CN107987277A - A kind of X-ray luminescence composite polyimide material and preparation method thereof - Google Patents

A kind of X-ray luminescence composite polyimide material and preparation method thereof Download PDF

Info

Publication number
CN107987277A
CN107987277A CN201711201437.1A CN201711201437A CN107987277A CN 107987277 A CN107987277 A CN 107987277A CN 201711201437 A CN201711201437 A CN 201711201437A CN 107987277 A CN107987277 A CN 107987277A
Authority
CN
China
Prior art keywords
polyimide resin
rare
earth oxide
oxide sulfate
dianhydride
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201711201437.1A
Other languages
Chinese (zh)
Other versions
CN107987277B (en
Inventor
周利庄
王洋
黄活阳
刘永亮
熊平
邱从章
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Aerospace Science and Industry Changsha New Materials Research Institute Co Ltd
Original Assignee
Changsha New Material Industry Research Institute Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Changsha New Material Industry Research Institute Co Ltd filed Critical Changsha New Material Industry Research Institute Co Ltd
Priority to CN201711201437.1A priority Critical patent/CN107987277B/en
Publication of CN107987277A publication Critical patent/CN107987277A/en
Application granted granted Critical
Publication of CN107987277B publication Critical patent/CN107987277B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1042—Copolyimides derived from at least two different tetracarboxylic compounds or two different diamino compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1046—Polyimides containing oxygen in the form of ether bonds in the main chain
    • C08G73/105—Polyimides containing oxygen in the form of ether bonds in the main chain with oxygen only in the diamino moiety
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1057—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain
    • C08G73/1064—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain containing sulfur
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
    • C08G73/1071—Wholly aromatic polyimides containing oxygen in the form of ether bonds in the main chain
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C08K9/06—Ingredients treated with organic substances with silicon-containing compounds

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The invention discloses a kind of X-ray luminescence composite polyimide material and preparation method thereof, the composite material includes polyimide resin and the modified RE oxysulfide being evenly distributed in the polyimide resin, the polyimide resin is aromatic diamine and the co-condensation polymer of aromatic dianhydride, and the modified RE oxysulfide refers to by silane coupler modified rare-earth oxide sulfate.The fluorescence efficiency of the polyimide resin luminescent material of the present invention is high, resistance to elevated temperatures is good, resistance to X penetrates performance good, good mechanical property.

Description

A kind of X-ray luminescence composite polyimide material and preparation method thereof
Technical field
The present invention relates to a kind of X-ray luminescence composite polyimide material and preparation method thereof, belong to luminous high polymer material Expect technical field.
Background technology
Polyimide resin is a kind of high-low temperature resistant, high intensity, radiation hardness, fire-retardant, good insulating high molecular material, is Temperature classification highest organic material in current industrialized high molecular material.Due to its excellent performance, it is widely used in Nuclear industry, spacecraft and medical instruments field, such as land on the moon outboard shell material, suit, spaceship cable insulation, resistance to universe Dirt overcoat, shading system, emergency oxygen system are all made with exclusion seal material of polyimide material.
X-ray is the very short electromagnetic wave of wavelength, is the ray that a kind of naked eyes can not be observed, is that one kind is hazardous to the human body Ray.X ray luminous material is a kind of material that can launch visible ray under excitation of X-rays, is penetrated when luminescent material is placed in X In thread environment, luminescent material can produce visible ray, and people can just can identification ring by the visible ray that radioluminescnet materials are sent The X-ray of harmful to human is whether there is in border, the X-ray track in environment can be also caught by the visible ray that radioluminescnet materials are sent And radiographic source.
Common high molecular polymer thermostabilization and radiation resistance with fat chain structure limit rare-earth luminescent material Practical application.Fluorescent material it is higher can only can not to be applied to environmental requirement in field applications such as false proof, night marks at present High temperature, ray radiation field.X-ray luminescence polyimide resin belongs to one kind of polyimides fluorescent material, open at present Polyimides fluorescence resin mainly realized by varying polyimide resin structure.Patent CN201611013214.8 is reported Lead, the building stone containing phenoxy group-diphenylamines-fluorenes is introduced in resin and is prepared for a kind of polyimides tree of electroluminescent fluorescent performance Fat material.Patent CN201380062274.7 is reported, and is prepared in resin the methods of introducing hexafluoroisopropanol structure, amide structure A kind of polyimide resin fluorescent material, but fluorescence efficiency is relatively low.
The content of the invention
Present invention solves the technical problem that being, the fluorescence efficiency of polyimide resin luminescent material is relatively low in the prior art, Resistance to elevated temperatures, resistance to X penetrate poor performance.
The technical scheme is that, there is provided a kind of X-ray luminescence composite polyimide material, including polyimide resin With the modified RE oxysulfide being evenly distributed in the polyimide resin, the polyimide resin is aromatic diamine With the co-condensation polymer of aromatic dianhydride, the modified RE oxysulfide refers to by silane coupler modified rare earth sulphur oxidation Thing.
Preferably, the rare earth element in the rare-earth oxide sulfate is La, Ce, Pr, Nd, Sm, the one or more in Eu.
Preferably, the mass ratio of modified RE oxysulfide and polyimide resin is：0.5%-10%, preferably 0.5%- 6%.The quality of polyimide resin may be approximately equal to the gross mass of aromatic diamine and aromatic dianhydride, modified RE sulphur oxygen Compound accounts for the 0.5-10% of the gross mass of aromatic diamine and aromatic dianhydride, preferably 0.5%-6%.
Preferably, the silane coupling agent is high temperature resistant silane coupling agent.
Preferably, the high temperature resistant silane coupling agent is phenyl oxyalkylene imide compound；Phenyl oxyalkylene imide Compound is preferably to be carried out by primary amino radical silicone compounds and phthalic anhydride obtained by hot imines cyclization.
Preferably, the primary amino radical silicone compounds are 3- aminopropyl trimethoxysilanes, 3- aminopropyl-triethoxies One or more in silane, 3- aminopropyltriethoxies dimethoxysilane, 3- aminopropyltriethoxy diethoxy silanes.
The present invention further provides a kind of preparation method of X-ray luminescence composite polyimide material, comprise the following steps：
A) silane coupler modified rare-earth oxide sulfate is added to aprotic polar solvent, then ultrasonic disperse, is formed The dispersion liquid of rare-earth oxide sulfate；
B) aromatic diamine is dissolved in the dispersion liquid obtained to step a), forms aromatic diamine and rare-earth oxide sulfate Mixed liquor；
C) aromatic dianhydride is added in the mixed liquor obtained to step b) and carries out polycondensation reaction, form the oxidation of rare earth sulphur The dispersion of thing-polyamic acid resin；
D) add in the dispersion obtained with aqueous solvent to c) step, then carry out hot imidization reaction, form rare earth sulphur oxygen Compound-polyimide resin solution, then through separating out, it is dry, obtain X-ray luminescence polyimide resin.
Preferably, aromatic diamine is phenylenediamine, diaminodiphenyl ether, diaminodiphenylmethane, diaminodiphenylsulfone, two One or more in amino-benzene oxygen diphenyl sulphone (DPS), diaminobenzophenone.It is preferred that p-phenylenediamine, m-phenylene diamine (MPD), 4,4 '-diamino Yl diphenyl ether, 3,4 '-diaminodiphenyl ether, 4,4 '-bis- (3- amino-benzene oxygens) diphenyl sulphone (DPS)s, 4,4 '-diaminodiphenylmethane, 4, 4 '-diaminobenzophenone.
Preferably, aromatic dianhydride is pyromellitic acid anhydride, bisphenol A dianhydride, diphenyl ether tetraformic dianhydride, biphenyl tetracarboxylic One or more in acid dianhydride, benzophenone tetracarboxylic dianhydride.It is preferred that pyromellitic acid anhydride, 3,3 ', 4,4 ' bisphenol-As two Acid anhydride, 3,3 ', 4,4 '-diphenyl ether tetraformic dianhydride, 3,3 ', 4,4 '-bibenzene tetracarboxylic dianhydride, 3,3 ', 4,4 '-benzophenone tetramethyl Acid dianhydride.
Preferably, aromatic diamine and the molar ratio of aromatic dianhydride are between 0.9-1.2, preferably 0.95-1.05.
Preferably, the aprotic solvent is dimethylacetylamide, dimethylformamide, 1-methyl-2-pyrrolidinone, diformazan Base sulfoxide, tetrahydrofuran, preferably dimethylacetylamide, dimethylformamide, 1-methyl-2-pyrrolidinone.The band aqueous solvent is first The mixture of benzene, dimethylbenzene or both.
Preferably, the mass ratio of the gross mass and solvent of the aromatic dianhydride and aromatic diamine is 15%-40%, excellent Select 20%-30%.
The specific implementation step of X-ray luminescence polyimide resin preparation method is：A) high temperature resistant silane coupling agent is changed Property rare-earth oxide sulfate add to aprotic polar solvent, then ultrasonic disperse 30-120min, form rare-earth oxide sulfate and disperse Liquid；B) aromatic diamine is added into the dispersion liquid described in step a), make diamines in a solvent fully dissolving formed diamines and Rare-earth oxide sulfate mixed liquor；C) it is aromatic dianhydride secondary addition in five batches progress polycondensation into the mixed liquor described in step b) is anti- Should, reaction time 3-8h, 5 DEG C -30 DEG C of reaction temperature, forms rare-earth oxide sulfate-polyamic acid resin dispersion；D) band is added In dispersion described in aqueous solvent to c) step, then carry out high temperature hot imidization reaction, reaction time 6-15h, reaction temperature 140 Between DEG C -190 DEG C, form rare-earth oxide sulfate-polyimide resin solution, resin solution again through separating out, dry, broken and sieve After point, X-ray luminescence polyimide resin is obtained.
By X-ray luminescence polyimide resin in mould it is hot-forming, temperature range is in 300-450 DEG C, pressure model It is trapped among in 5-60MPa, time range is in 30-180min, and then cool down pressure release, obtains X-ray luminescence polyimides composite wood Expect section bar, the composite material tensile strength ＞ 70MPa, impact strength ＞ 30kJ/m2, the composite material can be applied to detection not Know or known ray radiation space field.
The invention has the advantages that the fluorescence efficiency of polyimide resin luminescent material is high, resistance to elevated temperatures is good, resistance to X It is good to penetrate performance, good mechanical property.
Embodiment
In order to further illustrate the present invention, with reference to embodiments to polyimide resin provided by the invention and its preparation Method is described in detail with composite material, but does not limit and be used for the present invention.
Embodiment 1
3- is added to being equipped with mechanical agitation, water knockout drum, condensation reflux unit and four neck round-bottom flasks of nitrogen protection The Eu that phenyl acid imide propyl trimethoxy silicane is modified2O2S 1.5785g, dimethylacetylamide 146.71g, ultrasonic 60min, Stirring is opened, then adds p-phenylenediamine 11.0844g (0.1025mo1), to abundant dissolving, then adds 3,3 ' in five times, 4, Rare-earth oxide sulfate-polyamic acid solution is obtained when reaction 4 is small at 30 DEG C of 4 '-bisphenol A dianhydride 51.7887g (0.0995mo1). Dimethylbenzene 28.54g is added into obtained rare-earth oxide sulfate-polyamic acid solution, 155 DEG C of 8 hours of reflux band water obtain Rare-earth oxide sulfate-polyimide resin solution.Polyimide resin solution ethanol/water mixed liquor is separated out and filtered again and is obtained Rare-earth oxide sulfate-polyimide resin wet mash is obtained, wet mash filters after washing 2 times with ethanol again, and it is small that 5 are dried at 100 DEG C When, rare-earth oxide sulfate-polyimide resin powder end is obtained after broken sieving.Polyimide resin powder end is hot pressed into mould Type, 340 DEG C of temperature, pressure 12MPa, dwell time 45min, then cool down pressure release, obtains X-ray luminescence polyimides composite wood Expect section bar, the composite material section bar tensile strength 92MPa, impact strength 45kJ/m2。
Embodiment 2
3- is added to being equipped with mechanical agitation, water knockout drum, condensation reflux unit and four neck round-bottom flasks of nitrogen protection The Ce that phenyl acid imide hydroxypropyl methyl dimethoxysilane is modified2O2S 2.8564g, 1-methyl-2-pyrrolidinone 242.63g, ultrasound 90min, opens stirring, then adds 3,4 '-diaminodiphenyl ether 19.0628g (0.0952mo1), to abundant dissolving, then divides five It is secondary to add 3,3 ', 4,4 '-bibenzene tetracarboxylic dianhydride 29.8613g (0.1015mo1), obtain rare earth sulphur oxygen when reaction 5 is small at 25 DEG C Compound-polyamic acid solution.Toluene 45g, 170 DEG C of reflux bands are added into obtained rare-earth oxide sulfate-polyamic acid solution 4 hours of water obtain rare-earth oxide sulfate-polyimide resin solution.Polyimide resin solution is separated out with acetone solvent again And acquisition rare-earth oxide sulfate-polyimide resin wet mash is filtered, wet mash filters after washing 2 times with acetone again, at 90 DEG C Dry 5 it is small when, rare-earth oxide sulfate-polyimide resin powder end is obtained after broken sieving.Polyimide resin powder end is in mould Interior hot-forming, 370 DEG C of temperature, pressure 25MPa, dwell time 120min, then cool down pressure release, obtains X-ray luminescence polyamides Imines composite material section bar, the composite material section bar tensile strength 81MPa, impact strength 37kJ/m2。
Embodiment 3
3- is added to being equipped with mechanical agitation, water knockout drum, condensation reflux unit and four neck round-bottom flasks of nitrogen protection The Eu that phenyl acid imide propyl trimethoxy silicane is modified2O2S 6.702g, 1-methyl-2-pyrrolidinone 270.5g, ultrasonic 120min, Stirring is opened, then adds 4,4 ' into flask-bis- (3- amino-benzene oxygens) diphenyl sulphone (DPS) 44.1140g (0.1020mo1), to filling Divide dissolving, then add pyromellitic dianhydride 22.9026g (0.105mol) in five times, rare earth sulphur oxygen is obtained when reaction 5 is small at 20 DEG C Compound-polyamic acid solution.Dimethylbenzene 45.65g is added into obtained rare-earth oxide sulfate-polyamic acid solution, 180 DEG C are returned 4 hours of stream band water obtain rare-earth oxide sulfate-polyimide resin solution.Polyimide resin solution cooling is separated out simultaneously again Filtering obtains rare-earth oxide sulfate-polyimide resin wet mash, and wet mash is filtered after washing 4 times with ethanol again, dried at 100 DEG C It is dry 5 it is small when, rare-earth oxide sulfate-polyimide resin powder end is obtained after broken sieving.Polyimide resin powder end is in mould Hot-forming, 330 DEG C of temperature, pressure 12MPa, dwell time 60min, then cool down pressure release, obtains X-ray luminescence polyimides Composite material section bar, the composite material section bar tensile strength 105MPa, impact strength 52kJ/m2.The composite material is through 360 DEG C high temperature ageing 3000h, tensile strength 105MPa, impact strength 51kJ/m2。
Embodiment 4
3- is added to being equipped with mechanical agitation, water knockout drum, condensation reflux unit and four neck round-bottom flasks of nitrogen protection The Eu that aminopropyl trimethoxysilane is modified2O2S 6.702g, 1-methyl-2-pyrrolidinone 270.5g, ultrasonic 120min, unlatching are stirred Mix, then add 4,4 ' into flask-bis- (3- amino-benzene oxygens) diphenyl sulphone (DPS) 44.1140g (0.1020mo1), to abundant dissolving, Add pyromellitic dianhydride 22.9026g (0.105mol) in five times again, rare-earth oxide sulfate-poly- is obtained when reaction 5 is small at 20 DEG C Acid amides acid solution.Dimethylbenzene 45.65g, 180 DEG C of reflux band water 4 are added into obtained rare-earth oxide sulfate-polyamic acid solution Obtain rare-earth oxide sulfate-polyimide resin solution within a hour.Again polyimide resin solution is cooled down to separate out and filter and obtained Rare-earth oxide sulfate-polyimide resin wet mash is obtained, wet mash filters after washing 4 times with ethanol again, and it is small that 5 are dried at 100 DEG C When, rare-earth oxide sulfate-polyimide resin powder end is obtained after broken sieving.Polyimide resin powder end is hot pressed into mould Type, 330 DEG C of temperature, pressure 12MPa, dwell time 60min, then cool down pressure release, obtains X-ray luminescence polyimides composite wood Expect section bar, the composite material section bar tensile strength 95MPa, impact strength 46kJ/m2.The composite material is through 360 DEG C of high temperature Aging 3000h, tensile strength 89MPa, impact strength 40kJ/m2。
Embodiment 5
3- is added to being equipped with mechanical agitation, water knockout drum, condensation reflux unit and four neck round-bottom flasks of nitrogen protection The Ce that phenyl acid imide hydroxypropyl methyl dimethoxysilane is modified2O2S 2.1854g, dimethylformamide 220.98g, ultrasound 180min, opens stirring, then adds 4,4 '-diaminodiphenyl ether 22.0664g (0.1102mo1), to abundant dissolving, then divides Add 2,2,3 ', 4 '-diphenyl ether tetraformic acid anhydride 33.1625g (0.1069mol) five times, rare earth sulphur is obtained when reaction 6 is small at 15 DEG C Oxide-polyamic acid solution.Toluene 61.25g is added into obtained rare-earth oxide sulfate-polyamic acid solution, 145 DEG C are returned 12 hours of stream band water obtain rare-earth oxide sulfate-polyimide resin solution.Polyimide resin solution is analysed with acetone again Go out and filter acquisition rare-earth oxide sulfate-polyimide resin wet mash, wet mash filters after washing 3 times with acetone again, 100 DEG C When lower drying 4 is small, rare-earth oxide sulfate-polyimide resin powder end is obtained after broken sieving.Polyimide resin powder end is in mould Hot-forming in tool, 365 DEG C of temperature, pressure 35MPa, dwell time 75min, then cool down pressure release, obtains X-ray luminescence polyamides Imines composite material section bar, the composite material section bar tensile strength 85MPa, impact strength 265kJ/m2。
Embodiment 6
3- is added to being equipped with mechanical agitation, water knockout drum, condensation reflux unit and four neck round-bottom flasks of nitrogen protection The Ce that phenyl acid imide hydroxypropyl methyl diethoxy silane is modified2O2S 0.7854g and Eu2O2S 1.5042g, dimethylacetamide Amine 192.71g, ultrasonic 90min, open stirring, then add 4,4 '-diaminodiphenyl ether 10.0322g (0.0501mol), Phenylenediamine 5.3854 (0.0496mol), to abundant dissolving, then adds pyromellitic dianhydride 22.7498g in five times (0.1043mol), rare-earth oxide sulfate-polyamic acid solution is obtained when reaction 6 is small at 25 DEG C.Aoxidized to obtained rare earth sulphur Dimethylbenzene 38.91g is added in thing-polyamic acid solution, it is sub- that 150 DEG C of 8 hours of reflux band water obtain rare-earth oxide sulfate-polyamides Polyimide resin solution.Polyimide resin solution is cooled down again and is separated out and to filter acquisition rare-earth oxide sulfate-polyimide resin wet Powder, wet mash filter after washing 5 times with ethanol again, dried at 100 DEG C 5 it is small when, obtained after broken sieving rare-earth oxide sulfate- Polyimide resin powder end.Polyimide resin powder end is hot-forming in mould, 380 DEG C, pressure 45MPa of temperature, during pressurize Between 150min, then cool down pressure release, obtains X-ray luminescence composite polyimide material section bar, composite material section bar stretching Intensity 75MPa, impact strength 142kJ/m2。

Claims (10)

1. a kind of X-ray luminescence composite polyimide material, it is characterised in that including polyimide resin and be evenly distributed on institute The modified RE oxysulfide in polyimide resin is stated, the polyimide resin is aromatic diamine and aromatic dianhydride Co-condensation polymer, the modified RE oxysulfide refer to by silane coupler modified rare-earth oxide sulfate.
2. composite material as claimed in claim 1, it is characterised in that the rare earth element in the rare-earth oxide sulfate is La, One or more in Ce, Pr, Nd, Sm, Eu.
3. composite material as claimed in claim 1, it is characterised in that the matter of modified RE oxysulfide and polyimide resin Measuring ratio is：0.5%-10%.
4. composite material as claimed in claim 1, it is characterised in that the silane coupling agent is high temperature resistant silane coupling agent.
5. composite material as claimed in claim 4, it is characterised in that the high temperature resistant silane coupling agent is phenyl acid imide silicon Siloxane compound；Phenyl oxyalkylene imide compound is preferably to carry out hot imide ring by primary amino radical silicone compounds and phthalic anhydride Change reaction gained.
6. composite material as claimed in claim 5, it is characterised in that the primary amino radical silicone compounds are 3- aminopropyls three Methoxy silane, 3- aminopropyl triethoxysilanes, 3- aminopropyltriethoxies dimethoxysilane, 3- aminopropyltriethoxy diethoxies One or more in silane.
7. a kind of preparation method of X-ray luminescence composite polyimide material, it is characterised in that comprise the following steps：
A) silane coupler modified rare-earth oxide sulfate is added to aprotic polar solvent, then ultrasonic disperse, forms rare earth The dispersion liquid of oxysulfide；
B) aromatic diamine is dissolved in the dispersion liquid obtained to step a), forms the mixed of aromatic diamine and rare-earth oxide sulfate Close liquid；
C) aromatic dianhydride is added in the mixed liquor obtained to step b) and carries out polycondensation reaction, formation rare-earth oxide sulfate-poly- The dispersion of acid amides acid resin；
D) add in the dispersion obtained with aqueous solvent to c) step, then carry out hot imidization reaction, formation rare-earth oxide sulfate- Polyimide resin solution, then through separating out, it is dry, obtain X-ray luminescence polyimide resin.
8. preparation method as claimed in claim 7, it is characterised in that aromatic diamine is phenylenediamine, diaminodiphenyl ether, two One or more in diaminodiphenylmethane, diaminodiphenylsulfone, diamino phenoxy diphenyl sulphone (DPS), diaminobenzophenone.
9. preparation method as claimed in claim 7, it is characterised in that aromatic dianhydride is pyromellitic acid anhydride, bisphenol-A two One or more in acid anhydride, diphenyl ether tetraformic dianhydride, bibenzene tetracarboxylic dianhydride, benzophenone tetracarboxylic dianhydride.
10. preparation method as claimed in claim 7, it is characterised in that aromatic diamine and the molar ratio of aromatic dianhydride Between 0.9-1.2.
CN201711201437.1A 2017-11-27 2017-11-27 X-ray luminescent polyimide composite material and preparation method thereof Active CN107987277B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201711201437.1A CN107987277B (en) 2017-11-27 2017-11-27 X-ray luminescent polyimide composite material and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201711201437.1A CN107987277B (en) 2017-11-27 2017-11-27 X-ray luminescent polyimide composite material and preparation method thereof

Publications (2)

Publication Number Publication Date
CN107987277A true CN107987277A (en) 2018-05-04
CN107987277B CN107987277B (en) 2020-06-16

Family

ID=62032237

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201711201437.1A Active CN107987277B (en) 2017-11-27 2017-11-27 X-ray luminescent polyimide composite material and preparation method thereof

Country Status (1)

Country Link
CN (1) CN107987277B (en)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111100455A (en) * 2018-10-25 2020-05-05 中国石油化工股份有限公司 PBO fiber reinforced resin matrix composite material and preparation method thereof
CN111116908A (en) * 2019-12-20 2020-05-08 武汉华星光电半导体显示技术有限公司 Polyimide luminescent material, preparation method and application thereof
CN112778980A (en) * 2021-01-26 2021-05-11 山西万家暖节能科技有限公司 Energy storage new material for improving heat transfer and mass transfer efficiency
CN112812750A (en) * 2021-01-26 2021-05-18 山西万家暖节能科技有限公司 Application of silane coupling agent in new energy storage material and new solar energy heat supply system

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101544754A (en) * 2008-03-25 2009-09-30 中国科学院宁波材料技术与工程研究所 Polyimide and synthetic method thereof
CN102020847A (en) * 2008-12-02 2011-04-20 东丽纤维研究所（中国）有限公司 Polyimide/kieselguhr composite material and preparation method thereof
JP2012041531A (en) * 2010-07-22 2012-03-01 Ube Industries Ltd Polyimide precursor and polyimide
CN103668527A (en) * 2012-09-24 2014-03-26 江南大学 Yttrium oxysulfide red long-afterglow polypropylene fiber and preparation method thereof
CN103866418A (en) * 2012-12-10 2014-06-18 江南大学 Rare earth yttrium oxysulfide red long afterglow polyarmide fiber and preparation method thereof
CN103866419A (en) * 2012-12-10 2014-06-18 江南大学 Europium-doped yttrium oxysulfide red long afterglow color terylene
CN107118349A (en) * 2017-06-23 2017-09-01 中山大学 A kind of high-performance light-transmitting polyimide and its preparation method and application

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101544754A (en) * 2008-03-25 2009-09-30 中国科学院宁波材料技术与工程研究所 Polyimide and synthetic method thereof
CN102020847A (en) * 2008-12-02 2011-04-20 东丽纤维研究所（中国）有限公司 Polyimide/kieselguhr composite material and preparation method thereof
JP2012041531A (en) * 2010-07-22 2012-03-01 Ube Industries Ltd Polyimide precursor and polyimide
CN103668527A (en) * 2012-09-24 2014-03-26 江南大学 Yttrium oxysulfide red long-afterglow polypropylene fiber and preparation method thereof
CN103866418A (en) * 2012-12-10 2014-06-18 江南大学 Rare earth yttrium oxysulfide red long afterglow polyarmide fiber and preparation method thereof
CN103866419A (en) * 2012-12-10 2014-06-18 江南大学 Europium-doped yttrium oxysulfide red long afterglow color terylene
CN107118349A (en) * 2017-06-23 2017-09-01 中山大学 A kind of high-performance light-transmitting polyimide and its preparation method and application

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111100455A (en) * 2018-10-25 2020-05-05 中国石油化工股份有限公司 PBO fiber reinforced resin matrix composite material and preparation method thereof
CN111116908A (en) * 2019-12-20 2020-05-08 武汉华星光电半导体显示技术有限公司 Polyimide luminescent material, preparation method and application thereof
US11552249B2 (en) 2019-12-20 2023-01-10 Wuhan China Star Optoelectronics Semiconductor Display Technology Co., Ltd. Polyimide luminescent material, preparation method thereof, and device thereof
CN112778980A (en) * 2021-01-26 2021-05-11 山西万家暖节能科技有限公司 Energy storage new material for improving heat transfer and mass transfer efficiency
CN112812750A (en) * 2021-01-26 2021-05-18 山西万家暖节能科技有限公司 Application of silane coupling agent in new energy storage material and new solar energy heat supply system
CN112778980B (en) * 2021-01-26 2021-12-14 山西万家暖节能科技有限公司 Energy storage new material for improving heat transfer and mass transfer efficiency
CN112812750B (en) * 2021-01-26 2021-12-14 山西万家暖节能科技有限公司 Application of silane coupling agent in new energy storage material and new solar energy heat supply system

Also Published As

Publication number Publication date
CN107987277B (en) 2020-06-16

Similar Documents

Publication Publication Date Title
CN107987277A (en) A kind of X-ray luminescence composite polyimide material and preparation method thereof
CN106751516A (en) A kind of toughness reinforcing, heat-resisting modified epoxy and preparation method thereof
CN105906842A (en) Modified graphene oxide and epoxy resin composite material and method for preparing same
DE2342464C3 (en) Polyamide-polyamic acid block copolymers, processes for their production and their use for the production of industrial products
US20210125741A1 (en) Graphene Oxide-Filled Polyimide Films and Process
CN107955166A (en) A kind of cyanate ester resin and preparation method thereof, composite material
CN102677225B (en) Aromatic polyamide/aromatic polyimide blended fiber and preparation method thereof
CN105505289A (en) High-strength polysulfide waterproof structure adhesive and preparing method thereof
CN107245239B (en) Resin combination and prepreg, metal foil laminate and the interlayer dielectric made using it
CN105968355B (en) A kind of synthetic method of polyimides
CN112391114A (en) Insulating coating composition and insulating film
CN102644128A (en) Polyimide fiber spinning solution based on 2, 2-double [4-(2, 4-diaminophenoxy) phenyl group] hexafluoropropane and preparation method thereof
CN106496558B (en) One kind can response type poly (arylene ether nitrile) imide resin and preparation method thereof
CN112689656A (en) Method for producing polyamideimide film and polyamideimide film produced thereby
CN111057270B (en) Modified carbon black and preparation method thereof, resin composition and copper-clad plate
DE2345348A1 (en) HARDABLE MONOMERIC AROMATIC IMIDODICARBONIC ACID DIALLYLESTERS, PREPOLYMERS THEREOF, HARDENED RESINS THEREOF AND METHOD FOR THEIR PRODUCTION
DE1765738C3 (en) Insulating coating on an electrical conductor
CN108659527B (en) High-strength glass fiber composite material and preparation method thereof
DE2537305A1 (en) POLYTHIOAETHERIMIDE
CN108947918A (en) A kind of polyimides and preparation method thereof of diamine monomer of the structure containing pyrazine and preparation method thereof and a kind of structure containing pyrazine
TWI334434B (en) Adhesion aid composition
TWI843797B (en) Epoxy resin solution
CN112280464B (en) Method for improving storage stability of coating
JPH01259024A (en) Epoxy resin composition
JP2700703B2 (en) Polybenzobisoxazole molecular composite and method for producing the same

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant
CP01 Change in the name or title of a patent holder
CP01 Change in the name or title of a patent holder

Address after: 410205 7th floor, building B8, Lugu Enterprise Square, Yuelu District, Changsha City, Hunan Province

Patentee after: Aerospace Science and Industry (Changsha) New Materials Research Institute Co.,Ltd.

Address before: 410205 7th floor, building B8, Lugu Enterprise Square, Yuelu District, Changsha City, Hunan Province

Patentee before: CHANGSHA ADVANCED MATERIALS INDUSTRIAL RESEARCH INSTITUTE Co.,Ltd.