10-14 Nike, Inc. Golf Club Having Hydrophobic And Hydrophilic Portions
US8475296B2 (en) 2009-04-10 2013-07-02 Nike, Inc. Golf club having hydrophobic and hydrophilic portions
US9975605B2 (en) 2009-04-23 2018-05-22 Kebony Asa Decking
US9328024B2 (en) * 2010-04-29 2016-05-03 The Regents Of The University Of California Application of high toughness, low viscosity nano-molecular resin for reinforcing pothole patching materials in asphalt and concrete base pavement
US20110293954A1 (en) * 2010-04-29 2011-12-01 The Regents Of The University Of California Application of high toughness, low viscosity nano-molecular resin for reinforcing pothole patching materials in asphalt and concrete base pavement
CN103917500A (zh) * 2011-04-28 2014-07-09 加利福尼亚大学董事会 用于增强性凹坑修补材料的高韧性、低粘度纳米分子的树脂在沥青和混凝土基础路面中的应用
US8979679B2 (en) 2011-12-27 2015-03-17 Nike, Inc. Golf ball having hydrophilic and hydrophobic portions
US9498830B1 (en) * 2012-08-07 2016-11-22 Rawlings Sporting Goods Company, Inc. Automated boning machine for wooden bats
US10633484B2 (en) * 2014-01-10 2020-04-28 Materia, Inc. Method and composition for improving adhesion of metathesis compositions to substrates
US11384324B2 (en) 2015-02-24 2022-07-12 Albrecht Holdings Llc Reconditioned or infused fluid containers and related methods
US11135790B2 (en) * 2016-11-21 2021-10-05 Carbon, Inc. Method of making three-dimensional object by delivering reactive component for subsequent cure
WO2021236161A1 (fr) * 2020-05-22 2021-11-25 Halliburton Energy Services, Inc. Composition et procédés d'étanchéité de puits
US11414587B2 (en) 2020-05-22 2022-08-16 Halliburton Energy Services, Inc. Cycloalkene and transition metal compound catalyst resin for well sealing
WO2021242636A1 (fr) 2020-05-29 2021-12-02 Exxonmobil Chemical Patents Inc. Procédés de production d'oléfines cycliques à partir de polymères et leur re-polymérisation
CN113786589A (zh) * 2021-07-05 2021-12-14 厦门理工学院 一种体育用篮球自动清洁消毒装置
US20230050826A1 (en) * 2021-08-13 2023-02-16 Thomas Alexander MEYER Method and apparatus for producing cannabis smoke resin

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EP1446284A1 (fr) 2004-08-18
WO2003020504A1 (fr) 2003-03-13
CN101338062B (zh) 2012-09-05
DE60229158D1 (de) 2008-11-13
ATE409581T1 (de) 2008-10-15
CA2458904C (fr) 2012-07-17
EP1446284A4 (fr) 2005-12-07
CA2458904A1 (fr) 2003-03-13
EP1446284B1 (fr) 2008-10-01
NZ531455A (en) 2007-06-29
US20060052487A1 (en) 2006-03-09
CN1281405C (zh) 2006-10-25
CN1578726A (zh) 2005-02-09
BR0212392A (pt) 2004-08-17
CN101338062A (zh) 2009-01-07

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