CN110452251A - A kind of anhydride compounds and the preparation method and application thereof - Google Patents
A kind of anhydride compounds and the preparation method and application thereof Download PDFInfo
- Publication number
- CN110452251A CN110452251A CN201910822805.7A CN201910822805A CN110452251A CN 110452251 A CN110452251 A CN 110452251A CN 201910822805 A CN201910822805 A CN 201910822805A CN 110452251 A CN110452251 A CN 110452251A
- Authority
- CN
- China
- Prior art keywords
- compound
- carbon atom
- anhydride compounds
- preparation
- atom number
- 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
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D493/00—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system
- C07D493/02—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system in which the condensed system contains two hetero rings
- C07D493/10—Spiro-condensed systems
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D493/00—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system
- C07D493/12—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system in which the condensed system contains three hetero rings
- C07D493/20—Spiro-condensed systems
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D495/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms
- C07D495/12—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms in which the condensed system contains three hetero rings
- C07D495/20—Spiro-condensed systems
-
- 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
- C08G73/1003—Preparatory processes
- C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
-
- 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
- C08G73/1075—Partially aromatic polyimides
- C08G73/1078—Partially aromatic polyimides wholly aromatic in the diamino moiety
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
The present invention relates to a kind of anhydride compounds and the preparation method and application thereof, while anhydride compounds of the invention effectively destroy the conjugated structure in PI membrane molecular structure with its distinctive full-cream ring or half alicyclic structure, the charge transport capability in main structure is weakened, again to realize good transparence modified effect.The transparent polyimide film is light transmittance >=85% of 550mm light wave to wavelength.The application of transparent polyimide film is not particularly limited, can be applied to flexible and transparent display base plate, the photoelectric fields such as optical transparent film, optical communication material and solar cell substrate.Preparation method in the present invention can be stablized, be efficiently obtained anhydride compounds of the present invention, and raw material is easy to get, and preparation process is simple, convenient for the popularization of the anhydride compounds.
Description
Technical field
The invention belongs to technical field of polymer materials, and in particular to a kind of anhydride compounds and preparation method thereof with answer
With.
Background technique
Polyimides (Polyimide, PI) refers to a kind of high polymer on main chain containing imide ring, by containing diamines and dianhydride
Compound be prepared through gradually polymerizeing;Because of distinctive imide ring, aromatic ring structure and its conjugation on PI main chain, make it
Have a characteristics such as excellent thermal stability, mechanical strength, dielectric properties and low thermal coefficient of expansion, thus in aerospace, micro-
The fields such as electronics, mechanical engineering, petrochemical industry, liquid crystal display are widely used.
With the development of photoelectric field, on the basis of keeping original good hot property and mechanical performance, to polyimides
Optical property more stringent requirements are proposed, and distinctive kinds of aromatic ring conjugation structure in traditional polyimide structures results in molecule
Interior and Intermolecular charge transfer complex (CTC) formation, greatly affected the translucency of PI film, and show brown color
And poor light transmittance, PI film is limited in the development of photoelectric field.Meanwhile as intelligent electronic device in recent years is shown
Development of the device to bent direction opens high transparency PI film for the requirement for realizing this class of electronic devices Flexible Displays
Hair demand seems especially urgent.
To realize the good transparency of PI film, often realized by the design to PI molecular structure;Such as it introduces and can break
The group (curved ehter bond or sulfuryl can be achieved) of planar conjugate structure or structure (the big substituent group of spatial volume) in bad main chain,
Introduce aliphatic structure (alicyclic ring or aliphatic structure) and contain fluorine structure etc., to destroy the conjugation effect and symmetry of molecular structure,
Intramolecular or intermolecular load transfer effect are reduced, to realize good transparence modified effect;Often by select it is above-mentioned a kind of or
Various ways realize the raising of PI thin-film transparent.
For these reasons, the present invention is specifically proposed.
Summary of the invention
In order to solve problem above existing in the prior art, the first object of the present invention provides a kind of dicarboxylic anhydride chemical combination
Object, shown in the general structure of the anhydride compounds such as formula (I):
Wherein, X1、X2And X3It is identical or different, R1、R2And R3It is identical or different, n=0-12 integer;
The X1For CmR1, S atom, N atom or O atom, m=1-12 integer;
The X2For CmR1, S atom, N atom or O atom, m=1-12 integer;
The X3For CmR1, S atom, N atom or O atom, m=1-12 integer;
The R1、R2And R3It is independent represent hydrogen, heavy hydrogen, halogen, the alkyl containing 1-12 carbon atom or alkoxy,
Alkane alkenyl or alcoxyl alkenyl, the alkynyl that carbon atom number is 2 to 12 containing 2-12 carbon atom, the ring that carbon atom number is 3 to 12
Alkane-sulfur oxyl that the aryl or aryloxy group, carbon atom number that alkyl or cycloalkenyl, carbon atom number are 6 to 12 are 1 to 12, carbon atom number
For 6 to 12 fragrant sulphur oxygroup, carbon atom number be 1 to 12 alkylamino radical, carbon atom number be 6 to 12 aryl amine, carbon atom number 6
To 12 aryl, the carbon atom number with hetero atom O, N or S be 2 to 12 heteroaryl, carbon atom number be 1 to 12 alkyl
Silylation, carbon atom number are any one in 6 to 12 aryl-silane base;The wherein alkyl, alkoxy, alkane alkenyl, alkane
Oxy alkylene, alkynyl, naphthenic base, H can be replaced by F in cycloalkenyl, one or more non-conterminous-CH2It can be each independently
By-O- ,-N- ,-S- replace, and O atom, S atom are not directly connected each other;
Preferably, R1、R2And R3It is identical or different, R1、R2And R3The independent alkane for representing hydrogen, heavy hydrogen, F, 1-6 carbon atoms
Alkynyl that base or alkoxy, the alkane alkenyl containing 2-6 carbon atom or alcoxyl alkenyl, carbon atom number are 2 to 6, carbon atom number 3
To 12 naphthenic base or cycloalkenyl, carbon atom number be 6 to 12 aryl or aryloxy group in any one;Wherein the alkyl,
Alkoxy, alkane alkenyl, alcoxyl alkenyl, alkynyl, naphthenic base, H can be replaced by F in cycloalkenyl, it is one or more it is non-conterminous-
CH2It can be replaced each independently by-O-, but O atom is required to be not directly connected each other;
It is furthermore preferred that m=1-6 integer, n is 0 or 1.
Further, the anhydride compounds are such as any one in flowering structure:
The second object of the present invention provides the preparation method of anhydride compounds described in one kind, dicarboxylic anhydride conjunction
It is as follows at route:
Specific preparation method includes the following steps:
(1) using compound A-1 as raw material, by Mannich reaction, diamine compound A-2 is obtained;
(2) by compound A-2 deamination methyl, bifunctional vinyl compound A-3 is obtained;
(3) compound A-3 is carried out retaining ring with cyclopentadiene to react, obtains bicyclo hexene compound A-4;
(4) compound A-4 is carried out inserting carbonyl and oxidation reaction under catalyst, obtains compound A-5;
(5) hydrolysis and dehydration are occurred into for compound A-5, obtains compound A-6, the i.e. anhydride compounds.
Further, compound A-1 is reacted with the amine salt of secondary amine and formaldehyde derivatives in step (1), obtains chemical combination
Object A-2, it is preferred that the amine salt of secondary amine be secondary amine hydrochloride, the sulfate of secondary amine or the acetate of secondary amine, compound A-2 with
The molar ratio of the amine salt of secondary amine is 1:2-10, and the molar ratio of compound A-1 and formaldehyde derivatives is 1:2-10, it is furthermore preferred that changing
The molar ratio for closing object A-1 and formaldehyde derivatives is 1:1.5-5.0;
Further, the reaction condition in step (1) are as follows: heating reaction 0.5-10 hours under an inert atmosphere, heating temperature
Degree is 30-180 DEG C, it is preferred that heating temperature is 85-95 DEG C;
The reaction carries out in organic solvent, the organic solvent be tetrahydrofuran, methanol, ethyl alcohol, isopropanol,
Butanol, acetonitrile, methyl cellosolve, ethyl cellosolve, ethylene glycol, propylene glycol monomethyl ether, propylene glycol, methylene chloride, a fluorine three
One of chloromethanes, preferably isopropanol.
Further, the molar ratio of compound A-3 and cyclopentadiene is 1:2-10 in step (3), it is preferred that molar ratio is
1:2.5, reaction carries out under an inert atmosphere, water-bath 0.5-10 hours of 120-125 DEG C, it is preferred that in 85-95 DEG C of water
It is reacted in bath.
Further, step (4) makes alcoholic compound, carbon monoxide and compound A-4 under palladium catalyst and copper catalyst
Reaction;
The mass ratio of the compound A-4 and alcoholic compound are 1:1-100, preferably 1:5-50;
The alcoholic compound is selected from methanol, ethyl alcohol, normal propyl alcohol, isopropanol, n-butanol, sec-butyl alcohol, the tert-butyl alcohol, amylalcohol, first
The mixture of one or more of ethoxy-ethanol, ethoxy ethanol, ethylene glycol, triethylene glycol;It is preferred that methanol, ethyl alcohol, normal propyl alcohol,
The mixture of one or more of isopropanol;One of more preferable methanol, ethyl alcohol, isopropanol or several mixtures.
The molar ratio of the compound A-4 and palladium catalyst are 1:0.001-1, preferably 1:0.01-0.5;
The palladium catalyst used, is not particularly limited as long as comprising palladium.For example, palladium chloride, palladium bromide etc. can be enumerated
Halogenation palladium;The palladiums acylates such as acid chloride, oxalic acid palladium;The palladiums inorganic acid salt such as palladium nitrate, palladium sulfate;Palladium is set to be carried on carbon or oxidation
Palladium carbon or palladium aluminium oxide on the carriers such as aluminium etc. are, it is preferable to use palladium chloride or palladium carbon.
The molar ratio of the compound A-4 and copper catalyst are 1:1-50, preferably 1:4-20.
The copper catalyst is selected from monovalence copper oxide, monovalent copper chloride, monovalence copper bromide, divalent copper oxides, divalent chlorination
The mixture of one or more of copper, divalent copper bromide;It is preferred that in divalent copper oxides, divalent cupric chloride, divalent copper bromide
One or more of mixtures;More preferably divalent cupric chloride.
Further, in step (5) under an acid catalysis, heating carries out dehydration in organic solvent, and heating temperature is
50-130 DEG C, preferred heating temperature is 80-120 DEG C, and the mass ratio of compound A-5 and the organic solvent is 1:0.1-100,
Preferred mass ratio is 1:1-10.
Organic solvent described in step (5) is identical as the organic solvent in step (1).The acid is inorganic acid, has
One or more of machine sulfonic acid, halogenated carboxylic acids, ion exchange resin, sulfuric acid silica gel, zeolite, acidic alumina, the nothing
Machine acid is one or more of hydrochloric acid, hydrobromic acid, hydroiodic acid, sulfuric acid, sulfuric chlorohydrin, nitric acid, and the organic sulfonic acid is methylsulphur
It is acid, benzene sulfonic acid, one or more of in p-methyl benzenesulfonic acid, it is preferred that the acid is inorganic acid or organic sulfonic acid, it is furthermore preferred that
The acid is organic sulfonic acid.
The present invention illustrates the details of each reaction by embodiment.Those skilled in the art can change solvent, throw
Doses, reaction condition etc..In addition, respectively after reaction, such as filtering, extraction, distillation, distillation, recrystallization, column can be passed through
The common method such as chromatography carries out separation/purifying etc. of reaction product.
Raw material A -1 in the present invention can be synthesized by method known per se in public commercial source or document
It arrives.
Furthermore it is noted that part is not made used in each step being particularly limited in preparation method of the present invention
Solvent and its dosage, the separating-purifying of product, the rate of addition of reactant etc. are that those skilled in the art understand and grasp.
In the present invention, in addition to making special instruction, the volumetric usage of solvent is generally 5~15 times of reactant quality, specifically
Dosage can be according to the size appropriate adjustment of reaction substrate dosage and selected reaction flask;The rate of addition of reactant usually combines tool
Reaction speed comprehensively control of body etc..On the basis of disclosed by the invention, those skilled in the art can be corresponding according to the actual situation
Ground selects any available technical solution to realize the present invention.
Preparation method of the present invention can be stablized, be efficiently obtained anhydride compounds of the present invention.
The third object of the present invention provides the two of anhydride compounds described in one kind or preparation method preparation
Application of the anhydride compound in transparent polyimide film field.
Further, the transparent polyimide film is by the anhydride compounds, aliphatic or aromatic series two
Amine compounds are prepared.
Heretofore described diamine compound be selected from 4,4 '-diaminodiphenyl ethers (ODA), p-phenylenediamine (p-PDA),
Phenylenediamine (m-PDA), o-phenylenediamine (o-PDA), 4,4 '-diaminodiphenylmethane (MDA), anti-form-1,4- cyclohexanediamine (t-
DACH) and 2,2 '-bis- (trifluoromethyls) -4,4 '-benzidines) one of (TFMB) or a variety of.
Compared with prior art, the invention has the benefit that
(1) anhydride compounds provided by the invention can be used for transparent polyimide film field, distinctive full-cream with its
While ring or half alicyclic structure effectively destroy the conjugated structure in PI membrane molecular structure, and weaken the electricity in main structure
Lotus transfer ability, to realize good transparence modified effect.The transparent polyimide film is 550mm light wave to wavelength
Light transmittance >=85%.The application of transparent polyimide film is not particularly limited, flexible and transparent is can be applied to and shows
Substrate, the photoelectric fields such as optical transparent film, optical communication material and solar cell substrate.
(2) preparation method in the present invention can be stablized, be efficiently obtained anhydride compounds of the present invention, and former
Material is easy to get, and preparation process is simple, and the yield of target compound is high, convenient for the popularization of the anhydride compounds.
Specific embodiment
To make the object, technical solutions and advantages of the present invention clearer, technical solution of the present invention will be carried out below
Detailed description.Obviously, described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.Base
Embodiment in the present invention, those of ordinary skill in the art are obtained all without making creative work
Other embodiment belongs to the range that the present invention is protected.
Compound A-2 synthesis process is formed by hydrochloride in the present invention, unstable easy deamination in the state of heating
Methyl generates diene, obtains compound A-3, therefore compound A-2 and A-3 synthesis are written as single step reaction by following embodiment.
Embodiment 1
The structural formula of the anhydride compounds A1-6 of the present embodiment is as follows:
The synthetic route of the anhydride compounds of the present embodiment is as follows:
Specific preparation method includes the following steps:
(1) synthesis of compound A1-2 and compound A1-3
The aqueous dimethylamine that 24.0g mass fraction is 50% is added into the three-necked flask of 250ml, in cold
The lower aqueous hydrochloric acid solution that 33.2g mass fraction is added dropwise and is 30%, is added dropwise, is stirred to react 1 hour, the salt of dimethyl amine is made
Hydrochlorate is slowly added to 9.9g paraformaldehyde in the there-necked flask, 15.0g compound A1-1, is warming up under nitrogen protection
It 85-90 DEG C, reacts 3 hours, obtains reaction solution, for the synthesis of compound A1-4, carry out conventional post-processing, carry out HPLC analysis
Obtaining compound A1-1 conversion ratio is 99.3%.
(2) synthesis of compound A1-4
Above-mentioned reaction solution is cooled to 50 DEG C, is slowly added to 80ml methyl cellosolve, 3.8g mass fraction is 50%
Aqueous dimethylamine, 25.4g cyclopentadiene, nitrogen protection are warming up to 115-120 DEG C, and in this thermotonus 1.5h, will be upper
It states mixed liquor and is cooled to room temperature (25 DEG C).Conventional post-processing is carried out, through chromatogram purification, n-hexane elution, short-path distillation is obtained colourless
Oily liquids (A1-4) 22.8g, GC:98%, yield 71%.
(3) synthesis of compound A1-5
Methanol 50ml, chloroform 10ml, copper chloride (II) 0.5g, palladium chloride 0.8g are added in reaction flask, is stirred, an oxygen
Change carbon displacement three times, the mixed liquor of 20-25 DEG C of temperature control dropwise addition 20g compound A1-4 and 50ml chloroform are dripped off, controlled for about 3 hours
The reaction was continued at this temperature 4 hours for system, and nitrogen is replaced three times, is evaporated off solvent, carries out conventional post-processing, silica gel chromatography (hexane:
Ethyl acetate=10: 1) being purified, and obtaining compound as white solid A1-5 mass is 26.3g, LC:99.4%, yield 73%.
(4) synthesis of compound A1-6
A1-5 25.0g, formic acid 20.5g, p-methyl benzenesulfonic acid monohydrate 25.0mg are added in reaction flask, at 98 DEG C of temperature
Lower reaction 20 hours, after reaction, is distilled off formic acid, filters, and filter cake is eluted with toluene, gained crude product acetic anhydride
It is recrystallized, then is recrystallized with N ' N '-dimethyl acetamide, obtain white solid A1-6 16.9g, LC:99.5%, received
Rate 82%.
Embodiment 2
The structural formula of the anhydride compounds A2-6 of the present embodiment is as follows:
The synthetic route of the anhydride compounds of the present embodiment is as follows:
Specific preparation method includes the following steps:
(1) synthesis of compound A2-2 and compound A2-3
The aqueous dimethylamine that 48.0g mass fraction is 50% will be added in 250ml three-necked flask, under cold
The aqueous hydrochloric acid solution that 66.5g mass fraction is 30% is added dropwise, is added dropwise, is stirred to react 1 hour, the hydrochloric acid of dimethyl amine is made
Salt.In above-mentioned three-necked flask, it is slowly added to 19.8g paraformaldehyde, 35.8g compound A2-1 under nitrogen protection, is warming up to
80-90 DEG C is reacted 3 hours, carries out conventional post-processing, HPLC analyze compound A2-1 conversion ratio be 99.1% reaction solution, can
It direct plunges into next step.
(2) synthesis of compound A2-4
Above-mentioned reaction solution is cooled to 50 DEG C, is slowly added to 100ml methyl cellosolve, 7.2g mass fraction is the two of 50%
Methyl amine aqueous solution, 50.8g cyclopentadiene, nitrogen protection are warming up to 110-120 DEG C, and in this thermotonus 2.0h, will be above-mentioned
Mixed liquor is cooled to room temperature (25 DEG C).Conventional post-processing is carried out, through chromatogram purification, n-hexane elution, short-path distillation obtains colorless oil
Shape liquid (A2-4) 51.2g, GC:96%, yield: 75.5%.
(3) synthesis of compound A2-5
Methanol 200ml, chloroform 20ml, copper chloride (II) 0.6g, palladium chloride 0.7g are added in reaction flask, is stirred, one
Carbonoxide is replaced three times, and the mixed liquor of 20-25 DEG C of temperature control dropwise addition 50.5g compound A2-4 and 100ml chloroform drip for about 3 hours
Complete, the reaction was continued at this temperature 4 hours for control, and nitrogen is replaced three times, and solvent is evaporated off, and carries out conventional post-processing, silica gel chromatography
(hexane: ethyl acetate=10: 1) being purified, and obtains compound as white solid A2-5 63.8g, LC:99.6%, yield:
71.6%.
(4) synthesis of compound A2-6
Compound A2-5 63.5g, formic acid 240ml, p-methyl benzenesulfonic acid monohydrate 32mg are added in reaction flask, in temperature
It is reacted 22 hours at 100 DEG C, after reaction, formic acid is distilled off, filtered, filter cake is eluted with toluene, and gained crude product is used
Acetic anhydride is recrystallized, then is recrystallized with N ' N '-dimethyl acetamide, and compound as white solid A2-6 41.8g is obtained,
LC:99.4%, yield: 79.4%.GC-MS(m/z);452.50 (M+), elemental analysis: C:69.01, H:6.24, O:24.75.
Embodiment 3
The structural formula of the anhydride compounds A3-6 of the present embodiment is as follows:
The preparation method of the dicarboxylic anhydride of the present embodiment is same as Example 1, and test parameters and condition have carried out conventional tune
It is whole, anhydride compounds manufactured in the present embodiment are analyzed, GC-MS (m/z);438.47 (M+), elemental analysis: C:68.48,
H:5.98, O:25.52.
Embodiment 4
The structural formula of the anhydride compounds A4-6 of the present embodiment is as follows:
The preparation method of the dicarboxylic anhydride of the present embodiment is same as Example 1, and test parameters and condition have carried out conventional tune
It is whole, anhydride compounds manufactured in the present embodiment are analyzed, GC-MS (m/z);424.44 (M+), elemental analysis: C:67.91,
H:5.72, O:26.39.
The following are anhydride compounds prepared by the present invention to prepare the application in Kapton, and specific polyamides is sub-
Amine film the preparation method is as follows:
Embodiment 5
Reaction vessel is exhausted using nitrogen in advance, after 30min, 127.74g n,N-dimethylacetamide is added
(DMAc is removed water with molecular sieve for 24 hours in advance), then 4,4 '-diaminodiphenyl ether (ODA) of 10.01g (50mmol) is packed into and is dissolved
In DMAc, stirred at 25 DEG C to being completely dissolved;Gradually adding 21.92g (50mmol) anhydride compounds again, (embodiment 1 is made
Standby anhydride compounds A1-6), stir the insulation reaction 72h, so that it is molten to obtain 20wt% polyimide acid to after being completely dissolved
Liquid.
After reaction, it is separately added into the equimolar acetic anhydride of carboxylic acid group and isoquinolin, the DMAc removed water is added, is tuned into
The solution of 15~18wt%;On the glass substrate by obtained polyimide acid solution coating, it is transferred on needle plate after prebake,
It transfers in baking oven, is heat-treated 30min at 150 DEG C/250 DEG C/300 DEG C/350 DEG C respectively, hot imidization is carried out, to make
There must be the Kapton of about 25 μ m thicks.
Embodiment 6
Reaction vessel is exhausted using nitrogen in advance, after 30min, 130.55g n,N-dimethylacetamide is added
(DMAc is removed water with molecular sieve for 24 hours in advance), then 4,4 '-diaminodiphenyl ether (ODA) of 10.01g (50mmol) is packed into and is dissolved
In DMAc, stirred at 25 DEG C to being completely dissolved;Gradually adding 22.62g (50mmol) anhydride compounds again, (embodiment 2 is made
Standby anhydride compounds A2-6), stir the insulation reaction 72h, so that it is molten to obtain 20wt% polyimide acid to after being completely dissolved
Liquid.
Then, the Kapton of 25 μ m-thicks is prepared according to method identical in embodiment 5.
Embodiment 7
Reaction vessel is exhausted using nitrogen in advance, after 30min, 127.74g n,N-dimethylacetamide is added
(DMAc is removed water with molecular sieve for 24 hours in advance), then 4,4 '-diaminodiphenyl ether (ODA) of 10.01g (50mmol) is packed into and is dissolved
In DMAc, stirred at 25 DEG C to being completely dissolved;Gradually adding 21.92g (50mmol) anhydride compounds again, (embodiment 3 is made
Standby anhydride compounds A3-6), stir the insulation reaction 72h, so that it is molten to obtain 20wt% polyimide acid to after being completely dissolved
Liquid.
Then, the Kapton of 25 μ m-thicks is prepared according to method identical in embodiment 5.
Embodiment 8
Reaction vessel is exhausted using nitrogen in advance, after 30min, 124.94g n,N-dimethylacetamide is added
(DMAc is removed water with molecular sieve for 24 hours in advance), then 4,4 '-diaminodiphenyl ether (ODA) of 10.01g (50mmol) is packed into and is dissolved
In DMAc, stirred at 25 DEG C to being completely dissolved;Gradually adding 21.22g (50mmol) anhydride compounds again, (embodiment 4 is made
Standby anhydride compounds A4-6), stir the insulation reaction 72h, so that it is molten to obtain 20wt% polyimide acid to after being completely dissolved
Liquid.
Then, the Kapton of 25 μ m-thicks is prepared according to method identical in embodiment 5.
Comparative example 1
Reaction vessel is exhausted using nitrogen in advance, after 30min, 98.89g n,N-dimethylacetamide is added
(DMAc is removed water with molecular sieve for 24 hours in advance), then 4,4 '-diaminodiphenyl ether (ODA) of 10.01g (50mmol) is packed into and is dissolved
In DMAc, stirred at 25 DEG C to being completely dissolved;3,3 ', 4,4 '-biphenyltetracarboxyacid acid two of 14.71g (50mmol) is gradually added again
Acid anhydride (BPDA) stirs the insulation reaction 72h, to obtain 20wt% polyimides acid solution to after being completely dissolved.
Then, the Kapton of 25 μ m-thicks is prepared according to method identical in embodiment 5.
Comparative example 2
Reaction vessel is exhausted using nitrogen in advance, after 30min, 140.90g n,N-dimethylacetamide is added
(DMAc is removed water with molecular sieve for 24 hours in advance), then respectively by 8.00g (25mmol) 2,2 '-bis- (trifluoromethyl) -4,4 '-diamino
Biphenyl) (TFMB) and 4,4 '-diaminodiphenyl ether (ODA) of 5.00g (25mmol) be fitted into and be dissolved in DMAc, stir at 25 DEG C
To being completely dissolved;22.21g (50mmol) 2,2 '-bis- (3,4- dicarboxylic acids) hexafluoropropane dianhydrides are gradually added again) (6FDA), it stirs
It mixes to after being completely dissolved, insulation reaction 72h, so that 20wt% polyimides acid solution be made.
Then, the Kapton of 25 μ m-thicks is prepared according to method identical in embodiment 5.
Test example 1
The Kapton respectively prepared by embodiment 5-8 and comparative example 1-2 carries out following performance evaluation, as a result such as table
Shown in 1.
(1) thermal linear expansion coefficient (CTE)
According to thermomechanical analysis, polyamides is measured using thermomechanical analyzer (TA Instrument company, model Q400)
The thermal expansion coefficient of imines film.The condition of measurement is as follows: specimen size: 16mm × 4mm, atmosphere: under nitrogen atmosphere;Temperature: add
Heating rate 10 DEG C/min, 50 to 250 DEG C of scanning range;Drawing force: 0.05N, 50 to 200 DEG C of value range.
(2) yellowness index
Using ultraviolet spectrophotometer (Varian company, model C ary100), according to ASTM E313 canonical measure.
(3) light transmittance
The visible light transmittance rate of polyimide film is surveyed with ultraviolet spectrophotometer (Varian company, model C ary100)
.
(4) glass transition temperature (Tg)
It is measured using scan-type heating differential analysis instrument (TA Instrument company, model Q400).Atmosphere: nitrogen atmosphere
Under;Temperature: 5 DEG C/min of the rate of heat addition;Drawing force: 0.05N;Sample size: 16mm*4mm.
Table 1
From table 1 it follows that the light transmittance of the Kapton of embodiment 5-8 preparation is much higher than (the tradition of comparative example 1
Polyimides formula), illustrate to have when dicarboxylic anhydride prepared by the present invention is used to prepare Kapton apparent optical
Energy.
Thus it analyzes, anhydride compounds prepared by the present invention, when for polyimides preparation, polyamides Asia can be effectively improved
The light transmittance of amine film, it can be achieved that PI film light transmittance >=85% at 550mm optical characteristics;It has both simultaneously preferable heat-resisting
Property;Have on the basis of transparent polyimide film field application, in the photoelectricity such as flexible display apparatus and optical transparent film
Field has a good application prospect.
The above description is merely a specific embodiment, but scope of protection of the present invention is not limited thereto, any
Those familiar with the art in the technical scope disclosed by the present invention, can easily think of the change or the replacement, and should all contain
Lid is within protection scope of the present invention.Therefore, protection scope of the present invention should be based on the protection scope of the described claims.
Claims (10)
1. a kind of anhydride compounds, which is characterized in that shown in the general structure of the anhydride compounds such as formula (I):
Wherein, X1、X2And X3It is identical or different, R1、R2And R3It is identical or different, n=0-12 integer;
The X1For CmR1, S atom, N atom or O atom, m=1-12 integer;
The X2For CmR1, S atom, N atom or O atom, m=1-12 integer;
The X3For CmR1, S atom, N atom or O atom, m=1-12 integer;
The R1、R2And R3It is independent to represent hydrogen, heavy hydrogen, halogen, the alkyl containing 1-12 carbon atom or alkoxy, contain
The alkane alkenyl or alcoxyl alkenyl, the alkynyl that carbon atom number is 2 to 12 of 2-12 carbon atom, the naphthenic base that carbon atom number is 3 to 12
Cycloalkenyl, carbon atom number be 6 to 12 aryl or aryloxy group, carbon atom number be 1 to 12 alkane-sulfur oxyl, carbon atom number 6
To 12 fragrant sulphur oxygroup, carbon atom number be 1 to 12 alkylamino radical, carbon atom number be 6 to 12 aryl amine, carbon atom number be 6 to
The alkyl silicon that heteroaryl that 12 aryl, the carbon atom number with hetero atom O, N or S are 2 to 12, carbon atom number are 1 to 12
Alkyl, carbon atom number are any one in 6 to 12 aryl-silane base;The wherein alkyl, alkoxy, alkane alkenyl, alcoxyl
Alkenyl, alkynyl, naphthenic base, H can be replaced by F in cycloalkenyl, one or more non-conterminous-CH2It can be each independently
By-O- ,-N- ,-S- replace, and O atom, S atom are not directly connected each other;
Preferably, R1、R2And R3It is identical or different, R1、R2And R3It is independent represent hydrogen, heavy hydrogen, F, 1-6 carbon atoms alkyl or
Alkynyl that alkoxy, the alkane alkenyl containing 2-6 carbon atom or alcoxyl alkenyl, carbon atom number are 2 to 6, carbon atom number are 3 to 12
Naphthenic base or cycloalkenyl, carbon atom number be 6 to 12 aryl or aryloxy group in any one;The wherein alkyl, alcoxyl
Base, alkane alkenyl, alcoxyl alkenyl, alkynyl, naphthenic base, H can be replaced by F in cycloalkenyl, one or more non-conterminous-CH2It can
To be replaced each independently by-O-, but O atom is required to be not directly connected each other;
It is furthermore preferred that m=1-6 integer, n is 0 or 1.
2. anhydride compounds according to claim 1, which is characterized in that the anhydride compounds are such as flowering structure
In any one:
3. a kind of preparation method of anhydride compounds of any of claims 1 or 2, which is characterized in that dicarboxylic anhydride conjunction
It is as follows at route:
Specific preparation method includes the following steps:
(1) using compound A-1 as raw material, by Mannich reaction, diamine compound A-2 is obtained;
(2) by compound A-2 deamination methyl, bifunctional vinyl compound A-3 is obtained;
(3) compound A-3 is carried out retaining ring with cyclopentadiene to react, obtains bicyclo hexene compound A-4;
(4) compound A-4 is carried out inserting carbonyl and oxidation reaction under catalyst, obtains compound A-5;
(5) hydrolysis and dehydration are occurred into for compound A-5, obtains compound A-6, the i.e. anhydride compounds.
4. the preparation method of anhydride compounds according to claim 3, which is characterized in that compound A-1 in step (1)
It is reacted with the amine salt of secondary amine and formaldehyde derivatives, obtains compound A-2, it is preferred that the amine salt of secondary amine is the hydrochloric acid of secondary amine
The molar ratio of the amine salt of the acetate of salt, the sulfate of secondary amine or secondary amine, compound A-2 and secondary amine is 1:2-10, compound A-1
Molar ratio with formaldehyde derivatives is 1:2-10, it is furthermore preferred that the molar ratio of compound A-1 and formaldehyde derivatives is 1:1.5-
5.0。
5. the preparation method of anhydride compounds according to claim 3, which is characterized in that the reaction item in step (1)
Part are as follows: heating reaction 0.5-10 hours under an inert atmosphere, heating temperature are 30-180 DEG C, it is preferred that heating temperature 85-95
℃;
The reaction carries out in organic solvent, and the organic solvent is tetrahydrofuran, methanol, ethyl alcohol, isopropanol, fourth
Alcohol, acetonitrile, methyl cellosolve, ethyl cellosolve, ethylene glycol, propylene glycol monomethyl ether, propylene glycol, methylene chloride, a fluorine trichlorine
One of methane, preferably isopropanol.
6. the preparation method of anhydride compounds according to claim 3, which is characterized in that compound A-3 in step (3)
Molar ratio with cyclopentadiene is 1:2-10, it is preferred that molar ratio 1:2.5, reaction carries out under an inert atmosphere, in 120-
125 DEG C of water-bath 0.5-10 hours, it is preferred that reacted in 85-95 DEG C of water-bath.
7. the preparation method of anhydride compounds according to claim 3, which is characterized in that step (4) is in palladium catalyst
Under copper catalyst, make alcoholic compound, carbon monoxide and compound A-4 reaction;
The mass ratio of the compound A-4 and alcoholic compound are 1:1-100, preferably 1:5-50;
The molar ratio of the compound A-4 and palladium catalyst are 1:0.001-1, preferably 1:0.01-0.5;
The molar ratio of the compound A-4 and copper catalyst are 1:1-50, preferably 1:4-20.
8. the preparation method of anhydride compounds according to claim 3, which is characterized in that in acid catalysis in step (5)
Under agent, heating carries out dehydration in organic solvent, and heating temperature is 50-130 DEG C, and preferred heating temperature is 80-120 DEG C,
The mass ratio of compound A-5 and the organic solvent is 1:0.1-100, and preferred mass ratio is 1:1-10.
9. a kind of anhydride compounds of any of claims 1 or 2 or claim 3-8 any one preparation method preparation two
Application of the anhydride compound in transparent polyimide film field.
10. application according to claim 9, which is characterized in that the transparent polyimide film is by the diacid
Acid anhydride compound, aliphatic or aromatic diamine compound are prepared.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201910822805.7A CN110452251B (en) | 2019-09-02 | 2019-09-02 | Dianhydride compound and preparation method and application thereof |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201910822805.7A CN110452251B (en) | 2019-09-02 | 2019-09-02 | Dianhydride compound and preparation method and application thereof |
Publications (2)
Publication Number | Publication Date |
---|---|
CN110452251A true CN110452251A (en) | 2019-11-15 |
CN110452251B CN110452251B (en) | 2021-04-20 |
Family
ID=68490349
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201910822805.7A Active CN110452251B (en) | 2019-09-02 | 2019-09-02 | Dianhydride compound and preparation method and application thereof |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN110452251B (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN116970276A (en) * | 2023-09-25 | 2023-10-31 | 北京八亿时空液晶科技股份有限公司 | Polyimide resin, photosensitive resin composition containing polyimide resin and photosensitive cured film |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2006056944A (en) * | 2004-08-18 | 2006-03-02 | Chisso Corp | Tetracarboxylic dianhydride, polymer using the same as raw material, varnish, aligning film and liquid crystal display element using the polymer |
CN103733274A (en) * | 2011-08-08 | 2014-04-16 | 吉坤日矿日石能源株式会社 | Transparent film, transparent conductive laminate, and touch panel, solar cell and display device, using same |
CN109535171A (en) * | 2018-11-21 | 2019-03-29 | 华侨大学 | Fluoro triptycene tetracarboxylic acid dianhydride compound and preparation method thereof and polyimides and preparation method thereof |
CN109627253A (en) * | 2018-11-21 | 2019-04-16 | 中节能万润股份有限公司 | A kind of dicarboxylic anhydride containing butterfly structure and its synthetic method and polyimides based on dicarboxylic anhydride synthesis |
CN109912618A (en) * | 2019-03-20 | 2019-06-21 | 浙江福斯特新材料研究院有限公司 | Multifunctional organic acid anhydride and low-dielectric-constant hyperbranched polyimide film |
-
2019
- 2019-09-02 CN CN201910822805.7A patent/CN110452251B/en active Active
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2006056944A (en) * | 2004-08-18 | 2006-03-02 | Chisso Corp | Tetracarboxylic dianhydride, polymer using the same as raw material, varnish, aligning film and liquid crystal display element using the polymer |
CN103733274A (en) * | 2011-08-08 | 2014-04-16 | 吉坤日矿日石能源株式会社 | Transparent film, transparent conductive laminate, and touch panel, solar cell and display device, using same |
CN109535171A (en) * | 2018-11-21 | 2019-03-29 | 华侨大学 | Fluoro triptycene tetracarboxylic acid dianhydride compound and preparation method thereof and polyimides and preparation method thereof |
CN109627253A (en) * | 2018-11-21 | 2019-04-16 | 中节能万润股份有限公司 | A kind of dicarboxylic anhydride containing butterfly structure and its synthetic method and polyimides based on dicarboxylic anhydride synthesis |
CN109912618A (en) * | 2019-03-20 | 2019-06-21 | 浙江福斯特新材料研究院有限公司 | Multifunctional organic acid anhydride and low-dielectric-constant hyperbranched polyimide film |
Non-Patent Citations (3)
Title |
---|
张玲等: "可溶性透明聚酰亚胺薄膜的合成及性能研究", 《绝缘材料》 * |
潘霄等: "2 , 6 -双(4-氨基苯氧基)苯甲腈的合成及其聚酰亚胺薄膜", 《绝缘材料》 * |
赵世图等: "2,5-双(2-三氟甲基-4-氨基苯氧基)甲苯及其聚酰亚胺薄膜的合成与性能研究", 《绝缘材料》 * |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN116970276A (en) * | 2023-09-25 | 2023-10-31 | 北京八亿时空液晶科技股份有限公司 | Polyimide resin, photosensitive resin composition containing polyimide resin and photosensitive cured film |
CN116970276B (en) * | 2023-09-25 | 2024-01-09 | 上海八亿时空先进材料有限公司 | Polyimide resin, photosensitive resin composition containing polyimide resin and photosensitive cured film |
Also Published As
Publication number | Publication date |
---|---|
CN110452251B (en) | 2021-04-20 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP6077550B2 (en) | Polyimide and alicyclic tetracarboxylic dianhydride used in the production thereof | |
EP1810963B1 (en) | Fluorine-containing polymerizable monomer and polymer compound using same | |
US20130079490A1 (en) | NORBORNANE-2-SPIRO-alpha-CYCLOALKANONE-alpha'-SPIRO-2''-NORBORNANE-5,5'',6,6''-TETRACARBOXYLIC DIANHYDRIDE, NORBORNANE-2-SPIRO-alpha-CYCLOALKANONE-alpha'-SPIRO-2''-NORBORNANE-5,5'',6,6''-TETRACARBOXYLIC ACID AND ESTER THEREOF, METHOD FOR PRODUCING NORBORNANE-2-SPIRO-alpha-CYCLOALKANONE-alpha'-SPIRO-2''-NORBORNANE-5,5'',6,6''-TETRACARBOXYLIC DIANHYDRIDE, POLYIMIDE OBTAINED BY USING THE SAME, AND METHOD FOR PRODUCING POLYIMIDE | |
JP2014517820A (en) | Stannyl derivatives of naphthalene diimide and related compositions and methods | |
TW201718459A (en) | Tetracarboxylic dianhydride, carbonyl compound, polyamic acid and polyimide and methods respectively for producing these compounds, solution prepared using polyamic acid, and film produced using polyimide | |
CN108530304B (en) | Aromatic diamine and polyimide containing tolyl and non-coplanar structure and preparation method thereof | |
JP6635506B2 (en) | Diamine having fluorene skeleton, polyamic acid, and polyimide | |
JP7173204B2 (en) | Polyimide precursors, polyimides, polyimide films and substrates, and tetracarboxylic dianhydrides used in the production of polyimides | |
CN108383733A (en) | Diamine monomer containing tertiary butyl and cycloaliphatic ring and its preparation and application | |
CN106046376B (en) | The B of the B ' containing tert-butyl2Type Triamine monomer and its super-branched polyimide and preparation method | |
CN104557472A (en) | Adamantane derivative, preparation method and application in epoxy resin | |
CN110452251A (en) | A kind of anhydride compounds and the preparation method and application thereof | |
CN111961061B (en) | Dianhydride compound and preparation method and application thereof | |
WO1994025505A1 (en) | Perfluorocyclobutane ring-containing polyimides | |
JP6806089B2 (en) | Diamine and its use | |
CN112979582A (en) | Preparation method of diamine containing phenothiazine structure and synthetic polyimide | |
CN110511229A (en) | A kind of anhydride compounds and the preparation method and application thereof | |
JP2003096070A (en) | Alicyclic tetracarboxylic acid dianhydride and method for producing the same and polyimide | |
CN111116538A (en) | Diamine with antibacterial effect and preparation method thereof | |
JP7415218B2 (en) | Tetracarboxylic dianhydride, polyamic acid, polyimide and polyimide solution | |
JP2015155385A (en) | Tetracarboxylic acid dianhydride, polyamic acid and polyimide having fluorene skeleton | |
WO2023203897A1 (en) | Novel diamine, method for producing same, and polyamic acid and polyimide produced from said diamine | |
CN109627253A (en) | A kind of dicarboxylic anhydride containing butterfly structure and its synthetic method and polyimides based on dicarboxylic anhydride synthesis | |
CN114853615B (en) | Diamine monomer, polyimide film, and preparation methods and applications thereof | |
CN101560166A (en) | Method for preparing 1,3-di(2-trifluoromethyl-4-aminophenoxy) benzene |
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 | ||
TR01 | Transfer of patent right |
Effective date of registration: 20210722 Address after: 201203 Room 101 (duplex) and Room 102 (duplex) of building 50, No. 1387, Zhangdong Road, China (Shanghai) pilot Free Trade Zone, Pudong New Area, Shanghai Patentee after: Shanghai 800 million spacetime Advanced Material Co.,Ltd. Address before: 102488 Room 101, 1-5 / F, building 4, yard 20, dongliushui Road, Yanshan, Fangshan District, Beijing Patentee before: BEIJING BAYI SPACE LCD TECHNOLOGY Co.,Ltd. |
|
TR01 | Transfer of patent right |