• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
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    • 专利摘要:
    The invention relates to solid electric conductive polymeric materials prepared by growth of polyaniline side chains from non-conducting polymers with aminophenyl side groups in their structure, preferably in the form of films or coatings, as well as to the process for their preparation and their use in the development of sensors with resistive or conductive for substances of interest, both in gas phase and in solution, or for use in electrical and electronic systems. (Machine-translation by Google Translate, not legally binding)
    公开号:ES2657313A1
    申请号:ES201631147
    申请日:2016-09-02
    公开日:2018-03-02
    发明作者:Saúl Vallejos Calzada；Félix Clemente GARCÍA GARCÍA；Felipe Serna Arenas；José María CÁMARA NEBREDA；César REPRESA PÉREZ；Juan Carlos BERTOLÍN BURILLO；José Miguel GARCÍA PÉREZ；Blanca Sol PASCUAL PORTAL；Miriam TRIGO LÓPEZ
    申请人:Universidad de Burgos；
    IPC主号:
    专利说明:

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    DRIVING POLYMERS BASED ON POLYANILINE SEQUENCES AND PROCEDURE FOR OBTAINING
    DESCRIPTION
    TECHNICAL FIELD OF THE INVENTION
    The present invention relates to conductive polymers based on polyaniline sequences and, therefore, is encompassed in the field of conductive and semiconductor materials, as well as to the method of obtaining said conductive polymers.
    More specifically, the invention provides conductive polymeric materials and electrical semiconductors prepared by growing polyaniline side chains from non-conductive polymers with aminophenyl side groups in their structure, in the form of films or coatings.
    These films or coatings with polyaniline side sequences (PAni) are conductive and can be used in different technologies, for example in the development of resistive or conductive sensors for substances of interest, both in gas phase and in solution, or for use in electrical and electronic systems
    BACKGROUND OF THE INVENTION
    Organic polymers, due to the covalent nature of their bonds, have traditionally been considered as insulating materials, both thermal and electrical. Thus, commercial dielectric polymers are known, with resistivity values between 1012 and 1020 ohm cm.
    However, in the 1970s (H. Shirakawa, E. Louis, AG MacDiarmid, CK Chiang, AJ Heeger, J. Chem. Soc. Chem. Comm., 1977, 578) there was a significant advance in the science of Materials by discovering what are now called conductive polymers, organic polymeric conductors or synthetic metals, which have conductivity values that are in the range of inorganic semiconductors (102-10-5 S / m).
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    Among the polymers considered conductive is polyaniline (PAni). PAni is really a semiconductor polymer that has a different chemical structure depending on the pH of the medium and the oxidation state of its repetitive units, with protonated emeraldine being the only one of the forms that presents conductivity (S. Bhadra, D. Khastgir, NK Singha, JL Lee, Prog. Polym. Sci., 2009, 34, 783).
    Polymerization of aniline can be carried out chemically or electrochemically, as is the case in most synthetic metals, the first method being described in this specification for the growth of PAni sequences in the lateral structure of a non-polymer. driver.
    Previous studies show the potential of materials with PAni sequences transformed in the form of films and coatings, these materials being based on PAni dispersions. Thus, Dou et al. they refer to hydrogels of hierarchically structured PAni. These hydrogels have good conductive properties that make them suitable for applications such as energy storage and 3D multilayer printing, but have the disadvantage that, being hydrogels prepared with low molecular mass gelants, they lack good mechanical properties (P. Dou , Z. Liu, Z. Cao, J. Zheng, C. Wang, X. Xu, J. Mater. Sci., 2016, 51,4274).
    On the other hand, US6932921, "Electrically conductive polymer films" refers to the synthesis of conductive films based on dispersions of fluoropolymers and linear systems with n-conjugated electrons, such as PAni. This document uses a dispersion of PAni , that is, a mixture where there is no chemical bond between the fluorinated matrix and the PAni.
    In the same line M. Fabrizio et al. (M. Fabrizio, F. Furlanetto, G. Mengoli, M. M. Musiani, F. Paolucci, J. Electroanal. Chem. 1992, 323, 197) describe the preparation of PAni-based films. Three procedures are described: PAni dispersed in Nafion® (aniline monomers diffuse in Nafion® and then are oxidized to form dispersed PAni), solution-suspension on cellulose and subsequent evaporation (casting), and casting to give rise to PAni membranes.
    One of the main disadvantages of these known conductive polymeric materials is that, due to the nature of the PAni dispersions employed, which are based on hydrogels having the conductive material dispersed in their matrix, they can be produced.
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    migrations and aggregations of the PAni sequences dispersed in the polymeric film, causing a lack of homogeneity in the distribution of the conductive chains. This also causes that the films and coatings obtained do not have the desired mechanical properties for this type of materials, for example their elastic modulus or the maximum tension until breakage.
    DESCRIPTION OF THE INVENTION
    The present invention is established and characterized in the independent claims, while the dependent claims describe other features thereof.
    An objective of the present invention was to solve the problems of the conductive polymeric materials known in the state of the art, providing conductive polymeric materials that presented the advantages mentioned above and, at the same time, were formed in the form of a solid and manageable film, with Good mechanical properties Likewise, the conductive polymeric materials of the invention prevent the migration and aggregation of the PAni chains, since these PAni chains are chemically anchored to the polymeric main chain of the materials, which prevents their migration and aggregation, and in turn leads to a homogeneous dispersion of the conductive sequences throughout the material.
    Thus, in one aspect, the present invention provides conductive polymers whose structure consists of non-conductive chains on which conductive side groups are chemically anchored, specifically polyaniline (PAni) sequences. The structure of the main chain contains aminophenyl side groups so that, after the transformation of the material, the growth of the conductive polymer sequences is carried out. Preferably the main chain is chosen so that the transformed material is a film or coating and has a flexible nature.
    Thus, non-conductive polymers are transformed into conductors by growth of polyaniline side chains, the polyaniline sequences being conductive, as is known in the state of the art. The growth of the side chains occurs in a polymer whose main chain contains free aminophenyl side groups, where the amino group is a primary amine from which a conductive sequence of PAni grows by contacting aniline in acidic medium. presence of an oxidant.
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    In this context, the concepts polymer and polymerization are understood in the broadest sense, thus encompassing homopolymers and copolymers, homopolymerization and copolymerization, respectively.
    In the present invention, as a polymer whose main chain contains free aminophenyl side groups, in general, single vinyl-type comonomers with a small amount of a vinyl monomer with aminophenyl groups can be employed. The polymerization of these monomers allows to obtain polymers in the form of films and coatings, providing polymeric materials with good mechanical properties.
    In one embodiment, the non-conductive polymer is made up of simple vinyl-type comonomers, including at least one monomer with aromatic amines. The polymerization of these monomers allows to obtain polymers in the form of films or coatings with good mechanical properties, where the aminophenyl groups act as initiation or anchor points on which aniline is polymerized laterally to give rise to the lateral sequences of PAni.
    Preferably, the vinyl monomers used to obtain the non-conductive material on which the polymerization of aniline is carried out to give rise to the PAni side sequences are selected from N-vinylpyrrolidone (VP), 2-hydroxyethyl acrylate ( A2HE), methyl methacrylate (MMA), butyl acrylate (AB), 2- hydroxyethyl methacrylate (M2HE) and styrene (S).
    Preferably, a multifunctional monomer is incorporated into the formulation that results in the crosslinking of the material, for example ethylene glycol dimethacrylate (EGDMA).
    With respect to the monomer or monomers which have to contribute to the non-conductive polymer the initiation points of the PAni side sequences are preferably N- (4- aminophenyl) acrylamide, N- (3-aminophenyl) acrylamide, N- (2-aminophenyl) acrylamide, N- (4- aminophenyl) methacrylamide, N- (3-aminophenyl) methacrylamide and N- (2-aminophenyl) methacrylamide, in particular N- (4-aminophenyl) acrylamide, N- (4-aminophenyl) methacrylamide.
    The polymerization of this type of monomers to give rise to the non-conductive material and its subsequent treatment with aniline under conditions of coupling polymerization
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    Oxidative provides polymeric materials in the form of films and coatings with properties in relation to electrical conductivity.
    An important feature of the invention is in the selection of the non-conductive material, so that the films and coatings obtained are flexible and with good mechanical properties and are not substantially altered with the subsequent lateral polymerization of aniline to give rise to lateral sequences of polyaniline. Thus, the conductive materials that are obtained can be designed by selecting the monomers that make up the initial non-conductive structure so that they possess special characteristics, such as flexibility, stiffness, chemical resistance, thermal resistance, hydrophilicity, hydrophobia, to name some Relevant property in the field of polymeric material applications, where conductivity can play a special role in innovative applications.
    In this regard, and in a second aspect, the invention relates to a process for obtaining the above-mentioned conductive polymers, based on polyaniline sequences, where the non-conductive polymers are transformed according to the process of the invention into conductive by growth of polyaniline side chains. Side chain growth occurs in a polymer whose main chain contains free aminophenyl side groups, where the amino group is a primary amine from which a conductive sequence of PAni is grown by contacting aniline in acidic medium. in the presence of an oxidant. Polymerization of the aniline is initiated in the aminophenyl groups present in the non-conductive polymer structure, which results in polyaniline (PAni) conductive sequences chemically anchored to the macromolecular chemical structure. The size or length of the PAni side chains determines their electrical properties, so that the materials can be subjected to subsequent polymerization processes with aniline to increase this size.
    As mentioned above, as polymerizable monomers that give rise to polymeric materials, all commercialized and synthetic monomers can be used provided that a comonomer that adds the aminophenyl substructure, primary amine group, to the macromolecular sequence is already included. that this substructure is what acts as the initiator of the growth processes of lateral PAni chains. Preferably, given its versatility, the monomers used in greater proportion are vinyl and commercial, among which are mentioned without limitation, VP, A2HE, MMA, AB, M2HEA, and more preferably VP, MMA, as well as
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    Synthetic monomers containing primary aromatic amines such as N- (4- aminophenyl) acrylamide, N- (3-aminophenyl) acrylamide, N- (2-aminophenyl) acrylamide, N- (4- aminophenyl) methacrylamide (NAM), N- (3-Aminophenyl) methacrylamide and N- (2- aminophenyl) methacrylamide, preferably N- (4-aminophenyl) acrylamide, NAM, and more preferably NAM. In addition, given the importance of mechanical properties, including flexibility, in the applicability of such materials, formulations for obtaining the non-conductive polymer will include a crosslinker. As a non-limiting example of crosslinker, in particular ethylene glycol dimethacrylate (EGDMA) is cited.
    BRIEF DESCRIPTION OF THE FIGURES
    The present invention is complemented by a set of illustrative and non-limiting figures.
    Of the same. In the figures:
    Figure 1: Scheme of the general process according to the invention, of growth of conductive polymer from a non-conductive polymeric structure having aminophenyl side substructures, where the amino group is a primary amine.
    Figure 2: Characterization of the material designated as "WHITE": a) Differential Scanning Calorimetry (MDSC); b) Optical microscopy, A = 532 nm and 100 magnifications; c) Scanning electron microscopy, 500 magnification; d) Raman spectrum surface A = 785 nm, P = 60mW; e) Thermogravimetric nitrogen analysis.
    Figure 3: Characterization of the conductive material designated as "UNI": a) Differential Scanning Calorimetry (MDSC); b) Optical microscopy, A = 532 nm and 100 magnifications; c) Scanning electron microscopy, 500 magnification; d) Spectrum Superficial Raman A = 785 nm, P = 0.2 mW; e) Thermogravimetric nitrogen analysis.
    Figure 4: Characterization of the conductive material designated as "BIS": a) Differential Scanning Calorimetry (MDSC); b) Optical microscopy, A = 532 nm and 100 magnifications; c) Scanning electron microscopy, 500 magnification; d) Spectrum Superficial Raman A = 785 nm, P = 0.2 mW; e) Thermogravimetric nitrogen analysis.
    Figure 5: Characterization of the conductive material designated as "TRIS": a) Differential Scanning Calorimetry (MDSC); b) Optical microscopy, A = 532 nm and 100 magnification; c) Scanning electron microscopy, 500 magnification; d) Spectrum
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    Superficial Raman A = 785 nm, P = 0.2 mW; e) Thermogravimetric nitrogen analysis.
    Figure 6: Characterization of the conductive material designated as “TETRAKIS”: a) Differential Scanning Calorimetry (MDSC); b) Optical microscopy, A = 532 nm and 100 magnifications; c) Scanning electron microscopy, 500 magnifications; d) Raman surface spectrum A = 785 nm, P = 0.2 mW; e) Thermogravimetric nitrogen analysis.
    DETAILED EXHIBITION OF THE INVENTION
    In accordance with the first aspect of the invention, conductive polymers are provided whose structure consists of non-conductive chains containing free aminophenyl side groups, the amino group being a primary amine, on which conductive side groups are chemically anchored, specifically sequences of polyaniline (PAni).
    As polymers where the main chain contains free aminophenyl side groups, in general, single vinyl-type comonomers with a small amount of a vinyl monomer with aminophenyl groups can be used.
    Preferably, the non-conductive polymer is formed by simple vinyl-type comonomers, among which is at least one monomer with aromatic amines. The polymerization of these monomers allows to obtain polymers in the form of films or coatings with good mechanical properties, where the aminophenyl groups act as initiation or anchor points on which aniline is polymerized laterally to give rise to the lateral sequences of PAni.
    In a particularly preferred embodiment, the vinyl and commercial monomers used to obtain the non-conductive material on which the polymerization of aniline is carried out to give rise to the PAni side sequences are selected from N-vinylpyrrolidone (VP), 2-hydroxyethyl acrylate (A2HE), methyl methacrylate (MMA), butyl acrylate (AB), 2-hydroxyethyl methacrylate (M2HE) and styrene (S), with special preference between VP and MMA.
    Preferably, a cross-linking multifunctional monomer, in particular ethylene glycol dimethacrylate (EGDMA), is incorporated into the formulation.
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    With respect to the monomer or monomers that must provide the non-conductive polymer with the initiation points of the PAni side sequences, they are preferably selected from N- (4-aminophenyl) acrylamide, N- (3-aminophenyl) acrylamide, N- (2 -aminophenyl) acrylamide, N- (4-aminophenyl) methacrylamide, N- (3-aminophenyl) methacrylamide and N- (2-aminophenyl) methacrylamide, with particular preference from N- (4-aminophenyl) acrylamide, N- (4 -aminophenyl) methacrylamide and in particular is N- (4-aminophenyl) methacrylamide.
    According to the second aspect of the invention, there is provided a method for obtaining conductive polymers whose structure consists of non-conductive chains containing free aminophenyl side groups, the amino group being a primary amine, on which side groups are chemically anchored. conductors, specifically polyaniline (PAni) sequences.
    Thus, essentially the process of the invention includes a first step of providing a solid non-conductive polymeric material, preferably in the form of a film or coating, based on commercialized and synthetic monomers, especially vinyl, which further include a comonomer that adds the aminophenyl substructure , primary amine group, to the macromolecular sequence, since this substructure is what acts as the initiator of the growth processes of lateral PAni chains.
    This solid material, preferably in the form of a film or coating, is subjected to one or more side-growth reactions of PAni sequences by polymerization of aniline, in which conductive polymer chains chemically anchored to the said solid material are formed, submerging in a acidic water containing aniline and adding an oxidant that initiates polymerization in the lateral aminophenyl groups.
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    image 1
    The first lateral growth reaction of PAni sequences begins in the aminophenyl groups of the non-conductive polymer structure, while the following lateral growth reactions are continued in the lateral amino group of the PAni sequences generated in the previous growth. This is because the oxidation potential of the aniline is much greater than that of the substituted aminophenyl groups, especially in para, so that under the reaction conditions employed the free aniline molecules do not initiate polymerization.
    The successive phases to which the conductive polymer obtained in a first polymerization of aniline on the non-conductive polymer can be subjected to increase the size of the lateral conductive sequences of PAni, increasing the electrical conductivity, being able to achieve similar conductivity values, after obtaining the material to those of a semiconductor, with a minimum resistance below 20kQ per square (measured in relation to the surface resistance on a square surface of negligible thickness).
    Side chain growth occurs from the primary amino group, where a conductive sequence of PAni is grown by contacting aniline in an acid medium and in the presence of an oxidant. The size or length of the PAni side chains determines their electrical properties, so that the materials can be subjected to subsequent polymerization processes with aniline in acidic medium and in the presence of an oxidant to increase this size.
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    As indicated above in relation to the first aspect of the invention, as polymerizable monomers that give rise to polymeric materials, those monomers that also include a comonomer that adds the aminophenyl substructure, primary amine group, to the macromolecular sequence can be used, since this substructure is the one that acts as the initiator of the growth processes of the lateral PAni chains.
    Preferably, given its versatility, the monomers referred to and used in greater proportion are vinyl and commercial, preferably selected from VP, A2HE, MMA, AB, M2HEA, and more preferably VP, MMA, as well as synthesis monomers containing primary aromatic amines such as N- (4-aminophenyl) acrylamide, N- (3- aminophenyl) acrylamide, N- (2-aminophenyl) acrylamide, N- (4-aminophenyl) methacrylamide (NAM), N- (3-aminophenyl) methacrylamide and N - (2-Aminophenyl) methacrylamide, especially N- (4- aminophenyl) acrylamide, NAM, and in particular NAM.
    In addition, given the importance of mechanical properties, including flexibility, in the applicability of such materials, formulations for obtaining the non-conductive polymer will include a crosslinker. As a non-limiting example of crosslinker, in particular ethylene glycol dimethacrylate (EGDMA) is cited.
    Preferably, for the growth of the polyaniline conductive side chains from the primary amino group, upon contacting with aniline, the acidic medium is selected from any inorganic acid. Preferably, the pH of the acidic medium is less than 3. Particularly preferred is paratoluenesulfonic acid, hydrochloric acid or sulfuric acid, in particular sulfuric acid.
    As oxidants for the process of the invention, peroxides are used, such as hydrogen peroxide, or salts of metals in a high oxidation state, such as potassium dichromate, potassium permanganate, sodium persulfate or ammonium persulfate. In a preferred embodiment, 0.25M ammonium persulfate is used as oxidant.
    In a preferred embodiment of the process of the invention, the solid non-conductive material, preferably in the form of a film or coating, is prepared from comonomers of methyl methacrylate (MMA) and N-vinyl-2-pyrrolidone (VP) , a crosslinker such as ethylene glycol dimethacrylate (EGDMA) and the carrier monomer of the aminophenyl group is N- (4-aminophenyl) methacrylamide (NAM).
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    EXAMPLES
    The following examples show the obtaining of the solid non-conductive polymer, in this case in the form of a film, of the conductor after an initial aniline polymerization on the non-conductive and three more conductive materials obtained by successive aniline polymerization steps. Conductivity data is provided in the examples. The different polymerization steps of aniline on the non-conductive polymer and on the conductor allow obtaining polymers with the conductivity or semiconductivity suitable for the desired applications.
    In the examples, as preferred monomers that contribute to the non-conductive polymer side aminophenyl groups, the vinyl monomer N- (4-aminophenyl) methacrylamide (NAM) is used for: a) the preparation of a crosslinked film that results in a first material, which is designated as "WHITE"; b) polymerization on this aniline film, which gives rise to lateral sequences of PAni that provide conductive characteristics to the film, to give rise to a second material, which is designated as "UNI"; c) a new polymerization on the second material (conductive polymer UNI), to give rise to a third conductive material, which is designated as "BIS"; d) the polymerization of aniline on the third material to give rise to a fourth material, designated as "TRIS"; and e) the polymerization of aniline on the fourth material, to give rise to the fifth material, designated as "TETRAKIS".
    Example 1: Preparation of a film with lateral aminophenyl sequences (WHITE)
    A film with the following composition was prepared by radical polymerization:
     Monomers  VP, MMA, NAM, in a 50: 50: 1 molar ratio
     Crosslinker  EGDMMA, by 1% in moles with respect to total moles
     Thermal initiator  Azobisisobutyronitrile (AIBN) in a concentration of 1% by weight with respect to the total weight
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    The mixture of monomers, crosslinker and thermal initiator resulted in a solution, which was stirred at room temperature in an ultrasonic bath for 5 minutes and subsequently injected into a mold between silanized crystals, 100 ^ .m thick, in the absence of oxygen and placed in an oven at 60 ° C overnight. After demolding, a manageable film (WHITE) is obtained (elastic modulus = 780 MPa, tensile strength of = 50 MPa, elongation = 14%) of 110 ^ .m, which is left in the air for 24 hours. The additional characterization of the material is shown in Figure 2.
    Example 2: Polymerization of aniline on the "WHITE" film to give rise to the conductive material designated "UNI"
    First, the "WHITE" film was introduced into an aqueous solution of aniline (0.4M) in acidic medium (pH <3) for 2 hours. The system temperature was lowered to 0 ° C. Then, the system was added the oxidizing agent, in this example sodium persulfate dissolved in water, maintaining the temperature at 0 ° C. The polymerization of the aniline is initiated in the aminophenyl groups of the polymer chain of the film due to the lower oxidation potential of the groups aromatic amine substituted in respect to the aniline itself The polymerization reaction was maintained overnight.
    The formation reaction of the PAni side sequences is shown below:
    image2
    With this procedure, lateral sequences of green conductive PAni are chemically anchored to the film, sequences corresponding to protonated emeraldine, whose structure is as follows:
    image3
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    The material exhibits a conductivity of 0.02 S / m, an elastic modulus of 1,100 MPa, a tensile strength of 53 MPa and a elongation at break of 7%. The additional characterization is shown in Figure 3.
    Example 3: Additional polymerization of aniline on the "UNI" material to give rise to the "BIS" material
    The procedure was the same as in Example 2, by swelling the "UNI" material in an acidic aqueous solution of aniline and adding the oxidant at 0 ° C. In this polymerization reaction there is an increase in the size of the PAni chains that are chemically anchored to the dense membrane.
    The material exhibits a conductivity of 0.04 S / m, an elastic modulus of 855 MPa, a tensile strength of 38 MPa and a elongation at break of 9%. The additional characterization is shown in Figure 4.
    Example 4: Additional polymerization of aniline on the "BIS" material to give rise to the "TRIS" material
    The procedure was the same as in Example 2, by swelling the "BIS" material in an acidic aqueous solution of aniline and adding the oxidant at 0 ° C. In this polymerization reaction there is an increase in the size of the PAni chains that are chemically anchored to the dense membrane.
    The material exhibits a conductivity of 0.12 S / m, an elastic modulus of 840 MPa, a tensile strength of 46 MPa and an elongation at break of 8%. Additional characterization is shown in Figure 5.
    Example 5: Additional polymerization of aniline on the "TRIS" material to give rise to the "TETRAKIS" material
    The procedure was the same as in Example 2, by swelling the TRIS material in an aqueous aqueous solution of aniline and adding the oxidant at 0 ° C. In this polymerization reaction there is an increase in PAni chains that are chemically anchored to the dense membrane.
    The material exhibits a conductivity of 0.19 S / m, an elastic modulus of 890 MPa, a tensile strength of 44 MPa and an elongation at break of 7%. The additional characterization is shown in Figure 6.
    权利要求:
    Claims (18)
    [1]
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    1. Conductive polymers in solid form whose structure consists of polymeric chains based on non-conductive vinyl-type comonomers that include at least one free aminophenyl side group, the primary amino group, on which conductive side groups of sequence sequences are chemically anchored. polyaniline, the aminophenyl groups acting as initiation or anchor points on which aniline is polymerized laterally to give rise to the polyaniline side sequences.
    [2]
    2. - Conductive polymers in solid form according to claim 1, characterized in that
    vinyl type comonomers are selected from N-vinyl pyrrolidone (VP), 2-hydroxyethyl acrylate (A2HE), methyl methacrylate (MMA), butyl acrylate (AB), 2-hydroxyethyl methacrylate (M2HE) and styrene ( S).
    [3]
    3. - Conductive polymers in solid form according to claim 2, characterized in that
    vinyl type comonomers are selected from N-vinyl pyrrolidone and methyl methacrylate.
    [4]
    4. - Conductive polymers in solid form according to claim 1, characterized in that
    the aminophenyl groups as initiation or anchor points on which aniline is polymerized laterally to give rise to the polyaniline side sequences come from monomers selected from N- (4-aminophenyl) acrylamide, N- (3- aminophenyl) acrylamide, N - (2-Aminophenyl) acrylamide, N- (4-aminophenyl) methacrylamide, N- (3- aminophenyl) methacrylamide and N- (2-aminophenyl) methacrylamide.
    [5]
    5. - Conductive polymers in solid form according to claim 4, characterized in that
    the aminophenyl groups as initiation or anchor points on which aniline is polymerized laterally to give rise to the polyaniline side sequences come from monomers selected from N- (4-aminophenylacrylamide and N- (4- aminophenyl) methacrylamide.
    [6]
    6. - Conductive polymers in solid form according to claim 5, characterized in that
    the aminophenyl groups as initiation or anchor points on which aniline is polymerized laterally to give rise to the polyaniline side sequences come from N- (4-aminophenyl) methacrylamide.
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    [7]
    7. - Conductive polymers in solid form according to claim 5, characterized in that
    the aminophenyl groups are N- (4-aminophenyl) methacrylamide groups.
    [8]
    8. - Conductive polymers in solid form according to any of claims 1 to 7,
    characterized in that the solid non-conductive polymeric material is in the form of a film or coating.
    [9]
    9. - Conductive polymers in solid form according to any of claims 1 to 8,
    characterized in that they have a minimum resistance value below 20kQ per square, measured in relation to the surface resistance on a square surface of negligible thickness.
    [10]
    10. - Procedure for the production of a conductive polymer according to any of the
    claims 1 to 9, the method including a first step of providing a solid non-conductive polymeric material based on vinyl-type comonomers that include at least one free aminophenyl side group, the primary amino group being; a subsequent step of polymerization of aniline, in acidic medium and in the presence of an oxidant, initiated in the aminophenyl groups of the non-conductive polymer structure; and successive steps of polymerization of lateral growth aniline on the lateral amino group of the polyaniline sequences linked in the previous step, under the same conditions, increasing the size of the conductive lateral sequences of polyaniline.
    [11]
    11. - Method according to claim 10, characterized in that the acidic medium is
    Select from any inorganic acid that provides a pH below 3.
    12. Method according to claim 11, characterized in that the acid used is selected from paratoluenesulfonic acid, hydrochloric acid or sulfuric acid.
    [13]
    13. - Method according to claim 12, characterized in that the acid used is
    sulfuric acid.
    [14]
    14. - Method according to claim 10, characterized in that as oxidants are
    they use peroxides or salts of metals in a high oxidation state.
    [15]
    15. Process according to claim 14, characterized in that hydrogen peroxide is used as peroxide.
    [16]
    16. Process according to claim 14, characterized in that potassium dichromate, potassium permanganate, sodium persulfate or persulfate are used as oxidants.
    ammonium.
    [17]
    17. - Method according to claim 16, characterized in that the oxidant is
    employs 0.25M ammonium persulfate.
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    [18]
    18. - Method according to claim 10, characterized in that the solid material does not
    Conductive is prepared from comonomers of methyl methacrylate (MMA) and N-vinyl-2-pyrrolidone (VP) and the carrier monomer of the aminophenyl group is N- (4- aminophenyl) methacrylamide (NAM).
    fifteen
    [19]
    19. - Use of a solid conductive polymer according to any of claims 1 to
    9, for the manufacture are gas sensors, sensors in aqueous medium or in electrical and electronic systems.
    20 20.- Use of a solid conductive polymer obtained according to the process of
    Any of claims 10 to 18, for the manufacture are gas sensors, sensors in aqueous medium or in electrical and electronic systems.
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    CN102040695A|2010-11-26|2011-05-04|中国人民解放军国防科学技术大学|Preparation method of water-soluble polyvinylpyrrolidone grafted polyaniline copolymer|
    CN105506981A|2015-12-20|2016-04-20|青岛科技大学|Polyamide/polyaniline electric conduction composite and preparation method thereof|
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