CN116023650A - Process for producing polyphenyl ether by using tubular reactor - Google Patents
Process for producing polyphenyl ether by using tubular reactor Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 21
- 229920013636 polyphenyl ether polymer Polymers 0.000 title claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 36
- 239000007788 liquid Substances 0.000 claims abstract description 30
- 239000007791 liquid phase Substances 0.000 claims abstract description 27
- 239000003054 catalyst Substances 0.000 claims abstract description 24
- 239000011259 mixed solution Substances 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 238000000926 separation method Methods 0.000 claims abstract description 6
- 239000007789 gas Substances 0.000 claims description 40
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 26
- 239000001301 oxygen Substances 0.000 claims description 26
- 229910052760 oxygen Inorganic materials 0.000 claims description 25
- 239000003960 organic solvent Substances 0.000 claims description 14
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- 239000000178 monomer Substances 0.000 claims description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 8
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- 239000012295 chemical reaction liquid Substances 0.000 claims description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 claims description 4
- 229910021591 Copper(I) chloride Inorganic materials 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 150000001412 amines Chemical class 0.000 claims description 3
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims description 3
- 229940045803 cuprous chloride Drugs 0.000 claims description 3
- 230000000694 effects Effects 0.000 claims description 3
- 239000012071 phase Substances 0.000 claims description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 125000004103 aminoalkyl group Chemical group 0.000 claims description 2
- 125000001188 haloalkyl group Chemical group 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- 239000000463 material Substances 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- 229910001873 dinitrogen Inorganic materials 0.000 claims 1
- 229910001882 dioxygen Inorganic materials 0.000 claims 1
- 229920001955 polyphenylene ether Polymers 0.000 claims 1
- 238000009826 distribution Methods 0.000 abstract description 7
- NXXYKOUNUYWIHA-UHFFFAOYSA-N 2,6-Dimethylphenol Chemical compound CC1=CC=CC(C)=C1O NXXYKOUNUYWIHA-UHFFFAOYSA-N 0.000 abstract description 6
- 230000009286 beneficial effect Effects 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 238000009776 industrial production Methods 0.000 abstract description 3
- 239000002904 solvent Substances 0.000 abstract description 3
- 230000006583 body weight regulation Effects 0.000 abstract description 2
- 238000010924 continuous production Methods 0.000 abstract description 2
- 229920000642 polymer Polymers 0.000 abstract description 2
- 238000005691 oxidative coupling reaction Methods 0.000 abstract 1
- 239000000047 product Substances 0.000 description 15
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000007800 oxidant agent Substances 0.000 description 4
- 239000000376 reactant Substances 0.000 description 4
- 239000004721 Polyphenylene oxide Substances 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 229920006380 polyphenylene oxide Polymers 0.000 description 3
- 230000003321 amplification Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000003199 nucleic acid amplification method Methods 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000012265 solid product Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/18—Stationary reactors having moving elements inside
-
- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Polyethers (AREA)
Abstract
The invention discloses a process for producing polyphenyl ether by using a tubular reactor, and belongs to the technical field of polymer production and reactor design. The tubular reactor mainly comprises a liquid phase mixer, a reactor main body and a gas-liquid separator which are sequentially connected in series, wherein an outlet of the liquid phase mixer is connected with the side wall of the bottom of the reactor main body, the bottom of the reactor main body is connected with a gas inlet, a gas distributor is arranged between the gas inlet and the reactor main body, an inner member is arranged in the reactor main body, and the top outlet of the reactor main body is connected with the gas-liquid separator; and (3) performing oxidative coupling on the 2, 6-dimethylphenol by using a tubular reactor to prepare polyphenyl ether, and separating the obtained reaction mixed solution to obtain a polyphenyl ether product. The invention solves the problems of large back mixing degree, wide molecular weight distribution of products, difficult realization of molecular weight regulation and the like in the intermittent stirred tank reactor. The invention also realizes the continuous production operation of the reaction and the separation process of the catalyst, the solvent and the product, and is beneficial to industrial production.
Description
Technical Field
The invention belongs to the technical field of polymer production and reactor design, and particularly relates to a process for producing polyphenyl ether by using a tubular reactor.
Background
Polyphenylene Oxide (PPO) is engineering plastic with excellent comprehensive performance, not only has good mechanical properties, but also has outstanding properties of low dielectric constant, low dielectric loss, low hygroscopicity, high glass transition temperature, acid and alkali corrosion resistance and the like, thereby having wide application prospects in the fields of automobile parts, electronic devices, office equipment, paint and additives, photovoltaic junction boxes and the like. In the prior art, the process for producing the polyphenyl ether adopts a homogeneous intermittent kettle type reactor, the inside of the reactor belongs to a fully mixed flow state, a large amount of heat is generated in the reaction process, the mass and heat transfer effect is not ideal enough, the back mixing is serious, and the amplification and production operation are difficult in the industrial production process. Meanwhile, as the reacted product needs to be separated from the catalyst and the product rapidly, or the polyphenylene oxide generated by polymerization can be further crosslinked to generate a space net structure, the quality of the product is affected, and the intermittent kettle type reactor is not beneficial to the continuous operation of a system after the reaction, so that the industrial application difficulty of the process is high.
Disclosure of Invention
Aiming at the technical problems in the background art, the invention aims to provide a process for producing polyphenyl ether by using a tubular reactor. The reactor has the advantages of simple structure, simple and convenient operation and high operation elasticity, and can flexibly adjust the operation conditions according to the requirements to produce polyphenyl ether products with different molecular weight marks.
The invention aims at realizing the following steps:
the invention provides a process for producing polyphenyl ether by using a tubular reactor, wherein the tubular reactor mainly comprises a liquid phase mixer 5, a reactor main body 1 and a gas-liquid separator 8 which are sequentially connected in series through pipelines, and the inlet of the liquid phase mixer 5 is respectively communicated with a reaction liquid inlet 4 and a catalyst inlet 11; the reactor main body 1 is vertical, the outlet of the liquid phase mixer 5 is connected with the side wall of the bottom of the reactor main body 1 through a pipeline, the bottom of the reactor main body 1 is connected with a gas inlet 6, a gas distributor 7 is arranged on the cross section between the gas inlet 6 and the reactor main body 1, an inner member 2 is arranged in the reactor main body 1, a heat exchange jacket 3 is arranged outside the shell of the reactor main body 1 or/and a heat exchange pipe is arranged in the reactor main body 1 so as to control the temperature in the reactor, the top outlet of the reactor main body 1 is connected with a gas-liquid separator 8 through a pipeline, the top end of the gas-liquid separator 8 is provided with a gas outlet 9, and the bottom end is provided with a liquid outlet 10;
mainly comprises the following steps:
(1) The organic solvent dissolved with the phenol monomer is introduced into the liquid phase mixer 5 from the reaction liquid inlet 4 and is fully mixed with the organic solvent containing the catalyst introduced from the catalyst inlet 11 in the liquid phase mixer 5 to obtain a mixed solution of the reaction raw material and the catalyst;
(2) The mixed solution of the reaction raw materials and the catalyst enters the reactor body 1 through the bottom of the reactor body 1, fully contacts and reacts with the mixed gas containing oxygen of the bubbles which is introduced by the gas inlet 6 and dispersed by the gas distributor 7, and moves upwards along the axial direction of the reactor body 1; the heat exchange jacket 3 or/and the heat exchange tube maintain the reaction temperature in the reactor main body 1, and the inner member 2 in the reactor main body 1 increases the turbulence degree of the liquid phase, controls the size of bubbles and increases the mixing effect between the gas phase and the liquid phase;
(3) The mixture after reaction enters the gas-liquid separator 8 through the top of the reactor main body 1, gas is discharged from the gas outlet 9 at the top of the gas-liquid separator 8 through gas-liquid separation, and the mixed liquid flows out from the liquid phase outlet 10 at the bottom of the gas-liquid separator 8 and is separated and purified to obtain the polyphenyl ether.
Based on the technical scheme, the molecular weight of the polyphenyl ether product is further controlled by adjusting the amount of the mixed gas or the oxygen concentration introduced into the bottom of the reactor and the residence time of the materials in the reactor.
Based on the technical proposal, further, the structure of the phenol monomer in the step (1) is shown as the formula (I),
r in formula (I) 1 And R is 2 Are respectively and independently hydrogen, C 1-4 Alkyl, haloalkyl, aminoalkyl or alkoxy, R 3 Is hydrogen or halogen.
Based on the above technical scheme, further, the organic solvent in the step (1) is one or a mixture of more than two of toluene, xylene, benzene, nitrobenzene, methylene dichloride, chloroform and pyridine.
Based on the technical scheme, further, the concentration of the phenol monomer in the organic solvent dissolved with the phenol monomer in the step (1) is 10-300g/L.
Based on the technical scheme, the catalyst in the step (1) is a complex of cuprous chloride and organic amine, and the concentration of the catalyst in the organic solvent containing the catalyst is 0.1-20g/L.
Based on the technical scheme, further, the feeding flow ratio of the organic solvent in which the phenol monomer is dissolved in the step (1) to the organic solvent containing the catalyst is 1:5-5:1.
Based on the technical scheme, further, the reaction temperature in the reactor main body 1 in the step (1) is 20-150 ℃, the reaction pressure is 0.01-10MPa, and the liquid phase residence time is 0.1-24 hours.
Based on the above technical scheme, further, the oxygen-containing mixed gas in the step (2) is an oxygen/nitrogen mixed gas, the oxygen concentration is 5% -100%, and the introduced mixed gas is introduced from the bottom of the reactor main body 1 or respectively introduced at different heights of the reactor main body 1 according to a certain proportion.
Based on the technical scheme, the flow of the oxygen-containing gas mixture in the step (2) is 0.2-5000L/min.
Based on the technical scheme, further, the specific process of separation and purification in the step (3) is as follows: and adding the reaction mixed solution into a large amount of methanol solvent, filtering, washing and vacuum drying to obtain a solid product, namely the polyphenyl ether product.
Based on the technical scheme, the height of the reactor main body 1 is 0.5-50m, and the inner diameter is 10-6000mm.
Based on the above technical solution, further, the inner member 2 is one or a combination of two or more of a porous plate, a raschig ring, a pall ring and a θ ring.
Based on the above technical scheme, further, the reactor main body 1 is a section of reaction units or is formed by connecting 2-100 sections of reaction units in series, the inner diameter and the length of each section of reaction units are correspondingly adjusted according to the reaction process, and the sections of reaction units are coaxially arranged or arranged in parallel.
Compared with the prior art, the invention has the following beneficial effects:
the invention adopts the tubular reactor for producing polyphenyl ether by multiphase polymerization, can overcome the problems of serious back mixing, wide molecular weight distribution, difficult molecular weight regulation and control and the like of polyphenyl ether products in the stirred tank reactor, can realize continuous production operation of reaction and catalyst, solvent and product separation processes by adopting the tubular reactor, and is beneficial to engineering amplification and industrial production operation.
Drawings
In order to more clearly illustrate the embodiments of the present invention, the drawings to which the embodiments relate will be briefly described.
FIG. 1 is a tube reactor of example 1; in the figure: 1-a reactor body; 2-an inner member; 3-a heat exchange jacket; 4-a reaction liquid inlet; 5-a liquid phase mixer; 6-gas inlet; 7-a gas distributor; 8-a gas-liquid separator; 9-gas outlet; 10-liquid outlet; 11-catalyst inlet.
Detailed Description
The following detailed description of the invention is provided in connection with examples, but the implementation of the invention is not limited thereto, and it is obvious that the examples described below are only some examples of the invention, and that it is within the scope of protection of the invention to those skilled in the art to obtain other similar examples without inventive faculty.
Example 1
The embodiment provides a process for preparing polyphenyl ether by using a tubular reactor, wherein the total length of the tubular reactor used in the process is 2m, the inner diameter of the reactor is 50mm, the tubular reactor mainly comprises a liquid phase mixer 5, a reactor main body 1 and a gas-liquid separator 8 which are sequentially connected in series through pipelines, and the inlet of the liquid phase mixer 5 is respectively communicated with a reaction liquid inlet 4 and a catalyst inlet 11; the reactor main body 1 is vertical, the outlet of the liquid phase mixer 5 is connected with the side wall of the bottom of the reactor main body 1 through a pipeline, the bottom of the reactor main body 1 is connected with a gas inlet 6, a gas distributor 7 is arranged on the cross section between the gas inlet 6 and the reactor main body 1, an inner member 2 is arranged in the reactor main body 1, the inner member is a stainless steel pall ring, a heat exchange jacket 3 is arranged outside a shell of the reactor main body 1 to control the temperature in the reactor, the top outlet of the reactor main body 1 is connected with a gas-liquid separator 8 through a pipeline, the top end of the gas-liquid separator 8 is provided with a gas outlet 9, and the bottom end is provided with a liquid outlet 10;
with the reactor, the preparation process mainly comprises the following steps:
840g of 2, 6-dimethylphenol is dissolved in 3.75kg of toluene solvent, after the 2, 6-dimethylphenol is fully dissolved, the mixture is introduced into a liquid-phase mixer 5 at a flow rate of 17.3mL/min, and meanwhile, 35.0mL/min of mixed solution of cuprous chloride, an organic amine complex catalyst and toluene solvent is introduced into the liquid-phase mixer 5, wherein the raw material feeding amount is 4.7g/min; the reaction temperature is controlled to be 30 ℃, oxygen/nitrogen mixed gas is adopted at the bottom of the reactor, the oxygen concentration is 75%, the oxygen flow is 1.2L/min, the residence time is about 0.5 hour, gas-liquid separation is carried out at the outlet of the reactor through a gas-liquid separator, gas phase is discharged into the atmosphere through the gas outlet 9 through condensation and absorption, the liquid phase is subjected to collection of reactants through the liquid outlet 10, the reactants are dripped into a large amount of methanol, and the solid product is obtained after filtration, washing and vacuum drying to constant weight, thus obtaining the polyphenyl ether product, the yield is 78.57%, the number average molecular weight is 13000, the weight average molecular weight is 27000, and the molecular weight distribution is 2.1.
Examples 2 to 5
The feed composition of the gas was adjusted according to the protocol of example 1, the amounts of oxygen and nitrogen were adjusted, and other conditions were not adjusted, specifically as shown in table 1 below.
TABLE 1 intake air amount of oxygen and nitrogen and product parameters for examples 2-5
Examples 6 to 8
Following the protocol of example 1, pure oxygen was used as the reactant gas, with specific adjustments as shown in table 2 below.
TABLE 2 oxygen intake and product parameters for examples 6-8
| Examples | 6 | 7 | 8 |
| Oxygen flow (ml/min) | 900 | 1200 | 1500 |
| Number average molecular weight | 14000 | 16000 | 19000 |
| Weight average molecular weight | 27000 | 29000 | 36000 |
| Molecular weight distribution | 1.9 | 1.8 | 1.9 |
| Yield (%) | 78.79 | 80.45 | 82.58 |
Examples 9 to 12
The reactor was replaced with a 8m tubular reactor, the inside diameter of the reactor was unchanged, pure oxygen was used as an oxidizing agent, the feed ratio of each reaction substance was unchanged, the feed amount was adjusted to adjust the residence time, and the reaction temperature was controlled at 30 ℃, specifically adjusted as shown in table 3 below.
TABLE 3 oxygen intake, residence time and product parameters for examples 9-12
| Examples | 9 | 10 | 11 | 12 |
| Residence time (h) | 0.5 | 0.5 | 1 | 2 |
| Oxygen flow (ml/min) | 2800 | 3200 | 3600 | 4000 |
| Number average molecular weight | 38000 | 45000 | 53000 | 63000 |
| Weight average molecular weight | 129000 | 144000 | 179000 | 145000 |
| Molecular weight distribution | 1.8 | 1.8 | 2.0 | 2.3 |
| Yield (%) | 85.69 | 89.56 | 91.35 | 91.54 |
Examples 13 to 15
The reactor was replaced with a tubular reactor of 8m in diameter, pure oxygen was used as the oxidant, the total flow of oxygen was 3600ml/min, the residence time was 1h, the reaction temperature was controlled at 25-50℃and the specific adjustments were as shown in Table 4 below.
TABLE 4 reaction temperatures and product parameters for examples 13-15
| Examples | 13 | 14 | 15 |
| Reaction temperature (. Degree. C.) | 25 | 40 | 50 |
| Number average molecular weight | 35000 | 58000 | 60000 |
| Weight average molecular weight | 63000 | 197000 | 228000 |
| Molecular weight distribution | 1.8 | 3.4 | 3.8 |
| Yield (%) | 85.57 | 89.87 | 91.54 |
Examples 16 to 18
The reactor was replaced with a 4m tubular reactor with constant inside diameter, pure oxygen was used as the oxidant, the total flow rate of oxygen was 3000ml/min, the residence time was 0.5h, the reaction temperature was controlled at 30 ℃, the inlet position was adjusted, and a certain amount of oxygen was given to the 0,1,2,3m positions of the reactor, respectively, with the total flow rate of oxygen being 3000ml/min, and specific adjustments were shown in table 5 below.
TABLE 5 air intake and product parameters at different locations for examples 16-18
| Examples | 16 | 17 | 18 |
| Air inflow at 0m position (ml/min) | 3000 | 1500 | 1000 |
| 1m position air inflow (ml/min) | 0 | 0 | 1000 |
| 2m position air inflow (ml/min) | 0 | 1500 | 500 |
| Air inflow at 3m position (ml/min) | 0 | 0 | 500 |
| Number average molecular weight | 40000 | 39000 | 39000 |
| Weight average molecular weight | 100000 | 94000 | 82000 |
| Molecular weight distribution | 2.5 | 2.4 | 2.1 |
| Yield (%) | 88.95 | 88.65 | 88.73 |
Examples 19 to 23
The reactor was replaced with a 16m tubular reactor with constant inside diameter, pure oxygen was used as the oxidant, total oxygen flow was 4000ml/min, reaction temperature was controlled at 30 ℃, feed ratio of each reactant was constant, and feed amount was adjusted to adjust residence time, specifically adjusted as shown in table 6 below.
TABLE 6 different residence times and product parameters for examples 19-23
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and not for limiting the same; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the invention.
Claims (10)
1. A process for producing polyphenyl ether by using a tubular reactor is characterized in that the tubular reactor mainly comprises a liquid phase mixer, a reactor main body and a gas-liquid separator which are sequentially connected in series through pipelines, wherein the inlet of the liquid phase mixer is respectively communicated with a reaction liquid inlet and a catalyst inlet; the reactor main body is vertical, the outlet of the liquid phase mixer is connected with the side wall of the bottom of the reactor main body through a pipeline, the bottom of the reactor main body is connected with a gas inlet, a gas distributor is arranged on the cross section between the gas inlet and the reactor main body, an inner member is arranged in the reactor main body, a heat exchange jacket is arranged outside the shell of the reactor main body or/and a heat exchange pipe is arranged in the reactor main body, the top outlet of the reactor main body is connected with a gas-liquid separator through a pipeline, the top end of the gas-liquid separator is provided with a gas outlet, and the bottom end of the gas-liquid separator is provided with a liquid outlet;
the process mainly comprises the following steps:
(1) Introducing the organic solvent dissolved with the phenol monomer into a liquid phase mixer from a reaction liquid inlet, and fully mixing the organic solvent with the catalyst introduced from a catalyst inlet in the liquid phase mixer to obtain a mixed solution of reaction raw materials and the catalyst;
(2) The mixed solution of the reaction raw materials and the catalyst enters the reactor main body through the bottom of the reactor main body, fully contacts and reacts with the mixed gas containing oxygen of the bubbles which are introduced by the gas inlet and dispersed by the gas distributor, and moves upwards along the axial direction of the reactor main body; the heat exchange jacket or/and the heat exchange tube maintain the reaction temperature in the reactor main body, and the inner components in the reactor main body increase the turbulence degree of the liquid phase, control the size of bubbles and increase the mixing effect between the gas phase and the liquid phase;
(3) The mixture after reaction enters the gas-liquid separator through the top of the reactor main body, gas is discharged from a gas outlet at the top of the gas-liquid separator through gas-liquid separation, and the mixed liquid flows out from a liquid phase outlet at the bottom of the gas-liquid separator and is separated and purified to obtain the polyphenyl ether.
2. The process according to claim 1, wherein the molecular weight of the polyphenylene ether product is controlled by adjusting the amount of the mixture introduced at the bottom of the reactor, the oxygen concentration, and the residence time of the material in the reactor.
3. The process according to claim 1, wherein the phenol monomer in the step (1) has a structure represented by the formula (I),
r in formula (I) 1 And R is 2 Are respectively and independently hydrogen、C 1-4 Alkyl, haloalkyl, aminoalkyl or alkoxy, R 3 Is hydrogen or halogen.
4. The process according to claim 1, wherein the organic solvent in step (1) is one or more of toluene, xylene, benzene, nitrobenzene, methylene chloride, chloroform, pyridine.
5. The process according to claim 1, wherein the concentration of the phenol monomer in the organic solvent in which the phenol monomer is dissolved in step (1) is 10 to 300g/L; the catalyst is a complex of cuprous chloride and organic amine, and the concentration of the catalyst in the organic solvent containing the catalyst is 0.1-20g/L; the ratio of the feed flow rate of the organic solvent in which the phenol monomer is dissolved to the organic solvent containing the catalyst is 1:5 to 5:1.
6. The process according to claim 1, wherein the reaction temperature in the reactor body in step (1) is 20 to 150 ℃, the reaction pressure is 0.01 to 10MPa, and the liquid phase residence time is 0.1 to 24 hours.
7. The process according to claim 1, wherein the oxygen-containing gas mixture in step (2) is an oxygen/nitrogen gas mixture with an oxygen concentration of 5% -100%, and the introduced gas mixture is introduced from the bottom of the reactor main body 1 or is introduced at different heights of the reactor main body 1 according to a certain ratio; the flow rate of the mixed gas containing oxygen is 0.2-5000L/min.
8. The process according to claim 1, wherein the reactor body has a height of 0.5 to 50m and an inner diameter of 10 to 6000mm.
9. The process of claim 1 wherein the inner member is one or a combination of two or more of a perforated plate, a raschig ring, a pall ring, a θ ring.
10. The process according to claim 1, wherein the reactor body is a section of reaction units or is formed by connecting 2-100 sections of reaction units in series, the inner diameter and the length of each section of reaction units are correspondingly adjusted according to the reaction process, and each section of reaction units are coaxially arranged or arranged in parallel.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211584313.7A CN116023650A (en) | 2022-12-09 | 2022-12-09 | Process for producing polyphenyl ether by using tubular reactor |
| PCT/CN2022/138348 WO2024119526A1 (en) | 2022-12-09 | 2022-12-12 | Process for producing polyphenylene oxide by using tubular reactor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211584313.7A CN116023650A (en) | 2022-12-09 | 2022-12-09 | Process for producing polyphenyl ether by using tubular reactor |
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| CN116199875A (en) * | 2023-01-19 | 2023-06-02 | 北京中油创宇科技有限公司 | Method for preparing small-molecular-weight double-end hydroxyl polyphenyl ether by using micro-channel reactor |
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| US4477649A (en) * | 1983-03-25 | 1984-10-16 | General Electric Company | Two-stage continuous process for preparation of polyphenylene oxides |
| US4556699A (en) * | 1984-12-03 | 1985-12-03 | Enichimica S.P.A. | Process for the production of polyphenylene oxide |
| AU2002360970A1 (en) * | 2002-12-12 | 2004-06-30 | Man Dwe Gmbh | Shell-and-tube type reactor for catalytic gas phase reactions |
| CN208427016U (en) * | 2017-12-29 | 2019-01-25 | 安丽华 | A kind of production equipment of synthesized micromolecule amount polyphenylene oxide |
| CN114736367B (en) * | 2022-04-24 | 2024-03-01 | 常州中英科技股份有限公司 | Green and safe gas-liquid heterogeneous synthesis method for polyarylether |
| CN114716666B (en) * | 2022-04-24 | 2024-03-01 | 常州中英科技股份有限公司 | Polyarylether synthesis method based on gas-liquid heterogeneous method and continuous flow micro-channel reactor |
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| CN116199875A (en) * | 2023-01-19 | 2023-06-02 | 北京中油创宇科技有限公司 | Method for preparing small-molecular-weight double-end hydroxyl polyphenyl ether by using micro-channel reactor |
| CN116199875B (en) * | 2023-01-19 | 2023-11-17 | 北京中油创宇科技有限公司 | Method for preparing small-molecular-weight double-end hydroxyl polyphenyl ether by using micro-channel reactor |
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