DE102009004343A1 - Composition, based on (meth)acrylate, useful in producing clear moldings and semi-finished products such as pipes, plates, glazing or panels, furnitures and optical fibers, comprises polyhedral oligomeric silicon-oxygen clusters - Google Patents

Abstract

Composition based on (meth)acrylate, comprises polyhedral oligomeric silicon-oxygen clusters (I) (0.01-15 wt.%). Composition based on (meth)acrylate, comprises polyhedral oligomeric silicon-oxygen clusters of formula ((R aA bX iSiO 1.5) m(R cA dX jSiO) n(R eA fX kSi 2O 2.5) o(R gA hX lSi 2O 2) p)) (I) (0.01-15 wt.%). Either a, b, c, d, i : 0-1; f, h : 0-2; j : 1-2; and k : 0-3; or b+d+f+h : >= 1; i+j+k+l : >= 1; m+n+o+p : >= 4; a+b+i : 1; c+d : j = 2; e+f+k : 3; and g+h+l : 4; R : H, alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl or polymer unit (all are optionally substituted) or functionalized polyhedral oligomeric silicon-oxygen cluster units, which are bonded through a polymer unit or a bridging unit; X : at least one monomer building block with at least one double bond (optionally substituted with R) or optionally oxy, OH, alkoxy, carboxy, silyl, silyloxy, halo, epoxy, ester, fluoroalkyl, isocyanate, acrylate, methacrylate, mercapto, nitrile, amino or phosphine (all are optionally substituted with R); A : hydrophobic substituent comprising fluorinated hydrocarbon, preferably fluoro alkyl trialkoxysilane of formula (CF 3((CF 2) o(CH 2) p)Si(OR) 3; and o, p : 0-12.

Description

<stand of technology>

The The invention relates to acrylic glass or a methacrylate-based polymer with improved fire behavior.

Polymethyl methacrylate - PMMA for short - is a crystal-clear thermoplastic, which is known worldwide under the trade name Plexiglas ^® and comes because of its excellent optical and mechanical properties in a wide variety of applications. This is due in particular to the attractive combination of high optical transparency, high strength, high rigidity, high scratch resistance and outstanding weather resistance. The first work for the technical production of PMMA dates back to the end of the 20's and was carried out by the company Röhm in Darmstadt. In principle, for this purpose, a monomer based on acrylate and / or methacrylate - hereinafter described as (meth) acrylates - is radically polymerized in bulk, solution, emulsion or in suspension, wherein the monomers in detail of methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, iso-propyl (meth) acrylate, butyl (meth) acrylate, iso-butyl (meth) acrylate, tert-butyl (meth) acrylate, hexyl (meth) acrylate, heptyl ( meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, octyl (meth) acrylate, iso-octyl (meth) acrylate, decyl (meth) acrylate, benzyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, Octadecyl (meth) acrylate, dodecyl (meth) acrylate, tetradecyl (meth) acrylate, oleyl (meth) acrylate, 4-methylphenyl (meth) acrylate, benzyl (meth) acrylate, furfuryl (meth) acrylate, cetyl (meth) acrylate, Derive 2-phenylethyl (meth) acrylate, isobornyl (meth) acrylate, neopentyl (meth) acrylate.

The bulk polymerization is used to produce optically clear moldings such as plates, profiles and tubes. So-called acrylic glass GS is formed when the base materials in a form, for example, between two glass plates in a water bath, brought together and react to the polymer, while as acrylic glass XT z. B. in bags made in water-bath polymers, which are then extruded as acrylic granules to semi-finished products such as plates, rods tubes, etc. The mass polymerization between two plates usually leads to polymers of high molecular weight (> 10 ⁶ g / mol), so that the molded parts thus produced have better mechanical properties and a higher surface quality compared to extruded semi-finished products. Correspondingly, cast acrylic glass is easier to lift off and provides transparent cut edges, while extruded material is lower in molecular weight and therefore melts faster. This can smear the tools such as drills and saws during machining, leaving white cut edges, thereby eliminating various applications.

to Increasing toughness are meth) acrylates in various ways with z. For example, α-methylstyrene, styrene, acrylonitrile or other acrylic monomers. Elastomer modified, Impact-resistant polymer systems can by installation of elastomer particles - z. B. in the course of a two - or multistage suspension or emulsion polymerization become.

As a general rule For example, the polymerization of (meth) acrylates can be free-radical, anionic or cationic, being the most common in practice the radical method is used.

The Radical bulk polymerization usually proceeds at temperatures between 40 and 80 ° C, where in the Monomer mixture containing 0.01 to 2 wt .-% polymerization initiators are. Such polymerization initiators are, for example, peroxides such as benzoyl peroxide or azo compounds such as 2,2'-azobis (isobutyronitrile) or 2,2'-azobis (2,4-dimethylvaleronitrile).

As is known, when heating polymerized (meth) acrylates, ie PMMA, z. B. with a flame depolymerization, so that PMMA continues to burn after lighting by the resulting gases. That's why PMMA is after DIN 4102 Usually classified as a normal flammable in the building material class B2, wherein burning melt drips. Although only a few special varieties are available that meet building material class B1, they contain all conventional flame retardants ( http://www.ceficefra.com/faq ), which are currently critically discussed with regard to their environmental compatibility. For example, in DE 101 30 772 (2001) discloses a system which uses for (meth) acrylic polymers 4 to 15% by weight of phosphorus compounds in combination with a synergist such as 1 to 4% by weight of one or more cyclic organic sulfur compounds. This system meets the requirement of the UL 94 HB test, which requires, among other things, a combustion path of <100 mm for a sample of 30 seconds (UL = Underwriters Laboratories Inc .; http://www.ul-europe.com ; UL International Germany GmbH, 63263 Neu-Isenburg; Description of the test method: http://www.lairdtech.com/de/downloads/FA_UL_dt.pdf ). But if you have one in practice occurring fire case sets, where a self-extinction of the flame-retardant PMMA occurs less, since - as in the test case - the flame is stopped after 30 seconds, but in certain fire herds the PMMA is continuously flamed, are phosphorus and sulfur-containing Flame retardants release very toxic gases to the environment. When using nitrogen-containing flame retardants, for. As N-hydroxymethyl-3-dimethylphosphonpropionamid, the environment is also charged with the very toxic hydrocyanic acid and toxic nitrous gases ( André Leisewitz et al., Research Report 297 44 542, "Development of evaluation principles for the substitution of environmentally relevant flame retardants", Volume I 04 08, 2000 ; published on the internet: http://www.umweltdaten.de/publikationen/fpdf-l/1965.pdf ).

<Task>

The The task was to develop a PMMA type without addition a phosphorus compounds and / or sulfur compounds containing Flammschutzmittels when firing firstly not dripping and secondly in case of fire does not give off toxic gases to the environment. As a main goal is tracked that when used in the construction sector or roofing possibly necessary extinguishing work of the fire department neither by dripping and burning polymer still poisonous Gases are impaired.

<Solution>

Surprisingly was found to be the concomitant use of silicon-oxygen clusters as comonomers, although the burning process of burning PMMA is not absolute can stop, but in accordance with UL 94 V-0 a dripping when Burning process is completely prevented and also no toxic gases are released to the environment. The silicon-oxygen clusters surprisingly burn to the solid and completely harmless silica. For certain compositions and dosages of the silicon-oxygen clusters surprisingly occurs even a self extinguishing according to UL 94 V-0 on. The addition of the silicon-oxygen clusters are surprisingly the optical properties of PMMA are not adversely affected. In addition, this addition increases the scratch resistance of PMMA.

• a) aus mindestens einem monomeren Baustein des Typs (Meth)acryl-Z_m-SiY_n (1)hergestellt wurden, worin m = 0 oder 1 und n gleich 1, 2 oder 3 sind, mir der Maßgabe m + n = 4, Die Gruppen Y sind gleich oder verschieden, wobei Y für OH, ONa, OK, OR, OCOR, OSiR₃, Cl, Br, I oder NR₂ stehen. R ist dabei ein Wasserstoffatom, eine substituierte oder unsubstituierte Alkyl-, Cycloalkyl-, Alkenyl-, Cycloalkenyl-, Alkinyl-, Cycloalkinyl-, Aryl- oder Heteroarylgruppe. Z ist ein substituierter oder unsubstituierter Alkyl- oder Arylrest, ein Alkylsilyl-, ein Oxyalkyl- oder ein Oxyarylrest. Die (Meth)acrylgruppe ist unsubstituiert oder substituiert mit Halogenatomen und/oder Alkylgruppen und/oder Alkenylgruppen und/oder Arylgruppen;
• b) und/oder aus mindestens einem monomeren Baustein des Typs Vinyl-Z_m-SiY_n (2)hergestellt wurden, worin m = 0 oder 1 und n gleich 1,2 oder 3 sind, mir der Maßgabe m + n = 4. Die Gruppen Y sind gleich oder verschieden, wobei Y für OH, ONa, OK, OR, OCOR, OSiR₃, Cl, Br, I oder NR₂ stehen. R ist dabei ein Wasserstoffatom, eine substituierte oder unsubstituierte Alkyl-, Cycloalkyl-, Alkenyl-, Cycloalkenyl-, Alkinyl-, Cycloalkinyl-, Aryl- oder Heteroarylgruppe. Z ist ein substituierter oder unsubstituierter Alkyl- oder Arylrest, ein Alkylsilyl-, ein Oxyalkyl- oder ein Oxyarylrest. Die Vinylgruppe ist unsubstituiert oder substituiert mit Halogenatomen und/oder Alkylgruppen und/oder Alkenylgruppen und/oder Arylgruppen;
• c) und/oder aus mindestens einem monomeren Baustein des Typs Cycloalkenyl-Z_m-SiY_n (3)hergestellt wurden, worin m = 0 oder 1 und n gleich 1, 2 oder 3 sind, mir der Maßgabe m + n = 4. Die Gruppen Y sind gleich oder verschieden, wobei Y für OH, ONa, OK, OR, OCOR, OSiR₃, Cl, Br, I oder NR₂ stehen. R ist dabei ein Wasserstoffatom, eine substituierte oder unsubstituierte Alkyl-, Cycloalkyl-, Alkenyl-, Cycloalkenyl-, Alkinyl-, Cycloalkinyl-, Aryl- oder Heteroarylgruppe. Z ist ein substituierter oder unsubstituierter Alkyl- oder Arylrest, ein Alkylsilyl-, ein Oxyalkyl- oder ein Oxyarylrest. Die Cycloalkenylgruppe ist unsubstituiert oder substituiert mit Halogenatomen und/oder Alkylgruppen und/oder Alkenylgruppen und/oder Arylgruppen;
• d) und/oder aus mindestens einem monomeren Baustein des Typs Norbornenyl-Z_m-SiY_n (4)hergestellt wurden, worin m = 0 oder 1 und n gleich 1, 2 oder 3 sind, mir der Maßgabe m + n = 4. Die Gruppen Y sind gleich oder verschieden, wobei Y für OH, ONa, OK, OR, OCOR, OSiR₃, Cl, Br, I oder NR₂ stehen. R ist dabei ein Wasserstoffatom, eine substituierte oder unsubstituierte Alkyl-, Cycloalkyl-, Alkenyl-, Cycloalkenyl-, Alkinyl-, Cycloalkinyl-, Aryl- oder Heteroarylgruppe. Z ist ein substituierter oder unsubstituierter Alkyl- oder Arylrest, ein Alkylsilyl-, ein Oxyalkyl- oder ein Oxyarylrest. Die Norbornenylgruppe ist unsubstituiert oder substituiert mit Halogenatomen und/oder Alkylgruppen und/oder Alkenylgruppen und/oder Arylgruppen.
• e) und/oder aus mindestens einem monomeren ionischen Baustein des Typs [HR'C=C(R'')-Z'_m'-COO]^–[NHR₂]⁺-Z_m-SiY_n (5)hergestellt wurden, worin gleich oder unabhängig voneinander m und m' = 0 oder 1 und n gleich 1,2 oder 3 sind, mir der Maßgabe m + n = 4. Die Gruppen Y sind gleich oder verschieden, wobei Y für OH, ONa, OK, OR, OCOR, OSiR₃, Cl, Br, I oder NR₂ stehen. R ist dabei ein Wasserstoffatom, eine substituierte oder unsubstituierte Alkyl-, Cycloalkyl-, Alkenyl-, Cycloalkenyl-, Alkinyl-, Cycloalkinyl-, Aryl- oder Heteroarylgruppe. R' ist gleich oder unabhängig vor R und ist ein Wasserstoffatom, eine substituierte oder unsubstituierte Alkyl-, Cycloalkyl-, Alkenyl-, Cycloalkenyl-, Alkinyl-, Cycloalkinyl-, Aryl- oder Heteroarylgruppe. R” ist gleich oder unabhängig von R' oder R und ist ein Wasserstoffatom, eine substituierte oder unsubstituierte Alkyl-, Cycloalkyl-, Alkenyl-, Cycloalkenyl-, Alkinyl-, Cycloalkinyl-, Aryl- oder Heteroarylgruppe. Z und Z' sind gleich oder unabhängig voneinander und stellen einen substituierten oder unsubstituierten Alkyl- oder Arylrest, ein Alkylsilyl-, ein Oxyalkyl- oder ein Oxyarylrest dar.

This invention relates to (meth) acrylate-based polymers having from 0.01 to 15% by weight of ionic or covalently bonded polyhedral oligomeric silicon-oxygen clusters having at least 4 silicon atoms, which in turn

• a) from at least one monomeric building block of the type (Meth) acryl-Z _m -SiY _n (1) where m = 0 or 1 and n is 1, 2 or 3, with the proviso m + n = 4, the groups Y are the same or different, where Y is OH, ONa, OK, OR, OCOR, OSiR ₃ , Cl, Br, I or NR ₂ . R is a hydrogen atom, a substituted or unsubstituted alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl or heteroaryl group. Z is a substituted or unsubstituted alkyl or aryl radical, an alkylsilyl, an oxyalkyl or an oxyaryl radical. The (meth) acrylic group is unsubstituted or substituted with halogen atoms and / or alkyl groups and / or alkenyl groups and / or aryl groups;
• b) and / or at least one monomeric building block of the type Vinyl-Z _m -SiY _n (2) in which m = 0 or 1 and n are equal to 1, 2 or 3 with the proviso m + n = 4. The groups Y are identical or different, Y being OH, ONa, OK, OR, OCOR, OSiR ₃ , Cl, Br, I or NR ₂ . R is a hydrogen atom, a substituted or unsubstituted alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl or heteroaryl group. Z is a substituted or unsubstituted alkyl or aryl radical, an alkylsilyl, an oxyalkyl or an oxyaryl radical. The vinyl group is unsubstituted or substituted with halogen atoms and / or alkyl groups and / or alkenyl groups and / or aryl groups;
• c) and / or at least one monomeric building block of the type Cycloalkenyl-Z _m -SiY _n (3) where m = 0 or 1 and n is 1, 2 or 3 with the proviso m + n = 4. The groups Y are the same or different, where Y is OH, ONa, OK, OR, OCOR, OSiR ₃ , Cl, Br, I or NR ₂ . R is a hydrogen atom, a substituted or unsubstituted alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl or heteroaryl group. Z is a substituted or unsubstituted alkyl or aryl radical, an alkylsilyl, an oxyalkyl or an oxyaryl radical. The cycloalkenyl group is unsubstituted or substituted with halogen atoms and / or alkyl groups and / or alkenyl groups and / or aryl groups;
• d) and / or at least one monomeric building block of the type Norbornenyl-Z _m -SiY _n (4) where m = 0 or 1 and n is 1, 2 or 3 with the proviso m + n = 4. The groups Y are the same or different, where Y is OH, ONa, OK, OR, OCOR, OSiR ₃ , Cl, Br, I or NR ₂ . R is a hydrogen atom, a substituted or unsubstituted alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl or heteroaryl group. Z is a substituted or unsubstituted alkyl or aryl radical, an alkylsilyl, an oxyalkyl or an oxyaryl radical. The norbornenyl group is unsubstituted or substituted with halogen atoms and / or alkyl groups and / or alkenyl groups and / or aryl groups.
• e) and / or at least one monomeric ionic building block of the type [HR'C = C (R '') - Z '_m' --COO] ^- [NHR ₂ ] ⁺ - Z _m -SiY _n (5) where m is equal to or independently of one another and m '= 0 or 1 and n is equal to 1, 2 or 3, with the proviso m + n = 4. The groups Y are the same or different, where Y is OH, ONa, OK, OR, OCOR, OSiR ₃ , Cl, Br, I or NR ₂ . R is a hydrogen atom, a substituted or unsubstituted alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl or heteroaryl group. R 'is the same or independent of R and is a hydrogen atom, a substituted or unsubstituted alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl or heteroaryl group. R "is the same or independent of R 'or R and is a hydrogen atom, a substituted or unsubstituted alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl or heteroaryl group. Z and Z 'are the same or different and represent a substituted or unsubstituted alkyl or aryl radical, an alkylsilyl, an oxyalkyl or an oxyaryl radical.

Such monomeric building blocks or their precursors are sold mostly by Evonik Degussa GmbH under the trade names DYNASYLAN® ^® MEMO, DYNASYLAN® ^® VTMO, DYNASYLAN® ^® VTMOEO DYNASYLAN® ^® VTEO, DYNASYLAN® ^® AMEO and DYNASYLAN® ^® AMMO, but are also in the ABCR GmbH & Co KG such as 2- (3-cyclohexenyl) ethyltrichlorosilane, methacryloxymethyltriethoxysilane, methacryloxymethyltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3- (acryloxypropyl) dimethylmethoxysilane, 3- (acryloxypropyl) methyldimethoxysilane, cyclohexenyltrichlorosilane, or 5- (bicyloheptenyl) methyldichlorosilane. For the preparation of the monomeric building block 5 present in ionic form, an aliphatic or cyclic carboxylic acids having 3 to 20 carbon atoms substituted with alkyl groups, hydroxy groups or oxy groups and substituted by unsubstituted or unsubstituted aliphatic or cyclic carboxylic acids such as acrylic acid, methacrylic acid, pentenoic acid, 9-hydroxy-2 -decensic acid, 9-oxo-2-decenoic acid and oleic acid.

The silicon-oxygen clusters used according to the invention can be prepared by known methods. For example, Lichtenhan et al. in US 5,484,867 ; Comments Inorg. Chem. 17 (1995), 115-130; Macromolecules 29 (1996), 7302-7304 and in Macromolecules 28 (1995), 8435-8437 a synthetic route. For special silicon-oxygen clusters, the term "polyhedral, oligomeric silsesquioxanes" (POSS) can be found in the relevant literature. The structural formers are (RSiO _3/2 ) _n compounds, where n = 4, 6, 8, 10, 12, 14, 16, and 18. The resulting structures in the synthesis are of the order of nanosize (ca. 1 nm) and of the so-called T ₄ , T ₆ , T ₈ , T ₁₀ , T ₁₂ and T ₁₈ types, among which a 4-membered cage (tetrahedron), 6-membered cage (triangular prism) , 8-cage (cube), 10-cage (pentagonal prism), 12-cage (hexagonal prism) and so on. By far the most common form is the T ₈ structure.

The above literature describes silicon-oxygen clusters according to structure 6 with a functional Group X which was introduced by corner capping with trichlorosilanes, such as XSiCl ₃ , using an amine as the base, into the respective trisilanol precursor according to structure 7.

Preferred for the preparation of the silicon-oxygen clusters used in the invention is the in WO 03/064490 disclosed procedures. There, the functionalization of silicon-oxygen clusters of structure 7 by "corner capping" with alkoxysilanes, z. B. with monomeric building blocks of the type a), b), c) or d) described.

These However, methods only provide silicon-oxygen clusters with one functional group.

Particularly preferred for the preparation of the silicon-oxygen clusters used in the invention are the WO 2006/125707 and WO 2007/121908 documented processes using the monomeric building blocks of the type a), b), c) or d). This process is characterized in that at least two different silanes are reacted under base catalysis, wherein the rate constants with respect to the saponification reaction of the silanes used are of the same order of magnitude. In this way, it can be achieved that the silicon-oxygen clusters have a substituent distribution in accordance with the educt composition of the silanes. If, for example, the starting material used is the silane ASiY ₃ and the silane BSiY ₃ in a molar mixing ratio of 1: 1 in this process, the result is a composition which predominantly contains a silicon-oxygen cluster of the type A ₄ B ₄ Si ₈ O ₁₂ having. In different proportions by weight, but in parts by weight less than in the type A ₄ B ₄ Si ₈ O ₁₂ type silicon-oxygen cluster, the composition also has type A ₃ B ₅ Si ₈ O ₁₂ type A ₂ B ₆ Si silicon-oxygen clusters ₈ O ₁₂ , of the type A ₅ B ₃ Si ₈ O ₁₂ and of the type A ₆ B ₂ Si ₈ O ₁₂ .

To WO 2006/125707 and WO 2007/121908 in particular silanes according to the formula (R _a X _b ) _m SiY _n with: a, b = 0, 1; m, n = 1, 2 or 3;
a + b = 1 and m + n = 4,
in which
R = hydrogen, alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, heteroaryl or polymeric moiety, each being substituted or unsubstituted,
X = oxy, hydroxy, alkoxy, carboxy, silyl, silyloxy, halogen, epoxy, ester, fluoroalkyl, isocyanate, acrylate, methacrylate, mercapto, nitrile, amino, phosphine or at least one type X substituent of the type R,
Y = OH, ONa, OK, OR ', OCOR', OSiR ' ₃ , Cl, Br, I or NR' ₂ and
R 'is hydrogen, a substituted or unsubstituted alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl or heteroaryl radical,
used, preferably silanes are used which have substituents of the type Y selected from OH, OR ', OCOR' or Cl.

Particularly preferred in this process alkoxysilanes according to the formula (R _a X _b ) _m Si (OR ') _n with: a, b = 0, 1; m, n = 1, 2 or 3;
a + b = 1 and m + n = 4,
in which:
R = hydrogen, alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, heteroaryl or polymeric moiety, each being substituted or unsubstituted,
X = at least one monomeric building block having at least one double bond and optionally an oxy, hydroxy, alkoxy, carboxy, silyl, silyloxy, halogen, epoxy, ester, fluoroalkyl, isocyanate, acrylate, methacrylate , Mercapto, nitrile, amino, phosphine or at least one such type X substituent of type R,
R '= hydrogen, a substituted or unsubstituted alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl or heteroaryl radical. Here, the radicals R 'may be the same or different.

Trialkoxysilanes, in particular alkyltrialkoxysilanes RSi (OR ') _3, are particularly preferably used, the alkoxy group (OR') having from 1 to 4 carbon atoms, in particular methoxy or ethoxy group, and the alkyl group (R) having from 1 to 5 carbon atoms, in particular of 2 to 4 carbon atoms, but preferably has 3 carbon atoms. Examples of alkyltrialkoxysilanes of the formula RSi (OR ') ₃ are isobutyltrimethoxysilane (DYNASYLAN ^® IBTMO), isobutyltriethoxysilane, propyltrimethoxysilane (Dynasylan ^® PTMO) propyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, methyltrimethoxysilane (DYNASYLAN ^® MTMS), methyltriethoxysilane, Octyltrimethoxylsilan, octyltriethoxysilane, cyclopentyltrimethoxysilane, Cyclopentyltriethoxysilane, cyclohexyltrimethoxysilane and cyclohexyltriethoxysilane. In this method, trialkoxysilanes ₃ may be substituted with a substituent of the type X according to the formula XSi (OR '), such as 3-Aminopropytriethoxysilan (DYNASYLAN ^® AMEO) 3-chloropropyltrimethoxysilane (CPTMO), 3-glycidyloxypropyltrimethoxysilane (DYNASYLAN ^® GLYMO), 3 mercaptopropyltrimethoxysilane (DYNASYLAN ^® MTMO), 3-methacryloxypropyl-trimethoxysilane (Dynasylan ^® MEMO) and acryloxypropyltrimethoxysilane be used. In a particular embodiment, be (DYNASYLAN ^® VTMO) or vinyltriethoxysilane used such as vinyltrimethoxysilane alkenyltrialkoxysilanes. For the preparation of polyhedral oligomeric silsesquioxanes for hydrophobing, for example of polymers, preferably fluoroalkyltrialkoxysilanes, preferably according to the formula CF ₃ ((CF ₂ ) _o (CH ₂ ) _p ) Si (OR ') ₃ with 0, p = 0-12 such as 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyltriethoxysilane (DYNASYLAN ^® F 8261).

For the preparation of the silicon-oxygen clusters according to the invention having at least one functional group which have both substituents of type R and substituents of type X on the silicon-oxygen cluster, at least two different silanes are reacted under base catalysis. This base catalysis, during the process according to WO 2007/121908 can have different pH values, controls and accelerates the course of the reaction. As the basic catalyst, a compound having structural fragments selected from OH, R'O-, R'COO-, R'NH-, R'CONR'-, R'-, CO ₃ ^2- , PO ₄ is then preferably used ^3- , SO ₄ ^2- , NO ₃ ^- , F ^- , NR ' ₃ , R' ₃ NO, where R 'is hydrogen, a substituted or unsubstituted alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl , Aryl or heteroaryl radical. Base catalysis with a basic catalyst is preferably selected from alkali metal hydroxides, alkaline earth hydroxides, (C ₂ H ₅ ) ₄ NOH, (C ₆ H ₅ CH ₂ ) (CH ₃ ) ₃ NOH, aminosilanes, (CH ₃ ) ₄ NOH and / or ( C ₂ H ₅ ) ₃ N performed. This process is particularly preferably carried out with aminosilanes, NaOH, KOH or (C ₂ H ₅ ) ₄ NOH as the basic catalyst.

In a particular embodiment of the invention, a silicon-oxygen cluster is used which contains the ionic monomeric building block 5. The production of these ionic silicon-oxygen clusters is in WO 2006/125708 described.

object in particular PMMA or (meth) acrylate-based polymers of this invention, from 0.01 to 15% by weight of covalently bound polyhedral oligomeric silicon-oxygen clusters with at least 4 silicon atoms which in turn comprise at least one monomeric building block of the Type 1 to 5 included.

The at least 4 silicon atoms having silicon-oxygen clusters contain at least one free double bond. They are prepared before the polymerization of the (meth) acrylate mixture in a separate production step and can be described by the following general formula: [(R _a A _b X _i SiO _1.5 ) _m (R _c A _d X _j SiO) _n (R _e A _f X _k Si ₂ O _2.5 ) _o (R _g A _h X ₁ Si ₂ O ₂ ] _p ] With:
a, b, c, d, i = 0-1; j = 1-2; e, g, k = 0-3; f, h = 0-2; b + d + f + h ≥ 1, i + j + k + l ≥ 1; m + n + o + p ≥ 4; a + b + i = 1; c + d + j = 2; e + f + k = 3 and g + h + l = 4;
R = hydrogen atom, alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl or polymeric moiety, each being substituted or unsubstituted, or other functionalized polyhedral oligomeric silicon-oxygen cluster units attached via a polymer moiety or bridging moiety ,
X = at least one monomeric building block having at least one double bond and optionally an oxy, hydroxy, alkoxy, carboxy, silyl, silyloxy, halogen, epoxy, ester, fluoroalkyl, isocyanate, acrylate, methacrylate , Mercapto, nitrile, amino, phosphine or at least one such type X substituent of type R,
A = hydrophobic substituent selected from fluorinated hydrocarbon radicals, preferably fluoroalkyltrialkoxysilanes according to the formula CF ₃ ((CF ₂ ) _o (CH ₂ ) _p ) Si (OR) ₃ with o, p = 0-12,
wherein the substituents of the type R are the same or different.

The production of the silicon-oxygen clusters used according to the invention must necessarily be carried out in a separate production step, since otherwise the effect according to the invention is not obtained. The invention is therefore of OS DE 10212458 (2002), since unhydrolyzed silanes are added directly to a (meth) acrylate mixture to be polymerized.

In the composition of the invention have the used silicon-oxygen clusters preferably have a molecular weight of at least 400 g / mol, more preferably 600 to 3000 g / mol and most preferably 700 to 1500 g / mol. In a special Embodiment of the composition according to the invention are several polyhedral oligomeric silicon-oxygen cluster units condensed into a molecule.

The Molecular size of the silicon-oxygen clusters in the composition of the invention can be increased by adding several polyhedral oligomeric silicon-oxygen cluster units with substituents of type X by means of condensation z. B. over a spacer and / or the functional groups of the substituent of Type X, to be connected. Furthermore, an enlargement by a homo- or copolymerization - in the polymer phase takes place - enter. The inventive Composition preferably has polyhedral oligomeric silicon-oxygen clusters on, the size of a maximum of 100 nm, especially preferably from 2 to 50 nm.

The Silicon-oxygen clusters can be used directly in quantities of 0.01 to 15.0 wt .-%, preferably 0.1 to 7.5 wt .-%, in particular in amounts of 1 to 5 wt .-% of the reaction mixture are added. The reaction mixture according to the invention is based preferably on acrylates or methacrylates - in the following as (Meth) acrylates which are different from the monomers methyl (meth) acrylate, Ethyl (meth) acrylate, propyl (meth) acrylate, iso-propyl (meth) acrylate, Butyl (meth) acrylate, iso-butyl (meth) acrylate, tert-butyl (meth) acrylate, hexyl (meth) acrylate, Heptyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, Octyl (meth) acrylate, iso-octyl (meth) acrylate, decyl (meth) acrylate, Benzyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, octadecyl (meth) acrylate, Dodecyl (meth) acrylate, tetradecyl (meth) acrylate, oleyl (meth) acrylate, 4-methylphenyl (meth) acrylate, benzyl (meth) acrylate, Furfuryl (meth) acrylate, cetyl (meth) acrylate, 2-phenylethyl (meth) acrylate, Isobornyl (meth) acrylate, neopentyl (meth) acrylate can be derived.

In a particular embodiment of the invention Composition can this on the monomers (2-ethylhexyl) acrylate, (2-hydroxyhexyl) acrylate, hydroxyethyl acrylate, (2-hydroxyhexyl) acrylate phosphate, (2-hydroxypropyl) acrylate, (2-phenoxyethyl) acrylate, butyl acrylate, Butanediol dimethacrylate, hexanediol dimethacrylate, methylmethacrylate, [2- (tert -butylamino) ethyl] methacrylate, ethyltriglycol methacrylate, (2-hydroxyethyl) methacrylate, (2-hydroxyethyl) methacrylate phosphate, (2-hydroxypropyl) methacrylate or tetrahydrofurfuryl methacrylate or their polymers.

The Composition according to the invention can in addition to (Meth) acrylates also have other monomers with the (meth) acrylates are copolymerizable. These include preferably styrene, substituted styrenes having an alkyl substituent on the side chain, such as As α-methylstyrene, and substituted styrenes with an alkyl substituent on the ring, such as. For example, p-methylstyrene. But Other monomers such as vinyl halides, z. Vinyl chloride, vinyl fluoride, Vinylidene chloride, vinylidene fluoride, and vinyl esters such. B. vinyl acetate come into consideration. In addition, heterocyclic vinyl compounds may also be used z. V. substituted and substituted vinylpyridines, vinylpyrimidines, Vinylpiperidines, vinylcarbazoles, vinylprrolidines, N-vinylcaprolactams, Vinyl oxanes, vinyl furans, vinyl thiophenes, vinyl thiolanes, vinyl thiazoles, Vinyl and isoprenyl ethers are used. Furthermore, maleic acid and maleic acid derivatives.

Crucial to the feasibility of this invention is that the comonomers just mentioned no further functional groups, such as the functional vinyl group arising in the free-radical polymerization, such as. As acid or hydroxy groups have.

The mentioned monomers can in the inventive Composition may be contained individually or in mixtures, further may also homopolymer and / or copolymers of these monomers available.

The Polymerization of the composition of the invention can basically radical, anionic or cationic respectively. For certain compositions of the compositions are this even without polymerization catalyst reactive, the responsiveness of the combination used is dependent. This is - if products are longer stored or transported - an important fact. The Composition according to the invention may be optional Inhibitors or vinyl polymerization inhibitors such as tert-butyl catechol, Hydroquinone, hydroquinone monoethyl ether and 2,5-di-tert-butylhydroquinone contain. The required amounts vary depending on the monomer composition as well as storage and transport conditions and are usually in the range of 0.005 to 0.1 wt .-%, based on the total weight the composition

For the preferred free-radical polymerization or crosslinking of the composition according to the invention, these may contain what are known as polymerization initiators. In particular, the composition of the invention has a maximum of 5 wt .-%, preferably 0.01 to 2 wt .-%, in particular 0.015 to 1.0 wt .-% of initiator, based on the monomer mixture. As polymerization initiators, the composition according to the invention preferably azo compounds, such as 2,2'-azobis (isobutyronitrile) or 2,2'-azobis (2,4-dimethylvaleronitrile), redox systems, such as the combination of tertiary amines with peroxides on , The composition according to the invention preferably contains peroxides, particularly preferably dilauroyl peroxide, tert-butyl peroctoate, tert-butyl perisononanoate, dicyclohexyl peroxydicarbonate, dibenzoyl peroxide or 2,2-bis (tert-butylperoxy) butane (cf. H. Rauch-Puntigam, Th. Völker, "Acrylic and Methacrylic Compounds", Springer, Heidelberg, 1967 or Kirk-Othmer, Encyclopedia of Chemical Technology, Vol. 1, pp. 386ff, J. Wiley, New York, 1978 ). The composition according to the invention can also comprise a mixture of different polymerization initiators with different half-lives, such as, for example, dilauroyl peroxide and 2,2-bis (tert-butylperoxy) butane, in order to keep the radical stream constant during the polymerization and at different polymerization temperatures.

In a particular embodiment of the use of the composition according to the invention, it comprises a photoinitiator, for example, 2 wt .-% of DAROCUR ^® 1173 or a IRGACURE ^® type (Ciba Specialty Chemicals GmbH). These are, in particular, α-hydroxyketones, phenylglyoxylates, benzyldimethylketals or α-aminoketones. The polymerization of the composition according to the invention can now be carried out with a UV emitter, for example from the company Theimer or Lamp Express Inc. (USA), with a power of 100 W / cm.

For adjusting the molecular weights of the homopolymers or copolymers, the coating composition of the invention may preferably contain from 0.05 to 5% by weight, preferably from 0.1 to 2% by weight and more preferably from 0.2 to 1% by weight. % based on the monomer mixture having a molecular weight regulator. In particular, the composition of the invention has a molecular weight regulator selected from mercaptans, such as n-butyl mercaptan, n-dodecyl mercaptan, 2-mercaptoethanol, or 2-ethylhexyl thioglycolate. The composition according to the invention preferably comprises n-dodecylmercaptan (cf., for example H. Rauch-Puntigam, Th. Völker, "Acrylic and Methacrylic Compounds", Springer, Heidelberg, 1967 ; Houben-Weyl, Methods of Organic Chemistry, Vol. XIV / 1, page 66, Georg Thieme, Heidelberg, 1961 or Kirk-Othmer, Encyclopedia of Chemical Technology, Vol. 1, pp. 296ff, J. Wiley, New York, 1978 ).

to impact-modifying effect of the invention Crosslinkers such as di (meth) acrylates, Divinylbenzenes or allyl (meth) acrylates may be included.

Of course, the composition of the invention may contain other additives, such as heat and light stabilizers, especially UV absorbers, optical brighteners, antistatic agents, accelerators based on amine compounds, lubricants, antiblocking agents, nucleating agents, flame retardants, fillers and dyes and pigments. Reference is made to Hans Zweifel, Plastics Additives Handbook, 5th Edition, Carl Hanser Verlag 2001 , The coloring of polymers is in Vieweg-Esser, Kunststoffhandbuch, Volume IX, "Polymethacrylates", Carl Hanser Verlag 1975 and Batzer, Polymer Materials, Vol. II, Technology (337-353), Georg Thieme Verlag 1984 described. The composition of the invention has these additives - based on the particular additive - preferably in amounts of from 0.01 wt .-% to 5.0 wt .-%.

The The following examples are intended to illustrate the invention Explain composition without the Invention limited to this embodiment should be.

example 1

• 1a: MethacrylIsobutyl-POSS (MA0702)
• 1b: MonoVinylIsobutyl-POSS (OL1123)
• 1c: OctaCyclohexenyldimethylsilyl-POSS (OL1159)
• 1d: NorbornenylethylEthyl-POSS (NB1021)

The monomeric building blocks (1) (meth) acryl-Z _m -SiY _n , (2) vinyl-Z _m -SiY _n , (3) cycloalkenyl-Z _m -SiY _n and (4) norbornenyl-Z _m -SiY _n were from Hybrid Plastics ( 55 WL Runnels Industrial Drive, Hattiesburg, MS 39401, USA ) based:

• 1a: Methacrylic isobutyl POSS (MA0702)
• 1b: monoVinyl isobutyl POSS (OL1123)
• 1c: octa-cyclohexenyldimethylsilyl-POSS (OL1159)
• 1d: norbornenylethyl ethyl-POSS (NB1021)

Example 2

The monomeric building block (5) [HR'C = C (R '') - Z '_m' --COO] ^- [NHR ₂ ] ⁺ - Z _m -SiY _n was prepared according to WO 2006/125708 produced:

Synthesis of a composition (aminopropyl) _2.4 (propyl) _5.6 Si ₈ O ₁₂ and -Anteilen Methacrylresten

In 860 ml of ethanol 53.04 g (0.24 mol) of 3-aminopropyltriethoxysilane (Dynasylan AMEO ^®) are added under stirring at room temperature. These are quickly mixed with 20.66 g (0.24 mol) of methacrylic acid. Are then added to 91.99 g (0.56 mol) of propyltrimethoxysilane (Dynasylan ^® PTMEO) and then 64 g of water at room temperature. The temperature is then raised to 60 ° C and allowed to stir for 3 days at this temperature. After distilling off the solvent in vacuo and drying the product in a vacuum oven at 50 ° C to obtain 79.6 g (yield: 100%) of a white, water-soluble product (methacrylate salt), which in the MS-MALDI-TOF analysis (matrix Assisted laser desorption / ionization time of flight) predominantly T ₆ -, T ₈ -, T ₁₀ - and small amounts of T ₁₂ cages let recognize.

Example 3

Production of a silicon-oxygen cluster according to WO 2006/125707 :

Synthesis of a composition with (isobutyl) ₅ (3-methacryloxypropyl) ₃ Si ₈ O ₁₂ fractions

In 860 ml of acetone with stirring at room temperature 74.50 g (0.30 mol) of 3-methacryloxypropyltrimethoxysilane (DYNASYLAN ^® MEMO) with 89.15 g (0.50 mol) of isobutyltrimethoxysilane (DYNASYLAN ^® IBTMO) was added. With stirring, 2.038 g of KOH (0.0352 mol) dissolved in 64 g of water are added. The temperature is then raised to 40 ° C and allowed to stir at this temperature for 3 days. Thereafter, the solvent is distilled off in vacuo, the distillation residue is taken up in 300 ml of diethyl ether and concentrated in a separating funnel several times with 100 ml of water, the first time 2.11 g concentrated. Acetic acid was added, washed. After drying the organic phase over magnesium sulfate, the diethyl ether is distilled off in vacuo. This gives 106 g (yield: 98.1%) of a colorless, highly viscous mass, which in the MALDI-TOF analysis shows predominantly T ₈ , T ₁₀ and small amounts of T ₁₂ cages. The HPLC analysis shows predominantly trisubstituted cages which have three substituents of type X - in this example 3-methacryloxypropyl groups, but also cages having two or four substituents of type X.

Example 4

Preparation of inventive and non-inventive PMMA:

4.1 (not according to the invention):

A mixture of 3000 g of methyl methacrylate and 1.2 g of methacrylic acid with 0.9 g of azobis (isobutyronitrile) and 0.3 g of azobis (2,4-dimethylvaleronitrile) for 0.5 hours at room temperature with exclusion of air mixed with stirring. Thereafter, this mixture is filled in a polymerization chamber consisting of 2 discs of 8 mm thick glass. For sealing a PVC sealing cord is used between the two discs, the thickness of which can be varied. It is then polymerized in a water bath at 40 ° C for 35 hours. In this case, in the produced 18 mm PMMA core after 16 hours of polymerization, the sealing cord is removed in order to avoid destruction of the plate by shrinking. After the polymerization, the composite is annealed at 100 ° C. for 3 hours. After that, the discs are removed.

4.2 (according to the invention):

• 4.2.1: 150 g Silizium-Sauerstoffcluster aus Beispiel 1a
• 4.2.2: 75 g Silizium-Sauerstoffcluster aus Beispiel 1a
• 4.2.3: 75 g Silizium-Sauerstoffcluster aus Beispiel 1b
• 4.2.4: 75g Silizium-Sauerstoffcluster aus Beispiel 1c
• 4.2.5: 75 g Silizium-Sauerstoffcluster aus Beispiel 1d
• 4.2.6: 75 g Silizium-Sauerstoffcluster aus Beispiel 2
• 4.2.7: 75 g Silizium-Sauerstoffcluster aus Beispiel 3
• 4.2.8: 150 g Silizium-Sauerstoffcluster aus Beispiel 3

The procedure is as in Example 4.1, except that initially the mixture of 3000 g of methyl methacrylate and 1.2 g of methacrylic acid with 0.9 g of azobis (isobutyronitrile), 0.3 g of azobis (2,4-dimethylvaleronitrile) 0, Stir at room temperature with exclusion of air for 5 hours while stirring with:

• 4.2.1: 150 g silicon-oxygen cluster from example 1a
• 4.2.2: 75 g of silicon-oxygen clusters from Example 1a
• 4.2.3: 75 g silicon-oxygen cluster from example 1b
• 4.2.4: 75g silicon-oxygen cluster from Example 1c
• 4.2.5: 75 g of silicon-oxygen clusters from Example 1d
• 4.2.6: 75 g of silicon-oxygen clusters from Example 2
• 4.2.7: 75 g of silicon-oxygen clusters from Example 3
• 4.2.8: 150 g of silicon-oxygen clusters from Example 3

5. Exams

5.1 Measurement of scratch resistance

The scratch resistance is reduced with the Taber Abraser DIN 52347 with 5.4 N weight load at 100 revolutions through. A relatively high haze value means that the material is less scratch resistant.

5.2. Flammwidrigkeitsprüfung

The procedure is according to test UL 94 V-0 (eg published on the Internet: http://www.lairdtech.com/de/downloads/FA_UL_dt.pdf and http://www.geplastics.com/resins/de/devprod/flammabilityt.html ), in contrast, a continued burning of the vertically tested sample should be allowed here, but may not drip burning or burning material. 5.3 Test values according to 5.1 and 5.2 example Not according to the invention According to the invention Turbidity (%) UL 94 V-0 (modified) 4.1 (PMMA) X 20-30 Failed 4.2.1 X Not done passed 4.2.2 X Not done passed 4.2.3 X Not done passed 4.2.4 X Not done passed 4.2.5 X Not done passed 4.2.6 X Not done passed 4.2.7 X 10-20 passed 4.2.8 X about 10 passed

The Experimental results show that the inventively used Product in the burning state shows no dripping of the melt and further by the modification according to the invention the scratch resistance - d. H. the turbidity value after the abrasion test gets smaller - increases.

QUOTES INCLUDE IN THE DESCRIPTION

This list The documents listed by the applicant have been automated generated and is solely for better information recorded by the reader. The list is not part of the German Patent or utility model application. The DPMA takes over no liability for any errors or omissions.

Cited patent literature

• - DE 10130772 [0007]
• US 5484867 [0012]
• WO 03/064490 [0014]
• - WO 2006/125707 [0016, 0017, 0041]
• - WO 2007/121908 [0016, 0017, 0020]
• WO 2006/125708 [0021, 0040]
• - DE 10212458 [0024]

Cited non-patent literature

• - DIN 4102 [0007]
• - http://www.ceficefra.com/faq [0007]
• - http://www.ul-europe.com [0007]
• - http://www.lairdtech.com/en/downloads/FA_UL_dt.pdf [0007]
• - André Leisewitz et al., Research Report 297 44 542, "Development of evaluation principles for the substitution of environmentally relevant flame retardants", Volume I 04 08, 2000 [0007]
• - http://www.umweltdaten.de/publikationen/fpdf-l/1965.pdf [0007]
• - H. Rauch-Puntigam, Th. Völker, "Acrylic and Methacrylic Compounds ", Springer, Heidelberg, 1967 [0033]
• Kirk-Othmer, Encyclopedia of Chemical Technology, Vol. 1, pp. 386ff, J. Wiley, New York, 1978 [0033]
• - H. Rauch-Puntigam, Th. Völker, "Acrylic and Methacrylic Compounds", Springer, Heidelberg, 1967 [0035]
• - Houben-Weyl, Methods of Organic Chemistry, Vol. XIV / 1, page 66, Georg Thieme, Heidelberg, 1961 [0035]
• Kirk-Othmer, Encyclopedia of Chemical Technology, Vol. 1, pp. 296ff, J. Wiley, New York, 1978. [0035]
• - Hans Zweifel, Plastics Additives Handbook, 5th Edition, Carl Hanser Verlag 2001 [0037]
• - Vieweg-Esser, Kunststoffhandbuch, Volume IX, "Polymethacrylates", Carl Hanser Verlag 1975 [0037]
• Batzer, Polymeric Materials, Vol. II, Technology (337-353), Georg Thieme Verlag 1984 [0037]
• - 55 WL Runnels Industrial Drive, Hattiesburg, MS 39401, USA [0039]
• - DIN 52347 [0045]
• - http://www.lairdtech.com/en/downloads/FA_UL_dt.pdf [0046]
• - http://www.geplastics.com/resins/de/devprod/flammabilityt.html [0046]

Claims (17)

A composition based on (meth) acrylates, characterized in that said composition has from 0.01 to 15% by weight of polyhedral oligomeric silicon-oxygen clusters, according to the formula [(R _a A _b X _i SiO _1.5 ) _m (R _c A _d X _j SiO) _n (R _e A _f X _k Si ₂ O _2.5 ) _o (R _g A _h X ₁ Si ₂ O ₂ ] _p ] with: a, b, c, d, i = 0-1; j = 1-2; e, g, k = 0-3; f, h = 0-2; b + d + f + h ≥ 1, i + j + k + 1 ≥ 1; m + n + o + p ≥ 4; a + b + i = 1; c + d + j = 2; e + f + k = 3 and g + h + 1 = 4; R = hydrogen atom, alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl or polymeric moiety, each being substituted or unsubstituted, or other functionalized polyhedral oligomeric silicon-oxygen cluster units attached via a polymer moiety or bridging moiety , X = at least one monomeric building block having at least one double bond and optionally an oxy, hydroxy, alkoxy, carboxy, silyl, silyloxy, halogen, epoxy, ester, fluoroalkyl, isocyanate, acrylate, methacrylate , Mercapto, nitrile, amino, phosphine group or at least one type X substituent of the type R, A = hydrophobic substituent selected from fluorinated hydrocarbon radicals, preferably fluoroalkyltrialkoxysilanes according to the formula CF ₃ ((CF ₂ ) _o (CH ₂ ) _p ) Si (OR) ₃ with o, p = 0-12, wherein the substituents of the type R are the same or different. Composition according to Claim 1, characterized in that the double-bond-containing monomeric building block (Meth) acryl-Z _m -SiY _n (1) where m = 0 or 1 and n is equal to 1, 2 or 3, with the proviso m + n = 4, the groups Y are the same or different, where Y is OH, ONa, OK, OR, OCOR, OSiR ₃ , Cl, Br, I or NR ₂ . R is a hydrogen atom, a substituted or unsubstituted alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl or heteroaryl group. Z is a substituted or unsubstituted alkyl or aryl radical, an alkylsilyl, an oxyalkyl or an oxyaryl radical. The (meth) acrylic group is unsubstituted or substituted with halogen atoms and / or alkyl groups and / or alkenyl groups and / or aryl groups. Composition according to Claim 1, characterized in that the double-bond-containing monomeric building block Vinyl-Z _m -SiY _n (2) in which m = 0 or 1 and n are equal to 1, 2 or 3, with the proviso m + n = 4. The groups Y are identical or different, Y being OH, ONa, OK, OR, OCOR, OSiR ₃ , Cl, Br, I or NR ₂ . R is a hydrogen atom, a substituted or unsubstituted alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl or heteroaryl group. Z is a substituted or unsubstituted alkyl or aryl radical, an alkylsilyl, an oxyalkyl or an oxyaryl radical. The vinyl group is unsubstituted or substituted with halogen atoms and / or alkyl groups and / or alkenyl groups and / or aryl groups. Composition according to Claim 1, characterized in that the double-bond-containing monomeric building block Cycloalkenyl-Z _m -SiY _n (3) in which m = 0 or 1 and n are equal to 1, 2 or 3, with the proviso m + n = 4. The groups Y are identical or different, Y being OH, ONa, OK, OR, OCOR, OSiR ₃ , Cl, Br, I or NR ₂ . R is a hydrogen atom, a substituted or unsubstituted alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl or heteroaryl group. Z is a substituted or unsubstituted alkyl or aryl radical, an alkylsilyl, an oxyalkyl or an oxyaryl radical. The cycloalkenyl group is unsubstituted or substituted with halogen atoms and / or alkyl groups and / or alkenyl groups and / or aryl groups. Composition according to Claim 1, characterized in that the double-bond-containing monomeric building block Norbornenyl-Z _m -SiY _n (4) where m = 0 or 1 and n are equal to 1, 2 or 3, given m + n = The groups Y are the same or different, wherein Y is OH, ONa, OK, OR, OCOR, OSiR ₃ , Cl, Br, I or NR ₂ . R is a hydrogen atom, a substituted or unsubstituted alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl or heteroaryl group. Z is a substituted or unsubstituted alkyl or aryl radical, an alkylsilyl, an oxyalkyl or an oxyaryl radical. The norbornenyl group is unsubstituted or substituted with halogen atoms and / or alkyl groups and / or alkenyl groups and / or aryl groups. Composition according to Claim 1, characterized in that the double-bond-containing monomeric building block [HR'C = C (R '') - Z ' _m -COO] ^- [NHR ₂ ] ⁺ -Z _m -SiY _n (5) where m is equal to or independently of one another and m '= 0 or 1 and n is equal to 1, 2 or 3, then m + n = 4. The Y groups are the same or different, Y being OH, ONa, OK , OR, OCOR, OSiR ₃ , Cl, Br, I or NR ₂ . R is a hydrogen atom, a substituted or unsubstituted alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl or heteroaryl group. R 'is the same or independent of R and is a hydrogen atom, a substituted or unsubstituted alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl or heteroaryl group. R '' is the same or independent of R 'or R and is a hydrogen atom, a substituted or unsubstituted alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl or heteroaryl group. Z and Z 'are the same or different and represent a substituted or unsubstituted alkyl or aryl radical, an alkylsilyl, an oxyalkyl or an oxyaryl radical. Composition according to claim 1, characterized in that the polyhedral oligomeric silicon-oxygen cluster at least one alkenyl group polymerizable with a (meth) acrylic group is, has. Composition according to at least one of claims 1 or 7, characterized in that the composition of 0.05 to 5 wt .-% of a molecular weight regulator having. Composition according to at least one of claims 1 to 8, characterized in that the composition at most 5 wt .-% of polymerization initiator having. Composition according to at least one of claims 1 to 9, characterized in that the polyhedral oligomeric silicon-oxygen clusters in one separate production step and before the polymerization dispersed in the composition. Composition according to at least one of claims 1 to 10, characterized in that the polyhedral oligomeric silicon-oxygen clusters prior to polymerization dissolved in the composition. Composition according to at least one of Claims 1 to 11, characterized in that the (meth) acrylate polymer has a molecular weight of greater than 100,000 g / mol. Composition according to at least one of claims 1 to 12, characterized in that the (Meth) acrylate polymer has a molecular weight of the largest 1000 000 g / mol. Composition according to at least one of claims 1 to 13, characterized in that the the polyhedral, oligomeric silicon-oxygen cluster is a fluoroalkyl group having. Composition according to at least one of claims 1 to 14, characterized in that the polyhedral, oligomeric silicon-oxygen cluster is a mixture and according to WO 2006/125707 will be produced. Use of the composition according to the Claims 1 to 15 for the production of clear moldings and semi-finished products, such. Eg pipes, plates, glazings and windows, Furniture and optical fibers.