CN1176131C - Conjugated/unconjugated copolymer and its preparing process and application - Google Patents

Abstract

The chemical formula is disclosed in the specification. The present invention relates to a group of new copolymer with the simultaneous generation of a conjugated chain section and an unconjugated chain section. The copolymer integrates the advantages of photoelectric activity, solubility and processability. The copolymer can be used for organic/polymer semiconductor devices and can be particularly used as emulsifying agents for synthesizing nanometer particles in electroluminescence devices. Polymers of the present invention can be represented by the following constitutional formula; the polymer can be obtained by copolymerizing monomers in an oil phase path (tert-butanol potassium as catalysts) or a water phase path (sodium hydroxide as catalysts). The polymer has the characteristics of simple synthesizing path, etc. The polymer sending different color light can be prepared by controlling the quantity of polymerization monomers.

Description

A kind of conjugation/the preparation method of non-conjugated multipolymer in the oil phase system

Technical field:

The present invention relates to the preparation method of a kind of conjugation/non-conjugated multipolymer, particularly in the oil phase system, use the method for dichloride methyl benzene and incompatible this kind of preparation of vinyl monomer copolymerization conjugation/non-conjugated multipolymer.

Background technology:

Just synthesized PPV (poly-phenylene vinylene (ppv)) (J.Polymer Sci.:A-1 1966 as far back as people such as Gilch in 1966 with the method for a large amount of two monochloromethyl benzene of potassium tert.-butoxide processing, 4,1337), also there was human Witting condensation reaction to synthesize this polymkeric substance (J.Polymer Sci.:A-1 1968 afterwards, 6,1058; 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.Patens 3401152,1968 for the high PPV of support film; 3706677,1972).People such as nineteen ninety Swatos improve original Gilch method again, handle the dichloromethyl dialkyl benzene with the potassium tert.-butoxide of equimolar amount, obtain the high-molecular weight prepolymer earlier, and then are 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 Cambridge University 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 electroluminescent, 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 alkyl chain of synthesizing soluble, aryl derivatives, the method film forming with 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 electron donating groups, thereby change its level structure, regulate emission wavelength and electronics, hole injectability.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 copolymerization polymkeric substance, they can regard the high molecular of small molecules fluorescence dye as.

J.Am.Chem.Soc.1993，115，10117；J.Appl.Phys.1993，74，3584；Macromolecules，1993，26，1188；Chem?Mater.1995，7，1499；Adv.Mater.1995，7，1499；Adv.Mater.1997，9，639。

Though existing PPV and derivative kind thereof are a lot, the adjusting complexity of its glow color often needs from the beginning to synthesize, the polymkeric substance that is different glow colors need adopt different preparation methods, and complex process, polymkeric substance do not have good solvability, and production cost is high.

The present invention relates to the oil phase polymerization process of polymer materials, 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.

Patent of invention WO 98/13408 has proposed a kind of new conjugation/non-conjugated polymeric thing and aqueous polymerization method thereof.This synthetic method is the preceding aggressiveness for preparing the multipolymer of PPV and alkene class in the mixed system of water/organic solvent, then this prepolymer is spun in the ITO substrate, and heating is sloughed leavings group and formed polymeric film.But this method is owing to adopted aqueous phase system, can not in reaction, directly slough leavings group, so can not directly from reaction system, obtain polymkeric substance, must be with the preceding aggressiveness dialysis purification of the multipolymer of synthetic PPV and alkene class, be spun on then in the ITO substrate, heat is sloughed leavings group and is formed copolymer film.The preparation more complicated that causes this analog copolymer and electroluminescent device like this, and since in the heat film process leavings group slough the quality that has also influenced polymeric film.

Summary of the invention:

Purpose of the present invention just provides conjugation/non-conjugated multipolymer the preparation method in oil phase system of a kind of chemical formula shown in (1).

Wherein, Ar represents aromatic nucleus, and its structure can have following several variation:

M and n are integers

L is one and directly is connected in two singly-bound or groups between carbon atom

Or H

And, work as R ₁During for phenyl ring or carbazole, L is one and directly is connected two singly-bounds between carbon atom;

Work as R ₁During for H, L is a group

x+y＝1，0＜x＜1，0＜y＜1

The synthetic method of this base polymer in the oil phase system is as follows:

R=H, OC _nH _2n+1, R '=H, OC _mH _2m+1, x+y=1,0＜x＜1,0＜y＜1, m and n are integers;

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.

Compound shown in the structural formula (1) can also be by patent of invention WO 98/13408 disclosed water react method preparation, and its structural formula can be expressed as in water react:

Wherein,

R=H, OC _nH _2n+1, R '=H, OC _mH _2m+1, x+y=1,0＜x＜1,0＜y＜1, m and n are integers.

The water phase synthesis method of this base polymer is as follows:

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:

Polyreaction gained result under the different acrylamide consumptions of table 2.

The heavy color acrylamide of sample number acrylamide sample solvability fluorescence peak position

(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, the limiting viscosity that it records at aqueous phase is 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 20m] in water/methanol mixed solvent (volume ratio is 1/1); under nitrogen protection and zero degree; add the equimolar 1MNaOH 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 experimental result of table 3. gained after polymerization under the differing ethylene base pyrrolidone consumption

The heavy color vinyl pyrrole of sample number vinylpyridine sample 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 insolubles, filtrate is poured in the ethanol, separates out purer polymkeric substance once more, filters the dry and weighing of final vacuum.When the input amount of vinylcarbazole 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:

Table 4, the experimental result of gained after copolymerization under the differing ethylene base carbazole consumption

The heavy color vinyl of sample number vinyl sample 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

5 15 3.47 yellowish 73 21,000 1.7 483nm

The unitary weight percent of 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 the input amount of isoprene 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 experimental result of table 5. gained after copolymerization under the distinct isoprene consumption

The heavy color isoprene weight-average molecular weight polydispersity fluorescence peak position (nm) of sample number isoprene sample

(ml) (g) unit % (CHCl ₃)

12 1.55 orange red 32 36,000 2.2 532 (λ _Ex=420nm)

24 1.67 oranges, 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 2.9 591 (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 tetrahydrochysene and blow the middle recrystallization of muttering (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 of 4-dimethylene chlorination sulfonium salt and different amounts

Ester (MPEGA) is 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 experimental result of table 6. gained after copolymerization under the different amounts polyalkylene glycol acrylate monomethyl ether ester

The heavy color MPEGA weight-average molecular weight polydispersity fluorescence peak position (nm) of sample number MPEGA sample

(g) (g) wt％ (CHCl ₃)

12 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 ²

Example 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 2mlK 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 (1)

1, the oil phase system preparation method of polymkeric substance shown in a kind of structural formula (1),

It is characterized in that: polymerisable monomer has vinylbenzene, vinylcarbazole and isoprene; Reaction is carried out in two steps, the first step at room temperature, with dichloride methyl benzene and vinyl monomer mixed dissolution in 1, in the 4-dioxane, monomer weight concentration 20%-80%, logical nitrogen protection, with the effect of the potassium tert.-butoxide of dichloride methyl benzene equimolar amount under carry out copolymerization; It is the potassium tert.-butoxide of 5-10 times of molar weight of dichloride methyl benzene that second step added under 50-80 ℃ temperature, reacts dehydrohalogenation small molecules and form and have conjugation/subject polymer of unconjugated structure 2-4 hour;

Wherein, Ar represents aromatic nucleus, and its structure can have following several variation:

M and n are integers

L is one and directly is connected in two singly-bound or groups between carbon atom

Or H

And, work as R ₁During for phenyl ring or carbazole, L is one and directly is connected two singly-bounds between carbon atom;

Work as R ₁During for H, L is a group

R=H, OCnH2n+1 and R '=H, OCmH2m+1, x+y=1,0＜x＜1,0＜y＜1.