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EP1841804A1 - Thio(meth)acrylate, melanges destines a la production de matieres plastiques transparentes, matieres plastiques transparentes et leur procede de production et leur utilisation - Google Patents

Thio(meth)acrylate, melanges destines a la production de matieres plastiques transparentes, matieres plastiques transparentes et leur procede de production et leur utilisation

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Publication number
EP1841804A1
EP1841804A1 EP05814642A EP05814642A EP1841804A1 EP 1841804 A1 EP1841804 A1 EP 1841804A1 EP 05814642 A EP05814642 A EP 05814642A EP 05814642 A EP05814642 A EP 05814642A EP 1841804 A1 EP1841804 A1 EP 1841804A1
Authority
EP
European Patent Office
Prior art keywords
meth
compounds
thio
acrylates
formula
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP05814642A
Other languages
German (de)
English (en)
Inventor
Bardo Schmitt
Joachim Knebel
Patrik Hartmann
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Roehm GmbH Darmstadt
Original Assignee
Roehm GmbH Darmstadt
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 Roehm GmbH Darmstadt filed Critical Roehm GmbH Darmstadt
Publication of EP1841804A1 publication Critical patent/EP1841804A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C327/00—Thiocarboxylic acids
    • C07C327/20—Esters of monothiocarboxylic acids
    • C07C327/22—Esters of monothiocarboxylic acids having carbon atoms of esterified thiocarboxyl groups bound to hydrogen atoms or to acyclic carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10—Esters
    • C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10—Esters
    • C08F222/12—Esters of phenols or saturated alcohols
    • C08F222/24—Esters containing sulfur
    • 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
    • C08K11/00—Use of ingredients of unknown constitution, e.g. undefined reaction products
    • 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
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/38—Thiocarbonic acids; Derivatives thereof, e.g. xanthates ; i.e. compounds containing -X-C(=X)- groups, X being oxygen or sulfur, at least one X being sulfur
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L41/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a bond to sulfur or by a heterocyclic ring containing sulfur; Compositions of derivatives of such polymers
    • 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
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10—Esters
    • C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
    • C08F222/102—Esters of polyhydric alcohols or polyhydric phenols of dialcohols, e.g. ethylene glycol di(meth)acrylate or 1,4-butanediol dimethacrylate
    • C08F222/1025—Esters of polyhydric alcohols or polyhydric phenols of dialcohols, e.g. ethylene glycol di(meth)acrylate or 1,4-butanediol dimethacrylate of aromatic dialcohols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00—Properties characterising the ingredient of the composition

Definitions

  • the present invention relates to thio (meth) acrylates and mixtures for the production of transparent plastics containing these thio (meth) acrylates. Furthermore, the present invention relates to transparent plastics which can be prepared from the mixtures, and to processes for their preparation. Furthermore, the present invention relates to the use of transparent plastics for the production of optical, especially ophthalmic lenses.
  • Eyewear is an essential part of everyday life nowadays. Eyeglasses with plastic lenses in particular have gained in importance recently, because they are lighter and less fragile than spectacle lenses made of inorganic materials and can be dyed by means of suitable dyes.
  • plastic spectacle lenses highly transparent plastics which are obtainable, for example, from diethylene glycol bis (allyl carbonate) (DAC), thiourethane compounds having ⁇ , ⁇ -terminated multiple bonds or sulfur-containing (meth) acrylates.
  • DAC diethylene glycol bis (allyl carbonate)
  • thiourethane compounds having ⁇ , ⁇ -terminated multiple bonds or sulfur-containing (meth) acrylates.
  • DAC plastic has very good impact resistance, transparency and good processability.
  • the disadvantage is that due to the relatively low refractive index no of approximately 1.50, both the center and the edges of the respective plastic glasses must be reinforced, so that the spectacle lenses are accordingly thick and heavy. The wearing comfort of glasses with DAC plastic lenses is therefore significantly reduced.
  • DE 4234251 discloses sulfur-containing poly-methacrylates which are obtained by free-radical copolymerization of a monomer mixture of compounds of the formula (1) and (2).
  • Y denotes an optionally branched, optionally cyclic alkyl radical having 2 to 12 carbon atoms or an aryl radical having 6 to 14 carbon atoms or an alkaryl radical having 7 to 20 carbon atoms, wherein the carbon chains may be interrupted by one or more ether or thioether groups.
  • R is hydrogen or methyl and n is an integer in the range of 1 to 6.
  • the monomers of the formula (1) and (2) are generally in a molar ratio of 1: 0.5 to 0.5: 1.
  • the preparation of the monomer mixture is carried out by reacting at least two mols of (meth) acryloyl chloride or (meth) acrylic anhydride with one mol of a dithiois, the (meth) acryloyl chloride or (meth) acrylic anhydride in an inert organic solvent and the dithiol in aqueous solution.
  • alkaline solution brings to the reaction.
  • Suitable solvents are methyl tert-butyl ether, toluene and xylene called whose dielectric constant at 20 0 C 2.6, 2.4 and 2.3 to 2.6.
  • the plastics described in DE 4234251 are colorless, hard and slightly brittle and have a high refractive index no in the range of 1.602 to 1.608.
  • the Abbe number is between 35 and 38, so these too Plastics for spectacle lenses only conditionally suitable. Information on the glass transition temperature of the plastics can not be found in this document.
  • the publication WO 03/011925 describes the polymerization of thiomethacrylates with polyethylene glycol derivatives.
  • the ⁇ from plastics produced can u. a: used for the production of optical lenses.
  • a disadvantage of these lenses are their mechanical properties. In particular, the impact resistance does not meet many requirements.
  • plastic spectacle lenses should be produced which have a low dispersion and no color edges.
  • connection should allow good handling.
  • the compound should in particular have a low viscosity with a low volatility.
  • the compound should be added in a large amount of the mixture for the production of the plastic.
  • the object of the present invention was also to make available a compound for the production of a highly transparent plastic with improved mechanical properties even at temperatures above room temperature.
  • the compounds obtainable with the plastic should have a very high glass transition temperature, preferably greater than 80.0 0 C.
  • An object of the present invention was therefore to provide a highly transparent plastic, which can be prepared starting from the educt composition in a simple manner, on an industrial scale and inexpensively. In particular, it should be obtainable from a flowable at normal pressure and temperatures in the range of 20.0 to 80.0 C 0 0 C mixture via free radical polymerization starting.
  • the present invention also had the object of specifying fields of application and possible uses of the new compounds.
  • coating materials for plastic fibers which have a high refractive index.
  • these coating materials should have the highest possible adhesion and good processability.
  • thio (meth) acrylates having all the features of claim 1.
  • Advantageous modifications of the thio (meth) acrylates according to the invention are disclosed in US Pat to claim 1 dependent claims under protection.
  • the mixtures obtainable from the thio (meth) acrylates according to the invention and transparent plastics and processes for their preparation are claimed.
  • the claim of the use category protects a preferred use of the highly transparent plastic according to the invention.
  • An optical, preferably ophthalmic lens comprising the highly transparent plastic according to the invention is described in a further product claim.
  • the present invention relates to thio (meth) acrylates obtainable by reacting compounds of the formula (I) and / or (II)
  • each R 1 independently of one another is hydrogen or a methyl radical
  • R 2 are each independently a linear or branched, aliphatic or cycloaliphatic radical or a substituted or unsubstituted aromatic or heteroaromatic radical
  • m and n are each independently an integer greater than or equal to 0 with m + n> 0, with thiol compounds comprising at least two thiol groups.
  • mixtures comprising a) a prepolymer prepared from compounds of the formula (I) and / or (II)
  • R 1 are each independently of one another hydrogen or a methyl radical
  • R 2 each independently represent a linear or branched, aliphatic or cycloaliphatic radical or a substituted or unsubstituted aromatic or heteroaromatic radical and m and n are each independently an integer greater than or equal to 0 with m + n> 0, and alkyldithiols or polythiols, preferably Compounds of the formula (III)
  • aromatic vinyl compounds which are suitable for the production of transparent plastics and which have excellent mechanical and optical properties, the subject of the present invention.
  • the mixtures may optionally
  • the transparent plastics obtainable from the thio (meth) acrylates according to the invention have a hitherto unknown combination of outstanding properties, such as a high refractive index, a high Abbe number, a good impact strength and a high glass transition temperature.
  • the corresponding plastic spectacle lenses show a low dispersion; Color borders are not observed.
  • the transparent plastics obtainable from the thio (meth) acrylates according to the invention have further advantages. These include:
  • the very good impact resistance of the plastic according to the invention protects the corresponding plastic spectacle lenses from the "dangers of everyday life”. Damage or irreparable destruction, in particular of the thin spectacle lenses by mechanical violence is largely prevented.
  • the highly transparent plastic of the invention has a high glass transition temperature, preferably greater than 80.0 0 C, and retains Therefore, up to this temperature its excellent mechanical properties, in particular the high impact resistance and its hardness.
  • the highly transparent plastic of the invention is by free radical copolymerization of a preferably at normal pressure and temperatures in the range of 20.0 to 80.0 C 0 0 C fiplexTalken monomer mixture in a simple manner on an industrial scale and at low cost.
  • the thio (meth) acrylates according to the invention are obtainable by reacting compounds of the formula (I) and (II)
  • R 1 are each independently hydrogen or a methyl radical
  • R 2 are each independently a linear or branched, aliphatic or cycloaliphatic radical or a substituted or unsubstituted aromatic or heteroaromatic radical, wherein the radical R 2 may preferably comprise 1 to 100, in particular 1 to 20 carbon atoms, and m and n are each independently an integer greater than or equal to 0 with m + n> 0.
  • the preferred linear or branched, aliphatic or cycloaliphatic radicals include, for example, the methylene, ethylene, propylene, iso-propylene, n-butylene, iso-butylene, tert-butylene or cyclohexylene group.
  • the preferred divalent aromatic or heteroaromatic radicals include in particular groups which are derived from benzene, naphthalene, biphenyl, diphenyl ether, diphenylmethane, diphenyldimethylmethane, bisphenone, diphenylsulfone, quinoline, pyridine, anthracene and phenanthrene.
  • cycloaliphatic radicals also include bi-, tri- and polycyclic aliphatic radicals.
  • radical R 2 comprises radicals of the formula
  • R 4 are each independently a linear or branched, aliphatic or cycloaliphatic radical, such as a methylene, ethylene, propylene, isopropylene, n-butylene
  • the radical X is, in each case independently of one another, oxygen or sulfur and the radical R 5 is a linear or branched, aliphatic or cycloaliphatic radical, such as, for example, a methylene radical.
  • cycloaliphatic radicals also include bi-, tri- and polycyclic aliphatic radicals Radicals, y is an integer between 1 and 10, in particular 1, 2, 3 and 4.
  • Preferred radicals of the formula (Ia) include:
  • the radical R 2 is an aliphatic radical having 1 to 10 carbon atoms, preferably a linear aliphatic radical having 2 to 8 carbon atoms.
  • indices m and n are each independently an integer greater than or equal to 0, for example 0, 1, 2, 3, 4, 5 or 6.
  • the compounds of the formula (I) and (II) and the compounds of the formula (III) can each be used individually or as a mixture of several compounds of the formula (I) or (II) for the preparation of the thio (meth) acrylate.
  • the relative proportions of the compounds of the formula (I) and (II) for the preparation of the thio (meth) acrylates according to the invention are in principle arbitrary, they can be used to "tailor" the property profile of the plastic according to the invention according to the needs of the application.
  • the monomer mixture may be extremely expedient for the monomer mixture to contain a clear excess of compound (s) of the formula (I) or compound (s) of the formula (II), in each case based on the total amount of compounds of the formula (I) and (II) , contains.
  • R 2 is an ethylene radical
  • This corresponds to a weight fraction of (II) with m + n 3, when R 2 is an ethylene radical, of at least 6%.
  • the proportion of the compounds (I) is preferably 0.1 to 50.0 mol%, preferably 10.0 to 45.0 mol%, especially 20.0 to 35.0 mol%, based on the total amount of the compounds of the formula (I) and (II), which corresponds to a preferred range of the weight ratio of the compound (I) when R 2 is an ethylene radical of 15 to 40%.
  • This corresponds to a weight fraction of the compounds (II) with m + n 1, when R 2 is an ethylene radical, of preferably 10 to 45%.
  • the proportion of compounds (II) with m + n> 3 is preferably greater than 0 mol%, advantageously greater than 1 mol%, in particular greater than 2 mol%, based on the total amount of the compounds of the formula (I) and (II) , If R 2 is an ethylene radical, the proportion by weight of compounds (II) with m + n> 3 in the mixture is more than 2%, in particular more than 5%.
  • the radical X is halogen, in particular chlorine or bromine, or a radical
  • the compounds of formula (IX-a) include, inter alia, acrylic acid chloride, methacrylic acid chloride, acrylic anhydride and methacrylic anhydride, with the use of acrylic anhydride, methacrylic anhydride or mixtures of the two being particularly preferred.
  • Each M is independently hydrogen or a metal cation.
  • Preferred metal cations are derived from elements with an electronegativity of less than 2.0, advantageously less than 1, 5, from, with alkali metal cations, in particular Na +, K +, Rb +, Cs +, and alkaline earth metal cations, especially Mg 2+, Ca 2+, Sr 2+ , Ba 2+ , especially are preferred. Very favorable results can be achieved with the metal cations Na + and K + .
  • each R 4 is independently a linear or branched, aliphatic or cycloaliphatic radical, such as a methylene, ethylene, propylene, iso-propylene, n-butylene, iso-butylene, tert-butylene or cyclohexylene Group is.
  • cycloaliphatic radicals also include bi-, tri- and polycyclic aliphatic radicals.
  • the radical X is in each case independently of oxygen or sulfur and the radical R 5 is a linear or branched, aliphatic or cycloaliphatic radical, such as a methylene, ethylene, propylene, iso-propylene, n-butylene, iso Butylene, tert-butylene or cyclohexylene group.
  • cycloaliphatic radicals also include bi-, tri- and polycyclic aliphatic radicals, y is an integer between 1 and 10, in particular 1, 2, 3 and 4.
  • Preferred compounds of formula (IX-c) include:
  • 1,2-ethanedithiol is used as the compound of the formula (IX-b).
  • the (meth) acrylates of the formula (IX-a) are reacted in at least one inert organic solvent L and the polythiols of the formula (IX-b) in aqueous alkaline solution, the term "inert, organic Solvent "for such organic Solvent is that does not react under the reaction conditions with the compounds present in the reaction system.
  • At least one solvent L has a relative dielectric constant> 2.6, preferably> 3.0, suitably> 4.0, in particular> 5.0, in each case measured at 20 ° C.
  • the relative dielectric constant refers to a dimensionless number indicating how many times the capacitance C of a (theoretically) vacuum condenser increases when placing dielectrics with dielectric properties between the plates. This value is measured at 20 0 C and extrapolated to low frequencies ( ⁇ -> 0).
  • Dielectric values of solvent are disclosed, inter alia, in Handbook of Chemistry and Physics, 71st Edition, CRC Press, Baco Raton, Ann Arbor, Boston, 1990-1991, pp. 8-44, 8-46 and 9-9 to 9-12.
  • the solvent and the aqueous solution form two phases during the reaction and are not homogeneously miscible.
  • the solvent preferably has a water solubility, measured at 20 0 C, less than 10 g of water based on 100 g of solvent.
  • Preferred solvents L according to the invention include aliphatic ethers, such as diethyl ether (4.335), dipropyl ether, diisopropyl ether; cycloaliphatic ethers, such as tetrahydrofuran (7,6); aliphatic esters such as methyl formate (8.5), ethyl formate, propyl formate, methyl acetate, ethyl acetate, n-butyl acetate (5.01), methyl propionate, methyl butyrate (5.6), ethyl butyrate, 2-methoxyethyl acetate; aromatic esters such as benzyl acetate, dimethyl phthalate, methyl benzoate (6.59), ethyl benzoate (6.02), methyl salicylate, ethyl salicylate, phenyl acetate (5.23); aliphatic ketones such as acetone, methyl ethyl ketone (18.5),
  • Nitroaromatics such as nitrobenzene, o-nitrotoluene (27.4), m-nitrotoluene (23), p-nitrotoluene; halogenated aromatics such as chlorobenzene (5,708), o-chlorotoluene (4,45), m-chlorotoluene (5,55), p-chlorotoluene (6,08), o-dichlorobenzene, m-dichlorobenzene;
  • Heteroaromatics such as pyridine, 2-methylpyridine (9.8), quinoline, isoquinoline; or mixtures of these compounds, wherein the parentheses are the respective relative dielectric constants at 20 ° C.
  • Aliphatic esters and cycloaliphatic ethers are particularly suitable for the purposes of the present process.
  • the solvent L can be used both alone and a solvent mixture, wherein not all solvents contained in the mixture must meet the above dielectric criterion.
  • tetrahydrofuran / cyclohexane mixtures can also be used according to the invention.
  • the solvent mixture has a relative dielectric constant> 2.6, preferably> 3.0, advantageously> 4.0, in particular> 5.0, in each case measured at 20 ° C.
  • Particularly advantageous results can be achieved with solvent mixtures containing only solvents with a relative dielectric constant> 2.6, preferably> 3.0, suitably> 4.0, in particular> 5.0, in each case measured at 20 ° C.
  • the aqueous alkaline solution of the compound (s) of the formula (IX-b) preferably contains from 1.1 to 1.5 equivalents of at least one Bronsted base, based on the total amount of compound (s) of the formula (IX) b).
  • Preferred Bronsted bases in the context of the present invention include alkali hydroxides and alkaline earth hydroxides, especially sodium hydroxide and potassium hydroxide.
  • the implementation of the reaction can in principle be carried out in any way imaginable.
  • the compound (s) of the formula (IX-a) in at least one inert organic solvent L and the compound (s) of the formula (IX-b) in aqueous Alkaline solution to be metered parallel to the reaction vessel.
  • the reaction temperature can be varied over a wide range, but often the temperature is in the range of 20.0 0 C to 120.0 0 C, preferably in the range of 20.0 0 C to 80.0 0 C.
  • the reaction can take place both at low pressure and at overpressure. Preferably, however, it is carried out at atmospheric pressure.
  • the reaction can also take place under air, it has proven to be particularly advantageous in the context of the present process to carry out the reaction under a protective gas atmosphere, preferably nitrogen and / or argon, preferably with a low oxygen content.
  • the reaction mixture is reacted in a further step with a Bronsted acid, preferably until the aqueous solution at 20 0 C, a pH of less than 7.0, advantageously less than 6.0, in particular smaller than 5.0.
  • a Bronsted acid preferably until the aqueous solution at 20 0 C, a pH of less than 7.0, advantageously less than 6.0, in particular smaller than 5.0.
  • Useful acids in this context include inorganic mineral acids, such as hydrochloric acid, sulfuric acid, phosphoric acid, organic acids, such as acetic acid, propionic acid, and acidic ion exchangers, in particular acidic resin ion exchangers, such as ® Dowex M-31 (H).
  • acidic resin ion exchangers with loadings of at least 1, 0 meq, preferably at least 2.0 meq, in particular at least 4.0 meq, H + - ions based on 1 g of dried ion exchanger, particle sizes of 10- 50 mesh and porosities proven in the range of 10 to 50% based on the total volume of the ion exchanger very particularly.
  • the organic phase consisting of the solvent L is expediently separated off, optionally washed, dried and the solvent evaporated.
  • inhibitors which prevent free-radical polymerization of the (meth) acrylic groups during the reaction. These inhibitors are well known in the art.
  • inhibitors are used mainly 1, 4-dihydroxybenzenes. However, it is also possible to use differently substituted dihydroxybenzenes.
  • such inhibitors can be represented by the general formula (X)
  • R 6 represents a linear or branched alkyl radical having one to eight carbon atoms, halogen or aryl, preferably an alkyl radical having one to four carbon atoms, more preferably methyl, ethyl, n -propyl, iso -propyl, n -butyl, iso -butyl, sec -butyl, tert -butyl, Cl, F or Br;
  • o is an integer in the range of one to four, preferably one or two;
  • R 7 is hydrogen, a linear or branched alkyl radical having one to eight carbon atoms or aryl, preferably an alkyl radical having one to four carbon atoms, more preferably methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec Butyl or tert-butyl.
  • R 6 and o have the meaning given above.
  • R 8 denotes a linear or branched alkyl radical having one to eight carbon atoms, aryl or aralkyl, propionic acid esters with 1 to 4 valent alcohols, which may also contain heteroatoms such as S, O and N, preferably an alkyl radical having one to four carbon atoms, particularly preferably methyl, Ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl.
  • a further advantageous class of substances are hindered phenols based on triazine derivatives of the formula (XIII)
  • the proportion of inhibitors individually or as a mixture is generally 0.01-0.50% (wt / wt), wherein the concentration of the inhibitors is preferably selected so that the color number according to DIN 55945 is not impaired becomes. Many of these inhibitors are commercially available.
  • the mixture obtained in the preparation of the compounds according to the formulas (I) and / or (II) can be worked up according to prior art processes. For example, the different compounds of formulas (I) and / or (II) can be separated. Furthermore, residues and / or impurities can be removed.
  • reaction mixture obtained in the reaction can also be used without work-up for preparing the thio (meth) acrylates according to the invention.
  • thiol compounds comprising at least two thiol groups can be added to the reaction mixture.
  • the addition is preferably carried out after a large part of the compounds of the formulas (Ia) have been reacted with the compounds of the formulas (IX) to give compounds of the formulas (I) and / or (II).
  • the conversion of the compounds of formulas (Ia) on addition of the thiol compounds, which is at least two Thiol groups include at least 50%, more preferably at least 80%, and most preferably at least 95%.
  • the conversion is preferably calculated from the compounds of the formula (Ia) present in the reaction mixture with the addition of further thiol compounds which comprise at least two thiol groups, based on their originally used fraction.
  • the determination of this proportion can be carried out for example by chromatographic methods, in particular GC-MS, wherein a standard can be included.
  • the thiol compounds used to prepare the thio (meth) acrylates according to the invention which comprise at least two thiol groups, are known per se. These include in particular alkyldithiols and polythiols.
  • the thiol compounds also include thiolates formed upon reaction of compounds containing S-H groups with a base.
  • Preferred thiol compounds which comprise at least two thiol groups are compounds of the formula (IIIa)
  • MS-R 3 -SM (Ill-a), wherein R 3 represents a linear or branched, aliphatic or cycloaliphatic radical or a substituted or unsubstituted aromatic or heteroaromatic radical and each M independently denotes hydrogen, an ammonium ion or a metal cation.
  • Preferred metal cations are derived from elements with an electronegativity of less than 2.0, advantageously less than 1, 5, from, with alkali metal cations, in particular Na +, K +, Rb +, Cs +, and alkaline earth metal cations, especially Mg 2+, Ca 2+, Sr 2+ , Ba 2+ are particularly preferred. Very favorable results can be achieved with the metal cations Na + and K + .
  • the radical R 3 comprises radicals of the formula
  • each R 4 is independently a linear or branched, aliphatic or cycloaliphatic radical, such as a methylene, ethylene, propylene, iso-propylene, n-butylene, iso-butylene, tert-butylene or cyclohexylene Group is.
  • the radical X is in each case independently of oxygen or sulfur and the radical R 5 is a linear or branched, aliphatic or cycloaliphatic radical, such as a methylene, ethylene, propylene, iso-propylene, n-butylene, iso Butylene, tert-butylene or cyclohexylene group.
  • cycloaliphatic radicals also include bi-, tri- and polycyclic aliphatic radicals, y is an integer between 1 and 10, in particular 1, 2, 3 and 4.
  • Preferred radicals of the formula (III-b) include:
  • the radical R 3 is an aliphatic radical having 1 to 10 carbon atoms, preferably a linear aliphatic radical having 2 to 8 carbon atoms.
  • indices m and n are each independently an integer greater than or equal to 0, for example 0, 1, 2, 3, 4, 5 or 6.
  • the sum is m + n is greater than 0, preferably in the range of 1 to 6, suitably in the range of 1 to 4, in particular 1, 2 or 3.
  • each R 4 is independently a linear or branched, aliphatic or cycloaliphatic radical, such as a methylene, ethylene, propylene, iso-propylene, n-butylene, iso-butylene, tert-butylene or cyclohexylene Group is.
  • cycloaliphatic radicals also include bi-, tri- and polycyclic aliphatic radicals.
  • the radical X is in each case independently of oxygen or sulfur and the radical R 5 is a linear or branched, aliphatic or cycloaliphatic radical, such as a methylene, ethylene, propylene, iso-propylene, n-butylene, iso Butylene, tert-butylene or cyclohexylene group.
  • cycloaliphatic radicals also include bi-, tri- and polycyclic aliphatic radicals, y is an integer between 1 and 10, in particular 1, 2, 3 and 4.
  • Preferred compounds of formula (III-c) include:
  • 1,2-ethanedithiol is used as the compound of the formulas (III) or (III-a).
  • reaction of the compounds of the formula (I) and / or (II) with the thiol compounds which comprise at least two thiol groups can be carried out under the conditions described above for the preparation of the compounds according to the formulas (I) and / or (II), in particular from the compounds of the formulas (IX-a) and (IX-b).
  • At least one solvent L has a relative dielectric constant> 2.6, preferably> 3.0, suitably> 4.0, in particular> 5.0, in each case measured at 20 ° C.
  • the solvent and the aqueous solution form two phases during the reaction and are not homogeneously miscible.
  • the solvent preferably has a water solubility, measured at 20 0 C, less than 10 g of water based on 100 g of solvent.
  • the solvent L can be used both alone and a solvent mixture, wherein not all solvents contained in the mixture must meet the above dielectric criterion.
  • tetrahydrofuran / cyclohexane mixtures can also be used according to the invention.
  • the solvent mixture has a relative dielectric constant> 2.6, preferably> 3.0, advantageously> 4.0, in particular> 5.0, in each case measured at 20 ° C.
  • Particularly advantageous results can be achieved with solvent mixtures, which contain only solvents with a relative dielectric constant> 2.6, preferably> 3.0, suitably> 4.0, in particular> 5.0, in each case measured at 20 ° C.
  • the aqueous alkaline solution of the thiol compounds in particular compound (s) of the formula (III) or (IIIa), preferably contains 1.1 to 1.5 equivalents of at least one Bronsted base, based on the total amount of thiol compounds .
  • Preferred Bronsted bases in the context of the present invention include alkali hydroxides and alkaline earth hydroxides, especially sodium hydroxide and potassium hydroxide.
  • the molar ratio of compounds of formula (I) and / or (II) to thiol compounds comprising at least two thiol groups may range from 50: 1 to 1: 2, preferably 30: 1 to 2: 1 lie.
  • reaction it is possible to carry out the reaction in any conceivable manner.
  • the reaction temperature can be varied over a wide range, but often the temperature is in the range of 20.0 0 C to 120.0 0 C, preferably in the range of 20.0 0 C to 80.0 0 C.
  • the reaction can also take place under air, it has proven to be particularly advantageous in the context of the present process to carry out the reaction under a protective gas atmosphere, preferably nitrogen and / or argon, preferably with a low oxygen content.
  • the reaction mixture is reacted in a further step with a Bronsted acid, preferably until the aqueous solution at 20 0 C, a pH of less than 7.0, advantageously less than 6.0, in particular less than 5.0, has.
  • a Bronsted acid preferably until the aqueous solution at 20 0 C, a pH of less than 7.0, advantageously less than 6.0, in particular less than 5.0, has.
  • Useful acids in this context include inorganic mineral acids, such as hydrochloric acid, sulfuric acid, phosphoric acid, organic acids, such as acetic acid, propionic acid, and acidic ion exchangers, in particular acidic resin ion exchangers, such as ® Dowex M-31 (H).
  • acidic resin ion exchangers with loadings of at least 1, 0 meq, preferably at least 2.0 meq, in particular at least 4.0 meq, H + - ions based on 1 g of dried ion exchanger, particle sizes of 10- 50 mesh and porosities proven in the range of 10 to 50% based on the total volume of the ion exchanger very particularly.
  • the organic phase consisting of the solvent L can advantageously be separated off, optionally washed, dried and the solvent evaporated.
  • A is an end group of the formulas
  • Z is a linking group of formulas
  • Y is a linking group of formulas
  • Each R 1 is independently hydrogen or a methyl radical
  • Each R 2 is independently a linear or branched, aliphatic or cycloaliphatic radical or a substituted or unsubstituted aromatic or heteroaromatic radical and m and n are each independently an integer greater than or equal to 0 with m + n> 0, and
  • R 3 represents a linear or branched, aliphatic or cycloaliphatic radical or a substituted or unsubstituted aromatic or heteroaromatic radical.
  • the weight-average molecular weight of the thio (meth) acrylate according to the invention may preferably be in the range from 300 to 5000 Da, in particular in the range from 500 to 2000 Da.
  • the weight average molecular weight can be determined according to GPC or HPLC.
  • the viscosity of the thio (meth) acrylate (determined in substance according to DIN 53019) determined at 25 ° C. can be in the range from 100 to 1000 mPa.s, more preferably in the range from 200 to 600 mPa.s.
  • the adjustment of the molecular weight and the viscosity can be done by selecting the radicals R 2 and R 3 . Furthermore, these quantities can be effected by the molar ratio of compounds of the formulas (I) and / or (II) to the thiol compounds, in particular according to the formulas (III) or (III-a). According to a particular aspect of the present invention, the ratio of compounds of formula (IV-b), (IV-d) and (IV-e) to compounds of formula (IV-a) and (IV-c) is very small the conversion of the addition of thiol to the methacrylic double bond is complete. The proportion of compounds with thiol groups is preferably ⁇ 5%, in particular ⁇ 1%. The conversion of the thiol group can be monitored by IR spectroscopy.
  • Preferred thiomethacrylates of the present invention include, but are not limited to, compounds of the formula
  • radicals R 1 , R 2 and R 3 have the abovementioned meaning and the indices m and n in each case independently of one another denote an integer greater than or equal to 0.
  • Particularly preferred thio (meth) acrylates of the present invention may be considered as prepolymers.
  • the prepolymer of the present invention may comprise compounds of formula (I) and / or (II) and (III)
  • radical R 1 are each independently hydrogen or a methyl radical, preferably a methyl radical and the radical R 2 each independently a linear or branched, aliphatic or cycloaliphatic radical or a substituted or unsubstituted aromatic or heteroaromatic radical, wherein the radical R 2 is preferably 1 to 100, in particular 1 to 20 carbon atoms and wherein the radical R 3 each independently of R 2 denotes a linear or branched, aliphatic or cycloaliphatic radical or a substituted or unsubstituted aromatic or heteroaromatic radical, where the radical R 3 is preferably 1 to 100, in particular 1 to 20 carbon atoms.
  • the compounds of the formula (I) and (II) and the compounds of the formula (III) can each be used individually or as a mixture of several compounds of the formula (I), (II) or (III) for the preparation of the prepolymer.
  • the relative proportions of the compounds of the formula (I), (II) and (III) in the monomer mixture according to the invention are in principle arbitrary; they can be used to "tailor" the profile of properties of the plastic according to the invention according to the needs of the application.
  • the monomer mixture may be highly desirable for the monomer mixture to contain a marked excess of compound (s) of formula (I) or compound (s) of formula (II) or compound (s) of formula (III), respectively based on the total amount of compounds of the formula (I), (II) and (III) in the prepolymer contains.
  • the proportion of the compounds (III) in the prepolymer is preferably from 1 to 55.0 mol%, in particular from 10.0 to 50.0 mol%, based on the total amount of the compounds of the formula (I), (II) and (III ). If R 3 is a dimercaptodioxaoctane radical in the specific case, the proportion by weight of (III) in the prepolymer, based on the total amount of compounds (I), (II) and (III), is more than 0.5%, preferably more than 5%. ,
  • the thio (meth) acrylates according to the invention can be polymerized to give plastics which can be used in particular for the production of lenses.
  • the thio (meth) acrylates according to the invention can be mixed with other monomers.
  • a preferred mixture for the production of plastics in addition to thio (meth) acrylates which are preferably a prepolymer prepared from compounds of formula (I), (II) and (III) further comprises at least one radically polymerizable monomer (A ) containing at least two terminal methacrylate groups.
  • Di (meth) acrylates which are included are, for example, polyoxyethylene and polyoxypropylene derivatives of (meth) acrylic acid, such as triethylene glycol (meth) acrylate, tetraethylene glycol (meth) acrylate, tetrapropylene glycol (meth) acrylate, and 1,4-butanediol ( meth) acrylate, diethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, tetrapropylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate (preferably with weight average of Molecular weights in the range of 200-5000000 g / mol, suitably in the range of 200 to 25000 g / mol, in particular in the range of 200 to 1000
  • s and t are greater than or equal to zero and the sum s + 1 preferably in the range of 1 to 30, in particular in the range of 2 to 10, and by reaction of diisocyanates with 2 equivalents of hydroxyalkyl (meth) acrylate available di (meth) acrylates , especially
  • radical R 11 is, independently of one another, hydrogen or a methyl radical
  • Tri (meth) acrylates such as trimethyloylpropanetri (meth) acrylate and glycerol tri (meth) acrylate or (meth) acrylates of ethoxylated or propoxylated glycerol, trimethylolpropane or other alcohols having more than 2 hydroxy groups.
  • Each R 12 is independently hydrogen or methyl.
  • R 13 denotes a linear or branched alkyl, cycloalkyl radical or an aromatic radical having preferably 1 to 100, preferably 1 to 40, preferably 1 to 20, advantageously 1 to 8, in particular 1 to 6, carbon atoms, such as, for example, a methylethyl , Propyl, iso-propyl, n-butyl, iso-butyl, tert-butyl, cyclopentyl, cyclohexyl or phenyl.
  • cycloaliphatic radicals also include bi-, tri- and polycyclic aliphatic radicals. Linear or branched alkyl or cycloalkyl radicals having 1 to 6 carbon atoms are very particularly preferred as R 18 .
  • the radical R 13 is preferably a linear or branched, aliphatic or cycloaliphatic radical, such as, for example, a methylene, ethylene, propylene, iso-propylene, n-butylene, iso-butylene, tert-butylene or cyclohexylene group or a group of the general formula
  • radical R 15 is a linear or branched, aliphatic or cycloaliphatic radical or a substituted or unsubstituted aromatic or heteroaromatic radical, such as a methylene, ethylene, propylene, iso-propylene, n-butylene, iso-butylene , tert-butylene or cyclohexylene group, or divalent aromatic or heteroaromatic groups which are derived from benzene, naphthalene, biphenyl, diphenyl ether, diphenylmethane, diphenyldimethylmethane, bisphenone, diphenylsulfone, quinoline, pyridine, anthracene and phenanthrene.
  • aromatic or heteroaromatic radical such as a methylene, ethylene, propylene, iso-propylene, n-butylene, iso-butylene , tert-butylene or cyclohexylene group, or di
  • cycloaliphatic radicals also include bi-, tri- and polycyclic aliphatic radicals.
  • the radical R 14 each independently denotes a linear or branched, aliphatic or cycloaliphatic radical or a substituted or unsubstituted aromatic or heteroaromatic radical, such as a methylene, ethylene, propylene, iso-propylene, n-butylene, iso Butylene or cyclohexylene group, or divalent aromatic or heteroaromatic groups derived from benzene, naphthalene, biphenyl, diphenyl ether, diphenylmethane, diphenyldimethylmethane, bisphenone, diphenylsulfone, quinoline, pyridine, anthracene and phenanthrene.
  • cycloaliphatic radicals also include bi-, tri- and polycyclic aliphatic radicals. Each X 1 is
  • radical R 16 is a linear or branched, aliphatic or cycloaliphatic radical or a substituted or unsubstituted aromatic or heteroaromatic radical, such as, for example, a methyl, ethyl, propyl, iso-propyl, n-butyl, iso-butyl, tert-butyl or cyclohexyl group, or monovalent aromatic or heteroaromatic groups derived from benzene, naphthalene, biphenyl, diphenyl ether, diphenylmethane, diphenyldimethylmethane, bisphenone, diphenylsulfone, quinoline, pyridine, anthracene and phenanthrene ,
  • cycloaliphatic radicals also include bi-, tri- and polycyclic aliphatic radicals, z is an integer between 1 and 1000, suitably between 1 and 100, in particular between 1 and
  • di (meth) acrylates of the formula (XV) include ethylene glycol ide (meth) acrylate, ethoxylated bisphenol A di (meth) acrylate, in particular
  • s and t are greater than or equal to zero and the sum s + 1 preferably in the range of 1 to 30, in particular in the range of 2 to 10, and by reaction of diisocyanates with 2 equivalents of hydroxyalkyl (meth) acrylate available di (meth) acrylates , especially
  • R 17 is independently hydrogen or methyl, 3,8-di (meth) acryloyloxymethyltricyclo [5.2.1.0 (2.6)] decane, 3,9-Di (meth) acryloyloxymethyltricyclo [5.2.1.0 (2.6)] decane, 4,8-di (meth) acryloyloxymethyltricyclo [5.2.1.0 (2.6)] decane > 4,9-di (meth) acryloyloxymethyltricyclo [5.2.
  • the mixture may contain an aromatic vinyl compound.
  • aromatic vinyl compounds are preferably styrenes, substituted styrenes having an AI kylsubstituenten in the side chain, such as.
  • styrenes substituted styrenes having an AI kylsubstituenten in the side chain, such as.
  • ⁇ -methylstyrene and ⁇ -ethylstyrene substituted styrenes with a
  • Al kylsubstituenten on the ring such as vinyltoluene and p-methylstyrene, halogenated
  • Styrenes such as monochlorostyrenes, dichlorostyrenes, tribromostyrenes and
  • dienes such as 1, 2-divinylbenzene, 1, 3-divinylbenzene, 1, 4-divinylbenzene, 1, 2-diisopropenylbenzene, 1, 3-diisopropenylbenzene and 1, 4-diisopropenylbenzene used.
  • the proportion of the aromatic vinyl compounds is preferably 5-40 wt .-%, preferably 10-30 wt .-%, particularly preferably 15-25 wt .-%, based on the total amount of the compounds of formula (I), (II) and (III) which are used in the prepolymer, the radically polymerizable monomer (A) and the aromatic vinyl compounds and other optionally used monomers.
  • monomer (A) and the aromatic vinyl compound improves the mechanical properties of the plastic material according to the invention without adversely affecting its optical properties. In many cases, one can notice a favorable influence on the optical properties.
  • compounds may preferably contain linearly constructed molecules of different chain lengths (asymmetric crosslinkers) of the general formula (XVI)
  • radical R 19 is independently a hydrogen atom, a fluorine atom and / or a methyl group
  • the radical R 18 is a linking group which preferably comprises 1 to 1000, especially 2 to 100 carbon atoms
  • the radical Y is a bond or a linking group with 0 to 1000 carbon atoms, in particular 1 to 1000 carbon atoms and preferably 1 to 100 carbon atoms.
  • the molecular length R 18 can be used to vary the length of the molecule.
  • Compounds of formula (XVI) have at one end of the molecule a terminal (meth) acrylate function, on the other a terminal, different from a methacrylate group on.
  • the preferred groups Y include in particular a bond (vinyl group), a Chb group (allyl group) and aliphatic or aromatic groups having 1 to 20 carbon atoms, such as one derived from benzene Group, wherein the aliphatic or aromatic groups particularly preferably have a urethane group.
  • the radical R 18 is preferably a linear or branched, aliphatic or cycloaliphatic radical, such as a methylene, ethylene, propylene, iso-propylene, n-butylene, iso-butylene, tert-butylene or cyclohexylene Group or a group of the general formula
  • radical R 21 is a linear or branched, aliphatic or cycloaliphatic radical or a substituted or unsubstituted aromatic or heteroaromatic radical, such as a methylene, ethylene, propylene, iso-propylene, n-butylene, iso-butylene , tert-butylene or cyclohexylene group, or divalent aromatic or heteroaromatic groups which are derived from benzene, naphthalene, biphenyl, diphenyl ether, diphenylmethane, diphenyldimethylmethane, bisphenone, diphenylsulfone, quinoline, pyridine, anthracene and phenanthrene.
  • aromatic or heteroaromatic radical such as a methylene, ethylene, propylene, iso-propylene, n-butylene, iso-butylene , tert-butylene or cyclohexylene group, or di
  • cycloaliphatic radicals also include bi-, tri- and polycyclic aliphatic radicals.
  • the radical R 20 each independently denotes a linear or branched, aliphatic or cycloaliphatic radical or a substituted or unsubstituted aromatic or heteroaromatic radical, such as, for example, a methylene, ethylene, propylene, iso-propylene, n-butylene, iso Butylene or cyclohexylene group, or divalent aromatic or heteroaromatic groups derived from benzene, naphthalene, biphenyl, diphenyl ether, diphenylmethane, diphenyldimethylmethane, bisphenone, diphenylsulfone, quinoline, pyridine, anthracene and phenanthrene.
  • cycloaliphatic radicals also include bi-, tri- and polycyclic aliphatic radicals.
  • the radical X 1 is in each case independent oxygen, sulfur, an ester group of the general formula (XVIb), (XVIc),
  • radical R 22 is a linear or branched, aliphatic or cycloaliphatic radical or a substituted or unsubstituted aromatic or heteroaromatic Rest, such as a methyl, ethyl, propyl, iso-propyl, n-butyl, iso-B.utyl, tert-butyl or cyclohexyl group, or monovalent aromatic or heteroaromatic groups, the derived from benzene, naphthalene, biphenyl, diphenyl ether, diphenylmethane, diphenyldimethylmethane, bisphenone, diphenylsulfone, quinoline, pyridine, anthracene and phenanthrene.
  • cycloaliphatic radicals also include bi-, tri- and polycyclic aliphatic radicals, z is an integer between 1 and 1000, advantageously between 1 and 100, in particular between 1
  • R 23 and R 24 are each independently hydrogen or methyl
  • R 25 is a linear or branched, aliphatic or cycloaliphatic divalent radical or a substituted or unsubstituted aromatic or heteroaromatic divalent radical.
  • Preferred radicals have been previously set forth.
  • the length of the chain can be influenced by varying the number of polyalkylene oxide units, preferably polyethylene glycol units.
  • Compounds of the formula (XVII) and (XVIII) which are independent of one another from 1 to 40, preferably from 5 to 20, in particular from 7 to 15, and particularly preferably from the formula (XVII) and (XVIII) have proved to be particularly suitable for the solution described here - Have 12 polyalkylene oxide units.
  • Very particularly preferred asymmetric crosslinkers according to the invention include compounds of the formula (XVIII), in particular
  • the mixture preferably contains 0.5-40% by weight, in particular 5 to 15% by weight of compounds of the formula (XVI) and / or (XVII), based on the total weight of the monomer mixture.
  • the mixture according to the invention additionally contains at least one ethylenically unsaturated monomer (B).
  • monomers (B) are different from the asymmetric compounds of the formulas (XVII) and (XVIII) Monomers (A) and the thio (meth) acrylates of the formulas (I) and / or (II).
  • the monomers (B) are known in the art and preferably copolymerizable with the monomers (A) and the thio (meth) acrylates of the formulas (I) and / or (II).
  • These monomers (B) include in particular
  • Nitriles of (meth) acrylic acid and other nitrogen-containing methacrylates such as methacryloylamidoacetonitrile, 2-methacryloyloxyethylmethylcyanamide, cyanomethylmethacrylate;
  • (Meth) acrylates derived from saturated alcohols such as methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, iso-propyl (meth) acrylate, n-butyl (meth) acrylate, sec Butyl (meth) acrylate, tert-butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, nonyl ( meth) acrylate, iso-octyl (meth) acrylate, iso-nonyl (meth) acrylate, 2-tert-butylheptyl (meth) acrylate, 3-iso-propylheptyl (meth) acryl
  • Cycloalkyl (meth) acrylates such as cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, 3-vinyl-2-butylcyclohexyl (meth) acrylate and bornyl (meth) acrylate;
  • Aryl (meth) acrylates such as benzyl (meth) acrylate or phenyl (meth) acrylate, wherein the aryl radicals may each be unsubstituted or substituted up to four times;
  • Hydroxylalkyl (meth) acrylates such as 3-hydroxypropyl (meth) acrylate, 3,4-dihydroxybutyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2,5-dimethyl-1,6 hexanediol (meth) acrylate, 1, 10-decanediol (meth) acrylate, 1, 2-propanediol (meth) acrylate;
  • Aminoalkyl (meth) acrylates such as tris (2-methacryloxyethyl) amine, N-methylformamidoethyl (meth) acrylate, 2-ureidoethyl (meth) acrylate;
  • carbonyl-containing (meth) acrylates such as 2-carboxyethyl (meth) acrylate, carboxymethyl (meth) acrylate, oxazolidinylethyl (meth) acrylate, N- (methacryloyloxy) formamide, acetonyl (meth) acrylate, N-methacryloylmorpholine, N-methacryloyl-2- pyrrolidinone;
  • (Meth) acrylates of ether alcohols such as tetrahydrofurfuryl (meth) acrylate, vinyloxyethoxyethyl (meth) acrylate, methoxyethoxyethyl (meth) acrylate, 1-butoxypropyl (meth) acrylate, 1-methyl- (2-vinyloxy) ethyl (meth) acrylate, cyclohexyloxymethyl (meth) acrylate, methoxymethoxyethyl (meth) acrylate, benzyloxymethyl (meth) acrylate, furfuryl (meth) acrylate, 2-butoxyethyl (meth) acrylate, 2-ethoxyethoxymethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, allyloxymethyl (meth ) acrylate, 1-ethoxybutyl (meth) acrylate, methoxymethyl (meth) acrylate, 1-
  • (Meth) acrylates of halogenated alcohols such as 2,3-Dibromopropyl (meth) acrylate, 4-bromophenyl (meth) acrylate, 1,3-dichloro-2-propyl (meth) acrylate, 2-bromoethyl (meth) acrylate, 2-iodoethyl (meth) acrylate, chloromethyl ( meth) acrylate;
  • Oxiranyl (meth) acrylates such as 2,3-epoxybutyl (mth) acrylate, 3,4-epoxybutyl (meth) acrylate, glycidyl (meth) acrylate;
  • Amides of (meth) acrylic acid such as N- (3-dimethylaminopropyl) (meth) acrylamide, N- (diethylphosphono) (meth) acrylamide, 1- (meth) acryloylamido-2-methyl-2-propanol, N- (3-) Dibutylaminopropyl) (meth) acrylamide, Nt-butyl-N- (diethylphosphono) (meth) acrylamide, N, N-bis (2-diethylaminoethyl) (meth) acrylamide, 4- (meth) acryloylamido-4-methyl-2-pentanol , N- (methoxymethyl) (meth) acrylamide,
  • heterocyclic (meth) acrylates such as 2- (1-imidazolyl) ethyl (meth) acrylate, 2- (4-morpholinyl) ethyl (meth) acrylate and 1- (2-methacryloyloxyethyl) -2-pyrrolidone;
  • Phosphorus, boron and / or silicon-containing (meth) acrylates such as
  • Dipropyl (meth) acryloyl phosphate sulfur-containing (meth) acrylates such as ethylsulfinylethyl (meth) acrylate, 4-thiocyanatobutyl (meth) acrylate, ethylsulfonylethyl (meth) acrylate, thiocyanatomethyl (meth) acrylate, methylsulfinylmethyl (meth) acrylate, bis ((meth) acryloyloxyethyl) sulfide;
  • sulfur-containing (meth) acrylates such as ethylsulfinylethyl (meth) acrylate, 4-thiocyanatobutyl (meth) acrylate, ethylsulfonylethyl (meth) acrylate, thiocyanatomethyl (meth) acrylate, methylsulfinylmethyl (meth) acrylate, bis ((
  • Bis (allyl carbonates) such as ethylene glycol bis (allyl carbonate), 1,4-butanediol bis (allyl carbonate), diethylene glycol bis (allyl carbonate);
  • Vinyl halides such as vinyl chloride, vinyl fluoride, vinylidene chloride and vinylidene fluoride;
  • Vinyl esters such as vinyl acetate.
  • Heterocyclic vinyl compounds such as 2-vinylpyridine, 3-vinylpyridine, 2-methyl-5-vinylpyridine, 3-ethyl-4-vinylpyridine, 2,3-dimethyl-5-vinylpyridine, vinylpyrimidine, vinylpiperidine, 9-vinylcarbazole, 3-vinylcarbazole, 4-vinylcarbazole, 1-vinylimidazole, 2-methyl-1-vinylimidazole, N-vinylpyrrolidone, 2-vinylpyrrolidone, N-vinylpyrrolidine, 3-vinylpyrrolidine, N-vinylcaprolactam, N-vinylbutyrolactam, vinyloxolane, vinylfuran, vinylthiophene, vinylthiolane, vinylthiazoles and hydrogenated vinylthiazoles, vinyloxazoles and hydrogenated vinyloxazoles;
  • Maleic acid and maleic acid derivatives such as mono- and diesters of maleic acid, wherein the alcohol radicals have 1 to 9 carbon atoms,
  • Fumaric acid and fumaric acid derivatives such as mono- and diesters of fumaric acid, wherein the alcohol radicals have 1 to 9 carbon atoms.
  • a di (meth) acrylate listed under monomer (A) can also be used as the monomer (B).
  • (meth) acrylates include methacrylates and acrylates as well as mixtures of both.
  • (meth) acrylic acid includes methacrylic acid and acrylic acid and mixtures of both.
  • the ethylenically unsaturated monomers can be used individually or as mixtures.
  • composition of the monomer mixtures according to the invention is in principle arbitrary. It can be used to adapt the property profile of the plastic according to the invention to the needs of the application.
  • the composition of the monomer mixture such that the thio (meth) acrylate according to the invention, preferably prepolymer, is prepared from the compound (s) of the formula (I), (II) and (III) , and preferably at least one monomer (A) and optionally styrene homogeneously at the desired polymerization temperature mix, because such mixtures due to their i. a. low viscosity are easy to handle and beyond that can be polymerized to homogeneous plastics with improved material properties.
  • the monomer mixture comprises a prepolymer prepared from at least 5.0% by weight, preferably at least 20.0% by weight, particularly preferably at least 50.0% by weight, of compounds of the formula ( I), (II) and (III), in each case based on the total weight of the monomer mixture.
  • the proportion by weight of monomer (A) is preferably at least 2.0% by weight, preferably at least 10.0 wt .-%, particularly preferably at least 20.0 wt .-%, each based on the total weight of the monomer mixture.
  • the proportion by weight of aromatic vinyl compounds, in particular styrene is preferably at least 2.0 wt .-%, preferably at least 10.0 wt .-%, particularly preferably at least 20.0 wt .-%, each based on the total weight of the monomer mixture.
  • the preparation of the preferably used monomer mixture is known to the person skilled in the art. It can be prepared, for example, by mixing the thio (meth) acrylates according to the invention, preferably prepolymers, obtainable from the reaction of compounds of the formulas (I) and / or (II) with compounds (III), the aromatic vinyl compounds and the monomers (A) and ( B) take place in a known manner.
  • the monomer mixture is at atmospheric pressure and temperatures in the range of 20.0 0 C to 80.0 0 C. preferably flowable.
  • flowable is known to the person skilled in the art. It denotes a liquid, which can preferably be poured into various molds and stirred and homogenized using suitable auxiliaries.
  • Particular, flowable compositions according to the invention have, in particular at 25 ° C and at atmospheric pressure (101325 Pa) dynamic viscosities in the order of 0.1 mPa.s to 10 Pa.s, suitably in the range of 0.65 mPa.s to 1 Pa.s, up.
  • a cast monomer mixture has no bubbles, especially no air bubbles. Also preferred are those monomer mixtures from which bubbles, in particular air bubbles, can be removed by suitable methods, such as, for example, increasing the temperature and / or applying a vacuum.
  • the highly transparent plastic according to the invention is obtainable by free radical copolymerization of the above-described low-viscosity ( ⁇ ⁇ 200 mPa.s) monomer mixture.
  • Free radical copolymerization is a well-known free radical initiated process in which a mixture of low molecular weight monomers is converted into high molecular weight compounds, so-called polymers.
  • polymers for further details, reference is made to the disclosure of H.G. Elias, Macromolecules, Volumes 1 and 2, Basel, Heidelberg, New York Wegig, and Wepf. 1990 and Ullmann's Encyclopedia of Industrial Chemistry, 5th ed., Keyword "Polymerization Processes".
  • the plastic according to the invention is obtainable by mass or bulk polymerization of the monomer mixture.
  • Bulk or bulk polymerization is understood here to mean a polymerization process in which monomers are polymerized without a solvent, so that the polymerization reaction proceeds in bulk or in bulk.
  • the polymerization in emulsion silica
  • the polymerization in the dispersion silica
  • suspension polymerization in which the organic monomers are suspended with protective colloids and / or stabilizers in the aqueous phase and more or less coarse polymer particles are formed.
  • a particular form of heterogeneous phase polymerization is perl polymerization, which is essentially to be expected for suspension polymerization.
  • the polymerization reaction can in principle be initiated in any manner known to those skilled in the art, for example using a free-radical initiator (eg peroxide, azo compound) or by irradiation with UV rays, visible light, ⁇ rays, ⁇ rays or ⁇ rays, or a combination thereof.
  • a free-radical initiator eg peroxide, azo compound
  • UV rays visible light
  • ⁇ rays, ⁇ rays or ⁇ rays or a combination thereof.
  • lipophilic radical polymerization initiators are used to initiate the polymerization.
  • the radical polymerization initiators are therefore particularly lipophilic so that they dissolve in the mixture of bulk polymerization.
  • Useful compounds include, in addition to the classic azo initiators such as Azoisobutterklarenitril (AIBN) or 1, 1-Azobiscyclohexancarbonitril, u. a. aliphatic peroxy compounds, such as. B.
  • tert-amyl peroxyneodecanoate tert-amyl peroxypivalate, tert-butyl peroxypivalate, tert-amyl peroxy-2-ethylhexanoate, tert-butyl peroxy-2-ethylhexanoate, tert-amyl peroxy-3,5,5-trimethylhexanoate, ethyl 3,3-di- (tert-amyl peroxy) butyrate, tert-butyl perbenzoate, tert-butyl hydroperoxide, decanoyl peroxide, lauryl peroxide, benzoyl peroxide and any mixtures of the compounds mentioned. Of the aforementioned compounds, AIBN is most preferred.
  • the initiation of the polymerization takes place using known Photoinitiators by irradiation with UV rays or the like.
  • the common, commercially available compounds such. Benzophenone, ⁇ , ⁇ -diethoxyacetophenone, 4,4-diethylaminobenzophenone, 2,2-dimethoxy-2-phenylacetophenone, 4-isopropylphenyl-2-hydroxy-2-propyl ketone, 1-hydroxycyclohexylphenyl ketone, isoamyl-p-dimethylaminobenzoate, methyl 4-dimethylaminobenzoate, methyl o-benzoyl benzoate, benzoin, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-isopropylthioxanthone, dibenzosuberone
  • the amount of radical generators can vary within wide limits. For example, amounts in the range from 0.1 to 5.0% by weight, based on the weight of the total composition, are preferably used. Particularly preferred amounts in the range of 0.1 to 2.0 wt .-%, in particular amounts ranging from 0.1 to 0.5 wt .-%, each based on the weight of the total composition used.
  • the polymerization temperature to be chosen for the polymerization is obvious to the person skilled in the art. It is determined primarily by the initiator chosen and the way in which it is initiated (thermally, by irradiation, etc.). It is known that the polymerization temperature can influence the product properties of a polymer. Therefore, in the context of the present invention, polymerization temperatures in the range of 20.0 0 C to 100.0 0 C, advantageously in the range of 20.0 0 C to 80.0 ° C, in particular in the range of 20.0 0 C to 60 , 0 0 C preferred. In a particularly preferred embodiment of the present invention, the reaction temperature is increased during the reaction, preferably in stages. Furthermore, a tempering at elevated temperature, for example at 10O 0 C to 150 0 C, has proven to be useful towards the end of the reaction.
  • the reaction can take place both at negative pressure and at overpressure. Preferably, however, it is carried out at atmospheric pressure.
  • the reaction may take place under air as well as under a protective gas atmosphere, wherein preferably the lowest possible oxygen content is present, since this inhibits a possible polymerization.
  • the preparation of the highly transparent plastic according to the invention is carried out in such a way that a homogeneous mixture of the components monomer mixture, initiator and other additives, such. B. produces lubricant and then fills it between glass plates, whose shape by the subsequent application, eg. B. as lenses, lenses, prisms or other optical components, is predetermined.
  • the initiation of the bulk polymerization is carried out by supplying energy, for example by high-energy radiation, in particular with UV light, or by heating, expediently in a water bath and over several hours. Obtained in this way, the optical material in its desired form as a clear, transparent, colorless, hard plastic.
  • lubricants are additives for filled plastic masses, such as molding compounds and injection molding compounds, in order to make the fillers easier to slide and thus to make the molding compounds more easily deformable.
  • metal soaps and siloxane combinations are suitable. Due to its insolubility in plastics, some of the lubricant migrates to the surface during processing and acts as a release agent.
  • Particularly suitable lubricants such as non-ionic fluorosurfactants, non-ionic silicone surfactants, alkyl quaternary ammonium salts and acid phosphate esters, are described in EP 271839 A whose disclosure is explicitly referred to in the context of the present invention.
  • a highly transparent plastic with very good optical and mechanical properties is made available.
  • DIN 5036 it preferably has a transmission greater than 88.0%, advantageously greater than 89.0%.
  • Refractive index np of the plastic according to the invention is preferably greater than or equal to 1.59.
  • the refractive index of a medium is generally dependent on the wavelength of the incident radiation and on the temperature. The details of the refractive index according to the invention therefore relate to the standard data specified in DIN 53491 (standard wavelength of the (yellow) D line of sodium (about 589 nm)).
  • the plastic preferably has an Abbe number
  • the plastic has an Abbe number> 36.0, expediently
  • the mechanical properties are tested by the FDA ball drop test (ANSI Z 80.1). The test is passed if the test specimen withstands the load of a 16 mm diameter ball without damage. The material properties are the better, the larger the diameter of the ball, with which the sample is loaded and remains undamaged.
  • the plastic according to the invention is favorably characterized by a high glass transition temperature, so that it retains its excellent mechanical properties, in particular its impact resistance and hardness, even at temperatures above room temperature.
  • the glass transition temperature of the plastic material according to the invention is greater 8O 0 C, suitably greater than 90 0 C, in particular greater than 95 ° C.
  • the thio (meth) acrylates according to the invention Possible fields of use for the thio (meth) acrylates according to the invention and the transparent plastics obtainable therefrom are obvious to the person skilled in the art.
  • the plastics are particularly suitable for all applications that are predetermined for transparent plastics. Due to its characteristic properties, it is particularly suitable for optical lenses, in particular for ophthalmic lenses.
  • the thio (meth) acrylates are valuable substances that can be used in coating compositions for plastic fibers.
  • Another object of the invention is a mixture containing at least one photochromic dye.
  • All photochromic dyes known to the person skilled in the art and mixtures thereof can be used here.
  • Preferred are photochromic dyes such as e.g. Spiro (indoline) naphthoxazines, spiro (indolino) benzoxazines, spiropyrans, acetanilides, aldehyde hydrazones, thioindigo, stilbene, rhodamine and anthraquinone derivatives, benzofuroxanes, benzopyrans, naphthopyrans, organometallic dithiozonates, fulgides and fulgimides.
  • photochromic materials may be prepared, e.g. as lenses, preferably optical lenses, glass panes or glass inserts are used.
  • the batch is transferred to a separatory funnel, separated and drained the lower, aqueous phase.
  • the organic phase is transferred to an Erlenmeyer flask and stirred with ®Dowex M-31 for about 15 minutes, then filtered from the ion exchanger.
  • a polymer based on an oligomeric thiodimethacrylate for example, 7.2 g of the prepolymer, 2.4 g of styrene, 2.4 g of 10-times ethoxylated bisphenol A di (meth) acrylate, 0.1 g of hydroxyethyl methacrylate are mixed 36 mg of a UV initiator such.
  • the homogeneous casting resin mixture is placed in an appropriate mold and within 10 min. cured in a UV curing system with 1200 W high-pressure mercury radiator. Then it is tempered for about 2 h at about 120 ° C in a warming cabinet.
  • Plex 6931 O reaction product of methacrylic anhydride and ethanedithiol
  • E1 OBADMA ethoxylated bisphenol adimethacrylate with degree of ethoxylation of approx. 10
  • HEMA hydroxyethyl methacrylate
  • the mixture (B 1) according to the invention is odorless. Comparative Example CE I did not pass this test, so it was not further investigated. With a comparable refractive index (of B 1 with VB II and VB III), however, the Abbe number was better for the mixture according to the invention. In addition, the mixture according to the invention performed much better in the falling ball test.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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Abstract

La présente invention concerne des thio(meth)acrylates. On les obtient en faisant réagir les composés des formules (I) et (II) avec des composés thiol qui contiennent au moins deux groupes thiol. Dans les formules (I) et (II), R<SUP>1</SUP> représente respectivement et indépendemmant un hydrogène ou un groupe de méthyle, R<SUP>2</SUP> représente respectivement et indépendamment un groupe aliphatique ou cycloaliphatique linéaire ou ramifié ou un groupe aromatique ou hétéroaromatique substitué ou non substitué et m et n valent respectivement et indépendamment un nombre entier supérieur ou égal à 0, sous réserve que m + n > 0,.
EP05814642A 2005-01-24 2005-12-03 Thio(meth)acrylate, melanges destines a la production de matieres plastiques transparentes, matieres plastiques transparentes et leur procede de production et leur utilisation Withdrawn EP1841804A1 (fr)

Applications Claiming Priority (2)

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DE102005003303A DE102005003303A1 (de) 2005-01-24 2005-01-24 Thio(meth)acrylate, Mischungen zur Herstellung transparenter Kunststoffe, transparente Kunststoffe sowie Verfahren zu deren Herstellung und Verwendung
PCT/EP2005/012963 WO2006079387A1 (fr) 2005-01-24 2005-12-03 Thio(meth)acrylate, melanges destines a la production de matieres plastiques transparentes, matieres plastiques transparentes et leur procede de production et leur utilisation

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EP1841804A1 true EP1841804A1 (fr) 2007-10-10

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DE (1) DE102005003303A1 (fr)
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US9422502B2 (en) * 2014-03-31 2016-08-23 Exxonmobil Research And Engineering Company Low viscosity, low volatility lubricating oil basestocks
US9422498B2 (en) 2014-03-31 2016-08-23 Exxonmobil Research And Engineering Company Low viscosity, low volatility lubricating oil basestocks
CN110951162A (zh) * 2019-12-27 2020-04-03 王国银 一种耐刮擦聚丙烯材料及其制备方法

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KR20070094931A (ko) 2007-09-27
JP2008528711A (ja) 2008-07-31
DE102005003303A1 (de) 2006-07-27
WO2006079387A1 (fr) 2006-08-03
TW200634033A (en) 2006-10-01
CN101076547A (zh) 2007-11-21
US20080139771A1 (en) 2008-06-12

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