DE10318584A1 - Highly branched polymeric stabilizers - Google Patents

Abstract

The invention relates to stabilizers which are composed of structural units (I) to (III), namely DOLLAR A (I), a highly branched polymer with functional groups B as a highly branched anchor group; DOLLAR A (II) one or more groups of active ingredients which protect plastics against damage from heat, UV radiation, oxidation, hydrolysis or mechanical action during processing, the active ingredient groups via functional groups D which can react with functional groups B. the anchor group are coupled; DOLLAR A (III) optionally one or more auxiliary groups which modify the properties of the stabilizer, the auxiliary groups being coupled to the anchor group via functional groups E which can react with the functional groups B.

Description

The The invention relates to highly branched polymeric stabilizers.

plastics, e.g. Polyolefins, polyamides, polyurethanes, polyacrylates, polycarbonates, Find polyesters, polyoxymethylenes, polystyrenes and styrene copolymers in many areas of everyday life Life application. examples for these applications are foils and fibers, automotive interior applications, such as upholstery and cover fabrics, dashboard or airbag, or applications in the automotive exterior, like tires, bumpers or Protective strips, also cable sheaths, housings, shoe soles, dispersions, Varnishes or paints.

In These different applications are the most diverse plastics Exposed to stress. So must e.g. Plastics used in the engine compartment of a motor vehicle withstand high temperatures. Plastic films or varnishes, those exposed to sunlight are subject to the harmful ones Influence of UV light. UV light and lead to thermal stress generally discolored of the plastics and / or to a deterioration in the property profile of plastics. By impairing the visual appearance and the mechanical properties of the plastic can do that After all, the product they manufactured is no longer for the desired product Purpose.

by virtue of plastics have different chemical structures stabilities against damage by UV light and thermal stress or against damage from environmental influences generally on. However, it is desirable the scope of all plastics as wide as possible to shape, i.e. the stability of plastics against environmental influences such as heat, sunlight and UV light to improve.

Also During processing, plastics are often exposed to high processing temperatures and / or high shear forces impaired.

It is known to protect plastics from harm by adding stabilizers environmental influences to protect. For example, you can Plastics through a mixture of an antioxidant (AO) and a Hindererd Amine Light Stabilizer (HALS) or by a mixture from a UV absorber and a phenolic antioxidant or by Mixture of a phenolic antioxidant, a HALS and an UV absorber against UV damage protected become. To protect against damage due to thermal stress, the addition of antioxidants such as sterically hindered phenols, aromatic amines and phosphites or thiosynergists proven.

meanwhile is an unmistakable one size Number of different stabilizers and combinations of stabilizers commercially available. Examples for such compounds are given in Plastics Additive Handbook, 5th Edition, H. Doubt, ed., Hanser Publishers, Munich, 2001 ([1]), pp. 98-5136.

DE-A 39 14 945 discloses stabilized molding compositions made from asymmetrically branched branches Styrene-butadiene block copolymers and a sterically hindered Bisphenol monoacrylate.

WHERE 01/48057 discloses stabilizers made from amino-terminated dendrimers and 3- (3,5-di-t-butyl-4-hydroxyphenyl) propionic acid are available. Tris (2-aminoethyl) amine and 4-cascade: 1,4-diaminobutane [4] are used as dendrimers: called propylamine (n = 4).

On The problem with stabilizers is their migration behavior in the plastic, i.e. their volatility and their tendency to bloom, Bleeding or washing out. It has been shown that stabilizers, whose molar mass is too low, evaporate from the plastic. This is particularly a problem if the surface / volume ratio of a Plastic molding is very large. Evaporation of the stabilizer, the so-called "fogging", can occur with certain Applications, e.g. in the automotive interior, cause limit values for the total amount at fleeting Components exceeded be and the plastic for this application rejected becomes.

To reduce volatility, stabilizers are usually oligomerized, polymerized, or attached to an organic anchor group to increase the molecular weight. In this context, an organic anchor group is an organic radical, the function of which is to determine the molar mass of the To increase the stabilizer. One or more stabilizers can be connected to such an anchor group. By increasing the molar mass, however, the compatibility of the stabilizer with the polymer can decrease in such a way that efflorescence, that is to say the formation of deposits of the stabilizer on the surface of the product, occurs. These coverings lead to a visual impairment of the product and can therefore lead to complaints. In addition, the blooming reduces the concentration of the stabilizer and thus the effectiveness of the stabilizer mixture. Blooming is a relevant problem, especially for thick workpieces with a small surface / volume ratio.

The intolerance of a stabilizer with a polymer, and thus the risk of blooming of the stabilizer is heavily dependent of the combination stabilizer / polymer and is unpredictable. Sometimes a stabilizer can be used in a polymer without any problems can be used, lead to massive efflorescence in another polymer. This does not lead only that one manufacturer of different plastics one size Number of different stabilizers with the same active ingredient groups must also hold the tests to find the optimal stabilizers are very expensive because for each polymer also re-examined the migration properties Need to become.

moreover decreases if the molar masses are too high, e.g. in the polymerization of the active ingredient group, the mobility of the Stabilizer in such a way that its effectiveness decreases because of the stabilizer Differences in concentration caused by degradation reactions can no longer compensate through diffusion.

On Another problem is the washing out of a stabilizer Contact of the plastic with a liquid. This does not result only a reduction in the stabilizer content in the product, but also to contaminate the liquid with the stabilizer. This problem arises particularly in applications in the food sector.

on the other hand it may be necessary for applications in dispersions or paints, that the stabilizer can be emulsified or dissolved in a liquid in order to an even distribution to ensure.

• – eine geringe Flüchtigkeit aufweisen,
• – nicht zum Ausblühen oder Ausbluten neigen,
• – nicht aus dem Polymeren ausgewaschen werden,
• – gut mischbar und einarbeitbar sein,
• – eine hohe Mobilität im Polymeren besitzen,
• – eine hohe Wirkstoffgruppenkonzentration bezogen auf das Gesamtgewicht des Stabilisators haben,
• – sich anwendungsspezifisch in einer flüssigen Komponente emulgieren oder lösen lassen können,
• – sich leicht und nach gleichen oder ähnlichem Verfahren synthetisieren lassen.

The object of the present invention is to provide stabilizers which are effective against various damage mechanisms and have advantageous properties. The stabilizers are said to be effective against UV radiation, heat, hydrolysis, oxidation or ozone damage and to have one or more of the following advantageous properties, namely

• - have low volatility,
• - do not tend to bloom or bleed,
• - are not washed out of the polymer,
• - be easy to mix and incorporate,
• - have a high mobility in the polymer,
• Have a high concentration of active ingredient based on the total weight of the stabilizer,
• - can be emulsified or dissolved in a liquid component, depending on the application,
• - Can be easily synthesized using the same or a similar procedure.

• (I) einem hochverzweigten Polymer mit funktionellen Gruppen B als hochverzweigte Ankergruppe; das Polymer kann ein Dendrimer oder hyperverzweigtes Polymer sein; bevorzugt weist es im Mittel 3 bis 100, insbesondere 3 bis 50 funktionelle Gruppen B auf;
• (II) einer oder mehreren Wirkstoffgruppen, welche Kunststoffe gegen Schädigung durch Wärme, UV-Strahlung, Oxidation, Hydrolyse oder mechanische Einwirkung bei der Verarbeitung schützen, wobei die Wirkstoffgruppen über funktionelle Gruppen D, die mit den funktionellen Gruppen B reagieren können, an die Ankergruppe angekoppelt sind;
• (III) gegebenenfalls einer oder mehreren Hilfsgruppen, die die Eigenschaften des Stabilisators modifizieren, wobei die Hilfsgruppen über funktionelle Gruppen E, die mit den funktionellen Gruppen B reagieren können, an die Ankergruppe angekoppelt sind.

The problem was solved by stabilizers, which are composed of structural units I to (III), namely

• (I) a highly branched polymer with functional groups B as a highly branched anchor group; the polymer can be a dendrimer or hyperbranched polymer; it preferably has on average 3 to 100, in particular 3 to 50, functional groups B;
• (II) one or more groups of active ingredients which protect plastics against damage from heat, UV radiation, oxidation, hydrolysis or mechanical action during processing, the active ingredient groups via functional groups D, which can react with functional groups B, to the anchor group are coupled;
• (III) optionally one or more auxiliary groups which modify the properties of the stabilizer, the auxiliary groups being coupled to the anchor group via functional groups E which can react with the functional groups B.

characteristics the stabilizers, which are modified by the auxiliary groups, are, for example, emulsifiability or solubility in polar or non-polar solvents and / or the incorporation into a plastic or a plastic mixture.

anchor groups

As The stabilizers according to the invention contain highly branched anchor groups Polymers. Highly branched polymers are both dendrimers. symmetrical, structurally uniform branched polymers, as also hyperbranched polymers, i.e. irregularly structured, asymmetrical, structurally inconsistent polymers, but for cost reasons the hyperbranched polymers are preferred.

Functionally grouped hyperbranched polymers can be synthesized, for example, in a manner known per se using AB _x , preferably AB ₂ monomers. On the one hand, the AB ₂ monomers can be fully incorporated in the form of branches, they can be incorporated as terminal groups, that is to say they still have two free B groups, and they can be incorporated as linear groups with a free B group as a side group. Depending on the degree of polymerization, the highly branched polymers obtained have a more or less large number of B groups, either terminally or as side groups. Information on hyperbranched polymers and their synthesis are, for example, in JMS - Rev. Macromol. Chem. Phys., C37 (3), 555-579 (1997) and the literature cited therein.

The Selection of highly branched polymers for the production of stabilizers is principally not limited to a specific polymer class. The Expert meets depending on the desired Properties of the stabilizer and after use in the stabilizer Substrate among the principally possible Polymer classes a selection. As particularly suitable for the production Stabilizers have hyperbranched polyesters, hyperbranched Polyethers, hyperbranched polyurethanes, hyperbranched polyurea polyurethanes, hyperbranched polyureas, hyperbranched polyamines, hyperbranched Polyamides, hyperbranched polyetheramides and hyperbranched Polyesteramides proved. Hyperbranched are very particularly preferred Polyurethanes, hyperbranched polyurea polyurethanes, hyperbranched Polyethers, hyperbranched polyesters and hyperbranched polyesteramides.

Highly branched and highly functional polymers obtained by polymerizing AB _x molecules can in principle be used as such for the preparation of the stabilizers according to the invention, provided that the functional groups obtained in the course of the particular embodiment of the synthesis are suitable for the desired application.

The originally existing B groups can but advantageously also by polymer-analogous reaction with suitable ones Connections are functionalized. That way be for specially adapted the respective application of the stabilizer Polymers accessible.

Examples of suitable functional groups B which can be introduced into the highly branched polymer by means of suitable reactants include, in particular, NCO and epoxy groups, activated double bonds and acidic or basic groups containing H atoms or their derivatives such as -COOH, -COOR, -CONHR, -CONH ₂ , -OH, -SH, -NH ₂ , -NHR, -NR ₂ , -SO ₃ H, -SO ₃ R, -NHCOOR, -NHCONH ₂ , -NHCONHR, without being limited to this should be. If possible, the functional groups can also be converted into the corresponding salts using suitable acids or bases. The radicals R of the said groups are generally straight-chain or branched alkyl radicals or aryl radicals, which can also be further substituted. For example, they are C ₁ -C ₈ alkyl radicals or C ₅ -C ₁₂ aryl radicals. Other functional groups such as -CN or -OR can also be used.

The Functional groups of the highly branched polymers can optionally can also be functionalized. Used for re-functionalization Connections can on the one hand the desired new ones to be introduced functional group and a second group included with the B groups of the highly branched starting material Polymer is capable of reacting to form a bond. On Example of this is the reaction of an isocyanate group with a hydroxycarboxylic acid or an aminocarboxylic acid forming an acid functionality or the Implementation of an OH group with acrylic anhydride forming a responsive acrylic double bond.

It can but also monofunctional connections can be used with which existing groups B can only be modified. For example can Alkyl halides for the quaternization of existing primary, secondary or tertiary Amino groups are used.

The Refunctionalization of the highly branched polymers can be advantageous immediately following the polymerization reaction or in a separate reaction.

functional Groups over have sufficient acidic H atoms, can be converted into the corresponding salts by treatment with suitable bases. Analogously, functional basic groups can be used with suitable ones acids convert into the appropriate salts. Thereby can be, for example, water-soluble or water-dispersible Obtain hyperbranched polymers as anchor groups.

It can hyperbranched polymers are also generated as anchor groups which different functionalities exhibit. This can be done, for example, by reaction with a mixture different connections for re-functionalization take place, or also because only part of the originally existing functional Groups.

Mixed functional compounds can furthermore be produced by using monomers of the type ABC or AB ₂ C for the polymerization as AB _x compounds, C being a functional group which is not reactive with A or B under the chosen reaction conditions.

According to the invention the highly branched polymers having functional groups as Anchor groups used for the manufacture of stabilizers.

Of course you can too several different highly branched polymers as anchor groups for stabilizers be used.

polymerization, Molar mass as well as type and number of functional groups can from Specialist can be chosen depending on the intended application.

-NCO, -OH, -SH, -COOH, -COOR, -CONH ₂ , -NH ₂ , -NHR or -SO ₃ H have proven particularly useful as functional groups B. OH-terminated or NCO-terminated hyperbranched polymers have been found proven to be particularly advantageous for the production of stabilizers.

The The highly branched polymers used generally have at least 3 functional groups. The number of functional groups is principally not limited to above. However, products have an excessive number of functional groups often undesirable properties such as poor solubility or very high Viscosity. Therefore, the highly branched used according to the invention Polymers usually no more than an average of 100 functional Groups on. The highly branched polymers prefer on average 3 to 50 and particularly preferably 3 to 20 functional groups.

The molecular weights of the highly branched polymers used according to the invention depend on the respective polymer class and on the particular application and are selected accordingly by the person skilled in the art. However, products with a weight average M _W of 500 to 50,000 g / mol, preferably from 1000 to 20,000 g / mol, have proven successful.

• – hochverzweigte Polyisocyanate nach DE-A 100 13 187 und DE-A 100 13 186
• – hochverzweigte Polyurethane nach WO 97/02304 oder nach DE 199 04 444
• – hochverzweigte Polyester nach SE 468 771 oder nach SE 503 342
• – hochverzweigte Polyether nach DE 199 47 631
• – hochverzweigte Polyesteramide nach WO 99/16810
• – hochverzweigte Polyamine nach WO 93/14147
• - hochverzweigte Polyharnstoffe nach DE 102 04 979.3

Highly branched polymers can be produced, for example, as follows:

• - highly branched polyisocyanates according to DE-A 100 13 187 and DE-A 100 13 186
• - Highly branched polyurethanes according to WO 97/02304 or DE 199 04 444
• - highly branched polyester after SE 468 771 or after SE 503 342
• - highly branched polyethers DE 199 47 631
• - highly branched polyester amides according to WO 99/16810
• - highly branched polyamines according to WO 93/14147
• - highly branched polyureas after DE 102 04 979.3

An overview of highly branched Polymers is given for example in "Dendrimers And Other Dendritic Polymers ", by J.M.J. Féchet and since. Tomalia, John Wiley & Sons, Chichester 2001, or in “Dendrimers And Dendrons ", by G. R. Newkome, C.N. Morrefield and F. Vögtle, WILEY-VCH, Weinheim 2001.

following becomes representative of the production of highly branched polyurethanes explained in more detail.

The term “polyurethanes” in the sense of this invention encompasses, beyond the usual understanding, polymers which are obtained by reacting di- or polyisocyanates with compounds having active hydrogen can be, and which can be linked by urethane but also, for example, by urea, allophanate, biuret, carbodiimide, amide, uretonimine, uretdione, isocyanurate or oxazolidone structures.

For the synthesis of the hyperbranched polyurethanes used according to the invention, it is preferred to use AB _x monomers which have both isocyanate groups and groups which can react with isocyanate groups to form a link. x is a natural number between 2 and 8, preferably 2 or 3. Either A is an isocyanate group and B is a group reactive with it, or the reverse is the case.

The groups reactive with the isocyanate groups are preferably OH, NH ₂ , NHR or SH groups.

The AB _x monomers can be prepared in a known manner. AB _x monomers can be synthesized, for example, using the method described in WO 97/02304 using protective group techniques. This technique is exemplified by the preparation of an AB ₂ monomer from 2,4-tolylene diisocyanate (TDI) and trimethylolpropane. First, one of the TDI isocyanate groups is blocked in a known manner, for example by reaction with an oxime. The remaining free NCO group is reacted with trimethylolpropane, only one of the three OH groups reacting with the isocyanate group, while two OH groups are blocked by acetalization. After the protective group has been removed, a molecule with an isocyanate group and 2 OH groups is obtained.

The AB _x molecules can be synthesized particularly advantageously by the method described in DE-A 199 04 444, in which no protective groups are required. In this method, di- or polyisocyanates are used and reacted with compounds which have at least two groups reactive with isocyanate groups. At least one of the reactants has groups with different reactivities than the other reactants. Both reactants preferably have groups with different reactivities than the other reactants. The reaction conditions are chosen so that only certain reactive groups can react with each other.

Suitable di- and polyisocyanates are the aliphatic, cycloaliphatic and aromatic isocyanates known from the prior art. Preferred di- or polyisocyanates are 4,4'-diphenylmethane diisocyanate, the mixtures of monomeric diphenylmethane diisocyanates and oligomeric diphenylmethane diisocyanates (polymer MDI), tetramethylene diisocyanate, hexamethylene diisocyanate, 4,4'-methylenebis (cyclohexyl) diisocyanate, xylylene diisocyanate, tetra diisocyanate, tetrachloride , where alkyl is C ₁ - to C ₁₀ -alkyl, 2,2,4- or 2,4,4-trimethyl-1,6-hexamethylene diisocyanate, 1,4-diisocyanatocyclohexane or 4-isocyanatomethyl-1,8-octamethylene diisocyanate ,

Especially di- or polyisocyanates with different NCO groups are preferred Reactivity like 2,4-tolylene diisocyanate (2,4-TDI), 2,4'-diphenylmethane diisocyanate (2,4'-MDI), triisocyanatotoluene, phosphorus diisocyanate (IPDI), 2-butyl-2-ethylpentamethylene diisocyanate, 2-isocyanatopropylcyclohexyl isocyanate, 3 (4) -isocyanatomethyl-1-methylcyclohexyl isocyanate, 1,4-diisocyanato-4-methylpentane, 2,4'-methylenebis (cyclohexyl) diisocyanate and 4-methylcyclohexane-1,3-diisocyanate (H-TDI). Isocyanates whose NCO groups are also particularly preferred first are equally reactive, but in which the first addition of an alcohol or amine on one NCO group a decrease in reactivity in the second NCO group can induce. Examples are for that Isocyanates, whose NCO groups over a delocalized electron system are coupled, e.g. B. 1,3- and 1,4-phenylene diisocyanate, 1,5-naphthylene diisocyanate, diphenyl diisocyanate, tolidine diisocyanate or 2,6-tolylene diisocyanate.

Farther can For example, oligo- or polyisocyanates can be used themselves from the di- or polyisocyanates mentioned or mixtures thereof by linking by means of urethane, allophanate, urea, biuret, uretdione, amide, Isocyanurate, carbodiimide, uretonimine, oxadiazinetrione or iminooxadiazinedione structures have it made.

As Compounds with at least two groups reactive with isocyanates are preferably di-, tri- or tetrafunctional compounds used, the functional groups of which differ from NCO groups Reactivity exhibit. Compounds with at least one primary and at least one secondary Hydroxyl group, at least one hydroxyl group and at least one Mercapto group, particularly preferably with at least one hydroxyl group and at least one amino group in the molecule, in particular amino alcohols, Aminodiols and aminotriols, since the reactivity of the amino group towards the Hydroxyl group in the reaction with isocyanate is significantly higher.

Examples for the mentioned compounds with at least two reactive with isocyanates Groups are propylene glycol, glycerin, mercaptoethanol, ethanolamine, N-methylethanolamine, diethanolamine, ethanolpropanolamine, dipropanolamine, diisopropanolamine, 2-amino-1,3-propanediol, 2-amino-2-methyl-1,3-propanediol or tris (hydroxymethyl) aminomethane. Farther Mixtures of the compounds mentioned can also be used.

The preparation of an AB ₂ molecule is exemplified for the case of a diisocyanate with an aminodiol. Here, one mole of a diisocyanate is first reacted with one mole of an aminodiol at low temperatures, preferably in the range between -10 to 30 ° C. In this temperature range, the urethane formation reaction is virtually completely suppressed and the more reactive NCO groups of the isocyanate react exclusively with the amino group of the aminodiol. The AB _x molecule formed has one free NCO group and two free OH groups and can be used to synthesize a highly branched polyurethane.

This AB ₂ molecule can react intermolecularly to form a highly branched polyurethane by heating and / or adding catalyst. The highly branched polyurethane can advantageously be synthesized in a further reaction step at elevated temperature, preferably in the range between 30 and 80 ° C., without prior isolation of the AB _x molecule. When using the described AB ₂ molecule with two OH groups and one NCO group, a highly branched polymer is formed which has one free NCO group per molecule and - depending on the degree of polymerization - a more or less large number of OH groups. The reaction can be carried out up to high conversions, whereby very high molecular structures are obtained. However, it can also be terminated, for example, by adding suitable monofunctional compounds or by adding one of the starting compounds for the preparation of the AB ₂ molecule when the desired molecular weight has been reached. Depending on the starting compound used for the termination, either completely NCO-terminated or completely OH-terminated molecules are formed.

Alternatively, for example, an AB ₂ molecule can also be produced from one mole of glycerol and 2 moles of 2,4-TDI. At low temperature, the primary alcohol groups and the isocyanate group preferably react in the 4-position and an adduct is formed which has one OH group and two isocyanate groups and which, as described, can be converted to a highly branched polyurethane at higher temperatures. First, a highly branched polymer is formed which has a free OH group and - depending on the degree of polymerization - a more or less large number of NCO groups.

The Production of the highly branched polyurethanes can in principle without Solvent, but preferably in solution respectively. As a solvent in principle, all liquid and at the reaction temperature are suitable across from the monomers and polymers inert compounds.

Other products are accessible through further synthesis variants. AB ₃ molecules can be obtained, for example, by reacting diisocyanates with compounds having at least 4 groups that are reactive toward isocyanates. The reaction of 2,4-tolylene diisocyanate with tris (hydroxymethyl) aminomethane may be mentioned as an example.

To the Polymerization can be stopped polyfunctional compounds are also used, which with the respective A groups can react. That way you can several small highly branched molecules into one large highly branched molecule connected become.

Highly branched polymers with chain-extended branches can be obtained, for example, by using a 1: 1 molar ratio of a diisocyanate and a compound which has two groups reactive with isocyanate groups in addition to the AB _x molecules for the polymerization reaction. These additional AA or BB compounds can also have further functional groups, but these must not be reactive towards the A or B groups under the chosen reaction conditions. In this way, further functionalities can be introduced into the hyperbranched polymer.

Further synthesis variants for highly branched polyurethanes can be found in our previously unpublished applications with the file number DE 100 13 187.5 and DE 100 30 869.4 ,

However, as described above, the functional groups can also be hydrophobized, hydrophilized or functionalized. In this way, particularly suitable highly branched polyurethanes are accessible for use as a solution or aqueous dispersion. Are suitable for re-functionalization due to their reactivity, especially those highly branched polyurethanes which have isocyanate groups. OH or NH ₂ -terminated polyurethanes can also be functionalized using suitable reactants.

Preferred groups which are introduced into the highly branched polyurethanes are -COOH, -CONH ₂ , -OH, -NH ₂ , -NHR, -NR ₂ , -NR ₃ ⁺ , -SO ₃ H and their salts. Particularly preferred are -NH ₂ , -NHR, -NR ₂ , and -NR ₃ ⁺ according to one embodiment of the invention and -COOH, -OH and -SO ₃ H according to a further embodiment of the invention.

Groups, the above have sufficient acidic H atoms, can be converted into the corresponding salts by treatment with suitable bases. Analogously, basic groups with suitable acids can be added transfer the appropriate salts. Thereby can be water soluble obtained highly branched polyurethanes.

By reacting NCO-terminated products with alkanols and alkylamines, in particular alkanols and alkylamines with C ₈ -C ₄₀ -alkyl radicals, hydrophobized products can be obtained.

hydrophilicized but non-ionic products can be NCO-terminated by reaction Polymers with polyether alcohols, such as di-, tri- or Obtain tetra or polyethylene glycol.

acid groups can be, for example, by reaction with hydroxycarboxylic acids or amino acids introduce. Examples of suitable reactants are 2-hydroxyacetic acid, 4-hydroxybenzoic acid, 12-hydroxydodecanoic acid, 2-hydroxyethanesulfonic acid, glycine or called alanine.

By Implementation with compounds comprising acrylate groups such as acrylate groups comprehensive alcohols such as 2-hydroxyethyl acrylate or 2-hydroxyethyl methacrylate can be obtained highly branched polyurethanes, the polymerizable have olefinic groups.

It can also highly branched polyurethanes are produced, the different Have functionalities. This can be done, for example, by reaction with a mixture of different Connections are made, or also by having only a part the original existing functional groups, for example only a part the OH groups, implements.

The Refunctionalization of the highly branched polyurethane can be advantageous take place immediately after the polymerization reaction, without first isolating the NCO-terminated polyurethane. The Functionalization can also take place in a separate reaction.

drug groups

The stabilizers according to the invention contain one or more drug groups, these drug groups via functional Groups D that are reactive with the functional groups B the anchor group are coupled.

drug groups For the purposes of the present invention, groups are a plastic or protect a plastic mixture against harmful environmental influences. Examples are primary and secondary Antioxidants, hindered amine light stabilizers, UV absorbers, hydrolysis inhibitors, Quencher and flame retardant.

in principle can be a stabilizer according to the invention contain one or more, also different active ingredient groups. Number of drug groups and ratio of drug groups to each other are variable and only by the number of functional Groups B of the anchor group are limited. Not every functional must Group B can be implemented with an active ingredient group.

Should a stabilizer according to the invention e.g. act as an antioxidant, such can be attached to the anchor group Drug groups hanged that slow down the oxidative degradation of a plastic or stop.

On Classes of drugs that act as antioxidants are steric hindered phenols.

in gebundener Form.In one embodiment of the invention, the stabilizers according to the invention contain as active ingredient group of active compounds of the general formula (1)

in bound form.

Here, X and Y are each independently a hydrogen atom or a straight-chain, branched or cyclic alkyl radical having 1 to 12 carbon atoms, and Z is a radical of the formula -CR ¹ -D wherein R ^{1 is} a single bond, a linear or branched divalent organic radical with 1-100 C atoms, preferably 1-12 C atoms, particularly preferably 1-6 C atoms, or R ^{1 is} a divalent radical of the formula - (R ² -C ¹ -R ³ ) _m is
where R ² and R ^{3 may be the} same or different from one another and are each independently a single bond, a linear or branched divalent organic radical having 1-50 C atoms, preferably 1-10 C atoms, in particular 1-4 C atoms , and m is a number from 1-100, preferably from 1-10 and particularly preferably from 1-4.

C and C ¹ are each independently a single bond, an oxygen atom, a sulfur atom, an -NH or an -NR group, an ester group (-C (O) O- or -O (O) C-), an amide group ( -NHC (O) - or -C (O) NH-), a urethane group (-OC (O) NH- or -HNC (O) O-) or a urea group (-HNC (O) N- or NC (O ) NH-).

"Independent of one another" means that in each of the m repetition units C ¹ , R ² or R ³ can stand for a different residue.

D is a functional group, with which the active ingredient group to the Anchor group is tied. Examples of D are substituted and unsubstituted amino, hydroxyl, thiol, carboxyl, isocyanato, Epoxy groups or activated double bonds. Preferably functional Groups D are hydroxyl groups and substituted and unsubstituted Amino groups.

worin Z wie vorstehend definiert ist.The stabilizers preferably contain, as a phenolic active ingredient group, the sterically hindered phenol of the formula (1a) in bound form,

where Z is as defined above.

wobei R und R' unabhänig voneinander H, lineare oder verzweigte Alkylketten mit 1–10 C-Atomen, bevorzugt 1–4 C-Atomen sein können. Solche Gruppen Z werden erhalten durch Veresterung eines Carbonsäuregruppen enthaltenden sterisch gehinderten Phenols mit einem Oligo- oder Polyalkylenoxid-Diol oder durch Alkoxylierung eines OH-Gruppen aufweisenden sterisch gehinderten Phenols mittels Ethylenoxid, Propylenoxid, Butylenoxid oder deren Mischungen.Preferred groups Z are for example

where R and R 'independently of one another can be H, linear or branched alkyl chains with 1-10 C atoms, preferably 1-4 C atoms. Such groups Z are obtained by esterification of a sterically hindered phenol containing carboxylic acid groups with an oligo- or polyalkylene oxide diol or by alkoxylation of a sterically hindered phenol containing OH groups using ethylene oxide, propylene oxide, butylene oxide or mixtures thereof.

in gebundener Form. W¹, W² und W³ sind unabhängig voneinander ein geradkettiger, verzweigter oder cyclischer Alkylrest mit 1–30 Kohlenstoffatomen oder ein substituierter oder ein unsubstituierter Arylrest mit 3–30 Kohlenstoffatomen. W² und W³ können unab hängig voneinander ebenfalls Wasserstoff sein, die Bedeutung von Z ist wie vorstehend definiert.Another suitable class of active ingredients are phosphorus compounds, which are used, for example, as a secondary antioxidant. In a further embodiment of the invention, the stabilizers according to the invention contain, as active ingredient groups, groups which contain trivalent phosphorus, for example groups which are derived from organophosphorus compounds of trivalent phosphorus, such as phosphites and phosphonites. In a preferred embodiment of the invention, the stabilizers according to the invention contain a phosphorus active ingredient of the general formula (2)

in bound form. W ¹ , W ² and W ³ are, independently of one another, a straight-chain, branched or cyclic alkyl radical having 1-30 carbon atoms or a substituted or an unsubstituted aryl radical having 3-30 carbon atoms. W ² and W ³ can also be hydrogen independently of one another, the meaning of Z is as defined above.

An example of a phosphorus active ingredient is the following compound of formula (2a)

A another class of active ingredients, the polymers against oxidative degradation protect, are thio compounds. Thio compounds contain at least one Sulfur atom. If there are several sulfur atoms in the thio compound, so can these can be directly connected to one another or by an organic one Rest be separated. Thio compounds are preferred, in which the sulfur atoms are not directly connected to each other. Thio compounds which are used according to the invention to build up the stabilizers are used, contain a functional group D, with the functional groups B of the anchor group can react. suitable functional groups D are substituted and unsubstituted Amino, hydroxyl, thiol, carboxyl, isocyanato and epoxy groups and activated double bonds. Hydroxyl groups and are preferred substituted and unsubstituted amino groups.

In a further embodiment of the invention, the stabilizers contain thio-active substances of the general formula (3) as active substance group R ⁶ -SR ⁷ -Z (3) in bound form. R ^{6 is} a linear or branched aliphatic organic radical containing 1-100 C atoms, preferably 1-12 C atoms, in particular 1-6 C atoms, R ⁷ is a single bond or a divalent linear or branched aliphatic or aromatic radical with 1-100 C atoms, preferably 1-12 C atoms, in particular 1-6 C atoms, and Z is as defined above.

To the Can protect against UV degradation UV absorber as active ingredient group on the hyperbranched anchor group be bound. Suitable UV absorbers are those compounds that absorb in the UV-A and UV-B region of the spectrum.

In a further embodiment of the invention are the active ingredient groups which act as UV absorbers, Diphenylcyanoacrylates, benzotriazoles, benzophenones, cinnamic acid esters, Benzylidene malonates and diaryl butadienes. The UV absorbers mentioned contain functional groups D with the functional groups B of the anchor group react. Such functional groups are substituted and unsubstituted amino, hydroxyl, thiol, carboxyl, isocyanato and epoxy groups and activated double bonds. Are preferred Hydroxyl and substituted and unsubstituted amino groups.

in gebundener Form enthalten.Examples are stabilizers which, as an active ingredient group, contain active ingredients of the formulas (4) to (7)

contained in bound form.

Z ¹ and / or Z ² bind to the functional groups B of the anchor group and are independently Z or CX, where X is a hydrogen atom, a straight-chain branched alkyl radical or a cycloalkyl radical with 1 to 12 carbon atoms and C and Z are as defined above ,

Another group of active ingredients that stabilize polymers against the effects of UV light are the so-called hindered amine (light) stabilizers (HAS or HALS). The activity of the HALS compounds is based on their ability to form nitroxyl radicals which intervene in the mechanism of the oxidation of polymers. HALS are considered to be highly efficient UV stabilizers for most polymers. In one embodiment of the invention, the stabilizers contain a sterically hindered amine that is capable of nitroxylra to form dicals in bound form.

worin X¹, X², Y¹, Y² und X³ unabhängig voneinander ein Wasserstoffatom, ein geradkettiger oder verzweigter Alkylrest oder ein Cycloalkylrest mit 1 bis 12 Kohlenstoffatomen und X³ darüber hinaus ein Acylrest mit 2 bis 18 Kohlenstoffatomen, ein Alkoxyrest mit 1 bis 19 Kohlenstoffatomen und ein Aryloxycarbonylrest mit 7 bis 12 Kohlenstoffatomen sein kann, und Z wie vorstehend definiert ist.In a preferred embodiment of the invention, the stabilizers according to the invention contain HALS active ingredients of the general formula (8) in bound form as active ingredient groups,

wherein X ¹ , X ² , Y ¹ , Y ² and X ³ independently of one another are a hydrogen atom, a straight-chain or branched alkyl radical or a cycloalkyl radical with 1 to 12 carbon atoms and X ³ furthermore an acyl radical with 2 to 18 carbon atoms, an alkoxy radical with 1 to 19 carbon atoms and an aryloxycarbonyl group having 7 to 12 carbon atoms, and Z is as defined above.

A Another group of active ingredients are aromatic amines. Aromatic amines are all compounds that are substituted or not Have substituted amino group directly attached to an aromatic System are bound. Aromatic amines are used depending on the substitution as antioxidants or as an active ingredient against the harmful Influence of Ozone.

worin X¹, X², X³ und X⁴ unabhängig voneinander ein Wasserstoffatom, ein geradkettiger oder verzweigter Alkylrest oder ein Cycloalkylrest mit 1 bis 12 Kohlenstoffatomen oder Z sind, wobei Z wie obenstehen definiert ist, und
X⁴ darüber hinaus

sein kann.In a further embodiment of the invention, the stabilizers according to the invention contain aromatic amines in bound form as the active ingredient group. In a preferred embodiment, these are active compounds of the general formula (9)

wherein X ¹ , X ² , X ³ and X ^{4 are} independently a hydrogen atom, a straight-chain or branched alkyl radical or a cycloalkyl radical having 1 to 12 carbon atoms or Z, where Z is as defined above, and
X ⁴ beyond

can be.

X ⁵ and X ⁶ are independently a hydrogen atom, a straight-chain or branched alkyl radical or a cycloalkyl radical with 1 to 12 carbon atoms or Z, where Z is as defined above.

Another group of active ingredients are benzofuranones or indolenes. Such compounds are described, for example, in US 4,325,863 , In principle, benzofurans or indolenes are suitable as groups of active substances which carry a functional group which can react with the functional groups B of the anchor group. Examples of such functional groups are substituted and unsubstituted amino, hydroxyl, thiol, carboxyl, isocyanato or epoxy groups or activated double bonds. Hydroxyl groups and substituted and unsubstituted amino groups are preferred. In a further embodiment of the invention, the stabilizers according to the invention receive compounds of the general formula (10) in bound form as active ingredient group:

Z ¹ and / or Z ² bind to the functional groups B of the anchor group. Z ¹ and Z ² are independently Z or CX, where X is a hydrogen atom, a straight-chain or branched alkyl radical or a cycloalkyl radical with 1-12 C atoms, and C and Z are as defined above.

support groups

The stabilizers according to the invention can have one or more auxiliary groups (III).

(III) represents an auxiliary group within the meaning of the invention, the processing, Incorporation, emulsifiability or solubility of the stabilizer influenced in the sense of the user. For example, if the stabilizer is in an aqueous solution be dispersed, it may be helpful to have an auxiliary group built-in, which increases the emulsifiability of the stabilizer. Vice versa it can be used in hydrocarbon solvents be advantageous to increase the hydrophobicity of the product by preferably hydrophobic residues are incorporated as an auxiliary group. as it were can it for the processing of the stabilizer may be important, the glass temperature and viscosity lower. An auxiliary group can then also be deployed here come, which prevents the attachment of the stabilizer molecules to aggregates and so viscosity reducing acts. Finally the solubility of the stabilizer can also be determined by the choice of the auxiliary group be influenced in the interests of the user. This can e.g. the transition can be reduced from plastic into food or the distribution of the stabilizer for different polymer blends be steered in favor of one of the two blend components. by virtue of the diverse Tasks that can be assigned to the auxiliary group (III) is the type of structure the auxiliary group (III) very diverse.

The Auxiliary group (III) is like functional group (II) via functional Groups (functional groups E) with the functional groups B of the highly branched polymer react to the highly branched Polymer bound. examples for E are substituted and unsubstituted amino, hydroxyl, Thiol, carboxyl, isocyanato, epoxy groups or activated double bonds. Hydroxyl and substituted and unsubstituted are preferred Amino groups.

For example, auxiliary groups with a hydrophobic effect can have the following schematic structure: IT

S in this context is a non-polar residue, e.g. a straight chain, branched or cyclic alkyl radical with 1 to 10000 carbon atoms, preferably 1-1000 C-atoms.

Examples are for S. Hexyl, heptyl, octyl, nonyl, decyl, dodecyl, stearyl, oleyl, Palmityl, oligobutyl, oligobutadienyl, oligoisobutyl, polybutyl, Polybutadienyl, polyisobutyl, phenyl, naphthyl or nonylphenyl radicals.

Examples for one Auxiliaries with a hydrophobic effect (E-S) are stearic acid, oleic acid, palmitic acid, stearic acid chloride, Octylamine, stearylamine, polyisobutyleneamine, dipentylamine, diisopentylamine, Dihexylamine, octyl alcohol, stearyl alcohol, hexadecanol, octadecanol, Octadecenol, polyisobutylene alcohol, nonylphenol, hexyl isocyanate, Dodecyl isocyanate, phenyl isocyanate or naphthyl isocyanate.

If the auxiliary group is to have a hydrophilic effect, (III) can have the following schematic structure. ET

T in this context is a hydophilizing residue, e.g. a diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, Oligoethylene glycol monomethyl ether, polyethylene glycol monomethyl ether, Oligopropylene glycol monomethyl ether, polypropylene glycol monomethyl ether or a poly (ethylene) (propylene) glycol monomethyl ether residue.

Farther residues of aminocarboxylic acid, hydroxycarboxylic acids, mercaptocarboxylic acids, aminosulfonic acids or have a hydrophilic effect hydroxysulfonic or mercaptosulfonic acids.

Examples of auxiliaries which have a hydophilizing action are diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, oligoethylene glycol monomethyl ether, polyethylene glycol monomethyl ether, oligopropylene glycol monomethyl ether, polypropylene glycol monomethyl ether, poly (ethylene) - (propylene) glycol monomethyl methyl ether, 2 ) amine, 3- (2-methoxyethoxy) propylemine, 9-amino-3,6-dioxanonan-1-ol or higher molecular weight polyalkylene oxide amines, generally known under the name Jeffamine ^® from Huntsman, lactic acid, mercaptoacetic acid, hydroxypivalic acid, glycine, β-alanine or taurine.

Synthesis of the stabilizers according to the invention

The Production of the stabilizers according to the invention usually takes place via a Polyaddition or a polycondensation reaction such that at least one highly branched polymer (I) as an anchor group, if appropriate with the use of an organic solvent, under an inert gas atmosphere, preferably under nitrogen, placed in a reaction vessel and with stirring Reaction temperature is brought. Then one gives at reaction temperature at least one active ingredient (II) continuously or discontinuously to. The amount of active ingredient (II) depends on the number of functional Groups B of the anchor group and is usually chosen so that The relationship the number of moles of groups B to the number of moles of those reactive with these groups B. Groups D of the active ingredient are present in a ratio of 2: 1 to 1: 1. If several active ingredients are used simultaneously or in succession with the Anchor group implemented, or is still after coupling the active ingredients a further auxiliary (III) for the preparation of the stabilizer according to the invention needed so the total amount of reactive groups D of the active ingredients (II) and the reactive groups E of the auxiliary means (III) are dimensioned such that it corresponds to the total amount of reactive groups B of the anchor group.

The Response time is usually chosen so that the reactive groups B of the anchor group completely with the reactive groups D of the active substances and the reactive groups E of the auxiliary substances are implemented.

The aforementioned implementation with the active ingredient groups and the auxiliary substances can optionally be carried out in the presence of catalysts which in amounts of 0.0001 to 1% by weight, in particular 0.001 to 0.1 % By weight, based in each case on the amount of anchor group, used become. As catalysts for Polyaddition or polycondensation reactions occur organometallic Compounds, especially tin, zinc, titanium, bismuth or zircon organic Connections into consideration. For example, dibutyltin dilaurate, Dibutyltin oxide, titanium tetrabutylate, zinc acetylacetonate or zirconium acetylacetonate used. Can continue strong bases, preferably nitrogen-containing compounds, such as tributylamine, Chinnuclidine, diazabicyclooctane, diazabicyclononane or diazabicycloundecane be used.

As suitable solvents can those are used which under reaction conditions compared to the Feedstocks are inert. For example, acetone, 2-butanone, ethyl acetate, butyl acetate are suitable, Tetrahydrofuran, dioxane, benzene, toluene, xylene, ethylbenzene, chlorobenzene, Dichlorobenzene, dimethylformamide, dimethylacetamide or N-methylpyrrolidone.

The Reaction temperature for the polyaddition or polycondensation reaction is usually from -10 to 220 ° C, preferred 0 to 180 ° C. The reaction takes place both at atmospheric pressure and at a pressure above or below atmospheric pressure, for example at a pressure of 2-20 bar or at 0.1-0.001 bar.

example 1

manufacturing a hyperbranched polyisocyanate

In a reaction vessel with stirrer, gas inlet tube and dropping funnel with pressure equalization, 1000 g of IPDI are introduced under nitrogen and 300 g of trimethylolpropane, dissolved in 1300 g of dry ethyl acetate, are added at room temperature with vigorous stirring. After 0.3 g of dibutyltin dilaurate has been metered in, the reaction mixture is heated to 40 ° C. with stirring and the decrease in the NCO content is monitored titrimetrically. When an NCO content of 7.3% by weight is reached, the reaction product has an average functionality of 2 with respect to NCO and 1 with respect to OH. Now, the addition product will be 860 g BASONAT ^® HI 100 dissolved in 860 g of dry Essigester within 1 min added to the mixture at 60 ° C. and stirred for 3 h at this temperature. The end product has an NCO content of 6.2% by weight.

The average molar mass of the polyisocyanate is 2419 g / mol, which medium NCO functionality is 6.7.

BASONAT ^® HI 100 (BASF AG) is an aliphatic polyisocyanate based on hexamethylene diisocyanate, the average functionality is 3.7 NCO groups per molecule.

Example 2

manufacturing a hyperbranched polyisocyanate

In a reaction vessel with stirrer, gas inlet tube and dropping funnel with pressure equalization, 1000 g of IPDI are introduced with nitrogen injection and 300 g of trimethylolpropane, dissolved in 1300 g of dry ethyl acetate, are added at room temperature with thorough stirring within 1 min. After 0.12 g of dibutyltin dilaurate has been metered in, the reaction mixture is heated to 60 ° C. with stirring and the decrease in the NCO content is followed titrimetrically. When an NCO content of 7.3% by weight is reached, the reaction product has an average functionality of 2 with respect to NCO and 1 with respect to OH. Now, the addition product will be 1280 g BASONAT ^® HI 100 dissolved in 500 g of dry Essigester within 1 min added to the mixture at 60 ° C. and stirred for 3 h at this temperature. The end product has an NCO content of 8.5% by weight.

The average molar mass of the polyisocyanate is 1420 g / mol, which medium NCO functionality is 4.9.

Example 3

manufacturing of a phenolic active ingredient

In a 500 ml round bottom flask with stirrer, gas inlet tube and a distillation bridge are introduction of dry nitrogen 609 g Pluriol ^® E 200 (BASF AG), 175 g Ralox ^® 35 (Raschig) and 2.8 g Weston ^® DHOP (Messrs. General Electric ) given. The mixture is heated to 145 ° C. and 1.8 g of potassium methoxide are added. The resulting methanol is removed via the distillation bridge and collected in a cold trap.

To The reaction mixture is terminated at 145 ° C. (about 2 h) cooled to 80 ° C. Then be 2.5 g of 85% phosphoric acid added to neutralize the product. It will be another 15 min at 80 ° C touched and subsequently washed with water. To do this, add 1000 ml of distilled water a beaker at 40 ° C heated and that at 80 ° C warm product slowly added to the water with vigorous stirring. Subsequently becomes the watery Mixture stirred for 30 min, left until phase separation and the water phase from the product decanted. This washing process is repeated again. The product will then on a rotary evaporator at approx. 80 ° C and dried 10 mbar.

Example 4

Manufacture of the active substance 4-Hydroxyethyloxybenzophenon

520 g of diethylene glycol diethyl ether, 286 g of p-hydroxybenzophenone (1.44 mol) and 0.8 g of solid, finely ground potassium hydroxide are placed in a 2 l laboratory autoclave. This is followed by a 30-minute pressure test with dry nitrogen followed by inerting the reaction vessel. After the reaction mixture has been heated to 120 ° C., 95.4 g of ethylene oxide (2.2 mol) are continuously gassed in over a period of 1 h at a maximum internal pressure of 4 bar. After the end of the gassing with ethylene oxide, the reaction mixture is allowed to react until a constant pressure over 30 min occurs. The product is discharged hot from the autoclave with neutral aqueous hydrochloric acid siert, poured into 2 l ice water and brought to crystallization by constant stirring. The resulting solid is filtered off, washed with ice water and dried in vacuo.

Example 5

Stabilizer according to the invention A

In a reaction vessel with stirrer, gas inlet tube and dropping funnel with pressure equalization are 50 g of the solution of hyperbranched polyisocyanate in ethyl acetate from Example 1 below Nitrogen introduced at room temperature and 12.7 g of 1,2,2,6,6-pentamethylpiperidin-4-ol, solved in 50 g of dry ethyl acetate, added dropwise within 1 min. After encore 0.02 g of dibutyltin dilaurate is used to stir the mixture at 60 ° C. for 3 h. Then will the solvent removed on a rotary evaporator in vacuo. The product is a white powder with a calculated molar mass of 3565 g / mol and a number of on average 6.7 stabilizer groups per molecule.

Example 6

Stabilizer according to the invention B

In a reaction vessel with stirrer, gas inlet tube and dropping funnel with pressure equalization are 120 g of the solution of the hyperbranched polyisocyanate in ethyl acetate from Example 2 below Introduced nitrogen at room temperature and 42 g of 1,2,2,6,6-pentamethylpiperidin-4-ol, solved in 42 g of dry ethyl acetate, added dropwise within 1 min. After encore 0.02 g of dibutyltin dilaurate is used to stir the mixture at 60 ° C. for 6 h. Then will the solvent removed on a rotary evaporator in vacuo. The product has a calculated Molar mass of 2259 g / mol and a number of 4.9 stabilizer groups on average per molecule on.

Example 7

Stabilizer according to the invention C

In a reaction vessel with stirrer, gas inlet tube and dropping funnel with pressure equalization, 40 g of the solution of the hyperbranched polyisocyanate in ethyl acetate from Example 2 below Introduced nitrogen at room temperature and 25 g of the phenol from Example 3 in 25 g dry ethyl acetate and 8 g 1,2,2,6,6-pentamethylpiperidin-4-ol, solved in 8 g dry ethyl acetate, added dropwise within 1 min. After encore 0.02 g of dibutyltin dilaurate is used to stir the mixture at 60 ° C. for 6 h. Then will the solvent removed on a rotary evaporator in vacuo. The product has one calculated molar mass of 2350 g / mol and a number of on average 2.5 phenolic and 2.5 amine stabilizer groups per molecule.

Example 8

Stabilizer according to the invention D

In a reaction vessel with stirrer, gas inlet tube and dropping funnel with pressure equalization are 60 g of the solution of the hyperbranched polyisocyanate in ethyl acetate from Example 2 below Nitrogen introduced at room temperature and 16.6 g of 1,2,2,6,6-pentamethylpiperidin-4-ol, solved in 17 g dry ethyl acetate, added dropwise within 1 min. After encore 0.02 g of dibutyltin dilaurate is used to stir the mixture at 60 ° C. for 5 h. Then 6.1 g of 4-hydroxyethyloxy-benzophenone from Example 4, dissolved in 7 g of dry ethyl acetate, added and stirred at 60 ° C for 1 h. Then will the solvent removed on a rotary evaporator in vacuo. The product has one calculated molar mass of 2382 g / mol and a number of on average one benzophenonic and 4 amine stabilizer groups per molecule on.

Example 9

Manufacture of a thermoplastic Polyurethane (TPU) based on polyether

1000 g of a polytetrahydrofuran having a molecular weight of 1000 g / mol (PolyTHF ^® 1000, BASF AG) were heated in a tinplate bucket to about 90 ° C. Then additives such as. B. antioxidants and 125 g of butanediol are added. The solution was heated to 80 ° C with stirring. 600 g of 4,4'-diphenylmethane diisocyanate (4,4'-MDI) were then added and the mixture was stirred until the solution was homogeneous. The TPU was then poured into a flat dish and heated for 10 minutes at 125 ° C plate, then tempered for 15 h at 110 ° C in the heating cabinet.

Example 10

manufacturing of an antioxidant concentrate

1000 g of PTHF 1000 were heated in a tinplate bucket to approx. 90 ° C. Was then carried out with stirring, the addition of 8 g of Irganox ^® 1010 and Irganox ^® 1098 8 g and 125 g of butanediol. In addition, the stabilizers mentioned in Table 1 were incorporated in the amounts specified. The solution was heated to 80 ° C with stirring. Then 600 g of 4,4'-MDI were added and the mixture was stirred until the solution was homogeneous. The TPU was then poured into a flat dish and first heat-treated at 125 ° C. for 10 minutes on the hotplate, then at 110 ° C. for 15 hours in the heating cabinet. After the plates had cooled, they were ground into granules in a mill.

The Table 1 shows that the color of the cast stabilizer concentrate with the stabilizer according to the invention is significantly improved.

Table 1

Example 11

Production of an antioxidant concentrate in the kneader

45 g of a soft polyether TPU (Elastollan ^® 1185 A) were melted in a kneader at 200 ° C. The temperature was then reduced to 160 ° C. The amounts of stabilizers listed in Table 2 were then slowly metered in. After the substances had been mixed well, the product was removed from the kneader and annealed at 80 ° C. for two hours. It was found that the color of the concentrates with the stabilizers according to the invention is significantly better than that of the concentrates with the comparison stabilizers.

Table 2

Example 12

stabilization a TPU with stabilizer according to the invention containing HALS drug groups compared to commercial products

A Test series containing the stabilizers in Table 2 was the regulation prepared accordingly in Example 9. After granulation a series was blown into the casting rind into foils with a thickness of 100 μm. Another part was made with a yellow color concentrate of 2 mm test plates injection molded. Films and spray plates were exposed according to DIN 75202. Tables 3 and 4 show the results of the exposure. As can be clearly seen, the samples are the HALS according to the invention contain significantly more stable than the samples without HALS (Table 3). additionally indicate the colored ones Samples with the NECK has a significantly lower discoloration than the samples with the commercial HALS cast for comparison.

Stabilisatorenmischungen enthaltend einen erfindungsgemässen Stabilisator mit HALS-Wirkstoffgruppen Table 3

Stabilizer mixtures containing a stabilizer according to the invention with HALS active ingredient groups

The Products containing the HALS stabilizer according to the invention contain, show a significantly lower discoloration than the product without Hindered Amine Light Stabilizer (Table 4: Yellowness indices according to Exposure according to DIN 75202)

Table 4

at the yellow one Plates show the samples containing the HALS stabilizer according to the invention clearly smaller discoloration both compared to the samples that did not have a HALS stabilizer included as well as compared to the sample, which is a commercial Contains neck stabilizer. (Table 5: Yellowness indices after exposure according to DIN 75202)

Table 5:

Example 13

Manufacture of a thermoplastic Polyurethane (TPU) based on polyester

In a 2 liter metal bucket White, 1000 g of a polyesterol (Lupraphen ^® 1010 from BASF AG) were heated to 80 ° C. The various stabilizers were then added with stirring. The type and amount of stabilizers are summarized in Table 6. Thereafter, 88 g of 1,4-butanediol and 13.6 g Elastostab® ^® H 01 (Elastogran GmbH). After the solution had subsequently been heated to 75 ° C., 500 g of 4,4′-MDI were added and the mixture was stirred until the solution was homogeneous. The reaction mass was then poured into a flat dish and annealed at 125 ° C. on a hot plate for 10 minutes. The resulting rind was then tempered in a heating cabinet at 100 ° C for 24 h. After the mold plates had been granulated, they were processed into 2 injection plates on an injection molding machine. The product has a Shore hardness of 85 A.

Example 14

Stabilization of a polyester TPU with the stabilizers according to the invention

Corresponding Example 13 was cast with a polyester TPU using a UV stabilizing mixture was stabilized. Table 6 provides information about the amount of used Stabilizers.

Table 6

initial color is a crucial criterion for TPU. Table 7 shows 2 samples containing a commercial HALS stabilizer with compared a sample containing a stabilizer according to the invention. The The initial color of the sample with the stabilizer according to the invention is clear better.

Table 7

A Another important property of polyester TPU is its hydrolysis stability. For measurement this property, 2 rods were punched out of the spray plates and at 80 ° C over in water stored in the period specified in Table 8. Then was tensile strength measured according to DIN 53504 (Table 8). It shows that the tensile strength using the HALS stabilizer according to the invention the longest remains at a high level.

Table 8

The Main criterion for A good UV stabilization is the yellowing of the samples after exposure. For this the samples from Example 14 were exposed according to DIN 75202. It shows that the samples with the stabilizers according to the invention after the end less discolouration of the test (300 h) showed as those containing the commercial stabilizers. (Table 9: Yellowness index of the samples exposed according to DIN 75202 (total transmission))

Table 9

Example 15

Production of an aqueous stabilizer emulsion

10 g of stabilizer C from Example 7 were placed in a beaker to 90 ° C heated and with 40 g of an aqueous solution of 0.3% by weight of Mowiol 4088 (from Clariant). With help of a Ultraturrax (IKA, model T50) became an emulsion at 5000 rpm and 90 ° C made from the mixture. After cooling to room temperature one over stable oil-in-water for several days Emulsion with an average particle diameter of 1.6 μm. The middle one Particle diameter was determined by dynamic light scattering on a 0.005 to 0.01 wt .-% aqueous Dispersion at 23 ° C using an Autosizer IIC from Malvern Instruments, England, determined. The average diameter of the cumulative evaluation is given (cumulant z-average) of the measured autocorrelation function.

Example 16

Stabilization of a styrene-butadiene copolymer

The emulsion stabilizer from Example 15 was treated at room temperature with a mechanical overhead stirrer in 500 ml of a styrene-butadiene dispersion (LD Styronal ^® 906, BASF AG) are stirred in. The weight proportion of stabilizer was 0.5% based on the solid styrene-butadiene copolymer. The mixture was poured into flat molds and dried to a few millimeters thick films at room temperature.

• - stabilisiertes Produkt: 15
• - unstabilisiertes Produkt (Vergleich): 100

The films were stored together with unstabilized samples in a drying cabinet for one week at 150 ° C. in air. The yellowness index of the films was then determined in accordance with DIN 6167 and evaluated in accordance with DIN 6174. The following values were determined:

• - Stabilized product: 15
• - Unstabilized product (comparison): 100

Claims (17)

Stabilizers, which are composed of structural units (I) to (III), namely (I) a highly branched polymer with functional groups B as a highly branched anchor group; (II) one or more groups of active ingredients which protect plastics against damage from heat, UV radiation, oxidation, hydrolysis or mechanical action during processing, the active ingredient groups via functional groups D, which can react with functional groups B, to the anchor group are coupled; (III) optionally one or more auxiliary groups which modify the properties of the stabilizer, the auxiliary groups being coupled to the anchor group via functional groups E which can react with the functional groups B. Stabilizer according to claim 1, characterized in that the highly branched polymer is structurally irregular hyperbranched polymer or a structurally regular structure Is dendrimer. Stabilizer according to claim 1 or 2, characterized in that the highly branched anchor group has 3 to 100 groups B. Stabilizer according to one of claims 1 to 3, characterized in that that the highly branched polymer (I) is selected from hyperbranched Polyesters, hyperbranched polyethers, hyperbranched polyurethanes, hyperbranched polyurea polyurethanes, hyperbranched polyureas, hyperbranched polyamines, hyperbranched polyamides, hyperbranched Polyether amides and hyperbranched polyester amides. Stabilizer according to claim 4, characterized in that the highly branched polymer (I) is selected from hyperbranched Polyurethanes, hyperbranched polyureas, hyperbranched Polyethers, hyperbranched polyesters and hyperbranched polyester amides. Stabilizer according to one of claims 1 to 5, characterized in that the functional groups B are selected from -NCO, -OH, -SH, -COOH, -COOR, -CONH ₂ , -NH ₂ , -NHR, -SO ₃ H , Epoxy groups or activated double bonds. Stabilizer according to one of claims 1 to 6, characterized in that that the drug groups are selected are from sterically hindered phenols, organophosphorus compounds of trivalent phosphorus, thio compounds, diphenyl cyanoacrylates, Benzotriazoles, benzophenones, cinnamic acid esters, benzylidene malonates, Diarylbutadienes, HALS stabilizers, aromatic amines, benzofurans and indoles. Stabilizer according to one of claims 1 to 7, characterized in that it contains sterically hindered phenols of the general formula (1) as active ingredient groups

contained in bound form, wherein X and Y are each independently a hydrogen atom or a straight-chain, branched or cyclic alkyl radicals having 1 to 12 carbon atoms, and Z is a radical of the formula -CR ¹ -D is where R ^{1 is} a single bond, a linear or branched divalent organic radical having 1-100 C atoms, or R _{1 is} a divalent radical of the formula - (R ² -C ¹ -R ³ ) _m where R ² and R ^{3 may be the} same or different from one another and are each independently a single bond, a linear or branched divalent organic radical with 1-50 C atoms, and m is a number from 1-100, C and C ¹ independently of one another in each case a single bond, an oxygen atom, a sulfur atom, a -NH- or an -NR group, an ester group (-C (O) O- or -O (O) C-), an amide group (-NHC (O) - or -C (O) NH-), one Urethane group (-OC (O) NH- or -HNC (O) O-) or a urea group (-HNC (O) N- or -NC (O) NH-), and D is a functional group with which the Active ingredient group can be bound to the functional groups B of the anchor group. Stabilizer according to one of claims 1 to 7, characterized in that it contains, as active ingredient groups, phosphorus active ingredients of the general formula (2)

contains in bound form, in which W ¹ , W ² and W ^{3 are,} independently of one another, a straight-chain, branched or cyclic alkyl radical having 1-30 carbon atoms or a substituted or an unsubstituted aryl radical having 3-30 carbon atoms, W ² and W ³ also being independent can be hydrogen from one another and the meaning of Z is as defined in claim 6. Stabilizer according to one of claims 1 to 7, characterized in that it contains thio-active substances of the general formula (3) as active substance groups R ⁶ -SR ⁷ -Z (3) contains in bound form, in which R ^{6 is} a linear or branched aliphatic organic radical containing 1-100 C atoms and R ^{7 is} a single bond or a divalent linear or branched aliphatic or aromatic radical with 1-100 C atoms, and Z is as claimed 6 is defined. Stabilizer according to one of claims 1 to 7, characterized in that it contains one or more active substances of the formulas (4) to (7) as active substance groups

contains in bound form, in which Z ¹ and / or Z ² bind to the functional groups B of the anchor group and are independently Z or CX, where X is a hydrogen atom, a straight-chain branched alkyl radical or a cycloalkyl radical with 1 to 12 carbon atoms and C and Z are as defined in claim 6. Stabilizer according to one of claims 1 to 7, characterized in that it contains HALS active substances of the general formula (8) as active substance groups

contains in bound form, wherein X ¹ , X ² , Y ¹ , Y ² and X ³ independently of one another are a hydrogen atom, a straight-chain or branched alkyl radical or a cycloalkyl radical with 1 to 12 carbon atoms and X ³ furthermore an acyl radical with 2 to 18 carbon atoms , an alkoxy radical having 1 to 19 carbon atoms and an aryloxycarbonyl radical having 7 to 12 carbon atoms, and Z is as defined in claim 6. Stabilizer according to one of claims 1 to 7, characterized in that it contains aromatic amines of the general formula (9) as active ingredient groups

contains in bound form, wherein X ¹ , X ² , X ³ and X ^{4 are} independently a hydrogen atom, a straight-chain or branched alkyl radical or a cycloalkyl radical having 1 to 12 carbon atoms or Z, where Z is as defined in claim 6, and X ⁴ beyond

where X ⁵ and X ^{6 are} independently a hydrogen atom, a straight-chain or branched alkyl radical or a cycloalkyl radical having 1 to 12 carbon atoms or Z, where Z is as defined in claim 6. Stabilizer according to one of claims 1 to 7, characterized in that it contains compounds of the general formula (10) in bound form as active ingredient group,

wherein Z ¹ and / or Z ² bind to the functional groups B of the anchor group and Z ¹ and Z ^{2 are} independently Z or CX, where X is a hydrogen atom, a straight-chain or branched alkyl radical or a Is cycloalkyl with 1-12 C atoms, and C and Z are as defined in claim 6. Stabilizer according to one of claims 1 to 14, characterized in that it has a hydrophobic effect Auxiliary group E-S or a hydrophobic auxiliary group E-T contains in bound form, where S is a hydrophobic and T is a hydrophilic radical and E is a functional group that interacts with the functional Groups B of the anchor group can react. Stabilizer according to one of claims 1 to 15, characterized in that the groups D and E, with the functional groups B of the anchor group can react are selected from substituted and unsubstituted amino groups, hydroxyl, Thiol, carboxyl, isocyanato, epoxy groups or activated double bonds. Use of the stabilizers according to claims 1 to 16 for stabilizing polymers.