CN103408742B - A kind of preparation method of many carboxyls metal phthalocyanine-aromatic copolyester - Google Patents
A kind of preparation method of many carboxyls metal phthalocyanine-aromatic copolyester Download PDFInfo
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Abstract
The present invention relates to a kind of preparation method of the aromatic thermosetting resin containing many carboxyls metal phthalocyanine.The present invention adopts Phthalic Anhydride to prepare many carboxyls metal phthalocyanine, and metal phthalocyanine is added to Homogeneous phase mixing in aromatic thermosetting resin performed polymer monomer, pyroreaction, obtain two kinds of performed polymer Cx-MPc-COOH and Ax-MPc-COOH, by two kinds of performed polymer Homogeneous phase mixing, obtain the aromatic thermosetting resin matrix material containing many carboxyls metal phthalocyanine through hot setting.The various monomers of synthetic aroma race thermosetting resin are all with carboxyl and ester terminated, and many carboxyls metal phthalocyanine with it chain transfer reaction can occur, in the molecular network structure of access aromatic thermosetting resin.The electron donation that the present invention utilizes metal phthalocyanine excellent is coupled with the conjugated structure of aromatic thermosetting resin, reaches the object improving aromatic thermosetting resin dielectric properties.The present invention has high temperature resistant, resistance to ablation, and easily the performance such as bonding, has important application in fields such as microelectronics, semi-conductor, electromagnetic material, electric intelligent materials.
Description
Technical field
The invention belongs to technical field of material, be specifically related to a kind of preparation method of the aromatic thermosetting resin containing many carboxyls metal phthalocyanine.
Background technology
Along with the high speed development of information technology, the continuous progress of electronic technology, dielectric substance is widely used in devices such as preparing passive device (electric capacity and resistance etc.), embedded capacitor, ferroelectrics store-memory device, pyroelectric detector, ferroelectric optical device, electrically insulating material.Conventional dielectric material field, the ferroelectricss such as barium titanate are the Typical Representatives of high dielectric material, have very high specific inductivity, and dielectric properties are excellent, but have that matter is heavy, mold temperature is high, an easy shortcoming such as crisp, make it apply and are more and more restricted.And polymkeric substance has the advantages such as good mechanical property, excellent impact property, good electrical insulating property, low-dielectric loss, superior processing characteristics and low cost.This kind of high-k polymeric dielectrics material has become the propping material in current electronic science and technology field, has application prospect widely, causes at present and pays close attention to widely and research, achieve great progress.
Metal phthalocyanine is a kind of common chemical dye, and it has the structure of large plane of a loop conjugation, in the industry such as pigment, dyestuff and ink, occupy critical role.It is caused not only to have excellent dielectric properties because phthalein work copper molecule has large π-conjugated systems, chemical stability, thermostability, flame retardancy and fast light, radiation resistance, but also there are electroconductibility, photoconductivity, gas sensing property, Electroluminescence, optical storage, catalytic activity and bionical characteristic etc., just developing into a kind of multifunctional material at present, will be widely used in industry and daily life.
Aromatic thermosetting copolyesters is a kind of three-dimensional net structure be connected to form by aromatic nucleus and ester group, there is excellent mechanical property, thermal characteristics and flame retardant properties, and it has the advantage easily reclaimed, it is had becomes the potential quality of composite resin matrix of new generation.
Summary of the invention
The object of the present invention is to provide the preparation method of a kind of many carboxyls metal phthalocyanine-aromatic copolyester.
The preparation method of a kind of many carboxyls metal phthalocyanine-aromatic copolyester that the present invention proposes, adopt Phthalic Anhydride to synthesize many carboxyls metal phthalocyanine, respectively with the various monomer Homogeneous phase mixing of aromatic copolyester ester oligomer, pyroreaction obtains Cx-MPc-COOH and Ax-MPc-COOH two kinds of oligopolymer, again by these two kinds of oligopolymer Homogeneous phase mixing, be heating and curing, obtain many carboxyls metal phthalocyanine-aromatic copolyester.Metal phthalocyanine is excellent electron donor(ED), and aromatic thermosetting resin has conjugated structure, by both couplings, reaches the object maximizing and improve dielectric properties.
Concrete steps are as follows:
(1) many carboxyls metal phthalocyanine is synthesized
The raw material of synthesis many carboxyls metal phthalocyanine is placed in there-necked flask in proportion, churned mechanically while, is slowly heated to 190 ~ 250 DEG C, reaction 3 ~ 12h, cooling down, grinds to form powder; This powder hydrochloric acid soln boils, suction filtration while hot, dries porphyrize; To be hydrolyzed process with sodium hydroxide solution, suction filtration, washs three times with ethanolic soln again, dries porphyrize, is many carboxyls metal phthalocyanine;
(2) by the monomer Homogeneous phase mixing by a certain percentage of many carboxyls metal phthalocyanine of obtaining in step (1) and synthetic aroma race thermosetting resin prepolymer; make the condition of protective atmosphere with nitrogen under; 260 ~ 300 DEG C of reactions are heated in there-necked flask; mechanical stirring the 1 ~ 4h that refluxes, reduce the temperature to 200 ~ 220 DEG C and collect acetic acid.Again system is warmed up to 280 ~ 350 DEG C, reaction 4 ~ 8h obtains oligopolymer Cx-MPc-COOH.Oligopolymer Cx-MPc-COOH is ground into uniform powder, and successively through methanol-water solution extraction, distilled water wash, and vacuum-drying 1 ~ 48 hour at 50 ~ 200 DEG C of temperature, obtain the oligopolymer Cx-MPc-COOH of purifying; The quality adding many carboxyls metal phthalocyanine is 1 ~ 50% of the monomer total mass of end carboxyl oligopolymer in aromatic copolyester; Wherein: the monomer of described synthetic aroma race thermosetting resin prepolymer is benzene three carboxyl or benzene three ester group structures alone, dicarboxyl structures alone and contains carboxyl or ester group structures alone;
(3) by the monomer Homogeneous phase mixing in proportion of many carboxyls metal phthalocyanine of obtaining in step (1) and aromatic copolyester middle-end ester group oligopolymer, make the condition of protective atmosphere with nitrogen under, 260 ~ 300 DEG C of reactions are heated in there-necked flask, mechanical stirring the 1 ~ 4h that refluxes, reduce the temperature to 200 ~ 220 DEG C and collect acetic acid; Again system is warmed up to 280 ~ 350 DEG C, reaction 4 ~ 8h obtains oligopolymer Ax-MPc-COOH; Oligopolymer Ax-MPc-COOH is ground into uniform powder, and successively through methanol-water solution extraction, distilled water wash, and vacuum-drying 1 ~ 48 hour at 50 ~ 200 DEG C of temperature, obtain the oligopolymer Ax-MPc-COOH of purifying; The quality adding many carboxyls metal phthalocyanine is 1 ~ 50% of the monomer total mass of aromatic copolyester middle-end ester group oligopolymer; Wherein: the monomer of described aromatic copolyester middle-end ester group oligopolymer is benzene three carboxyl or benzene three ester group structures alone, dicarboxyl structures alone and contains carboxyl or ester group structures alone;
(4) the oligopolymer Ax-MPc-COOH of the oligopolymer Cx-MPc-COOH of step (2) gained and step (3) gained is compared Homogeneous phase mixing according to the quality of 1.1:1 ~ 5.5:1,3h is maintained to 270 ~ 300 DEG C with the ramp of 10 ~ 20 DEG C/min, 3h is maintained to 330 ~ 350 DEG C again with the ramp of 5 ~ 15 DEG C/min, finally complete solidification with the speed cool to room temperature of 5 ~ 15 DEG C/min, obtain the aromatic thermosetting resin containing many carboxyls metal phthalocyanine.
In the present invention, many carboxyls metal phthalocyanine described in step (1) comprises any one in tetracarboxylic metal phthalocyanine structure, eight carboxyl metal phthalocyanine structures or Asymmetrical substitute carboxyl metal phthalocyanine structure; Center coordination particle comprises: in cupric ion, iron ion, cobalt ion, aluminum ion, nickel ion, calcium particle or sodium ion etc. any one, by in feed change, the kind of coordination particlized compound is provided, is aided with the metal phthalocyanine compound changing reaction conditions and prepare different central ion.
In the present invention, described in step (1), the synthesis material of many carboxyls metal phthalocyanine comprises: the chlorate of pyromellitic dianhydride, urea, metal or vitriol; Or the chlorate of TMA, urea, metal or vitriol; Catalyzer adopts Ammonium Molybdate Tetrahydrate; Described metal is any one in copper, iron, cobalt, aluminium, nickel, calcium or sodium etc.
In the present invention, in the synthesis material of many carboxyls metal phthalocyanine described in step (1), the mol ratio of the chlorate of pyromellitic dianhydride, urea, metal or vitriol and catalyzer is 4:4:1:0.01; Or TMA, urea, the chlorate of metal or the mol ratio of vitriol and catalyzer are 4:4:1:0.01.
In the present invention, described in step (1), the molar fraction of hydrochloric acid soln is 2 ~ 6mol/L, and the massfraction of sodium hydroxide solution is 30 ~ 60%; The ratio of powder and solution is that 10g powder adds 100ml solution, and pickling is seethed with excitement, and hydrolysis temperature is 80 ~ 100 DEG C, and hydrolysis time is 2 ~ 10h.
In the present invention, benzene three carboxyl or the benzene three ester group structures alone of the Cx-MPc-COOH of the Ax-MPc-COOH that step (2) is synthesized and the middle synthesis of step (3) are: trimesic acid or trimesic acid ethyl ester; Dicarboxyl structures alone is: 2-carboxyl propanedioic acid, m-phthalic acid, terephthalic acid, phthalic acid, succinic acid, tartrate, maleic acid, FUMARIC ACID TECH GRADE, 1, in 4-cyclohexane cyclohexanedimethanodibasic, 1,8-naphthalic acid, 3-carboxymethyl hexanodioic acid or hexanodioic acid any one; Containing carboxyl, ester group structures alone be: dimethyl phthalate, dimethyl terephthalate (DMT), dimethyl isophthalate, acetoxybenzoic acid, to acetoxy-benzoic acid, acetoxyl group naphthoic acid, hydroquinone diaeetate or the third oxalic acid diethyl ester or diacetoxy biphenol two or more.
In the present invention, in oligopolymer Cx-MPc-COOH described in step (2), trimesic acid (TMA): to acetoxy-benzoic acid (ABA): the mol ratio of m-phthalic acid (IPA) and hydroquinone diaeetate (HQDA) is any one in 1:1:1:1,1:3:4:3,2:5:4:3,2:1:6:4,2:2:3:2,2:6:3:1,3:4:3:1 or 4:3:2:1 etc.
In the present invention, in oligopolymer Ax-CNTs-COOH described in step (3), trimesic acid (TMA): to acetoxy-benzoic acid (ABA): the mol ratio of m-phthalic acid (IPA) and hydroquinone diaeetate (HQDA) is any one in 1:2:4:6,2:3:1:5 or 3:3:2:6 etc., or 1,2,4-benzenetricarboxylic anhydride (TMA): to acetoxy-benzoic acid (ABA): the mol ratio of m-phthalic acid (IPA) and hydroquinone diaeetate (HQDA) is any one in 2:4:1:3,1:2:3:6,1:2:2:4 or 2:5:1:6.
In the present invention, the volume ratio of step (2) and the first alcohol and water described in step (3) is 3:1.
In the present invention, this many carboxyls metal phthalocyanine-aromatic copolyester is 10
2~ 10
8in the range of frequency of Hz, specific inductivity changes in 10 ~ 1000.
Beneficial effect of the present invention is: aromatic thermosetting resin is all the conjugated structure that phenyl ring is connected with ester group, and metal phthalocyanine is the macromole of planar conjugate, has very high specific inductivity, is excellent electron donor(ED).This invents the electron donation utilizing metal phthalocyanine excellent and is coupled with the conjugated structure of aromatic thermosetting resin, reaches the object improving aromatic thermosetting resin dielectric properties, thus widens the range of application of aromatic thermosetting resin.The metal phthalocyanine of this invention preparation and the matrix material of aromatic thermosetting resin possess excellent dielectric properties, and have high temperature resistant, resistance to ablation, easily the performance such as bonding, can have important application in fields such as microelectronics, semi-conductor, electromagnetic material, electric intelligent materials.
Embodiment
The following examples further illustrate of the present invention, instead of limit the scope of the invention.
EXAMPLE l: with eight carboxyl CuPcs for initial raw material, Cx-CuPc-COOH and Ax-CuPc-COOH two kinds of oligopolymer are obtained by reacting respectively with the monomer Homogeneous phase mixing of aromatic copolyester ester oligomer, again by these two kinds of oligopolymer Homogeneous phase mixing, be heating and curing and obtain CuPc-aromatic copolyester.
Step (1): with pyromellitic dianhydride, urea, cuprous chloride for raw material, Ammonium Molybdate Tetrahydrate is catalyzer, Solid phase synthesis eight carboxyl CuPc.To be equipped with thermometer, stirring rod, prolong 500ml there-necked flask in, add 10.9g (0.05mol) pyromellitic dianhydride, 3g (0.05mol) urea, 1.24g (0.0125mol) cuprous chloride, 0.1g Ammonium Molybdate Tetrahydrate.Mechanical stirring, is slowly heated to 190 DEG C, reaction 3h, then is warming up to 210 DEG C, reaction 6h, cooling porphyrize.Boil powder with the hydrochloric acid soln of 4mol/L, while hot suction filtration, washing with alcohol, 80 DEG C are dried 10h.Be hydrolyzed powder with the sodium hydroxide solution of 40% again, temperature is 80 DEG C, hydrolysis 4h, suction filtration, and washing with alcohol, dries, be eight carboxyl CuPc crystal.
Step (2): in the 2000ml four-hole bottle that stirring rod, thermometer, prolong and inert gas entrance are housed, adds the eight equal tricarboxylic acid of carboxyl CuPc 0.76g, 21g (0.1mol) benzene (TMA), 18g (0.1mol) acetoxy-benzoic acid (ABA), 16.6g (0.1mol) m-phthalic acid (IPA) and 19.4g (0.1mol) Resorcinol oxalic acid fat (HQDA) that obtain in step (1).Be under the condition of protective atmosphere with nitrogen; reaction system is heated to 280 DEG C; stirring and refluxing 1h obtains low viscosity melt; reflux condensing tube is changed into collector when reducing the temperature to 200 DEG C; collect acetic acid; treat that system viscosity increases and again system is warmed up to 300 DEG C, reaction 1h obtains oligopolymer Cx-CuPc-COOH.Cx-CuPc-COOH is ground into uniform powder, and through the extraction of methanol-water, distilled water wash, and vacuum-drying 24 hours at 80 DEG C of temperature, obtain pure Cx-CuPc-COOH.
(3) in the 1000ml four-hole bottle that stirring rod, thermometer, prolong and inert gas entrance are housed, add the eight equal tricarboxylic acid of carboxyl CuPc 1.12g, 21g (0.1mol) benzene (TMA), 36g (0.2mol) acetoxy-benzoic acid (ABA), 16.6g (0.1mol) m-phthalic acid (IPA) and 38.8g (0.2mol) Resorcinol oxalic acid fat (HQDA) in step (1).Be under the condition of protective atmosphere with nitrogen, reaction system be heated to 280 DEG C, backflow 1h obtains low viscosity melt; reflux condensing tube is changed into collector when reducing the temperature to 200 DEG C; collect acetic acid, again system is warmed up to 300 DEG C when viscosity increases, reaction 1h obtains oligopolymer Ax-CuPc-COOH.Ax-CuPc-COOH is ground into uniform powder, and through the extraction of methanol-water, distilled water wash, and vacuum-drying 24 hours at 80 DEG C of temperature, obtain pure Ax-CuPc-COOH.
(4) be 1.1:1 by the oligopolymer Ax-CuPc-COOH(mass ratio obtained in the oligopolymer Cx-CuPc-COOH of step (2) gained and step (3)) Homogeneous phase mixing, 3h is maintained to 280 DEG C with the ramp of 15 DEG C/min, 3h is maintained to 330 DEG C again with the ramp of 10 DEG C/min, finally complete with the speed cool to room temperature of 5 DEG C/min CuPc-aromatic copolyester that solidification obtains containing 1wt%, during 100Hz frequency, specific inductivity is 800.
Embodiment 2: with tetracarboxylic CuPc for raw material, respectively with the monomer Homogeneous phase mixing of aromatic copolyester ester oligomer, pyroreaction obtains Cx-CuPc-COOH and Ax-CuPc-COOH two kinds of oligopolymer, then by these two kinds of oligopolymer Homogeneous phase mixing, be heating and curing, obtain CuPc-aromatic copolyester.
Step (1): with TMA, urea, cuprous chloride for raw material, Ammonium Molybdate Tetrahydrate is catalyzer, Solid phase synthesis tetracarboxylic CuPc.To be equipped with thermometer, stirring rod, prolong 500ml there-necked flask in, add 9.6g (0.05mol) 1,2,4-benzenetricarboxylic anhydride, 3g (0.05mol) urea, 1.24g (0.0125mol) cuprous chloride, 0.1g Ammonium Molybdate Tetrahydrate.Mechanical stirring, is slowly heated to 240 DEG C, reaction 3h, cooling porphyrize.Boil powder with the hydrochloric acid soln of 5mol/L, while hot suction filtration, washing with alcohol, 80 DEG C are dried 10h.Be hydrolyzed powder with the sodium hydroxide solution of 50% again, temperature is 90 DEG C, hydrolysis 2h, suction filtration, and washing with alcohol, dries, be tetracarboxylic CuPc crystal.
Step (2): add step (1) middle tetracarboxylic CuPc 37.84g, 84g (0.4mol) benzene equal tricarboxylic acid TMA, 54g (0.3mol) Resorcinol oxalic acid fat HQDA, 33.2g (0.2mol) m-phthalic acid IPA, 18g (0.1mol) to acetoxy-benzoic acid ABA, 50mlNMP in the 500ml there-necked flask that stirring rod, nitrogen inlet and prolong are housed.Not easily melt because TMA and IPA consumption is more, therefore need to dissolve with solvent, in this example, select NMP as solvent.Immersed by reaction mixture in the salt bath of 300 DEG C, NMP can vaporize very soon, collects NMP and be about 45ml in 30min, and the 4h of mechanical stirring backflow afterwards, obtains low viscosity melt Cx-CuPc-COOH.Cx-FePc-COOH is ground into uniform powder, and through the extraction of methanol-water, distilled water wash, and vacuum-drying 12 hours at 100 DEG C of temperature, obtain pure Cx-CuPc-COOH.
Step (3): stirring rod is being housed, tetracarboxylic CuPc 26.64g in step (1) is added in the 500ml there-necked flask of nitrogen inlet and prolong, the equal tricarboxylic acid of 21g (0.1mol) benzene (TMA), 18g (0.1mol) is to acetoxy-benzoic acid (ABA), 16.6g (0.1mol) m-phthalic acid (IPA) and 77.6g (0.4mol) Resorcinol oxalic acid fat (HQDA), make the condition of protective atmosphere with nitrogen under, reaction system is heated to 300 DEG C, mechanical stirring backflow 4h obtains low viscosity melt, reflux condensing tube is changed into collector when temperature drops to 200 DEG C, collect acetic acid, treat that system is warmed up to 350 DEG C by system viscosity increase again, reaction 6h obtains oligopolymer Ax-CuPc-COOH.Ax-CuPc-COOH is ground into uniform powder, and through the extraction of methanol-water, distilled water wash, and vacuum-drying 12 hours at 100 DEG C of temperature, obtain pure Ax-CuPc-COOH.
Step (4): by the oligopolymer Cx-CuPc-COOH of step (2) and step (3) gained and oligopolymer Ax-CuPc-COOH(mass ratio 2.2:1) Homogeneous phase mixing, 2h is maintained to 300 DEG C with the ramp of 10 DEG C/min, 2h is maintained to 350 DEG C again with the ramp of 8 DEG C/min, finally complete solidification with the speed cool to room temperature of 15 DEG C/min to obtain containing 20wt% CuPc-aromatic copolyester, under 100Hz frequency, specific inductivity is 2000.
Embodiment 3: with eight carboxyl Cobalt Phthalocyanines for initial raw material, respectively with the monomer Homogeneous phase mixing of the oligopolymer of aromatic copolyester, pyroreaction obtains Cx-CoPc-COOH and Ax-CoPc-COOH two kinds of oligopolymer, again by these two kinds of oligopolymer Homogeneous phase mixing, be heating and curing, obtain eight carboxyl Cobalt Phthalocyanine-aromatic copolyesters.
Step (1): with pyromellitic dianhydride, urea, cobalt chloride for raw material, Ammonium Molybdate Tetrahydrate is catalyzer, and oil of mirbane synthesizes eight carboxyl Cobalt Phthalocyanines as solvent.To be equipped with thermometer, stirring rod, prolong 500ml there-necked flask in, add 10.9g (0.05mol) pyromellitic dianhydride, 3g (0.05mol) urea, 1.625g (0.0125mol) cobalt chloride, 0.1g Ammonium Molybdate Tetrahydrate, 50ml oil of mirbane.Mechanical stirring, is slowly heated to 200 DEG C, reaction 1h, then is warming up to 240 DEG C, reaction 3h, cooling porphyrize.Boil powder with the hydrochloric acid soln of 4mol/L, while hot suction filtration, washing with alcohol, 80 DEG C are dried 10h.Be hydrolyzed powder with the sodium hydroxide solution of 50% again, temperature is 100 DEG C, hydrolysis 6h, suction filtration, and washing with alcohol, dries, be eight carboxyl Cobalt Phthalocyanine crystal.
Step (2): add eight carboxyl Cobalt Phthalocyanine 4.8g, 27g (0.1mol) diacetoxies biphenol (BPDA), 18g (0.1mol) ABA, 52g (0.4mol) acetoxyl group naphthoic acid (ANA) in step (1) in the 500ml four-hole bottle that thermometer, stirring rod, nitrogen inlet and prolong are housed.Be under the condition of protective atmosphere with nitrogen, reaction system be heated to 320 DEG C, stirring and refluxing 1h obtains low viscosity melt, cools to 220 DEG C and collects acetic acid, treat that viscosity increase is warming up to 380 DEG C again, and reaction 3h obtains oligopolymer Cx-CoPc-COOH.Cx-CoPc-COOH is ground into uniform powder, through the extraction of methanol-water, distilled water wash, and at 120 DEG C of temperature vacuum-drying 10h, obtain pure Cx-CoPc-COOH.
Step (3): add eight carboxyl Cobalt Phthalocyanine 3.35g, 27g (0.1mol) diacetoxies biphenol (BPDA), 27g (0.15mol) ABA, 13g (0.1mol) acetoxyl group naphthoic acid (ANA) in step (1) in the 500ml there-necked flask that thermometer, stirring rod, nitrogen inlet and prolong are housed.Be under the condition of protective atmosphere with nitrogen, reaction system be heated to 320 DEG C, stirring and refluxing 1h obtains low viscosity melt, cools to 220 DEG C and collects acetic acid, treat that viscosity increase is warming up to 380 DEG C again, and reaction 3h obtains oligopolymer Ax-CoPc-COOH.Ax-CoPc-COOH is ground into uniform powder, through the extraction of methanol-water, distilled water wash, and at 120 DEG C of temperature vacuum-drying 10h, obtain pure Ax-CoPc-COOH.
Step (4): be 3.3:1 by the oligopolymer Cx-CoPc-COOH of step (2) and step (3) gained and oligopolymer Ax-CoPc-COOH(quality) Homogeneous phase mixing, 2h is maintained to 310 DEG C with the ramp of 15 DEG C/min, 2h is maintained to 340 DEG C again with the ramp of 12 DEG C/min, finally complete solidification with the speed cool to room temperature of 12 DEG C/min to obtain containing 5wt% Cobalt Phthalocyanine-aromatic copolyester, under 100Hz frequency, specific inductivity is 1200.
Embodiment 4: take four carboxyl phthalocyanine cobalt as initial raw material, Cx-CoPc-COOH and Ax-CoPc-COOH two kinds of oligopolymer are obtained by reacting respectively with the monomer Homogeneous phase mixing of aromatic copolyester ester oligomer, again by these two kinds of oligopolymer Homogeneous phase mixing, be heating and curing, obtain eight carboxyl Cobalt Phthalocyanine-aromatic copolyesters.
Step (1): with TMA, urea, cobalt chloride for raw material, Ammonium Molybdate Tetrahydrate is catalyzer, and oil of mirbane makes solvent synthesis four carboxyl phthalocyanine cobalt.To be equipped with thermometer, stirring rod, prolong 500ml there-necked flask in, add 9.6g (0.05mol) 1,2,4-benzenetricarboxylic anhydride, 3g (0.05mol) urea, 1.625g (0.0125mol) cobalt chloride, 0.1g Ammonium Molybdate Tetrahydrate.Mechanical stirring, is slowly heated to 220 DEG C, reaction 5h, cooling porphyrize.Boil powder with the hydrochloric acid soln of 6mol/L, while hot suction filtration, washing with alcohol, 80 DEG C are dried 10h.Be hydrolyzed powder with the sodium hydroxide solution of 60% again, temperature is 80 DEG C, hydrolysis 6h, suction filtration, and washing with alcohol, dries, be four carboxyl phthalocyanine cobalt crystal.
Step (2): stirring rod is being housed, thermometer, four carboxyl phthalocyanine cobalt 18.44g in step (1) is added in the four-hole bottle of the 2000ml of inert gas entrance and prolong, the equal tricarboxylic acid of 21g (0.1mol) benzene (TMA), 36g (0.2mol) acetoxy-benzoic acid (ABA), 49.8g (0.3mol) m-phthalic acid (IPA) and 77.6g (0.4mol) Resorcinol oxalic acid fat (HQDA), under the condition constantly passing into nitrogen, reaction system is heated to 370 DEG C, backflow 3h obtains low viscosity melt, reflux condensing tube is changed into collector when temperature drops to 225 DEG C, collect acetic acid, again system is warmed up to 360 DEG C, reaction 3h obtains oligopolymer Cx-CoPc-COOH.Cx-CoPc-COOH is ground into uniform powder, and through the extraction of methanol-water, distilled water wash, and vacuum-drying 12 hours at 120 DEG C of temperature, obtain pure Cx-CoPc-COOH.
(3) in the four-hole bottle of 2000ml that stirring rod, thermometer, inert gas entrance and prolong are housed, add four carboxyl phthalocyanine cobalt 12.92g, 42g (0.2mol) 1 in step (1); 3; 5-triacetyl phenol (TBA), 18g (0.1mol) acetoxy-benzoic acid (ABA), 49.8g (0.3mol) m-phthalic acid (IPA) and 19.4g (0.1mol) Resorcinol oxalic acid fat (HQDA); plus solvent is not adopted in present method; and adopting the TAB monomer of low melting point, it can as the linking agent of trifunctional.Under the condition constantly passing into nitrogen, reaction system is heated to 320 DEG C, backflow 3h obtains low viscosity melt, changes reflux condensing tube into collector when temperature drops to 230 DEG C, collects acetic acid, again system is warmed up to 340 DEG C, reaction 3h obtains oligopolymer Ax-CoPc-COOH.Ax-CoPc-COOH is ground into uniform powder, and through the extraction of methanol-water, distilled water wash, and vacuum-drying 12 hours at 120 DEG C of temperature, obtain the Ax-CoPc-COOH of purifying.
Step (4): be 4.4:1 by the oligopolymer Cx-CoPc-COOH of step (2) and step (3) gained and oligopolymer Ax-CoPc-COOH(quality) Homogeneous phase mixing, 2h is maintained to 300 DEG C with the ramp of 8 DEG C/min, 3h is maintained to 350 DEG C again with the ramp of 10 DEG C/min, finally complete with the speed cool to room temperature of 10 DEG C/min Cobalt Phthalocyanine-aromatic copolyester that solidification obtains containing 10wt%, under 100Hz frequency, specific inductivity is 1000.
Claims (5)
1. the preparation method of the aromatic thermosetting resin material containing many carboxyls metal phthalocyanine, is characterized in that concrete steps are as follows:
(1) many carboxyls metal phthalocyanine is synthesized
The raw material of synthesis many carboxyls metal phthalocyanine is placed in there-necked flask in proportion, churned mechanically while, is slowly heated to 190 ~ 250 DEG C, reaction 3 ~ 12h, cooling down, grinds to form powder; This powder hydrochloric acid soln boils, suction filtration while hot, dries porphyrize; To be hydrolyzed process with sodium hydroxide solution, suction filtration, washs three times with ethanolic soln again, dries porphyrize, is many carboxyls metal phthalocyanine; The synthesis material of described many carboxyls metal phthalocyanine comprises: the chlorate of pyromellitic dianhydride, urea, metal or vitriol; Or the chlorate of TMA, urea, metal or vitriol; Catalyzer adopts Ammonium Molybdate Tetrahydrate; Described metal is any one in copper, iron, cobalt, aluminium, nickel, calcium or sodium; The mol ratio of the chlorate of pyromellitic dianhydride, urea, metal or vitriol and catalyzer is 4:4:1:0.01; Or TMA, urea, the chlorate of metal or the mol ratio of vitriol and catalyzer are 4:4:1:0.01;
(2) by the monomer Homogeneous phase mixing by a certain percentage of many carboxyls metal phthalocyanine of obtaining in step (1) and synthetic aroma race thermosetting resin prepolymer, make the condition of protective atmosphere with nitrogen under, 260 ~ 300 DEG C of reactions are heated in there-necked flask, mechanical stirring the 1 ~ 4h that refluxes, reduce the temperature to 200 ~ 220 DEG C and collect acetic acid; Again system is warmed up to 280 ~ 350 DEG C, reaction 4 ~ 8h obtains oligopolymer Cx-MPc-COOH; Oligopolymer Cx-MPc-COOH is ground into uniform powder, and successively through methanol-water solution extraction, distilled water wash, and vacuum-drying 1 ~ 48 hour at 50 ~ 200 DEG C of temperature, obtain the oligopolymer Cx-MPc-COOH of purifying; The quality adding many carboxyls metal phthalocyanine is 1 ~ 50% of the monomer total mass of end carboxyl oligopolymer in aromatic copolyester; Wherein: the monomer of described synthetic aroma race thermosetting resin prepolymer is benzene three carboxyl or benzene three ester group structures alone, dicarboxyl structures alone and contains carboxyl or ester group structures alone; In described oligopolymer Cx-MPc-COOH, trimesic acid: to acetoxy-benzoic acid: the mol ratio of m-phthalic acid and hydroquinone diaeetate is any one in 1:1:1:1,1:3:4:3,2:5:4:3,2:1:6:4,2:2:3:2,2:6:3:1,3:4:3:1 or 4:3:2:1;
(3) by the monomer Homogeneous phase mixing in proportion of many carboxyls metal phthalocyanine of obtaining in step (1) and aromatic copolyester middle-end ester group oligopolymer, make the condition of protective atmosphere with nitrogen under, 260 ~ 300 DEG C of reactions are heated in there-necked flask, mechanical stirring the 1 ~ 4h that refluxes, reduce the temperature to 200 ~ 220 DEG C and collect acetic acid; Again system is warmed up to 280 ~ 350 DEG C, reaction 4 ~ 8h obtains oligopolymer Ax-MPc-COOH; Oligopolymer Ax-MPc-COOH is ground into uniform powder, and successively through methanol-water solution extraction, distilled water wash, and vacuum-drying 1 ~ 48 hour at 50 ~ 200 DEG C of temperature, obtain the oligopolymer Ax-MPc-COOH of purifying; The quality adding many carboxyls metal phthalocyanine is 1 ~ 50% of the monomer total mass of aromatic copolyester middle-end ester group oligopolymer; Wherein: the monomer of described aromatic copolyester middle-end ester group oligopolymer is benzene three carboxyl or benzene three ester group structures alone, dicarboxyl structures alone and contains carboxyl or ester group structures alone; In described oligopolymer Ax-CNTs-COOH, trimesic acid: to acetoxy-benzoic acid: the mol ratio of m-phthalic acid and hydroquinone diaeetate is any one in 1:2:4:6,2:3:1:5 or 3:3:2:6, or 1,2,4-benzenetricarboxylic anhydride: to acetoxy-benzoic acid: the mol ratio of m-phthalic acid and hydroquinone diaeetate is any one in 2:4:1:3,1:2:3:6,1:2:2:4 or 2:5:1:6;
(4) the oligopolymer Ax-MPc-COOH of the oligopolymer Cx-MPc-COOH of step (2) gained and step (3) gained is compared Homogeneous phase mixing according to the quality of 1.1:1 ~ 5.5:1,3h is maintained to 270 ~ 300 DEG C with the ramp of 10 ~ 20 DEG C/min, 3h is maintained to 330 ~ 350 DEG C again with the ramp of 5 ~ 15 DEG C/min, finally complete solidification with the speed cool to room temperature of 5 ~ 15 DEG C/min, obtain the aromatic thermosetting resin containing many carboxyls metal phthalocyanine.
2. the preparation method of a kind of many carboxyls metal phthalocyanine-aromatic copolyester according to claim 1, is characterized in that many carboxyls metal phthalocyanine described in step (1) comprises any one in tetracarboxylic metal phthalocyanine structure, eight carboxyl metal phthalocyanine structures or Asymmetrical substitute carboxyl metal phthalocyanine structure; Center coordination particle comprises: in cupric ion, iron ion, cobalt ion, aluminum ion, nickel ion, calcium particle or sodium ion etc. any one, by in feed change, the kind of coordination particlized compound is provided, is aided with the metal phthalocyanine compound changing reaction conditions and prepare different central ion.
3. the preparation method of a kind of many carboxyls metal phthalocyanine-aromatic copolyester according to claim 1, is characterized in that the molar fraction of hydrochloric acid soln described in step (1) is 2 ~ 6mol/L, and the massfraction of sodium hydroxide solution is 30 ~ 60%; The ratio of powder and solution is that 10g powder adds 100ml solution, and pickling is seethed with excitement, and hydrolysis temperature is 80 ~ 100 DEG C, and hydrolysis time is 2 ~ 10h.
4. the preparation method of a kind of many carboxyls metal phthalocyanine-aromatic copolyester according to claim 1, is characterized in that the volume ratio of step (2) and the first alcohol and water described in step (3) is 3:1.
5. the preparation method of a kind of many carboxyls metal phthalocyanine-aromatic copolyester according to claim 1, is characterized in that this many carboxyls metal phthalocyanine-aromatic copolyester is 10
2~ 10
8in the range of frequency of Hz, specific inductivity changes in 10 ~ 1000.
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