DE102017010165A1 - Self-healing polymers and their use - Google Patents

Abstract

Described are polymers containing functional groups of the formula I. -NR ₁ -CO-X-Ar ₁ - (X-CO-NR ₂ ) _n - (I) wherein
X is a bivalent radical of the formula -O-, -S- or -NR ₂ -,
R ₁ and R ₂ independently of one another are hydrogen, C ₁ -C ₆ -alkyl or aryl,
Ar _{1 is} an n + 1-valent carbocyclic-aromatic radical or an n + 1-valent radical
Ar ₄ - (C _a H _2a ) _b , wherein a is an integer from 1 to 4, and b is an integer from 1 to 4
is n, Ar _{4 is} an n + 1-valent carbocyclic-aromatic radical and wherein the radicals
Ar ₁ and Ar ₄ bear at least one substituent selected from the group haloalkyl, nitro, nitrile, fluorine, chlorine, bromine, carboxyl, carboxyl ester, carboxylamide, sulfonic acid, sulfonic acid ester, sulfonamide, formyl or alkylcarbonyl, or A _{1 is} an n + Is a monovalent heterocyclic aromatic radical or an n + 1-valent radical Ar ₅ - (C _a H _2a ) _b, wherein a is an integer from 1 to 4, and b is an integer from 1 to n, Ar _{5 is} an n + 1-valent heterocyclic aromatic radical and wherein the radicals Ar ₁ and Ar ₅ optionally carry one or more substituents which are preferably selected from the group haloalkyl, nitro, nitrile, fluorine, chlorine, bromine, carboxyl, carboxyl ester , Carboxylamide, sulfonic acid, sulfonic acid ester, sulfonic acid amide, formyl or alkylcarbonyl, and
n is an integer from 1 to 4.
The polymers have self-healing properties and in the form of polymer networks also vitrimeres behavior. They can be used in particular for the production of coatings.

Description

The invention relates to self-healing polymers which are crosslinked by at least one reversible urethane bond, their preparation and use, for example as construction materials or as coating materials.

Self-healing polymers are already known. These materials are able to partially or completely heal mechanical damage and thus at least partially regenerate the original material properties. They are therefore particularly suitable as a coating material to prevent corrosion occurring or make it difficult. Furthermore, applications as a construction material are possible.

From an economic point of view it is crucial that self-healing polymers are synthetically readily accessible and that it is possible to repair damage (healing) under relatively simple conditions.

Vitrimerartige polymers, also called vitrimers, are polymers which behave like a thermoset at room temperature, so form a highly crosslinked polymer. By increasing the temperature, reversible groups present in the polymer are split, as a result of which a partial dissolution of the polymer network takes place, thereby softening the material. This allows a variety of properties, such as a slight thermal processability or the possibility of recycling, which is not possible with ordinary thermosets.

Known self-healing polymers can basically be subdivided into two types. On the one hand there are extrinsic and on the other hand intrinsic self-healing polymers. In the case of extrinsic healing, a cure is needed which must be present in a reservoir in the polymer matrix. This embedding can be done in different ways.

On the one hand, the use of (nano) capsules is possible ( SR White, NR Sottos, PH Geubelle, JS Moore, MR Kessler, SR Sriram, EN Brown, S. Viswanathan: "Autonomic Healing of Polymer Composites", Nature, 409, 2001, 794-797 ) or on the other hand, vascular networks are possible ( KS Toohey, NR Sottos, JA Lewis, JS Moore, SR White: "Self-healing materials with microvascular networks", Nat. Mater., 6, 2007, 581-585 and KS Toohey, NR Sottos, JA Lewis, JS Moore, SR White: "Self-healing materials with microfluidic networks" . WO 2009029319 A2 ). Various polymer matrices are used, such as epoxy resins ( SR White, NR Sottos, PH Geubelle, JS Moore, MR Kessler, SR Sriram, EN Brown, S. Viswanathan: "Autonomic Healing of Polymer Composites", Nature, 409, 2001, 794-797 ), Polyurethanes ( JF Patrick, NR Sottos, SR White: "Microvascular based self-healing polymeric foam", Polymer, 53, 2012, 4231-4240 ) or polysiloxanes ( MW Keller, SR White, NR Sottos: "A self-healing poly (dimethylsiloxane) elastomer", Adv. Funct. Mater. 17, 2007, 2399-2404 ). Healing agents used are mainly derivatives which are suitable for a ring-opening polymerization ( SR White, NR Sottos, PH Geubelle, JS Moore, MR Kessler, SR Sriram, EN Brown, S. Viswanathan: "Autonomy healing of polymer composites", Nature, 409, 2001, 794-797 ). In addition, a catalyst is necessary, which induces cross-linking after the capsule has opened, thus enabling healing ( PV Brown, SH Cho, SR White, NR Sottos, HM Andersson: "Self-healing polymers" . WO2006 / 121609 A1 ).

Examples of further crosslinking reaction are Michael additions, but also the reaction of isocyanates with alcohols (formation of urethanes) ( J. Yang, MW Keller, JS Moore, SR Wwhite, NR Sottos: "Microencapsulation of isocyanates for self-healing polymers", Macromolecules 41, 2008, 9650-9655 ) or thiols (formation of thiourethanes) ( XKD Hillewaere, RFA Teixeira, LTT Nguyen, JA Ramos, H. Rahier, FE Du Prez: "Autonomous self-healing of epoxy thermosets with thiol-isocyanate chemistry", Adv. Funct. Mater., 24, 2014, 5575-5583 ). The capsules are usually made of polyureas, polyurethanes or mixtures of these two.

The concept of intrinsic self-healing is based on the ability of a material to crack without additional encapsulated healing agent. For this, however, reversible chemical processes are necessary to enable a cure.

These may be on the one hand supramolecular interactions, such as metal-ligand bonds ( M. Burnworth, L. Tang, JR Kumpfer, AJ Duncan, FL Beyer, GL Fiore, SJ Rowan, C. Neither: "Optically Healable Supramolecular Polymers", Nature, 472, 2011, 334-337 ) or ionic interactions ( SJ Kalista Jr., JR Pflug, RJ Varley: "Effect of ionic content on ballistic self-healing in EMAA copolymer and ionomers", Polym. Chem, 4, 2013, 4910-4926 ). In addition, π-π interactions can also be used ( S. Burattini, BW Greenland, DH Merino, W. Weng, J, Seppala, HW Colquhoun, W. Hayes, ME Mackay, IW Hamley, SJ Rowan: "A Healable Supramolecular Polymer Blend Based on Aromatic π-π Stacking and Hydrogen bonding interactions ", J. Am. Chem. Soc., 132, 2010, 12051-12058 ).

Another important supramolecular dynamic system is hydrogen bonding. These can have different molecular structures to generate the necessary reversibility of the interaction, such as ureidopyrimidine ( A. Faghihnejad, KE Feldman, J. Yu, MV Tirrell, JN Israelachvili, CJ Hawker, EJ Kramer, H. Zeng: "Adhesion and surface interactions of a self-healing polymer having multiple hydrogen-bonding groups", Adv. Funct. Mater., 24, 2014, 2322-2333 ), Thymine ( D. Döhler, H. Peterlik, WH Binder: "A dual crosslinked self-healing system: supramolecular and covalent network formation of four-arm star polymers", Polymer, 69, 2015, 264-273 ) or amides ( Y. Chen, Z. Guan: "Self-healing thermoplastic elastomeric elastomer with a glassy polymethylmethacrylate backbone and rubbery polyacrylate-amide brushes", Polymer, 69, 2015, 249-254 ).

In addition, the hydrogen bonds between ureas ( P. Cordier, F. Tournilhac, C. Soulie-Ziakovic, L. Leibler: "Self-healing and thermoreversible rubber from supramolecular assembly", Nature, 451, 2007, 977-980 ) and urethanes (C.T. Ho: "Reactive two-part polyurethane compositions and optionally self-releasable and scratch-resistant coatings prepared therefrom", WO 1996/10595 A1 and JP Harmon, R. Bass: "Self-healing polycarbonate containing polyurethane nanotube composite", US 8,846,801 B1 ), most of which are low glass point polymers to allow self-healing.

In addition to these supramolecular interactions, it is also possible to use reversible covalent systems. For this, mostly the Diels-Alder reaction has been used ( X. Chen, MA Dam, K. Ono, H. Shen, SR Nutt, K. Sheran, F. Wudl: "A thermally remanent cross-linked polymeric material", Science, 295, 2002, 1698-1702 ), but also dynamic imine reactions ( H. Li, J. Bai, Z. Shi, Yin: "Environmental friendly polymer based on ship-base reaction with self-healing, remolding and degradable ability", Polymer, 85, 2016, 106-113 ). Furthermore, acylhydrazone bonds ( Kuhl, S. Bode, RK Bose, J Vitz, A. Seifert, S. Hoeppener, SJ Garcia, S. Spange, S. van der Zwaag, MD Hager, US Schubert: "Acylhydrazones as reversible covalent crosslinkers for self- healing polymers ", Adv. Funct. Mater., 25, 2015, 3295-3301 ) are used for self-healing polymers. Finally, it is also possible to use reversible urea bonds (U. Burckhardt: "Polyurethane polymer for reversible adhesive bonds", US 2010/0273008 A1 However, sterically hindered amines must be used to provide an opening by increasing the temperature (Cheng J., Ying: "Dynamic urea bonds for reversible and self-healing polymers"). WO2014 / 144539 A2 and J. Cheng, H. Ying, Y. Zhang: Dynamic urea bonds for polymers. WO 2016 / - 069582 A1 or by addition of water (MW Urban, Y. Yang: "Self-repairing polyurethane networks", WO 2015/073075 A1 ) to effect.

Similar groups are also used in the production of vitrimers. Again, dynamic bonds in a polymer network are necessary, such as esters ( D. Montarnal, M. Capelot, F. Tournilhac, L. Leibler: "Silica-like malleable materials from permanent organic networks", Science, 334, 2011, 965-968 and C. Duquenne, M. Melas, S. Beaudrais: "Composition for manufacturing vitrimer resins of epoxy / anhydride type comprising a polyol", WO2015 / 162356 A2 ) and imines (W. Zhang, P. Taynton: "Covalently cross-linked malleable polymers and methods for use", US 9,453,099 B2 and A. Chao, I. Negulescu, D. Zhang: "Dynamic covalent polymer networks based on degenerative imine bond exchange: tuning the malleability and self-healing properties by solvent", Macromolecules, 49, 2016, 6277-6284 ).

It was also possible to use polyhydroxyurethanes for the production ( DJ Fortman, J P. Brutman, CJ Cramer, MA Hillmyer, WR Dichtel: "Mechanically Activated, Catalyst-Free Polyhydroxyurethane Vitrimers", J. Am. Chem. Soc., 137, 2015, 14019-14022 and G. Beniah, K. Lun, WH Heath, MD Miller, KA Scheidt, JM Torkelson: "Novel thermoplastic polyhdroxyurethane elastomers as effective damping materials over broad-temperature ranges", Eur. Polym. J., 84, 2016, 770-783 ), although additional hydroxyl groups allowed an exchange at very high temperatures (above 180 ° C) in the first place. Finally, vinylogous urethanes can also be used for the production of vitrimers, whereby additional hydroxyl or amino groups are necessary in order to generate the properties ( W. Denissen, G. Rivero, R. Nicolay, L. Leibler, JM Winne, FE Du Prez: "Vinylogous urethane vitrimers", Adv. Funct. Mater., 25, 2015, 2451-2457 ).

Here, however, the actual urethane bond is not involved in the reversibility of the bond, it merely increases the reactivity of the exchange reaction.

Even urethane bonds per se can be thermally reversible under certain circumstances. However, this effect has hitherto been used only to allow improved processing of such polymers at very high temperatures (RA Markle, PL Brusky, GE Cremeans: "Thermally-reversible isocyanate polymers", WO1991 / 011476 A2 and RA Markle, JD Elhard, D.M, Bigg, S. Sowell, PL Brusky, GE Cremeans: "Thermally-reversible isocyanate polymers", US 5,387,667 A ). However, only very high opening temperatures (well over 150 ° C) have been described so far (FC Onwumere, JF Pazos: "Thermally reversible polymers", US 5,491,210 A ). Thus, in the current state of the art self-healing at temperatures of up to 150 ° C is not possible with such systems.

The invention is based on the object of providing polymers with a significantly reduced opening temperature of the urethane bond, for example with an opening temperature of 150 ° C. or below.

The invention is also based on the object to provide self-healing polymers with vitrimeren properties.

The invention relates to polymers containing functional groups of the formula I. -NR ₁ -CO-X-Ar ₁ - (X-CO-NR ₂ ) _n - (I) wherein
X is a bivalent radical of the formula -O-, -S- or -NR ₂ -,
R ₁ and R ₂ independently of one another are hydrogen, C ₁ -C ₆ -alkyl or aryl,
Ar _{1 is} an n + 1-valent carbocyclic aromatic radical or an n + 1-valent radical Ar ₄ - (C _a H _2a ) _b , wherein a is an integer from 1 to 4, preferably from 1 to 2, and especially preferred is 1, and b is an integer from 1 to n, preferably 1 or 2 and especially 1, Ar _{4 is} an n + 1-valent carbocyclic aromatic radical and wherein Ar ₁ and Ar ₄ bear at least one substituent, which is selected from the group haloalkyl, preferably mono- or perfluoroalkyl, nitro, nitrile, fluorine, chlorine, bromine, carboxyl, carboxyl ester, carboxylamide, sulfonic acid, sulfonic acid ester, sulfonamide, formyl or alkylcarbonyl, or A _{1 is} an n + 1- is a valent heterocyclic aromatic radical or an n + 1-valent radical Ar ₅ - (C _a H _2a ) _b , wherein a is an integer from 1 to 4, preferably from 1 to 2 and more preferably from 1, and b is one is an integer from 1 to n, preferably 1 or 2 and especially 1, Ar _{5 is} an n + 1-valent heterocyclic-aromatic radical and wherein the radicals Ar ₁ and Ar ₅ optionally carry one or more substituents which are preferably selected from the group haloalkyl, preferably mono- or perfluoroalkyl, nitro, nitrile, fluorine, chlorine, bromine, carboxyl, carboxyl ester, carboxylamide, sulfonic acid, Sulfonic acid ester, sulfonic acid amide, formyl or alkylcarbonyl, and
n is an integer from 1 to 4, and particularly preferably 1 or 2.

The polymers according to the invention have self-healing properties and can be processed thermoplastically at comparatively low temperatures.

Surprisingly, this is also possible when the polymers according to the invention are in the form of a polymer network. By using electron-deficient aromatic compounds as a functional building block of urethane, thiourethane or urea bonding, it is possible to create covalent bonds that can be reversibly opened at comparatively low temperatures.

The polymer networks according to the invention exhibit vitrimeric behavior. Thus, these polymers have thermoset properties, but at the same time they can be processed as thermoplastics using high temperatures, but well below the decomposition temperature.

In order to generate the self-healing properties and the vitrimere behavior, according to the invention as a component an electron-poor aromatic amino or hydroxy compound having at least one further hydroxy, thiol or amino group is used, which in combination with a polyisocyanate compound, a polymer containing functional groups of the formula I trains.

To produce the functional groups of the formula I-containing polymers, compounds of the formula II can be reacted with compounds of the formula IIa to give polymers containing the structural unit of the formula III HX-Ar ₁ - (XH) _n (II), OCN-R ₃ - (NCO) _m (IIa), -X-Ar ₁ - (X-CO-NH-R ₃ - (NH-CO-) _m ) _n - (III) wherein
X, R ₂ and Ar ₁ and n have the meaning defined above,
R _{3 is} an m + 1-valent aliphatic, cycloaliphatic, carbocyclic-aromatic radical, heterocyclic-aromatic radical or aralkyl radical which is unsubstituted or bears at least one substituent selected from the group alkyl, alkoxy, haloalkyl, cycloalkyl, aryl , Heterocyclyl, halogen, amino, hydroxy, nitro, nitrile, carboxyl, carboxyl ester, carboxylamide, sulfonic acid, sulfonic acid ester, sulfonic acid amide, formyl or alkylcarbonyl, and
m is an integer from 1 to 4, preferably 1 or 2.

Alternatively, functionalized monomers of formula IIIa can be reacted with compounds of formula II to form monomers of formula I containing polymers containing isocyanate functional groups of formula I to give monomers of formula IIIb, which are then polymerized HX-Ar ₁ - (XH) _n (II), M-BG-R ₃ - (NCO) _m (purple), M-BG-R ₃ - ((NH-CO-X-Ar ₁ - (X-CO-NH) -R ₃ -BG-M) _n ) _m (IIIb), wherein
X, Ar ₁ , R ₃ , m and n have the meanings defined above,
M is an organic radical having at least one polymerizable double bond, and
BG is a covalent bond or a divalent organic radical.

In a further embodiment, to produce the polymers containing functional groups of the formula I, polyisocyanates of the formula III can be reacted with monomers of the formula IIIc functionalized with HX groups to give monomers of the formula IIId, which are subsequently polymerized OCN-R ₃ - (NCO) _m (III), M-BG-X-Ar ₁ (XH) _n (IIIc), M-BG-X-Ar ₁ - (X-CO-NH-R ₃ - (NH-CO-X-Ar ₁ - (X-BG-M) _m ) _n ) _m (IIId) wherein
X, Ar ₁ , R ₃ , BG, M, m and n have the meanings defined above.

In this description, if one of the radicals is alkyl, then the alkyl group can be both branched and unbranched. An alkyl group typically contains one to twenty carbon atoms, preferably one to ten carbon atoms. Examples of alkyl groups are: methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, pentyl, n-hexyl, n-heptyl, 2-ethylhexyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl or eicosyl. Particularly preferred are alkyl groups having one to six carbon atoms. Alkyl groups may be optionally substituted, for example, with alkoxy, haloalkyl, cycloalkyl, aryl, heterocyclyl, halogen, amino, hydroxy, nitro, nitrile, carboxyl, carboxyl, carboxylamide, sulfonic, sulfonic, sulfonic, formyl or alkylcarbonyl.

In this description, if one of the radicals alkoxy, the alkoxy group may consist of an alkyl moiety, which may be both branched and unbranched. An alkoxy group typically contains one to twenty carbon atoms, preferably one to ten carbon atoms. Examples of alkoxy groups are: methoxy, ethoxy, isopropoxy, n-butoxy, sec-butoxy, tert-butoxy, pentyloxy, n-hexyloxy, n-heptyloxy, 2-ethylhexyloxy, n-octyloxy, n-nonyloxy, n-decyloxy , n-Tridecyloxy, n-tetradecyloxy, n-pentadecyloxy, n-hexadecyloxy, n-octadecyloxy or eicosyloxy. Particularly preferred are alkoxy groups having one to six carbon atoms.

In this description, if one of the radicals haloalkyl, the haloalkyl group may be both branched and unbranched. A haloalkyl group typically contains one to twenty carbon atoms, which in turn are independently substituted with one or more halogen atoms, preferably one to ten carbon atoms. Examples of halogen atoms are fluorine, chlorine, bromine or iodine. Preference is given to fluorine and chlorine. Examples of haloalkyl groups are: trifluoromethyl, difluoromethyl, fluoromethyl, bromodifluoromethyl, 2-chloroethyl, 2-bromoethyl, 1,1-difluoroethyl, 2,2,2-trifluoroethyl, 1,1,2,2-tetrafluoroethyl, 2-chloro-1 , 1,2-trifluoroethyl, pentafluoroethyl, 3-bromopropyl, 2,2,3,3-tetrafluoropropyl, 1,1,2,3,3,3-hexafluoropropyl, 1,1,1,3,3,3-hexafluoropropyl , 3-bromo-2-methylpropyl, 4-bromobutyl, perfluoropentyl.

Preferred haloalkyl groups are part or perfluoroalkyl groups having one to six carbon atoms, in particular pentafluoroethyl or trifluoromethyl.

In this specification, when one of the radicals is cycloalkyl, the cycloalkyl group is typically a cyclic group containing three to eight, preferably five, six or seven ring carbon atoms, each of which may be independently substituted. Examples of substituents are alkyl groups or two alkyl groups which can form another ring together with the ring carbons to which they are attached. Examples of cycloalkyl groups are cyclopropyl, cyclopentyl or cyclohexyl. Cycloalkyl groups may be optionally substituted, for example, with alkyl, alkoxy, haloalkyl, cycloalkyl, aryl, heterocyclyl, halogen, amino, hydroxy, nitro, nitrile, carboxyl, carboxyl, carboxylamide, sulfonic, sulfonic, sulfonic, formyl or alkylcarbonyl.

In this specification, when one of aryl or a carbocyclic aromatic group is used, the aryl group is typically a cyclic aromatic group containing five to fourteen ring carbon atoms, each of which may be independently substituted. Examples of substituents are alkyl groups or two alkyl groups which together with the ring carbon atoms to which they are attached can form a further ring. Examples of aryl groups are naphthyl, biphenyl, anthryl or especially phenyl. Aryl groups may be optionally substituted, for example, with alkyl, alkoxy, haloalkyl, cycloalkyl, aryl, heterocyclyl, halogen, amino, hydroxy, nitro, nitrile, carboxyl, carboxyl, carboxylamide, sulfonic, sulfonic, sulfonic, formyl or alkylcarbonyl. Aryl radicals Ar ₁ have at least one electron-withdrawing substituent selected from the group haloalkyl, nitro, nitrile, fluorine, chlorine, bromine, carboxyl, carboxyl ester, carboxylamide, sulfonic acid, sulfonic acid ester, sulfonic acid amide, formyl or alkylcarbonyl.

In this description, if one of the radicals heterocyclyl, this is typically a cyclic group having three to ten ring carbon atoms and having at least one ring heteroatom, each of which may be substituted independently of one another. Examples of substituents are alkyl groups, or two alkyl groups which together with the ring carbons to which they are attached can form a further ring. Examples of heteroatoms are oxygen, nitrogen, phosphorus, boron, selenium or sulfur. Examples of heterocyclyl groups are furyl, thienyl, pyrrolyl, imidazolyl, pyridyl or piperidinyl. Heterocyclyl groups are preferably aromatic and are also referred to as heteroaryl groups. Heterocyclyl groups may optionally be substituted, for example with alkyl, alkoxy, haloalkyl, cycloalkyl, aryl, heterocyclyl, halogen, amino, hydroxy, nitro, nitrile, carboxyl, carboxyl ester, carboxylamide, sulfonic acid, sulfonic acid ester, sulfonamide, formyl or alkylcarbonyl. Heteroaryl radicals Ar ₁ can be unsubstituted or substituted. Substituted heteroaryl radicals preferably have at least one electron-withdrawing substituent selected from the group haloalkyl, nitro, nitrile, fluorine, chlorine, bromine, carboxyl, carboxyl ester, carboxylamide, sulfonic acid, sulfonic acid ester, sulfonic acid amide, formyl or alkylcarbonyl. Preferred heteroaryl radicals are unsubstituted radicals having one to three ring nitrogen atoms or having at least one electron-withdrawing substituent selected from the group haloalkyl, nitro, nitrile, fluorine, chlorine, bromine, carboxyl, carboxyl ester, carboxylamide, sulfonic acid, sulfonic acid ester, sulfonic acid amide, Formyl or alkylcarbonyl substituted radicals having one to three ring nitrogen atoms.

In this description, if one of the radicals is an aralkyl radical, then the aralkyl group is typically an aryl group, wherein aryl has previously been defined, to which at least one alkyl group is covalently bonded. The aralkyl group may be substituted on the aromatic ring, for example with alkyl groups or with halogen atoms. An example of an aralkyl group is benzyl. Aralkyl groups may be optionally substituted, for example, with alkyl, alkoxy, haloalkyl, cycloalkyl, aryl, heterocyclyl, halogen, amino, hydroxy, nitro, nitrile, carboxyl, carboxyl, carboxylamide, sulfonic, sulfonic, sulfonic, formyl or alkylcarbonyl.

In this description, if a radical is amino, it is a radical of the formula -NR ₄ R ₅ , in which R ₄ and R _5, independently of one another, denote hydrogen or an organic radical, preferably hydrogen or an alkyl group having one to six carbon atoms.

In this description, if one of the radicals is halogen, then it is understood to mean a covalently bonded fluorine, chlorine, bromine or iodine atom. Preference is given to fluorine or chlorine.

In this description, a radical carboxyl ester, it is a radical of the formula -CO-OR ₆ , wherein R _{6 is} an organic radical, preferably an alkyl group and in particular an alkyl group having one to six carbon atoms.

In this description, a radical carboxamide, it is a radical of the formula -CO-NR ₄ R ₅ , wherein R ₄ and R _{5 are} independently hydrogen or an organic radical, preferably hydrogen or an alkyl group having one to six carbon atoms.

In this description, a radical sulfonic acid ester, so it is a radical of the formula -SO ₂ -OR ₆ , wherein R _{6 is} an organic radical, preferably an alkyl group and especially an alkyl group having one to six carbon atoms.

In this description, a radical sulfonic acid amide, it is a radical of the formula -SO ₂ -NR ₄ R ₅ , wherein R ₄ and R _{5 are} independently hydrogen or an organic radical, preferably hydrogen or an alkyl group having a six carbon atoms.

In this description, a radical alkylcarbonyl, it is a radical of the formula -CO-R ₆ , wherein R _{6 is} an alkyl radical, preferably an alkyl group having one to six carbon atoms.

Preference is given to polymers in which X is a bivalent radical of the formula -O- and / or -NH-.

Very particular preference is given to polymers in which X is -O-.

Also preferred are polymers in which R ₁ and R _{2 are} hydrogen.

Further preferred polymers contain radicals of the formula I in which Ar _{1 is} a divalent or trivalent carbocyclic aromatic radical, a divalent or trivalent heterocyclic aromatic radical, a radical -Ar ₄ -CH ₂ -,> Ar ₄ -CH ₂ - , -Ar ₅ -CH ₂ - or> Ar ₅ -CH ₂ -, wherein Ar ₄ is a divalent or trivalent carbocyclic aromatic radical and Ar ₅ divalent or trivalent heterocyclic-aromatic radical and in which the radicals Ar _1, Ar ₄ and Ar ₅ carry one or two substituents which are selected from the group haloalkyl, in particular para or perfluoroalkyl, nitro, nitrile, fluorine, chlorine, bromine, carboxyl, carboxyl ester, carboxylamide, sulfonic acid, sulfonic acid ester, sulfonic acid amide, formyl or alkylcarbonyl or in which Ar _{1 is} an unsubstituted divalent or trivalent heterocyclic aromatic radical or an unsubstituted radical -Ar ₅ -CH ₂ - or> Ar ₅ -CH ₂ -, where Ar _{5 is} a di- or trihydric heterocyclic-aromatic radical is, in particular a two- or trivalent heterocyclic-aromatic radical having one to three, in particular having one or two ring nitrogen atoms.

Further preferred polymers contain di- or trivalent radicals R ₃ which are unsubstituted or which have one or two radicals selected from the group consisting of alkyl, alkoxy, haloalkyl, in particular perfluoroalkyl, cycloalkyl, aryl, heterocyclyl, halogen, amino, hydroxyl, nitro, nitrile , Carboxyl, carboxyl ester, carboxylamide, sulfonic acid, sulfonic acid ester, sulfonic acid amide, formyl or alkylcarbonyl.

As stated above, the polymers of the invention contain structural units of the formula I which are derived from selected electron-poor aromatic amino, thiol or hydroxy compounds and from polyisocyanates.

worin X, Ar₁, n und m die oben definierten Bedeutungen besitzen,
R₇ ein m+1-wertiger organischer Rest ist, und
o eine Zahl von größer gleich 2 ist.The polymers according to the invention can be in the form of polymer chains in which groups of the formula I are present. Examples of polymers of this type are compounds of the formula IV

wherein X, Ar ₁ , n and m have the meanings defined above,
R _{7 is} an m + 1-valent organic radical, and
o is a number greater than or equal to 2.

worin X, Ar₁, n und m die oben definierten Bedeutungen besitzen,
R₇ ein 2-wertiger organischer Rest ist, und
o eine Zahl von größer gleich 1, insbesondere von 10 bis 100000 ist, und ganz besonders bevorzugt von 10 bis 1000.Preferred polymers of this type are those of the formula IVa

wherein X, Ar ₁ , n and m have the meanings defined above,
R _{7 is} a divalent organic radical, and
o is a number greater than or equal to 1, in particular from 10 to 100,000, and most preferably from 10 to 1000.

worin X, Ar₁, n und m die oben definierten Bedeutungen besitzen,
R₇ ein n+1-wertiger organischer Rest ist,
o eine Zahl von größer gleich 1 ist,
ME eine von einem polymerisierbaren Monomer abgeleitete wiederkehrende Struktureinheit ist,
BG eine kovalente Bindung oder ein zweiwertiger organischer Rest ist, und
p eine ganze Zahl von 2 bis 10000000, vorzugsweise von 10 bis 100000, besonders bevorzugt von 20 bis 50000, und ganz besonders bevorzugt von 20 bis 1000 ist.The polymers of the present invention may also be in the form of main chain and one or more side chain polymer chains containing groups of formula I in the backbone and / or side chains. Examples of polymers of this type are compounds of the formula V or compounds of the formula VI

wherein X, Ar ₁ , n and m have the meanings defined above,
R _{7 is} an n + 1-valent organic radical,
o is a number greater than or equal to 1,
ME is a repeating structural unit derived from a polymerizable monomer,
BG is a covalent bond or a divalent organic radical, and
p is an integer from 2 to 10,000,000, preferably from 10 to 100,000, more preferably from 20 to 50,000, and most preferably from 20 to 1,000.

Examples of divalent groups BG are alkylene, alkenylene or arylene radicals, where alkylene radicals may have one or more oxygen atoms which are not directly adjacent to one another or imino groups in the alkylene chain.

Preferably, bridging groups BG are attached to the polymer backbone ME via functional groups. Examples of functional groups are -CO-O-, -CO-, -CO-NH-, -NH- or -S-, preferably -O- or -CO-O-. Functional groups may themselves be bridging groups BG or, together with the remainder -BG-X, bring about a binding of the radical Ar ₁ to the polymer skeleton.

Preferably, bridging groups BG are alkylene radicals having from one to twenty carbon atoms, alkenylene or alkynylene radicals having from two to twenty carbon atoms and a double or triple bond, polyalkylene glycol radicals having from one to fifty alkylene oxide repeating units, radicals of the formulas -O-, -S-, -NH-, -Si (CH ₃ ) ₂ -O-, -CO-, -CO-O-, -CO-NR ₂₁ - with R ₂₁ as hydrogen, alkyl or aryl, -CO-, - C ₆ H ₄ - in which the two free bonds are in the ortho-meta or para position, or -C ₆ H ₄ -CH ₂ - in which the free bond and the -CH ₂ - group in ortho, meta - or para-position to each other.

Bridging groups BG are particularly preferably alkylene radicals having from one to six carbon atoms, bivalent polyethyleneglycol radicals having from one to twenty ethylene oxide repeat units, zeolitic polypropylene glycol radicals having from one to twenty propylene oxide repeat units, or ortho, meta or para radicals. phenylene.

worin R₂₁ Wasserstoff, Aryl oder Alkyl bedeutet, insbesondere Wasserstoff oder C₁-C₆-Alkyl, und ganz besonders bevorzugt Wasserstoff oder Methyl,
p eine ganze Zahl von 1 bis 6 ist und
q eine Zahl von mindestens 1, vorzugsweise von 1 bis 50 und insbesonder von 1 bis 20 ist.Examples of particularly preferred bridging groups BG are those of the formulas listed below

in which R _{21 is} hydrogen, aryl or alkyl, in particular hydrogen or C ₁ -C ₆ -alkyl, and very particularly preferably hydrogen or methyl,
p is an integer from 1 to 6 and
q is a number of at least 1, preferably from 1 to 50 and especially from 1 to 20.

worin X, ME, BG, o und p die oben definierten Bedeutungen besitzen,
Ar₂ ein zweiwertiger carbocyclisch-aromatischer Rest, ein zweiwertiger heterocyclisch-aromatischer Rest, ein Rest -Ar₄-CH₂- oder -Ar₅-CH₂-, wobei Ar₄ ein zweiwertiger carbocyclisch-aromatischer Rest ist und Ar₅ ein zweiwertiger heterocyclisch-aromatischer Rest ist und wobei die Reste Ar₂, Ar₄ und Ar₅ mindestens einen Substituenten tragen, der ausgewählt wird aus der Gruppe Haloalkyl, insbesondere Teil- oder Perfluoroalkyl, Nitro, Nitril, Fluor, Chlor, Brom, Carboxyl, Carboxylester, Carboxylamid, Sulfonsäure, Sulfonsäureester, Sulfonsäureamid, Formyl oder Alkylcarbonyl,
R₇ ein 2-wertiger organischer Rest ist, und
o eine Zahl von größer gleich 1, insbesondere von 10 bis 100000 ist.Preferred polymers of the above-mentioned type of the formula V or VI are those of the formula Va or VIa

wherein X, ME, BG, o and p have the meanings defined above,
Ar _{2 is} a divalent carbocyclic aromatic radical, a divalent heterocyclic aromatic radical, a radical -Ar ₄ -CH ₂ - or -Ar ₅ -CH ₂ -, wherein Ar _{4 is} a divalent carbocyclic aromatic radical and Ar _{5 is} a divalent heterocyclic -aromatic radical and wherein the radicals Ar ₂ , Ar ₄ and Ar ₅ carry at least one substituent which is selected from the group haloalkyl, especially partial or perfluoroalkyl, nitro, nitrile, fluorine, chlorine, bromine, carboxyl, carboxyl ester, carboxylamide , Sulfonic acid, sulfonic acid ester, sulfonic acid amide, formyl or alkylcarbonyl,
R _{7 is} a divalent organic radical, and
o is a number greater than or equal to 1, in particular from 10 to 100,000.

The polymers according to the invention can also be present in the form of a polymer network in which individual polymer chains are covalently bonded to one another by functional groups of the formula I and, if appropriate, functional groups of the formula I additionally occur in the individual polymer chains.

worin X, Ar₁, Ar₂, ME, BG, R₇, n und m die oben definierten Bedeutungen besitzen, und p eine ganze Zahl von 2 bis 10000000, vorzugsweise von 10 bis 100000 und ganz besonders bevorzugt von 20 bis 50000 ist.Examples of polymers of this type are compounds of the formula VII or of the formula VIII

wherein X, Ar ₁ , Ar ₂ , ME, BG, R ₇ , n and m have the meanings defined above, and p is an integer from 2 to 10,000,000, preferably from 10 to 100,000 and most preferably from 20 to 50,000.

worin X, Ar₂, ME, BG und p die oben definierten Bedeutungen besitzen und R₈ ein 2-wertiger organischer Rest ist.Preferred polymers of this type are those of the formula VIIa or of the formula VIIIa

wherein X, Ar ₂ , ME, BG and p have the meanings defined above and R _{8 is} a 2-valent organic radical.

The polymers according to the invention are preferably in the form of a polymer network.

Very particular preference is given to polymer networks comprising the structures of the formulas VIIa or VIIIa.

The repeating units ME and BG form the backbone of the polymer of the formulas V, VI, Va, VIa, VII, VIII, VIIa or VIIIa.

Examples of classes of compounds which can form the backbone of the polymer are polymers derived from ethylenically unsaturated carboxylic acids or their esters or amides, such as polymethacrylate, polyacrylate, polymethacrylamide, polyacrylamide or polymaleinate, or polymers derived from ethylenically unsaturated aryl compounds, such as polystyrene, or polyurethanes or Polyvinyl ethers, or polymers derived from aliphatic polyenes, such as polybutadiene or polyisoprene.

Polyacrylat BG = -CO- X = -O- ME =

Polymethacrylamid BG = -CO- X = -NH- ME =

Polymaleinat BG = -CO- X = -O- ME =

R = C₁-C₆-Alkyl Polyacrylamid BG = -CO- X = -NH- ME =

Poly(4-hydroxystyrol) BG = kovalente Bindung X = -O- ME =

Polyvinylether BG = kovalente Bindung X = -O- ME =

Polybutadien BG = kovalente X = -O- ME Bindung

Polyisopren BG = kovalente X = -O- ME = Bindung

The following are examples of combinations of the structural units ME and the bridging groups BG for some of the abovementioned classes of substances. It refers to polymethacrylate BG = -CO- X = -O- ME =

polyacrylate BG = -CO- X = -O- ME =

polymethacrylamide BG = -CO- X = -NH- ME =

polymaleate BG = -CO- X = -O- ME =

R = C ₁ -C ₆ -alkyl polyacrylamide BG = -CO- X = -NH- ME =

Poly (4-hydroxystyrene) BG = covalent bond X = -O- ME =

polyvinyl BG = covalent bond X = -O- ME =

polybutadiene BG = covalent X = -O- ME binding

polyisoprene BG = covalent X = -O- ME = binding

Particularly preferred classes of substances which form the backbone of the polymer are polymethacrylates, polyacrylates, polymaleinates, poly (4-hydroxystyrene), polyvinyl ethers, polybutadiene and polyisoprene.

The structural units of the formula I are covalently bonded to the polymer backbone.

The structural units of the formula I-containing polymers can be in the form of linear or three-dimensionally crosslinked polymers, or they can be comb and star polymers, dendrimers, ladder polymers, ring-shaped polymers, polycatenans or polyrotaxanes.

In addition to the above-described structural units, the polymers according to the invention may have further structural units which have been obtained by the use of further comonomers in the polymerization or by functionalization of the (co) polymer.

Examples of such further structural units are those derived from esters or amides of ethylenically unsaturated mono- or dicarboxylic acids, in particular esters or amides of acrylic acid, esters or amides of methacrylic acid, esters or amides of maleic acid, esters or amides of itaconic acid, derived from vinyl esters of saturated aliphatic carboxylic acids and / or of ethylenically unsaturated mono- or dicarboxylic acids.

The preparation of the polymers of the invention can be carried out by the usual polymerization. Examples of these are the bulk polymerization, the polymerization in solution or the emulsion or suspension polymerization. The person skilled in these procedures are known.

For the preparation of the polymers according to the invention, selected electron-poor phenols, thiophenols, amines or aminophenols of the formulas II and / or IIIc defined above can be used and reacted with polyisocyanates of the formulas III and / or IIIa defined above.

Preference is given to using electron-poor compounds of the formula II. These are characterized in that at least one hydroxyl group, amino group or thiol group is bonded to a carbocyclic-aromatic radical which additionally has at least one electron-withdrawing radical, or in that at least one hydroxyl group, amino group or thiol group is bonded to a heterocyclic-aromatic radical, which optionally carries one or more substituents, in particular one or more electron-withdrawing radicals.

Preferred electron-deficient compounds of the formula II are those of the formula IXa or IXb or IXc HO-Ar ₃ -Y (IXa) HS-Ar ₃ -Y (IXb) H ₂ N-Ar ₃ -Y (IXc) wherein
Ar _{3 is} a divalent or trivalent carbocyclic aromatic radical which, besides the groups OH and Y or the groups SH and Y or the groups NH ₂ and Y, bears a substituent which is selected from the group haloalkyl, nitro, nitrile, fluorine , Chlorine, bromine, carboxyl, carboxyl ester, carboxylamide, sulfonic acid, sulfonic acid ester, sulfonic acid amide, formyl or alkylcarbonyl, or Ar _{3 is} a di- or trihydric heterocyclic aromatic radical which in addition to the groups OH and Y or the groups SH and Y or den Groups NH ₂ and Y optionally carries a further substituent which is selected from the group haloalkyl, nitro, nitrile, fluorine, chlorine, bromine, carboxyl, carboxyl esters, carboxylamide, sulfonic acid, sulfonic acid esters, sulfonic acid amide, formyl or alkylcarbonyl, and
Y is a group of the formula -OH, -SH, -NH ₂ , -N (CH ₃ ) H, -alkylene-OH, phenylene-OH, alkylene-NH ₂ , alkylene-N (CH ₃ ) H, alkylene-SH, Phenylene-SH, phenylene-N (CH ₃ ) H or phenylene-NH ₂ .

worin Y die oben definierte Bedeutung hat und
R₉ Haloalkyl, Nitro, Nitril-, Fluor, Chlor, Brom, Carboxyl, Carboxylester, Carboxylamid, Sulfonsäure, Sulfonsäureester, Sulfonsäureamid, Formyl oder Alkylcarbonyl bedeutet.Preferred carbocyclic aromatic compounds of the formula IXa are those of the following formulas

wherein Y has the meaning defined above and
R _{9 is} haloalkyl, nitro, nitrile, fluorine, chlorine, bromine, carboxyl, carboxyl esters, carboxylamide, sulfonic acid, sulfonic acid esters, sulfonic acid amide, formyl or alkylcarbonyl.

worin Y die oben definierte Bedeutung hat und
Rg Haloalkyl, Nitro, Nitril-, Fluor, Chlor, Brom, Carboxyl, Carboxylester, Carboxylamid, Sulfonsäure, Sulfonsäureester, Sulfonsäureamid, Formyl oder Alkylcarbonyl bedeutet.Preferred carbocyclic aromatic compounds of the formula IXb are those of the following formulas

wherein Y has the meaning defined above and
Rg is haloalkyl, nitro, nitrile, fluorine, chlorine, bromine, carboxyl, carboxyl esters, carboxylamide, sulfonic acid, sulfonic acid esters, sulfonic acid amide, formyl or alkylcarbonyl.

worin Y die oben definierte Bedeutung hat und
R₉ Haloalkyl, Nitro, Nitril-, Fluor, Chlor, Brom, Carboxyl, Carboxylester, Carboxylamid, Sulfonsäure, Sulfonsäureester, Sulfonsäureamid, Formyl oder Alkylcarbonyl bedeutet.Preferred carbocyclic aromatic compounds of the formula IXc are those of the following formulas

wherein Y has the meaning defined above and
R _{9 is} haloalkyl, nitro, nitrile, fluorine, chlorine, bromine, carboxyl, carboxyl esters, carboxylamide, sulfonic acid, sulfonic acid esters, sulfonic acid amide, formyl or alkylcarbonyl.

worin Y und Rg die oben definierte Bedeutung haben oder R₉ zusätzlich Wasserstoff bedeuten kann. Preferred heterocyclic aromatic compounds of the formula IXa are those of the following formulas

wherein Y and Rg have the meaning defined above or R _{9 can} additionally denote hydrogen.

worin Y und Rg die oben definierte Bedeutung haben oder Rg zusätzlich Wasserstoff bedeuten kann.Preferred heterocyclic aromatic compounds of the formula IXb are those of the following formulas

wherein Y and Rg have the meaning defined above or Rg may additionally denote hydrogen.

worin Y und R₉ die oben definierte Bedeutung haben oder R₉ zusätzlich Wasserstoff bedeuten kann.Preferred heterocyclic aromatic compounds of the formula IXc are those of the following formulas

wherein Y and R _{9 have} the meaning defined above or R _{9 can} additionally be hydrogen.

wobei mindestens einer der Reste R₁₀, R₁₁, R₁₂ und R₁₃ Nitro, Teil- oder Perfluoralkyl, Nitril, Fluor, Chlor, Brom, Carboxy, Carboxylester, Carboxyl-amid, Alkylcarbonyl oder Formyl ist und die übrigen dieser Reste und die Reste R₁₈ und R₁₉ unabhängig voneinander Wasserstoff, Alkyl, Alkoxy, Cycloalkyl, Aryl oder Aralkyl bedeuten.Examples of particularly preferred electron-deficient compounds of the formula II are those of the formulas below

wherein at least one of R ₁₀ , R ₁₁ , R ₁₂ and R _{13 is} nitro, partial or perfluoroalkyl, nitrile, fluorine, chlorine, bromine, carboxyl, carboxyl, carboxyl amide, alkylcarbonyl or formyl and the remaining of these radicals and the Radicals R ₁₈ and R ₁₉ independently of one another are hydrogen, alkyl, alkoxy, cycloalkyl, aryl or aralkyl.

It is also possible to use mixtures of different electron-poor compounds of the formula II, in particular those of the formulas IXa, IXb or IXc.

These electron-poor compounds of the formula II, in particular those of the formulas IXa, IXb or IXc, can be used for the preparation of self-healing polymers, in particular of polymer networks. For this purpose, it is possible to crosslink with isocyanate groups or thioisocyanate functionalized polymers, such as polyacrylates, polymethacrylates or polyacrylamides, using low-electron aromatic amino or hydroxy compounds by means of urethane thiourethane or urea bonds. Crosslinking can also be achieved by reacting monomers or comonomers functionalized with isocyanate or thioisocyanate groups, for example 2-isocyanatoethyl acrylate and / or 2-isocyanatoethyl methacrylate, with electron-poor aromatic amino or hydroxy compounds and subsequent polymerization. Further, cross-linking can be achieved by reacting compounds functionalized with a plurality of isocyanate or thioisocyanate groups with electron-deficient aromatic amino or hydroxy compounds.

Preferably, these monomers functionalized with isocyanate or thioisocyanate groups and electron-deficient aromatic amino, thiol or hydroxy compounds are reacted with further comonomers.

In these copolymers, the proportion of structural units derived from isocyanate or thioisocyanate functionalized monomers is typically between 1 mol% and 50 mol%, in particular 2 to 10 mol%, of the copolymer.

As further comonomers, esters or amides of ethylenically unsaturated carboxylic acids or ethylenically unsaturated sulfonic acids can be used.

Preference is given to using acrylic acid or methacrylic acid esters or acrylic or methacrylic acid amides and corresponding mixtures thereof. These compounds should be selected so that self-healing of the derived copolymer is possible. For this purpose, the homopolymers prepared from these comonomers should have a lower glass transition temperature than the temperature required for self-healing of the copolymers.

Particularly preferred further comonomers are alkyl esters and alkylamides of acrylic acid and of methacrylic acid. Both branched and unbranched alkyl esters or amides of any chain length are possible. Furthermore, it is also possible to use polyalkylene glycols, such as ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol and relatively long-chain polyethylene glycols, and their unilateral ethers as comonomers.

wobei der Rest R₂₀ entweder Wasserstoff oder Alkyl, der Rest R₂₁ entweder Wasserstoff, Aryl oder Alkyl bedeutet, n 0 bis 21, m 2 bis 6 und x≥1 bedeutet.Preferred examples of ester comonomers are:

where the radical R _{20 is} either hydrogen or alkyl, the radical R _{21 is} either hydrogen, aryl or alkyl, n is 0 to 21, m is 2 to 6 and x≥1.

wobei der Rest R₂₀ Wasserstoff oder Alkyl bedeutet, der Rest R₂₁ Wasserstoff, Alkyl oder Aryl ist, n 0 bis 21, m 2 bis 6 und x eine Zahl von ≥1 ist.Preferred examples of amide comonomers are:

wherein the radical R _{20 is} hydrogen or alkyl, the radical R _{21 is} hydrogen, alkyl or aryl, n is 0 to 21, m is 2 to 6 and x is a number of ≥1.

The invention also includes polyurethanes, polythiourethanes or polyureas, which may preferably be present as polymer networks. In addition to the electron-poor aromatic amino or hydroxy compounds, polyvalent isocyanates or mixtures of different isocyanates or the corresponding thioisocyanates are used for this purpose. The number of (thio) isocyanate units per molecule may vary, but is at least two. Polyisocyanates or polythioisocyanates can also be used. In addition, polyols and mixtures thereof may additionally be used. Again, the number of hydroxyl groups is variable. The proportion of the electron-deficient aromatic amino or hydroxy compounds with respect to the additionally used polyols may vary between 1 and 100 mol%, and is preferably 1 to 20 mol%. The molar ratio of the functionalities (thio) isocyanate to hydroxyl group is usually 1 :1.

Preferably used polyisocyanates are those of formula III defined above.

wobei n ≥ 2 und m ≥ 1 ist.Examples of particularly preferably used polyisocyanates are:

where n ≥ 2 and m ≥ 1.

Preferably, poly [methylene (polyphenyl) isocyanate] can also be used.

Furthermore, it is also possible to use biobased polyisocyanates, these also having to have two or more than two isocyanate units.

For example, esters of lysine, isosorbides and dimers of fatty acids can be used as basic building blocks for these isocyanates. Particularly preferred fatty acids are capric acid, lauric acid, myristic acid, myristoleic acid, palmitic acid, palmitoleic acid, stearic acid, oleic acid, linoleic acid, α-linoleic acid, γ-linoleic acid, stearidonic acid, rumen acid, β-calendulic acid, elaeostearic acid, pinolenic acid, eicosanoic acid, eicosenoic acid, eicosdienoic acid, eicostrienic acid Eicosatetraenoic acid, Eicospenic acid, Mead's acid, Dihomogammalinolenic acid and Arachidonic acid.

wobei R₂₂ Alkyl ist, und
R₂₃ und R₂₄ unabhängig voneinander Wasserstoff, Aryl, Alkoxy oder Alkyl bedeuten.Examples of preferred bio-based polyisocyanates are:

wherein R _{22 is} alkyl, and
R ₂₃ and R ₂₄ independently of one another are hydrogen, aryl, alkoxy or alkyl.

In addition, it is also possible to use blocked multifunctional isocyanates or thioisocyanates, which can be converted by heating in isocyanates or thioisocyanates. Alcohols, phenols, amines, oximes, amides, imides, imidazoles, pyrazoles and triazoles may be mentioned as blocking agents.

Preferably used polyols are those of the formula X. HO-R ₁₀ - (OH) _p (X), wherein R _{10 is} a p + 1-valent alkyl, cycloalkyl, aryl, arylalkyl or heterocyclyl radical, and
p is 1 to 6, in particular 1 or 2.

mit n und m zwischen 0 und 17.Examples of particularly preferably used polyols are:

with n and m between 0 and 17.

It is also possible to use mono- and disaccharides and their completely reduced forms as polyols.

mit m ≥ 1. Weiterhin sind auch verzweigte Polymere mit mehreren Armen, beispielsweise mit 3, 4, 6 oder 8 Armen möglich.Similarly, polymer-based multifunctional alcohols can be used as polyols, the alcohol groups preferably forming the end groups of the polymer chains. These include polyethylene glycol, polypropylene glycol, polytetrahydrofuran and hydroxyl-terminated polyester. Examples for this are:

with m ≥ 1. Furthermore, branched polymers with multiple arms, for example, with 3, 4, 6 or 8 arms are possible.

Likewise, polyhydric aromatic alcohols can be used as polyols. This results in the same basic structures as those of the electron-poor aromatic hydroxyl compounds, but no electron-withdrawing radicals must be present. Instead, any substitution pattern is possible.

The polymers and polymer networks generated in this way have the ability to self-heal. By this is meant in the context of this description that the polymers and polymer networks on the one hand are able to close cracks, and on the other hand are able to regenerate the mechanical properties of the damaged material. This could be proven by tensile test. In addition to self-healing, it is also possible to thermoplastically process these polymers, regardless of whether they are polymer chains or polymer networks. Despite its thermoset nature at room temperature, the polymer networks have a thermoplastic behavior at higher temperatures. These polymer networks can therefore be assigned to the class of vitrimers. This is evident, for example, from the distinctly lower viscosity that could be detected by dynamic mechanical thermal analysis (DMTA).

The polymers of the invention can be formed into moldings of any shape. Examples of these are fibers, films or moldings obtainable from the polymers according to the invention by any desired molding processes, for example by injection molding, pressing, foam injection, internal gas pressure injection molding, blow molding, film casting, calendering, lamination or coating of any desired substrates at elevated temperatures with the polymers according to the invention.

The polymers according to the invention are particularly suitable for the production of coatings.

The invention also relates to the use of the polymers according to the invention for the production of coatings or for the production of moldings.

The following examples illustrate the invention without limiting it.

example 1

As an electron-poor phenol derivative, 4- (hydroxymethyl) -3- (trifluoromethyl) phenol was used. The synthesis was carried out analogously to the procedure of Allen et al. DG Allen, DM Coe, AWJ Cooper, PM Gore, D. House, S. Senger, SL Sollis, S. Vile, C. Wilson, "N-pyrazolyl carboxamides as crac channel inhibitors", WO 2010122089 A1 ), whereby the purification of the synthesis product was changed.

Synthesis of 4- (hydroxymethyl) -3- (trifluoromethyl) phenol:

5.00 g of 4- (hydroxymethyl) -3- (trifluoromethyl) benzoic acid were dissolved in 65 mL of dry tetrahydrofuran under a nitrogen atmosphere and at room temperature. Subsequently, 52 mL borane-THF complex ( 1 M) was added dropwise. Thereafter, the solution was heated at 80 ° C for two hours. After cooling to room temperature, the reaction was quenched by the dropwise addition of dry methanol (43 mL) and finally heated again to 80 ° C for 30 minutes. Finally, the solvent was removed in vacuo and the product was purified by silica column chromatography (chloroform / ethyl acetate 2: 1). The product was obtained as a colorless solid (4.51 g, 98% yield).
¹ H NMR (300 MHz, DMSO d ₆ ): δ = 9.95 (s, 1H, -OH), 7.52 (d, 11-1, Ar-H), 7.01 (m, 2H, Ar-H), 5.27 ( s, 1H, -OH), 4.53 (s, 2H, -CH ₂ ) ppm.
¹³ C NMR (300 MHz, DMSO d ₆ ): δ = 156.6, 131.0, 130.9, 127.1, 126.7, 126.6, 122.9, 119.3, 112.5, 112.4, 59.3, 59.2 ppm.

Elemental analysis:

Calculated C ₈ H ₇ F ₃ O ₂ : C 50.01% H 3.67%
(192.14) found: C 50.21% H 3.71%

Synthesis of a polymer network

4- (Hydroxymethyl) -3- (trifluoromethyl) phenol (0.5 eq.), Butyl methacrylate (20 eq.) And 2-isocyanoethyl methacrylate (1 eq.) Were mixed. Then, 1,4-diazabicyclo [2.2.2] octane (1 wt%) was added as a catalyst, and the solution was allowed to stand at room temperature for 15 minutes and at 70 ° C for additional 15 minutes.

Then benzoin methyl ether (M / I = 200) was added and the solution was polymerized by means of a Dentacolor XS Kulzer for 30 minutes. The resulting polymer network was finally annealed overnight at 100 ° C.

Elemental analysis:

calculated: C 66.36% H 9.53% N 0.45%
found: C 66.71% H 9.60% N 0.80%
Glass transition temperature: 44 ° C
Decomposition temperature: 270 ° C

Thermomechanical analysis

The mechanical properties were determined by means of rheology (temperature-dependent). Here, a softening of the polymer is observed above 70 ° C, indicating vitrimerartiges behavior.

shows some mechanical properties of the polymer as a function of the temperature.

shows the dependence of the viscosity of the polymer as a function of the temperature.

Self-healing of the polymer network

The prepared specimens were cut into two parts by means of a scalpel. Subsequently, the parts of the sample body were brought back into contact and heated to 100 ° C and 150 ° C for two days. As a result, most of the mechanical properties could be restored (see Tables 1 and ) Table 1: Overview of mechanical characteristics for example 1. The values obtained represent average values of several measurements. sample _σmax [MPa] E-module [GPa] Healing efficiency [%] original material 10.4 0.25 - Annealed at 100 ° C for 48 hours 14.3 0.32 - Cured at 100 ° C for 48 hours 1.7 0.49 16 ^a and 12 ^b Annealed at 150 ° C for 48 hours 24.7 0.51 Healed at 150 ° C for 48 hours 7.0 0.51 67 ^a and 28 ^b a: Healing efficiency relative to the original values b: Healing efficiency based on the tempered values at the respective temperature

Example 2

The electron-deficient phenol derivative used was 4-nitrocatechol.

Synthesis of a polymer network

Under an inert gas atmosphere, 153.68 mg of 4-nitrocatechol (0.99 mmol) were dissolved in 5.80 g of polyethylene glycol (M _n = 400 g / mol, 13.87 mmol). Then, 5.40 g of hexamethylene diisocyanate trimer (10.70 mmol) was added and the mixture was filled into the appropriate sample mold. Thereafter, the reaction was allowed to stand under inert conditions for at least four days. The resulting polymer network was finally annealed at 100 ° C overnight.

Elemental analysis:

calculated: C 54.41% H 8.44% N 6.45%
found: C 54.91% H 8.52% N 8.60%
Glass transition temperature: -18 ° C
Decomposition temperature: 302 ° C
Thermomechanical analysis

The mechanical properties were determined by means of rheology (temperature-dependent). Here, a softening of the polyimers is observed above 0 ° C, indicating vitrimerartiges behavior.

shows some mechanical properties of the polymer as a function of the temperature.

shows the dependence of the viscosity of the polymer as a function of the temperature.

Self-healing of the polymer network

The prepared specimens were cut into two parts by means of a scalpel. Subsequently, the parts of the sample body were brought back into contact and heated to 150 ° C for two days. As a result, most of the mechanical properties could be restored (see Table 2): Table 2: Overview of the mechanical characteristics for Example 2. The values obtained represent average values of several measurements. sample _σmax [MPa] E-module [GPa] Healing efficiency [%] Original material 0.9 4.6 - Annealed at 150 ° C for 48 hours 7.8 22.1 - Healed at 150 ° C for 48 hours 3.2 23.6 356 ^a or 41 ^b a: Healing efficiency relative to the original values b: Healing efficiency based on the annealed values at 150 ° C

Example 3

The electron-deficient phenol derivative used was 4-nitrocatechol.

Synthesis of a polymer network

Under a protective gas atmosphere, 76.84 mg of 4-nitrocatechol (0.50 mmol) were dissolved in 6.01 g of polyethylene glycol (M _n = 400 g / mol, 14.37 mmol). Then, 5.40 g of hexamethylene diisocyanate trimer (10.70 was added and the mixture was filled into the appropriate sample mold, after which the reaction was allowed to stand under inert conditions for at least four days, and the resulting polymer network finally became 100 ° C overnight annealed.

Elemental analysis:

calculated: C 53.70% H 8.40% N 6.37%
found: C 54.19% H 8.65% N 7.07%
Glass transition temperature: -19 ° C
Decomposition temperature: 303 ° C

Thermomechanical analysis

The mechanical properties were determined by means of rheology (temperature-dependent). Here, a softening of the polymer is observed above 0 ° C, indicating vitrimerartiges behavior

shows some mechanical properties of the polymer as a function of the temperature.

shows the dependence of the viscosity of the polymer as a function of the temperature.

Self-healing of the polymer network

The prepared specimens were cut into two parts by means of a scalpel. Subsequently, the parts of the sample body were brought back into contact and heated to 150 ° C for two days. As a result, the mechanical properties could largely be restored (see Table 3): Table 3: Overview of the mechanical characteristics for example 3. The values determined represent average values of several measurements. sample _σmax [MPa] E-module [GPa] Healing efficiency [%] Original material 1.0 4.3 - Annealed at 150 ° C for 48 hours 5.3 16.5 - Healed at 150 ° C for 48 hours 2.7 14.9 270 ^a and 51 ^{b ,} respectively a: Healing efficiency relative to the original values b: Healing efficiency based on the annealed values at 150 ° C

Example 4

The electron-deficient phenol derivative used was 2,2'-dinitro-4,4'-biphenol. The synthesis was from the regulation of Liang et al. (Y. Liang, S. Gao, H. Wan, J. Wang, H. Chen, Z. Zheng, X. Hu: "Syntheses and resolutions of new chiral biphenyl backbones: 2-amino-2'-hydroxy-6, 6'-dimethy1-1, 1'-biphenyl and 2-amino-2'-hydroxy-4,4 ', 6,6'-tetramethyl-1,1'-biphenyl ", Tetrahedron: Asymmetry 14, 2003, 1267 1273 ) as well as from Kulkarni et al. (PP Kulkarni, A. Kadam, RB Mane, UV Desai, PP Wadgaonkar: "Demethylation of methyl aryl ethers using pyridine hydrochloride in solvent-free conditions under microwave irradiation", J. Chem. Res., 1999, 394-395 ) adapted.

Synthesis of 4,4'-dimethoxy-2,2'-dinitro-1,1'-biphenyl

5.00 g of 4-iodo-3-nitroanisole (17.92 mmol) were dissolved in 10 mL of dry DMF. The brown solution was heated to 100 ° C. Subsequently, 4.68 g of copper powder (73.63 mmol) was added and the reaction mixture was refluxed for six hours. Thereafter, the copper powder was filtered off and washed with DMF. The solvent was removed in vacuo and 20 mL of distilled water was added. This forms a yellow-brown solid, which was filtered off and recrystallized from ethanol. Finally, the product was purified by silica column chromatography (chloroform).
¹ H NMR (300 MHz, CD ₂ Cl ₂ ): δ = 7.69 (s, 2H, Ar-H), 7.24 (s, 4H, Ar-H), 3.95 (s, 6H, -CH ₃ ) ppm
¹³ C NMR (300 MHz, CD ₂ Cl ₂ ): δ = 159.7, 148.3, 132.3, 125.6, 119.5, 109.5, 56.1 ppm.

Elemental analysis

Calculated C ₁₄ H ₁₂ N ₂ O ₆ : C 55.27% H 3.98% N 9.21%
(304.26) found: C 55.48% H 3.88% N 9.41%
Synthesis of 2,2'-dinitro-4,4'-biphenol

In a 20 mL microwave vessel, 4.30 g of 4,4'-dimethoxy-2,2'-dinitro-1,1'-biphenyl (14.13 mmol) and 8.17 g of pyridine hydrochloride (70.66 mmol) were mixed and heated to 160 ° C in an oil bath. The The reaction mixture was stirred at this temperature for 21 hours and then cooled to room temperature. The resulting solid was dissolved in chloroform and placed in 300 mL of ice-water. The phases were separated and the product extracted with chloroform (3 x 100 mL) and diethyl ether (3 x 50 mL). The combined organic phases were washed with water and dried over sodium sulfate. Subsequently, the solvent was removed in vacuo and the crude product was purified by silica column chromatography (chloroform / ethyl acetate 3: 1).
¹ H NMR (300 MHz, DMSO d ₆ ): δ = 10.58 (s, 2H, -OH), 7.46 (s, 2H, Ar-H), 7.13-7.22 (m, 4H, Ar-H) ppm.
¹³ C NMR (300 MHz, DMSO d ₆ ): δ = 158.1, 148.5, 133.3, 123.4, 121.2, 111.1 ppm.

Elemental analysis:

Calculated C ₁₂ H ₈ N ₂ O ₆ : C 52.18% H 2.92% N 10.14%
(276.20) found: C 52.39%. H 2.87% N 10.18%

Synthesis of a polymer network

Under a protective gas atmosphere, 136.84 mg of 2,2'-dinitro-4,4'-biphenol (0.50 mmol) were dissolved in 6.01 g of polyethylene glycol (M _n = 400 g / mol, 14.37 mmol). Then, 5.40 g of hexamethylene diisocyanate trimer (10.70 mmol) was added and the mixture was transferred to the appropriate sample form. Thereafter, the reaction was allowed to stand under inert conditions for at least four days. The resulting polymer network was finally annealed at 100 ° C overnight.

Elemental analysis:

calculated: C 54.04% H 8.16% N 7.56%
found: C 53.70% H 8.63% N 8.20%
Glass transition temperature: -18 ° C
Decomposition temperature: 360 ° C

Thermomechanical analysis

The mechanical properties determined by rheology (temperature dependent). Here, a softening of the polymer is observed above 0 ° C, indicating vitrimerartiges behavior.

shows some mechanical properties of the polymer as a function of the temperature.

shows the dependence of the viscosity of the polymer as a function of the temperature.

Self-healing of the polymer network

The prepared specimens were cut into two parts by means of a scalpel. Subsequently, the parts of the sample body were brought back into contact and heated to 150 ° C for two days. As a result, most of the mechanical properties were restored (see Table 4). Table 4: Overview of the mechanical characteristics for Example 4. The values obtained represent average values of several measurements. sample _σmax [MPa] E-module [GPa] Healing efficiency [%] Original material 1.3 4.7 - Annealed at 150 ° C for 48 hours 1.4 3.6 - Healed at 150 ° C for 48 hours 0.6 3.6 46 ^a and 43 ^b a: Healing efficiency relative to the original values b: Healing efficiency based on the annealed values at 150 ° C

QUOTES INCLUDE IN THE DESCRIPTION

This list of the documents listed by the applicant has been generated automatically and is included solely for the better information of the reader. The list is not part of the German patent or utility model application. The DPMA assumes no liability for any errors or omissions.

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Claims (18)

Polymers containing functional groups of the formula I. -NR ₁ -CO-X-Ar ₁ (X-CO-NR ₂ ) _n - (I) wherein X is a bivalent radical of the formula -O-, -S- or -NR ₂ -, R ₁ and R _{2 are} independently hydrogen, C ₁ -C ₆ alkyl or aryl, Ar _{1 is} an n + 1-valent carbocyclic -aromatic radical or an n + 1-valent radical Ar ₄ - (C _a H _2a ) _b , wherein a is an integer from 1 to 4, and b is an integer from 1 to n, Ar _{4 is} an n + Is a monovalent carbocyclic aromatic radical and in which the radicals Ar ₁ and Ar ₄ carry at least one substituent which is selected from the group haloalkyl, nitro, nitrile, fluorine, chlorine, bromine, carboxyl, carboxyl ester, carboxylamide, sulfonic acid, sulfonic acid ester, Sulfonic acid amide, formyl or alkylcarbonyl, or A _{1 is} an n + 1-valent heterocyclic-aromatic radical or an n + 1-valent radical Ar ₅ - (C _a H _2a ) _b , wherein a is an integer from 1 to 4, and b is an integer of 1 to n, Ar _{5 is} an n + 1-valent heterocyclic aromatic radical and wherein Ar ₁ and Ar ₅ optionally carry one or more substituents n, which are preferably selected from the group haloalkyl, nitro, nitrile, fluorine, chlorine, bromine, carboxyl, carboxyl ester, carboxylamide, sulfonic acid, sulfonic acid ester, sulfonic acid amide, formyl or alkylcarbonyl, and n is an integer from 1 to 4, preferably 1 or 2. Polymers after Claim 1 , characterized in that X is a bivalent radical of the formula -O- and / or -NH-. Polymers after Claim 1 , characterized in that X is -O-. Polymers according to at least one of Claims 1 to 3 , characterized in that R ₁ and R _{2 are} hydrogen. Polymers according to at least one of Claims 1 to 4 , characterized in that Ar _{1 is} a divalent or trivalent carbocyclic aromatic radical, a divalent or trivalent heterocyclic aromatic radical, a radical -Ar ₄ -CH ₂ -,> Ar ₄ -CH ₂ -, -Ar ₅ -CH ₂ - or> Ar ₅ -CH ₂ -, wherein Ar _{4 is} a di- or trihydric carbocyclic-aromatic radical and Ar _{5 is a} di- or trihydric heterocyclic-aromatic radical and wherein the radicals Ar ₁ , Ar ₄ and Ar _{5 is} a or two substituents selected from the group haloalkyl, in particular partial or perfluoroalkyl, nitro, nitrile, fluorine, chlorine, bromine, carboxyl, carboxyl esters, carboxylamide, sulfonic acid, sulfonic acid esters, sulfonic acid amide, formyl or alkylcarbonyl or that Ar _{1 is} an unsubstituted two- or trivalent heterocyclic aromatic radical or an unsubstituted radical - Ar _{5 is} -CH ₂ - or> Ar ₅ -CH ₂ -, wherein Ar _{5 is} a di- or trihydric heterocyclic-aromatic radical, in particular a di- or trihydric heterocyclic-aromatic radical with one to three, in particular with one or two ring nitrogen atoms. Polymers according to at least one of Claims 1 to 5 , characterized in that they contain the structural unit of the formula III -X-Ar ₁ - (X-CO-NH-R ₃ - (NH-CO-) _m ) _n - (III) wherein X, R ₂ and Ar ₁ and n are the in Claim 1 have defined meaning, R _{3 is} an m + 1-valent aliphatic, cycloaliphatic, carbocyclic-aromatic radical, heterocyclic-aromatic radical or aralkyl radical which is unsubstituted or carries at least one substituent selected from the group alkyl, alkoxy, haloalkyl , Cycloalkyl, aryl, heterocyclyl, halogen, amino, hydroxy, nitro, nitrile, carboxyl, carboxyl ester, carboxylamide, sulfonic acid, sulfonic acid ester, sulfonic acid amide, formyl or alkylcarbonyl, and m is an integer from 1 to 4. Polymers after Claim 6 , characterized in that R _{3 is} a divalent or trivalent radical which is unsubstituted or one or two radicals selected from the group alkyl, alkoxy, haloalkyl, cycloalkyl, aryl, heterocyclyl, halogen, amino, hydroxy, nitro, nitrile , Carboxyl, carboxyl ester, carboxylamide, sulfonic acid, sulfonic acid ester, sulfonic acid amide, formyl or alkylcarbonyl. Polymers according to at least one of Claims 1 to 7 , characterized in that they are in the form of polymer chains in which groups of the formula I are contained Polymers after Claim 8 , characterized in that these compounds of the formula IV

wherein X, Ar ₁ and n are those in Claim 1 have defined meanings, m is an integer from 1 to 4, R _{7 is} an m + 1-valent organic radical, and o is a number greater than or equal to 2. Polymers after Claim 9 , characterized in that these compounds of formula IVa

wherein X, Ar ₁ and n are those in Claim 1 have defined meanings, R _{7 is} a 2-valent organic radical, and o is a number greater than or equal to 1. Polymers according to at least one of Claims 1 to 7 , characterized in that these structural units of the formula V or the formula VI

where X, Ar ₁ , n are those in Claim 1 have defined meanings, m is an integer from 1 to 4, o is a number greater than or equal to 1, R _{7 is} an n + 1-valent organic radical, ME is a repeating structural unit derived from a polymerizable monomer, BG is a covalent bond or a divalent organic radical, and p is an integer from 2 to 10,000,000. Polymers after Claim 11 , characterized in that these structural units of the formula Va or of the formula VIa

where X, ME, BG, o and p are those in Claim 11 Ar _{2 is} a divalent carbocyclic aromatic radical, a divalent heterocyclic aromatic radical, a radical -Ar ₄ -CH ₂ - or -Ar ₅ -CH ₂ -, wherein Ar _{4 is} a divalent carbocyclic-aromatic radical and Ar _{5 is} a divalent heterocyclic aromatic radical and wherein the radicals Ar ₂ , Ar ₄ and Ar ₅ carry at least one substituent selected from the group haloalkyl, in particular partial or perfluoroalkyl, nitro, nitrile, fluorine, chlorine, bromine, carboxyl , Carboxyl ester, carboxylamide, sulfonic acid, sulfonic acid ester, sulfonic acid amide, formyl or alkylcarbonyl, and R _{7 is} a divalent organic radical. Polymers according to at least one of Claims 1 to 7 , characterized in that they are in the form of a polymer network. Polymers after Claim 13 , characterized in that these structural units of the formula VII or the formula VIII

wherein X, Ar ₁ and n are those in Claim 1 Ar _{2 is} a divalent carbocyclic aromatic radical or a divalent heterocyclic aromatic radical bearing at least one substituent selected from the group haloalkyl, nitro, nitrile, fluorine, chlorine, bromine, carboxyl, carboxyl ester, carboxylamide , Sulfonic acid, sulfonic acid ester, sulfonic acid amide, formyl or alkylcarbonyl, R _{7 is} an m + 1-valent organic radical ME is a repeating structural unit derived from a polymerizable monomer, BG is a covalent bond or a divalent organic radical, m is an integer of 1 to 4, and p is an integer of 2 to 10,000,000. Polymers after Claim 14 , characterized in that these structural units of formula VIIa or of formula VIIIa

wherein X, Ar ₂ , ME, BG and p are those in Claim 14 have defined meanings and R _{8 is} a divalent organic radical. Polymers according to at least one of Claims 11 to 15 , characterized in that ME and BG are derived from ethylenically unsaturated carboxylic acids or their esters or amides, in particular a polymer backbone selected from the group consisting of polymethacrylate, polyacrylate, polymethacrylamide, polyacrylamide or polymaladate, or derived from ethylenically unsaturated aryl compounds polymers, in particular polystyrene, polyurethanes or polyvinyl ethers, or polymers derived from aliphatic polyenes, in particular polybutadiene or polyisoprene. Polymers according to at least one of Claims 1 to 16 , which in addition to the structural units of the formula I have further structural units which are derived from esters or amides of ethylenically unsaturated mono- or dicarboxylic acids, in particular esters or amides of acrylic acid, esters or amides of methacrylic acid, esters or amides of maleic acid, esters or amides of itaconic acid, of vinyl esters of saturated aliphatic carboxylic acids and / or of ethylenically unsaturated mono- or dicarboxylic acids. Use of the polymers according to at least one of Claims 1 to 17 for the production of coatings or for the production of moldings.

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