CN100503655C - Luminescent organic-polymer/metal complex, luminescent organic-polymer/metal complex composition capable of forming film by wet process, and process for producing the same - Google Patents
Luminescent organic-polymer/metal complex, luminescent organic-polymer/metal complex composition capable of forming film by wet process, and process for producing the same Download PDFInfo
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- CN100503655C CN100503655C CNB200480014974XA CN200480014974A CN100503655C CN 100503655 C CN100503655 C CN 100503655C CN B200480014974X A CNB200480014974X A CN B200480014974XA CN 200480014974 A CN200480014974 A CN 200480014974A CN 100503655 C CN100503655 C CN 100503655C
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Abstract
This invention provides a luminescent organic polymer metal complex represented by polyQ M K n-1 (1) which is obtained by the reaction of a polymer ligand (polyQ) with an 8-hydroxyquinoline derivative introduced to its side chain through a spacer group, an 8-hydroxyquinoline derivative ligand (K) and a divalent to tetravalent metal ion (M n+ ) wherein the 8-hydroxyquinoline derivative ligand (K) has a bulky substituent. This invention also provides a luminescent organic polymer metal complex composition comprising said luminescent organic polymer metal complex and additionally a low-molecular-weight ligand and a process for producing the same.
Description
Technical field
The present invention relates to novel luminous organic polymer metal complexes (or claim " coordination compound ") and comprise this organic polymer metal complexes can film by wet luminous organic polymer metal complex composition and manufacture method thereof, particularly as the luminescent layer material of organic electroluminescent device (organic EL) and useful luminous organic polymer metal complexes and luminous organic polymer metal complex composition and manufacture method thereof that can film by wet.
Background technology
Therefore organic EL waits in expectation and much uses in the purposes at indicating meter and the back light of liquid crystal indicator, various advertising tower and the exhibited light etc. of TV, Personal Computer and family computer etc. because the possibility that can make surface light emitting, large-area luminous element is arranged.
Particularly as the material that has electron transport ability and luminous power simultaneously, initial report three (oxine base) aluminium (Alq
3) since, studied aluminum complex and derivative thereof as its part (or title " dentate ") with oxine morely, in addition, at this compound (Alq
3) and derivative beyond also reported more organometallic complex as the material of organic EL.
, this compound (Alq
3Though) excellent on aspects such as its fastness, polychromatism, high brightness, do not lose its importance now yet, but situation as the organic EL use, need on substrate, vacuum evaporation form film, will make large-area luminous element more, the device that is used for vacuum evaporation maximizes more, except the making that is unsuitable for large-area luminous element, also in as the action of luminous element, make luminous molecule crystallization lentamente, have to lack weather resistance or short problem of life-span by thermal motion.
As the method that solves such problem, known polymer self is made it method with metallic ion coordination as part, such scheme has for example been proposed: will be to Alq
3The solution of three (5-(methacryloxy ethoxyl methyl)-oxine base) aluminium of introducing the polymerizability part and obtaining is spin-coated on the substrate, then adopt light to carry out polymerization in this case, thus the insoluble film of on substrate, making crosslinked to heavens (W002/068560 brochure).; in this method in order on substrate, to adopt light to make polymerizability partially polymerized and use photoreaction initiator in this case; but this photoreaction initiator enters into the film on the substrate; might hinder luminous; volume change during in addition because of polymerization makes film produce strain, might produce film and easily peel off.
In addition, also know the organic polymer metal complexes of making solvent soluble with macromolecule ligand and low molecule ligand, and use its film forming method on substrate, for example proposed: the material (the 2887th page of Journal of Polymer Science:PartA:Polymer Chemistry the 38th volume (2000)) of having introduced the oxine position at the side chain of polyethersulfone by imide bond; Make Alq
35 of an oxine position and 5 of norbornylene between by spacer (CH
2NH (CH
2)
6-) and bonded XAlq
2The material of the coordination compound monomer open loop metathesis polymerizable of type (the 1766th page of Macromolecules the 36th volume (2003))., these materials all are to have repeating unit that combines aluminum complex and the multipolymer that does not have the repeating unit of aluminum complex, can not introduce aluminum complex with high ratio to high molecular repeating unit, have inefficient problem as electric-field light-emitting element.
Organic polymer metal complexes about solvent soluble with macromolecule ligand and low molecule ligand, also proposed: will have the material (spy open 2001-131542 communique and spy open 2001-185357 communique) of the resultant of reaction of amino high molecular polymer and aromatics as macromolecule ligand with aldehyde radical and hydroxyl, with the material (spy opens the 2001-185357 communique and the spy opens the 2001-220579 communique) that has as the beta-diketon base of the part of polymer side chain, but these materials are not to use the material of oxine derivative as the part of polymer side chain, because Alq
3Be excellent especially electron transport luminescent material, therefore wish to take into account previous narration high-molecular luminous material advantage and have the exploitation of the part of oxine derivative at side chain.
Summary of the invention
Therefore, the inventor (it is Alq about a kind of luminous organic polymer metal complexes
3The organometallic complex of type has this Alq
3The speciality that all fastness, polychromatism, high brightness etc. are excellent, in addition, have macromolecule ligand and low molecule ligand and excellent solvent soluble is arranged, can adopt the wet type legal system film that is suitable for big area system film in view of the above) result of diligent investigation is surprised to find that, has bulky substituent oxine derivative as low molecule ligand by use, even use the macromolecule ligand of homopolymer also to demonstrate excellent solvent soluble with oxine position, can adopt wet type legal system film, thereby finish the present invention.
In addition, the inventor finds, by only making by having low molecule ligand that bulky substituent oxine derivative the constitutes Alq as part
3The luminous organometallic complex of type and Alq with macromolecule ligand and low molecule ligand
3The luminous organic polymer metal complexes coexistence of type, above-mentioned luminous organic polymer metal complexes is enhanced for the solvability of solvent, becomes the luminous organic polymer metal complexes that is suitable for wet type legal system film, thereby has finished the present invention.
Therefore, the objective of the invention is to, provide to have macromolecule ligand and low molecule ligand and excellent solvent soluble is arranged, be suitable for the Alq of wet type legal system film
3The luminous organic polymer metal complexes of type.
In addition, another object of the present invention is to, provide and contain above-mentioned Alq with macromolecule ligand and low molecule ligand
3The luminous organic polymer metal complexes of type has the also luminous organic polymer metal complex composition of energy film by wet of excellent solvent soluble.
And, the present invention also aims to, the manufacture method of these luminous organic polymer metal complexess and composition thereof is provided.
Promptly, the present invention is a kind of luminous organic polymer metal complexes, it is characterized in that, be to make in the side chain of the high molecular polymer with repeating unit (Y) as required by spacer (X) to have introduced the macromolecule ligand (polyQ) of oxine derivative (Q) and the low molecule ligand (K) that is made of oxine derivative (K) and the metal ion (M of 2～4 valencys
N+) reaction and the organic polymer metal complexes of the following general formula of usefulness (1) that obtains expression, above-mentioned oxine derivative (K) is the oxine derivative of representing with following general formula (2),
polyQ·M·K
n-1 (1)
Wherein, R in the formula
1～R
6Be to be selected from hydrogen; halogen; carbon number is 1～20 and by the straight chain shape; prop up chain; ring-type or their the saturated or undersaturated alkyl that constitutes; the alkoxyl group of carbon number 1～20; the alkylamino of carbon number 1～20; the alkyl sulfenyl of carbon number 1～20; the alkyl sulphonyl of carbon number 1～20; the alkoxyalkyl of carbon number 2～20; the alkyl-thio-alkyl of carbon number 2～20; the alkyloyl of carbon number 2～20; aroyl; the alkyl monosubstituted amino alkyl of carbon number 2～20; the dialkyl aminoalkyl of carbon number 3～20; the phenylazo of functional group's replacement or non-replacement; functional group replace or the anilino alkyl of non-replacement and-SO
3The substituting group of Na, substituent R
1, R
3, R
4And R
6Among at least 1 be hydrogen, halogen and-SO
3Bulky substituting group beyond the Na.
In addition, the present invention is a kind of luminous organic polymer metal complex composition, the low molecular metal title complex (LM-C) that it comprises with the high molecular metal complex (HM-C) of above-mentioned general formula (1) expression and only has the low molecule ligand (K) that is made of above-mentioned oxine derivative (K) and metal ion (Mn+) coordinate of 2～4 valencys to represent with following general formula (3).
M·K
n (3)
And then, the present invention is a kind of manufacture method of luminous organometallic complex composition of energy film by wet, it is characterized in that, metallic compound 1 equivalent with respect to the metal of 2～4 valencys, in solvent, make macromolecule ligand (polyQ) 0.1～1 equivalent of having introduced oxine derivative (Q) at the side chain of high molecular polymer as required by spacer (X) with repeating unit (Y), react with low molecule ligand (K) 1～3.9 equivalent that constitutes by oxine derivative (K), make the metal ion (M that comprises macromolecule ligand (polyQ) and low molecule ligand (K) and 2～4 valencys with above-mentioned general formula (2) expression
N+) coordinate is with the high molecular metal complex (HM-C) of above-mentioned general formula (1) expression and only low molecule ligand (K) metal ion (M with 2～4 valencys
N+) coordinate is with the organic polymer metal complex composition of the low molecular metal title complex (LM-C) of above-mentioned general formula (3) expression.
In the present invention, being used to make the macromolecule ligand (polyQ) of the high molecular metal complex (HM-C) of general formula (1), is to have introduced the part that forms the oxine derivative (Q) of title complex by spacer (X) in the repeating unit (Y) of high molecular polymer as required.This macromolecule ligand (polyQ), its high molecular polymer can be the polymkeric substance that is made of the repeating unit of single kind (Y), can also be the multipolymers with the repeating unit (Y) more than 2 kinds.
Repeating unit (Y) as the high molecular polymer that forms this high molecular metal complex (HM-C), if can introduce oxine derivative (Q) by spacer (X) as required just is not particularly limited, for example can enumerate by addition polymerization, polycondensation, the repeating unit that open loop metathesis polymerizable etc. are made, specifically can exemplify out: from acrylate, methacrylic ester, acrylamide, the acrylic compound class of Methacrylamide etc., the vinyl ester of vinyl-acetic ester etc., the N-vinyl lactam class of N-vinyl pyrrolidone etc., vinyl ethers, the allyl ester class, allyl ether series, the repeating unit (ethylenic linkage) of all olefines derived polymers of the vinyl aromatic compounds class of vinylbenzene etc. etc., all dienes repeat units derived from divinyl and isoprene etc., and acid amides, imide, ester, the ether sulfone, vinyl pentamethylene etc., preferably methacrylic ester, vinylbenzene, vinyl pentamethylene etc.
In addition, the spacer (X) that when forming above-mentioned macromolecule ligand (polyQ), is provided with as required be between the quinoline nuclei of the main chain of the high molecular polymer that will constitute by repeating unit (Y) and oxine derivative (Q) bonded in conjunction with base, can introduce with oxine derivative (Q) bonded substituting group in the monomer side of the repeating unit (Y) that forms high molecular polymer by polyreaction and be provided with, on the contrary, also can introduce with above-mentioned monomer side bonded substituting group and be provided with in oxine derivative (Q) side, can also introduce respectively in above-mentioned monomer side and oxine derivative (Q) side and react to each other and bonded substituting group and being provided with, specifically preferably by carbon, hydrogen, halogen, oxygen, nitrogen, sulphur, silicon, atomic buildings such as phosphorus, and straight chain shape ground bonded atomicity is 0～15 mutually, preferred 5～10 combination base also can be glycolss such as ethylene glycol, two amines of quadrol etc., alkyl chain etc.
And; as the oxine derivative (Q) that constitutes above-mentioned macromolecule ligand (polyQ); can enumerate oxine; with have in its wantonly position more than 1 or 2 of 2～7 1 or the mutual identical or different substituent derivative more than 2, described substituting group is selected from halogen; carbon number is 1～20 and by the straight chain shape; prop up chain; ring-type or their the saturated or undersaturated alkyl that constitutes; the alkoxyl group of carbon number 1～20; the alkylamino of carbon number 1～20; the alkyl sulfenyl of carbon number 1～20; the alkyl sulphonyl of carbon number 1～20; the alkoxyalkyl of carbon number 2～20; the alkyl-thio-alkyl of carbon number 2～20; the alkyloyl of carbon number 2～20; aroyl; the alkyl monosubstituted amino alkyl of carbon number 2～20; the dialkyl aminoalkyl of carbon number 3～20; the phenylazo of functional group's replacement or non-replacement; the anilino alkyl of functional group's replacement or non-replacement; and-SO
3The substituting group of Na.
Also be not particularly limited about the method for making this macromolecule ligand (polyQ), for example oxine derivative (Q) chloro is methylated, then make the reaction of (methyl) vinylformic acid hydroxyalkyl acrylate, thereby introduce (methyl) vinylformic acid alcoxyl base ester group of polymerizability, in the presence of free radical reaction initiators such as AIBN, make the resulting substituent oxine derivative of polymerizability (Q) polymerization that contains, can make thus, in addition, adopt and use diamines, be synthesized by polycondensation the method for polymeric amide or polyimide with oxine position, also can easily make with method of the norbornene derivative open loop metathesis polymerizable that will have the oxine position by ruthenium catalyst etc.
At this, in the presence of the free radical reaction initiator with above-mentioned contain the substituent oxine derivative of polymerizability (Q) thus when macromolecule ligand (polyQ) is made in polymerization, for example oxine derivative (Q) is the phenoloid that the radical-scavenging ability is arranged, strip out make it polymerization under the former state state of its 8 hydroxyls when, because of the seizure of free radical makes the situation that polyreaction is hindered, the such method manufacturing of preferred employing: make trialkylsilkl halogenide and 8 hydroxyl reactions that contain the substituent oxine derivative of polymerizability (Q), thereby introducing trialkylsilkl, then in the presence of free radical reaction initiators such as AIBN, make (methyl) vinylformic acid alcoxyl base ester group partly carry out polymerization, slough trialkylsilkl from resulting polymkeric substance.
In addition, about being used to form low molecule ligand (K), be in above-mentioned general formula (2) by oxine derivative (K) formation with the high molecular metal complex (HM-C) of above-mentioned general formula (1) expression, its substituent R
1～R
6For being selected from hydrogen; halogen; carbon number is 1～20 and by the straight chain shape; prop up chain; ring-type or their the saturated or undersaturated alkyl that constitutes; the alkoxyl group of carbon number 1～20; the alkylamino of carbon number 1～20; the alkyl sulfenyl of carbon number 1～20; the alkyl sulphonyl of carbon number 1～20; the alkoxyalkyl of carbon number 2～20; the alkyl-thio-alkyl of carbon number 2～20; the alkyloyl of carbon number 2～20; aroyl; the alkyl monosubstituted amino alkyl of carbon number 2～20; the dialkyl aminoalkyl of carbon number 3～20; the phenylazo of functional group's replacement or non-replacement; the anilino alkyl of functional group's replacement or non-replacement; and-SO
3The substituting group of Na, and substituent R
1, R
3, R
4And R
6Among at least 1 be hydrogen, halogen and-SO
3Bulky substituent oxine derivative beyond the Na, preferably above-mentioned substituent R
1, R
4And R
6Among at least 1 substituting group be 6～20 and for being selected from carbon number by the straight chain shape; prop up chain; ring-type or their the saturated or undersaturated alkyl that constitutes; the alkoxyalkyl of carbon number 2～20; the alkyloyl of carbon number 2～20; the dialkyl aminoalkyl of carbon number 3～20; the phenylazo of functional group's replacement or non-replacement; and functional group replaces or the bulky substituent oxine derivative of the anilino alkyl of non-replacement; as particularly preferred 7-(4-ethyl-1-the Methyl Octyl)-oxine of enumerating; 7-(1-vinyl-3; 3; 6,6-tetramethyl-hexyl)-oxine etc.
And, as the metal ion (M of 2～4 valencys that form above-mentioned high molecular metal complex (HM-C)
N+), can restrictedly not use the metal ion (M of 2～4 valencys that in this organometallic complex, use up to now
N+), specifically can enumerate: aluminum ion (Al
3+), beryllium ion (Be
2+), cadmium ion (Cd
2+), cerium ion (Ce
3+), cobalt ion (Co
3+), chromium ion (Cr
3+), cupric ion (Cu
2+), iron ion (Fe
3+), gallium ion (Ga
3+), germanium ion (Ge
4+), indium ion (In
2+), mn ion (Mn
2+), nickel ion (Ni
2+), ruthenium ion (Ru
3+), osmium ion (Os
3+), titanium ion (Ti
4+) etc., preferably can enumerate aluminum ion (Al
3+), gallium ion (Ga
3+), beryllium ion (Be
2+) etc.Metal ion (the M of 2～4 valencys
N+) be aluminum ion (Al
3+) situation, as the aluminum compound that uses for synthetic above-mentioned high molecular metal complex (HM-C), the tri-alkoxy aluminium of the particularly preferred trialkyl aluminium of enumerating trimethylammonium aluminium, triethyl aluminium etc. and three isopropoxy aluminium etc.
In the present invention, organic polymer metal complexes (HM-C) with above-mentioned general formula (1) expression, also have and himself demonstrate excellent solvability for all solvents, can adopt wet type legal system film separately, but, given play to more excellent solvent soluble sometimes by mixing with the low molecular metal conjunction with figs. exponent of representing with above-mentioned general formula (3) (LM-C).
Promptly, luminous organometallic complex composition of the present invention, be being principal constituent with the high molecular metal complex (HM-C) of above-mentioned general formula (1) expression with the low molecular metal title complex (LM-C) that above-mentioned general formula (3) is represented, should low molecular metal title complex (LM-C), be only have by the low molecule ligand (K) that constitutes with the same oxine derivative (K) of the situation of high molecular metal complex (HM-C) with and the metal ion (M of same 2～4 valencys of the situation of high molecular metal complex (HM-C)
N+) the coordinate compound.
About this luminous organometallic complex composition, can make high molecular metal complex (HM-C) and low molecular metal title complex (LM-C) respectively, resulting high molecular metal complex (HM-C) and low molecular metal title complex (LM-C) ratio with defined is dissolved in the solvent of defined, can makes thus by having identical or different metal ion (M mutually
N+) or the high molecular metal complex (HM-C) of mutually identical or different low molecule ligand (K) and the composition of low molecular metal title complex (LM-C) composition, but about the metal ion (M in high molecular metal complex (HM-C) and the low molecular metal title complex (LM-C)
N+) and the mutual identical composition of low molecule ligand (K), metallic compound 1 equivalent with respect to the metal of 2～4 valencys, in the solvent of defined, make 0.1～1 equivalent, preferred 0.2～0.5 normal macromolecule ligand (polyQ) and 1～3.9 equivalent, the reaction of preferred 1.5～2.8 normal low molecule ligands (K), can easily make thus.
In addition, in this luminous organometallic complex composition, cooperation ratio about above-mentioned high molecular metal complex (HM-C) and low molecular metal title complex (LM-C), be not specially limited, but viewpoint from the physical strength of solvent soluble and film, the mol ratio (HM-C/LM-C) of high molecular metal complex (HM-C) and low molecular metal title complex (LM-C) is normally more than 0.2, preferably more than 0.5.
And, as the solvent that in above-mentioned luminous organometallic complex composition, uses, if do not have reactivity for high molecular metal complex (HM-C) and low molecular metal title complex (LM-C), the solvent that can also dissolve these high molecular metal complexes (HM-C) and low molecular metal title complex (LM-C) just is not particularly limited, and for example can enumerate chloroform, methylene dichloride, the chlorine series solvent of ethylene dichloride etc., the ether series solvent of tetrahydrofuran (THF) etc., toluene, the aromatic hydrocarbons series solvent of dimethylbenzene etc., acetone, the ketone series solvent of methylethylketone etc., ethyl acetate, butylacetate, the ester series solvent of ethyl cellosolve acetate etc. etc.
About luminous organic polymer metal complexes of the present invention (HM-C) or comprise this high molecular metal complex (HM-C) and the luminous organometallic complex composition of low molecular metal title complex (LM-C), with the situation of its system film, also can in its solvent solution, add low molecular pigment or low molecular positive charge conveying property compound as required.
As the pigment that adds for this purpose, for example can enumerate Nile red, coumarin 6, quinacridone etc., in addition, for example can enumerate 1 as positive charge conveying property compound, two [the 4-[N of 1-, N '-two (p-methylphenyl) amino] phenyl] hexanaphthene, N, N '-phenylbenzene-N, N '-two (tolyl) p-diaminodiphenyl etc.
As using luminous organic polymer metal complexes of the present invention (HM-C) or comprising this high molecular metal complex (HM-C) and the method for the luminous organometallic complex composition system film of low molecular metal title complex (LM-C), can adopt known method in the past according to purpose, for example can enumerate spin-coating method, teeming practice, photogravure and be coated with method, little photogravure and be coated with method, rod and be coated with method, coiling rod and be coated with that method, rolling method, dipping are coated with method, spraying is coated with method, silk screen print method, offset printing method, lithography, ink jet printing method etc.
Luminous organic polymer metal complexes of the present invention and luminous organic polymer metal complex composition are by Alq
3The organometallic complex of type is formed, and not only has this Alq
3The excellent speciality of all fastness, polychromatism, high brightness etc., and have excellent solvent soluble, can adopt the wet type legal system film that is suitable for making large area film, be industrial extremely useful.
Description of drawings
Fig. 1 is the explanatory view of synthetic method of the luminous organic polymer metal complexes of the expression embodiment of the invention.
Fig. 2 is the reaction mixture (organic polymer metal complex composition) of embodiment 1
1H-NMR (400MHz; CDCl
3) spectrogram (A), and the low molecular metal title complex (LM-C of data; Al-K
3) spectrogram (B).
Fig. 3 is
1The H-NMR data are reaction mixture and the low molecular metal title complex (LM-C of the embodiment 2 of presentation graphs 1; Al-K
3) different spectrographic spectrograms (A), and macromolecule ligand (polyQ
1) independent spectrogram (B).
Fig. 4 is the high molecular metal complex (polyQ of expression embodiment 3
2-Al-K
2)
1H-NMR (400MHz; CDCl
3) spectrogram of data.
Fig. 5 is the high molecular metal complex (polyQ of expression embodiment 3
2-Al-K
2) the spectrogram of IR analytical data.
Embodiment
Below based on the synthetic method of the luminous organic polymer metal complexes of the embodiment of the invention shown in Figure 1, specify the preferred embodiments of the invention.
[synthesizing of macromolecule ligand (polyQ)]
Synthesis example 1 (polyQ
1Synthetic)
Oxine (Q packs in reaction vessel
1) 26.2g (0.201mol), concentrated hydrochloric acid 36mL, and 28wt%-formalin 32mL (0.3mol), in resulting mixed solution, imported at 90 minutes hydrogen chloride gas of drying at room temperature.
After reaction finishes, with the throw out that generates filter, drying, the chloro that the obtains amorphous yellow solid resultant (Q that methylates
1-CH
2ClHCl) 37.2g (yield 80%).The fusing point of resulting resultant is 280 ℃ (decomposition), with literature value (J.Org.Chem.26, p4078 (1961); 280 ℃ (decomposition) is very consistent.
Then, the chloro resultant (Q that methylates that in reaction vessel, packs into
1-CH
2ClHCl) 14.5g (0.0629mol) and superfluous methacrylic acid 2-hydroxyethyl ester (HMA) 60mL (0.43mol) make it to react 2 days at 60 ℃ under argon atmospher.
After turning back to room temperature after reaction finishes, add entry 150mL, then adopting weak ammonia to make reaction mixture is alkalescence, the throw out that generates is filtered, and after cleaning with weak ammonia again, the vacuum-drying of spending the night.
Resulting thick resultant is put in the tetrahydrofuran (THF) (THF) of 650mL, make it dissolving, after insoluble composition filtration, removing, under reduced pressure concentrate, resulting solid is carried out recrystallize 2 times from hexane, obtained introducing the resultant (Q of the colourless acicular crystal of methacrylic acid 2-oxyethyl group ester group
1-CH
2-HMA) 12.5g (43.5mmol; Yield 69%).The fusing point of resulting resultant is 89.2～89.5 ℃, and is very consistent with literature value (89 ℃).
With synthetic like this resultant (Q
1-CH
2-HMA) 7.00g (24.4mmol) and AIBN 231mg (1.4mmol) are dissolved among the benzene 55mL, put under argon atmospher in the narrow-necked bottle, and tube sealing 65 ℃ of heating 20 minutes, was put cold 1 hour in oil bath then, turned back to room temperature.
Remove benzene after the Kaifeng, the arborescens light green solid that remains in the narrow-necked bottle bottom is dissolved among the DMF of 50mL, after then filtering, make it redeposition, obtained the polymkeric substance (macromolecule ligand of white solid with the methyl alcohol of 2L; PolyQ
1) 3.75g (yield 54%).
Resulting polymkeric substance (polyQ
1)
1The H-NMR data are as follows.
1H-NMR(400MHz；CDCl
3)δ(ppm)＝0.75(br.s，3H)，1.67(br.s，2H)、3.35(br.s，2H)、3.90(br.s，2H)、4.58(br.s，2H)、6.89(br.s，1H)、7.21(br.s，1H)、7.33(br.s，1H)、8.25(br.s，1H)、8.66(br.s，1H)、9.73(br.s，1H)。
Synthesis example 2 (polyQ
2Synthetic)
7-(4-ethyl-1-Methyl Octyl)-oxine (Q packs in reaction vessel
2) 45.0g (0.15mol), concentrated hydrochloric acid 75mL, and 28wt%-formalin 25mL (0.23mol), in resulting mixed solution, imported at 17 hours hydrogen chloride gas of 65～75 ℃ of dryings.Resulting reactant is water layer and dark yellow ashen solid mixture.
After reaction finishes, extract 4 times with the chloroform 100mL that removes stablizer in advance, adopt the ether of 4L to make resulting extracting solution redeposition, obtain the resultant 23g of amorphous yellow solid.
Resulting resultant by
1H-NMR reaches
13Each spectrum of C-NMR confirms it is 5 resultant (Q that methylated by chloro
2-CH
2ClHCl) (yield 57%).
1H-NMR(400MHz；CDCl
3)δ(ppm)＝9.14(1H，d，J＝7.2Hz)，9.04(1H，br.s)、7.99(1H，br.s)、7.75(1H，s)、8.06(2H，s)、3.68(1H，m)、1.64(2H，br.d，J＝5.6Hz)、1.31-1.18(14H，m)、0.87-0.75(6H，m)。
13C-NMR(400MHz；CDCl
3)δ(ppm)＝146、142、141、140、132、130、127、125、120、43、39、34、32.9、32.6、31、29、26、23、21、14、11。
Then, the resulting chloro resultant (Q that methylates that in reaction vessel, packs into
2-CH
2ClHCl) 10.0g (0.026mol) and superfluous methacrylic acid 2-hydroxyethyl ester (HMA) 25mL (0.21mol) make it to react about 60 hours at 60～65 ℃ under argon atmospher.
Reaction under agitation adds entry 400mL after finishing, then add 5wt%-ammoniacal liquor, be adjusted to about pH10, leave standstill, remove water layer through decant, with the residual white viscous solid of chloroform extraction, isolate the resultant 6.2g (yield 54%) of light green viscous liquid with silica dioxide gel chromatographic column (benzol-cyclohexane).
Resulting resultant by
1H-NMR reaches
13Each spectrum of C-NMR confirms it is the resultant (Q that has introduced methacrylic acid 2-oxyethyl group ester group
2-CH
2ClHMA).
1H-NMR(400MHz；CDCl
3)δ(ppm)＝8.76(1H，d，4Hz)，8.46(1H，d，8.4Hz)，7.90(1H，dd，8.4，4.2Hz)，7.26(1H，s)，6.07(1H，s)，5.55(1H，s)，4.90(2H，s)，4.31(2H，t，4.8Hz)，3.73(2H，t，4.8Hz)，3.36(1H，q)，1.92(3H，s)，1.69-1.62(2H，m)，1.32-0.75(20H，m)。
13C-NMR(400MHz；CDCl
3)δ(ppm)＝167，149，147，139，136，133，127.9，127.6，126，123，121，72，67，64，39，34，33，31，29，26，23，21，18，14，11。
With synthetic like this resultant (Q
2-CH
2-HMA) 6.2g (14mmol) and AIBN155mg (1mmol) are dissolved among the benzene 35mL, put under argon atmospher in the narrow-necked bottle, and tube sealing made it reaction in 10 hours 65～75 ℃ of heating.
Reaction finishes to add benzene 100mL dilution after the Kaifeng, back, Yi Bian stir attentively, Yi Bian be added drop-wise among the methyl alcohol 1L, makes the resultant redeposition.Remove methyl alcohol through decant, use the benzene extraction throw out, heat up in a steamer the solvent of extracting solution,, obtain arborescens light green solid polymkeric substance (macromolecule ligand 60 ℃ of vacuum-dryings 12 hours; PolyQ
2) 2.9g (yield 47%).
Resulting polymkeric substance (polyQ
2)
1The H-NMR data are as follows.
1H-NMR(400MHz；CDCl
3)δ(ppm)＝8.5?&?8.3(2H，br)，7.25(2H，br)，4.69(2H，br)，4.00(2H，br)，3.5?&?3.3(2H，br)，1.5-2.5(3H，br)，1.5-0.7(25H，br.m)
Synthesis example 3 (polyQ
2Synthetic)
Resultant (the Q that will similarly obtain with above-mentioned synthesis example 2
2-CH
2HMA) 2.13g (4.82mmol) and tert-butyldimethylsilyl chloride thing 0.872g (5.79mmol) are dissolved among the dry DMF (5mL), at room temperature stir on one side and in resulting solution, add imidazoles 0.82g (12.0mmol) on one side, after then at room temperature stirring 10 hours then, add saturated sodium bicarbonate water, reaction is stopped, then extracting with hexane.Behind the dry resulting organic layer, refining with silica dioxide gel chromatographic column (hexane-ethyl acetate), obtain 8 hydroxyls by silylanizing the resultant [Q of colorless oil
2(OSi)-CH
2-HMA] 2.68g (yield is more than 99%).
Resulting resultant [Q
2(OSi)-CH
2-HMA]
1The H-NMR data are as follows.
1H-NMR(400MHz；CDCl
3)δ(ppm)＝8.76(1H，dd，2，4Hz)，8.41(1H，dd，2，9Hz)，7.35(1H，s)，7.32(1H，dd，4，9Hz)，6.08(1H，br.s)，5.55(1H，quintet，1Hz)，4.91(2H，s)，4.32(2H，t，5Hz)，3.74(2H，t，5Hz)，3.62(1H，sextet，7Hz)，1.93(3H，s)，1.7-0.7(22H，m)，1.08(9H，m)，0.38(3H，s)，0.30(3H，s)。
Then, with the above-mentioned resultant [Q that obtains
2(OSi)-CH
2-HMA] 1.5g (2.7mmol) and AIBN22mg (0.14mmol) be dissolved among the benzene 20mL, puts under argon atmospher in the narrow-necked bottle, and tube sealing was 65～75 ℃ of heating 10 hours.Reaction mixture is diluted to 50mL with benzene, Yi Bian stir attentively, Yi Bian be added drop-wise among the methyl alcohol 400mL, makes the resultant redeposition.After decant has been removed methyl alcohol, extract throw out with ether, heat up in a steamer desolvate after, obtained the polymkeric substance [polyQ of faint yellow amorphous solid shape by drying under reduced pressure
2(OSi)] 600mg.
Resulting polymkeric substance [polyQ
2(OSi)]
1The H-NMR data are as follows.
1H-NMR(400MHz；CDCl
3)δ(ppm)＝8.7-8.5(1H，br)，8.4-8.2(1H，br)，7.4-7.1(2H，br)，4.75(2H，br)、4.05(2H，br)、3.54(2H，br)、1.96(1H，br)、1.5-0.9(29H，br.m)、0.8-0.6(6H，br.m)、0.4-0.2(6H，br.m)。
With the polymkeric substance [polyQ that obtains like this
2(OSi)] 300mg was dissolved among the THF of 30mL, adds tetrabutylammonium 2 equivalents, stirring at room 10 minutes.Add saturated aqueous ammonium chloride reaction is stopped, carrying out separatory with ether and water.Heat up in a steamer behind the dry organic layer and desolvate, the residue that resulting viscosity is high is dissolved in the ether once again.Add methyl alcohol to it, separated out the light green solid lentamente.Filtration, drying obtain polymkeric substance (macromolecule ligand; PolyQ
2) 215mg.
Resulting polymkeric substance (polyQ
2)
1The H-NMR data are as follows.
1H-NMR(400MHz；CDCl
3)δ(ppm)＝8.66(1H，br.s)，8.37(1H，br.s)，8.37(1H，br.s)，7.28(2H，br)，4.77(2H，br.s)，4.04(2H，br)，3.55(2H，br)，3.32(1H，br.s)，2.1-0.7(27H，br.m)。
In addition, the intrinsic viscosity [η] that adopts viscosimetry to measure is 0.24 (THF).
Embodiment 1[polyQ
1-Al-K
2+ Al-K
3Synthesizing of composition]
In reaction vessel, put into the macromolecule ligand (polyQ that in above-mentioned synthesis example 1, obtains
1) 800mg (2.78mmol) and low molecule ligand (K) 6.64g (22.3mmol) and the exsiccant THF100mL that constitute by 7-(4-ethyl-1-Methyl Octyl)-oxine, dissolving, under argon atmospher, in the dry ice-propanone cryostat, cool off, under agitation add trimethylammonium aluminium (AlMe on a small quantity
3) hexane solution (concentration 1.00mol/L) 8.4mL (8.4mmol), add to finish the back and continue to stir 30 minutes, make it reaction.The painted gradually yellow that becomes of reaction solution therebetween.
After this reaction finishes, remove cryostat and return room temperature, former state ground at room temperature continues reaction 3 days, but only the solid of trace is separated out, and reactive system be can't see variation in appearance.Then, add a spot of methyl alcohol, reaction is stopped, having obtained proterties is the reaction mixture of yellow uniform solution.
Resulting reaction mixture
1H-NMR (400MHz; CDCl
3) data see shown in Fig. 2 (A), comprise 3 normal low molecule ligand (K) coordinations low molecular metal title complex (LM-C; Al-K
3) spectrum [Fig. 2 (B)], in addition, above-mentioned reaction mixture and low molecular metal title complex (LM-C; Al-K
3) different spectrum [Fig. 3 (A)] and macromolecule ligand (polyQ
1) independent spectrum [Fig. 3 (B)] is inconsistent.
Therefore, the macromolecule ligand (polyQ in the reaction mixture
1) exist as aluminum complex, infer in theory and be: 1 normal macromolecule ligand (polyQ
1) and 2 normal low molecule ligands (K) and aluminum ion (Al
3+) coordination high molecular metal complex (HM-C) 2.53g (2.78mmol) and 3 normal low molecule ligands (K) and aluminum ion (Al
3+) coordination low molecular metal title complex (LM-C) 5.12g (5.62mmol) be dissolved in solvent (THF:100mL+C
6H
14: the organic polymer metal complex composition 8.4mL+MeOH:0.1mL) [mol ratio (HM-C/LM-C): 0.5].
The organic polymer metal complex composition solution 0.05mL that will obtain in this embodiment 1 is dissolved among the chloroform 3mL, (Shimadzu Seisakusho Ltd.'s corporate system, SHIMADZURF-5300PC) result of mensuration fluorescence spectrum can confirm fluorescence [(λ ex=400nm): λ em-533nm in CHCl to use the fluorescence spectrometry device
3], in addition, the solution-cast of the foregoing description 1 on sheet glass, after the air-dry evening, 50 ℃ of vacuum-dryings 12 hours, has also been seen fluorescence [(λ ex=400nm): λ em-533nm] about the yellow transparent film that obtains thus.
Embodiment 2[polyQ
2-Al-K
2+ Al-K
3Synthesizing of composition]
Macromolecule ligand (the polyQ that in reaction vessel, will in above-mentioned synthesis example 2, obtain
2) 1.12g (2.5mmol) and low molecule ligand (K) 4.48g (15.1mmol) that is made of 7-(4-ethyl-1-Methyl Octyl)-oxine be dissolved among the exsiccant THF20mL, similarly having obtained proterties with the foregoing description 1 in addition is the reaction mixture of even yellow solution.
Resulting reaction mixture is: 1 normal macromolecule ligand (polyQ
2) and 2 normal low molecule ligands (K) and aluminum ion (Al
3+) coordination high molecular metal complex (HM-C) 2.11g (1.98mmol) and 3 normal low molecule ligands (K) and aluminum ion (Al
3+) coordination low molecular metal title complex (LM-C) 1.56g (1.70mmol) be dissolved in solvent (THF:20mL+C
6H
14: the organic polymer metal complex composition of the embodiment 2 6mL+MeOH:0.1mL) [mol ratio (HM-C/LM-C): 1.16].
Embodiment 3[polyQ
2-Al-K
2Separation]
The drips of solution of the organic polymer metal complex composition that will obtain in the foregoing description 2 is added among the methyl alcohol 500mL and mixes, the low molecular metal title complex (LM-C:Al-K in making solvent in the dissolving said composition
3) time, make high molecular metal complex (HM-C:polyQ
2-Al-K
2) precipitation, filter, reclaim yellow solid 2.87g, further make with extra care by redeposition, obtained the high molecular metal complex (polyQ of yellow solid shape
2-Al-K
2) 2.11g (yield 79%).
High molecular metal complex (the polyQ of this embodiment 3
2-Al-K
2) to methyl alcohol, ethanol, hexane equal solvent indissoluble, THF, benzene, chloroform equal solvent are demonstrated good solubility.In addition, with the foregoing description 1 similarly measured fluorescence spectrum results verification fluorescence [(λ ex=400nm): λ em=537nm in CHCl
3], in addition, cast on the sheet glass, after the air-dry evening,, also confirmed fluorescence [(λ ex=400nm): λ em=537nm] about the yellow transparent film that obtains thus 50 ℃ of vacuum-dryings 12 hours.
In the situation of this embodiment 3, the methanol solution that obtains has obtained the low molecular metal title complex (Al-K of yellow viscous liquid from separating out above-mentioned high molecular metal complex (HM-C)
3) 1.56g (yield 34%).
About resulting low molecular metal title complex (Al-K
3), the result who has similarly measured fluorescence spectrum with the foregoing description 1 has observed fluorescence [(λ ex=400nm): λ em=533nmin CHCl
3].
About the high molecular metal complex (polyQ that in the foregoing description 3, obtains
2-Al-K
2), express the result of the ultimate analysis of having carried out its carbon (C), hydrogen (H) and nitrogen (N) below.
[ultimate analysis value]
found；C：73.80；H：9.39；N：3.75
Calcd.for?C
67H
94N
3O
6Al·1.2H
2O；
C：74.07；H：8.95；N：3.87
In addition, Fig. 4 expresses
1H-NMR (400MHz; CDCl
3) data, and then Fig. 5 expresses the IR analytical data.
Embodiment 4[polyQ
2-Al-K
2Synthetic]
Macromolecule ligand (the polyQ that will in above-mentioned synthesis example 3, obtain
2) 252mg (0.57mmol) and low molecule ligand (K) 1.36g (4.55mmol) that is made of 7-(4-ethyl-1-Methyl Octyl)-oxine be dissolved among the exsiccant THF of 15mL, similarly at room temperature carry out 5 hours reaction in addition with trimethyl ammonium with the foregoing description 1, add methyl alcohol 3mL, reaction is stopped, having obtained the xanchromatic reaction mixture.
After filtering resulting reaction mixture, add methyl alcohol 200mL in filtrate, filtration obtains the solid of separating out, and vacuum-drying obtains the high molecular metal complex (polyQ of yellow solid shape
2-Al-K
2) 456mg (yield 75%).
High molecular metal complex (the polyQ that obtains like this
2-Al-K
2)
1H-NMR (400MHz; CDCl
3) data, with the high molecular metal complex (polyQ of embodiment 3 shown in Figure 4
2-Al-K
2) very consistent.
In addition, the high molecular metal complex (polyQ of this embodiment 4
2-Al-K
2) to methyl alcohol, ethanol, hexane, and dimethyl formamide indissoluble, other common organic solvent (for example THF, benzene, chloroform etc.) is demonstrated good solubility.In addition, similarly its THF solution is spin-coated on the sheet glass with the foregoing description 1, air-dry and yellow transparent film that obtain demonstrates fluorescence [(λ ex=400nm): λ em=537nm].
Embodiment 5[polyQ
2-Al-K
2Synthetic]
Polymkeric substance (the polyQ that will in above-mentioned synthesis example 3, obtain
2) 500mg (1.13mmol) and low molecule ligand (K) 2.70g (9.04mmol) and the three isopropoxy aluminium [Al (OiPr) that constitute by 7-(4-ethyl-1-Methyl Octyl)-oxine
3] 0.70g (3.39mmol) is dissolved among the exsiccant THF of 30mL, at room temperature makes it to react 1 hour, then under agitation makes it to react 12 hours under reflux temperature, obtained muddy a little yellow reaction solution.
After filtering resulting reaction soln, filtrate is added in the methyl alcohol of 800mL and make it redeposition, filtration obtains the throw out of separating out, and makes it dry, has obtained the high molecular metal complex (polyQ of yellow amorphous solid shape
2-Al-K
2) 430mg (yield 36%).
High molecular metal complex (the polyQ that obtains like this
2-Al-K
2)
1H-NMR (400MHz; CDCl
3), the fluorescence spectrum of solvability, film-forming properties and film is very consistent with embodiment 3 and 4.
Utilizability on the industry
Photism organic polymer metal complex of the present invention and photism organic polymer metal complex composition are Alq3The organometallic complex of type, have fastness, pleochroism, In the time of the excellent speciality such as high brightness, have excellent solvent soluble, can adopt to be suitable for Make the wet type legal system film of large tracts of land film processed, therefore particularly (have as organic electroluminescent device The machine EL element) luminescent layer material industrial be extremely useful.
Claims (10)
1. luminous organic polymer metal complexes, it is characterized in that, be make on the side chain of the repeating unit (Y) that constitutes high molecular polymer by spacer (X) introduced the macromolecule ligand (polyQ) of oxine derivative (Q), the low molecule ligand (K) that constitutes by the oxine derivative and the metal ion (M of 2～4 valencys
N+) reaction and the organic polymer metal complexes of the following general formula of usefulness (1) that obtains expression, the oxine derivative that constitutes above-mentioned low molecule ligand (K) is the oxine derivative of representing with following general formula (2),
polyQ·M·K
n-1 (1)
Wherein, R in the formula
1～R
6Be to be selected from hydrogen; halogen; carbon number is 1～20 and by the straight chain shape; prop up chain; ring-type or their the saturated or undersaturated alkyl that constitutes; the alkoxyl group of carbon number 1～20; the alkylamino of carbon number 1～20; the alkyl sulfenyl of carbon number 1～20; the alkyl sulphonyl of carbon number 1～20; the alkoxyalkyl of carbon number 2～20; the alkyl-thio-alkyl of carbon number 2～20; the alkyloyl of carbon number 2～20; aroyl; the alkyl monosubstituted amino alkyl of carbon number 2～20; the dialkyl aminoalkyl of carbon number 3～20; the phenylazo of functional group's replacement or non-replacement; functional group replace or the anilino alkyl of non-replacement and-SO
3The substituting group of Na, substituent R
1, R
4And R
6Among at least 1 be selected from carbon number be 6～20 and by alkyloyl, the dialkyl aminoalkyl of carbon number 3～20 of the alkoxyalkyl of straight chain shape, chain, ring-type or their the saturated or undersaturated alkyl that constitutes, carbon number 2～20, carbon number 2～20, functional group replaces or the phenylazo of non-replacement, and functional group replaces or the bulky substituting group of the anilino alkyl of non-replacement.
2. luminous organic polymer metal complexes according to claim 1, wherein, the oxine derivative that constitutes the general formula (2) of low molecule ligand (K) is 7-(4-ethyl-1-Methyl Octyl)-oxine or 7-(1-vinyl-3,3,6,6-tetramethyl-hexyl)-oxine.
3. luminous organic polymer metal complexes according to claim 1 and 2, wherein, the metal ion (M of 2～4 valencys
N+) be Al
3+, Ga
3+, or Be
2+
4. the luminous organic polymer metal complex composition of an energy film by wet, it is characterized in that, be the metal ion (M that comprises low molecule ligand (K) that the high molecular metal complex (HM-C) and only having of wantonly 1 described general formula (1) of claim 1～3 is made of the oxine derivative and 2～4 valencys
N+) carry out the organic polymer metal complex composition of coordinate with the low molecular metal title complex (LM-C) of following general formula (3) expression, the oxine derivative that constitutes above-mentioned low molecule ligand (K) is the oxine derivative with following general formula (2) expression
M·K
n (3)
Wherein, R in the formula
1～R
6Be to be selected from hydrogen; halogen; carbon number is 1～20 and by the straight chain shape; prop up chain; ring-type or their the saturated or undersaturated alkyl that constitutes; the alkoxyl group of carbon number 1～20; the alkylamino of carbon number 1～20; the alkyl sulfenyl of carbon number 1～20; the alkyl sulphonyl of carbon number 1～20; the alkoxyalkyl of carbon number 2～20; the alkyl-thio-alkyl of carbon number 2～20; the alkyloyl of carbon number 2～20; aroyl; the alkyl monosubstituted amino alkyl of carbon number 2～20; the dialkyl aminoalkyl of carbon number 3～20; the phenylazo of functional group's replacement or non-replacement; functional group replace or the anilino alkyl of non-replacement and-SO
3The substituting group of Na, substituent R
1, R
4And R
6Among at least 1 be selected from carbon number be 6～20 and by alkyloyl, the dialkyl aminoalkyl of carbon number 3～20 of the alkoxyalkyl of straight chain shape, chain, ring-type or their the saturated or undersaturated alkyl that constitutes, carbon number 2～20, carbon number 2～20, functional group replaces or the phenylazo of non-replacement, and functional group replaces or the bulky substituting group of the anilino alkyl of non-replacement.
5. the luminous organic polymer metal complex composition of energy film by wet according to claim 4, wherein, the oxine derivative that constitutes the general formula (2) of low molecule ligand (K) is 7-(4-ethyl-1-Methyl Octyl)-oxine or 7-(1-vinyl-3,3,6,6-tetramethyl-hexyl)-oxine.
6. according to claim 4 or 5 described luminous organic polymer metal complex compositions that can film by wet, wherein, the metal ion (M of 2～4 valencys
N+) be Al
3+, Ga
3+, or Be
2+
7. according to claim 4 or 5 described luminous organic polymer metal complex compositions that can film by wet, wherein, the mol ratio HM-C/LM-C with general formula (1) high molecular metal complex of representing (HM-C) and the low molecular metal title complex of representing with general formula (3) (LM-C) is more than 0.2.
8. the manufacture method of the luminous organometallic complex composition of an energy film by wet, it is characterized in that, with respect to metallic compound 1 equivalent of the metal of 2～4 valencys, in solvent, make on the side chain of the repeating unit (Y) that constitutes high molecular polymer by spacer (X) and introduced macromolecule ligand (polyQ) 0.1～1 equivalent of oxine derivative (Q) and by with following general formula (2)
Low molecule ligand (K) 1～3.9 equivalent that the oxine derivative of expression constitutes reacts, and makes the metal ion (M that comprises macromolecule ligand (polyQ) and low molecule ligand (K) and 2～4 valencys
N+) coordinate is with following general formula (1)
polyQ·M·K
n-1 (1)
Metal ion (the M of the high molecular metal complex (HM-C) of expression and only above-mentioned low molecule ligand (K) and 2～4 valencys
N+) coordinate is with following general formula (3)
M·K
n (3)
The organic polymer metal complex composition of the low molecular metal title complex (LM-C) of expression,
Wherein, in the formula (2), R
1～R
6Be to be selected from hydrogen; halogen; carbon number is 1～20 and by the straight chain shape; prop up chain; ring-type or their the saturated or undersaturated alkyl that constitutes; the alkoxyl group of carbon number 1～20; the alkylamino of carbon number 1～20; the alkyl sulfenyl of carbon number 1～20; the alkoxyalkyl of carbon number 2～20; the alkyl-thio-alkyl of carbon number 2～20; the alkyloyl of carbon number 2～20; aroyl; the alkyl monosubstituted amino alkyl of carbon number 2～20; the dialkyl aminoalkyl of carbon number 3～20; the phenylazo of functional group's replacement or non-replacement; functional group replace or the anilino alkyl of non-replacement and-SO
3The substituting group of Na, substituent R
1, R
4And R
6Among at least 1 be selected from carbon number be 6～20 and by alkyloyl, the dialkyl aminoalkyl of carbon number 3～20 of the alkoxyalkyl of straight chain shape, chain, ring-type or their the saturated or undersaturated alkyl that constitutes, carbon number 2～20, carbon number 2～20, functional group replaces or the phenylazo of non-replacement, and functional group replaces or the bulky substituting group of the anilino alkyl of non-replacement.
9. the manufacture method of the luminous organic polymer metal complex composition of energy film by wet according to claim 8, wherein, the metallic compound of the metal of 2～4 valencys is trialkyl aluminium or tri-alkoxy aluminium.
10. the manufacture method of a macromolecule ligand, it is characterized in that, it is the manufacture method of on the side chain of the repeating unit (Y) that constitutes high molecular polymer, having introduced the macromolecule ligand (polyQ) of oxine derivative (Q) by spacer (X), oxine derivative (Q) chloro is methylated, then on methylating resultant, the chloro that obtains makes the reaction of (methyl) vinylformic acid hydroxyalkyl acrylate, synthetic contain (methyl) vinylformic acid alcoxyl base ester group contain the substituent oxine derivative of polymerizability (Q), make this contain (methyl) vinylformic acid alcoxyl base ester group polymerization of the substituent oxine derivative of polymerizability (Q), thereby make when the macromolecule ligand (polyQ), make trialkylsilkl halogenide and above-mentioned 8 hydroxyl reactions that contain the substituent oxine derivative of polymerizability (Q), thereby introducing trialkylsilkl, then in the presence of reaction initiator, (methyl) vinylformic acid alcoxyl base ester group is partly carried out polymerization, and then slough trialkylsilkl from resulting polymkeric substance.
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