TWI279407B - Mixtures for preparing transparent plastics, transparent plastics, and process for their preparation, and use - Google Patents

Abstract

The present invention relates to mixtures for preparing transparent plastics, encompassing (a) a prepolymer prepared from compounds of the formula (I) and (II), where each R1, independently of the others, is hydrogen or a methyl radical, each R2, independently of the others, is a linear or branched, aliphatic or cycloaliphatic radical, or a substituted or unsubstituted aromatic or heteroaromatic radical, and each of m and n, independently of the other, is a whole number greater than or equal to 0, where m+n > 0, and from compounds of the formula (III), or from alkyl dithiols or from polythiols, preferably HS-R3-SH (III) where R3, identical with or different from R2, can be as defined for R2, and (b) at least one monomer (A) capable of free-radical polymerization and having at least 2 methacrylate groups, and (c) aromatic vinyl compounds, such as styrene, and (d) if appropriate, a monomer capable of free-radical polymerization and having at least two terminal olefinic groups whose reactivity differs, and/or (e) if appropriate, at least one monomer (B) from the group of the methacrylates, preferably 2-hydroxyethyl methacrylate.

Description

(1) .1279407 m ^ IX. Description of the Invention [Technical Field of the Invention] The present invention relates to a mixture for preparing a transparent plastic. The present invention further relates to a transparent plastic which can be prepared from a mixture and a process for the preparation thereof. The present invention also relates to the use of transparent plastics for the production of optical (especially ophthalmic) lenses. [Prior Art] Glasses have become a necessary accessory for daily life. Among them, a lens having a plastic lens is particularly important because it is lighter in weight and less susceptible to breakage than a lens for an eyeglass composed of an inorganic material, and can be colored in a suitable dye manner. The production of lenses for plastic spectacles usually uses, for example, thiocarbamate or sulphur-containing (meth) which can be derived from diethylene glycol bis(allyl carbonate) (DAC), having α, ω-terminal type multiple bonds. A highly transparent plastic that is achievable with acrylates. DAC plastics have excellent impact strength and transparency, as well as good processing capabilities. However, the disadvantage is that the relatively low refractive index nD of about 1,500 requires the center and edge of these plastic lenses to be strengthened so that the lens for lenses has a relative thickness and weight. This significantly reduces the comfort of the wearer of the DAC plastic lens. The specification of DE 423 425 1 discloses the capture of sulfur-containing polymethacrylates via free radical copolymerization of monomer mixtures consisting of compounds of formula (1) and (2) 8 -5- (2) 1279407

(2) wherein Y is an unbranched or branched alicyclic or cyclic alkyl group having from 2 to 12 carbon atoms, or an aryl group having from 6 to 14 carbon atoms or having from 7 to 20 carbons An alkaryl group of an atom, and the carbon chain may be interrupted by one or more ether or thioether groups. R is hydrogen or methyl, and η is an integer ranging from 1 to 6. According to DE 4234251, the monomers of the formulae (1) and (2) generally have a molar ratio of from 1:0.5 to 0.5:1. A monomer mixture is prepared by reacting at least 2 moles of (meth)acrylofluorene chloride or (meth)acrylic anhydride with 1 mole of dithiol by means of (meth)acryloyl hydrazine in an inert organic solvent Chlorine or (meth)acrylic anhydride is reacted with a dithiol in an aqueous alkaline solution. Suitable for the solvent methyl tert-butyl ether, toluene and xylene, the dielectric constant of these monomers at 20 ° C is 2.6, 2.4 and respectively from 2.3 to 2.6 DE in DE 42 3 425 1 The plastic is colorless, rigid and slightly brittle, and has a high refractive index nr) ranging from 1.602 to 1.608. The Abbe number is from 35 to 38. These plastics are therefore only limited in their ability to be used with special lenses for glasses. This specification also does not provide any information on the glass transition temperature of the plastic. -6 - 1279407 (3) • WO 0 3 /0 1 1 92 5 The specification describes the polymerization of thiomethacrylate and polyethylene-diol derivatives. The resulting plastic can be used, for example, to produce an optical 'lens. The disadvantages of these lenses are their mechanical properties. In particular, for example, the impact strength is not sufficient for many needs. SUMMARY OF THE INVENTION In accordance with the prior art, it is therefore an object of the present invention to provide a mixture for the preparation of a transparent plastic which is suitable as a material for an optical lens wherein the plastic has desirable mechanical properties (especially high impact strength) and high refraction. The rate (more preferably greater than 1.59) and the largest yawbike number (more preferably greater than 36). In particular, it should be possible to produce lenses for plastic glasses with low dispersion and no coloration at the edges. The present invention is also primarily directed to providing a raw material composition for the preparation of highly transparent plastics having improved mechanical properties, even at temperatures above room temperature. In particular, the glass transition temperature of the plastic of the present invention should be φ to a maximum of greater than 8 0.0. (: Preferably. Therefore, the object of the present invention is to provide a highly transparent plastic which can be prepared from a raw material composition in a simple manner, industrial specifications and at a low cost. In particular, 'via at atmospheric pressure and from 20.0 to 80.0 ° C The plastic can be obtained by free radical polymerization of the flowing mixture at a range of temperatures. _ Another object of the present invention is to provide a type of application and possible use of the highly transparent plastic of the present invention. A mixture of all the features of the first item of the scope achieves these objectives, and also achieves other purposes for the discussion of the content discussed in the introduction, -7-(4) 1279407 - although not explicitly stated. Mixing the invention ^ The advantageous improvement of the object is protected by the scope of the patent application of the scope of claim 1 of the patent application. The subject matter of the other application is a highly transparent plastic obtainable from the mixture of the present invention, and its preparation is also proposed. Method. The use of the high-transparency plastic of the present invention is protected by the application patent scope. Another product application patent scope description package Optical (preferably ophthalmic) lens comprising the highly transparent plastic of the present invention. [Embodiment] The mixture of the present invention comprises: a compound of the formula (I) and (II)

0)

(wherein each R1 is independently hydrogen or methyl, and each R2 is independently of one another a straight or branched aliphatic or cycloaliphatic group, or a substituted or unsubstituted aromatic or heteroaromatic group, And each m and η are independently of each other an integer greater than 〇 or equal to 0, wherein m + n > 〇) and a pre-polymerized by a dithiol or a polythiol (preferably a compound of the formula (111)) , HS-R3-SH (III ) (5) '1279407 , wherein R3 may be the same or different from the definition of R2, b) at least one capable of free radical polymerization and having at least 2 methacrylate groups Monomer (A), and c) an aromatic vinyl compound suitable for the preparation of transparent plastics having excellent mechanical and optical properties. If appropriate, the mixture may comprise: φ d ) a monomer capable of free radical polymerization and having at least 2 terminal olefin groups which are not reactive, for example, having a methacrylate end group and a vinyl terminal group The functional monomer, and/or e) at least one ethylenically unsaturated monomer (B), preferably from the methacrylate, is particularly preferably 2-hydroxyethyl methacrylate. The transparent plastic of the present invention has a combination of previously unknown special characteristics such as high refractive index, elegant ratio, good impact strength and also high glass transition temperature. The corresponding lens for plastic glasses has a low dispersion; no φ is found to be colored on the edge. The transparent plastic of the present invention also has more advantages. These advantages are: = > Since the plastic of the present invention has a high refractive index, there is no need for any reinforcement and thus a thickening of the center and edge of the lens for the corresponding plastic spectacles, and since the weight is relatively light, it is markedly increased. The wearer's comfort is provided by these glasses. = > The lens of the corresponding plastic glasses is protected from the "life risk" by the very good impact strength of the plastic of the present invention. Particularly in the case of a thin lens for glasses, it is highly unlikely that mechanical damage will cause damage or irreparable damage. -9 - (6) 1279407 = > The highly transparent plastic of the present invention has a high glass transition temperature, preferably greater than 80.0 ° C, and thus retains its special mechanical properties up to this temperature, particularly high impact strength. And its hardness. = > The high aspect of the invention can be prepared in a simple manner, in an industrial form, and at a low cost by free radical copolymerization, preferably via a monomer mixture flowable at atmospheric pressure and at a temperature ranging from 20.0 to 80.0 °C. Transparency plastic. = > The following monomer mixture can be prepared in a simple manner, in an industrial form, and at a low cost. The prepolymer of the present invention comprises the compounds of formula (I) and (11) and (111):

(I)

Hs-r3-sh (III) (Η),

Rl is independently hydrogen or methyl, preferably methyl; and §-R2 are independently of each other, straight or branched aliphatic or cycloaliphatic '^ @ $ or unsubstituted aromatic or hetero An aromatic group, wherein a preferred R 2 group may contain from 1 to 100 carbon atoms, particularly from 1 to 20, and -10 (7) Ί 279407 g for each r3 linear or branched fat of R2 a family or cyclic aliphatic 矣S ' or a substituted or unsubstituted aromatic or heteroaromatic group, wherein a preferred R3 group may contain from i to one carbon atom, particularly from i to 2 〇 . & Examples illustrate preferred linear or branched aliphatic or cycloaliphatic methyl, ethylene, propylene, isopropylene, n-butyl, isobutyl, tertylene or cyclohexene . Preferred among the preferred divalent aromatic or heteroaromatic groups are derived from benzene, naphthalene, biphenyl, diphenyl ether, diphenylmethane, diphenyldimethylmethane, bisphenol ketone, diphenyl hydrazine, Quinoline, pyridine, fluorene and phenanthrene. For the purposes of the present invention, wherein the cycloaliphatic group also contains a di-, tri-, and polycyclic aliphatic group, the R2 or R3 group also includes a group of the formula

(la), wherein each R4 is independently of one another a straight or branched aliphatic or cycloaliphatic group, for example, methyl, ethylene, propylene, isopropene, n-butyl, isobutyl, tert Support or cyclohexene. Each of the X groups is independently of each other oxygen or sulfur, and the R5 group is a linear or branched aliphatic or cycloaliphatic group 'for example, methyl, ethylene, propylene, isopropylene, n-butyl, isobutyl Support, special support or cyclohexene. For the purposes of the present invention, the cycloaliphatic group also contains di-, tri- and polycyclic aliphatic groups. Y is an integer from 1 to 1 ,, especially 1, 2, 3 or 4. -11 - (8) 1279407 The preferred formula (I a ) group comprises:

The φ r2 group is preferably an aliphatic group having from 1 to 10 carbon atoms, and preferably a linear aliphatic group having from 2 to 8 carbon atoms. Each of the indices m and η is independent of each other by an integer greater than or equal to 〇, such as 〇, 1, 2, 3, 4, 5 or 6. among them! The sum of 11 + 11 is greater than 0, preferably in the range from 1 to 6, and is advantageously in the range from 1 to 4, particularly 1, 2 or 3. For the preparation of the prepolymers, it is possible to use each of the compounds of the formulae (I) and (II) individually and also each of the compounds of the formula (III), φ or additionally two or more of the formulae (I), (II) And a mixture of the various compounds of formula (III). The relative proportions of the compounds of the formulae (I), (II) and (m) in the monomer mixture of the invention can be substantially as desired, and the ratio of the properties of the plastic of the invention can be advantageously used, Suitable, as required by the application. By way of example, a very advantageous monomer mixture may comprise a significant excess of the compound (class) or formula of formula (I) based on the total amount of the compounds of formula (1), (11) and (III) in each case. (II) a compound (class) or a compound of the formula (类). -12- (9) (9) 1279407 However, it is particularly advantageous for the purposes of the present invention that the mixture comprises more than 10 mol% based on the total amount of the compounds of formula (I) and (II). The compound of formula (II) with + n = 2 is preferably more than 12 mol%, especially more than 14 mol%. If R2 is an ethylene group, the weight ratio of the compound of the formula (II) wherein m + n = 2 in the mixture exceeds 丨〇%, especially more than 15%. Moreover, it is particularly advantageous according to the invention to use a compound of formula (II) wherein m + n = 3 in excess of 5.8 mol% based on the total amount of the compound of formula (n and (II) to exceed 6.5 Molar% is more advantageous, in particular more than 7.5 mol%. If R2 is an ethylene group, it corresponds to a weight ratio of formula (II) wherein at least 6% of m + n = 3. Formula (I) The ratio is preferably from 0.1 to 50.0 mol% based on the total amount of the compounds of the formulae (I) and (II), and is more preferably from 1 〇. to 45.0 mol%, particularly from 20,000 to If the R2 is an ethylene group, the compound of the formula (I) is from 15 to 40%, which corresponds to a preferred weight range for preparation, wherein m + n = 1 of the compound of the formula (II) The ratio is preferably from 1 to 40.0 mol% based on the total amount of the compounds of the formulae (I) and (II), and is preferably from 5 to 35.0 mol%, particularly from 1 3 to 3 0.0 mol. %. If R2 is an ethylene group, it corresponds to a preferred weight ratio of from 10 to 45 wt% of the compound of formula (II) wherein m + n = l. wherein m + n > Compound ratio Preferably, it is greater than 〇mol% based on the total amount of the compounds of formula (I) and (II), more preferably greater than 1 mol%, especially more than 2 mol%. If R2 is methylene, Then in the mixture, the weight ratio of the compound of the formula (II) wherein m + n>3 exceeds -13 - (10) • 1279407 2%, especially more than 5%. The proportion of the compound of the formula (ΠΙ) in the prepolymer It is preferably from 1 to 55.0 mol% based on the total amount of the compounds of the formulae (I), (II) and (III), particularly from 1 〇.〇 to 50.0 mol%. In special cases. In the case where R3 is a dinonyldioxaoctyl group, the weight ratio of the formula (ΠΙ) based on the total amount of the compounds of the formulae (I), (II) and (III) in the prepolymer exceeds 0.5%, preferably more than 5%. The method for preparing the compounds of the formula () and (Π) is known to the skilled person, for example, from DE 42342 5 1, the disclosure of which is incorporated herein by reference. However, for the purposes of the present invention, it has proven to be very particularly advantageous to pass from 丨.〇 to <2 · 〇莫耳(from 丨.丨 to i · 8 摩尔) Good 'from 1.2 to 1.6 mole advantageously, particularly compounds based Dae ear from 1.2 to 1.5) is at least one of formula (IV)

(IV) with at least one polythiol of formula (V) m/S, j^S, M (7) (wherein X-based halogen, especially chlorine or bromine), or phenyl-14- (11) 1279407

Rl

Ο A method of reacting a mixture of compounds of formula (I) and (II). The method of the formula (IV) comprises, for example, propyl chlorobenzene, methacrylic chlorohydrin, acrylic anhydride and methacrylic anhydride, with particular preference to the use of acrylic anhydride, methacrylic anhydride or a mixture of the two. Each of the oximes independently represents hydrogen or a metal cation. Preferred metal cations are derived from elements having an anion of less than 2.0, and are advantageously less than 1>5, with particular preference to alkali metal cations (especially Na+, K+, Rb+, +) and alkaline earth metal cations (especially Mg2+, Ca2+). , Sr2+, Ba2+彡. The metal cations Na + and K + can be used to achieve very particularly advantageous results. The polythiol of formula (V) which is particularly suitable for the present invention comprises 1,2-ethanedithiol, 1,2 - propane dithiol, 1,3-propane dithiol, l52-butane dithiol, 1:3, butane dithiol, 1,4-butane dithiol, 2·methylpropane丨? ^ -- Mercaptan, 2-methylpropane-1,3-dithiol, 3,6-dioxa-1,8-octyl dithiol (didecyldioxooctane = DMDO Ethylcyclohexyldithiol, o-(indolyl)benzene, m-bis(S-methyl)benzene, p-bis (obtained via 4-vinylcyclohexan and bisulfite)酼methyl)benzene, compound of formula (V)-15- (12) (12)1279407

Each of the R4 systems is independently of one another a straight or branched aliphatic or cycloaliphatic group, for example, methyl, ethylene, propylene, isopropylene, n-butyl, isobutyl, tertylene or cyclohexene. Support base. For the purposes of the present invention, the cycloaliphatic group also contains di-, tri- and polycyclic aliphatic groups. Each of the X groups is independently of each other oxygen or sulfur, and the R5 group is a linear or branched aliphatic or cycloaliphatic group such as methyl, ethylene, propylene, isopropylene, n-butyl, isobutylene. , special support or cyclohexyl. For the purposes of the present invention, the cycloaliphatic-16-(13)(13)1279407 group also contains a di-, tri- and polycyclic aliphatic group. y is an integer from 1 to 10 'special system 1, 2, 3 or 4. Preferred compounds of formula (Va) comprise: f 9 For the purposes of a particularly preferred embodiment of the invention, the compound of formula (V) used comprises 1,2-ethanedithiol. This method reacts a compound of the formula (IV) in at least one inert organic solvent S with a compound of the formula (V) in an aqueous alkaline solution, and the term "inert organic solvent" is used under the respective reaction conditions. An organic solvent that does not react with a compound present in the reaction system. Preferably, at least one of the solvents S has a relative dielectric constant of > 2.6, preferably > 3.0, more preferably > 4.0, especially > 5.0, and each case is measured at 20 °C. Herein, the relative dielectric constant represents a dimensionless enthalpy, which illustrates the capacitance C of a capacitor located in a vacuum when a substance having a dielectric property (known as a dielectric) is introduced between the metal plates (theoretical 値Increase the multiple. The tether was measured at 20 ° C and extrapolated to a low frequency (ω 0 ). For more details, refer to the familiar technical literature, especially Ullmann Encyklopadie der technischen Chemie [Uman's Encyclopedia of Industrial Chemistry] 2 /1 A nwendu 11 g physikalischer und -17- • 1279407 • (14) - Physikalisch- chemise her Methoden im Laboratorium [Application of physical and physical chemistry in the laboratory], Title: • Dielektrizitatskonstante [Dielectric constant], pp. 455-479. For example, in the Baco Raton, Ann Arbor, CRC Press, 71 edition (1990-1991), Chemistry and Physics Handbook, pages 8-44, 8-46 and 9-9 to 9-12, provide solvent. Dielectric 値. Further, for the purpose of the method, it is particularly advantageous to form a two-phase and a solvent and an aqueous solution which are not uniformly mixed during the reaction. Finally, the water-soluble lanthanide of the solvent measured at 20 ° C is preferably less than 1 〇g of water based on 100 gram of solvent. Preferred solvent S according to the invention comprises: an aliphatic ether such as diethyl ether (4·335), dipropyl ether, diisopropyl ether 9-cycloaliphatic ether, such as tetrahydrofuran (7·6); aliphatic Ester, such as methyl formate (8 · 5), ethyl formate, propionate propyl ester, 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 · 0) 2), methyl salicylate, ethyl salicylate, phenyl acetate (5 · 2 3 ); ^ aliphatic ketones, such as acetone, methyl ethyl ketone (18.5), 2-pentanone (15.4), 3-pentanone (17·〇), methyl isoamyl ketone, methyl isobutyl ketone (13.1) aromatic ketone, such as acetophenone; -18- (15) 1279407 • nitroaromatics, such as nitrobenzene, o-nitride Toluene (27.4), meta-nitrate, toluene (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), morpholine, iso-II-quinoline; and mixtures of these compounds, the data in parentheses are divided into two at 25 °C. The dielectric constant is related to the data. The compounds which are very particularly suitable for the purposes of the present invention are aliphatic esters and cycloaliphatic ethers, in particular ethyl acetate and tetrahydrofuran. For the purpose of the process of the invention, it is possible to use solvent S alone or in addition to a solvent mixture, in which case it is not necessary to match all of the solvents present in the mixture with the above mentioned dielectric standards. According to the invention, it is also possible to use a mixture of tetrahydrofuran/cyclohexane as an example. However, a solvent mixture which has proven to be advantageous has a relative dielectric constant of > 2.6, preferably φ > 3.0, more advantageously > 4.0, especially > 5.0, in each case 2 (TC measurement. A solvent mixture comprising only a solvent having a relative dielectric constant > 2.6 can achieve particularly advantageous results, preferably > 3.0, more advantageously > 4.0, especially > 5.0, in each case 20 ° C The alkaline aqueous solution of the compound of the formula (V) comprises from 1.1 to 1.5 equivalents of at least one Bronsted base based on the total amount of the compound of the formula (IV). For the purposes of the present invention, Preferred brunite bases comprise alkali metal hydroxides and alkaline earth metal hydroxides, especially sodium hydroxide and potassium hydroxide. -19- (16) (16) Ί 279407 can basically be carried out using any conceivable method. The reaction can be illustrated by way of example. The compound of formula (IV) can be formed into a preliminary charge in a solvent (mixture) S, and an aqueous test solution of the compound of formula (V) can be added stepwise or continuously. However, for the purposes of the present invention, Proven to be very special The compound of the formula (IV) in at least one inert organic solvent S and the compound of the formula (V) in an aqueous alkaline solution are simultaneously metered into the reaction vessel. The reaction temperature can be widely used. Change, but the temperature is usually in the range from 2 0.0 to 120.0 ° C, preferably in the range from 20.0 to 80. CTC. The same applies to the pressure at which the reaction is completed. The reaction can therefore occur at or under atmospheric pressure or Under superatmospheric pressure, however, it is preferably carried out under atmospheric pressure. Although the reaction can also take place in the air, for the purposes of the present invention, it has proven to be very particularly advantageous to carry out the reaction under inert gas with nitrogen. Preferably, argon is preferably present in a very small proportion. The reaction mixture is preferably reacted with brunite base in a further step, preferably until an aqueous solution at 20 ° C. When the pH is less than 7.5, it is advantageous to be less than 6.0, especially less than 5.00. The acid used herein includes inorganic acids (such as hydrochloric acid, sulfuric acid, phosphoric acid), organic acids (such as acetic acid, propionic acid). And acidic ion exchangers (especially acidic synthetic resin ion exchangers, for example, ® Dowex M-31 ( Η )). Very successful methods have been proven to use at least 1 gram of dry ion exchanger. An acidic synthetic resin ion exchanger containing Η-equivalent Η + ions (at least 2.0 equivalents, particularly at least 4. 〇 milliequivalents) having from -20-(17) •1279407 1 〇 to 5 0 The particle size of the mesh and the porosity in the range of from 10 to 50% based on the total volume of the ion exchanger. In a process advantageous for the separation of the compounds of the formula (I) and (II), the organic phase consisting of the solvent S is separated, washed and dried as appropriate, and the solvent is evaporated. During the reaction of the compound of the formula (IV) with the compound of the formula (V), it is possible to add an inhibitor which inhibits the radical polymerization of the (meth)acrylic group during the reaction. Those skilled in the art are familiar with these inhibitors. Mainly 1,4-dihydroxybenzene is used. However, it is also possible to use dihydroxybenzene having other substitutions. Generally, the formula (VI) can represent these inhibitors r7o

(VI),

Wherein R6 is a linear or branched alkyl group having from 1 to 8 carbon atoms, a halogen or an aryl group, preferably having an alkyl group of from 1 to 4 carbon atoms, and a methyl group, an ethyl group, a n-propyl group. , isopropyl, n-butyl, isobutyl, t-butyl, tert-butyl, Cl, F or Br are particularly preferred;

The lanthanide is an integer ranging from 1 to 4, preferably 1 or 2; and R7 is hydrogen, a linear or branched alkyl or aryl group having from 1 to 8 carbon atoms, having from 1 to 4 The alkyl group of the carbon atom is preferably a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a second butyl group or a tert- 21 - (18) 1279407 group. However, it is also possible to use a compound in which the parent compound is 1,4-benzoquinone. These compounds can be illustrated by formula (VII): 〇 ==/ \==〇 (VII) R〇 wherein R6 and oxime are as defined above. Phenols of the general structure (VIII) are also used.

• wherein R8 is a linear or branched alkyl, aryl or aralkyl group having from 1 to 8 carbon atoms, a propionate having a mono- to tetrahydric alcohol, which may also include a hetero atom such as S, 0 and N, preferably having an alkyl group of from 1 to 4 carbon atoms, with methyl, ethyl, n-propyl 'isopropyl, n-butyl, isobutyl, t-butyl, tert-butyl The base is especially good. A hindered phenol based on the three-till derivative of formula (IX) represents another advantageous substance class: -22- •1279407 ' (19)

Where R10 = CpH2p+i; where p = 1 or 2. Particularly successful compounds are 1,4-dihydroxybenzene, 4-methoxyphenol, 2,5-dichloro-3,6-dihydroxy-1,4-benzoquinone, 1,3,5-three Methyl-2,4,6-gin (3,5-di-tert-butyl-4-hydroxybenzyl)benzene, 2,6-di-tert-butyl-4-methylphenol, 2,4-di Methyl-6-tert-butylphenol, 2,2-bis[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl-1-oxypropoxymethyl]-1, 3-propane diester, 2,2'-thiodiethyl bis[3-(3,5-di-tert-butyl-4.hydroxyphenyl)propionate], 3-(3,5-di-te) Octadecyl butyl-4-hydroxyphenyl)propionate, 3,5-bis( " 1,1-dimethylethyl-2,2'-methylenebis(4-methyl-6- Tert-butyl)phenol, ginseng-(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-s-three-plowing - 2,4,6-( 11^3}1,511 a triketone, ginseng (3,5-di-tert-butyl-4-hydroxy)-3-tris-2,4,6-(1}1,3:9,5:9)trione or tert-butyl -3,5-dihydroxybenzene. The ratio of inhibitors, either alone or in a mixture, is usually from 0. 0 1 to 0 · 50 weight based on the weight of the mixture. %, preferably - the concentration of the inhibitor selected in this way is not impaired DIN 5 5945. Many of these inhibitors are commercially available. ' For the purposes of the present invention, the mixture also comprises a prepolymer prepared from a compound of formula (I), (1〇 and (III), at least A monomer capable of radical polymerization and having at least two terminal methacrylates (A) 〇 φ. Examples of these di(meth) acrylates are polyoxymethylene-(meth)acrylic acid derivatives and polyoxypropylene. a (meth)acrylic acid derivative, for example, triethylene glycol (meth) acrylate, tetraethylene glycol (meth) acrylate, tetrapropylene glycol (meth) acrylate; and also 4-butane Diol (meth) acrylate, diethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tripropylene glycol di (methyl) Acrylate, tetraethylene glycol di(meth)acrylate, tetrapropylene glycol di(meth)acrylate, polyethylene glycol bis(meth) acrylate (having a range from 200 to 5,000,000 g/mole) The weight average molar amount is preferably from 200 to 25000 g/ The ear is in a favorable range, in particular from 200 to 1 gram/mole, and polypropylene glycol di(meth)acrylate (having a weight average molar amount ranging from 200 to 5,000,000 g/mole) Preferably, from 250 to 4000 g/mole is advantageous, especially from 25 to 100 g/mole, 2,2'-thiodiethanol (meth) acrylate (thio Diethylene glycol di(meth)acrylate), 3,9-bis(methyl)propenyloxymethyltricyclo[5.2.1.0 ( 2.6)]-nonane, especially -24- (21) 1279407

3,8-bis(methyl)propenyloxymethyltricyclo[5.2.1.0(2.6)]-nonane, 4,8-di(methyl)propenyloxymethyltricyclo[5·2 ·1·0(2·6 )]-decane, 4,9-di(methyl)propenyloxymethyltricyclo[5·2·1.0( 2.6 )]-decane, ethoxylated double Phenolphthalein di(meth)acrylate, special

Wherein s and t are integers greater than 0 or equal to 0, and the sum of s and t is preferably in the range from 1 to 30, in particular from 2 to 10, and from the diisocyanate to 2 equivalents ( Di(meth)acrylate obtainable by reaction of hydroxyalkyl methacrylate, especially -25-1 (22) 1279407

Wherein each R1] is independently hydrogen or methyl; tris(methyl)propanate hydrazide such as dimethylolpropane tri(meth) acrylate and glycerol tri(meth) acrylate; or Ethoxylated or propoxylated glycerol, trimethoprim or (meth) propionate of other alcohols having more than 2 hydroxyl groups

It has been confirmed that the bis(meth) acrylate of the formula (XI) is particularly successful as a monomer (Α):

Each of the R12 systems is independently hydrogen or methyl, representing a

Up to 1 carbon atom (preferably from 丨 to 40 carbon atoms, from 1 to 2 较佳 preferably 'from 1 to 8 is more favorable, especially from 】 to 6) straight -26- (23 1279407 • A chain or branched alkyl or cycloalkyl or aryl group, for example, methyl, ethyl-, isopropyl, n-butyl, isobutyl, tert-butyl, cyclopentyl, benzene, For the purposes of the invention, cycloaliphatic: * di-, tri- and polycyclic aliphatic groups. It is particularly preferred to have from 1 to 6 carbon chains or branched alkyl groups or cycloalkyl groups as RlS. The R13 group is a linear or branched aliphatic or cycloaliphatic methyl, ethylene, propylene, isopropylene, n-butyl, isobutylene, Φ or cyclohexylene group, or a base of the following formula (Xla) wherein R15 is a linear or branched aliphatic or cycloaliphatic group, or an unsubstituted aromatic or heteroaromatic group, for example, methyl, ethyl, isopropene, n-butyl, isobutyl Propylene, tertylene or cyclohexene from benzene, naphthalene, biphenyl, diphenyl ether, diphenylmethane, diphenyl φ methane, bisphenol ketone, diphenyl hydrazine, quinoline, pyridine, hydrazine or phenanthrene Family or heteroaromatic group. For the purposes of the present invention, the cycloaliphatic comprises di-, tri- and polycyclic aliphatic groups. Each R14 group is a linear or branched aliphatic or cycloaliphatic group, or a substituted or aromatic or heteroaromatic group, for example, methyl, ethylene, propylene, n-butyl, isobutylene , tertylene or cyclohexylene, or derivatized, biphenyl, diphenyl ether, diphenylmethane, diphenyldimethyl ketone, diphenyl maple, quinoline, pyridine, hydrazine or phenanthrene Valence aromatic group. For the purposes of the present invention, the cycloaliphatic group is also a tri- and polycyclic aliphatic group. Each of the X1 groups independently of each other is a -27-yl group, a propylcyclohexyl group or S also preferably contains an atom, such as a dibutyl group or a substituted phenyl group, a propylene group, or a divalent dimethyl group. Aromatic aliphatic groups are also independent of each other, unsubstituted isophthalic, self-benzene, decalin, bisphenol or heteroaromatic I containing two... oxygen, sulfur,

(24) 1279407 Ester ester group of formula (Xlb), (XIc): 0 II —〇—c—(Xlb) —(!]—〇—(XIc) (Xld), (Xle), (Xlf Or (Xlg) di-OH II ! - 0 - C - N - (Xld) 〒 - C - 0 - (Xle) 〇 R16 (Xlf) II 1 - 0 - C - N - r16o (Xig) ~ N - ·C_O— General formula (Xlh carboxylic acid ester group: (Xli (Xlj) or (Xlk) thioamine (25) ^ 1279407 (Xlh) (Xli) (xij) (XVk) Ο Η

Li I —s—c—Ν—?—Ν—C—S—? f—S—C—N—16—N—C—S—

Dithiocarbamate group of the formula (XII), (Xlm), (XIn) or (XIo): (XII) S Η

II I —s—c—Ν—H S I II —N—C—S—

—S—C—N—(Xlm) (XIn) (XI〇) ff or a thiocarbamate group of the formula (xip), (Xlq), (XIr) or (XIs): -29- * 1279407 • (26)

(Xlp) (Xlq) (Xlr) (Xls) /Φ.w 13⁄4 'where R1 6 is a linear or branched aliphatic or cyclic aliphatic 矣S $ substituted or unsubstituted aromatic or heteroaromatic Base, for example, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl or cyclohexyl' or derived from benzene, naphthalene, biphenyl, diphenyl ether, diphenylmethane a monovalent aromatic or heteroaromatic group of diphenyldimethylmethane, bisphenol ketone, diphenyl hydrazine, quinoline, pyridine, hydrazine or hydrazine. For the purposes of the present invention, the cycloaliphatic group also contains di-, tri- and polycyclic aliphatic groups. The Z series is an integer from 1 to 1000, and is advantageously from 1 to 100, particularly from 1 to 25. Particularly preferred (meth) acrylate of formula (XI) comprises ethylene glycol di(meth)acrylate, ethoxylated bisphenol A di(meth)acrylic acid > ester, especially

(27) 1279407 where s and t are integers greater than 0 or equal to 0, and the sum of s and t is preferably from 1 t to 〇, particularly from 2 to 10 in range, and via $ = isocyanate 2 equivalents of hydroxyalkyl (meth) acrylate can be obtained by % @ (meth) acrylate, especially

• /, Zhongmu~R17 are independent of each other as hydrogen or methyl, 3,8_di(methyl) oxa methoxymethyl tricyclic [5·2·1·〇(2·6) ]_ Decane, 3,9·di(methyl vaporcanoxymethyl tricyclo[5·2·1·〇(2·6)]-decane, bismuth di(methyl) & Oxymethyltricyclo[5·2·1·〇(2.6)]-nonane, 4,9-di(methyl, y-), dilute oxymethylbicyclo[5.2.1.0 ( 2.6) ] · brothel, thio-ethylene glycol di(meth)acrylate (having a weight average from 200 to i gram / #马 range) and / or polyethylene glycol II (A Acrylate (having a weight average from 200 to 1 000 g/mole). Use polyethylene glycol dimethacrylate (having from 200 to 1 gram per gram) The average weight of the ear is in the range of -31 - (28) (28) 1279407. A very particularly advantageous result is achieved. The ratio of monomer (A) is based on all monomers used in the mixture. From 2 to 50% by weight, in particular from 1 to 30% by weight. / For the purposes of the present invention, the mixture is also a prepolymer comprising a compound of the formula (j), (Π) and (III), at least one monomer capable of radically polymerizing (A) and an aromatic vinyl compound. Among the aromatic vinyl compounds, Preference is given to using styrene, substituted styrenes having an alkyl substituent in the side chain (for example, α-methylphenethyl and α-ethylstyrene), substituted styrenes having an alkyl substituent on the ring. (for example, vinyl toluene and p-methylstyrene), halogenated styrene (such as monochlorostyrene, dichlorostyrene, tribromostyrene, and tetrabromostyrene); Classes such as 1,2-divinylbenzene, 1,3-divinylbenzene, 1,4-divinylbenzene, anthracene, 2-diisopropenylbenzene, 1,3-diisopropenylbenzene And 1,4-diisopropyl pyridylbenzene. The proportion of the aromatic vinyl compound is a compound of the formula (Ϊ), (Π) and (111) used in the prepolymer, and a monomer capable of radical polymerization. (A), the total amount of the aromatic vinyl compound and other monomers optionally selected is from 5 to 40% by weight based on the total amount, from 1 3 to 30% by weight. Preferably, it is particularly preferred from 15 to 25% by weight. Surprisingly, the addition of the monomer (A) and the aromatic vinyl compound improves the mechanical properties of the plastic material of the present invention without adversely affecting its optical properties. Advantageous optical property effects are found in many examples. According to a particular aspect of the invention, there may be the presence of a compound of the formula (X Π ) (asymmetric crosslinker) to have a linear structure and a different -32- 0 ( 29) • 1279407 The chain length of the molecule is better:

(XII), wherein the R19 group is independently a hydrogen atom, a fluorine atom and/or a methyl group, and the R18 group is a linking group to preferably contain from 1 to 1 carbon atoms, particularly from 2 至 to 100 And a Y-based bond or a linking group having from 1 to 1 carbon atom, particularly preferably from 1 to 1 carbon atoms, and preferably from 1 to 100 carbon atoms. The length of the molecule can vary depending on the molecular component R18. The compound of the formula (XII) has a terminal (meth) acrylate functional group at one terminal end and a terminal group other than the methacrylate functional group at the other terminal. Preferred among them are a γ group-specific bond (vinyl group), a ch2 group (allyl group), and also an aliphatic or aromatic group having from 1 to 20 carbon atoms, for example, a group derived from benzene, to include The urethane-based fat φ is particularly preferred as an aliphatic or aromatic group. The R18 group is preferably a linear or branched aliphatic or cycloaliphatic group, such as methyl, ethylene, propylene, isopropylene, n-butylene, isobutylene, tertylene or cyclohexylene. Or a radical or branched aliphatic or cycloaliphatic radical of the R21 radical of the formula: or substituted by an unsubstituted aromatic or heteroaromatic radical, for example, methyl, ethylene, or propyl support

'Isobutylene, n-butylene, isobutylene, tertylene or cyclohexylene, or derivative-33- (30) • 1279407 - from benzene, naphthalene, biphenyl, diphenyl ether, di-based A divalent aromatic or heteroaromatic group of formazan, diphenyl dimethyl, ketone, diacid ketone, diphenyl hydrazine, hydrazine, hydrazine, hydrazine or phenanthrene. For the purposes of the present invention, the cycloaliphatic group also contains a di-, tri- and polycyclic aliphatic group. Each of the R2G radicals is independently of a straight or branched bond aliphatic or anthraquinone aliphatic group or a substituted or unsubstituted aromatic or heteroaromatic group, for example, methyl, ethylene, propylene, or different Propylene, n-butylene, isobutylene, tertylene or cyclohexylene, or derived from benzene, Cai, Lianben, an acid, a base, a phenyldimethylformamidine, A divalent aromatic or heteroaromatic group of diindolone, diphenylanthracene, quinoline, pyridine, indole or phenanthrene. For the purposes of the present invention, the cycloaliphatic group also contains a di-, di- and polycyclic aliphatic group. Each of the X1 groups is independently of each other, oxygen, sulfur, an ester group of the formula (Xllb), (XIIc)·· _ · "〇-1

(Xllb) (XIIc) Amine of the formula (Xlld) (Xlle xnf) or (xiig)-34- (31)1279407 OH -0-(i-N-(Xlld) π (Xlle) ? f -〇-C N-f? __ -N-C-O- (XHf) (Xiig) General formula (Xllh) urethane group: ΧΙΠ) (Xllj) or (Xllk) sulfur OH II I -S-C N - (Xllh) Η 0 } lj - N - C - S - (XHi) 0 I^2 II I - s - c - N - (Xllj) f? - N - C - S - (Xllk) , (Xllm), (Xlln) or formula (XIII) thiocarbamate-35 - (32)1279407

—S—C—N—(XIII)—N—(J—S—(Xllm) ff—S—C—N—“(XI In) fl—N—C—S—(Xllo) or Formula (XIIp) a thiocarbamate group of (Xllq), (Xllr) or (XIIs)

(Xiip) (XHq) (XHr) (XIIs) is preferably oxygen, wherein R22 is a linear or branched aliphatic or cycloaliphatic group, or a substituted or unsubstituted aromatic or heteroaromatic group, For example, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl or cyclohexyl, or derived from benzene, naphthalene, biphenyl, diphenyl ether, diphenylmethane, two Phenyldimethylmethane, bisphenol ketone, diphenyl hydrazine, hydrazine, pyridinium, hydrazine or -36- (33) 1279407 phenanthrene monovalent aromatic or heteroaromatic group. For the purposes of the present invention, the cycloaliphatic group also contains di-, tri- and polycyclic aliphatic groups. The Z series is an integer from 1 to 1 000, and is advantageously from 1 to 1 , especially from 1 to 25. In a particularly preferred embodiment of formula (XII), the compounds comprise those compounds of formula (XIII)

Each of the R23 and R24 groups is independently hydrogen or methyl, and the r25 φ group is a linear or branched aliphatic or cycloaliphatic divalent group, or a substituted or substituted aromatic or heteroaromatic group. Divalent base. The preferred base has been described above. The length of the chain can be influenced by the amount of different polyalkylene oxide hydroxy units (in terms of polyethylene glycol units & amps). The compounds of the formulae (XIII) and (XIV) which have proven to be particularly suitable for achieving the present invention have the number of r, p and q polyoxyalkylene oxide hydroxy units independently from 1 to 40, It is preferably from 5 to 20, particularly from 7 to 15 and particularly preferably from 8 to 12. A very heterogeneous crosslinking agent according to the invention comprises a compound of the formula (Xlv), in particular -37- (34) • 1279407

Wherein S and t are greater than or equal to 0, and the sum of s + t is preferably in the range of from 1 to 20, particularly in the range from 2 to 1 ,, and the compound of formula (X111), especially

(XlVb) wherein S and t are greater than or equal to 0, and the sum of s + t is preferably in the range of from 1 to 20, particularly in the range of from 2 to 10. According to a particular aspect, the mixture comprises from 0.5 to 40% by weight, based on the total weight of the monomer mixture, of a compound of the formula (ΧΠ) and/or (ΧΠΙ) φ, particularly from 5 to 15% by weight. For the purposes of a particularly preferred embodiment of the invention, the mixture of the invention also comprises at least one ethylenically unsaturated monomer (B). These monomers (B) are different from the asymmetric compounds of the formula (ΧΠΙ) and (XIV) and are not compatible with the monomers (A) and the thio(meth)acrylates of the formula (I) and/or (11). the same. The monomer (B) is known to those skilled in the art, and is preferably copolymerized with the monomer (A) and the thio(meth)acrylate of the formula (I) and/or (II). Among them, these monomers (B) are especially: nitrile of (meth)acrylic acid and other nitrogen-containing methacrylates, -38-(35) 1279407. For example, methacryl fluorenyl amide acetonitrile, 2-methyl Alkyl propylene oxide ethyl methyl cyanoamine, cyanomethyl methacrylate; '(meth) acrylate derived from a saturated alcohol, for example, (meth) - methyl acrylate, (meth) acrylate Ester, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, dibutyl (meth)acrylate, tert-butyl (meth)acrylate, (a) Ethyl pentyl acrylate, hexyl (meth) acrylate, p- φ (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, decyl (meth) acrylate, ( Isooctyl methacrylate, isodecyl (meth) acrylate, 2-tert-butyl heptyl (meth) acrylate, 3-isopropyl heptyl (meth) acrylate, decyl (meth) acrylate, ( Undecyl (meth) acrylate, 5-methyl undecyl (meth) acrylate, (methyl) Dodecyl acrylate, methyl dodecyl (meth) acrylate, tridecyl (meth) acrylate, 5-methyltridecyl (meth) acrylate, (methyl) Tetradecyl acrylate, pentadecyl (meth) propylene pentanoate, cetyl (meth) acrylate, 2-methyl hexadecyl (meth) acrylate, (methyl) Heptadecyl acrylate, 5-isopropylheptadecyl (meth) acrylate, 4-tert-octadecyl (meth) acrylate, 5-ethyl octyl (meth) acrylate Alkyl ester, (meth)acrylic acid 3 isopropyl octadecyl acrylate, octadecyl (meth) acrylate, hexadecyl (meth) acrylate, (meth) acrylate Decaalkyl ester, cetyl eicosyl (meth)acrylate, stearyl amyl (meth)acrylate, behenyl (meth)acrylate and/or (methyl) Ethylene alkyl tetra-t-butylalkyl acrylate; -39- (36) (36) 1279407 cycloalkyl (meth) acrylate, such as cyclopentyl (meth) acrylate, (methyl) Cyclohexyl acrylate, 3-vinyl-2-butylcyclohexyl (meth)acrylate and borneol (meth)acrylate; (meth) acrylate derived from an unsaturated alcohol, for example, (methyl) 2-propynyl acrylate, allyl (meth) acrylate, oleyl (meth) acrylate, vinyl (meth) acrylate; if appropriate, the mixture may comprise: d) a radical polymerizable and a monomer having at least 2 terminal olefin groups having different reactivity, for example, a difunctional monomer having a methacrylate terminal group and a vinyl terminal group, and/or e) at least one ethylenically unsaturated monomer ( B), preferably from the group of methacrylates, especially 2-hydroxyethyl methacrylate; amine alkyl (meth) acrylate, such as ginseng (2-methyl propyleneoxyethyl) amine, N-methylformamidoethyl (meth)acrylate, 2-ureidoethyl (meth)acrylate; (meth)acrylate containing carbonyl, such as 2-carboxyethyl (meth)acrylate, Carboxymethyl (meth)acrylate, oxazolidinium (meth)acrylate, N-(methacryloquinone) (oxy)methanamine, acetone (meth)acrylate, N-methylpropenyloxymorpholine, N-methylpropenyl-2-pyrrolidone 9 ether alcohol (meth) acrylate, For example, tetrahydrofurfuryl (meth)acrylate, vinyloxyethoxyethyl (meth)acrylate, methoxyethoxyethyl (meth)acrylate, 1-butoxy (meth)acrylate Propyl ester, (meth)acrylic acid methyl-(2-vinyloxy)ethyl ester, (methyl-40- 8 (37) • 1279407 1 ) propylene hexanoate, (methyl) propyl Acid methoxymethoxyethyl ester, benzyloxymethyl (meth)acrylate, decyl (meth)acrylate* 2-butoxyethyl (meth)acrylate, (meth)acrylic acid 2 - ethoxy, ethoxymethyl ester, 2-ethoxyethyl (meth) acrylate, allyloxymethyl (meth) acrylate, 1-ethoxybutyl (meth) acrylate, ( Methyl) methoxymethyl acrylate, 1-ethoxyethyl (meth) acrylate, ethoxymethyl (meth) acrylate; ( (meth) acrylate of a halogenated alcohol, such as (methyl) 2,3-dibromopropyl acrylate, 4-bromophenyl (meth)acrylate, 1,3-dichloro-2-propyl (meth)acrylate, 2-bromoethyl (meth)acrylate, (fluorenyl) 2-iodoethyl acrylate, chloromethyl (meth) acrylate; epoxyethyl (meth) acrylate, such as 2,3-butyl butyl (meth) acrylate, (meth) acrylate 3,4-epoxybutyl acrylate, glycidyl (meth) acrylate; decylamine (meth) acrylate, for example, Ν-( 3 -dimethylaminopropyl propyl ) (meth) acrylamide , Ν-(diethylphosphorus carboxy) (methyl) acrylamide, 1-(methyl)propenyl decylamino-2-methyl-2-propanol, Ν-(3-dibutyl Aminopropyl)(meth)acrylamide, Ν-tert-butyl-hydrazine-(diethylphosphiniumcarboxy)(meth)acrylamide, hydrazine, hydrazine-bis(2·diethylamino) Ethyl)(meth)acrylamide, 4-(methyl)propenylnonylamino-4-methyl-2-pentanol, Ν-(methoxymethyl)(methyl) acrylamide , Ν-(2-hydroxyethyl)(methyl) acrylamide, Ν·ethoxymethyl (meth) acrylamide, hydrazine-(dimethylamino) Ethyl)(meth)acrylamide, Ν-methylphenyl(meth)acrylamide, hydrazine, hydrazine-diethyl (-41 - (38) 1279407 methyl) acrylamide, N-A (meth)acrylamide, ν, Ν-(meth) acrylamide, hydrazine-isopropyl (meth) acrylamide; heterocyclic (meth) acrylate such as (meth) acrylate Imidazolyl)ethyl ester, (meth)acrylic acid 2 _( 4 -morpholinyl)ethyl (2-methylpropane; (3⁄4 acid oxyethyl)-2-indole quinone ketone; phosphorus and boron And/or a (meth)propionic acid ester of sand, such as (2-(dimethylphosphonate) propyl acrylate, (meth) propyl methacrylate) propyl ester, (meth)acrylic acid Dimethylphosphonium methyl methacrylate, dimethylphosphinoethyl acrylate, (meth) propylene decylphosphine, (meth) propylene decyl phosphate; sulfur-containing (meth) acrylate, such as Methyl) thiodecyl ethyl acrylate, 4-thiocyanobutyl (meth) acrylate, ethyl sulfonyl acrylate, thiocyanate (meth) acrylate Methyl sulfinyl methyl ester, double (a a decyloxyethyl) sulfide; a bis(allyl carbonate) such as ethylene glycol bis(propylene carbonate 1,4-butanediol bis(allyl carbonate), diethylene glycol bis (carbonic acid); Ethylene halides such as vinyl chloride, vinyl fluoride, vinylidene chloride and ethylene; vinyl esters such as vinyl acetate; heterocyclic vinyl compounds such as 2-vinylpyridine, 3-ethidine, 2-methylvinyl Pyridine, 3-ethyl-4-vinylpyridine, methyl-5-vinylpyridinium, vinylpyrimidine, vinylhexahydropyridinedimethyl 2-(1-ester and 1-methyl) 2-( Ester, (diethylethyl (methyloxyethyl) propyl), allyl difluoroethenyl 2,3-di, 9 • B-42 - (39) 1279407 • alkenyl Carbazole, 3-vinylcarbazole, 4-vinylcarbazole, 1-vinylimidazole, 2-methyl-1-vinylimidazole, N-vinylpyrrolidone, 2-vinylpyrrolidone , N-vinylpyrrolidone, 3-vinylpyrrolidone, N-vinyl caprolactam, N-vinyl butyrolactam, vinyl oxane, vinyl furan, vinyl thiophene, vinyl Thiadiene, vinylthiazole and Hydrogenated vinyl thiazole, vinyl oxazole and hydrogenated vinyl oxazole; vinyl ether and isoprene diene ether; B maleic acid and maleic acid derivatives, such as mono- and di-esters of maleic acid, having Alcohol groups of 1 to 9 carbon atoms, maleic anhydride, methyl maleic anhydride, melamine, methyl melamine; fumaric acid and fumaric acid derivatives, such as mono- and di-esters of fumaric acid, having An alcohol group of 1 to 9 carbon atoms. As the integrity, it is also possible to use the bis(meth)acrylate listed as the monomer (A) as the monomer (B). As used herein, the term (meth) acrylate includes methacrylate φ and acrylate, and mixtures of the two. The corresponding (meth)acrylic acid term includes methacrylic acid and acrylic acid, and a mixture of the two. The ethylenically unsaturated monomer may be used alone or in the form of a mixture. Substantially the composition of the monomer mixture of the present invention can be as desired. The characteristic distribution of the plastic of the invention according to the application requirements can be used. However, it has proven to be highly advantageous to uniformly mix the prepolymer consisting of the compounds of the formulae (I), (II) and (III) with at least one monomer (A) and styrene at the desired polymerization temperature. The choice of the composition of the monomer mixture 'because the mixture of this type is easy to handle due to their generally low viscosity - 43- (40) 1279407 * 'and can be polymerized to give a uniform plastic with better properties. According to a particularly preferred embodiment of the invention, the monomer mixture comprises at least 5.0% by weight, based on the total weight of the monomer mixture in each case, of the compounds of formula (I), (II) and (III) The composition of the prepolymer is preferably at least 20.0% by weight, at least 50.0% by weight, particularly preferably, the weight ratio of the monomer (A) is at least 2.0% by weight based on the total weight of the monomer mixture in each case. Preferably, it is particularly preferably at least 10.0% by weight p, preferably at least 20.0% by weight. The weight ratio of the aromatic vinyl compound (particularly styrene) is preferably at least 2.0% by weight based on the total weight of the monomer mixture in each case, preferably at least 10.0% by weight, preferably At least 20.0% by weight is particularly good. According to a particular aspect of the invention, the mixture comprises from 5 to 9% by weight, based on the total weight of the monomer mixture in each case, of the monomers of formula (I) and/or (II) and (III). a prepolymer, from 2 to 50% by weight of monomer (A) (particularly preferably from 1 Torr to 30% by weight) and from 2 to 50 φ% by weight of an aromatic vinyl compound (especially from 10 to 30% by weight) 'Specially styrene, and from 0 to 45% by weight of the formula (XII) and (XIII) monomer and/or monomer (B) (especially from 1 to 10% by weight). ^ The skilled artisan will understand the preparation of the monomer mixture to be used in accordance with the present invention. By way of example, a prepolymer, an aromatic vinyl monomer and a monomer composed of a thio(meth)acrylate of the formula (I) and/or (II) and (m) are mixed in a manner known per se. (A) and monomer (B), the preparation can occur. For the purposes of the invention, preferred monomer mixtures are flowable at atmospheric pressures of -44 - (41) (41) - 1279407 and temperatures ranging from 20.0 to 80.0 ° C. The term "flowable" is known to those skilled in the art. Preferably, it is characterized by a liquid that can be cast into a variety of shapes and agitated and homogenized using a suitable aid. For the purposes of the present invention, the particular flowable material has a specificity at 25 ° C and at atmospheric pressure (1 0 1 3 2 5 Bass) equal to from 1 MPa. Baska·Second dynamic viscosity, from 0 · 6 5 millibass·second to 1 Baska. Second is advantageous. In a particularly preferred embodiment of the invention, the monomer mixture for casting is free of any air bubbles, particularly without any air bubbles. It is also preferred to remove the monomer mixture of bubbles (especially air bubbles) via a suitable process, such as to increase the temperature and/or use a vacuum. The highly transparent plastic of the present invention can be obtained by the above-described free radical copolymerization of a low viscosity (77 < 200 millibass per second) monomer mixture. Free radical copolymerization converts a low molecular weight monomer mixture into a high molecular weight compound, known as a polymer, by well known methods starting with free radicals. For further details, refer to H. G · E1 ias, Volumes 1 and 2, Makr 〇m ο 1 eku 1 e [Giant], B as 1 e, Heide 1 berg, N ew Y 〇rk Huthig und Wepf· 1 990 und The fifth edition of the Ullmann, s industrial chemistry encyclopedia is titled "Polymerization (p〇lymerizati〇11pr〇cesses)". In a preferred embodiment of the invention, the plastic of the invention is obtained via bulk or bulk polymerization of the monomer mixture. In this context, bulk or bulk polymerization represents a polymerization which polymerizes the monomer in the absence of a solvent. Thus, the polymerization is carried out as an undiluted material or as a bulk. The opposite method is the polymerization in the emulsion (known as emulsion polymerization -45- •1279407 * (42) <) and the polymerization in the dispersion (known as suspension polymerization), The organic monomer and the protective colloid and/or stabilizer are suspended in the aqueous phase, and a relatively coarse polymer particle is formed. A special form of heterophasic polymerization system. Pearlization polymerization, which is basically a suspension polymerization mode. The polymerization can be initiated substantially in any manner familiar to those skilled in the art, for example, using a free radical initiator (e.g., a peroxide, an azo compound) or via UV radiation or by visible light, alpha radiation, yg radiation. φ or r - radiation or irradiation in these combinations. In a preferred embodiment of the invention, the polymerization is initiated using a lipophilic free radical polymerization initiator. The radical polymerization initiator is particularly lipophilic to facilitate dissolution in the overall polymerization mixture. In addition to conventional azo initiators such as azoisobutyronitrile (AIBN) or 1,1-azobiscyclohexanecarbonitrile, the compounds which can be used are aliphatic peroxy compounds (such as peroxy neodecanoic acid). Pentyl ester, pivalyl peroxypivalate, tert-butyl peroxypivalate, p-amyl 2-ethylperoxyhexanoate, tert-butyl 2-ethylperoxyhexanoate, 3,5 , 5-trimethylperoxyperoxypivalate, 3,3-di(p-pentylperoxy)ethyl butyrate, tert-butyl perbenzoate, tert-butylperoxide-hydrogen, peroxidation Anthraquinone, oxidized laurel, benzoquinone peroxide, and any desired mixture of said compounds. Among the above compounds, a very preferred preference is for AIBN. In another preferred embodiment of the invention, The polymerization initiator is known to initiate polymerization via irradiation with UV rays or the like. A familiar commercially available compound such as benzophenone, α,α-diethoxyethyl benzene, 4, 4 can be used herein. -diethylaminobenzophenone, 2,2-di-46- (43) •1279407 • methoxy-2-phenylethyl benzene, 4-iso Phenyl-2-hydroxy-2·acetone, 1- • hydroxycyclohexyl benzophenone, isoamyl p-dimethylaminobenzoate, methyl 4-dimethylaminobenzoate, o-benzoquinone Methyl benzoate, benzoin, benzoic acid, diethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, 2-hydroxy-2-methyl-1-propenyl-1-one, 2 -Isopropyl thioxanthone | 'dibenzocycloheptanone, 2,4,6-trimethylphenylnonyldiphenylphosphine oxide, bis-indenyl-ortho-oxygen and other compounds, and can be used alone a photoinitiator, or a combination of two or more of the B composition or one of the above-mentioned polymerization initiators. The radical generating dose can be widely varied. The amount used is based on the weight of the entire composition by way of example. The range is preferably from 〇·1 to 5.00% by weight, particularly preferably in an amount ranging from 〇·1 to 2.0% by weight, based on the weight of the entire composition in each case, particularly The amount is from 〇.; [to 0.5% by weight of the range. The skilled artisan understands that the polymerization temperature to be selected for polymerization is mainly selected. The initiator and the mode of initiation (heat, via irradiation, etc.) are determined. It is known that the polymerization temperature can affect the properties of the polymer product. For the purposes of the present invention, therefore, the preference is from 2 0 · 0 to 1 〇〇 · 〇 ° C The range of polymerization temperatures, from 20.0 to 80. (TC is a range of favor, particularly in the range of from 20.0 to 60.0 ° C. In a particularly preferred embodiment of the invention, the reaction temperature is increased during the reaction, It is preferred to increase in stages. _ It has also been shown to be advantageous for thermal conditioning at elevated temperatures, for example, from 100 to 150 ° C towards the end of the reaction. The reaction can occur at or under atmospheric pressure or otherwise at superatmospheric pressure. However, it is best to carry out under atmospheric pressure. The reaction can occur in air or -47-(44) 1279407 ‘In addition, in an inert gas, it is preferred to minimize the amount of oxygen present, ^ because this content has an inhibitory effect on any polymerization. In a particularly preferred embodiment of the invention, the step of preparing the highly transparent plastic of the present invention is prepared by combining components (these monomer mixtures), initiators and other additives (e.g., lubricants). The mixture 'and then these are mounted between glass plates having a shape predetermined for subsequent application', for example, lenses for lenses or other lenses, iridium or their optical components. The overall polymerization is initiated via the introduction of energy, for example, via high energy radiation (especially using UV lamps) or via heating (in a water bath and for 2 or more hours). An optical material having a desired shape such as bright, transparent, colorless, and hard plastic is obtained. For the purposes of the present invention, lubricants are additives for plastic material sizing agents, such as compression molding materials and injection molding materials, which function to increase the sliding ability of the mounted material and thus to facilitate molding of the molding material. Examples of materials suitable for this purpose are metal soap and sap composition. The insolubility of the lubricant in the plastic causes some lubricant to move to the surface during processing as a release agent. Particularly suitable lubricants are described in EP 2 7 1 8 3 9 A, such as surface-active nonionic fluorinating agents, surface active fluorenone agents, quaternary alkyl ammonium salts and acid phosphates, which are disclosed The contents are specifically incorporated by reference for the purpose of the present invention. The present invention provides a highly transparent plastic having very good optical and mechanical properties. For example, its transparency with respect to DIN 5 03 65 is preferably greater than 88 〇%, and more preferably greater than 8 9 · 0. The refractive index nD of the plastic of the present invention is preferably greater than or equal to 1.59. The refractive index of -48- (45) 1279407 is usually determined by the wavelength and temperature of the incident light. The refractive index data of the present invention is therefore predominantly based on the standard data specified in DIN 5 3 49 1 (sodium (yellow) D line standard wavelength (about 589 nm)). According to the invention, the plastic yaw number relative to DIN 5 3 49 1 is preferably > 3 6.0. More information about the Jabe number can be found in the literature by the skilled person, for example, in Lexikon der Physik [Physical Dictionary] (Walter Greulich (e d. ); Lexikon der Physik [Physical Dictionary]; Heidelberg; Spektrum , Akademischer Verlag ; Volume 1 ; 1 9 9 8 ). According to a particularly preferred embodiment of the invention, the plastic has an yaw ratio of > 36.0, which is advantageous with > 37.0, especially > 38.0. Mechanical properties were tested using the FDA drop ball test (ANSI Z 80.1). If the test sample is not damaged by a ball with a diameter of 16 mm, pass the test. The larger the diameter of the ball used in the test without damaging the sample, the better the mechanical strength. The plastic of the present invention also preferably has a high glass transition temperature and thus maintains its remarkable mechanical properties, particularly its impact strength and hardness, even at temperatures above room temperature. The glass transition temperature of the plastic of the present invention is preferably greater than 80 ° C, more preferably greater than 90 ° C, especially greater than 95 ° C. Those skilled in the art will appreciate the possible fields of application of the highly transparent plastics of the present invention. Particularly suitable for any application where transparent plastic is intended. Its characteristic features make it particularly suitable for optical lenses, especially ophthalmic lenses. The following examples of the invention and comparative examples are intended to be illustrative of the invention and are not intended to be limiting. -49- .1279407 (46) Preparation of a sample thiomethacrylate mixture 7.5.3 g of 1,2-ethanedithiol was weighed into an Erlenmeyer flask with an inert gas feed and stirred, and 4 1 6.4 3 g of a 13% strong NaOH solution was metered in over a period of 30 minutes from 25 to 30 ° C (cooled with water). A brown clear solution formed. Next, 1 78.64 g of methacrylic anhydride and sodium thiolate solution were metered into the initial charge of ethyl acetate/water stirred in the reaction flask over the period of 45 minutes at the desired metering temperature. The inert gas is passed through the mixture where appropriate. The contents of the flask are typically cooled to about 2 ° C at the beginning of the feed and a microexothermic reaction is initiated after about 5-10 minutes with the aim of applying appropriate cooling to maintain the desired reaction temperature (3 5 (:) Once the feed has been added, the mixture is stirred for an additional 5 minutes at 35 ° C and then cooled to about 25 t with stirring: Transfer the mixture to a separatory funnel and separate and The lower aqueous phase is discharged. For the sake of sorting, the organic phase is transferred to an Erlenmeyer flask and stirred with ® Do Wex®-31 for about 15 minutes, followed by filtration of the ion exchanger. Next, some misty to almost clear crude ester The solution was stabilized at 1 〇〇 ppm HQ Μ E and concentrated on a rotary evaporator at no more than 5 。. The final colorless product was filtered at room temperature (20 - 25 ° C) to give about 140 grams. Colorless clarified ester. Preparation of prepolymer: 6.84 g of thiobis(meth)acrylic acid vinegar and 〇36 g of DMDO are reacted in the presence of an amine as a catalyst, -50-(47) 1279407 Based on EP 284374. It is based on oligomer thiodimethacrylate. In the preparation example of the compound, 7.2 g of prepolymer, 2.4 g of styrene, 2.4 g of deethoxylated bisphenol A di(meth)acrylate, 1.1 g of hydroxyethyl methacrylate, 36 mg A UV initiator (for example, Irgacur 819) is mixed with 24 mg of tert-butyl peroctoate or a similar initiator (refer to Example 1 of the present invention). The homogeneous cast resin mixture is placed in a suitable mold and used at 1 200 watts. The UV curing system of high pressure mercury source hardens during a period of 10 minutes. The material is then thermally conditioned for approximately 2 hours in an oven at approximately 120 ° C. -51 - 1279407 \ly 48

The average ball diameter in millimeters is 〇〇1 Ό FDA landing ball test diameter ANSI Z80.1 by hiring through On 〇〇1 a 00 OO Λ Λ Λ 1 - Sichuan 1 inch (N 00 m 1 ON inch cn v〇ON <N refractive index system! DIN 5 5 8 9 nanometer 1.5 93 9 1 1.5 95 9 1.608 9 system κ 丨丨< Ο 仞S g age s ΐ π.S ο ^ Κ] Q Η X 龄 S ·· w 〇 〇 口 η — & meal ω ·· 〇§ _ Q ^ ^ ^ ^ ·· < 一居j <NS $船S ω Χ^Λ-'t ω 擀5 «> + d ...〇d, P<$ pq ll (N net ί Κ)<π® ^ ^ m 5 * * Q 〇^ X PQ · · Woo i-) 1 'O Oh W !| o in < 2 ^ w $ m + n3 〇r^\ W 〇J ^ r- ~ 丨丨 丨丨 experiment Example IE 1 Comparative example HH UQ U h—(1—1 ω o CE III 骝酲Loading E t to Φ S listening 1 _ bottom i > lt tension 伥 (#) Distillation N] 氍 tir slightly ffi-: vs3H carbonyl secret H «fJn: ocma 01 stroll side problem Cui slightly secret K) · retanning E slightly in v 螽 翠 翠 slightly secret K]: vsavPQOIa 1 991 £ 301 inlaid * loose side 鹳吆 ^ 氍 :::: 遁 ^ 鄯 overflow _ system ^ slightly & dish embedded: 〇 1 £ 69 〆 ^ ^ -52- (49) 1279407 The mixture of the invention (IE) is odorless. The comparative example CE I did not pass the test and therefore no further investigation. Comparing the refractive indices (IE 1 with CE II and CE III ), the mixtures of the invention thus have a better yaw number. The mixtures of the invention also exhibited substantially better results in the ball drop test.

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Claims (1)

1279407 (1) Month W曰修(更)ΐ本10, the scope of application for patents Annex 2 Patent application No. 94 1 05068 Patent application scope of the patent application for the amendment of the Republic of China on August 31, 1995 1 · A method for preparing transparent plastic a mixture comprising: a) a compound of formula (I) and (II) (wherein each Ri is independently hydrogen or methyl, and each r2 is independently of a straight or branched aliphatic or cycloaliphatic group, or a substituted or unsubstituted aromatic or heteroaromatic group, And each m and η are independently of each other an integer greater than 〇 or equal to 0, wherein m + n > 〇) and alkyl dithiol or pre-prepared from polythiol (preferably a compound of formula (III)) Polymer, HS-R3-SH (III) wherein R3 is the same or different from R2, as defined by R2, and b) at least one capable of free radical polymerization and having at least 2 methyl propyl (2) 1279407 enoic acid a monomer (A) of an ester group, and c) an aromatic vinyl compound, d) a monomer capable of radically polymerizing and having at least two terminal olefin groups having different reactivity, and/or e, if appropriate ) at least one ethylenically unsaturated monomer (B), if appropriate. 2. The mixture of claim 1 of the patent application comprising more than 10 mol% of the total of the compounds of the formulae (I), (II) and (III) • m + n = 2 (II) ) compound. 3. A mixture according to claim 1, wherein the R2 group of the formula (I) and/or (Π) has an aliphatic group of from 1 to 1 carbon atoms. 4) A mixture of claim 1 of the patent, comprising more than 5.8 moles based on the total amount of the compounds of formula (I), (II) and (III). The compound of formula (II) wherein m + n = 3. 5 · As claimed in the scope of claim 1, the mixture comprises from 〇.1 to 〇5〇mol% based on the total amount of the compounds of formula (I), (II) and (III) (I ) compound. 6 · As in the mixture of claim 1 of the patent range, the mixture comprises from 1 to 40 mol% of m + (+) based on the total amount of the compounds of the formula (Ϊ), (II) and (III) Compound. 7. A mixture of claim 1 of the patent, the mixture comprising a compound of formula (II) of m + n > 3. 8. A mixture as claimed in claim 1, wherein the total content of the compounds of the formulae (I), (11) and (111) is at least 5% by weight based on the total weight of the mixture. -2- (3) 1279407 9. The mixture of claim 1 containing at least one prepolymer copolymerizable with monomers of formula (I), (II) and (III) Monomer (A). 1 〇 · As a mixture of claim 9 of the patent, the mixture contains di(meth)acrylate. 1 1 . The mixture of claim 1 wherein the aromatic vinyl compound present in the mixture is preferably styrene. 1 2 - A mixture according to claim 1 which comprises a monomer of the following formula which is capable of free radical polymerization and has at least 2 terminal olefin groups which are not reactively different. Wherein the R19 group is independently a hydrogen atom, a fluorine atom and/or a methyl group, and the R18 group is a linking group, preferably from 1 to 1000 carbon atoms, and particularly preferably from 2 to 100 carbon atoms. The Y group is a bond or a linking group having from 〇 to 10,000 carbon atoms, particularly preferably from 1 to 1,000 carbon atoms, and more preferably from 1 to 100 carbon atoms. A mixture of claim 12, which comprises allyl polyethylene glycol methacrylate. A mixture of claim 1 comprising at least one ethylenically unsaturated monomer (B), preferably a methacrylate. A mixture of claim 14 of the patent application comprising methyl propyl- 3 - (4) 1279407 enoic acid 2 · hydroxyethyl ester. A method for producing a transparent plastic, which is characterized in that the mixture of any of the above-mentioned patents is polymerized. 1 7 · A kind of transparent plastic, which can be obtained by the method of claim 16th. 18. If the plastic of claim 17 is applied, the plastic has a refractive index greater than 1 · 5 9 as measured by DIN 5 3 4 9 1 . 1 9 · If the plastics of the patent application No. 17 or 18 are applied, the number of Abbes measured by this plastic according to DIN 53491 is greater than 36. 2〇·For example, the plastic of the 17th or 18th patent application, wherein the average diameter of the ball which does not damage the sample in the ball drop test is 2 18 . 2 1 · If the plastic of the patent application No. 17 or 18 is applied, the transmittance of this plastic measured according to DIN 5 03 6 is $89%. 22. If the plastic is applied for in the 17th or 18th patent, the glass conversion temperature is greater than 80.0 °C. 2 3 - The use of a highly transparent plastic material as claimed in any one of claims 17 to 22 is an optical lens. 24 · An optical (especially ophthalmic) lens comprising a transparent plastic of at least one of claims 17 to 22 of the patent application.