CN104974341A - Cross-linked polyarylether polymer and preparation method thereof - Google Patents
Cross-linked polyarylether polymer and preparation method thereof Download PDFInfo
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- CN104974341A CN104974341A CN201510400364.3A CN201510400364A CN104974341A CN 104974341 A CN104974341 A CN 104974341A CN 201510400364 A CN201510400364 A CN 201510400364A CN 104974341 A CN104974341 A CN 104974341A
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Abstract
The invention relates to a cross-linked polyarylether polymer and a preparation method thereof, and belongs to the technical field of polymer materials and preparations thereof. According to the present invention, a bisphenol monomer and a dihalogen monomer are adopted as reactants, potassium carbonate is adopted as a catalyst, tetramethylene sulfone is adopted as a solvent, toluene or xylene is adopted as an azeotropic dehydrating agent, and reaction is performed under the nitrogen protection and mechanical stirring to obtain a linear polyarylether polymer, the polymer is washed with distilled water and ethanol and then is completely dissolved with N-methyl pyrrolidone, dibromo alkane is added to the system, uniform stirring is performed, a film is casted by using a casting method, the film is placed into a vacuum oven to react and then is immersed in N-methyl pyrrolidone so as to remove the unreacted linear polymer, and finally vacuumizing is performed to remove the solvent and the unreacted dibromo alkane to obtain the cross-linked polyarylether polymer. According to the present invention, the pyridine salt structure can be generated while the cross-linked polymer is formed, the film-forming ability is strong, and the thermal stability and the chemical stability required by the anion membrane material in the 80 DEG C fuel cell working environment can be met.
Description
Technical field
The invention belongs to macromolecular material and preparing technical field thereof, be specifically related to a kind of crosslinked polyarylether polymer and preparation method thereof.
Background technology
Fuel cell, due to its less energy-consumption, pollution-free, obtains increasing concern and research.Be developed so far, its Proton Exchange Membrane Fuel Cells mainly applied and alkaline fuel cell.Alkaline fuel cell in use can produce sour gas, causes ionic conductivity to decline; The acidic medium of Proton Exchange Membrane Fuel Cells defines noble metals such as only having platinum and could use as eelctro-catalyst.
In order to integrate both advantages, anion-exchange membrane fuel cells is arisen at the historic moment, and it is using alkaline polymer film as ionogen, negatively charged ion as improved in two interpolar conduct charges.This fuel cell can use non-precious metal as electrode catalyst, avoids the problem that electrolysis of solutions matter carbonating analyses salt simultaneously, has higher power density and lower production cost.The present invention can generate pyridinium salt ion while formation cross-linked polymer, and film forming ability is strong, meets the thermostability of anionic membrane material in fuel cell operating conditions needed for 80 DEG C and chemical stability.
Summary of the invention
Anion-exchange membrane material require has enough physical strengths and dimensional stability, therefore, the invention provides a kind of crosslinked polyarylether polymer and preparation method.Crosslinked polyarylether polymer of the present invention is a kind of anionresin mould material of excellent properties, the present invention can generate pyridinium salt ion while formation cross-linked polymer, film forming ability is strong, meets the thermostability of anionic membrane material in fuel cell operating conditions needed for 80 DEG C and chemical stability.
A kind of crosslinked polyarylether polymer, described crosslinked polyarylether polymer comprises crosslinked polyaryletherketone and crosslinked polyether sulphone.
A preparation method for crosslinked polyarylether polymer, its step is as follows:
(1) with biphenol monomer A, biphenol monomer B and two halogen monomer C for reactant, take salt of wormwood as catalyzer, take tetramethylene sulfone as solvent, with toluene or dimethylbenzene for azeotropy dehydrant, under nitrogen protection, mechanical agitation, reaction system is warming up to azeotropy dehydrant backflow, reacts and discharge dewatering agent in 2 ~ 3 hours, then continue to be warming up to 180 DEG C ~ 200 DEG C reactions 7 ~ 10 hours; The solution obtained is poured in distilled water, obtains white solid, be i.e. linear polyarylether polymer;
(2) after linear polyarylether polymer distilled water step (1) obtained and washing with alcohol are clean, after fully dissolving with N-Methyl pyrrolidone, dibromoalkane is added in system, casting method casting film is used after stirring, then vacuum drying oven 50 ~ 80 DEG C of isothermal reactions 20 ~ 30 hours are placed in, again film to be immersed in N-Methyl pyrrolidone 8 ~ 15 hours, to remove unreacted linear polymer; Finally vacuumize at 60 ~ 80 DEG C except desolventizing and unreacted dibromoalkane, obtain described crosslinked polyarylether polymer.
Its preparation process and product structure formula as follows:
The integer of n=1 ~ 4, represents the C atom number in dibromoalkane;
M=p/ (p+q)=10% ~ 100%, represents the molecular fraction that this segment is shared in repeating unit;
Wavy line represents possible continuation crosslinking structure;
Described biphenol monomer mole dosage (biphenol monomer A+ biphenol monomer B) is 1:1 with the ratio of two halogen monomer C mole dosage, and in biphenol monomer, the consumption of biphenol monomer A is 10% ~ 100%.
Described salt of wormwood molar weight is 1.1 ~ 1.5 times of two halogen monomer C molar weight, and tetramethylene sulfone quality is 1.5 ~ 4 times of described reactant total mass, and toluene or xylene mass are 0.8 ~ 1.2 times of described reactant total mass.
The molar weight of described dibromoalkane is 0.25 ~ 2.0 times of biphenol monomer A molar weight.
Described biphenol monomer A is 4-pyridine Resorcinol, 3-pyridine Resorcinol, 2-pyridine Resorcinol, 2,5-bis-(4-pyridine) Resorcinol, 2, one or more in 5-bis-(3-pyridine) Resorcinol or 2,5-bis-(2-pyridine) Resorcinol.
Described biphenol monomer B is one or more in '-biphenyl diphenol, Resorcinol, dihydroxyphenyl propane or 4,4-dihydroxy benaophenonel.
Described two halogen monomer C are one or more in 4,4-difluorodiphenyl sulfone, DDS, 4,4-difluoro benzophenones or 4,4-dichloro benzophenone.
Described dibromoalkane is one or more in glycol dibromide, 1,3-dibromopropane, Isosorbide-5-Nitrae-dibromobutane or pentamethylene bromide.
Accompanying drawing explanation
Fig. 1: Py20 and XLPy20 infrared spectrogram;
Infrared spectrogram before and after contrast is crosslinked can see that XLPy20 is at 2960cm
-1there is the stretching vibration peak of saturated carbon hydrogen bond, proved the existence of the methylene radical in 1,3-dibromopropane, be namely cross-linked and successfully occur; At 1675cm
-1having there is the special absorption peak of pyridinium salt in place, proves to generate pyridinium salt in crosslinked process.
Fig. 2: Py20 and XLPy20 thermogravimetric curve
As can be seen from curve in figure 1, linear Py20 is very stable before 450 DEG C, and when 485 DEG C, the main chain of Py20 starts to decompose, and shows excellent thermal characteristics; Occur 2 thermal weight loss platforms as can be seen from curve in figure 2, XLPy20, all very stable before 100 DEG C, pyridinium salt structure starts to decompose at 115 DEG C, enters second platform to 340 DEG C, and finally 485 DEG C time, XLPy20 main chain starts to decompose.Meet the use temperature 80 DEG C of anion-exchange membrane, thermal characteristics is excellent.
Fig. 3: Py20 and XLPy20 DSC figure;
Fig. 4: the relation curve of dibromoalkane add-on and crosslinked massfraction.
Crosslinked massfraction=M
1/ M
2
M
1for film is immersed in the quality of N-Methyl pyrrolidone after 10 hours; M
2for film is immersed in the quality before N-Methyl pyrrolidone;
Embodiment
Embodiment 1
(1) be equipped with in the 100mL there-necked flask that machinery stirs, add 0.7488g (0.004mol) 4-pyridine Resorcinol, 2.9794g (0.016mol) '-biphenyl diphenol, 5.0850g (0.02mol) 4,4-difluorodiphenyl sulfone, 3.04g (0.022mol) salt of wormwood, tetramethylene sulfone 25mL, toluene 10mL.Under mechanical stirring, nitrogen protection, be warming up to 150 DEG C of backflows 2 hours, discharge toluene, continue to be warming up to that 180 DEG C of reactions 7 are little no longer increases up to soltion viscosity (torque levels of mechanical stirring head, is substantially just judged as that viscosity no longer adds).
(2) solution in step (1) is slowly poured in distilled water, namely obtain white polymer after cooling, be labeled as Py20, use deionized water and washing with alcohol 5 times post-dryings respectively, productive rate more than 95%.
(3) Py20 getting 1g is dissolved in the N-Methyl pyrrolidone of 10mL, 0.076g 1 is added after abundant dissolving, 3-dibromopropane, use casting method casting film, be placed in vacuum drying oven 50 DEG C of isothermal reactions 24 hours, film to be immersed in N-Methyl pyrrolidone 10 hours, to remove unreacted linear polymer.Then 60 DEG C vacuumize 24 hours, except desolventizing and 1,3-dibromopropane, obtain 0.930g crosslinked polyethers sulfone, are labeled as XLPy20.
The infrared spectrogram of Py20 and XLPy20 can see that XLPy20 is respectively at 2960cm as shown in Figure 1
-1and 1675cm
-1having there is the stretching vibration peak of methylene radical and the absorption peak of pyridinium salt in place, proves successfully to generate pyridinium salt structure in crosslinked process.
Py20 and XLPy20DSC shown in Py20 and XLPy20 thermogravimetic analysis (TGA) figure and Fig. 3 as shown in Figure 2 schemes, and can find out that the decomposition temperature of XLPy20 pyridinium salt is 115 DEG C, meets the use temperature 80 DEG C of anionic membrane fuel cell completely.Good Heat-resistance.
Embodiment 2
0.7488g (0.004mol) 4-pyridine Resorcinol in embodiment 1 is changed to 0.3744g (0.002mol) 4-pyridine Resorcinol; 2.9794g (0.016mol) '-biphenyl diphenol is changed to 3.3518g (0.018mol) '-biphenyl diphenol; Dibromopropane quality 0.076g is changed to 0.038g, the other the same as in Example 1, obtains 0.912g crosslinked polyethers sulfone.
Embodiment 3
0.7488g (0.004mol) 4-pyridine Resorcinol in embodiment 1 is changed to 3.7438g (0.02mol) 4-pyridine Resorcinol; '-biphenyl diphenol does not add; Dibromopropane quality 0.076g is changed to 0.38g, the other the same as in Example 1, obtains 0.948g crosslinked polyethers sulfone.
Embodiment 4
0.7488g (0.004mol) 4-pyridine Resorcinol in embodiment 1 is changed to 0.7488g (0.004mol) 3-pyridine Resorcinol, and the other the same as in Example 1, obtains 0.916g crosslinked polyethers sulfone.
Embodiment 5
0.7488g (0.004mol) 4-pyridine Resorcinol in embodiment 1 is changed to 0.7488g (0.004mol) 2-pyridine Resorcinol, and the other the same as in Example 1, obtains 0.915g crosslinked polyethers sulfone.
Embodiment 6
0.7488g (0.004mol) 4-pyridine Resorcinol in embodiment 1 is changed to 1.0572g (0.004mol) 2,5-bis-(4-pyridine) Resorcinol; Dibromopropane quality 0.076g is changed to 0.152g the other the same as in Example 1, obtains 0.958g crosslinked polyethers sulfone.
Embodiment 7
0.7488g (0.004mol) 4-pyridine Resorcinol in embodiment 1 is changed to 1.0572g (0.004mol) 2,5-bis-(3-pyridine) Resorcinol; Dibromopropane quality 0.076g is changed to 0.152g the other the same as in Example 1, obtains 0.955g crosslinked polyethers sulfone.
Embodiment 8
0.7488g (0.004mol) 4-pyridine Resorcinol in embodiment 1 is changed to 1.0572g (0.004mol) 2,5-bis-(4-pyridine) Resorcinol; Dibromopropane quality 0.076g is changed to 0.152g the other the same as in Example 1, obtains 0.954g crosslinked polyethers sulfone.
Embodiment 9
5.0850g (0.02mol) 4,4-difluorodiphenyl sulfone in embodiment 1 is changed to 5.7432g (0.02mol) DDS; Polymerization temperature 180 DEG C is changed to 200 DEG C; The other the same as in Example 1, obtains 0.936g crosslinked polyethers ketone.
Embodiment 10
5.0850g (0.02mol) 4,4-difluorodiphenyl sulfone in embodiment 1 is changed to 4.3640g (0.02mol) 4,4-difluoro benzophenone; Polymerization temperature 180 DEG C is changed to 200 DEG C; The other the same as in Example 1, obtains 0.896g crosslinked polyethers ketone.
Embodiment 11
5.0850g (0.02mol) 4,4-difluorodiphenyl sulfone in embodiment 1 is changed to 5.0222g (0.02mol) 4,4-dichloro benzophenone; Polymerization temperature 180 DEG C is changed to 200 DEG C; The other the same as in Example 1, obtains 0.897g crosslinked polyethers ether ketone.
Embodiment 12
Be changed to respectively shown in following table by 0.076g 1,3-dibromopropane in embodiment 1, the other the same as in Example 1, gained cross-linked polymer productive rate lists in table 1.
Table 1: embodiment 12 data
| Glycol dibromide | 1,3-dibromopropane | Isosorbide-5-Nitrae-dibromobutane | Pentamethylene bromide | |
| Raw materials quality/g | 0.023g | 0.025g | 0.027g | 0.029g |
| Product quality/g | 0.401g | 0.402g | 0.402g | 0.404g |
Note: dihalo hydrocarbon molar weight 0.125mmol is 0.25 times of biphenol monomer A molar weight 0.5mmol in the Py20 of 1g.
Embodiment 13
Be changed to respectively shown in following table by 0.076g 1,3-dibromopropane in embodiment 1, the other the same as in Example 1, gained cross-linked polymer productive rate also lists in table 2.
Table 2: embodiment 13 data
| Glycol dibromide | 1,3-dibromopropane | Isosorbide-5-Nitrae-dibromobutane | Pentamethylene bromide | |
| Raw materials quality/g | 0.046g | 0.050g | 0.054g | 0.058g |
| Product quality/g | 0.830g | 0.832g | 0.832g | 0.834g |
Note: dihalo hydrocarbon molar weight 0.25mmol is 0.5 times of biphenol monomer A molar weight 0.5mmol in 1gPy20.
Embodiment 14
Be changed to respectively shown in following table by 0.076g 1,3-dibromopropane in embodiment 1, the other the same as in Example 1, gained cross-linked polymer productive rate also lists in table 3.
Table 3: embodiment 14 data
| Glycol dibromide | 1,3-dibromopropane | Isosorbide-5-Nitrae-dibromobutane | Pentamethylene bromide | |
| Raw materials quality/g | 0.069g | 0.075g | 0.081g | 0.087g |
| Product quality/g | 0.930g | 0.930g | 0.931g | 0.931g |
Note: dihalo hydrocarbon molar weight 0.375mmol is 0.75 times of biphenol monomer A molar weight 0.5mmol in 1gPy20.
Embodiment 15
Be changed to respectively shown in following table by 0.076g 1,3-dibromopropane in embodiment 1, temperature of reaction is changed to 80 DEG C, the other the same as in Example 1, and gained cross-linked polymer productive rate also lists in table 3.
Table 4: embodiment 15 data
| Glycol dibromide | 1,3-dibromopropane | Isosorbide-5-Nitrae-dibromobutane | Pentamethylene bromide | |
| Raw materials quality/g | 0.094g | 0.101g | 0.108g | 0.115g |
| Product quality/g | 0.810g | 0.811g | 0.812g | 0.814g |
Note: dihalo hydrocarbon molar weight 0.50mmol is 1.0 times of biphenol monomer A molar weight 0.5mmol in 1gPy20.
Embodiment 16
Be changed to respectively shown in following table by 0.076g 1,3-dibromopropane in embodiment 1, temperature of reaction is changed to 80 DEG C, the other the same as in Example 1, and gained cross-linked polymer productive rate also lists in table 3.
Table 5: embodiment 16 data
| Glycol dibromide | 1,3-dibromopropane | Isosorbide-5-Nitrae-dibromobutane | Pentamethylene bromide | |
| Raw materials quality/g | 0.141g | 0.151g | 0.162g | 0.172g |
| Product treatment/g | 0.669g | 0.670g | 0.670g | 0.671g |
Note: dihalo hydrocarbon molar weight 0.75mmol is 1.5 times of biphenol monomer A molar weight 0.5mmol in 1gPy20.
Embodiment 17
Be changed to respectively shown in following table by 0.076g 1,3-dibromopropane in embodiment 1, temperature of reaction is changed to 80 DEG C, the other the same as in Example 1, and gained cross-linked polymer productive rate also lists in table 3.
Table 6: embodiment 17 data
| Glycol dibromide | 1,3-dibromopropane | Isosorbide-5-Nitrae-dibromobutane | Pentamethylene bromide | |
| Raw materials quality/g | 0.188g | 0.202g | 0.216g | 0.230g |
| Product quality/g | 0.500g | 0.502g | 0.502g | 0.503g |
Note: dihalo hydrocarbon molar weight 1.0mmol is 2.0 times of biphenol monomer A molar weight 0.5mmol in 1gPy20.
For Py20, dibromoalkane as shown in Figure 4 and crosslinked massfraction relation curve can be found out, along with the increase of dibromoalkane add-on, crosslinked massfraction presents the rear downward trend that first rises.This is because along with the increase of dibromoalkane, in linear polymer, pyridine groups participates in the quantity increase of crosslinking reaction, and crosslinked massfraction rises; After dibromoalkane is excessive greatly, dibromoalkane just occupies a large amount of reaction site, thus the generation that impact is crosslinked, cause crosslinked massfraction to decline.
Reaction formula in low cross-linking massfraction situation is as follows:
The integer of n=1 ~ 4, represents the C atom number in dibromoalkane;
M=p/ (p+q)=10% ~ 100%, represents the molecular fraction that this segment is shared in repeating unit.
Claims (7)
1. a crosslinked polyarylether polymer, its structural formula is as follows:
The integer of n=1 ~ 4, represents the C atom number in dibromoalkane;
M=10% ~ 100%, represents the molecular fraction that this segment is shared in repeating unit;
Wavy line represents possible continuation crosslinking structure;
2. the preparation method of crosslinked polyarylether polymer according to claim 1, its step is as follows:
(1) with biphenol monomer A, biphenol monomer B and two halogen monomer C for reactant, take salt of wormwood as catalyzer, take tetramethylene sulfone as solvent, with toluene or dimethylbenzene for azeotropy dehydrant, under nitrogen protection, mechanical agitation, reaction system is warming up to azeotropy dehydrant backflow, reacts and discharge dewatering agent in 2 ~ 3 hours, then continue to be warming up to 180 DEG C ~ 200 DEG C reactions 7 ~ 10 hours; The solution obtained is poured in distilled water, obtains white solid, be i.e. linear polyarylether polymer;
(2) after linear polyarylether polymer distilled water step (1) obtained and washing with alcohol are clean, after fully dissolving with N-Methyl pyrrolidone, dibromoalkane is added in system, casting method casting film is used after stirring, then vacuum drying oven 50 ~ 80 DEG C of isothermal reactions 20 ~ 30 hours are placed in, again film to be immersed in N-Methyl pyrrolidone 8 ~ 15 hours, to remove unreacted linear polymer; Finally vacuumize at 60 ~ 80 DEG C except desolventizing and unreacted dibromoalkane, obtain described crosslinked polyarylether polymer;
Biphenol monomer A is 4-pyridine Resorcinol, 3-pyridine Resorcinol, 2-pyridine Resorcinol, 2,5-bis-(4-pyridine) Resorcinol, 2, one or more in 5-bis-(3-pyridine) Resorcinol or 2,5-bis-(2-pyridine) Resorcinol; Biphenol monomer B is one or more in '-biphenyl diphenol, Resorcinol, dihydroxyphenyl propane or 4,4-dihydroxy benaophenonel; Two halogen monomer C is one or more in 4,4-difluorodiphenyl sulfone, DDS, 4,4-difluoro benzophenones or 4,4-dichloro benzophenone.
3. the preparation method of crosslinked polyarylether polymer as claimed in claim 2, is characterized in that: dibromoalkane is one or more in glycol dibromide, 1,3-dibromopropane, Isosorbide-5-Nitrae-dibromobutane or pentamethylene bromide.
4. the preparation method of crosslinked polyarylether polymer as claimed in claim 2, it is characterized in that: biphenol monomer mole dosage is 1:1 with the ratio of two halogen monomer C mole dosage, in biphenol monomer, the consumption of biphenol monomer A is 10% ~ 100%.
5. the preparation method of crosslinked polyarylether polymer as claimed in claim 2, is characterized in that: salt of wormwood molar weight is 1.1 ~ 1.5 times of two halogen monomer C molar weight.
6. the preparation method of crosslinked polyarylether polymer as claimed in claim 2, it is characterized in that: tetramethylene sulfone quality is 1.5 ~ 4 times of described reactant total mass, toluene or xylene mass are 0.8 ~ 1.2 times of described reactant total mass.
7. the preparation method of crosslinked polyarylether polymer as claimed in claim 2, is characterized in that: the molar weight of dibromoalkane is 0.25 ~ 2.0 times of biphenol monomer A molar weight.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2019145235A1 (en) * | 2018-01-23 | 2019-08-01 | Solvay Specialty Polymers Usa, Llc | Process for preparing functionalized poly(aryl ether sulfones) polymers and block copolymers resulting therefrom |
| CN110294845A (en) * | 2019-07-03 | 2019-10-01 | 中国科学院长春应用化学研究所 | A kind of tertiary amine-type polyether sulphone (ketone) fluoropolymer resin and preparation method thereof and anion-exchange membrane |
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| CN101302335A (en) * | 2008-06-25 | 2008-11-12 | 吉林大学 | Bisphenol A type polyaromatic ether ketone water-based fluid dispersion and preparation thereof |
| CN102585204A (en) * | 2012-02-26 | 2012-07-18 | 吉林大学 | Side-chain sulfonic acid type polyarylether, preparation method thereof and application of polyarylether in preparation of proton exchange membrane |
| CN104558586A (en) * | 2015-01-12 | 2015-04-29 | 吉林大学 | Allyl containing crosslinkable azo polyarylether and preparation method thereof |
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| CN101302335A (en) * | 2008-06-25 | 2008-11-12 | 吉林大学 | Bisphenol A type polyaromatic ether ketone water-based fluid dispersion and preparation thereof |
| CN102585204A (en) * | 2012-02-26 | 2012-07-18 | 吉林大学 | Side-chain sulfonic acid type polyarylether, preparation method thereof and application of polyarylether in preparation of proton exchange membrane |
| CN104558586A (en) * | 2015-01-12 | 2015-04-29 | 吉林大学 | Allyl containing crosslinkable azo polyarylether and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2019145235A1 (en) * | 2018-01-23 | 2019-08-01 | Solvay Specialty Polymers Usa, Llc | Process for preparing functionalized poly(aryl ether sulfones) polymers and block copolymers resulting therefrom |
| US11572443B2 (en) | 2018-01-23 | 2023-02-07 | Solvay Specialty Polymers Usa, Llc | Process for preparing functionalized poly(aryl ether sulfones) polymers and block copolymers resulting therefrom |
| CN110294845A (en) * | 2019-07-03 | 2019-10-01 | 中国科学院长春应用化学研究所 | A kind of tertiary amine-type polyether sulphone (ketone) fluoropolymer resin and preparation method thereof and anion-exchange membrane |
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