Blends of thermoplastic polymers with covalent adaptable networks

Abstract

The invention relates to a thermoplastic composition comprising A) a non-crosslinked polymer and B) a covalent adaptable network, wherein the covalent adaptable network is the reaction product of B1) a component comprising at least two acid anhydride groups or comprising at least two pairs of carboxyl groups or comprising at least two pairs of derivatives of carboxyl groups and B2) a component with at least two functional groups independently from each other selected from -OH, -NHR and -SH, wherein R stands for an optionally substituted alkyl, aryl or arylalkyl residue, and wherein at least one of the components B1 and B2 has a functionality of >2, a process for preparing a thermoplastic molding compound from these thermoplastic compositions and molded articles comprising the thermoplastic compositions or thermoplastic molding compounds. The invention also relates to a thermoplastic molding compound comprising A) an amorphous non-crosslinked polymer as matrix phase B') a polymer different from polymer A which is characterized by a two phase morphology with a matrix phase i) containing component A, a phase ii) dispersed therein containing component B' and an interphase layer iii) of a defined thickness. In a particular embodiment of the invention the gradient of the ratio of components A and B' in the interphase layer iii) is in a certain range.

Description

[0001] 2024PF30097-Foreign Countries

[0002] - 1 -

[0003] Blends of thermoplastic polymers with covalent adaptable networks

[0004] The present invention relates to a thermoplastic composition comprising a non-crosslinked polymer and a specific covalent adaptable network, a process for preparation of a molding compound from the composition and an article comprising the thermoplastic molding composition or molding compound. The invention also relates to a thermoplastic molding compound comprising an amorphous non-crosslinked polymer and a second polymer, wherein the molding compound is characterized by a two phase morphology comprising a matrix phase, a dispersed phase and an interphase layer, wherein the interphase layer is characterized by a gradient change of the contents of the two polymers of the composition from the according values in the matrix phase to the according values in the dispersed phase and wherein the thickness of the interphase exceeds a certain minimum value.

[0005] Thermoplastic polymers are used for a wide range of applications for example in the automotive industry, for electro / electronic parts and in the construction area. In case the polymer is amorphous and non-crosslinked the molded articles made thereof are typically translucent or even transparent.

[0006] For many applications such as large and / or thin parts produced by injection molding processes a low melt viscosity of the thermoplastic material at high shear rates is desirable. This requirement is not easily fulfilled for some transparent polymers such as polycarbonate. Reduction of molecular weight is not an option for all applications as other properties would be negatively affected. Whereas injection molding operates at high shear rates and benefits from low melt viscosities other methods for producing finished parts such as compression molding, extrusion and blow-molding require good melt stability, i.e. high melt viscosity at low shear rates. For universal suitability for any kind of industrial molding processes the thermoplastic material should combine these two properties, i.e. show structural viscous behavior.

[0007] To adjust the rheological, mechanical, thermal and further properties, the polymers are often mixed and compounded with polymeric blend partners and further additives. In this way polymer blends covering a broad variety of property profiles can be obtained. However, due to the often limited miscibility of the blended polymers, this process in most cases results in compound materials with a two-phase morphology on a mesoscopic scale. Blending a transparent or translucent polymer with another polymer in such cases typically leads to significantly reduced transparency of the obtained compound materials due to differences in refractive indices of the blend partners resulting in light scattering at the interphases of the two polymers. The interphases are also often weak spots with regard to mechanical properties. If the compatibility of the mixed polymers is very low even phase delamination may occur. 2024PF30097-Foreign Countries

[0008] - 2 -

[0009] A promising new class of blend partners are covalent adaptable networks (CAN). These polymers comprise crosslinks between different polymer chains which can be covalently opened and thus dynamically activated by stimuli such as light, pH changes, ultrasonic waves and, most typically, by heat. In the latter case the CANs become thermoplastic at elevated temperatures. CANs with different mechanism of covalent dynamics are known. In dissociative CANs covalent bonds participating in crosslinking are completely opened e.g. triggered by increasing temperature above a critical value. Above this critical temperature there is a dynamic equilibrium of covalent opening and reforming of crosslinks. The density of crosslinks in such materials above the critical temperature is thus a function of temperature. In associative CANs, such as vitrimers, on the other hand crosslink bonds simultaneously open and reform with the same or other pending functional groups, i.e. crosslinks just exchange between different areas of a polymer chain or between different polymer chains, and thus density of crosslinks in the material remains nearly constant even above the temperature triggering the polymer dynamics.

[0010] A variety of chemistries (chemical groups) have been identified to access CANs from different starting materials. The majority of those chemistries require the use of catalysts to promote the desired exchange reactions and thus to make the CANs industrially processable under typical polymer processing conditions (temperatures). Those catalysts often however have detrimental effects on the stability and properties of the matrix polymers and thus on the polymer blends when the CANs containing the catalysts are used as blend partners.

[0011] The covalent adaptable networks have the potential to combine advantages of conventional (permanent) polymer networks such as chemical stability and dimensional stability at higher application temperatures with the recyclability and processability of non-crosslinked thermoplastics. They also have the potential to impart compatibilization between immiscible polymers in polymer blends.

[0012] Covalent adaptable networks and blends thereof with thermoplastic polymers have been reported in the scientific and patent literature.

[0013] A. Hernandez et al. disclose “Design and Continuous (Re)Processing of Thermally Resilient Poly(Styrene-co-Maleic Maleate)-Based Covalent Adaptable Networks” (Chemistry of Materials 2024 36 (15), 7487-7503). The disclosed CANs have the advantage that they show sufficient dynamic behavior required for established industrial thermoplastic molding processes already at quite low temperatures even in the absence of any catalysts. 2024PF30097-Foreign Countries

[0014] - 3 -

[0015] WO 2021 / 074290 Al discloses a covalent adaptable network, a method for the preparation thereof and the use of the covalent adaptable network in extrusion, injection molding and other molding processes as well as 3D printing.

[0016] WO 2024 / 182665 Al discloses a polymer blend composition comprising a thermoplastic resin matrix and a dynamically crosslinked polymer.

[0017] The state of the art is silent with regard to polymeric materials comprising non-crosslinked polymers, such as polycarbonate, with improved rheological properties which allow them to be used in processing with a wide range of different industrially established molding techniques. Further, the state of the art is silent with regard to the balance of rheological and optical features such as light transparency. Although it was known that polymeric blend partners may improve melt flowability, no teaching was available as to achieving suitable rheological behavior in a wide range of shear rates and preferably at the same time minimizing the reduction of light transparency when such blend partners are present.

[0018] Therefore, it was desirable to provide a polymeric material that is characterized by a combination of high viscosity at low shear rates and low viscosity at high shear rates, which makes it suitable for a variety of different thermoplastic molding processes including injection molding, extrusion, blow molding and compressing molding. In other words, it is desirable to provide a polymeric material with structural viscosity over the complete shear range as indicated by a large slope value of the dynamic melt viscosity also in the low shear rate regime. Preferably this desired rheological behavior should be achieved in combination with a high level of light transparency of the parts made from the polymeric material by any of these forming processes.

[0019] Surprisingly, it was found, that a thermoplastic composition comprising

[0020] A) a non-crosslinked polymer and

[0021] B) a covalent adaptable network, wherein the covalent adaptable network is the reaction product of

[0022] B 1) a component comprising at least two acid anhydride groups or comprising at least two pairs of carboxyl groups or comprising at least two pairs of derivatives of carboxyl groups and

[0023] B2) a component with at least two functional groups independently from each other selected from -OH, -NHR and -SH, wherein R stands for an optionally substituted alkyl, aryl or arylalkyl residue wherein at least one of the components B 1 and B2 has a functionality of >2, 2024PF30097-Foreign Countries

[0024] - 4 - shows the desired properties.

[0025] The term "a non-crosslinked polymer" for component A also includes mixtures of two or more noncrosslinked polymers. "A non-crosslinked polymer" is therefore to be understood as "at least one non-crosslinked polymer" . This applies analogously to the component B, to the components B 1 and B2 from which component B is formed by reaction, to the components Bl.l and Bl.2 which form polymers according to component Bl and to the (optional) component C.

[0026] In case that more than one component B 1 and / or B2 are used in the reaction forming the covalently adaptable network according to component B, the term “functionality” individually for B 1 and / or B2 refers to the molar average functionality of the according building blocks Bl and / or B2.

[0027] In a preferred embodiment the thermoplastic composition comprises

[0028] 50 to 99 parts per weight, more preferably 60 to 98 parts per weight, even more preferably 70 to 97 parts per weight and most preferably 80 to 95 parts per weight, each based on in sum 100 parts by weight of component A and B, of component A and

[0029] 1 to 50 parts per by weight, more preferably 2 to 40 parts per weight, even more preferably 3 to 30 parts per weight and most preferably 5 to 20 parts per weight, each based on in sum 100 parts by weight of component A and B, of component B.

[0030] The thermoplastic composition may also comprise one or more polymer additives according to component C as described below. The content of component C is preferably not more than 25 parts by weight, more preferably not more than 10 parts by weight, most preferred not more than 5 parts by weight, each based on in sum 100 parts by weight of component A and B. In case the thermoplastic molding compound comprises component C, this component C is preferably comprised therein in an amount of 0.02 to 25 parts per weight, more preferably 0.05 to 10 parts per weight, even more preferably 0.1 to 5 parts by weight and most preferably 0.2 to 3 parts by weight, each based on in sum 100 parts by weight of component A and B.

[0031] In a preferred embodiment, the thermoplastic composition is free from catalysts promoting the exchange reactions in the covalent adaptable network.

[0032] In a preferred embodiment, the thermoplastic molding composition comprises in sum at least 90 % by weight, more preferably at least 99 % by weight of components A, B and C; most preferably the thermoplastic molding composition consists of components A, B and C.

[0033] It was also surprisingly found that a molding compound comprising 2024PF30097-Foreign Countries

[0034] - 5 - i) a matrix phase containing an amorphous non-crosslinked polymer A, ii) a phase dispersed in that matrix phase according to i) containing a polymer B’ which is different from polymer A, and iii) an interphase layer between the matrix phase i) and the dispersed phase ii) containing both polymers A and B’, wherein the interphase layer iii) is characterized by a gradient change of the contents of components A and B’ from the according values in the matrix phase according to i) to the according values in the dispersed phase according to ii), and wherein the thickness of that interphase layer Ax is larger than 30 nm, preferably larger than 40 nm, most preferably larger than 50 nm, and wherein Ax is determined via photo-induced force microscopy exhibits a combination of structural viscosity and an improved level of light transmission of parts molded therefrom.

[0035] In a preferred embodiment the dispersed phase ii) contains both polymers A and B’. In another preferred embodiment, the matrix phase i) contains both polymers A and B '.

[0036] In another preferred embodiment component B’ is a covalent adaptable network.

[0037] In a more preferred embodiment, the covalent adaptable network according to component B’ is the reaction product of

[0038] B 1) a polymer comprising at least two acid anhydride groups or comprising at least two pairs of carboxyl groups or comprising at least two pairs of derivatives of carboxyl groups and

[0039] B2) a component with at least two functional groups independently from each other selected from -OH, -NHR and -SH, wherein R stands for an optionally substituted alkyl, aryl or arylalkyl residue, and wherein at least one of the components Bl and B2 has a functionality of >2.

[0040] For the molding compound, any of the preferred embodiments with regard to the nature of component B disclosed below does also apply as preferred embodiment for component B’.

[0041] In another preferred embodiment the polymer A in the thermoplastic molding compound contains carbonate structural units -O-C(O)-O-, 2024PF30097-Foreign Countries

[0042] - 6 - and AU / Ax is in the range of 0. 1 to 0.9, preferably in the range of 0.3 to 0.7, more preferably in the range of 0.4 to 0.6, wherein AU = 100 • (UM - UD) / U is the relative difference of the photoinduced forces in the matrix and dispersed phases, wherein UM is the photoinduced force of the matrix phase, wherein UD is the photoinduced force of the dispersed phase, and wherein Ax, UM and UD are determined via photo-induced force microscopy with laser excitation at a wavelength of 1775 cm1.

[0043] In the latter preferred embodiment polymer A is preferentially a polycarbonate, a polyestercarbonate or a mixture of both, more preferentially a polycarbonate, most preferentially an aromatic polycarbonate.

[0044] Component A

[0045] Component A is a non-crosslinked polymer or a mixture of more than one non-crosslinked polymers. In case component A is a mixture of non-crosslinked polymers, this mixture can be either homogenous or heterogenous, i.e. the polymers can be either miscible, partly miscible or immiscible and thus form a one-phase or multi-phase morphology. In case component A is a mixture of more than two non-crosslinked polymers, some of the components of such polymer mixture may be miscible with each other, while they and / or their mixture might not be miscible with the other components or with a miscible sub-mixture of some of the other components of that polymer mixture . In a preferred embodiment component A is a single non-crosslinked polymer or a mixture of at least two fully miscible non-crosslinked polymers, most preferably it is a single non-crosslinked polymer.

[0046] Preferably, component A is comprising a polymer selected from, more preferably it is consisting of at least one polymer selected from the group consisting of polycarbonates, polyestercarbonates, vinylpolymers and olefinic polymers, more preferably selected from the group consisting of polycarbonates, polyestercarbonates and vinylpolymers.

[0047] In a preferred embodiment, component A is an amorphous non-crosslinked polymer or a mixture of amorphous non-crosslinked polymers.

[0048] In a further preferred embodiment component A is containing a polymer selected from, more preferably it is consisting of a polymer selected from the group consisting of polycarbonates and polyestercarbonates. More preferably component A is a polycarbonate, polyestercarbonate or a mixture of both, even more preferably a polycarbonate and most preferably an aromatic polycarbonate. 2024PF30097-Foreign Countries

[0049] - 7 -

[0050] Vinylpolymers that in the context of this invention are suitable as component A may mean vinyl homopolymers or vinylcopolymers. They may be produced e.g. by free-radical polymerization, in particular emulsion-, suspension-, solution- or bulk polymerization, of the respective monomers, preferably selected from the group consisting of vinylaromatics and / or ring-substituted vinylaromatics (such as styrene, a -methylstyrene, p-methylstyrene, p-chlorostyrene), (Ci-Cs)-alkyl (meth)acrylates (such as methyl methacrylate, ethyl methacrylate, n-butyl acrylate and t-butyl acrylate, vinyl cyanides (unsaturated nitriles such as acrylonitrile and methacrylonitrile) and mixtures thereof. Also olefinic monomers such as e.g. ethylene, propylene or octene isomers can be used as comonomers in these vinylpolymers. The polymerization of the vinylmonomers can be executed in the presence of a cross-linked particulate or a non-crosslinked dissolved rubber, for example and preferably a polybutadiene-containing rubber.

[0051] The vinylpolymers are resinous, maybe either rubber-free or rubber modified, preferably they are rubber-free, and have a weight-average molecular weight Mwof preferably 10 to 500 kg / mol, more preferably of 30 to 250 kg / mol, in particular of 50 to 200 kg / mol.

[0052] In the context of the present invention the weight average molecular weight Mwof the free vinyl (co)polymer in component A is measured by gel permeation chromatography (GPC) in tetrahydrofuran against a polystyrene standard at room temperature.

[0053] Polycarbonates suitable and preferred as component A in the context of the present invention include homopolycarbonates and copolycarbonates. Polycarbonates may be linear or branched in a known manner.

[0054] The thermoplastic polycarbonates preferably have weight-average molecular weights Mwof 15 000 g / mol to 40 000 g / mol, more preferably to 34 000 g / mol, particularly preferably of 17 000 g / mol to 33 000 g / mol, in particular of 19 000 g / mol to 32 000 g / mol, determined by gel permeation chromatography (GPC) at room temperature, calibrated against bisphenol A-based polycarbonate standards using dichloromethane as eluent, calibration with linear polycarbonates (formed from bisphenol A and phosgene) of known molar mass distribution from PSS Polymer Standards Service GmbH, Germany, and calibration by method 2301-0257502-09D (2009 German- language edition) from Currenta GmbH & Co. OHG, Leverkusen. Column combination of crosslinked styrene-divinylbenzene resins. Diameter of analytical columns: 7.5 mm; length: 300 mm. Particle sizes of column material: 3 pm to 20 pm. Concentration of solutions: 0.2% by weight. Flow rate: 1.0 ml / min, temperature of solutions: 30°C. Use of UV and / or RI detection.

[0055] A portion of up to 80 mol%, preferably of 20 mol% to 50 mol%, of the carbonate groups in the polycarbonates that are suitable as component A according to the invention may be replaced by aromatic dicarboxylic ester groups. Polycarbonates of this type that have not only acid moieties 2024PF30097-Foreign Countries

[0056] - 8 - derived from carbonic acid but also acid moieties derived from aromatic dicarboxylic acids incorporated into the molecular chain are termed aromatic polyestercarbonates.

[0057] The polycarbonates are produced in a known manner from dihydroxyaryl compounds (also denoted as aromatic diols) and / or aliphatic diols with carbonic acid derivatives, optionally chain terminators and optionally branching agents, and the polyestercarbonates are produced by replacing a portion of the carbonic acid derivatives with aromatic dicarboxylic acids or derivatives of the dicarboxylic acids.

[0058] Suitable dihydroxyaryl compounds for producing the preferred aromatic polycarbonates are those of formula (1)

[0059] HO-Z-OH (1), in which

[0060] Z is an aromatic radical which has 6 to 30 carbon atoms and may contain one or more aromatic rings, may be substituted, and may contain aliphatic or cycloaliphatic radicals or alkylaryls or heteroatoms as bridging elements.

[0061] It is preferable for Z in formula (1) to be a radical of formula (2) in which

[0062] R6and R7independently of one another are H, Ci- to Cis-alkyl, Ci- to Cis-alkoxy, halogen such as Cl or Br or in each case optionally substituted aryl or aralkyl, preferably H or Ci- to Ci2-alkyl, particularly preferably H or Ci- to Cs-alkyl and very particularly preferably H or methyl, and

[0063] X is a single bond, -SO2-, -CO-, -O-, -S-, Ci- to Ce-alkylene, C2- to Cs-alkylidene or

[0064] C5- to Ce-cycloalkylidene which may be substituted by Ci- to Ce -alkyl, preferably methyl or ethyl, or else Ce- to Ci2-arylene which may optionally be fused to further aromatic rings containing heteroatoms.

[0065] X is preferably a single bond, Ci- to Cs-alkylene, C2- to Cs-alkylidene, C5- to Ce-cycloalkylidene, - O-, -SO-, -CO-, -S-, -SO2- 2024PF30097-Foreign Countries

[0066] - 9 - or a radical of formula (3)

[0067] (3).

[0068] Examples of dihydroxyaryl compounds are: dihydroxybenzenes, dihydroxydiphenyls, bis(hydroxyphenyl)alkanes, bis(hydroxyphenyl)cycloalkanes, bis(hydroxyphenyl)aryls, bis(hydroxyphenyl) ethers, bis(hydroxyphenyl) ketones, bis(hydroxyphenyl) sulfides, bis(hydroxyphenyl) sulfones, bis(hydroxyphenyl) sulfoxides, 1,1'- bis(hydroxyphenyl)diisopropylbenzenes and the ring-alkylated and ring-halogenated compounds thereof.

[0069] Suitable dihydroxyaryl compounds for the production of the polycarbonates and copolycarbonates for use in accordance with the invention are for example hydroquinone, resorcinol, dihydroxydiphenyl, bis(hydroxyphenyl)alkanes, bis(hydroxyphenyl)cycloalkanes, bis(hydroxyphenyl) sulfides, bis(hydroxyphenyl) ethers, bis(hydroxyphenyl) ketones, bis(hydroxyphenyl) sulfones, bis(hydroxyphenyl) sulfoxides, a,a'- bis(hydroxyphenyl)diisopropylbenzenes and the alkylated, ring-alkylated and ring-halogenated compounds thereof. Copolycarbonates may also be produced using Si-containing telechelics to obtain what are known as Si-copoly carbonates.

[0070] Preferably used dihydroxyaryl compounds are 4,4'-dihydroxydiphenyl, 2,2-bis(4-hydroxyphenyl)-l- phenylpropane, bisphenol-A, l,l-bis(4-hydroxyphenyl)phenylethane, 2,4-bis(4-hydroxyphenyl)-2- methylbutane, l,3-bis[2-(4-hydroxyphenyl)-2-propyl]benzene (bisphenol M), 2,2-bis(3-methyl-4- hydroxyphenyl)propane, bis(3,5-dimethyl-4-hydroxyphenyl)methane, 2,2-bis(3,5-dimethyl-4- hydroxyphenyl)propane, bis(3, 5 -dimethyl -4-hydroxyphenyl) sulfone, 2,4-bis(3,5-dimethyl-4- hydroxyphenyl)-2 -methylbutane, l,3-bis[2-(3,5-dimethyl-4-hydroxyphenyl)-2-propyl]benzene and l,l-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane (bisphenol TMC), and also the bisphenols of formulae (I) to (III) 2024PF30097-Foreign Countries

[0071] - 10 - in which each R' represents a Ci- to C4-alkyl radical, aralkyl radical or aryl radical, preferably a methyl radical or phenyl radical, very particularly preferably a methyl radical.

[0072] Particularly preferred dihydroxyaryl compounds are bisphenol-A, 4,4'-dihydroxydiphenyl, 1 , 1 -bis(4- hydroxyphenyl)phenylethane, 2,2-bis(3,5-dimethyl-4-hydroxyphenyl)propane, 1, 1 -bis(4- hydroxyphenyl)cyclohexane and l,l-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane (bisphenol TMC), and also the dihydroxyaryl compounds of formulae (I), (II) and / or (III).

[0073] These and further suitable dihydroxyaryl compounds are described, for example, in US 2 999 835 A, 3 148 172 A, 2 991 273 A, 3 271 367 A, 4 982 014 A and 2 999 846 A, in German laid-open specifications 1 570 703 A, 2 063 050 A, 2 036 052 A, 2 211 956 A and 3 832 396 A, in French patent specification 1 561 518 Al, in the monograph "H. Schnell, Chemistry and Physics of Polycarbonates, Interscience Publishers, New York 1964, p. 28 ff; p. 102 ff", and in "D.G. Legrand, J.T. Bendler, Handbook of Polycarbonate Science and Technology, Marcel Dekker New York 2000, p. 72ff".

[0074] Suitable aliphatic diols are selected from the group consisting of 1,2-cyclohexanediol, 1,3- cyclohexanediol, 1,4-cyclohexanediol, 1,2-cyclohexandimethanol, 1,3-cyclohexandimethanol, 1,4- cyclohexandimethanol, 2,2-bis(4-hydroxycyclohexyl)propane, tetrahydro-2, 5 -furandimethanol, 2- butyl-2-ethyl-l,3-propanediol, 2-(2-hydroxy-ethoxy)ethanol, 2,2,4,4-tetramethyl-l,3- cyclobutanediol, 2,2,4-trimethyl-l,3-pentanediol, 2,2-dimethylpropane-l,3-diol, cyclobutane- 1,1- diyldimethanol, 8-(hydroxymethyl)-3-tricyclo[5.2.1.02,6]decanyl]methanol, 1,2-propanediol, 1,3- propanediol, 1,4-butanediol, 1,5 -pentanediol, 1,6-hexanediol, 1,8-octanediol, isosorbide and any mixtures thereof.

[0075] Also mixtures of dihydroxyaryl compounds, mixtures of aliphatic diols and mixtures of one or more dihydroxyaryl compound with one or more aliphatic diol may be used.

[0076] Particularly preferred copolycarbonates are based on the two monomers bisphenol A and 1 , 1 -bis(4- hydroxyphenyl)-3,3,5-trimethylcyclohexane or the two monomers bisphenol A and 4,4'- dihydroxydiphenyl, and copolycarbonates derived from bisphenol A and the dihydroxyaryl compounds of formulae (I), (II) and / or (III) 2024PF30097-Foreign Countries

[0077] - 11 - in which each R' is Ci- to C4-alkyl, aralkyl or aryl, preferably methyl or phenyl, very particularly preferably methyl.

[0078] The total proportion of the monomer units based on the formulae (I), (II), (III), 4,4'- dihydroxydiphenyl and / or bisphenol TMC in the copolycarbonate is preferably 0.1-88 mol%, particularly preferably 1-86 mol%, very particularly preferably 5-84 mol% and in particular 10- 82 mol% (based on the sum total of the moles of dihydroxyaryl compounds used).

[0079] The dihydroxyaryl compounds used, similarly to all other chemicals and auxiliaries added to the synthesis, may be contaminated with the contaminants from their own synthesis, handling and storage. It is however desirable to work with the purest possible raw materials.

[0080] The copolycarbonates may be in the form of block copolycarbonate and random copolycarbonate. Random copolycarbonates are particularly preferred.

[0081] The relative solution viscosity of the copolycarbonates, determined in accordance with ISO 1628- 4: 1999, is preferably in the range of 1.15 - 1.35.

[0082] The monofunctional chain terminators needed to regulate the molecular weight, such as phenols or alkylphenols, especially phenol, p-tert-butylphenol, isooctylphenol, cumylphenol, their chlorocarbonic esters or acyl chlorides of monocarboxylic acids or mixtures of these chain terminators, are either supplied to the reaction together with the bisphenoxide(s) or else added to the synthesis at any time, provided that phosgene or chlorocarbonic acid end groups are still present in the reaction mixture, or, in the case of the acyl chlorides and chlorocarbonic esters as chain terminators, provided that sufficient phenolic end groups of the incipient polymer are available. However, it is preferable for the chain terminator(s) to be added after the phosgenation at a location or at a juncture at which phosgene is no longer present but the catalyst has not yet been metered in, or for them to be metered in before the catalyst or together or in parallel with the catalyst.

[0083] Any branching agents or branching agent mixtures to be used are added to the synthesis in the same manner, but typically before the chain terminators. Compounds typically used are trisphenols, quaterphenols or acyl chlorides of tri- or tetracarboxylic acids, or else mixtures of the polyphenols or of the acyl chlorides.

[0084] Examples of some of the compounds usable as branching agents and having three or more phenolic hydroxyl groups include phloroglucinol, 4,6-dimethyl-2,4,6-tri(4-hydroxyphenyl)hept-2-ene, 4,6- dimethyl-2,4,6-tri(4-hydroxyphenyl)heptane, l,3,5-tris(4-hydroxyphenyl)benzene, 1, 1, l-tri(4- hydroxyphenyljethane, tris(4-hydroxyphenyl)phenylmethane, 2,2-bis[4,4-bis(4- hydroxyphenyl)cyclohexyl]propane, 2,4-bis(4-hydroxyphenylisopropyl)phenol, tetra(4- hydroxyphenyljmethane . 2024PF30097-Foreign Countries

[0085] - 12 -

[0086] Some of the other trifunctional compounds are 2,4-dihydroxybenzoic acid, trimesic acid, cyanuric chloride and 3 ,3 -bis (3 -methyl -4-hydroxyphenyl)-2-oxo-2, 3 -dihydroindole .

[0087] Preferred branching agents are 3,3-bis(3-methyl-4-hydroxyphenyl)-2-oxo-2,3-dihydroindole and 1,1,1 -tri(4-hydroxyphenyl)ethane .

[0088] The amount of any branching agents to be used is 0.05 mol% to 2 mol%, based in turn on moles of diphenols used in each case.

[0089] The branching agents may either be initially charged with the diphenols and the chain terminators in the aqueous alkaline phase or added dissolved in an organic solvent before the phosgenation.

[0090] All of these measures for preparing the polycarbonates are familiar to those skilled in the art.

[0091] Examples of aromatic dicarboxylic acids that are suitable for the preparation of the polyestercarbonates include orthophthalic acid, terephthalic acid, isophthalic acid, tertbutylisophthalic acid, 3,3'-diphenyldicarboxylic acid, 4,4'-diphenyldicarboxylic acid, 4,4- benzophenonedicarboxylic acid, 3,4'-benzophenonedicarboxylic acid, 4,4'-diphenyl ether dicarboxylic acid, 4,4'-diphenyl sulfone dicarboxylic acid, 2,2-bis(4-carboxyphenyl)propane, trimethyl-3-phenylindane-4,5'-dicarboxylic acid.

[0092] Among the aromatic dicarboxylic acids, particular preference is given to using terephthalic acid and / or isophthalic acid.

[0093] Derivatives of dicarboxylic acids are dicarbonyl dihalides and dialkyl dicarboxylates, especially dicarbonyl dichlorides and dimethyl dicarboxylates.

[0094] Replacement of the carbonate groups by the aromatic dicarboxylic ester groups is substantially stoichiometric, and also quantitative, and the molar ratio of the reactants is therefore also maintained in the final polyestercarbonate. The aromatic dicarboxylic ester groups may be incorporated either randomly or in blocks.

[0095] Preferred modes of preparation of the polycarbonates to be used in the invention, including the polyestercarbonates, are the known interfacial process and the known melt transesterification process (cf. e.g. WO 2004 / 063249 Al, WO 2001 / 05866 Al, US 5,340,905 A, US 5,097,002 A, US-A 5,717,057 A).

[0096] In the former case the acid derivatives used are preferably phosgene and optionally dicarbonyl dichlorides and in the latter case preferably diphenyl carbonate and optionally dicarboxylic diesters. Catalysts, solvents, workup, reaction conditions etc. for polycarbonate preparation or polyestercarbonate preparation are sufficiently well described and known for both cases. 2024PF30097-Foreign Countries

[0097] - 13 -

[0098] Also preferred are copolycarbonates prepared using diphenols of general formula (la):

[0099] (la), in which

[0100] R5is hydrogen or Ci - to C4-alkyl, Ci - to Cs-alkoxy, preferably hydrogen, methoxy or methyl,

[0101] R6, R7, R8and R9each independently of one another are Ci- to C4-alkyl or Ce- to Cn-aryl, preferably methyl or phenyl,

[0102] Y is a single bond, SO2-, -S-, -CO-, -O-, Ci- to Ce-alkylene, C2- to Cs-alkylidene, Ce- to Ci2-arylene which may optionally be fused to further aromatic rings containing heteroatoms or is a C5- to Ce- cycloalkylidene radical which may be mono- or polysubstituted by Ci- to C4-alkyl, preferably is a single bond, -O-, isopropylidene or a C5- to Ce-cycloalkylidene radical which may be mono- or polysubstituted by Ci- to C4-alkyl,

[0103] V is oxygen, C2- to Ce-alkylene or C3- to Ce-alkylidene, preferably oxygen or Cs-alkylene, p, q and r are each independently 0 or 1, when q = 0, W is a single bond, when q = 1 and r = 0, W is oxygen, C2- to Ce-alkylene or C3- to Ce- alkylidene, preferably oxygen or C’s-alkylcnc. when q = 1 and r = 1, W and V each independently are C2- to Ce-alkylene or C3- to Ce-alkylidene, preferably C’s-alkylcnc.

[0104] Z is a Ci - to Ce-alkylene, preferably C2-alkylene, o is an average number of repeating units of from 10 to 500, preferably 10 to 100, and m is an average number of repeating units of from 1 to 10, preferably 1 to 6, more preferably 1.5 to 5. It is likewise possible to use diphenols in which two or more siloxane blocks of general formula (la) are joined to one another via terephthalic acid and / or isophthalic acid to form ester groups.

[0105] Especial preference is given to (poly)siloxanes of formulae (4) and (5) 2024PF30097-Foreign Countries

[0106] - 14 - in which R1 is hydrogen, Ci- to C4-alkyl, preferably hydrogen or methyl and especially preferably hydrogen, each R2 independently is aryl or alkyl, preferably methyl,

[0107] X is a single bond, -SO2-, -CO-, -O-, -S-, Ci- to Ce-alkylene, C2- to Cs-alkylidene or Ce- to C12- arylene which may optionally be fused to further aromatic rings containing heteroatoms,

[0108] X preferably is a single bond, Ci- to Cs-alkylene, C2- to Cs-alkylidene, C5- to Cn-cycloalkylidene, - O-, -SO- -CO-, -S-, -SO2-, particularly preferably X is a single bond, isopropylidene, C5- to C12- cycloalkylidene or oxygen, and very particularly preferably is isopropylidene, n is an average number of from 10 to 400, preferably 10 to 100, especially preferably 15 to 50 and m is an average number of from 1 to 10, preferably from 1 to 6 and especially preferably from 1.5 to 5.

[0109] The siloxane block may likewise preferably be derived from the following structure 2024PF30097-Foreign Countries

[0110] - 15 - wherein a in formulae (6), (7) and (8) is an average number of from 10 to 400, preferably 10 to 100 and particularly preferably 15 to 50.

[0111] It is likewise preferable when at least two identical or different siloxane blocks of general formulae (6), (7) or (8) are joined to one another via terephthalic acid and / or isophthalic acid to form ester groups.

[0112] It is likewise preferable when in formula (la) p = 0, V is Cs-alkylene, r = 1, Z is C2-alkylene, R8and R9are methyl, q = 1, W is Cs-alkylene, m = 1, R5is hydrogen or Ci- to C4-alkyl, preferably hydrogen or methyl, R6and R7each independently of one another are Ci- to C4-alkyl, preferably methyl, and o is 10 to 500.

[0113] Copolycarbonates having monomer units of formula (la) and in particular also the preparation thereof are described in WO 2015 / 052106 A2.

[0114] Copolycarbonates having monomer units of formula (6), (7) and (8) and in particular also the preparation thereof are also described in WO 2015 / 052106 A2.

[0115] Polyolefins (also referred to as olefinic polymers) that are suitable as component A are usually produced by chain polymerization, for example by radical or anionic polymerization of olefin monomers. The monomers can be polymerized individually or as a mixture of different monomers. Preferred monomers are ethylene, propylene, 1 -butene, isobutene, 1 -pentene, 1 -heptene, 1 -octene and 4-methyl-l -pentene.

[0116] The polyolefins can be semi-crystalline or amorphous as well as linear or branched. Preferably, the polyolefins are amorphous. The production of polyolefins has been known to the skilled person for a long time. By changing the polymerization conditions and the catalyst system, the crystallinity, the molecular weight distribution and the density of the polyolefins can be varied over a wide range. These measures are also familiar to the skilled person. 2024PF30097-Foreign Countries

[0117] - 16 -

[0118] Component B

[0119] Component B is a covalent adaptable network (CAN).

[0120] The covalent adaptable network according to component B comprises a network of crosslinked polymer chains which can rearrange through reversible de-cross-linking. This reversible de-cross- linking is preferably triggered by a thermal stimulus. The reversible de-crosslinking results from a reversible equilibrium following an associative or a dissociative, preferably a dissociative mechanism.

[0121] The CAN is a reaction product of

[0122] B 1) a component comprising at least two acid anhydride groups or comprising at least two pairs of carboxyl groups or comprising at least two pairs of derivatives of carboxyl groups and

[0123] B2) a component with at least two functional groups independently from each other selected from -OH, -NHR and -SH, wherein R stands for an optionally substituted alkyl, aryl or arylalkyl residue, and wherein at least one of the components Bl and B2 has a functionality of >2.

[0124] In a preferred embodiment at least one of the components Bl and B2 has a functionality of >2.5, most preferably at least one of the components B 1 and B2 has a functionality of 3 or higher.

[0125] The functionality of B 1 is the number of acid anhydride groups or the number of pairs of carboxyl groups or the number of pairs of derivatives of carboxyl groups per molecule of B 1.

[0126] The functionality of B2 is the sum of functional groups selected from -OH, -NHR and -SH per molecule of B2.

[0127] In case that more than one component B 1 and / or B2 are used in the reaction forming the covalently adaptable network according to component B, the term “functionality” individually for Bl and / or B2 refers to the molar average functionality of the according building blocks Bl and / or B2.

[0128] In the preferred case that exactly one component B 1 and one component B2 are used in the reaction forming the covalently adaptable network according to component B, at least one of the components B 1 and B2 has a functionality of 3 or higher.

[0129] Preferably, the molar ratio of the functional groups of component B2 to the carboxylic acid anhydride groups or the pairs of carboxyl groups or the pairs of derivatives of carboxyl groups in component 2024PF30097-Foreign Countries

[0130] - 17 -

[0131] Bl is in the range of 0.05 to 0.75, more preferably in the range of 0.08 to 0.45, most preferably in the range of 0. 15 to 0.40. In the more and most narrow range the rheological properties are more and most suited, respectively, for production of molded parts from the composition with a wide range of industrial molding processes.

[0132] The reaction of Bl with B2 resulting in component B as reaction product can be performed either in solution using a suitable solvent or in a melt mixture. From an industrial point of view it is advantageous to carry out the reaction in a melt mixture. Such a process does not require an energy intensive additional work-up step in which the solvent is removed and therefore reaction in a melt mixture will result in a product that is not contaminated with residuals of that solvent.

[0133] Bl

[0134] B 1 can be a non-polymeric component or a (co)polymer.

[0135] In case B 1 is a non-polymeric component, it comprises at least two anhydride groups or at least two pairs of carboxyl groups or at least two pairs of derivatives of carboxyl groups. Examples of suitable non-polymeric components Bl are all molecules described below as Bl.l which fulfill this requirement.

[0136] Preferred examples of non-polymeric components Bl are pyromellitic dianhydride, benzophenone- 3,3',4,4'-tetracarboxylic dianhydride, 4,4'-(4,4'-isopropylidenediphenoxy)bis(phthalic anhydride), 3,3',4,4'-biphenyltetracarboxylic dianhydride, bicyclo[2.2.2]oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, cyclobutane-l,2,3,4-tetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, perylene-3,4,9,10-tetracarboxylic dianhydride, mellitic trianhydride, pyromellitic acid, 1,2,4,5-cyclohexanetetracarboxylic acid, mellitic acid, cyclohexane-l,2,3,4,5,6-hexacarboxylic acid and 1,2,3,4-butanetetracarboxylic acid.

[0137] Preferably, Bl is a (co)polymer comprising structural units derived from Bl.l and optionally Bl.2. More preferably, B 1 is a (co)polymer consisting of - beyond endgroups - structural units derived from Bl. l and optionally B 1.2. In a preferred embodiment B 1 is a copolymer of B 1.1 and B 1.2.

[0138] Bl. l

[0139] Bl. l is a monomer comprising an acid anhydride group or comprising a pair of carboxyl groups or comprising a pair of derivatives of carboxyl groups. Thus in a preferred embodiment Bl is a copolymer comprising structural units derived from a monomer Bl.l, wherein Bl.l comprises an acid anhydride group or a pair of carboxyl groups or a pair of derivatives of carboxyl groups, and a further monomer B 1.2. 2024PF30097-Foreign Countries

[0140] - 18 -

[0141] Derivatives of a carboxyl group are for example acyl halides (-COX, with X being a halogen) and esters (-COR, with R being an organic residue), preferably esters.

[0142] An organic residue in this context is an optionally substituted hydrocarbon residue that may contain heterogen atoms such as oxygen, nitrogen, sulfur or halogens, preferably it is an optionally substituted hydrocarbon residue that does not contain heterogen atoms, most preferably it is an alkyl, aryl or arylalkyl residue.

[0143] The anhydride group, the pair of carboxyl groups or the pair of derivatives of a carboxyl group comprises two or three carbon atoms, preferably two carbon atoms, between the two carbonyl groups of the anhydride group, between the two carbonyl groups of the pair of carboxyl groups or between the two carbonyl groups of the pair of derivatives of carboxyl groups.

[0144] The two or three atoms between the carbonyl groups can be independently of each other substituted or unsubstituted. The bonds between these two or three carbon atoms can be saturated or unsaturated or one or more of the two or three carbon atoms can be part of an aromatic or cyclic structure.

[0145] Bl.l additionally comprises a further functionality which enables polymerization of this monomer. This functionality can be either a suitable polymerizable group such as an unsaturated carbon-carbon double bond or an anhydride group or can be a pair of two equal or different functional groups selected from the group consisting of carboxyl groups, derivatives of carboxyl groups and hydroxyl groups.

[0146] Examples of monomers B.1.1 wherein the further polymerizable group is an anhydride group are pyromellitic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 4,4'-oxydiphthalic anhydride, benzophenone-3,3',4,4'-tetracarboxylic dianhydride, 4,4'-(4,4'- isopropylidenediphenoxy)bis(phthalic anhydride), 3,3',4,4'-biphenyltetracarboxylic dianhydride, bicyclo[2.2.2]oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, cyclobutane- 1,2, 3, 4-tetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, perylene-3,4,9,10-tetracarboxylic dianhydride, difuro[3,4-b:3',4'-d]furan-l,3,5,7-tetrone and mellitic trianhydride.

[0147] Examples of monomers Bl. l wherein the further polymerizable group is a pair of carboxyl groups are pyromellitic acid, 1,2, 4, 5 -cyclohexanetetracarboxylic acid, mellitic acid, cyclohexane- 1,2,3,4,5,6-hexacarboxylic acid and 1,2,3,4-butanetetracarboxylic acid.

[0148] Examples of monomers Bl.l wherein the further polymerizable group is an unsaturated carboncarbon bond are itaconic acid and anhydrides comprising unsaturated carbon-carbon bonds. 2024PF30097-Foreign Countries

[0149] - 19 -

[0150] Preferably, B 1. 1 is a monoanhydride having one cyclic anhydride group, and a further polymerizable group. Preferentially the polymerizable group is an unsaturated carbon-carbon bond and even more preferentially this is participating in the cyclic anhydride ring as for example in the case of maleic anhydride, which is most preferred component B 1.1.

[0151] Bl, 2

[0152] B 1.2 is an additional component that does not contain anhydride groups or pairs of carboxyl groups or pairs of derivatives of carboxyl groups.

[0153] Preferably Bl is obtained from Bl.l and Bl.2. In this case the content of structural units derived from Bl. l in B 1 is 1 to 50 % by weight, preferably 2 to 35 % by weight, in each case based on the total composition of B 1.

[0154] Bl.l may be copolymerized with B1.2. In this case Bl.2 has functional groups capable of reacting with the further functional groups of B 1.1.

[0155] It is also possible to graft Bl. l onto polymers obtained from B 1.2 through radical mediated reactions. As a preferred example maleic anhydride can be grafted onto polyolefins to obtain component B 1.

[0156] Component Bl may be a block copolymer or a random copolymer, preferably it is a random copolymer or a graft copolymer, most preferably a random copolymer.

[0157] A copolymerization of Bl.l with Bl.2 is preferred. It is further preferred that Bl.2 comprises unsaturated carbon-carbon bonds. The copolymerization in such case may be carried out by free- radical polymerization.

[0158] Examples of preferred monomers B 1.2 include vinylaromatics and / or ring-substituted vinylaromatics (such as styrene, a -methylstyrene, p-methylstyrene, p-chlorostyrene), (Ci-Cs)-alkyl (meth)acrylates (such as methyl methacrylate, ethyl methacrylate, n-butyl acrylate and t-butyl acrylate, vinyl cyanides (unsaturated nitriles such as acrylonitrile and methacrylonitrile), olefins (such as ethylene and propylene) and mixtures thereof. More preferred monomers B.1.2 are selected from the group consisting of vinylaromatics, (Ci-Cs)-alkyl (meth)acrylates, olefins and mixtures thereof. Most preferred monomer Bl.2 is styrene.

[0159] In a further preferred embodiment component B 1 is a copolymer of, most preferentially exclusively of B 1.1 maleic anhydride and B 1.2 styrene . 2024PF30097-Foreign Countries

[0160] - 20 -

[0161] Another preferred component B 1 is a copolymer of B 1. 1 maleic anhydride and B 1.2 being a mixture of at least one olefin and at least one (Ci-Cs)-alkyl (meth)acrylate.

[0162] Component Bl has preferably a weight average molecular weight Mwin the range of 50 to 500 kg / mol, measured by gel permeation chromatography in tetrahydrofuran at ambient temperature with calibration against polystyrene standard.

[0163] B2

[0164] B2 is a component with at least two functional groups independently from each other selected from -OH, -NHR and -SH, wherein R stands for an optionally substituted alkyl, aryl or arylalkyl residue.

[0165] Examples of components according to component B2 with two different functional groups are 3- hydroxypiperidine and 4-hydroxypiperidine.

[0166] Preferably, the at least two functional groups are all identical and therefore B2 is selected from the group of alcohols, secondary amines and thiols with at least two of these respective functional groups.

[0167] The functional groups in component B2 may be aliphatic or aromatic. Aliphatic functional groups are preferred due to their higher reactivity. This is particulary the case for -OH functional groups.

[0168] Examples of organic components according to component B2 comprising two -SH groups are 1,2- ethanedithiol, 1,3 -propanedithiol, 1,4-butanedithiol and 1,6-hexanedithiol.

[0169] Examples of secondary diamines suitable as component B2 are N,N'-dimethylethylendiamine (DMEDA), N,N'-diethylethylendiamine, N,N'-dimethylhexane-l,6-diamine, N,N'-diethylhexane- 1,6-diamine, N,N'-diisopropylhexane-l,6-diamine, N,N'-diisopropylethylendiamine, piperazine, N,N'-di-sec-butylethylendiamine and 4,4 ’-trimethylenedipiperidine.

[0170] Preferably B2 is a component comprising at least two hydroxyl groups, in case B 1 is a (co)polymer, B2 is preferably a component comprising two hydroxyl groups (i.e. a diol). Further preferred, the hydroxy groups are primary hydroxy group, i.e. B2 is a primary diol or primary alcohol containing more than two hydroxyl groups.

[0171] Preferably B2 is an organic component containing at least two aliphatic hydroxyl groups, in case B 1 is a (co)polymer, B2 is preferably a component containing two aliphatic hydroxyl groups.

[0172] Examples of diols that are preferred as component B2 are 1,10-decanediol, 1,6-hexanediol, 1,5- pentanediol, 1,4-butanediol, 1,2-ethanediol, 2,4-diethyl 1,5-pentanediol, 2,5-tetrahydrofuranediol, tetrahydrofuran-2,5-dimethanol, 1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4- 2024PF30097-Foreign Countries

[0173] - 21 - benzenedimethanol, 1,3 -benzenedimethanol, 1,2-benzenedimethanol, 1,4-cyclohexanediol, 1,3- cyclohexandiol, 1,2-cyclohexandiol, larger aliphatic dialcohols such as Pripol™ 2033, polymeric diols or oligomeric diols such as triethylene glycol. Non-limiting examples of suitable polymeric diols include a hydroxyl terminated polyether (polyether polyols); hydroxyl terminated polyester (polyester polyols) or mixture thereof, with one or more chain extenders, all of which are well known to those skilled in the art.

[0174] Examples of components suitable as component B2 that comprise three or more hydroxyl groups are pentaerythritol, benzene-l,3,5-triyltrimethanol, xylitol, erythritol, trimethylolpropane, di- (trimethylolpropan) and polymeric polyols such as polyvinylalcohol and cellulose.

[0175] It is also possible to use a mixture of a diol and a component with more than two hydroxyl groups as component B2.

[0176] In a preferred embodiment component B2 contains at least two aliphatic hydroxyl groups and does not contain any functional groups selected from the group consisting of -NH2, -NHR and -SH, wherein R stands for an optionally substituted alkyl, aryl or arylalkyl residue.

[0177] Also preferred B2 is an alicyclic diol. Most preferably component B2 is cyclohexanedimethanol, in particular 1,4 cyclohexanedimethanol.

[0178] Preferably, component B comprises polymer chains crosslinked by ester groups and a carboxyl group or a derivate of a carboxyl group in -position to the carbon atom bearing the crosslinking ester according to formula (9) wherein Ri is an organic residue and R2 and R3 are independently from each other organic residues, halogen or hydrogen, preferably R2 and R3 are independently from each other organic residues or hydrogen.

[0179] An organic residue in this context is an optionally substituted hydrocarbon residue that may contain heterogen atoms such as oxygen, nitrogen, sulfur or halogens.

[0180] Details on the production of exemplary CANs can be found in “Design and Continuous (Re)Processing of Thermally Resilient Poly(Styrene-co-Maleic Maleate)-Based Covalent Adaptable 2024PF30097-Foreign Countries

[0181] - 22 -

[0182] Networks”; A. Hernandez et. Al (Chemistry of Materials 2024 36 (15), 7487-7503).

[0183] Component C

[0184] As component C the composition according to the invention may contain at least one polymer additive. Examples of polymer additives suitable as component C are heat stabilizers, light and UV stabilizers, hydrolytic stabilizers, antioxidants, transesterification inhibitors, catalyst quenchers (the former will hereinafter be summarized as “stabilizers”), mould release agents, colorants and pigments, compatibilizers, (functional) fillers and reinforcement agents, electrical conductivity enhancing additives and antistatic agents, impact modifiers, flame retardants and flame retardancy synergists, antidripping agents and melt flow improvers. Preferably component C is selected from the group consisting of stabilizers, mould release agents, colorants and pigments.

[0185] Production of the molding compounds and molded articles

[0186] The compositions according to the invention may be used to produce thermoplastic molding compounds. The thermoplastic molding compounds may be produced for example when the respective constituents A and B, optionally C and optionally additional components of the composition are in conventional fashion mixed and melt-compounded and melt-extruded at temperatures of preferably 200°C to 350°C, particularly preferably at 230°C to 320°C, very particularly preferably at 240°C to 300°C, in customary apparatuses such as internal kneaders and any kind of extruders, e.g. twin-screw extruders. The residence time of the components in the melt is preferably in the range of 15 seconds to 5 minutes, more preferably in the range of 20 seconds to 2 minutes. In the context of the present application this process is generally referred to as compounding or melt-compounding. The term “molding compound” is thus to be understood as meaning the product obtained when the constituents of the composition are melt-compounded and melt-extruded.

[0187] The mixing of the individual constituents of the compositions may be carried out in a known manner, either successively or simultaneously, either at about 20°C (room temperature) or at a higher temperature. This means that for example some of the constituents, individually or as one or more physical premix(es), may be added via the main intake of an extruder and the remaining constituents, individually or as one or more physical premix(es), may be supplied subsequently in the compounding process via one or more than one ancillary extruder(s). It is also possible to meltcompound only part of the components A to D, e.g. components A and B, in a first compounding step and add the other components in one or more additional (succeeding) compounding step(s).

[0188] The component B can be produced either prior to mixing with the other components of the composition or in a one-step compounding process by mixing B 1 and B2 in the presence of the other components of the composition. Component B is preferably produced in a separate step by reacting 2024PF30097-Foreign Countries

[0189] - 23 -

[0190] B 1 and B2 prior to mixing with the other components of the composition. This reaction can occur in solution as well as in a melt mixture. In case the reaction is processed in solution, the solvent preferentially, but not necessarily, is removed from the reaction product via drying in hot atmosphere of air or an inert gas such as nitrogen prior to compounding with the other components of the composition. In this way undesired side reactions of Bl and B2 with A and / or C are minimized. However, in cases where such undesired side reactions of Bl and B2 with A and / or C are not an issue, it might be an advantage and thus preferential to produce component B from Bl and B2 in- situ in an reactive extrusion process in the presence of components A and / or C.

[0191] The invention therefore also provides a process for producing a thermoplastic molding compound comprising

[0192] A) a non-crosslinked polymer and

[0193] B) a covalent adaptable network, and

[0194] C) optionally a polymer additive, wherein the covalent adaptable network is the reaction product of

[0195] B 1) a polymer comprising at least two acid anhydride groups or comprising at least two pairs of carboxyl groups or comprising at least two pairs of derivatives of carboxyl groups and

[0196] B2) a component with at least two functional groups independently from each other selected from -OH, -NHR and -SH, wherein R stands for an optionally substituted alkyl, aryl or arylalkyl residue, and wherein at least one of the components Bl and B2 has a functionality of >2, comprising the steps a) reacting components B 1 and B2 to form the covalent adaptable network B b) melt compounding component A and B in a temperature range of 200 to 350°C c) solidifying the molding compound via cooling, wherein steps a) and b) can either occur simultaneously or sequentially.

[0197] Preferentially steps a) and b) occur sequentially.

[0198] The molding compounds according to the invention may be used to produce molded articles of any kind. These may be produced for example by injection molding, extrusion and blow-molding processes. A further form of processing is the production of molded articles by compression molding 2024PF30097-Foreign Countries

[0199] - 24 - from previously produced sheets or fdms. As a consequence of their structural viscous behaviour, the molding compounds according to the invention are equally suitable for processing both by extrusion and injection molding methods.

[0200] The constituents of the compositions may also be metered directly into an injection molding machine or into an extrusion apparatus and thereby processed into molded articles.

[0201] Examples of such molded articles are foils, profiles, housing parts of all kinds, e.g. for household appliances, for office machines, panels, pipes, electrical ducts, windows, doors and other profiles for the construction sector, automotive interior and exterior parts such as decorative elements, headlamps and glazing elements as well as electrical and electronic parts such as switches, plugs and sockets, housings of electrical appliances, housings and cladding of medical equipment, massagers and housings therefor, children's play vehicles, flat wall elements, housings for safety devices, thermally insulated transport containers, molded parts for sanitary and bathroom equipment, cover grilles for fan openings and housings for garden tools.

[0202] Specific embodiments of the invention are disclosed hereinafter:

[0203] 1. Thermoplastic composition comprising

[0204] A) a non-crosslinked polymer and

[0205] B) a covalent adaptable network, wherein the covalent adaptable network is the reaction product of

[0206] B 1) a component comprising at least two acid anhydride groups or comprising at least two pairs of carboxyl groups or comprising at least two pairs of derivatives of carboxyl groups and

[0207] B2) a component with at least two functional groups independently from each other selected from -OH, -NHR and -SH, wherein R stands for an optionally substituted alkyl, aryl or arylalkyl residue, wherein at least one of the components Bl and B2 has a functionality of >2.

[0208] 2. Thermoplastic composition according to embodiment 1, wherein component A is selected from the group consisting of polycarbonates, polyestercarbonates, vinylpolymers, olefinic polymers and mixtures thereof.

[0209] 3. Thermoplastic composition according to embodiments 1 or 2, wherein component A is amorphous. 2024PF30097-Foreign Countries

[0210] - 25 -

[0211] 4. Thermoplastic composition according to embodiment 1, wherein component A is selected from the group consisting of polycarbonates, polyestercarbonates, vinylpolymers and mixtures thereof.

[0212] 5. Thermoplastic composition according to embodiment 1, wherein component A is comprising a polycarbonate, polyestercarbonate or a mixture of both.

[0213] 6. Thermoplastic composition according to embodiment 5, wherein component A is a polycarbonate.

[0214] 7. Thermoplastic composition according to embodiment 6, wherein component A is an aromatic polycarbonate.

[0215] 8. Thermoplastic composition according to any of the preceding embodiments, wherein the molar ratio of the functional groups of component B2 to the carboxylic acid anhydride groups or the pairs of carboxyl groups or the pairs of derivatives of carboxyl groups in component B 1 is in the range of 0.05 to 0.75.

[0216] 9. Thermoplastic composition according to any of the preceding embodiments, wherein the molar ratio of the functional groups of component B2 to the carboxylic acid anhydride groups or the pairs of carboxyl groups or the pairs of derivatives of carboxyl groups in component B 1 is in the range of 0.15 to 0.40.

[0217] 10. Thermoplastic composition according to any of the preceding embodiments, wherein B 1 is a non- polymeric component comprising at least two anhydride groups or at least two pairs of carboxyl groups or at least two pairs of derivatives of carboxyl groups.

[0218] 11. Thermoplastic composition according to any of the preceding embodiments 1 - 9, wherein component B 1 is a copolymer comprising structural units derived from a monomer B 1. 1 and a further monomer B 1.2, wherein B 1.1 comprises an acid anhydride group or a pair of carboxyl groups or a pair of derivatives of carboxyl groups.

[0219] 12. Thermoplastic composition according to embodiment 11, wherein B 1.1 is maleic anhydride.

[0220] 13. Thermoplastic composition according to any of the embodiments 11 or 12, wherein B1.2 is a monomer selected from the group consisting of vinylaromatics, (Ci-Cs)-alkyl (meth)acrylates, olefins and mixtures thereof.

[0221] 14. Thermoplastic composition according to embodiment 11, wherein component Bl is a copolymer comprising structural units derived from styrene and structural units derived from maleic anhydride. 2024PF30097-Foreign Countries

[0222] - 26 -

[0223] 15. Thermoplastic composition according to any of the preceding embodiments, wherein component Bl has a weight average molecular weight Mwin the range of 50 to 500 kg / mol, measured by gel permeation chromatography in tetrahydrofuran at ambient temperature with calibration against polystyrene standard.

[0224] 16. Thermoplastic composition according to any of the preceding embodiments, wherein component B2 contains at least two aliphatic hydroxyl groups.

[0225] 17. Thermoplastic composition according to embodiment 16, wherein component B2 is a diol containing two aliphatic hydroxyl groups.

[0226] 18. Thermoplastic composition according to embodiment 17, wherein component B2 is a diol containing two primary aliphatic hydroxyl groups.

[0227] 19. Thermoplastic composition according to any of the embodiments 16 - 18, wherein component B2 is an alicyclic diol.

[0228] 20. Thermoplastic composition according to any of the embodiments 16 - 19, wherein the component B2 contains at least two aliphatic hydroxyl groups and does not contain any functional groups selected from the group consisting of -NH2, -NHR and -SH, wherein R stands for an optionally substituted alkyl, aryl or arylalkyl residue.

[0229] 21. Thermoplastic composition according to any of the preceding embodiments, wherein component B2 is 1,4-cyclohexanedimethanol.

[0230] 22. Thermoplastic composition according to any of the preceding embodiments, comprising

[0231] 50 to 99 parts per weight, based on in sum 100 parts by weight of component A and B, of component A and

[0232] 1 to 50 parts per by weight, based on in sum 100 parts by weight of component A and B, of component B.

[0233] 23. Thermoplastic composition according to any of the preceding embodiments, comprising

[0234] 60 to 98 parts by weight, based on in sum 100 parts by weight of component A and B, of component A and

[0235] 2 to 40 parts by weight, based on in sum 100 parts by weight of component A and B, of component B. 2024PF30097-Foreign Countries

[0236] - 27 -

[0237] 24. Thermoplastic composition according to any of the preceding embodiments, comprising

[0238] 70 to 97 parts by weight, based on in sum 100 parts by weight of component A and B, of component A and

[0239] 3 to 30 parts by weight, based on in sum 100 parts by weight of component A and B, of component B.

[0240] 25. Thermoplastic composition according to any of the preceding embodiments, comprising

[0241] 80 to 95 parts by weight, based on in sum 100 parts by weight of component A and B, of component A and

[0242] 5 to 20 parts by weight, based on in sum 100 parts by weight of component A and B, of component B.

[0243] 26. Thermoplastic composition according to any of the preceding embodiments further comprising at least one polymer additive as component C.

[0244] 27. Thermoplastic composition according to embodiment 26, wherein the at least one polymer additive is selected from the group consisting of stabilizers, mould release agents, colorants and pigments.

[0245] 28. Thermoplastic composition according to any of the embodiments 26 or 27, comprising component C in an amount of not more than 25 parts by weight, based on in sum 100 parts by weight of components A and B.

[0246] 29. Thermoplastic composition according to any of the embodiments 26 - 28, comprising component C in an amount of 0.02 to 25 parts by weight, based on in sum 100 parts by weight of components A and B.

[0247] 30. Thermoplastic composition according to any of the embodiments 26 - 29, comprising component C in an amount of 0.05 to 10 parts by weight, based on in sum 100 parts by weight of components A and B.

[0248] 31. Thermoplastic composition according to any of the embodiments 26 - 30, comprising component C in an amount of 0. 1 to 5 parts by weight, based on in sum 100 parts by weight of components A and B.

[0249] 32. Thermoplastic composition according to any of the preceding embodiments comprising in sum at least 90 % by weight of components A, B and C. 2024PF30097-Foreign Countries

[0250] - 28 -

[0251] 33. Thermoplastic composition according to any of the preceding embodiments comprising in sum at least 99 % by weight of components A, B and C.

[0252] 34. Thermoplastic composition according to any of the preceding embodiments consisting of components A, B and C.

[0253] 35. Thermoplastic composition according to any of the preceding claims wherein component

[0254] B comprises structural units according to formula (9) wherein Ri is an organic residue and R2 and R3 are independently from each other organic residues or hydrogen.

[0255] 36. Thermoplastic composition according to any of the preceding embodiments comprising i) a matrix phase containing component A, ii) a phase dispersed in that matrix phase according to i) containing component B iii) an interphase layer between the matrix phase i) and the dispersed phase ii) containing both component A and component B, wherein the interphase layer iii) is characterized by a gradient change of the contents of components A and B from the according values in the matrix phase according to i) to the according values in the dispersed phase according to ii), and wherein the thickness of that interphase layer Ax is larger than 30 nm determined via photo-induced force microscopy.

[0256] 37. Thermoplastic composition according to embodiment 36, wherein AU / Ax is in the range of 0.1 to 0.9, wherein AU = 100 • (UM- UD) / U is the relative difference of the photoinduced forces in the matrix and dispersed phases, wherein UM is the photoinduced force of the matrix phase, wherein UD is the photoinduced force of the dispersed phase, and wherein Ax, UM and UD are determined via photo-induced force microscopy with laser excitation at a wavelength of 1775 cm1. 2024PF30097-Foreign Countries

[0257] - 29 -

[0258] 38. Thermoplastic molding compound comprising a composition according to any of the preceding embodiments 1 to 35, comprising i) a matrix phase containing component A ii) a phase dispersed in that matrix phase according to i) containing component B iii) an interphase layer between the matrix phase and the dispersed phase containing both components A and B wherein the interphase layer iii) is characterized by a gradient change of the contents of components A and B from the according values in the matrix phase i) to the according values in the dispersed phase according to ii), and wherein the thickness of that interphase layer Ax is larger than 30 nm determined via photo-induced force microscopy.

[0259] 39. Thermoplastic molding compound according to embodiment 38, wherein AU / Ax is in the range of 0.1 to 0.9, wherein AU = 100 • (UM- UD) / U is the relative difference of the photoinduced forces in the matrix and dispersed phases, wherein UM is the photoinduced force of the matrix phase, wherein UD is the photoinduced force of the dispersed phase, and wherein Ax, UM and UD are determined via photo-induced force microscopy with laser excitation at a wavelength of 1775 cm1.

[0260] 40. Thermoplastic molding compound comprising i) a matrix phase containing an amorphous non-crosslinked polymer A, ii) a phase dispersed in that matrix phase according to i) containing a polymer B’ which is different from polymer A, and iii) an interphase layer between the matrix phase i) and the dispersed phase ii) containing both polymers A and B’, wherein the interphase layer iii) is characterized by a gradient change of the contents of components A and B’ from the according values in the matrix phase according to i) to the according values in the dispersed phase according to ii), and wherein the thickness of that interphase layer Ax is larger than 30 nm determined via photoinduced force microscopy.

[0261] 41. Thermoplastic molding compound according to the embodiment 40, wherein Ax is larger than 40 nm. 2024PF30097-Foreign Countries

[0262] - 30 -

[0263] 42. Thermoplastic molding compound according to the embodiment 40, wherein Ax is larger than 50 nm.

[0264] 43. Thermoplastic molding compound according to any of the embodiments 40- 42, wherein the dispersed phase ii) contains both polymers A and B’.

[0265] 44. Thermoplastic molding compound according to any of the embodiments 40 - 43, wherein component B’ is a covalent adaptable network.

[0266] 45. Thermoplastic molding compound according to embodiment 44, wherein the covalent adaptable network according to component B’ is the reaction product of

[0267] B 1) a component comprising at least two acid anhydride groups or comprising at least two pairs of carboxyl groups or comprising at least two pairs of derivatives of carboxyl groups and

[0268] B2) a component with at least two functional groups independently from each other selected from -OH, -NHR and -SH, wherein R stands for an optionally substituted alkyl, aryl or arylalkyl residue, and wherein at least one of the components Bl and B2 has a functionality of >2.

[0269] 46. Thermoplastic molding compound according to any of the embodiments 40 - 45, wherein polymer A contains carbonate structural units -O-C(O)-O-, and AU / Ax is in the range of 0.1 to 0.9, wherein AU = 100 • (UM - UD) / U is the relative difference of the photoinduced forces in the matrix and dispersed phases, wherein UM is the photoinduced force of the matrix phase, wherein UD is the photoinduced force of the dispersed phase, and wherein Ax, UM and UD are determined via photo-induced force microscopy with laser excitation at a wavelength of 1775 cm1.

[0270] 47. Thermoplastic molding compound according to embodiment 46, wherein AU / Ax is in the range of 0.3 to 0.7.

[0271] 48. Thermoplastic molding compound according to embodiment 46, wherein AU / Ax is in the range of 0.4 to 0.6.

[0272] 49. Thermoplastic molding compound according to any of the embodiments 40 - 48, wherein polymer A is a polycarbonate, a polyestercarbonate or a mixture of both. 2024PF30097-Foreign Countries

[0273] - 31 -

[0274] 50. Thermoplastic molding compound according to any of the embodiments 40 - 49, wherein polymer A is a polycarbonate.

[0275] 51. Thermoplastic molding compound according to any of the embodiments 40 - 50, wherein polymer A is an aromatic polycarbonate.

[0276] 52. Process for the preparation of a thermoplastic molding compound from a composition comprising

[0277] A) a non-crosslinked polymer and

[0278] B) a covalent adaptable network, and

[0279] C) optionally a polymer additive, wherein the covalent adaptable network is the reaction product of

[0280] B 1) a component comprising at least two acid anhydride groups or comprising at least two pairs of carboxyl groups or comprising at least two pairs of derivatives of carboxyl groups and

[0281] B2) a component with at least two functional groups independently from each other selected from -OH, -NHR and -SH, wherein R stands for an optionally substituted alkyl, aryl or arylalkyl residue, and wherein at least one of the components B 1 and B2 has a functionality of >2, comprising the steps a) reacting components B 1 and B2 to form the covalent adaptable network B, b) melt compounding component A, B and optionally C in a temperature range of 200 to 350°C, c) solidifying the molding compound via cooling, wherein steps a) and b) either occur simultaneously or sequentially.

[0282] 53. Process according to embodiment 52, wherein steps a) and b) occur sequentially.

[0283] 54. Process according to embodiment 52 or 53, wherein component A is an amorphous polymer.

[0284] 55. Molded article comprising a thermoplastic composition according to any of the embodiments 1 - 37 or a thermoplastic molding compound according to any of the embodiments 38 - 51 ora molding compound obtained by a process according to any of the embodiments 52 - 54. 2024PF30097-Foreign Countries

[0285] - 32 -

[0286] Examples

[0287] Component A

[0288] Bisphenol-A based polycarbonate in powder form with weight-averaged molecular weight Mwof 25.000 g / mol (measured by GPC in methylene chloride at room temperature and with calibration against Bisphenol-A based polycarbonate standard)

[0289] Component B-l

[0290] Xibond™ 120 (Aurorium, Indianapolis, US): Random copolymer of styrene and maleic anhydride (PSMA) with a weight-averaged molecular weight Mwof 190 kg / mol (measured by GPC in THF at ambient temperature with calibration against polystyrene standard) and with a content of structural units derived from maleic anhydride of 8.7 % by weight. The glass transition temperature of the copolymer is 120°C.

[0291] Component B-2, B-3 and B-4

[0292] The styrene-maleic anhydride copolymer based Covalent Adaptable Networks and, in specific, the Components B-2 (O10), B-3 (025) and B-4 (050) were prepared as follows:

[0293] To a Teflon® beaker immersed in an oil bath and equipped with a magnetic stirrer, 3 m of tetrahydrofuran (THF) were added per gram of Xibond™ 120 (further referred to as XI 20) to be used. Afterwards, the X120 beads were slowly poured into the beaker while stirring at room temperature. Once the beads had completely dissolved, targeting adequate stoichiometric ratios, the specified amount of diol crosslinker was added to the beaker as 0.2 g / mL in THF solutions (see Table 1 for the specific formulations of Components B-2, B-3 and B-4 using 1,4-cyclohexanedimethanol (CHDM) as cross-linker and targeting stoichiometric ratios [OH] / [Anhydride] of 0.10 eq / eq, 0.25 eq / eq and 0.50 eq / eq, respectively). The temperature was then set to 70°C and the solution left to stir and concentrate overnight. Finally, the remaining solvent was removed by heating the mixture inside a 2 L polypropylene container in an oven at 100°C for 1 h and afterwards eventually for 4 h at 140°C under vacuum. The X120 and diol-derived Covalently Adaptable Networks (Components B-2, B-3 and B-4) were obtained as colorless, glassy and transparent foams. 2024PF30097-Foreign Countries

[0294] - 33 -

[0295] Table 1. Formulations used in the synthesis of diol-derived Covalent Adaptable Networks

[0296] (Components B-2, B-3 and B-4).

[0297] Network [0H] / [MA] XI 20 MA MA Crosslinker Crosslinker Crosslinker eq / eq mass (mmol) mass (mmol) mass (g)

[0298] Scheme 1. Schematic representation of Covalent Adaptable Networks derived from random styrenemaleic anhydride copolymer via crosslinking with diols.

[0299] Component B-5

[0300] The styrene-maleic anhydride copolymer based Covalent Adaptable Network N25 (Component B- 5) was prepared as follows:

[0301] To a Teflon® beaker immersed in an oil bath and equipped with a magnetic stirrer, 3 mb of THF were added per gram of Xibond® 120 to be used. Afterwards, the X120 beads were slowly poured into the beaker while stirring at room temperature. Once the beads had completely dissolved, targeting adequate stoichiometric ratios, the specified amount of secondary bisamine crosslinker was added to the beaker as 0.2 g / mL in THF solution (see Table 2 for the specific formulation of Component B-5 using 4,4-trimethylenedipiperidine (DPP) as cross-linker and targeting a stoichiometric ratio [NH] / [Anhydride] of 0.25 eq / eq). The beaker was covered for 5 min to let the organogel form slowly at room temperature. The resulting transparent gel was heated at 60°C for 10 min and afterwards extracted from the beaker and broken into small fragments (diameter <5mm) with the help of a stainless steel spatula. Finally, the remaining solvent was removed by heating the obtained gel fragments inside the beaker in an oven at 80°C for 1 h and afterwards eventually for 4 h under vacuum at 140°C. The XI 20 and secondary amine-derived Covalently Adaptable Network (Components B-5) was obtained as colorless glassy transparent material. 2024PF30097-Foreign Countries

[0302] - 34 -

[0303] Table 2. Formulation used in the synthesis of secondary diamine-derived Covalent Adaptable Network (Component B-5).

[0304] Network [NHR] / [MA] Method XI 20 MA MA Crosslinker Crosslinker Crosslinker g)

[0305] Scheme 2. Schematic representation of Covalent Adaptable Network derived from random styrenemaleic anhydride copolymer via crosslinking with a secondary diamine.

[0306] Component B-6

[0307] The non-inventive, permanently crosslinked styrene-maleic anhydride copolymer (Component B-6) was prepared as follows:

[0308] To a Teflon® beaker immersed in an oil bath and equipped with a magnetic stirrer, 6 mb of THF were added per gram of X120 to be used. Afterwards, the X120 beads were slowly poured into the beaker while stirring at room temperature. Once the beads had completely dissolved, targeting adequate stoichiometric ratios, the specified amount of secondary bisamine crosslinker was added to the beaker as 0.2 g / mL in THF solutions (see Table 3 for the specific formulation of Component B- 6 using l,3-bis(aminomethyl)cyclohexane (1,3-BAC) as crosslinker and targeting a stoichiometric ratio of [NH2] / [Anhydride] = 0.25 eq / eq). The beaker was covered for 5 min to let the organo-gel form slowly at room temperature. The resulting transparent gel was heated at 60°C for 10 min and afterwards extracted from the beaker and broken into small fragments (diameter <5mm) with the help of a stainless steel spatula. Finally, the remaining solvent was removed by heating the obtained gel fragments inside a 250 mb polypropylene container in an oven at 80°C for 1 h and afterwards eventually for 4 h under vacuum at 160°C. The imide-based permanently crosslinked polymer network derived from X120 (Component B-6) was obtained as faint yellow, glassy and transparent material. 2024PF30097-Foreign Countries

[0309] - 35 -

[0310] Table 3. Formulation used in the synthesis of imid-based non-adaptable polymer network (Component B-6) derived from random styrene-maleic anhydride copolymer via crosslinking with primary diamine.

[0311] Xibond® 120 (X120)

[0312] High Mw ~ 200 kg / mol

[0313] MA = 8.7 wt%

[0314] Tg = 120°C

[0315] D » 1.9

[0316] Scheme 3. Schematic representation of a permanent (i.e. non dynamic / covalently adaptable) polymer network derived from random styrene-maleic anhydride copolymer via crosslinking with a primary diamine.

[0317] Preparation of the thermoplastic compositions and injection molded test specimens

[0318] Components B-l, B-2, B-3, B-4, B-5 and B-6 were cryo-milled to fine powders prior to use in compound preparation. 90 % by weight of component A with 10 % by weight of components B-l (comparison example 1), B-2, B-3, B-4 and B-5 (inventive examples 2 - 5) and B-6 (comparative example 6) were homogeneously premixed. The thus obtained powder premixes were fed into the main feed of a laboratory-scale Thermo Scientific™ Process 11 parallel twin-screw extruder equipped with co-rotating compounding screws of diameter D=l l mm and with L / D=5 (Thermo Fisher Scientific Inc., Waltham, US). Throughput was set at 150 g / h, rotational screw speed at 75 rounds per minute, and barrels in the melt zone heated to 260°C. After leaving the extruder through a die plate, the suspended melt strands were allowed to cool and thus vitrify under ambient temperature in air as they were drawn and cut by a rotary pelletizer that was positioned about 0.8 m away from the extruder die.

[0319] Rectangular plate specimens for light transmission measurements with dimensions of 60 mm x 60 mm x 2 mm were prepared by injection molding at a melt temperature of 280°C using a laboratory scale injection molding machine Boy Procan ALPHA® 4 (Dr. Boy GmbH & Co. KG, Neustadt- 2024PF30097-Foreign Countries

[0320] - 36 -

[0321] Femthal, Germany). Mold temperature was set to 80°C. Before injection molding pellets were dried in vacuum at 120°C for about 4 hours.

[0322] Rheological characterization of the thermoplastic compositions and assessment of optical properties of test specimens molded thereof

[0323] The visual transmission Yio values of the injection molded 2 mm thick rectangular plate specimens were calculated based on the measured transmittance spectra with the observer 10° and illuminant D65 according to industry standard DIN EN ISO / CIE 11664-3:2020-03.

[0324] The dynamic melt viscosities were measured as function of shear rate directly on the molten compounded pellets in plate-to-plate geometry at a melt temperature of 260°C and with a plate to plate clearance of 1.5 mm. Before the measurement the pellets were dried in vacuum at 110°C for about 4 hours. As measure of the structurally viscous behavior of the compositions the slopes Ar| / Ay of the dynamic melt viscosity versus shear rate curves in the range of low shear rates are calculated based on the formula

[0325] Ar| / Ay = [ q( l s’1) - r|(3 S’1) ] / 2 S’1.

[0326] Large slope values of the dynamic melt viscosity vs. shear rate function in the low shear rate region are an indicator for structural viscosity of the investigated material.

[0327] Photo-induced force microscopical (PiFM) characterization of phase morphology

[0328] Smooth sample surfaces of the compounded pellets were prepared using Leica EM UC7 ultramicrotome (Leica microsystems) under cryo-condition (-130°C). Afterwards the blockface was investigated using Vista 75 microscope (Molecular Vista, Inc.) to obtain height and mechanical phase information, as well as the near field optical response. Laser wavelength was tuned from 800 to 1800 cm’1(with spectral line width of 1 cm’1) using the MIRcatTM mid-IR quantum cascade laser (QCL). A Platinum-Iridium coated AFM cantilever (type: NCH 300 kHz from Nanosensors) was used and oscillated at the second mechanical resonance (fl) to detect surface topography and at the first mechanical resonance (fO) to detect photo-induced force as voltage (U), while the laser is modulated at a frequency that equals to the difference between fl and fO with a power in the range of 0.5 to 1.5 mW. All PiFM images were recorded at 256 x 256 pixels using a scan rate of 0.5 Hz with a setpoint of 75% and amplitude of 2 nm. The photo-induced force (PiF) spectra were acquired using acquisition time of 26 s / spectrum over the set spectral range and were laser power normalized and smoothened. 2024PF30097-Foreign Countries

[0329] - 37 -

[0330] Characteristic peak assignments

[0331] Characterization of the thickness of the interphase layer and the compositional gradient within the interphase

[0332] The morphology of the blend shows clearly two phases (shown in the images of figure 1, i.e. left side): the matrix (the continuous) phase and the dispersed (discontinuous, isolated) phase. This results in two distinctive levels of photo-induced force (as voltage U) under set laser wavelength, with the higher level originated from the matrix phase and the lower level originated from the dispersed phase. In order to quantitatively assess the interdiffusion of the two polymers within and in the vicinity of the interphase area between the polycarbonate matrix and the polystyrene-maleic anhydride copolymer dispersed domains, a line profile was created across the matrix and the dispersed domain in the optical image (black lines in the images) measured with a laser wavelength of 1775 cm1, i.e. with a resonance frequency that essentially selectively detects the polycarbonate (see table “Characteristic peak assignments” above). Two levels of photo-induced force signals are clearly visible in the surface profile (as shown in the graphs next to the images). Subsequently the arithmetic mean value of the matrix phase is calculated using the part of surface profile with high photo-induced force (number of data points > 20) and the arithmetic mean value of the dispersed phase is calculated using the part of surface profile with low photo-induced force (number of data points > 20). These arithmetic mean values are displayed in the graphs by horizontal solid lines. + / - 5% error range is applied on the arithmetic mean values and shown in the figures as grey bands around the lines. One marker was placed at the matrix end of the profile with its value equals the arithmetic mean value of the matrix phase while a second marker was placed at the starting position of the dispersed phase with its value equals the arithmetic mean value of the dispersed phase. The distance Ax between these two markers was determined and is a measure for the thickness of the interphase. The relative difference AU of the voltages (indicating the photo-induced forces) in percent of the average voltage measured in the matrix phase is calculated from the difference between the arithmetic mean values in the matrix phase UM and in the dispersed phase UD using the formula

[0333] AU = 100 • (UM- UD) / UM. 2024PF30097-Foreign Countries

[0334] - 38 -

[0335] AU is an indicator for the relative compositional change in polycarbonate content between the two markers referred to the respective polycarbonate content of the composition in the matrix phase. The slope of the selected line profde, calculated as the ratio AU / Ax, is a measure for the size of the gradient in polycarbonate content within the interphase layer, i.e. a measure for the gradient of the polycarbonate / styrene-maleic anhydride copolymer ratio therein. In other words, the lower the value of AU / Ax, the more diffuse is the transition of the polymer composition in the interphase between the matrix and the dispersed phase. The values of AU / Ax can theoretically vary from 0 to infinity. However, both limit values are rather theoretical. The value of 0 would result from a perfectly homogenous distribution of both polymers of the blend between the matrix and dispersed phase, i.e. in case of equal compositions in the matrix and dispersed phase, or in case of an infinitely large interphase thickness. Essentially this means that both polymers are fully miscible. The value of infinity would mean that the interphase between the matrix and the dispersed phase is infinitely thin which means that the polymers are completely immiscible. Thus, the value of AU / Ax can be regarded as a parameter describing the compatibility of the polymers.

[0336] The values of Ax and AU are reported as numerical averages of a triple determination at different positions of the recorded PiFM images.

[0337] Figure 1, for comparative example Cl and inventive example 3, shows two examples of PiFM images both measured with laser wavelength of 1775 cm'1and illustrates the definition of Ax and AU as well as the procedure of determination of these values from the respective line profiles of the photoinduced forces determined for the lines depicted in the PiFM images.

[0338] Table 4 summarizes the formulations of the exemplary inventive and comparative thermoplastic molding compositions as well as their morphological features and rheological as well as optical properties.

[0339] Table 4: Compositions and their rheological, optical and morphological characteristics n.a. = not applicable 2024PF30097-Foreign Countries

[0340] - 39 -

[0341] The data in Table 4 demonstrates that the thermoplastic compositions 2 - 5 according to the invention allow for an improved balance of their rheological properties and light transmittance of parts obtained from them by injection molding. Compared to thermoplastic compositions comprising the noncrosslinked polymer B-l (Cl) or the permanently crosslinked polymer B-6 (C6), light transmission is significantly improved. Melt viscosities at high shear rate are on a low level compared to the pure polycarbonate (C7) which is good for injection molding. At the same time structural viscosity Aq / Ay is increased with the inventive compositions 2 - 5 versus both Cl, C6 and C7. This allows the inventive materials to be processed over a broad processing window not only by injection molding where low viscosities at high shear rates are required, but also by extrusion, blow molding or compression molding where high viscosities at low shear rates are a prerequisite. Without component B, i.e. in the pure polycarbonate (C7), light transmission is superior but melt viscosity is on a very high level at high shear rates and, at the same time, structural viscosity is very low (C7). Thus, the rheology limits the processing window of the composition C7 both for injection molding as well as extrusion, blow molding or compression molding.

[0342] It can be also seen that the favorable optical performance (high light transmission) is achieved by thermoplastic compositions with a thick interphase (where Ax is large) and with a small gradient AU / Ax indicating a more diffuse interphase layer.

Claims

2024PF30097-Foreign Countries- 40 -Patent Claims1. Thermoplastic composition comprisingA) a non-crosslinked polymer andB) a covalent adaptable network, wherein the covalent adaptable network is the reaction product ofB 1) a component comprising at least two acid anhydride groups or comprising at least two pairs of carboxyl groups or comprising at least two pairs of derivatives of carboxyl groups andB2) a component with at least two functional groups independently from each other selected from -OH, -NHR and -SH, wherein R stands for an optionally substituted alkyl, aryl or arylalkyl residue, and wherein at least one of the components Bl and B2 has a functionality of >2.

2. Thermoplastic composition according to claim 1, wherein component A is selected from the group consisting of polycarbonates, polyestercarbonates, vinylpolymers, and mixtures thereof.

3. Thermoplastic composition according to claim 1, wherein component A is a polycarbonate.

4. Thermoplastic composition according to any of the preceding claims, wherein the molar ratio of the functional groups of component B2 to the carboxylic acid anhydride groups or the pairs of carboxyl groups or the pairs of derivatives of carboxyl groups in component B 1 is in the range of 0.05 to 0.75.

5. Thermoplastic composition according to any of the preceding claims, wherein component B 1 is a copolymer comprising structural units derived from a monomer B 1. 1 and a further monomer B 1.2, wherein B 1. 1 comprises an acid anhydride group or a pair of carboxyl groups or a pair of derivatives of carboxyl groups.

6. Thermoplastic composition according to claim 5, wherein B 1.1 is maleic anhydride.

7. Thermoplastic composition according to any of the preceding 5 or 6, wherein Bl.2 is a monomer selected from the group consisting of vinylaromatics, (Ci-Cs)-alkyl (meth)acrylates, olefins and mixtures thereof.2024PF30097-Foreign Countries- 41 -8. Thermoplastic composition according to any of the preceding claims, wherein component B2 contains at least two aliphatic hydroxyl groups and does not contain any functional groups selected from the group consisting of -NH2, -NHR and -SH, wherein R stands for an optionally substituted alkyl, aryl or arylalkyl residue.

9. Thermoplastic composition according to claim 8, wherein component B2 is 1,4- cyclohexanedimethanol .

10. Thermoplastic composition according to any of the preceding claims, comprising50 to 99 parts per weight, based on in sum 100 parts by weight of component A and B, of component A and1 to 50 parts per by weight, based on in sum 100 parts by weight of component A and B, of component B.

11. Thermoplastic composition according to any of the preceding claims wherein componentB comprises structural units according to formula (9)wherein Ri is an organic residue and R2 and R3 are independently from each other organic residues or hydrogen.

12. Thermoplastic molding compound comprising i) a matrix phase containing an amorphous non-crosslinked polymer A, ii) a phase dispersed in that matrix phase according to i) containing a polymer B ’ which is different from polymer A, and iii) an interphase layer between the matrix phase i) and the dispersed phase ii) containing both polymers A and B’, wherein the interphase layer iii) is characterized by a gradient change of the contents of components A and B’ from the according values in the matrix phase according to i) to the according values in the dispersed phase according to ii), and wherein the thickness of that interphase layer Ax is larger than 30 nm determined via photoinduced force microscopy.2024PF30097-Foreign Countries- 42 -13. Thermoplastic molding compound according to claim 12 wherein polymer A contains carbonate structural units -O-C(O)-O-, and AU / Ax is in the range of 0.1 to 0.9, wherein AU = 100 • (UM - UD) / U is the relative difference of the photoinduced forces in the matrix and dispersed phases, wherein UM is the photoinduced force of the matrix phase, wherein UD is the photoinduced force of the dispersed phase, and wherein Ax, UM and UD are determined via photo-induced force microscopy with laser excitation at a wavelength of 1775 cm1.

14. Process for the preparation of a thermoplastic molding compound from a composition comprisingA) a non-crosslinked polymer andB) a covalent adaptable network, andC) optionally a polymer additive, wherein the covalent adaptable network is the reaction product ofB 1) a component comprising at least two acid anhydride groups or comprising at least two pairs of carboxyl groups or comprising at least two pairs of derivatives of carboxyl groups andB2) a component with at least two functional groups independently from each other selected from -OH, -NHR and -SH, wherein R stands for an optionally substituted alkyl, aryl or arylalkyl residue and wherein at least one of the components B 1 and B2 has a functionality of >2, comprising the steps a) reacting components B 1 and B2 to form the covalent adaptable network B, b) melt compounding component A, B and optionally C in a temperature range of 200 to 350°C, c) solidifying the molding compound via cooling, wherein steps a) and b) either occur simultaneously or sequentially.

15. Molded article comprising a thermoplastic composition according to any of the preceding claims 1 to 11 or a thermoplastic molding compound according to any of claims 12 and 13 or obtained by a process according to claim 14.