CN107793566A - A kind of thermoplastic poly benzimidazole acid imide and preparation method thereof - Google Patents
A kind of thermoplastic poly benzimidazole acid imide and preparation method thereof Download PDFInfo
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- CN107793566A CN107793566A CN201711044352.7A CN201711044352A CN107793566A CN 107793566 A CN107793566 A CN 107793566A CN 201711044352 A CN201711044352 A CN 201711044352A CN 107793566 A CN107793566 A CN 107793566A
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- 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
- C08G73/18—Polybenzimidazoles
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- 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
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- 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
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Abstract
The invention provides a kind of thermoplastic poly benzimidazole acid imide and preparation method thereof, structural formula is as follows, m be 1~1000 integer, n be 0~1000 integer, Ar1It is the residue of diamine compounds, Ar2It is the residue of two compound anhydrides, the thermoplastic poly benzimidazole acid imide is prepared by the way of benzimidazole diamine and the ether dianhydride homopolymerization of triphen two or the dianhydride common with other and diamines through polycondensation reaction.Polybenzimidazoles acid imide material provided by the invention combines the ether dianhydride construction unit of triphen two of the stronger benzimidazole unit of rigidity and relative flexibility, and with the carbonylic oxygen atom in imide group interaction of hydrogen bond can occur for the hydrogen atom in imidazole group, increase intermolecular interaction, therefore higher glass transition temperature (Tg) and the characteristic being easily worked are had concurrently, have the characteristics that good mechanical property, heat resistance are high, processability is good, be adapted to injection, extrusion, molding, dissolving film, melt spinning and solution-polymerized SBR processing.
Description
Technical field
The invention belongs to polyimides and the preparation method technical field of correlation, and in particular to a kind of thermoplastic poly benzo miaow
Azoles acid imide and preparation method thereof.
Background technology
Polyimides is the resin material of a kind of excellent combination property, has good heat endurance, excellent mechanicalness
Energy, preferable dimensional stability, excellent chemical stability, high-breakdown-voltage, low-k, high flame retardant, low bulk system
The advantages that number, it is widely used in the high-tech areas such as electronic apparatus, Aero-Space, automobile, chemical machinery.It is but most of
Polyimide resin makes it difficult to be melted or dissolves processing because molecule chain rigidity is stronger, by introducing flexible ehter bond
The polyimide resin that can be easily worked, such as the Ultem resins that GE companies of the U.S. develop, its Tg is 217 DEG C, by Japan
The crystalline thermoplastic polyimide Aurum of Mitsui's exploitation, its Tg are 250 DEG C, and still, excessive introducing flexible group is again
It can decline its glass transition temperature (Tg) more, it is difficult to find the polyimide resin for not only meeting high Tg but also being easily worked.
Polybenzimidazoles is the high performance engineering plastics of a kind of excellent combination property, especially its heat resistance and mechanical performance
It is prominent, it is widely used in the fields such as Aero-Space, electronic apparatus, fuel battery proton exchange film, existing oneself turns into national economy, point
The important materials of end technology and new high-tech industry.
With the development of Electronic Packaging field greenization, the heat resistance of the matrix resin used at present in package substrate by
Great challenge.The peak temperature of Reflow Soldering reaches 260 DEG C in packaging technology, and thermoplastic is in more than Tg, and it resists shape
The ability of change can decline rapidly so that and the reliability of package substrate is affected, so, it would be highly desirable to exploitation has high Tg (Tg>260
DEG C), the polyimide resin of easy processing.It is sub- that Chinese patent CN103992478A discloses a kind of resistant to elevated temperatures solvable fusible polyamides
Polyimide resin and preparation method thereof, it is by equimolar Bisphenol A Type Diether Dianhydride and 2- (4- aminophenyls) -5- amino benzo miaows
Prepared by azoles, the glass transition temperature of the polyimide resin can reach more than 300 DEG C, still, in Bisphenol A Type Diether Dianhydride
The presence of isopropyl group, it is very easy to decompose in the process of resin, has a strong impact on the performance of final products.
The content of the invention
The purpose of the present invention is to be directed to the above-mentioned existing state of the art, there is provided a kind of high Tg (Tg>260 DEG C), easy processing
Thermoplastic poly benzimidazole acid imide, the polybenzimidazoles acid imide material is with reference to the stronger imidazole structure unit of rigidity and relatively
The flexible ether dianhydride construction unit of triphen two, have the characteristic of high glass-transition temperature (Tg) and easy processing concurrently, and with very
High heat decomposition temperature.
Technical scheme is used by the present invention realizes above-mentioned technical purpose：A kind of thermoplastic poly benzimidazole acid imide,
Its structural formula is：
Wherein, Ar1The residue of diamine compounds, Ar2 is the residue of two compound anhydrides, m be 1~1000 it is whole
Number, n are 0~1000 integer.
When n is 0, the imido structural formula of polybenzimidazoles is as follows：
M is 1~1000 integer, and n is 0~1000 integer；The oxygen atom of the ether dianhydride part of triphen two is deposited in strand
It is that 3- positions or 4- positions, the concrete structure of phenyl ring are as follows：
Described Ar1It can be one kind in following groups：
Preferably, Ar1It can be one of following group：
Described Ar2It can be one kind in following groups：
Preferably, Ar2It can be one of following group：
When concentration of the polybenzimidazoles acid imide provided by the invention in 1-METHYLPYRROLIDONE is 0.5g/dL, pass through
Ubbelohde viscometer determines its logarithmic viscosity number at 30 DEG C between 0.2dL/g~1.5dL/g；Preferably 0.3dL/g~
1.2dL/g, more preferably 0.4~0.8dL/g.By differential scanning calorimetry determine its glass transition temperature for 260 DEG C~
400℃；Preferably 270 DEG C~380 DEG C, more preferably 280 DEG C~350 DEG C.Its 5% thermal decomposition is determined by thermal gravimetric analyzer
Temperature is 400 DEG C~600 DEG C；Preferably 420 DEG C~570 DEG C, more preferably 450 DEG C~560 DEG C.Determined by melting means instrument molten
It is 0.1~80g/10min, preferably 1~50g/10min, more preferably 2~30g/10min to melt index.
Present invention also offers the preparation method of two kinds of above-mentioned polybenzimidazoles imide resin materials, the preparation method
Can be one of following two methods：
Method one：In reaction vessel, under inert gas shielding, dianhydride monomer, diamine monomer, organic solvent are added, is filled
Divide and mix, under base catalyst existence condition, polycondensation reaction occurs for heating, then cools down reaction product, pours into precipitating reagent
In, filtering, fully wash, dry after collecting precipitation, polybenzimidazoles acid imide is made.
Method two：In the reactor, diamine monomer is added in the polar non-solute of inert gas shielding, stirred
It is set to add dianhydride monomer and polar non-solute after being completely dissolved, at room temperature stirring reaction 3 hours~48 hours (preferably 15
~25 hours), obtain polyamic acid solution；The mixed solution of acetic anhydride and organic base is added into this polyamic acid solution again,
The organic base is pyridine or triethylamine, and stirring reaction 2 hours~24 hours (preferably 10~20 hours), carry out chemistry at room temperature
Imidization, polyimide solution is obtained, the polyimide solution is poured into precipitating reagent and separated out, fully washed after collecting precipitation
Wash, dry, polybenzimidazoles acid imide is made.
In methods described one and method two, the diamine monomer is 2- (4- aminophenyls) -5- aminobenzimidazole monomers
Or 2- (4- aminophenyls) -5- aminobenzimidazoles monomers and a kind of mixing in compound shown in following formula A.
H2N-Ar1-NH2
A
In formula A, Ar1It is as defined above.
Further, the structural formula of compound is as follows shown in formula A：
The dianhydride monomer is a kind of in compound shown in the ether dianhydride of triphen two or the ether dianhydride of triphen two and following formula B
Mixing.
The ether dianhydride of triphen two is the ether dianhydride of 3,3 '-triphen two, the ether dianhydride of 3,4 '-triphen two or 4,4 '-triphen diether
Dianhydride, concrete structure formula are as follows：
The formula of compound is as follows shown in formula B：
In formula B, Ar2It is as defined above.
Further, the structural formula of compound is for example one of following shown in formula B：
In methods described one and method two, the diamine monomer is 2- (4- aminophenyls) -5- aminobenzimidazole monomers,
When the dianhydride monomer is two ether dianhydride of triphen, that is, the polybenzimidazoles acid imide of n=0 in formula is prepared.
The diamine monomer is in compound shown in 2- (4- aminophenyls) -5- aminobenzimidazoles monomers and following formula A
A kind of mixing, when dianhydride monomer is two ether dianhydride of triphen, be made formula in n ＞ 0 polybenzimidazoles acid imide；Or two
Amine monomers are 2- (4- aminophenyls) -5- aminobenzimidazole monomers, and dianhydride monomer is shown in the ether dianhydride of triphen two and following formula B
During a kind of mixing in compound, the polybenzimidazoles acid imide of n ＞ 0 in formula is made.
In methods described one or method two, the diamine monomer, the ratio between the amount of material of dianhydride monomer are 1：0.9~1.1,
It is preferred that 1：0.9~1.
In methods described one, described organic solvent can be DMF, DMA, ring
Fourth sulfone, metacresol, methyl sulfoxide, 1-METHYLPYRROLIDONE or diphenyl sulphone (DPS) etc., preferably metacresol.
The volumetric usage of the organic solvent is typically calculated as 3~10mL/mmol with the amount of the material of diamine monomer.
And water entrainer can be added in the reaction system of method one, described water entrainer can be toluene, chlorobenzene, diformazan
Benzene or dichloro-benzenes etc..
In methods described one, described base catalyst may be selected from but be not limited to carbonate, bicarbonate, hydroxide
The alkali compounds, preferably isoquinolin such as thing, organic base, the alkali metal salt of alcohol, metal hydride, pyridine, isoquinolin, triethylamine.
In methods described one, the dosage of the base catalyst is generally the 10-150% of the amount of the material of diamine monomer.
In methods described one, described precipitating reagent may be selected from but be not limited to ethanol, acetone, deionized water etc..
In methods described one, described polycondensation reaction is carried out in nitrogen or other inert gas shielding atmosphere；
In course of reaction, temperature of reaction system is between 130 DEG C~250 DEG C.
End-capping reagent can be added after the completion of described polycondensation reaction to be blocked, described end-capping reagent is phthalic acid
Acid anhydride, its structural formula are：
The ratio between the amount dosage of the material of the end-capping reagent and the amount of material of diamine monomer are generally 0.05~0.5:1, it is excellent
Select 0.1~0.3:1
Further, the course of reaction of preferably methods described one is, in reaction vessel, add dianhydride monomer, diamine monomer,
Organic solvent, fully mix, under base catalyst existence condition, be heated to 130~150 DEG C (preferably 130~140 DEG C) reaction
1~5 hour, then it is warming up to 150~250 DEG C (preferably 180~200 DEG C) 8~10 hours, then cools down 100~120 DEG C, add
Enter end-capping reagent, continue reaction 1~3 hour, be cooled to room temperature, pour into precipitating reagent, filter, fully washed after collecting precipitation, done
It is dry, be made in polybenzimidazoles imide resin methods described two, the polar non-solute be DMA,
1-METHYLPYRROLIDONE, N,N-dimethylformamide or dimethyl sulfoxide (DMSO) etc..
Total volumetric usage of the polar non-solute is typically calculated as 1~5mL/ with the amount of the material of diamine monomer
Mmol, typically add in two steps, a part is used to dissolve diamine monomer, and a part and dianhydride monomer add reaction system together.
In methods described two, in the mixed solution of the acetic anhydride and organic base, the volume ratio of acetic anhydride and organic base is
1.5~5:1, preferably 2~3:1.
In methods described two, the volumetric usage of the mixed solution of the acetic anhydride and organic base is typically with the thing of diamine monomer
The amount of matter is calculated as 0.3~0.8mL/mmol
In summary, the present invention combines the triphen diether of the stronger benzimidazole unit of rigidity and relative flexibility
Dianhydride construction unit, and the hydrogen atom in imidazole group can be mutual with the carbonylic oxygen atom generation hydrogen bond in imide group
Effect, increase intermolecular interaction, be prepared for a kind of thermoplastic poly benzimidazole imide resin material, have high glass concurrently
Change the characteristic of transition temperature (Tg) and easy processing, have the following advantages that：
(1) because the introducing of benzimidazole unit, the benzimidazole polyimide type resin can significantly improve glass
Glass transition temperature, while with preferable fluidity of molten, heat endurance；
(2) molecular weight can be regulated and controled by end-capping reagent, be easy to prepare fibre-grade, injection grade, molding level, coating level etc. no
The imidazole type copolymer polyimide resin of same level；
(3) the polybenzimidazoles imide structure can be able to by common dianhydride, the structure of diamine monomer and ratio
Change, therefore the controllable space of structure is big.
Therefore, polybenzimidazoles imide resin provided by the invention has good mechanical property, heat-resist, processability is good
The features such as, be adapted to injection, extrusion, molding, dissolving film, melt spinning and solution-polymerized SBR processing, resistant to elevated temperatures engineering plastics,
The association areas such as film, fiber, adhesive, coating and advanced composite material, there is good application prospect.
Embodiment
The present invention is described in further detail below in conjunction with specific embodiment, it is necessary to be pointed out that the present embodiment is only used
It is further detailed in the present invention, it is impossible to be interpreted as limiting the scope of the invention.Technology in the field is ripe
Some nonessential modifications and adaptations can be made according to the content of foregoing invention by practicing personnel.
Embodiment 1：
In the present embodiment, polybenzimidazoles acid imide has following structural formula：
The above-mentioned imido preparation method of polybenzimidazoles is as follows：
11.2130g (0.05mol) 2- (4- aminophenyls) -5- aminobenzenes are added in the 500mL there-necked flasks of dried and clean
And imidazoles monomer and 18.9086g (0.047mol) 3,3 '-triphen diether dianhydride monomer, 270mL metacresols, 8 drop isoquinolin,
Under nitrogen protection, 130 DEG C are reacted 1 hour；Then heat to 200 DEG C to react 8 hours, be cooled to 110 DEG C, add 1.3331g
(0.009mol) phthalic anhydride, continue reaction 2 hours, be cooled to room temperature, reaction solution is poured slowly into 2L ethanol and separated out,
Filtering, gained filter cake is boiled with ethanol to be washed 2 times, is placed in 160 DEG C of vacuum drying ovens and is dried 8 hours afterwards, obtains faint yellow polyphenyl simultaneously
Imidazoles acid imide powder 26.78g, yield 94.2%.
The polybenzimidazoles acid imide is subjected to performance test, test result is shown in Table 1.
Comparative example 1：
In this comparative example, polyimides has following structural formula：
The preparation method of above-mentioned polyimides is as follows：
0.05mol 4,4 '-diaminodiphenyl ether monomer and 0.047mol are added in the 500mL there-necked flasks of dried and clean
The equal anhydride monomer of benzene four, 270mL metacresols, 8 drop isoquinolin, under nitrogen protection, 130 DEG C are reacted 1 hour；Then heat to 200
DEG C reaction 8 hours, is cooled to 110 DEG C, adds 0.009mol phthalic anhydrides, continue reaction 2 hours, be cooled to room temperature, will
Reaction solution is poured slowly into 2L ethanol and separated out, and filtering, gained filter cake is boiled with ethanol to be washed 2 times, is placed in afterwards in 160 DEG C of vacuum drying ovens
Dry 8 hours, obtain faint yellow polyimide powder.
The polyimides is subjected to performance test, test result is shown in Table 1.
Comparative example 2：
In this comparative example, polyimides has following structural formula：
The preparation method of above-mentioned polyimides is as follows：
0.05mol 4,4 '-diaminodiphenyl ether monomer and 0.047mol are added in the 500mL there-necked flasks of dried and clean
3,3 '-triphen diether dianhydride monomer, 270mL metacresols, 8 drop isoquinolin, under nitrogen protection, 130 DEG C are reacted 1 hour；Then
It is warming up to 200 DEG C to react 8 hours, is cooled to 110 DEG C, add 0.009mol phthalic anhydrides, continues reaction 2 hours, cooling
To room temperature, reaction solution is poured slowly into 2L ethanol and separated out, filtered, gained filter cake is boiled with ethanol to be washed 2 times, is placed in 160 DEG C afterwards
Dried 8 hours in vacuum drying oven, obtain faint yellow polyimide powder.
The polyimides is subjected to performance test, test result is shown in Table 1.
Embodiment 2：
In the present embodiment, polybenzimidazoles acid imide has following structural formula：
The above-mentioned imido preparation method of polybenzimidazoles is as follows：
10.0917g (0.045mol) 2- (4- aminophenyls) -5- amino is added in the 500mL there-necked flasks of dried and clean
Benzimidazole monomer, 1.0016g (0.005mol) 4,4 '-diaminodiphenyl ether monomer, 19.3109g (0.048mol) 3,3 '-three
Benzene diether dianhydride monomer, 260mL metacresols, 10 drop isoquinolin, under nitrogen protection, 140 DEG C are reacted 1 hour；Then heat to
195 DEG C are reacted 10 hours, are cooled to 120 DEG C, add 1.1850g (0.008mol) phthalic anhydride, continue reaction 2 hours,
Room temperature is cooled to, reaction solution is poured slowly into 1.5L acetone and separated out, is filtered, gained filter cake is boiled with ethanol to be washed 2 times, is placed in afterwards
Dried 4 hours in 160 DEG C of vacuum drying ovens, obtain faint yellow polybenzimidazoles acid imide powder 28.68g, yield 92.3%.
The polybenzimidazoles acid imide is subjected to performance test, test result is shown in Table 1.
Embodiment 3：
In the present embodiment, polybenzimidazoles acid imide has following structural formula：
The above-mentioned imido preparation method of polybenzimidazoles is as follows：
11.2130g (0.05mol) 2- (4- aminophenyls) -5- aminobenzenes are added in the 500mL there-necked flasks of dried and clean
And imidazoles monomer, 10.0578g (0.025mol) 3,3 '-triphen diether dianhydride monomer, 8.4487g (0.021mol) 4,4 '-triphen
Diether dianhydride monomer, 250mL metacresols, 12 drop isoquinolin, under nitrogen protection, 140 DEG C are reacted 3 hours；Then heat to 180
DEG C reaction 10 hours, is cooled to 100 DEG C, adds 1.7774g (0.012mol) phthalic anhydride, continue reaction 3 hours, cooling
To room temperature, reaction solution is poured slowly into 2.0L ethanol and separated out, filtered, gained filter cake is boiled with ethanol to be washed 2 times, is placed in 180 afterwards
Dried 4 hours in DEG C vacuum drying oven, obtain faint yellow polybenzimidazoles acid imide powder 26.49g, yield 93.8%.
The polybenzimidazoles acid imide is subjected to performance test, test result is shown in Table 1.
Embodiment 4：
In the present embodiment, polybenzimidazoles acid imide has following structural formula：
The above-mentioned imido preparation method of polybenzimidazoles is as follows：
11.2130g (0.05mol) 2- (4- aminophenyls) -5- aminobenzenes are added in the 250mL there-necked flasks of dried and clean
And imidazoles monomer, 100mL DMAs, stirring at normal temperature under nitrogen protection, after diamine monomer all dissolving,
Add 18.1044g (0.045mol) 3,3 '-triphen diether dianhydride monomer, 1.5512g (0.005mol) 3,3, ' 4,4 '-diphenyl ether
Tetracarboxylic acid dianhydride monomer, 20mL DMAs, normal-temperature reaction 20 hours, add the mixing of acetic anhydride and triethylamine
Solution 28ml (wherein 20mL acetic anhydrides, 8mL triethylamines), continue normal-temperature reaction 12 hours, by reaction solution be poured slowly into 1L go from
Separate out, filter in sub- water, gained filter cake is boiled with ethanol to be washed 2 times, is placed in 140 DEG C of vacuum drying ovens and is dried 8 hours afterwards, obtains light
Yellow polybenzimidazoles acid imide powder 26.89g, yield 92.5%.
The polybenzimidazoles acid imide is subjected to performance test, test result is shown in Table 1.
Embodiment 5：
In the present embodiment, polybenzimidazoles acid imide has following structural formula：
The above-mentioned imido preparation method of polybenzimidazoles is as follows：
6.7278g (0.03mol) 2- (4- aminophenyls) -5- aminobenzenes are added in the 250mL there-necked flasks of dried and clean
And imidazoles monomer, 3.9652g (0.02mol) 4,4 ,-two amido diphenyl-methane monomers, 90mL DMAs, in nitrogen
Stirring at normal temperature under gas shielded, after diamine monomer all dissolving, add 20.1155g (0.05mol) 3, the ether dianhydride of 3 '-triphen two
Mixed solution 30ml (its of monomer, 40mL DMAs, normal-temperature reaction 18 hours, addition acetic anhydride and triethylamine
Middle 22mL acetic anhydrides, 8mL triethylamines), continue normal-temperature reaction 12 hours, reaction solution is poured slowly into 1.5L ethanol and separated out, mistake
Filter, gained filter cake is boiled with ethanol to be washed 2 times, is placed in 180 DEG C of vacuum drying ovens and is dried 4 hours afterwards, obtains faint yellow polyphenyl and miaow
Azoles acid imide powder 27.15g, yield 93.6%.
The polybenzimidazoles acid imide is subjected to performance test, test result is shown in Table 1.
Embodiment 6：
In the present embodiment, polybenzimidazoles acid imide has following structural formula：
The above-mentioned imido preparation method of polybenzimidazoles is as follows：
6.7278g (0.03mol) 2- (4- aminophenyls) -5- aminobenzenes are added in the 250mL there-necked flasks of dried and clean
And imidazoles monomer, double (3- amino-benzene oxygens) benzene monomers of 5.8466g (0.02mmol) 1,3-, 90mL 1-METHYLPYRROLIDONEs,
The lower stirring at normal temperature of nitrogen protection, after diamine monomer all dissolving, adds 20.1155g (0.05mol) 3,3 '-triphen diether two
The mixed solution 30ml of anhydride monomer, 40mL 1-METHYLPYRROLIDONEs, normal-temperature reaction 18 hours, addition acetic anhydride and pyridine is (wherein
20mL acetic anhydrides, 10mL pyridines), continue normal-temperature reaction 16 hours, reaction solution is poured slowly into 1.5L ethanol and separated out, filter,
Gained filter cake is boiled with ethanol to be washed 2 times, is placed in 180 DEG C of vacuum drying ovens and is dried 4 hours afterwards, obtains faint yellow polybenzimidazoles acyl
Imines powder 28.60g, yield 92.6%.
The polybenzimidazoles acid imide is subjected to performance test, test result is shown in Table 1.
Although the glass transition temperature of comparative example 1 is higher (367 DEG C), there is no processing characteristics (melt index 0), it is right
Although processing characteristics (the melt index of ratio 2>70g/10min), but glass transition temperature is low (245 DEG C).
Table 1
Note：
1. logarithmic viscosity number is to be determined in the 1-METHYLPYRROLIDONE that 30 DEG C of concentration are 0.5g/dL.
2. glass transition temperature is to be determined by differential scanning calorimetry.
3.5% heat decomposition temperature is to be determined by thermal gravimetric analyzer.
4. melt index is determines by melting means instrument, test condition is pressure 12.5Kg, and 380 DEG C of temperature, fusion time 2 divides
Clock.
Claims (10)
1. a kind of thermoplastic poly benzimidazole acid imide, general structure are shown below：
Wherein, Ar1It is the residue of diamine compounds, Ar2It is the residue of two compound anhydrides, m is 1~1000 integer, n 0
~1000 integer；The oxygen atom of the ether dianhydride part of triphen two is present in the 3- positions or 4- positions of phenyl ring in strand.
2. thermoplastic poly benzimidazole acid imide according to claim 1, it is characterised in that：Described Ar1It is following groups
In one kind：
3. thermoplastic poly benzimidazole acid imide according to claim 1, it is characterised in that：Described Ar2It is following groups
In one kind：
4. thermoplastic poly benzimidazole acid imide according to claim 1, it is characterised in that triphen diether two in strand
The oxygen atom of anhydride component be present in phenyl ring 3- positions or 4- positions, concrete structure it is as follows：
5. the thermoplastic poly benzimidazole acid imide according to one of Claims 1 to 4, it is characterised in that：Polybenzimidazoles
When concentration of the acid imide in 1-METHYLPYRROLIDONE is 0.5g/dL, it is determined than dense logarithm at 30 DEG C by Ubbelohde viscometer
Viscosity is between 0.2dL/g~1.5dL/g.
6. the thermoplastic poly benzimidazole acid imide according to one of Claims 1 to 4, it is characterised in that：Swept by differential
Its glass transition temperature of calorimetric determination is retouched as 260 DEG C~400 DEG C；Its 5% thermal decomposition temperature is determined by thermal gravimetric analyzer
Spend for 400 DEG C~600 DEG C.
7. the thermoplastic poly benzimidazole acid imide according to one of Claims 1 to 4, it is characterised in that：Pass through melting means instrument
The melt index of measure is 0.1~80g/10min.
8. the imido preparation method of thermoplastic poly benzimidazole as described in one of Claims 1 to 4, it is characterised in that described
Method is one of following：
Method one：In reaction vessel, under inert gas shielding, dianhydride monomer, diamine monomer, organic solvent are added, it is fully mixed
Even, under base catalyst existence condition, polycondensation reaction occurs for heating, then cools down reaction product, pours into precipitating reagent, mistake
Filter, fully wash, dry after collecting precipitation, polybenzimidazoles acid imide is made；
Method two：In the reactor, diamine monomer is added in the polar non-solute of inert gas shielding, stirring makes it
Dianhydride monomer and polar non-solute are added after being completely dissolved, stirring reaction 3 hours~48 hours, obtain polyamide at room temperature
Acid solution；The mixed solution of acetic anhydride and organic base is added into this polyamic acid solution again, the organic base is pyridine or three
Ethamine, stirring reaction 2 hours~24 hours, carry out chemical imidization reaction, polyimide solution are obtained, by the polyamides at room temperature
Imide liquor is poured into precipitating reagent and separated out, and is fully washed after collecting precipitation, is dried, and polybenzimidazoles acid imide is made.
9. according to the method for claim 8, it is characterised in that：In methods described one and method two, the diamine monomer is
2- (4- aminophenyls) -5- aminobenzimidazoles monomers or 2- (4- aminophenyls) -5- aminobenzimidazoles monomers and following formula A
A kind of mixing in shown compound
H2N-Ar1-NH2
A
In formula A, Ar1It is one kind in following groups：
The dianhydride monomer is the ether dianhydride of triphen two or the ether dianhydride of triphen two and a kind of mixing in compound shown in following formula B
The formula of compound is as follows shown in formula B：
In formula B, Ar2It is one kind in following groups：
10. method according to claim 8 or claim 9, it is characterised in that：In methods described one or method two, the diamines list
Body, the ratio between the amount of material of dianhydride monomer are 1：0.9~1.1.
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