EP1088000A1 - Compositions de polyolefine a resistance et/ou durete variable - Google Patents

Compositions de polyolefine a resistance et/ou durete variable

Info

Publication number
EP1088000A1
EP1088000A1 EP99923165A EP99923165A EP1088000A1 EP 1088000 A1 EP1088000 A1 EP 1088000A1 EP 99923165 A EP99923165 A EP 99923165A EP 99923165 A EP99923165 A EP 99923165A EP 1088000 A1 EP1088000 A1 EP 1088000A1
Authority
EP
European Patent Office
Prior art keywords
solution
mold
resin
mixture
approximately
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP99923165A
Other languages
German (de)
English (en)
Other versions
EP1088000A4 (fr
Inventor
Michael A. Giardello
Jonathan G. Lasch
Christopher J. Cruce
Jessie G. Macleod
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Materia Inc
Original Assignee
Materia Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Materia Inc filed Critical Materia Inc
Publication of EP1088000A1 publication Critical patent/EP1088000A1/fr
Publication of EP1088000A4 publication Critical patent/EP1088000A4/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • 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
    • C08K5/13—Phenols; Phenolates
    • A—HUMAN NECESSITIES
    • A63—SPORTS; GAMES; AMUSEMENTS
    • A63B—APPARATUS FOR PHYSICAL TRAINING, GYMNASTICS, SWIMMING, CLIMBING, OR FENCING; BALL GAMES; TRAINING EQUIPMENT
    • A63B60/00—Details or accessories of golf clubs, bats, rackets or the like
    • A—HUMAN NECESSITIES
    • A63—SPORTS; GAMES; AMUSEMENTS
    • A63B—APPARATUS FOR PHYSICAL TRAINING, GYMNASTICS, SWIMMING, CLIMBING, OR FENCING; BALL GAMES; TRAINING EQUIPMENT
    • A63B53/00—Golf clubs
    • A63B53/04—Heads
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G61/02—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes
    • C08G61/04—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms
    • C08G61/06—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms prepared by ring-opening of carbocyclic compounds
    • C08G61/08—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms prepared by ring-opening of carbocyclic compounds of carbocyclic compounds containing one or more carbon-to-carbon double bonds in the ring
    • A—HUMAN NECESSITIES
    • A63—SPORTS; GAMES; AMUSEMENTS
    • A63B—APPARATUS FOR PHYSICAL TRAINING, GYMNASTICS, SWIMMING, CLIMBING, OR FENCING; BALL GAMES; TRAINING EQUIPMENT
    • A63B2209/00—Characteristics of used materials
    • A—HUMAN NECESSITIES
    • A63—SPORTS; GAMES; AMUSEMENTS
    • A63B—APPARATUS FOR PHYSICAL TRAINING, GYMNASTICS, SWIMMING, CLIMBING, OR FENCING; BALL GAMES; TRAINING EQUIPMENT
    • A63B53/00—Golf clubs
    • A63B53/12—Metallic shafts

Definitions

  • the present invention is directed generally to novel polyolefin compositions having variable toughness and/or hardness properties, and to articles of manufacture produced therefrom. More specifically, the present invention relates to dicyclopentadiene-based polymers (poly-DCPD) comprising various toughness and/or hardness modulators. BACKGROUND OF THE INVENTION
  • Examples of olefin monomers that may be polymerized using the aforementioned metathesis catalysts include dicyclopentadiene (DCPD), in addition to other strained cyclic olefin compounds.
  • DCPD dicyclopentadiene
  • Polymer compositions, and articles or parts produced therefrom, are useful in a wide variety of applications because of their unique physical properties and ease of fabrication.
  • poly-DCPD compositions show promise for applications requiring a combination of toughness, hardness, elasticity, rebounding qualities, marine anti-fouling and/or corrosion resistance, among other properties.
  • the low viscosity of DCPD-based compositions makes these resins particularly well-suited to the fabrication of complex shapes and composites.
  • compositions, and articles of manufacture thereof which may be formulated to have variable toughness and/or hardness for use in a wide range of commercial applications. This is especially so for materials related to the sports, recreational and marine industries.
  • the compositions' properties are not compromised by the incorporation of additives giving rise to the beneficial toughness and/or hardness characteristics.
  • the present invention relates to novel polyolefin compositions having variable toughness and/or hardness properties, to methods of making the compositions, and to articles of manufacture produced therefrom.
  • the present invention provides for toughness/hardness modulating additives, which may be added to polyolefin resins. These toughness/hardness modulators permit controllable modulation of the surface "feel", toughness and/or hardness of a polyolefin article or part.
  • Such modified polyolefin compositions are useful in a variety of applications and products, particularly those in the sports, recreational, and marine fields.
  • the polyolefin compositions of the present invention are prepared by the ring-opening metathesis polymerization (ROMP) of dicyclopentadiene (DCPD) and related strained cyclic olefins, polymerized with a metal catalyst system.
  • ROMP ring-opening metathesis polymerization
  • DCPD dicyclopentadiene
  • strained cyclic olefins polymerized with a metal catalyst system.
  • Ruthenium and osmium carbene compounds have been identified as effective catalysts for olefin metathesis reactions such as, for example, ROMP.
  • Such metathesis catalysts are now well known in the art.
  • the present invention involves ROMP reactions where DCPD resin compositions are cast into product molds or infused into a fiber preform.
  • pigments, dyes, antiozonants and/or antioxidants, among other additives may optionally be included.
  • the present invention provides, in certain preferred embodiments, polyolefin compositions containing toughness and or hardness modulators. These polymer compositions produce articles or parts that are, for example, as tough and impact resistant as the best thermoplastics, but have the ease of fabrication of thermosets.
  • the resin system of the present invention is tolerant to additives, fillers and fibers, such as glass, carbon, fiberglass and Kevlar, among others. As such, the modulating additives are dispersed in the polyolefin resin matrix to controllably alter various physical properties of the native polyolefin.
  • One aspect of the present invention is a novel composition
  • a polyolefin prepared by the metathesis of an olefin monomer using a ruthenium or osmium carbene catalyst, and one or more toughness and/or hardness modulators.
  • These compositions possess variable hardness, toughness and/or surface "feel" properties.
  • the polyolefin is poly-DCPD.
  • Another aspect of the present invention is an article of manufacture, such as a molded part, comprising a polyolefin, prepared by the metathesis of an olefin monomer using a ruthenium or osmium carbene catalyst, and one or more toughness and/or hardness modulators.
  • the present invention is directed to polyolefin compositions having variable toughness and/or hardness properties, and to articles of manufacture made therefrom.
  • the present invention provides toughness/hardness modulaing additives, which may be added to polyolefin resins to alter various physical properties. More specifically, addition of toughness and/or hardness modulators allows controllable modulation of the surface "feel", hardness and/or toughness of a polyolefin article. In particular cases, a modulator may serve as both a toughness and as a hardness modulator.
  • the polyolefin compositions of the present invention are useful in a wide variety of applications, particularly for use in sports, recreational and marine equipment products.
  • the polyolefin compositions of the present invention may be prepared by the metathesis of olefin monomers (e.g., DCPD) and related strained cyclic olefins, polymerized with a metal catalyst system.
  • olefin monomers e.g., DCPD
  • strained cyclic olefins polymerized with a metal catalyst system.
  • Ruthenium and osmium carbene compounds have been identified as effective catalysts for olefin metathesis reactions such as, for example, ring opening metathesis polymerization (ROMP).
  • ROMP ring opening metathesis polymerization
  • Such metathesis catalysts are known in the art and have been previously described in, for example, United States Patent Nos.
  • the catalys olefin monomer ratio in the present invention is preferably between about 1 : 100 and about 1 : 100000.
  • the catalyst-.monomer ratio is between about 1 : 1000 and about 1 : 10000 and, most preferably, is between about 1:3000 and about 1:8000.
  • Particularly preferred metal catalysts include, but are not limited to, bis(tricyclohexylphosphine) benzylidene ruthenium dichloride, bis(tricyclohexylphosphine) dimethylvinylmethylidene ruthenium dichloride and bis(tricyclopentylphosphine) dimethylvinylmethylidene ruthenium dichloride.
  • Preferred hardness modulators include, for example, rubber-like or elastomeric additiv s such as polybutadienes, polyisoprenes, and the like.
  • Polybutadienes and polyisoprenes of various sources, and of various number-average molecular weights (M n ) or weight-average molecular weights (M w ), may be utilized in the present invention as hardness modulators.
  • M n number-average molecular weights
  • M w weight-average molecular weights
  • the poly-DCPD resins of the present invention allow compositions containing polybutadiene to be clear or transparent, rather than opaque or translucent. This is a result of the fact that polybutadiene becomes incorporated into the polymer backbone during the metathesis reaction, leading to little or no phase separation of the polybutadiene particles.
  • hardness modulators of the present invention when added to a polyolefin resin composition, alter the hardness and/or surface "feel" of the composition compared to the unmodified or native polyolefin.
  • other hardness modulators include plasticizers such as dioctyl phthalate and various molecular weight hydrocarbon, fluorocarbon or similar jellies, greases and waxes; carboxylic acids and salts thereof; and co-monomers such as norbornene, cyclooctadiene, cyclooctene, cyclohexenylnorbornene, norbornadiene, di(methylcyclopentadiene), cyclopentene and/or methylcyclopentene.
  • the amount of hardness modulator included in the polyolefin compositions of the present invention is preferably about 0.1%-60% by weight of the olefin monomer to which it is added. More preferably, the amount of hardness modulator is about 1%- 20% by weight of the olefin monomer and, most preferably, is about 2%-10%. In certain cases, hardness modulators may be included in amounts outside the preferred ranges. The determination of the appropriate amount of hardness modulator in a given polyolefin composition can be readily determined by one skilled in the art based on, for example, the degree of microphase separation desired.
  • Preferred toughness modulators include silicones such as, for example, polysiloxane compositions of various viscosities, molecular weights and functionalities.
  • Particularly preferred toughness modulators include poly(dimethylsiloxane) and poly(diphenylsiloxane).
  • Polyolefin compositions comprising such toughness modulators possess significantly increased toughness properties without significant concomitant losses in heat distortion temperature (HDT).
  • HDT heat distortion temperature
  • poly-DCPD compositions comprising low molecular weight poly(dimethylsiloxane)
  • the amount of toughness modulator included in the polyolefin compositions of the present invention is preferably about 0.1%-20% by weight of the olefin monomer to which it is added. More preferably, the amount of toughness modulator is about 0.5%- 10% by weight of the olefin monomer and, most preferably, is about l%-5%.
  • 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.
  • toughness modulators may be included in amounts outside the preferred ranges.
  • the determination of the appropriate amount of toughness modulator in a given polyolefin composition can be readily determined by one skilled in the art based on, for example, the degree of phase separation desired and the degree of transparency/translucency desired. It is well known in the art that phase separation contributes to the toughness of a polyolefin material.
  • the foregoing preferred ranges have been determined to provide polyolefin articles possessing increased toughness.
  • polyolefin hybrid compositions further comprising density modulators may be preferred.
  • Hybrid modified poly-DCPD articles can combine, for example, increased density with increased toughness.
  • preferred density modulators include metallic density modulators where increased density polyolefin compositions are desired, and microparticulate (e.g., microsphere) density modulators where either increased or decreased density polyolefin compositions are desired.
  • metallic density modulators include, but are not limited to, powdered, sintered, shaved, filed, particulated or granulated metals, metal oxides, metal nitrides and/or metal carbides, and the like.
  • Preferred metallic density modulators include, among others, tungsten, tungsten carbide, aluminum, titanium, iron, lead, silicon oxide, and aluminum oxide.
  • the density modulator is dispersed in the polyolefin resin matrix by stirring or mixing.
  • the density, wear resistance and/or "feel" of a metal-filled poly-DCPD composite may be varied in a controllable manner.
  • poly-DCPD compositions containing aluminum metal powder have a soft surface "feel", while poly-DCPD compositions containing aluminum oxide have a rough surface and are extremely wear-resistant.
  • articles or parts made therefrom may be produced to be isotropic, where the metallic density modulator is dispersed evenly throughout the article or part, or anisotropic, where the metallic density modulator is dispersed unevenly (either through the use of layers or a density gradient).
  • the amount of metallic density modulator included in the polyolefin compositions of the present invention is preferably about 1-5400 parts per hundred parts resin (phr), by weight. More preferably, the amount of metallic density modulator is about 200-2000 phr and, most preferably, is about 300-1000 phr.
  • the poly-DCPD resin compositions of the present invention have numerous advantages over traditional thermoset polymers (e.g., epoxies, vinyl esters, unsaturated polyesters, urethanes, and silicones) in the fabrication of low- to medium-density syntactic foams. Specifically, these poly-DCPD resins combine low viscosity ( ⁇ 20 centipoise), long gelling times (>20 minutes), high inherent toughness, and high tensile strength.
  • traditional thermoset polymers e.g., epoxies, vinyl esters, unsaturated polyesters, urethanes, and silicones
  • microparticulate density modulators include, but are not limited to, glass, thermoplastic (either expandable or pre-expanded), thermoset, and/or ceramic/silicate microspheres.
  • the amount of microparticulate density modulator included in the polyolefin compositions of the present invention is preferably about 1-100 phr by weight. More preferably, the amount of microparticulate density modulator is about 10-60 phr and, most preferably, is about 20-50 phr.
  • the compositions of the present invention possess the following properties: tensile strength of at least about 9000 psi; elongation of at least about 4.5%; tensile modulus of at least about 350,000 psi; flexural strength of at least about 14,000 psi; and flexural modulus of at least about 30,000 psi. These values are typically 25-30% greater than those of commercially available poly-DCPD materials, such as Meton ® or Telene ® .
  • the most preferred olefin monomer for use in the present invention is dicyclopentadiene (DCPD).
  • DCPD suppliers and purities may be used, such as Lyondell 108 (94.6% purity), Velsicol UHP (99+% purity), B.F. Goodrich Ultrene 18 (97% and 99% purities), and Hitachi (99+% purity).
  • DCPD sources of lower purities may also be used.
  • Other suitable olefin monomers include cyclooctadiene (COD, DuPont), cyclooctene (COE, Alfa Aesar), cyclohexenylnorbornene (Shell), norbornene, di(methylcyclopentadiene) (Aldrich), and norbornadiene (Elf Atochem).
  • the UV and oxidative resistance of the polyolefin compositions of the present invention may be enhanced by the addition of various antioxidants.
  • one or more antioxidants are included in the polyolefin resin composition at a level of about 0.1- 15 phr. More preferably, the antioxidant(s) are present at a level of about 1-10 phr and, most preferably, 3-8 phr.
  • antioxidants include, for example, 4,4'- methylenebis (2,6-di-tertiary-butylphenol) (Ethanox 702 ® ; Albemarle Corporation), l,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), as well as Irganox 1135 ® (Ciba-Geigy), and the Tinuvin ® (Ciba-Geigy) series of UV stabilizers.
  • Antiozonants such as Flexzone ® (Uniroyal) may also be added.
  • TPP triphenylphosphine
  • TPP inhibitor it is preferably included in an amount of about 10-200 mg: per 64 g olefin monomer. More preferably, the amount of TPP is about 30-100 mg per 64 g olefin monomer and, most preferably, is about 50-80 mg per 64 g olefin monomer.
  • the amount of inhibitor is preferably about 0.1-50 mg per 64 g olefin monomer, more preferably about 1-40 mg:64 g olefin monomer, and most preferably is about 1-30 mg per 64 g olefin monomer.
  • pigments or dyes may be included in the polyolefin resin compositions of the present invention for applications where color is desired.
  • Preferred pigments include Ferro ® and Dayglo ® products, in an amount of about 0.05- 0.5 parts per hundred of polyolefin resin.
  • a particularly preferred class of dyes are photochromic dyes.
  • the polyolefin resins of the present invention are amenable to the manufacture of composites and are tolerant of additives, fillers and fibers including, but not limited to, carbon, glass, fiberglass and aramid (e.g., Kevlar ® and Twaron ) and other polyme:' fibers (e.g., Spectra ® ).
  • the polyolefin compositions, and parts or articles of manufacture prepared therefrom may be processed in a variety of ways including, for example, Reaction Injection Molding (RIM), Resin Transfer Molding (RTM) and vacuum-assisted variants such as SCRIMP (Seemann Composite Resin Infusion Molding Process), open casting, rotational molding, centrifugal casting, filament winding, and mechanical machining.
  • RIM Reaction Injection Molding
  • RTM Resin Transfer Molding
  • SCRIMP Seemann Composite Resin Infusion Molding Process
  • the 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.
  • 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 20-100°C, more preferably about 30-80°C, and most preferably about 40-60°C.
  • the molded polyolefin part or article of the present invention may also be subjected to a post-cure heating step.
  • the post-cure involves heating to about 60-160°C for about 10 minutes - 3 hours. More preferably, the post-cure involves heating to about 80-150°C for about 30 minutes - 2 hours and, and most preferably, involves heating to about 100-140°C for between about 45 and about 90 minutes.
  • the polyolefin compositions of the present invention are useful in the production of sports, recreational, and marine products and equipment which may provide performance advantages over other materials already in use.
  • Examples of such products and applications include, but are not limited to, the following: golf tees, clubs (including weighted club heads), shafts, gradient shafts (where the formulation varies along the length of the club shaft), balls, and carts; basketball backboards; tennis rackets, squash rackets, racquetball rackets, and badminton racquets; snow boards, surfboards, boogie boards, skis, backboards, sleds, toboggans, snow shoes; baseball bats, bat coatings and end-caps, balls, and helmets; football helmets; hockey helmets, sticks, pads, and pucks; roller blade shoes, wheels, pads, and helmets; bicycle parts, frames, helmets, and trispokes; marine applications (e.g., hulls, coatings, oars, propellers,
  • the polyolefin compositions of the present invention are useful in the production of foams of various densities which are useful in numerous applications where properties such as weight, buoyancy, acoustic impedance, anticorrosion, antifouling, and low moisture absorption are considerations.
  • the polyolefin compositions of the present invention are particularly useful in the production of golf club driver heads, exhibiting the performance of titanium drivers with the sound and "feel" of wood drivers.
  • compositions of the present invention are useful in polymer mixtures, interpenetrating polymer networks, fabrics, composites (fiber- or particle-reinforced), blends, alloys, elastomers, ionomers, and dendrimers, among others.
  • compositions of the present invention are also useful in the manufacture of wafer carriers and other semiconductor handling equipment, as well as parts for the construction of semiconductor fabrication facilities, such as walls, fascia, sinks, and decking. Additionally, these materials are useful as low k dielectrics and components for chemical/mechanical planarization (CMP).
  • CMP chemical/mechanical planarization
  • the present invention permits the advantageous control of balance, weight and density localization. These capabilities provide for the enhancement of the performance of, for example, golf club heads and putters and composite tooling, through selective addition and location of metallic density modulators.
  • syntactic foam In the case of polyolefin compositions or parts comprising microparticulate density modulators (i.e., syntactic foam), advantages of the compositions of the present invention are evidenced in the lightweight support and flexion enhancement of sports equipment such as archery bows, bats, sticks, and shafts.
  • Other preferred uses for the syntactic foams of the present invention include hulls and other components of boats and submersibles, core materials for skis and surf-, snow-, and skateboards, and lightweight reinforcement of safety equipment such as pads and helmets.
  • Example 1 A 500 mL round bottom (RB) flask was charged with 250g DCPD (Velsicol UHP), 15g Ethanox ® 702 (Albemarle), and a magnetic stir-bar. The mixture was stirred and heated to 35°C to yield a clear light yellow solution. A separate 100 mL RB flask was charged with 50g DCPD (Velsicol UHP), 280mg triphenylphosphine (TPP) inhibitor, and a magnetic stir-bar. The mixture was stirred and heated to 35°C to yield a clear colorless solution.
  • DCPD Veelsicol UHP
  • Ethanox ® 702 Albemarle
  • TPP triphenylphosphine
  • a 500 mL RB flask was charged with 250g DCPD (Velsicol UHP), 15g Ethanox ® 702 (Albemarle), and a magnetic stir-bar. The mixture was stirred and heated to 35°C to yield a clear light yellow solution.
  • a separate 100 mL RB flask was charged with 50g DCPD (Velsicol UHP), 400mg triphenylphosphine (TPP), and a magnetic stir-bar. The mixture was stirred and heated to 35°C to yield a clear colorless solution. To this latter solution was added (with stirring) 350mg bis(tricyclohexylphosphine) benzylidene ruthenium dichloride (sieved through a 45 mesh size sieve).
  • Example 3 A 500 mL RB flask was charged with 300g DCPD (Velsicol UHP), 35g
  • Irganox ® 1076 (Ciba), and a magnetic stir-bar. The mixture was stirred and heated to 30°C to yield a clear light yellow solution.
  • a separate 100 mL RB flask was charged with 50g DCPD (Velsicol UHP), 450mg triphenylphosphine (TPP), and a magnetic stir-bar. The mixture was stirred and heated to 35°C to yield a clear colorless solution. To this latter solution was added (with stirring) 400mg bis(tricyclohexylphosphine) benzylidene ruthenium dichloride (sieved through a 45 mesh size sieve). After approximately 5 minutes, the mixture evolved a clear dark amber/purple color.
  • This solution was then added to the solution in the 500ml RB flask with continued stirring. After approximately 3 minutes, the mixture turned into a clear amber solution.
  • the resin solution was then poured into a mold that had been previously formed into the shape of a golf club head. The mold had been heated to approximately 40°C prior to the addition of the resin. Within 30 minutes, the resin appeared to be gelled and within 1 hour the molded golf club head was removed from the mold. The golf club head was then subjected to a post-cure at 130°C for a period of 1 hour and cooled to ambient temperature before a golf club shaft was attached thereto. This club head exhibited a slightly softer feel than samples prepared in Examples 1 and 2, probably due, in part, to the greater amount of Irganox ® 1076, which has a plasticizing effect on the formulation.
  • Example 4 A 1000 mL RB flask was charged with 400g DCPD (Velsicol UHP), 25g
  • Ethanox ® 702 (Albemarle), 50g polybutadiene (Aldrich, 38,369-4), and a magnetic stir-bar. The mixture was stirred and heated to 35°C to yield a clear light yellow solution.
  • a separate 100 mL RB flask was charged with 50g DCPD (Velsicol UHP), 750mg triphenylphosphine, and a magnetic stir-bar. The mixture was stirred and heated to 35°C to yield a clear colorless solution. To this latter solution was added (with stirring) 600mg bis(tricyclohexylphosphine) benzylidene ruthenium dichloride (sieved through a 45 mesh size sieve).
  • Example 5 This club head exhibited a softer feel than Example 3 because of the addition of polybutadiene. Additionally, when this formulation was poured into small ( ⁇ 50 mL) sample containers, gelation was accompanied by phase separation. Interestingly, upon post-cure (130°C for 1 hour), the golf club head was homogenous in appearance, despite the inclusion of polybutadiene in the formulation.
  • Example 5
  • a 1000 mL RB flask was charged with 400g DCPD (Ultrene ® 97 from B.F. Goodrich), 25g Ethanox ® 702 (Albemarle), 50g polybutadiene (Aldrich, 38,369-4) and a magnetic stir-bar. The mixture was stirred and heated to 35°C to yield a clear light yellow solution.
  • a separate 100 mL RB flask was charged with 50g DCPD (Ultrene ® 97 from B.F. Goodrich), 750mg triphenylphosphine, and a magnetic stir-bar. The mixture was stirred and heated to 35°C to yield a clear colorless solution.
  • the golf club head was then subjected to a post-cure at 130°C for a period of 1 hour and cooled to ambient temperature before a golf club shaft was attached thereto.
  • This club head exhibited a softer feel (similar to the sample from Example 4) due to the addition of polybutadiene.
  • gelation was accompanied by phase separation.
  • post-cure 130°C for 1 hour
  • the golf club head was homogenous in appearance, despite the inclusion of polybutadiene in the formulation.
  • a 1000 mL RB flask was charged with 400g DCPD (Ultrene ® 99 from B.F. Goodrich), 25g Ethanox ® 702 (Albemarle), 50g polybutadiene (Aldrich, 38,369-4) and a magnetic stir-bar. The mixture was stirred and heated to 35°C to yield a clear light yellow solution.
  • a separate 100 mL RB flask was charged with 50g DCPD (Ultrene ® 99 from B.F. Goodrich), 750mg triphenylphosphine, and a magnetic stir-bar. The mixture was stirred and heated to 35°C to yield a clear colorless solution.
  • the golf club head was then subjected to a post-cure at 130°C for a period of 1 hour and cooled to ambient temperature before a golf club shaft was attached thereto.
  • This club head exhibited a softer feel (similar to the sample from Example 4) because of the addition of polybutadiene.
  • gelation was accompanied by phase separation.
  • post-cure 130°C for 1 hour
  • the golf club head was homogenous in appearance, despite the inclusion of polybutadiene in the formulation.
  • a 1000 mL RB flask was charged with 400g DCPD (Lyondell 108, filtered through activated alumina), 25g Ethanox ® 702 (Albemarle), 50g polybutadiene (Aldrich, 38,369-4) and a magnetic stir-bar. The mixture was stirred and heated to 35°C to yield a clear light yellow solution.
  • a separate 100 mL RB flask was charged with 50g DCPD (Lyondell 108, filtered through activated alumina), 750mg triphenylphosphine, and a magnetic stir-bar. The mixture was stirred and heated to 35°C to yield a clear colorless solution.
  • the golf club head was then subjected to a post-cure at 130°C for a period of 1 hour and cooled to ambient temperature before a golf club shaft was attached thereto.
  • This club head exhibited a softer feel (similar to the sample from Example 4) because of the addition of polybutadiene.
  • gelation was accompanied by phase separation.
  • post-cure 130°C for 1 hour
  • the golf club head was homogenous in appearance, despite the inclusion of polybutadiene in the formulation.
  • a 1000 mL RB flask was charged with 400g DCPD (Hitachi 99), 25g Ethanox ® 702 (Albemarle), 50g polybutadiene (Aldrich, 38,369-4) and a magnetic stir- bar. The mixture was stirred and heated to 35°C to yield a clear light yellow solution.
  • a separate 100 mL RB flask was charged with 50g DCPD (Hitachi high purity), 750mg triphenylphosphine, and a magnetic stir-bar. The mixture was stirred and heated to 35°C to yield a clear colorless solution.
  • the golf club head was then subjected to a post-cure at 130°C for a period of 1 hour and cooled to ambient temperature before a golf club shaft was attached thereto.
  • This club head exhibited a softer feel (similar to the sample from Example 4) because of the addition of polybutadiene.
  • gelation was accompanied by phase separation.
  • post-cure 130°C for 1 hour
  • the golf club head was homogenous in appearance, despite the inclusion of polybutadiene in the formulation.
  • a 1000 mL RB flask was charged with 250g DCPD (Velsicol UHP), 15g Ethanox ® 702 (Albemarle), and a magnetic stir-bar. The mixture was stirred and heated to 35°C to yield a clear light yellow solution.
  • a separate 100 mL RB flask was charged with 50g DCPD (Velsicol UHP), 280mg triphenylphosphine, and a magnetic stir-bar. The mixture was stirred and heated to 35°C to yield a clear colorless solution. To this latter solution was added (with stirring) 300mg bis(tricyclohexylphosphine) benzylidene ruthenium dichloride (sieved through a 45 mesh size sieve).
  • a 1000 mL RB flask was charged with 250g DCPD (Velsicol UHP), 15g Ethanox ® 702 (Albemarle), 1.5g Tinuvin ® 213 (Ciba) and a magnetic stir-bar. The mixture was stirred and heated to 35°C to yield a clear light yellow solution.
  • a separate 100 mL RB flask was charged with 50g DCPD (Velsicol UHP), 280mg triphenylphosphine, and a magnetic stir-bar. The mixture was stirred and heated to

Landscapes

  • Health & Medical Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Physical Education & Sports Medicine (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne des compositions de polyoléfine à dureté et/ou résistance variable, qui comprennent: une polyoléfine obtenue par métathèse d'un monomère d'oléfine, avec un catalyseur au ruthénium ou à l'osmium; et un ou plusieurs modulateurs de dureté et/ou de résistance. De préférence, la polyoléfine est poly(dicyclopentadiène), ou poly-DCPD. L'invention concerne également des produits fabriqués à partir desdites compositions, du type éléments moulés. Les compositions considérées sont utiles pour la fabrication d'articles à usage maritime, récréatif et sportif.
EP99923165A 1998-05-19 1999-05-18 Compositions de polyolefine a resistance et/ou durete variable Withdrawn EP1088000A4 (fr)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
US8598198P 1998-05-19 1998-05-19
US85981P 1998-05-19
US11886599P 1999-02-05 1999-02-05
US118865P 1999-02-05
PCT/US1999/010910 WO1999060030A1 (fr) 1998-05-19 1999-05-18 Compositions de polyolefine a resistance et/ou durete variable

Publications (2)

Publication Number Publication Date
EP1088000A1 true EP1088000A1 (fr) 2001-04-04
EP1088000A4 EP1088000A4 (fr) 2002-03-06

Family

ID=26773300

Family Applications (1)

Application Number Title Priority Date Filing Date
EP99923165A Withdrawn EP1088000A4 (fr) 1998-05-19 1999-05-18 Compositions de polyolefine a resistance et/ou durete variable

Country Status (4)

Country Link
EP (1) EP1088000A4 (fr)
AU (1) AU3999599A (fr)
CA (1) CA2333034A1 (fr)
WO (1) WO1999060030A1 (fr)

Families Citing this family (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7963868B2 (en) 2000-09-15 2011-06-21 Easton Sports, Inc. Hockey stick
BRPI0212392B1 (pt) * 2001-08-30 2015-09-15 Materia Inc processo para preparação de um material poroso infundido com poliolefina e artigo manufaturado.
US6844409B2 (en) 2002-05-06 2005-01-18 Kerr Corporation Composition curable by metathesis reaction
US7060770B2 (en) 2003-05-06 2006-06-13 Kerr Corporation Metathesis-curable composition with a reaction control agent
US7060769B2 (en) 2003-05-06 2006-06-13 Kerr Corporation Method of curing composition by metathesis reaction using reaction control agent
US7173097B2 (en) 2003-05-06 2007-02-06 Kerr Corporation Metathesis-curable composition with a reaction control agent
US7683148B2 (en) 2003-05-06 2010-03-23 Kerr Corporation Metathesis-curable composition with a reaction control agent
US7232386B2 (en) 2003-05-15 2007-06-19 Easton Sports, Inc. Hockey stick
US7645443B2 (en) 2004-11-15 2010-01-12 Kerr Corporation Polyether-based composition curable by metathesis reaction
US7625551B2 (en) 2004-11-15 2009-12-01 Kerr Corporation Polyether-based dental impression material curable by metathesis reaction
US7001590B1 (en) 2004-11-15 2006-02-21 Kerr Corporation Metathesis-curable composition
EP1847245A1 (fr) 2006-02-21 2007-10-24 Kerr Corporation Méthode de préparation des alkoxy-siloxanes polyéther carboxylates avec des groupements fonctionnels d'oléfine
WO2008064223A1 (fr) * 2006-11-21 2008-05-29 California Institute Of Technology Initiateurs de métathèse d'oléfine portant des ligands thiazol-2-ylidène
US7914403B2 (en) 2008-08-06 2011-03-29 Easton Sports, Inc. Hockey stick
RU2402572C1 (ru) 2009-07-09 2010-10-27 Общество с ограниченной ответственностью "Объединенный центр исследований и разработок" Способ получения полидициклопентадиена и материалов на его основе

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4485208A (en) * 1982-05-14 1984-11-27 Hercules Incorporated Plasticized polydicyclopentadiene and a method for making the same
US5171776A (en) * 1991-06-19 1992-12-15 Hercules Incorporated Use of chlorinated polymers to increase the hdt and tg of dicyclopentadiene polymers
US5312940A (en) * 1992-04-03 1994-05-17 California Institute Of Technology Ruthenium and osmium metal carbene complexes for olefin metathesis polymerization

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
No further relevant documents disclosed *
See also references of WO9960030A1 *

Also Published As

Publication number Publication date
CA2333034A1 (fr) 1999-11-25
WO1999060030A1 (fr) 1999-11-25
AU3999599A (en) 1999-12-06
EP1088000A4 (fr) 2002-03-06

Similar Documents

Publication Publication Date Title
AU779888B2 (en) Polyolefin compositions having variable density and methods for their production and use
EP1088000A1 (fr) Compositions de polyolefine a resistance et/ou durete variable
US7285593B1 (en) Polyolefin compositions optionally having variable toughness and/or hardness
US3507495A (en) Lacrosse stick
EP1446284B1 (fr) Infusion de resines d'olefines cycliques dans des materiaux poreux
Easterling Advanced materials for sports equipment: how advanced materials help optimize sporting performance and make sport safer
EP3630871B1 (fr) Équipement sportif comprenant un élastomère de polycarbonate silicone
Laad Polymers in sports
JP2008136872A (ja) ゴルフボール層に対するエンジニアリング熱可塑性加硫ゴムの使用
US20080064535A1 (en) Weighted Training Ball
RU2718831C1 (ru) Эпоксидное связующее, препрег на его основе и изделие, выполненное из него
MX2019002896A (es) Termoplastico pur con alto tg para el moldeo de transferencia por reaccion (rtm).
JPS636201B2 (fr)
WO2001030461A1 (fr) Canne de golf
GB2085885A (en) Foamed polymer sports balls
JP2517924B2 (ja) グリツプ
JPS58124463A (ja) ポリウレタンゴルフクラブ
WO2001012271A1 (fr) Balle biodegradable et moyen d'attaque
Tusim Polyolefins in sports equipment.
Froes et al. Third International Conference On The Engineering Of Sport Research, Development And Innovation
JPS6338054B2 (fr)
TW200500408A (en) Epoxy resin/nano rubber powder hybrid composite material

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20001212

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE

A4 Supplementary search report drawn up and despatched

Effective date: 20020117

AK Designated contracting states

Kind code of ref document: A4

Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE

17Q First examination report despatched

Effective date: 20020724

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN

18D Application deemed to be withdrawn

Effective date: 20030204