CN109251316A - A kind of synthesis preparation method of polybenzimidazole resin - Google Patents
A kind of synthesis preparation method of polybenzimidazole resin Download PDFInfo
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- CN109251316A CN109251316A CN201810928812.0A CN201810928812A CN109251316A CN 109251316 A CN109251316 A CN 109251316A CN 201810928812 A CN201810928812 A CN 201810928812A CN 109251316 A CN109251316 A CN 109251316A
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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
- C08G73/18—Polybenzimidazoles
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Abstract
The present invention provides a kind of synthesis preparation methods of polybenzimidazole resin, the following steps are included: step 1: PPA 300ml, 3 being added in dry four-hole bottle, 3 ', 4,4 '-tetramino diphenyl ether 46g, 1,4 naphthalenedicarboxylic acids or 2,6-naphthalenedicarboxylic acid 43g, crosslinking agent 2,6- pyridinedicarboxylic acid 33g；Step 2: being passed through nitrogen into the four-hole bottle of step 1, be then slowly heated, and is warming up to certain temperature and keeps the temperature a period of time；Step 3: then being heated again, is warming up to certain temperature and is kept the temperature a period of time；Step 4: and then the reaction solution for obtaining step 3 pours into deionized water, red brown solid is precipitated in stirring；Step 5: the red brown solid that step 4 is obtained filters, then with sodium bicarbonate aqueous solution soaking certain time, is then washed with deionized water out, is finally dried, polybenzimidazole resin can be obtained.
Description
Technical field
The present invention relates to new material technology field more particularly to a kind of synthesis preparation methods of polybenzimidazole resin.
Background technique
With the development of space technology, the especially raising of spacecraft flight speed and payload and architecture quality ratio,
High temperature resistant advanced composite material is becoming most important space structure new material.Polybenzimidazoles (PBI) still has at 400 DEG C
Good mechanics, electricity, self-lubricating, radiation hardness, hydrolysis and the fire-retardant resistance to characteristics such as burn.Polybenzimidazoles (PBI) resin glass
Glass fiber pressurized layer material has good high temperature bend strength at 425 DEG C, now has been supplied in the radar antenna of supersonic vehicle
Cover, resistance to burns coating, the radiation hardness material of space ship, printed wiring board, C grades of electrically insulating materials and micro- at radome fairing and empennage
Electronic field FPC substrate and semiconductor interlayer dielectic.Cruise is led in the 21st century, the United States, Russia, day, the plan of Fa Deng state
The flying speed of bullet is increased to 2000m/s or more, and polybenzimidazole material resistant to high temperature will have wider development prospect, will
It can be more widely used in space flight, aviation, microelectronic field.
A variety of tetra-amino compounds, such as tetra-amino-biphenyl and tetra-amino-biphenyl ether chemical combination usually can be used in polybenzimidazoles
Object is made with terephthalic acid (TPA), toluene dioctyl phthalate, naphthalene diacid and its derivative polycondensation.Different unit structures can cause performance
On some variations, such as fragrant increasing for phenyl ring can improve its thermal stability, and processing performance declines；Main chain introduces ether, side
Chain, which introduces methyl, will increase its soluble and flexibility, but reduce heat resistance, it is therefore desirable to according to the difference of polymer material
Purposes selects suitable chemical structure.
Such as Chinese patent CN201210069763.2 discloses a kind of polybenzimidazole high temperature resistant material and its preparation side
Method: by aliphatic dicarboxylic acid acid anhydride or aromatic dicarboxylic or polybasic acid anhydride, aromatic series tetra-amino compound and phosphorus-containing catalyst
It is added according to molar ratio 1:0.5-3:0.001-0.05 into reaction vessel, it is lasting to stir, vacuumize the vacuum for making reaction vessel
Degree is maintained at 0.2-5.0KPa, then heats to 210-270 DEG C, raw material reacts, and after block product to appear, is warming up to
320-520 DEG C, continues to vacuumize the vacuum degree for making reaction vessel and be maintained at 0.2-5.0KPa and react 1-6 hours, finally to reaction
Distilled water is added in container is totally submerged product, smashs reaction products therefrom to pieces, is impregnated with sodium bicarbonate solution, is washed to
Property, it is drying to obtain after filtering.The technical solution replaces binary acid and corresponding ester using with binary or polybasic acid anhydride, but
Reaction process temperature is higher, and needs to keep high pressure conditions, is unfavorable for industrialized production.
In another example patent CN201480040106.2 discloses a kind of preparation method of polybenzimidazoles: making to have in the solution
There is the organic compound of at least two amino group to react with organic aldehyde adducts, reactant accounts at least based on the weight of solution
8%.The solvent of solution can be selected from: DMAC N,N' dimethyl acetamide (DMAc), N,N-dimethylformamide (DMF), dimethyl sulfoxide
(DMSO), n-methyl-2-pyrrolidone (NMP), tetramethylene sulfone and their combination.Organic aldehyde adducts can be organic
Aldehyde bisulfite adduct.The organic aldehyde part of organic aldehyde adducts is aliphatic, alicyclic, aromatics, heterocycle or heteroaromatic aldehyde
Or their mixture.Polybenzimidazoles can have at least inherent viscosity of 0.40dl/g.Reaction solution used in the technical solution is dense
It spends lower, be easy to cause waste of raw materials, be unfavorable for industrialized production.
Summary of the invention
To overcome the problems, such as that reaction existing in the prior art needs high temperature and pressure, unsuitable industrialized production, the present invention
Provide a kind of synthesis preparation method of polybenzimidazole resin.
Above-mentioned purpose that the invention is realized by the following technical scheme: a kind of synthesis preparation method of polybenzimidazole resin,
The following steps are included:
Step 1: being added polyphosphoric acids 300ml, 3,3 ', 4,4 '-tetramino diphenyl ether 46g, 1 in dry four-hole bottle,
4 naphthalenedicarboxylic acids or 2,6- naphthalenedicarboxylic acid 43g, crosslinking agent 2,6- pyridinedicarboxylic acid 33g；
Step 2: being passed through nitrogen into the four-hole bottle of step 1, be then slowly heated, and is warming up to certain temperature and protects
Warm a period of time；
Step 3: then being heated again, is warming up to certain temperature and is kept the temperature a period of time；
Step 4: and then the reaction solution for obtaining step 3 pours into deionized water, red brown solid is precipitated in stirring；
Step 5: the red brown solid that step 4 is obtained filters, then with sodium bicarbonate aqueous solution soaking certain time,
Then it is washed with deionized water out, is finally dried, polybenzimidazole resin can be obtained.
On this basis, in the step 13,3 ', 4,4 '-tetramino diphenyl ether synthetic method the following steps are included:
Step 1: 4,4 '-diaminodiphenyl ether 100g are added in 2L four-hole boiling flask, glacial acetic acid 600g is heated to reflux 8-10
Hour, raw material fully reacting is tracked using thin-layer chromatography, without processing, direct cools to 50 DEG C hereinafter, being added dropwise in the system
Nitric acid 100g is added dropwise and continues heat preservation 2 hours, then pours into this reaction solution in 2000ml water, and solid is precipitated, and washes, and dries
Do to obtain solid 140g.
Step 2: 2L four-hole bottle is added in the solid that the first step is obtained, water 100g, hydrochloric acid 30ml, ethyl alcohol 600ml together
In be heated to reflux to raw material fully reacting, reduced iron powder 250g is then added portionwise again, the reaction was continued 5 hours, heat filtering, filter cake
Primary, merging filtrate is rinsed with 300ml hot ethanol, after decompression removes ethyl alcohol, raffinate is added in 100ml water, and stirring is precipitated reddish brown
Color solid 80g i.e. 3,3 ', 4,4 '-tetramino diphenyl ether.
On this basis, 3,3 ', 4,4 '-tetramino diphenyl ether, Isosorbide-5-Nitrae naphthalenedicarboxylic acid or 2 in the step 1,6- naphthalene diformazan
Sour, 2,6- pyridinedicarboxylic acid molal weight is 0.2mol.
On this basis, warming temperature is 180-220 DEG C in the step 2, and soaking time is 3 hours.
On this basis, warming temperature is 260-280 DEG C in the step 3, and soaking time is at least 10 hours.
On this basis, small aqueous soda solution concentration is 10% in the step 5, and soaking time is at least 12 hours.
On this basis, the molal weight of 4,4 '-diaminodiphenyl ethers is 0.5mol in the first step, and glacial acetic acid rubs
Your quality is 10mol, concentration of nitric acid 65%, molal weight 1.5mol.
On this basis, solvent is ethyl acetate and n-hexane in the first step.
On this basis, the ratio of the ethyl acetate and n-hexane is 5:1.
On this basis, concentration of hydrochloric acid is 30% in the second step, concentration of alcohol 95%.
Compared with prior art, the beneficial effects of the present invention are: the method for the binary copolymerization of abandoning tradition of the present invention, uses
The method of ternary polymerization prepares polybenzimidazole resin, the degree of polymerization and molecular weight of polybenzimidazole resin is increased, due to drawing
Pyridyl group is entered, the rigidity of molecule is weakened, improves the machinability of polybenzimidazole resin, mention for subsequent machining operations
Convenience has been supplied, while polybenzimidazole resin is prepared in dimethyl sulfoxide high temperature slightly soluble using the method for ternary polymerization, has also been made
This product has the prospect for preparing industrial coating, high-temperaure coating.
Specific embodiment
With reference to embodiments, the present invention will be described in further detail.It should be appreciated that specific reality described herein
Example is applied only to explain the present invention, is not intended to limit the present invention.
The present invention schematically illustrates a kind of synthesis preparation method of polybenzimidazole resin.
Embodiment 1
4, the 4 '-diaminodiphenyl ether 100g that molal weight is 0.5mol are added in 2L four-hole boiling flask, molal weight is
The glacial acetic acid 600g of 10mol is heated to reflux 8-10 hours, tracks raw material fully reacting, solvent used using thin-layer chromatography
And proportion are as follows: ethyl acetate: n-hexane=5:1 direct cools to 50 DEG C hereinafter, concentration is added dropwise in the system without processing
The nitric acid 100g for being 1.5mol for 65%, molal weight is added dropwise and continues heat preservation 2 hours, then pours into this reaction solution
In 2000ml water, solid is precipitated, solid 140g is dried to obtain in washing.
Then the solid that will be obtained, water 100g, the hydrochloric acid 30ml that concentration is 30%, the ethyl alcohol 600ml that concentration is 95%, one
It rises to be added in 2L four-hole bottle and be heated to reflux to raw material fully reacting, reduced iron powder 250g is then added portionwise again, it is 5 small that the reaction was continued
When, heat filtering, filter cake rinses primary, merging filtrate with 300ml hot ethanol, and after decompression removes ethyl alcohol, 100ml water is added in raffinate
In, brown-red solid 80g i.e. 3,3 ', 4,4 '-tetramino diphenyl ether are precipitated in stirring.
Polyphosphoric acids 300ml, 3,3 ', 4,4 '-tetramino diphenyl ether 46g, 1,4 naphthalene diformazans are added in dry four-hole bottle
Sour 43g, crosslinking agent 2,6- pyridinedicarboxylic acid 33g, the above raw material molal weight is 0.2mol；Nitrogen is passed through into four-hole bottle
Then gas is slowly heated, be warming up to 180-220 DEG C and keep the temperature 3 hours；It is then heated again, is warming up to 260-280
DEG C and keep the temperature 10 hours or more；Then obtained reaction solution is poured into deionized water, red brown solid is precipitated in stirring；It will obtain
Red brown solid filtered, then with sodium bicarbonate aqueous solution soaking 12 hours or more of 10%, be then washed with deionized water out,
It is finally dried, ternary polybenzimidazole resin can be obtained.
Embodiment 2
4, the 4 '-diaminodiphenyl ether 100g that molal weight is 0.5mol are added in 2L four-hole boiling flask, molal weight is
The glacial acetic acid 600g of 10mol is heated to reflux 8-10 hours, tracks raw material fully reacting, solvent used using thin-layer chromatography
And proportion are as follows: ethyl acetate: n-hexane=5:1 direct cools to 50 DEG C hereinafter, concentration is added dropwise in the system without processing
The nitric acid 100g for being 1.5mol for 65%, molal weight is added dropwise and continues heat preservation 2 hours, then pours into this reaction solution
In 2000ml water, solid is precipitated, solid 140g is dried to obtain in washing.
Then the solid that will be obtained, water 100g, the hydrochloric acid 30ml that concentration is 30%, the ethyl alcohol 600ml that concentration is 95%, one
It rises to be added in 2L four-hole bottle and be heated to reflux to raw material fully reacting, reduced iron powder 250g is then added portionwise again, it is 5 small that the reaction was continued
When, heat filtering, filter cake rinses primary, merging filtrate with 300ml hot ethanol, and after decompression removes ethyl alcohol, 100ml water is added in raffinate
In, brown-red solid 80g i.e. 3,3 ', 4,4 '-tetramino diphenyl ether are precipitated in stirring.
Polyphosphoric acids 300ml, 3,3 ', 4,4 '-tetramino diphenyl ether 46g, 2,6- naphthalenes two are added in dry four-hole bottle
Formic acid 43g, crosslinking agent 2,6- pyridinedicarboxylic acid 33g, the above raw material molal weight is 0.2mol；Nitrogen is passed through into four-hole bottle
Then gas is slowly heated, be warming up to 180-220 DEG C and keep the temperature 3 hours；It is then heated again, is warming up to 260-280
DEG C and keep the temperature 10 hours or more；Then obtained reaction solution is poured into deionized water, red brown solid is precipitated in stirring；It will obtain
Red brown solid filtered, then with sodium bicarbonate aqueous solution soaking 12 hours or more of 10%, be then washed with deionized water out,
It is finally dried, ternary polybenzimidazole resin can be obtained.
The method of the binary copolymerization of abandoning tradition of the present invention prepares polybenzimidazole resin using the method for ternary polymerization,
The degree of polymerization and molecular weight for increasing polybenzimidazole resin, due to introducing pyridyl group, the rigidity of molecule is weakened, and is promoted
The machinability of polybenzimidazole resin, provides convenience for subsequent machining operations, while using the method system of ternary polymerization
Standby polybenzimidazole resin also has this product and prepares industrial coating, high-temperaure coating in dimethyl sulfoxide high temperature slightly soluble
Prospect.
The preferred embodiment of the present invention has shown and described in above description, as previously described, it should be understood that the present invention is not office
Be limited to form disclosed herein, should not be regarded as an exclusion of other examples, and can be used for various other combinations, modification and
Environment, and can be changed within that scope of the inventive concept describe herein by the above teachings or related fields of technology or knowledge
It is dynamic.And changes and modifications made by those skilled in the art do not depart from the spirit and scope of the present invention, then it all should be appended by the present invention
In scope of protection of the claims.
Claims (10)
1. a kind of synthesis preparation method of polybenzimidazole resin, which comprises the following steps:
Step 1: polyphosphoric acids 300ml, 3,3 ', 4,4 '-tetramino diphenyl ether 46g, 1,4 naphthalenes are added in dry four-hole bottle
Dioctyl phthalate or 2,6- naphthalenedicarboxylic acid 43g, crosslinking agent 2,6- pyridinedicarboxylic acid 33g；
Step 2: being passed through nitrogen into the four-hole bottle of step 1, be then slowly heated, and is warming up to certain temperature and keeps the temperature one
The section time；
Step 3: then being heated again, is warming up to certain temperature and is kept the temperature a period of time；
Step 4: and then the reaction solution for obtaining step 3 pours into deionized water, red brown solid is precipitated in stirring；
Step 5: the red brown solid that step 4 is obtained filters, then with sodium bicarbonate aqueous solution soaking certain time, then
It is washed with deionized water out, is finally dried, polybenzimidazole resin can be obtained.
2. a kind of synthesis preparation method of polybenzimidazole resin according to claim 1, it is characterised in that: the step
In one 3,3 ', 4,4 '-tetramino diphenyl ether synthetic method the following steps are included:
Step 1: 4,4 '-diaminodiphenyl ether 100g, glacial acetic acid 600g are added in 2L four-hole boiling flask, it is heated to reflux 8-10 hours,
Raw material fully reacting is tracked using thin-layer chromatography, without processing, direct cools to 50 DEG C hereinafter, nitric acid is added dropwise in the system
100g is added dropwise and continues heat preservation 2 hours, then pours into this reaction solution in 2000ml water, and solid is precipitated, and washing is dried
Solid 140g.
Step 2: the solid that the first step is obtained, water 100g, hydrochloric acid 30ml, ethyl alcohol 600ml are added in 2L four-hole bottle add together
Heat is back to raw material fully reacting, and reduced iron powder 250g is then added portionwise again, and the reaction was continued 5 hours, heat filtering, and filter cake is used
300ml hot ethanol rinses primary, merging filtrate, and after decompression removes ethyl alcohol, raffinate is added in 100ml water, and brownish red is precipitated in stirring
Solid 80g i.e. 3,3 ', 4,4 '-tetramino diphenyl ether.
3. a kind of synthesis preparation method of polybenzimidazole resin according to claim 1, it is characterised in that: the step
The molal weight of 3,3 ', 4,4 '-tetramino diphenyl ether, 1,4 naphthalenedicarboxylic acids or 2,6- naphthalenedicarboxylic acid, 2,6- pyridinedicarboxylic acid in one
It is 0.2mol.
4. a kind of synthesis preparation method of polybenzimidazole resin according to claim 1, it is characterised in that: the step
Warming temperature is 180-220 DEG C in two, and soaking time is 3 hours.
5. a kind of synthesis preparation method of polybenzimidazole resin according to claim 1, it is characterised in that: the step
Warming temperature is 260-280 DEG C in three, and soaking time is at least 10 hours.
6. a kind of synthesis preparation method of polybenzimidazole resin according to claim 1, it is characterised in that: the step
Five medium and small aqueous soda solution concentration are 10%, and soaking time is at least 12 hours.
7. a kind of synthesis preparation method of polybenzimidazole resin according to claim 2, it is characterised in that: described first
The molal weight of 4,4 '-diaminodiphenyl ethers is 0.5mol in step, and the molal weight of glacial acetic acid is 10mol, and concentration of nitric acid is
65%, molal weight 1.5mol.
8. a kind of synthesis preparation method of polybenzimidazole resin according to claim 2, it is characterised in that: described first
Use thin-layer chromatography tracking raw material reaction using solvent for ethyl acetate and n-hexane in step.
9. a kind of synthesis preparation method of polybenzimidazole resin according to claim 8, it is characterised in that: the acetic acid
The ratio of ethyl ester and n-hexane is 5:1.
10. a kind of synthesis preparation method of polybenzimidazole resin according to claim 2, it is characterised in that: described
Concentration of hydrochloric acid is 30% in two steps, concentration of alcohol 95%.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101392060A (en) * | 2008-10-21 | 2009-03-25 | 东华大学 | Quaternized polybenzimidazoles and preparation method thereof |
| CN101805448A (en) * | 2010-04-21 | 2010-08-18 | 上海交通大学 | Polybenzimidazole containing phenylsulfonyl side groups and preparation method thereof |
| CN102643426A (en) * | 2012-05-11 | 2012-08-22 | 北京化工大学 | Preparation method of novel polybenzimidazole resin |
| US20140004432A1 (en) * | 2012-05-08 | 2014-01-02 | Basf Se | Membrane electrode assemblies and fuel cells with long lifetime |
| KR20170012974A (en) * | 2015-07-27 | 2017-02-06 | 한국과학기술연구원 | Novel method for preparation of polybenzimidazole under mild condition |
-
2018
- 2018-08-15 CN CN201810928812.0A patent/CN109251316B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101392060A (en) * | 2008-10-21 | 2009-03-25 | 东华大学 | Quaternized polybenzimidazoles and preparation method thereof |
| CN101805448A (en) * | 2010-04-21 | 2010-08-18 | 上海交通大学 | Polybenzimidazole containing phenylsulfonyl side groups and preparation method thereof |
| US20140004432A1 (en) * | 2012-05-08 | 2014-01-02 | Basf Se | Membrane electrode assemblies and fuel cells with long lifetime |
| CN102643426A (en) * | 2012-05-11 | 2012-08-22 | 北京化工大学 | Preparation method of novel polybenzimidazole resin |
| KR20170012974A (en) * | 2015-07-27 | 2017-02-06 | 한국과학기술연구원 | Novel method for preparation of polybenzimidazole under mild condition |
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