White electroluminescent polymeric material and preparation thereof

Abstract

This invention relates to a white electroluminescent polymeric material and preparation thereof. Based on the physical idea that white light emission can be achieved by regulating the relative luminous intensities of blue- and orange-light emitting units located in a single polymer molecule, the present invention provides three types (main chain type, pendant chain type, and terminal group type) of high efficiency and stable white electroluminescent polymeric material systems.

1 . A white electroluminescent polymeric material, which comprising a single white electroluminescent polymeric material selected from a group consisting of: 
 type (A): pendant chain type single white electroluminescent polymeric material                          Wherein:    R 1  is alkyl or aryl;    R 2  is selected from a group consisting of alkyl, alkoxy, phenyl, and phenyl substituted by alkyl or alkoxy;    Ar1 is a naphthalimide derivative basic unit and has one or more structures as listed below:                                                                                                  wherein R 6  is alkyl, phenyl, naphthyl, a phenyl or naphthyl group substituted by alkyl or alkoxy, wherein the chain lengths of the alkyl and the alkoxy are 1-18; and    Ar2 is an electron transport basic unit, a hole transport basic unit or a luminescence basic unit and has one or more structural units selected from the following units:                                                                                wherein R 5  is selected from a group consisting of alkyl, phenyl, naphthyl, and phenyl or naphthyl substituted by alkyl or alkoxy, m=0-20; wherein, the chain lengths of the alkyl and the alkoxy are 1-18;    each basic unit content—x, y and z satisfy 0<x≦1, 0<y<1, 0≦z<1, x+y+z=1, m=0-20, n=1-300; and    the chain lengths of the alkyl and the alkoxy are 1-18; and    type (B): terminal group type single white electroluminescent polymeric material                          wherein:    R 1  is alkyl or aryl;    Ar1 is a naphthalimide derivative basic unit and has one or more structures as listed below:                                                              wherein R 7  is alkyl, phenyl, naphthyl, or a phenyl or naphthyl group substituted by alkyl or alkoxy;    the structure of Ar2 is the same as the Ar2 in the type (A) single white luminescent polymeric material;    x and y are basic unit contents and satisfy 0<x≦1, 0<y<1, x+y=1; n=1-300; and    the chain length of alkyl and alkoxy is 1-18.    
   
   
       2 . A method for preparing the white electroluminescent polymeric material according to  claim 1 , the method comprising steps of: 
 d. providing a monomer selected from a group consisting of:    (5) monomers with a formula as follows:                          wherein, Ar1 is the same as that in the main chain type single white luminescent polymeric material according to  claim 1;     (6) monomers with a formula as follows:                          wherein, Ar1 is the same as that in the pendant chain type single white luminescent polymeric material according to  claim 1 , m=0-20;    (7) monomers with a formula as follows:                          wherein, Ar1 is the same as that in the pendant chain type single white luminescent polymeric material according to  claim 1 , m=0-20; and    (8) monomers with a formula as follows:                          wherein, Ar1 is the same as that in the pendant chain type single white luminescent polymeric material according to  claim 1 , m=0-20;    e. providing a monomer selected from a group consisting of:                          wherein, Ar1 is the same as that in the terminal group type single white luminescent polymeric material defined in  claim 1;  and    f. polymerizing a monomer obtained in step (a) and a monomer obtained in step (b) using the Yamamoto polymerization method or the Suzuki polymerization method.    
   
   
       3 . The method according to  claim 2 , wherein the monomer (1) in step a is prepared by a method comprising steps of: 
 dissolving naphthalimide derivative Ar1 and 2-4 mole equivalents of tetrabutyltriammonium bromide in a dichloromethane;    reacting the resulting solution, preferably at room temperature, for 10-1200 min; and    separating the reaction product.    
   
   
       4 . The method according to  claim 2 , wherein the monomer (2) in step a is prepared by a method comprising steps of: 
 dissolving 4-amino-1,8-naphthalimide and 1-5 mole equivalents of 2-(m-bromoalkoxy)-5-substituted-1,4-dibromobenzene in dimethyl sulfoxide;    adding 1-10 mole equivalents of MOH wherein M represents Li, Na or K;    reacting at 50-150° C. for 1-120 hr;    stopping the reaction and separating the intermediate product;    dissolving the intermediate product, 2-20 mole equivalents of iodobenzene, 2-20 mole equivalents of carbonate, 1-5% mole equivalent of 18-crown-6 and 1-5% mole equivalent of cuprous iodide in a solvent; heating to 140-200° C. under N 2  gas to react for 5-50 hr; and    separating the product.    
   
   
       5 . The method according to  claim 2 , wherein the monomer (3) in step a is prepared by a method comprising steps of: 
 contacting N,N-diphenyl-1,8-naphthalimide derivative with 15-80 mole equivalents of POCl 3  in dimethyl formamide at 50˜100° C. for 20-100 hr to produce 4-aldo or 4,4′-dialdo-N,N-diphenyl-1,8-naphthalimide derivative;    dissolving the resulting product and 0.5-1 mole equivalents of 9-phenyl-9-(4-bromotributylphosphino-methylenephenyl)-2,7-dibromofluorene or 9,9-(4-bromotributylphosphino-methylenephenyl)-2,7-dibromofluorene in a chloroform solution;    adding a solution of 4-10 mole equivalents of sodium ethoxide;    reacting at room temperature for 10-50 hr; and    separating the reaction product.    
   
   
       6 . The method according to  claim 2 , wherein the monomer (4) in step a is prepared by a method comprising the steps of: 
 dissolving 9,9-(m-bromoalkyl)-2,7-dibromofluorene and 2-3 mole equivalents of 4-amino-1,8-naphthalimide in a solvent;    adding 2-20 mole equivalents of MOH wherein M represents Li, Na or K;    reacting at 50-150° C. for 1-120 hr;    separating the intermediate product;    dissolving the intermediate product, 4-20 mole equivalents of iodobenzene, 6-20 mole equivalents of potassium carbonate, 2-10% mole equivalents of 18-crown-6, 2-10% mole equivalent of cuprous iodide in a solvent;    heating the solution to 140-200° C. to react for 5-50 hr; and    separating the product.    
   
   
       7 . The method according to  claim 2 , wherein the monomer b in step b is prepared using a method comprising steps of: 
 dissolving naphthalimide derivative Ar1H and 1-2 mole equivalents of tetrabutyltriammonium bromide in a solvent, preferably, dichloromethane;    reacting for 10-1200 min; and    separating the product.    
   
   
       8 . The method according to  claim 2 , wherein, for obtaining the main chain type single white light polymeric material, the Yamamoto polymerization method comprising steps of: 
 dissolving 2,7-dibromofluorene derivative monomer, 0.01%-10% mole equivalent of dibromonaphthalimide derivative monomer and 0-30% mole equivalent of dibromoaromatic monomer in a solvent, preferably anhydrous toluene, under the protection of N 2  gas;    dropping the resulting solution into a solution of 2-3 mole equivalents of Ni (0) in a solvent;    reacting at 50-100° C. for 24-120 hr; and    separating the product.    
   
   
       9 . The method according to  claim 2 , wherein, for obtaining the main chain type single white light polymeric material, the Suzuki polymerization method comprising steps of: 
 dissolving 2,7-diborate fluorene derivative monomer, 0.01-10% mole equivalent of dibromonaphthalimide derivative monomer and 0-20% mole equivalent of dibromoaromatic monomer in a solvent;    adding 3 mole equivalents of carbonate in a solution form;    under the protection of inert gas and at 50-100° C., adding 0.05% mole equivalent of tetra(triphenylphosphino) palladium (0);    reacting for 1-200 hr; and    separating the product.    
   
   
       10 . The method according to  claim 2 , wherein, for obtaining the pendant chain type single white light polymeric material, the Yamamoto polymerization method comprising steps of: 
 dissolving 2,7-dibromofluorene derivative monomer, 0.01%-10% mole equivalent of any one of monomers (2)-(4) in step a, and 0-30% mole equivalent of dibromoaromatic monomer in a solvent;    dropping the resulting solution into a solution of 2-3 mole equivalents of Ni (0) in a solvent;    reacting at 50-100° C. for 24-120 hr; and    separating the product.    
   
   
       11 . The method according to  claim 2 , wherein, for obtaining the pendant chain type single white light polymeric material, the Suzuki polymerization method comprising steps of: 
 dissolving 2,7-diborate fluorene derivative monomer, 0.01-10 mole equivalent of any one of monomers (2)-(4) in step a, and 0-20% mole equivalent of dibromoaromatic monomer in a solvent;    adding 3 mole equivalents of carbonate in a solution form;    under the protection of inert gas and at 50-100° C., adding 0.05% mole equivalent of tetra(triphenylphosphino) palladium (0);    reacting for 1-200 hr; and    separating the product.    
   
   
       12 . The method according to  claim 2 , wherein, for obtaining the terminal group type single white light polymeric material, the Yamamoto polymerization method comprising steps of: 
 dissolving 2,7-dibromofluorene derivative monomer and 0-30% mole equivalent of dibromoaromatic monomer in a solvent under the protection of an inert gas;    dropping the resulting solution into a solution of 2-3 mole equivalents of Ni (0) in a solvent;    reacting at 50-100° C. for 24-120 hr; and    separating the product.    
   
   
       13 . The method according to  claim 2 , wherein, for obtaining the terminal group type single white light polymeric material, the Suzuki polymerization method comprising steps of: 
 dissolving 2,7-diborate fluorene derivative monomer and 0-30% mole equivalent of dibromoaromatic monomer in a solvent;    adding 3 mole equivalents of carbonate in a solution form;    under the protection of N 2  gas and at 50-100° C., adding 0.050% mole equivalent of tetra(triphenylphosphino) palladium (0);    reacting for 24-120 hr;    adding 0.01-10% mole equivalent of monobromonaphthalimide derivative monomer;    reacting at 50-100° C. for 1-48 hr; and    separating the product.