Classifications

• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
  • C09D175/04—Polyurethanes
  • C09D175/06—Polyurethanes from polyesters
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
  • C08K5/005—Stabilisers against oxidation, heat, light, ozone
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/16—Nitrogen-containing compounds
  • C08K5/315—Compounds containing carbon-to-nitrogen triple bonds
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K15/00—Anti-oxidant compositions; Compositions inhibiting chemical change
  • C09K15/04—Anti-oxidant compositions; Compositions inhibiting chemical change containing organic compounds
  • C09K15/20—Anti-oxidant compositions; Compositions inhibiting chemical change containing organic compounds containing nitrogen and oxygen
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G2290/00—Compositions for creating anti-fogging

Definitions

• the present invention relates to a stabilizer composition consisting of mindes ⁇ least a solid under standard conditions UV absorber from the group of diphenylcyanoacrylates having a molecular weight of at least 500 g / mol and least min ⁇ a liquid at 50 0 C and standard pressure UV absorber and their use for the stabilization of polymer compositions.
• the present invention relates to a process for the preparation of polyisocyanate polyaddition products by reacting polyisocyanates with isocyanate-reactive polyvalent compounds, the reaction taking place in the presence of such a stabilizer composition.
• UV radiation ultraviolet radiation
• plastics can be stabilized with at least one UV absorber.
• suitable UV absorbers a large number of different solid and liquid compounds are known, for example from the group of the benzotriazoles, diphenylcyanoacrylates, cinnamic acid esters, hydroxybenzophenones or hydroxyphenyltriazines.
• liquid UV absorbers have the technical disadvantage of a relatively high volatility.
• they since they are only partially compatible with many plastics, they tend to migrate, in particular under the influence of heat, and exhibit exudation effects. This leads to a loss of stabilization and an unwanted release of the UV absorber.
• the substances emerging from the plastic strike, for example, as a misty coating on the inside of windshields. This effect is called "fogging".
• the precipitation affects the transparency, especially in direct sunlight or at night by glare from headlights of oncoming vehicles. There is therefore a need for UV stabilizer compositions which avoid the disadvantages mentioned above.
• WO 96/15102 describes high molecular weight 2-cyanoacrylic acid esters, which u. a. for the stabilization of plastics. Quite generally, without a sample Ausry ⁇ example, a possible combination of high molecular weight 2-cyanoacrylic acid esters with other light stabilizers such as derivatives of ⁇ -cyanocinnamic acid, 2-hydroxybenzophenones and 2- (2'-hydroxyphenyl) benzotriazoles is mentioned.
• US Pat. No. 6,297,300 describes carbonate polymers which contain as light stabilizer composition at least two UV light stabilizers selected from various groups and having a molecular weight of at least 400 g / mol in each case.
• Suitable groups are cyanoacrylates, hydroxyphenylbenzotriazoles and hydroxyphenyltriazines.
• As a suitable high molecular weight cyanoacrylate there is cited 1,3-bis - [(2 1 -cyano-3 ', 3'-diphenylacryloyooxyj ⁇ to bis'-cyano-S'.S'-diphenylacryloyooxy ⁇ methylpropane.
• WO 01/57125 describes a benzotriazole-stabilized candle wax.
• UV stabilizers such as s-triazines, benzoates, ⁇ -cyanoacrylates, benzophenones, malonates, oxanilides and salicylates.
• No. 5,821,292 describes the use of 3-arylacrylic acid esters as light stabilizers. These can be used in combination with other light stabilizers such as 2- (2-hydroxyphenyl) benzotriazoles, 2-hydroxybenzophenones, aryl esters of hydroxybenzoic acids, derivatives of ⁇ -cyanocinnamic acid, benzimidazolecarboxanilides, nickel compounds and oxanilides. Among other things, they find use for stabilizing polyurethanes.
• EP 1 323 743 describes a resin composition containing a mixture of UV absorbers comprising a cyanoacrylate and a benzotriazole.
• EP 0 992 533 describes polyisocyanate polyaddition products which contain a covalently bonded dye and at least one UV absorber selected from the group of benzotriazoles, cinnamic acid esters, diphenylcyanoacrylates and benzophenones, at least one antioxidant and at least one radical scavenger.
• a preferred UV absorber is u. a. 2-ethylhexyl-p-methoxycinnamate.
• US Pat. No. 4,935,275 discloses a stabilizer composition for stabilizing polyurethanes, the stabilizer composition being a ternary system comprising a sterically hindered amine, a C 2 -C 8 -alkyl 2-cyano-3,3-diphenylacrylic acid such as 2-ethylhexyl-2 cyan-3,3-diphenyl acrylate and a hindered phenol.
• the object of the present invention is to provide a novel stabilizer composition having good performance properties.
• the composition should have a high protective effect against the damaging effect of light and be present in a form which can be easily incorporated into the material to be stabilized and homogeneously distributed.
• the specifically mentioned disadvantages, in particular the fogging from the plastic should be avoided.
• the stabilizer composition should be particularly effective for stabilizing polyisocyanate polyaddition products and polyvinyl chloride.
• the object is surprisingly achieved by a stabilizer composition (S) consisting of:
• the present invention therefore provides a stabilizer composition (S) as defined above and its use in a polymer composition containing at least one polymer which is preferably selected from polyesters, polycarbonates, polyamides, polyolefins, polyvinyl acetals, polystyrene, copolymers of styrene or ⁇ - Methylstyrene with dienes and / or acrylic derivatives, halogen-containing polymers, polyisocyanate polyaddition products and mixtures thereof.
• a polymer composition containing at least one polymer which is preferably selected from polyesters, polycarbonates, polyamides, polyolefins, polyvinyl acetals, polystyrene, copolymers of styrene or ⁇ - Methylstyrene with dienes and / or acrylic derivatives, halogen-containing polymers, polyisocyanate polyaddition products and mixtures thereof.
• Another object of the present invention is a process for the preparation of polyisocyanate polyaddition products by reacting polyisocyanates with isocyanate-reactive compounds, wherein the reaction in Ge the presence of the stabilizer composition (S), as defined above takes place.
• polyisocyanate polyaddition product is understood to mean oligomeric and polymeric compounds which are obtained in the reaction of di- or polyfunctional isocyanates with compounds which have at least two groups which are reactive toward NCO groups.
• the resulting oligomeric and polymeric compounds may thus contain polyurethane and optionally polyisocyanate structures, polyurea structures, polyalphanate structures and polybiuretstructures.
• liquid is understood to mean rheological properties which range from low-viscosity over pasty / ointment-like to gel-like.
• Gel-like consistency show compounds or compositions which have a higher viscosity than a liquid and which are self-supporting, i. However, in contrast to solid compounds or compositions, gel-like compounds or compositions can be deformed by the application of shear forces.
• the term “flowable” can also be used in the context of the present invention.
• alkyl includes straight or branched chain hydrocarbon radicals.
• these are straight-chain or branched Ci-C 20 -AlkyI and particularly preferably C r C 12 alkyl groups.
• alkyl groups are in particular methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, 2-pentyl, 3-pentyl, 2-methylbutyl, 3-methylbutyl, 1 , 2-dimethylpropyl, 1, 1-dimethylpropyl, 2,2-dimethylpropyl, n-hexyl, 2-hexyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1, 2-dimethylbutyl, 1, 3-dimethylbutyl, 2 , 3-Dimethylbutyl, 1, 1-dimethylbutyl, 2,2-dimethylbutyl, 3,3-dimethylbutyl, 1, 1, 2-trimethylpropyl, 1, 2,2-trimethylpropyl, 1-ethylbutyl, 2-ethylbutyl, 1-ethyl 2-methylpropyl,
• alkyl also includes alkyl whose carbon chain is replaced by one or more nonadjacent groups selected from -O-, -S-, -NR 10 - (wherein R 10 is hydrogen or C 1 -C 4 -alkyl), -CO- and / or -SO 2 - may be interrupted, ie the termini of the acyl group are formed by carbon atoms.
• alkenyl in the context of the present invention comprises straight-chain and branched alkenyl groups which, depending on the chain length, can carry one or more double bonds. Preference is given to C 2 -C 2O- , particularly preferably C 2 -C 10 -alkenyl groups, such as vinyl, allyl or methallyl.
• alkenyl also includes substituted alkenyl groups which are e.g. B. 1, 2, 3, 4 or 5 substituents formerly ⁇ NEN. Suitable substituents are, for. Cycloalkyl, heterocycloalkyl, aryl, heteroaryl, cyano, halo, amino, mono- or di- (C 1 -C 20 -alkyl) -amino.
• cycloalkyl in the context of the present invention comprises unsubstituted or substituted mono- or polynuclear cycloalkyl groups, preferably C 3 -C 10 -cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, Hydrindanyl, decalinyl, bicyclo [2.2.1] hept-1-yl, bicyclo [2.2.1] hept-2-yl, bicyclo [2.2.1] hept-7-yl, bicyclo [2.2.2] oct-1 yl, bicyclo [2.2.2] oct-2-yl, bicyclo [3.3.0] octyl and bicyclo [4.4.0] decyl.
• the cycloalkyl groups may have one or more, spielmud one
• cycloalkenyl in the context of the present invention comprises unsubstituted as well as substituted mono- or polynuclear cycloalkenyl groups, preferably C 3 -C 10 -cycloalkenyl groups such as cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, cycloheptenyl, cyclooctenyl, cyclononenyl, cyclodecenyl, indenyl or tetralinyl.
• the cycloalkenyl groups may contain one or more, for example 1, 2, 3 or 4 double bonds.
• the cycloalkenyl groups can in the case of a substitution or more, for example one, two, three, four or five support a group selected from C r c o 2 alkyl and C 1 -C 6 -alkoxy substituents.
• aryl in the context of the present invention comprises mononuclear or polynuclear aromatic hydrocarbon radicals, for example mono-, di- or tri-nuclear aromatic hydrocarbon radicals which may be unsubstituted or substituted.
• the aryl group may generally bear 1, 2, 3, 4 or 5, preferably 1, 2 or 3, substituents selected from C 1 -C 20 -alkyl and C 1 -C 6 -alkoxy.
• aryl preferably phenyl, ToIyI, XyIyI, Mesi tyl, duryl, naphthyl, fluorenyl, anthracenyl, phenanthrenyl or naphthyl, more preferably phenyl or naphthyl.
• Aryl is unsubstituted or which bears one or more radicals which are independent of one another selected from C r C 20 alkyl and C 1 -C 6 -alkoxy, represents, for example 2-, 3- and 4-methylphenyl, 2, 4-, 2,5-, 3,5- and 2,6-dimethylphenyl, 2, 4,6-trimethylphenyl, 2-, 3- and 4-ethylphenyl, 2,4-, 2,5-, 3,5 and 2,6-diethylphenyl, 2,4,6-triethylphenyl, 2-, 3- and 4-propylphenyl, 2,4-, 2,5-, 3,5- and 2,6-dipropylphenyl, 2,4 , 6-tripropylphenyl, 2-, 3- and 4-isopropylphenyl, 2,4-, 2,5-, 3,5- and 2,6-diisopropylphenyl, 2,4,6-triisopropylphenyl, 2-, 3- and 4-butylphenyl, 2,4-
• heterocycloalkyl in the context of the present invention comprises non-aromatic, unsaturated or fully saturated, cycloaliphatic groups having generally 5 to 8 ring atoms, preferably 5 or 6 ring atoms, in which 1, 2 or 3 of the ring carbon atoms by heteroatoms selected from Oxygen, nitrogen, sulfur and a group -NR 10 - (wherein R 10 has the abovementioned meaning) and are unsubstituted or with one or more, for example 1, 2, 3, 4, 5 or 6 CrC 2 o-alkyl and C 1 -C 6 -alkoxy is substituted.
• heterocycloaliphatic groups are pyrrolidinyl, piperidinyl, 2,2,6,6-tetramethylpiperidinyl, imidazolidinyl, pyrazolidinyl, oxazolidinyl, morpholidinyl, thiazolidinyl, isothiazolidinyl, isoxazolidinyl, piperazinyl, tetrahydrothiophenyl, dihydrothienyl, tetrahydrofuranyl, dihydrofuranyl Tetrahydropyranyl, isoxazolinyl, oxazolinyl and dioxanyl.
• heteroaryl in the context of the present invention comprises unsubstituted or substituted, heteroaromatic, mononuclear or polynuclear groups having in general 5 to 14 ring atoms, preferably 5 or 6 ring atoms, in which 1, 2 or 3 of the ring carbon atoms Heteroatoms selected from oxygen, nitrogen, sulfur and a group -NR 10 - (wherein R 10 has the aforementioned meaning importance) replaced and which is unsubstituted or with one or more, for example 1, 2, 3, 4, 5 or 6 C r C 2 o-alkyl and C 1 -C 6 -alkoxy is substituted.
• the groups furyl, thienyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, benzofuranyl, benzothiophenyl, pyridyl, quinolinyl, acridinyl, pyridazinyl, pyrimidinyl, pyrazinyl, pyrryl, imidazolyl, pyrazolyl, indolyl, puryl, indazolyl, benzotriazolyl are examples of such heteroaryl groups , 1, 2,3-triazolyl, 1, 2,4-triazolyl and carbazolyl, these heterocycloaromatic groups in the case of a substitution generally 1, 2 or 3 substituents, may carry called.
• the substituents are selected un ⁇ ter d-Ce-alkyl, and C r C 6 alkoxy.
• acyl encompasses alkanoyl, heteroaryl and aroyl groups having generally 1 to 11, preferably 2 to 8, carbon atoms, for example the formyl, acetyl, propionyl, butyryl, Pentanoyl, hexanoyl, heptanoyl, 2-ethylhexanoyl, 2-propylheptanoyl, benzoyl or naphthoyl group.
• halogen includes fluoro, chloro, bromo and iodo, preferably chloro and bromo.
• the stabilizer composition (S) according to the invention is preferably present under standard conditions as a viscous liquid and can therefore easily be incorporated into the material to be stabilized and distributed homogeneously.
• the stabilizer composition (S) which is liquid under standard conditions according to the invention may be a solution or dispersion. Preferred are solutions.
• component i) comprises only those compounds which have a molecular weight of at least 650 g / mol, in particular at least 800 g / mol and very particularly preferably at least 1000 g / mol.
• Preferred UV absorbers which are suitable as component i) of the stabilizer composition (S) according to the invention have the general formula (I): wherein
• R 1a , R 1b , R 1C , R 1d , R 1e , R 2a , R 2b , R 2c , R 2d and R 2e are each independently hydrogen, alkyl, alkenyl, halo, cyano, nitro, amino, monoalkylamino, dial - kylamino, hydroxy, acyl, acyloxy, alkoxy, alkoxycarbonyl, cycloalkyl, cycloalkoxycarbonyl, cycloalkenyl, aryl, heteroaryl or heterocycloalkyl;
• n is an integer from 3 to 10;
• X is an n-valent aliphatic or cycloaliphatic radical having 3-20 Kohlen ⁇ atoms, wherein a cycloaliphatic radical is also by 1 to 2 and an aliphatic radical by 1, 2, 3, 4, 5, 6, 7, 8 or 9 non-adjacent oxygen atoms, sulfur atoms, imino or C 1 -C 4 -alkylimino groups may be interrupted
• R 1a , R 1b , R 1c , R 1d , R 1e , R 2a , R 2b , R 2c , R 2d and R 2e is alkyl, it is preferably dC 2 o-alkyl.
• Alkenyl is preferably C 2 -C 10 -alkenyl.
• Halogen is preferably chlorine or bromine.
• Monoalkylamino is preferably mono (C 1 -C 4 -alkyl) amino.
• Dialkylamino is preferably also di (C 1 -C 4 -alkyl) amino.
• Acyl is preferably C 1 -C 8 -acyl.
• Acyloxy is preferably C 1 -C 8 acyloxy.
• Alkoxy is preferably C 1 -C 18 -alkoxy.
• Alkoxycarbonyl is preferably C 1 -C 4 -alkoxycarbonyl.
• Cycloalkyl is preferably C 3 -C 10 -cycloalkyl which is unsubstituted or carries one, two, three, four or five substituents selected from C 1 -C 6 -alkyl and C 1 -C 6 -alkoxy.
• Cycloalkoxycarbonyl is preferably Ca-C ⁇ -cycloalkoxycarbonyl which is unsubstituted or carries one, two, three, four or five substituents selected from C 1 -C 10 -alkyl and C 1 -C 6 -alkoxy.
• Cycloalkenyl is preferably C 3 -C 10 cycloalkenyl which is unsubstituted or carries one, two, three, four or five substituents selected from (C 1-4 alkyl and C 1 -C 6 alkoxy)
• Aryl is preferably phenyl or naphthyl , the unsubstituted or carries one, two, three, four or five substituents selected from C 1 -C 10 -alkyl and C 1 -C 6 -alkoxy.
• X is an n-valent aliphatic or cycloaliphatic radical.
• X is derived from the corresponding n-valent aliphatic or cycloaliphatic alcohols by removal of the OH group. These alcohols may be linear or branched, and their carbon chains may be interrupted by one or more oxygen or sulfur atoms, by imino groups or by C 1 -C 4 -alkylimino groups.
• the group X is preferably derived from the following known polyols:
• diphenylcyanoacrylates are known, for example, from WO 96/15102 and DE 44 40 055, to the disclosure of which reference is hereby fully made.
• Diphenylcyanoacrylates of the formula (I) in which R 1a , R 1b , R 1c , R 1d , R 1e , R 2a , R 2b , R 20 , R 2d and R 2e have a different meaning can be prepared by corresponding processes become.
• a particularly preferred diphenylcyanoacrylate is 1-bis-bis-cyano-S, S, S-diphenylacryloyl, oxy! -2,2-bis ⁇ [2 1- cyano-3 ', 3'-diphenylacryloyl) oxy] methyl ⁇ propane (CAS No. [178671-58-4], which is commercially available, for example, as Uvinul® 3030 from BASF AG, Ludwigshafen.
• component ii) are in principle all UV absorbers are suitable, which are liquid at 50 0 C under standard pressure.
• component ii) is selected from the group of benzotriazoles, diphenylcyanoacrylates, cinnamic acid esters, hydroxybenzophenones, hydroxyphenyltriazines and mixtures thereof.
• component ii) comprises only those UV absorbers which are liquid under standard conditions.
• the component ii) comprises UV absorbers of the general formula (II)
• R 3 is hydrogen or a group A stands
• # is the point of attachment to the acrylic backbone
• R 3a , R 3b , R 3c , R 3d and R 3e are each independently hydrogen, alkyl, alkenyl, halogen, cyano, nitro, amino, monoalkylamino, dialkylamino, hydroxy, acyl, acyloxy, alkoxy, alkoxycarbonyl, cycloalkyl, Cycloalkoxycarbonyl, cycloalkenyl, aryl, heteroaryl or heterocycloalkyl;
• R 4a , R 4b , R 4c , R 4d and R 4e are each independently of one another hydrogen, alkyl, alkenyl, halogen, cyano, nitro, amino, monoalkylamino, dialkylamino, hydroxy, acyl, acyloxy, alkoxy, alkoxycarbonyl, cycloalkyl, cycloalkoxycarbonyl, Cycloalkenyl, aryl, heteroaryl or heterocycloalkyl;
• R 5 is hydrogen or cyano
• R 6 is OR 7 or NR 8 R 9 ,
• R 7 is hydrogen, alkyl, alkenyl, cycloalkyl, cycloalkenyl, aryl, heteroaryl, heterocycloalkyl or (CH 2 CH 2 -O) 0 -R ";
• R 8 , R 9 are each independently of one another hydrogen, alkyl, alkenyl, cycloalkyl,
• R 3 , R 4a , R 4b , R 40 , R 4d , R 4e and R 5 have the abovementioned meaning aufwei ⁇ sen;
• o stands for an integer from 1 to 10.
• R 3a , R 3b , R 3c , R 3d , R 3e , R 4a , R 4b , R 4c , R 4d and R 4e is alkyl, it is preferably C 1 -C 20 - -alkyl.
• Alkenyl is preferably C 2 -C -alkenyl.
• Halogen is preferably chlorine or bromine.
• Monoalkyl amino is preferably mono (C r C 4 alkyl) amino.
• Dialkylamino is preferably also di (C 1 -C 4 -alkyl) amino.
• Acyl is preferably Ci-C 8 -Acyl.
• Acyloxy is preferably C 1 -C 8 acyloxy.
• Alkoxy is preferably C 1 -C 18 -alkoxy.
• Alkoxycar- carbonyl is preferably C r C 2 alkoxycarbonyl.
• Cycloalkyl preferably is C 3 -C 10 cycloalkyl which is unsubstituted or which bears one, two, three, four or five selected from C r C 10 alkyl and C 1 -C 6 -alkoxy substituents.
• Cycloalkoxycarbonyl is preferably C 3 -C 6 cycloalkoxycarbonyl which is unsubstituted or carries one, two, three, four or five under CRCI ⁇ alkyl and -C 6 alkoxy substituents selected.
• Cycloalkenyl is preferably C 3 -C 10 cycloalkenyl which is unsubstituted or one, two, three, four or five under -C 10 alkyl and -C 6 alkoxy selected substituents.
• Aryl is preferably phenyl or naphthyl, which is ated unsubstitu ⁇ or one, two, three, four or five sub-Ci-Ci o alkyl, and Ci-C 6 alkoxy transmits easily ⁇ selected substituents.
• R 7 or at least one of R 8 or R 9 is alkyl, it is preferably C 1 -C 20 -alkyl whose carbon chain is replaced by one or more nonadjacent groups selected from -O-, -S-, -NR 10 - (wherein R 10 is hydrogen or C r C 4 alkyl), -CO- and / or -SO 2 - may be interrupted.
• Alkenyl is preferably C 2 -C 10 alkenyl.
• Cycloalkenyl stands preferably C 3 -C 10 -cycloalkenyl which is unsubstituted or carries one, two, three, four or five substituents selected from C 1 -C 10 -alkyl and C 1 -C 6 -alkoxy.
• Aryl is preferably phenyl or naphthyl which is unsubstituted or carries one, two, three, four or five substituents selected from C 1 -C 10 -alkyl and C 1 -C 6 -alkoxy.
• R 3 is a radical of the formula A in which up to three, particularly preferably one of the radicals R 3a , R 3b , R 30 , R 3d and R 3e is C 1 -C 4 -alkyl, C 1 -C 12 -alkoxy or di (C 1 -C 4 -alkylamino) and the remaining of these radicals are hydrogen.
• R 3c is C r C 4 alkyl, C r C 4 alkoxy or di (C 1 -C 4 alkyl) amino, especially methyl, ethyl, methoxy or dimethylamino and the remaining of these radicals for hydrogen ,
• R 3a , R 3b , R 3c , R 3d and R 3e are each hydrogen.
• R 4a, R 4b, R 4c, R 4d and R 12 alkyl, C r C 4e -C 12 alkoxy or di (C 1 -C 4 alkylamino ) and the rest of these radicals are hydrogen.
• R 40 is C r C 4 alkyl, C 1 -C 4 -alkoxy or di (CrC 4 alkyl) amino, especially methyl, ethyl, methoxy or dimethyl amino and the remainder of these radicals are hydrogen.
• R 4a , R 4b , R 4c , R 4d and R 48 are each hydrogen.
• R 5 is cyano. Equally preferred are compounds II, wherein R 5 is hydrogen.
• R 6 is OR 7 or NR 8 R 9 wherein R 7 and R 8 and R 9 are each independently preferably C 4 -C 8 alkyl, in particular C 4 -C 12 alkyl whose carbon chain can be interrupted by one, two, three, four, five, six or seven non-adjacent oxygen atoms, imino groups or C 1 -C 4 -alkylimino groups.
• Particularly preferred are branched C 4 -C 18 -alkyl groups and chains, which are described by the general formula (CH 2 CH 2 -O) 0 -R ", wherein R" is hydrogen, alkyl, preferably CrC 18 alkyl or a radical of the formula B,
• R 3 , R 4a , R 4b , R 4c , R 4d , R 4e and R 5 have the abovementioned and in particular the preferred meanings, and o is a number of 1 to 10, preferably 2 to 8 stands.
• R 7 is 3 -C 8 -cycloalkyl, which may optionally bear one or two among C r C 4 -AlkyI or -C 4 alkoxy substituents selected C.
• Such diphenylcyanoacrylates or amides or phenylacrylic acid esters or amides are known, for example, from US Pat. Nos. 5,821,292, DE 10058290, EP 1323743 and US Pat. No. 4,935,275 or can be prepared on the basis of the processes described therein.
• R 4a, R 4b, R 4d and R 4e each represent hydrogen, R 4c is methoxy, R 3 is hydrogen, if is preferably p-methoxycinnamate (compound II, R 5 is hydrogen and R 6 is isoamyl)
• 2-cyano-3,3-diphenylacrylic acid 2'-ethylhexyl ester is commercially available as Uvinul® 3039 from BASF AG.
• p-methoxycinnamic acid 2-ethylhexyl ester is commercially available as Uvinul® 3088 from BASF AG, Ludwigshafen.
• isoamyl p-methoxycinnamate is available from Symrise as Neo Heliopan® E1000.
• the stabilizer composition (S) according to the invention may also comprise benzotriazoles as component ii).
• a suitable benzotriazole is, for example, 2- (2H-benzotriazol-2-yl) -6-dodecyl-4-methylphenol, which is commercially available as Tinuvin® 571 from Ciba Specialty Chemicals, Inc.
• the stabilizer composition (S) according to the invention may also comprise 2-hydroxybenzophenones as component ii).
• a suitable 2-hydroxybenzophenone is, for example, 2-hydroxy-4-octoxybenzophenone, which is commercially available as Uvinul® 3008 from BASF AG, Ludwigshafen.
• the solid component i) is brought into intimate contact with the liquid component ii), for example by mixing.
• suitable mixing devices for the preparation of mixtures of liquid / solid educts or solid starting materials under standard conditions are known to the person skilled in the art. These include, for example, mixing devices based on static or dynamic mixers, such as stirred tanks, dispersing machines, ultrasonic or high-pressure homogenizers.
• mixing devices based on static or dynamic mixers such as stirred tanks, dispersing machines, ultrasonic or high-pressure homogenizers.
• one of the components i) or ii) present partially and the remaining component (s) added by conventional methods.
• the liquid component ii) is at least partially vorge ⁇ sets.
• the addition of the solid component i) can then be carried out, for example, continuously or in portions.
• the bringing into contact can take place, for example, at ambient temperature or with the supply of heat.
• the components i) and ii) can be heated together and then allowed to cool, or the component ii) is heated and then the solid component i) is added to the liquid component ii).
• the Her ⁇ position of the stabilizer composition (S) is generally carried out at a Tempera ⁇ tur above ambient temperature, preferably at temperatures ranging from 25 0 C to 200 0 C, preferably between 100 0 C and 180 0 C.
• solutions or dispersions are formed.
• component i) is completely soluble in component ii)
• the use of auxiliaries in the preparation of the stabilizer composition (S) according to the invention can as a rule be dispensed with.
• This also generally applies to the preparation of stable stabilizer dispersions.
• it is generally sufficient to expose components i) and ii) to sufficiently strong shearing forces in order to produce stable disperse mixtures, preferably molecular disperse mixtures.
• At least one solvent is used as auxiliary for preparing the stabilizer composition (S) according to the invention.
• Preferred solvents are those which are more volatile than the most volatile component of the stabilizer composition (S). These include aliphatic, cycloaliphatic or aromatic hydrocarbons, such as pentane, hexane, petroleum ether, cyclohexane, toluene, ethers, such as diethyl ether, tert-butyl methyl ether, tetrahydrofuran, ketones, such as Acetone, diethyl ketone or methyl ethyl ketone, carboxylic acid alkyl esters such as ethyl acetate or halogenated hydrocarbons such as dichloromethane or trichloromethane. Solvents used in the preparation can be removed by conventional methods known to those skilled in the art after preparation of the stabilizer composition (S), for. B. by evaporation under reduced pressure.
• the finished stabilizer compositions (S) according to the invention preferably contain essentially no solvent, ie. H. the proportion of solvent is less than 1% by weight, based on the total weight of the stabilizer composition (S).
• Further suitable auxiliaries in the preparation of the stabilizer composition (S) according to the invention are emulsifiers, protective colloids and dispersants.
• the stabilizer compositions (S) according to the invention contain no additional auxiliaries.
• stabilizer compositions wherein the Kompo ⁇ component i) 1, 3-bis - [(2-cyano-I 3 1, 3 1 -diphenylacryloyl) oxy] -2,2-bis ⁇ [2'-cyano -3 1 , 3 1 -diphenyl-acryloyl) oxy] methyl ⁇ propane and component ii) is selected from 2-cyano-3,3-diphenylacrylic acid 2'-ethylhexyl ester, p-methoxycinnamic acid 2-ethylhexyl ester, Hydroxy-4-octoxybenzophenone, p-Methoxycinnamic acid isoamyl ester and
• stabilizer compositions (S) in which component i) 1, 3-bis - [(2 1 -cyano-3 ', 3 1 -diphenylacryloyl) oxy] -2,2-bis ⁇ [2 1 -cyano -3 I , 3 is 1 -diphenylacryloyl) oxy] methyl ⁇ propane and component ii) is 2-cyano-3,3-diphenyl-2-ethylhexyl acrylate.
• stabilizer compositions (S) in which component i) contains 1, 3-bis - [(2'-cyano-3 ', 3'-diphenylacryloyOxyJ ⁇ - bisJP'-cyano-S'.S' -diphenylacryloyoxy methyl-propane and component ii) is 2-ethylhexyl p-methoxycinnamate.
• stabilizer compositions (S) in which component i) 1, 3-bis - [(2 l -cyano-3 ', 3 l -diphenylacryloyl) oxy] -2,2-bis ⁇ [2 l -cyano -3 ', 3 l -diphenyl-acryloyl) oxy] methyl ⁇ propane and component ii) is 2- (2H-benzotriazol-2-yl) -6-dodecyl-4-methylphenol.
• stabilizer compositions (S) in which component i) 1, 3-bis - [(2'-cyano-3 ', 3'-diphenylacryloyl) oxy] -2,2-bis ⁇ [2' cyano-3 1 , 3 l -diphenylacryloyl) oxy] methyl ⁇ propane and component ii) is 2-hydroxy-4-octoxybenzophenone.
• the stabilizer composition (S), based on the total weight of the components i) and ii) is preferably from 0.001 to 50 wt., In particular 0.1 to 40 wt .-% and most preferably 1 to 30 wt .-% of component i ) and from 50 to 99.999% by weight, in particular 60 to 99.9% by weight and very particularly preferably 70 to 99% of component ii).
• the stabilizer composition (S) according to the invention is suitable for stabilizing inanimate organic and revived organic material, in particular for stabilizing inanimate organic material, such as plastics.
• a further subject of the present invention therefore relates to a polymer composition
• a polymer composition comprising a stabilizer composition (S) as defined above and at least one polymer selected from polyesters, polycarbonates, polyamides, polyolefins, polyvinyl acetals, polystyrene, copolymers of styrene or ⁇ -methylstyrene with dienes and / or acrylic derivatives, halogen-containing polymers, polyisocyanate polyaddition products and mixtures thereof.
• S stabilizer composition
• the polymer composition contains 0.005 to 10 wt .-%, preferably 0.01 to 5 wt .-%, in particular 0.05 to 2 wt .-% of the stabilizer composition (S), based on the weight of the polymer composition.
• the weight of the polymer composition is understood as meaning the weight of the polymer composition, including added additives, stabilizers, auxiliaries or additives.
• the polymer composition contains, as polymer, at least one polyester, preferably at least one linear polyester.
• polyesters and copolyesters are described in EP-A-0678376, EP-A-0 595 413 and US 6,096,854, to which reference is hereby made.
• Polyesters are known to be condensation products of one or more polyols and one or more polycarboxylic acids.
• the polyol is a diol and the polycarboxylic acid is a dicarboxylic acid.
• the polymer composition contains a polycarbonate as polymer.
• Polycarbonates are formed z. B. by condensation of phosgene or carbonic acid esters such as diphenyl carbonate or
• Dimethyl carbonate with dihydroxy compounds are aliphatic or aromatic dihydroxy compounds.
• aromatic dihydroxy compounds are bisphenols, such as 2,2-bis- (4-hydroxyphenyl) -propane (bisphenol-A), tetraalkylbisphenol-A, 4,4- (meta-phenylenediisopropyl) diphenol (bisphenol M), 4,4 - (para-phenylenediisopropyl) diphenol, 1, 1-bis (4-hydroxyphenyl) - 3,3,5-trimethylcyclohexane (BP-TMC), 2,2-bis (4-hydroxyphenyl) -2-phenylethane, 1, 1-bis (4-hydroxyphenyl) -cyclohexane (bisphenol-Z) and optionally their Called Gemi ⁇ cal.
• the polycarbonates can be branched by using small amounts of branching agents.
• the polymer composition contains at least one polyamide as polymer.
• Polyamides can be prepared, for example, by polycondensation from diamines, for example hexamethylenediamine, and dicarboxylic acids, such as adipic acid. Polyamides are also by polycondensation of amino acids or by ring-opening polymerization of lactams, eg. B. caprolactam available.
• the polymer composition contains at least one polyolefin as polymer.
• polyolefin encompasses all polymers which are synthesized from olefins without further functionality, such as low or high density polyethylene, polypropylenes, linear polybutene-1 or polyisobutylene or polybutadiene and also copolymers of monoolefins or diolefins , Preferred polyolefins are the homopolymers and copolymers of ethylene, as well as the homopolymers and copolymers of propylene.
• the polymer composition as polymer contains at least one polyvinyl acetal.
• Polyvinyl acetals are the reaction products of polyvinyl alcohol with aldehydes.
• the polymer composition as polymer contains at least one copolymer of styrene or of ⁇ -methylstyrene with dienes and / or acrylic derivatives.
• Suitable copolymers of styrene or of ⁇ -methylstyrene are, for example, styrene-butadiene copolymers, styrene-acrylonitrile copolymers (SAN), styrene-ethyl methacrylate copolymers, styrene-butadiene-ethylacrylate copolymers, styrene-acrylonitrile-methacrylate copolymers, Acrylonitrile-butadiene-styrene copolymers (ABS) or methyl methacrylate-butadiene-styrene copolymers (MBS).
• the polymer composition contains as polymer at least one halogen-containing polymer such as copolymers of ethylene and chlorinated ethylene, polymers of halogenated vinyl compounds such.
• halogen-containing polymer such as copolymers of ethylene and chlorinated ethylene, polymers of halogenated vinyl compounds such.
• polyvinyl chloride, polyvinylidene chloride, polyvinyl fluoride, polyvinylidene fluoride and their copolymers such as vinyl chloride / ethylene / vinyl acetate graft copolymers, acrylic ester / vinyl chloride graft copolymers, vinyl chloride / vinyl acetate copolymers, vinyl chloride RID / styrene copolymers, vinyl chloride / acrylonitrile copolymers, vinyl chloride / vinylidene copolymers.
• the halogen-containing polymer is polyvinyl chloride (PVC).
• PVC is formed by free-radical polymerization of vinyl chloride.
• Polyvinyl chloride is usually prepared by the emulsion polymerization, suspension polymerization and bulk polymerization processes. The polymerization is often initiated by peroxides.
• Polyvinyl chloride is used with different content of plasticizers, with a content of plasticizers of 0 - 12% as rigid PVC, of more than 12% as soft PVC or with a very high content of plasticizers as PVC paste.
• the stabilizer composition (S) according to the invention can be added to the finished polyvinyl chloride. The addition is done in the usual way. Alternatively, the stabilizer composition (S) according to the invention can be added to the monomer and the mixture of monomer and stabilizer composition (S) according to the invention polymerized or the stabilizer composition (S) according to the invention added during the polymerization of the polyvinyl chloride. Furthermore, the addition of the stabilizer composition (S) according to the invention can be carried out together with a plasticizer. If appropriate, it may be advantageous to heat the mixture before addition, for example to temperatures above 50 ° C.
• polymer compositions in which the polymer is selected from polyisocyanate polyaddition products (polyurethanes).
• Suitable polyisocyanate polyaddition products are, for example, cellular polyurethanes, eg. As hard or soft polyurethane foams, compact polyurethanes, thermoplastic polyurethanes (TPU), thermosetting or elastic polyurethanes or polyisocyanurates. These are well known and their preparation is described many times. It is usually carried out by reacting dihydric and higher isocyanates or corresponding isocyanate analogues with isocyanate-reactive compounds. The preparation is carried out by customary processes, for example by the one-shot process or by the prepolymer process, eg. B. in forms, in a reaction extruder or a belt system.
• a special manufacturing process is the reaction injection molding (RIM) process, which is preferably used for the production of polyurethanes having a foamed or compact core and a predominantly compact, non-porous surface.
• the stabilizer compositions (S) according to the invention are advantageously suitable for all these processes.
• Polyurethanes are generally composed of at least one polyisocyanate and at least one compound having at least two groups reactive toward isocyanate groups per molecule. Suitable polyisocyanates preferably have 2 to 5 NGO groups.
• the isocyanate-reactive groups are preferably selected from hydroxyl, mercapto, primary and secondary amino groups. These preferably include di- or higher polyols.
• Suitable polyisocyanates are aliphatic, cycloaliphatic, araliphatic and aromatic isocyanates.
• Suitable aromatic diisocyanates are, for example, 2,2'-, 2,4'- and / or 4,4'-diphenylmethane diisocyanate (MDI), 1, 5-naphthylene diisocyanate (NDI), 2,4- and / or 2,6-toluene diisocyanate (TDI), diphenylmethane diisocyanate, 3,3'-dimethyl-diphenyl-diisocyanate, 1, 2-diphenylethane diisocyanate and / or phenylene diisocyanate.
• MDI 2,2'-, 2,4'- and / or 4,4'-diphenylmethane diisocyanate
• NDI 1, 5-naphthylene diisocyanate
• TDI 2,6-toluene diisocyanate
• Aliphatic and cycloaliphatic diisocyanates include, for example, tri-, tetra-, penta-, hexa-, hepta- and / or octamethylene diisocyanate, 2-methyl-pentamethylene-1,5-diisocyanate, 2-ethylbutylene-1,4-diisocyanate, 1-isocyanato - SS ⁇ -trimethyl- ⁇ -isocyanatomethyl-cyclohexane (isophorone diisocyanate, IPDI), 1, 4- and / or 1, 3-bis (isocyanatomethyl) cyclohexane (HXDI), cyclohexane-1, 4-diisocyanate, 1-methyl- 2,4- and / or 2,6-cyclohexanediisocyanato and / or 4,4'-, 2,4'- and / or 2,2'-dicyclohexylmethane diisocyanate ,
• Preferred diisocyanates include hexamethylene diisocyanate (HMDI) and isophorone diisocyanate.
• HMDI hexamethylene diisocyanate
• isophorone diisocyanate examples of higher functionality isocyanates are triisocyanates, e.g. B. Triphenylmethan- 4 j 4 1 j 4 "triisocyant, furthermore the cyanurates of the abovementioned diisocyanates, as well as the oligomers obtainable by partial reaction of diisocyanates with water, eg the biurets of the abovementioned diisocyanates, furthermore oligomers obtained by specific order - Setting of semi-blocked diisocyanates with polyols having an average of more than 2 and preferably 3 or more hydroxyl groups are available.
• Polyol components used for rigid polyurethane foams which may optionally have isocyanurate structures, are highly functional polyols, in particular polyether polyols based on high-functional alcohols, sugar alcohols and / or saccharides as starter molecules.
• polystyrene foams or RIM materials For flexible polyisocyanate polyaddition products, for example flexible polyurethane foams or RIM materials, 2- and / or 3-functional polyether polyols based on glycerol and / or trimethylolpropane and / or glycols as starter molecules are polyols and 2- and / or 3-functional Polyetherherpolyols based on glycerol and / or trimethylolpropane and / or glycols as alcohols to be esterified are preferred as polyols.
• Thermoplastic polyurethanes are usually based on predominantly difunctional polyester polyalcohols and / or polyether polyalcohols which preferably have an average functionality of from 1.8 to 2.5, particularly preferably from 1.9 to 2.1.
• the preparation of the polyether polyols is carried out according to a known technology.
• Suitable alkylene oxides for the preparation of the polyols are, for example, 1,3-propylene oxide, 1,2- or 2,3-butylene oxide, styrene oxide and preferably ethylene oxide and 1,2-propylene oxide.
• the alkylene oxides can be used individually, alternately in succession or as mixtures.
• alkylene oxides are used which lead to primary hydroxyl groups in the polyol.
• Particularly preferred polyols used are those which have been alkoxylated with ethylene oxide to complete the alkoxylation and thus have primary hydroxyl groups.
• Further suitable polyetherols are polytetrahydrofurans and polyoxymethylenes.
• the polyether polyols have a functionality of preferably 2 to 6 and in particular 2 to 4 and molecular weights of 200 to 10,000, preferably 200 to 8,000.
• Suitable polyester polyols may be prepared, for example, from organic dicarboxylic acids having 2 to 12 carbon atoms, preferably aliphatic dicarboxylic acids having 4 to 6 carbon atoms, and polyhydric alcohols, preferably diols having 2 to 12 carbon atoms, preferably 2 to 6 carbon atoms.
• the polyester polyols preferably have a functionality of 2 to 4, in particular 2 to 3, and a molecular weight of 480 to 3000, preferably 600 to 2000 and in particular 600 to 1500.
• the polyol component may also include diols or higher alcohols. Suitable diols are glycols preferably having 2 to 25 carbon atoms. Hier ⁇ to count 1, 2-ethanediol, 1, 2-propanediol, 1, 3-propanediol, 1, 4-butanediol, 1, 5-pentanediol, 1, 6-hexanediol, 1, 10-decanediol, diethylene glycol, 2, 2,4-trimethylpentanediol-1, 5, 2,2-dimethylpropanediol-1,3,3,4-dimethylolcyclohexane, 1,6-dimethylolcyclohexane, 2,2-bis (4-hydroxyphenyl) -propane (bisphenol A), 2 , 2-bis (4-hydroxyphenyl) butane (bisphenol B) or 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane (bisphenol C).
• Suitable higher alcohols are for.
• pentavalent alcohols pentoles. They usually have 3 to 25, preferably 3 to 18 carbon atoms. These include glycerol, trimethylolethane, trimethylolpropane, erythritol, pentaerythritol, sorbitol and their alkoxylates.
• chain extenders e.g., a molecular weight of 40 to 300.
• Suitable examples include aliphatic, cycloaliphatic and / or araliphatic diols having 2 to 14, preferably 2 to 10 carbon atoms, such as ethylene glycol, 1, 3-propanediol, 1, 2-propanediol, 1, 10-decanediol, 1, 2 , 1, 3, 1, 4-dihydroxycyclohexane, diethylene glycol, dipropylene glycol and preferably ethylene glycol, 1,4-butanediol, 1,6-hexanediol and bis (2-hydroxyethyl) hydroquinone, triols, such as 1, 2,4-, 1, 3,5-trihydroxycyclohexane, glycerol, trimethylolpropane, triethanolamine and low molecular weight hydroxyl-containing polyalkylene oxides based on ethylene and / or 1, 2-propylene oxide and the aforementioned diols and / or triols as starter molecules.
• Suitable stoppers include, for
• Another object of the present invention is therefore a process for the preparation of polyisocyanate polyaddition by reaction of isocyanates with isocyanate-reactive compounds, wherein the reaction in the presence of a stabilizer composition (S), as defined above takes place.
• S stabilizer composition
• the isocyanates and the isocyanate-reactive compounds are preferably reacted in amounts such that the equivalence ratio of NCO groups of the isocyanate to the sum of the reactive hydrogen atoms of the isocyanate-reactive compounds 0.85 to 1, 25: 1, preferably 0.95 to 1, 15: 1 and in particular 1 to 1, 05: 1, is. If in particular the rigid polyurethane foams contain at least partially bound isocyanurate groups, a ratio of NCO groups to the sum of the reactive hydrogen atoms of from 1.5 to 60: 1, preferably from 1.5 to 8: 1, is usually used.
• the stabilizer composition (S) may be added to the isocyanate component, the isocyanate-reactive component or both the isocyanate component and the isocyanate-reactive component.
• the stabilizer composition (S) according to the invention is preferably added in the process according to the invention to the isocyanate-reactive component, the so-called polyol component.
• heating the stabilizer composition (S) prior to the addition for example, to a temperature above 50 0 C.
• the Stabilisatorzu ⁇ composition can be easily homogeneously dispersed in the isocyanate-reactive component there are suitable split by a rule.
• the mixing of the stabilizer composition (S) with the poly-ol component can be carried out, for example, in a stirred tank.
• Suitable additional stabilizers comprise at least one antioxidant, the is selected from the group of phosphites, sulfites, phenothiazine, aromatic amines, benzofuranones and / or dilauryl-3,3'-thiodipropionate and mixtures thereof.
• Suitable phosphites are trisnonylphenyl phosphite, triphenyl phosphite, didecylphenyl phosphite and tris- (2,4-di-tert-butylphenyl) phosphite and mixtures thereof.
• a suitable aromatic amine is, for example, di- (4- (1,1,3,3-tetramethylbutyl) phenyl) amine (available, for example, as Irganox® 5077 from Ciba Specialty Chemicals, Inc.).
• Suitable benzofuranones are, for example, 3- [4- (2-acetoxyethoxy) phenyl] -5,7-di-tert-butylbenzofuran-2-one, 5,7-di-tert-butyl-3- [4- (2 -stearoyloxyethoxy) phenyl] -benzofuran-2-one, 3,3'-bis [5,7-di-tert-butyl-3- (4- [2-hydroxyethoxy] phenyl) benzofuran-2-one], 5, 7-di-tert-butyl-3- (4-ethoxyphenyl) benzofuran-2-one, 3- (4-acetoxy-3,5-dimethylphenyl) -5,7-di-tert-butylbenzofuran-2 -on, 3- (3,5-dimethyl-4-pivaloyloxyphenyl) -5,7-di-tert-butylbenzofuran-2-one and mixture
• antioxidants are trisnonylphenyl phosphite, triphenyl phosphite, phenothiazine, tris- (2,4-di-tert-butylphenyl) phosphite, didecylphenyl phosphite and / or dilauryl-3,3'-thiodipropionate, and mixtures thereof.
• the proportion of antioxidant, based on the weight of the polymer composition is from 0.0001 to 10% by weight, preferably from 0.01 to 1% by weight.
• the reaction between the polyol component and the isocyanate component may additionally be carried out in the presence of at least one further component which is selected from costabilizers, blowing agents, catalysts, colorants and additives.
• Suitable costabilizers include sterically hindered amines and sterically hindered phenols.
• Suitable sterically hindered amines are diphenylamine, bis (4-octylphenyl) amine, bis (2,2,6,6-tetramethylpiperidyl) sebacate, bis (1, 2,2,6,6-pentamethylpiperidyl) sebacate, bis (1 , 2,2,6,6-pentamethylpiperidyl) ester, N, N'-bis (formyl) -bis (2,2,6,6-tetramethyl-4-piperidyl) -1, 6-hexanediamine, the Kondensati ⁇ onsomme of 1, 4-dihydroxy-2,2,6,6-tetramethylpiperidine and succinic acid, the condensation product of N, N '- (2,2,6,6-tetramethylpiperidyl) hexamethylenediamine and 4-tert-octylamino-2,6- dichloro-1, 3,5-s-triazine, poly [3- (eicosyl / tetracosyl) -1 -
• Bis- (2,2,6,6-tetramethyl-1-octoxypiperidyl) sebacyt (commercially available, for example, under the name Tinuvin® 123 from Ciba Specialty Chemicals, Inc.), the condensate of 4-amino-2,2 , 6,6-tetramethylpiperidines and tetramethylolacetylenediureas and mixtures thereof.
• the amount of sterically hindered amine is 0.0001 to 10% by weight, preferably 0.01 to 1% by weight.
• reaction is carried out both in the presence of at least one sterically hindered amine and in the presence of at least one antioxidant.
• Suitable sterically hindered phenols are, for example
• Triethylene glycol bis [3- (5-tert-butyl-4-hydroxy-m-tolyl) propionate] available, for example, as Irganox® 245 from Ciba Specialty Chem., Inc.) bis- (2- [3- ( 3,5-di-tert-butyl-4-hydroxy-phenyl) -propionyloxy] -ethyl) -sulfide (for example, available as Irganox® 1035 from Ciba Specialty Chemicals, Inc.), octadecyl-3- (3,5 di-tert-butyl-4-hydroxyphenyl) -propionate (available, for example, as Irganox® 1076 from Ciba Specialty Chemicals, Inc.), N, N-hexamethylene-bis- (3,5-di-t-butyl) 4-hydroxyphenyl) propionamide (for example, available as Irganox® 1098 from Ciba Specialty Chemicals, Inc.
• the proportion of sterically hindered phenol, based on the weight of the polymer composition is 0.0001 to 10% by weight, preferably 0.01 to 1% by weight.
• blowing agents in particular for the production of polyurethane foams, conventional chemical, for example water, and / or physically acting blowing agents be used.
• physical blowing agent makes suitable as such physical blowing agent prises ⁇ fluids, which cyanates toward the organic, modified or unmodified polyisobutylene, are inert and have boiling points below 100 0 C, preferably below 50 0 C, more particularly sondere between -50 0 C and 30 0 C in Standard pressure, so that they evaporate under the influence of the exothermic polyaddition reaction.
• alkanes such as heptane, hexane, n- and iso-pentane, preferably technical mixtures of n- and iso-pentanes, n- and iso-butane and propane, cycloalkanes, such as cyclopentane and / or cyclohexane, Ethers, such as furan, dimethyl ether and diethyl ether, ketones, such as acetone and methyl ethyl ketone, carboxylic acid alkyl esters, such as methyl formate, dimethyl oxalate and ethyl acetate, and halogenated hydrocarbons, for example customary fluorohydrocarbons and / or chlorohydrocarbons, for example dichloromethane.
• alkanes such as heptane, hexane, n- and iso-pentane, preferably technical mixtures of n- and iso-pentanes,
• low-boiling liquids with one another and / or with other substituted or unsubstituted hydrocarbons.
• organic carboxylic acids such as. For example, formic acid, acetic acid, oxalic acid, ricinoleic acid and carboxyl group-containing compounds.
• the blowing agents are usually added to the isocyanate-reactive compounds. However, they may be added to the isocyanate component or as a combination of both the polyol component and the isocyanate component or premixes of these components with the other constituent components.
• the amount of physical blowing agent used is preferably 0 to 25 wt .-%, particularly preferably 0 to 15 wt .-%, each based on the weight of the total isocyanate-reactive compounds.
• water is used as the blowing agent, preferably in an amount of 0.1 to 10% by weight of water, more preferably in an amount of 0.1 to 7% by weight of water, in each case based on the weight of the total used Isocyanate-reactive compounds, it is preferably added to the polyol component, wherein water is preferably used in combination with at least one of said physical blowing agents, for example cyclopentane, n- and / or iso-pentane.
• catalysts it is possible to use generally known compounds which greatly accelerate the reaction of isocyanates with the compounds reactive toward isocyanates, preferably having a total catalyst content of from 0.001 to 0.1% by weight, based on the weight of the total isocyanate-reactive compounds Connections, is used.
• the following compounds can be used: triethylamine, tributylamine, dimethylbenzylamine, dicyclohexylmethylamine, dimethylcyclohexylamine, N, N, N ', N'-tetramethyl-diaminodiethylether, bis (dimethylaminopropyl) -urea, N-methyl- or N Ethylmorpholine, N-cyclohexylmorpholine, N 1 N 1 N ', N'-tetramethylethylenediamine, NNN'.N'-tetramethylbutanediamine, N, N, N 1 , N'-tetramethylhexanediamine-1, 6, Pentamethyldiethylenetriamine, dimethylpiperazine, N-dimethylaminoethylpiperidine, 1,2-dimethylimidazole, 1-azabicyclo [2.2.0] octane, 1,4-diazabicyclo [2.2.2] octtan
• colorant is understood in the context of the present invention, both dyes and inorganic and organic pigments.
• the proportion of colorant, based on the Intelge ⁇ weight of isocyanate-reactive compounds is usually 1 to 6% by weight.
• Suitable additives are, for example, surface-active substances, foam stabilizers, cell regulators, fillers, flame retardants, hydrolysis protectants, fungicidal and bacteriostatic substances and mold release agents.
• z. B. compounds which serve to assist the homogenization of the starting materials and optionally are also suitable to regulate the cell structure of the plastics. Mention may be spielvati emulsifiers, such as the sodium salts of castor oil or of fatty acids and salts of fatty acids with amines, eg. As diethylamine, stearic acid diethanolamine, ricinolsaures diethanolamine, salts of sulfonic acids, eg. B.
• Foam stabilizers such as siloxane-oxalkylene copolymers and other organopolysiloxanes, ethoxylated alkylphenols, ethoxylated fatty alcohols, paraffin oils, castor oil or ricinoleic acid esters, turkey red oil and peanut oil, and cell regulators, such as paraffins, fatty alcohols and dimethylpolysiloxanes.
• the above-described oligomeric acrylates having polyoxyalkylene and fluoroalkane radicals are also suitable as side groups.
• the surface-active substances are usually used in amounts of 0.01 to 5 wt .-%, based on 100 wt .-% of the total used gegen ⁇ isocyanate-reactive compounds.
• Fillers, in particular reinforcing fillers are to be understood as meaning the conventional organic and inorganic fillers, reinforcing agents, hardening agents, agents for improving the abrasion behavior in paints, coating agents, etc., which are known per se.
• inorganic fillers such as carbon and in particular carbon fibers, silicate minerals, for example phyllosilicates such as antigorite, serpentine, hornblende, amphiboles, chrysotile and talc, metal oxides such as kaolin, aluminum oxides, titanium oxides and iron oxides, metal salts, such as Chalk, barite and inorganic pigments, such as cadmium sulfide and zinc sulfide, as well as glass, etc.
• silicate minerals for example phyllosilicates such as antigorite, serpentine, hornblende, amphiboles, chrysotile and talc
• metal oxides such as kaolin, aluminum oxides, titanium oxides and iron oxides
• metal salts such as Chalk
• barite and inorganic pigments such as cadmium sulfide and zinc sulfide, as well as glass, etc.
• kaolin China Clay
• aluminum silicate and coprecipitates of barium sulfate and aluminum silicate and natural and synthetic fibrous minerals such as wollastonite, metal fibers and in particular glass fibers of various lengths, which may optionally be sized.
• Suitable organic fillers are, for example: melamine, rosin, cyclopentadienyl resins and graft polymers and cellulose fibers, polyamide, polyacrylonitrile, polyurethane, polyester fibers based on aromatic and / or aliphatic dicarboxylic esters.
• the inorganic and organic fillers can be used individually or as mixtures and are advantageously added to the reaction mixture in amounts of from 0.5 to 50% by weight, preferably from 1 to 40% by weight, based on the weight of the isocyanates and the weight of the total isocyanate-reactive compounds incorporated, whereby, however, the content of mats, nonwovens and woven fabrics of natural and synthetic fibers can reach values of up to 80% by weight.
• Suitable flame retardants are, for example, tricresyl phosphate, tris (2-chloroethyl) phosphate, tris (2-chloropropyl) phosphate,
• Suitable mold release agents are, for example, silicones, waxes, metal salts of fatty acids such as calcium, lead, magnesium, aluminum, zinc stearate, fats, talc or mica.
• the optionally used antioxidant and the optionally used further component (s) may in principle be added to the isocyanate component and / or the polyol component.
• the addition can be made simultaneously with the addition, before addition, or after the addition of the stabilizer composition (S) to the isocyanate component and / or polyol component.
• the polyisocyanate polyaddition products are advantageously prepared by the one-shot process, for example by means of the high-pressure or low-pressure technique in open or closed molds, for example metallic molds or reaction extruders, in particular for the production of thermoplastic polyurethanes. Also customary is the continuous application of the reaction mixture on suitable strip conveyors for the production of panels.
• the starting components A and B are, depending on the application, at a temperature of 0 to 100 0 C, preferably from 20 to 60 ° C, mixed and introduced into the open or optionally under increased pressure in the closed Formwerk ⁇ convincing or in a continuous workstation on a tape which receives the reaction mass applied.
• the mixing can be carried out mechanically by means of a stirrer or a stirring screw.
• the temperature of the mold or, if no mold is used of which temperature at which the reduction takes place Um ⁇ is usually at least 30 0 C, preferably 35 to 110 0 C.
• the present invention also provides the use of a stabilizer composition (S), as defined above, for stabilizing polymer compositions which contain at least one of polyesters, polycarbonates, polyamides, polyolefins and polyesters.
• S stabilizer composition
• polymer compositions which contain at least one of polyesters, polycarbonates, polyamides, polyolefins and polyesters.
• NEN polyvinyl acetals, polystyrene, copolymers of styrene or ⁇ -methyl styrene with dienes and / or acrylic derivatives, polyisocyanate polyaddition products, halogen-containing polymers and mixtures thereof contain polymer, against the action of light.
• the stabilizer composition (S) according to the invention is well-suited for stabilizing moldings made from polyisocyanate polyaddition products, since it can be readily dissolved or dispersed in the isocyanate-reactive component and thus a homogeneous distribution of the stabilizer composition in the polyisocyanate polyaddition product can be achieved.
• Equally suitable is the stabilization of moldings made of polyvinyl chloride. Moldings of polyisocyanate polyaddition products, polyvinylamide or polyvinyl chloride are used, for example, as housings, covers or dashboards in means of transport.
• the means of transport include, for example, means of transport such as passenger cars, lorries, buses, rail vehicles such as trams, levitation trains, railways, rack railways, water transport such as ships and air kiosk, as well as aviation equipment such as aircraft and helicopters.
• means of transport such as passenger cars, lorries, buses, rail vehicles such as trams, levitation trains, railways, rack railways, water transport such as ships and air kiosk, as well as aviation equipment such as aircraft and helicopters.
• the molded parts stabilized according to the invention are used in the interior of means of transport.
• the stabilized using the Stabilizerzu ⁇ composition according to the invention (S) moldings of polyvinyl chloride or a polyisocyanate polyaddition product are preferably used for the production of dashboards for passenger and trucks, for aircraft or ships, especially for passenger cars and trucks.
• the polymer compositions stabilized according to the invention have low fogging values in comparison to polymer compositions stabilized with the stabilizers or stabilizer compositions known from the prior art.
• the fogging value is determined at 100 0 C over a period of 16 hours in accordance with DIN 75201, at a present invention stabili ⁇ classified polymer composition to 1, 5 mg, preferably 1 0 mg, and in particular less than 0.8 mg , at a stabilizer concentration of 0.5 wt .-% based on the weight of the polyol component.
• the stabilizer composition (S) according to the invention is distinguished by good compatibility and solubility in the abovementioned polymer compositions. They are usually weakly yellowish and in the usual plastic processing temperatures stable and non-volatile.
• the polymer compositions stabilized according to the invention and the moldings produced therefrom are characterized by a longer service life since the stabilizer composition (S) according to the invention evaporates more slowly from the polymer composition or from the moldings produced therefrom than those known from the prior art Light stabilizers.
• the 0.5% by weight of stabilizer or 0.5% by weight of stabilizer composition (S1) was dissolved in the polyol component (polyesterpolyol) of the polyurethane to be prepared and subsequently afterlaid together with an aliphatic isocyanate as a mixture with a spray gun the spray technology process into a black colored skin.
• the polyurethane does not contain a stabilizer.
• Comparative Examples 3 stabilizer is
• the fogging value of the stabilized polyurethane skins from Examples 3, 4 and 6 was determined.
• the specimen was placed on the bottom of a standard cup made of glass.
• the beaker is covered with a glass plate on which volatiles can condense out of the sample. This glass plate is cooled.
• the thus prepared beaker is placed 16 hours in a structure located on educatempera ⁇ of 100 0 C (+ 0.3 0 C) bath thermostat.
• the amount of fogging precipitate on the glass plate is measured by measuring the 60 ° reflectometer values. Reference is made to the 60 ° reflectometer values of the same glass plate without precipitate, which was thoroughly cleaned before the experiment. Table 2 shows the measured fogging values. Table 2:
• a stabilizer mixture (S) according to the invention has a significantly lower fogging than stabilizers from the prior art. Accordingly, the polymer compositions stabilized using the stabilizer composition (S) according to the invention show markedly improved quality properties in comparison to polymer compositions which are stabilized with conventional UV absorbers.
• the stabilizer evaporates from the stabilized polymer according to the invention to a significantly lower extent than the stabilizers known from the prior art.

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• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
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• Chemical Kinetics & Catalysis (AREA)
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• Polymers & Plastics (AREA)
• Engineering & Computer Science (AREA)
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• Life Sciences & Earth Sciences (AREA)
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• Compositions Of Macromolecular Compounds (AREA)
• Polyurethanes Or Polyureas (AREA)

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• 2004
  • 2004-07-30 DE DE102004036965A patent/DE102004036965A1/de not_active Withdrawn
• 2005
  • 2005-07-29 EP EP05772510A patent/EP1773929A1/de not_active Withdrawn
  • 2005-07-29 WO PCT/EP2005/008271 patent/WO2006013071A1/de active Application Filing
  • 2005-07-29 US US11/658,884 patent/US20090264566A1/en not_active Abandoned
  • 2005-07-29 CN CNA2005800330227A patent/CN101031613A/zh active Pending
  • 2005-07-29 MX MX2007000994A patent/MX2007000994A/es unknown
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