CN108409959B - Bromomethylated polyphenyl ether and preparation method thereof - Google Patents
Bromomethylated polyphenyl ether and preparation method thereof Download PDFInfo
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- CN108409959B CN108409959B CN201810312742.6A CN201810312742A CN108409959B CN 108409959 B CN108409959 B CN 108409959B CN 201810312742 A CN201810312742 A CN 201810312742A CN 108409959 B CN108409959 B CN 108409959B
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- bromomethylated
- source reagent
- methylene
- polyphenyl ether
- polyphenylene ether
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- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 229920013636 polyphenyl ether polymer Polymers 0.000 title claims description 26
- 125000005997 bromomethyl group Chemical group 0.000 claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 10
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 8
- 239000003153 chemical reaction reagent Substances 0.000 claims description 25
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 claims description 18
- 229920001955 polyphenylene ether Polymers 0.000 claims description 14
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical group Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 claims description 12
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 12
- 229910052794 bromium Inorganic materials 0.000 claims description 11
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 229910000042 hydrogen bromide Inorganic materials 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- 239000012716 precipitator Substances 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical group ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- 230000007935 neutral effect Effects 0.000 claims description 4
- BGJSXRVXTHVRSN-UHFFFAOYSA-N 1,3,5-trioxane Chemical group C1OCOCO1 BGJSXRVXTHVRSN-UHFFFAOYSA-N 0.000 claims description 3
- 229930040373 Paraformaldehyde Natural products 0.000 claims description 3
- IYYIVELXUANFED-UHFFFAOYSA-N bromo(trimethyl)silane Chemical compound C[Si](C)(C)Br IYYIVELXUANFED-UHFFFAOYSA-N 0.000 claims description 3
- 239000012295 chemical reaction liquid Substances 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 239000007789 gas Substances 0.000 claims description 3
- 229920002866 paraformaldehyde Polymers 0.000 claims description 3
- 239000002244 precipitate Substances 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 2
- 125000001246 bromo group Chemical group Br* 0.000 claims description 2
- 239000012046 mixed solvent Substances 0.000 claims description 2
- 238000006116 polymerization reaction Methods 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 14
- 239000004721 Polyphenylene oxide Substances 0.000 abstract description 7
- 229920006380 polyphenylene oxide Polymers 0.000 abstract description 7
- 229920001002 functional polymer Polymers 0.000 abstract description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 3
- 239000001257 hydrogen Substances 0.000 abstract description 3
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 3
- 238000003547 Friedel-Crafts alkylation reaction Methods 0.000 abstract description 2
- 239000002841 Lewis acid Substances 0.000 abstract description 2
- 239000003377 acid catalyst Substances 0.000 abstract description 2
- -1 benzyl halide Chemical class 0.000 abstract description 2
- 239000003054 catalyst Substances 0.000 abstract description 2
- 238000004132 cross linking Methods 0.000 abstract description 2
- 150000007517 lewis acids Chemical class 0.000 abstract description 2
- 239000003011 anion exchange membrane Substances 0.000 description 6
- 239000002904 solvent Substances 0.000 description 5
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 4
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000031709 bromination Effects 0.000 description 2
- 238000005893 bromination reaction Methods 0.000 description 2
- 238000005341 cation exchange Methods 0.000 description 2
- 229920006351 engineering plastic Polymers 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 230000011987 methylation Effects 0.000 description 2
- 238000007069 methylation reaction Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229920013638 modified polyphenyl ether Polymers 0.000 description 2
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 229920001169 thermoplastic Polymers 0.000 description 2
- 239000004416 thermosoftening plastic Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 125000005002 aryl methyl group Chemical group 0.000 description 1
- AGEZXYOZHKGVCM-UHFFFAOYSA-N benzyl bromide Chemical compound BrCC1=CC=CC=C1 AGEZXYOZHKGVCM-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 238000005956 quaternization reaction Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 231100000167 toxic agent Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
Classifications
-
- 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
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
- C08G65/48—Polymers modified by chemical after-treatment
Landscapes
- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyethers (AREA)
Abstract
The invention provides bromomethylated polyphenylene oxide and a preparation method thereof, belonging to the field of functional polymers. The bromomethylation degree of the bromomethylated polyphenylene oxide obtained by the invention can reach very high, even 200%, namely hydrogen on a benzene ring of the polyphenylene oxide is completely replaced by bromomethyl, which is far higher than that of the existing bromomethylation method, and compared with the existing polyphenylene oxide halomethylation method, the invention avoids the use of Lewis acid or strong protonic acid catalyst in the general halomethylation process, and avoids the crosslinking reaction caused by the further friedel-crafts alkylation of benzyl halide caused by the catalyst.
Description
Technical Field
The invention belongs to the field of functional polymers, and particularly relates to bromomethylation polyphenyl ether and a preparation method thereof.
Background
Polyphenylene oxide is an excellent thermoplastic engineering plastic, has good mechanical property, thermal property and electrical property and is low in price. In order to improve the properties of polyphenylene ethers and expand the application fields thereof, extensive studies have been made on the functional modification of polyphenylene ethers. Wherein, the halogen methylation modified polyphenyl ether is an important intermediate for preparing functional polymer materials such as polyphenyl ether-based anion exchange membranes, phosphonated cation exchange membranes, phosphine-containing flame-retardant polyphenyl ethers and the like. For example, XunnalofMembranance, 2001, 190: 159-166, etc. firstly performs bromomethylation on arylmethyl groups on polyphenylene ether, then reacts with tertiary ammonium to convert benzyl bromide into quaternary ammonium groups, and finally prepares the anion exchange membrane. The DF120 anion exchange membrane of Shandong Tianwei company is the anion exchange membrane at present. However, the bromine used in the bromomethylation process is a toxic substance and requires the use of chlorobenzene, a high boiling point toxic solvent, since the reaction is carried out at higher temperatures. Nanwen Li (Energy & environmental science, 2012, 5: 7888-; ShuangGu (ChemSusChem, 2012, 5: 843-.
Patent document CN106432744A discloses a highly alkali-resistant polyphenylene ether anion exchange membrane and a preparation method thereof. Dissolving polyphenyl ether in a solvent to obtain a polyphenyl ether solution, adding a brominating reagent into the polyphenyl ether solution, reacting under the condition of introducing nitrogen to obtain a bromomethylated polyphenyl ether solution, and drying to obtain the bromomethylated polyphenyl ether. However, according to the method, chlorobenzene is used as a solvent, liquid bromine is used as a bromination reagent, and the prepared bromomethylation polyphenyl ether has low bromomethylation degree.
Disclosure of Invention
The invention aims to solve the technical problem of providing bromomethylation polyphenyl ether and a preparation method thereof aiming at the defects of the prior art.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
the bromomethylated polyphenyl ether has a chemical structural general formula as follows:
wherein n represents the polymerization degree of the polyphenyl ether and is an integer of 10-400; x represents the number of bromomethyl groups on average per benzene ring, and is 1% to 200%.
Preferably, the preparation method of the bromomethylated polyphenylene ether comprises the following steps:
s1: adding polyphenyl ether and an organic solvent into a reactor, and stirring and dissolving to prepare a solution;
s2: adding a methylene source reagent and a bromine source reagent into the solution obtained in the step S1, and stirring and reacting at 20-80 ℃ for 1-24 hours to prepare a reaction solution;
s3: and (4) slowly dropping the reaction liquid obtained in the step (S2) into a precipitator, filtering, washing with the precipitator until the pH value is close to neutral, collecting the precipitate, and drying to obtain the bromomethylated polyphenylene ether.
Preferably, in step S1, the organic solvent is chloroform or 1, 2-dichloroethane.
Preferably, in step S2, the bromine source reagent is hydrogen bromide gas, acetic acid solution of hydrogen bromide or trimethyl bromosilane; the methylene source reagent is paraformaldehyde or trioxymethylene.
Preferably, the molar ratio of methylene contained in the methylene source reagent to benzene rings contained in the polyphenylene ether is 1: 0.01-2.5; the molar ratio of bromine atoms contained in the bromine source reagent to methylene contained in the methylene source reagent is 1: 1-1.5.
Preferably, in step S3, the precipitant is ethanol, methanol, acetone or a mixed solvent of each component and water.
The invention has the beneficial effects that: polyphenylene oxide is an excellent thermoplastic engineering plastic, has good mechanical property, thermal property and electrical property and is low in price. Wherein, the halogen methylation modified polyphenyl ether is an important intermediate for preparing functional polymer materials such as polyphenyl ether-based anion exchange membranes, phosphonated cation exchange membranes, phosphine-containing flame-retardant polyphenyl ethers and the like. The bromomethylation degree of the bromomethylated polyphenyl ether obtained by the invention can reach very high, the bromomethyl content is increased along with the increase of the addition amount of a methylene source reagent, even 200 percent of the bromomethyl content can be reached, namely, all hydrogen on a benzene ring is replaced by bromomethyl, which is far higher than that of the existing bromomethylation method, and the high bromomethylation degree is very beneficial to further functionalization such as phosphonation, quaternization and the like. Compared with the prior polyphenylene ether halomethylation method, the method avoids the use of Lewis acid or strong protonic acid catalyst in the general halomethylation process, thereby avoiding the crosslinking reaction caused by the further friedel-crafts alkylation of benzyl halide caused by the catalyst; compared with the existing method for methyl bromination on polyphenyl ether, the method has the advantages that the price of the used reagent is relatively low, and the reaction temperature is relatively low.
Firstly, adding polyphenyl ether and an organic solvent into a reactor, and stirring and dissolving to prepare a solution; adding a methylene source reagent and a bromine source reagent into the solution, and stirring and reacting at 20-80 ℃ for 1-24 hours to prepare a reaction solution; and then slowly dripping the reaction liquid into a precipitator, filtering, washing with the precipitator until the pH value is close to neutral, collecting the precipitate, and drying to obtain the bromomethylated polyphenylene oxide. The method has the advantages of simple steps, simple process and low cost.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions of the embodiments of the present invention are clearly and completely described below. It is to be understood that the embodiments described are only a few embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the described embodiments of the invention, are within the scope of the invention.
The hydrogen nuclear magnetic resonance spectrum adopts deuterated chloroform as a solvent and tetramethylsilane as an internal standard.
Examples 1 to 13:
1.2015 g of polyphenyl ether (containing 10mmol of phenyl, sold on the market) and amL of organic solvent are stirred and dissolved at room temperature, then a methylene source reagent (containing bmmol of methylene) and a bromine source reagent (containing c mmol of bromine atoms) are added into a round-bottom flask provided with a condensing tube and a drying tube, stirring reaction is carried out for a plurality of hours at a certain temperature, then the reaction solution is slowly dropped into ethanol, filtered, washed until the pH value is close to neutral, and dried to obtain a series of bromomethylated polyphenyl ethers with different bromomethyl contents.
The influence of the amount of each component added, the kind of solvent, the reaction temperature and the time on the bromomethyl group content (obtained by integrating the corresponding nuclear magnetic spectrum) in the obtained bromomethylated polyphenylene ether, that is, the influence of x in formula 1 is shown in table 1.
TABLE 1
It can be seen from examples 3 and 4 that whether the methylene source reagent is paraformaldehyde or trioxymethylene has no significant effect; it can be seen from examples 5, 6 and 7 that no matter the acetic acid solution of hydrogen bromide, trimethyl bromosilane or hydrogen bromide gas is selected as the bromine source reagent, the product with 100% bromomethyl group content can be obtained; it can be seen from examples 4, 10 and 11 that the bromomethyl content increases with the addition of the methylene source reagent, and even can reach 200%, that is, all the hydrogens on the benzene ring are replaced by bromomethyl, which is far higher than that of the existing bromomethylation method.
Finally, the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting, and other modifications or equivalent substitutions made by the technical solutions of the present invention by those of ordinary skill in the art should be covered within the scope of the claims of the present invention as long as they do not depart from the spirit and scope of the technical solutions of the present invention.
Claims (4)
1. A bromomethylated polyphenylene ether characterized by: the chemical structural general formula is as follows:
the preparation method of the bromomethylated polyphenylene ether comprises the following steps:
s1: adding polyphenyl ether and an organic solvent into a reactor, and stirring and dissolving to prepare a solution;
s2: adding a methylene source reagent and a bromine source reagent into the solution obtained in the step S1, and stirring and reacting at 20-80 ℃ for 1-24 hours to prepare a reaction solution;
s3: slowly dripping the reaction liquid obtained in the step S2 into a precipitator, filtering, washing with the precipitator until the pH value is close to neutral, collecting the precipitate, and drying to obtain bromomethylated polyphenyl ether;
the molar ratio of methylene contained in the methylene source reagent to benzene rings contained in the polyphenyl ether is 1: 0.01-2.5; the molar ratio of bromine atoms contained in the bromine source reagent to methylene contained in the methylene source reagent is 1: 1-1.5.
2. The bromomethylated polyphenylene ether according to claim 1, wherein: in the step S1, the organic solvent is chloroform or 1, 2-dichloroethane.
3. The bromomethylated polyphenylene ether according to claim 1, wherein: in the step S2, the bromine source reagent is hydrogen bromide gas, acetic acid solution of hydrogen bromide, or trimethyl bromosilane; the methylene source reagent is paraformaldehyde or trioxymethylene.
4. The bromomethylated polyphenylene ether according to claim 1, wherein: in the step S3, the precipitant is ethanol, methanol, acetone or a mixed solvent of each component and water.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3334068A1 (en) * | 1983-09-21 | 1985-04-11 | Chemische Werke Hüls AG, 4370 Marl | METHOD FOR BROMMETHYLATING POLYPHENYLENE ETHERS |
| WO2008103599A3 (en) * | 2007-02-22 | 2008-11-06 | Sabic Innovative Plastics Ip | Composition, its use in the preparation of membranes, and systems comprising the membranes |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1295268C (en) * | 2004-03-23 | 2007-01-17 | 华东理工大学 | Preparing thermosetting phlyphenylether through Geliya reagent in polyphenylether halide and allyl group type |
| CN101284216B (en) * | 2008-05-08 | 2011-05-18 | 中国科学技术大学 | Hollow fiber anion-exchange membrane and preparation method thereof |
| CN103372381B (en) * | 2012-04-19 | 2015-04-08 | 中国科学技术大学 | Anion-exchange film, preparation method thereof and fuel cell |
| US10023672B2 (en) * | 2016-05-24 | 2018-07-17 | Elite Material Co., Ltd. | Polyphenylene oxide prepolymer, method of making the same, resin composition and product made therefrom |
| CN106188525A (en) * | 2016-07-18 | 2016-12-07 | 江苏三吉利化工股份有限公司 | A kind of synthetic method of polyphenylene oxide |
| CN106243345B (en) * | 2016-08-04 | 2018-11-30 | 潍坊鑫洋化工有限公司 | A kind of brominated polyphenylether synthesis technology |
| CN106632747B (en) * | 2016-12-28 | 2020-03-06 | 四川大学 | Bromomethylated styrene thermoplastic elastomer and preparation method and application thereof |
| CN107602848B (en) * | 2017-10-09 | 2019-05-28 | 山东日兴新材料股份有限公司 | A kind of preparation method of water process Noryl film |
| CN107694346B (en) * | 2017-10-09 | 2020-11-06 | 山东日兴新材料股份有限公司 | Preparation method of brominated polyphenylene oxide asymmetric membrane for water treatment |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3334068A1 (en) * | 1983-09-21 | 1985-04-11 | Chemische Werke Hüls AG, 4370 Marl | METHOD FOR BROMMETHYLATING POLYPHENYLENE ETHERS |
| WO2008103599A3 (en) * | 2007-02-22 | 2008-11-06 | Sabic Innovative Plastics Ip | Composition, its use in the preparation of membranes, and systems comprising the membranes |
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