WO2007097798A1 - High impact poly (urethane urea) polysulfides - Google Patents

High impact poly (urethane urea) polysulfides Download PDF

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Publication number
WO2007097798A1
WO2007097798A1 PCT/US2006/046649 US2006046649W WO2007097798A1 WO 2007097798 A1 WO2007097798 A1 WO 2007097798A1 US 2006046649 W US2006046649 W US 2006046649W WO 2007097798 A1 WO2007097798 A1 WO 2007097798A1
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WO
WIPO (PCT)
Prior art keywords
sulfur
polyureaurethane
amine
polythiol
mixture
Prior art date
Application number
PCT/US2006/046649
Other languages
English (en)
French (fr)
Inventor
Nina V. Bojkova
Robert A. Smith
Robert D. Herold
Chandra B. Rao
William H. Mcdonald
Vidhu J. Nagpal
Marvin J. Graham
Phillip C. Yu
Suresh Sawant
Michael O. Okoroafor
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
Application filed by Ppg Industries Ohio, Inc. filed Critical Ppg Industries Ohio, Inc.
Priority to CN2006800503771A priority Critical patent/CN101356209B/zh
Priority to JP2008552292A priority patent/JP5191905B2/ja
Priority to EP06839138A priority patent/EP1987074B1/en
Publication of WO2007097798A1 publication Critical patent/WO2007097798A1/en
Priority to IL191777A priority patent/IL191777A/en
Priority to HK09102393.0A priority patent/HK1127778A1/xx

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    • 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
    • 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
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    • 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
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    • 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
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    • 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
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    • 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
    • C08G18/4202—Two or more polyesters of different physical or chemical nature
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • 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
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    • 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
    • C08G18/4837—Polyethers containing oxyethylene units and other oxyalkylene 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
    • C08G18/40—High-molecular-weight compounds
    • C08G18/52—Polythioethers
    • 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
    • C08G18/6603—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/6607—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
    • C08G18/6611—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203 having at least three hydroxy 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
    • C08G18/65—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
    • C08G18/6644—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203 having at least three hydroxy 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
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/721—Two or more polyisocyanates not provided for in one single group C08G18/73 - C08G18/80
    • C08G18/722—Combination of two or more aliphatic and/or cycloaliphatic polyisocyanates
    • 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
    • C08G18/721—Two or more polyisocyanates not provided for in one single group C08G18/73 - C08G18/80
    • C08G18/724—Combination of aromatic polyisocyanates with (cyclo)aliphatic polyisocyanates
    • 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
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • 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
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
    • G02B1/041—Lenses
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2375/04—Polyurethanes

Definitions

  • the present invention relates to sulfur-containing polyureaurethanes and methods for their preparation.
  • a number of organic polymeric materials, such as plastics, have been developed as alternatives and replacements for glass in applications such as optical lenses, fiber optics, windows and automotive, nautical and aviation transparencies. These polymeric materials can provide advantages relative to glass, including, shatter resistance, lighter weight for a given application, ease of molding and ease of dying.
  • the refractive indices of many polymeric materials are generally lower than that of glass. In ophthalmic applications, the use of a polymeric material having a lower refractive index will require a thicker lens relative to a material having a higher refractive index. A thicker lens is not desirable .
  • the present invention is directed to a sulfur- containing polyureaurethane when at least partially cured having a refractive index of at least 1.55, or at least 1.56, or at least 1.57, or at least 1.58, or at least 1.59, or at least 1.60, or at least 1.62, or at least 1.65; an Abbe number of at least 32 and a density of at least 1.0, or at least 1.1, or less than 1.2 grams/cm 3 , or less than 1.3 grams/cm 3 .
  • curing of a polymerizable composition refers to subjecting said composition to curing conditions such as but not limited to thermal curing, leading to the reaction of the reactive end- groups of said composition, and resulting in polymerization and formation of a solid polymerizate.
  • curing conditions such as but not limited to thermal curing, leading to the reaction of the reactive end- groups of said composition, and resulting in polymerization and formation of a solid polymerizate.
  • the term "at least partially cured” means subjecting the polymerizable composition to curing conditions, wherein reaction of at least a portion of the reactive end-groups of said composition occurs, to form a solid polymerizate, such that said polymerizate can be demolded, and cut into test pieces, or such that it may be subjected to machining operations, including optical lens processing.
  • the polymerizable composition can be subjected to curing conditions, such that a substantially complete cure is attained and wherein further curing results in no significant further improvement in polymer properties, such as hardness.
  • the sulfur-containing polyureaurethane of the present invention can be prepared by combining polyisocyanate and/or polyisothiocyanate; active hydrogen-containing material, and amine-containing curing agent .
  • the terms "isocyanate” and “isothiocyanate” include unblocked compounds capable of forming a covalent bond with a reactive group such as a thiol, hydroxyl , or amine functional group.
  • the polyisocyanate of the present invention can contain at least two functional groups chosen from isocyanate (NCO)
  • the polyisothiocyanate can contain at least two functional groups chosen from isothiocyanate (NCS)
  • the isocyanate and isothiocyanate materials can each include combinations of isocyanate and isothiocyanate functional groups .
  • the polyureaurethane of the invention when polymerized can produce a polymerizate having a refractive index of at least 1.55, or at least 1.56, or at least 1.57, or at least 1.58, or at least 1.59, or at least 1.60, or at least 1.62, or at least 1.65.
  • the polyureaurethane of the invention when polymerized can produce a polymerizate having an Abbe number of at least 32, or at least 35, or at least 38, or at least 39, or at least 40, or at least 44.
  • the refractive index and Abbe number can be determined by methods known in the art such as American -Standard Test Method (ASTM) Number D 542-00.
  • the refractive index and Abbe number can be determined using various known instruments.
  • the refractive index and Abbe number can be measured in accordance with ASTM D 542-00 with the following exceptions: (i) test one to two samples/specimens instead of the minimum of three specimens specified in Section 7.3; and (ii) test the samples unconditioned instead of conditioning the samples/specimens prior to testing as specified in Section 8.1.
  • an Atago, model DR-M2 Multi-Wavelength Digital Abbe Refractometer can be used to measure the refractive index and Abbe number of the samples/specimens.
  • the sulfur-containing polyureaurethane of the present invention can be prepared by reacting polyisocyanate and/or polyisothiocyanate with active hydrogen-containing material selected from polyol, polythiol, or combination thereof, to form polyurethane prepolymer or sulfur-containing polyurethane prepolymer; and chain extending (i.e., reacting) said prepolymer with amine-containing curing agent, wherein said amine-containing curing agent optionally includes active hydrogen-containing material selected from polyol, polythiol, or combination thereof.
  • the amount of polyisocyanate and the amount of active hydrogen-containing material used to prepare isocyanate terminated polyurethane prepolymer or sulfur-containing polyurethane prepolymer can be selected such that the equivalent ratio of (NCO) : (SH + OH) can be greater than 1.0:1.0, or at least 2.0:1.0, or at least 2.5:1.0, or less than 4.5:1.0, or less than 5.5:1.0,- or the amount of polyisothiocyanate and the amount of active hydrogen-containing material used to prepare isothiocyanate terminated sulfur-containing polyurethane prepolymer can be selected such that the equivalent ratio of (NCS) : (SH + OH) can be greater than 1.0:1.0, or at least 2.0:1.0, or at least 2.5:1.0, or less than 4.5:1.0, or less than 5.5:1.0; or the amount of a combination of polyisothiocyanate and polyisocyanate and the amount of active hydrogen-containing material used to prepare is
  • the amount of isocyanate terminated polyurethane prepolymer or sulfur- containing prepolymer and the amount of amine-containing curing agent used to prepare sulfur-containing polyureaurethane can be selected such that the equivalent ratio of (NH + SH + OH) : (NCO) can range from 0.80:1.0 to 1.1:1.0, or from 0.85:1.0 to 1.0:1.0, or from 0.90:1.0 to 1.0:1.0, or from 0.90:1.0 to 0.95:1.0, or from 0.95:1.0 to 1.0:1.0.
  • the amount of isothiocyanate or isothiocyanate/isocyanate terminated sulfur- containing polyurethane prepolymer and the amount of amine- containing curing agent used to prepare sulfur-containing polyureaurethane can be selected such that the equivalent ratio of (NH + SH + OH) : (NCO + NCS) can range from 0.80:1.0 to 1.1:1.0, or from 0.85:1.0 to 1.0:1.0, or from 0.90:1.0 to 1.0:1.0, or from 0.90:1.0 to 0.95:1.0, or from 0.95:1.0 to 1.0:1.0.
  • Polyisocyanates and polyisothiocyanates useful in the preparation of the polyureaurethane of the present invention are numerous and widely varied.
  • Suitable polyisocyanates for use in the present invention can include but are not limited to polymeric and C 2 -C 2O linear, branched, cycloaliphatic and aromatic polyisocyanates.
  • Suitable polyisothiocyanates for use in the present invention can include but are not limited to polymeric and C 2 -C 20 linear, branched, cyclic and aromatic polyisothiocyanates .
  • Non- limiting examples can include polyisocyanates and polyisothiocyanates having backbone linkages chosen from urethane linkages (-NH-C (0) -O- ) , thiourethane linkages (-NH- C(O)-S-), thiocarbamate linkages ( -NH-C (S) -0-) , dithiourethane linkages (-NH-C (S) -S-) and combinations thereof.
  • the molecular weight of the polyisocyanate and polyisothiocyanate can vary widely.
  • the number average molecular weight (Mn) of each can be at least 100 grams/mole, or at least 150 grams/mole, or less than 15,000 grams/mole, or less than 5000 grams/mole.
  • the number average molecular weight can be determined using known methods .
  • the number average molecular weight values recited herein and the claims were determined by gel permeation chromatography (GPC) using polystyrene standards.
  • Non-limiting examples of suitable polyisocyanates and polyisothiocyanates can include but are not limited to polyisocyanates having at least two isocyanate groups,- polyisothiocyanates having at least two isothiocyanate groups ; mixtures thereof; and combinations thereof, such as a material having isocyanate and isothiocyanate functionality.
  • Non-limiting examples of polyisocyanates and polyisothiocyanates can include but are not limited to those described in WO 2004/060951 Al at paragraphs [0014] to [0035] , incorporated by reference herein.
  • the polyisocyanate can include meta-tetramethylxylylene diisocyanate (1 , 3-bis (1-isocyanato-1-methylethyl-benzene) ; 3- isocyanato-methyl-3, 5,5, -trimethyl-cyclohexyl isocyanate; 4,4 - methylene bis (cyclohexyl isocyanate) ; meta-xylylene diisocyanate; and mixtures thereof.
  • the polyisocyanate and/or polyisothiocyanate can be reacted with an active hydrogen-containing material to form a polyurethane prepolymer.
  • Active hydrogen-containing materials are varied and k.nown in the art.
  • Non-limiting examples can include hydroxyl-containing materials such as but not limited to polyols,- sulfur-containing materials such as but not limited to hydroxyl functional polysulfides, and SH-containing materials such as but not limited to polythiols; and materials having both hydroxyl and thiol functional groups .
  • Suitable hydroxyl-containing materials for use in the present invention can include a wide variety of materials known in the art.
  • Non-limiting examples can include but are not limited to polyether polyols, polyester polyols, polycaprolactone polyols, polycarbonate polyols, polyurethane polyols, poly vinyl alcohols, polymers containing hydroxy functional acrylates, polymers containing hydroxy functional methacrylates, polymers containing allyl alcohols and mixtures thereof .
  • Polyether polyols and methods for their preparation are known to one skilled in the art . Many polyether polyols of various types and molecular weight are commercially available from various manufacturers. Non-limiting examples of polyether polyols can include but are not limited to those described in WO 2004/060951 Al at paragraphs [0038] to [0040] incorporated herein by reference. Compatible mixtures of polyether polyols can also be used. As used herein, "compatible" means that two or more materials are mutually soluble in each other so as to essentially form a single phase .
  • polyester polyols and polycaprolactone polyols suitable for use in the present invention are known in the art .
  • Suitable polyester polyols and polycaprolactone polyols can include but are not limited to those described in WO 2004/060951 Al at paragraphs [0041] and [0042] , respectively, incorporated by reference herein.
  • Polycarbonate polyols for use in the present invention are varied and known to one skilled in the art. Suitable polycarbonate polyols can include those described in WO 2004/060951 Al at paragraphs [0043] , incorporated by reference herein.
  • active hydrogen-containing materials can include low molecular weight di- functional and higher functional polyols and mixtures thereof .
  • these low molecular weight materials can have a number average molecular weight of less than 500 grams/mole.
  • the amount of low molecular weight material chosen can be such to avoid a high degree of cross-linking in the polyurethane .
  • the di-functional polyols typically contain from 2 to 16, or from 2 to 6, or from 2 to 10, carbon atoms.
  • Non-limiting examples of such difunctional polyols can include but are not limited to ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, 1,2-, 1,3- and 1 , 4-butanediol, 2,2,4-trimethyl-1,3 -pentanediol , 2 -methyl-1,3-pentanediol , 1,3- 2,4- and 1 , 5 -pentanediol, 2,5- and 1, 6-hexanediol, 2,4- heptanediol, 2 -ethyl- 1, 3-hexanediol , 2 , 2 -dimethyl -1 , 3- propanediol, 1, 8-octanediol, 1, 9-nonanediol, 1, 10-decanediol, 1, 4-cyclohexaned
  • Non- limiting examples of trifunctional or tetrafunctional polyols can include glycerin, tetramethylolmethane, pentaerythritol, trimethylolethane, tritnethylolpropane, alkoxylated polyols such as but not limited to ethoxylated trimethylolpropane, propoxylated trimethylolpropane, ethoxylated trimethylolethane; and mixtures thereof.
  • the active hydrogen-containing material can have a number average molecular weight of at least 200 grams/mole, or at least 400 grams/mole, or at least 1000 grams/mole, or at least 2000 grams/mole. In alternate non-limiting embodiments, the active hydrogen-containing material can have a number average molecular weight of less than 5,000 grams/mole, or less than 10,000 grams/mole, or less than 15,000 grams/mole, or less than 20,000 grams/mole, or less than 32,000 grams/mole. [0029] In a non-limiting embodiment, the active hydrogen- containing material can comprise block polymers including blocks of ethylene oxide-propylene oxide and/or ethylene oxide-butylene oxide. In a non-limiting embodiment, the active hydrogen-containing material can comprise a block copolymer of the following' chemical formula:
  • R 1 through R 6 can each independently represent hydrogen or methyl; a, b, and c can each be independently an integer from 0 to 300. wherein a, b and c are chosen such that the number average molecular weight of the polyol does not exceed 32,000 grams/mole, as determined by GPC. In another non- limiting embodiment, a, b, and c can be chosen such that the number average molecular weight of the polyol does not exceed 10,000 grams/mole, as determined by GPC. In another non- limiting embodiment, a, b, and c each can be independently an integer from 1 to 300.
  • R 1 , R 2 , R 5 , and R 6 can be hydrogen, and R 3 and R 4 each can be independently chosen from hydrogen and methyl, with the proviso that R 3 and R 4 are different from one another.
  • R 3 and R 4 can be hydrogen, and R 1 and R 2 each can be independently chosen from hydrogen and methyl, with the proviso that R 1 and R 2 are different from one another, and R 5 and R 6 each can be independently chosen from hydrogen and methyl, with the proviso that R 5 and R 6 are different from one another.
  • Pluronic R, Pluronic L62D, Tetronic R or Tetronic which are commercially available from BASF
  • suitable polyols for use in the present invention can include but are not limited to those described in WO 2004/060951 Al at paragraphs [0050J at page 17 to page 18, line 6, incorporated by reference herein.
  • the polyol can be a polyurethane prepolytner having two or more hydroxy functional groups .
  • Such polyurethane prepolymers can be prepared from any of the polyols and polyisocyanates previously described herein.
  • the OH:NCO equivalent ratio can be chosen such that essentially no free NCO groups are produced in preparing the polyurethane prepolymer.
  • the equivalent ratio of OH to NCO (i.e., isocyanate) present in the polyurethane prepolymer can be an amount of from 2.0 to less than 5.5 OH/1.0 NCO.
  • the polyurethane prepolymer can have a number average molecular weight (Mn) of less than 50,000 grams/mole, or less than 20,000 grams/mole, or less than 10,000 grams/mole, or less than 5,000 grams/mole, or greater than 1,000 grams/mole or greater than 2,000 grams/mole.
  • Mn number average molecular weight
  • the active hydrogen- containing material for use in the present invention can include sulfur-containing materials such as SH-containing materials, such as but not limited to polythiols having at least two thiol groups.
  • suitable polythiols can include but are not limited to aliphatic polythiols, cycloaliphatic polythiols, aromatic polythiols, heterocyclic polythiols, polymeric polythiols, oligomeric polythiols and mixtures thereof .
  • the sulfur-containing active hydrogen-containing material can have linkages including but not limited to ether linkages (-O-), sulfide linkages (-S-), polysulfide linkages (-S x -, wherein x is at least 2, or from 2 to 4) and combinations of such linkages.
  • thiol refers to an -SH group which is capable of forming a thiourethane linkage, (i.e., -NH-C(O)-S-) with an isocyanate group or a dithioruethane linkage (i.e., -NH-C(S)- S-) with an isothiocyanate group.
  • Non-limiting examples of suitable polythiols can include but are not limited to 2 , 5-dimercaptomethyl-l,4- dithiane, dimercaptoethylsulfide, pentaerythritol tetrakis(3- mercaptopropionate) , pentaerythritol tetrakis(2- mercaptoacetate) , trimethylolpropane tris(3- tnercaptopropionate) , trimethylolpropane tris(2- mercaptoacetate) , 4-mercaptomethyl-3 , 6-dithia-l, 8- octanedithiol, 4-tert-butyl-l, 2-benzenedithiol , 4,4'- thiodibenzenethiol , ethanedithiol , benzenedithiol, ethylene glycol di (2-mercaptoacetate) , ethylene glycol di
  • the polythiol can be chosen from materials described in WO 2004/060951 Al at paragraphs [0056] to [0061] , incorporated by reference herein.
  • the nature of the SH group of polythiols is such that oxidative coupling can occur readily, leading to formation of disulfide linkages.
  • Various oxidizing agents can lead to such oxidative coupling.
  • the oxygen in the air can in some cases lead to such oxidative ' coupling during storage of the polythiol- It is believed that a possible mechanism for the coupling of thiol groups involves the formation of thiyl radicals, followed by coupling of said thiyl radicals, to form disulfide linkage.
  • the polythiol for use in the present invention can include species containing disulfide linkage formed during storage.
  • the polythiol for use in the present invention can include species containing disulfide linkage formed during synthesis of said polythiol .
  • the polythiol for use in the present invention can include at least one polythiol described in WO 2004/060951 Al at paragraphs [0062] to [0093] , incorporated by reference herein.
  • polythiol for use in the present invention can include polythiol oligomer formed by the reaction of dithiol with diene, via thiol-ene type reaction of SH groups of said dithiol with double bond groups of said diene.
  • polythiol for use in the present invention can include at least one oligomeric polythiol as follows:
  • R 1 can be C 2 to C 5 n-alkylene; C 3 to C 6 alkylene unsubstituted or substituted wherein substituents can be hydroxyl , methyl, ethyl, methoxy or ethoxy,- or C 6 to C 3 cycloalkylene,- R 2 can be C 2 to C 6 n-alkylene, C 2 to C 6 branched alkylene, C 6 to C 8 cycloalkylene, C 6 to Ci 0 alkylcycloalkylene or --[(CH 2 --)p --O--] q --(--CH 2 --) r --; m can be a rational number from 0 to 10, n can be an integer from 1 to 20, p can be an integer from 2 to 6, q can be an integer from 1 to 5, and r can be an integer from 2 to 10.
  • polystyrene resin Various methods of preparing the polythiol of formula (IVf) are described in detail in United States Patent 6,509,418Bl, column 4, line 52 through column 8, line 25, which disclosure is herein incorporated by reference.
  • this polythiol can be prepared by combining reactants comprising one or more polyvinyl ether monomer, and one or more polythiol .
  • Useful polyvinyl ether monomers can include but are not limited to divinyl ethers represented by structural formula (V ) :
  • m can be two (2) .
  • Non-limiting examples of suitable polyvinyl ether monomers for use can include divinyl ether monomers , such as but not limited to ethylene glycol divinyl ether, diethylene glycol divinyl ether, butane diol divinyl ether and mixtures thereof .
  • the polyvinyl ether monomer can constitute from 10 to less than 50 mole percent of the reactants used to prepare the polythiol, or from 30 to less than 50 mole percent.
  • the divinyl ether of formula (V ) can be reacted with polythiol such as but not limited to dithiol represented by the formula (VI'):
  • Ri can be C 2 to C s n-alkylene group,- C 3 to C s branched alkylene group, having one or more pendant groups which can include but are not limited to hydroxyl, alkyl such as methyl or ethyl; alkoxy, or C 6 to C 8 cycloalkylene.
  • suitable polythiols for reaction with Formula (V ) can include those polythiols represented by Formula 2_ herein.
  • Non-limiting examples of suitable polythiols for reaction with Formula (V ) can include but are not limited to dithiols such as 1, 2-ethanedithiol, 1, 2-propanedithiol, 1,3- propanedithiol, 1 , 3-butanedithiol , 1, 4-butanedithiol , 2,3- butanedithiol , 1 , 3-pentanedithiol , 1 , 5-pentanedithiol, 1,6- hexanedithiol , 1,3 -dimercapto-3 -methylbutane, dipentenedimercaptan, ethylcyclohexyldithiol (ECHDT) , dimercaptodiethylsulfide (DMDS) , methyl-substituted dimercaptodiethylsulfide, dimethyl-substituted dimercaptodiethylsulfide, dimer
  • the polythiol for reaction with Formula (V ) can have a number average molecular weight ranging from 90 to 1000 grams/mole, or from 90 to 500 grams/mole.
  • the stoichiometric ratio of polythiol to divinyl ether can be less than one equivalent of polyvinyl ether to one equivalent of polythiol .
  • the polythiol and divinyl ether mixture can further include one or more free radical initiators.
  • suitable free radical initiators can include azo compounds, such as azobis- nitrile compounds such as but not limited to azo (bis) isobutyronitrile (AIBN),- organic peroxides such as but not limited to benzoyl peroxide and t-butyl peroxide; inorganic peroxides and similar free-radical generators .
  • the reaction to produce the material represented by Formula (IVf) can include irradiation with ultraviolet light either with or without a photoinitiator .
  • the polythiol for use in the present invention can include materials, their preparation, and reaction mixture ingredients therefore described in WO 2004/060951 Al at paragraphs [00102] to [00108] , incorporated by reference herein.
  • n+1" moles of dimercaptoethylsulfide can be reacted with "n” moles of 4- vinyl-1-cyclohexene, as shown above, in the presence of VAZO- 52 radical initiator.
  • the polythiol for use in the present invention can include a material represented by the following structural formula and reaction scheme:
  • R 1 and R 3 each can be independently Ci to C 6 n-alkylene, C 2 to C 6 branched alkylene, C 6 to C 8 cycloalkylene , C 6 to C 10 alkylcycloalkylene, C 6 to C 8 aryl , C 6 to C 10 alkyl-aryl, C 1 -C 10 alkyl containing ether linkages or thioether linkages or ester linkages or thioester linkages or combinations thereof, --[(CH 2 --)p --X--] q --(--CH 2 --)r --/ wherein X can be 0 or S, p can be an integer from 2 to 6, q can be an integer from 1 to 5 , r can be an integer from 0 to 10,- R 2 can be hydrogen or methyl; and n can be an integer from 1 to 20.
  • the polythiol of formula (IVj) can be prepared by reacting di (meth) acrylate monomer and one or more polythiols .
  • suitable di (meth) acrylate monomers can vary widely and can include those known in the art, such as but not limited to ethylene glycol di (meth (acrylate, 1,3 -butylene glycol di (meth) acrylate, 1, 4-butanediol di (meth) acrylate, 2 , 3-dimethylpropane 1,3- di (meth) acrylate, 1 , 6-hexanediol di (meth) acrylate, propylene glcol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, tetrapropylene glycol di (meth) acrylate , ethoxylated hexanediol di (meth)
  • Non-limiting examples of suitable polythiols for use as reactants in preparing polythiol of Formula (IVj) can vary widely and can include those known in the art , such as but not limited to 1, 2-ethanedithiol , 1 , 2-propanedithiol, 1,3- propanedithiol, 1, 3-butanedithiol , 1, 4-butanedithiol , 2,3- butanedithiol, 1, 3-pentanedithiol , 1, 5-pentanedithiol , 1,6- hexanedithiol , 1, 3-dimercapto-3 -tnethylbutane, dipentenedimercaptan, ethylcyclohexyldithiol (ECHDT) , dimercaptodiethylsulfide (DMDS) , methyl-substituted dimercaptodiethylsulfide, dimethyl -substituted
  • the polythiol used to prepare the polythiol of formula (IVj) can be dimercaptodiethylsulfide (DMDS) .
  • DMDS dimercaptodiethylsulfide
  • the reaction to produce the polythiol of formula (IVj) can be carried out in the presence of base catalyst .
  • Suitable base catalysts for use in this reaction can vary widely and can be selected from those known in the art. Non-limiting examples can include but are not limited to tertiary amine bases such as 1,8- diazabicyclo [5.4.0] undec-7-ene (DBU) and N, N- dimethylbenzylamine.
  • DBU 1,8- diazabicyclo [5.4.0] undec-7-ene
  • the amount of base catalyst used can vary widely. In a non-limiting embodiment, base catalyst can be present in an amount of from 0.001 to 5.0% by weight of the reaction mixture.
  • the double bonds can be at least partially consumed by reaction with the SH groups of the polythiol.
  • the mixture can be reacted for a period of time such that the double bonds are substantially consumed and a pre-calculated theoretical value for SH content is achieved.
  • the mixture can be reacted for a time period of from 1 hour to 5 days.
  • the mixture can be reacted at a temperature of from 20 0 C to 100 0 C.
  • the mixture can be reacted until a theoretical value for SH content of from 0.5% to 20% is achieved.
  • the number average molecular weight (M n ) of the resulting polythiol can vary widely.
  • the number average molecular weight (M n ) of polythiol can be determined by the stoichiometry of the reaction.
  • the M n of polythiol can be at least 400 g/mole, or less than or equal to 5000 g/mole, or from 1000 to 3000 g/mole.
  • the polythiol for use in the present invention can include a material represented by the following structural formula and reaction scheme:
  • Ri and R 3 each can be independently C 1 to C 6 n-alkylene , C 2 to C e branched alkylene , C 6 to C 8 cycloalkylene , C 6 to C 10 alkylcycloalkylene , C e to C 8 aryl , C 6 to C 10 alkyl -aryl , C x -C 10 alkyl containing ether linkages or thioether linkages or ester linkages or thioester linkages or combinations thereof, --[(CH 2 --) p --X--]q --(--CH 2 --) r --/ wherein X can be O or S, p can be an integer from 2 to 6, q can be an integer from 1 to 5 , r can be an integer from 0 to 10; R 2 can be hydrogen or methyl, and n can be an integer from 1 to 20.
  • the polythiol of formula (IVk) can be prepared by reacting polythio (meth) acrylate monomer, and one or more polythiols .
  • suitable polythio (meth) acrylate monomers can vary widely and can include those known in the art such as but not limited to di (meth) acrylate of 1 , 2-ethanedithiol including oligomers thereof, di (meth) acrylate of dimercaptodiethyl sulfide (i.e., 2 , 2 ' -thioethanedithiol di (meth) acrylate) including oligomers thereof, di (meth) acrylate of 3 , 6-dioxa-l, 8-octanedithiol including oligomers thereof, di (meth) acrylate of 2- mercaptoethyl ether including oligomers thereof, di (meth) acrylate of 4 , 4 '
  • the polythio (meth) acrylate monomer can be prepared from polythiol using methods known to those skilled in the art, including but not limited to those methods disclosed in US 4,810,812, US 6,342,571; and WO 03/011925.
  • Non-limiting examples of suitable polythiol for use as reactant(s) in preparing polythiols can include a wide variety of polythiols known in the art, such as but not limited to 1,2- ethanedithiol, 1, 2-propanedithiol, 1, 3-propanedithiol, 1,3- butanedithiol, 1, 4-butanedithiol, 2 , 3-butanedithiol, 1,3- pentanedithiol, 1, 5-pentanedithiol, 1, 6-hexanedithiol, 1,3- dimercapto-3-methylbutane, dipentenedimercaptan, ethylcyclohexyldithiol (ECHDT) , dimercaptodiethylsulfide, methyl-substituted dimercaptodiethylsulfide, dimethyl- substituted dimercaptodiethylsulfide, dimercaptodioxa
  • the polythio (meth) acrylate used to prepare the polythiol of formula (IV k) can be di (meth) acrylate of dimercaptodiethylsulfide, i.e., 2 , 2 ' -thiodiethanethiol dimethacrylate .
  • the polythiol used to prepare the polythiol of formula (IV k) can be dimercaptodiethylsulfide (DMDS) .
  • this reaction can be carried out in the presence of base catalyst.
  • suitable base catalysts for use can vary widely and can be selected from those known in the art.
  • Non-limiting examples can include but are not limited to tertiary amine bases such as 1 , 8-diazabicyclo [5.4.0] undec-7-ene (DBU) and N, N-dimethylbenzylamine .
  • the amount of base catalyst used can vary widely.
  • the base catalyst can be present in an amount of from 0.001 to 5.0% by weight of the reaction mixture.
  • the mixture can be reacted for a time period of from 1 hour to 5 days .
  • the mixture can be reacted at a temperature of from 20 0 C to 100 0 C.
  • the mixture can be heated until a precalculated theoretical value for SH content of from 0.5% to 20% is achieved.
  • the number average molecular weight (M n ) of the resulting polythiol can vary widely.
  • the number average molecular weight (M n ) of polythiol can be determined by the stoichiometry of the reaction.
  • the M n of polythiol can be at least 400 g/mole, or less than or equal to 5000g/mole, or from 1000 to 3000g/mole.
  • the polythiol for use in the present invention can include a material represented by the following structural formula and reaction:
  • R 1 can be hydrogen or methyl
  • R 2 can be C 1 to C 5 n- alkylene, C 2 to C 5 branched alkylene, C 6 to C 8 cycloalkylene, C ⁇ to C 10 alkylcycloalkylene , C 6 to C 8 aryl , C 6 to C 10 alkyl-aryl, C 1 -C 10 alkyl containing ether linkages or thioether linkages or ester linkages or thioester linkages or combinations thereof, or --[(CH 2 --) P --X--] q --(--CH 2 --) r --, wherein X can be O or S , p can be an integer from 2 to 6 , q can be an integer from 1 to 5, r can be an integer from 0 to 10; and n can be an integer from 1 to 20.
  • the polythiol of formula (IV 1 I) can be prepared by reacting allyl (raeth) acrylate, and one or more polythiols .
  • Non-limiting examples of suitable polythiols for use as reactant(s) in preparing polythiols can include a wide variety of known polythiols such as but not limited to 1,2- ethanedithiol, 1, 2-propanedithiol , 1, 3-propanedithiol , 1,3- butanedithiol , 1, 4-butanedithiol, 2, 3-butanedithiol, 1,3- pentanedithiol, 1, 5-pentanedithiol, 1, 6-hexanedithiol, 1,3- dimercapto-3 -methylbutane, dipentenedimercaptan, ethylcyclohexyldithiol (ECHDT) , dimercaptodiethylsulfide, methyl-substituted dimercaptodiethylsulfide, dimethyl- substituted dimercaptodiethylsulfide, dimercaptodio
  • the (meth) acrylic double bonds of allyl (meth) acrylate can be first reacted with polythiol in the presence of base catalyst.
  • suitable base catalysts can vary widely and can be selected from those known in the art.
  • Non-limiting examples can include but are not limited to tertiary amine bases such as 1, 8-diazabicyclo [5.4.0] undec-7-ene (DBU) and N, N- dimethylbenzylamine .
  • the amount of base catalyst used can vary widely. In a non-limiting embodiment, base catalyst can be present in an amount of from 0.001 to 5.0% by weight of the reaction mixture.
  • the mixture can be reacted for a time period of from 1 hour to 5 days . In another non-limiting embodiment, the mixture can be reacted at a temperature of from 20 0 C to 100 0 C. In a further non- limiting embodiment, following the reaction of the SH groups of the polythiol with substantially all of the available (meth) acrylate double bonds of the allyl (meth) acrylate, the allyl double bonds can then be reacted with the remaining SH groups in the presence of radical initiator.
  • Non-limiting examples of suitable radical initiators can include but are not limited to azo or peroxide type free-radical initiators such as azobisalkylenenitriles .
  • the free-radical initiator can be azobisalkylenenitrile which is commercially available from DuPont under the trade name VAZOTM.
  • VAZO-52, VAZO-64, VAZO- 67, or VAZO-88 can be used as radical initiators.
  • the mixture can be heated for a period of time such that the double bonds are substantially consumed and a desired pre-calculated theoretical value for SH content is achieved.
  • the mixture can be heated for a time period of from 1 hour to 5 days.
  • the mixture can be heated at a temperature of from 40 0 C to 100°C.
  • the mixture can be heated until a theoretical value for SH content of from 0.5% to 20% is achieved.
  • the number average molecular weight (M n ) of the resulting polythiol can vary widely.
  • the number average molecular weight (M n ) of polythiol can be determined by the stoichiometry of the reaction.
  • the M n of polythiol can be at least 400 g/mole, or less than or equal to 5000g/mole, or from 1000 to 3000g/mole.
  • the polythiol for use in the present invention can include polythiol oligomer produced by the reaction of at least two or more different dienes with one or more dithiol; wherein the stoichiometric ratio of the sum of the number of equivalents of dithiol present to the sum of the number of equivalents of diene present is greater than 1.0 : l.o.
  • the term "different dienes” can include the following embodiments: at least one non-cyclic diene and at least one cyclic diene which can be selected from non-aromatic ring-containing dienes including but not limited to non-aromatic monocyclic dienes, non-aromatic polycyclic dienes or combinations thereof, and/or aromatic ring-containing dienes; at least one aromatic ring-containing diene and at least one diene selected from the non-aromatic cyclic dienes described above; at least one non-aromatic monocyclic diene and at least one non-aromatic polycyclic diene.
  • the molar ratio of polythiol to diene in the reaction mixture can be
  • n can represent an integer from 2 to 30.
  • the two or more different dienes can each be independently chosen from non-cyclic dienes, including straight chain and/or branched aliphatic non-cyclic dienes, non-aromatic ring-containing dienes, including non-aromatic ring-containing dienes wherein the double bonds can be contained within the ring or not contained within the ring or any combination thereof, and wherein said non-aromatic ring- containing dienes can contain non-aromatic monocyclic groups or non-aromatic polycyclic groups or combinations thereof ; aromatic ring-containing dienes; or heterocyclic ring- containing dienes; or dienes containing any combination of such non-cyclic and/or cyclic groups, and wherein said two or more different dienes can optionally contain thioether, disulfide, polysulfide, sulfone, ester, thioester, carbonate, thiocarbonate, urethane, or thiourethane linkages, or halogen substituents , or combinations
  • said ratio can be within the range of from greater than 1:1 to 3:1, or from 1.01:1 to 3:1, or from 1.01:1 to 2:1, or from 1.05:1 to 2:1, or from 1.1:1 to 1.5:1, or from 1.25:1 to 1.5:1.
  • number of equivalents refers to the number of moles of a particular diene or polythiol, multiplied by the average number of thiol groups or double bond groups per molecule of said diene or polythiol, respectively.
  • reaction mixture that consists of the group of two or more different dienes and the group of one or more dithiol and the corresponding number of equivalents of each diene and dithiol that is used to prepare the polythiol oligomer can be depicted as shown in Scheme I below:
  • y is an integer greater than or equal to 1, that represents the total number of different dienes that are present; d x through d x represent the number of equivalents of each corresponding diene; T 1 through T y represent one or more dithiol; and t x through t y represent the number of equivalents of each corresponding dithiol; and y is an integer greater than or equal to 1 that represents the total number of dithiols present .
  • a group of two or more different dienes and the corresponding number of equivalents of each diene can be described by the term diDi (such as diD ⁇ through d x D x , as shown in Scheme I above) , wherein D 1 represents the i ch diene and di represents the number of equivalents of D 1 , i being can be an integer ranging from 1 to x, wherein x is an integer, greater than or equal to 2, that defines the total number of different dienes that are present.
  • the sum of the number of equivalents of all dienes present can be represented by the term d, defined according to Expression
  • t- j T- (such as ⁇ T 1 through t y T y , as shown m Scheme I above)
  • T- represents the j th dithiol
  • t D represents the number of equivalents of the corresponding dithiol T-
  • j being an integer ranging from 1 to y
  • y is an integer that defines the total number of dithiols present, and y has a value greater than or equal to 1.
  • the sum of the number of equivalents of all dithiols present can be represented by the term t, defined according to Expression (II) ,
  • the ratio of the sum of the number of equivalents of all dithiols present to the sum of the number of equivalents of all dienes present can. be characterized by the term t : d, wherein t and d are as defined above.
  • the ratio t : d can have values greater than 1:1.
  • the ratio t : d can have values within the range of from greater than 1:1 to 3:1, or from 1.01:1 to 3:1, or from 1.01:1 to 2:1, or from 1.05:1 to 2:1, or from 1.1:1 to 1.5:1, or from 1.25:1 to 1.5:1.
  • dienej has a molecular weight (MW) of 100, diene 2 has a molecular weight of 150, dithiol has a molecular weight of 200; and dien ⁇ j , diene 2 , and dithiol are present in the following molar amounts: 2 moles of diene ⁇ 4 moles of diene 2/ and 8 moles of dithiol; then the number average molecular weight (M n ) of the resulting polythiol oligomer is calculated as follows:
  • M n ⁇ (moles dlenel x MW diene i) + (moles die ne2 x MW dlene2 ) + (moles dithiol x MW dit:hi oi) ⁇ / m;
  • m is the number of moles of the material that is present in the smallest molar amount .
  • the term "different dienes” refers to dienes that can be different from one another in various aspects.
  • the "different dienes” can be different from one another as follows: a) non-cyclic vs. cyclic; b) aromatic ring- containing vs. non-aromatic ring-containing,- or c) monocyclic non-aromatic vs.
  • non-limiting embodiments of this invention can include the following: a) at least one non-cyclic diene and at least one cyclic diene selected from non-aromatic ring-containing dienes, including but not limited to dienes containing non-aromatic monocyclic groups or dienes containing non-aromatic polycyclic groups, or combinations thereof, and/or aromatic ring- containing dienes ; or b) at least one aromatic ring-containing diene and at least one diene selected from non-aromatic cyclic dienes, as described above,- or c) at least one non-aromatic diene containing non- aromatic monocyclic group, and at least one non-aromatic diene containing polycyclic non-aromatic group.
  • the polythiol oligomer can be as depicted in Formula (AA') in Scheme II below, produced from the reaction of Dienei and Diene 2 with a dithiol; wherein R 2 , R 4 , R 6 , and R 7 can be independently chosen from H, methyl, or ethyl, and R x and R 3 can be independently chosen from straight chain and/or branched aliphatic non-cyclic moieties, non-aromatic ring-containing moieties, including non-aromatic monocyclic moieties or non-aromatic polycyclic moieties or combinations thereof,- aromatic ring-containing moieties; or heterocyclic ring-containing moieties; or moieties containing any combination of such non-cyclic and/or cyclic groups; with the proviso that Diene x and Diene 2 are different from one another, and contain double bonds capable of undergoing reaction with SH groups of dithiol, and forming co
  • the polythiol oligomer can be as depicted in Formula (AA' ' ) in Scheme III below, produced from the reaction of Diene x and 5-vinyl-2- norbornene (VNB) with a dithiol; wherein R 2 and R 4 can be independently chosen from H, methyl, or ethyl, and R 1 can be chosen from straight chain and/or branched aliphatic non- cyclic moieties, non-aromatic monocyclic ring-containing moieties; aromatic ring-containing moieties,- or heterocyclic ring-containing moieties; or include moieties containing any combination of such non-cyclic and/or cyclic groups; with the proviso that Diene x is different from'VNB, and contains double bonds capable of reacting with SH groups of dithiol, and forming covalent C-S bonds; and wherein R 3 can be chosen from divalent groups containing straight chain and/or branched
  • the polythiol oligomer can be as depicted in Formula (AA' ' ' ) in Scheme IV below, produced from the reaction of Diene ! and 4-vinyl -1- cyclohexene (VCH) with a dithiol; wherein R 2 and R 4 can be independently chosen from H, methyl, or ethyl, and R 1 can be chosen from straight chain and/or branched aliphatic non- cyclic moieties, non-aromatic polycyclic ring-containing moieties; aromatic ring-containing moieties; or heterocyclic ring-containing moieties,- or moieties containing any combination of such non-cyclic and/or cyclic groups ; with the proviso that Diene x is different from VCH, and contains double bonds capable of reacting with SH group of dithiol, and forming covalent C-S bonds; and wherein R 3 can be chosen from divalent groups containing straight chain and
  • the polythiol for use in the present invention can include polythiol oligomer produced by the reaction of at least two or more different dienes with with at least one or more dithiol, and, optionally, one or more trifunctional or higher functional polythiol; wherein the stoichiometric ratio of the sum of the number of equivalents of polythiol present to the sum of the number of equivalents of diene present is greater than 1.0 : 1.0; and wherein the two or more different dienes can each be independently chosen from non-cyclic dienes, including straight chain and/or branched aliphatic non-cyclic dienes; non-aromatic ring-containing dienes, including non-aromatic ring-containing dienes wherein the double bonds can be contained within the ring or not contained within the ring or any combination thereof, and wherein said non-aromatic ring- containing dienes can contain non-aromatic monocyclic groups or non-aromatic polycyclic groups
  • Suitable dithiols for use in preparing the polythiol oligomer can be selected from a wide variety known in the art. Non-limiting examples can include those disclosed herein. Further non-limiting examples of suitable dithiols for use in preparing the polythiol oligomer can include but are not limited to 1, 2-ethanedithiol , 1, 2-propanedithiol , 1,3- propanedithiol, 1 , 3-butanedithiol, 1, 4-butanedithiol , 2,3- butanedithiol , 1, 3-pentanedithiol, 1, 5-pentanedithiol, 1,6- hexanedithiol, I 1 3-dimercapto-3-methylbutane, dipentenedimercaptan, ethylcyclohexyldithiol (ECHDT) , 2- mercaptoethylsulfide (DMDS) , methyl-substi
  • the dithiol can be 2, 5-di ⁇ nercaptomethyl-l,4- dithiane, ethylene glycol di (2-mercaptoacetate) , ethylene glycol di (3-mercaptopropionate) , poly (ethylene glycol) di (2- mercaptoacetate) , poly (ethylene glycol) di(3- mercaptopropionate) , dipentene dimercaptan (DPDM) , and mixtures thereof .
  • DPDM dipentene dimercaptan
  • Suitable trifunctional and higher-functional polythiols for use in preparing the polythiol oligomer can be selected from a wide variety known in the art. Non-limiting examples can include those disclosed herein. Further non- limiting examples of suitable trifunctional and higher- functional polythiols for use in preparing the polythiol oligomer can include but are not limited to pentaerythritol tetrakis (2 -mercaptoacetate) , pentaerythritol tetrakis (3- mercaptopropionate) , trimethylolpropane tris(2- mercaptoacetate) , trimethylolpropane tris(3- mercaptopropionate) , thioglycerol bis (2-mercaptoacetate) , and mixtures thereof .
  • Suitable dienes for use in preparing the polythiol oligomer can vary widely and can be selected from those known in the art.
  • suitable dienes can include but are not limited to acyclic non-conjugated dienes, acyclic polyvinyl ethers, allyl- and vinyl-acrylates, allyl- and vinyl-methacrylates, diacrylate and dimethacrylate esters of linear diols and dithiols, diacrylate and dimethacrylate esters of poly (alkyleneglycol) diols, monocyclic aliphatic dienes, polycyclic aliphatic dienes, aromatic ring-containing dienes, diallyl and divinyl esters of aromatic ring dicarboxylic acids, and mixtures thereof.
  • Non-limiting examples of acyclic non-conjugated dienes can include those represented by the following general formula:
  • R can represent C 2 to C 30 linear branched divalent saturated alkylene radical, or C 2 to C 30 divalent organic radical containing at least one element selected from the group consisting of sulfur, oxygen and silicon in addition to carbon and hydrogen atoms .
  • the acyclic non-conjugated dienes can be selected from 1, 5-hexadiene, 1,6- heptadiene, 1, 7-octadiene and mixtures thereof.
  • Non-limiting examples of suitable acyclic polyvinyl ethers can include but are not limited to those represented by structural formula (V ) :
  • R 2 can be C 2 to C 5 n-alkylene, C 2 to C 6 branched alkylene group, or --[(CH 2 --) p --O--] q --(--CH 2 --) r --, m can be a rational number from 0 to 10, p can be an integer from 2 to 6 , q can be an integer from 1 to 5 and r can be an integer from 2 to 10.
  • m can be two (2) .
  • Non-limiting examples of suitable polyvinyl ether monomers for use can include divinyl ether monomers, such as but not limited to ethylene glycol divinyl ether, diethylene glycol divinyl ether, triethyleneglycol divinyl ether, and mixtures thereof.
  • Non-limiting examples of suitable allyl- and vinyl- acrylates and methacrylates can include but are not limited to those represented by the following formulas:
  • R 1 each independently can be hydrogen or methyl .
  • the acrylate and methacrylate monomers can include monomers such as but not limited to allyl methacrylate, allyl acrylate and mixtures thereof .
  • Non-limiting examples of diacrylate and dimethacrylate esters of linear diols can include but are not limited to those represented by the following structural formula :
  • R can represent C 1 to C 30 divalent saturated alkylene radical; branched divalent saturated alkylene radical; or C 2 to C 30 divalent organic radical containing at least one element selected from sulfur, oxygen and silicon in addition to carbon and hydrogen atoms,- and R 2 can represent hydrogen or methyl.
  • the diacrylate and dimethacrylate esters of linear diols can include ethanediol dimethacrylate, 1 , 3 -propanediol diacrylate, 1, 3-propanediol dimethacrylate, 1 , 2-propanediol diacrylate, 1, 2-propanediol dimethacrylate, 1, 4-butanediol diacrylate, 1, 4-butanediol dimethacrylate, 1, 3-butanediol diacrylate, 1,3- butanediol dimethacrylate, 1, 2-butanediol diacrylate, 1,2- butanediol dimethacrylate, and mixtures thereof.
  • Non-limiting examples of diacrylate and dimethacrylate esters of poly (alkyleneglycol) diols can include but are not limited to those represented by the following structural formula:
  • R 2 can represent hydrogen or methyl and p can represent an integer from 1 to 5.
  • the diacrylate and dimethacrylate esters of poly (alkyleneglycol) diols can include ethylene glycol dimethacrylate, ethylene glycol diacrylate, diethylene glycol dimethacrylate, diethylene glycol diacrylate, and mixtures thereof.
  • suitable dienes can include monocyclic aliphatic dienes such as but not limited to those represented by the following structural formulas:
  • X and Y each independently can represent Ci-I 0 divalent saturated alkylene radical; or Ci -5 divalent saturated alkylene radical, containing at least one element selected from the group of sulfur, oxygen and silicon in addition to the carbon and hydrogen atoms; and R 1 can represent H, or Ci-C 10 alkyl,- and
  • R 1 can be as defined above and R 2 can represent C 2 -Ci 0 alkenyl .
  • the monocyclic aliphatic dienes can include 1, 4-cyclohexadiene, 4- vinyl-1-cyclohexene, dipentene and terpinene.
  • Non- limiting examples of polycyclic aliphatic dienes can include but are not limited to 5-vinyl-2-norbornene; 2,5- norbornadiene,- dicyclopentadiene and mixtures thereof.
  • Non-limiting examples of aromatic ring-containing dienes can include but are not limited to those represented by the following structural formula:
  • the aromatic ring-containing dienes can include monomers such as 1,3- diispropenyl benzene, divinyl benzene and mixtures thereof.
  • diallyl esters of aromatic ring dicarboxylic acids can include but are not limited to those represented by the following structural formula :
  • n each independently can be an integer fro ⁇ n 0 to 5.
  • diallyl esters of aromatic ring dicarboxylic acids can include o- diallyl phthalate, m-diallyl phthalate, p-diallyl phthalate and mixtures thereof .
  • reaction of at least one polythiol with two or more different dienes can be carried out in the presence of radical initiator.
  • Suitable radical initiators for use in the present invention can vary widely and can include those known to one of ordinary skill in the art.
  • Non-limiting examples of radical initiators can include but are not limited to azo or peroxide type free-radical initiators such as azobisalkalenenitriles .
  • the free-radical initiator can be azobisalkalenenitrile which is commercially available from DuPont under the trade name VAZOTM.
  • VAZO-52, VAZO-64, VAZO-67, VAZO-88 and mixtures thereof can be used as radical initiators.
  • selection of the free- radical initiator can depend on reaction temperature.
  • the reaction temperature can vary from room temperature to 100 0 C.
  • Vazo 52 can be used at a temperature of from 50-60 0 C, or Vazo 64 or Vazo 67 can be used at a temperature of 60 0 C to 75 0 C, or Vazo 88 can be used at a temperature of 75-100 0 C.
  • the reaction of at least one polythiol and two or more different dienes can be carried out under a variety of reaction conditions. In alternate non-limiting embodiments, such conditions can depend on the degree of reactivity of the dienes and the desired structure of the resulting polythiol oligomer.
  • polythiol, two or more different dienes and radical initiator can be combined together while heating the mixture.
  • polythiol and radical initiator can be combined together and added in relatively small amounts over a period of time to a mixture of two or more dienes .
  • two or more dienes can be combined with polythiol in a stepwise manner under radical initiation.
  • polythiol can be mixed with one diene and optionally free radical initiator; the diene and polythiol and optionally free radical initiator can be allowed to react and then a second diene can be added to the mixture, followed by addition of the radical initiator to the mixture.
  • the mixture is allowed to react until the double bonds are essentially consumed and a pre-calculated ⁇ e.g., by titration based on stoichiometry) theoretical SH equivalent weight is obtained.
  • the reaction time for completion can vary from one hour to five days depending on the reactivity of the dienes used.
  • the final oligomeric product of the stepwise addition process can be a block-type copolymer
  • the reaction of at least one polythiol with two or more different dienes can be carried out in the presence of a catalyst .
  • Suitable catalysts for use in the reaction can vary widely and can be selected from those known in the art .
  • the amount of catalyst used in the reaction of the present invention can vary widely and can depend on the catalyst selected. In a non-limiting embodiment, the amount of catalyst can be present in an amount of from 0.01% by weight to 5% by weight of the reaction mixture .
  • the acrylic monomers can be reacted with polythiol in the presence of a base catalyst .
  • Suitable base catalysts for use in this reaction vary widely and can be selected from those known in the art. Non-limiting examples can include but are not limited to tertiary amine bases such as 1,8- diazabicyclo[5.4.0] undec-7-ene (DBU) and N, N- dimethylbenzylamine .
  • the amount of base catalyst used can vary widely. In a non-limiting embodiment, the base catalyst can be present in an amount of from 0.01 to 5.0% by weight of the reaction mixture.
  • the reaction of the acrylic monomers with polythiol in the presence of a base catalyst can substantially minimize or essentially preclude double bond polymerization .
  • acrylic double bonds in order to substantially minimize or essentially preclude double bond polymerization, acrylic double bonds can be first reacted with polythiol under basic catalysis conditions and then, electron- rich reactive double bond dienes can be added to the intermediate product and reacted under radical initiation conditions .
  • electron-rich reactive double bond dienes can include materials such as but not limited to vinyl ethers, aliphatic dienes and cycloaliphatic dienes .
  • the mixture of polythiol, dienes and radical intiator is heated, the double bonds are at least partially consumed by reaction with the SH groups of the polythiol.
  • the mixture can be heated for a sufficient period of time such that the double bonds are essentially consumed and a pre-calculated theoretical value for SH content is reached.
  • the mixture can be heated for a time period of from 1 hour to 5 days .
  • the mixture can be heated at a temperature of from 40 0 C to 100 0 C.
  • the mixture can be heated until a theoretical value for SH content of from 0.7% to 17% is reached.
  • the number average molecular weight (M n ) of the resulting polythiol oligomer can vary widely.
  • the number average molecular weight (M n ) of polythiol oligomer can be predicted based on the stoichiometry of the reaction.
  • the M n of polythiol oligomer can vary from 400 to 10,000 g/mole, or from 1000 to 3000 g/mole.
  • the viscosity of the resulting polythiol oligomer can vary widely.
  • the viscosity can be from 40 cP to 4000 cP at 73°C, or from 40 cP to 2000 cP at 73°C, or from 150 cP to 1500 cP at 73°C .
  • vinylcyclohexene (VCH) and I 1 5-hexadiene (1,5-HD) can be combined together, and 2- mercaptoethylsulfide (DMDS) and a radical initiator (such as Vazo 52) can be mixed together, and this mixture can be added dropwise to the mixture of dienes at a rate such that a temperature of 60 0 C is not exceeded. After the addition is completed, the mixture can be heated to maintain a temperature of 60°C until the double bonds are essentially consumed and the pre-calculated theoretical value for SH content is reached.
  • polythiol oligomer can be prepared from the following combinations of dienes and polythiol :
  • VNB 5-vinyl-2-norbornene
  • DEGDVE diethylene glycol divinyl ether
  • DMDS diethylene glycol divinyl ether
  • VNB butanediol divinylether (BDDVE), DMDS
  • the polythiol for use in the present invention can be polythiol oligomer prepared by reacting one or more dithiol and, optionally, one or more trifunctional or higher functional polythiol with two or more dienes, wherein said dienes can be selected such that at least one diene has refractive index of at least 1.52 and at least one other diene has Abbe number of at least 40, wherein said dienes contain double bonds capable of reacting with SH groups of polythiol, and forming covalent C-S bonds; and wherein the stoichiometric ratio of the sum of the number of equivalents of all polythiols present to the sum of the number of equivalents of all dienes present is greater than 1.0 : 1.0.
  • the diene with refractive index of at least 1.52 can be selected from dienes containing at least one aromatic ring, and/or dienes containing at least one sulfur-containing substituent, with the proviso that said diene has refractive index of at least 1.52; and the diene with Abbe number of at least 40 can be selected from cyclic or non-cyclic dienes not containing an aromatic ring, with the proviso that said diene has Abbe number of at least 40.
  • the diene with refractive index of at least 1.52 can be selected from diallylphthalate and 1, 3-diisopropenyl benzene; and the diene with Abbe number of at least 40 can be selected from 5-vinyl-2-norbornene, 4-vinyl-l-cyclohexene, limonene, diethylene glycol divinyl ether, and allyl methacrylate .
  • tthe nature of the SH group of polythiols is such that oxidative coupling can occur readily, leading to formation of disulfide linkages.
  • Various oxidizing agents can lead to such oxidative coupling.
  • the oxygen in the air can in some cases lead to such oxidative coupling during storage of the polythiol .
  • a possible mechanism for the coupling of thiol groups involves the formation of thiyl radicals, followed by coupling of said thiyl radicals, to form disulfide linkage. It is further believed that formation of disulfide linkage can occur under conditions that can lead to the formation of thiyl radical, including but not limited to reaction conditions involving free radical initiation.
  • the polythiol oligomer for use in the present invention can contain disulfide linkages present in the dithiols and/or polythiols used to prepare said polythiol oligomer.
  • the polythiol oligomer for use in the present invention can contain disulfide linkage formed during the synthesis of said polythiol oligomer.
  • the polythiol oligomer for use in the present invention can contain disulfide linkages formed during storage of said polythiol oligomer.
  • polythiol for use in the present invention can include a material represented by the following structural formula and reaction scheme :
  • n can be an integer from 1 to 20.
  • the polythiol of formula (IVm) can be prepared by reacting "n" moles of 1,2,4- trivinylcyclohexane with "3n” moles of dimercaptodiethylsulfide (DMDS) , and heating the mixture in the presence of a suitable free radical initiator, such as but not limited to VAZO 64.
  • DMDS dimercaptodiethylsulfide
  • the polythiol for use in the present invention can include a material represented by the following structural formula:
  • n can be an integer from 1 to 20
  • Various methods of preparing the polythiol of the formula (IVi) are described in detail in United States Patent 5,225,472, from column 2, line 8 to column 5, line 8.
  • "3n" moles of 1,8- dimercapto-3 , 6-dioxaooctane (DMDO) can be reacted with "n” moles of ethyl formate, as shown above, in the presence of anhydrous zinc chloride .
  • the active hydrogen-containing material for use in the present invention can be chosen from polyether glycols and polyester glycols having a number average molecular weight of at least 200 grams/mole, or at least 300 grams/mole, or at least 750 grams/mole,- or no greater than 1,500 grams/mole, or no greater than 2,500 grams/mole, or no greater than 4,000 grams/mole.
  • Non-limiting examples of suitable active hydrogen- containing materials having both hydroxyl and thiol groups can include but are not limited to 2-mercaptoethanol , 3-mercapto- 1 , 2 -propanediol, glycerin bis (2-mercaptoacetate) , glycerin bis (3-mercaptopropionate) , l-hydroxy-4-mercaptocyclohexane, , 1, 3 -dimercapto-2-propanol, 2, 3-dimercapto-l-propanol, 1,2- dimercapto-1, 3-butanediol , trimethylolpropane bis (2- mercaptoacetate) , trimethylolpropane bis (3- mercaptopropionate) , pentaerythritol mono (2-mercaptoacetate) , pentaerythritol bis (2-mercaptoacetate) , pentaerythritol tris (2 -mercaptoethanol
  • the sulfur-containing polyureaurethane of the present invention can be prepared using a variety of techniques known in the art.
  • polyisocyanate, polyisothiocyanate or mixtures thereof and at least one active hydrogen-containing material can be reacted to form polyurethane prepolymer, and the polyurethane prepolymer can be reacted with an amine- containing curing agent.
  • the active hydrogen-containing material can include at least one material chosen from polyol, polythiol, polythiol oligomer and mixtures thereof.
  • the polyurethane prepolymer can be reacted with amine-containing curing agent.
  • said amine-containing curing agent can comprise a combination of amine-containing material and active hydrogen-containing material chosen from polyol, polythiol, polythiol oligomer and mixtures thereof.
  • said active hydrogen-containing material can further comprise material containing both hydroxy1 and SH groups .
  • said polyurethane prepolymer can contain disulfide linkages due to disulfide linkages contained in polythiol and/or polythiol oligomer used to prepare the polyurethane prepolymer.
  • polyisocyanate, polyisothiocyanate, or mixtures thereof, at least one active hydrogen-containing material and amine-containing curing agent can be reacted together in a "one pot" process.
  • the active hydrogen-containing material can include at least one material chosen from polyol, polythiol, polythiol oligomer and mixtures thereof.
  • the polyisocyanate can include meta-tetramethylxylylene diisocyanate (1, 3-bis (1-isocyanato-l-methylethyl-benzene) ; 3- isocyanato-methyl-3 , 5 , 5, -trimethyl-cyclohexyl isocyanate ;
  • Amine-containing curing agents for use in the present invention are numerous and widely varied.
  • suitable amine-containing curing agents can include but are not limited to those described in WO 2004/060951 Al at paragraphs [00116] to [00125] , incorporated by reference herein.
  • the atnine- containing curing agent can include a combination of polyamine and material selected from polyol, polythiol, polythiol oligomer, materials containing both hydroxyl and SH groups, and mixtures thereof.
  • Non-limiting examples of suitable polyamines , polythiols, polythiol oligomers, polyols, and/or materials containing both hydroxyl and SH groups for use in the curing agent mixture can include those previously recited herein.
  • the amine-containing curing agent for use in the present invention can be a combination of polyamine and polythiol and/or polythiol oligomer.
  • the sulfur-containing polyureaurethane of the present invention can be polymerized using a variety of techniques known in the art.
  • the polyureaurethane can be prepared by combining polyisocyanate, polyisothiocyanate, or mixtures thereof and active hydrogen-containing material to form polyurethane prepolymer, and then introducing amine-containing curing agent, and polymerizing the resulting mixture.
  • the prepolymer and the amine-containing curing agent each can be degassed (e.g. under vacuum) prior to mixing them and carrying out the polymerization.
  • the amine-containing curing agent can be mixed with the prepolymer using a variety of methods and equipment, such as but not limited to an impeller or extruder.
  • the sulfur-containing polyureaurethane can be prepared by a one- pot process, the polyisocyanate and/or polyisothiocyanate, active hydrogen-containing material, amine-containing curing agent and optionally catalyst can be degassed and then combined, and the mixture then can be polymerized.
  • Suitable catalysts can be selected from those known in the art. Non-limiting examples can include but are not limited to tertiary amine catalysts or tin compounds or mixtures thereof. In alternate non-limiting embodiments, the catalysts can be dimethyl cyclohexylamine or dibutyl tin dilaurate or mixtures thereof. In further non-limiting embodiments, degassing can take place prior to or following addition of catalyst.
  • the mixture which can be optionally degassed, can be introduced into a mold and the mold can be heated (i.e., using a thermal cure cycle) using a variety of conventional techniques known in the art.
  • the thermal cure cycle can vary depending on the reactivity and molar ratio of the reactants, and the presence of catalyst (s) .
  • the thermal cure cycle can include heating the mixture of polyurethane prepolymer and amine- containing curing agent, wherein said curing agent can include primary diamine or mixture of primary diamine and trifunctional or higher functional polyamine and optionally polyol and/or polythiol and/or polythiol oligomer,- or heating the mixture of polyisocyanate and/or polyisothiocyanate, polyol and/or polythiol and/or polythiol oligomer, and amine- containing material; from room temperature to a temperature of 200 0 C over a period of from 0.5 hours to 120 hours,- or from 80 to 150 0 C for a period of from 5 hours to 72 hours.
  • said curing agent can include primary diamine or mixture of primary diamine and trifunctional or higher functional polyamine and optionally polyol and/or polythiol and/or polythiol oligomer,- or heating the mixture of polyisocyanate and/or polyisothiocyanate, polyol and/or
  • a urethanation catalyst can be used in the present invention to enhance the reaction of the polyurethane-forming materials.
  • Suitable urethanation catalysts can vary; for example, suitable urethanation catalysts can include those catalysts that are useful for the formation of urethane by reaction of the NCO and OH-containing materials and/or the reaction of the NCO and SH-containing materials.
  • suitable catalysts can be chosen from the group of Lewis bases, Lewis acids and insertion catalysts as described in Ullmann's Encyclopedia of Industrial Chemistry, 5 th Edition, 1992, Volume A21, pp. 673 to 674.
  • the catalyst can be a stannous salt of an organic acid, such as but not limited to stannous octoate, dibutyl tin dilaurate, dibutyl tin diacetate, dibutyl tin mercaptide, dibutyl tin dimaleate, dimethyl tin diacetate, dimethyl tin dilaurate.
  • stannous octoate dibutyl tin dilaurate
  • dibutyl tin diacetate dibutyl tin mercaptide
  • dibutyl tin dimaleate dimethyl tin diacetate, dimethyl tin dilaurate.
  • I 7 4-diazabicyclo [2.2.2] octane, and mixtures thereof-
  • the catalyst can be zinc octoate, bismuth, or ferric acetylacetonate.
  • Suitable catalysts can include tin compounds such as but not limited to dibutyl tin dilaurate, phosphines, tertiary ammonium salts and tertiary amines such as but not limited to triethylamine, triisopropylamine, dimethyl cyclohexylamine, N, N- dimethylbenzylamine and mixtures thereof .
  • tin compounds such as but not limited to dibutyl tin dilaurate, phosphines, tertiary ammonium salts and tertiary amines
  • tertiary amines such as but not limited to triethylamine, triisopropylamine, dimethyl cyclohexylamine, N, N- dimethylbenzylamine and mixtures thereof .
  • tertiary amines are disclosed in United States Patent 5,693,738 at column 10, lines 6-38, the disclosure of which is incorporated herein by reference .
  • sulfur-containing polyureaurethane of the present invention can be prepared using the various combinations of ingredients shown in Table A below:
  • A dithiol oligomer made from DMDS + VNB + DEGDVE
  • VNB 5-vinyl-2-norbornene
  • DEGDVE di (ethylene glycol) divinyl ether
  • DIPEB 1, 3-diisopropenylbenzene
  • DMDS dimercaptodiethyl sulfide
  • HITT polythiol made by reacting "3n” moles DMDS with "n” moles of
  • PTMA pentaerythritol tetrakis (2-mercaptoacetate)
  • TMP trimethylolpropane
  • Des W 4 , 4 ' -methylene bis (cyclohexyl isocyanate)
  • the sulfur- containing polyureaurethane can be prepared by introducing together a polyurethane prepoly ⁇ ner and an amine-containing curing agent
  • the polyurethane prepolymer can be reacted with at least one episulfide-containing material prior to being introduced together with amine-containing curing agent.
  • Suitable episulfide-containing materials can vary, and can include but are not limited to materials having at least one, or two, or more episulfide functional groups.
  • the episulfide-containing material can have two or more moieties represented by the following general formula :
  • the numerical ratio of S is 50% or more, on the average, of the total amount of S and O constituting a three-membered ring.
  • the episulfide-containing material having two or more moieties represented by the formula (V) can be attached to an acyclic and/or cyclic skeleton.
  • the acyclic skeleton can be branched or unbranched, and it can contain sulfide and/or ether linkages.
  • the episulfide-containing material can be obtained by replacing the oxygen in an epoxy ring-containing acyclic material using sulfur, thiourea, thiocyanate, triphenylphosphine sulfide or other such reagents known in the art .
  • alkylsulfide-type episulfide-containing materials can be obtained by reacting various known acyclic polythiols with epichlorohydrin in the presence of an alkali to obtain an alkylsulfide-type epoxy material; and then replacing the oxygen in the epoxy ring as described above .
  • the cyclic skeleton can include the following materials:
  • each of the above materials can contain a linkage of a sulfide, an ether, a sulfone, a ketone, and/or an ester.
  • Non-limiting examples of suitable episulfide- containing materials having an alicyclic skeleton can include but are not limited to 1,3- and 1,4 -bis (/3- epithiopropylthio) cyclohexane, 1,3- and l,4-bis ⁇ /3- epithiopropylthiomethyl) cyclohexane, bis [4- ( ⁇ - epithiopropylthio) cyclohexyl] methane, 2 , 2-bis [4- ⁇ - epithiopropylthio) cyclohexyl] propane, bis [4- ( ⁇ - epithiopropylthio) cyclohexyl] sulfide, 4-vinyl-l-cyclohexene diepisulfide, 4-epithioethyl-l-cyclohexene sulfide, 4-epoxy- 1 , 2-cyclohexene sulfide, 2, 5-bis (/3-
  • Non-limiting examples of suitable episulfide- containing materials having an aromatic skeleton can include but are not limited to 1,3- and l,4-bis(/3- epithiopropylthio) benzene, 1,3- and l,4-bis(/3- epithiopropylthiomethyl) benzene, bis [4- ⁇ - epithiopropylthio) phenyl] methane, 2, 2-bis [4- ( ⁇ - epithiopropylthio) phenyl] propane, bis [4- ( ⁇ - epithiopropylthio) phenyl] sulfide, bis [4-(/S- epithiopropylthio) phenyl] sulfone, and 4,4-bis(/3- epithiopropylthio) biphenyl .
  • Non-limiting examples of suitable episulfide- containing materials having a heterocyclic skeleton including the sulfur atom as the hetero-atom can include but are not limited to the materials represented by the following general formulas :
  • X can be 0 or S .
  • suitable episulfide-containing materials can include but are not limited to 2, 5-bis ( / S-epithiopropylthiomethyl) -1, 4-dithiane; 2 , 5-bis (jS-epithiopropylthioethylthiomethyl) -1, 4-dithiane; 2 , 5- bis (jS-epithiopropylthioethyl) -1, 4-dithiane; 2,3,5-tri ( ⁇ - epithiopropylthioethyl) -1, 4-dithiane; 2,4,6-tris ( ⁇ - epithiopropylmethyl) -1, 3 , 5-trithiane; 2,4, 6-tris (/3- epithiopropylthioethyl) -1,3 , 5-trithiane; 2 , 4 , 6-tris ( ⁇ - epithiopropylthiomethyl) -1,3, ⁇ -trithiane,- 2,4, 6-tritris ( ⁇ - epithioprop
  • X can be as defined above .
  • the polyurethane prepolymer can be reacted with an episulfide-containing material of the structural formula XXXII : SH2 -VH-CH, - CH 2 -ZH- CH 5
  • additives can be incorporated into the sulfur-containing polyureaurethane of the present invention.
  • additives can include but are not limited to light stabilizers, heat stabilizers, antioxidants, ultraviolet light absorbers, mold release agents, static (non-photochromic) dyes, pigments and flexibilizing additives, such as but not limited to alkoxylated phenol benzoates and poly (alkylene glycol) dibenzoates .
  • Non-limiting examples of anti-yellowing additives can include 3- ⁇ ethyl-2-butenol , organo pyrocarbonates and triphenyl phosphite (CAS registry no. 101- 02-0) .
  • Such additives can be present in an amount such that the additive constitutes less than 10 percent by weight, or less than 5 percent by weight, or less than 3 percent by weight , based on the total weight of the prepolymer .
  • the aforementioned optional additives can be mixed with the polyisocyanate and/or polyisothiocyanate .
  • the optional additives can be mixed with active hydrogen- containing material .
  • the resulting sulfur- containing polyureaurethane of the present invention when at least partially cured can be solid and essentially transparent such that it is suitable for optical or ophthalmic applications.
  • the sulfur-containing polyureaurethane can have a refractive index of at least 1.55, or at least 1.56, or at least 1.57, or at least 1.58, or at least 1.59, or at least 1.60, or at least 1.62, or at least 1.65.
  • the sulfur-containing polyureaurethane can have an Abbe number of at least 32, or at least 35, or at least 38, or at least 39, or at least 40, or at least 44.
  • the sulfur-containing polyureaurethane when polymerized and at least partially cured can demonstrate good impact resistance/strength.
  • Impact resistance can be measured using a variety of conventional methods known to one skilled in the art.
  • the impact resistance is measured using the Impact Energy Test which consists of testing a flat sheet sample of polymerizate having a thickness of 3mm, and cut into a square piece approximately 4cm x 4cm. The flat sheet sample of polymerizate is supported on a flat O-ring which is attached to top of the pedestal of a steel holder, as defined below.
  • the O-ring is constructed of neoprene having a hardness of 40 +_ 5 Shore A durometer, a minimum tensile strength of 8.3 MPa, and a minimum ultimate elongation of 400 percent, and has an inner diameter of 25 mm, an outer diameter of 31 mm, and a thickness of 2.3 mm.
  • The. steel holder consists of a steel base, with a mass of approximately 12 kg, and a steel pedestal affixed to the steel base.
  • the shape of said steel pedestal is approximated by the solid shape which would result from adjoining onto the top of a cylinder, having an outer diameter of 75 mm and a height of 10 mm, the frustum of a right circular cone, having a bottom diameter of 75 mm, a top diameter of 25 mm, and a height of 8 mm, wherein the center of said frustum coincides with the center of said cylinder.
  • the bottom of said steel pedestal is affixed to said steel base, and the neoprene O-ring is affixed to the top of the steel pedestal, with the center of said O-ring coinciding with the center of the steel pedestal.
  • the flat sheet sample of polymerizate is set on top of the O-ring with the center of said flat sheet sample coinciding with the center of said O- ring.
  • the Impact Energy Test is carried out by dropping steel balls of increasing weight from a distance of 50 inches (1.27 meters) onto the center of the flat sheet sample.
  • the sheet is determined to have passed the test if the sheet does not fracture.
  • the sheet is determined to have failed the test when the sheet fractures.
  • the term "fracture” refers to a crack through the entire thickness of the sheet into two or more separate pieces , or detachment of one or more pieces of material from the backside of the sheet (i.e., the side of the sheet opposite the side of impact) .
  • the impact strength of the sheet is reported as the impact energy that corresponds to the highest level (i.e., largest ball) at which the sheet passes the test, and it is calculated accordinging to the following formula:
  • E impact energy in Joules (J)
  • m mass of the ball in kilograms (kg)
  • g represents acceleration due to gravity (i.e., 9.80665 m/sec 2 )
  • d represents the distance of the ball drop in meters (i.e., 1.27 m) .
  • the impact strength can be at least 2.0 joules, or at least 4.95 joules.
  • the sulfur- containing polyureaurethane of the present invention when at least partially cured can have low density.
  • the density can be at least 1.0, or at least 1.1 g/cm 3 , or less than 1.3, or less than 1.25, or less than 1.2 g/cm 3 , or from 1.0 to 1.2 grams/cm 3 , or from 1.0 to 1.25 grams/cm 3 , or from 1.0 to less than 1.3 grams/cm 3 .
  • the density is measured using a DensiTECH instrument manufactured by Tech Pro, Incorporated in accordance with ASTM D297.
  • Solid articles that can be prepared using the sulfur-containing polyureaurethane of the present invention include but are not limited to optical lenses, such as piano and ophthalmic lenses, sun lenses, windows, automotive transparencies, such as windshields, sidelights and backlights, and aircraft transparencies.
  • optical lenses such as piano and ophthalmic lenses, sun lenses, windows, automotive transparencies, such as windshields, sidelights and backlights, and aircraft transparencies.
  • the sulfur-containing polyureaurethane polymerizate of the present invention can be used to prepare photochromic articles, such as lenses.
  • the polymerizate can be transparent to that portion of the electromagnetic spectrum which activates the photochromic substance (s) , i.e., that wavelength of ultraviolet (UV) light that produces the colored or open form of the photochromic substance and that portion of the visible spectrum that includes the absorption maximum wavelength of the photochromic substance in its UV activated form, i.e., the open form .
  • UV ultraviolet
  • photochromic substances can be used in the present invention. Suitable photochromic substances, suitable amounts thereof, and methods of incorporation into the polymerizate are described in WO 2004/060951 Al at [00151] to [00161] , incorporated herein by reference .
  • the photochromic substance can be added to the sulfur-containing polyureaurethane prior to polymerizing and/or cast curing the material.
  • the photochromic substance used can be chosen such that it is resistant to potentially adverse interactions with, for example, the isocyanate, isothiocyante and amine groups present. Such adverse interactions can result in deactivation of the photochromic substance, for example, by trapping them in either an open or closed form.
  • suitable photochromic substances for use in the present invention can include photochromic pigments and organic photochromic substances encapsulated in metal oxides such as those disclosed in U.S. Patents 4,166,043 and 4,367,170; organic photochromic substances encapsulated in an organic polymerizate such as those disclosed in U.S. Patent 4,931,220.
  • the IH NMR and 13C NMR were measured on a Varian Unity Plus (200 MHz) machine; the Mass Spectra were measured on a Mariner Bio Systems apparatus; the refractive index and Abbe number were measured on a multiple wavelength Abbe Refractoraeter Model DR-M2 manufactured by ATAGO Co., Ltd.; the refractive index and Abbe number of liquids were measured in accordance with ASTM-D1218; the refractive index and Abbe number of solids was measured in accordance with ASTM-D542; the refractive index (e-line or d-line) was measured at a temperature of 20 0 C; the density of solids was measured in accordance with ASTM-D792; and the viscosity was measured using a Brookfield CAP 2000+ Viscometer.
  • Desmodur W (4,4'- methylenebis (cyclohexyl isocyanate) containing 20% of the trans, trans isomer and 80% of the cis,cis and cis, trans isomers) was obtained from Bayer Corporation.
  • the contents of the reactor were stirred at a rate of 150 rpm and a nitrogen blanket was applied as the reactor contents were heated to a temperature of 120 "C at which time the reaction mixture began to exotherm. The heat was removed and the temperature rose to a peak of 140 0 C for 30 minutes and then began to cool. Heat was applied to the reactor when the temperature reached 120 0 C and was maintained at that temperature for 4 hours to form the prepolymer (Component A) .
  • THF Tetrahydrofuran
  • Blank determination Into a 220-mL polyethylene beaker was added 50 mL THF followed by 10.0 mL DBA/THF solution. The solution was capped and allowed to mix with magnetic stirring for 5 minutes. 50 mL of the 80/20 THF/PG mix was added and titrated using the standardized alcoholic HCl solution and this volume was recorded. This procedure was repeated and these values averaged for use as the blank value . In a polyethylene beaker was weighed 1.0 gram of the prepolymer sample and this weight was recorded to the nearest 0.1 mg. 50 mL THF was added, the sample was capped and allowed to dissolve with magnetic stirring .
  • the reaction mixture was heated to a temperature of 65 0 C and then 30 ppm of dibutyltindilaurate catalyst (obtained from Aldrich) was added and the heat source was removed. The resulting exotherm raised the temperature of the mixture to 112°C.
  • the reaction was then allowed to cool to a temperature of 100 0 C, and 131 grams of UV absorber Cyasorb 5411 (obtained from American Cyanamid/Cytec) and 32.66 grams of Irganox 1010 (obtained from Ciba Geigy) were added with 0.98 grams of one weight percent solution of Exalite Blue 78-13 (obtained from Exciton) dissolved in Desmodur W (4,4'- methylenebis (cylohexylisocyanate) ) . The mixture was stirred for an additional two hours at 100 0 C and then allowed to cool to room temperature. The isocyanate (NCO) concentration of the prepolymer was 10.8% as measured in accordance with the procedure described above (see Example 1) .
  • NCO isocyanate
  • the reaction mixture was heated to a temperature of 65°C and then 30 ppm of dibutyltindilaurate catalyst (obtained from Aldrich) was added and the heat source was removed. The resulting exotherm raised the temperature of the mixture to 112°C.
  • the reaction was then allowed to cool to a temperature of 100 0 C, and 150 grams of UV absorber Cyasorb 5411 (obtained from American Cyanamid/Cytec) and 37.5 grams of Irganox 1010 (obtained from Ciba Geigy) were added with 1.13 grams of one weight percent solution of Exalite Blue 78-13 (obtained from Exciton) dissolved in Desmodur W, 4,4'- methylenebis (cylohexylisocyanate) . The mixture was stirred for an additional two hours at 100 0 C and then allowed to cool to room temperature . The isocyanate (NCO) concentration of the prepolymer was 12.2% as measured in accordance with the procedure described above (see Example 1) .
  • NCO isocyanate
  • the resulting clear mixture was immediately charged between two flat glass molds.
  • the molds were heated to a temperature of 130 0 C for 5 hours, yielding a transparent plastic sheet with the refractive index (e-line) , Abbe number, density and impact resistance values shown in Table 1.
  • reaction mixture was stirred for an additional 20 hours at room temperature.
  • the organic phase was than separated, washed with 2x100 ml of H 2 O, 1x100 ml of brine and dried over anhydrous MgSO 4 .
  • the drying agent was filtered off and the toluene was evaporated using a Buchi Rotaevaporator .
  • the hazy residue was filtered through Celite to provide 182 g (96% yield) of PTE Dithiol 1 as a colorless clear oily liquid.
  • the SH groups within the product were determined using the following procedure. A sample size (0.1 g) of the product was combined with 50 mL of tetrahydrofuran
  • a blank value was initially obtained by titrating 25.0 mL of iodine (including 1 mL of concentrated hydrochloric acid) with sodium thiosulfate in the same manner as conducted with the product sample. This resulting volume of titrant is represented as "mLs Blank" in the below equation.
  • the refractive index was 1.618 (20 0 C) and the Abbe number was 35.
  • the product sample (lOOmg, 0.28 mmol) was acetylated by dissolving it in 2 ml of dichloromethane at room temperature. Acetic anhydride (0.058 ml, 0.6 mmol) was added to the reaction mixture, and triethylamine (0.09 ml, 0.67 mmol) and dimethylaminopyridine (1 drop) were then added. The mixture was maintained at room temperature for 2 hours. The mixture was then diluted with 20 ml of ethyl ether, washed with aqueous NaHCO 3 and dried over MgSO 4 .
  • the mixture was transferred to a separatory funnel, shaken well, and following phase separation, 200 ml toluene were added to the organic layer; it was then washed with 150 ml H 2 O, 50 ml 5% HCl and 2x100 ml H 2 O and dried over anhydrous MgSO 4 .
  • the drying agent was filtered off and the solvent was evaporated on rotaevaporator to yield 80 g (32% yield) of transparent liquid having viscosity (73°C) of 56 cP; refractive index (e-line) of 1.635 (20 0 C), Abbe number of 36; and SH group analysis of 7.95%.
  • PTUPP 1 (30 g) was degassed under vacuum at a temperature of 70 0 C for 2 hours.
  • DETDA (7.11 g) and PTE Dithiol 1 (1.0 g) were mixed and degassed under vacuum at a temperature of 70 0 C for 2 hours.
  • the two mixtures were then mixed together at the same temperature and charged between a preheated glass plates mold.
  • the material was cured in a preheated oven at a temperature of 130°C for 5 hours.
  • the cured material was transparent and had a refractive index (e- line) of 1.585 (20 0 C), Abbe number of 39 and density of 1.174 g/cm 3 .
  • PTUPP 2 25 g was degassed under vacuum at a temperature of 65°C for 3 hours.
  • DETDA 3.88 g
  • PTE Dithiol 1 3.83 g were mixed and degassed under vacuum at a temperature of 65°C for 2 hours .
  • the two mixtures were then mixed together at the same temperature and charged between a preheated glass plates mold.
  • the material was cured in a preheated oven at a temperature of 130 0 C for 10 hours.
  • the cured material was transparent and had refractive index (e- line) of 1.599 (20 0 C), Abbe number of 39 and density of 1.202 g/cm 3 .
  • PTUPP 3 (40 g) was degassed under vacuum at a temperature of 65°C for 2 hours.
  • DETDA (3.89 g) and PTE Dithiol 1 (3.84 g) were mixed and degassed under vacuum at a temperature of 65°C for 2 hours.
  • the two mixtures were then mixed together at the same temperature and charged between a preheated glass plates mold.
  • the material was cured in a preheated oven at a temperature of 130 0 C for 10 hours.
  • the cured material was transparent and had refractive index feline) of 1.609 (20 0 C), Abbe number of 39 and density of 1.195 g/cm 3 .
  • reaction mixture was then heated to a temperature of 60 0 C, and five 0.25g-portions of free radical initiator Vazo-52 (2 , 2 ' -azobis (2 , 4-dimethylpentanenitrile) obtained from DuPont) were added. Each portion was added after an interval of one hour.
  • the reaction mixture was evacuated at 60°C/4-5mm Hg for one hour to yield 1.2 kg (yield: 100%) of colorless liquid with the following properties: viscosity of 300 cps @ 25°C refractive index (e-line) of 1.597 (20 0 C),- Abbe Number of 39; and SH groups content of 16.7%.
  • a colorless, viscous oligomeric product was obtained, having the following properties: viscosity of 10860, cps O 25 0 C; refractive index (e-line) of 1.604 (20 0 C),- Abbe Number of 41; and SH groups content of 5.1%.
  • EXAMPLE 26 Synthesis of Star Polymer (SP)
  • liquid polythioether with the following properties: viscosity of 320 cps @ 25 0 C; n D ao of 1.553; Abbe Number of 42; and SH groups content of 11.8% (thiol equivalent weight . of 280) .
  • Dimercaptodiethyl sulfide (16.20 grams, 0.105 mole) and ethylene glycol dimethacrylate (13.83 grams, 0.0698 mole) were charged into a small glass jar and mixed together using a magnetic stirrer.
  • N,N-dimethylbenzylamine (0.3007 gram) obtained from Aldrich was added, and the resulting mixture was stirred and heated using an oil bath at a temperature of 75°C for 52 hours.
  • a colorless to slightly yellow liquid was obtained having thiol equivalent weight of 314, viscosity of 1434 cps at 25°C and SH group content of 10.53%.
  • a colorless to slightly yellow liquid was obtained having thiol equivalent weight of 488, viscosity of 1470 cps at 25°C, refractive index n D 20 of 1.6100, Abbe Number of 36, and SH group content of 6.76%.
  • the UV light source used was a 300-watt FUSION SYSTEMS UV lamp, with a D-BuIb, which was positioned at a distance of 19 cm above the sample.
  • the sample was passed beneath the UV light source at a linear rate of 30.5 cm / minute using a model no. C636R conveyor belt system, available commercially from LESCO, Inc.
  • a single pass beneath the UV light source as described imparted 16 Joules / cm 2 of UV energy (UVA) to the sample.
  • a SH titration analysis conducted 10 minutes following the UV irradiation, showed SH group content of 6.4% and SH equivalent weight of 515 g/equivalent .
  • the viscosity of this product was 215 cps at 73 ⁇ C the refractive index was n D was 1.5825, and the Abbe number was 40.
  • PTUPP 4 (30 g) was degassed under vacuum at a temperature of 60 0 C for two hours.
  • DETDA (7.57 g) and PTE Dithiol 6 (2.02g) were mixed and degassed under vacuum at a temperature of 60 0 C for 2 hours .
  • the two mixtures were then mixed together at the same temperature and charged between a preheated glass plates mold.
  • the material was cured in a preheated oven at a temperature of 130 0 C for five hours. The cured material was clear and had refractive index (e-line) of 1.574 (20 0 C) and Abbe number of 40.
  • PTUPP 5 (30 g) was degassed under vacuum at a temperature of 60 0 C for two hours.
  • DETDA (5.94 g) and DMDS (1.13g) were mixed together and degassed under vacuum at a temperature of SO 0 C for two hours.
  • the two mixtures were then mixed together at the same temperature and charged between preheated glass plates mold.
  • the material was cured in a preheated oven at a temperature of 130 0 C for five hours.
  • the cured material was clear and had refractive index (e-line) of 1.575 (20 0 C) and Abbe number of 41.
  • EXAMPLE 36 Synthesis of dithiol oligomers [00212]
  • the starting materials shown in Table 2 were prepared according to the method specified in Table 2 and described below to yield a resulting dithiol oligomer having the properties shown in Table 2 for Entries 1-16.
  • DMDS - 2-mercaptoethy1sulfide obtained from Nisso-
  • AM - allyl methacrylate from Sartomer, USA
  • O VNB 5-vinyl-2-norbornene (mixture of endo and exo isomers from Ineos Oxide, Belgium)
  • EGDM ethylene glycol dimethacrylate
  • BDDVE 1,4-butanediol divinyl Ether (from BASF, Germany) 1,5-HD - 1,5-hexadiene (from Aldrich, USA)
  • DIPEB 1,3-diisopropenylbenzene (from Cytec) L -(R)- (+) -Limonene, 97% (from Aldrich, USA)
  • Table 2, Entry 8 In a three-necked glass flask equipped with thermometer, using a magnetic stirrer, were mixed 48.0 grams (0.4 mole) of VNB and 28.4 grams (0.2 mole) of (BDDVE) . The flask was emersed in an oil bath having a temperature between 40-42 0 C. With slight heating, 0.400 grams (0.5%) Vazo 52 radical initiator (2 , 2 ' -azobis (2 , 4- dimethylpentanenitrile, obtained from DuPont) was dissolved in 107.8 grams (0.7 mole) of DMDS. This solution was charged in a dropping funnel and the solution was added drop-wise to the mixture of two dienes .
  • Vazo 52 radical initiator 2 , 2 ' -azobis (2 , 4- dimethylpentanenitrile, obtained from DuPont
  • the reaction was exothermic and the temperature of the mixture did not exceed 60 0 C.
  • the temperature of the oil bath was increased to a temperature of 60 0 C and the mixture was- stirred at this temperature for 16 hours.
  • the temperature was then increased to 75°C and the mixture was stirred for another 4 hours.
  • the SH analysis was conducted and showed SHEW (SH (mercaptan) equivalent weight) of 894.
  • the mixture was stirred at a temperature of 60 0 C for another 24 hours.
  • the SH analysis was conducted and showed SHEW of 896.
  • the M n for the oligomeric mixture was calculated based on SHEW as 1792.
  • the measured refractive index n D (at 20 0 C) was 1.606 and the viscosity of the mixture at 73°C was 993 cP.
  • the temperature of the mixture increased slightly due to the exothermic reaction.
  • the mixture was stirred at room temperature for 2 hours, and then 60 grams (0.5 mole) of VNB were added drop-wise with a rate such that the temperature of the reaction did not exceed 70 0 C- After the addition was completed (over a time period of 2 hours), 0.180 grams (0.5%) radical initiator Vazo 64 (2 , 2 ' -azobisisobutyronitrile, obtained from DuPont) was added and the mixture was heated at 70 0 C for 15 hours .
  • the SH group analysis was conducted and showed SHEW of 636 and viscosity at 73°C of 291 cP.
  • the mixture was heated for another 15 hours at 65°C and the SH analysis then showed SHEW of 646 and viscosity of 329 cP at 73°C.
  • the M n for the oligomeric mixture based on SHEW was calculated as 1292.
  • the measured refractive index n D (at 20 0 C) was 1.593 and the Abbe number was 41.
  • Vazo 52 radical initiator 0.100 grams (0.03%) of Vazo 52 radical initiator was added and the mixture was stirred for 4 hours at a temperature of 60 0 C. To this mixture was added drop- wise at the same temperature, 63.2 grams (0.4 mole) of DEGDVE. After the addition was completed (total addition time was 1 hour) . The mixture was stirred at this temperature for 1 hour. Then 0.100 grams (0.03%) of Vazo 52 radical initiator was added and the mixture was stirred for 15 hours at a temperature of 60 0 C. The SH analysis was conducted and showed SHEW of 943 and viscosity at 73°C of 861 cP . The M n for the oligomeric mixture based on SHEW was measured as 1887. The measured refractive index n D (at 20 0 C) was 1.595 and the Abbe number was 42.
  • VAZO 52 0.1 g VAZO 52 was dissolved into the reaction mixture, which was then returned to the oven. Over a time period of 8 hours, the reaction mixture was kept in the 60 0 C oven, and two more additions of 0.2 g VAZO 52 were made. After 17 hours, the final addition of VAZO 52 (0.2 g) was made, and the resulting sample was titrated, giving an equivalent weight of 238 g/equivalent. The viscosity of the material at 25 0 C was 490 cps.
  • DIPEP.2DMDS refers to dithiol oligomer prepared with 2 eq. Of DMDS with 1 eq. Of DIPEB Des W - 4,4-dicyclohexylmethane diisocyanate (from Bayer, USA)
  • IPDI 3-isocyanato-methyl-3,5, 5-trimethyl cyclohexyl-isocyanate (from Degussa, Germany)
  • TMXDI 1, 3 -bis (1-isocyanato-l-methylethyl) benzene ( from Cytec, USA)
  • DETDA 2,4-diamino-3, 5-diethyl-toluene, 2, 6-dia ⁇ nino-3 , 5-diethyl-toluene and mixtures thereof (collectively "diethyltoluenediamine” or "DETDA”) , which is commercially available from Albemarle Corporation under the trade name Ethacure 100 00 OO DBTDL - dibutyltin dilaurate (obtained from Aldrich) Polycat 8 - N,N-dimethylcyclohexylamine (from Air
  • the prepolymer was chain extended with diamine and polythiol, the prepolymer was degassed under vacuum at a temperature of 60 0 C for two hours and diamine and polythiol were mixed and degassed under vacuum at room temperature for 2 hours.
  • the weight ratio of diamine/polythiol was as shown in Table 3 for each experiment .
  • the molar ratio (NH 2 +SH) /NCO was in all cases 0.95.
  • the two mixtures were then mixed together at a temperature of 60 0 C and charged between a preheated glass plates mold.
  • the material was cured in a preheated oven at a temperature of 130 0 C for 16 hours.
  • the cured material had the appearance, refractive index, density and impact resistence as shown in Table 3.
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WO2018079518A1 (ja) 2016-10-25 2018-05-03 三井化学株式会社 光学材料用重合性組成物、該組成物から得られた光学材料及びその製造方法
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