US20170029552A1 - Composition containing aromatic nitriles for the production of transparent polythiourethane bodies - Google Patents

Composition containing aromatic nitriles for the production of transparent polythiourethane bodies Download PDF

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US20170029552A1
US20170029552A1 US15/303,119 US201515303119A US2017029552A1 US 20170029552 A1 US20170029552 A1 US 20170029552A1 US 201515303119 A US201515303119 A US 201515303119A US 2017029552 A1 US2017029552 A1 US 2017029552A1
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composition
bis
polyisocyanate
isocyanatomethyl
nitrile
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Inventor
Robert Maleika
Fredie LANGENSTUECK
Christoph Eggert
Irene C. LATORRE MARTINEZ
Frank-Stefan STERN
Josef Sanders
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Covestro Deutschland AG
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Covestro Deutschland AG
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Assigned to COVESTRO DEUTSCHLAND AG reassignment COVESTRO DEUTSCHLAND AG ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: SANDERS, JOSEF, LATORRE MARTINEZ, IRENE CRISTINA, EGGERT, CHRISTOPH, LANGENSTUECK, FREDIE, MALEIKA, ROBERT, STERN, Frank-Stefan
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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
    • C08G18/70—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
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C263/00—Preparation of derivatives of isocyanic acid
    • C07C263/10—Preparation of derivatives of isocyanic acid by reaction of amines with carbonyl halides, e.g. with phosgene
    • 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
    • C08G18/16—Catalysts
    • C08G18/22—Catalysts containing metal compounds
    • C08G18/24—Catalysts containing metal compounds of tin
    • C08G18/242—Catalysts containing metal compounds of tin organometallic compounds containing tin-carbon bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
    • C08G18/3855—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur
    • C08G18/3863—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur containing groups having sulfur atoms between two carbon atoms, the sulfur atoms being directly linked to carbon atoms or other sulfur atoms
    • C08G18/3865—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur containing groups having sulfur atoms between two carbon atoms, the sulfur atoms being directly linked to carbon atoms or other sulfur atoms containing groups having one sulfur atom between two carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
    • C08G18/3855—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur
    • C08G18/3863—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur containing groups having sulfur atoms between two carbon atoms, the sulfur atoms being directly linked to carbon atoms or other sulfur atoms
    • C08G18/3865—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur containing groups having sulfur atoms between two carbon atoms, the sulfur atoms being directly linked to carbon atoms or other sulfur atoms containing groups having one sulfur atom between two carbon atoms
    • C08G18/3868—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur containing groups having sulfur atoms between two carbon atoms, the sulfur atoms being directly linked to carbon atoms or other sulfur atoms containing groups having one sulfur atom between two carbon atoms the sulfur atom belonging to a sulfide group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
    • C08G18/3855—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur
    • C08G18/3876—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur containing mercapto groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/71—Monoisocyanates or monoisothiocyanates
    • C08G18/714—Monoisocyanates or monoisothiocyanates containing nitrogen in addition to isocyanate or isothiocyanate nitrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
    • C08G18/7628—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring containing at least one isocyanate or isothiocyanate group linked to the aromatic ring by means of an aliphatic group
    • C08G18/7642—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring containing at least one isocyanate or isothiocyanate group linked to the aromatic ring by means of an aliphatic group containing at least two isocyanate or isothiocyanate groups linked to the aromatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate groups, e.g. xylylene diisocyanate or homologues substituted on the aromatic ring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/315—Compounds containing carbon-to-nitrogen triple bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
    • 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
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2125/00—Compositions for processes using internal mould release agents

Definitions

  • the present invention relates to compositions for producing transparent polythiourethane articles containing or consisting of
  • the invention further relates to a process for producing transparent polythiourethane articles by reaction of such a composition and to the thus manufactured polythiourethane articles and also to the use of aromatic nitriles for producing transparent polythiourethane articles and, in addition, to a mixture of a polyisocyanate and an aromatic nitrile for producing compact transparent polythiourethane articles.
  • U.S. Pat. No. 4,680,369 and U.S. Pat. No. 4,689,387 describe polyurethanes/polythhiourethanes suitable as lens materials for example, the production of which involves combining special sulfur-containing polyols or mercapto-functional aliphatic compounds with monomeric araliphatic diisocyanates, for example 1,3-bis(isocyanatomethyl)benzene (m-xylylene diisocyanate, m-XDI), 1,4-bis(isocyanatomethyl)benzene (p-xylylene diisocyanate, p-XDI), 1,3-bis(2-isocyanatopropan-2-yl)benzene (m-tetramethylxylylene diisocyanate, m-TMXDI) or 1,3-bis(isocyanatomethyl)-2,4,5,6-tetrachlorobenzene, in order to achieve particularly high refractive indices.
  • the present invention accordingly has for its object to specify a composition for producing transparent polythiourethane articles which makes it possible to manufacture such articles with improved optical properties, in particular improved transparency and freedom from cloudiness.
  • composition of the type mentioned at the outset when the composition further contains D) at least one aromatic nitrile.
  • the present invention accordingly provides a composition for producing transparent polythiourethane articles containing or consisting of
  • composition according to the invention is less sensitive to entrained water than prior art systems as are described in U.S. Pat. No. 8,044,165 B2 for example.
  • the thiol component in particular must be dried to remove excess water which could otherwise impair the optical properties of manufactured optical components.
  • the water content of the thiol component in the compositions according to the invention may be >600 ppm, in particular >800 ppm or even more than 900 ppm.
  • nitrile addition may preferably be effected during formulation of the composition, it being particularly preferable when the nitrile is premixed with the polyisocyanate component before the reaction with the thiol component is effected.
  • the invention is in no way limited to this option.
  • nitrile addition may also be effected before or during manufacture of the polyisocyanate which is typically effected by a liquid-phase or gas-phase phosgenation of the corresponding polyamines.
  • the addition of portions of the aromatic nitrile at any desired timepoints is also possible.
  • This option is very preferably applied in the gas-phase phosgenation of 1,3-xylylenediamine (1,3-XDA) and/or 1,4-xylylenediamine (1,4-XDA) to afford 1,3-bis(isocyanatomethyl)benzene (1,3-XDI) and/or 1,4-bis(isocyanatomethyl)benzene (1,4-XDI).
  • the thus manufactured araliphatic diisocyanate or a mixture of the compounds mentioned with the production-dependent amount of aromatic nitriles present may be employed in a composition according to the invention or else the nitrile amount may be increased by addition of further aromatic nitriles which may be identical or different to the nitriles present.
  • compositions according to the invention may contain not only the aromatic nitriles but, in addition, also other organic nitriles, for example aliphatic, cycloaliphatic or araliphatic nitriles.
  • the polyisocyanate component contains at least one polyisocyanate having at least two isocyanate groups per molecule, in particular from 2 to 6, preferably from 2 to 4, particularly preferably from 2 to 3. It is also possible to employ mixtures of polyisocyanates of different functionality and odd-numbered average functionalities may therefore arise.
  • polyisocyanate is to be understood as meaning organic isocyanates having two or more free isocyanate groups.
  • the polyisocyanate may be in monomeric form or else in oligomeric form.
  • Modification reactions suitable therefor are for example the customary processes for catalytic oligomerization of isocyanates to form uretdione, isocyanurate, iminooxadiazinedione and/or oxadiazinetrione structures or for biuretization of diisocyanates such as are described by way of example in Laas et al., J. Prakt. Chem. 336, 1994, 185-200, in DE-A 1 670 666 and in EP-A 0 798 299 for example.
  • poly-isocyanates based on araliphatic diisocyanates may also be found in EP-A 0 081 713, EP-A 0 197 543, GB-A 1 034 152 and JP-A 05286978 for example.
  • the syllable “poly” accordingly relates essentially to the number of isocyanate groups per molecule and does not necessarily mean that the polyisocyanate must have an oligomeric, much less a polymeric, structure.
  • Polyisocyanates that may be employed in the context of the present invention in principle include all polyisocyanates known per se. These are for example polyisocyanates in the molecular weight range 140 to 400 g/mol, for example 1,4-diisocyanatobutane, 1,5-diisocyanatopentane, 1,6-diisocyanatohexane (HDI), 1,5-diisocyanato-2,2-dimethylpentane, 2,2,4- or 2,4,4-trimethyl-1,6-diisocyanatohexane, 1,8-diisocyanatooctane, 1,9-diisocyanatononane, 1,10-diisocyanatodecane, 1,3- and 1,4-diisocyanatocyclohexane, 1,4-diisocyanato-3,3,5-trimethylcyclohexane, 1,3-diisocyanato-2-methylcyclohexan
  • polyisocyanates may have been produced by any desired processes, for example by phosgenation of the corresponding amines in the gas or liquid phase but also by phosgene-free methods, for example by carbamate cleavage.
  • the polyisocyanates are preferably selected from 1,3-bis(isocyanatomethyl)benzene (1,3-XDI), 1,4-bis(isocyanatomethyl)benzene (1,4-XDI), 2,5-bis(isocyanatomethyl)bicyclo[2.2.1]heptane, 2,6-bis(isocyanatomethyl)bicyclo[2.2.1]heptane, 1,4-bis(isocyanatomethyl)cyclohexane, 1,3-bis(isocyanatomethyl)cyclohexane, 2,2′-diisocyanatodicyclohexylmethane, 2,4′-diisocyanatodicyclohexylmethane, 4,4′-diisocyanatodicyclohexylmethane (H12-MDI), 1-isocyanato-3,3,5-trimethyl-5-isocyanato ethylcyclohexane (isophoronediis
  • poly- and diisocyanates are preferred because they make it possible to obtain lens materials having particularly good optical properties, such as a high refractive index and high transparency. These advantages are particularly pronounced for the diisocyanates mentioned as preferable 1,3-bis(isocyanatomethyl)benzene (1,3-XDI) and 1,4-bis(isocyanatomethyl)benzene (1,4-XDI).
  • the average isocyanate functionality of the polyisocyanate component A) is preferably 1.8 to 4.0, in particular 1.9 to 3.5, particularly preferably 2.0 to 3.0.
  • the present invention may provide that at least one polyisocyanate of the polyisocyanate component A) has been produced by gas-phase phosgenation of aliphatic, cycloaliphatic, aromatic or araliphatic polyamines.
  • gas-phase phosgenation of aliphatic, cycloaliphatic, aromatic or araliphatic polyamines.
  • Such a process for manufacturing the polyisocyanates to be employed in accordance with the invention is described in EP 1 754 698 B1.
  • Also employable is a process for gas-phase phosgenation as is disclosed in WO 2013/079517 A1.
  • the gas phase phosgenation procedure is preferably conducted such that the relevant starting substances, i.e. the polyamines upon which the polyisocyanates to be produced are based, are evaporated, optionally with addition of stabilizers and/or an inert gas, this being done at a pressure of ⁇ 1000 mbar if necessary.
  • the polyamines evaporated in this way are passed through a circuit with an average residence time of 5 to 90 minutes and a temperature of 40° C. to 190° C. and reacted with phosgene in accordance with processes of gas-phase phosgenation known per se at a temperature of 10 to 100 K above the evaporation temperature of the amines at the prevailing pressure.
  • Suitable modification reactions for producing the polyisocyanate components A) are, if desired, urethanization and/or allophanatization of araliphatic diisocyanates after addition of a molar deficiency of hydroxyl-functional coreactants, in particular low molecular weight mono- or polyhdric alcohols in the molecular weight range 32 to 300 g/mol, for example methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, secbutanol, the isomeric pentanols, hexanols, octanols and nonanols, n-decanol, ndodecanol, n-tetradecanol, n-hexadecanol, n-octadecanol, cyclohexanol, the isomeric methylcyclohexanols, hydroxymethylcyclo
  • urethane- and/or allophanate-modified polyisocyanates based on araliphatic diisocyanates may be found in EP-A 1 437 371, EP-A 1 443 067, JP-A 2005161611691, JP-A 2005162271 for example.
  • a preferred configuration of the composition according to the invention specifies that the polyisocyanate component contains at least 30 wt % based on the polyisocyanate component of polyisocyanate produced by gas-phase phosgenation, in particular at least 50 wt %, more preferably at least 80 wt % or even at least 90 wt %, particularly preferably at least 95 wt % or even at least 96 or at least 98 wt %.
  • polyisocyanate manufactured by gas-phase phosgenation it is preferable for least one nitrile present as a byproduct in the polyisocyanate component present by gas-phase phosgenation to form a further constituent of the polyisocyanate component.
  • the polyisocyanate component may quite possibly also have had a polyisocyanate manufactured by a different production route added to it, for example a polyisocyanate produced by liquid-phase phosgenation.
  • the proportion of polyisocyanates produced by routes other than gas-phase phosgenation may be for example up to 19 wt % based on the polyisocyanate component A), or else up to 14 wt %, up to 9 wt %, up to 4 wt % or up to 3 wt %.
  • the polyisocyanate component contains at least 0.005 wt % based on the polyisocyanate component A) of at least one aromatic nitrile, in particular at least 0.01 wt %, preferably 0.005 to 15 wt %, more preferably 0.01 to 5 wt %, particularly preferably 0.1 to 2 wt % or even 0.1 to 1 wt %.
  • the polyisocyanate components employed in accordance with the invention and manufactured by gas-phase phosgenation may already contain a certain proportion of nitriles as a result of the production process which may be influenced inter alia by the nature of the polyamines employed in the reaction and moreover by the choice of the reaction conditions, in particular the pressure and the reaction temperature.
  • This applies in particular for the polyisocyanates particularly preferred in the context of the present invention 1,3-bis(isocyanatomethyl)benzene (1,3-XDI) and 1,4-bis(isocyanatomethyl)benzene (1,4-XDI) which after the gas-phase phosgenation generally exhibit comparatively high contents of corresponding nitriles.
  • the composition preferably contains 0.0025 to 10 wt % based on the total composition of aromatic nitrile, in particular 0.005 to 5 wt %, more preferably 0.01 to 3 wt % and particularly preferably 0.05 to 2 wt %.
  • aromatic nitriles are particularly advantageous because this makes it possible to produce optical molded articles that are particularly transparent and free from cloudiness from polythiourethanes, for example lenses.
  • the content of nitriles is determined by derivatization with diethylamine and subsequent HPLC-MS by integration of the areas of the signals in the UV range.
  • the HPLC-MS measurement may be performed with the following program for example:
  • the mobile phase consisted of:
  • the nitrile is derived from the same polyamine as the polyisocyanate. This applies both for the nitriles present as a result of the production process and for any subsequently added nitriles. This is particularly advantageous since the identical basic chemical structure to that of the polyisocyanate manufactured during the gas-phase phosgenation ensures that a particularly good promotion effect is achieved by the nitrile.
  • the nitrile may contain at least one further functional group which is in particular a group that can be incorporated into the polythiourethane network to prevent later migration of the nitrile out of the molded article and may particularly preferably be an isocyanate group.
  • This diisocyanate may be manufactured by gas-phase phosgenation of 1,3-bis(aminomethyl)benzene.
  • the particularly preferred isocyanatonitrile in this case is 3-(isocyantomethyl)benzonitrile.
  • R2 represents the radical of the polythiol employed.
  • R2 represents the radical of the polythiol employed.
  • DMPT 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane
  • R2 represents the following structural unit, wherein the left-hand bond line in the formula represents the bond to the sulfur atom in the above structure.
  • Analogous compounds may also be formed with optionally employed polyols.
  • a nitrile-modified urethane is thus formed.
  • a diol it is also possible for both OH groups to react with one molecule of 3-(isocyantomethyl)benzonitrile respectively, thus forming the structure:
  • aromatic nitriles is to be understood as meaning compounds having a nitrile group bonded directly to an aromatic and preferably having a molar mass of ⁇ 1000 g/mol, particularly preferably ⁇ 500 g/mol.
  • the nitrile is selected from benzonitrile, 3-(isocyanatomethyl)benzonitrile, 4-(isocyanatomethyl)benzonitrile, 3-(chloromethyl)benzonitrile, 4-(chloromethyl)benzonitrile, 3-cyanobenzoic acid, 4-cyanobenzoic acid, 2-hydroxybenzonitrile, 3-hydroxybenzonitrile, 4-hydroxybenzonitrile, 3-cyanobenzoyl chloride, 4-cyanobenzoyl chloride or mixtures thereof, in particular benzonitrile, 3-(chloromethyl)benzonitrile, 4-(chloromethyl)benzonitrile, 3-(isocyanatomethyl)benzonitrile, and/or 4-(isocyanatomethyl)benzonitrile, particularly preferably 3-(isocyanatomethyl)benzonitrile, and/or 4-(isocyanatomethyl)benzonitrile.
  • nitriles are advantageous particularly when a polyisocyanate component which has relatively large proportions of 1,3-XDI and/or 1,4-XDI, such as >50 wt % based on the polyisocyanate component A), or which in terms of the polyisocyanates consists completely of these compounds, is used. In these cases a particularly pronounced improvement in the optical properties of a polythiourethane article manufactured therefrom may be observed, especially as regards transparency thereof.
  • the polyisocyanate is selected from 1,3-bis(isocyanatomethyl)benzene (1,3-XDI) and the nitrile from 3-(isocyanatomethyl)benzonitrile and/or that the polyisocyanate is selected from 1,4-bis(isocyanatomethyl)benzene (1,4-XDI) and the nitrile from 4-(isocyanatomethyl)benzonitrile.
  • composition according to the invention further contains a thiol component B).
  • Said component contains or consists of at least one polythiol having a functionality of thiol groups of at least two per molecule, in particular from 2 to 6, preferably from 2 to 4, particularly preferably from 3 to 4. It is also possible to employ mixtures of polythiols of different functionality and odd-numbered average functionalities may therefore arise.
  • polythiol is to be understood as meaning organic thiols having two or more thiol groups.
  • the syllable “poly” accordingly relates essentially to the number of thiol groups per molecule and, as stated above for the polyisocyanate compounds, does not necessarily mean that the polythiol must have an oligomeric, much less a polymeric, structure. Notwithstanding, the polythiols used according to the invention may quite possibly also have a polyether basic structure, a polythioether basic structure or a mixed basic structure composed of O-ether and S-ether units.
  • the polythiol may have an average molecular weight of 80 (methanedithiol) to about 12000 g/mol, preferably 250 to 8000 g/mol.
  • Suitable polythiols include for example methanedithiol, 1,2-ethanedithiol, 1,1-propanedithiol, 1,2-propanedithiol, 1,3-propanedithiol, 2,2-propanedithiol, 1,4-butanedithiol, 2,3-butanedithiol, 1,5-pentanedithiol, 1,6-hexanedithiol, 1,2,3-propanetrithiol, 1,1-cyclohexanedithiol, 1,2-cyclohexanedithiol, 2,2-dimethylpropane-1,3-dithiol, 3,4-dimethoxybutane-1,2-dithiol and 2-methylcyclohexane-2,3-dithiol, polythiols containing thioether groups, for example 2,4-dimercaptomethyl-1,5-dimercapto-3-thiapentane, 4-mercap
  • the polythiol is selected from 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, 2,5-bismercaptomethyl-1,4-dithiane, 1,1,3,3-tetrakis(mercaptomethylthio)propane, 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, trimethylolpropane tris(3-mercaptopropionate), trimethylolethane tris(2-mercaptoacetate), pentaerythritol tetrakis(2-mercaptoacetate) and/or pentaerythritol tetrakis(3-mercapto
  • composition according to the invention may also contain other components typically reacted with polyisocyanates.
  • these are in particular the customary polyetherpolyols, polyesterpolyols, polyetherpolyesterpolyols, polythioetherpolyols, polymer-modified polyetherpolyols, graft polyetherpolyols, in particular those based on styrene and/or acrylonitrile, polyetherpolyamines, hydroxyl-containing polyacetals and/or hydroxyl-containing aliphatic polycarbonates known from polyurethane chemistry which typically have a weight-average molecular weight of 106 to 12 000 g/mol, preferably 250 to 8000 g/mol.
  • polythiourethane is to be understood as meaning a polymer where more than half to all of the bonds between the polyisocyanate and the isocyanate-reactive component(s) are thiourethane groups. Thus, other bonds may be present in a proportion of less than half, for example urethane or urea bridges.
  • the composition according to the invention also contains other isocyanate-reactive component(s). These merely optional components are more particularly described hereinbelow.
  • Suitable polyetherpolyols are for example those of the type referred to in DE-A 2 622 951, column 6, line 65-column 7, line 47, or EP-A 0 978 523, page 4, line 45 to page 5, line 14, provided that they conform to the above indications relating to functionality and molecular weight.
  • Particularly preferred polyetherpolyols B) are addition products of ethylene oxide and/or propylene oxide onto glycerol, trimethylolpropane, ethylenediamine and/or pentaerythritol.
  • Suitable polyesterpolyols are for example those of the type referred to in EP-A 0 978 523, page 5, lines 17 to 47, or EP-A 0 659 792, page 6, lines 8 to 19, provided that they conform to the above indications, preferably those having a hydroxyl number of 20 to 650 mg KOH/g.
  • Suitable polyacetalpolyols are for example the known reaction products of simple glycols, for example diethylene glycol, triethylene glycol, 4,4′-dioxyethoxydiphenyldimethylmethane (adduct of 2 mol of ethylene oxide onto bisphenol A) or hexanediol, with formaldehyde, or else polyacetals produced by polycondensation of cyclic acetals, for example trioxane.
  • Aminopolyethers or mixtures of aminopolyethers may likewise be suitable, i.e. polyethers having isocyanate-reactive groups which are composed of primary and/or secondary, aromatic or aliphatic amino groups to an extent of at least 50 equivalent %, preferably at least 80 equivalent %, and of primary and/or secondary, aliphatic hydroxyl groups as the remainder.
  • Suitable aminopolyethers of this type are for example the compounds referred to in EP-A 0 081 701, column 4, line 26 to column 5, line 40.
  • starting component E are amino-functional polyetherurethanes or -ureas such as are producible for example by the process of DE-A 2 948 419 by hydrolysis of isocyanate-functional polyether prepolymers or else amino-containing polyesters of the abovementioned molecular weight range.
  • isocyanate-reactive components are, for example, also those described in EP-A 0 689 556 and EP-A 0 937 110, for example special polyols obtainable by reaction of epoxidized fatty acid esters with aliphatic or aromatic polyols to bring about epoxide ring opening.
  • Hydroxyl-containing polybutadienes too may optionally be employed.
  • Sulfur-containing hydroxyl compounds are moreover also suitable as isocyanate-reactive components.
  • examples that may be mentioned here are mercaptoalcohols, for example 2-mercaptoethanol, 3-mercaptopropanol, 1,3-dimercapto-2-propanol, 2,3-dimercaptopropanol and dithioerythritol, thioether-containing alcohols, for example di(2-hydroxyethyl)sulfide, 1,2-bis(2-hydroxyethylmercapto)ethane, bis(2-hydroxyethyl)disulfide and 1,4-dithiane-2,5-diol, or sulfur-containing diols having a polyesterurethane-, polythioesterurethane-, polyesterthiourethane- or Polythioesterthiourethane structure of the type referred to in EP-A 1 640 394.
  • compositions according to the invention may also contain as isocyanate-reactive compounds low molecular weight, hydroxyl- and/or amino-functional components, i.e. those in a molecular weight range from 60 to 500 g/mol, preferably from 62 to 400 g/mol.
  • suitable low molecular weight amino-functional compounds are aliphatic and cycloaliphatic amines and aminoalcohols having primary and/or secondary amino groups, for example cyclohexylamine, 2-methyl-1,5-pentanediamine, diethanolamine, monoethanolamine, propylamine, butylamine, dibutylamine, hexylamine, monoisopropanolamine, diisopropanolamine, ethylenediamine, 1,3-diaminopropane, 1,4-diaminobutane, isophoronediamine, diethylenetriamine, ethanolamine, aminoethylethanolamine, diaminocyclohexane, hexamethylenediamine, methyliminobispropylarmine, iminobispropylamine, bis(aminopropyl)piperazine, aminoethylpiperazine, 1,2-diaminocyclohexane, triethylenetetramine, te
  • aromatic polyamines in particular diamines, having molecular weights below 500 which are suitable isocyanate-reactive compounds B) are for example 1,2- and 1,4-diaminobenzene, 2,4- and 2,6-diaminotoluene, 2,4′- and/or 4,4′-diaminodiphenylmethane, 1,5-diaminonaphthalene, 4,4′,4′′-triaminotriphenylmethane, 4,4′-bis(methylamino)diphenylmethane or 1-methyl-2-methylamino-4-aminobenzene, 1-methyl-3,5-diethyl-2,4-diaminobenzene, 1-methyl-3,5-diethyl-2,6-diaminobenzene, 1,3,5-trimethyl-2,4-diaminobenzene, 1,3,5-triethyl-2,4-diaminobenzene, 3,5,3′,5′-
  • low molecular weight amino-functional polyethers having molecular weights below 500 g/mol is likewise possible.
  • These are for example those which have primary and/or secondary, aromatic or aliphatic amino groups, said amino groups optionally being bonded to the polyether chains via urethane or ester groups, and which are obtainable by known processes already described above in connection with production of the higher molecular weight aminopolyethers.
  • Sterically hindered aliphatic diamines having two secondary amino groups may optionally also be employed as isocyanate-reactive components, for example the reaction products of aliphatic and/or cycloaliphatic diamines with maleic or fumaric esters disclosed in EP-A 0 403 921 or the hydrogenation products of Schiff bases obtainable from aliphatic and/or cycloaliphatic diamines and ketones, for example diisopropyl ketone, described in DE-A 19 701 835 for example.
  • auxiliary and additive agents for example catalysts, surface-active agents, UV stabilizers, antioxidants, fragrances, mold release agents, fillers and/or pigments, may optionally be co-used.
  • tertiary amines for example triethylamine, tributylamine, dimethylbenzylamine, diethylbenzylamine, pyridine, methylpyridine, dicyclohexylmethylamine, dimethylcyclohexylamine, N,N,N′,N′-tetramethyldiaminodiethyl ether, bis(dimethylaminopropyl)urea, N-methyl-1 N-ethylmorpholine, N-cocomorpholine, N-cyclohexylmorpholine, N,N,N,N′-tetramethylethylenediamine, N,N,N′,N′-tetramethyl-1,3-butanediamine, N,N,N′,N′-tetramethyl-1,6-hexanediamine, pentamethyldiethylene
  • Preferred catalysts C) for use are tertiary amines, bismuth and tin compounds of the type mentioned.
  • the catalysts mentioned by way of example may be used in the production of the lightfast polyurethane, polythiourethane and/or polyurea masses according to the invention individually or in the form of any desired mixtures with one another and are optionally employed in amounts of 0.001 to 5.0 wt %, preferably 0.002 to 2 wt %, calculated as the total amount of catalysts employed based on the total amount of the starting compounds employed.
  • compositions according to the invention are preferably used to produce transparent, compact moldings having a high refractive index.
  • compositions according to the invention feature very good light resistance even as such, i.e. without addition of appropriate stabilizers. Nevertheless, known UV-protectants (light stabilizers) or antioxidants may be co-used as auxiliary and additive agents C).
  • Suitable UV stabilizers C) are for example piperidine derivatives, for example 4-benzoyloxy-2,2,6,6-tetramethylpiperidine, 4-benzoyloxy-1,2,2,6,6-pentamethylpiperidine, bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, methyl (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis(2,2,6,6-tetramethyl-4-piperidyl) suberate or bis(2,2,6,6-tetramethyl-4-piperidyl) dodecanedioate, benzophenone derivatives, for example 2,4-dihydroxy-, 2-hydroxy-4-methoxy-, 2-hydroxy-4-octoxy-, 2-hydroxy-4-dodecyloxy- or 2,2′-dihydroxy-4-dodecyloxybenzophenone, benzotriazole derivative
  • Suitable antioxidants C) are for example the known sterically hindered phenols, for example 2,6-di-tert-butyl-4-methylphenol (lonol), pentaerythritol tetrakis(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate), octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, triethylene glycol bis(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate, 2,2′-thiobis(4-methyl-6-tert-butylphenol), 2,2′-thiodiethylbis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate), which may be employed either individually or in any desired combinations with one another.
  • sterically hindered phenols for example 2,6-di-tert-butyl-4-methylphenol (
  • auxiliary and additive agents C) for optional co-use are for example the known flame retardants, for example trischlorethyl phosphate, ammonium phosphate or polyphosphate, fillers, for example barium sulfate, diatomaceous earth, carbon black, whiting or else reinforcing glass fibers.
  • flame retardants for example trischlorethyl phosphate, ammonium phosphate or polyphosphate
  • fillers for example barium sulfate, diatomaceous earth, carbon black, whiting or else reinforcing glass fibers.
  • Suitable mold release agents are for example methyl phosphate, dimethyl phosphate, methoxyethyl phosphate, methoxypropyl phosphate, di(methoxyethyl) phosphate, methoxyethyl ethoxyethyl phosphate, methoxyethyl propoxyethyl phosphate, di(methoxypropyl) phosphate, ethyl phosphate, diethyl phosphate, ethoxyethyl phosphate, di(ethoxyethyl) phosphate, ethoxypropyl phosphate, ethoxyethyl propoxyethyl phosphate, di(ethoxypropyl) phosphate, ethoxyethyl butoxyethyl phosphate, isopropyl phosphate, diisopropyl phosphate, propoxyethyl phosphate, di(propoxyethyl) phosphate, propoxypropyl
  • compositions according to the invention advantageously contain 0.01 to 4 wt % of mono-/dialkylphosphates and/or mono-/dialkylalkoxyphosphates, preferably 0.02 to 2 wt %, based on the overall composition.
  • the abovementioned usage amounts relate to the total content of these substances as mold release agents.
  • a particularly preferable composition according to the invention for producing transparent polythiourethane articles contains or consists of
  • the process may in particular be performed without solvent addition, i.e. in solvent-free fashion, and the nitrile addition is not to be understood as solvent addition in this context.
  • the reaction of the polyisocyanate mixtures A) with the thiol component B) and optionally further isocyanate-reactive components is effected adhering to an equivalent ratio of isocyanate groups to isocyanate-reactive groups of 0.5:1 to 2.0:1, preferably of 0.7:1 to 1.3:1, more preferably of 0.8:1 to 1.2:1.
  • the components of the composition according to the invention are preferably mixed, optionally in solvent-free form, in the abovestated equivalent ratio of isocyanate groups to isocyanate-reactive groups using suitable mixing apparatuses and charged into open or closed molds by any desired method, for example by simple hand-pouring but preferably using suitable machines, for example the low-pressure or high-pressure machines customary in polyurethane technology, or by the RIM process.
  • Curing may be performed in a temperature range of 40° C. to 180° C., preferably of 50° C. to 140° C., particularly preferably of 60° C. to 120° C., and optionally under elevated pressure of up to 300 bar, preferably up to 100 bar, particularly preferably up to 40 bar.
  • the molded articles thus produced from the according to the invention can generally be demolded after a short time, for example after 2 to 60 min.
  • a post-curing at a temperature of 50° C. to 100° C., preferably at 60° C. to 90° C., may optionally follow.
  • a particularly preferred field of application for the molded polythiourethane articles according to the invention obtainable from the compositions according to the invention is the production of lightweight plastic spectacle glasses having a high refractive index and a high Abbe number.
  • Spectacle glasses produced according to the invention feature outstanding mechanical properties, in particular hardness and impact resistance and also good scratch resistance and are moreover easy to process and colorable as desired.
  • the present invention further relates to the use of aromatic nitriles for producing transparent polythiourethane articles.
  • the present invention further provides a mixture of a polyisocyanate having a functionality of isocyanate groups of at least 2 per molecule and at least one aromatic nitrile for producing compact transparent polythiourethane articles.
  • FIG. 1 depicts a schematic diagram of a suitable plant for gas-phase phosgenation. This plant is particularly suitable for manufacturing 1,3-XDI and 1,4-XDI with contents of nitriles >0.1 wt % based on the manufactured isocyanate.
  • the NCO contents were determined by titrimetry as per DIN EN ISO 11909.
  • Tinuvin® 571 alkylphenol-substituted benzotriazole (BASF)
  • Zelec UN mixture of long-chain mono- and dialkyl phosphate (Steppan)
  • DBC dibutyltin dichloride (Acros Organics)
  • DMPT 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane (Bruno Bock GmbH)
  • the supply temperature to the evaporator (V) was 255° C.
  • the entry temperature of the cooling medium into the heat exchanger (WT) was 40° C.
  • the average residence time of the 1,3-XDA in the pumped circulation circuit was 35 minutes.
  • the stream composed of gaseous 1,3-XDA and nitrogen was heated to 280° C. in a further heat exchanger and supplied to the reactor via the coaxial nozzle.
  • 750 kg/h of phosgene were heated to 310° C. and on the annular space left free by the nozzle likewise continuously supplied to the reactor in which the two reactant streams were mixed and brought to reaction.
  • the velocity of the gas stream in the reactor was about 20 m/s and the velocity ratio of the amine/nitrogen stream to the phosgene stream was 8,8.
  • the pressure at the vacuum pump was 600 mbar abs.
  • the mobile phase consisted of:
  • the sample was found to contain 98.4% 1,3-XDI and 0.7% 3-isocyanatomethylbenzonitrile.
  • DRC dibutyltin dichloride
  • 1,3-XDI 1,3-XDI from example 4
  • DMPT 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane
  • the mixture was then filtered through a 5 ⁇ m filter, drawn into a syringe and the casting mold was completely filled therewith.
  • the casting mold was prepared by clamping together two glass shell molds (85 mm diameter, internal radius 88 mm, Shamir Insight, Inc., IL) with a gap of 8 mm and a plastic sealing ring to form a casting cavity.
  • the mold gap is 8 mm at each point of the lens.
  • the filled casting mold was cured in a drying cabinet with the temperature profile: 15 hours at 65° C.; 2 hours at 100° C. and a further 2 hours at 120′C.
  • the casting mold was then cooled to room temperature and, after complete cooling, first the sleeve and then the two glass articles were manually removed.
  • a spectacle glass blank that was completely clear, transparent and free from cloudiness was obtained in this way.
  • Transmission was 90.3% for standard light type D65, haze was 2.1.
  • the refractive index nE was 1.67 at 23° C.
  • a spectacle glass blank was produced using 1,3-XDI from example 5. This spectacle glass blank was completely cloudy, transmission was only 29.7%, haze was 100.
  • a spectacle glass blank that was completely clear, transparent and free from cloudiness was obtained in this way.
  • Transmission was 86.3% for standard light type D65, haze was 2.9.
  • the refractive index nE was 1.67 at 23° C.
  • DRC dibutyltin dichloride
  • DRC dibutyltin dichloride
  • DMPT 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane

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  • General Physics & Mathematics (AREA)
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