CN103923316A - Carbon nano ring-grafted modified plumbous oxide (PBO) polymer and preparation method thereof - Google Patents
Carbon nano ring-grafted modified plumbous oxide (PBO) polymer and preparation method thereof Download PDFInfo
- Publication number
- CN103923316A CN103923316A CN201410174136.4A CN201410174136A CN103923316A CN 103923316 A CN103923316 A CN 103923316A CN 201410174136 A CN201410174136 A CN 201410174136A CN 103923316 A CN103923316 A CN 103923316A
- Authority
- CN
- China
- Prior art keywords
- carbon nano
- nano ring
- polymkeric substance
- pbo
- preparation
- 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
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention discloses a carbon nano ring-grafted modified plumbous oxide (PBO) polymer and a preparation method thereof, relates to a modified PBO polymer and a preparation method thereof, and aims at solving the technical problem of low tensile strength of the existing PBO fiber. The structural formula of the carbon nano ring-grafted modified PBO polymer disclosed by the invention is as shown in the specification, wherein A is a carbon nano ring, n=30-100, and s=30-100. The preparation method comprises the following steps: adding a carboxyl carbon nano ring to a polyphosphoric acid liquid to obtain a dispersion liquid of the carboxyl carbon nano ring; mixing and stirring the PBO polymer with a methanesulfonic acid to obtain a PBO liquid; mixing the carboxyl carbon nano ring dispersion liquid with the PBO liquid; and washing and drying to obtain the carbon nano ring-grafted modified PBO polymer after heating reaction. The tensile strength of the polymer is improved to 8-9 GPa, and the carbon nano ring-grafted modified PBO polymer can be applied to production of heat resistant textiles or utilization as a fiber reinforced material.
Description
Technical field
The present invention relates to modification PBO polymkeric substance and preparation method thereof.
Background technology
Polyparaphenylene Ben Bing bis-oxazole (PBO) entrusts the SRI of U.S. Stanford Research Institute to test chamber the beginning of the sixties in last century by United States Air Force material laboratory at first, in order to meet the needs of aerospace material, design and prepare polymkeric substance, this polymkeric substance is high temperature resistant, high-performance polymer.Be described as 21 century super fiber.In existing man-made fiber, tensile property is the highest, not only surpasses steel fiber, and can outmatch on carbon fiber.Its intensity, modulus are Kafra fiber 2 times, and there is the performance of heat-proof combustion-resistant.Can the sling weight of 450kg of the PBO filament that diameter is 1mm.In addition, the shock-resistance of pbo fiber, rub resistance and dimensional stability are all very excellent, and light weight and softness.In fields such as aerospace vehicle, guided missile, opportunity of combat, bullet proof clothing, bulletproof halmet and protective garment for high-temp working, optical fiber, rope, sports equipments, have a wide range of applications.But at present, the tensile strength of the pbo fiber of preparing is 5.5～5.8GPa, also there is a big difference with the intensity of Theoretical Calculation, is badly in need of improving.
Summary of the invention
The present invention will solve the technical problem that the tensile strength of existing pbo fiber is low, and kind of carbon nano ring graft modification PBO polymkeric substance and preparation method thereof is provided.
The structural formula of a kind of carbon nano ring graft modification PBO polymkeric substance of the present invention is as follows:
Wherein A is carbon nano ring, n=30～100, and s=30～100, n, s all represents the polymerization degree.
The preparation method of above-mentioned carbon nano ring graft modification PBO polymkeric substance, carries out according to the following steps:
One, Vanadium Pentoxide in FLAKES is added in phosphoric acid, stirring and dissolving obtains poly phosphoric acid solution;
Two, carboxylated carbon nano ring is added in poly phosphoric acid solution prepared by step 1, stir 0.5～2 hour, obtain the dispersion soln of carboxylated carbon nano ring;
Three, by PBO polymkeric substance and methylsulfonic acid mix and blend 4～24 hours, obtain PBO solution;
Four, the PBO solution that carboxylated carbon nano ring dispersion liquid step 2 being obtained obtains with step 3 mixes, then stirring reaction 12～48 hours at 100 ℃～180 ℃ temperature, obtain reaction product, by dry after reaction product washing, the carbon nano ring graft modification PBO polymkeric substance obtaining.
The carbon nano ring consisting of 10 phenyl ring of take is example, and the preparation process of carbon nano ring graft modification PBO polymkeric substance of the present invention is described, this preparation process can be represented by the formula:
PPA wherein represents poly phosphoric acid solution, and MSA represents methylsulfonic acid;
for carboxylated carbon nano ring;
The present invention adopts carbon nano ring to carry out graft modification to PBO polymkeric substance, and the tensile strength of the carbon nano ring graft modification PBO polymkeric substance obtaining is increased to 8～9GPa, compares with existing PBO polymer fiber, has improved 30%～55%.
Accompanying drawing explanation
Fig. 1 tests the carbon nano ring graft modification PBO polymkeric substance infrared spectrogram of 1 preparation.
Embodiment
Embodiment one: the structural formula of a kind of carbon nano ring graft modification PBO polymkeric substance of present embodiment is as follows:
Wherein A is carbon nano ring, n=30～100, s=30～100.
In present embodiment, n, s all represents the polymerization degree.
Embodiment two: present embodiment is different from embodiment one is that the structural representation of carbon nano ring A is:
m is wherein 1～100, represents the polymerization degree.Other is identical with embodiment one.
Embodiment three: present embodiment is different from embodiment one is that the structural representation of carbon nano ring A is:
m is wherein 1～95, represents the polymerization degree.Other is identical with embodiment one.
Embodiment four: the preparation method of the carbon nano ring graft modification PBO polymkeric substance described in embodiment one, carries out according to the following steps:
One, Vanadium Pentoxide in FLAKES is added in phosphoric acid, stirring and dissolving obtains poly phosphoric acid solution;
Two, carboxylated carbon nano ring is added in poly phosphoric acid solution prepared by step 1, stir 0.5～2 hour, obtain the dispersion soln of carboxylated carbon nano ring;
Three, by PBO polymkeric substance and methylsulfonic acid mix and blend 4～24 hours, obtain PBO solution;
Four, the PBO solution that carboxylated carbon nano ring dispersion liquid step 2 being obtained obtains with step 3 mixes, then stirring reaction 12～48 hours at 100 ℃～180 ℃ temperature, obtain reaction product, by dry after reaction product washing, the carbon nano ring graft modification PBO polymkeric substance obtaining.
Embodiment five: present embodiment is different from embodiment four is that in step 1, the mass ratio of Vanadium Pentoxide in FLAKES and phosphoric acid is 1:(1～2); Other is identical with embodiment four.
Embodiment six: present embodiment is different from embodiment four or five is that carbon nano ring carboxylated in step 2 and the mass ratio of poly phosphoric acid solution are 1:(50～1000); Other is identical with embodiment four or five.
Embodiment seven: present embodiment is different from one of embodiment four to six is that in step 3, the mass ratio of PBO polymkeric substance and methylsulfonic acid is 1:(20～100); Other is identical with one of embodiment four to six.
Embodiment eight: present embodiment is different from one of embodiment four to seven is that carbon nano ring dispersion liquid carboxylated in step 4 and the mass ratio of PBO solution are 1:(1～2).Other is identical with one of embodiment four to seven.
Embodiment nine: present embodiment is different from one of embodiment four to eight is that the preparation method of carbon nano ring carboxylated in step 2 carries out according to the following steps:
A, carbon nano ring is joined in mixing acid, be warming up to 90～100 ℃, at this temperature, stirring reaction is 40～48 hours, then is cooled to room temperature, obtains mixture solution; Wherein mixing acid is 1:(3～4 by concentrated nitric acid and the vitriol oil by volume) mix; Ratio 1g:(40mL～the 50mL of the quality of carbon nano ring and the volume of mixing acid);
In b, the mixture solution that obtains to step a, add distilled water, stir after 30～50 minutes, by millipore filtration suction filtration, then use distilled water rinse throw out, until leaching the pH value of liquid, suction filter lower end is neutral, then by solid formation vacuum drying at 80～90 ℃, obtain carboxylated carbon nano ring.Other is identical with one of embodiment four to eight.
Embodiment ten: that present embodiment is different from one of embodiment four to nine is the preparation method of the PBO polymkeric substance in step 3, carries out according to the following steps:
1., under nitrogen atmosphere, in the poly phosphoric acid solution that is 83.7% to the massfraction of Vanadium Pentoxide in FLAKES, add 4,6-diamino resorcin hydrochlorate, terephthalic acid and tindichloride, mixture A stirs to obtain, then mixture A heated and stirred at 60 ℃～80 ℃ is reacted 12～36 hours, obtain mixture B;
2., mixture B that 1. step is obtained is warming up to 110～120 ℃, then adds Vanadium Pentoxide in FLAKES, then insulated and stirred reaction 5～6 hours, obtains mixture C;
3., mixture C that 2. step is obtained is warming up to 150 ℃, then insulation reaction is 5～6 hours, then is warming up to 180 ℃, insulation reaction 5～6 hours, and then reaction product is cooled to after room temperature, be washed to neutrality, vacuum-drying 20～24 hours at 70～80 ℃ again, obtains PBO polymkeric substance.Other is identical with one of embodiment four to nine.
Embodiment 11: present embodiment is different from embodiment ten be step 1. in the mol ratio of 4,6-diaminoresorcinol hydrochloride and terephthalic acid be 1:1, they are monomer; Other is identical with embodiment ten.
Embodiment 12: present embodiment is different from embodiment ten or 11 be step 1. in the mass ratio of tindichloride and terephthalic acid be 0.003:1; Other is identical with embodiment ten or 11.
Embodiment 13: present embodiment is different from one of embodiment ten to 12 be step 1. in 4,6-diaminoresorcinol hydrochloride, terephthalic acid and the total mass of tindichloride and the mass ratio of poly phosphoric acid solution be 0.2:1; Other is identical with one of embodiment two to 12.
Embodiment 14: present embodiment is different from one of embodiment two to 13 be the Vanadium Pentoxide in FLAKES that adds in 2. of step and step 1. in the mol ratio of terephthalic acid monomers be 1:0.7～0.8; Other is identical with one of embodiment ten to 13.
With following verification experimental verification beneficial effect of the present invention:
Test 1: first prepare carbon nano ring, concrete steps are as follows:
One, in 500mL round-bottomed flask, the 4'-bromo-(1 that adds 50.5g, 1'-biphenyl)-4-alcohol, and under 0 ℃, the condition that stirs, add the trimethylchlorosilane of 22.1g imidazoles, 300ml methylene dichloride and 33ml, then mixing solutions is stirred to 16h at ambient temperature, under in whipping process, the concentration that adds 150ml is 1mol/L sodium bicarbonate aqueous solution, solution layering, be divided into organic layer and water layer, organic layer is washed with water, by dried over sodium sulfate concentrating under reduced pressure for organic layer, is pale solid A;
Two, 5g pale solid A is joined in the round-bottomed flask of 250ml, the acetonitrile solution that adds tetrahydrofuran (THF), 35ml deionized water and the 20ml of 80ml in the situation that stirring, in solution, add slowly afterwards 7.5g (diacetoxy iodine) benzene, stirring reaction 16h, obtains orange solid B by reaction product concentrating under reduced pressure;
Three, the sodium hydride of 3.9g is joined in the round-bottomed flask of 2L, and add the tetrahydrofuran (THF) of 400mL, and mixing solutions is cooled to subzero-78 ℃, at this temperature, slowly add the solid B of 20.0g and the tetrahydrofuran solution of 200mL, stirring reaction 2h, obtains solution M;
On the other hand, in 500mL round-bottomed flask, add 4-bromochlorophene and the 200mL tetrahydrofuran (THF) of 34.7g to obtain mixing solutions, under the condition stirring, adding 73.9mL concentration is the hexane solution of 2.5mol/L n-Butyl Lithium, at subzero-78 ℃, reacts 0.5h, obtains solution C; Obtain after solution C, solution C is transferred in the round-bottomed flask of the 2L that fills solution M, mix and blend, is evaporated to the volume half of solution, obtains brown solution D;
Four, the sodium hydride of 7.84g, 400mL tetrahydrofuran solution are joined in 1L round-bottomed flask, add afterwards 200ml brown solution D, at 0 ℃, stir 0.5h, in the solution of the reaction afterwards methyl-iodide of 18.8ml being added, at room temperature stir 16h, dried over sodium sulfate concentrating under reduced pressure for the mixing solutions obtaining, obtain a kind of yellow solid, with hexane, yellow solid is carried out to recrystallization, obtain white crystals E;
Five, 2g white crystals E is dissolved in the middle of the tetrahydrofuran solution of 56mL, and be cooled to subzero-78 ℃, adding 3mL concentration is the hexane solution of 2.5mol/L n-Butyl Lithium, adds subsequently the isopropyl alcohol boric acid of 2mL at once, stir 0.5h, with chromatography purification, obtain product F;
Six, by the Pd (PPh of white crystals E, the 0.312g of product F, the 1.27g of 1.96g
3)
4join in 250mL three-necked bottle, the isopropanol water solution that the sodium bicarbonate aqueous solution that is 0.5mol/L to the mass percentage concentration that adds 44mL in reactor more afterwards and 150mL concentration are 1mol/L, by reaction soln stirring reaction 16 hours at 85 ℃, obtain carbon nano ring afterwards.
The structural formula of the carbon nano ring that this test obtains is as follows:
m=0～3 wherein.The carbon nano ring obtaining with this test carries out following test.
Test 2: the preparation method of the carbon nano ring graft modification PBO polymkeric substance of this test, carries out according to the following steps:
One, the preparation of carboxylated carbon nano ring: concrete grammar is as follows:
A, 2g carbon nano ring is joined in mixing acid, be warming up to 100 ℃, at this temperature, stirring reaction is 48 hours, then is cooled to room temperature, obtains mixture solution; Wherein mixing acid by concentrated nitric acid and the vitriol oil by volume for 1:3 mixes; The ratio 1g:50mL of the quality of carbon nano ring and the volume of mixing acid;
In b, the mixture solution that obtains to step a, add distilled water, stir after 30 minutes, by millipore filtration suction filtration, then use distilled water rinse throw out, until suction filter lower end leaches the pH value of liquid, be neutral, then, by solid formation vacuum drying at 90 ℃, obtain carboxylated carbon nano ring.
Two, the preparation of PBO polymkeric substance: concrete grammar is as follows:
1., under nitrogen atmosphere, in the poly phosphoric acid solution that is 83.7% to the massfraction of Vanadium Pentoxide in FLAKES, add 4,6-diamino resorcin hydrochlorate, terephthalic acid and tindichloride, mixture A stirs to obtain, then mixture A heated and stirred at 70 ℃ is reacted 20 hours, obtain mixture B; Wherein the mol ratio of 4,6-diaminoresorcinol hydrochloride and terephthalic acid is 1:1, and they are monomer; The mass ratio of tindichloride and terephthalic acid is 0.003:1; The total mass of 4,6-diaminoresorcinol hydrochloride, terephthalic acid and tindichloride and the mass ratio of poly phosphoric acid solution are 0.2:1;
2., mixture B that 1. step is obtained is warming up to 120 ℃, then adds Vanadium Pentoxide in FLAKES, then insulated and stirred reaction 6 hours, obtains mixture C; In the Vanadium Pentoxide in FLAKES wherein adding and step a, the mol ratio of terephthalic acid monomers is 1:0.8;
3., mixture C that 2. step is obtained is warming up to 150 ℃, then insulation reaction is 5 hours, then is warming up to 180 ℃, insulation reaction 5 hours, and then reaction product is cooled to after room temperature, be washed to neutrality, vacuum-drying 24 hours at 80 ℃ again, obtains PBO polymkeric substance.
Three, the preparation of carbon nano ring graft modification PBO polymkeric substance, concrete steps are as follows:
(1), 193.34g Vanadium Pentoxide in FLAKES being added to 145.55g mass percentage concentration is that in 85% phosphoric acid, stirring and dissolving obtains poly phosphoric acid solution;
(2), the carboxylated carbon nano ring of 0.5g is added in poly phosphoric acid solution prepared by step (), stir 1 hour, obtain the dispersion soln of carboxylated carbon nano ring;
(3), by 10g PBO polymkeric substance and 338.89g methylsulfonic acid mix and blend 12 hours, obtain PBO solution;
(4) the carboxylated carbon nano ring dispersion liquid, step (two) being obtained mixes with the PBO solution that step (three) obtains, then stirring reaction 24 hours at 130 ℃ of temperature, obtain reaction product, reaction product is added in 2L water to agitator treating 24 hours, dry, to obtain carbon nano ring graft modification PBO polymkeric substance.
The carbon nano ring graft modification PBO polymkeric substance that this test is obtained carries out Infrared spectroscopy, and the infrared spectrogram obtaining as shown in Figure 1, as can be seen from Figure 1, has two obvious absorption peaks of carbon nano ring in spectrogram, and one is at 1554cm
-1near-C=C-stretching vibration peak, another is at 1124cm
-1near, i.e. C-C stretching vibration.3068cm
-1peak be C-H on aromatic ring, secondly in fingerprint region, have 845cm
-1the peak that has obvious phenyl ring.At 1628cm
-1c=N peak, 1050cm
-1-C-O-C peak and-3068cm
-1aromatic ring on C-H, be the charateristic avsorption band of PBO.Infrared spectrum has shown carbon nano ring and the successful copolymerization of PBO together.
After the carbon nano ring graft modification PBO polymkeric substance drawing fiber that this test is obtained, with stretching testing machine, carry out tensile strength test, test result shows, the tensile strength of carbon nano ring graft modification PBO polymer fiber is 8.3GPa.
Test 3: the preparation method of the carbon nano ring graft modification PBO polymkeric substance of this test, carries out according to the following steps:
One, the preparation of carboxylated carbon nano ring: concrete grammar is as follows:
A, 2g carbon nano ring is joined in mixing acid, be warming up to 100 ℃, at this temperature, stirring reaction is 48 hours, then is cooled to room temperature, obtains mixture solution; Wherein mixing acid by concentrated nitric acid and the vitriol oil by volume for 1:4 mixes; The ratio 1g:50mL of the quality of carbon nano ring and the volume of mixing acid;
In b, the mixture solution that obtains to step a, add distilled water, stir after 50 minutes, by millipore filtration suction filtration, then use distilled water rinse throw out, until suction filter lower end leaches the pH value of liquid, be neutral, then, by solid formation vacuum drying at 90 ℃, obtain carboxylated carbon nano ring.
Two, the preparation of PBO polymkeric substance: concrete grammar is as follows:
1., under nitrogen atmosphere, in the poly phosphoric acid solution that is 83.7% to the massfraction of Vanadium Pentoxide in FLAKES, add 4,6-diamino resorcin hydrochlorate, terephthalic acid and tindichloride, mixture A stirs to obtain, then mixture A heated and stirred at 80 ℃ is reacted 30 hours, obtain mixture B; Wherein the mol ratio of 4,6-diaminoresorcinol hydrochloride and terephthalic acid is 1:1, and they are monomer; The mass ratio of tindichloride and terephthalic acid is 0.003:1; The total mass of 4,6-diaminoresorcinol hydrochloride, terephthalic acid and tindichloride and the mass ratio of poly phosphoric acid solution are 0.2:1;
2., mixture B that 1. step is obtained is warming up to 120 ℃, then adds Vanadium Pentoxide in FLAKES, then insulated and stirred reaction 6 hours, obtains mixture C; In the Vanadium Pentoxide in FLAKES wherein adding and step a, the mol ratio of terephthalic acid monomers is 1:0.8;
3., mixture C that 2. step is obtained is warming up to 150 ℃, then insulation reaction is 5 hours, then is warming up to 180 ℃, insulation reaction 6 hours, and then reaction product is cooled to after room temperature, be washed to neutrality, vacuum-drying 24 hours at 80 ℃ again, obtains PBO polymkeric substance.
Three, the preparation of carbon nano ring graft modification PBO polymkeric substance, concrete steps are as follows:
(1), 195.23g Vanadium Pentoxide in FLAKES being added to 148.24g mass percentage concentration is that in 85% phosphoric acid, stirring and dissolving obtains poly phosphoric acid solution;
(2), the carboxylated carbon nano ring of 0.5g is added in poly phosphoric acid solution prepared by step (), stir 1 hour, obtain the dispersion soln of carboxylated carbon nano ring;
(3), by 10g PBO polymkeric substance and 334.57g methylsulfonic acid mix and blend 12 hours, obtain PBO solution;
(4) the carboxylated carbon nano ring dispersion liquid, step (two) being obtained mixes with the PBO solution that step (three) obtains, then stirring reaction 30 hours at 170 ℃ of temperature, obtain reaction product, reaction product is added in 2L water to agitator treating 24 hours, dry, to obtain carbon nano ring graft modification PBO polymkeric substance.
After the carbon nano ring graft modification PBO polymkeric substance drawing fiber that this test is obtained, with stretching testing machine, carry out tensile strength test, test result shows, the tensile strength of carbon nano ring graft modification PBO polymer fiber is 8.83GPa.
Claims (10)
1. a carbon nano ring graft modification PBO polymkeric substance, is characterized in that the structural formula of this polymkeric substance is as follows:
Wherein A is carbon nano ring, n=30～100, s=30～100.
2. the method for preparation carbon nano ring graft modification PBO polymkeric substance claimed in claim 1, is characterized in that the method carries out according to the following steps:
One, Vanadium Pentoxide in FLAKES is added in phosphoric acid, stirring and dissolving obtains poly phosphoric acid solution;
Two, carboxylated carbon nano ring is added in poly phosphoric acid solution prepared by step 1, stir 0.5～2 hour, obtain the dispersion soln of carboxylated carbon nano ring;
Three, by PBO polymkeric substance and methylsulfonic acid mix and blend 4～24 hours, obtain PBO solution;
Four, the PBO solution that carboxylated carbon nano ring dispersion liquid step 2 being obtained obtains with step 3 mixes, then stirring reaction 12～48 hours at 100 ℃～180 ℃ temperature, obtain reaction product, by dry after reaction product washing, the carbon nano ring graft modification PBO polymkeric substance obtaining.
3. the preparation method of carbon nano ring graft modification PBO polymkeric substance according to claim 2, is characterized in that in step 1, the mass ratio of Vanadium Pentoxide in FLAKES and phosphoric acid is 1:(1～2).
4. according to the preparation method of the carbon nano ring graft modification PBO polymkeric substance described in claim 2 or 3, the mass ratio that it is characterized in that carbon nano ring carboxylated in step 2 and poly phosphoric acid solution is 1:(50～1000).
5. according to the preparation method of the carbon nano ring graft modification PBO polymkeric substance described in claim 2 or 3, it is characterized in that in step 3, the mass ratio of PBO polymkeric substance and methylsulfonic acid is 1:(20～100).
6. according to the preparation method of the carbon nano ring graft modification PBO polymkeric substance described in claim 2 or 3, it is characterized in that the preparation method of carbon nano ring carboxylated in step 2 carries out according to the following steps:
A, carbon nano ring is joined in mixing acid, be warming up to 90～100 ℃, at this temperature, stirring reaction is 40～48 hours, then is cooled to room temperature, obtains mixture solution; Wherein mixing acid is 1:(3～4 by concentrated nitric acid and the vitriol oil by volume) mix; Ratio 1g:(40mL～the 50mL of the quality of carbon nano ring and the volume of mixing acid);
In b, the mixture solution that obtains to step a, add distilled water, stir after 30～50 minutes, by millipore filtration suction filtration, then use distilled water rinse throw out, until leaching the pH value of liquid, suction filter lower end is neutral, then by solid formation vacuum drying at 80～90 ℃, obtain carboxylated carbon nano ring.
7. according to the preparation method of the carbon nano ring graft modification PBO polymkeric substance described in claim 2 or 3, it is characterized in that the preparation method of the PBO polymkeric substance in step 3, carry out according to the following steps:
1., under nitrogen atmosphere, in the poly phosphoric acid solution that is 83.7% to the massfraction of Vanadium Pentoxide in FLAKES, add 4,6-diamino resorcin hydrochlorate, terephthalic acid and tindichloride, mixture A stirs to obtain, then mixture A heated and stirred at 60 ℃～80 ℃ is reacted 12～36 hours, obtain mixture B;
2., mixture B that 1. step is obtained is warming up to 110～120 ℃, then adds Vanadium Pentoxide in FLAKES, then insulated and stirred reaction 5～6 hours, obtains mixture C;
3., mixture C that 2. step is obtained is warming up to 150 ℃, then insulation reaction is 5～6 hours, then is warming up to 180 ℃, insulation reaction 5～6 hours, and then reaction product is cooled to after room temperature, be washed to neutrality, vacuum-drying 20～24 hours at 70～80 ℃ again, obtains PBO polymkeric substance.
8. according to the preparation method of the carbon nano ring graft modification PBO polymkeric substance described in claim 2 or 3, it is characterized in that during step 1., the mol ratio of 4,6-diaminoresorcinol hydrochloride and terephthalic acid is 1:1.
9. according to the preparation method of the carbon nano ring graft modification PBO polymkeric substance described in claim 2 or 3, it is characterized in that during step 1. that 4,6-diaminoresorcinol hydrochloride, terephthalic acid and the total mass of tindichloride and the mass ratio of poly phosphoric acid solution are 0.2:1.
10. according to the preparation method of the carbon nano ring graft modification PBO polymkeric substance described in claim 2 or 3, it is characterized in that during the Vanadium Pentoxide in FLAKES that adds during step 2. and step are 1., the mol ratio of terephthalic acid monomers is 1:0.7～0.8.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410174136.4A CN103923316B (en) | 2014-04-28 | 2014-04-28 | A kind of carbon nano ring graft modification PBO polymkeric substance and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410174136.4A CN103923316B (en) | 2014-04-28 | 2014-04-28 | A kind of carbon nano ring graft modification PBO polymkeric substance and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103923316A true CN103923316A (en) | 2014-07-16 |
| CN103923316B CN103923316B (en) | 2016-03-09 |
Family
ID=51141727
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410174136.4A Active CN103923316B (en) | 2014-04-28 | 2014-04-28 | A kind of carbon nano ring graft modification PBO polymkeric substance and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103923316B (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1478818A (en) * | 2003-07-18 | 2004-03-03 | 哈尔滨工业大学 | Synthesis method of PBO/carbon nanometer pipe composite material |
| US20050070657A1 (en) * | 2003-09-29 | 2005-03-31 | Mark Elkovitch | Conductive thermoplastic compositions, methods of manufacture and articles derived from such compositions |
| CN101274983B (en) * | 2008-05-21 | 2010-06-02 | 哈尔滨工业大学 | Preparation for single wall carbon nano-tube monomer-containing compound for PBO polymerization |
| CN102491309A (en) * | 2011-12-07 | 2012-06-13 | 北京化工大学 | Carbon nanometer ring and preparation method thereof |
-
2014
- 2014-04-28 CN CN201410174136.4A patent/CN103923316B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1478818A (en) * | 2003-07-18 | 2004-03-03 | 哈尔滨工业大学 | Synthesis method of PBO/carbon nanometer pipe composite material |
| US20050070657A1 (en) * | 2003-09-29 | 2005-03-31 | Mark Elkovitch | Conductive thermoplastic compositions, methods of manufacture and articles derived from such compositions |
| CN101274983B (en) * | 2008-05-21 | 2010-06-02 | 哈尔滨工业大学 | Preparation for single wall carbon nano-tube monomer-containing compound for PBO polymerization |
| CN102491309A (en) * | 2011-12-07 | 2012-06-13 | 北京化工大学 | Carbon nanometer ring and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| X.LI, ET AL: "Preparation of multiwall carbon nanotubes/poly(p-phenylene benzobisoxazole) nanocomposites and analysis of their physical properties", 《JOURNAL OF APPLIED POLYMER SCIENCE》, vol. 102, 31 December 2006 (2006-12-31), pages 2500 - 2508 * |
| 李霞, 等: "酸处理碳纳米管/PBO复合材料的制备与表征", 《高分子材料科学与工程》, vol. 23, no. 1, 31 January 2007 (2007-01-31), pages 192 - 195 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103923316B (en) | 2016-03-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103184588B (en) | Manufacturing method of 12K quaternary polyacrylonitrile-based carbon fiber | |
| CN100564413C (en) | The preparation method of polymer for polyacrylonitrile base carbon fiber precursors | |
| CN101910480B (en) | Processes for producing flameproof fiber and carbon fiber | |
| CN107163250A (en) | A kind of preparation and application for 4,6 diamino resorcin hydrochlorates and its compound salt monomer that PBO is modified for monohydroxy | |
| CN109881280A (en) | A kind of preparation method of polyacrylonitrile fibre, preparation method and its carbon fiber | |
| CN103936988B (en) | A kind of graphene nanobelt graft modification PBO polymer and preparation method thereof | |
| CN104231158B (en) | A kind of preparation method of carbon fiber PAN precursor | |
| CN111172745A (en) | Preparation method of graphene, polyaniline and polyester composite conductive fiber | |
| CN104231159B (en) | A kind of preparation method of carbon fiber PAN polymer | |
| CN110105397B (en) | Multi-reaction-functionality phosphaphenanthrene/siloxane bi-based macromolecular flame retardant and preparation method thereof | |
| CN103923316B (en) | A kind of carbon nano ring graft modification PBO polymkeric substance and preparation method thereof | |
| CN105820343B (en) | A kind of borosilicate polymer, preparation method and applications | |
| CN107653520A (en) | A kind of preparation method of cost degradation polyacrylonitrile-based carbon fibre | |
| CN104031271B (en) | A kind of preparation method of Nano carbon balls modification by copolymerization PBO polymer | |
| CN103342812A (en) | Aromatic polyamide sulfamide and preparation method thereof | |
| CN110747647A (en) | Antibacterial carbon fiber sizing agent emulsion and preparation method and application thereof | |
| CN103132327A (en) | Sizing agent applied to constant SiC (Silicon Carbide) fiber and preparation method and application thereof | |
| CN103668524B (en) | Low viscosity, high-performance binary acrylonitrile copolymer spinning solution preparation method | |
| CN105442076B (en) | A kind of preparation method of graphene quantum dot enhancing para-aramid fiber | |
| CN110724262B (en) | Ternary light-resistant liquid crystal copolymer containing oxazole structure and preparation and application thereof | |
| US20120319315A1 (en) | Polyacrylonitrile-based polymer solution, preparing method of the same, carbon fiber precursor, manufacturing method of the same and manufacturing method of carbon fiber using the same | |
| CN106835351B (en) | A kind of preparation method of ultra-fine pbo fiber | |
| CN109790648B (en) | Method for producing polyacrylonitrile-based fiber and polyacrylonitrile-based copolymer used therein | |
| CN102391511B (en) | Novel polytriazole resins with rigid structure and preparation method thereof | |
| CN102634023A (en) | Preparation method of poly-p-phenylenebenzobisthiazole (PBO) polymer |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |