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WO2007139586A2 - Poly(urée-uréthane)s, articles et revêtements préparés à partir de ceux-ci et leurs procédés de fabrication - Google Patents

Poly(urée-uréthane)s, articles et revêtements préparés à partir de ceux-ci et leurs procédés de fabrication Download PDF

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Publication number
WO2007139586A2
WO2007139586A2 PCT/US2006/047755 US2006047755W WO2007139586A2 WO 2007139586 A2 WO2007139586 A2 WO 2007139586A2 US 2006047755 W US2006047755 W US 2006047755W WO 2007139586 A2 WO2007139586 A2 WO 2007139586A2
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WO
WIPO (PCT)
Prior art keywords
polyol
group
ureaurethane
limiting embodiments
poly
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.)
Ceased
Application number
PCT/US2006/047755
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English (en)
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WO2007139586A3 (fr
WO2007139586A8 (fr
Inventor
Thomas G. Rukavina
Robert Hunia
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.)
PPG Industries Ohio Inc
Original Assignee
PPG Industries Ohio 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 US11/303,671 external-priority patent/US20070142604A1/en
Priority claimed from US11/303,892 external-priority patent/US20070142606A1/en
Priority claimed from US11/303,422 external-priority patent/US20070142602A1/en
Priority claimed from US11/303,670 external-priority patent/US20070142603A1/en
Priority claimed from US11/303,832 external-priority patent/US20070238848A1/en
Priority to ES06851307T priority Critical patent/ES2408598T3/es
Application filed by PPG Industries Ohio Inc filed Critical PPG Industries Ohio Inc
Priority to EP06851307.6A priority patent/EP2004717B1/fr
Priority to CA2647094A priority patent/CA2647094C/fr
Publication of WO2007139586A2 publication Critical patent/WO2007139586A2/fr
Publication of WO2007139586A3 publication Critical patent/WO2007139586A3/fr
Anticipated expiration legal-status Critical
Publication of WO2007139586A8 publication Critical patent/WO2007139586A8/fr
Ceased legal-status Critical Current

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
    • B32B17/1055—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer
    • B32B17/1077—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer containing polyurethane
    • 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
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
    • 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
    • C08G18/3203—Polyhydroxy compounds
    • C08G18/3206—Polyhydroxy compounds aliphatic
    • 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
    • C08G18/3203—Polyhydroxy compounds
    • C08G18/3212—Polyhydroxy compounds containing cycloaliphatic groups
    • 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
    • C08G18/3203—Polyhydroxy compounds
    • C08G18/3215—Polyhydroxy compounds containing aromatic groups or benzoquinone groups
    • 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
    • C08G18/3271—Hydroxyamines
    • C08G18/3293—Hydroxyamines containing heterocyclic groups
    • 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
    • C08G18/3855—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur
    • 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
    • C08G18/3855—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur
    • C08G18/3863—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur containing groups having sulfur atoms between two carbon atoms, the sulfur atoms being directly linked to carbon atoms or other sulfur atoms
    • C08G18/3865—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur containing groups having sulfur atoms between two carbon atoms, the sulfur atoms being directly linked to carbon atoms or other sulfur atoms containing groups having one sulfur atom between two carbon atoms
    • C08G18/3872—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur containing groups having sulfur atoms between two carbon atoms, the sulfur atoms being directly linked to carbon atoms or other sulfur atoms containing groups having one sulfur atom between two carbon atoms the sulfur atom belonging to a sulfoxide or sulfone group
    • 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
    • C08G18/3855—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur
    • C08G18/3876—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur containing mercapto groups
    • 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
    • C08G18/40—High-molecular-weight compounds
    • C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
    • C08G18/4018—Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
    • 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
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
    • C08G18/4269—Lactones
    • C08G18/4277—Caprolactone and/or substituted caprolactone
    • 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
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4833—Polyethers containing oxyethylene units
    • 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
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6633—Compounds of group C08G18/42
    • C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/664—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
    • 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
    • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
    • C08G18/758—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing two or more cycloaliphatic rings
    • 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
    • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
    • C08G18/78—Nitrogen
    • C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
    • C08G18/791—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups
    • C08G18/792—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups formed by oligomerisation of aliphatic and/or cycloaliphatic isocyanates or isothiocyanates
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F41—WEAPONS
    • F41H—ARMOUR; ARMOURED TURRETS; ARMOURED OR ARMED VEHICLES; MEANS OF ATTACK OR DEFENCE, e.g. CAMOUFLAGE, IN GENERAL
    • F41H5/00—Armour; Armour plates
    • F41H5/02—Plate construction
    • F41H5/04—Plate construction composed of more than one layer
    • F41H5/0407—Transparent bullet-proof laminatesinformative reference: layered products essentially comprising glass in general B32B17/06, e.g. B32B17/10009; manufacture or composition of glass, e.g. joining glass to glass C03; permanent multiple-glazing windows, e.g. with spacing therebetween, E06B3/66

Definitions

  • the present invention provides methods of preparing polyurethane comprising the steps of:
  • the present invention provides methods of preparing poly(ureaurethane) comprising the steps of:
  • the present invention provides poly(ureaurethane)s comprising a reaction product of components comprising:
  • Fig. 2 is a graph of G 1 and G" as a function of temperature measured using Dynamic Mechanical Analysis (DMA) showing storage modulus, loss modulus and tan Delta for a casting of a polyurethane according to Example A, Formulation 2 of the present invention;
  • DMA Dynamic Mechanical Analysis
  • Fig. 5 is a TEM photomicrograph showing a casting of a polyurethane according to Example A 1 Formulation 2 analyzed about three weeks after formation according to the present invention
  • Example A after shooting of the sample with a 12 gauge shotgun shot from 20 feet (6.1 m) at a velocity of 1290 ft/sec (393.2 m/sec) using heavy game lead shot pellets;
  • Fig. 19 is a photograph of a front elevational view of a test sample of
  • Non-limiting examples of suitable heteroaryls include pyridyl, pyrazinyl, furanyl, thienyl, pyrimidinyl, pyridone (including N-substituted pyridones), isoxazolyl, isothiazolyl, oxazolyl, thiazolyl, pyrazolyl, furazanyl, pyrrolyl, pyrazolyl, triazolyl, 1,2,4-thiadiazolyl, pyrazinyl, pyridaz ⁇ nyl, quinoxalinyl, phthalazinyl, oxindolyl, imidazo[1,2-a]pyridinyl, imidazo[2,1- bjthiazolyl, benzofurazanyl, indolyl, azaindolyl, benzimidazolyl, benzothie ⁇ yl, quinolinyl, imidazolyl, thienopyrid
  • Alkoxy means an alkyl-O- group in which the alkyl group is as previously described.
  • suitable alkoxy groups include methoxy, ethoxy, n-propoxy, isopropoxy and n-butoxy.
  • the bond to the parent moiety is through the ether oxygen.
  • substituted means that one or more hydrogens on the designated atom is replaced with a selection from the indicated group, provided that the designated atom's normal valency under the existing circumstances is not exceeded, and that the substitution results in a stable compound. Combinations of substituents and/or variables are permissible only if such combinations result in stable compounds.
  • thermoset polymer Once cured, a crosslinked thermoset polymer will not melt upon the application of heat and is generally insoluble in solvents.
  • the term "cure” as used in connection with a composition shall mean that any curable or crosslinkable components of the composition are at least partially cured or crosslinked.
  • the crosslink density of the crosslinkable components i.e., the degree of crosslinking, ranges from about 5% to about 100% of complete crosslinking. In other non-limiting embodiments, the crosslink density ranges from about 35% to about 85% of full crosslinking. In other non-limiting embodiments, the crosslink density ranges from about 50% to about 85% of full crosslinking.
  • polyurethane is intended to include not only polyurethanes that are formed from the reaction of polyisocyanates and polyols but also poly(ureaurethane)(s) that are prepared from the reaction of polyisocyanates with polyols and water and/or polyamines.
  • stretched acrylic will absorb enough water to cause severe swelling of the plastic, to the point that it cracks in-plane, like layers of onion skin separating until it falls apart.
  • the low water absorption can also mitigate any hydrolysis degradation of the urethane groups in the polymer.
  • Cycloaliphatic diisocyanates are desirable for use in the present invention because they are not adversely affected by ultraviolet light and can yield polyurethanes having high impact energy absorption levels, which make them desirable for glass replacements and bilayer safety glass applications. Also, polyurethanes prepared with cycloaliphatic diisocyanates are not adversely affected by conventional processing temperatures. When an aromatic polyisocyanate is used, generally care should be taken to select a material that does not cause the polyurethane to color (e.g., yellow).
  • Non-limiting examples of suitable aromatic polyisocyanates wherein the isocyanate groups are not bonded directly to the aromatic ring ⁇ include ⁇ , ⁇ '- xylene diisocyanate, bis(isocyanatoethyl)benzene, ⁇ . ⁇ . ⁇ '. ⁇ '-tetramethylxylene diisocyanate, 1 ,3-bis(1-isocyanato-1-methylethyl)benzene, bis(isocyanatobutyl)benzene, bis(isocyanatomethyl)naphthalene, bis(isocyanatomethyl)diphenyl ether, bis(isocyanatoethyl) phthalate, mesitylene triisocyanate and 2,5-di(isocyanatomethyl)furan.
  • Non-limiting examples of suitable carbonyl isothiocyanates include hexane-dioyl diisothiocyanate, nonanedioyl diisothiocyanate, carbonic diisothiocyanate, 1 ,3-benzenedicarbonyl diisothiocyanate, 1 ,4-benzenedicarbonyl diisothiocyanate and (2,2'-bipyridine)-4,4'-dicarbonyl diisothiocyanate.
  • Non-limiting examples of suitable polyols include aliphatic, cycloaliphatic, aromatic, heterocyclic, oligomeric, and polymeric polyols and mixtures thereof. In some embodiments, such as for transparencies or windows exposed to sunlight, aliphatic or cycloaliphatic polyols can be used.
  • the polyol can be a cycloalkane polyol, such as trimethylene bis(1,3,5-cyc!ohexanetriol).
  • suitable polyols include the aforementioned polyols which can be alkoxylated derivatives, such as ethoxylated, propoxylated and butoxylated.
  • the following polyols can be alkoxylated with from 1 to 10 alkoxy groups: glycerol, trimethylolethane, trimethylolpropane, benzenetriol, cyclohexanetriol, erythritol, pentaerythritol, sorbitol, mannitol, sorbitan, dipentaerythritol and tripentaerythritol.
  • the polyuretha ⁇ es of the present invention can be thermoplastics, for example those polyurethanes having a molecular weight per crosslink of at least about 6000 g/mole.
  • the branched polyol having 4 to 18 carbon atoms can have a number average molecular weight of about 100 to about 500 grams/mole. In some non-limiting embodiments, the polyol can have a number average molecular weight of less than about 450 grams/mole. In other non-limiting embodiments, the polyol can have a number average molecular weight of less than about 200 grams/mole.
  • the reaction components for preparing the polyurethane of Group A also comprise about 0.1 to about 0.9 equivalents of at least one diol having 2 to 18 carbon atoms, or from about 2 to about 14 carbon atoms, or from 2 to 10 carbon atoms, or from 2 to 6 carbon atoms.
  • one or more carbon atoms in the diol can be replaced with one or more heteroatoms, such as N, S, or O.
  • the components of the polyurethane are essentially free of SH-containing materials, i.e., comprise less than
  • the diol having 4 to 18 carbon atoms can have a number average molecular weight of about 200 to about 10,000 grams/mole, or less than about 500 grams/mole, or less than about 200 grams/mole. [00207] Mixtures of any of the above diols can be used.
  • the amount of branched polyol used to form the polyurethane is about 0.3 equivalents.
  • the present invention provides polyurethanes of Group A comprising a reaction product of components consisting of: about 1 equivalent of 4,4'-methylene-bis-(cyclohexyl isocyanate); about 0.3 equivalents of trimethylolpropane; and about 0.7 equivalents of 1 ,5-pentanediol, wherein the reaction components are maintained at a temperature of at least about 100°C for at least about 10 minutes.
  • the present invention provides polyurethanes of Group A comprising a reaction product of components consisting of: about 1 equivalent of 4,4'-methylene-bis-(cyclohexyl isocyanate); about 0.4 equivalents of trimethylolpropane; about 0.6 equivalents of 1,18-octadecanediol, wherein the reaction components are maintained at a temperature of at least about 100 0 C for at least about 10 minutes.
  • Non-limiting examples of polycaprolactone polyols include those prepared by condensing caprolactone in the presence of difunctional active hydrogen material such as water or low molecular weight glycols, for example ethylene glycol and propylene glycol.
  • difunctional active hydrogen material such as water or low molecular weight glycols, for example ethylene glycol and propylene glycol.
  • suitable polycaprolactone polyols can include commercially available materials designated as the CAPA series from
  • the polycaprolactone polyol has a molecular weight ranging from about 500 to about 2000 grams per mole, or about 500 to about 1000 grams per mole.
  • Non-limiting examples of suitable polyisocyanates, branched polyols having 4 to 18 carbon atoms and at least 3 hydroxyl groups, polycarbonate diols and diol having 2 to 18 carbon atoms for use in as reaction products for preparing the polyurethanes of Group F are discussed in detail above with respect to Group A.
  • the amount of branched polyol used to form the polyurethane of Group F can range from about 0.3 to about 0.98 equivalents, or about 0.5 to about 0.98 equivalents, or about 0.9 to about 0.98 equivalents.
  • the amount of aliphatic diol used to form the polyurethane of Group G can range from about 0.1 to about 0.6 equivalents, or about 0.1 to about 0.5 equivalents, or about 0.5 equivalents.
  • the polyurethanes of Group G are essentially free of or free of polyether polyol and/or amine curing agent, the types and amounts of polyether polyol and amine curing agent being described above with respect to Groups A-D. .
  • the present invention provides methods of preparing polyurethanes of Group G comprising the steps of: reacting at least one polyisocyanate and at least one branched polyol having 4 to 18 carbon atoms and at least 3 hydroxyl groups to form a polyurethane prepolymer; and reacting the polyurethane prepolymer with at least one polyol selected from the group consisting of polyester polyol, polycaprolactone polyol and mixtures thereof and about 0.1 to about 0.7 equivalents of at least one aliphatic diol to form the polyurethane.
  • the polyol and/or diol can be reacted with the isocyanate functional urea prepolymer(s) to form poly(ureaurethane)s of the present invention.
  • suitable polyols can be any of the polyos discussed above.
  • the polyol can be
  • the filled mold or cell can be placed in an oven at a temperature of about 250 0 F (121 0 C) to about 320 0 F (160 0 C) and cured for about 24 to about 48 hours, for example.
  • the cell can be removed from the oven and cooled to a temperature of about 25°C and the cured polymer released from the casting mold.
  • reaction synthesis can be as described above with respect to Poly(ureaurethane) Synthesis A.
  • a portion of one or more polyols or diols as described above can be included in this reaction to form isocyanate functional urethane prepolymer which is then further reacted with another portion of polyol and/or diol, as shown in Poly(ureaurethane) Synthesis B, desc ⁇ bed in further detail below.
  • urea linkages or units can be formed within the polyurethane matrix to the extent desired by reacting polyisocyanate(s) and a portion of the polyol(s) to form at least one isocyanate functional urethane prepolymer, and then reacting the isocyanate functional urethane prepolymer(s) with water.
  • the isocyanate shown in Step 1 is a diisocyanate in which R is any linking group, such as aliphatic, cycloaiiphatic, aromatic, heterocycle, etc. as described in detail above.
  • R is any linking group, such as aliphatic, cycloaiiphatic, aromatic, heterocycle, etc. as described in detail above.
  • the isocyanate can have one or more, two or more, three or more or a higher number of isocyanate functional groups, as desired.
  • suitable isocyanates can be any of the polyisocyanates discussed above.
  • the polyisocyanate is one or more aliphatic polyisocyanates.
  • the polyisocyanate is 4,4'-methylene-bis-(cyclohexyl isocyanate) (such as DESMODUR W).
  • Non-limiting examples of suitable polyisocyanates, branched polyols having 4 to 18 carbon atoms and at least 3 hydroxyl groups, aliphatic diols and amine curing agents for use as reaction components for preparing the pofyurethanes of Group M are discussed in detail above with respect to Group A.
  • the amount of branched polyol used to form the polyurethane of Group M can be about 0.3 to about 0.98 equivalents, in other non-limiting embodiments about 0.5 to about 0.98 equivalents, and in other non-limiting embodiments about 0.3 equivalents or about 0.9 or about 0.98 equivalents.
  • the present invention provides methods of preparing a polyurethane powder coating composition comprising the steps of: reacting at least one polyisocyanate with at least one aliphatic polyol to form a generally solid, hydroxy functional prepolymer; melting the hydroxy functional prepolymer; melting at least one generally solid polyisocyanate to form a melted polyisocyanate; mixing the melted hydroxy functional prepolymer and melted polyisocyanate to form a mixture; and solidifying the mixture to form a generally solid powder coating composition.
  • organic material means any material that is not an organic material.
  • the mixture can be heated to initiate the formation of the nanoparticles.
  • the mixture can be heated to any one
  • the concentration of the nanostructures in the polymer matrix can range from 0.1% to 90%, for example from 3% to 85% or from 15% to 80% based on total volume.
  • the nanostructures in the polymer matrix can have the following shapes: spherical, polyhedral-like cubic, triangular, pentagonal, diamond shaped, needle shaped, rod shaped, disc shaped etc.
  • ITO or ATO nanostructures are formed from the precursor.
  • the nanostructure formation can be caused by adjusting the pH of the solution by introducing an agent, such as ammonia, into the mixture followed by heating the mixture.
  • an agent such as ammonia
  • the ITO nanostructures start to form at pH > 8.
  • the mixture is heated to a temperature of up to 100°C. As discussed above, heating the mixture for a longer time period can increase the size of the nanostructures.
  • the reinforcement material is a nanostructural reinforcement material formed in situ by swelling the polyurethane in a solvent comprising a precursor for the nanostructures, and forming nanostructures in the matrix of the polyurethane from the precursor of the nanostructures.
  • suitable solvents for mild swelling of the polymer include methanol, propylene glycol methyl ether such as DOWANOL PM (commercially available from Dow Chemical Co. of Midland, Michigan), diacetone alcohol, 2-propanol, 1-propanol and acetylpropanol.
  • the particles are formed from solid lubricant materials.
  • solid lubricant means any solid used between two surfaces to provide protection from damage during relative movement and/or to reduce friction and wear.
  • the solid lubricants are inorganic solid lubricants.
  • inorganic solid lubricant means that the solid lubricants have a characteristic crystalline habit which causes them to shear into thin, flat plates which readily slide over one another and thus produce an antifriction lubricating effect. See R. Lewis, Sr., Hawlev's Condensed Chemical Dictionary. (12th Ed. 1993) at page 712, incorporated by reference herein. Friction is the resistance to sliding one solid over another. F. Clauss, Solid Lubricants and Self-Lubricating Solids (1972) at page 1, incorporated by reference herein.
  • Inorganic solid particles having a lamellar fullerene (i.e., buckyball) structure can also be useful in the present invention.
  • the reinforcing material can be glass fiber strands.
  • the glass fiber strands are formed from glass filaments, a class of filaments generally accepted to be based upon oxide compositions such as silicates selectively modified with other oxide and non-oxide compositions.
  • Useful glass filaments can be formed from any type of fiberizable glass composition known to those skilled in the art, and include those prepared from fiberizable glass compositions such as "E-glass”, “A-gtass", "C-glass”, “D-glass”, “R-glass”, “S-glass”, and E-glass derivatives that are fluorine-free and/or boron-free.
  • the polymeric organic material is a
  • Non-limiting examples of suitable fiberizable organic materials include cotton, cellulose, natural rubber, flax, ramie, hemp, sisal and wool.
  • suitable fiberizable organic polymeric materials include those formed

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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • General Engineering & Computer Science (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

La présente invention concerne des poly(urée-uréthane)s comprenant un produit de réaction des composants comprenant : (a) au moins un prépolymère d'urée-uréthane à fonction isocyanate comprenant le produit de réaction de : (1) au moins un prépolymère d'uréthane à fonction isocyanate comprenant le produit de réaction de : (i) une première quantité d'au moins un polyisocyanate; et (ii) une première quantité d'au moins un polyol ramifié; et (2) de l'eau, pour former un prépolymère d'urée-uréthane à fonction isocyanate; et (b) une seconde quantité d'au moins un polyisocyanate et une seconde quantité d'au moins un polyol ramifié; des compositions, revêtements et articles préparés à partir de ceux-ci et leurs procédés de fabrication.
PCT/US2006/047755 2005-12-16 2006-12-14 Poly(urée-uréthane)s, articles et revêtements préparés à partir de ceux-ci et leurs procédés de fabrication Ceased WO2007139586A2 (fr)

Priority Applications (3)

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CA2647094A CA2647094C (fr) 2005-12-16 2006-12-14 Poly(uree-urethane)s, articles et revetements prepares a partir de ceux-ci et leurs procedes de fabrication
EP06851307.6A EP2004717B1 (fr) 2005-12-16 2006-12-14 Poly(urée-uréthane)s, articles et revêtements préparés à partir de ceux-ci et leurs procédés de fabrication
ES06851307T ES2408598T3 (es) 2005-12-16 2006-12-14 Poli(ureauretano)s, artículos y revestimientos preparados a partir de los mismos, y procedimientos de fabricación de los mismos

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US11/303,422 2005-12-16
US11/303,892 2005-12-16
US11/303,671 US20070142604A1 (en) 2005-12-16 2005-12-16 Polyurethanes and sulfur-containing polyurethanes and methods of preparation
US11/303,832 US20070238848A1 (en) 2001-11-16 2005-12-16 High impact poly (urethane urea) polysulfides
US11/303,670 US20070142603A1 (en) 2005-12-16 2005-12-16 Polyurethane(urea) and sulfur-containing polyurethane(urea) and methods of preparation
US11/303,670 2005-12-16
US11/303,832 2005-12-16
US11/303,422 US20070142602A1 (en) 2005-12-16 2005-12-16 Polyurethanes and sulfur-containing polyurethanes and methods of preparation
US11/303,892 US20070142606A1 (en) 2005-12-16 2005-12-16 Polyurethane (ureas) and sulfur-containing polyurethane (ureas) methods of preparation
US11/303,671 2005-12-16

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PCT/US2006/047674 Ceased WO2007070627A2 (fr) 2005-12-16 2006-12-14 Polyurethanes, articles et revetements les utilisant et procedes pour les fabriquer
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2602300A4 (fr) * 2010-08-06 2014-07-23 Tokuyama Corp Composition photochromique

Families Citing this family (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11248083B2 (en) 2004-09-01 2022-02-15 Ppg Industries Ohio, Inc. Aircraft windows
US20090280709A1 (en) 2004-09-01 2009-11-12 Ppg Industries Ohio, Inc. Polyurethanes, Articles and Coatings Prepared Therefrom and Methods of Making the Same
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
US11591436B2 (en) 2004-09-01 2023-02-28 Ppg Industries Ohio, Inc. Polyurethane article and methods of making the same
US11008418B2 (en) 2004-09-01 2021-05-18 Ppg Industries Ohio, Inc. Polyurethanes, articles and coatings prepared therefrom and methods of making the same
US9464169B2 (en) 2004-09-01 2016-10-11 Ppg Industries Ohio, Inc. Polyurethanes, articles and coatings prepared therefrom and methods of making the same
US9598527B2 (en) 2004-09-01 2017-03-21 Ppg Industries Ohio, Inc. Polyurethanes, articles and coatings prepared therefrom and methods of making the same
US8933166B2 (en) 2004-09-01 2015-01-13 Ppg Industries Ohio, Inc. Poly(ureaurethane)s, articles and coatings prepared therefrom and methods of making the same
US8889815B2 (en) 2004-09-01 2014-11-18 Ppg Industries Ohio, Inc. Reinforced polyurethanes and poly(ureaurethane)s, methods of making the same and articles prepared therefrom
US8859680B2 (en) 2004-09-01 2014-10-14 Ppg Industries Ohio, Inc Poly(ureaurethane)s, articles and coatings prepared therefrom and methods of making the same
US20090280329A1 (en) 2004-09-01 2009-11-12 Ppg Industries Ohio, Inc. Polyurethanes, Articles and Coatings Prepared Therefrom and Methods of Making the Same
US11149107B2 (en) 2004-09-01 2021-10-19 Ppg Industries Ohio, Inc. Polyurethanes, articles and coatings prepared therefrom and methods of making the same
US20080171197A1 (en) * 2007-01-12 2008-07-17 Rukavina Thomas G Automotive window, high impact interlayer
US8608988B2 (en) * 2010-11-23 2013-12-17 Transitions Optical, Inc. Curable photochromic compositions and optical articles prepared therefrom
US9139571B2 (en) 2010-12-16 2015-09-22 Transitions Optical, Inc. Methods of making fused ring compounds
CA2904414C (fr) * 2013-03-14 2019-01-15 Ppg Industries Ohio, Inc. Polyurethanes, articles et revetements prepares avec ceux-ci et procedes de fabrication associes
EP3337841A1 (fr) * 2015-08-21 2018-06-27 Covestro Deutschland AG Matériau composite polyuréthane

Citations (27)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2644007A (en) 1951-10-08 1953-06-30 Du Pont Preparation of polyamine hydrochlorides and polyisocyanates
US2680127A (en) 1952-01-02 1954-06-01 Monsanto Chemicals Method of making organic isocyanates
US3361706A (en) 1964-03-06 1968-01-02 American Cyanamid Co Control of the photochromic return rate of (arylazo) thioformic arylhydrazidates
US3562172A (en) 1968-10-28 1971-02-09 Fuji Photo Film Co Ltd Photochromic compound and composition containing the same
US3567605A (en) 1966-03-30 1971-03-02 Ralph S Becker Photochemical process
US3578602A (en) 1967-08-30 1971-05-11 Fuji Photo Film Co Ltd Photochromic compound
US4160853A (en) 1976-04-28 1979-07-10 Ppg Industries, Inc. Catalyst for making polycarbonate diols for use in polycarbonate urethanes
US4166043A (en) 1974-12-23 1979-08-28 American Optical Corporation Stabilized photochromic materials
US4215010A (en) 1978-09-08 1980-07-29 American Optical Corporation Photochromic compounds
US4342668A (en) 1978-09-08 1982-08-03 American Optical Corporation Photochromic compounds
US4367170A (en) 1975-01-24 1983-01-04 American Optical Corporation Stabilized photochromic materials
US4637698A (en) 1983-11-04 1987-01-20 Ppg Industries, Inc. Photochromic compound and articles containing the same
US4680204A (en) 1983-09-06 1987-07-14 Ppg Industries, Inc. Color plus clear coating system utilizing inorganic microparticles
US4816584A (en) 1986-11-12 1989-03-28 Ppg Industries, Inc. Photochromic spiro(indoline)benzoxazines
US4818096A (en) 1986-06-17 1989-04-04 The Plessey Company Plc Photoreactive lenses with adamantane spiro compounds
US4826977A (en) 1986-05-15 1989-05-02 The Plessey Company Plc Photochromic spiropyran compounds
US4880667A (en) 1985-09-24 1989-11-14 Ppg Industries, Inc. Photochromic plastic article and method for preparing same
US4931220A (en) 1987-11-24 1990-06-05 Ppg Industries, Inc. Organic photochromic pigment particulates
US4931219A (en) 1987-07-27 1990-06-05 Ppg Industries, Inc. Photochromic compound and articles containing the same
US5066818A (en) 1990-03-07 1991-11-19 Ppg Industries, Inc. Photochromic naphthopyran compounds
US5238931A (en) 1990-07-06 1993-08-24 Zeria Pharmaceutical Co., Ltd. Inflammatory bowel disease preventive and curative agent containing zinc l-carnosine salt as active ingredient
US5274132A (en) 1992-09-30 1993-12-28 Transitions Optical, Inc. Photochromic naphthopyran compounds
US5384077A (en) 1993-06-21 1995-01-24 Transitions Optical, Inc. Photochromic naphthopyran compounds
US5405958A (en) 1992-12-21 1995-04-11 Transitions Optical, Inc. Photochromic spiro(indoline)naphthoxazine compounds
US5429774A (en) 1993-03-12 1995-07-04 Transitions Optical, Inc. Benzopyran compounds
US5466398A (en) 1993-06-21 1995-11-14 Transitions Optical, Inc. Photochromic substituted naphthopyran compounds
US5853809A (en) 1996-09-30 1998-12-29 Basf Corporation Scratch resistant clearcoats containing suface reactive microparticles and method therefore

Family Cites Families (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3664909A (en) 1970-03-25 1972-05-23 Ppg Industries Inc Needled resin fibrous article
US3713962A (en) 1970-03-25 1973-01-30 Ppg Industries Inc Composite mat structure
US3850723A (en) 1971-09-20 1974-11-26 Ppg Industries Inc Method of making a stampable reinforced sheet
US4085092A (en) * 1974-05-30 1978-04-18 Ppg Industries, Inc. Transparent, optically clear poly(lactone-urethane) interlayers for laminated safety glass
US4153777A (en) * 1975-10-01 1979-05-08 Goodyear Aerospace Corporation Polyurethane and method of making
US4101529A (en) * 1976-02-04 1978-07-18 Ppg Industries, Inc. Hard, optically clear polyurethane articles
US4024113A (en) * 1976-04-28 1977-05-17 Ppg Industries, Inc. Polycarbonate polyurethanes based on particular aliphatic/cycloaliphatic polycarbonates
US4360653A (en) 1981-10-23 1982-11-23 Ppg Industries, Inc. Polymerizate of (allyl carbonate) and aliphatic polyurethane having acrylic unsaturation
US4652494A (en) * 1983-07-11 1987-03-24 Saint-Gobain Vitrage Bilayer laminate and preformed sheet for use therein
US4847140A (en) 1985-04-08 1989-07-11 Helmic, Inc. Nonwoven fibrous insulation material
US5098624A (en) 1987-07-10 1992-03-24 C.H. Masland & Sons Glossy finish fiber reinforced molded product and processes of construction
US5011737A (en) 1987-07-10 1991-04-30 C. H. Masland & Sons Glossy finish fiber reinforced molded product and processes of construction
US5071608A (en) 1987-07-10 1991-12-10 C. H. Masland & Sons Glossy finish fiber reinforced molded product and processes of construction
US4948661A (en) 1987-07-10 1990-08-14 C. H. Masland & Sons Glossy finish fiber reinforced molded product and processes of construction
US4808690A (en) * 1988-02-29 1989-02-28 Loral Corporation High heat distortion temperature transparent polyurethanes
US4994208A (en) 1989-04-18 1991-02-19 Ppg Industries, Inc. Photochromic polymeric article
US5200483A (en) 1991-11-07 1993-04-06 Ppg Industries, Inc. Polyol(allyl carbonate) composiitons and articles prepared there from
US6127505A (en) * 1995-02-02 2000-10-03 Simula Inc. Impact resistant polyurethane and method of manufacture thereof

Patent Citations (27)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2644007A (en) 1951-10-08 1953-06-30 Du Pont Preparation of polyamine hydrochlorides and polyisocyanates
US2680127A (en) 1952-01-02 1954-06-01 Monsanto Chemicals Method of making organic isocyanates
US3361706A (en) 1964-03-06 1968-01-02 American Cyanamid Co Control of the photochromic return rate of (arylazo) thioformic arylhydrazidates
US3567605A (en) 1966-03-30 1971-03-02 Ralph S Becker Photochemical process
US3578602A (en) 1967-08-30 1971-05-11 Fuji Photo Film Co Ltd Photochromic compound
US3562172A (en) 1968-10-28 1971-02-09 Fuji Photo Film Co Ltd Photochromic compound and composition containing the same
US4166043A (en) 1974-12-23 1979-08-28 American Optical Corporation Stabilized photochromic materials
US4367170A (en) 1975-01-24 1983-01-04 American Optical Corporation Stabilized photochromic materials
US4160853A (en) 1976-04-28 1979-07-10 Ppg Industries, Inc. Catalyst for making polycarbonate diols for use in polycarbonate urethanes
US4215010A (en) 1978-09-08 1980-07-29 American Optical Corporation Photochromic compounds
US4342668A (en) 1978-09-08 1982-08-03 American Optical Corporation Photochromic compounds
US4680204A (en) 1983-09-06 1987-07-14 Ppg Industries, Inc. Color plus clear coating system utilizing inorganic microparticles
US4637698A (en) 1983-11-04 1987-01-20 Ppg Industries, Inc. Photochromic compound and articles containing the same
US4880667A (en) 1985-09-24 1989-11-14 Ppg Industries, Inc. Photochromic plastic article and method for preparing same
US4826977A (en) 1986-05-15 1989-05-02 The Plessey Company Plc Photochromic spiropyran compounds
US4818096A (en) 1986-06-17 1989-04-04 The Plessey Company Plc Photoreactive lenses with adamantane spiro compounds
US4816584A (en) 1986-11-12 1989-03-28 Ppg Industries, Inc. Photochromic spiro(indoline)benzoxazines
US4931219A (en) 1987-07-27 1990-06-05 Ppg Industries, Inc. Photochromic compound and articles containing the same
US4931220A (en) 1987-11-24 1990-06-05 Ppg Industries, Inc. Organic photochromic pigment particulates
US5066818A (en) 1990-03-07 1991-11-19 Ppg Industries, Inc. Photochromic naphthopyran compounds
US5238931A (en) 1990-07-06 1993-08-24 Zeria Pharmaceutical Co., Ltd. Inflammatory bowel disease preventive and curative agent containing zinc l-carnosine salt as active ingredient
US5274132A (en) 1992-09-30 1993-12-28 Transitions Optical, Inc. Photochromic naphthopyran compounds
US5405958A (en) 1992-12-21 1995-04-11 Transitions Optical, Inc. Photochromic spiro(indoline)naphthoxazine compounds
US5429774A (en) 1993-03-12 1995-07-04 Transitions Optical, Inc. Benzopyran compounds
US5384077A (en) 1993-06-21 1995-01-24 Transitions Optical, Inc. Photochromic naphthopyran compounds
US5466398A (en) 1993-06-21 1995-11-14 Transitions Optical, Inc. Photochromic substituted naphthopyran compounds
US5853809A (en) 1996-09-30 1998-12-29 Basf Corporation Scratch resistant clearcoats containing suface reactive microparticles and method therefore

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
G. WYPYCH: "Handbook of Fillers", 1999, pages: 15 - 202
JOHN C. CRANO: "Chromogenic Materials (Photochromic", KIRK-OTHMER ENCYCLOPEDIA OF CHEMICAL TECHNOLOGY, 1993, pages 321 - 332
T. W. GREENE ET AL.: "Protective Groups in organic Synthesis", 1991, WILEY

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2602300A4 (fr) * 2010-08-06 2014-07-23 Tokuyama Corp Composition photochromique
US9234984B2 (en) 2010-08-06 2016-01-12 Tokuyama Corporation Photochromic composition

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WO2007139586A8 (fr) 2008-10-16

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