CN105820572A - Preparation method of polyimide/graphene nanoribbon composite film - Google Patents
Preparation method of polyimide/graphene nanoribbon composite film Download PDFInfo
- Publication number
- CN105820572A CN105820572A CN201610388416.4A CN201610388416A CN105820572A CN 105820572 A CN105820572 A CN 105820572A CN 201610388416 A CN201610388416 A CN 201610388416A CN 105820572 A CN105820572 A CN 105820572A
- Authority
- CN
- China
- Prior art keywords
- graphene nanobelt
- laminated film
- preparation
- polyimides
- solution
- 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
Links
Classifications
-
- 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
- C08K3/02—Elements
- C08K3/04—Carbon
-
- 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
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
- C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
-
- 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
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/16—Applications used for films
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention relates to a method for preparing water-soluble polyimide and a method for preparing a composite film, in particular to a preparation method of a polyimide/graphene nanoribbon composite film. The preparation method aims at solving the problems that existing carbon nanotubes and graphene can not be uniformly dispersed in a polyimide matrix, a prepared composite film has high electroconductibility, and application of the prepared composite film to the field of electrical insulation is limited. The preparation method includes the steps that firstly, water-soluble polyimide is prepared; secondly, a graphene nanoribbon solution is prepared; thirdly, a composite film is prepared, and the polyimide/graphene nanoribbon composite film is obtained. The prepared polyimide/graphene nanoribbon composite film has a good insulating property, a low dielectric constant and high and excellent mechanical properties, which is of great promoting significance in expanding the wide industrial application prospects of a polyimide-based composite. The polyimide/graphene nanoribbon composite film can be obtained through the preparation method.
Description
Technical field
The present invention relates to a kind of prepare the imido method of water-soluble poly and the method preparing laminated film.
Background technology
nullPolyimides is a kind of high-fire resistance insulative polymer material containing imide ring，The most also have good mechanical performance concurrently，High electrical insulation properties，Excellent chemical stability、Strong radiation resistance etc.，Along with power electronics，Aero-Space、The high speed development of flexible electronic industry，This tool is considered as that " expert solving problem " polyimides macromolecular material has industrially obtained quick development，It has been widely used at frequency conversion motor，Military project、Aero-Space、Microelectronics、Nano-liquid crystal、Separate multiple fields such as film，In order to meet its multifarious application demand，Various polyimide-based composite materials have obtained the extensive concern of industrial quarters and scholars，The most studied polyimides majority is at N-methyl ketopyrrolidine (NMP)、The organic solvents such as dimethylformamide (DMF) or dimethyl acetylamide (DMAC) are obtained by monomer polymerization，These organic solvents are the most expensive and have certain toxicity，This is to limiting its industrial applicability，Hinder some hydrophilic modification applications strengthening relative polyimides，The preparation of organic solvent type polyimide precursor is replaced to have become as a research direction widely paid close attention to of current chemical field hence with water.Utilizing CNT to prepare polyimide-based composite material with Graphene etc. for reinforcement, have been obtained for the widely studied of scholar, but also face main two problems, first is exactly CNT and Graphene scattering problem in polyimide matrix；Second is that polyimides/material with carbon element is combined the electric conductivity that can improve composite, and these application many with polyimides are conflicting with electric insulation field.
Summary of the invention
The invention aims to solve existing CNT and Graphene can not be dispersed in polyimide matrix, the laminated film electric conductivity of preparation is high, it is applied to electric insulation field and receives the problem of restriction, and the preparation method of a kind of polyimides/graphene nanobelt laminated film is provided.
The preparation method of a kind of polyimides/graphene nanobelt laminated film, completes according to the following steps:
One, water-soluble poly acid imide is prepared:
1., polyamic acid solution is prepared:
4，4′-diaminodipohenyl ether is joined in organic solvent, then low whipping speed is stirring reaction 60min under 100r/min～300r/min, more ultrasonic 6h～12h under ultrasonic power is 300W, obtain two amine aqueous solutions；Dianhydride is divided 5 times under conditions of ice-water bath and mixing speed are 100r/min and join in two amine aqueous solutions, obtain thick polyamic acid solution；
Step one 1. described in the quality of 4,4 '-diaminodiphenyl ether and the volume ratio of organic solvent be 3g:(40mL～60mL)；
Step one 1. described in organic solvent be N-Methyl pyrrolidone or dinethylformamide；
Step one 1. described in dianhydride be biphenyl type dianhydride or equal benzene-type dianhydrides；Described biphenyl type dianhydride is 3,3', 4,4'-biphenyl tetracarboxylic dianhydride；Described equal benzene-type dianhydride is pyromellitic acid anhydride；
Step one 1. described in dianhydride and the mol ratio of 4,4 '-diaminodiphenyl ether be 1:1；
2., to step one 1. in the thick polyamic acid solution that obtains adds alkalescence reagent, again nitrogen atmosphere and mixing speed be under 100r/min～300r/min stirring reaction 20h～30h, again with deionized water as abluent, eccentric cleaning 5 times～10 times, remove supernatant, obtain water-soluble poly acid imide；
Step one 2. described in the volume ratio of polyamic acid solution and alkalescence reagent be 10:1；
Two, graphene nanobelt solution is prepared:
CNT and oxidant are joined in concentrated acid, obtains mixture A；By mixture A ice-water bath and mixing speed be under 100r/min～300r/min stirring reaction 1h～2h；Again mixture A is heated to 60 DEG C, then at 60 DEG C, is incubated 1h～3h, more centrifugal 10min～15min under centrifugal speed is 6000r/min～8000r/min, remove supernatant, obtain solid B；Clean solid B1 time～2 times first by hydrochloric acid that mass fraction is 5%～10%, re-use distilled water cleaning solid B5 time～10 times, obtain graphene nanobelt；Graphene nanobelt is dissolved in deionized water, obtains graphene nanobelt solution；
The quality of the CNT described in step 2 and the volume ratio of concentrated acid are 1g:(80mL～100mL)；
The quality of the CNT described in step 2 and the mass ratio of oxidant are 1:(5～8)；
In graphene nanobelt solution described in step 2, the mass fraction of graphene nanobelt is 1%～5%；
Three, laminated film is prepared:
1., by step one 2. in the water-soluble poly acid imide that obtains be dissolved in deionized water, obtain water-soluble poly imide solution；
Step 3 1. described in the volume ratio of the imido quality of water-soluble poly and deionized water be 5g:(10mL～20mL)；
2., by the graphene nanobelt solution obtained in step 2 join step 3 1. in the water-soluble poly imide solution that obtains, obtain mixed solution C；It is stirring reaction 24h～36h under 100r/min～300r/min by mixed solution C low whipping speed, obtains graphene nanobelt/polyamic acid solution；By in graphene nanobelt/polyamic acid solution spin coating, curtain coating or plastic film mulch to clean glass plate, again glass plate is placed in the high temperature furnace that temperature is 60 DEG C, again high temperature furnace is warming up to 100 DEG C with the heating rate of 5 DEG C/min～10 DEG C/min, 2h it is incubated again at temperature is 100 DEG C, it is warming up to 350 DEG C from 100 DEG C again with the heating rate of 5 DEG C/min of high temperature furnace～10 DEG C/min, at temperature is 350 DEG C, it is incubated 2h again, obtains polyimides/graphene nanobelt laminated film；
Step 3 2. described in mixed solution C in the mass fraction of graphene nanobelt be 0.1%～3%.
Advantages of the present invention:
One, the present invention utilizes compound having prepared of the graphene nanobelt in aqueous with good dispersion and hypotoxic water miscible polyimide precursor to have good insulating performance, strong mechanical performance, low-k, the polyimides/graphene nanobelt laminated film of very good mechanical properties, this has important promotion meaning to the wide range of industrial applications prospect expanding polyimide-based composite material；
Two, the hot strength of polyimides prepared by the present invention/graphene nanobelt laminated film is more than 140MPa；
Three, the resistivity of polyimides prepared by the present invention/graphene nanobelt laminated film is 6 × 10 to the maximum16Ω m, improves 1.6 times compared with the resistivity of pure polyimides.
The present invention can obtain the preparation method of a kind of polyimides/graphene nanobelt laminated film.
Accompanying drawing explanation
Fig. 1 is the SEM figure of the polyimides/graphene nanobelt laminated film of embodiment one preparation；
Fig. 2 is the hot strength variation diagram with elongation at break, in Fig. 2,1 is the hot strength change curve with elongation at break of the polyimides/graphene nanobelt laminated film of embodiment one preparation, 2 is the hot strength change curve with elongation at break of the polyimides/graphene nanobelt laminated film of embodiment two preparation, 3 is the hot strength change curve with elongation at break of the polyimides/graphene nanobelt laminated film of embodiment three preparation, and 4 is the hot strength change curve with elongation at break of the Kapton of contrast test one preparation；
Fig. 3 is the resistivity variation diagram with voltage, in Fig. 3,1 is the resistivity change curve with voltage of the polyimides/graphene nanobelt laminated film of embodiment one preparation, 2 is the resistivity change curve with voltage of the polyimides/graphene nanobelt laminated film of embodiment two preparation, 3 is the resistivity change curve with voltage of the polyimides/graphene nanobelt laminated film of embodiment three preparation, and 4 is the resistivity change curve with voltage of the Kapton of contrast test one preparation；
Fig. 4 is the dielectric constant variation diagram with frequency, in Fig. 4,1 is the dielectric constant change curve with frequency of the polyimides/graphene nanobelt laminated film of embodiment one preparation, 2 is the dielectric constant change curve with frequency of the polyimides/graphene nanobelt laminated film of embodiment two preparation, 3 is the dielectric constant change curve with frequency of the polyimides/graphene nanobelt laminated film of embodiment three preparation, and 4 is the dielectric constant change curve with frequency of the Kapton of contrast test one preparation.
Detailed description of the invention
Detailed description of the invention one: present embodiment is that the preparation method of a kind of polyimides/graphene nanobelt laminated film completes according to the following steps:
The preparation method of a kind of polyimides/graphene nanobelt laminated film completes according to the following steps:
One, water-soluble poly acid imide is prepared:
1., polyamic acid solution is prepared:
4，4′-diaminodipohenyl ether is joined in organic solvent, then low whipping speed is stirring reaction 60min under 100r/min～300r/min, more ultrasonic 6h～12h under ultrasonic power is 300W, obtain two amine aqueous solutions；Dianhydride is divided 5 times under conditions of ice-water bath and mixing speed are 100r/min and join in two amine aqueous solutions, obtain thick polyamic acid solution；
Step one 1. described in the quality of 4,4 '-diaminodiphenyl ether and the volume ratio of organic solvent be 3g:(40mL～60mL)；
Step one 1. described in organic solvent be N-Methyl pyrrolidone or dinethylformamide；
Step one 1. described in dianhydride be biphenyl type dianhydride or equal benzene-type dianhydrides；Described biphenyl type dianhydride is 3,3', 4,4'-biphenyl tetracarboxylic dianhydride；Described equal benzene-type dianhydride is pyromellitic acid anhydride；
Step one 1. described in dianhydride and the mol ratio of 4,4 '-diaminodiphenyl ether be 1:1；
2., to step one 1. in the thick polyamic acid solution that obtains adds alkalescence reagent, again nitrogen atmosphere and mixing speed be under 100r/min～300r/min stirring reaction 20h～30h, again with deionized water as abluent, eccentric cleaning 5 times～10 times, remove supernatant, obtain water-soluble poly acid imide；
Step one 2. described in the volume ratio of polyamic acid solution and alkalescence reagent be 10:1；
Two, graphene nanobelt solution is prepared:
CNT and oxidant are joined in concentrated acid, obtains mixture A；By mixture A ice-water bath and mixing speed be under 100r/min～300r/min stirring reaction 1h～2h；Again mixture A is heated to 60 DEG C, then at 60 DEG C, is incubated 1h～3h, more centrifugal 10min～15min under centrifugal speed is 6000r/min～8000r/min, remove supernatant, obtain solid B；Clean solid B1 time～2 times first by hydrochloric acid that mass fraction is 5%～10%, re-use distilled water cleaning solid B5 time～10 times, obtain graphene nanobelt；Graphene nanobelt is dissolved in deionized water, obtains graphene nanobelt solution；
The quality of the CNT described in step 2 and the volume ratio of concentrated acid are 1g:(80mL～100mL)；
The quality of the CNT described in step 2 and the mass ratio of oxidant are 1:(5～8)；
In graphene nanobelt solution described in step 2, the mass fraction of graphene nanobelt is 1%～5%；
Three, laminated film is prepared:
1., by step one 2. in the water-soluble poly acid imide that obtains be dissolved in deionized water, obtain water-soluble poly imide solution；
Step 3 1. described in the volume ratio of the imido quality of water-soluble poly and deionized water be 5g:(10mL～20mL)；
2., by the graphene nanobelt solution obtained in step 2 join step 3 1. in the water-soluble poly imide solution that obtains, obtain mixed solution C；It is stirring reaction 24h～36h under 100r/min～300r/min by mixed solution C low whipping speed, obtains graphene nanobelt/polyamic acid solution；By in graphene nanobelt/polyamic acid solution spin coating, curtain coating or plastic film mulch to clean glass plate, again glass plate is placed in the high temperature furnace that temperature is 60 DEG C, again high temperature furnace is warming up to 100 DEG C with the heating rate of 5 DEG C/min～10 DEG C/min, 2h it is incubated again at temperature is 100 DEG C, it is warming up to 350 DEG C from 100 DEG C again with the heating rate of 5 DEG C/min of high temperature furnace～10 DEG C/min, at temperature is 350 DEG C, it is incubated 2h again, obtains polyimides/graphene nanobelt laminated film；
Step 3 2. described in mixed solution C in the mass fraction of graphene nanobelt be 0.1%～3%.
The advantage of present embodiment:
One, present embodiment utilizes compound having prepared of the graphene nanobelt in aqueous with good dispersion and hypotoxic water miscible polyimide precursor to have good insulating performance, strong mechanical performance, low-k, the polyimides/graphene nanobelt laminated film of very good mechanical properties, this has important promotion meaning to the wide range of industrial applications prospect expanding polyimide-based composite material；
Two, the hot strength of polyimides prepared by present embodiment/graphene nanobelt laminated film is more than 140MPa；
Three, the resistivity of polyimides prepared by present embodiment/graphene nanobelt laminated film is 6 × 10 to the maximum16Ω m, improves 1.6 times compared with the resistivity of pure polyimides.
Present embodiment can obtain the preparation method of a kind of polyimides/graphene nanobelt laminated film.
Detailed description of the invention two: present embodiment with detailed description of the invention one difference is: step one 2. described in the centrifugal speed of each eccentric cleaning be 6000r/min～8000r/min, each centrifugation time is 10min～20min.Other steps are identical with detailed description of the invention one.
Detailed description of the invention three: present embodiment with one of detailed description of the invention one or two difference is: step one 2. described in alkalescence reagent be triethanolamine, tripropyl amine (TPA) or triethylamine.Other steps are identical with detailed description of the invention one or two.
Detailed description of the invention four: present embodiment with one of detailed description of the invention one to three difference is: the oxidant described in step 2 is that potassium ferrate, ferric acid are received or potassium permanganate.Other steps are identical with detailed description of the invention one to three.
Detailed description of the invention five: present embodiment with one of detailed description of the invention one to four difference is: the concentrated acid described in step 2 be mass fraction be the sulphuric acid of 98%.Other steps are identical with detailed description of the invention one to four.
Detailed description of the invention six: present embodiment with one of detailed description of the invention one to five difference is: step 3 2. described in mixed solution C in the mass fraction of graphene nanobelt be 0.1%.Other steps are identical with detailed description of the invention one to five.
Detailed description of the invention seven: present embodiment with one of detailed description of the invention one to six difference is: step 3 2. described in mixed solution C in the mass fraction of graphene nanobelt be 0.3%.Other steps are identical with detailed description of the invention one to six.
Detailed description of the invention eight: present embodiment with one of detailed description of the invention one to seven difference is: step 3 2. described in mixed solution C in the mass fraction of graphene nanobelt be 1%.Other steps are identical with detailed description of the invention one to seven.
Detailed description of the invention nine: present embodiment with one of detailed description of the invention one to eight difference is: step 3 2. in the graphene nanobelt solution obtained in step 2 joined step 3 1. in the water-soluble poly imide solution that obtains, obtain mixed solution C；It is stirring reaction 24h under 300r/min by mixed solution C low whipping speed, obtains graphene nanobelt/polyamic acid solution；By in graphene nanobelt/polyamic acid solution spin coating, curtain coating or plastic film mulch to clean glass plate, again glass plate is placed in the high temperature furnace that temperature is 60 DEG C, again high temperature furnace is warming up to 100 DEG C with the heating rate of 5 DEG C/min, 2h it is incubated again at temperature is 100 DEG C, it is warming up to 350 DEG C from 100 DEG C again with the heating rate of 5 DEG C/min of high temperature furnace, at temperature is 350 DEG C, it is incubated 2h again, obtains polyimides/graphene nanobelt laminated film.Other steps are identical with detailed description of the invention one to eight.
Detailed description of the invention ten: present embodiment with one of detailed description of the invention one to nine difference is: the thickness of the graphene nanobelt laminated film that 2. step 3 obtains is 30 μm～40 μm.Other steps are identical with detailed description of the invention one to nine.
Employing following example checking beneficial effects of the present invention:
Embodiment one: the preparation method of a kind of polyimides/graphene nanobelt laminated film completes according to the following steps:
One, water-soluble poly acid imide is prepared:
1., polyamic acid solution is prepared:
4，4′-diaminodipohenyl ether is joined in organic solvent, then low whipping speed is stirring reaction 60min under 100r/min～300r/min, more ultrasonic 6h～12h under ultrasonic power is 300W, obtain two amine aqueous solutions；Dianhydride is divided 5 times under conditions of ice-water bath and mixing speed are 100r/min and join in two amine aqueous solutions, obtain thick polyamic acid solution；
Step one 1. described in the quality of 4,4 '-diaminodiphenyl ether and the volume ratio of organic solvent be 3g:50mL；
Step one 1. described in organic solvent be N-Methyl pyrrolidone；
Step one 1. described in dianhydride be equal benzene-type dianhydride；Described equal benzene-type dianhydride is pyromellitic acid anhydride；
Step one 1. described in dianhydride and the mol ratio of 4,4 '-diaminodiphenyl ether be 1:1；
2., to step one 1. in the polyamic acid solution that obtains adds alkalescence reagent, then be stirring reaction 20h under 200r/min at nitrogen atmosphere and mixing speed, then with deionized water as abluent, eccentric cleaning 8 times, remove supernatant, obtain water-soluble poly acid imide；
Step one 2. described in the volume ratio of polyamic acid solution and alkalescence reagent be 10:1；
Step one 2. described in alkalescence reagent be triethanolamine；
Two, graphene nanobelt solution is prepared:
CNT and oxidant are joined in concentrated acid, obtains mixture A；By mixture A ice-water bath and mixing speed be under 200r/min stirring reaction 2h；Again mixture A is heated to 60 DEG C, then at 60 DEG C, is incubated 2h, more centrifugal 10min under centrifugal speed is 6000r/min, remove supernatant, obtain solid B；Clean solid B2 time first by the hydrochloric acid that mass fraction is 8%, re-use distilled water and clean solid B8 time, obtain graphene nanobelt；Graphene nanobelt is dissolved in deionized water, obtains graphene nanobelt solution；
Concentrated acid described in step 2 be mass fraction be the sulphuric acid of 98%；
Oxidant described in step 2 is potassium ferrate；
The quality of the CNT described in step 2 and the volume ratio of concentrated acid are 1g:100mL；
The quality of the CNT described in step 2 and the mass ratio of oxidant are 1:6；
In graphene nanobelt solution described in step 2, the mass fraction of graphene nanobelt is 3%；
Three, laminated film is prepared:
1., by step one 2. in the water-soluble poly acid imide that obtains be dissolved in deionized water, obtain water-soluble poly imide solution；
Step 3 1. described in the volume ratio of the imido quality of water-soluble poly and deionized water be 5g:15mL；
2., by the graphene nanobelt solution obtained in step 2 join step 3 1. in the water-soluble poly imide solution that obtains, obtain mixed solution C；It is stirring reaction 24h under 300r/min by mixed solution C low whipping speed, obtains graphene nanobelt/polyamic acid solution；Graphene nanobelt/polyamic acid solution is spun on the glass plate of cleaning, again glass plate is placed in the high temperature furnace that temperature is 60 DEG C, again high temperature furnace is warming up to 100 DEG C with the heating rate of 5 DEG C/min, 2h it is incubated again at temperature is 100 DEG C, it is warming up to 350 DEG C from 100 DEG C again with the heating rate of 5 DEG C/min of high temperature furnace, at temperature is 350 DEG C, it is incubated 2h again, obtains polyimides/graphene nanobelt laminated film；
The thickness of the graphene nanobelt laminated film that 2. step 3 obtains is 40 μm；
Step 3 2. described in mixed solution C in the mass fraction of graphene nanobelt be 0.1%.
Embodiment two: the preparation method of a kind of polyimides/graphene nanobelt laminated film completes according to the following steps:
One, water-soluble poly acid imide is prepared:
1., polyamic acid solution is prepared:
4，4′-diaminodipohenyl ether is joined in organic solvent, then low whipping speed is stirring reaction 60min under 100r/min～300r/min, more ultrasonic 6h～12h under ultrasonic power is 300W, obtain two amine aqueous solutions；Dianhydride is divided 5 times under conditions of ice-water bath and mixing speed are 100r/min and join in two amine aqueous solutions, obtain thick polyamic acid solution；
Step one 1. described in the quality of 4,4 '-diaminodiphenyl ether and the volume ratio of organic solvent be 3g:50mL；
Step one 1. described in organic solvent be N-Methyl pyrrolidone；
Step one 1. described in dianhydride be equal benzene-type dianhydride；Described equal benzene-type dianhydride is pyromellitic acid anhydride；
Step one 1. described in dianhydride and the mol ratio of 4,4 '-diaminodiphenyl ether be 1:1；
2., to step one 1. in the polyamic acid solution that obtains adds alkalescence reagent, then be stirring reaction 20h under 200r/min at nitrogen atmosphere and mixing speed, then with deionized water as abluent, eccentric cleaning 8 times, remove supernatant, obtain water-soluble poly acid imide；
Step one 2. described in the volume ratio of polyamic acid solution and alkalescence reagent be 10:1；
Step one 2. described in alkalescence reagent be tripropyl amine (TPA)；
Two, graphene nanobelt solution is prepared:
CNT and oxidant are joined in concentrated acid, obtains mixture A；By mixture A ice-water bath and mixing speed be under 200r/min stirring reaction 2h；Again mixture A is heated to 60 DEG C, then at 60 DEG C, is incubated 2h, more centrifugal 10min under centrifugal speed is 6000r/min, remove supernatant, obtain solid B；Clean solid B2 time first by the hydrochloric acid that mass fraction is 8%, re-use distilled water and clean solid B8 time, obtain graphene nanobelt；Graphene nanobelt is dissolved in deionized water, obtains graphene nanobelt solution；
Concentrated acid described in step 2 be mass fraction be the sulphuric acid of 98%；
Oxidant described in step 2 is potassium ferrate；
The quality of the CNT described in step 2 and the volume ratio of concentrated acid are 1g:100mL；
The quality of the CNT described in step 2 and the mass ratio of oxidant are 1:6；
In graphene nanobelt solution described in step 2, the mass fraction of graphene nanobelt is 5%；
Three, laminated film is prepared:
1., by step one 2. in the water-soluble poly acid imide that obtains be dissolved in deionized water, obtain water-soluble poly imide solution；
Step 3 1. described in the volume ratio of the imido quality of water-soluble poly and deionized water be 5g:15mL；
2., by the graphene nanobelt solution obtained in step 2 join step 3 1. in the water-soluble poly imide solution that obtains, obtain mixed solution C；It is stirring reaction 24h under 300r/min by mixed solution C low whipping speed, obtains graphene nanobelt/polyamic acid solution；Graphene nanobelt/polyamic acid solution is spun on the glass plate of cleaning, again glass plate is placed in the high temperature furnace that temperature is 60 DEG C, again high temperature furnace is warming up to 100 DEG C with the heating rate of 5 DEG C/min, 2h it is incubated again at temperature is 100 DEG C, it is warming up to 350 DEG C from 100 DEG C again with the heating rate of 5 DEG C/min of high temperature furnace, at temperature is 350 DEG C, it is incubated 2h again, obtains polyimides/graphene nanobelt laminated film；
The thickness of the graphene nanobelt laminated film that 2. step 3 obtains is 40 μm；
Step 3 2. described in mixed solution C in the mass fraction of graphene nanobelt be 0.3%.
Embodiment three: the preparation method of a kind of polyimides/graphene nanobelt laminated film completes according to the following steps:
One, water-soluble poly acid imide is prepared:
1., polyamic acid solution is prepared:
4，4′-diaminodipohenyl ether is joined in organic solvent, then low whipping speed is stirring reaction 60min under 100r/min～300r/min, more ultrasonic 6h～12h under ultrasonic power is 300W, obtain two amine aqueous solutions；Dianhydride is divided 5 times under conditions of ice-water bath and mixing speed are 100r/min and join in two amine aqueous solutions, obtain thick polyamic acid solution；
Step one 1. described in the quality of 4,4 '-diaminodiphenyl ether and the volume ratio of organic solvent be 3g:50mL；
Step one 1. described in organic solvent be N-Methyl pyrrolidone；
Step one 1. described in dianhydride be equal benzene-type dianhydride；Described equal benzene-type dianhydride is pyromellitic acid anhydride；
Step one 1. described in dianhydride and the mol ratio of 4,4 '-diaminodiphenyl ether be 1:1；
2., to step one 1. in the polyamic acid solution that obtains adds alkalescence reagent, then be stirring reaction 20h under 200r/min at nitrogen atmosphere and mixing speed, then with deionized water as abluent, eccentric cleaning 8 times, remove supernatant, obtain water-soluble poly acid imide；
Step one 2. described in the volume ratio of polyamic acid solution and alkalescence reagent be 10:1；
Step one 2. described in alkalescence reagent be triethylamine；
Two, graphene nanobelt solution is prepared:
CNT and oxidant are joined in concentrated acid, obtains mixture A；By mixture A ice-water bath and mixing speed be under 200r/min stirring reaction 2h；Again mixture A is heated to 60 DEG C, then at 60 DEG C, is incubated 2h, more centrifugal 10min under centrifugal speed is 6000r/min, remove supernatant, obtain solid B；Clean solid B2 time first by the hydrochloric acid that mass fraction is 8%, re-use distilled water and clean solid B8 time, obtain graphene nanobelt；Graphene nanobelt is dissolved in deionized water, obtains graphene nanobelt solution；
Concentrated acid described in step 2 be mass fraction be the sulphuric acid of 98%；
Oxidant described in step 2 is potassium ferrate；
The quality of the CNT described in step 2 and the volume ratio of concentrated acid are 1g:100mL；
The quality of the CNT described in step 2 and the mass ratio of oxidant are 1:6；
In graphene nanobelt solution described in step 2, the mass fraction of graphene nanobelt is 1%；
Three, laminated film is prepared:
1., by step one 2. in the water-soluble poly acid imide that obtains be dissolved in deionized water, obtain water-soluble poly imide solution；
Step 3 1. described in the volume ratio of the imido quality of water-soluble poly and deionized water be 5g:15mL；
2., by the graphene nanobelt solution obtained in step 2 join step 3 1. in the water-soluble poly imide solution that obtains, obtain mixed solution C；It is stirring reaction 24h under 300r/min by mixed solution C low whipping speed, obtains graphene nanobelt/polyamic acid solution；Graphene nanobelt/polyamic acid solution is spun on the glass plate of cleaning, again glass plate is placed in the high temperature furnace that temperature is 60 DEG C, again high temperature furnace is warming up to 100 DEG C with the heating rate of 5 DEG C/min, 2h it is incubated again at temperature is 100 DEG C, it is warming up to 350 DEG C from 100 DEG C again with the heating rate of 5 DEG C/min of high temperature furnace, at temperature is 350 DEG C, it is incubated 2h again, obtains polyimides/graphene nanobelt laminated film；
The thickness of the graphene nanobelt laminated film that 2. step 3 obtains is 40 μm；
Step 3 2. described in mixed solution C in the mass fraction of graphene nanobelt be 1%.
Contrast test one: the preparation method of a kind of Kapton, it is characterised in that the preparation method of Kapton completes according to the following steps:
One, water-soluble poly acid imide is prepared:
1., polyamic acid solution is prepared:
4，4′-diaminodipohenyl ether is joined in organic solvent, then low whipping speed is stirring reaction 60min under 100r/min～300r/min, more ultrasonic 6h～12h under ultrasonic power is 300W, obtain two amine aqueous solutions；Dianhydride is divided 5 times under conditions of ice-water bath and mixing speed are 100r/min and join in two amine aqueous solutions, obtain thick polyamic acid solution；
Step one 1. described in the quality of 4,4 '-diaminodiphenyl ether and the volume ratio of organic solvent be 3g:50mL；
Step one 1. described in organic solvent be N-Methyl pyrrolidone；
Step one 1. described in dianhydride be equal benzene-type dianhydride；Described equal benzene-type dianhydride is pyromellitic acid anhydride；
Step one 1. described in dianhydride and the mol ratio of 4,4 '-diaminodiphenyl ether be 1:1；
2., to step one 1. in the polyamic acid solution that obtains adds alkalescence reagent, again nitrogen atmosphere and mixing speed be under 100r/min～300r/min stirring reaction 20h～30h, again with deionized water as abluent, eccentric cleaning 5 times～10 times, remove supernatant, obtain water-soluble poly acid imide；
Step one 2. described in the volume ratio of polyamic acid solution and alkalescence reagent be 10:1；
Two, by water-soluble poly acid imide low whipping speed be under 300r/min stirring reaction 24h, again water-soluble poly acid imide is spun on the glass plate of cleaning, again glass plate is placed in the high temperature furnace that temperature is 60 DEG C, again high temperature furnace is warming up to 100 DEG C with the heating rate of 5 DEG C/min, 2h it is incubated again at temperature is 100 DEG C, it is warming up to 350 DEG C with the heating rate of 5 DEG C/min of high temperature furnace from 100 DEG C again, then at temperature is 350 DEG C, is incubated 2h, obtain Kapton；
The thickness of the Kapton that 2. step 3 obtains is 40 μm.
Fig. 1 is the SEM figure of the polyimides/graphene nanobelt laminated film of embodiment one preparation；
From fig. 1, it can be seen that graphene nanobelt is uniformly dispersed in polyimide matrix, be uniformly dispersed be macro property promote micro-foundation.
Fig. 2 is the hot strength variation diagram with elongation at break, in Fig. 2,1 is the hot strength change curve with elongation at break of the polyimides/graphene nanobelt laminated film of embodiment one preparation, 2 is the hot strength change curve with elongation at break of the polyimides/graphene nanobelt laminated film of embodiment two preparation, 3 is the hot strength change curve with elongation at break of the polyimides/graphene nanobelt laminated film of embodiment three preparation, and 4 is the hot strength change curve with elongation at break of the Kapton of contrast test one preparation；
As can be seen from Figure 2, the doping of the graphene nanobelt of trace, the mechanical performance that composite polyimide material is greatly improved is conducive to improving the middle physical life of its following application.
Fig. 3 is the resistivity variation diagram with voltage, in Fig. 3,1 is the resistivity change curve with voltage of the polyimides/graphene nanobelt laminated film of embodiment one preparation, 2 is the resistivity change curve with voltage of the polyimides/graphene nanobelt laminated film of embodiment two preparation, 3 is the resistivity change curve with voltage of the polyimides/graphene nanobelt laminated film of embodiment three preparation, and 4 is the resistivity change curve with voltage of the Kapton of contrast test one preparation；
As can be seen from Figure 3, the doping of the graphene nanobelt of trace, improves the resistivity of composite polyimide material, is conducive to the application in electrical apparatus insulation field in its future.
Fig. 4 is the dielectric constant variation diagram with frequency, in Fig. 4,1 is the dielectric constant change curve with frequency of the polyimides/graphene nanobelt laminated film of embodiment one preparation, 2 is the dielectric constant change curve with frequency of the polyimides/graphene nanobelt laminated film of embodiment two preparation, 3 is the dielectric constant change curve with frequency of the polyimides/graphene nanobelt laminated film of embodiment three preparation, and 4 is the dielectric constant change curve with frequency of the Kapton of contrast test one preparation；
As can be seen from Figure 4, the doping of the graphene nanobelt of trace, reduce the dielectric constant of composite polyimide material, be conducive to it in the following application of microelectronic.
Claims (10)
1. the preparation method of polyimides/graphene nanobelt laminated film, it is characterised in that the preparation method of a kind of polyimides/graphene nanobelt laminated film completes according to the following steps:
One, water-soluble poly acid imide is prepared:
1., polyamic acid solution is prepared:
4，4′-diaminodipohenyl ether is joined in organic solvent, then low whipping speed is stirring reaction 60min under 100r/min～300r/min, more ultrasonic 6h～12h under ultrasonic power is 300W, obtain two amine aqueous solutions；Dianhydride is divided 5 times under conditions of ice-water bath and mixing speed are 100r/min and join in two amine aqueous solutions, obtain thick polyamic acid solution；
Step one 1. described in the quality of 4,4 '-diaminodiphenyl ether and the volume ratio of organic solvent be 3g:(40mL～60mL)；
Step one 1. described in organic solvent be N-Methyl pyrrolidone or dinethylformamide；
Step one 1. described in dianhydride be biphenyl type dianhydride or equal benzene-type dianhydrides；Described biphenyl type dianhydride is 3,3', 4,4'-biphenyl tetracarboxylic dianhydride；Described equal benzene-type dianhydride is pyromellitic acid anhydride；
Step one 1. described in dianhydride and the mol ratio of 4,4 '-diaminodiphenyl ether be 1:1；
2., to step one 1. in the thick polyamic acid solution that obtains adds alkalescence reagent, again nitrogen atmosphere and mixing speed be under 100r/min～300r/min stirring reaction 20h～30h, again with deionized water as abluent, eccentric cleaning 5 times～10 times, remove supernatant, obtain water-soluble poly acid imide；
Step one 2. described in the volume ratio of polyamic acid solution and alkalescence reagent be 10:1；
Two, graphene nanobelt solution is prepared:
CNT and oxidant are joined in concentrated acid, obtains mixture A；By mixture A ice-water bath and mixing speed be under 100r/min～300r/min stirring reaction 1h～2h；Again mixture A is heated to 60 DEG C, then at 60 DEG C, is incubated 1h～3h, more centrifugal 10min～15min under centrifugal speed is 6000r/min～8000r/min, remove supernatant, obtain solid B；Clean solid B1 time～2 times first by hydrochloric acid that mass fraction is 5%～10%, re-use distilled water cleaning solid B5 time～10 times, obtain graphene nanobelt；Graphene nanobelt is dissolved in deionized water, obtains graphene nanobelt solution；
The quality of the CNT described in step 2 and the volume ratio of concentrated acid are 1g:(80mL～100mL)；
The quality of the CNT described in step 2 and the mass ratio of oxidant are 1:(5～8)；
In graphene nanobelt solution described in step 2, the mass fraction of graphene nanobelt is 1%～5%；
Three, laminated film is prepared:
1., by step one 2. in the water-soluble poly acid imide that obtains be dissolved in deionized water, obtain water-soluble poly imide solution；
Step 3 1. described in the volume ratio of the imido quality of water-soluble poly and deionized water be 5g:(10mL～20mL)；
2., by the graphene nanobelt solution obtained in step 2 join step 3 1. in the water-soluble poly imide solution that obtains, obtain mixed solution C；It is stirring reaction 24h～36h under 100r/min～300r/min by mixed solution C low whipping speed, obtains graphene nanobelt/polyamic acid solution；By in graphene nanobelt/polyamic acid solution spin coating, curtain coating or plastic film mulch to clean glass plate, again glass plate is placed in the high temperature furnace that temperature is 60 DEG C, again high temperature furnace is warming up to 100 DEG C with the heating rate of 5 DEG C/min～10 DEG C/min, 2h it is incubated again at temperature is 100 DEG C, it is warming up to 350 DEG C from 100 DEG C again with the heating rate of 5 DEG C/min of high temperature furnace～10 DEG C/min, at temperature is 350 DEG C, it is incubated 2h again, obtains polyimides/graphene nanobelt laminated film；
Step 3 2. described in mixed solution C in the mass fraction of graphene nanobelt be 0.1%～3%.
The preparation method of a kind of polyimides/graphene nanobelt laminated film the most according to claim 1, the centrifugal speed that it is characterized in that each eccentric cleaning described in step one is 2. is 6000r/min～8000r/min, and each centrifugation time is 10min～20min.
The preparation method of a kind of polyimides/graphene nanobelt laminated film the most according to claim 1, it is characterised in that step one 2. described in alkalescence reagent be triethanolamine, tripropyl amine (TPA) or triethylamine.
The preparation method of a kind of polyimides/graphene nanobelt laminated film the most according to claim 1, it is characterised in that the oxidant described in step 2 is that potassium ferrate, ferric acid are received or potassium permanganate.
The preparation method of a kind of polyimides/graphene nanobelt laminated film the most according to claim 1, it is characterised in that the concentrated acid described in step 2 be mass fraction be the sulphuric acid of 98%.
The preparation method of a kind of polyimides/graphene nanobelt laminated film the most according to claim 1, it is characterised in that step 3 2. described in mixed solution C in the mass fraction of graphene nanobelt be 0.1%.
The preparation method of a kind of polyimides/graphene nanobelt laminated film the most according to claim 1, it is characterised in that step 3 2. described in mixed solution C in the mass fraction of graphene nanobelt be 0.3%.
The preparation method of a kind of polyimides/graphene nanobelt laminated film the most according to claim 1, it is characterised in that step 3 2. described in mixed solution C in the mass fraction of graphene nanobelt be 1%.
The preparation method of a kind of polyimides/graphene nanobelt laminated film the most according to claim 1, it is characterized in that being joined by the graphene nanobelt solution obtained in step 2 during step 3 is 2. step 3 1. in the water-soluble poly imide solution that obtains, obtain mixed solution C；It is stirring reaction 24h under 300r/min by mixed solution C low whipping speed, obtains graphene nanobelt/polyamic acid solution；By in graphene nanobelt/polyamic acid solution spin coating, curtain coating or plastic film mulch to clean glass plate, again glass plate is placed in the high temperature furnace that temperature is 60 DEG C, again high temperature furnace is warming up to 100 DEG C with the heating rate of 5 DEG C/min, 2h it is incubated again at temperature is 100 DEG C, it is warming up to 350 DEG C from 100 DEG C again with the heating rate of 5 DEG C/min of high temperature furnace, at temperature is 350 DEG C, it is incubated 2h again, obtains polyimides/graphene nanobelt laminated film.
The preparation method of a kind of polyimides/graphene nanobelt laminated film the most according to claim 1, it is characterised in that the thickness of the graphene nanobelt laminated film that 2. step 3 obtains is 30 μm～40 μm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610388416.4A CN105820572B (en) | 2016-06-02 | 2016-06-02 | A kind of preparation method of polyimides/graphene nanobelt laminated film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610388416.4A CN105820572B (en) | 2016-06-02 | 2016-06-02 | A kind of preparation method of polyimides/graphene nanobelt laminated film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105820572A true CN105820572A (en) | 2016-08-03 |
| CN105820572B CN105820572B (en) | 2018-03-27 |
Family
ID=56531962
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610388416.4A Active CN105820572B (en) | 2016-06-02 | 2016-06-02 | A kind of preparation method of polyimides/graphene nanobelt laminated film |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105820572B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110894292A (en) * | 2019-10-31 | 2020-03-20 | 安徽国风塑业股份有限公司 | Fluorescent polyimide film and preparation method thereof |
| CN111470876A (en) * | 2020-03-16 | 2020-07-31 | 中山大学 | High-graphitization polyimide-based graphite thick film and preparation method thereof |
| CN114804097A (en) * | 2022-05-12 | 2022-07-29 | 重庆锦添翼新能源科技有限公司 | Nitrogen-doped spherical porous carbon and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104448824A (en) * | 2015-01-05 | 2015-03-25 | 福州大学 | Polyimide-based composite film with optical limiting performance |
| CN105197909A (en) * | 2015-09-24 | 2015-12-30 | 复旦大学 | Graphene nanoribbon/carbon nanotube/polyimide-based compound carbon aerogel and preparation method thereof |
-
2016
- 2016-06-02 CN CN201610388416.4A patent/CN105820572B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104448824A (en) * | 2015-01-05 | 2015-03-25 | 福州大学 | Polyimide-based composite film with optical limiting performance |
| CN105197909A (en) * | 2015-09-24 | 2015-12-30 | 复旦大学 | Graphene nanoribbon/carbon nanotube/polyimide-based compound carbon aerogel and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| S. ANAND ET AL.: "《Graphene nanoribbon based terahertz antenna on polyimide substrate》", 《OPTIK》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110894292A (en) * | 2019-10-31 | 2020-03-20 | 安徽国风塑业股份有限公司 | Fluorescent polyimide film and preparation method thereof |
| CN111470876A (en) * | 2020-03-16 | 2020-07-31 | 中山大学 | High-graphitization polyimide-based graphite thick film and preparation method thereof |
| CN111470876B (en) * | 2020-03-16 | 2021-10-19 | 中山大学 | High-graphitization polyimide-based graphite thick film and preparation method thereof |
| CN114804097A (en) * | 2022-05-12 | 2022-07-29 | 重庆锦添翼新能源科技有限公司 | Nitrogen-doped spherical porous carbon and preparation method thereof |
| CN114804097B (en) * | 2022-05-12 | 2024-03-22 | 重庆锦添翼新能源科技有限公司 | Nitrogen-doped spherical porous carbon and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105820572B (en) | 2018-03-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110550956B (en) | Preparation method of graphene-polyimide-based composite sponge precursor heat-conducting film | |
| CN100441652C (en) | Method for preparing binder of polyimide of containing phenolic hydroxyl group | |
| CN101798462B (en) | Graphene/conductive polymer composite film and preparation method thereof | |
| CN109401314B (en) | Preparation method of graphene/polyimide composite material | |
| CN101289542B (en) | Spherical silica/polyimides composite membrane, preparation thereof and applications | |
| CN106283659B (en) | A kind of preparation method of electric-conducting polyimide fiber material | |
| CN106629699B (en) | A kind of preparation method of high thermal conductivity graphite film | |
| CN109929129A (en) | A kind of carboxylic carbon nano-tube/polyimide composite film and preparation method thereof | |
| CN106084219B (en) | A kind of preparation method of high-performance polyimide/ultrathin boron nitride laminated film | |
| CN105820572A (en) | Preparation method of polyimide/graphene nanoribbon composite film | |
| JP2013516509A (en) | Method for producing wholly aromatic polyimide powder having antistatic properties or electrical conductivity properties | |
| CN105968393A (en) | Preparation method of polyimide and fluorinated graphene oxide composite material | |
| CN105566630A (en) | Polyimide film and preparation method thereof | |
| CN110272552B (en) | Preparation method of polyimide film for graphite sintering | |
| CN110172151A (en) | A kind of preparation method of graphene/carbon nano-tube/polyimide composite film | |
| CN103889196A (en) | Manufacturing method of high thermal conductivity artificial graphite film | |
| CN103923330A (en) | Method for preparing high-thermal conductivity polyimide/magnesium oxide composite film | |
| CN102120826A (en) | Preparation method of antistatic polyimide film | |
| CN105330878A (en) | Preparation method of fluororesin-containing modified polyimide film | |
| CN106497054A (en) | Nano-TiO2/ polyimide composite film and preparation method thereof | |
| CN105348551A (en) | Polyimide porous membrane and preparation method thereof | |
| CN105566906A (en) | Black conductive polyimide film | |
| CN107286651B (en) | A kind of preparation method of Nano diamond/Kapton | |
| CN107189092A (en) | A kind of preparation method of high heat conduction type Kapton | |
| CN115558292B (en) | Polyimide film with high heat conductivity and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20190116 Address after: 710000 Weiyang University Park, Xi'an City, Shaanxi Province Patentee after: SHAANXI University OF SCIENCE & TECHNOLOGY Address before: 150022 No. 2468 Puyuan Road, Songbei District, Harbin City, Heilongjiang Province Patentee before: Heilongjiang University of Science and Technology |
|
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20221129 Address after: Room 1f412, room c0101, building 1, Chuangye Plaza, No. 48, Keji Road, high tech Zone, Xi'an, Shaanxi 710075 Patentee after: Datong copolymerization (Xi'an) Technology Co.,Ltd. Address before: 710000 Weiyang University Park, Xi'an City, Shaanxi Province Patentee before: SHAANXI University OF SCIENCE & TECHNOLOGY |