BRPI0216123B1 - COMPOSITION COMPOSING COMPOSITION OF POROUS MATERIAL INFUSED WITH POLYOLEFIN - Google Patents

Description

Report of the Invention Patent for "COMPOSITION UNDERSTANDING POLY-OLEPHINE INFOSED POROUS MATERIAL".

Divided from PI 0212392-4, filed on August 30, 2002.

This patent application claims the benefit of co-pending provisional patent application U.S. 60 / 316,290 filed August 30, 2001, the contents of which are incorporated herein by reference.

Background The invention is generally directed to methods and systems for infusing cyclic olefin resins into self-supporting porous materials, together with ring-opening metathesis polymerization (ROMP) catalysts, to polymerize these olefins into porous materials. to produce specific composite structures and new derivatives.

A wide range of both natural and synthetic materials has 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 modes of origin or may be a deliberate design aspect. Depending on the intended use of a particular material, such porosity may offer advantages such as lower weight, absorbency, breathability or unique conductivity or insulating characteristics. However, for many applications, porosity can also lead to problems such as poor mechanical performance and durability. As a common example, water or moisture routinely enters and exits the pores of porous materials. Apart from affecting the mechanical properties resulting from the material, this moisture often also accelerates chemical and / or mechanical degradation.

Many types of treatments are designed to try to protect and improve the performance of porous materials. Paints and other coatings are often applied for surface protection, but provide little improvement or mechanical performance. Various chemical agents may be impregnated into porous materials such as preservatives, flame retardants, water repellents or biocides, however generally to the detriment of mechanical strength and stiffness. In addition, most of these agents are slowly leached over time, decreasing their efficiency and creating environmental consequences. Polymeric impregnants potentially alleviate some of these consequences, but may be difficult to apply, especially with microporous materials. The viscosities of thermoplastic and even very thermosetting resins are very high, making impregnation and wetting of porous materials very difficult. Low viscosity thermosetting resins, which would be easier to infuse, typically form brittle polymers upon curing. In addition, the chemical properties of thermoset resins may be incompatible with the portions present in the interstices or surfaces of porous materials (porous materials having very large surface areas) and are often susceptible to hydrolysis, thereby limiting their long term durability. .

Low viscosity thermosetting resins, which produce moisture resistant polymers, would appear to be ideal candidates for infusion into porous materials such as mechanical performance enhancers and protectors. Such polymers may be obtained by ring-opening metathesis (ROMP) polymerization of cyclic olefin monomers. The resulting ROMP polymers have non-hydrolysable hydrocarbon backbones and are generally very hard. ROMP, however, typically depends on transition metal catalysts, which are extremely sensitive to air, moisture, and functional groups that may be present in the porous material monomers. Thus, ROMP polymers are not commonly considered as candidate impregnants for porous materials.

Recently, however, certain ruthenium and osmium carbene compounds have been identified as effective catalysts for ROMP, even in the presence of air, water, and most functional groups. Examples of such metathesis catalysts have been described previously in, for example, US Patents 5,312,940, 5,969,170, 5,917,071, 5,977,393, 6,111,121, 6,211,391, 6,225,488 and 6,306,987 and in PCT publications WO 98/39346, WO 99/00396, WO 99/00397, WO 99/28330, WO 99/29701, WO 99/50330, WO 99/51344, WO 00/15339, WO 00/58322, WO 00 / 71554 and WO 02/14376, the descriptions of which are incorporated herein by reference. Surprisingly, these catalysts were then found to provide ROMP of cyclic olefin monomers, which were infused into various porous materials, including, for example, such highly functional materials as concrete and wood.

Brief Description of the Drawings Figure 1 shows a preferred method of infusing DCPD resin baseball bats.

Detailed Description The present invention encompasses novel compositions comprising polymer infused porous materials 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 carbide metathesis catalysts, useful for infusion of porous materials. Another embodiment of the invention includes methods for preparing porous materials infused with cyclic olefin resin formulations. Other embodiments of the present invention are specific composite structures and articles made of porous materials infused with cyclic olefin polymers. Several catalysts have recently been developed for initiation of olefin metathesis reactions, including cyclic olefin ring opening metathesis (ROMP) polymerization, diene ring closure metathesis (ROM) to form closed ring products, acyclic dienes (ADMET), depolymerization of unsaturated polymers to form depolymerized products, synthesis of telequelic polymers by reaction of a cyclic olefin with a functionalized olefin, and synthesis of cyclic olefins by self-metathesis of an acyclic oil or cross-metathesis. two acyclic olefins.

Any suitable metathesis catalyst may be used. Preferred metathesis catalysts include, but are not limited to, neutral ruthenium or osmium carbene complexes, which have metal centers, which are formally in the +2 oxidation state, have an electron count of 16, are pentacoordinated and Other preferred metathesis catalysts include, but are not limited to, cationic ruthenium or osmium carbene complexes, which have metal centers that are formally in the +2 oxidation state, have a count of 14 electrons, are tetracoordinated and are of formula II. Still other preferred metathesis catalysts include, but are not limited to, neutral ruthenium or osmium carbene complexes, which have metal centers that are formally in the +2 oxidation state, have an electron count of 18, are hexacoordinated and are of general formula III. where: M is ruthenium or os; n is an integer between 0 and 5; L, L1 and L2 are independently any neutral electron donor ligand;

R 1 and R 1 are independently hydrogen or any hydrocarbyl or silyl moiety; X and X1 are independently any anionic ligand; Y is any non-coordinating anion;

ZeZ1 are independently any binding agent selected from the group of null, -O-, -S-, -NR2-, -PR2-, -P (= 0) R2-, -P (OR2) -, -P (= 0 ) (0R2) -, -C (= 0) -, -0 (= 0) 0-, -00 (= 0) -, -00 (= 0) 0-, -S (= 0) - or -S (= 0) 2; and wherein any two or more of X, X1, L, L1, L2, Z, Z \ R, R1 and R2 may be joined to form a multidentate ligand and wherein any or more of X, X1, L, L1 L 2, Z, Z 1, R and R 1 may optionally be chemically bonded to a solid or vitreous support.

In preferred embodiments of these catalysts, L, L1 and L2 are 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 formula IV or V: wherein: A is carbon or nitrogen; R3, R4, R5 and R6 are independently hydrogen or any hydrocarbyl moiety, except that where A is nitrogen, R5 is nothing; Z2 and Z3 are independently any binding agent selected from the group of null, -O-, -S-, -NR2-, -PR2-, -P (= 0) R2-, -P (OR2) -, -P ( = 0) (OR2) -, -C (= 0) -, -C (= 0) 0-, -0C (= 0) -, -0C (= 0) 0-, -S (= 0) - or -S (= 0) 2, except that where A is nitrogen, Z3 is null; and Z 2, Z 3, R 4 and R 5 may optionally together form a cyclic moiety optionally substituted by 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 which It consists of hydroxyl, thiol, thioether, ketone, aldehyde, ester, ether, amine, imine, amide, nitro, carboxylic acid, disulfide, carbonate, isocyanate, carbodiimide, carboalkoxy, carbamate and halogen.

In particularly preferred embodiments, L and L1 are each phosphine of formula PR7R8R9, wherein R7, R8 and R9 are independently any moiety of hydrocarbyl, particularly aryl, C1 -C10 primary alkyl, secondary alkyl or cycloalkyl. In especially preferred embodiments, L and Li 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: PCy3, PCp3, P (i-Pr) 3, PBu3 and PPh3, respectively.

In especially preferred embodiments, L is a phosphine and L1 is a nucleophilic carbene of formula III. Preferably, 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 L1 is selected from group consisting of structures VI, VII or VIII (where m is an integer between 0 and 5): Ligand L1 of structure VII is commonly referred to as "I-MES", where m = 3. The saturated variant of structure VI is similarly referred to as "s-IMES" where m = 3.

In other preferred embodiments, L is a phosphine or a nucleophilic carbene of formula IV and L1 and L2 are independently a substituted pyridine or pyridine ligand or L1 and L2 together form a chelating bispyridine or phenanthroline ligand, either of which may be substituted. or unsubstituted.

With respect to R and R1 - R9, examples of hydrocarbyl moieties include, but are not limited to, the group consisting of C1 -C20 alkyl, C3 -C20 cycloalkyl, C2 -C20 alkenyl, C2 -C20 alkynyl, aryl, heteroaryl , aralkyl or arylalkyl. Examples of silyl moieties include, but are not limited to, the group consisting of tri (hydrocarbyl) silyl, tri (hydrocarbyloxy) silyl or mixed (hydrocarbyl) (hydrocarbyloxy) silyl. Optionally, each of the substituent groups of R, R1 or R2 may be substituted by one or more hydrocarbyl or silyl moieties, which may in turn be substituted by one or more groups selected from a halogen, a C1 -C5 alkyl, C1 -C5 alkoxy and phenyl. Furthermore, any of the catalyst ligands may further include one or more functional groups. Examples of 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, carbodiimidate, carboalkoxy carbamate and halogen. Further, any of R, R1 and R2 may be joined to form a bridged or cyclic structure.

In preferred embodiments of such catalysts, the substituent R1 is hydrogen and the substituent R1 is selected from the group consisting of C1 -C20 alkyl, C2 -C20 alkenyl, aryl, alkaryl, aralkyl, trialkylsilyl and trialkoxysilyl. In particularly preferred embodiments, n is 0, 1 or 2 and the substituent R 1 is phenyl, tert-butyl or vinyl, optionally substituted by 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. In especially preferred embodiments, n is 0 or 1 and R 1 is phenyl, tert-butyl or vinyl substituted by one or more moieties selected from the group consisting of chloride, bromide, iodide, fluoride, -NO 2 -, -NMe 2, methyl, methoxy and phenyl.

In preferred embodiments of these catalysts, X and X 1 are 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 alkyl dicetonate, aryldiketonate, C 1 -C 20 carboxylate, arylsulfonate, C1 -C20 alkylsulfonate, C1 -C20 alkylthiol, arylthiol, C1 -C20 alkylsulfonyl or C1 -C20 alkylsulfinyl. Optionally, X and X1 may be substituted by one or more selected portions of the group consisting of C1 - C10 alkyl, C1 - C10 alkoxy and aryl which may in turn be further substituted by one or more selected halogen groups, C1 - C10. C5 alkyl, C1 -C5 alkoxy and phenyl. In particularly preferred embodiments, 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, arylthiol, aryl and C 1 -C 5 alkylsulfonate. In more particularly preferred embodiments, each of X and X1 is halide, CF3 CO2, CH3 CO2, CFH2 CO2, (CH3) 3 CO, (CF3) 3 CO, (CF3) 2 (CH3) CO, (CF3) (CH3) 2 CO, PhO, MeO, EtO, tosylate, mesylate or trifluoromethanesulfonate. In especially preferred embodiments, each of X and X1 is chloride, bromide or iodide. Furthermore, X and X1 may together comprise a bidentate ligand. Y may be derived from any tetracoordinate boron compound or any hexacoordinated phosphorus compound. Preferred boron compounds include BF4 ', BPh4' and fluorinated derivatives of BPh4. Preferred phosphorus compounds include PF'6 and P0'4. The non-coordinating anion can also be one of the following: CI04 ', S04', N03 ', OTeF5', F3CS03 ', H3CS03', CF3COO ", PhS03 'or (CH3) C6H5S03'. Y can also be derived from char- boranes, fullerides or aluminoxanes The catalyst: olefin monomer ratio in the invention is preferably from about 1: 5 to about 1: 1,000,000, particularly the catalyst: olefin ratio is from about 1: 100 to about especially from about 1: 1,000 to about 1: 30,000. Particularly preferred metal catalysts include, but are not limited to: (PCy3) 2CI2Ru = CHPh, (PCy3) 2CI2Ru = CH-CH = CMe2, (PCy3) 2Cl2Ru = C = CHCMe3, (PCy3) 2Cl2Ru = C = CHSiMe3, (PCy3) (s-IMES) CI2Ru = CH-CH = CMe2, (PCp3) 2CI2Ru = CH-CH = CMe2, (PCp3 ) 2CI2Ru = C = CHPh, (PCp3) (s-IMES) CI2Ru = CH-CH = CMe2, (PPh3) (s-IMES) CI2Ru = C-CHCMe3, (PPh3) 2CI2Ru = C = CHSiMe3, (P (- iPr) 3) 2Cl2Ru = C = CHPh, (PPh3) (s-IMES) CI2Ru = C = CHSiMe3, (PBu3) 2CI2Ru = C = CHPh, (PPh3) (s-IMES) CI2Ru = CH-CH = CMe2, ( PCy3) (s-IMES) CI2Ru = C = CHPh, (PCp3) (s- IMES) CI2Ru = C = CHPh, (PBu3) (s-IMES) CI2Ru = C = CHPh, (PCy3) (s-IMES) CI2Ru = CHPh, (PBu3) (s-IMES) CI2Ru = CH-CH = CMe2, (PCy3) (IMES) CI2Ru = C = CHPh, (PPh3) 2CI2Ru = C = CHCMe3, (PCy3) (IMES) CI2Ru = C = CHCMe3, (PCp3) CI2Ru = CH-CH = CMe2, (PBu3) (IMES) CI2Ru = C = CHPh, (s-IMES) (C5H5N) CI2Ru = CHPh and (s-IMES) (3-Br-C5H4N) CI2Ru = CH-CH = CMe2.

Resins of the inventive formulations include any olefin monomer and metathesis catalyst. Olefin monomers may be used alone or mixed together in various combinations to adjust the properties of the olefin monomer composition. For example, cyclopentadiene oligomer blends offer a low melting point and produce cured olefin copolymers with greater mechanical strength and stiffness than pure poly-DCPD. As another example, incorporation of COD, norbornene or alkyl and norbornene comonomers tends to produce cured olefin copolymers that are relatively soft and rubbery. The polyolefin resins of the invention are receptive to heat curing and are tolerant to various additives, stabilizers, speed modifiers, hardness and / or stiffness modifiers, viscosity modifiers, adhesion or coupling agents and fillers.

Any suitable cyclic olefin monomer may be used with the present invention. Within the scope of this invention, the olefin infusion monomers include at least one of all "firm" cycloolefins described in US 6,001,909 and at least one of all cycloolefins described in US 5,840,238 and US 5,922,802 and at least least one of all Diels-Alder adducts described in US 6,100,323. The particularly preferred olefin monomer for use in the invention is dicyclopentadiene (DCPD). Various suppliers and purity of DCPD can be used such as Lyondell 108 (94.6% purity), Velsicol UHP (99% purity), Cy-metech Ultrene® (97% and 99% purity) and Hitachi ( equal purity 99 +%).

High purity grades of DCPD, such as Ultrene® 99, are preferred. In certain preferred formulations, the DCPD resin may optionally contain other cyclopentadiene oligomers, including trimers, trimers, pentamers and the like. Such oligomers may be introduced into DCPD by heat treatment of DCPD, as described in U.S. Patent 4,899,005 to Lane (et al.) And U.S. Patent 4,751,337 to Espy (et al.). Oligomer content may be controlled by varying heat treatment conditions or by combining oligomer mixtures of known compositions with DCPD until the desired oligomer concentration is obtained. Advantages of using these oligomer mixtures include a lower melting point of the monomer mixture and higher mechanical properties and glass transition temperature of the cured resin.

Other preferred olefin monomers include cyclooctadiene (COD; DuPont), cyclooctene (COE), cyclohexenylnorbornene; norbornene, norbornene dicarboxylic anhydride (noic anhydride); norbornadiene (Elf Ato-chem) and substituted norbornenes including ethylidene norbornene (ENB), butyl norbornene, hexyl norbornene, octyl norbornene, decyl norbornene and the like. Preferably, the olefin moieties include mono- or disubstituted olefins and cycloolefins containing from 3 to 200 carbon atoms. Particularly, the olefinic active moieties for metathesis include cyclic or multicyclic olefins, for example cyclopropenes, cyclubutenes, cycloepenes, cycloocenes, [2.2.1] bicycloepenes, [2.2.2] bicycloocenes, benzocyclobenenes, cyclopentenes; cyclopentadiene oligomers including trimers, tetramers, pentamers and the like; and cyclohexenes. It is also to be understood that such compositions include structures in which one or more 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 wherein one or more carbon atoms have been replaced by, for example, silicon, oxygen, sulfur, nitrogen, phosphorus, antimony or boron. For example, the olefin may be substituted with one or more groups such as thiol, thioether, keto, aldehyde, ester, ether, amine, amide, nitro, carboxylic acid, disulfide, carbonate, isocyanate, phosphate, phosphite , sulphate, sulphite, sulphonyl, carbodiimide, carboalkoxy, carbamate, halogen or pseudohalogen. Similarly, the olefin may be substituted by one or more groups, such as C1 -C20 alkyl, aryl, acyl, C1 -C20 alkoxide, aryloxide, C3 -C20 alkylhydricetonate, arylthio tonate, C1 -C20 carboxylate, aryl sulfonate , C1 -C20 alkylsulfonate, C1 -C20 alkylthio, arylthio, C1 -C20 alkylsulfonyl, and C1 -C20 alkylsulfinyl, C1 -C20 alkylphosphate and arylphosphate, wherein the moiety may be substituted or unsubstituted.

In the invention, the viscosity of formulated olefin monomers (e.g., olefin monomers combined with any additives, stabilizers or modifiers other than density, filler or fiber modulators) is typically less than about 500 centipoise at temperatures close to room temperature (e.g., about 25 to 35 ° C). Preferably, the viscosity of the formulated olefin monomers is less than about 200 centipoises, particularly less than about 75 centipoises and especially less than about 50 centipoises. In many circumstances, the viscosity is less than 25 centipoises to promote easy infusion. The viscosity of formulated olefin monomers can be controlled by selecting the combination of monomers and additives, stabilizers and modifiers used. The viscosity of the formulated resin may be increased or decreased by temperature variation or by the use of additives such as thixotropes, thickeners or diluents.

Preferred hardness modulators include, for example, elastomeric additives such as polybutadienes, polyisoprenes and the like. Polybutadienes and polyisoprenes from various sources, as well as various number average molecular weight (Mn) or weight average molecular weight (Mw), may be used in the invention as rubber-shaped hardness modulators. Unexpectedly, the poly-DCPD resins of the invention provide polybutadiene-containing compositions 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 unmodified or native polyolefin. In addition to butadiene and isoprene elastomers, other hardness modulators include plasticizers such as dioctyl phthalate and hydrocarbons of various molecular weights and the like, gelatins, greases and waxes, carboxylic acids and their salts, and comonomers such as norbornene, cyclooctadiene , cyclooctene, cyclohexenylnorbornene, nor-bornadiene, cyclopentene and / or methylcyclopentene. The proportion of hardness modulator included in the polyolefin compositions of the invention is preferably about 0.1% to 20% by weight of the olefin monomer to which it is added. Particularly, the hardness modulator ratio is about 1 to 10% by weight of the olefin monomer and especially about 2.5 to 7.5%.

Especially preferred toughness modulators are triblock rubber copolymers such as styrene-butadiene-styrene, styrene-isoprene-styrene, styrene-ethylene / butylene-styrene, styrene-ethylene / propylene-styrene and the like. An example of such toughness modulators is Kraton® commercially available polymers. Other preferred toughness modulators include polysiloxanes, because the resulting polyolefin compositions have significantly higher toughness properties, without significant concomitant thermal distortion temperature (HDT) losses. The proportion of toughness modulator included in the polyolefin compositions of the invention is preferably about 0.1-10% by weight of olefin monomer to which it is added. Particularly, the toughness modulator ratio is about 0.5 to 6% by weight of the olefin monomer, and particularly it is about 2% to 4%. For example, poly-DCPD resins containing 3 parts percent low molecular weight (MW) polydimethylsiloxane (Shin Etsu DMF-50) have notched Izod impact values greater than 21.8 (cm - kg) / cm [ 4 ft. / Inches] and HDT values above 130 ° C. Hardness and toughness modulators are further described in PCT publication WO 99/60030, the contents of which are incorporated herein by reference.

UV and oxidation resistances of the polyolefin compositions of the invention can be optimized by the addition of various stabilizing additives such as primary antioxidants (e.g. sterically hindered phenols), secondary antioxidants (e.g. organophosphites, thioesters and light stabilizers (for example, hindered amine light stabilizers or HALS) and UV light absorbers (for example hydroxybenzophenone absorbers, hydroxyphenylbenzotriazole absorbers and the like). Preferably, one or more stabilizing additives are included in the polyolefin resin composition at a level of about 0.01 - 15 phr. In particular, the antioxidant (s) is present at a level of about 0.05 to 10 phr, and more particularly 0.1-8 phr. Exemplary primary antioxidants include, for example, 4,4'-methylenebis (2,6-di-tert-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 tetracis (3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate) (Irganox® 1010®; Ciba-Geigy). Exemplary secondary antioxidants include phosphite of tris (2,4-di-tert-butylphenyl) (Irgafos® 168; Ciba-Geigy), 1:11 (3,6,9-trioxaudecyl) bis (dodecylthio) propionate (Wingstay® SN-1; Goodyear) Light stabilizers and light absorbers include bis (1,2,2,6,6-pentamethyl-4-piperidinyl) - [[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl ] methyljbutylmalonate (Tinuvin® 144 HALS; Ciba-Geigy), 2- (2H-benzotriazol-2-yl) -4,6-di-tert-pentylphenol (Tinuvin® 328 absorbent; Ciba-Geigy), 2,4-di -tert-butyl-6- (5-chlorob enzotriazol-2-yl) phenyl (Tinuvin® 327 absorbent; Ciba-Geigy), 2-hydroxy-4- (octyloxy) benzophenone (Chimassorb® 81 absorbent; Ciba-Geigy) and the like. UV and oxidation resistances of polyolefin compositions are further discussed in PCT publication WO 00/46256, the contents of which are incorporated herein by reference.

In addition, a suitable speed modifier, such as, for example triphenylphosphine (TPP), tricyclopentylphosphine, tricyclohexylphosphine, triisopropylphosphine, trialkylphosphites, mixed phosphites or other Lewis base, may be added to the olefin retarder monomer. or accelerate the polymerization rate if necessary. In the case of a TPP speed modifier, it is preferably included in a ratio of about 10 - 200 mg per 64 g of olefin monomer. Particularly, the ratio of TPP is around 20- 100 mg per 64 g olefin monomer and especially it is around 30 - 80 mg per 64 mg olefin monomer. In the case of other velocity modifiers, such as alkylphosphine and pyridine, the rate of velocity modifier is preferably about 0.1 - 50 mg per 64 g of olefin monomer, particularly about 1 - 40. mg per 64 g olefin monomer and especially is around 1 - 30 mg per 64 mg olefin monomer. A detailed description of the speed modifiers can be seen in U.S. Patent 5,939,504 and U.S. Patent Application 09 / 130,586, the contents of which are incorporated herein by reference.

Also, 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 a ratio of about 0.05 - 2 percent parts of polyolefin resin. The cyclic olefin resin formulation may also contain coupling agents or adhesives which promote bonding between the substrate walls and the infused resin. U.S. Patent Nos. 6,040,363 and 6,001,909, the disclosures of which are incorporated herein by reference, describe various sizing or coupling agents useful with cyclic olefin resin formulations. Especially preferred coupling agents are the metathesis active adhesives described in International Patent Application WO 00/46257, the contents of which are incorporated herein by reference, and organotitanates and organozirconates, such as Ken-React® products available from Kenrich Petrochemicals. Especially preferred organotitanates and organozirconates are those containing olefin groups, which 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) phosphite titanate (Ken-React® KR 55), tetra (2,2-diallyloxymethyl) butyl di (ditridecyl) phosphite zenconate (Ken -React® KZ 55) and cyclo [dineopentyl (diallyl)] dioneopentyl (diallyl) zirconate pyrophosphate (Ken-React® KZ TPP). Especially preferred active adhesives for metathesis are olefin-containing silanes such as allyl trimethoxysilane, butenyltriethoxysilane, hexenyltriethoxysilane, octenyltriethoxysilane, norbornenyltriethoxysilane, norbornenylethyltriethoxysilane and the like.

A wide range of porous materials may be used in the present invention as long as these materials are prior to the depolymerized cyclic olefin resin formulation and do not contain certain chemical groups that are incompatible with the olefin metathesis catalyst. Such porous materials include, but are not limited to, wood, cement, concrete, open and crosslinked cell foams and sponges, paper, cardboard, felt, string or braided natural or synthetic fibers, and various sintered materials. Preferred non-organic materials include non-vitrified porous ceramics, compacted self-supporting metal powder objects and porous concrete aggregates such as slag 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, particle board, and chipboard objects and products. Especially preferred porous materials are the various types of wood.

Portland cement or concrete has an open pore structure that is woven and interconnected. A particular form of cement called Optimized Porosity Cement (EPC) uses little or no sand and has a void volume of 20-25%. The significantly porous structure of all cements and related materials provides for the ready diffusion of air, other gases and water vapor. This porous structure also facilitates moisture migration and water soaking. These 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 the rusting of embedded steel reinforcement materials, which expand by oxidation and promote the formation of very thin fractures and cracks. Acid rain surface water and saline water in marine applications present a particularly difficult and corrosive physical medium for concrete use. These problems are alleviated by the use of infused composites of the present invention. Catalyzed cyclic olefin monomer formulations effectively infuse the pore structure, fractures and cracks of concrete and related materials to provide chemically stable ROMP polymers, which provide a barrier to water, water vapor and dissolved salts, as well as less permeability to corrosive gases such as NOx and SO2. Infused concrete can also show up to three to fourfold increase in compressive strength, flexural strength and durability, along with a 50 - 100% increase in modulus of elasticity. These aspects, together with lower water permeability, greatly optimize durability to freeze and thaw cycles.

In the practice of the present invention, the high reactivity and functional group tolerance of the preferred metathesis catalysts enables polymerization within the porous structures of a wide range of porous materials. These catalysts are effective at a relatively low resin loading, operate at a relatively low temperature, and are tolerant to reactive molecules absorbed superficially in the porous structure and to reactive functional groups on these surfaces, as well as to these functional groups in resin materials. The initiation and polymerization rates of cyclic olefin monomers can be controlled over a wide range by carefully selecting the chemical structure of the preferred metathesis catalyst and / or using rate modifying additives, as is well known in the art.

In the practice of the present invention, the low viscosity of preferred cyclic olefin resin formulations facilitates infusion of porous material. For example, 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 the porous and microporous structures characteristic of powdery materials such as wood. The high reactivity of ROMP catalysts, coupled with the low viscosity of the DCPD resin, allows resins to cure without the extreme temperatures and pressures required for other phenol, polyester, epoxy, resorcinol or urea derived polymers, which may cause structure decomposition. porous material, especially for sensitive organic substrates such as wood. Unlike many other resinous materials, polymers derived from cyclic olefin monomer polymerization are stable to hydrolysis and are insoluble in polar organic solvents and thus produce infused products which are stable to leaching and decomposition. of the polymer. Preferred resins are also compatible with, and will accommodate, a variety of additives and additional fillers to impart additional properties to the infused composites.

The resulting infused composites are generally tougher, harder, denser and stiffer than the starting porous substrate alone. For example, in the case of wood, more economical softer woods are therefore able to replace more expensive hardwoods in various applications such as sports equipment, tool handles, furniture, floors, rails, window frames, steps, platforms, etc .; and marine applications such as boats, breakwaters and piling. This treated and infused wood will be water resistant and resistant to rot and insect damage. Surface wear characteristics will generally be improved for these applications. In applications where an optimal level of water absorbed within the wood must be maintained to prevent further wood drying and cracking, suitably stable ROMP catalysts and resins are available for use within wood with varying proportions of water absorbed to stabilize the wood against loss of this water.

The resulting compositions exhibit unique properties of the composite for the portion of material that is infused, while the shape of the final product is determined by that of the starting self-sustaining object. Thus, the invention enables a wide range 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 various products in the areas of sports and recreational equipment, marine infrastructure and construction articles and for the consumer for which optimal mechanical performance, durability and / or moisture resistance. is required. Examples of sporting and recreational products include, but are not limited to, the following: golf clubs, golf clubs, clubs (including weighted club heads), graded axes and axles (when formulation or density varies over time). club shaft length); basketball tables; tennis rackets, squash rackets, racketball rackets and badminton rackets; snowboards, surfboards, boogie boards, skis, support boards, sledges, slides; baseball and cricket bats; hockey sticks; pool cues; bows and arrows for bow equipment; rifle tips; polo and croque clubs; and tent pegs. Examples of marine infrastructure applications include, but are not limited to, the following: breakwaters, docks, decks, hulls, oars, thrusters, rudders, keels, masts, sides of boats, kayaks, canoes, and boats. ferrocement. Examples of construction and consumer goods applications include, but are not limited to, the following: hand tool handles, knife handles, ladders, wood floor panels, platform construction timbers, treated concrete or slag, door and window frames, office furniture, concrete bridge decks, parking frame ramps, post-beam beams and plates, treated pipe linings and concrete channels for aggressive and acidic fluids, sewage pipes , retaining structures, paving agents, stone consolidation (eg, James R. Clifton, "National Bureau of Standards", Technical Note 1118, May 1980, Government Documents C 13.46: 1118), stucco or concrete ornamental objects and other precast concrete objects.

Other ROMP polymer infused porous materials, to provide novel 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 mica capacitors. and paper. Various open cell plastic foams, including, but not limited to, those derived from polyurethane, provide novel compositions with a wide range of applications. Graphite foams with continuous porous structures have a variety of new applications, such as thermal outlets, and in thermal control technology. This material has the thermal conductivity of aluminum at approximately 20% of its weight. However, graphite foam applications are limited by the inherently brittle and friable nature of this material and corresponding incidental damage in use. The infusion of ROMP polymers in graphite foam provides an effective means of reinforcing structures and objects as formed and producing new composites. Various processing techniques, depending on the nature of the porous substrate and cyclic olefin resin formulation, may be used to prepare the resin infused composites of the present invention. For highly porous materials, it may be sufficient to place the porous substrate in a container and simply pour the formulated resin. For medium porosity materials, a simple soaking or soaking process may be feasible. For low porosity or microporous materials, pressure or a combination of pressure and vacuum may be required to obtain the formulated resin to completely permeate the porous substrate. This can be done by variations of the usual processing techniques such as resin transfer molding (RTM) or vacuum assisted RTM (VARTM or SCRIMP®, Seemann Composite Resin Infusion Molding Process). If a mold or container is required, that mold may be constructed of various materials including, for example, aluminum, teflon, delrin and high and low density polyethylenes (HDPE and LDPE, respectively), silicone, epoxy, epoxy charged. aluminum, polyurethane and polyurethane with aluminum filler, stucco, polyvinyl chloride (PVC) and various stainless steel alloys. The temperature of the mold is preferably around 20 - 150 ° C, particularly around 30 - 100 ° C and especially around 40 - 60 ° C. The infused part or article of the invention may also be subjected to a post-cure heating step. Preferably, post curing involves heating at about 60 - 200 ° C for about 10 minutes - 3 hours. Particularly, post curing involves heating around 80 - 160 ° C for about 30 minutes - 2 hours and especially heating around 140 ° C for about 1 hour.

In the case of microporous substrates, such as wood or concrete, the use of a vacuum / pressure process is preferred to obtain good infusion with the cyclic olefin resin formulation. The vacuum process helps remove air and water vapor from the pores of the substrate. After evacuation of the substrate, the resin formulation is applied and pulled into the empty pores. Applying moderate pressure (typically between about 34.47 and 1,379 kPa (5 to 200 psi) and preferably between about 275.8 to 413.7 kPa (40 - 60 psi) helps the resin to The time required to fully infuse the particular article may vary widely, based on the shape and pore structure of the article and the viscosity of the resin formulation, but will typically range from about 30 seconds to The progress of infusion can be determined and / or controlled by monitoring the weight of the substrate. Pressure alone can be effective in infusing microporous substrates if their internal structures and / or infusion technology are such that any gas displaced by the infused resin may escape rather than pressurize.If pressurization occurs, then typically low viscosity cyclic olefin resin formulations (at least before they are cured) may be at least partially and expelled from the pores of the substrate by releasing externally applied pressure due to the counter-pressure exerted by the compressed gases trapped within the pores.

Certain porous substrates may require chemical or mechanical pretreatment prior to the resin infusion process. For example, the pores of precast (e.g. machined) wood dowels tend to be at least partially blocked by sawdust and other particulate impurities that prevent resin from entering during infusion. Careful mechanical cleaning of the surface of these wooden billets with a wire brush has been found to be effective, although a labor intensive pretreatment process. Surprisingly, it has been found that a high pressure water spray treatment that can clean and wet an object followed by careful drying serves as an excellent pretreatment method for wood substrates. While not wishing to be bound by theory, it is believed that this methodology opens the pores of water-expandable substrates, such as wood, more deeply because of both the mechanical cleaning action of water droplets that collide on the substrate surface, as well as the expansion and contraction of substrate mass during the overall wetting and drying process. This methodology has the advantages that it is prone to automation and that adhesion or coupling agents, which will facilitate chemical bonding between the resin and the substrate, can be easily incorporated into the water treatment rather than as a separate step.

The following examples are illustrative of the invention and it should be understood that the invention is not limited to the described embodiments, but that various modifications and substitutions may be made therein, as will be apparent to those skilled in the art.

Examples Example 1 Stiffness and impact resistance of low grade white ash Several 7,62 cm (3 inch) diameters of low grade northern white ash (grain spacing <0.158 cm - 1/16 inch) were turned 1/8-inch (2.86 cm) diameter billets and cut to lengths of 10- to 12-inch (25.4 - 30.5 cm) (three per billet, marked A - C). The rigidity of each specimen was measured by centering the billet on a pair of support rods spaced 22.8 centimeters (9 inches) apart. A load of 22.7 kilograms (50 pounds) was applied to the center of the billet, in the radial direction of the grain, and billet deflection was measured. The impact strength of each billet was determined by centering it on the same 9-inch (22.86 cm) support and dropping a heavy impactor of increasing weights until sample failure was observed. Impact resistance is recorded as the maximum impact level and the sum of all impacts obtained to failure. Data for the various samples are recorded in Table 1.

Table 1 ______________________________________________________________ * pcf = pounds per cubic foot Example 2 Stiffness and impact resistance of medium grade white ash Two billets of 7.62 cm (3 inch) diameter of mid grade northern white ash (grain spacing <0.317 cm - 1/8 inches) were turned to 2.86 cm (1 1/8 inch) diameter billets and cut to lengths of 25.4 - 30.5 cm (10 - 12 inches) (three per billet marked A - C). The stiffness and impact strength of each specimen were measured as in Example 1. Data for the various samples are recorded in Table 2. Medium grade wood has consistently density, stiffness (eg lower deflection) and impact strength. higher than low grade wood.

Table 2 ________________________________________________________ Example 3 Pressure Treatment of White Ash with DCPD Resin

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 blue PDI® Iron dye Type 34 (to allow improved visualization of the degree of resin infusion in the wood grain) and 0.11 grams of metathesis catalyst (PCp3) 2Cl2Ru = CH-CH = CMe2 was prepared and poured into a cylindrical mold. The resin and mold temperature was 21 ° C. A low grade ash billet (1A) as described in Example 1 was placed in the mold. The mold was sealed and pressurized at 413.7 kPa (60 psi) for one hour. The pressure was relieved and the billet removed from the mold and heated in an oven at 60 ° C for eight hours to cure the resin. After curing, the billet surface was lightly sanded to remove excess resin. The sanded billet was then post-cured in a kiln for one hour at 140 ° C. Billet density increased from 0.6531 to 0.7361 g / cm3 (40.77 pcf to 45.95 pcf) due to the infused resin.

Example 4 Vacuum / Pressure Treatment of White Ash with DCPD Resin

A mixture comprising 500 grams Ultrene®-99 dicyclopentadiene (BF Goodrich), 15 grams Ethanox® 702 primary antioxidant (Albemarle), 0.5 grams triphenylphosphine inhibitor, 5.0 grams Iron PDI® Type 34 blue dye ( to allow improved visualization of the degree of resin infusion in the wood grain) and 0.55 grams of metathesis catalyst (PCp3) 2Cl2Ru = CH-CH = CMe2 was prepared and poured into a cylindrical mold. The resin and mold temperature was 20 ° C. A low grade ash billet (1C) as described in Example 1 was placed in the mold. The mold was sealed, evacuated to degass the resin and billet pores, and then pressurized to 413.7 kPa (60 psi) for one hour. The pressure was relieved and the billet removed from the mold and heated in an oven at 60 ° C for 6.5 hours to cure the resin. After lightly sanding to remove excess resin, the billet was then post-cured in an oven for one hour at 140 ° C. Billet density increased from 0.6562 to 0.7965 g / cm3 (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 deflection measured from 0.0330 centimeter (0.013 inch) before treatment to 0.0279 centimeter (0.011 inch) after treatment.

Example 5 Vacuum / modified pressure treatment of white ash with DCPD resin

A mixture comprising 100 grams of Ultrene®-99 dicyclopentadiene (BF Goodrich), 3 grams of Ethanox® 702 primary antioxidant (Albemarle), 0.1 grams of triphenylphosphine inhibitor, 1.0 grams of Iron PDI® Type 34 blue dye ( to allow improved visualization of the degree of resin infusion in the wood grain) and 0.11 grams of metathesis catalyst (PCp3) 2Cl2Ru = CH-CH = CMe2 was prepared and poured into a cylindrical mold. The resin and mold temperature was 22 ° C. A low grade ash billet (1C) as described in Example 1 was placed in the mold. The mold was sealed, evacuated to degass the resin and billet pores, and then pressurized to 413.7 kPa (60 psi) for seven hours. The pressure was relieved and the billet removed from the mold and heated in an oven at 60 ° C for eight hours to cure the resin. After lightly sanding to remove excess resin, the billet was then post-cured in an oven for one hour at 140 ° C. Billet density increased from 0.6015 to 0.7353 g / cm3 (37.55 pcf to 45.90 pcf) due to the infused resin. The stiffness of treated wood also increased, as evidenced by the decrease in deflection measured from 0.0165 centimeter (0.026 inch) before treatment to 0.033 centimeter (0.013 inch) after treatment.

Example 6 White Ash Pressure Treatment with Modified DCPD Resin A DCPD resin formulation comprising approximately 3.5% trimeric CPD isomers, together with lower higher oligomer proportions, was prepared by mixing 44 grams of Ultrene®. -99 DCPD with 6 grams CM15T (heat treated DCPD containing approximately 29% trimeric CPD and lower proportions of higher oligomers obtained from BF Goodrich), 1.5 grams Ethanox®-702 primary antioxidant (Albermarle) 0.05 grams of triphenylphosphine inhibitor, 0.518 grams of Iron PDI® Type 34 blue dye (to allow improved visualization of the degree of resin infusion in the wood grain) and 0.062 grams of metathesis catalyst (PCp3) 2CI2Ru = CH-CH = CMe2. Thirty grams of this formulation was poured into a cylindrical mold. The resin and mold temperature was 20 ° C. A low grade white ash billet (40C) as described in Example 1 was placed in the mold. The 2.54 cm (1 inch) top of the billet was not submerged in the resin. The mold was sealed and then pressurized at 413.7 kPa (60 psi) for seven hours. The pressure was relieved and the billet removed from the mold and heated in an oven at 140 ° C for one hour to cure / post-cure the resin. Billet density increased from 0.6139 to 0.6883 g / cm3 (38.32 pcf to 42.97 pcf) due to the infused resin. The portion of the billet that was not submerged in the resin appeared to contain less resin than the rest of the billet.

Example 7 Impact Strength of DCPD-Infused White Ash The stiffness and impact resistance of DCPD-infused white ash billets from Example 3 - Example 6 were measured as described in Example 1. The data are summarized in Table 3, compared to the untreated samples 1B and 40B of Example 1 and demonstrate the highest impact performance of the infused wood.

Table 3 _______________i_________________________________________i Example 8 Test for measuring wood adhesion - resin The adhesion between resin and wood using a 2.54 cm (1 inch) long wood billet (2.86 cm - 1.125 inch diameter) with a 1.27 centimeter (0.5 inch) diameter hole drilled through its center. The specimen may optionally be conditioned before the desired resin formulation is poured into the hole and cured in place. The adhesion between wood and resin is then assessed by determining the force required to push the resin plug out of the hole. A baseline DCPD resin formulation comprising approximately 3.5% trimeric CPD isomers along with lower higher oligomer ratios was prepared by mixing 1.759 grams of Ultrene®-99 DCPD with 241 grams of CM15T (DCPD). heat treated containing approximately 29% trimeric CPD and lower proportions of higher oligomers obtained from BF Goodrich). Shortly before specimen fabrication, appropriate amounts of the baseline resin were removed and mixed with 3 phr Ethanox®-702 (Albermarle), 0.10 phr triphenylphosphine moderator and 0.11 phr metathesis catalyst (PCp3 ) 2Cl 2 Ru = CH-CH = CMe 2. This mixture was poured into the hole and cured for 1 hour at 40 ° C to form a solid plug within the wood billet. After 5 hours, the specimens were post-cured at 140 ° C for 1 hour. Results for a series of 32 specimens of white ash wood and the 3.5% trimer / DCPD baseline resin averaged 5.57 ± 1.01 MPa (808 ± 147 psi).

Example 9 Wood silane treatment to improve wood-resin adhesion Five white ash wood specimens as described in Example 8 were soaked in a 2 phr solution of allyltriethoxysilane (Gelest) in aqueous acetic acid solution 0.6 millimolar 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 hole and cured for 1 hour at 40 ° C to form a solid plug within the wood billet. After 5 hours, the specimens were post-cured at 140 ° C for 1 hour. Results for these specimens averaged 18.76 ± 1.21 MPa (2,721 ± 176 psi).

Example 10 Treatment with Wood Acetic Acid to Improve Wood-Resin Adhesion Two specimens of white ash wood as described in Example 8 were soaked in a 0.6 millimolar aqueous acetic acid solution 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 hole and cured for 1 hour at 40 ° C to form a solid plug within the wood billet. After 5 hours, the specimens were post-cured at 140 ° C for 1 hour. Results for these specimens averaged 17.88 ± 0.07 MPa (2,593 ± 11 psi).

Example 11 Wood Water Treatment to Improve Wood-Resin Adhesion 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 hole and cured for 1 hour at 40 ° C to form a solid plug within the wood billet. Results for these specimens averaged 17.97 ± 1.33 MPa (2,606 ± 193 psi). Example 12 Treatment with aqueous wood isopropanol to improve wood-resin adhesion Two specimens of white ash wood 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 hole and cured for 1 hour at 40 ° C to form a solid plug within the wood billet. Results for these specimens averaged 17.42 ± 0.303 MPa (2.526 ± 44 psi). Example 13 Treatment of wood norbornene to improve wood-resin adhesion Two specimens of white ash wood as described in Example 8 were soaked in a solution of 0.2 gram monomethyl-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 hole and cured for 1 hour at 40 ° C to form a solid plug within the wood billet. Results for these specimens averaged 15.91 ± 1.27 MPa (2,308 ± 184 psi).

Example 14 Dependence of wood - resin adhesion on wood density Two specimens from each of the nine different low density white ash billets, ranging in density from 0.6408 to 0.6327 g / cm3 (35.3 to 39.5 pcf) were prepared as in Example 8. The results of the adhesion test with this series averaged 4.95 ± 1.47 MPa (718 ± 213 psi). As can be seen in Graph 1, there is little dependence on the adhesion result in wood density, by this density range.

Graph 1 Example 15 Effect of coupling additives on adhesion of white ash-resin wood Specimens, as described in Example 8, were prepared using low grade white ash wood billets 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. The evaluated coupling agents included isopropyl triisostearoyl titanate (Ken-React® KR TTS); tetraoctyl (ditridecyl) phosphite titanate (Ken-React® KR 46B), diallyloxineopentyl tri (N-ethylenediaminoethyl) titanate (Ken-React® Ll-CA 38), tetra (2,2-diallyloxymethyl) di (ditridecyl) phosphite titanate ) butyl (Ken-React® KZ 55) and tetra (2,2-diallyloxymethyl) butyl di (ditridecyl) phosphite zirconate (Ken-React® KZ 55). Three specimens were prepared and tested using each of the additives and the results are summarized in Table 4. Additives KR 55 and KZ 55, with metathesis reactive allyl groups, significantly increased wood - resin adhesion. The LICA 38 additive, although also containing metathesis-reactive allyl groups, also gave poor results, presumably due to the presence of the basic amine groups, which may poison the metathesis catalysts.

Example 16 Wood adhesion - resin with white ash, pine and poplar Specimens, as described in Example 8, were prepared using pine and poplar together with white ash. Both the standard resin formulation and the modified formulation containing 0.5 phr Ken-React® KR 55 coupling agent were used. The results are summarized in Table 5 and show that these woods behave similarly to white ash.

Table 5____________________________________________________________________ Example 17 DCPD Resin Retention by White Ash Baseball Bats Resin retention for a series of ten net-shaped white ash bats is shown in Graph 2. While covering results involving many different parameter variations, The data seem to suggest that less resin can be infused into higher density wood. Although not entirely unexpected, it seems perhaps to be a preferred weight for infused wood (around 1,000 grams - a bit heavy for stick application), suggesting that it may be possible to refine a wide range of wood densities to a density of more consistent end product.

Graph 2 Graph 3 summarizes the results obtained for variations in infusion time. All of these experiments were conducted using mesh rods with a uniform infusion pressure of 413.7 kPa (60 psi). Data for rods of high density (eg above 800 grams) and low density (eg below 800 grams) were analyzed separately. The data suggest that infusion occurs fairly rapidly, as aided by the very low viscosity of DCPD resins, although slightly higher resin loads may be achieved with extended infusion times.

Graph 3 Example 18 Method of pre-infused spray-washing of baseball bats Models of preformed small-grade white-gray wooden baseball bats were weighed and then subjected to surface treatment. spraying high pressure water with tap water, under a pressure of approximately 344.7 kPa (50 psi) by the rod from the protrusion into the cable to the rod drum, as the rod was rotated manually to completely cover the long axis and along the shaft of the rod for approximately 30 seconds. The cup-shaped end of the baton drum and the end of the protrusion and the wood shaft received special attention with approximately 15 seconds of washing. This water spray treatment appeared to mechanically remove loose material, sand or sawdust and open the wood end shaft. The weight of stick models prior to water treatment ranged from approximately 700 to 800 grams and approximately 725 to 825 grams after water washing. Each stick was then allowed to air dry for approximately 24 hours at ambient temperature and humidity, during which the weight of the stick fell to a range of approximately 710 to 810 grams. To complete the drying process, the sticks were then placed in an oven at 60 ° C for 30 minutes. The oven temperature was then increased for a period of five minutes at 100 ° C and held there for an additional 60 minutes. After cooling, the rods were weighed to be close to or slightly below the original 700 - 800 gram range.

Example 19 DCPD Resin Baseball Bats Infusion Method

One goal of the infusion process is to place each wooden staff at a weight of 900 grams, regardless of the starting weight of the staff. The step-by-step process using the equipment as shown in Figure 1 achieves this goal by using a system of two separate metal chambers, which are connected by flexible high pressure tubing. One chamber is used to conduct the infusion process (the "Mold") and the other is used to store the DCPD resin formulation (the "Resin Chamber"). The process enables a variety of DCPD resin formulations to be introduced into vacuum self-supporting porous wooden rods to completely coat or cover the rod, followed by increased pressure of the liquid resin to facilitate infusion into the voids. of wood.

In a typical example, the mid-grade, single-ended, ash-shaped wooden rod models are weighed and then subjected to a high pressure water spray treatment as described in Example 18. After complete drying, each rod is then placed in the cylindrical mold, sufficiently to close the rod completely and completely and with a removable end to allow the rod to be placed in the container. The Mold is mounted vertically to allow the rod to be completely submerged in the resin with the removable end at the top of the cylinder. The removable end of the Mold is equipped with two valves (V3 and V4) with removable pipe fittings in one to allow the chamber to be placed under vacuum and the other to allow the introduction of a pressurized gas to discharge chamber resin. A third pressure fitting and valve (V2) at the bottom of the Mold allows the introduction of separate Resin Chamber DCPD resin formulations. The Resin Chamber has a removable end portion equipped with a dip tube (V1) to allow resin from the bottom of the chamber to be introduced into the bottom of the infusion chamber by means of a flexible pressure tube. Additional valves (V5 and V6) are used to apply or discharge pressure to the resin chamber. The Resin Chamber can be periodically refilled with freshly mixed DCPD resin formulation by valve V7.

In the infusion process, the rod-containing mold and resin transfer tube are evacuated by valve V3, with valve V2 open and valves V1 and V4 closed, with a mechanical pump at approximately 101.3 Pa (10 '3 atmospheres), which results in the removal of air from the pores of the wood. The vacuum valve V3 is then closed and the weighing mechanism is tared. The mold is then completely refilled with resin from the resin chamber by opening valves V1 and V5. The infusion pressure is controlled by the inlet gas pressure at valve V5 and is usually equal to or greater than 379.2 kPa (55 psi) to promote infusion of the formulated DCPD resin into the porous structure of the wood. The total weight of the mold is continuously monitored until the resin retention is sufficient to place the weight of each stick at a weight of 900 grams. This can be easily calculated for each rod if the volume of the Mold and the volume and weight of the rod are known. The time this can take typically ranges from as short as 10 seconds to as long as 7 minutes. Once the desired amount of resin has been introduced into the Mold, valves V2 and V5 are closed and pressure is relieved from the Resin Chamber by opening the pressure release valve V6. After a slight delay, excess DCPD resin in the mold is then reinjected into the resin chamber by opening valves V2 and V4. Once all excess resin has been returned to the Resin Chamber, Valves V1 and V4 and then Valves V2 and V6 are closed. The mold is then opened, the infused rod is removed to a curing oven, and the next rod is placed in the mold so that the cycle can be repeated. If necessary, further DCPD resin formulation may also be added to the Resin Chamber at this time. The resin cure process is promoted by placing the infused rod in a 60 ° C oven 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 stick is then ready for finishing in a commercial product by final sanding, painting and / or adding illustrations, and applying a polyurethane topcoat for UV protection and improved appearance.

Example 20 Durability of DCPD Infused Wooden Baseball Bats

A sample of precast but unfinished wooden sticks was obtained and classified in three degrees according to the number of grains counted on the overhang. Long time experience with baseball bats indicates that lower grain counts correspond to greater durability. Therefore, high grade canes had grain counts around 16 or less, medium grade canes had grain counts around 17 to 28 and low grade canes had grain counts around 29 or more. Half of the sticks were usually finished with a polyurethane topcoat, while the other half was infused with DCPD resin, as described in Example 19. Figure 4 shows the number of "hits to failure" for these non-stick wood sticks. treated and infused with DCPD in relation to grain count. Of course, there is considerable natural variation within the wood, but untreated high grade baseball bats were expected to deliver approximately 200 - 250 strokes to failure, while low or medium grade bats would typically fail after a few hits. Infused sticks would typically have a longer durability (usually greater than 300 hits to failure) than comparable untreated sticks and would allow a much lower grade of wood to perform as well or better than untreated sticks. high grade wood.

Graph 4 Example 21 Notch Resistance of DCPD Infused Wooden Baseball Bats

One of the unexpected aspects of DCPD-infused wood is its greater surface "toughness" or its ability to resist notching compared to untreated wood. Since surface grooving is a significant contributor to the failure of wooden rods, increased surface hardness is a desirable aspect. Graph 5 shows the thickness of the notches measured on both untreated and DCPD-infused baseball bats in relation to the number of strikes sustained. These measurements were made with a baseball colliding at 217.2 kilometers per hour (136 miles per hour), 12.7 centimeters (5 inches) from the end of the drum and with the wood grains parallel to the point of impact. The data demonstrate the significant notch resistance of the infused wood.

Example 5 Infusion of a Porous Concrete Block A DCPD resin formulation comprising approximately 3.5% trimeric CPD isomers, together with lower proportions of higher oligomers, was prepared by combining a 88/12 mixture of Ultrene®-99 and CM15T DCPD (heat treated DCPD containing approximately 29% trimeric CPD and lower proportions of higher oligomers obtained from BF Goodrich) with 3 phr primary antioxidant Ethanox®-702 (Albermale), 0.1 phr inhibitor triphenylphosphine and 0.124 phr metathesis catalyst (PCp3) 2 Cl 2 R 2 = CH-CH = CMe 2. The resin mixture was poured onto small pieces of porous concrete block in a mold. The mold was sealed and then pressurized to 379.2 kPa (55 psi). The pressure was relieved 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 retention by the concrete block pieces and there was no depolymerized DCPD odor. The infused pieces were normal in appearance but had a higher hydrophobicity.

Example 23 Properties of DCPD Infused Wood

Samples of birch, cherry, North American conifer, maple, poplar, red oak, southern yellow pine, and white ash woods were cut into rectangular 1 "x 2.54" x 30.48 cm (1 ") billets. x 1 "x 12"). The cut samples were washed using pressurized tap water (620.5 kPa - 90 psi) for 1 minute and then air dried for 48 hours at room temperature (20 - 24 ° C). The specimens were then split in a vacuum oven for 48 hours at room temperature and then for a further 48 hours at 40 ° C. The weight of each billet after this treatment ranged from 4 - 6% less than its weight. Once removed from the mold, the samples were kept under static vacuum at room temperature until infused.For infusion, a billet was placed in a 1.17 cm x 3.17 cm x 45.72 cm (1 cm) chamber. , 25 "x 1.25" x 18 "), which was then evacuated at a vacuum between 3.33 - 3.86 kPa (25 - 29 mm Hg) (usually about 1 minute). The resin was then refilled in the chamber and then pressurized at 275.8 - 310.3 kPa (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 from the chamber. The specimen was then moved to a greenhouse and cured at 60 ° C for 1 hour and then post-cured at 160 ° C for an additional hour. Four variations were tested for each type of wood: (a) a control that was washed and dried but not infused; (b) a baseline resin formulation comprising DCPD with a 10% trimeric CPD content, 3 phr Ethanox®-702 antioxidant, 0.2 phr triphenylphosphine inhibitor and 0.104 phr metathesis catalyst (PCp3) 2Cl 2 Ru = CH-CH = CMe 2; (c) a modified resin formulation comprising DCPD with a 10% trimeric CPD content, 3 phr Ethanox®-702 antioxidant, 0.2 phr triphenylphosphine inhibitor, 1 phr Ken-React® KR 55 organotitanate and 0.104 metathesis catalyst phr (PCp3) 2 Cl 2 Ru = CH-CH = CMe 2; and (d) a modified resin formulation comprising DCPD with a 10% trimeric CPD content, 3 phr Ethanox®-702 antioxidant, 0.2 phr triphenylphosphine inhibitor, 1 phr Ken-React® KR 55 organotitanate and 0.104 phr metathesis catalyst (PCp3) 2Cl 2 Ru = CH-CH = CMe 2. The final resin retention for each specimen is summarized in Table 6. Bending properties were tested using a specimen from 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 grain direction and are summarized in Table 8. Shore D hardness was measured for one specimen of each wood and is summarized in Table 9. Table 6 Table 8 Compressive strength (MPa, psi) for infused wood Table 9 Shore A Hardness for Infused Wood Example 24 Properties of DCPD Infused Cardboard

A resin formulation comprising DCPD with a 10% trimeric CPD content, 3 phr Ethanox®-702 antioxidant, 0.2 phr triphenylphosphine inhibitor, 1 phr Ken-React® KR 55 organotitanate and 0.104 phr Metathesis (PCp3) 2Cl2Ru = CH-CH = CMe2 was applied to 0.010 inch thick pre-dried pieces of cardboard cut into a dog bone shape suitable for tensile testing. The resin appeared to wet the porous tissue rapidly. 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. Using this methodology, a series of 6 specimens seized an average of 3.37 ± 0.54% resin. Dry but untreated cardboard had the following tensile properties: 41.1 MPa (5,979 psi) tensile strength, 2,162.2 MPa (313,597 psi) tensile modulus and 3.60% rupture deformation. The treated cardboard had the following improved tensile properties: 45.9 MPa (6,663 psi) tensile strength, 2,468 MPa (375,936 psi) tensile modulus and 3.20% rupture deformation.

Claims (10)

Composition, characterized in that it comprises a porous material infused with a metathesis derived polyolefin. Composition according to Claim 1, characterized in that it further comprises a coupling agent. Composition according to Claim 2, characterized in that the coupling agent is selected from the group consisting of organotitanates, organozirconates and silanes. Composition according to Claim 1, characterized in that the porous material is selected from the group consisting of a non-organic material and an organic material. Composition according to Claim 1, characterized in that the porous material is selected from the group consisting of wood, cement, concrete, open and cross-linked foam and sponge, paper, cardboard, felt, string and braided material. natural or synthetic fibers, sintered materials, non-vetrified porous ceramics, self-supporting metal objects and powders, compacted porous concrete aggregates, wood, wood products and cellulosic materials. Composition according to Claim 1, characterized in that the metathesis-derived polyolefin is selected from the group consisting of a ROMP polymer and an ADMET polymer. Composition according to Claim 1, characterized in that the metathesis-derived polyolefin is selected from the group consisting of norbornenes, cyclopropenes, cyclobutenes, benzocyclobutenes, cyclopentenes, cyclopentadiene oligomers, cyclohexenes, cycloepenes, cycloocenes, cyclooctadienes, norbornadienes, [2.2.1] bicycloeptenes and [2.2.2] bicyclooctene, cyclohexenylnorbornenes and norbornene dicarboxylic anhydrides. Composition according to Claim 1, characterized in that the metathesis-derived polyolefin is polydicyclopentadiene. Composition according to Claim 1, characterized in that the metathesis-derived polyolefin is polymerized using a ruthenium or osmium metal carbene catalyst. Composition according to Claim 1, characterized in that the metathesis-derived polyolefin is polymerized using a catalyst selected from the group consisting of a catalyst of formula:. 9 a catalyst of formula: a catalyst of formula: 9 a catalyst of formula: a catalyst of formula: and a catalyst of formula: wherein: M is ruthenium or osmium; n is an integer between 0 and 5; L, L1 and L2 are independently any neutral electron donor binder; ReR1 are independently hydrogen or any hydrocarbyl or silyl moiety; X and X1 are independently any anionic ligand; Y is any non-coordinating anion; and ZeZ1 are independently any binding agent selected from the group consisting of -O-, -S-, -NR2-, -PR2-, -P (= O) R2-, -P (OR2) -, -P ( = 0) (0R2) -, -C (= 0) -, -C (= 0) 0-, -0C (= 0) -, -0C (= 0) 0-, -S (= 0) -or -S (= 0) 2.