• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    Obtaining metallic nano-particles by using copolymers in membrane form. Procedures for obtaining nano-particles of a metal M from a solution of a salt of said metal M by using copolymers in the form of dense membranes (films or films of metallic nano-particles.) These copolymers are obtained by putting in contact an initiator, photochemical or thermal, with at least monomers of formula (1), and where said initiator is decomposed by light or temperature forming radicals The copolymers obtained in the described process are characterized by an increase of between 1 % and 200% of its initial weight when submerged in water The uses of said copolymers in obtaining metal nanoparticles are also described. (Machine-translation by Google Translate, not legally binding)
    公开号:ES2684426A1
    申请号:ES201730551
    申请日:2017-03-31
    公开日:2018-10-02
    发明作者:Saúl Vallejos Calzada；José Miguel GARCÍA PÉREZ；Félix GARCÍA GARCÍA；Felipe Serna Arenas；Patricia CALVO GREDILLA；José GARCÍA CALVO；Tomás TORROBA PÉREZ；Víctor GARCÍA CALVO；Manuel Pedro AVELLA ROMERO
    申请人:Fundacion Parque Cientifico Uva；Fund Parque Cientifico Uva；Universidad de Burgos；
    IPC主号:
    专利说明:

    image 1
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    methylenebutanonitrile, 2-methylbut-2-enonitrile, 2,3-bis (2-methoxy-2-methylpropyl) -2,3-dimethylsuccinonitrile.
    In a preferred embodiment of the process for obtaining nano-particles of the invention, obtaining the copolymer of step (a) is carried out with the use of an initiator that decomposes forming radicals due to the effect of light or temperature, where said initiator it is in an amount between 0.0075% molar and 7.5% molar, preferably in an amount between 0.5 and 2.5% molar, more preferably 0.75% molar.
    By varying the amounts and type of monomers with which the copolymers are manufactured, it is possible to control the shape and size of the nano-particles deposited on the surface of the membrane. For the purposes of the present invention are non-limiting examples of M metals, which can be deposited in the form of nano-particles: gold [Au], platinum [Pt], palladium [Pd], silver [Ag], copper [Cu], nickel [Ni], cobalt [Co], rhodium [Rh], iridium [Go], zinc [Zn], cadmium [Cd], aluminum [Al], titanium [ Ti], vanadium [V], chromium [Cr], manganese [Mn] or iron [Fe]. In a preferred embodiment, the metal M is selected from: gold [Au], platinum [Pt], palladium [Pd], silver [Ag], copper [Cu], nickel [Ni] or cobalt [Co]. More preferably the metal M is selected from: gold [Au], platinum [Pt], palladium [Pd], silver [Ag]
    or copper [Cu]. Even more preferably the metal M is selected from gold [Au] or palladium [Pd].
    The formation of nano-particles occurs when the membranes are immersed in metal salt solutions, without the need for any other laboratory operation. The process of reduction of metal cations to metals, as well as homogeneous deposition on the surface of the material, occurs without controlled atmosphere and at room temperature, between 1 ̊̊̊̊
    C at 50 C, more preferably between 15 C and 30 C, even more preferably at 20 C. Therefore, the copolymers described in the present invention can be used as materials for direct obtaining of metal nano-particles, also obtaining both different forms and different size of them, by variation in the conditions and copolymer used.
    For the purposes of the present invention, a nanoparticle of a metal M is defined as a particle of said metal M having a size between 1x 10-5 and 1x10-9m. More preferably, the nano-particles have a size between 10x10-6 and 1x10-7 m.
    7
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    In another preferred embodiment of step (b) of the process of the present invention, the metal salt is nickel (II) perchlorate hexahydrate (Ni (ClO4) 2 · 6H2O).
    The chemical structure of the copolymers obtained in step (a) of the process of the invention
    5 (ie copolymers comprising N-vinyl pyrrolidone monomers), and the conditions for obtaining it (ie use of an initiator which, by the effect of light or temperature, decomposes to form radicals), results in obtaining the nano-particles of according to the process of the present invention. The following embodiments include obtaining copolymers according to step (a) of the process of the invention, in which it is used
    10 an initiator that by the effect of light or temperature decomposes forming radicals and also monomers of N-vinyl pyrrolidone. The processes for obtaining these copolymers are collected illustratively in examples 1 to 4. Said copolymers are used in the preparation of metal nano-particles in accordance with the process of the invention as set out in illustrative manner in examples 5 and 6. Said nano-particles have
    15 different shapes and sizes depending on the structure of the copolymer used and the conditions for obtaining said copolymer.
    In a preferred embodiment of the process for obtaining nano-particles of the invention, obtaining the copolymer of step (a) comprises contacting an initiator
    20 photochemical that by the effect of light or temperature decomposes forming radicals with monomers of formula (I), described above, monomers of formula (IV) and cross-linking monomers of formula (V), obtaining a copolymer of formula (VI):
    image11
    image12
    image13
    where each R1 is independently selected from H or CH3, Z represents between 0.1% and 25% of the total number of monomers; and where the ratio of X to Y is 1:10 to 10: 1.
    13


    In a preferred embodiment of the process for obtaining nano-particles of the invention, step (a) described in the present invention is carried out by contacting an initiator which, by the effect of light or temperature, decomposes forming radicals with of ethylene glycol dimethacrylate, N-vinyl pyrrolidone and butyl acrylate. In said preferred embodiment and the copolymer obtained in step (a) is a copolymer of formula (VII):
    image14
    image15
    image16
    image17
    where Z represents between 0.1% and 20% of the total number of monomers, and where the ratio of X to Y is 1:10 to 10: 1.
    In said preferred embodiment of the process for obtaining nano-particles of the present invention, the commercial monomers N-vinyl pyrrolidone (where R1 is H), butyl acrylate (where R1 is H), and ethylene glycol dimethacrylate (where R1 is CH3).
    In a preferred embodiment of the process for obtaining nano-particles from the
    In the invention, the copolymer obtained in step (a) is a copolymer of formula (VII) where Z is 10% of the total number of monomers and the ratio of X to Y is 1: 4.
    In a preferred embodiment of the process for obtaining nano-particles of the invention, in step (b), the copolymer of formula (VII) is immersed in a
    20 aqueous solution of palladium (II) chloride di-sodium chloride at a concentration of 5 · 10-3 M.
    In another preferred embodiment of the process for obtaining nano-particles of the invention, obtaining the copolymer of step (a) comprises contacting an initiator which, by effect of light or temperature, decomposes forming radicals, with N-vinyl
    14


    pyrrolidone and butyl acrylate. In said preferred embodiment the copolymer obtained in step (a) is a copolymer of formula (IX):
    image18
    where the ratio of X to Y is 1:10 to 10: 1.
    In said preferred embodiment of the process for obtaining nano-particles of the present invention, the commercial monomers N-vinyl pyrrolidone (where R 1 is H) and butyl acrylate are used.
    In a preferred embodiment, the copolymer obtained in step (a) is a copolymer of formula (IX), where the ratio of X to Y is 1.5: 1.
    In a preferred embodiment of the process for obtaining nano-particles of the invention, in step (b), the copolymer obtained in step (a) is immersed in an aqueous solution of tetrachlorouric acid at a concentration of 5 · 10-3 M.
    In another preferred embodiment of the process for obtaining nano-particles of the invention, obtaining the copolymer of step (a) comprises contacting an initiator which, by effect of light or temperature, decomposes forming radicals, with N-vinyl 20 pyrrolidone, butyl acrylate, ethylene glycol dimethacrylate and methacryloyl chloride. In said preferred embodiment, the copolymer obtained in step (a) is a copolymer of formula (X):
    image19
    image20


    where Z represents between 0.1% to 20% of the total number of monomers, where K represents between 0.1% to 10% of the total number of monomers and where the ratio of X to Y is from 1:10 to 10: one.
    In a preferred embodiment of the process for obtaining nano-particles of the invention, the copolymer obtained in step (a) is a copolymer of formula (XII), where Z represents 5% of the total number of monomers, K represents 5 % of the total number of monomers, and the ratio of X to Y is 1.5: 1.
    In a preferred embodiment, immersion of the copolymer obtained in step (a) is carried out in an aqueous solution of palladium (II) chloride in step (b) of the process for obtaining nanoparticles described in the present invention. sodium chloride at a concentration of 5 · 10-3 M.
    An embodiment of the invention relates to copolymers of formula (VII):
    image21
    X
    Y
    image22 image23 Z
    N
    OR
    OR
    image24
    image25
    OR
    OO
    image26
    image27
    image28 OO
    image29 (VII)
    where Z represents between 0.1% and 20% of the total number of monomers, and where the ratio of X to Y is 1:10 to 10: 1.
    Another preferred embodiment of the invention relates to copolymers of formula (IX):
    image30
    image31
    image32
    17


    where the ratio of X to Y is 1:10 to 10: 1. Another preferred embodiment of the invention relates to copolymers of formula (X):
    image33
    It is from 1:10 to 10: 1. Another preferred embodiment of the invention relates to copolymers of formula (XII):
    image34
    It is from 1:10 to 10: 1.
    An embodiment of the invention relates to the nano-particles of a metal M obtainable according to the method of obtaining described in the present invention.
    An embodiment of the invention relates to the use of any of the copolymers obtained in step (a) in obtaining nano-particles of a metal M according to the obtaining process 20 described in the present invention.
    18


    Another preferred embodiment of the present invention relates to the use of any of the copolymers of formula (VII), (IX), (X) or (XII) in obtaining nano-particles of a metal
    M.
    Another preferred embodiment of the present invention relates to the use of any of the copolymers of formula (VII), (IX), (X) or (XII) in obtaining nano-particles of a metal M according to the process of Obtaining described in the present invention.
    A preferred embodiment of the invention relates to the use of any of the copolymers of formula (VII), (IX), (X) or (XII) in obtaining nano-particles of: gold [Au], platinum [Pt] , palladium [Pd], silver [Ag], copper [Cu], nickel [Ni], cobalt [Co], rhodium [Rh], iridium [Ir], zinc [Zn], cadmium [Cd], aluminum [Al] , titanium [Ti], vanadium [V], chromium [Cr], manganese [Mn] or iron [Fe]. In a preferred embodiment, the metal M is selected from gold [Au], platinum [Pt], palladium [Pd], silver [Ag], copper [Cu], nickel [Ni] or cobalt [Co]. More preferably the metal M is selected from gold [Au], platinum [Pt], palladium [Pd], silver [Ag] or copper [Cu]. Even more preferably the metal M is selected from gold [Au] or palladium [Pd].
    In general, the copolymer obtained in step (a) of the process for obtaining nanoparticles of the present invention, whether it comprises commercial monomers or not, can be carried out by any of the methods described in the literature for the polymerization of multiple bonds.
    The copolymers obtained in step (a) of the process for obtaining nano-particles of the present invention, as well as the membranes, films, coatings and solid state materials obtained therefrom, are characterized by a combination of properties mechanical both dry and swollen (that is, with water within the polymeric network), which makes them suitable materials for the development of dense membranes that can be used to obtain nano-particles of different metals with different morphology and size, as described in the present invention.
    That is, the copolymers obtained in step (a) of the process for obtaining nanoparticles of the invention act as a substrate for the formation and growth of metal nanoparticles with different shapes and sizes.
    19
    image35
    image36


    Example 2. Preparation of a copolymer of formula (IX).
    A block copolymer was prepared according to step (a) of the process of the invention with the following monomers: N-vinyl pyrrolidone and acrylate of
    5 butyl, with a 60, 40 molar ratio, respectively. Photochemical initiator 2,2-dimethoxy-2-phenylacetophenone with a weight percentage of 1.56%. The synthetic scheme is described in fig. 2A. The resulting solution was injected into a mold of silanized crystals, 100 µm thick, in the absence of oxygen, and placed under an ultraviolet radiation lamp at 365 nm for one hour.
    Example 3. Preparation of a copolymer of formula (X).
    A block copolymer was prepared according to step (a) of the process of the invention with the following monomers: N-vinyl pyrrolidone and 15-butyl acrylate, ethylene glycol dimethacrylate and methacryloyl chloride with a molar ratio 54, 36 , 5, 5, respectively. Photochemical initiator 2,2-dimethoxy-2-phenylacetophenone with a weight percentage of 1.56%. The synthetic scheme is described in fig. 3A. The resulting solution was injected into a mold of silanized crystals, 100 µm thick, in the absence of oxygen, and placed under an ultraviolet radiation lamp at 365 nm for one hour.
    Example 4. Preparation of a copolymer of formula (XII).
    I. Preparation of compound PC53. The synthesis of compound PC53 was performed in 4
    synthetic steps detailed below: 25
    22
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    权利要求:
    Claims (12)
    [1]
    image 1

    [6]
    6. Procedure for obtaining nano-particles according to any of claims 1 to 5, wherein the copolymer obtained in step (a) is a copolymer of formula (VII):
    image2
    5 where Z represents between 0.1% to 20% of the total number of monomers; and where the ratio of X to Y is 1:10 to 10: 1.
    [7]
    7. Procedure for obtaining nano-particles according to claim 6, Z represents 10% of the total monomers and where the ratio of X to Y is
     10 1: 4.
    [8]
    8. Procedure for obtaining nano-particles according to any of claims 1 to 5, wherein the copolymer obtained in step (a) is a copolymer of formula (IX):
    image3
    image4
    where the ratio of X to Y is 1:10 to 10: 1.
    [9]
    9. Procedure for obtaining nano-particles according to claim 8, wherein the ratio of X to Y is 1.5: 1.
    31
    image5

    where Z represents between 0.1% to 20% of the total number of monomers, K represents between 0.1% to 10% of the total number of monomers, and the ratio of X to Y is at least
    1:10 and up to 10: 1.
    [13]
    13. Procedure for obtaining nano-particles according to claim 12, wherein Z represents 5% of the total number of monomers, K represents 5% of the total number of monomers, and the ratio of X to Y is 1.5: 1.
    [14]
    14.  Copolymer of formula (VII):
    image6
    where Z represents between 0.1% to 20% of the total number of monomers; and where the ratio of X to Y is 1:10 to 10: 1.
    [15]
    15. Copolymer of formula (IX):
    image7
    image8
    fifteen
    where the ratio of X to Y is 1:10 to 10: 1.
    twenty
    33

    [16]
    16. Copolymer of formula (X):
    image9
    1:10 and up to 10: 1.
    [17]
    17. Copolymer of formula (XII):
    image10
    1:10 and up to 10: 1.
    [18]
    18. Nano-particles of a metal M obtainable according to the method of production according to any one of claims 1 to 13.
    [19]
    19. Use of copolymers of formula (VII), (IX), (X) or (XII) of claims 14 to 17, in obtaining nano-particles of an M metal.
    3. 4
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    同族专利:
    公开号 | 公开日
    ES2684426B1|2019-07-10|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    EP0252254A1|1986-07-01|1988-01-13|HIRAI, Hidefumi|A colloidal metal dispersion, and a colloidal metal complex|
    US20140207000A1|2011-04-26|2014-07-24|Encapson B.V.|Coating for improving the ultrasound visibility|
    WO2014070131A1|2012-10-29|2014-05-08|Unipixel Displays, Inc.|Coated nano-particle catalytically active composite inks|
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