Classifications

• • 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
  • C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
  • C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
  • C08F236/20—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds unconjugated
• • 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
  • C08G18/81—Unsaturated isocyanates or isothiocyanates
  • C08G18/8141—Unsaturated isocyanates or isothiocyanates masked
  • C08G18/815—Polyisocyanates or polyisothiocyanates masked with unsaturated compounds having active hydrogen
  • C08G18/8158—Polyisocyanates or polyisothiocyanates masked with unsaturated compounds having active hydrogen with unsaturated compounds having only one group containing active hydrogen
  • C08G18/8175—Polyisocyanates or polyisothiocyanates masked with unsaturated compounds having active hydrogen with unsaturated compounds having only one group containing active hydrogen with esters of acrylic or alkylacrylic acid having only one group containing active hydrogen
• • 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
  • 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
  • C08G18/72—Polyisocyanates or polyisothiocyanates
  • C08G18/73—Polyisocyanates or polyisothiocyanates acyclic
• • 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
  • C08L75/12—Polyurethanes from compounds containing nitrogen and active hydrogen, the nitrogen atom not being part of an isocyanate group

Definitions

• the present invention relates to the field of transparent plastics.
• the invention relates to highly transparent plastics that can be used for the production of optical, especially ophthalmic lenses.
• plastic eyeglass lenses are an integral part of everyday life. Spectacles with plastic lenses in particular have recently gained in importance because they are lighter and less fragile than spectacle lenses made from inorganic materials and can be colored using suitable dyes.
• plastic eyeglass lenses generally highly transparent plastics are used, which are available, for example, starting from diethylene glycol bis (allyl carbonate) (DAC), thiourethane compounds with ⁇ , ⁇ -terminated multiple bonds or sulfur-containing (meth) acrylates.
• DAC diethylene glycol bis (allyl carbonate)
• thiourethane compounds with ⁇ , ⁇ -terminated multiple bonds or sulfur-containing (meth) acrylates.
• DAC plastic has very good impact strength, transparency and good processability. It is disadvantageous, however, that due to the relatively low refractive index no of approximately 1.50, both the center and the edges of the plastic lenses in question must be reinforced, so that the lenses are accordingly thick and heavy. The wearing comfort of glasses with DAC plastic lenses is therefore significantly reduced.
• Thiourethane prepolymers with ⁇ , ⁇ -terminated multiple bonds which are obtained by reacting ⁇ , ⁇ -difunctional thiourethane prepolymers which carry two isocyanate groups with unsaturated compounds which have zerewitinow-active H atoms are described, for example, in DD 298645 described. Possible applications of the thiourethane prepolymers are transparent layers or well-adhering films. A use as optical and ophthalmic lenses is not disclosed in DD 298645.
• the plastic eyeglass lenses described in JP 5-215995 are trimethylolpropane tris (beta.) By radical copolymerization of a temporary composition from an ⁇ , ⁇ -di (meth) acrylate-terminated thiourethane compound which has S- (phenyl-S) 2 units -thiopropionate) and divinylbenzene.
• the refractive index of the resulting plastics is relatively large (np> 1, 58)
• the glasses have the disadvantage of a comparatively low Abbeschen number in the range from 28 to 36.
• a too low Abbesche number leads to higher dispersion and color edges, Corresponding plastic glasses are therefore only of limited use as visual aids.
• plastics disclosed in WO 01/36506 which are obtained by free-radical polymerization of monomers with at least two (meth) acryloyl groups, the monomers furthermore having thiourethane and / or dithiourethane linkages within the molecule.
• the exemplified polymer has a refractive index of 1.60 and an Abbe number of 34 to 35. Information on the Vicat temperature of the plastics cannot be found in this publication either.
• the plastics described in EP 0810210 have improved impact strength and a high refractive index n D in the range from 1,589 to 1,637.
• the Abbe number is compared to that in JP 5-215995 described plastics only slightly increased, it is between 27.5 and 40.7. Therefore, the plastics disclosed in EP 0810210 are only suitable to a limited extent for spectacle lenses. Information on the Vicat temperature of the plastics cannot be found in this publication either.
• DE 4234251 discloses sulfur-containing polymethacrylates which are obtained by radical copolymerization of a monomer mixture of compounds of the formulas (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, it being possible for the carbon chains to be interrupted by one or more ether or thioether groups.
• R represents hydrogen or methyl and n is an integer ranging from 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 monomer mixture is prepared by reacting at least two moles of (meth) acrylic acid chloride or (meth) acrylic anhydride with one mole of a dithiol, the (meth) acrylic chloride or (meth) acrylic anhydride in an inert organic solvent and the dithiol in aqueous brings alkaline solution to the reaction.
• Suitable solvents are methyl tert-butyl ether, toluene and xylene, the dielectric constant of which is 2.6, 2.4 or 2.3 to 2.6 at 20 ° C.
• the plastics described in DE 4234251 are colorless, hard and slightly brittle and have a high refractive index np in the range from 1.602 to 1.608.
• the Abbe number is between 35 and 38. Therefore, these plastics are only of limited suitability for spectacle lenses. Information on the Vicat temperature of the plastics cannot be found in this publication either.
• Another object was to provide a starting material composition for the production of a highly transparent plastic with improved mechanical properties, such as good impact strength.
• the Charpy impact strength of the plastic measured according to ISO 179 / 1fU, should preferably be greater than 3.0 kJ / m 2 .
• the present invention was also based on the object of making a starting material composition for the production of a highly transparent plastic with improved mechanical properties accessible even at temperatures above room temperature.
• the plastic according to the invention should have a Vicat temperature as high as possible, preferably greater than 50.0 ° C. measured according to ISO 306.
• the highly transparent plastic according to the invention based on the starting material composition, in a simple manner, on an industrial scale and is inexpensive to manufacture.
• it should be available starting from a mixture which is flowable at normal pressure and temperatures in the range from 20.0 ° C. to 80.0 ° C. via free radical polymerization.
• the present invention was also based on the object of specifying areas of application and possible uses of the highly transparent plastic according to the invention.
• R 1 each independently of one another is hydrogen or a methyl radical
• R 2 each independently of one another is a linear or branched, aliphatic or cycloaliphatic radical or a substituted or unsubstituted aromatic or heteroaromatic radical and m and n each independently represent an integer greater than or equal to 0 with m + n> 0, and
• the highly transparent plastic according to the invention has a previously unknown combination of outstanding properties, such as a high refractive index, a high Abbe number, good Charpy impact strength and a high Vicat temperature.
• the corresponding plastic glasses show a low dispersion; There are no color borders.
• the highly transparent plastic according to the invention has further advantages. These include:
• the highly transparent plastic according to the invention has a high Vicat temperature in accordance with ISO 306, preferably greater than 50.0 ° C., and therefore retains its excellent mechanical properties, in particular its high impact resistance and hardness, up to this temperature.
• the highly transparent plastic according to the invention can be produced in a simple manner, on an industrial scale and inexpensively by free radical copolymerization of a monomer mixture which is preferably flowable at normal pressure and temperatures in the range from 20.0 ° C. to 80.0 ° C.
• the production of the underlying monomer mixture is also possible in a simple manner, on an industrial scale and at low cost.
• the present invention relates to mixtures, the compounds of the formula (I) and (II)
• the radical R 1 is in each case independently of one another hydrogen or a methyl radical, preferably a methyl radical.
• the radical R 2 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 or iso -Butylene, t-butylene or cyclohexylene group, or divalent aromatic or heteroaromatic groups derived from benzene, naphthalene, biphenyl, diphenyl ether, diphenyl methane, diphenyldimethyl methane, bisphenone, diphenyl sulfone, quinoline, pyridine, anthracene and phenanthrene.
• cycloaliphatic radicals also include bi-, tri- and polycyclic aliphatic radicals.
• the radical R furthermore also comprises radicals of the formula
• R 3 each independently is a linear or branched, aliphatic or cycloaliphatic radical, such as, for example, a methylene, ethylene, propylene, iso-propylene, n-butylene, iso-butylene, t-butylene or cyclohexylene Group is.
• the radical X is in each case independently of one another oxygen or sulfur and the radical R 4 stands for a linear or branched, aliphatic or cycloaliphatic radical, such as, for example, a methylene, ethylene, propylene, iso-propylene, n-butylene or iso -Butylene, t-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 (Ia) include:
• the radical R 2 is preferably an aliphatic radical with 1 to 10 carbon atoms, preferably a linear aliphatic radical with 2 to 8 carbon atoms.
• the 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 m + n is advantageously greater than 0, preferably in the range from 1 to 6 in the range from 1 to 4, in particular 1, 2 or 3.
• the compounds of formula (I) and the compounds of formula (II) can each be used individually or as a mixture of several compounds of formula (I) or (II).
• the relative proportions of the compounds of the formula (I) and (II) in the monomer mixture according to the invention are in principle arbitrary, they can be used to "tailor" the property profile of the plastic according to the invention in accordance with the needs of the application.
• the proportion of the compounds (I) is preferably 0.1 to 50.0 mol%, advantageously 10.0 to 45.0 mol%, in particular 20.0 to 35.0 mol%, based on the total amount of the compounds of the formula (I) and (II).
• the proportion of the 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) ,
• the radical X stands for chlorine or for a radical
• the compounds of formula (III) include acrylic acid chloride, methacrylic acid chloride, acrylic acid anhydride and methacrylic anhydride, the use of acrylic acid anhydride, methacrylic acid anhydride or mixtures of the two being particularly preferred.
• M independently of one another denotes hydrogen or a metal cation.
• Preferred metal cations are derived from elements with an electronegativity less than 2.0, advantageously less than 1.5, alkali metal cations, in particular Na + , K + , Rb + , Cs + , and alkaline earth metal cations, in particular Mg 2+ , Ca 2+ , Sr 2+ , Ba 2+ , are particularly preferred. Particularly favorable results can be achieved with the metal cations Na + and K + .
• Polythiols of the formula (IV) which are particularly suitable in this context include 1,2-ethanedithiol, 1,2-propanedithiol, 1,3-propanedithiol, 1,2-butanedithiol, 1,3-butanedithiol, 1,4-butanedithiol, 2- Methylpropane-1,2-dithiol, 2-methylpropane-1,3-dithiol, 3,6-dioxa-1,8-octanedithiol,
• Ethylcyclohexyldimercaptans which can be obtained by reacting 4-ethenylcyclohexene with hydrogen sulfide, ortho-bis (mercaptomethyl) benzene, meta-bis (mercaptomethyl) benzene, para-bis (mercaptomethyl) benzene, compounds of the formula
• R 3 each independently is a linear or branched, aliphatic or cycloaliphatic radical, such as, for example, a methylene, ethylene, propylene, iso-propylene, n-butylene, iso-butylene, t-butylene or cyclohexylene Group is.
• cycloaliphatic radicals also include bi-, tri- and polycyclic aliphatic radicals.
• the radical X is in each case independently of one another oxygen or sulfur and the radical R 4 stands for a linear or branched, aliphatic or cycloaliphatic radical, such as, for example, a methylene, ethylene, propylene, iso-propylene, n-butylene or iso -Butylene, t-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 (IVa) include: .S ⁇ ⁇ SH
• 1,2-ethanedithiol is used as the compound of the formula (IV).
• the compound (s) of formula (III) in at least one inert organic solvent L and the compound (s) of formula (IV) in aqueous alkaline solution for the reaction brought, the term "inert organic solvent” for those organic solvents that do not react under the respective reaction conditions with the compounds present in the reaction system.
• At least one solvent L must have a relative dielectric constant> 2.6, preferably> 3.0, expediently> 4.0, in particular> 5.0, in each case measured at 20 ° C.
• the relative dielectric constant denotes a dimensionless number, which indicates how many times the capacitance C of a (theoretically) capacitor is in vacuum if substances with dielectric properties, so-called dielectrics, are placed between the plates. This value is measured at 20 ° C and extrapolated to low frequencies ( ⁇ ⁇ 0).
• Dielectric values of solvents are u. a. in the 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 ° C., less than 10 g water based on 100 g 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), pentanone-2 (15.4), pentanone-3 (17.0), methyl isoamyl ketone, methyl isobutyl ketone (13.1); aromatic ketones such as acetophenone;
• Nitro aromatics 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, the information in parentheses being the respective associated relative dielectric constant at 20 ° C.
• Aliphatic esters and cycloaliphatic ethers are very particularly suitable for the purposes of the present process.
• the solvent L can be used both on its own and a solvent mixture, it not being necessary for all of the solvents contained in the mixture to meet the above dielectric criterion.
• tetrahydrofuran / cyclohexane mixtures can also be used according to the invention.
• the solvent mixture it has proven to be expedient for the solvent mixture to have 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, advantageously> 4.0, in particular> 5.0, in each case measured at 20 ° C.
• the aqueous alkaline solution of the compound (s) of the formula (IV) preferably contains 1.1 to 1.5 equivalents of at least one Bronsted base, based on the total amount of compound (s) of the formula (III).
• Preferred Bronsted bases for the purposes of the present invention include alkali hydroxides and alkaline earth hydroxides, in particular sodium hydroxide and potassium hydroxide.
• the reaction can be carried out in any conceivable manner.
• the reaction temperature can be varied over a wide range, but the temperature is frequently in the range from 20.0 ° C. to 120.0 ° C., preferably in the range from 20.0 ° C. to 80.0 ° C.
• the reaction can therefore take place both under negative pressure and under positive pressure. However, it is preferably carried out at normal pressure.
• the reaction can also take place in 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 small proportion of oxygen.
• the reaction mixture is advantageously reacted with a Bronsted acid, preferably until the aqueous solution has a pH of less than 7.0, advantageously less than 6.0, in particular less than 5.0, at 20 ° C.
• usable acids include inorganic mineral acids such as hydrochloric acid, sulfuric acid, phosphoric acid, organic acids such as acetic acid, propionic acid and acidic Ion exchangers, especially acid synthetic resin ion exchangers, such as ® Dowex M-31 (H).
• acidic synthetic resin ion exchangers with loads 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 in the range from 10 to 50%, based on the total volume of the ion exchanger, has proven particularly useful.
• the organic phase consisting of the solvent L is expediently separated off, optionally washed, dried and the solvent is evaporated.
• inhibitors can be added which prevent free-radical polymerization of the (meth) acrylic groups during the reaction. These inhibitors are well known in the art.
• R 5 is 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, particularly 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 from one to four, preferably one or two; and
• R 6 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, particularly preferably methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec -Butyl or tert-butyl.
• R 5 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, particularly preferably methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, Cl, F or Br; and
• o is an integer in the range from one to four, preferably one or two.
• R 5 is a linear or branched alkyl radical with one to eight carbon atoms, aryl or aralkyl, propionic acid ester with 1 to 4 polyhydric alcohols, which may also contain heteroatoms such as S, O and N, preferably an alkyl radical with one to four carbon atoms, particularly preferably methyl , Ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert. Butyl means.
• Another advantageous class of substances are hindered phenols based on triazine derivatives of the formula (VIII)
• the proportion of the inhibitors is generally 0.01-0.50% (wt / wt), the concentration of the inhibitors preferably being selected so that the color number according to DIN 55945 is not impaired becomes. Many of these inhibitors are commercially available.
• the mixture further comprises at least one ethylenically unsaturated monomer (A) which is different from the compounds of the formulas (I) and (II).
• the monomer (A) can also be regarded as a reactive diluent for the compounds of the formula (I) and (II).
• the addition of monomer (A) improves the mechanical properties of the plastic material according to the invention without adversely affecting its optical properties. In many cases, the opposite can also be found, namely a favorable influence on the optical properties.
• Ethylenically unsaturated monomers (A) are well known to the person skilled in the art, they comprise all the organic compounds which have at least one ethylenic double bond. These include:
• Nitriles of (meth) acrylic acid and other nitrogen-containing methacrylates such as methacryloylamidoacetonitrile, 2-methacryloyloxyethylmethylcyanamide, cyanomethyl methacrylate;
• (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
• Cycloalkyl (meth) acrylates such as cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, 3-vinyl-2-butylcyclohexyl (meth) acrylate and bomyl (meth) acrylate;
• Aryl (meth) acrylates such as benzyl (meth) acrylate or phenyl (meth) acrylate, it being possible for the aryl radicals to 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;
• Polyoxyethylene and polyoxypropylene derivatives of (meth) acrylic acid such as triethylene glycol (meth) acrylate, tetraethylene glycol (meth) acrylate, tetrapropylene glycol (meth) acrylate;
• Di (meth) acrylates such as 1,2-ethanediol di (meth) acrylate, 1,4-butanediol di (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 molecular weights in the range from 200 to 5000000 g / mol, advantageously in the range from 200 to 25000 g / mol, in particular in the range from 200 up to 1000 g / mol), polypropylene glycol di (meth) acrylate (preferably with a weight average molecular weight in the range from 200 to 5000000 g / mol, advantageously in the range from 250
• s and t are greater than or equal to zero and the sum s + 1 is preferably in the range from 1 to 20, in particular in the range from 2 to 10, and di (meth) acrylates obtainable by reacting diisocyanates with 2 equivalents of hydroxyalkyl (meth) acrylate , in particular
• radical R 1 each independently represents hydrogen or a methyl radical
• Aminoalkyl (meth) acylates 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, Furfuryi (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 -lodoethyl (meth) acrylate, chloromethyl (meth) acrylate;
• Oxiranyl (meth) acrylates such as 2,3-epoxybutyl (meth) acrylate, 3,4-epoxybutyl (meth) acrylate, glycidyl (meth) acrylate;
• heterocyclic (meth) acrylates such as 2- (1-imidazolyl) ethyl (meth) acrylate, 2- (4-morpholinyl) ethyl (meth) acrylate and 1 - (2-methacryloyloxyethyl) -2-pyrro! idon;
• Phosphorus, boron and / or silicon-containing (meth) acrylates such as
• 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; Tri (meth) acrylates such as trimethyloylpropane tri (meth) acrylate and glycerol tri (meth) acrylate;
• Vinyl halides such as vinyl chloride, vinyl fluoride, vinylidene chloride and vinylidene fluoride;
• Vinyl esters such as vinyl acetate
• Styrene substituted styrenes with an alkyl substituent in the side chain, such as. B. ⁇ -methylstyrene and oc-ethylstyrene, substituted styrenes with an alkyl substituent on the ring, such as vinyltoluene and p-methylstyrene, halogenated styrenes such as monochlorostyrenes, dichlorostyrenes, tribromostyrenes and tetrabromostyrenes;
• 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, vinylthiophene, vinylthiophene, vinylthiophene, vinylthiophene, vinylthiazhen hydrogenated vinyl thiazoles, vinyl oxazoles and hydrogenated vinyl oxazoles;
• Maleic acid and maleic acid derivatives such as, for example, mono- and diesters of maleic acid, the alcohol residues having 1 to 9 carbon atoms, Maleic anhydride, methyl maleic anhydride, maleimide, methyl maleimide;
• Fumaric acid and fumaric acid derivatives such as, for example, mono- and diesters of fumaric acid, the alcohol residues having 1 to 9 carbon atoms;
• dienes such as, for example, 1,2-divinylbenzene, 1,3-divinylbenzene, 1,4-divinylbenzene, 1,2-diisopropenylbenzene, 1,3-diisopropenylbenzene and 1,4-diisopropenylbenzene.
• the expression (meth) acrylates includes methacrylates and acrylates and mixtures of the two. Accordingly, the expression (meth) acrylic acid encompasses methacrylic acid and acrylic acid and mixtures of the two.
• the ethylenically unsaturated monomers can be used individually or as mixtures.
• the monomer (A) in particular comprises ethylenically unsaturated monomers which can be copolymerized with the compounds of the formulas (I) and (II).
• the mixture according to the invention contains at least one thiourethane compound (T) as monomer (A), which in turn can be obtained by a) reacting one equivalent of at least one diisocyanate of the formula
• the R 9 radical is 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, t -Butylene, cyclohexylene or divalent aromatic or heteroaromatic groups derived from benzene, naphthalene, biphenyl, diphenyl ether, diphenyl methane, diphenyldimethyl methane, bisphenone, diphenyl sulfone, quinoline, pyridine, anthracene and phenanthrene.
• cycloaliphatic radicals also include bi-, tri- and polycyclic aliphatic radicals.
• the radical R 9 is preferably an aliphatic radical, advantageously with 2 to 9 carbon atoms.
• VD is a number in the range from 0.1 to 0.9, preferably in the range from 0.5 to 0.9, in particular a number in the range from 0.5 to 0.6.
• v D 0.5 has proven to be particularly useful according to the invention.
• the R 10 radical is 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 , t-butylene or cyclohexylene group, or divalent aromatic or heteroaromatic groups derived from benzene, naphthalene, biphenyl, diphenyl ether, diphenyl methane, diphenyldimethyl methane, bisphenone, diphenyl sulfone, quinoline, pyridine, anthracene and phenanthrene
• the radical R 10 also comprises radicals of the formula
• R 14 is, independently of one another, a linear or branched, aliphatic or cycloaliphatic radical, such as, for example, a methylene, ethylene, propylene, iso-propylene, n-butylene, iso-butylene, t-butylene or cyclohexylene or Group is.
• the radical X is in each case independently of one another oxygen or sulfur and the radical R 15 stands for a linear or branched, aliphatic or cycloaliphatic radical, such as, for example, a methylene, ethylene, propylene, iso-propylene, n-butylene or iso -Butylene, t-butylene or cyclohexylene group.
• cycloaliphatic radicals also include bi-, tri- and polycyclic aliphatic radicals, r is an integer between 1 and 10, in particular 1, 2, 3 and 4.
• Preferred radicals of the formula (Xla) include:
• the radical R 10 is preferably an aliphatic radical with 1 to 10 carbon atoms, preferably a linear aliphatic radical with 2 to 8 carbon atoms.
• the rest Z stands for oxygen or sulfur.
• the at least one compound of the general formula (XII) thus comprises diols of the general formula (XI la)
• the R 11 radical is 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 , t-butylene or cyclohexylene group, or divalent aromatic or heteroaromatic groups derived from benzene, naphthalene, biphenyl, diphenyl ether, diphenyl methane, diphenyldimethyl methane, bisphenone, diphenyl sulfone, quinoline, pyridine, anthracene and phenanthrene.
• cycloaliphatic radicals also include bi-, tri- and polycyclic aliphatic radicals.
• the radical R 11 also comprises radicals of the formula (XI Ic)
• R 16 each independently of one another is a linear or branched, aliphatic or cycloaliphatic radical, such as, for example, a methylene, ethylene, propylene, iso-propylene, n-butylene, iso-butylene, t-butylene or cyclohexylene Group is.
• the radical X is in each case independently of one another oxygen or sulfur and the radical R 17 represents a linear or branched, aliphatic or cycloaliphatic radical, such as, for example, a methylene, ethylene, propylene, iso-propylene, n-butylene or iso -Butylene, t-butylene or cyclohexylene group.
• cycloaliphatic radicals also include bi-, tri- and polycyclic aliphatic radicals.
• r a is an integer between 1 and 20, especially between 1 and 10.
• Preferred residues of formula (Xllc) include:
• diisocyanates of the formula (X) are the following diisocyanates: aliphatic diisocyanates, such as hexamethylene diisocyanate, 2,2,4- and 2,4,4-trimethylhexamethylene diisocyanate, cycloaliphatic diisocyanates such as isophorone diisocyanate, 1,4-cyclohexane diisocyanate, 1-methyl-2,4- and -2,6-cyclohexane diisocyanate, 4,4'-dicyclohexyl diisocyanate and the corresponding positional isomer mixtures , 4,4'-, 2,4'- and 2,2'-dicyclohexylmethane diisocyanate and the corresponding positional isomer mixtures, di- (2-isocyanatoethyl) bicyclo [2.2.1] -hept-5-ene-2,3 dicarboxylate and aromatic diisocyanates, such as 2,4-tolylene diiso
• Suitable dithiols include, for example, 1,2-ethanedithiol, 1,2-propanedithiol, 1,3-propanedithiol, 1,2-butanedithiol, 1,3-butanedithiol, 1,4-butanedithiol, 2-methylpropane-1,2-dithiol, 2-methylpropane-1,3-dithiol, 3,6-dioxa-1,8-octanedithiol, ethylcyclohexyldimercaptans, which can be obtained by reacting 4-ethenylcyclohexene with hydrogen sulfide, ortho-bis (mercaptomethyl) benzene, meta-bis ( mercaptomethyl) benzene, para-bis (mercaptomethyl) benzene, compounds of the formula
• R 14 is, independently of one another, a linear or branched, aliphatic or cycloaliphatic radical, such as, for example, a methylene, ethylene, propylene, iso-propylene, n-butylene, iso-butylene, t-butylene or cyclohexylene or Group is.
• cycloaliphatic radicals also include bi-, tri- and polycyclic aliphatic radicals.
• the radical X is in each case independently of one another oxygen or sulfur and the radical R 15 stands for a linear or branched, aliphatic or cycloaliphatic radical, such as, for example, a methylene, ethylene, propylene, iso-propylene, n-butylene or iso -Butylene, t-butylene or cyclohexylene group.
• cycloaliphatic radicals also include bi-, tri- and polycyclic aliphatic radicals, r is an integer between 1 and 10, in particular 1, 2, 3 and 4.
• Preferred compounds of formula (Xlb) include: ⁇ / ⁇ SH
• R 16 each independently of one another is a linear or branched, aliphatic or cycloaliphatic radical, such as, for example, a methylene, ethylene, propylene, iso-propylene, n-butylene, iso-butylene, t-butylene or cyclohexylene Group is.
• cycloaliphatic radicals also include bi-, tri- and polycyclic aliphatic radicals.
• the radical X is in each case independently of one another oxygen or sulfur and the radical R 17 represents a linear or branched, aliphatic or cycloaliphatic radical, such as, for example, a methylene, ethylene, propylene, iso-propylene, n-butylene or iso -Butylene, t-butylene or cyclohexylene group.
• cycloaliphatic radicals also include bi-, tri- and polycyclic aliphatic radicals.
• r a is an integer between 1 and 20, especially between 1 and 10.
• Preferred compounds of formula (Xlld) include: ⁇ / ⁇ OH
• Suitable hydroxy-mercapto compounds of the general formula (Xllb) include, for example, 2-mercaptoethanol, 2-mercaptopropanol, 1-mercapto-isopropanol, 3-mercaptopropanol, 2-mercaptobutanol, 1-mercaptobutanol- (2), 3-mercaptobutanol, 1-mercaptobutanol- (3), 4-mercaptobutanol, 2-mercapto-2-methylpropanol, 1-mercapto-2-methylpropanol- (2), 3-mercapto-2-methylpropanol, 8-mercapto-3,6-dioxa-1, 8- octanol, ortho- (mercaptomethyl) benzyl alcohol, meta- (mercaptomethyl) benzyl alcohol, para- (mercaptomethyl) benzy
• R 16 each independently of one another is a linear or branched, aliphatic or cycloaliphatic radical, such as, for example, a methylene, ethylene, propylene, iso-propylene, n-butylene, iso-butylene, t-butylene or cyclohexylene Group is.
• cycloaliphatic radicals also include bi-, tri- and polycyclic aliphatic radicals.
• the radical X is in each case independently of one another oxygen or sulfur and the radical R 17 represents a linear or branched, aliphatic or cycloaliphatic radical, such as, for example, a methylene, ethylene, propylene, iso-propylene, n-butylene or iso -Butylene, t-butylene or cyclohexylene group.
• cycloaliphatic radicals also include bi-, tri- and polycyclic aliphatic radicals.
• r a ⁇ st is an integer between 1 and 20, especially between 1 and 10.
• Preferred compounds of formula (Xlle) include:
• the reaction of the at least one isocyanate with the at least one thiol and the at least one compound of the general formula (XII) can be carried out in bulk, ie without the use of a further solvent.
• an inert solvent can also be used. These include benzene, toluene, tetrahydrofuran, methyl isobutyl ketone (MIBK) and methyl ethyl ketone (MEK).
• the reaction temperature can be varied over a wide range, but the temperature is frequently in the range from 20.0 ° C. to 120.0 ° C., preferably in the range from 20.0 ° C. to 80.0 ° C.
• the reaction can therefore take place both under negative pressure and under positive pressure. However, it is preferably carried out at normal pressure.
• the reaction can take place in air as well as in a protective gas atmosphere, a small amount of oxygen preferably being present.
• catalysts such as tertiary amines are often used, these include, among others, triethylamine, 1,4-diazabicyclo [2.2.2] octane, N-methylmorpholine, N, N-diethylcyclohexylamine, N, N, N ', N'-tetramethyldiaminomethane, N, N '-dimethylpiperazine, 2- (dimethylaminoethoxy) ethanol, pyridine, collidine and picoline, organic metal compounds such as titanium acid esters, iron compounds such as e.g. B. iron (III) acetylacetonate, tin compounds, e.g. B.
• the presence of a catalytically effective amount of a catalyst known from urethane chemistry, in particular pyridine, DABCO (diazobicyclo (2.2.2) octane), collidine and / or picoline, is particularly preferred during the reaction of the isocyanate groups with the thiol groups and the hydroxyl groups.
• a catalyst known from urethane chemistry in particular pyridine, DABCO (diazobicyclo (2.2.2) octane), collidine and / or picoline.
• the hydroxyalkyl (meth) acrylates suitable for the reaction with the at least one ⁇ , ⁇ -difunctional thiourethane compound from step a) are esters of (meth) acrylic acid with dihydric, aliphatic alcohols.
• hydroxyalkyl (meth) acrylate includes hydroxyalkyl methacrylates and hydroxyalkyl acrylates, and also mixtures of the two. Hydroxyalkyl (meth) acrylates which can be used according to the invention satisfy the general formula (XIII)
• the radical R 12 is hydrogen or a methyl radical.
• the radical R 13 is hydrogen or a linear or branched alkyl radical having 1 to 4 carbon atoms, such as, for example, a methyl, ethyl, propyl, isopropyl, n-butylene, isobutylene or a t-butyl radical.
• the radical R 13 is preferably hydrogen.
• q is 1, 2 or 3.
• the oxirane compounds include ethylene oxide, propylene oxide, 1, 2-butylene oxide and / or 2,3-butylene oxide. These compounds can be used both individually and as a mixture.
• the conversion to the hydroxyalkyl (meth) acrylates is described for example in DE-A-24 39 352, DE-15 68 838 and GB 1 308 250.
• hydroxyalkyl (meth) acrylates thus obtainable are frequently commercially available and are therefore particularly suitable for the purposes according to the invention.
• Preferred hydroxyalkyl (meth) acrylates include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 2-hydroxybutyl acrylate, 2-hydroxybutyl methacrylate, 3-hydroxybutyl acrylate, 3-hydroxybutyl methacrylate, 4-hydroxybutyl acrylate and 4-hydroxybutyl methacrylate, of which are 2-hydroxyethyl methacrylate,
• the at least one ⁇ , ⁇ -difunctional thiourethane compound from step a) is reacted with the at least one hydroxyalkyl (meth) acrylate of the general formula (XIII) in the presence of customary compounds which catalyze and stabilize the reaction.
• the reaction can be carried out in bulk, i.e. be carried out without the use of another solvent. If desired, an inert solvent can also be used. These include benzene, toluene, tetrahydrofuran, methyl isobutyl ketone (MIBK) and methyl ethyl ketone (MEK).
• MIBK methyl isobutyl ketone
• MEK methyl ethyl ketone
• the reaction of the isocyanate groups with the hydroxyl groups is widely known in the art.
• the reaction temperature can vary over a wide range, but often the temperature is in the range from 20.0 ° C to 120.0 ° C, preferably in the range from 20.0 ° C to 80.0 ° C.
• the reaction can therefore take place both under negative pressure and under positive pressure. However, it is preferably carried out at normal pressure.
• the reaction can take place in air as well as in a protective gas atmosphere, a small amount of oxygen preferably being present.
• catalysts such as tertiary amines
• tertiary amines including triethylamine, 1,4-diazabicyclo [2.2.2] octane (DABCO), N-methylmorpholine, N, N-diethylcyclohexylamine, NNN'.N '-Tetramethyldiaminomethane, N, N' -Dimethylpiperazin, 2- (Dimethyl-aminoethoxy) -ethanol, pyridine, collidine and picoline, organic metal compounds such as titanium esters, iron compounds such as. B. iron (III) acetylacetonate, tin compounds, e.g. B.
• DABCO 1,4-diazabicyclo [2.2.2] octane
• N-methylmorpholine N, N-diethylcyclohexylamine
• NNN'.N '-Tetramethyldiaminomethane N, N' -D
• inhibitors can be added which prevent free-radical polymerization of the (meth) acrylates during the reaction .
• Suitable inhibitors include the compounds mentioned above in connection with the compounds of the formula (I) and (II).
• auxiliaries and / or additives may also be expedient during the reaction of the at least one ⁇ , ⁇ -difunctional thiourethane compound from step a) with the at least one hydroxyalkyl (meth) acrylate of the general formula (XIII) .
• Lubricants, stabilizers against hydrolysis, light, heat or discoloration and plasticizers may be mentioned, for example.
• Further information on the above-mentioned auxiliaries and additives can be found in the specialist literature, for example the monograph by JH Saunders and KC Frisch "High Polymers", Volume XVI, Polyurethane, Parts 1 and 2, Interscience Publishers 1962 and 1964 or DE-OS 29 01 774.
• the thiourethane compound (T) is obtainable by reacting one equivalent of at least one diisocyanate with VD equivalents of at least one dithiol (XI) or a mixture comprising at least one dithiol (XI) and at least one compound ( XII) and subsequent reaction with VH equivalents of at least one hydroxyalkyl (meth) acrylate, at least one mixture of two or more diisocyanates, two or more dithiols and / or two or more hydroxyalkyl (meth) acrylates being used.
• composition of the respective mixtures is in principle arbitrary, i. H. it can contain a significant excess of a main component in comparison with the other components.
• Equimolar mixtures of two or more components are also possible.
• mixtures of two to five, preferably two or three, in particular two, components have proven particularly useful.
• the main component denotes the component which is numerically in excess compared to the other components. In the event that two or more components can be considered as the main component, the choice among the relevant components is arbitrary.
• the at least one thiourethane compound (T) is obtained by reacting one equivalent of a diisocyanate of the general formula (X) with VD equivalents of a dithiol of the general formula (XI) or a mixture consisting of a dithiol of the general formula (XI) and at least one compound of the general formula (XII) and the subsequent reaction with v H equivalents of a mixture of at least two hydroxyalkyl (meth) acrylates of the general formula (XIII).
• a mixture of at least two thiourethane compounds (T) is preferred, which advantageously differ in R 12 , R 13 and / or q.
• the use of mixtures of 2-hydroxyethyl methacrylate and 4-hydroxybutyl acrylate has proven to be particularly useful in this context.
• the at least one thiourethane compound (T) is obtained by reacting one equivalent of a diisocyanate of the general formula (X) with v D equivalents of a mixture of at least two dithiols of the general formula (XI) and, if appropriate at least one compound of the general formula (XII) and the subsequent reaction with v H equivalents of a hydroxyalkyl (meth) acrylate of the general formula (XIII) are obtainable.
• a mixture of at least two thiourethane compounds (T), which advantageously differ in R 10 is preferred.
• mixtures of 3,6-dioxa-1, 8-octanedithiol and 1, 2-ethanedithiol or of a product mixture obtainable by reacting 4-ethenylcyclohexene with hydrogen sulfide in particular the use of mixtures of 3,6-dioxa-1, 8-octanedithiol and 1,2-ethanedithiol as dithiol (II) have proven particularly useful in this context.
• the at least one thiourethane compound (T) consists of reacting one equivalent of a mixture of at least two diisocyanates of the general formula (I) with VD equivalents of a dithiol of the general formula (XI) or a mixture from a dithiol of the general formula (XI) and at least one compound of the general formula (XII) and the subsequent reaction with VH equivalents
• a mixture of at least two thiourethane compounds (T) is preferred, which advantageously differ in R 9 .
• the use of mixtures of a positional isomer mixture of 2,2,4- and 2,4,4-trimethylhexamethylene diisocyanate (CAS-34992-02-4) and isophorone diisocyanate (obtainable by reacting 1-amino-3-aminomethyl-3,5, 5-trimethylcyclohexane with phosgene) has proven to be particularly useful in this context.
• thiourethane compound (T) Alternative ways of producing the thiourethane compound (T) are obvious to the person skilled in the art. For example, it can also be carried out by reacting one equivalent of at least one diisocyanate (X) with VH equivalents of at least one hydroxyalkyl (meth) acrylate (XIII) and subsequent coupling with v D equivalents of a dithiol of the general formula (XI) or a mixture comprising at least one dithiol (XI) and at least one compound (XII) can be obtained.
• X diisocyanate
• v D equivalents of a dithiol of the general formula (XI) or a mixture comprising at least one dithiol (XI) and at least one compound (XII) can be obtained.
• the mixture according to the invention contains an ethylenically unsaturated monomer (B) which is different from the thiourethane compound (T) as monomer (A).
• B ethylenically unsaturated monomer
• R 1 denotes independently of one another hydrogen or methyl.
• R 19 denotes a linear or branched alkyl, cycloalkyl or an aromatic radical having 1 to 40, preferably 1 to 20, advantageously 1 to 8, in particular 1 to 6, carbon atoms, such as, for example, a methyl, ethyl, propyl, iso- Propyl, n-butyl, iso-butyl, t-butyl, cyclopentyl, cyclohexyl or phenyl group.
• cycloaliphatic radicals also include bi-, tri- and polycyclic aliphatic radicals.
• R 20 is a linear or branched, aliphatic or cycloaliphatic radical, such as, for example, a methylene, ethylene, propylene, iso-propylene, n-butylene, iso-butylene, t-butylene or cyclohexylene group or a radical of the general formula
• radical R 22 is 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 -, t-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, for example, a methylene, ethylene, propylene, iso-propylene, n-butylene, iso-butylene -, t-Butylene or cycl
• cycloaliphatic radicals also include bi-, tri- and polycyclic aliphatic radicals.
• the radical R 21 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 or iso -Butylene, t-butylene or cyclohexylene group, or divalent aromatic or heteroaromatic groups derived from benzene, naphthalene, biphenyl, diphenyl ether, diphenyl methane, diphenyldimethyl methane, bisphenone, diphenyl sulfone, quinoline, pyridine, anthracene and phenanthrene.
• cycloaliphatic radicals also include bi-, tri- and polycyclic aliphatic radicals.
• the radical X 1 is in each case independently of one another oxygen, sulfur, an ester group of the general formula (XVb), (XVc),
• radical R 23 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, t-butyl or cyclohexyl group, or monovalent aromatic or heteroaromatic 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, z is an integer between 1 and 1000, advantageously between 1 and 100, in particular between 1
• Monomers (B) which are very particularly preferred according to the invention include (meth) acrylates of the formula (XIV) and di (meth) acrylates of the formula (XV), in particular di (meth) acrylates of the formula (XV).
• Particularly preferred (meth) acrylates of the formula (XIV) include methyl (meth) acrylate and cyclohexyl (meth) acrylate, in particular the methacrylates of the compounds mentioned.
• Particularly preferred di (meth) acrylates of the formula (XV) include ethylene glycol di (meth) acrylate, ethoxylated bisphenol A di (meth) acrylate, in particular
• radical R 1 each independently represents hydrogen or a methyl radical
• composition of the monomer mixtures according to the invention is in principle arbitrary, it 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 can be extremely expedient for the monomer mixture to contain a clear excess of compounds of the formula (I) and (II) or of monomer (A).
• composition of the monomer mixture such that the compound (s) of the formulas (I) and (II) and the at least one monomer (A) mix homogeneously at the desired polymerization temperature, because such Mixtures due to their i. a. low viscosity are easy to handle and can also be polymerized into homogeneous plastics with improved material properties.
• the monomer mixture contains at least 5.0% by weight, preferably at least 20.0% by weight, particularly preferably at least 50.0% by weight, advantageously at least 60.0% by weight , in particular at least 80.0 wt .-%, compounds of formula (I) and (II), each based on the total weight of the monomer mixture.
• the weight fraction of monomer (A) is preferably at least 5.0% by weight, preferably at least 20.0% by weight, particularly preferably at least 40.0% by weight, advantageously at least 50.0% by weight, in particular at least 80.0% by weight, based in each case on the total weight of the monomer mixture.
• the preparation of the monomer mixture to be used according to the invention is obvious to the person skilled in the art. It can be done, for example, by mixing the two monomers (A) and (B) in a manner known per se.
• the monomer mixture is preferably flowable at normal pressure and temperatures in the range from 20.0 ° C to 80.0 ° C.
• flowable is known to the person skilled in the art. It identifies a more or less viscous liquid, which can preferably be poured into various forms and stirred and homogenized using suitable aids.
• Special, flowable compositions in the sense of the invention have dynamic viscosities in the range from 0.1 mPa.s to 10 Pa.s, expediently in the range from 0.65 mPa.s to, in particular at 25 ° C. and at normal pressure (101325 Pa) 1 Pa.s, on.
• a cast monomer mixture has no bubbles, in particular 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 can be obtained by free radical copolymerization of the monomer mixture described above.
• Free radical copolymerization is a well-known process initiated by free radicals, in which a mixture of low-molecular monomers is converted into high-molecular compounds, so-called polymers.
• free radicals in which a mixture of low-molecular monomers is converted into high-molecular compounds, so-called polymers.
• the plastic according to the invention can be obtained by bulk or bulk polymerization of the monomer mixture.
• Bulk or bulk polymerization is understood to mean a polymerization process in which monomers are polymerized without a solvent, so that the polymerization reaction takes place in bulk or in bulk.
• the polymerization can be seen in emulsion (so-called emulsion polymerization) and the polymerization in dispersion (so-called suspension polymerization), in which the organic monomers are suspended in a water phase with protective colloids and / or stabilizers and more or less coarse polymer particles are formed.
• a special form of polymerization in the heterogeneous phase is bead polymerization, which is essentially to be counted as suspension polymerization.
• the polymerization reaction can in principle be triggered in any manner familiar to the person skilled in the art, for example using a radical initiator (e.g. peroxide, azo compound) or by irradiation with UV rays, visible light, rays, ⁇ rays or ⁇ rays, or one Combination of the same.
• a radical initiator e.g. peroxide, azo compound
• UV rays visible light, rays, ⁇ rays or ⁇ rays, or one Combination of the same.
• lipophilic radical polymerization initiators are used to initiate the polymerization.
• the radical polymerization initiators are lipophilic in particular because they dissolve in the mixture of the bulk polymerization.
• compounds which can be used include aliphatic peroxy compounds, such as B.
• tert-amyl peroxy neodecanoate tert-amyl peroxypivalate, tert-butyl peroxypivalate, tert-amyl peroxy-2-ethylhexanoate, tert-butyl peroxy-2-ethyl hexanoate, tert-amyl peroxy-3,5,5, -trimethyl hexanoate, ethyl -3,3-di- (tert-amylperoxy) butyrate, tert-butyl perbenzoate, tert-butyl hydroperoxide, decanoyl peroxide, lauryl peroxide, benzoyl peroxide and any mixtures of the compounds mentioned.
• AIBN is very particularly preferred.
• the polymerization is initiated using known photoinitiators by irradiation with UV rays or the like.
• the common, commercially available compounds such.
• the amount of radical formers can vary widely. For example, amounts in the range from 0.1 to 5.0% by weight, based on the weight of the overall composition, are preferably used. Amounts in the range from 0.1 to 2.0% by weight, in particular amounts in the range from 0.1 to 0.5% by weight, in each case based on the weight of the total composition, are particularly preferred.
• the polymerization temperature to be selected for the polymerization is obvious to the person skilled in the art. It is primarily determined by the initiator chosen and the type of initiation (thermal, by radiation, etc.). It is known that the polymerization temperature can influence the product properties of a polymer.
• polymerization temperatures in the range from 20.0 ° C to 100.0 ° C, advantageously in the range from 20.0 ° C to 80.0 ° C, in particular in the range from 20.0 ° C to 60 , 0 ° C preferred.
• the reaction temperature is preferably increased stepwise during the reaction. Annealing at elevated temperature, for example at 100 ° C. to 150 ° C., towards the end of the reaction has also proven to be expedient.
• the reaction can take place under negative pressure as well as under positive pressure. However, it is preferably carried out at normal pressure.
• the reaction can take place in air as well as under a protective gas atmosphere, preferably as little oxygen as possible being present, since this inhibits a possible polymerization.
• the procedure for producing the highly transparent plastic according to the invention is that a homogeneous mixture of the components monomer mixture, initiator and other additives, such as, for. B. produces lubricant and then fills it between glass plates, the shape of which by later use, e.g. B. as lenses, glasses, prisms or other optical components is predetermined.
• the substance polymerization is initiated by supplying energy, for example by high-energy radiation, in particular using UV light, or by heating, expediently in a water bath and over several hours. In this way, the optical material is obtained in its desired shape as a clear, transparent, colorless, hard plastic.
• lubricants refer to additives for filled plastic compositions, such as molding compositions and injection molding compositions, in order to make the fillers easier to slide and thus to make the molding compositions easier to deform.
• Metal soaps and siloxane combinations are suitable for this. 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, quaternary alkylammonium salts and acidic phosphate esters are described in EP 271839 A, the disclosure of which is explicitly referred to in the context of the present invention.
• a highly transparent plastic with very good optical and mechanical properties is provided.
• DIN 5036 it preferably has a transmission greater than 88.5%, suitably greater 89.0%, preferably greater than 89.5%, in particular greater than 90.0%.
• Refractive index n D of the plastic according to the invention is preferably greater than 1.6.
• ni and n 2 denote the refractive indices of the two media 1 and 2, ⁇ the angle of the light beam to the incident perpendicular in medium 1 and ⁇ the corresponding angle in medium 2.
• the refractive index of a medium is generally dependent on the wavelength of the incident radiation and on the temperature.
• the refractive index data according to the invention therefore relate to the standard data specified in DIN 53491 (standard wavelength of the (yellow) D line of sodium (approx. 589 nm)).
• the plastic preferably has an Abbe number> 36.0, in particular> 37.0, in accordance with DIN 53491.
• the Abbesche number denotes a size VD introduced by E.
• ⁇ F and nc are the refractive indices of the medium for Fraunhofer D, F and C lines.
• a large Abbe number means a low dispersion.
• the person skilled in the literature can obtain further information on the Abbeschen number, for example from the Lexikon der Physik (Walter Greulich (ed.); Lexikon der Physik; Heidelberg; Spektrum, Akademischer Verlag; Volume 1; 1998).
• the plastic has an Abbe number> 38.0, advantageously> 39.0, in particular> 40.0.
• plastics with an Abbe number> 41.0, preferably> 42.0 have proven to be very particularly advantageous.
• plastics with an Abbe number> 43.0, in particular> 44.0 are plastics with an Abbe number> 43.0, in particular> 44.0.
• the Charpy impact strength of the plastic according to the invention is preferably greater than 3.0 kJ / m 2 .
• the plastic according to the invention is advantageously characterized by a high Vicat temperature measured according to ISO 306, so that it retains its excellent mechanical properties, in particular its Charpy impact strength and its hardness, even at temperatures above room temperature.
• the Vicat temperature of the plastic according to the invention, measured according to ISO 30 * 6, is preferably greater than 50 ° C., suitably greater than 60 ° C., in particular greater than 70 ° C.
• the plastic has a Vicat temperature measured according to ISO 306 greater than 140 ° C., preferably greater than 160 ° C., in particular greater than 180 ° C.
• the maximum of the tangent delta of the plastic according to the invention is preferably greater than 50, suitably greater than 60. Possible areas of use for the highly transparent plastic according to the invention are obvious to the person skilled in the art. It is particularly suitable for all applications designed for transparent plastics. Because of its characteristic properties, it is particularly suitable for optical lenses, in particular for ophthalmic lenses.
• the mixture is transferred to a separatory funnel, separated and the lower, aqueous phase is drained off.
• the organic phase is transferred to an Erlenmeyer flask and stirred with Dowex M31 for about 15 minutes, after which the ion exchanger is filtered off.
• the somewhat cloudy to almost clear crude ester solution is now stabilized with 100 ppm HQME and on a rotary evaporator at max. Concentrated at 50 ° C.
• the colorless end product is optionally mixed with 0.5% kieselguhr at room temperature (20-25 ° C) and stirred for about 10 minutes. Then filter through a Seitz filter layer K800 and a 0.45 ⁇ m filter membrane at approx. 1 bar. About 140 g of colorless, clear ester are obtained.
• TMDI position isomer mixture of 2,2,4- and 2,4,4-trimethylhexamethylene diisocyanate (CAS-34992-02-4)
• DABCO position isomer mixture of 2,2,4- and 2,4,4-trimethylhexamethylene diisocyanate
• the viscous casting resin is then poured into a mold and polymerized using 0.2% by weight of AIBN.

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• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
• Macromonomer-Based Addition Polymer (AREA)

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• 2002
  • 2002-11-06 DE DE10252006A patent/DE10252006A1/de not_active Withdrawn
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