Polymeric compositions containing polymers and ionic liquids

0001The present invention relates to a polymer composition which has at least one at least partially crystalline polymer without ionic groups and at least one compound with plasticizing properties, the polymer composition having 0.1% to 30% by weight of ionic liquid as plasticizer, and a method for their manufacture and their use.

0002Ionic liquids have been the subject of various research projects for several years. An ionic liquid is generally understood to be a liquid that consists exclusively of ions. In contrast to the classic concept of molten salt, which is usually a high-melting, highly viscous and usually very corrosive medium, ionic liquids are liquid and relatively low-viscosity even at low temperatures (&lt;100 ° C). Even if there are some examples in which high-temperature salt melts have been successfully used as reaction media in preparative applications, the fact that ionic liquids are already in the liquid state below 100 ° C allows their use as a replacement for conventional organic solvents in chemical processes. Although ionic liquids have been known since 1914, they have only been intensively investigated as solvents and / or catalysts in organic syntheses in the last 10 years (review by <nplcit id="ncit0001" npl-type="s"><text>KR Seddon in J. Chem. Technol. Biotechnol. 68: 351-356 (1997)</text></nplcit>; <nplcit id="ncit0002" npl-type="s"><text>T. Welton, in Chem. Rev. 99 (1999), 2071-2083</text></nplcit>; <nplcit id="ncit0003" npl-type="s"><text>JD Holbrey, KR Seddon in Clean Products and Processes 1 (1999) 223-236</text></nplcit>; <nplcit id="ncit0004" npl-type="s"><text>P. Wasserscheid, W. Keim in Angew. Chem. 112 (2000), 3926-3945</text></nplcit> and <nplcit id="ncit0005" npl-type="s"><text>R. Sheldon in Chem. Comm. (2001), 2399-2407</text></nplcit>).

0003<nplcit id="ncit0006" npl-type="s"><text>S. Fischer et al. report in ACS Symp. Ser. 737: 143-150 (1999)</text></nplcit> about melting hydrates of inorganic salts, namely LiJ · 2H₂O, LiClO₄3H₂O, NaSCN / KSCN / LiSCN · 2H₂O and LiClO₄3H₂O / Mg (ClO₄)₂, as a solvent for cellulose.

0004Polymer extractions with chloroaluminate salts melted at room temperature are the subject of the work of <nplcit id="ncit0007" npl-type="s"><text>JS Wilkes et al. (Electrochem. Soc. Proceed. (2000) Volume 99-41 (Molten Salts XII), 65</text></nplcit>). 1-Ethyl-2-methylimidazolium chloride / aluminum chloride mixtures were used as ionic liquids and various polymers, including nylon, polyethylene, PVC and butyl rubber, were investigated.

0005<patcit id="pcit0001" dnum="WO0016902A"><text>WO 00/16902</text></patcit> and also <patcit id="pcit0002" dnum="WO0020115A"><text>WO 00/20115</text></patcit> deal with special ionic liquids which are used as catalysts or as solvents for catalysts in various organic syntheses.

0006It can be advantageous to immobilize the ionic liquid both for use as a solvent for catalytic reactions and for other areas of use. The advantages of immobilization in catalytic syntheses are the simplified separation, recovery and regeneration of the catalyst and the lower product contamination.

0007Immobilized ionic liquids are, for example, from <patcit id="pcit0003" dnum="EP0553009A"><text>EP-A-0 553 009</text></patcit> and <patcit id="pcit0004" dnum="US5693585A"><text>US-A-5,693,585</text></patcit> known. Both references describe a calcined support containing an ionic liquid consisting of aluminum chloride and an alkylated ammonium chloride or imidazolinium chloride. The immobilized ionic liquids are used as catalysts in alkylation reactions.

0008<patcit id="pcit0005" dnum="WO0132308A"><text>WO-A-01/32308</text></patcit> describes ionic liquids which are immobilized on a functionalized carrier which carries or contains a component of the ionic liquid or a precursor of such a component. The ionic liquid can be immobilized over the anion by treating a carrier with an anion source before the ionic liquid is applied or formed. Alternatively, the ionic liquid can be immobilized by the cation being covalently bound to the support or embedded in the support. The immobilized ionic liquids are used as catalysts, for example for the Friedel-Crafts reaction.

0009The work of <nplcit id="ncit0008" npl-type="s"><text>N. Ogata, K. Sanui, M. Rikukawa, S. Yamada and M. Watanabe (Synthetic Metals 69 (1995), 521-524</text></nplcit> and Mat. Res. Soc. Symp. Proc. 293, 135 ff.) Deal with "immobilized" ionic liquids, specifically with new polymer electrolytes, which are ion-conductive polymer complexes and are formed by dissolving various polycationic salts in ionic liquids (also referred to herein as "molten salts") which contain aluminum chloride . The polycationic salts can be polyammonium, polypyridinium, polysulfonium and / or polyphosphonium salts. A polymer complex consisting of a polypyridinium salt and, as an ionic liquid, a pyridinium salt and aluminum chloride was investigated in more detail. The polypyridinium salt in this case represents the ionic liquid instead of the pyridinium salt and enables the polymer complexes to form thin layers, which results from the enormous increase in viscosity compared to the pure ionic liquid. The new polymer complexes have a high ionic conductivity and, like other polymer electrolytes, are of interest for use in batteries and display devices.

0010In <patcit id="pcit0006" dnum="US6025457A"><text>US-A-6,025,457</text></patcit> "Molten salt type" polyelectrolytes are disclosed which contain a molten salt polymer which is formed by reacting an imidazolium derivative bearing a substituent at the 1- and 3-positions with at least one organic acid or organic acid compound which forms a Has acid amide or acid imide bond is obtained, with at least one component, ie said imidazolium derivative or said organic acid compound is a polymerizable monomer or a polymer. These polyelectrolytes also show high ion conductivity at room temperature and have good mechanical properties.

0011Furthermore, the prior art describes many polymer electrolytes with high conductivity, which consist of a nonionic polymer in combination with an ionic liquid.

0012Describe like this <nplcit id="ncit0009" npl-type="s"><text>J. Fuller et al. in J. Electrochem. Soc. 144 (4) (1997), L67-L70</text></nplcit> rubber-like gel electrolytes from poly (vinylidene fluoride-hexafluoropropyl) copolymers and ionic liquids based on 1-ethyl-3-methylimidazolium triflate or tetrafluoroborate.

0013In <patcit id="pcit0007" dnum="JP10265673A"><text>JP-A-10265673</text></patcit> discloses the production of solid polymer electrolytes in the form of ion-conducting films by polymerizing hydroxyethyl methacrylate and ethylene glycol dimethacrylate in the presence of an ionic liquid based on 1-butylpyridinium tetrafluoroborate.

0014Subject of <patcit id="pcit0008" dnum="JP10265674A"><text>JP-A-10265674</text></patcit> are compositions of polymers, eg polyacrylonitrile and polyethylene oxide, and ionic liquids. The ionic liquids contain, for example, LiBF₄ and 1-ethyl-3-methylimidazolium tetrafluoroborate. Solid electrolytes, antistatic agents and shields are given as uses.

0015<nplcit id="ncit0010" npl-type="s"><text>Noda et al. report in Electrochim. Acta 45 (2000), 1265-1270</text></nplcit>that certain vinyl monomers can be polymerized in situ from 1-ethyl-3-methylimidazolium tetrafluoroborate or 1-butylpyridinium tetrafluoroborate in molten salt melts at room temperature and produce transparent, highly conductive and mechanically stable polymer electrolyte films.

0016<nplcit id="ncit0011" npl-type="s"><text>Fuller et al. (Molten Salt Forum 5-6 (1998), 605-608</text></nplcit>) investigated mixtures of ionic liquids or other imidazolium salts and poly (vinylidene fluoride-hexafluoropropyl) copolymers. These mixtures show high conductivity, thermal stability and dimensional stability for applications in batteries, fuel cells or capacitive units as highly conductive polymer electrolytes.

0017<nplcit id="ncit0012" npl-type="s"><text>Watanabe et al. in Solid State Ionics 86-88 (1996), 353-356</text></nplcit>that at temperatures below 100 ° C liquid salt mixtures of trimethylammonium benzoate, lithium acetate and lithium bis (trifluoromethylsulfonyl) imide are compatible with polyacrylonitrile and polyvinyl butyral and result in systems from which film-forming polymer electrolytes can be produced.

0018<nplcit id="ncit0013" npl-type="s"><text>Humphrey et al. (Book of Abstracts, 215th ACS National Meeting, Dallas. March 29-April 2 (1998</text></nplcit>), CHED-332, ACS, Washington DC) describe the solution and extraction of polymers with molten salts of aluminum chloride and an organic chloride salt that are liquid at room temperature. The ionic liquids are adjustable with regard to their Lewis acidity and become superacids by adding hydrogen chloride. In <nplcit id="ncit0014" npl-type="s"><text>Chem. Commun. (2002), 1370-1371</text></nplcit> PMMA is produced by radical polymerization in an ionic liquid. However, the production of plasticized polymers by polymerization in ionic liquids is not suitable for all types of polymers.

0019Many polymers, such as polyaramides, polyesters, polyamides, polyether (ether) ketones, can only be processed with the aid of certain processes or only with difficulty.

0020In some cases, the thermoplastic processing of these polymer materials as such is not possible without decomposition of the polymer chain. Processing of polymers is often only possible by mixing in plasticizers. Many of the known plasticizers are not suitable for the high temperature range. This can be due, on the one hand, to the fact that the plasticizers are too volatile or, on the other hand, to an incompatibility with the polymer. In particular for polymers which have polar groups, such as, for example, in the case of the polyamides or polyesters, it is frequently not possible to find suitable, non-corrosive plasticizers which do not outgas during processing.

0021It was therefore the object of the present invention to provide a polymer composition which has a plasticizer which improves the properties of at least partially crystalline polymers which have no ionic groups, in particular with regard to their thermoplastic processability, and not or only to a small extent in particular in the case of current processing temperatures of

0022Thermoplastics is volatile. Surprisingly, it was found that polymers which do not contain any ionic groups can be improved by adding ionic liquids according to claims 1-12 in their processability, preferably in their thermoplastic processability, in their electrical properties and in their compatibility with other systems. Although the use of ionic liquids as a catalyst or for the production of polymer electrolytes has long been known from the literature, it has not hitherto been recognized that the presence of ionic liquids in polymers which have no ionic groups improve the thermoplastic processability and therefore ionic liquids as Plasticizers can be used. The solution was all the more surprising since it was shown that the ionic liquids can also be used as solvents for these polymers, which are insoluble or only insoluble in organic or aqueous solvents, and thus plasticized polymer compositions can be obtained.

0023The present invention therefore relates to a polymer composition according to claim 1, consisting of at least one at least partially crystalline polymer without ionic groups and at least one compound with plasticizing properties, the polymer composition comprising 0.1% to 30% by weight of ionic liquid as plasticizer .

0024The invention furthermore relates to a process according to claim 13 for producing a polymer composition which has at least one polymer without ionic groups and at least one compound with plasticizing properties, the polymer composition as a plasticizer being 0.1% by weight to 30% by weight ionic Has liquid.

0025The invention furthermore relates to the use of a polymer composition according to claim 1 and the use of a polymer composition which has been prepared by the process according to the invention.

0026The polymer composition according to the invention has the advantage that the solvent-like character of the ionic liquid increases the flowability of the melts of this polymer composition, the particular advantage being the non-volatility of the ionic liquid even at the processing temperatures of the polymer blends. This means that either processing temperatures can be used at which the plasticizers or Processing aids already have too high a vapor pressure and lead to outgassing and / or formation of molds or tooling, or the polymers can be processed at lower temperatures due to the softening effect. This is particularly advantageous in the case of partially crystalline or crystalline polymers since, owing to their morphology, they usually have higher melting temperatures and, associated therewith, higher processing temperatures (compared to an amorphous polymer such as PMMA). The use of non-volatile plasticizers for partially crystalline or crystalline polymers makes it possible to process or use these polymers at higher temperatures. Through the use of ionic liquids as a plasticizer , the flowability of the polymer materials in the molten state is increased. Because of their non-volatile and ionic character and their special dissolving properties, ionic liquids can be used as plasticizers or solvents, especially for polymers or substances that are not or only insufficiently soluble in organic or aqueous solvents. If crosslinked or crosslinking polymers are used in a mixture of substances, the ionic liquid can also be used as a plasticizer which lowers the glass transition temperature.

0027The polymer composition according to the invention, which has at least one at least partially crystalline polymer without ionic groups and at least one compound with plasticizing properties, is characterized in that the polymer composition as a plasticizer is 0.1% by weight to 30% by weight, preferably 0, 5% by weight to 25% by weight and particularly preferably from 1% by weight to 16% by weight of ionic liquid. The concentration of the ionic liquid in the case of the polyamide as a thermoplastically processable polymer, in which the ionic liquid is used as a plasticizer, is preferably from 1% by weight to 25% by weight, preferably from 3% by weight to 16% by weight. -%.

0028The ionic liquid according to the invention has a salt with a cation, according to the structures below <b>2</b> to <b>9</b> and <b>12</b> on,<chemistry id="chem0001" num="0001"><img file="EP1519988B2_D0001.tif" /></chemistry><chemistry id="chem0002" num="0002"><img file="EP1519988B2_D0002.tif" /></chemistry><chemistry id="chem0003" num="0003"><img file="EP1519988B2_D0003.tif" /></chemistry><chemistry id="chem0004" num="0004"><img file="EP1519988B2_D0004.tif" /></chemistry><chemistry id="chem0005" num="0005"><img file="EP1519988B2_D0005.tif" /></chemistry><chemistry id="chem0006" num="0006"><img file="EP1519988B2_D0006.tif" /></chemistry>wherein R1, R2, R3, R4, R5 and, identical or different and hydrogen, a linear or branched aliphatic hydrocarbon radical having 1 to 20 carbon atoms, a cycloaliphatic hydrocarbon radical having 5 to 30 carbon atoms, an aromatic hydrocarbon radical having 6 to 30 carbon atoms, an alkylaryl radical with 7 to 40 carbon atoms, one through one or more heteroatoms (oxygen, NH, NCH₃) interrupted linear or branched aliphatic hydrocarbon radical having 2 to 20 carbon atoms, one by one or more functionalities, selected from the group -OC (O) -, - (O) CO-, -NH-C (O) -, - (O ) C-NH, - (CH₃) NC (O) -, - (O) CN (CH₃) -, -S (O)₂-O-, -OS (O)₂-, -S (O)₂-NH-, -NH-S (O)₂-, -S (O)₂-N (CH₃) -, -N (CH₃)-SO)₂-, interrupted linear or branched aliphatic hydrocarbon radical with 2 to 20 carbon atoms, a terminal -OH, -NH₂, -N (H) CH₃ Functionalized linear or branched aliphatic hydrocarbon radical with 1 to 20 carbon atoms or a block or random polyether according to - (R⁷-O)_n-R⁸ mean, where R⁷ is a linear or branched hydrocarbon radical containing 2 to 4 carbon atoms, n = 1 to 30 and R⁸ Is hydrogen, a linear or branched aliphatic hydrocarbon group having 1 to 20 carbon atoms, a cycloaliphatic hydrocarbon group having 5 to 30 carbon atoms, an aromatic hydrocarbon group having 6 to 30 carbon atoms, an alkylaryl group having 7 to 40 carbon atoms, or a group -C (O) -R⁹ with R⁹ are a linear or branched aliphatic hydrocarbon group having 1 to 20 carbon atoms, a cycloaliphatic hydrocarbon group having 5 to 30 carbon atoms, an aromatic hydrocarbon group having 6 to 30 carbon atoms, an alkylaryl group having 7 to 40 carbon atoms; and an anion selected from the group consisting of halides, ie Chloride, bromide and iodide, preferably iodide; Phosphate; Alkyl phosphates; Nitrate; Sulfate; Hydrogen sulfate; Alkyl sulfates, preferably octyl sulfate; Aryl sulfates; perfluorinated aryl and alkyl sulfates; Sulfonate, alkyl sulfonates; Aryl sulfonates; perfluorinated aryl sulfonates, perchlorate; Tetrachloroaluminate; Alkyl borates, preferably B (C₂H₅)₃C.₆H₁₃ ; Tosylate; Saccharinate; Alkyl carboxylates and, or a mixture of several such salts.

0029In a preferred embodiment of the polymer composition according to the invention, the ionic liquid has halogen-free anions selected from the group consisting of phosphate, alkyl phosphates, nitrate, sulfate, alkyl sulfates, aryl sulfates, sulfonate, alkyl sulfonates, aryl sulfonates, alkyl borates, tosylate, saccharinate and alkyl carboxylates, are particularly preferred Alkyl sulfates, especially octyl sulfate, and tosylate.

0030In a further preferred embodiment of the polymer composition according to the invention, the ionic liquid has different anions and / or cations. The ionic liquids used, for example, as plasticizers can thus be used individually or in a mixture in the polymer composition according to the invention.

0031The ionic liquid is prepared as described in the literature, inter alia in <nplcit id="ncit0015" npl-type="s"><text>S. Saba, A. Brescia, M. Kaloustian, Tetrahedron Letters 32 (38) (1991), 5031-5034</text></nplcit>, <patcit id="pcit0009" dnum="EP1072654A"><text>EP 1 072 654</text></patcit> and <patcit id="pcit0010" dnum="EP1178106A"><text>EP 1 178 106</text></patcit>, is described.

0032The polymer composition according to the invention preferably has at least one thermoplastically processable polymer selected from the group of (co) polyamides, (co) polyesters, polyurethanes, polyphenylene ethers, polyolefins, (co) polyether amides, polyaramides, polyether (ether) ketones, polyether ester amides.

0033In a particular embodiment of the polymer composition according to the invention, it has at least one thermoplastically processable polymer from the group of homopolyamides. Homopolyamides according to the structure are preferred<b>13</b> or structure <b>14</b>, where both n ≥ 2 and k ≥ 2 (independently of one another) and m> 3.<chemistry id="chem0007" num="0007"><img file="EP1519988B2_D0007.tif" /></chemistry>

0034Examples of polymers according to the structures <b>13</b> and <b>14</b> are polyamide 46, polyamide 66, polyamide 69, polyamide 612, polyamide 1012, polyamide 1212, polyamide 6, polyamide 11 and polyamide 12.

0035In a further embodiment of the polymer composition according to the invention, it has aromatic polyamides based on aromatic dicarboxylic acids and / or aromatic diamines; preference is given to aromatic polyamides based on terephthalic acid, for example polyamide PA-6.3T, isophthalic acid and naphthalenedicarboxylic acids. The polymer composition according to the invention preferably has a thermoplastically processable polymer in accordance with the structures below<b>15</b>, <b>16</b> and <b>17</b> where x = 2 to 22 and y = 2 to 22:<chemistry id="chem0008" num="0008"><img file="EP1519988B2_D0008.tif" /></chemistry>or<chemistry id="chem0009" num="0009"><img file="EP1519988B2_D0009.tif" /></chemistry>

0036In a particularly preferred embodiment of the polymer composition according to the invention, it has aliphatic polyamides and / or copolyamides. As the polyamide-forming monomer, the polyamides of the polymer composition according to the invention preferably have lactams or ω-aminocarboxylic acids which contain 4 to 19 and in particular 6 to 12 carbon atoms. Ε-Caprolactam, ε-aminocaproic acid, capryllactam, ω-aminocaprylic acid, laurolactam, ω-aminododecanoic acid and / or ω-aminoundecanoic acid are particularly preferably used.

0037Combinations of diamine and dicarboxylic acid are, for example, hexamethylene diamine / adipic acid, hexamethylene diamine / dodecanedioic acid, octamethylene diamine / sebacic acid, decamethylene diamine / sebacic acid, decamethylene diamine / dodecanedioic acid, dodecamethylene diamine / dodecanedioic acid and dodecane diamine diamine acid. In addition, however, all other combinations can also be used, such as decamethylenediamine / dodecanedioic acid / terephthalic acid, hexamethylenediamine / adipic acid / terephthalic acid, hexamethylenediamine / adipic acid / caprolactam, decamethylenediamine / dodecanedioic acid / ω-aminoundecanoic acid / decamethylenediamine diamine amine / decamethylenediamine diamine amine / decamethylenediamine diamine amine / decamethylenediamine diamine amine / decamethylenediamine diamine amine / decamethylenediamine diamine amine / decamethylenediamine diamine / 2,6-naphthalenedicarboxylic acid / laurolactam.

0038The polymer composition according to the invention can contain copolyamides as the thermoplastically processable polymer. For this purpose, preference is given to those which contain basic monomers which lead to the homopolyamides mentioned above. Laurin lactam, 11-aminoundecanoic acid, caprolactam, adipic acid / hexamethylenediamine, dodecanedioic acid / hexamethylenediamine, dodecanedioic acid / methylpentanediamine, dodecanedioic acid / decamethylenediamine and dodecanedioic acid / isophoronediamine can be used as co-components. Such copolyamides are, for example, in <patcit id="pcit0011" dnum="DE3921164"><text>DE 39 21 164</text></patcit>, <patcit id="pcit0012" dnum="DE2324160"><text>DE 23 24 160</text></patcit>, <patcit id="pcit0013" dnum="DE1939758"><text>DE 19 39 758</text></patcit> and <patcit id="pcit0014" dnum="DE3248776"><text>DE 32 48 776</text></patcit> described. The copolyamides listed can be used individually or in a mixture for the polymer composition according to the invention. Both the homopolyamides and the copolyamides can be linear or branched.

0039The polymer composition according to the invention can, as a thermoplastically processable polymer, be homo- and / or copolyesters, such as polyalkylene terephthalates; in particular polyethylene terephthalate and polybutylene terephthalate, polybutylene naphthalate, polyethylene naphthalate, 1,4-cyclohexanedimethanol (co) polyester, polycaprolactone, polyoxytetramethylene-b-polybutylene terephthalate, polylactides. These are preferably copolyesters according to the structure<b>18</b>: <chemistry id="chem0010" num="0010"><img file="EP1519988B2_D0010.tif" /></chemistry>where d = 2 to 6, e = 2 to 4, a> 20, b = 0 to 40, c = 1 to 40 and the structural units, which are based on monomers each having two hydroxyl groups, can be linear or branched. Copolyesters according to the structure are preferred<b>19</b>: <chemistry id="chem0011" num="0011"><img file="EP1519988B2_D0011.tif" /></chemistry>where g = 1 to 5, f = 1 to 5 and Q and S independently of one another bivalent radicals, for example according to the structures <b>20</b>, <b>21</b>, <b>22</b> and <b>23</b>, could be:<chemistry id="chem0012" num="0012"><img file="EP1519988B2_D0012.tif" /></chemistry><chemistry id="chem0013" num="0013"><img file="EP1519988B2_D0013.tif" /></chemistry>

0040According to the structure, copolyesters which arise from different hydroxycarboxylic acids and / or lactones are particularly preferred <b>24</b>: <chemistry id="chem0014" num="0014"><img file="EP1519988B2_D0014.tif" /></chemistry>where both R10 and R11 can be linear or branched alkyl radicals, preferably o> 1 and q <200 and preferably, however, o> 10 and q <70.

0041Copolyesters according to the structure are very particularly preferred <b>25</b>: <chemistry id="chem0015" num="0015"><img file="EP1519988B2_D0015.tif" /></chemistry>where R12 is linear or branched alkyl radicals, which can either be the same or different, R13 is a hydrocarbon group having 2 to 4 carbon atoms, for example - (CH₂)₂-, -CH₂-CH (CH₃) -, - (CH₂)₄- and p = 1 to 40 can be. In a particular embodiment, various lactones can be used as monomers.

0042A polymer composition according to the invention can also preferably be thermoplastically processable polymers selected from the group of polyolefins, polyurethanes which can be thermoplastically processed, polyphenylene ethers as described in <patcit id="pcit0015" dnum="EP0657519A"><text>EP 0 657 519</text></patcit> copolyether amides and copolyether ester amides.

0043In a further embodiment, the polymer composition according to the invention has at least one crosslinked or at least one polymer to be crosslinked. The polymer composition according to the invention preferably has at least one polymer selected from the group of (co) polyamides, (co) polyesters, polyurethanes or polyphenylene ethers. This polymer composition according to the invention makes it possible to produce a crosslinked plasticized polymer with a non-volatile plasticizer, the ionic liquid.

0044The polymers contained in the polymer composition according to the invention can be linear or branched. The polymer compositions according to the invention can contain one or more polymers, whether as a polymer blend, copolymer or physical mixture, preferably the polymer composition according to the invention has at least one polymer mixture or at least one polymer blend. The polymeric component can have additives such as UV stabilizers, fillers, flame retardants, antioxidants. In a particular embodiment, the polymer composition according to the invention can have modified, for example end-group-modified, polymers.

0045The polymer composition according to the invention preferably has a glass temperature which is 18K lower than that of a polymer without the presence of the ionic liquid, as measured by differential scanning calorimetry (DSC).

0046Furthermore, the polymer composition according to the invention, which has a crystalline or partially crystalline polymer - in comparison to the polymer without the presence of the ionic liquid - has a higher recrystallization capacity, measured by the onset of recrystallization at a higher temperature in a DSC cooling test from the polymer melt.

0047These morphological properties can improve the processability, in particular the thermoplastic processability, of the polymer composition according to the invention compared to a polymer composition without an ionic liquid. This can be seen, for example in that the polymer composition according to the invention can be molded at lower temperatures without the polymer chain being decomposed, or the molding process can be carried out at higher temperatures without the plasticizer - the ionic liquid - being volatile.

0048The polymer composition according to the invention can additionally have microbicidal properties. These polymer compositions according to the invention with microbicidal properties preferably have an ionic liquid with a quaternary ammonium ion, but particularly preferably TEGOTAIN^® 3300, which itself already has microbicidal properties. In a particular embodiment of the polymer composition according to the invention, at least one of the polymers used may already have microbicidal properties. Polymers that have microbicidal properties are, inter alia, in<patcit id="pcit0016" dnum="DE19952221"><text>DE 199 52 221</text></patcit>, <patcit id="pcit0017" dnum="DE19943344"><text>DE 199 43 344</text></patcit> or <patcit id="pcit0018" dnum="DE19940023"><text>DE 199 40 023</text></patcit> described.

0049Furthermore, the polymer composition according to the invention can additionally have antistatic properties. The antistatic properties can either be due to the addition of water molecules (increased water absorption) and thus according to the principle of the generally known conductivity improvement of polymeric materials by adding salts, such as, for example Potassium formate, or be caused by one of the added ionic liquids intrinsically assignable ion conductivity.

0050In the process according to the invention for producing a polymer composition which has at least one polymer without ionic groups and at least one compound with plasticizing properties, the polymer composition having 0.1 to 30% by weight of ionic liquid as plasticizer, in particular the one according to the invention Polymer composition is preferably first the ionic liquid with a polymeric component of the polymer composition, for example, brought into contact with at least one of the polymers and then the ionic liquid is distributed in the polymer composition. Here, one of the components of the polymer composition according to the invention can be in the molten or solid state or dissolved in a solvent. In the event that one of the components of the polymer composition according to the invention is used dissolved in a solvent, the solvent can then be separated off from the precursor of the polymer composition according to the invention, preferably by a thermal separation process, such as distillation, or by precipitation of the polymer composition according to the invention, eg by adding a non-solvent or by lowering the temperature.

0051In a particular embodiment of the process according to the invention, the solvent or swelling agent, which in this case is the same as the ionic liquid, can remain in the polymer composition according to the invention. This is particularly advantageous in the case of multiphase polymer systems in which, for example only one of the polymeric components is compatible with the ionic liquid; this can result in additional new properties for the multiphase system, preferably at the phase boundaries. Another possible use of the polymer composition according to the invention, in which the ionic liquid remains, is the dissolving or swelling of a polymer component of a multiphase system, a further polymer component being incompatible with the pure ionic liquid. By mixing or kneading this multiphase system, it can be achieved that the ionic liquid passes into the phase which is incompatible with the pure ionic liquid.

0052In a special embodiment of the method according to the invention, the ionic liquid is distributed in the polymer composition by means of a mixing process. Here, the ionic liquid can be brought into contact with the molten phase of the polymeric component and then mixed. Another possibility is to bring the ionic liquid into contact with the solid phase of the polymeric component, then to melt it and then to mix it. For example, this can be done by mechanical mixing of the polymeric component and the ionic liquid using an extruder or stirrer at appropriate temperatures; preference is given to mixing the individual components of the polymer composition according to the invention in a 1- or 2-shaft kneader, the polymeric component being in the molten state is present. Furthermore, in the mixing process, the polymeric component can be dissolved in the ionic liquid at higher temperatures, or both the polymeric component and the ionic liquid are dissolved in a solvent. In a special embodiment of this partial process step, the polymeric component, for example precipitated, spray-dried or (cold) ground polymer, mixed with the ionic liquid, optionally by adding a solvent for the ionic liquid, which is a non-solvent for the polymeric component, in order thus to have a homogeneous distribution of the ionic liquid in the invention Obtain polymer composition.

0053In a further preferred embodiment of the method according to the invention, the ionic liquid is distributed in the polymer composition by means of diffusion. Preference is given here to impregnating polymer powders using an ionic liquid; impregnation of foils, fibers, foams or injection-molded parts using auxiliaries, such as solvents, is particularly preferred.

0054The polymer composition according to the invention or the polymer composition produced according to the method according to the invention can be used, for example, in a molding process. In the shaping, a plastic which has a polymer composition according to the invention or a polymer composition produced according to the method according to the invention or which is the inventive polymer composition itself can be, for example, by means of Injection molding, extrusion or blow molding are thermally molded. When processing thermoplastics, it is particularly important that the polymer materials are easy to process. This can be limited when using polymers with a strong polarity due to the intra- and intermolecular interactions. By using the polymer compositions according to the invention or of the polymer composition produced according to the process according to the invention, in which ionic liquids are used as plasticizers, the interactions between the polymer-bound functional groups are reduced and thus an improved processability is achieved.

0055The polymer composition according to the invention or the polymer composition produced according to the method according to the invention can also be used as a starting material in spinning processes. In the case of polymers to be spun into fibers, the ionic liquid can enable or facilitate the spinning process. Due to the lowering of the melt viscosity due to the addition of ionic liquids, the processing window for the spinning process can be expanded; the same applies to film production or other extrusion processes.

0056The ionic liquids contained as plasticizing processing aids in the polymer compositions according to the invention or in the polymer compositions produced according to the method according to the invention can, if they are miscible with water or another solvent incompatible with the polymer, also be extracted again from the polymers after processing, so that Structure and properties of the polymer can be changed. This can open up new areas of application for individual types of polymer.

0057Another object of the invention is the use of the polymer composition according to the invention or the polymer composition produced according to the method according to the invention for the production of films, films, sports shoes, coatings, preferably in sports equipment or articles, such as the coatings of snowboards, and membranes. The use of the polymer composition according to the invention or the polymer composition produced according to the method of the invention as a hot melt adhesive, adhesion promoter, binder, filler or packaging material. The use of the polymer composition according to the invention or of the polymer composition produced according to the method according to the invention as an adhesion promoter is preferably used in polymer multicomponent systems, such as, for example, in multilayer pipes or compound systems. In displays or other electronic components, the polymer composition according to the invention or the polymer composition produced according to the method according to the invention can be used as a binder, filler material or as packaging material. In the production of membranes, preferably ceramic membranes, the polymer composition according to the invention or the polymer composition prepared according to the inventive method can be used, an improvement in the separating effect of the membrane can result therefrom.

0058The polymer composition according to the invention or the polymer composition produced according to the method according to the invention can be used as a constituent of a mixture of polymers which are not miscible or incompatible, as a compatibility improver for the production of a polymer blend, preferably of homogeneous polymer blends.

0059In a further use of the polymer composition according to the invention or of the polymer composition produced according to the method according to the invention, this can be used as a viscosity and / or conductivity modifier in polymer mixtures or compositions. The polymer composition according to the invention or the polymer composition produced according to the method according to the invention can be used as a so-called masterbatch.

0060The polymer composition according to the invention or the polymer composition produced according to the method according to the invention can be used in these uses in a mixture with other polymers or directly.

0061The polymer composition according to the invention or the polymer composition produced according to the method according to the invention makes it possible to produce novel binder or adhesive systems. Due to the presence of ionic groups by the ionic liquid, the adhesive behavior of the polymer composition according to the invention or the polymer composition produced according to the method according to the invention can be polar or swollen or swollen by the ionic liquids. loosened surfaces can be improved.

0062Conductive binder systems and adhesives are manufactured according to the current state of the art by adding special conductivity fillers. Antistatic finishes for molding compounds, varnishes, rubber and foams are produced either by incorporating fillers, fibers, such as carbon black or graphite, or low-molecular salts such as potassium formate. Electrically conductive adhesives have proven to be an alternative or introduced in addition to soft soldering, especially in electronics. Epoxy resins are predominantly used as base polymers; In addition, adhesive systems based on cyanoacrylate, silicone and polyimide are known. Gold, silver, copper or nickel in platelet or Known flake shape, also e.g. silver-coated glass beads (<patcit id="pcit0019" dnum="EP0195859A"><text>EP 0 195 859</text></patcit>).

0063In addition to the state of the art in the case of conductive polymer materials for electronic applications, it should be mentioned that there are materials that either contain an addition of intrinsically conductive polymer materials (eg BF₄-doped poly (ethoxythiophene)) as an additive for heat-sealable antistatic films (<patcit id="pcit0020" dnum="DE4219410"><text>DE 42 19 410</text></patcit>) or increase the conductivity of the polymer blend with the addition of conductive particles or antistatic or conductive fibers.

0064The electrical properties of the polymer composition according to the invention or of the polymer composition produced according to the method according to the invention can be adapted over a wide range by introducing the ionic groups into the polymer composition by means of the ionic liquids. This is an additional antistatic or partly also semiconducting property of the polymer composition according to the invention or the polymer composition produced according to the inventive method can be produced. The polymer composition according to the invention or the polymer composition produced according to the method according to the invention can therefore be used in electrical and electronic components as a semiconducting or antistatic binder or adhesive for (co) extrusion or injection molding processing. The use of the polymer composition according to the invention or The polymer composition produced according to the method according to the invention, for example in electronic components, can be particularly advantageous on account of the variable electrical and thermal properties of these systems.

0065The following examples are intended to explain the invention in more detail without restricting its scope:

<i>Example: Production of a polymer composition according to the invention</i>

00665 g VESTAMELT, a hot melt adhesive based on copolyamides from Degussa AG and 15% by weight of ionic liquid based on VESTAMELT (corresponds to 0.75 g of ionic liquid) in 25 g of acetone were intimately mixed in a shaker and then the acetone was in a rotary evaporator away.

0067The following were used as ionic liquids:<ul id="ul0001" list-style="bullet" compact="compact"><li>1-ethyl-3-methylimidazolinium tosylate</li><li>Trioctylammonium octyl sulfate (reference example)</li><li>1,3-dimethylimidazolinium octyl sulfate</li></ul>

0068The following were used as VESTAMELT powders:<ul id="ul0002" list-style="bullet"><li>VESTAMELT VM 250-P2</li><li>VESTAMELT VM 430-P2</li><li>VESTAMELT VM 470-P830</li></ul>

0069The following table shows the lowering of the melting or glass temperature and the simultaneous increase in the melting enthalpy compared to the original powders.<tables id="tabl0001" num="0001"><table frame="all"><tgroup cols="5"><colspec colnum="1" colname="col1" colwidth="25mm" /><colspec colnum="2" colname="col2" colwidth="58mm" /><colspec colnum="3" colname="col3" colwidth="17mm" /><colspec colnum="4" colname="col4" colwidth="17mm" /><colspec colnum="5" colname="col5" colwidth="21mm" /><thead><row><entry align="center" valign="middle"><b>ESTABLISHED</b></entry><entry align="center" valign="middle"><b>Ionic liquid</b></entry><entry align="center" valign="middle"><b>ΔTm (K)</b></entry><entry align="center" valign="middle"><b>ΔTg (K)</b></entry><entry align="center" valign="middle"><b>Δ (ΔH) (J / g)</b></entry></row></thead><tbody><row><entry align="center" valign="middle">VM250</entry><entry align="center" valign="middle">Trioctylammonium octyl sulfate</entry><entry align="center" valign="middle">-4,8</entry><entry align="center" valign="middle">nb</entry><entry align="center" valign="middle">14,5</entry></row><row><entry morerows="2" align="center" valign="middle">VM430</entry><entry align="center" valign="middle">1-ethyl-3-methylimidazolinium tosylate</entry><entry align="center" valign="middle">-5,4</entry><entry align="center" valign="middle">-14,3</entry><entry align="center" valign="middle">16,3</entry></row><row><entry align="center" valign="middle">Trioctylammonium octyl sulfate *</entry><entry align="center" valign="middle">-5,7</entry><entry align="center" valign="middle">-10,0</entry><entry align="center" valign="middle">1,7</entry></row><row><entry align="center" valign="middle">1,3-dimethylimidazolinium octyl sulfate</entry><entry align="center" valign="middle">-6,0</entry><entry align="center" valign="middle">-16,6</entry><entry align="center" valign="middle">11,5</entry></row><row><entry morerows="1" align="center" valign="middle">VM470</entry><entry align="center" valign="middle">1-ethyl-3-methylimidazolinium tosylate</entry><entry align="center" valign="middle">-4,0</entry><entry align="center" valign="middle">-14,9</entry><entry align="center" valign="middle">10,3</entry></row><row><entry align="center" valign="middle">1,3-dimethylimidazolinium octyl sulfate</entry><entry align="center" valign="middle">-4,5</entry><entry align="center" valign="middle">-18,0</entry><entry align="center" valign="middle">13,6</entry></row></tbody></tgroup><tgroup cols="5" rowsep="0"><colspec colnum="1" colname="col1" colwidth="25mm" /><colspec colnum="2" colname="col2" colwidth="58mm" /><colspec colnum="3" colname="col3" colwidth="17mm" /><colspec colnum="4" colname="col4" colwidth="17mm" /><colspec colnum="5" colname="col5" colwidth="21mm" /><tbody><row><entry namest="col1" nameend="col5" align="justify">* Reference example</entry></row></tbody></tgroup></table></tables>

0070By using ionic liquids as plasticizers, a lowering of the melting and glass temperature is achieved and thus an improved thermoplastic processing is possible.