CN106188525A - A kind of synthetic method of polyphenylene oxide - Google Patents
A kind of synthetic method of polyphenylene oxide Download PDFInfo
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- CN106188525A CN106188525A CN201610563702.XA CN201610563702A CN106188525A CN 106188525 A CN106188525 A CN 106188525A CN 201610563702 A CN201610563702 A CN 201610563702A CN 106188525 A CN106188525 A CN 106188525A
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- polyphenylene oxide
- synthetic method
- red copper
- oxide
- hydrogen bromide
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- 239000004721 Polyphenylene oxide Substances 0.000 title claims abstract description 29
- 229920006380 polyphenylene oxide Polymers 0.000 title claims abstract description 29
- 238000010189 synthetic method Methods 0.000 title claims abstract description 13
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 claims abstract description 36
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 19
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 claims abstract description 19
- LBJNMUFDOHXDFG-UHFFFAOYSA-N copper;hydrate Chemical compound O.[Cu].[Cu] LBJNMUFDOHXDFG-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910000042 hydrogen bromide Inorganic materials 0.000 claims abstract description 18
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 16
- 150000000345 2,6-xylenols Chemical class 0.000 claims abstract description 10
- 239000003054 catalyst Substances 0.000 claims abstract description 10
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 10
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 8
- 230000001590 oxidative effect Effects 0.000 claims abstract 2
- 238000006243 chemical reaction Methods 0.000 claims description 30
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 claims description 24
- NXXYKOUNUYWIHA-UHFFFAOYSA-N 2,6-Dimethylphenol Chemical compound CC1=CC=CC(C)=C1O NXXYKOUNUYWIHA-UHFFFAOYSA-N 0.000 claims description 22
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 239000000463 material Substances 0.000 claims description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 8
- 239000001301 oxygen Substances 0.000 claims description 8
- 229910052760 oxygen Inorganic materials 0.000 claims description 8
- 238000007664 blowing Methods 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- 238000011084 recovery Methods 0.000 claims description 3
- JEFSTMHERNSDBC-UHFFFAOYSA-N 1,2-dimethylcyclohexa-2,4-dien-1-ol Chemical compound CC1=CC=CCC1(C)O JEFSTMHERNSDBC-UHFFFAOYSA-N 0.000 claims description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 2
- 229910001882 dioxygen Inorganic materials 0.000 claims description 2
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 2
- 230000004044 response Effects 0.000 claims description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims 1
- 229910052794 bromium Inorganic materials 0.000 claims 1
- 239000001257 hydrogen Substances 0.000 claims 1
- 229910052739 hydrogen Inorganic materials 0.000 claims 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 abstract description 15
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 abstract description 12
- 239000002904 solvent Substances 0.000 abstract description 11
- 238000000034 method Methods 0.000 abstract description 7
- 230000003647 oxidation Effects 0.000 abstract description 7
- 238000007254 oxidation reaction Methods 0.000 abstract description 7
- 239000012530 fluid Substances 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 4
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 abstract description 4
- 230000008569 process Effects 0.000 abstract description 4
- 230000001988 toxicity Effects 0.000 abstract description 3
- 231100000419 toxicity Toxicity 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 238000003889 chemical engineering Methods 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 229960004424 carbon dioxide Drugs 0.000 description 8
- 238000010668 complexation reaction Methods 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 229920013636 polyphenyl ether polymer Polymers 0.000 description 5
- 230000008901 benefit Effects 0.000 description 3
- 229910002090 carbon oxide Inorganic materials 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 229920006351 engineering plastic Polymers 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 241000790917 Dioxys <bee> Species 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 229920006038 crystalline resin Polymers 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 230000009965 odorless effect Effects 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000004017 vitrification Methods 0.000 description 1
- 238000005303 weighing Methods 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
- C08G65/38—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols
- C08G65/44—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols by oxidation of phenols
-
- 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
- C08G2650/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G2650/28—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type
- C08G2650/56—Polyhydroxyethers, e.g. phenoxy resins
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
Landscapes
- 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 discloses the synthetic method of a kind of polyphenylene oxide.By at supercritical CO2Fluid, as under the effect of solvent, uses Red copper oxide, hydrogen bromide and the catalyst of secondary monoamine composition, and to 2,6 xylenols carry out oxidative polymerization, thus synthesize polyphenylene oxide.The present invention uses supercritical CO2As 2,6 xylenols carry out the solvent of oxidation polymerization, replace Nitrobenzol that toxicity is bigger, benzene, toluene, Isosorbide-5-Nitrae dioxane etc., reduce the harm to human body and environment, optimize the synthesis technique of polyphenylene oxide；Meanwhile, CO2It is prone to separate with product, and can be recycled, useless carbon dioxide will not be discharged and cause greenhouse effect to affect environment, be a kind of Green Chemical Engineering Process.
Description
Technical field
The present invention relates to macromolecular polymerization reaction field, be specifically related to the synthetic method of a kind of polyphenylene oxide.
Background technology
Polyphenylene oxide (PPO) is one of big general engineering plastic in the world five, it has, and rigidity is big, thermostability is high, difficult combustion, intensity
The advantages such as higher, electrical property is excellent.It addition, polyphenylene oxide also has the advantages such as wear-resisting, nontoxic, anti-pollution.
Polyphenylene oxide is non-crystalline resin, and without water-disintegrable Ji Xuan in molecular structure, water resistance is preferable, in high steam
The change of Reusability performance is little.
Without highly polar Ji Xuan in polyphenylene oxide molecular structure, its dielectric constant and dielectric loss are minimum in engineering plastics
One of kind, is little affected by the impact of temperature, humidity, can be used for basic, normal, high frequency electric field field.
Polyphenylene oxide has higher thermostability, vitrification point 211 DEG C, fusing point 268 DEG C, and being heated to 330 DEG C has decomposition tendency,
Content its thermostability the highest of PPO is the best, and heat distortion temperature is up to 190 DEG C.Heat distortion temperature, can be from 75-under 1.82MPa
170 DEG C of consecutive variations, along with PPO content increases, the heat distortion temperature of material constantly raises, for meeting the performance of different occasion
Demand.
The range of polyphenylene oxide is extensive, and electric aspect disclosure satisfy that have under conditions of moist, load, high temperature
Excellent electrical insulating property, utilization is prepared TV and is amassed machine tuning sheet, coil core, insulating microwave part, housing, high frequency printed circuit
Plate, various high-pressure electronic components and parts, television set, computer, facsimile machine, copy machine housings etc.；Auto industry aspect is applicable to instrument
Plate, window frame, amortisseur, pump screen etc.；Mechanical industry aspect is used as gear, bearing, impeller of pump, blower wheel sheet etc.；
Chemical field aspect is used for making the corrosion-resistant parts such as pipeline, valve, filter disc and immersible pump.
Traditional polyphenylene oxide preparation method is mainly special by benzene phenoloid in a solvent under copper-amine complex is catalyzed
Being not 2,6-xylenol carries out oxidation polymerization and synthesizes, if patent US3306875 is using Nitrobenzol as solvent, cuprous halide
With aniline as catalyst, 2,6-xylenols carry out oxidation polymerization and prepare polyphenylene oxide；Patent CN103642847B with Isosorbide-5-Nitrae-
Dioxane is as solvent, Cu-lyt. and pyridine as catalyst, and by hydrogen peroxide oxidation 2,6-xylenol carries out oxygen
Change polymerization and prepare polyphenylene oxide；Using the aromatic hydrocarbon particularly benzene of C6 ~ C18 or toluene as solvent, copper and C4 in patent CN1612910
The secondary monoamine of ~ C12 is as catalyst, and 2,6-xylenols carry out oxidation polymerization and prepare polyphenylene oxide.
Solvent used in any of the above preparation method such as Nitrobenzol, benzene, toluene, Isosorbide-5-Nitrae-dioxane etc. all have relatively
, there is bigger risk in big toxicity in reaction and separation process, gives to produce and bring difficulty, to health with solvent recovery
Work the mischief, simultaneously to environment, it is therefore desirable to find a kind of safer synthetic method.
Summary of the invention
In order to solve above-mentioned technical problem, the invention provides the synthetic method of a kind of polyphenylene oxide.Supercritical CO2Fluid
It is the gas that colorless and odorless is nontoxic under normality, and after isolation entirely without the residual of solvent, can be effectively prevented from above-mentioned
The shortcoming of solvent, also prevent the murder by poisoning to human body of the use process and the pollution to environment simultaneously.CO2Critical temperature be
31.265 DEG C, critical pressure is 72.9atm, range of reaction temperature prepared by applicable polyphenylene oxide, and after the completion of reaction, works as bag
When Co 2 supercritical fluid containing product flows through separator, make CO owing to pressure declines2Rapidly become with product
Separate biphase and separate immediately, there is not the phase transition process of material, be not required to recycling design, easy to operate；This technique is not only imitated
Rate is high, and energy consumption is less, cost-effective, and meets the trend of environmental protection and energy saving.Fluid CO2Can be recycled, can't arrange
Putting useless carbon dioxide causes greenhouse effect to affect environment, is the production process of green chemical industry.
Technical scheme is as follows:
The synthetic method of a kind of polyphenylene oxide, by using catalyst and oxygen to 2,6-xylenol carries out oxidation polymerization production
Obtain, specifically include following step:
(1) catalyst is made up of Red copper oxide, hydrogen bromide and secondary monoamine, and mol ratio is 1:1 ~ 5:2 ~ 10；At autoclave
Red copper oxide and hydrogen bromide are mixed by nitrogen atmosphere, is subsequently adding secondary monoamine, prepares catalyst；
(2) 2 are added in a kettle., 6-xylenol, and be passed through carbon dioxide and dissolve material to critical point, then pass to oxygen
Gas starts reaction, and polymeric reaction temperature is maintained at 32 ~ 50 DEG C, response time 50min；
(3) reaction terminates rear pressure release blowing, and carbon dioxide recovery utilizes, and product is dried after washing with methanol and water, is gathered
Phenylate product.
Wherein:
Hydrogen bromide described in step (1) is aqueous solution, and its mass concentration is 40 ~ 49%；
Secondary monoamine described in step (1) is di-n-butyl amine；
The mol ratio of Red copper oxide, hydrogen bromide and secondary monoamine described in step (1) is 1:1 ~ 3:2 ~ 5；
Polymeric reaction temperature described in step (2) is 35 ~ 40 DEG C；
The mol ratio of 2,6-xylenols and Red copper oxide is 100:0.05 ~ 5.
Beneficial effects of the present invention:
1) it is an advantage of the current invention that to use supercritical CO2As 2,6-xylenol carries out the solvent of oxidation polymerization, replaces
Nitrobenzol that toxicity is bigger, benzene, toluene, Isosorbide-5-Nitrae-dioxane etc., reduce the harm to human body and environment, optimize polyphenylene oxide
Synthesis technique；
2) fluid CO2It is prone to separate with product, and can be recycled, useless carbon dioxide can't be discharged and cause greenhouse effect shadow
Ring environment, be a kind of Green Chemical Engineering Process.
Detailed description of the invention
Below in conjunction with embodiment, the invention will be further described, in order to those skilled in the art know more about the present invention, but also
It is not so limited the present invention.
Embodiment 1
At room temperature weigh Red copper oxide 0.143g and hydrogen bromide 0.303g that mass percent is 40%, put into the high pressure of nitrogen charging
In reactor, add di-n-butyl amine 0.323g after dissolving and carry out complexation, be subsequently adding 2,6-xylenol 122.0g, wherein
2,6-xylenols: Red copper oxide: hydrogen bromide: the mol ratio of di-n-butyl amine is 100:0.1:0.15:0.25.It is passed through dioxy
Change carbon and dissolve material to critical point, then pass to oxygen and start reaction, exothermic heat of reaction, to cool down water insulation 35 DEG C of reactions, time
Between 50min terminate, reaction terminates rear pressure release blowing, and product is dried after washing with methanol and water, obtains polyphenyl ether product.
Embodiment 2
At room temperature weigh Red copper oxide 0.215g and hydrogen bromide 0.405g that mass percent is 40%, put into the high pressure of nitrogen charging
In reactor, add di-n-butyl amine 0.387g after dissolving and carry out complexation, be subsequently adding 2,6-xylenol 122.0g, wherein
2,6-xylenols: Red copper oxide: hydrogen bromide: the mol ratio of di-n-butyl amine is 100:0.15:0.20:0.30.It is passed through two
Carbonoxide dissolves material to critical point, then pass to oxygen start reaction, exothermic heat of reaction, with cool down water be incubated 38 DEG C of reactions,
Time, 50min terminated, and reaction terminates rear pressure release blowing, and product is dried after washing with methanol and water, obtains polyphenyl ether product.
Embodiment 3
At room temperature weigh Red copper oxide 0.286g and hydrogen bromide 0.330g that mass percent is 49%, put into the high pressure of nitrogen charging
In reactor, add di-n-butyl amine 0.516g after dissolving and carry out complexation, be subsequently adding 2,6-xylenol 122.0g, wherein
2,6-xylenols: Red copper oxide: hydrogen bromide: the mol ratio of di-n-butyl amine is 100:0.20:0.20:0.40.It is passed through two
Carbonoxide dissolves material to critical point, then pass to oxygen start reaction, exothermic heat of reaction, with cool down water be incubated 40 DEG C of reactions,
Time, 50min terminated, and reaction terminates rear pressure release blowing, and product is dried after washing with methanol and water, obtains polyphenyl ether product.
Embodiment 4
At room temperature weighing Red copper oxide 7.15g and hydrogen bromide 41.25g that mass percent is 49%, the high pressure putting into nitrogen charging is anti-
Answer in still, add di-n-butyl amine 64.5g after dissolving and carry out complexation, be subsequently adding 2,6-xylenol 122.0g, wherein 2,
6-xylenol: Red copper oxide: hydrogen bromide: the mol ratio of di-n-butyl amine is 100:5:25:50.It is passed through carbon dioxide to facing
Boundary's point dissolves material, then passes to oxygen and starts reaction, and exothermic heat of reaction, to cool down water insulation at 32 DEG C of reactions, time 50min knot
Bundle, reaction terminates rear pressure release blowing, and product is dried after washing with methanol and water, obtains polyphenyl ether product.
Embodiment 5
At room temperature weigh Red copper oxide 0.072g and hydrogen bromide 0.248g that mass percent is 49%, put into the high pressure of nitrogen charging
In reactor, add di-n-butyl amine 0.323g after dissolving and carry out complexation, be subsequently adding 2,6-xylenol 122.0g, wherein
2,6-xylenols: Red copper oxide: hydrogen bromide: the mol ratio of di-n-butyl amine is 100:0.05:0.15:0.25.It is passed through two
Carbonoxide dissolves material to critical point, then pass to oxygen start reaction, exothermic heat of reaction, with cool down water be incubated 50 DEG C of reactions,
Time, 50min terminated, and reaction terminates rear pressure release blowing, and product is dried after washing with methanol and water, obtains polyphenyl ether product.
Claims (6)
1. a synthetic method for polyphenylene oxide, by catalyst and oxygen to 2,6-xylenol carry out oxidative polymerization and
Obtain, it is characterised in that specifically include following step:
(1) catalyst is made up of Red copper oxide, hydrogen bromide and secondary monoamine, and mol ratio is 1:1 ~ 5:2 ~ 10；At autoclave
Red copper oxide and hydrogen bromide are mixed by nitrogen atmosphere, is subsequently adding secondary monoamine, prepares catalyst；
(2) 2 are added in a kettle., 6-xylenol, and be passed through carbon dioxide and dissolve material to critical point, then pass to oxygen
Gas starts reaction, and polymeric reaction temperature is maintained at 32 ~ 50 DEG C, 50 minutes response time；
(3) reaction terminates rear pressure release blowing, and carbon dioxide recovery utilizes, and product is dried after washing with methanol and water, is gathered
Phenylate product.
The synthetic method of polyphenylene oxide the most according to claim 1, it is characterised in that the hydrogen bromide described in step (1) is water
Solution, its mass concentration is 40 ~ 49%.
The synthetic method of polyphenylene oxide the most according to claim 1, it is characterised in that the secondary monoamine described in step (1) is
Di-n-butyl amine.
The synthetic method of polyphenylene oxide the most according to claim 1, it is characterised in that the Red copper oxide described in step (1), bromine
The mol ratio changing hydrogen and secondary monoamine is 1:1 ~ 3:2 ~ 5.
The synthetic method of polyphenylene oxide the most according to claim 1, it is characterised in that the polyreaction temperature described in step (2)
Degree is 35 ~ 40 DEG C.
The synthetic method of polyphenylene oxide the most according to claim 1, it is characterised in that 2,6-xylenols and Red copper oxide
Mol ratio be 100:0.05 ~ 5.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610563702.XA CN106188525A (en) | 2016-07-18 | 2016-07-18 | A kind of synthetic method of polyphenylene oxide |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201610563702.XA CN106188525A (en) | 2016-07-18 | 2016-07-18 | A kind of synthetic method of polyphenylene oxide |
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| CN106188525A true CN106188525A (en) | 2016-12-07 |
Family
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| CN201610563702.XA Pending CN106188525A (en) | 2016-07-18 | 2016-07-18 | A kind of synthetic method of polyphenylene oxide |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108409959A (en) * | 2018-04-09 | 2018-08-17 | 南阳师范学院 | A kind of bromomethylation polyphenylene oxide and preparation method thereof |
| WO2019127645A1 (en) * | 2017-12-29 | 2019-07-04 | 安丽华 | Reaction system and method for preparing polyphenyl ether having small molecular weight |
-
2016
- 2016-07-18 CN CN201610563702.XA patent/CN106188525A/en active Pending
Non-Patent Citations (5)
| Title |
|---|
| KAPELLEN K K, ET AL: "Synthesis of Poly(2,6-dimethylphenylene oxide) in Carbon Dioxide", 《MACROMOLECULES》 * |
| MURATA HIDENORI, ET AL: "Synthesis of Poly(2,6-dimethyl-1,4-phenylene oxide) by Double-Step Polymerization in Supercritical Carbon Dioxide", 《KOBUNSHI RONBUNSHU》 * |
| 王稼书，等: "催化剂对2,6-二甲酚聚合反应速度的影响", 《化学世界》 * |
| 范洪琼: "《无机及分析化学》", 31 August 2015, 重庆大学出版社 * |
| 韦军主: "《高分子合成工艺学》", 28 February 2011, 华东理工大学出版社 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2019127645A1 (en) * | 2017-12-29 | 2019-07-04 | 安丽华 | Reaction system and method for preparing polyphenyl ether having small molecular weight |
| CN108409959A (en) * | 2018-04-09 | 2018-08-17 | 南阳师范学院 | A kind of bromomethylation polyphenylene oxide and preparation method thereof |
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