WO2000024478A1 - Golf ball containing plastomer and method of making same - Google Patents
Golf ball containing plastomer and method of making same Download PDFInfo
- Publication number
- WO2000024478A1 WO2000024478A1 PCT/US1999/018121 US9918121W WO0024478A1 WO 2000024478 A1 WO2000024478 A1 WO 2000024478A1 US 9918121 W US9918121 W US 9918121W WO 0024478 A1 WO0024478 A1 WO 0024478A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- golf ball
- plastomer
- ball according
- peroxide
- ethylene
- Prior art date
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- 229920000034 Plastomer Polymers 0.000 title claims abstract description 121
- 238000004519 manufacturing process Methods 0.000 title claims description 12
- 239000000203 mixture Substances 0.000 claims abstract description 58
- 238000009826 distribution Methods 0.000 claims abstract description 29
- 239000003795 chemical substances by application Substances 0.000 claims description 28
- 229920001577 copolymer Polymers 0.000 claims description 21
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 18
- 239000005977 Ethylene Substances 0.000 claims description 18
- 238000012360 testing method Methods 0.000 claims description 16
- 150000002978 peroxides Chemical class 0.000 claims description 15
- 239000004711 α-olefin Substances 0.000 claims description 11
- UVWVIEBLYRKAFQ-UHFFFAOYSA-N 4,4-bis(tert-butylperoxy)butyl pentanoate Chemical compound CCCCC(=O)OCCCC(OOC(C)(C)C)OOC(C)(C)C UVWVIEBLYRKAFQ-UHFFFAOYSA-N 0.000 claims description 9
- 238000004132 cross linking Methods 0.000 claims description 8
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 claims description 6
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 6
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 6
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 6
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- -1 butyl peroxy Chemical group 0.000 claims description 6
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 claims description 6
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- RIPYNJLMMFGZSX-UHFFFAOYSA-N (5-benzoylperoxy-2,5-dimethylhexan-2-yl) benzenecarboperoxoate Chemical compound C=1C=CC=CC=1C(=O)OOC(C)(C)CCC(C)(C)OOC(=O)C1=CC=CC=C1 RIPYNJLMMFGZSX-UHFFFAOYSA-N 0.000 claims description 3
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- 239000012975 dibutyltin dilaurate Substances 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- LRCFXGAMWKDGLA-UHFFFAOYSA-N dioxosilane;hydrate Chemical compound O.O=[Si]=O LRCFXGAMWKDGLA-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229920006226 ethylene-acrylic acid Polymers 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- UMKARVFXJJITLN-UHFFFAOYSA-N lead;phosphorous acid Chemical compound [Pb].OP(O)O UMKARVFXJJITLN-UHFFFAOYSA-N 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 230000013011 mating Effects 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000012968 metallocene catalyst Substances 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- 125000005394 methallyl group Chemical group 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- DYUWTXWIYMHBQS-UHFFFAOYSA-N n-prop-2-enylprop-2-en-1-amine Chemical compound C=CCNCC=C DYUWTXWIYMHBQS-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 229920006285 olefinic elastomer Polymers 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000002516 radical scavenger Substances 0.000 description 1
- 239000012858 resilient material Substances 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 238000005488 sandblasting Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 229960004029 silicic acid Drugs 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- GTZCVFVGUGFEME-UHFFFAOYSA-N trans-aconitic acid Natural products OC(=O)CC(C(O)=O)=CC(O)=O GTZCVFVGUGFEME-UHFFFAOYSA-N 0.000 description 1
- 238000001721 transfer moulding Methods 0.000 description 1
- 229940096522 trimethylolpropane triacrylate Drugs 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000004636 vulcanized rubber Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
- 229910052984 zinc sulfide Inorganic materials 0.000 description 1
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
- C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
- C08L23/0815—Copolymers of ethene with aliphatic 1-olefins
-
- A—HUMAN NECESSITIES
- A63—SPORTS; GAMES; AMUSEMENTS
- A63B—APPARATUS FOR PHYSICAL TRAINING, GYMNASTICS, SWIMMING, CLIMBING, OR FENCING; BALL GAMES; TRAINING EQUIPMENT
- A63B37/00—Solid balls; Rigid hollow balls; Marbles
- A63B37/0003—Golf balls
-
- A—HUMAN NECESSITIES
- A63—SPORTS; GAMES; AMUSEMENTS
- A63B—APPARATUS FOR PHYSICAL TRAINING, GYMNASTICS, SWIMMING, CLIMBING, OR FENCING; BALL GAMES; TRAINING EQUIPMENT
- A63B37/00—Solid balls; Rigid hollow balls; Marbles
- A63B37/0003—Golf balls
- A63B37/0023—Covers
- A63B37/0024—Materials other than ionomers or polyurethane
-
- A—HUMAN NECESSITIES
- A63—SPORTS; GAMES; AMUSEMENTS
- A63B—APPARATUS FOR PHYSICAL TRAINING, GYMNASTICS, SWIMMING, CLIMBING, OR FENCING; BALL GAMES; TRAINING EQUIPMENT
- A63B37/00—Solid balls; Rigid hollow balls; Marbles
- A63B37/0003—Golf balls
- A63B37/0038—Intermediate layers, e.g. inner cover, outer core, mantle
- A63B37/0039—Intermediate layers, e.g. inner cover, outer core, mantle characterised by the material
-
- A—HUMAN NECESSITIES
- A63—SPORTS; GAMES; AMUSEMENTS
- A63B—APPARATUS FOR PHYSICAL TRAINING, GYMNASTICS, SWIMMING, CLIMBING, OR FENCING; BALL GAMES; TRAINING EQUIPMENT
- A63B37/00—Solid balls; Rigid hollow balls; Marbles
- A63B37/0003—Golf balls
- A63B37/005—Cores
- A63B37/0051—Materials other than polybutadienes; Constructional details
-
- A—HUMAN NECESSITIES
- A63—SPORTS; GAMES; AMUSEMENTS
- A63B—APPARATUS FOR PHYSICAL TRAINING, GYMNASTICS, SWIMMING, CLIMBING, OR FENCING; BALL GAMES; TRAINING EQUIPMENT
- A63B37/00—Solid balls; Rigid hollow balls; Marbles
- A63B37/0003—Golf balls
- A63B37/007—Characteristics of the ball as a whole
- A63B37/0072—Characteristics of the ball as a whole with a specified number of layers
- A63B37/0073—Solid, i.e. formed of a single piece
-
- A—HUMAN NECESSITIES
- A63—SPORTS; GAMES; AMUSEMENTS
- A63B—APPARATUS FOR PHYSICAL TRAINING, GYMNASTICS, SWIMMING, CLIMBING, OR FENCING; BALL GAMES; TRAINING EQUIPMENT
- A63B37/00—Solid balls; Rigid hollow balls; Marbles
- A63B37/0003—Golf balls
- A63B37/007—Characteristics of the ball as a whole
- A63B37/0072—Characteristics of the ball as a whole with a specified number of layers
- A63B37/0074—Two piece balls, i.e. cover and core
-
- A—HUMAN NECESSITIES
- A63—SPORTS; GAMES; AMUSEMENTS
- A63B—APPARATUS FOR PHYSICAL TRAINING, GYMNASTICS, SWIMMING, CLIMBING, OR FENCING; BALL GAMES; TRAINING EQUIPMENT
- A63B37/00—Solid balls; Rigid hollow balls; Marbles
- A63B37/0003—Golf balls
- A63B37/007—Characteristics of the ball as a whole
- A63B37/0072—Characteristics of the ball as a whole with a specified number of layers
- A63B37/0075—Three piece balls, i.e. cover, intermediate layer and core
-
- A—HUMAN NECESSITIES
- A63—SPORTS; GAMES; AMUSEMENTS
- A63B—APPARATUS FOR PHYSICAL TRAINING, GYMNASTICS, SWIMMING, CLIMBING, OR FENCING; BALL GAMES; TRAINING EQUIPMENT
- A63B37/00—Solid balls; Rigid hollow balls; Marbles
- A63B37/0003—Golf balls
- A63B37/007—Characteristics of the ball as a whole
- A63B37/0077—Physical properties
- A63B37/0078—Coefficient of restitution
-
- A—HUMAN NECESSITIES
- A63—SPORTS; GAMES; AMUSEMENTS
- A63B—APPARATUS FOR PHYSICAL TRAINING, GYMNASTICS, SWIMMING, CLIMBING, OR FENCING; BALL GAMES; TRAINING EQUIPMENT
- A63B37/00—Solid balls; Rigid hollow balls; Marbles
- A63B37/0003—Golf balls
- A63B37/007—Characteristics of the ball as a whole
- A63B37/0072—Characteristics of the ball as a whole with a specified number of layers
- A63B37/0076—Multi-piece balls, i.e. having two or more intermediate layers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L21/00—Compositions of unspecified rubbers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2314/00—Polymer mixtures characterised by way of preparation
- C08L2314/06—Metallocene or single site catalysts
Definitions
- the invention generally relates to golf balls, and more particularly to golf balls having cores and/or covers made of plastomers.
- a wound ball is difficult to 5 manufacture due to the number of production steps required and the careful control which must be exercised in each stage of manufacture to achieve suitable roundness, velocity or rebound, "click", "feel” and the like.
- “Click” is the term applied to the sound produced by the ball when dropped on a hard surface or when struck with a golf club.
- “Feel” refers to how impact of the ball is transmitted through the club to the hands of the golfer.
- the balata cover material for the wound ball is susceptible to cutting when struck by a golf club.
- the one-piece ball and the core for a multi-piece non- wound ball frequently are formed from a combination of materials such as polybutadiene, zinc diacrylate or zinc dimethacrylate, fillers and curing agents which are molded under high pressure and temperature to provide a ball of suitable hardness and resilience.
- One-piece balls are described, for example, in U.S. Patent No. 3,313,545, U.S. Patent No. 3,373,123 and U.S. Patent No. 3,384,612.
- Multi-piece non- wound golf balls typically have a cover which contains a substantial quantity of ionomer.
- Useful ionomers include those sold by E.I.
- An object of the invention is to provide a golf ball containing reduced quantities of ionomer. Yet another object of the invention is to provide a golf ball containing reduced quantities of polybutadiene.
- a further object of the invention is to provide a golf ball having payability characteristics similar to those of golf balls with ionomeric covers while containing reduced quantities of ionomer.
- Another object of the invention is to provide a golf ball which does not contain polybutadiene.
- a further object of the invention is to provide a method of making a golf ball product having reduced quantities of ionomer.
- a further object of the invention is to provide a method of making a golf ball product having reduced quantities of polybutadiene.
- Yet another particularly preferred form of the invention is a one-piece golf ball comprising a plastomer.
- the plastomer in at least the outer surface of the one-piece ball is cured.
- the plastomer used to form the golf ball preferably is a copolymer formed from ethylene. More preferably the plastomer is a copolymer of ethylene and at least one of butene, hexene and octene.
- the ball is provided with good cut resistance, thereby meeting the payability standards of commercial golf balls.
- any peroxide curing agent having an activation temperature higher than the melting point of the plastomer can be used if the plastomer is to be cured, e.g. a one hour half life at 112°C or higher
- a preferred curing agent is 4,4 bis(tert- butylperoxy) butylvalerate having about 40% peroxide content.
- the curing or crosslinking agent is employed in an amount appropriate to impart to the golf ball a crosslink density which is sufficient to provide the desired cut resistance, scuff resistance and surface hardness to the outside of the ball.
- the amount of peroxide is sufficient to provide a usable compression, i.e. 60 -110 PGA compression in addition to appropriate cut resistance, scuff resistance and hardness.
- a plastomer core or an inner cover layer of a multi-layer ball may not require crosslinking or curing.
- Another preferred form of the invention is a method of making a golf ball product comprising forming a mixture comprising a plastomer with a molecular weight distribution of about 1.5 - 4 and a composition distribution breadth index of at least 30%, the quantity of plastomer being appropriate to form a golf ball product having a coefficient of restitution of at least 0.600, and molding the mixture to form a golf ball product.
- the golf ball product is a golf ball core, a one-piece golf ball, or a multi-piece golf ball with plastomer in at least one of the core and cover.
- the mixture includes a curing agent for curing the plastomer.
- copolymer includes (1) copolymers having two types of monomers which are polymerized together, (2) terpolymers (which are formed by the polymerization of three types of monomers), and (3) copolymers which are formed by the polymerization of more than three types of monomers.
- the compositions of the invention further may include additives and fillers as well as a co-agent for use with a curing agent to aid in crosslinking the plastomer or to improve processability.
- the plastomers employed in the invention preferably are formed by a single-site metallocene catalyst such as those disclosed in EP 29368, USP 4752597, USP 4808561 , and USP 4937299, the teachings of which are incorporated herein by reference.
- plastomers can be produced by metallocene catalysis using a high pressure process by polymerizing ethylene in combination with other monomers such as butene-1, hexene-1 , octene-1 and 4-methyl-1-pentene in the presence of catalyst system comprising a cyclopentadienyl- transition metal compound and an alumoxane.
- EXACT 4011 having a density of about 0.887 gms/cc (ASTM D-1505) and a melt index of about 2.2 g/10 min. (ASTM D-2839); and EXACT 4049 having a density of about 0.873 gms/cc (ASTM D-1505) and a melt index of about 4.5 g/10min. (ASTM D-2839); and ethylene-hexene copolymers such as EXACT 3031 having a density of about 0.900 gms/cc (ASTM D-1505) and a melt index of about 3.5 g/10min. (ASTM D-2839).
- EXACT plastomers are EXACT 4005 and EXACT 5010. Terpolymers of e.g. ethylene, butene and hexene also can be used. All of the above EXACT series plastomers are available from EXXON Chemical Co.
- EXACT plastomers typically have a molecular weight distribution (MJM n ) of about 1.5 to 2.4, where M w is weight average molecular weight and M n is number average molecular weight, a density of about 0.86 to about 0.91 g/cc, preferably about 0.87 g/cc to about 0.91 g/cc, a molecular weight of about 5,000 to about 50,000, preferably about 20,000 to about 30,000, a melting point of about 140-220°F, and a melt index above about 0.50 g/10mins, preferably about 1 - 10 g/10mins as determined by ASTM D-1238, condition E.
- M w weight average molecular weight
- M n number average molecular weight
- a density of about 0.86 to about 0.91 g/cc preferably about 0.87 g/cc to about 0.91 g/cc
- a molecular weight of about 5,000 to about 50,000 preferably about 20,000 to about 30,000
- Plastomers which may be employed in the invention include copolymers of ethylene and at least one C 3 -C 20 ⁇ -olefin, preferably a C 4 -C 8 ⁇ - olefin present in an amount of about 5 to about 32 mole %, preferably about 7 to about 22 mole %, more preferably about
- Plastomers such as those sold by Dow Chemical Co. under the tradename ENGAGE also may be employed in the invention. These plastomers are believed to be produced in accordance with USP 5,272,236, the teachings of which are incorporated herein in their entirety by reference.
- These plastomers include homopolymers of C 2 -C 20 olefins such as ethylene, propylene, 4- methyl-1-pentene, and the like, or they can be interpolymers of ethylene with at least one C 3 -C 20 ⁇ -olefin and/or C 2 -C 20 acetylenically unsaturated monomer and/or C 4 -C 18 diolefins.
- These plastomers generally have a polymer backbone that is either unsubstituted or substituted with up to 3 long chain branches/1000 carbons.
- long chain branching means a chain length of at least about 6 carbons, above which the length cannot be distinguished using 13 C nuclear magnetic resonance spectroscopy.
- the preferred ENGAGE plastomers are characterized by a saturated ethylene-octene backbone, a narrow molecular weight distribution M M n of about 2, and a narrow level of crystallinity. These plastomers also are compatible with pigments, brightening agents, fillers such as carbon black, calcium carbonate and silica, as well as with plasticizers such as paraffinic process oil and naphthenic process oil. Other commercially available plastomers may be useful in the invention, including those manufactured by Mitsui.
- the molecular weight distribution, (MJM ⁇ ), of plastomers made in accordance with USP 5,272,236 most preferably is about 2.0.
- Non-limiting examples of these plastomers include
- ENGAGE CL 8001 having a density of about 0.868 gms/cc, a melt index of about 0.5 g/10mins, and a Shore A hardness of about 75
- ENGAGE CL 8002 having a density of about 0.87 gms/cc, a melt index of about 1gms/10min, Shore A hardness of about 75
- ENGAGE CL 8003 having a density of about 0.885 gms/cc, melt index of about 1.0 gms/10min, and a Shore A hardness of about 86
- ENGAGE EG 8100 having a density of about 0.87 gms/cc, a melt index of about 1gms/10min., and a Shore A hardness of about 87
- ENGAGE 8150 having a density of about 0.868 gms/cc, a melt index of about 0.5gms/10min, and a Shore A hardness of about 75
- ENGAGE 8200 having a density of about 0.87
- the plastomer When the plastomer is used in a one-piece ball or in the outer cover of a multi-piece ball, it is crosslinked at the outer surface, and preferably throughout the plastomer-containing thickness, in order to provide the surface of the ball with good cut resistance.
- Surface-crosslinking can be effected using electron beam treatment and the like.
- curing agents useful in the compositions of the invention when the entire plastomer-containing layer is to be crosslinked include but are not limited to di-tert-butyl peroxide, dicumyl peroxide, benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, t-butyl-cumyl peroxide, t-butyl perbenzoate, t-butyl peroxide, t-butylperoxy (2- ethyl hexanoate), 2,5-dimethyl-2,5-di(benzoylperoxy)-hexane, benzoyl peroxide, 2,5-dimethyl-2,5-(6-butylperoxy)-hexane, 1,1- di-t-butylperoxy-3,3,5-trimethylcyclohexane,4,4-di-t-butylperoxy n-butyl valerate, 4,4 bis(-t-butylperoxy
- Coagents which may be used with the aforementioned curing agents include, for example, zinc diacrylate, zinc dimethacrylate, zinc monomethacrylate, trimethylol propane triacrylate, trimethylol propane trimethacrylate, vinyl, allyl, methallyl, furfuryl, crotyl and cinnamyl esters of the following acids: oxatic, maioic, succinic, glutaric, adipic, pimelic, suberic, azelaic, sebacic, maleic, itaconic, citraconic, mesaconic, fumaric, aconitic, phthalic, isophthalic, terephthalic, naphthalene, dicarboxylic mellitic, pyromellitic, trimesic, acrylic methacrylic, cennamic, and crotonic.
- coagents which may be employed include di- and triallyl cyanurate, di- and triallylmelamine, divinyl benzene; diallyl benzene; diallyl amine; allyl ether; allyl gycolates; di, tri and tetravinyl and allyl silanes, as well as polyamides and imides of maleic, itaconic, acrylic, methacrylic crotonic, citaconic, aconitic and cinnamic acid as well as polyol esters and anhydrides of acrylic methacrylic, crontic and cinnamic acids. All of these co-agents are commercially available.
- filler materials can be employed in the compositions to control the weight of the ball and increase hardness or compression.
- Fillers which may be employed are in finely divided form, for example, in a size generally less than about 20 mesh, preferably less than about 100 mesh U.S. standard size.
- the filler preferably is a precipitated hydrated silica such as that sold under the trademark HiSil by the Pittsburgh Plate Glass Company.
- fillers which may be employed include, but are not limited to, clay, talc, asbestos, graphite, glass, mica, calcium metasilicate, barium sulfate, zinc sulfide, aluminum hydroxide, silicates, diatomaceous earth, carbonates such as calcium carbonate, magnesium carbonate and the like, metals and metal alloys, such as titanium, tungsten, aluminum, bismuth, nickel, molybdenum, iron, copper, brass, boron, bronze, cobalt and beryllium, and alloys of the above metals, metal oxides such as zinc oxide, iron oxide, aluminum oxide, titanium oxide, magnesium oxide, zirconium oxide and the like, particulate synthetic plastic such as high molecular weight polyethylene, polystyrene, polyethylene ionomer resins and the like, particulate carbonaceous materials such as carbon black, natural bitumen and the like, as well as cotton flock, cellulose flock, and leather fiber. Dark colored fillers generally are not preferred for use in outer cover compositions
- compositions of the invention also may include various processing aids and activators known in the rubber and molding arts such as fatty acids.
- processing aids include 24478
- fatty acids having from about 10 to about 40 carbon atoms, preferably from about 15 to about 20 carbon atoms.
- useful fatty acids include stearic acid and linoleic acid, as well as mixtures thereof.
- the fatty acid may be present in the s compositions of the invention in amounts of from about 1 to about 15, preferably from about 2 to about 5 parts by weight per 100 parts olefin elastomer.
- processing aids and activators include, for example, calcium stearate, barium stearate, zinc stearate, lead stearate, basic lead sulfite, dibasic lead phosphite, o dibutyl tin dilaurate, dibutyltin dimaleate, and dibutyltin mercaptide.
- Coloring pigments and optical brighteners also may be included in the compositions of the invention.
- Useful coloring pigments include, for example, titanium dioxide, the presence of which simplifies the surface painting operation of the finished ball.
- the plastomer-containing golf balls of the invention have a coefficient of restitution of at least 0.600, preferably at least 0.700, and more preferably at least 0.740, a PGA compression of about 60 - 110 and preferably 80 - 90, a ball size of 1.680" -
- plastomer When plastomer is used in a core or an inner cover layer of a multi-layer golf ball, it is not necessary to crosslink the cover layer.
- an initiator such as 4,4 bis (tert-butylperoxy) butylvalerate having 40% peroxide therein, preferably are employed.
- a curing or crosslinking agent optionally is used in forming a core or an inner cover layer for a multi-piece ball, it generally is employed in an amount of about 1 - 10 parts by weight of 40% active peroxide per 100 parts by weight of plastomer.
- the curing agent can be omitted and the outer surface of the core, or the entire core, can be treated by electron beam treatment or the like to induce crosslinking.
- the amount of filler which can be employed in these compositions is primarily a function of weight restrictions on the ball.
- the filler is included in amounts of from about 10 to about 100 parts by weight per 100 parts by weight of plastomer.
- Processing aids and activators such as fatty acids, metal stearates and the like may be employed in these compositions in amounts of from about 1 to about 15, preferably in amounts of from about 2 to about 5 parts by weight per 100 parts by weight of plastomer.
- Wide latitude may be taken in the production of balls from the compositions of the invention to provide balls of various compressions suitable for every type of golfer.
- Low compression balls generally preferred by "soft” hitters, may be made by increasing the proportion of the olefin copolymer component.
- Medium compression balls preferred by average golfers, may be made by balancing the quantities of the olefin copolymer, co-agent and peroxide initiator.
- High compression balls preferred by "hard” hitters may be made by increasing the proportion of co-agent and peroxide curing agent.
- compositions useful as golf balls are intimately mixed, using, for example, a two roll mill or an internal mixer such as a Banbury® mixer until the mixture is uniform. This usually can be accomplished in a period of from about 5 to about 20 minutes.
- a preferred mixing sequence is one wherein the metallocene catalyzed olefin copolymer is mixed for about 5 minutes in a Banbury® mixer.
- the curing agent (if used), co-agent and fillers are then added, whereafter mixing is continued for about one minute, whereupon the batch is discharged onto a two roll mill, mixed for about an additional minute and formed into a sheet.
- the temperature of the mixing is not critical, but should, of course, be below the curing temperature. Mixing is usually done at room temperature, although, through friction, the ingredients will be slightly warmed.
- the resulting composition can be formed into one-piece golf balls and centers for multi-piece balls by any one of a variety of known techniques such as injection, compression or transfer molding.
- a preform of the composition of the invention can be compression molded and cured under 8
- the mold has dimpled golf ball cavities therein.
- the volume of the preform portion placed in the mold cavity is slightly in excess of the actual volume of the ball cavity to enable the cavity to be completely filled when the mold is closed.
- an extrudate or flash of excess composition typically is formed at the mating surfaces of the closed cavities.
- the composition is compression molded at about 290° F to about 330°F, preferably about 315°F, under a pressure of about 100 - 500 PSI, preferably about 500 PSI.
- the time required for curing is normally about 10 minutes to about 20 minutes, preferably about 14 minutes depending upon the amount and activity of the selected curing agent and any co-agents.
- the resulting golf balls or cores are cooled for about 10 minutes in the mold by circulating cold water through the mold. If a core has been made, the core optionally can be subjected to known centerless grinding operations whereby a thin layer of the molded center is removed. The center can be converted into a two-piece ball by providing a layer of covering material thereon.
- a number of 1.545 inch golf ball cores were made using EXACT resins compounded without peroxide.
- a warm soft slug for each core was heated 4 mins @ 320 then cooled for 10 minutes using cooling water. All of the uncured cores passed the Guillotine Cut Test.
- metallocene catalyzed polyolefins can be used in golf ball cores and covers, and to form one-piece golf balls as long as sufficiently high values of COR, cut resistance and compression are achieved.
Abstract
Description
Claims
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CA002345259A CA2345259A1 (en) | 1998-10-26 | 1999-08-09 | Golf ball containing plastomer and method of making same |
PCT/US1999/018121 WO2000024478A1 (en) | 1998-10-26 | 1999-08-09 | Golf ball containing plastomer and method of making same |
GB0108523A GB2363577A (en) | 1998-10-26 | 1999-08-09 | Golf ball containing plastomer and method of making same |
JP2000578079A JP2003525649A (en) | 1998-10-26 | 1999-08-09 | Golf ball containing plastomer and method for producing the same |
AU56719/99A AU761460B2 (en) | 1998-10-26 | 1999-08-09 | Golf ball containing plastomer and method of making same |
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
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US74312298A | 1998-10-26 | 1998-10-26 | |
US08/743,122 | 1998-10-26 | ||
PCT/US1999/018121 WO2000024478A1 (en) | 1998-10-26 | 1999-08-09 | Golf ball containing plastomer and method of making same |
Publications (1)
Publication Number | Publication Date |
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WO2000024478A1 true WO2000024478A1 (en) | 2000-05-04 |
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Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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PCT/US1999/018121 WO2000024478A1 (en) | 1998-10-26 | 1999-08-09 | Golf ball containing plastomer and method of making same |
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WO (1) | WO2000024478A1 (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2002083433A1 (en) * | 2001-04-13 | 2002-10-24 | Pirelli Pneumatici S.P.A. | Tyre comprising an ethylene copolymer, tread band and elastomeric composition used therein |
Citations (4)
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US5272236A (en) * | 1991-10-15 | 1993-12-21 | The Dow Chemical Company | Elastic substantially linear olefin polymers |
US5703166A (en) * | 1995-01-24 | 1997-12-30 | Acushnet Company | Golf ball compositions based on blends of olefinic ionomers and metallocene catalyzed polymers |
US5779561A (en) * | 1995-06-26 | 1998-07-14 | Sullivan; Michael J. | Golf ball and method of making same |
US5824746A (en) * | 1995-01-24 | 1998-10-20 | Acushnet Company | Golf balls incorporating foamed metallocene catalyzed polymer |
-
1999
- 1999-08-09 WO PCT/US1999/018121 patent/WO2000024478A1/en active IP Right Grant
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5272236A (en) * | 1991-10-15 | 1993-12-21 | The Dow Chemical Company | Elastic substantially linear olefin polymers |
US5703166A (en) * | 1995-01-24 | 1997-12-30 | Acushnet Company | Golf ball compositions based on blends of olefinic ionomers and metallocene catalyzed polymers |
US5824746A (en) * | 1995-01-24 | 1998-10-20 | Acushnet Company | Golf balls incorporating foamed metallocene catalyzed polymer |
US5779561A (en) * | 1995-06-26 | 1998-07-14 | Sullivan; Michael J. | Golf ball and method of making same |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2002083433A1 (en) * | 2001-04-13 | 2002-10-24 | Pirelli Pneumatici S.P.A. | Tyre comprising an ethylene copolymer, tread band and elastomeric composition used therein |
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