US20100323056A1 - Cross-linked thermoplastic polyurethane/polyurea and method of making same - Google Patents

Cross-linked thermoplastic polyurethane/polyurea and method of making same Download PDF

Info

Publication number
US20100323056A1
US20100323056A1 US12/871,726 US87172610A US2010323056A1 US 20100323056 A1 US20100323056 A1 US 20100323056A1 US 87172610 A US87172610 A US 87172610A US 2010323056 A1 US2010323056 A1 US 2010323056A1
Authority
US
United States
Prior art keywords
mixture
cross
heated
thermoplastic
create
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.)
Abandoned
Application number
US12/871,726
Inventor
Pijush K. Dewanjee
John G. Guard
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.)
PriPro Polymer Inc
Topgolf Callaway Brands Corp
Original Assignee
Callaway Golf Co
PriPro Polymer 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
Priority claimed from US10/992,907 external-priority patent/US7417094B2/en
Application filed by Callaway Golf Co, PriPro Polymer Inc filed Critical Callaway Golf Co
Priority to US12/871,726 priority Critical patent/US20100323056A1/en
Assigned to CALLAWAY GOLF COMPANY, PRIPRO POLYMERS, INC. reassignment CALLAWAY GOLF COMPANY ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: DEWANJEE, PIJUSH K., GUARD, JOHN G.
Publication of US20100323056A1 publication Critical patent/US20100323056A1/en
Priority to US13/292,996 priority patent/US20120056354A1/en
Abandoned legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/0895—Manufacture of polymers by continuous processes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3225—Polyamines
    • C08G18/3237—Polyamines aromatic
    • C08G18/324—Polyamines aromatic containing only one aromatic ring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
    • C08G18/3802—Low-molecular-weight compounds having heteroatoms other than oxygen having halogens
    • C08G18/3814—Polyamines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
    • C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
    • C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • 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
    • C08G2120/00—Compositions for reaction injection moulding processes
    • 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
    • C08G2310/00—Agricultural use or equipment
    • 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
    • C08G2380/00—Tyres
    • 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
    • C08G2410/00—Soles

Definitions

  • the field of the invention generally relates to thermoplastic polyurethanes and thermoplastic polyureas having properties similar to those of castable or cross-linked polyurethanes or polyureas.
  • the field of the invention also includes methods of making the same.
  • thermoplastic polyurethanes or polyureas
  • thermoset polyurethanes or polyureas
  • Thermoplastic polyurethanes generally have linear molecular structures and are able to flow freely at elevated temperatures. For this reason, thermoplastic polyurethanes are preferred for products which are produced by injection molding or other extrusion techniques, where flowability of the reactants are of paramount importance.
  • thermoplastic polyurethanes typically exhibit poor performance characteristics with respect to abrasion, tensile strength, rebound, and compression set compared to castable poluurethanes.
  • thermoset polyurethanes In contrast to current thermoplastic polyurethanes, thermoset polyurethanes have particularly good characteristics with respect to abrasion, tensile strength, rebound, and compression set.
  • Thermoset polyurethanes generally have a network structure that incorporates irreversible chemical cross-linking.
  • the downside of thermoset polyurethanes is that the irreversible chemical cross-linking reaction makes it unsuitable for use in injection molding and extrusion applications.
  • thermoset polyurethanes are formed using a casting process. Unfortunately, casting processes require costly equipment and usually involve a large number of processing steps. Casting is thus a less efficient and more expensive method of producing polyurethane-based and polyurea-based products as compared to injection molding and extrusion systems.
  • a di-isocyanate component is first pre-polymerized with a polyol having either a polyester or polyether backbone. The remaining di-isocyanate of the pre-polymer is reacted with a chain extender or a cross-linking agent or a blend of cross-linking agents. Catalysts are added to control the reaction rate. If the cross-linking agent has a dihydroxy functional component, a polyurethane will be formed. If the cross-linking agent has diamine functionality, a polyurea is formed.
  • thermoplastic polyurethanes With respect to thermoplastic polyurethanes, a diol or polyol is reacted with an isocyanate. This reaction typically takes place in large commercial reactors. As stated above, thermoplastic polyurethanes, while not cross-linked, are usable in injection molding and other extrusion methods. Because of the lack of cross-linking, these materials have abrasion, tensile, and compression set properties that are not as good as thermoset polyurethane or polyurea systems.
  • thermoplastic polyurethane or polyurea material which exhibits good abrasion, tensile strength, rebound, and compression set characteristics which are similar to those found in thermoset urethanes.
  • Such a material could be produced using conventional injection molding and/or extrusion techniques, thereby reducing the cost of manufacture for the material.
  • the conventional solution has been to add a cross-linking agent to a thermoplastic resin, either post-injection molding or pre-injection molding. Adding the cross-linking agent pre-injection molding allows for a greater dispersion of the cross-linking agent within the thermoplastic resin material.
  • many cross-linking agents have low boiling temperatures and will “flash off” prior to dispersion, especially at room temperatures. Trying to add other agents to resolve the flash off problems leads to other processing issues, especially with injection molding machines which melt processing materials (thermoplastic resins) and inject the melted materials under high pressures to form various articles, which can lead to a build up of materials in the injection molding barrel.
  • the present invention provides a solution for forming cross-linked thermoplastic polymers.
  • the present invention adds a cross-linking agent a thermoplastic resin in the pre-injection molding stage.
  • a second mixture is added during the injection molding stage. This second mixture prevents the flashing off of the cross-linking agent while allowing for processing without a build-up of material.
  • One aspect of the present invention is a method for forming an article composed of a cross-linked thermoplastic polymer.
  • the method includes mixing a thermoplastic urethane based material and a monomeric diisocyanate to create a first mixture.
  • the monomeric diisocynate comprises between 1% to 10% of the total mass of the first mixture, the diisocyanate.
  • the method also includes mixing 4,4′methylene-bis-(3-chloro-2,6-diethylaniline) and diethyl 2,4-toluenediamine to create a second mixture.
  • the 4,4′methylene-bis-(3-chloro-2,6-diethylaniline) is 75% to 95% of the total mass of the second mixture and diethyl 2,4-toluenediamine is 25% to 5% of the total mass of the second mixture.
  • the method also includes heating the first mixture to a temperature within the range of 250° F. to 550° F. to created a heated first mixture.
  • the method also includes heating the second mixture to a temperature greater than the melting point of the second mixture and less than 225° F. to create a liquid second mixture having a volume.
  • the method also includes injecting the heated first mixture into a barrel of an injection molding machine through a first opening.
  • the method also includes injecting the liquid second mixture into the barrel of the injection molding machine in a plurality of dispensing shots of approximately equal amounts of the volume of the liquid second mixture during a predetermined time period.
  • the method also includes injecting a reaction product into at least one injection mold cavity, the reaction product formed by the reaction of the heated first mixture and the liquid second mixture.
  • the method also includes forming an article composed of the reaction product.
  • FIG. 1 schematically illustrates an injection molding device which can be used to produce products made from cross-linked thermoplastic polyurethanes/polyureas according to the present invention.
  • FIG. 2 is a flow chart of a method of the present invention.
  • the method for forming a cross-linked thermoplastic polyurethane or polyurea generally involves four different components.
  • the first component is a thermoplastic polyurethane resin material.
  • the second component is a diisocyanate.
  • the third component is a diamine.
  • the fourth component is a diamine.
  • thermoplastic polyurethane resin material and the diisocynate are preferably mixed in a dry state to create a first dry mixture.
  • the third and fourth components, the diamines, are mixed together to create a liquid second mixture.
  • the dry mixture is heated into a flowable form and the liquid second mixture is introduced at predetermined intervals of equal amounts to create a homogeneous reaction product.
  • the thermoplastic polyurethane base material may include TEXIN 985, an aromatic polyether-based thermoplastic polyurethane available from Bayer Corporation.
  • the thermoplastic urethane base material may include NOVEON ST80A, which is available from Noveon Incorporated.
  • Another thermoplastic polyurethane is IROGAN A 95 P 4021 from Huntsman Chemical.
  • IROGAN A 95 P 4021 is a thermoplastic polyether-polyurethane having a Shore A hardness of approximately 95, a Shore D hardness of approximately 46, a melt index of 210° C./21.6 kilograms at 5-15 grams/10 minutes.
  • Another thermoplastic polyurethane is TEXIN DP7 1197 from Bayer Corporation.
  • TEXIN DP7-1197 is a thermoplastic polyester polyurethane having a Shore A hardness of 88.
  • Another thermoplastic polyurethane is DESMOPAN 445 from Bayer Corporation.
  • DESMOPAN is a thermoplastic polyester polyurethane having a Shore D hardness of 45.
  • thermoplastic urethane base material is preferably dried prior to adding the additional components described in detail below. This can be accomplished, for example, by heating the thermoplastic base material to a temperature between about 100° F. to 200° F. in a separate container.
  • a monomeric diisocyanate is added to the dried thermoplastic urethane base material.
  • the diisocyanate used in the process is a solid at room temperature.
  • the diisocyanate is 4,4′ diphenylmethane diisocyanate, which has a sublimation point of approximately 392° F.
  • MONDUR M CAS No. 101-68-8
  • the flaked or fused form of MONDUR M is used in connection with the process described herein.
  • the diisocyanate is preferably stored at about ⁇ 20° C.
  • Diisocyanate materials which are solid at room temperature and may be used in accordance with the invention include: Toluene Diisocyanates (TDI), Toluene ortho Diisocyanates (TODI), Naphthalene Diisocyantaes (NDI), Hydrogenated Methylene Diisocyantaes (H12MDI), Iso Phorone Diisocyanates (IPDI), Hexamethylene Diisocyantes (HDI).
  • TDI Toluene Diisocyanates
  • TODI Toluene ortho Diisocyanates
  • NDI Naphthalene Diisocyantaes
  • H12MDI Hydrogenated Methylene Diisocyantaes
  • IPDI Iso Phorone Diisocyanates
  • HDI Hexamethylene Diisocyantes
  • the diisocyanate comprises between 1% to 10% of the total weight of the mixture forming the cross-linked thermoplastic polyurethane/polyurea. Even more preferably, the diisocyanate comprises between 1% to 2% of the total weight of the mixture forming the cross-linked thermoplastic polyurethane/polyurea.
  • the diisocyanate materials other than those specifically identified above may also be used in accordance with the invention, provided they exist as a solid at room temperature.
  • One preferred diamine is 4,4′ methylene-bis-(3-chloro-2,6-diethylaniline), available commercially as LONZACURE M-CDEA (CAS No. 106246-33-7).
  • Another diamine which can be employed with the present invention is 4,4′ Methylene-bis-(2,6-diethylaniline), available commercially as LONZACURE M-DEA (CAS No. 13680-35-8). Both diamines have melting points at approximately 90° C.
  • the diamine is added in solid form and dry blended with the MDI and thermoplastic urethane base material.
  • a second diamine for the second mixture is preferably diethyl 2,4-toluenediamine, which is available under the brandname ETHACURE 100, or E100, from Albermarle of Baton Rouge, La.
  • the diethyl toluene diamine prevents build-up due to the first diamine, preferably 4,4′ methylene-bis-(3-chloro-2,6-diethylaniline).
  • the second mixture is preferably 75 to 95 parts by weight 4,4′ methylene-bis-(3-chloro-2,6-diethylaniline) and 5 to 25 parts by weight diethyl 2,4-toluenediamine, and more preferably 80 to 90 parts by weight 4,4′ methylene-bis-(3-chloro-2,6-diethylaniline) and 10 to 20 parts by weight diethyl 2,4-toluenediamine, and most preferably 85 parts by weight 4,4′ methylene-bis-(3-chloro-2,6-diethylaniline) and 15 parts by weight diethyl 2,4-toluenediamine.
  • the second mixture is preferably utilized to prevent the diisocynate from “flashing off” during the processing.
  • the second mixture provides heat stability to the diisocynate during the processing.
  • the second mixture also allows the temperature of the reaction to be reduced substantially which provides for a more favorable viscosity.
  • 4,4′ methylene-bis-(3-chloro-2,6-diethylaniline) allows for the diisocynate to be utilized at a higher temperature since the 4,4′ methylene-bis-(3-chloro-2,6-diethylaniline) essentially increasing the boiling temperature of the diisocynate.
  • the diamines comprises between 1% to 10% of the total weight of the mixture forming the cross-linked thermoplastic polyurea. Even more preferably, diamine comprises between 1% to 2% of the total weight of the mixture forming the cross-linked thermoplastic polyurea. Diamines other than those specifically identified above may also be used in accordance with the invention, provided they exist as a solid at a temperature within the range of 50° F. to 150° F.
  • hydroquinone replaces the diamine constituent and is added to the mixture of MDI and thermoplastic urethane.
  • HQEE is added to the mixture in solid form and dry blended with the MDI and thermoplastic urethane base material.
  • HQEE is added in conjunction with a diamine.
  • thermoplastic urethane base material MDI, and diamine (and/or HQEE)
  • the mixture of thermoplastic urethane base material, MDI, and diamine (and/or HQEE) is then mixed and heated to a temperature within the range of 250° F. to 550° F.
  • the solid thermoplastic urethane base material, MDI, and diamine (and/or HDEE) melt and partially cross-link.
  • the partially cross-linked thermoplastic polyurethane/polyurea is post-cured by heating the same to a temperature within the range of 150° F. to 250° F. for a period of time ranging between 2 and 36 hours.
  • FIG. 1 illustrates an injection molding device 10 capable of producing cross-linked thermoplastic polymers in accordance with the present invention.
  • the injection molding device 10 includes a hopper 12 for loading the various components (e.g., a first mixture of thermoplastic urethane resins and MONDUR flakes).
  • the hopper 12 preferably includes a rotating mixer therein for dry mixing the first mixture materials.
  • the hopper 12 is in flow communication with a mixing barrel 16 having a screw (not shown).
  • the screw is disposed inside the mixing barrel 16 , and both rotates and reciprocates within the mixing barrel 16 .
  • the distal end of the mixing barrel 16 terminates into an injection chamber and injection nozzle.
  • the injection nozzle is preferably disposed inside a stationary platen and is in flow communication with a mold 18 .
  • the mold 18 preferably includes one or more cavities (not shown) having a pre-formed shape.
  • the injection molding device 10 may be used to form any number of products including, for example, skateboard wheels, in-line skate wheels, roller coaster wheels, caster wheels, golf ball layers, and golf club components, and the like.
  • the injection molding device also includes a secondary mixing chamber 20 for mixing and heating a second mixture for introduction into the barrel 16 .
  • the secondary mixing chamber 20 is in flow communication with the barrel 16 through a flow pipe 22 .
  • FIG. 2 is a flow chart of a preferred method 200 of the present invention.
  • the thermoplastic polyurethane (“TPU”) resin and a diisocynate are mixed to create a first mixture.
  • the monomeric diisocynate comprises between 1% to 10% of the total mass of the first mixture, and most preferably 6% by weight of the first mixture.
  • the diisocynate is MONDUR flakes.
  • 4,4′ methylene-bis-(3-chloro-2,6-diethylaniline) and diethyl 2,4-toluenediamine are mixed to create a second mixture.
  • the second mixture is preferably mixed in the secondary mixing chamber 20 as described in reference to FIG. 1 .
  • the 4,4′ methylene-bis-(3-chloro-2,6-diethylaniline) is preferably 75% to 95% of the total mass of the second mixture and diethyl 2,4-toluenediamine is 25% to 5% of the total mass of the second mixture.
  • the first mixture is heated to create a first heated mixture.
  • the first mixture is heated to a temperature preferably within the range of 250° F. to 550° F. to create a heated first mixture.
  • the second mixture is heated to create a liquid second mixture.
  • the liquid second mixture is preferably created in the secondary mixing chamber 20 .
  • the second mixture is preferably heated to a temperature greater than the melting point of the second mixture and less than 225° F.
  • the heated first mixture is injected into a barrel through an opening at one end of the barrel, preferably the barrel 16 as described in reference to FIG. 1 .
  • the liquid second mixture is injected into the barrel at predetermined intervals and in predetermined amounts. In a preferred embodiment, the liquid second mixture is injected into the barrel four times in four equal amounts of the volume of the liquid second mixture in order to create a homogeneous reaction product. Each of the four injections of the liquid second mixture is preferably 1 to 20 grams of the liquid second mixture.
  • the reaction product is injected into a mold cavity, preferably a cavity of a mold 18 as described in reference to FIG. 1 .
  • an article is formed from the reaction product within the mold 18 . The article is preferably an article such as discussed above.
  • Example 1 is a control of TEXIN DP7-1197 thermoplastic polyurethane.
  • Example 2 is TEXIN DP7-1197 thermoplastic polyurethane crosslinked at 2/2.
  • Example 3 is TEXIN DP7-1197 thermoplastic polyurethane crosslinked at 2/3.
  • Example 4 is TEXIN DP7-1197 thermoplastic polyurethane crosslinked at 2.5/3.
  • Example 5 is a control of DESMOPAN 445 thermoplastic polyurethane.
  • Example 6 is DESMOPAN 445 thermoplastic polyurethane crosslinked at 2/2.
  • Example 7 is DESMOPAN 445 thermoplastic polyurethane crosslinked at 2/3.
  • Example 8 is DESMOPAN 445 thermoplastic polyurethane crosslinked at 2.5/3.
  • Example 9 is DESMOPAN 445 thermoplastic polyurethane crosslinked at 2.5/5.
  • Example 8 is DESMOPAN 445 thermoplastic polyurethane crosslinked at 2.5/7.
  • the thermoplastic polyurethanes crosslinked according to the present invention demonstrate much better properties than the control samples (Examples 1 and 5).

Abstract

A process for forming a cross-linked thermoplastic polymer is disclosed herein. The cross-linked thermoplastic polymer is formed by heating a first mixture containing a thermoplastic urethane base material, a monomeric diisocyanate comprising between 1 to 10% of the total weight of the first mixture, and a second mixture of a first diamine and a second diamine comprising between 1 to 10% of the total weight of a total reaction product. The heated first mixture, which is flowable, is injected into at least one injection molding device, with the second mixture injected at predetermined intervals to create a homogeneous reaction product.

Description

    CROSS REFERENCES TO RELATED APPLICATIONS
  • The Present Application is a divisional application of U.S. patent application Ser. No. 12/471,659, filed on May 26, 2009, which is a continuation application of U.S. patent application Ser. No. 12/260,279 filed on Oct. 29, 2008, now U.S. Pat. No. 7,540,990, which is a continuation-in-part application of U.S. patent application Ser. No. 12/184,394, filed on Aug. 1, 2008, which is a divisional application of U.S. patent application Ser. No. 10/992,907 filed on Nov. 18, 2004, now U.S. Pat. No. 7,417,094.
    • STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH OR DEVELOPMENT
  • Not Applicable
    • BACKGROUND OF THE INVENTION
  • 1. Field of the Invention
  • The field of the invention generally relates to thermoplastic polyurethanes and thermoplastic polyureas having properties similar to those of castable or cross-linked polyurethanes or polyureas. The field of the invention also includes methods of making the same.
  • 2. Description of the Related Art
  • There currently are a number of commercialized products made from polyurethanes and polyureas. Typically, these products made from either thermoplastic polyurethanes (or polyureas) or thermoset polyurethanes (or polyureas). Thermoplastic polyurethanes generally have linear molecular structures and are able to flow freely at elevated temperatures. For this reason, thermoplastic polyurethanes are preferred for products which are produced by injection molding or other extrusion techniques, where flowability of the reactants are of paramount importance. Unfortunately, thermoplastic polyurethanes typically exhibit poor performance characteristics with respect to abrasion, tensile strength, rebound, and compression set compared to castable poluurethanes.
  • In contrast to current thermoplastic polyurethanes, thermoset polyurethanes have particularly good characteristics with respect to abrasion, tensile strength, rebound, and compression set. Thermoset polyurethanes generally have a network structure that incorporates irreversible chemical cross-linking. The downside of thermoset polyurethanes is that the irreversible chemical cross-linking reaction makes it unsuitable for use in injection molding and extrusion applications. Typically, thermoset polyurethanes are formed using a casting process. Unfortunately, casting processes require costly equipment and usually involve a large number of processing steps. Casting is thus a less efficient and more expensive method of producing polyurethane-based and polyurea-based products as compared to injection molding and extrusion systems.
  • In a typical process for making a thermoset (i.e., castable) polyurethane, a di-isocyanate component is first pre-polymerized with a polyol having either a polyester or polyether backbone. The remaining di-isocyanate of the pre-polymer is reacted with a chain extender or a cross-linking agent or a blend of cross-linking agents. Catalysts are added to control the reaction rate. If the cross-linking agent has a dihydroxy functional component, a polyurethane will be formed. If the cross-linking agent has diamine functionality, a polyurea is formed.
  • With respect to thermoplastic polyurethanes, a diol or polyol is reacted with an isocyanate. This reaction typically takes place in large commercial reactors. As stated above, thermoplastic polyurethanes, while not cross-linked, are usable in injection molding and other extrusion methods. Because of the lack of cross-linking, these materials have abrasion, tensile, and compression set properties that are not as good as thermoset polyurethane or polyurea systems.
  • There thus is a need for a thermoplastic polyurethane or polyurea material which exhibits good abrasion, tensile strength, rebound, and compression set characteristics which are similar to those found in thermoset urethanes. Such a material could be produced using conventional injection molding and/or extrusion techniques, thereby reducing the cost of manufacture for the material.
  • The conventional solution has been to add a cross-linking agent to a thermoplastic resin, either post-injection molding or pre-injection molding. Adding the cross-linking agent pre-injection molding allows for a greater dispersion of the cross-linking agent within the thermoplastic resin material. However, many cross-linking agents have low boiling temperatures and will “flash off” prior to dispersion, especially at room temperatures. Trying to add other agents to resolve the flash off problems leads to other processing issues, especially with injection molding machines which melt processing materials (thermoplastic resins) and inject the melted materials under high pressures to form various articles, which can lead to a build up of materials in the injection molding barrel.
    • BRIEF SUMMARY OF THE INVENTION
  • The present invention provides a solution for forming cross-linked thermoplastic polymers. The present invention adds a cross-linking agent a thermoplastic resin in the pre-injection molding stage. In order to prevent the cross-linking agent from flashing-off, a second mixture is added during the injection molding stage. This second mixture prevents the flashing off of the cross-linking agent while allowing for processing without a build-up of material.
  • One aspect of the present invention is a method for forming an article composed of a cross-linked thermoplastic polymer. The method includes mixing a thermoplastic urethane based material and a monomeric diisocyanate to create a first mixture. The monomeric diisocynate comprises between 1% to 10% of the total mass of the first mixture, the diisocyanate. The method also includes mixing 4,4′methylene-bis-(3-chloro-2,6-diethylaniline) and diethyl 2,4-toluenediamine to create a second mixture. The 4,4′methylene-bis-(3-chloro-2,6-diethylaniline) is 75% to 95% of the total mass of the second mixture and diethyl 2,4-toluenediamine is 25% to 5% of the total mass of the second mixture. The method also includes heating the first mixture to a temperature within the range of 250° F. to 550° F. to created a heated first mixture. The method also includes heating the second mixture to a temperature greater than the melting point of the second mixture and less than 225° F. to create a liquid second mixture having a volume. The method also includes injecting the heated first mixture into a barrel of an injection molding machine through a first opening. The method also includes injecting the liquid second mixture into the barrel of the injection molding machine in a plurality of dispensing shots of approximately equal amounts of the volume of the liquid second mixture during a predetermined time period. The method also includes injecting a reaction product into at least one injection mold cavity, the reaction product formed by the reaction of the heated first mixture and the liquid second mixture. The method also includes forming an article composed of the reaction product.
  • Having briefly described the present invention, the above and further objects, features and advantages thereof will be recognized by those skilled in the pertinent art from the following detailed description of the invention when taken in conjunction with the accompanying drawings.
    • BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWINGS
  • FIG. 1 schematically illustrates an injection molding device which can be used to produce products made from cross-linked thermoplastic polyurethanes/polyureas according to the present invention.
  • FIG. 2 is a flow chart of a method of the present invention.
    •  DETAILED DESCRIPTION OF THE INVENTION
  • The method for forming a cross-linked thermoplastic polyurethane or polyurea generally involves four different components. The first component is a thermoplastic polyurethane resin material. The second component is a diisocyanate. The third component is a diamine. The fourth component is a diamine.
  • The thermoplastic polyurethane resin material and the diisocynate are preferably mixed in a dry state to create a first dry mixture. The third and fourth components, the diamines, are mixed together to create a liquid second mixture. The dry mixture is heated into a flowable form and the liquid second mixture is introduced at predetermined intervals of equal amounts to create a homogeneous reaction product.
  • The thermoplastic polyurethane base material may include TEXIN 985, an aromatic polyether-based thermoplastic polyurethane available from Bayer Corporation. As another example, the thermoplastic urethane base material may include NOVEON ST80A, which is available from Noveon Incorporated. Another thermoplastic polyurethane is IROGAN A 95 P 4021 from Huntsman Chemical. IROGAN A 95 P 4021 is a thermoplastic polyether-polyurethane having a Shore A hardness of approximately 95, a Shore D hardness of approximately 46, a melt index of 210° C./21.6 kilograms at 5-15 grams/10 minutes. Another thermoplastic polyurethane is TEXIN DP7 1197 from Bayer Corporation. TEXIN DP7-1197 is a thermoplastic polyester polyurethane having a Shore A hardness of 88. Another thermoplastic polyurethane is DESMOPAN 445 from Bayer Corporation. DESMOPAN is a thermoplastic polyester polyurethane having a Shore D hardness of 45.
  • The thermoplastic urethane base material is preferably dried prior to adding the additional components described in detail below. This can be accomplished, for example, by heating the thermoplastic base material to a temperature between about 100° F. to 200° F. in a separate container.
  • A monomeric diisocyanate is added to the dried thermoplastic urethane base material. Preferably, the diisocyanate used in the process is a solid at room temperature. In one preferred aspect of the invention, the diisocyanate is 4,4′ diphenylmethane diisocyanate, which has a sublimation point of approximately 392° F. This can be commercially obtained from Bayer Corporation under the trade name, MONDUR M (CAS No. 101-68-8). Preferably, the flaked or fused form of MONDUR M is used in connection with the process described herein. The diisocyanate is preferably stored at about −20° C. By adding diisocyanate to the thermoplastic urethane base material, isocyanate functionality is added to the system. Other Diisocyanate materials which are solid at room temperature and may be used in accordance with the invention include: Toluene Diisocyanates (TDI), Toluene ortho Diisocyanates (TODI), Naphthalene Diisocyantaes (NDI), Hydrogenated Methylene Diisocyantaes (H12MDI), Iso Phorone Diisocyanates (IPDI), Hexamethylene Diisocyantes (HDI). These isocyanate-based compounds can be made in solid crystalline form suitable for dry blending. These isocyanates can also be added in the liquid and semi-liquid form.
  • Preferably, the diisocyanate comprises between 1% to 10% of the total weight of the mixture forming the cross-linked thermoplastic polyurethane/polyurea. Even more preferably, the diisocyanate comprises between 1% to 2% of the total weight of the mixture forming the cross-linked thermoplastic polyurethane/polyurea. The diisocyanate materials other than those specifically identified above may also be used in accordance with the invention, provided they exist as a solid at room temperature.
  • One preferred diamine is 4,4′ methylene-bis-(3-chloro-2,6-diethylaniline), available commercially as LONZACURE M-CDEA (CAS No. 106246-33-7). Another diamine which can be employed with the present invention is 4,4′ Methylene-bis-(2,6-diethylaniline), available commercially as LONZACURE M-DEA (CAS No. 13680-35-8). Both diamines have melting points at approximately 90° C. Preferably, the diamine is added in solid form and dry blended with the MDI and thermoplastic urethane base material. Alternative cross-linking agents and other solid or crystalline Diamines which may be used in the present invention include: MOCA (4,4′-Methylenebis-(O-Chloroaniline)), MDA (Methylene Dianiline), as well as any other methylene bis aniline like LONZACURE M-CDEA described above. Any other diamine-based compounds can be made in solid crystalline form suitable for dry blending can also be used. The diamines above can also be added in the liquid or semi-liquid form.
  • A second diamine for the second mixture is preferably diethyl 2,4-toluenediamine, which is available under the brandname ETHACURE 100, or E100, from Albermarle of Baton Rouge, La. The diethyl toluene diamine prevents build-up due to the first diamine, preferably 4,4′ methylene-bis-(3-chloro-2,6-diethylaniline). The second mixture is preferably 75 to 95 parts by weight 4,4′ methylene-bis-(3-chloro-2,6-diethylaniline) and 5 to 25 parts by weight diethyl 2,4-toluenediamine, and more preferably 80 to 90 parts by weight 4,4′ methylene-bis-(3-chloro-2,6-diethylaniline) and 10 to 20 parts by weight diethyl 2,4-toluenediamine, and most preferably 85 parts by weight 4,4′ methylene-bis-(3-chloro-2,6-diethylaniline) and 15 parts by weight diethyl 2,4-toluenediamine.
  • The second mixture is preferably utilized to prevent the diisocynate from “flashing off” during the processing. The second mixture provides heat stability to the diisocynate during the processing. The second mixture also allows the temperature of the reaction to be reduced substantially which provides for a more favorable viscosity. Further, the use of 4,4′ methylene-bis-(3-chloro-2,6-diethylaniline) allows for the diisocynate to be utilized at a higher temperature since the 4,4′ methylene-bis-(3-chloro-2,6-diethylaniline) essentially increasing the boiling temperature of the diisocynate.
  • Preferably, the diamines comprises between 1% to 10% of the total weight of the mixture forming the cross-linked thermoplastic polyurea. Even more preferably, diamine comprises between 1% to 2% of the total weight of the mixture forming the cross-linked thermoplastic polyurea. Diamines other than those specifically identified above may also be used in accordance with the invention, provided they exist as a solid at a temperature within the range of 50° F. to 150° F.
  • In an alternative embodiment, hydroquinone (HQEE) replaces the diamine constituent and is added to the mixture of MDI and thermoplastic urethane. As with the prior embodiment, HQEE is added to the mixture in solid form and dry blended with the MDI and thermoplastic urethane base material. In yet another alternative embodiment, HQEE is added in conjunction with a diamine.
  • The mixture of thermoplastic urethane base material, MDI, and diamine (and/or HQEE) is then mixed and heated to a temperature within the range of 250° F. to 550° F. The solid thermoplastic urethane base material, MDI, and diamine (and/or HDEE) melt and partially cross-link. Preferably, the partially cross-linked thermoplastic polyurethane/polyurea is post-cured by heating the same to a temperature within the range of 150° F. to 250° F. for a period of time ranging between 2 and 36 hours.
  • FIG. 1 illustrates an injection molding device 10 capable of producing cross-linked thermoplastic polymers in accordance with the present invention. The injection molding device 10 includes a hopper 12 for loading the various components (e.g., a first mixture of thermoplastic urethane resins and MONDUR flakes). The hopper 12 preferably includes a rotating mixer therein for dry mixing the first mixture materials.
  • The hopper 12 is in flow communication with a mixing barrel 16 having a screw (not shown). The screw is disposed inside the mixing barrel 16, and both rotates and reciprocates within the mixing barrel 16. The distal end of the mixing barrel 16 terminates into an injection chamber and injection nozzle. The injection nozzle is preferably disposed inside a stationary platen and is in flow communication with a mold 18. The mold 18 preferably includes one or more cavities (not shown) having a pre-formed shape. The injection molding device 10 may be used to form any number of products including, for example, skateboard wheels, in-line skate wheels, roller coaster wheels, caster wheels, golf ball layers, and golf club components, and the like. Products in the automotive industry such as seals, O-rings, gaskets, bushings, CV-joint cover, and tires may also be made using the methods described herein. For agricultural applications, the methods can be used in silo liners, plow parts, pipe, and pipe liners. The invention also has utility in mining applications, where the methods and processes described herein can be used to produce mining screens, material moving buckets, pump parts and liners, pulleys, and bumpers. The materials and methods can also be used in footwear applications such as, for example, shoe soles and the like. The invention can also be used in general purpose applications such as press pads, abrasion-resistant silo or hopper liner sheets, gears, hammers, metal forming parts, etc. The injection molding device also includes a secondary mixing chamber 20 for mixing and heating a second mixture for introduction into the barrel 16. The secondary mixing chamber 20 is in flow communication with the barrel 16 through a flow pipe 22.
  • FIG. 2 is a flow chart of a preferred method 200 of the present invention. At block 202, the thermoplastic polyurethane (“TPU”) resin and a diisocynate are mixed to create a first mixture. The monomeric diisocynate comprises between 1% to 10% of the total mass of the first mixture, and most preferably 6% by weight of the first mixture. Preferably the diisocynate is MONDUR flakes. At block 204, 4,4′ methylene-bis-(3-chloro-2,6-diethylaniline) and diethyl 2,4-toluenediamine are mixed to create a second mixture. The second mixture is preferably mixed in the secondary mixing chamber 20 as described in reference to FIG. 1. The 4,4′ methylene-bis-(3-chloro-2,6-diethylaniline) is preferably 75% to 95% of the total mass of the second mixture and diethyl 2,4-toluenediamine is 25% to 5% of the total mass of the second mixture. At block 206, the first mixture is heated to create a first heated mixture. The first mixture is heated to a temperature preferably within the range of 250° F. to 550° F. to create a heated first mixture. At block 208, the second mixture is heated to create a liquid second mixture. The liquid second mixture is preferably created in the secondary mixing chamber 20. The second mixture is preferably heated to a temperature greater than the melting point of the second mixture and less than 225° F. to create a liquid second mixture having a predetermined volume. At block 210, the heated first mixture is injected into a barrel through an opening at one end of the barrel, preferably the barrel 16 as described in reference to FIG. 1. At block 212, the liquid second mixture is injected into the barrel at predetermined intervals and in predetermined amounts. In a preferred embodiment, the liquid second mixture is injected into the barrel four times in four equal amounts of the volume of the liquid second mixture in order to create a homogeneous reaction product. Each of the four injections of the liquid second mixture is preferably 1 to 20 grams of the liquid second mixture. At block 214, the reaction product is injected into a mold cavity, preferably a cavity of a mold 18 as described in reference to FIG. 1. At block 216, an article is formed from the reaction product within the mold 18. The article is preferably an article such as discussed above.
  • The following are experimental test results of various cross-linked thermoplastic urethanes/ureas in accordance with the present invention. Example 1 is a control of TEXIN DP7-1197 thermoplastic polyurethane. Example 2 is TEXIN DP7-1197 thermoplastic polyurethane crosslinked at 2/2. Example 3 is TEXIN DP7-1197 thermoplastic polyurethane crosslinked at 2/3. Example 4 is TEXIN DP7-1197 thermoplastic polyurethane crosslinked at 2.5/3. Example 5 is a control of DESMOPAN 445 thermoplastic polyurethane. Example 6 is DESMOPAN 445 thermoplastic polyurethane crosslinked at 2/2. Example 7 is DESMOPAN 445 thermoplastic polyurethane crosslinked at 2/3. Example 8 is DESMOPAN 445 thermoplastic polyurethane crosslinked at 2.5/3. Example 9 is DESMOPAN 445 thermoplastic polyurethane crosslinked at 2.5/5. Example 8 is DESMOPAN 445 thermoplastic polyurethane crosslinked at 2.5/7. The thermoplastic polyurethanes crosslinked according to the present invention (Examples 2-4 and 6-10) demonstrate much better properties than the control samples (Examples 1 and 5).
  • TABLE ONE
    TEST 1 2 3 4 5 6 7 8 9 10
    Tensile Test-ASTM D 885 psi 1007 1042 1074 1499 1566 1715 1714 1849 2090
    412-Die C-strength
    at 100% elongation
    Tensile Test-ASTM D 2004 psi 2239 2360 2447 2360 2514 3046 3015 3232 3736
    412-Die C-strength
    at 300% elongation
    Tensile Test-ASTM D 675%  598 621 619 641 547 510 499 422 364
    412-Die C-ultimate
    elongation
    Tensile Test-ASTM 6040 psi 6212 6963 6493 4109 3799 4714 4684 4325 4396
    D 412-Die C-ultimate
    tensile strength
    Die “C” Tear 686 pli 676 641 615 706 710 707 693 702 715
    ASTM D 624-D
    3489-tear resistance
    Durometer Hardness, 89 90 90 91 94 94 94 94 96 97
    Shore A-ASTM D 2240-
    hardness at 5 secs.
    Durometer Hardness, 31 33 34 34 37 39 39 39 42 44
    Shore D-ASTM D 2240-
    hardness at 5 secs.
    Vicat Softening (10N 129° C. 145 152 152 141 147 158 159 162 166
    load, 50C rate of
    rise) ASTM D 1525-
    softening temperature
    Compression Set, Test 34% 28 23 18 28 22 20 17 15 15
    Meth B, 25% Defl., 70C,
    22 hrs, ASTM D 395-
    percent set
    Compression Set, Test 13% 17 9 9 13 14 9 11 12 12
    Meth B, 25% Defl., RT,
    22 hrs, ASTM D 395-
    percent set
  • From the foregoing it is believed that those skilled in the pertinent art will recognize the meritorious advancement of this invention and will readily understand that while the present invention has been described in association with a preferred embodiment thereof, and other embodiments illustrated in the accompanying drawings, numerous changes, modifications and substitutions of equivalents may be made therein without departing from the spirit and scope of this invention which is intended to be unlimited by the foregoing except as may appear in the following appended claims. Therefore, the embodiments of the invention in which an exclusive property or privilege is claimed are defined in the following appended claims.

Claims (1)

1. An apparatus for forming a golf ball layer composed of a cross-linked thermoplastic polymer, the apparatus comprising:
a hopper for mixing a thermoplastic urethane based material and a monomeric diisocyanate to create a first mixture, the monomeric diisocynate comprising between 1% to 10% of the total mass of the first mixture, wherein the first mixture is heated within the hopper to a temperature within the range of 250° F. to 550° F. to create a heated first mixture;
a mixing chamber for mixing 4,4′ methylene-bis-(3-chloro-2,6-diethylaniline) and diethyl 2,4-toluenediamine to create a second mixture, wherein the 4,4′ methylene-bis-(3-chloro-2,6-diethylaniline) is 75% to 95% of the total mass of the second mixture and diethyl 2,4-toluenediamine is 25% to 5% of the total mass of the second mixture, wherein the second mixture is heated to a temperature greater than the melting point of the second mixture and less than 225° F. to create a liquid second mixture having a volume;
a barrel having a first opening in flow communication with the hopper for receiving the heated first mixture, the barrel in flow communication with the mixing chamber for receiving injections of the liquid second mixture into the barrel in a plurality of dispensing shots of approximately equal amounts of the volume of the liquid second mixture during a predetermined time period;
at least one injection mold cavity in flow communication with the barrel to receive the reaction product formed by the reaction of the heated first mixture and the liquid second mixture and to form a golf ball layer composed of the reaction product.
US12/871,726 2004-11-18 2010-08-30 Cross-linked thermoplastic polyurethane/polyurea and method of making same Abandoned US20100323056A1 (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
US12/871,726 US20100323056A1 (en) 2004-11-18 2010-08-30 Cross-linked thermoplastic polyurethane/polyurea and method of making same
US13/292,996 US20120056354A1 (en) 2004-11-18 2011-11-09 Cross-linked thermoplastic polyurethane/polyurea and method of making same

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
US10/992,907 US7417094B2 (en) 2004-11-18 2004-11-18 Cross-linked thermoplastic polyurethane/polyurea and method of making same
US12/184,394 US8003747B2 (en) 2004-11-18 2008-08-01 Cross-linked thermoplastic polyurethane/polyurea and method of making same
US12/260,279 US7540990B1 (en) 2004-11-18 2008-10-29 Cross-linked thermoplastic polyurethane/polyurea and method of making same
US12/471,659 US7785522B2 (en) 2004-11-18 2009-05-26 Cross-linked thermoplastic polyurethane/polyurea and method of making same
US12/871,726 US20100323056A1 (en) 2004-11-18 2010-08-30 Cross-linked thermoplastic polyurethane/polyurea and method of making same

Related Parent Applications (1)

Application Number Title Priority Date Filing Date
US12/471,659 Division US7785522B2 (en) 2004-11-18 2009-05-26 Cross-linked thermoplastic polyurethane/polyurea and method of making same

Related Child Applications (1)

Application Number Title Priority Date Filing Date
US13/292,996 Continuation US20120056354A1 (en) 2004-11-18 2011-11-09 Cross-linked thermoplastic polyurethane/polyurea and method of making same

Publications (1)

Publication Number Publication Date
US20100323056A1 true US20100323056A1 (en) 2010-12-23

Family

ID=40672392

Family Applications (5)

Application Number Title Priority Date Filing Date
US12/260,279 Active US7540990B1 (en) 2004-11-18 2008-10-29 Cross-linked thermoplastic polyurethane/polyurea and method of making same
US12/471,659 Active US7785522B2 (en) 2004-11-18 2009-05-26 Cross-linked thermoplastic polyurethane/polyurea and method of making same
US12/855,130 Abandoned US20100303950A1 (en) 2004-11-18 2010-08-12 Cross-linked thermoplastic polyurethane/polyurea and method of making same
US12/871,726 Abandoned US20100323056A1 (en) 2004-11-18 2010-08-30 Cross-linked thermoplastic polyurethane/polyurea and method of making same
US13/292,996 Abandoned US20120056354A1 (en) 2004-11-18 2011-11-09 Cross-linked thermoplastic polyurethane/polyurea and method of making same

Family Applications Before (3)

Application Number Title Priority Date Filing Date
US12/260,279 Active US7540990B1 (en) 2004-11-18 2008-10-29 Cross-linked thermoplastic polyurethane/polyurea and method of making same
US12/471,659 Active US7785522B2 (en) 2004-11-18 2009-05-26 Cross-linked thermoplastic polyurethane/polyurea and method of making same
US12/855,130 Abandoned US20100303950A1 (en) 2004-11-18 2010-08-12 Cross-linked thermoplastic polyurethane/polyurea and method of making same

Family Applications After (1)

Application Number Title Priority Date Filing Date
US13/292,996 Abandoned US20120056354A1 (en) 2004-11-18 2011-11-09 Cross-linked thermoplastic polyurethane/polyurea and method of making same

Country Status (1)

Country Link
US (5) US7540990B1 (en)

Families Citing this family (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6344745B1 (en) * 1998-11-25 2002-02-05 Medrad, Inc. Tapered birdcage resonator for improved homogeneity in MRI
EP2595710A1 (en) 2010-07-21 2013-05-29 Nike International Ltd. Golf ball and method of manufacturing a golf ball
EP2426157A1 (en) * 2010-09-02 2012-03-07 Lonza Ltd. Diamine compositions and use thereof
US10570244B2 (en) 2012-08-09 2020-02-25 Pennsy Corporation Cross-linked thermoplastic co-polyester elastomer, method of making same, and articles composed thereof
US10518136B2 (en) 2017-09-21 2019-12-31 Acushnet Company Methods for cross-linking thermoplastic polyurethane covers for golf balls
US10729938B2 (en) 2017-09-21 2020-08-04 Acushnet Company Gold balls having covers made with thermoplastic polyurethane and polydimethylsiloxane blend compositions
US10363458B2 (en) 2017-09-21 2019-07-30 Acushnet Company Methods for treating golf balls having a thermoplastic polyurethane cover
US10661123B2 (en) 2017-09-21 2020-05-26 Acushnet Company Methods and compositions for cross-linking thermoplastic polyurethane covers for golf balls
US10821327B2 (en) 2017-09-21 2020-11-03 Acushnet Company Methods for cross-linking thermoplastic polyurethane golf ball covers and resultant golf balls
US10688366B1 (en) 2018-07-13 2020-06-23 Callaway Golf Company Golf ball with electrical components
EP4041791A1 (en) * 2019-10-09 2022-08-17 Dupont Polymers, Inc. Improved thermoplastic polyurethane
US11779814B2 (en) 2020-08-26 2023-10-10 Volvik Inc. Polyurethane golf ball

Citations (69)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2151476A (en) * 1936-03-23 1939-03-21 Eastman Kodak Co Molding method
US2873790A (en) * 1953-04-20 1959-02-17 Us Rubber Co Method of making pneumatic tires by casting a liquid polyester-diisocyanate composition
US3084004A (en) * 1960-10-14 1963-04-02 Eagle Picher Co Elastomeric bearing races
US3218215A (en) * 1960-04-27 1965-11-16 Eagle Picher Co Adhering polyurethane to metal
US3387074A (en) * 1963-12-16 1968-06-04 Edward D. Hill Ink transfer member
US3427386A (en) * 1961-06-01 1969-02-11 Syntex Corp 3-methylene-androstan-17beta-ols and 17-alkyl derivatives thereof
US3472826A (en) * 1968-05-23 1969-10-14 Union Carbide Corp Saturated hydrocarbon prepolymer and reaction products thereof
US3477097A (en) * 1965-04-01 1969-11-11 Owens Illinois Inc System for dispensing material accurately through multiple orifices
US3542718A (en) * 1966-08-15 1970-11-24 Wyandotte Chemicals Corp Urethane compositions
US3632245A (en) * 1970-05-13 1972-01-04 Vroman Foods Inc Apparatus for the production of frozen confections
US3828661A (en) * 1971-09-03 1974-08-13 Cpm Europ Nv Apparatus for the production of food pellets from a flour product
US3845021A (en) * 1970-09-11 1974-10-29 Goodyear Tire & Rubber Polyurea-urethane shock absorbing compositions
US4029300A (en) * 1975-10-17 1977-06-14 The Japan Steel Works Ltd. Extruder of the degassing and modification type
US4089917A (en) * 1974-05-16 1978-05-16 Ikegai Tekko Kabushiki Kaisha Process of cross-linking and extrusion molding thermoplastic polymers
US4107101A (en) * 1974-06-05 1978-08-15 Bayer Aktiengesellschaft Process for the production of crosslinked, urethane-containing plastics
US4144012A (en) * 1977-08-05 1979-03-13 Pinkley Paul D Material hopper translatable unit
US4195132A (en) * 1976-05-08 1980-03-25 Bayer Aktiengesellschaft Cross-linked plastics based on cyanic acid esters and method of production thereof
US4199343A (en) * 1977-08-29 1980-04-22 Corning Glass Works Mixing and injection molding hydrosilicates
US4247354A (en) * 1978-10-02 1981-01-27 Union Carbide Corporation Bonding thermoplastic or thermosetting resins
US4265798A (en) * 1980-01-28 1981-05-05 Uniroyal Ltd. Isocyanurate products and polyurethanes therefrom
US4302171A (en) * 1979-05-14 1981-11-24 Peltsman Michael I Level control for ceramic slurry working tank in ceramic hot molding machine
US4315724A (en) * 1979-12-19 1982-02-16 Kamaya Kagaku Kogyo Co., Ltd. Process and machine for multi-color injection molding
US4438225A (en) * 1983-04-12 1984-03-20 Henkel Corporation Polyester polyols from bishydroxymethyl tricyclo compounds and caprolactone and polyurethanes based thereon
US4444704A (en) * 1981-01-26 1984-04-24 Hitachi, Ltd. Process for producing integral skin polyurethane foam
US4529568A (en) * 1982-11-23 1985-07-16 Saipem S.P.A. System for coating welded pipe joints with weighting material
US4573897A (en) * 1983-03-17 1986-03-04 Gaetano Piazzola System for hot extruding, drawing, and similarly processing plastomers or elastomers, incorporating a means of recovering and utilizing heated air from the cooling of heated parts
US4591475A (en) * 1982-03-26 1986-05-27 Warner-Lambert Company Method for molding capsules
US4605681A (en) * 1984-06-26 1986-08-12 Btr Plc. Thermosetting polyurethanes
US4728476A (en) * 1984-10-12 1988-03-01 Resin Stretchers Method of supplying a moldable mixture of materials to an article forming mold of an injection molding machine
US4786657A (en) * 1987-07-02 1988-11-22 Minnesota Mining And Manufacturing Company Polyurethanes and polyurethane/polyureas crosslinked using 2-glyceryl acrylate or 2-glyceryl methacrylate
US4931249A (en) * 1987-04-20 1990-06-05 Thermal Designs, Inc. Apparatus and process for mixing and dispensing high viscosity, multiple component reactive liquids into a mold
US4944880A (en) * 1989-10-16 1990-07-31 Exxon Research And Engineering Company Polyimide/aliphatic polyester copolymers
US4975207A (en) * 1988-08-01 1990-12-04 The B. F. Goodrich Company Impact modified polyurethane blends
US4980445A (en) * 1989-01-17 1990-12-25 The Dow Chemical Company Thermoplastic polyurethanes
US5028685A (en) * 1989-10-16 1991-07-02 Exxon Research & Engineering Company Halogenated polyurethanes
US5040963A (en) * 1990-04-24 1991-08-20 Devtech Labs, Inc. Apparatus for coinjection molding of preforms for multi-layer containers
US5169582A (en) * 1985-05-08 1992-12-08 Ems-Inventa Ag Method and apparatus for the production of thermoplastic caprolactam containing molding compositions
US5286187A (en) * 1988-12-20 1994-02-15 Mitsui Petrochemical Co., Ltd. Method for molding saturated crystalline polyesters and molding equipment therefor
US5393213A (en) * 1992-02-27 1995-02-28 Mitsubishi Jukogyo Kabushiki Kaisha Serial two-stage extruder
US5516873A (en) * 1994-07-11 1996-05-14 Bayer Corporation Polyisocyanate/polyamine mixtures and their use for the production of polyurea coatings
US5559204A (en) * 1994-08-29 1996-09-24 Bayer Corporation Polyisocyanate/polyamine mixtures and their use for the production of polyurea coatings
US5635125A (en) * 1995-02-24 1997-06-03 Re-New Wood, Incorporated Method for forming simulated shake shingles
US5773042A (en) * 1994-10-14 1998-06-30 Kabushiki Kaisha Kobe Seiko Sho Injection molding unit for long fiber-reinforced thermoplastic resin
US5776395A (en) * 1994-06-07 1998-07-07 Bando Kagaku Kabushiki Kaisha Method and apparatus for making a blade for electrophotographic devices
US5811164A (en) * 1996-09-27 1998-09-22 Plastic Specialties And Technologies Investments, Inc. Aeration pipe and method of making same
US5811038A (en) * 1996-09-27 1998-09-22 Plastic Specialties And Technologies Investments, Inc. Method of blending components for porous plastic pipe processing
US5861117A (en) * 1991-08-01 1999-01-19 Rumber Materials, Inc. Process and apparatus for cooling an extrudate
US5908894A (en) * 1996-11-21 1999-06-01 Basf Aktiengesellschaft Thermoplastic polyurethanes and their preparation
US5976435A (en) * 1994-03-01 1999-11-02 Evergreen Global Resources, Inc. Method and apparatus for producing composite materials
US5985200A (en) * 1997-12-12 1999-11-16 Owens Corning Fiberglass Technology, Inc. Injection molding of asphalt-based compositions
US6037440A (en) * 1997-07-31 2000-03-14 Eastman Kodak Company Cross-linked linear (2-cyanoacetamido) reactive polyurethanes
US6074190A (en) * 1996-10-29 2000-06-13 Kabushiki Kaisha Kobe Seiko Sho Multilayer injection molding machine and injection unit connecting device
US6075113A (en) * 1998-10-05 2000-06-13 Mirror Image Technologies, Inc. Wheel composition
US6143214A (en) * 1998-03-09 2000-11-07 Board Of Regents Of The University Of Texas System Mixing and dispensing system for rapidly polymerizing materials
US6166166A (en) * 1998-08-26 2000-12-26 Bayer Corporation Composition and process for preparation of thermoplastic polyurethanes (TPU based on a polybutadiene soft segment)
US6186769B1 (en) * 1999-04-06 2001-02-13 Woodshed Technologies Resin and fiber compounding apparatus for molding operations
US6207752B1 (en) * 1997-12-10 2001-03-27 Advanced Elastomer Systems Lp Thermoplastic vulcanizates of carboxylated nitrile rubber and thermoplastic polyurethanes
US6224526B1 (en) * 1997-12-19 2001-05-01 H.B. Fuller Licensing & Financing, Inc. Printing rollers
US6355406B2 (en) * 1998-10-15 2002-03-12 Eastman Kodak Company Process for forming abrasion-resistant antistatic layer with polyurethane for imaging element
US6450739B1 (en) * 1999-07-02 2002-09-17 Seco Tools Ab Tool for chip removing machining and methods and apparatus for making the tool
US20030065124A1 (en) * 1999-11-30 2003-04-03 Rosenberg Ronald O. High performance polyurethane elastomers from MDI prepolymers with reduced content of free MDI monomer
US20030064833A1 (en) * 2001-05-17 2003-04-03 Bridgestone Sports Co.,Ltd. Composition for improving the property of a golf ball cover
US6716954B2 (en) * 1998-03-18 2004-04-06 Callaway Golf Company Golf ball formed from a polyisocyanate copolymer and method of making same
US20040108611A1 (en) * 2002-12-10 2004-06-10 Dennis Michael D. Injecting liquid additives into plastic extruders
US6790020B2 (en) * 2000-12-12 2004-09-14 Sumitomo Chemical Company, Limited System for producing foamed article, a molten resin preparing apparatus and a molding apparatus for use in foamed article production system
US20050067729A1 (en) * 2001-04-26 2005-03-31 Laver Terry C. Apparatus and method for low-density cellular wood plastic composites
US20050212159A1 (en) * 2004-03-25 2005-09-29 Richards George E Process for manufacturing powder coating compositions introducing hard to incorporate additives and/or providing dynamic color control
US7037985B2 (en) * 2003-04-24 2006-05-02 Taylor Made Golf Company, Inc. Urethane sporting equipment composition incorporating nitroso compound
US7417094B2 (en) * 2004-11-18 2008-08-26 Pripro Polymer, Inc. Cross-linked thermoplastic polyurethane/polyurea and method of making same

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL295726A (en) 1962-07-25
BE759829A (en) * 1969-12-03 1971-06-03 Upjohn Co PREPARATION OF POLYURETHANES
US6592472B2 (en) * 1999-04-20 2003-07-15 Callaway Golf Company Golf ball having a non-yellowing cover
US6943213B2 (en) * 2003-08-13 2005-09-13 Acushnet Company Polyalkylacrylate compounds for use in golf balls
JP4051374B2 (en) 2002-07-25 2008-02-20 キャラウェイ・ゴルフ・カンパニ Golf ball
US6939924B2 (en) 2003-03-10 2005-09-06 Hyun Jin Kim Golf ball incorporating urethane composition
US8927675B2 (en) 2004-09-01 2015-01-06 Ppg Industries Ohio, Inc. Poly(ureaurethane)s, articles and coatings prepared therefrom and methods of making the same

Patent Citations (71)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2151476A (en) * 1936-03-23 1939-03-21 Eastman Kodak Co Molding method
US2873790A (en) * 1953-04-20 1959-02-17 Us Rubber Co Method of making pneumatic tires by casting a liquid polyester-diisocyanate composition
US3218215A (en) * 1960-04-27 1965-11-16 Eagle Picher Co Adhering polyurethane to metal
US3084004A (en) * 1960-10-14 1963-04-02 Eagle Picher Co Elastomeric bearing races
US3427386A (en) * 1961-06-01 1969-02-11 Syntex Corp 3-methylene-androstan-17beta-ols and 17-alkyl derivatives thereof
US3387074A (en) * 1963-12-16 1968-06-04 Edward D. Hill Ink transfer member
US3477097A (en) * 1965-04-01 1969-11-11 Owens Illinois Inc System for dispensing material accurately through multiple orifices
US3542718A (en) * 1966-08-15 1970-11-24 Wyandotte Chemicals Corp Urethane compositions
US3472826A (en) * 1968-05-23 1969-10-14 Union Carbide Corp Saturated hydrocarbon prepolymer and reaction products thereof
US3632245A (en) * 1970-05-13 1972-01-04 Vroman Foods Inc Apparatus for the production of frozen confections
US3845021A (en) * 1970-09-11 1974-10-29 Goodyear Tire & Rubber Polyurea-urethane shock absorbing compositions
US3828661A (en) * 1971-09-03 1974-08-13 Cpm Europ Nv Apparatus for the production of food pellets from a flour product
US4089917A (en) * 1974-05-16 1978-05-16 Ikegai Tekko Kabushiki Kaisha Process of cross-linking and extrusion molding thermoplastic polymers
US4107101A (en) * 1974-06-05 1978-08-15 Bayer Aktiengesellschaft Process for the production of crosslinked, urethane-containing plastics
US4029300A (en) * 1975-10-17 1977-06-14 The Japan Steel Works Ltd. Extruder of the degassing and modification type
US4195132A (en) * 1976-05-08 1980-03-25 Bayer Aktiengesellschaft Cross-linked plastics based on cyanic acid esters and method of production thereof
US4144012A (en) * 1977-08-05 1979-03-13 Pinkley Paul D Material hopper translatable unit
US4199343A (en) * 1977-08-29 1980-04-22 Corning Glass Works Mixing and injection molding hydrosilicates
US4247354A (en) * 1978-10-02 1981-01-27 Union Carbide Corporation Bonding thermoplastic or thermosetting resins
US4302171A (en) * 1979-05-14 1981-11-24 Peltsman Michael I Level control for ceramic slurry working tank in ceramic hot molding machine
US4315724A (en) * 1979-12-19 1982-02-16 Kamaya Kagaku Kogyo Co., Ltd. Process and machine for multi-color injection molding
US4265798A (en) * 1980-01-28 1981-05-05 Uniroyal Ltd. Isocyanurate products and polyurethanes therefrom
US4444704A (en) * 1981-01-26 1984-04-24 Hitachi, Ltd. Process for producing integral skin polyurethane foam
US4591475A (en) * 1982-03-26 1986-05-27 Warner-Lambert Company Method for molding capsules
US4529568A (en) * 1982-11-23 1985-07-16 Saipem S.P.A. System for coating welded pipe joints with weighting material
US4573897A (en) * 1983-03-17 1986-03-04 Gaetano Piazzola System for hot extruding, drawing, and similarly processing plastomers or elastomers, incorporating a means of recovering and utilizing heated air from the cooling of heated parts
US4438225A (en) * 1983-04-12 1984-03-20 Henkel Corporation Polyester polyols from bishydroxymethyl tricyclo compounds and caprolactone and polyurethanes based thereon
US4605681A (en) * 1984-06-26 1986-08-12 Btr Plc. Thermosetting polyurethanes
US4728476A (en) * 1984-10-12 1988-03-01 Resin Stretchers Method of supplying a moldable mixture of materials to an article forming mold of an injection molding machine
US5169582A (en) * 1985-05-08 1992-12-08 Ems-Inventa Ag Method and apparatus for the production of thermoplastic caprolactam containing molding compositions
US4931249A (en) * 1987-04-20 1990-06-05 Thermal Designs, Inc. Apparatus and process for mixing and dispensing high viscosity, multiple component reactive liquids into a mold
US4786657A (en) * 1987-07-02 1988-11-22 Minnesota Mining And Manufacturing Company Polyurethanes and polyurethane/polyureas crosslinked using 2-glyceryl acrylate or 2-glyceryl methacrylate
US4975207A (en) * 1988-08-01 1990-12-04 The B. F. Goodrich Company Impact modified polyurethane blends
US5286187A (en) * 1988-12-20 1994-02-15 Mitsui Petrochemical Co., Ltd. Method for molding saturated crystalline polyesters and molding equipment therefor
US4980445A (en) * 1989-01-17 1990-12-25 The Dow Chemical Company Thermoplastic polyurethanes
US5028685A (en) * 1989-10-16 1991-07-02 Exxon Research & Engineering Company Halogenated polyurethanes
US4944880A (en) * 1989-10-16 1990-07-31 Exxon Research And Engineering Company Polyimide/aliphatic polyester copolymers
US5040963A (en) * 1990-04-24 1991-08-20 Devtech Labs, Inc. Apparatus for coinjection molding of preforms for multi-layer containers
US5861117A (en) * 1991-08-01 1999-01-19 Rumber Materials, Inc. Process and apparatus for cooling an extrudate
US5393213A (en) * 1992-02-27 1995-02-28 Mitsubishi Jukogyo Kabushiki Kaisha Serial two-stage extruder
US5976435A (en) * 1994-03-01 1999-11-02 Evergreen Global Resources, Inc. Method and apparatus for producing composite materials
US5776395A (en) * 1994-06-07 1998-07-07 Bando Kagaku Kabushiki Kaisha Method and apparatus for making a blade for electrophotographic devices
US5516873A (en) * 1994-07-11 1996-05-14 Bayer Corporation Polyisocyanate/polyamine mixtures and their use for the production of polyurea coatings
US5559204A (en) * 1994-08-29 1996-09-24 Bayer Corporation Polyisocyanate/polyamine mixtures and their use for the production of polyurea coatings
US5773042A (en) * 1994-10-14 1998-06-30 Kabushiki Kaisha Kobe Seiko Sho Injection molding unit for long fiber-reinforced thermoplastic resin
US5635125A (en) * 1995-02-24 1997-06-03 Re-New Wood, Incorporated Method for forming simulated shake shingles
US5811038A (en) * 1996-09-27 1998-09-22 Plastic Specialties And Technologies Investments, Inc. Method of blending components for porous plastic pipe processing
US5811164A (en) * 1996-09-27 1998-09-22 Plastic Specialties And Technologies Investments, Inc. Aeration pipe and method of making same
US6074190A (en) * 1996-10-29 2000-06-13 Kabushiki Kaisha Kobe Seiko Sho Multilayer injection molding machine and injection unit connecting device
US6555041B1 (en) * 1996-10-29 2003-04-29 Kabushiki Kaisha Kobe Seiko Sho Method of injection molding a skin layer around a core resin
US5908894A (en) * 1996-11-21 1999-06-01 Basf Aktiengesellschaft Thermoplastic polyurethanes and their preparation
US6037440A (en) * 1997-07-31 2000-03-14 Eastman Kodak Company Cross-linked linear (2-cyanoacetamido) reactive polyurethanes
US6207752B1 (en) * 1997-12-10 2001-03-27 Advanced Elastomer Systems Lp Thermoplastic vulcanizates of carboxylated nitrile rubber and thermoplastic polyurethanes
US5985200A (en) * 1997-12-12 1999-11-16 Owens Corning Fiberglass Technology, Inc. Injection molding of asphalt-based compositions
US6224526B1 (en) * 1997-12-19 2001-05-01 H.B. Fuller Licensing & Financing, Inc. Printing rollers
US6143214A (en) * 1998-03-09 2000-11-07 Board Of Regents Of The University Of Texas System Mixing and dispensing system for rapidly polymerizing materials
US6716954B2 (en) * 1998-03-18 2004-04-06 Callaway Golf Company Golf ball formed from a polyisocyanate copolymer and method of making same
US6166166A (en) * 1998-08-26 2000-12-26 Bayer Corporation Composition and process for preparation of thermoplastic polyurethanes (TPU based on a polybutadiene soft segment)
US6075113A (en) * 1998-10-05 2000-06-13 Mirror Image Technologies, Inc. Wheel composition
US6355406B2 (en) * 1998-10-15 2002-03-12 Eastman Kodak Company Process for forming abrasion-resistant antistatic layer with polyurethane for imaging element
US6186769B1 (en) * 1999-04-06 2001-02-13 Woodshed Technologies Resin and fiber compounding apparatus for molding operations
US6450739B1 (en) * 1999-07-02 2002-09-17 Seco Tools Ab Tool for chip removing machining and methods and apparatus for making the tool
US20030065124A1 (en) * 1999-11-30 2003-04-03 Rosenberg Ronald O. High performance polyurethane elastomers from MDI prepolymers with reduced content of free MDI monomer
US6790020B2 (en) * 2000-12-12 2004-09-14 Sumitomo Chemical Company, Limited System for producing foamed article, a molten resin preparing apparatus and a molding apparatus for use in foamed article production system
US20050067729A1 (en) * 2001-04-26 2005-03-31 Laver Terry C. Apparatus and method for low-density cellular wood plastic composites
US7186102B2 (en) * 2001-04-26 2007-03-06 Strandex Corporation Apparatus and method for low-density cellular wood plastic composites
US20030064833A1 (en) * 2001-05-17 2003-04-03 Bridgestone Sports Co.,Ltd. Composition for improving the property of a golf ball cover
US20040108611A1 (en) * 2002-12-10 2004-06-10 Dennis Michael D. Injecting liquid additives into plastic extruders
US7037985B2 (en) * 2003-04-24 2006-05-02 Taylor Made Golf Company, Inc. Urethane sporting equipment composition incorporating nitroso compound
US20050212159A1 (en) * 2004-03-25 2005-09-29 Richards George E Process for manufacturing powder coating compositions introducing hard to incorporate additives and/or providing dynamic color control
US7417094B2 (en) * 2004-11-18 2008-08-26 Pripro Polymer, Inc. Cross-linked thermoplastic polyurethane/polyurea and method of making same

Also Published As

Publication number Publication date
US20090230587A1 (en) 2009-09-17
US20100303950A1 (en) 2010-12-02
US20120056354A1 (en) 2012-03-08
US7540990B1 (en) 2009-06-02
US7785522B2 (en) 2010-08-31

Similar Documents

Publication Publication Date Title
US7540990B1 (en) Cross-linked thermoplastic polyurethane/polyurea and method of making same
US8003747B2 (en) Cross-linked thermoplastic polyurethane/polyurea and method of making same
US9708438B2 (en) Thermoplastic polyurethane copolymer molding compositions
CN104755521A (en) Thermoplastic polyurethane from low free monomer prepolymer
EP0379149A2 (en) Thermoplastic polyurethanes
JP5606753B2 (en) High elasticity transparent thermoplastic polyurethane characterized by heat resistance and chemical resistance
GB2046281A (en) Process for producing polyurethane elastomer
US9790365B2 (en) Thermoplastic polyurethane composition
EP3808532A1 (en) Recycling of cast polyurethane
KR101799927B1 (en) Melt processable copolyurea elastomers
US10570244B2 (en) Cross-linked thermoplastic co-polyester elastomer, method of making same, and articles composed thereof
US11312816B2 (en) Thermoplastic polyurethane and composite article
WO2021202876A1 (en) Polyurethane prepolymer composition comprising an alkyl benzoate
WO2021050620A1 (en) Thermoplastic polyurethane composition

Legal Events

Date Code Title Description
AS Assignment

Owner name: CALLAWAY GOLF COMPANY, CALIFORNIA

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:DEWANJEE, PIJUSH K.;GUARD, JOHN G.;REEL/FRAME:024911/0831

Effective date: 20081021

Owner name: PRIPRO POLYMERS, INC., CALIFORNIA

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:DEWANJEE, PIJUSH K.;GUARD, JOHN G.;REEL/FRAME:024911/0831

Effective date: 20081021

STCB Information on status: application discontinuation

Free format text: ABANDONED -- FAILURE TO RESPOND TO AN OFFICE ACTION