CN1264715A - Conjugated/unconjugated copolymer and its preparing process and application - Google Patents
Conjugated/unconjugated copolymer and its preparing process and application Download PDFInfo
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Abstract
The present invention relates to a copolymer with both conjugated chain segment and unconjugated chain segment, which has the advantages of photoelectric activity, solubility and processability, and can be used for organic/polymer semiconductor device (especially electroluminescent element) or in the synthesis of nm particles. Said copolymer is obtained by copolymerization with monomer via oil-phase approach (using tert-butanol potassium as catalyst) or water-phase approach (using sodium hydroxide as catalyst). Its advantage is simple synthsis. Said polymer can emit light with different colours by controlling the amount of monomer.
Description
The present invention relates to a kind of conjugation/non-conjugated multipolymer and preparation method thereof and application, particularly relate to p-phenylene ethylene and vinyl monomer copolymerization and preparation method thereof, these polymkeric substance both can be used as luminescent material and had been used in the luminescent device, can be used as emulsifying agent again and were used in the preparation of polymer nano particle.
Just synthesized poly-phenylene vinylene (ppv) (J.Polymer Sci.:A-1 1966 as far back as people such as Gilch in 1966 with the method that big excessive potassium tert.-butoxide is handled two monochloromethyl benzene, 4,1337), also there was human Wittig condensation reaction to synthesize this polymkeric substance (J.Polymer Sci.:A-1,1968,6 afterwards, 1058:Macromolecules, 1984,17,1025; ).But resulting product all is low-molecular-weight oligopolymer, and solvability is relatively poor.Nineteen sixty-eight Wessling and Zimmermann invented a kind of new water-soluble before the method for aggressiveness synthesized high molecular, high orientation, (U.S.Patents 3401152,1968 for self-supporting PPV film; 3706677,1972).People such as nineteen ninety Swatos improve original Gilch method again, handle the dichloride methyl dialkoxy benzene with equimolar potassium tert.-butoxide, obtain the prepolymer of high-molecular weight solubility earlier, and then be transformed into PPV derivative (Polymer Prepr.1990,31,505).Since then, this conjugated polymers begins to be subjected to people's attention and begins to move towards applied research.People such as the nineteen ninety Friend of univ cambridge uk have made high performance polymer electroluminescent diode (Nature with PPV first, 1990,347,539), the PPV derivative of the human solubilities such as Heeger of U.S. Uniax company in 1991 has been made electroluminescent device (Appl.Phys.Lett.1991,58,1982), and luminescent device (Nature, 1992 of developing the straight polymer flexible substrates on this basis, 357,477).Owing to aspect electroluminescence, found using value, the research of PPV and derivative thereof is become focus very soon.
Generally speaking, the research of the material aspect of carrying out around PPV mainly contains following several direction:
1. the alkoxyl group of synthesizing soluble, aryl derivatives, with the method film forming of spin coating, need not thermal treatment.
Synth.Met.1993，57，4174；Appl.Phys.Lett.1991，58，1982；Nature，1992，
357，477；Synth?Met.1993，55，914；U.S.Patent?5189136，1990.Synth.Met.
1994，66，75；Polym.Prepr.1993，34，197；Macromolecules，1995，28，6151；
Adv.Mater.1995，7，36；Adv.Mater.1997，9，551；Polym.Prepr.1999，40，
1200
2. introduce some push-and-pull electron groups, thereby change its level structure, regulate emission wavelength and electronics, hole injection energy
Power.
Synth.Met.1995，71，2117；Chem.Mater.1994，6，171；Makromol.Chem.
Macromol.Symp.1987，12，229；Thin?Solid?Films?1996，276，13；Macromolecules，
1998，31，7566.
3. develop conjugation, non-conjugated main chain segment copoly type polymkeric substance, its door also can be regarded the small molecules fluorescence dye as
High molecular.
J.Am.Chem.Soc.1993，115，10117；J.Appl.Phys.1993，74，3584；
macromolecules，1993，26，1188；Chem?Mater.1995，7，1499；Adv.Mater.1995，
7，388；Adv.Mater.1997.9，639.
Existing PPV (phenylenevinylene) though and the derivative kind a lot, but the adjusting more complicated of its glow color, often need from the beginning to synthesize, both the polymkeric substance of different glow colors need adopt different preparation methods, and complex process, polymkeric substance does not have good solvability, and production cost is high.
The objective of the invention is to develop a kind of new multipolymer, multipolymer has simple, the low cost and other advantages of production technique, by the monomeric consumption of controlled polymerization, can regulate the glow color of multipolymer easily.
Polymer materials involved in the present invention and polymerization process also do not have bibliographical information at present.It is to add alkene class and diene class monomer and the copolyreaction that produces on the basis of Gilch method and Wessling-Zimmermann method, is to the development of forefathers' method and replenishes.Its successful part is to have found that methylene radical quinoid active intermediate can cause alkene class and this fact of diene class monomer polymerization, thereby this important material system of PPV and traditional polymer materials are combined, the solvability of regulating glow color and polymkeric substance by a kind of different ratios of raw materials of polyreaction is for further this polymer semiconductor's material of development and utilization PPV has been opened new way.
The present invention wants the synthetic subject polymer as follows:
X+y=1 wherein, the Ar shown in 0＜x＜1,0＜y＜1 structural formula (1) and the two kinds of route of synthesis, X
1, X
2, R
1, R
2Represent following meaning:
Ar represents aromatic nucleus, and its structure can have following several variation:
X
1=Cl, Br
M, n=1,2,3 ... when
The time, the structural formula of polymkeric substance should be written as:
Composite structure formula (1) has following two kinds of methods usually:
1. oil phase reaction system:
R=H, OCnH2n+1, R '=H, OCmH2m+1, x+y=1,0＜x＜1,0＜y＜1, m, n are natural number
Polymerisable monomer has vinylbenzene, vinylcarbazole, and isoprene, they all have high polymerization activity, and can not caused by potassium tert.-butoxide and anionoid polymerization takes place.Above-mentioned reaction is carried out in two steps, and in lower temperature (20 ℃ of room temperatures), two kinds of monomers were dissolved in the dioxane before this, monomer concentration 20-80% (weight), and alkali (potassium tert.-butoxide) the effect copolymerization down of logical nitrogen protection and equivalent was reacted 3-5 hour; Be at higher temperature (50-80 ℃) then, add excessive potassium tert.-butoxide (mol ratio 5-10 doubly) reaction 2-4 hour, dehydrohalogenation small molecules and form conjugated structure.In general, have only the solvability of multipolymer when the second monomeric introducing amount acquires a certain degree (about 30%) obviously to improve.The color of polymkeric substance shoals with the raising of non-conjugated degree.
2. water react system:
R=H, OCnH2n+1, R '=H, OCmH2m+1, x+y=1,0＜x＜1,0＜y＜1, m, n are natural number
R in the formula
2Represent polar group, polymerisable monomer is water miscible, as acrylamide, and sodium acrylate, vinyl pyrrolidone, Hydroxyethyl acrylate, polyalkylene glycol acrylate ester etc.Reaction divides two stages to carry out; fs (0 ℃), nitrogen protection at a lower temperature, two kinds of monomers are water-soluble with the methanol mixed solvent in (water/methyl alcohol=1: 1 volume ratio); monomer concentration is 20-80% in the control solution; add and the equimolar aqueous sodium hydroxide solution of sulfonium salt; violent stirring 2-4 hour, form prepolymer.Second stage (40-60 ℃) under high slightly temperature sloughed small molecules with sodium-hydroxide treatment 2-4 hour of 1 to 2 times of amount (mol ratio), formed conjugated structure.It must be noted that because the concentration of alkali is lower in the medium, and temperature of reaction is far less than the degree of boiling reflux, so amides and esters monomer can not be hydrolyzed.From reaction formula as can be seen, slough small molecules after, hydrophilic unit has originally become hydrophobic units, multipolymer has also become amphipathic thereupon.When second monomeric the gathering when surpassing certain value into amount, multipolymer has become water-soluble, and forms hydrophobic microcell at aqueous phase, the opalescence phenomenon occurs, and the viscosity of system is surprisingly big, and this is the universal phenomenon of this type of system.In addition, second monomer seldom forms independent homopolymer in polymerization process, so need not make special separating treatment.In solid state, this base polymer all has heterogeneous structure.This is because hydrophilic segment and the mutual exclusive cause of hydrophobic segment.
More than the first used monomer of reaction obtains by following synthetic method, and these methods and characterization data all can check in (for example: J.Am.Chem.Soc.1993,115,10117) in the literature, so no longer carefully state here.
Below further illustrate concrete enforcement of the present invention and result by some examples, rather than to limit the present invention with these examples.Example 1:Poly's (p-PV-co-St) is synthetic
With 1.0 grams 2; 5-dibutoxy-1; the vinylbenzene of 4-dichloride methyl benzene and different volumes is dissolved in 10ml 1; in the 4-dioxane, under nitrogen protection, splash into the dioxane solution of equimolar potassium tert.-butoxide earlier; reacted at normal temperatures 4 hours; and then add excessive potassium tert.-butoxide, and be heated to 60 ℃ of afterreactions 2 hours, obtain orange or orange-yellow polymers soln.Reaction solution is poured in the big excessive methyl alcohol, separated out the polymkeric substance of band fluorescence immediately, this polymkeric substance is dissolved in the chloroform, remove by filter insolubles, filtrate is poured in the ether, separates out purer polymkeric substance once more, filters the dry and weighing of final vacuum.When cinnamic input amount is big, should suitably reduces the consumption of dioxane, and add an amount of hexaoxacyclooctadecane-6-6 to increase the solubleness of potassium tert.-butoxide.The results list of reaction conditions and resulting polymers is as follows:
Wherein the molar content of styrol structural unit is to calculate by the nuclear-magnetism spectrum, and molecular weight records with the gel chromatography method.According to fluorescent spectroscopy, the photoluminescence peak position of polymkeric substance can move to about 450nm from 550nm with the increase of styrene units content, promptly moves to blueness gradually from yellow.
The experimental result of Table 1. gained after copolymerization under the different vinylbenzene consumptions
The heavy color styrene units of sample number vinylbenzene sample weight-average molecular weight polydispersity
(ml) (g) mol％
13 1.45 orange red 48 15,000 2.4
26 1.98 oranges 57 22,000 2.1
39 2.46 orange 64 18,000 1.8
4 12 3.15 yellow 76 24,000 2.9
5 24 4.31 yellowish 83 43,000 2.3 example 2:Poly's (p-PV-co-Am) is synthetic
1.0 2 of gram; 5-Oxy-1 in two heptan; the acrylamide of 4-dimethylene chlorination sulfonium salt and different amounts is dissolved in (volume ratio is 1/1) in 25ml water/methanol mixed solvent; under nitrogen protection and zero degree; add the equimolar 1M NaOH aqueous solution, reaction is after 2 hours under brute force stirs, and temperature rises to 40 ℃ gradually; the NaOH aqueous solution that adds qdx again continues reaction and stops after 2 hours.Product in two kinds of situation, when the acrylamide consumption obtains orange sedimentable matter more after a little while; When the large usage quantity of acrylamide, obtain the jellylike water-sol.The previous case product is handled simpler, and water and methanol wash after drying get final product; To latter event, earlier reaction solution is poured in a large amount of methyl alcohol, obtain solid polymer, and then soluble in water, in methyl alcohol, settle out, thoroughly to remove small-molecule substance.Obtain lurid solid matter through vacuum-drying.Reaction result under the different condition sees the following form:
The heavy color acrylamide of polyreaction gained results sample acrylamide sample solvability fluorescence peak position under the Table 2. different acrylamide consumptions
(g) (g) (wt%) (in CHCl
3) in CHCl
3(nm) 10 0.76 red 0 molten 550 (λ
Ex=420nm) 25 1.05 orange red 38 slightly solubles, 542 (λ
Ex=420nm) 3 10 1.58 orange 47 slightly solubles, 536 (λ
Ex=420nm) 4 15 2.46 yellow 64 slightly solubles, 524 (λ
Ex=420nm) 5 20 3.85 pale yellow 82 water-soluble 509 (in water,
λ
ex＝400nm)
Because amphipathic nature polyalcohol solubleness in chloroform or tetrahydrofuran (THF) is very little, so molecular weight data can't be provided, but water solubility copolymer has good solubleness in water, it aqueous phase survey limiting viscosity be 700dL/g, and the limiting viscosity that records polyacrylamide (weight-average molecular weight is 40,000 3 thousand) under the same conditions is 28dL/g, the weight-average molecular weight that records this multipolymer with gel chromatography is about 100,000 (doing standard with sulfonated phenylethylene), is up to a million as if the viscosity-average molecular weight that calculates this polymkeric substance by the identical formula of polyacrylamide.This shows that this polymkeric substance has extraordinary viscosity feature, this mainly is because aqueous phase exists hydrophobic microcell to cause.This polymkeric substance in concentrated base under the high temperature hydrolysis can obtain corresponding sodium acrylate copolymer, it can be water-soluble, but generate water-fast acrylic copolymer after the acidifying, if handle with barium salt or lead salt, then can obtain white precipitate.Find that with transmission electron microscope observation back the multipolymer of band heavy metal ion has many microfacies structure.Example 3:Poly's (p-PV-co-VP) is synthetic
1.0 2 of gram; 5-Oxy-1 in two heptan; the vinyl pyrrolidone of 4-dimethylene chlorination sulfonium salt and different amounts is dissolved in (volume ratio is 1/1) in 20ml water/methanol mixed solvent; under nitrogen protection and zero degree; add the equimolar 1M NaOH aqueous solution, reaction is after 2 hours under brute force stirs, and temperature rises to 40 ℃ gradually; the NaOH aqueous solution that adds qdx again continues reaction and stops after 2 hours.When the consumption of vinyl pyrrolidone more after a little while, product is a sedimentable matter, water and methanol wash after centrifugation, centrifugal final vacuum drying.When the large usage quantity of vinyl pyrrolidone, product is a water-soluble polymers, with dialysis membrane reaction solution is dialysed to water earlier, remove all small-molecule substances, with rotatory evaporator water is removed then and do, finally obtain the xanchromatic solid polymer, put into the vacuum finish-drying.All multipolymers all have good solubility in chloroform and tetrahydrofuran (THF), product characterizes with infrared, nuclear-magnetism, gel chromatography, ultimate analysis, visible-ultraviolet, fluorescence.Gained the results are shown in following table:
The heavy color vinyl pyrrole of the experimental result sample number vinylpyridine sample of Table 3. gained after copolymerization under differing ethylene base pyrrolidone consumption weight-average molecular weight polydispersity fluorescence peak position (CHCl
3)
Pyrrolidone (ml) is alkane ketone unit % (λ (g)
Ex=420nm) 13 1.24 orange red 38 35,000 2.1 542nm, 25 1.48 oranges, 46 32,000 2.3 535nm, 38 1.72 orange 56 38,000 1.9 528nm, 4 12 2.15 yellow 66 26,000 2.6 504nm, 5 20 3.61 yellowish 77 36,000 2.0 475nm example 4:Poly's (p-PV-co-VK) is synthetic
With 1.0 grams 2; 5-dibutoxy-1; the vinylcarbazole of 4-dichloride methyl benzene and different amounts is dissolved in 15ml 1; in the 4-dioxane, under nitrogen protection, splash into the dioxane solution of equimolar potassium tert.-butoxide earlier; reacted at normal temperatures 4 hours; and then add excessive potassium tert.-butoxide, and be heated to 60 ℃ of afterreactions 3 hours, obtain orange or orange-yellow polymers soln.Reaction solution is poured in the big excessive methyl alcohol, separated out the polymkeric substance of band hyperfluorescence immediately, this polymkeric substance is dissolved in the chloroform, remove by filter not tolerantly, filtrate is poured in the ethanol, separates out purer polymkeric substance once more, filters the dry and weighing of final vacuum.When cinnamic input amount was big, the consumption that should suitably increase dioxane was to 20ml or 25ml, and added an amount of hexaoxacyclooctadecane-6-6 to increase the solubleness of potassium tert.-butoxide.The characterizing method of this series copolymer is identical with example 1, and the characterization result of resulting polymers is listed as follows:
The heavy color vinyl of the experimental result sample number vinyl sample of Table 4. gained after copolymerization under differing ethylene base carbazole consumption click weight-average molecular weight polydispersity fluorescence peak position (CHCl
3)
Carbazole (g) is azoles unit % (λ (g)
Ex=420nm)
12 1.15 orange red 39 11,000 1.4 543nm
24 1.67 oranges, 46 13,000 1.5 538nm
38 2.76 orange 55 17,000 2.1 526nm
4 12 3.25 yellow 63 14,000 1.9 511nm
The unitary weight percent of 5 15 3.47 yellowish 73 21,000 1.7 483nm vinylcarbazole calculates by results of elemental analyses and obtains.Example 5:Poly's (p-PV-co-IP) is synthetic
With 1.0 grams 2; 5-dimethoxy-1, the isoprene of 4-dichloride methyl benzene and different volumes is dissolved in 10ml 1, in the 4-dioxane; join in three mouthfuls of reaction flasks that prolong is housed; under nitrogen protection, splash into the dioxane solution of equimolar potassium tert.-butoxide earlier, stirred at normal temperatures 4 hours; and then add excessive potassium tert.-butoxide; and being heated to 40 ℃ of afterreactions gradually 2 hours, cool to room temperature obtains orange-yellow or the xanchromatic polymers soln.Reaction solution is poured in the big excessive methyl alcohol, separated out the polymkeric substance of band fluorescence immediately, this polymkeric substance is dissolved in the chloroform, remove by filter insolubles, filtrate is poured in the ether, separates out purer polymkeric substance once more, filters the dry and weighing of final vacuum.When cinnamic input amount is big, should suitably reduces the consumption of dioxane, and add an amount of hexaoxacyclooctadecane-6-6 to increase the solubleness of potassium tert.-butoxide.The results list of reaction conditions and resulting polymers is as follows:
The heavy color isoprene weight-average molecular weight polydispersity fluorescence peak position (nm) of the experimental result sample number isoprene sample of table 5. gained after copolymerization under the distinct isoprene consumption
(ml) (g) unit % (CHCl
3) 12 1.55 orange red 32 36,000 2.2 532 (λ
Ex=420nm) 24 1.67 the orange 48 33,000 2.5 525 (λ
Ex=420nm) 36 2.76 orange 54 42,000 3.1 510 (λ
Ex=400nm) 48 3.25 yellow 62 44,000 2.9 491 (λ
Ex=380nm) 5 10 3.47 yellowish 78 47,000 2.7 463 (λ
Ex=360nm)
The multipolymer of PPV and PIP demonstrates the characteristic of rubber, is the polymer materials that a kind of existing flexibility has physical strength again, is suitable for making the large area light emitting significant screen.With perosmic anhydride dyeing back electron microscopic observation, the result shows that hard section of PPV and PIP exist tangible microphase-separated behavior for soft section, and this feature just is being used to make the electroluminescence device of doping small molecular semiconductor in the polymeric matrix.
Example 6:Poly's (p-PV-co-MPEGA) is synthetic:
40 gram poly glycol monomethyl ethers (number-average molecular weight is 2000) are dissolved in the 100ml methylene dichloride, add the 2ml triethylamine, solution is transferred to Erlenmeyer flask, under agitation dropwise add excessive acrylate chloride (0.1mol), capping is 3 hours under the normal temperature, steaming vibrating dichloromethane behind the insoluble solid salt of elimination, residue are dissolved in recrystallization in the tetrahydrofuran (THF) (is precipitation agent with the hexanaphthene), obtain the polyalkylene glycol acrylate monomethyl ether ester solid of white at last.With 2 grams 2,5-dimethoxy-1, the polyalkylene glycol acrylate monomethyl ether ester of 4-dimethylene chlorination sulfonium salt and different amounts
(MPEGA) be dissolved in (volume ratio is 1/1) in 20ml water/alcohol mixed solvent.Use nitrogen protection at normal temperatures, add equimolar 1M NaOH solution gradually, stirring reaction adds the 1M NaOH solution of double amount after 3 hours again, and makes temperature rise to 40 ℃ of maintenances 2 hours gradually.Finally obtain the orange-red shape material that freezes.Product is handled with the methyl alcohol of heat, and thoroughly flush away small-molecule substance and unpolymerized polyalkylene glycol acrylate ester are weighed after the vacuum-drying.When the second monomer large usage quantity, can suitably increase the amount of solvent.Reaction result shows that (greater than 35%) polymkeric substance dissolves in chloroform, dimethyl formamide when MPEGA content is higher, otherwise then sample is difficult to be dissolved in various organic solvents.The composition of solubility sample is calculated with the integral area of characteristic peak in the nuclear-magnetism spectrum, and molecular weight records with GPC.
This series polymer also belongs to amphipathic nature polyalcohol, thereby has very strong microphase-separated phenomenon, can produce various self-assembly behaviors under different conditions, because the research of these character has exceeded the scope of this patent, so here do not describe in detail.The polymer architecture characterization data is as follows:
The heavy color MPEGA weight-average molecular weight polydispersity fluorescence peak position (nm) of the experimental result sample number MPEGA sample of table 6. gained after copolymerization under the different amounts polyalkylene glycol acrylate monomethyl ether ester
(g) (g) wt％ (CHCl
3)
14 1.85 orange red insoluble--
28 2.67 orange red 38 36,000 2.4 524 (λ
Ex=420nm)
3 12 3.76 orange red 52 47,000 2.1 520 (λ
Ex=420nm)
4 16 4.55 oranges, 67 54,000 2.5 511 (λ
Ex=420nm)
5 20 5.37 orange 85 68,000 2.7 503 (λ
Ex=400nm)
Synthetic method by polymkeric substance and preparation example are as can be seen, this polymkeric substance have reparation technology simple, can regulate the effect of shiner color by changing the polymerization single polymerization monomer component concentration, polymkeric substance has the advantage that photoelectric activity and solubility, workability combine.The light emitting electrochemical cell device research of example 7:Poly (p-PV-co-MPEGA)
Owing in multipolymer, has introduced PPV component simultaneously and had the PEG component of ion transmission performance, so it is suitable for doing light emitting electrochemical cell with luminescent properties.Select the sample 3 in the example 6,4 and 5 experimentize, polymkeric substance is dissolved in is made into the solution that concentration is 2mg/ml among the DMF, add the trifluoromethyl sulfonic acid lithium that is equivalent to polymer weight 5% again, solution is spin-coated on the ITO conductive glass sheet, film forming after the solvent evaporates, the thickness of film is about 250nm, and steaming last layer thickness on the surface of film is the aluminium electrode of 40nm.Add on ITO and Al electrode that respectively forward and reverse electric current obtains symmetric I-V curve, battery all sends yellow or yellowish green light under voltage forward or backwards, and cut-in voltage is 3 to 4 volts, and maximum brightness can reach 300cd/m
2Example 8:Poly (p-PV-co-Am) is as the application of emulsifying agent synthesis of nano particulate
Polymkeric substance in the example 2 is worked as X=0.18, and during Y=0.82, polymkeric substance is a kind of water miscible emulsifying agent.1ml vinylbenzene is dispersed in the aqueous solutions of polymers of 100ml 5%, under nitrogen protection, adds 2ml K
2S
2O
8/ Na
2SO
3The aqueous solution (concentration all is 2mol/L).Reacted 1 hour down at 40-50 ℃ then, obtain the microemulsion of Bluish white.Find with transmission electron microscope observation, exist particle diameter in the emulsion at the particulate of 50 nanometers to 100 nanometer range, and in the surface coverage of particle the polymer emulsifier of one deck 5-10 nanometer thickness, the core of particle is a polystyrene.Traditional letex polymerization all uses the small molecules tensio-active agent as emulsifying agent, and this experimental result shows that the synthetic polymkeric substance has very strong emulsifying effect in the example 2, can be used for the synthetic polymer nanoparticle.
Claims (5)
1. the polymkeric substance of a structural formula shown in (1) formula:
Wherein: Ar represents aromatic nucleus, and its structure can have following several variation:
M, n=1,2,3,
X+y=1, work as 0＜x＜1,0＜y＜1
The time, the structural formula of polymkeric substance should be written as:
2. the oil phase reaction system of polymkeric substance shown in synthetic claim 1 structural formula is as follows:
R＝H，OCnH2n+1；R′＝H，OCmH2m+1；x+y＝1，0＜x＜1，0＜y＜1，
R
1Meaning such as claim 1
Polymerisable monomer has vinylbenzene, vinylcarbazole, isoprene; Above-mentioned reaction is carried out in two steps, and the first step is before this in room temperature, and two kinds of monomers are dissolved in the dioxane solution, monomer weight concentration 20-80%, and logical nitrogen protection, copolymerization under the potassium tert.-butoxide effect of equivalent was reacted 3-5 hour; Then at 50-80 ℃ of adding and the first monomer dichloride methyl benzene mole than for 5-10 potassium tert.-butoxide doubly, reacted dehydrohalogenation small molecules and form partly conjugated structure 2-4 hour.
3. the water react system of the polymkeric substance shown in synthetic claim 1 structural formula:
R＝H，OCnH2n+1；R′＝H，OCmH2m+1；x+y＝1，0＜x＜1，0＜y＜1，
R in the formula
2Represent polar group, polymerisable monomer is water miscible, as acrylamide, and sodium acrylate, vinyl pyrrolidone, Hydroxyethyl acrylate, polyalkylene glycol acrylate ester etc.;
Reaction is same to divide two stages to carry out, fs is at 0 ℃, monomer water-soluble with the methyl alcohol volume ratio be in 1: 1 the mixed solvent, monomer concentration is 20-80% in the control mixed solution, logical nitrogen protection, add with the equimolar aqueous sodium hydroxide solution of sulfonium salt, the powerful stirring 2-4 hour forms prepolymer again; Second stage under 40-60 ℃, use again with the sulfonium salt mol ratio be that 1-2 aqueous sodium hydroxide solution was doubly handled 2-4 hour, slough small molecules, form partly conjugated structure.
Shown in claim 1 or by claim 2 method prepared or by the prepared polymkeric substance of claim 3 method as the application of luminescent material in luminescent device.
As the prepared polymkeric substance of claim 3 method as the application of emulsifying agent in the synthetic polymer nanoparticle.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2484537A (en) * | 2010-10-15 | 2012-04-18 | Cambridge Display Tech Ltd | Light-emitting composition |
| CN103739762A (en) * | 2013-12-09 | 2014-04-23 | 中北大学 | Preparation method of near-ultraviolet polystyrene copolymerization fluorescence microsphere |
| CN109046472A (en) * | 2018-08-10 | 2018-12-21 | 宁波帝杨电子科技有限公司 | A kind of pulping wastewater treatment photoactivation agent and preparation method thereof |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2484537A (en) * | 2010-10-15 | 2012-04-18 | Cambridge Display Tech Ltd | Light-emitting composition |
| CN103154191A (en) * | 2010-10-15 | 2013-06-12 | 剑桥显示技术有限公司 | Polymer and organic light-emitting device |
| CN103154191B (en) * | 2010-10-15 | 2016-07-06 | 剑桥显示技术有限公司 | Polymer and organic luminescent device |
| CN103739762A (en) * | 2013-12-09 | 2014-04-23 | 中北大学 | Preparation method of near-ultraviolet polystyrene copolymerization fluorescence microsphere |
| CN103739762B (en) * | 2013-12-09 | 2016-04-06 | 中北大学 | A kind of preparation method of near-ultraviolet polystyrene copolymerization fluorescence microsphere |
| CN109046472A (en) * | 2018-08-10 | 2018-12-21 | 宁波帝杨电子科技有限公司 | A kind of pulping wastewater treatment photoactivation agent and preparation method thereof |
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