`
`
`
`
`
`
`
`Title of Invention: METHOD OF MANUFACTURING POLYMER/SILICA
`
`
`
`
`
`
` CA COMPOSITE
`
`COMPOSITE NANO STRUCTURE, POLYMER/METAL/SII
`
`
`E
`
`
`
`
`
`AND SILICA INORGANIC STRUCTUR
`
`
`
`
`
`
`
`
`
`NANO STRUCTUR
`
`
`
` GI
`
`
`
`
`
`
` —
`Detailed Description of the Invention]
`
`
`
`
`
`DESCRIPTION
`
`
`
`
`
`
`the Invention]
`
`
`
`
`
`
`
`[Field of
`
`
`
`[0001]
`
`
`The crystalline association body formed in the aqueous
`
`
`
`
`
`
`
`medium of the polymer which has a straight—chain-shape
`
`polyethyleneimine
`skeleton is used for the present invention
`
`
`
`
`
`as a reaction field, The structure with which the polymer
`
`and silica by making it mix water glass were compounded by
`
`
`
`
`
`(hereinafter,
`nanometer order. To the manufacturing method of
`
`calling nanostructure in the present invention), and also
`
`
`its polymer / silica composite-construction inside of the
`
`
`
`body, metal
`
`
`
`ion, It is related with the manufacturing method
`
`
`of polymer / sorted metals / silica compound nanostructure
`
`with which the metal nano particle (metal
`
`
`
`
`nano particle are hereafter called sorted metals
`
`
`collectively.) of number nanometer order is contained, and
`
`
`
`the manufacturing method of the silica system inorganic
`
`
`structure produced by carrying out heat calcination of
`
`these.
`
`
`
`
`
`— Background of the Invention]
`
`[0002]
`
`ion and a metal
`
`
`
`
`
`
`Silicon is abundant existences which are proud of
`
`the second
`
`which ranks second to oxygen on earth crust,
`
`
`and quartz of a
`
`nature,
`
`crystal, an opal,
`
`mica, a diatom,
`
`e tc.
`
`are the
`
`
`oxides of
`
`the silicon known well.
`
`The inventtion of silica
`
`
`
`material which has regular space structure and pattern
`
`structure is a big research task in the material science
`
`
`field,
`
`and the technical development about this is
`
`progressing largely.
`
`[0003]
`
`
`
`
`
`
`the method of
`ica around the organism is widely
`
`
`
`a certain kind reveal,
`
`used
`
`
`for silica material
`
`in the
`
`organism as a
`
`(mold).
`
`see nonpatent literature 1.),
`
`see nonpatent literature 2.),
`
` field,
`using a molecule
`
`
`A surfactant
`(for example,
`
`
`
`(for example,
`
`
`
`block polymer
`
`a virus,
`
`bact
`
`
`eria (for example,
`
`As a method for making a structure of
`fixing sil
`template
`
`
`
`see nonpatent
`
`literature 3.),
`
`etc. are used
`
` for this
`
`template.
`
`Application to a catalyst,
`
`an electronic industry material,
`
`a nano filter, bio-engineering,
`
`etc.
`
`is possible
`
` for silica
`
`
`
`which has a nano cavity synthesized considering these as a
`
`template,
`
`
`for
`
`example,
`
`
`material of
`
`MCM-41
`
`(meso-porous)
`
`series.
`
`
`Research towards control of
`
`a more precise structure is made
`
`about
`
`these materials,
`
`
`
`
`
`a cavity, how
`
`to be located in a line,
`
`or spherical silica
`
`and cavernous control in
`
`
`the size of
`
`
`
`
`
`etc. are considered.
`
`[0004]
`
`
`
`On the other hand,
`
`in parallel to control of
`
`
`
`suc
`
`Nn a nano
`
`cavity,
`
`the technology
`
`
`which controls the form o
`
`silica by
`
`a micron and also macroscale
`
` from nano attracts
`
`attention.
`
`
`
`
`
`for by the bio-silica in
`
`for example, see nonpaten
`
`the bodily shape
`
`
`
`taken up as bio-silica of
`
` from sil
`ica,
`
`the t literature
`
`a nature.
`
`and has
`
`construction
`
`concerned
`
`ese act as a
`
`What this was educated
`
`ecosystem has a cause (
`
`4
`
`.).
`
`The diatom can be
`
`The diatom constitutes
`
`
` (for example,
`
`
`
`
`
` polyamine.
`
`complicated and precise
`
` form and pattern on it.
`
`of
`
`the silica -—- protei
`
`n or polypeptide -- being
`
`literature 5.) -- th
`
`see nonpatent
`
`
`fixed r
`catalyst of the
`
`eaction of silica,
`
`sca
`
`
` Fold of
`
`Silica
`form growt
`
`th.
`
`or provide the
`
`
`
`In formation of
`
`such living
`
`
`
`organism bio-silica, on
`
`e of
`
`the indispensable ch
`
`emical
`
` fixed mo
`
`structure is long chain
`
`Polyamine works by being
`
`included in pept
`
`tide structure,
`
`or works with polypeptide as
`
`
`
`polyamine of a
`
`lecular weight uniquely (
`
` for example,
`
`see nonpatent literature 6.).
`
`[0005]
`
`As described above,
`
`it has come to be widely known under
`
`in the past several years
`existence of polyamine
`
`
`
`
`
`example that silica sources,
`
`,
`
`
`for
`
`such as silicic acid,
`
`a sodium
`
`Silicate, or
`
`alkoxysilane,
`
`
`are fixable as silica
`
`gel ata
`
`room temperature.
`
`However,
`
`Since it was what
`
`they make
`
`
`
`
`usually carry out the underwater dissolution of the
`
`
`
`polyamine, and is performed by the sol-gel reaction of the
`
`
`
`Silica source in the inside of
`the aqueous solution, even if
`
`
`
`
`
`
`
`
`
`the realization of silica gel
`it could form silica gel,
`
`
`
`form of the silica gel but has a
`which cannot control
`
`
`regular structure was difficult.
`
`
`
`[0006]
`
`Unlike the above-mentioned method,
`
`the inventors by using
`
`the unique molecular association object which the straight-—
`
`chain-shape polyethyleneimine which comprised secondary
`
`
`
`amine reveals in an aqueous medium as a reaction field of
`
`Silica precipitation, The silica content nanostructure which
`
`
`
`(a Patent document
`
`1 -
`
`
`has various form represented by silica nanofiber, and its
`
`
`
`manufacturing method were found out
`
`
`
`four references.). If the silane compound of alkoxysilane is
`
`
`
`
`
`
`
`
`
`
`mixed in the association body liquid after making the
`
`polymer which has a straight-chain-shape polyethyleneimine
`
`
`
`skeleton associate spontaneously underwater in these
`
`
`invention, It is invention completed by having found out
`
`that the nanostructure which the Silang condensed in
`
`
` of silica system nanostructure, as a silica source to be
`
`
`
`hydrolysis on the polymer association body surface
`
`selectively, and polymer and silica compounded generated.
`
`
`
`Although this process is efficient to the structure control
`
`
`used, it is alkoxysilane. Therefore,
`
`
`the manufacturing cost
`
`
`
`
`
`of the nanostructure to manufacture is high, alcohols arise
`
`
`
`from alkoxysilane being expensive by hydrolysis of
`
`
`
`alkoxysilane
`
`further, and the problem to an environmental
`
`impact is not avoided for this disposal treatment, either.
`
` i
`
`
`
`
`is
`inexpensive and the nanostructure of silica can be
`
`built
`
`
`th water glass of non-carbon, etc., it has an
`
`important meaning industrially.
`
`[0007]
`
`[Nonpa
`
`tent literature 1] C.T.Kresge et
`
`al.,Na
`
`1992,359,p.710
`
`tent literature 2] A.Monnier et
`
`al.,Science,1993,261,p1299
`
`[Nonpa
`
`
`tent literature 3] S.A.Davis et
`
`al.,Na
`
`1997,385,p420
`
`[Nonpa ture,
`
` Biotechnol logy, 2003, Springer
`
`
`tent literature 4] W.E.G.Muller Ed.,Silicon
`
`
`
`
`Biomineralizattion:
`Biology-Biotechnology-—Molecular Biology-
`
`
`
`[Nonpatent literature 5] N.Kroger et
`
`al.,Science,1999,286,p.1129
`
`[Nonpatent literature 6] N.Kroger et
`
`
`[Nonpa ture,
`
`
`
`
`
`
`wi
`
`al.,Proc.Natl.Acad.Sci.USA, 2000,97,p14133
`
`[Paten
`
`[Paten
`
`[Paten
`
`document
`
`
`
`
`
`document [Paten document
`
`document
`
`1]
`
`2]
`
`JP,2005-264421,A
`
`JP,2005-336440,A
`
`3]
`
`JP,2006-063097,A
`
`4)
`
`JP,2007-051056,A
`
`
`
`
`
`
`[Description of the Invention]
`
`
`
`[Problem to be solved by the invention]
`
` It is based on the process which the issue which the present
`
`[0008]
`
`
`
`
`invention tends to solve has a low manufacturing cost, and
`
`
`
`the waste of an organic substance does not generate, It is
`
`
`
`
`in providing the simple manufacturing method of the silica
`
`system inorganic structure produced by carrying out heat
`
`
`calcination of the polymer / silica compound nanostructure,
`
`
`
`the polymer / sorted metals / silica compound nanostructure,
`
`
`and these which have various form.
`
`
`[Means for solving problem]
`
`[0009]
`
`
`
`
`
`If it mixes with the water glass which carried out pH
`
`
`
`adjustment preliminarily under the conditions in which the
`
`inventors make a template the crystalline association body
`
`
`
`which specific polymer forms underwater when it inquires
`
`intensively, and it exists stably in order to solve the
`
`
`above-mentioned problem, Silicon of water glass deposits as
`
`Silica around the association body,
`
`there is no generating
`
`
`
`
`
` of an organic matter, and it found out that the
`
`nanostructure which polymer and silica compounded was
`
`obtained, and completed the present invention.
`
`[0010]
`
`Namely,
`
`the present
`
`invention uses as a crystalline
`
`
`
`association body the polymer
`
`shape polyethyleneimine
`skeleton (al)
`
`(A) which has a straight-chain-
`
`in an aqueous medium,
`
`
`and it mixes the water glass (B) which adjusted this and pH
`
`
`
`to 8.5 or more, A manufacturing method of the polymer /
`
`Silica compound nanostructure depositing silica (bl), The
`
`
`
` manufacturing method of polymer / sorted metals / silica
`
`
`
`
`
`compound nanostructure with which metal
`
`ion (cl) or a metal
`
`nano particle (c2)
`
`is contained in the polymer / silica
`
`
`
`compound nanostructure, and the manufacturing method of the
`
`Silica system inorganic structure produced by carrying out
`
`
`heat calcination of
`these are provided.
`
`
`
`
`CT]
`
`
`
`
`(3 Fect of the Invention]
`
`[O011]
`
`Using water glass with the industrially cheapest
`
`
`
` manufacturing method of the present invention, and high
`
` flexibility as a silica source, it is simple and obtains
`
`polymer / silica compound nanostructure, and polymer /
`
`sorted metals / silica compound nanostructure by the method
`
`
`which abandonment of an organic matter twists. The
`
`
`
`nanostructure obtained from this manufacturing method is a
`
`silica system material which the fiber of a nano dimension
`
`
`
`
`
`
`
`
`
`and a unit construction like lamellae spread largely to
`
`three-dimensional space, and has various complicated shape
`
`
`and structures and which carries out the main component of
`
`the silica.
`
`
`
`
`
`Since the polymer which has a straight-chain-shape
`
`
`polyethyleneimine
`skeleton is contained in the inside of
`
`
`
`
`
`
`
`[0012]
`
` Silica,
`
`by the present
`
`the polymer / silica compound nanostructure obtained
`
`
`
`invention can employ efficiently the function
`
`in which the polymer carries out peculiar. For example,
`
`
`Since polyethyleneimine can form metal
`
`ion and a polymer
`
`the polymer / silica compound nanostructure
`
`
`
`metal complex,
`
` of the present
`
`
`separation of metal
`
`invention can be used for concentration and
`
`
`ion, and fixing of a metal complex, and
`
`
`
` forms polymer / sorted metals / silica compound
`
`nanostructure.
`
`[0013]
`
`
`Since polyethyleneimine can form living body polymer, etc.
`
`and the acid / base complex which has an acidic organic
`
`the polymer / silica
`
`
`compound and an acid functional group,
`
`
`compound nanostructure of
`the present invention can be used
`
`
`for separation or fixing of many acid.
`
`
`
`
`
` [0014]
`
`Since polyethyleneimine has sterilization and an antivirotic
`
`function,
`
`the polymer / silica compound nanostructure, and
`
` the polymer / sorted metals / silica compound nanostructure
` antimicrobic agent, a germicide, antiviral, and a cosmetics
`
`obtained by the present
`
`invention can be used as an
`
`additive agent,
`
`
`for example.
`
`
`
`[0015]
`
`
`Since it has the characteristics constituted from a tangle
`
`
`
`of silica nanofiber,
`
`the polymer / silica compound
`
`nanostructure obtained by the present invention can also be
`
`
`
`
`
`
`used as water and a nano filter for purification of air.
`
`[0016]
`
`Since the silica system inorganic structure produced by
`
`
`calcinating the aforementioned polymer / silica compound
`
`nanostructure, or polymer / sorted metals / silica compound
`
`
`nanostructure has high specific surface area, it can be
`
`
`
`
`
`Suitably used for a filter, a catalyst base material, a
`
`
`
`
`filler, etc.
`
` [0017]
`
`
`
` [Best Mode of Carrying Out the Invention]
`
`
`
`The present invention uses as a crystalline association body
`
`(A) which has a straight-—chain-shape
`the polymer
`
`polyethyleneimine
`skeleton (al)
`
`in an aqueous medium, Using
`
`this as a template, by depositing silica (bl) around the
`
`
`
`association body from the water glass (B) which adjusted pH
`
`to 8.5 or more, polymer
`
`(A) and silica (bl) are compounded
`
`
`
`and nanostructure is obtained.
`
`[0018]
`
`
`
`
`
`
`
`In manufacture of the structure which contains silica,
`
`in
`
`order to lose the abandonment
`
`
`to the environment of an
`
`organic substance,
`
`the reaction which does not use
`
`
`
`alkoxysilane must be realized. This is dramatically
`
`
`
` difficult in order to build the silica content nanostructure
`
`
`
`
`which has fixed form and structure in three dimensional
`
`space.
`
`[0019]
`
`
`
`A specific structure which polymer forms in a medium
`
`
`generates fundamentally the nanostructure which polymer and
`
`
`Silica have compounded by functioning as a template which
`
`deposits silica. The more the form of the polymer template
`
`is stable,
`
`the more the polymer / silica compound
`
`nanostructure obtained will have clear nano structure.
`
`
`
`
` In order to complete silica to a certain specific shape,
`
`
`
`
`
`
`[0020]
`
`speaking specifically,
`
`that the polymer template which
`
`
`
`form forms
`derives the three following conditions and (1)
`
`Stably, and (2) -- that the template can condense a silica
`
`source and (3) -- it 1s necessary to arrange that the
`
`
`
`
`
`
`
`
`template promotes the polymerization of a silica source etc.
`
`When alkoxysilane is used for a silica source at this time,
`
`
`
`
`
`in order to fulfill
`the conditions of a lever to
`
`comparatively extensive polymer,
`
`
`for obtaining the compound
`
`nanostructure by which structure was controlled, it was
`
`convenient. As a silica source instead of alkoxysilane,
`
`
`
`
`
`
`
`there are only things,
`
`such as water-soluble silicates (a
`
`sodium silicate, a potassium silicate, etc.) or moisture
`
`
`
`11
`
`
`
`
`powder silica colloid particles. If
`
`such a silica source
`
`is
`
`used,
`
`it will be thought
`
`that the abandonment problem to the
`
`
`environment of
`
`
`the alcohols which arise by hydrolysis of
`
`
`
`alkoxysilane is solvable.
`
`However,
`
`when using water-sol
`
`uble
`
`water glass which is especially a thick solution
`
`
`silicates,
`
`is water solubility, but.
`
`Since it destabilizes by minute
`
`
`
`change (for example, change of pH,
`
`
`mixing of
`
`an additive,
`
`etc.) of an aqueous medium and
`
`
`deposits as a lump of-less
`
`rule silica spontaneously,
`
`water gl]
`
`lass can be mixed stably,
`
`Unless a polymer template and
`
`it is
`
`impossible to
`
`
`
`
`
`te on the ten
`
`
`nplate surface,
`
`to deposit
`
`
`
`Silica, and to obtain polymer / silica compound
`
`condense a silicat
`
`
`
`nanostructure.
`
`[0021]
`
`
`
`
`
`
`
`
`
`In the present
`
`invention,
`
`in order to solve the above-
`
`mentioned problem,
`
`the polymer
`
`(A)
`
`which has a straight-—
`
`chain-shape polyethyleneimine
`
`skeleton
`
`(al) uses as a
`
`template the crystalline association body
`
` formed in an
`
`aqueous medium. Although the polymer
`(A)
`
`t-chain-shape polyethyleneimin
`skel
`
`straight
`
`
`
`underwater soluble,
`
`at a room temperature,
`
`which has a
`
`(al)
`
`is
`
`ton it exists asa
`
`
`
`crystall
`
`line molecular association object.
`
`Also when the
`
`water glass (
`
`B)
`
`which adjusted pH here 8
`
`.5 OF more is mixed,
`
`
`
`It is possible to prevent precipitate of
`
`the silicate in the
`
`aqueous medium which the stability o!
`
`
`
`fF this crystalline
`
`
`
`association body is maintained, and contains the crystalline
`
`
`association body itself, and a silicate makes this
`
`
`
`
`
`
`
`
`crystalline association body a template, By having found out
`
`depositing as silica (silicon oxide)
`
`(bl) selectively around
`
`the template, it came to complete the present invention.
`
`[0022]
`
`Polymer
`
`(A) and silica (bl) which have a straight-—chain-
`
`shape polyethyleneimine
`skeleton are compounded, and the
`
`
`
`nanostructure obtained by the present invention has various
`
` form to which nano structure spreads to space by the
`
`
`hardness of silica (bl).
`
`[0023]
`
`[Polymer which has a straight-chain-shape polyethyleneimine
`
`skeleton]
`
`
`
`
`The straight-chain-shape polyethyleneimine
`
`
`
`
`used in the field of
`the present invention is a polymer
`
`
`skeleton which makes th
`thyleneimine unit of the second
`
`skeleton (al) as
`
`class amine a main structural unit. Although structural
`
`units other than an ethyleneimine unit may exist in the
`
`skeleton (al),
`
`
`
`body form, it is preferable that the fixed chain length in
`
`
`
`in order to make a crystalline association
`
`the polymer skeleton (al)
`
`iS a continuous ethyleneimine unit.
`
`
`
`
`The length of the straight-chain-shape polyethyleneimine
`
`
`skeleton (al), Especially if the polymer
`
`
`
`(A) which has the
`
`
`
`
`
`
`skeleton is a range which can form a crystal, it will not be
`
`
`
`
`
`in order to form a crystal suitably,
`restricted, but
`
`
`
`preferable that
`the number of repeating units of
`the
`
`
`
`
`
`it is
`
`
`
`
`
`
`ethyleneimine unit of the skeleton (al) portion is ten or
`
`
`more, and it is preferable that it is especially the range
`
`
`of 20-10,000.
`
`[0024]
`
`skeleton (al)
`
`
`
` Even if it has a straight-chain-shape polyethyleneimine
`
`
`
`
`in the structure and the form of the whole
`
`
`
`
`
`
`the shape of a star, or a
`
`polymer
`
`(A) should just be a line,
`
`
`pectinate form,
`
`the polymer
`
`(A) used in the present
`
`invention, A crystalline association body can be given in
`
`
`the aqueous medium (both are hereafter called aqueous medium
`
`
`collectively) which is a mixed solvent of water or water,
`
`and a hydrophilic organic solvent.
`
`[0025]
`
`
`
`
`the shape of a star, or a pectinate
`
`
`
`Polymer of these lines,
`
`
` form, It may consist only of a straight-chain-shape
`
`polyethyleneimine
`skeleton (al), and may be a thing which
`
`
`
`consists of the block copolymer of the block (it is
`
`
`hereafter written as a polyethyleneimine block.) which
`
`
`
`
`consists of a straight-chain-shape polyethyleneimine
`
`skeleton (al), and other polymer blocks. As other polymer
`
`
`
`blocks, it is a polymer block of water solubility for
`
`example,
`
`such as a polyethylene glycol,
`
`polypropionylethyleneimine, and polyacrylamide. Or
`
`the
`
`
`
`hydrophobic polym
`
`
`
`er block of the polymethylmethacrylate of
`
`polystyrene, polyphenyl oxazoline of poly oxazoline,
`
`
`
`
`polyoctyl oxazoli
`
`
`
`polyacrylates, po
`
`
`
`ne, polydodecyl oxazoline, and
`
`ly butyl methacrylate, etc., etc. can be
`
`
`mentioned. By con
`
`polymer block bes
`
`association body
`
`sidering it as block copolymer with a
`
`
`the form of
`the crystalline
`
`ides these,
`
`
`
`
`
`
`
`
`formed from polymer and the characteristic
`
`
`of nanostructure obtained can be adjusted.
`
`[0026]
`
`
`
`
`case of being block copolymer
`
`(A) which has a straight-—chain-shape
`The polymer
`
`
`polyethyleneimin
`skeleton the ratio of the straight-—chain-
`
`in the polymer in the
`imine
`skeleton (al)
`shape polyethylen
`
`
`(A), Especially if it is a
`
`
`
`
`range which can form a crystalline association body, it will
`
`
`in order to form the association body
`
`not be restricted
`
`, but
`
`
`
`Suitably,
`
`
`
`it is preferable that the ratio of the straight-
`
`chain-shape polyethyleneimine
`skeleton (al)
`
`
`is 40 mol % or more, and it is still more preferable that it
`
`
`
`is 50 mol % or more.
`
`in polymer
`
`(A)
`
`[0027]
`
`The polymer
`
`chain-shape poly
`
`(A) w hich has the above-mentioned straight-—
`
`thyleneimine
`skeleton (al), The polymer (it
`
` traight chain shape which consists of the
`
`
`is hereafter written as precursor polymer.) which has a
`
`skeleton of the s
`
`
`
`
`
`poly oxazoline used as the precursor can be easily obtained
`
`
`
`
`
`by hydrolyzing under an acid condition or alkali conditions.
`
`
`
`Therefore,
`form,
`
`the
`
`
`(A) which has a
`such as a line of polymer
`
`straight—-chain-shape polyethyleneimine
`skeleton (al),
`
`
`shape of a star, or a pectinate form, can be easily designed
`
`
`
`
`
`by controlling the form of this precursor polymer. A degree
`
` of polymerization and terminal structures can also be easily
`
`
`
`
`
`
`
`adjusted by controlling the degree of polymerization and end
`
`
`
`
`functional team of precursor polymer. When forming the block
`
`
`
`copolymer which has a straight-chain-shape polyethyleneimine
`
`skeleton (al), precursor polymer can be made into block
`
`
`copolymer and the skeleton of the straight chain shape which
`
`
`consists of the poly oxazoline in the precursor can be
`
`obtained by hydrolyzing selectively.
`
`
`
`[0028]
`
`
`
`The monomer of oxazoline can be used for precursor polymer,
`
`it can synthesize it with synthesizing methods,
`
`such as a
`
`
`
`method of polymerizing a cation form, or the macro monomer
`
`
`
`method, and can synthesize precursor polymer of various form,
`
`
`
`
`
`such as a line,
`
`
`
`the shape of a star, or a pectinate form, by
`
`choosing a synthesizing method and an initiator suitably.
`
`[0029]
`
`
`
`As a monomer which forms the skeleton of the straight chain
`
`shape which consists of poly oxazoline, oxazoline monomers,
`
`such as methyl oxazoline, ethyl oxazoline, methylvinyl
`
`oxazoline, and phenyl oxazoline, can be used.
`
`
`
`
`
`
`
`[0030]
`
`As a polymerization initiator,
`
`the compound which has
`
` functional groups,
`
`such as an alkyl chloride group, an alkyl
`
`bromide group, an iodination alkyl group, a
`
`
`
`
`toluenesulfonyloxy group, or an trifluoromethyl sulfonyloxy
`
`group, can be used into a molecule. These polymerization
`
`
`initiators are obtained by making the hydroxyl group of many
`
`
`alcohols compounds convert to other functional groups.
`
`
`
`Especially, as functional group conversion, since
`
`
`toluenesulfonic-acid-izing, and the
`bromination,
`iodination,
`
`
`
`
`thing formed into trifluoro methylsulfonic acid have high
`
`
`
`polymerization start efficiency, it is preferable, and it is
`
`
`
`
`
`
` preferable to consider it as an alkyl bromide group and a
`
`
`toluenesulfonic acid alkyl group especially.
`
`[0031]
`
`The thing which converted poly (ethylene glycol)
`
`terminal
`
`hydroxyl groups to bromine or iodine, or the thing converted
`
`to the tosyl group can also be used as a polymerization
`
`In that case, it is preferable that it is the
`
`
`
`initiator.
`
`
`
`
`
`
`
`
`range of 5-100, and especially if the ranges of a poly
`
`
`(ethylene glycol) degree of polymerization are 10-50, it is
`
` preferable.
`
`[0032]
`
`
`
`
`The luminescence function have a functional group which has
`
`cation ring opening living polymerization start ability, and
`
`
`
`
`
`
`
`
`
`
`
`
`according to light, The pigments which have a skeleton of
`
`
`either the porphyrin skeleton which has an energy transfer
`
`
`
`function and an electronic transition function, a
`
`phthalocyanine skeleton or a pyrene skeleton can give a
`
`
`special function to polymer
`
`(A) and nanostructure which are
`
`obtained.
`
`[0033]
`
`Linear precursor polymer
`
`oxazoline monomer by polymerizing with the polymerization
`
`
`initiator which has a univalent or divalent functional group.
`
`is obtained in the above-mentioned
`
`
`
`As such a polymerization initiator,
`
`they are methylbenzene
`
`chloride and methylbenzene bromide,
`
`
`for example. Iodination
`
`
`methylbenzene, methylbenzene toluenesulfonic acid, and
`
`
`
`trifluoromethylsulfonate, Methane bromide,
`
`
`
`
`
`methylbenzene,
`
`Llodination methane, methanetoluenesulfonic acid, or a
`
`
`
`
`
`toluenesulfonic anhydride, A trifluoro methylsulfonic
`
`
`
`
`
`
`
`
`anhydride, 5-(4-bromomethyl phenyl)-10,15,20-bird (phenyl)
`
`
`
`porphyrin, Or divalent things,
`
`such as univalent things,
`
`
`such as bromomethyl pyrene, dibromomethylbenzene, JIYOU-ized
`
`
`
`methylbenzene, dibromomethyl biphenylene, or
`
`dibromomethylazobenzene, are mentioned. The linear poly
`
`oxazoline currently used industrially [ poly (methyl
`
`oxazoline), poly (ethyl oxazoline), or poly (methylvinyl
`
`oxazoline)
`
`] can also be used as precursor polymer as it
`
`is.
`
`[0034]
`
`
`
`Star-like precursor polymer is obtained in an oxazoline
`
`monomer which was described above by polymerizing with the
`
`
`polymerization initiator which has a functional group more
`
`than trivalent. As a polymerization initiator more than
`
`trivalent, it is a thing trivalent
`
`[,
`
`such as
`
` tribromomethylbenzene,
`
`
`
`]
`
`for example. Tetrabromo
`
`
`
`methylbenzene,
`
`tetra(4-chloromethyl phenyl) porphyrin, The
`
`thing more than pentavalence,
`
`such as tetravalent things,
`
`such as tetrabromo ethoxyphthalocyanine, hexa bromomethyl
`
`
`
`
`
`benzene, and tetra(3,5-JITOSHIRIRU ethyloxy phenyl)
`
`porphyrin,
`
`is mentioned.
`
`[0035]
`
`
`
`
`
`In order to obtain precursor polymer of a pectinate form,
`
`are obtained by polymerizing an oxazoline monomer
`
`
`from the
`
`polymerization start group using the linear polymer which
`
`
`
`
`
`
`
`
`
`
`has a polymerization start group of ** value, but. For
`
`example, after halogenating the hydroxyl group of the
`
`polymer which carries out
`
`
`two or more owners of
`
`the hydroxyl
`
`group to side chains,
`
`such as a linear epoxy resin and
`
`polyvinyl alcohol, with bromine,
`
`iodine, etc. or making it
`
`convert to a tosyl group, using as a polymerization start
`
`
`
`group can also obtain the conversion portion.
`
`[0036]
`
`
`A polyamine type terminator can also be used as a method of
`
`
`
`obtaining precursor polymer of a pectinate form. For example,
`
`
`
`
`
`poly oxazoline of a pectinate form can be obtained by
`
`
`polymerizing oxazoline and combining the end of the poly
`
`
`
`
`oxazoline with the amino group of polyamine,
`
`such as
`
`polyethyleneimine, polyvinyl amine, and poly propylamine,
`
`
`using the polymerization initiator of monovalence.
`
`[0037]
`
`
`
`Hydrolysis of the skeletal part of the straight chain shape
`
`
`
`
`which consists of the poly oxazoline of
`the precursor
`
`
`
`
`
`polymer obtained by the above may be under which [ under an
`
`acid condition or alkali conditions ] condition. The
`
`
`
`
`
`hydrolysis under acid conditions can obtain the
`
`
`hydrochloride of polyethyleneimine,
`
`
`for example by stirring
`
`precursor polymer under heating in a hydrochloric acid
`
`aqueous solution. By processing the obtained hydrochloride
`
`
`
`
`
`with excessive ammonium water,
`
`
`the crystal powder of the
`
`polymer which has a basic polyethyleneimine
`skeleton can be
`
`
`
`obtained. Although concentrated hydrochloric acid or an
`
`
`
`
`1 mol/L aqueous solution may be sufficient as the
`
`about
`
`hydrochloric acid aqueous solution to be used,
`
`
`
`
`hydrolyze efficiently, it is desirable to use a 5 mol/L
`
`in order to
`
`
`hydrochloric acid aqueous solution. Around 80 degrees C of
`
`reaction temperature are desirable.
`
`[0038]
`
`For example,
`
`the hydrolysis under alkali conditions can make
`
`
`the skeleton which consists of poly oxazoline convert to a
`
`
`
`-—- 20 -
`
`
`polyethyleneimine
`skeleton by using a sodium hydroxide
`
`
`aqueous solution. After making it react under alkali
`
`conditions, by washing reaction mixture in permeable
`
`
`
`
`
`membrane, excessive sodium hydroxide can be removed and the
`
`
`crystal powder of
`the polymer which has a polyethyleneimine
`
`
`
`skeleton can be obtained. The range of the concentration of
`
`
`
`the sodium hydroxide to be used may be 1-10 mol/L, and it is
`
`
`
`
`
`
`preferable for performing a more efficient reaction that it
`
`
`
`is the range of 3-5 mol/L. Around 80 degrees C of reaction
`
`
`
`
`
`
`temperature are preferable.
`
`[0039]
`
`
`
`As amount of
`the acid used or alkali in the hydrolysis under
`
`
`
`
`an acid condition or alkali conditions, 1-10 Eq may be
`
`
`
`
`sufficient to the oxazoline unit in precursor polymer, and
`
`
`
`
`
`in reaction efficiency, and
`it is preferable for improvement
`
`facilitation of post-processing to consider it as about
`
`
`
`
`
` [0040]
`
`
`
`
`
`3 Eq.
`
`The polymer
`
`
`(A) which has the polyethyleneimine
`skeleton
`
`
`(al) by the above-mentioned hydrolysis by the skeleton of
`
`
`
`
`
`the straight chain shape which consists of the poly
`
`oxazoline in precursor polymer turning into a straight-—
`
`chain-shape polyethyleneimine
`skeleton (al)
`
`is obtained.
`
`[0041]
`
`
`
`
`
`
`In forming the block copolymer of a straight-chain-shape
`
`polyethyleneimine block and other polymer blocks, Precursor
`
`
`
`
`
`
`
`
`
`- ?1 -
`
`polymer can be made into the block copolymer which consists
`
`
`
`of a polymer block of
`
`
`consists of poly oxazoline, and other polymer blocks, and
`
`the straight chain shape which
`
`
`
`the block of the straight chain shape which consists of the
`
`
`
`poly oxazoline in the precursor polymer can be acquired by
`
`hydrolyzing selectively.
`
`[0042]
`
`
`When other polymer blocks are water-soluble polymer blocks,
`
`such as poly (N-propionylethyleneimine), Poly (N-
`
`
`
`
`propionylethyleneimine) can form block copolymer using the
`
`solubility to an organic solvent being high compared with
`
`
`poly (N-formylethyleneimine) or poly (N-acetylethylenimine).
`
`
`Namely, after carrying out cation ring opening living
`
`
`
`
`
`
`
`polymerization of 2-oxazoline or the 2-methyl-2-oxazoline
`
`
`under existence of
`the above-mentioned polymerization start
`
`
`
`compound, To the obtained living polymer, by polymerizing 2-
`
`
`ethyl-2-oxazoline, The precursor polymer which consists of a
`
`
`poly (N-formylethyleneimine) block or a poly (N-
`
`
`
`acetylethylenimine) block, and a poly (N-
`
`propionylethyleneimine) block is obtained. An emulsion is
`
` formed by mixing an immiscible organic solvent with the
`
`water which dissolves the precursor polymer
`
`in water and
`
`
`
`dissolves a poly (N-propionylethyleneimine) block in the
`
`aqueous solution, and stirring. By hydrolyzing
`
`
`
`preferentially a poly (N-formylethyleneimine) block or a
`
`
`
`
`
`—- 22 -
`
`
`poly (N-acetylethylenimine) block in the aqueous phase of
`
`the emulsion by adding acid or alkali, The block copolymer
`
`which has a straight-chain-shape polyethyleneimine block and
`
`
`a poly (N-propionylethyleneimine) block can be formed.
`
`
`
`[0043]
`
`When the valences of the polymerization start compound used
`
`
`here are 1 and 2, it becomes the block copolymer of straight
`
`
`
`
`chain shape, and if it is a valence beyond it,
`
`the block
`
`
`
`copolymer of a star shape will be obtained. It is also
`
`possible the polymer obtained by making precursor polymer
`
`into the block copolymer of multistage and to consider it as
`
`the block structure of multistage.
`
`
`
`
`[0044]
`
`[Crystalline association body]
`
`The polymer
`
`(A) which has the above-mentioned straight-
`
`chain-shape polyethyleneimine
`skeleton (al) derives the
`
`
`crystal of the polymer
`
`polyethyleneimine
`skeleton (al)
`
`reveals crystallinity in an aqueous medium. The polymer
`
`(A), when the straight-—chain-shape
`
`in the primary structure
`
`
`crystal can also form the hydrogel which has a three-
`
`
`
`
`
`
`dimensional network by physical combination of
`
`the polymer
`
`
`crystals under existence of an aqueous medium, and can also
`
` form the cross-bridging hydrogel which has a chemical
`
`crosslinking bond by cross-bridging polymer crystals by a
`
`
`cross linking agent further.
`
`
`
`-— 23
`
`[0045]
`
`The polyethyleneimine used widely conventionally is branched
`
`
`state polymer obtained by the ring opening pol
`ymerization of
`
`
`
`annular ethyleneimine,
`
`and prima
`
`ry amine,
`
`the second class
`
`amine,
`
`and a tertiary amine exis
`
`
`Therefore,
`
` although branched sta
`
`
`water solubility,
`
`Since it does
`
`order to make hydrogel using bra
`
`f
`polyethyl neimin
`the
`network s
`
`
`
`the covalent bond by a cross
`
`straight—-chain-shape polyethylen
`
`lin
`
`for the present invention h
`
`
`
`
`
`t
`
`in the primary structure.
`
`te polyethyleneimine is
`
`not have crystallinity,
`
`in
`
`nched state
`
`
`
`tructure must be given by
`
`king agent. However,
`
`the
`
`eimine which the polymer
`
`as as a skeleton comprises
`
`
`
`used
`
`only the second class amine,
`
`and
`
`second class amine [
`
`the ]
`
`type straight-—chain-shape polyethyleneimine has the
`
`outstanding crystallinity,
`
`thoug
`
`h it is water solubility.
`
`[0046]
`
`such a crys
`
`
`
`tal of straight-chain
`
`-—shape polyethyleneimine,
`
`
`
`
`
` 14 th volume,
`
` it is known that polymer
`
`is known wi
`
`
`th the number of crys
`
`
`ethyleneimi
`ne of the polymer tha
`
`
` er
`di
`largely (Y. Chatani et al
`
`
`p.315 -321 referenc
`
`hyleneimine gives priority
`polyet
`
` t
`
`tal water contained per
`
`polymer crystal
`
`structures
`
`oT
`
`Macromolecules, 1981,
`
`the
`
`e). Although anhydrous
`
`to the crystal structure
`
`charac
`
`terized by double helical
`
`conformation,
`
`
`if dyad water
`
`is contained in a monomeric unit,
`
`will grow up to be a crystalline characterized by zigzag
`
`
`
`structure.
`
`
`fF the straight-—chain-shape
`the crystal ot!
`
`polyethyleneimine obtained
`
`
`from the water is actually a
`
`
`
`crystal which contains dyad water in one monomeric unit —--
`
`underwater
`
`the crystal -- a room temperature stat
`
`it
`
`
`
`is insoluble.
`
`[0047]
`
`has a straight
`
`in the present
`
`
`(A) which
`The crystalline association body of the polymer
`
`
`-chain-shape polyethyleneimine
`skeleton (al)
`
`
`
`if it is formed by the
`invention, Even
`
`
`
`
`
`
`crystal manifestation o
`
`polyethyleneimine
`skel
`
`
`
`f a straight-chain-shape
`
`ton (al)
`
`like the above-mentioned
`
`
`
`
`case and polymer form ij
`such as a line,
`form,
`s
`
`
`a star, or a pectinate
`If it has a straight-chain-
`form,
`
`shape polyethyleneimin
`skeleton (al)
`
`
`the shape of
`
`in the primary
`
`
`
`structure,
`
`
`the crystalline association body of polymer
`
`(A)
`
`will be obtained.
`
`[0048]
`
`
`
`
` Existence of
`the crystalline association body of polymer
`
`(A)
`
`in the present
`
`t
`
`invention can be checked
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