CN116199875A - Method for preparing small-molecular-weight double-end hydroxyl polyphenyl ether by using micro-channel reactor - Google Patents
Method for preparing small-molecular-weight double-end hydroxyl polyphenyl ether by using micro-channel reactor Download PDFInfo
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- CN116199875A CN116199875A CN202310062546.9A CN202310062546A CN116199875A CN 116199875 A CN116199875 A CN 116199875A CN 202310062546 A CN202310062546 A CN 202310062546A CN 116199875 A CN116199875 A CN 116199875A
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- 238000000034 method Methods 0.000 title claims abstract description 53
- 229920013636 polyphenyl ether polymer Polymers 0.000 title claims abstract description 30
- 125000002887 hydroxy group Chemical group [H]O* 0.000 title claims abstract description 27
- 238000006243 chemical reaction Methods 0.000 claims abstract description 212
- 239000000463 material Substances 0.000 claims abstract description 43
- 239000003054 catalyst Substances 0.000 claims abstract description 34
- 239000000047 product Substances 0.000 claims abstract description 23
- 238000003756 stirring Methods 0.000 claims abstract description 17
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 51
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 40
- 239000007789 gas Substances 0.000 claims description 34
- 239000007788 liquid Substances 0.000 claims description 25
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 24
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 24
- 239000001301 oxygen Substances 0.000 claims description 24
- 229910052760 oxygen Inorganic materials 0.000 claims description 24
- 230000003068 static effect Effects 0.000 claims description 23
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 22
- 150000001412 amines Chemical class 0.000 claims description 21
- 238000002360 preparation method Methods 0.000 claims description 20
- 239000002994 raw material Substances 0.000 claims description 19
- ODJUOZPKKHIEOZ-UHFFFAOYSA-N 4-[2-(4-hydroxy-3,5-dimethylphenyl)propan-2-yl]-2,6-dimethylphenol Chemical compound CC1=C(O)C(C)=CC(C(C)(C)C=2C=C(C)C(O)=C(C)C=2)=C1 ODJUOZPKKHIEOZ-UHFFFAOYSA-N 0.000 claims description 15
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 14
- 239000007795 chemical reaction product Substances 0.000 claims description 14
- 229910001431 copper ion Inorganic materials 0.000 claims description 14
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 14
- 229910052757 nitrogen Inorganic materials 0.000 claims description 13
- 230000036284 oxygen consumption Effects 0.000 claims description 13
- 230000001105 regulatory effect Effects 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 12
- XFNJVJPLKCPIBV-UHFFFAOYSA-N trimethylenediamine Chemical compound NCCCN XFNJVJPLKCPIBV-UHFFFAOYSA-N 0.000 claims description 12
- 229930185605 Bisphenol Natural products 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- NXXYKOUNUYWIHA-UHFFFAOYSA-N 2,6-Dimethylphenol Chemical compound CC1=CC=CC(C)=C1O NXXYKOUNUYWIHA-UHFFFAOYSA-N 0.000 claims description 10
- 238000007599 discharging Methods 0.000 claims description 10
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 9
- 239000004615 ingredient Substances 0.000 claims description 9
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 claims description 9
- 239000000498 cooling water Substances 0.000 claims description 8
- 239000012495 reaction gas Substances 0.000 claims description 8
- 229960003280 cupric chloride Drugs 0.000 claims description 7
- -1 dipropenyl bisphenol A Chemical compound 0.000 claims description 7
- 230000035484 reaction time Effects 0.000 claims description 7
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- 239000007791 liquid phase Substances 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- CFNHVUGPXZUTRR-UHFFFAOYSA-N n'-propylethane-1,2-diamine Chemical compound CCCNCCN CFNHVUGPXZUTRR-UHFFFAOYSA-N 0.000 claims description 5
- HDCAZTXEZQWTIJ-UHFFFAOYSA-N n,n',n'-triethylethane-1,2-diamine Chemical compound CCNCCN(CC)CC HDCAZTXEZQWTIJ-UHFFFAOYSA-N 0.000 claims description 5
- 238000005086 pumping Methods 0.000 claims description 5
- 229910021591 Copper(I) chloride Inorganic materials 0.000 claims description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims description 4
- 229940045803 cuprous chloride Drugs 0.000 claims description 4
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 claims description 4
- 239000000376 reactant Substances 0.000 claims description 4
- DDHUNHGZUHZNKB-UHFFFAOYSA-N 2,2-dimethylpropane-1,3-diamine Chemical compound NCC(C)(C)CN DDHUNHGZUHZNKB-UHFFFAOYSA-N 0.000 claims description 3
- 230000009920 chelation Effects 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 3
- 229910000366 copper(II) sulfate Inorganic materials 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 230000007423 decrease Effects 0.000 claims description 2
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 claims description 2
- KGHYGBGIWLNFAV-UHFFFAOYSA-N n,n'-ditert-butylethane-1,2-diamine Chemical compound CC(C)(C)NCCNC(C)(C)C KGHYGBGIWLNFAV-UHFFFAOYSA-N 0.000 claims description 2
- 238000010926 purge Methods 0.000 claims description 2
- 230000000087 stabilizing effect Effects 0.000 claims description 2
- 238000009826 distribution Methods 0.000 abstract description 6
- 238000006116 polymerization reaction Methods 0.000 abstract description 5
- 230000008569 process Effects 0.000 abstract description 4
- 238000005691 oxidative coupling reaction Methods 0.000 abstract description 3
- 230000000149 penetrating effect Effects 0.000 abstract description 2
- 239000012264 purified product Substances 0.000 abstract description 2
- QWBBPBRQALCEIZ-UHFFFAOYSA-N 2,3-dimethylphenol Chemical compound CC1=CC=CC(O)=C1C QWBBPBRQALCEIZ-UHFFFAOYSA-N 0.000 description 23
- 230000015572 biosynthetic process Effects 0.000 description 14
- 238000003786 synthesis reaction Methods 0.000 description 14
- 238000012360 testing method Methods 0.000 description 13
- 238000013329 compounding Methods 0.000 description 12
- 238000007385 chemical modification Methods 0.000 description 5
- 230000001276 controlling effect Effects 0.000 description 5
- 238000005070 sampling Methods 0.000 description 4
- 238000012546 transfer Methods 0.000 description 4
- 239000005749 Copper compound Substances 0.000 description 3
- 150000001880 copper compounds Chemical class 0.000 description 3
- 150000004985 diamines Chemical class 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 150000001335 aliphatic alkanes Chemical group 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000012668 chain scission Methods 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 229920001955 polyphenylene ether Polymers 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000001174 ascending effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 150000004699 copper complex Chemical class 0.000 description 1
- 230000027734 detection of oxygen Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- PYGSKMBEVAICCR-UHFFFAOYSA-N hexa-1,5-diene Chemical group C=CCCC=C PYGSKMBEVAICCR-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- DCUFMVPCXCSVNP-UHFFFAOYSA-N methacrylic anhydride Chemical compound CC(=C)C(=O)OC(=O)C(C)=C DCUFMVPCXCSVNP-UHFFFAOYSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 230000002000 scavenging effect Effects 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
Images
Classifications
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- 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
-
- 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
- B01J19/0093—Microreactors, e.g. miniaturised or microfabricated reactors
-
- 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
- C08G65/46—Post-polymerisation treatment, e.g. recovery, purification, drying
-
- 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
- C08G65/485—Polyphenylene oxides
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for preparing small molecular weight double-end hydroxyl polyphenyl ether by a microchannel reactor, which uses the microchannel reactor as a main reactor for polymerization reaction, wherein the tail end of the outlet of the reactor is connected with a distributor in a penetrating way into a reaction kettle, reaction materials sprayed out of the distributor enter a circulating pump from the outlet of the reaction kettle in the stirring process of the reaction kettle, the materials pressurized by the circulating pump are mixed with air from a gas distributor at the inlet of the microchannel reactor, and the materials doped with the air are fully contacted with a catalyst in the microchannel reactor for oxidative coupling polymerization reaction, so that a material reaction cycle is formed; after a large amount of material reaction circulation, the reaction is close to the theoretical reaction balance, and the reaction is finished. The low molecular weight double-end hydroxyl polyphenyl ether prepared by the invention has relatively stable molecular weight and small molecular weight distribution range, the hydroxyl value of the product is reduced along with the increase of the molecular weight, and the yield of the purified product is high.
Description
Technical Field
The invention belongs to the field of new materials for organic polymer synthesis, and particularly relates to a method for preparing small-molecular-weight double-end hydroxyl polyphenyl ether by a micro-channel reactor.
Background
In the technical development of the modern information industry, the original circuit board technical base material mainly adopts epoxy resin as a chemical modification material, and the characteristics of high dielectric constant and high electric loss can not meet the requirements of high-speed high-frequency communication, and the original circuit board technical base material has the physical characteristics of high glass transition temperature, high heat resistance and low water absorption, and more importantly, has low dielectric constant and dielectric loss. The low molecular weight dihydroxy polyphenyl ether has the excellent properties, and is an ideal material for high-frequency and high-speed circuit board substrates.
In the prior art disclosed, low molecular weight bishydroxy polyphenylene ethers are typically prepared by redistribution methods. In the patent with publication number of CN104231259B, a commercially available polyphenyl ether resin with number average molecular weight of 20000 is adopted for dissolution, peroxide is added under certain conditions to perform chain scission reaction and react with bisphenol A structural compounds to prepare the dihydroxyl polyphenyl ether, the redistribution reaction is critical, the control of the chain scission reaction is critical, and the molecular weight distribution prepared by the reaction is generally wider. In the patent with publication No. CN113698591B, the synthesis of important monomer 2,6 dimethylphenol of synthesized polyphenyl ether and important copolymer tetramethyl bisphenol A of synthesized dihydroxy polyphenyl ether are completed simultaneously in one reactor, so that the reaction flow is shortened, but the high selectivity and high yield of the synthesis are worth researching.
In summary, in the prior art, batch reaction direct synthesis or redistribution synthesis of a reaction kettle is mostly adopted, and the reaction technology has no quality improvement on the control of reaction heat and molecular weight, and has certain limitation on the selectivity of a dihydroxyl structure of the reaction. In addition, the purification effect of the product is poor, the high quality requirement of the next chemical modification cannot be met, and the product cannot be used for manufacturing a substrate of the copper-clad plate.
Disclosure of Invention
The invention aims to provide a method for preparing small-molecular-weight double-end hydroxyl polyphenyl ether by a microchannel reactor, which aims to solve the problems in the prior art.
The invention is realized by the following technical scheme: a method for preparing small molecular weight double-end hydroxyl polyphenyl ether by a micro-channel reactor is characterized by comprising the following steps: the reaction system adopted by the method is as follows: the system comprises a circulating system consisting of a reaction kettle and a micro-channel reactor unit; a tubular distributor is arranged from the outlet of the microchannel reactor unit to the inside of the reaction kettle, is positioned at a position which is far from the center of the height of the reaction kettle and is submerged in the material filled in the reaction kettle;
the method comprises the following steps:
step 1, preparation: starting an air compressor and adjusting the outlet pressure of the pressure regulating valve to 0.3-0.8 Mpa; starting a steam tracing or circulating hot water tracing system to heat a jacket of the reaction kettle; a cooling system connected with the microchannel reactor; starting the reaction kettle to empty a tail gas condenser cold source;
step 2, feeding: quantitatively preparing a toluene solution of monophenol with the mass concentration of 15% in a preparation tank, adding the toluene solution into the preparation tank according to the molar ratio of monophenol to bisphenol of 11:1, and stirring until the toluene solution is dissolved; closing an outlet valve of the reaction kettle, and pumping the ingredients into the reaction kettle;
step 3, starting the reaction kettle for stirring, when the temperature of materials in the reaction kettle reaches 37-40 ℃, then starting a discharge valve of the reaction kettle, starting a circulating pump, keeping circulating until the temperature of the reaction kettle and the outlet temperature of the microchannel reactor reach 37-40 ℃, after the temperature reaches the temperature, closing the circulating pump and the outlet valve of the pump, keeping the reaction kettle for stirring operation, opening a charging hole cover of the reaction kettle, and pouring catalyst liquid into the reaction kettle and closing the charging hole or pumping the catalyst liquid into the reaction kettle by using a metering pump;
step 4, slowly opening an air supply valve to be fully opened, then starting a circulating pump, rapidly opening a pump outlet valve after 2 seconds, observing that a flowmeter starts to indicate the upper amount and display the stable flow, and regulating the flow of tail gas of a condenser to calculate the required gas flow according to the flow value of the reaction gas required by each mole of monophenol reactant;
step 5, observing an oxygen analyzer, recording reaction time when the oxygen content value begins to decline after stabilizing, adjusting the temperature of a hot water system in the reaction process, and intermittently introducing cooling water into the microchannel reactor to control the reaction temperature; the reaction temperature of the reaction kettle and the micro-channel reactor is kept at 39-42 ℃;
step 6, the real-time database system collects the oxygen content in real time and calculates the total oxygen consumption, and when the total oxygen consumption reaches the theoretical total oxygen consumption and the reaction time is 3.5-4.5 hours, the device stops to run and the reaction is ended; after the reaction is finished, closing the air supply system, closing the circulating pump and stirring the reaction kettle, opening a discharge valve at an outlet of the reaction kettle for discharging after the gas of the system is discharged, and purging the residual materials in the system by adopting nitrogen after the discharging is finished;
and 7, discharging the reaction product from the system, pouring the reaction product into a conical bottom tank, standing for more than 10 hours, settling the catalyst from the reaction product liquid, discharging the catalyst from the bottom, collecting and then carrying out additional treatment, enabling the oily liquid at the upper part to enter a chelating procedure, separating out the purified reaction product after chelation by adopting methanol, and drying the separated solid to obtain the dihydroxypolyphenyl ether product.
Further: the microchannel reactor comprises one or more microchannel reactor units, each microchannel reactor unit is formed by connecting one or two or more microchannel reactor units in parallel, and the microchannel reactor is one of the following three types: 1 or more AFR gas-liquid phase micro-channel reactors are combined in parallel; b, combining 1 or more MF-X microchannel static mixer type reactors in parallel; a combination of 1 or more parallel static mixers. Any of the above microchannel reactors must have only one material inlet and material outlet.
Further: the catalyst is a coordination compound formed by copper ions and ethylenediamine organic amine or propylenediamine organic amine; the molar ratio of the organic amine to the copper ions in the catalyst is in the range of: (2-20) 1) wherein the compound containing copper ions is cuprous chloride or one of cupric chloride, cupric chloride hydrate, cupric sulfate and cupric nitrate;
the ethylenediamine organic amine is one of the following:
N，N , -dimethylethylenediamine, N , -trimethylethylenediamine, N , ,N , -tetramethyl ethylenediamine, N ’ -diethyl ethylenediamine, N ’ Triethylethylenediamine, N ’ ,N ’ -tetraethyl ethylenediamine, N-propylethylenediamine, N-diisopropylethylenediamine, N ， -di-tert-butylethylenediamine
The propylenediamine organic amine is one of the following:
1, 2-propanediamine, 1, 3-propanediamine or 2, 2-dimethyl 1, 3-propanediamine.
Further: the organic amine is as follows: 1, 2-propanediamine, 1, 3-propanediamine, 2-dimethyl 1, 3-propanediamine, N , -dimethylethylenediamine, N , -trimethylethylenediamine, N , ,N , -tetramethyl ethylenediamine, N ’ -diethyl ethylenediamine, N ’ Triethylethylenediamine, N ’ ,N ’ -tetraethyl ethylenediamine, N-propylethylenediamine, N-diisopropylethylenediamine, N ， -one of di-tert-butylethylenediamine;
the monophenol is as follows: one of 2, 6-dimethylphenol, o-methylphenol, m-methylphenol; the bisphenol raw material is one of tetramethyl bisphenol A, dipropenyl bisphenol A, tetrapropenyl bisphenol A and bisphenol A.
The solvent prepared from the reaction raw materials is toluene or dimethylbenzene, and the mass concentration of the monophenol raw material is 10% -30%; the molar ratio of monophenol to bisphenol is in the range of n Monophenol :n Bisphenol A =7:1—19:1。
Further: the molar ratio of the copper ions added to the catalyst in the reaction to the monophenol compound in the reaction mass is: n is n Cu :n Monophenol =0.003:1—0.021:1。
Further: the reaction gas is air or the mixture of air and oxygen, and the pressure range of the introduced gas is as follows: 0.3Mpa-0.7Mpa; the temperature of the reaction kettle is 34-45 ℃; the outlet temperature of the microchannel reactor is 34-47 ℃.
Further: the reaction system comprises one or more groups of micro-channel reactors.
Further: a tubular distributor is arranged from the outlet of the microchannel reactor unit to the inside of the reaction kettle, is positioned at a position which is far from the center of the height of the reaction kettle and is submerged in the material filled in the reaction kettle; the tube distributor has one or more.
The invention has the advantages that: after the low molecular weight double-end hydroxyl polyphenyl ether prepared by the method is subjected to purification treatment, the double-end hydroxyl groups of the polyphenyl ether can be subjected to chemical reaction with part of double-bond-containing compounds to carry out chemical modification, and the generated polyphenyl ether with a multiple double-bond structure and other components are subjected to high-temperature vulcanization lamination technology to prepare the substrate of the copper-clad plate.
The invention adopts the micro-channel reactor to effectively control the reaction process and generate the product with narrow molecular weight distribution, the product has the characteristic of high dihydroxy content value, and the synthesized low molecular weight dihydroxy polyphenyl ether can meet the quality requirement of the existing high-frequency high-speed plate base material after chemical modification, thereby completely replacing epoxy resin chemical modified materials.
In addition, the proposal adopts the micro-channel reactor, thereby solving the limitations of micron-level high-efficiency dispersion, mass transfer and heat transfer in the reaction kettle type polymerization reaction. The synthesized product has narrower molecular weight distribution, can provide higher glass transition temperature, and is very beneficial to the high-temperature stability of the prepared circuit board. The catalyst can be precipitated, so that the product post-treatment easiness is improved, and the post-treatment environmental protection pressure is reduced. The reaction is completed in the microchannel reactor by adopting air or the mixed gas of air and oxygen as the reaction gas, so that no high-content oxygen exists in the space of the reaction kettle, the potential danger of oxidative coupling reaction is avoided, and the intrinsically safe production is realized.
Drawings
FIG. 1 is a reaction scheme of the present invention.
In the figure: r1-a microchannel reactor; r2-a reaction kettle; t1-measuring the temperature of the reaction kettle;
t2-reactor inlet temperature; t3-reactor outlet temperature;
t4-the temperature of a reaction kettle gas condenser; d1-online detection of oxygen content of tail gas of the reaction kettle;
d2-an oxygen-air ratio mixer; s-a liquid distributor in the reaction kettle;
p1, P2, P3-gas pressure gauge; ZX-centrifugal turbine pump; f-vortex shedding flowmeter;
surpass-is a real-time database collection analysis system.
Description of the embodiments
The invention will be further clarified and fully explained below in connection with the technical solutions of specific embodiments, it being evident that the embodiments described are only some of the embodiments of the invention. Based on the embodiments of the present invention, other embodiments that may be obtained by those of ordinary skill in the art without making any inventive effort are within the scope of the present invention.
The invention discloses a method for preparing small molecular weight double-end hydroxyl polyphenyl ether by a micro-channel reactor, which uses the micro-channel reactor as a main reactor for polymerization reaction, and the reactor is characterized in that the specific surface area of a contact material flow is abnormally large, ideal mass transfer and heat transfer can be provided, and very high reaction selectivity can be realized; the tail end of the outlet of the reactor is connected with a distributor in a penetrating way, reaction materials sprayed out of the distributor enter a circulating pump from the outlet of the reactor in the stirring process of the reactor, the materials pressurized by the circulating pump are mixed with air from the gas distributor at the inlet of the microchannel reactor, and the materials doped with the air are fully contacted with a catalyst in the microchannel reactor to perform oxidative coupling polymerization reaction, so that a material reaction cycle is formed; after a large amount of material reaction circulation, the reaction is close to the theoretical reaction balance, and the reaction is finished.
The micro-channel reactor in the preparation process of the invention can be realized by the following equipment: 1. AFR gas-liquid phase micro-channel reactor of corning company; 2. an MF-X microchannel static mixer type reactor from Michauchoi micro (microflu); 3. 1 static mixer or a combination of multiple parallel static mixers. Any of the above microchannel reactors must have only one material inlet and material outlet. Any one of the three micro-channel reactors is connected with the reaction kettle in series to realize the preparation process.
The process flow of the invention is shown in figure 1: r1 is a microchannel reactor; r2 is a reaction kettle; ZX is a circulating pump; V1-V11 are valves; after reaction materials are pumped into a reaction kettle for 5 minutes, a pump is stopped for adding a catalyst, air or the mixed gas of the air and oxygen is pumped in, the pump circulation is started, the continuous flow reaction can be started by controlling the reaction temperature, when a real-time database detects that the total oxygen consumption reaches the theoretical oxygen consumption, the reaction is carried out for 3.5 to 4.5 hours, the reaction reaches the end condition, sampling is carried out, methanol precipitation and filtration are adopted, the preliminary yield reaches more than 90 percent according to the solid content of 40 percent of a filter cake, the reaction can be stopped, an air inlet valve is closed, and the circulation pump and the reaction kettle are stopped for stirring.
The preferred monophenol reactant material involved in the practice of this invention is 2,6 Dimethylphenol (DMP); preferred bisphenol starting materials are tetramethyl bisphenol A (TMBPA), diallyl double A (DBA), tetrapropenyl Bisphenol A (TBA) and bisphenol A (BPA) as shown in the following reaction equations:
the invention can be realized by adopting various material combinations: 1. DMP and TMBPA react; 2. DMP and DBA reactions; 3. reaction of DMP with TBA; 4. DMP and BPA reactions, and the like.
The final product synthesized by the technical route of the invention is low molecular weight double-end hydroxyl polyphenyl ether, and the specific synthetic route depends on the performance of the product required after the chemical modification of the product.
The catalyst in the preparation method of the invention belongs to a composition prepared by a coordination compound formed by copper ions and organic amine; the copper ion realizing the catalyst is provided by a compound such as cuprous chloride, cupric chloride hydrate (commercial cupric chloride dihydrate or hydrate prepared by cupric chloride), cupric sulfate and cupric nitrate, and one or more than one of the five copper compounds can not be selected if cuprous chloride is selected; the catalyst is a complex formed by copper ions and ethylenediamine organic amine or propylene organic amine, and the ethylenediamine organic amine of the catalyst is realized to be the organic amine which accords with the following structure:
wherein:
r1, R2, R3 and R4 are C n H 2n+1 N ranges from 1 to 4; for each ethylenediamine compound, the alkane substituents R1, R2, R3, R4 constituting the structure are the same, except that the number of alkane substituents varies, such as from 2 to 4; such as the following compounds corresponding to the above structural formula, e.g. N, N , -dimethylethylenediamine, N, N, N , -trimethylethylenediamine, N , ,N , -tetramethyl ethylenediamine, N ’ -diethyl ethylenediamine, N ’ Triethylethylenediamine, N ’ ,N ’ -tetraethyl ethylenediamine, N-propylethylenediamine, N-diisopropylethylenediamine, N ， -di-tert-butylethylenediamine; 1, 2-propanediamine, 1, 3-propanediamine or 2, 2-dimethyl 1, 3-propanediamine.
One or more than one of the diamine organic amine is selected as a ligand of copper ions, one of the diamine organic amine and the copper compound are selected to prepare a coordination compound, and the other diamine organic amine and the copper compound are selected to prepare the coordination compound, wherein the two coordination compounds can be used singly or in a mixed mode. The molar ratio of the organic amine to the copper ions in the catalyst copper complex is in the range of: (2-20): 1.
The method comprises the following steps:
the preparation of the reaction raw materials, namely toluene is selected as a solvent for dissolving the monophenol raw materials, the mass concentration of the prepared solution ranges from 10% to 30%, one type of copolymer is selected, and bisphenol with the required proportion is only required to be dissolved into the monophenol solution, and the DMP solution and TMBPA raw materials are preferably selected for combination.
The molar ratio of the synthetic raw materials is in the range of n DMP :n TMBPA =7:1 to 19:1, suitable for any one of the above raw material combinations.
The molar ratio of the copper ions added into the catalyst to the monophenol added into the reaction mass is as follows: n is n Cu :n Monophenol =0.003:1—0.021:1。
The pressure range of the reaction system maintained by air or the mixed gas of air and oxygen is as follows: air is used as a reaction gas at 0.3-0.7 Mpa, preferably 0.35-0.50 Mpa, the air flow is calculated according to the mole number of monophenol in the reaction material, the exhaust gas control flow of the air is required to be 0.08-0.5L/min per 1 mole Shan Fen, the mixed flow of air and oxygen is used as the reaction gas, the flow of the mixed oxygen in the gas proportion mixer is set to be 1/5-2/5 of the air flow, and the exhaust gas control flow of the mixed gas is required to be 0.03-0.2L/min per 1 mole Shan Fen.
The temperature control range of the reaction system is as follows: the temperature of the reaction kettle is controlled within 34-45 ℃; the outlet temperature of the microchannel reactor is controlled within the range of 34-47 ℃; the above two temperatures are preferably controlled at 39-41 ℃. The temperature in the condenser is controlled below-12 ℃.
The explosion-proof centrifugal vortex pump with high lift is adopted, the lift exceeds 40m, the flow is determined according to the quantity of reactant flow, the pump head and the impeller are required to meet SUS304, SUS316 or SUS316L stainless steel specifications, and the motor is preferably an explosion-proof variable frequency motor.
The operation procedure is as follows: 1. Preparation of synthesis: starting an air compressor to increase the air pressure in the air tank to 0.8Mpa, and regulating the outlet pressure of an air pressure regulating valve of the device to 0.4Mpa; starting a circulating hot water system, heating until the temperature of materials in the reaction kettle reaches 38 ℃, and then keeping the temperature of a hot water heat tracing system at 38-42 ℃; the cooling system of the reactor R1 micro-channel reactor is connected, the temperature of cooling water is about 10 ℃, and the cooling water can keep circulating after being started and is started intermittently; starting a condenser cold source, and keeping the temperature in the condenser at about minus 15 ℃. 2. Feeding: quantitatively preparing a DMP toluene solution with the mass concentration of 15% in a preparation tank, adding the calculated bisphenol (one or two) into the preparation tank, and stirring until the bisphenol is completely dissolved. Closing the outlet valve V1 of the reaction kettle, and pumping the prepared materials into the reaction kettle. 3. And (3) starting the reaction kettle for stirring, then starting a valve V1 and a pump outlet valve V4, starting a circulating pump ZX, keeping circulating to the temperature T1 of the reaction kettle and the temperature T3-38-40 ℃ of the outlet of the microchannel reactor, closing the circulating pump and the valve V4 after the temperature reaches the temperature, keeping the reaction stirring, opening a charging hole of the reaction kettle, pouring quantitative catalyst liquid into the reaction kettle, and closing a charging hole cover. 4. Slowly opening an air supply valve to be fully opened, then starting a circulating pump, rapidly opening a pump outlet valve V4 after about 2 seconds, observing that the flowmeter starts to display flow and display flow stability, and regulating the flow of tail gas of the condenser to a required value. 5. After the value of the oxygen tester is observed to rise and stabilize, the reaction time is recorded when the oxygen tester starts to fall, the reaction temperature is kept between 39 ℃ and 42 ℃, the temperature of a hot water system is regulated in the reaction process, and cooling water can be intermittently introduced into the microchannel reactor R1 to control the reaction temperature. 6. Collecting oxygen content by a real-time database collection system (Surpass of Beijing stone Saipu Co.) and automatically calculating total oxygen consumption in real time, when the total oxygen consumption reaches theoretical oxygen consumption, the reaction time is generally 3.5-4.5 hours, sampling and verifying, stopping the device operation and ending the reaction; after the reaction is finished, the gas supply system is closed, the circulating pump and the reaction kettle are closed for stirring, after the gas of the system is discharged, the discharge valve V2 is opened for discharging, and the residual materials in the system are swept by adopting nitrogen (the air inlet valve is closed and the nitrogen valve is opened).
Post-treatment of the reaction product; and after the reaction product is discharged from the system, pouring the reaction product into a conical bottom tank, standing for more than 10 hours, settling the catalyst out of the reaction product liquid, discharging the catalyst from the bottom, collecting and post-treating the catalyst, enabling the oily liquid at the upper part to enter a chelating process (not described herein), separating out the purified reaction product after chelation by adopting methanol, and drying the separated solid to obtain the dihydroxyl polyphenyl ether product. The product can be used for physical index analysis and structure test.
And (3) product index test: for testing the products of the invention, most important are molecular weight and distribution tests and hydroxyl number content determination. Molecular weight and distribution are determined by GPC chromatography; the hydroxyl value content was determined using method A in GB/T12008.3-2009.
The invention is further illustrated by the following specific examples.
Examples
The embodiment discloses a method for preparing small-molecular-weight double-end hydroxyl polyphenyl ether by a microchannel reactor, wherein in a reaction system of the method, an AFR gas-liquid-phase microchannel reactor of corning company and a 100 liter reaction kettle are adopted as main reaction equipment. The reaction raw materials are DMP and TMBPA, the generated products are as follows,
the method comprises the following steps:
1. preparation of synthesis: starting an air compressor to increase the air pressure in the air tank to 0.8Mpa, and regulating the outlet pressure of an air pressure regulating valve of the device to 0.4Mpa; starting a circulating hot water system, and keeping the temperature of the hot water carried by the reaction kettle at 41 ℃; the cooling system of the reactor R1 micro-channel reactor is connected, the temperature of cooling water is about 10 ℃, and the cooling water can keep circulating after being started and is started intermittently; starting a condenser cold source, and keeping the temperature in the condenser at about minus 15 ℃. 2. Feeding: 30 liters of a 15% strength DMP toluene solution was quantitatively prepared in a compounding tank, and 800g of tetramethyl bisphenol A was added to the compounding tank and stirred until dissolved. Closing the outlet valve V1 of the reaction kettle, and adding the ingredients into the reaction kettle from a feed inlet. 3. And (3) starting the reaction kettle for stirring until the temperature of materials in the reaction kettle reaches 38-40 ℃, then starting a valve V1 and a pump outlet valve V4, starting a circulating pump ZX, keeping circulating until the temperature T1 of the reaction kettle and the outlet temperature T3 of the microchannel reactor reach 38-39 ℃, and closing the circulating pump and the valve V4 after the temperature reaches the temperature, so as to keep the reaction stirring operation. 4. The reactor feed hole was opened, 1120ml of catalyst liquid was poured into the reactor, and the feed hole cover was closed. Slowly opening an air supply valve to be fully opened, then starting a circulating pump, rapidly opening a pump outlet valve V4 in about 2 seconds, observing the start indication flow of a liquid flowmeter, displaying stable flow, controlling the flow of tail gas of a condenser to be 6L/min, wherein the pump flow is 1.6 cubic meters per hour. 5. And (3) observing the rising and stable value of the oxygen analyzer, recording the reaction time when the value is reduced, keeping the reaction temperature between 40 ℃ and 42 ℃, adjusting the temperature of a hot water system in the reaction process, and introducing cooling water into the microchannel reactor R1 to control the reaction temperature. 6. After 3.5 hours of reaction, 100ml of the reaction mixture is sampled from a sampling port, 1000ml of methanol is added into a 1500ml beaker, a stirrer is started, 100ml of the reaction mixture is slowly added into the methanol, then the methanol mixture is poured into a vacuum funnel for suction filtration until no methanol is dropped out, solids on a filter cloth are collected into a glass vessel, the weight of the solids is calculated according to 40% of the weight, and the yield is initially calculated. After the reaction is carried out for 4 hours, the oxygen content value of the tail gas oxygen content tester is observed to be in an ascending stage, a Surpass real-time data acquisition system displays that the total oxygen consumption reaches the theoretical oxygen consumption value, the sampling calculation yield reaches 90%, the reaction can be ended, the air supply valve, the circulating pump and the reaction kettle are closed to be stirred, the air in the discharge device is discharged, the valve V2 is opened to discharge the material from the discharge port, the air inlet valve V10 is closed to be confirmed to be closed after the material is discharged, and the nitrogen scavenging valve V11 is opened to use the nitrogen to accelerate the residual materials in the device. If this yield is not achieved, the reaction can be continued for 30 minutes. 7. And separating out and drying the chelated product to obtain the small-molecular-weight double-end hydroxyl polyphenyl ether.
Molecular weight was determined by GPC and hydroxyl number by titration. The data are shown in Table 1.
Example 2
The embodiment discloses a method for preparing small-molecular-weight double-end hydroxyl polyphenyl ether by a microchannel reactor, wherein a reaction device adopts three static mixers which are parallelly connected to form a static mixer unit, inlets and outlets of the three static mixers are respectively connected in parallel, and the microchannel reactor and a 100 liter reaction kettle are used as main reaction equipment. The reaction raw materials are DMP and TMBPA. The reaction equation is shown in example 1.
The method comprises the following steps:
1. preparation of synthesis: the procedure is the same as in example 1,2, charging: a60 liter 15% strength DMP toluene solution was quantitatively prepared in a compounding tank, 1600g of tetramethyl bisphenol A was added to the compounding tank, and stirred until dissolved. Closing the outlet valve V1 of the reaction kettle, and adding the ingredients into the reaction kettle from a feed inlet. 3. And 4, opening a charging hole of the reaction kettle, pouring 2250ml of catalyst liquid into the reaction kettle, and closing the charging hole. Slowly opening an air supply valve to be fully opened, then starting a circulating pump, rapidly opening a pump outlet valve V4 in about 2 seconds, observing that the liquid flowmeter starts to display the upper amount and the parallel flow is stable, controlling the pump flow to be 2.3 cubic/hour, and regulating the flow of tail gas of the condenser to be 13L/min. The remaining steps are the same as those of example 1. The test data are shown in Table 1.
Example 3
The embodiment discloses a method for preparing small-molecular-weight double-end hydroxyl polyphenyl ether by a microchannel reactor, wherein a reaction device adopts three static mixers which are parallelly connected to form a static mixer unit, inlets and outlets of the three static mixers are respectively connected in parallel, and the microchannel reactor and a 100 liter reaction kettle are used as main reaction equipment. The reaction raw materials are DMP and DBA, and the generated product has the following equation:
the method comprises the following steps:
1. preparation of synthesis: the procedure is the same as in example 1,2, charging: 60 liters of a 15% strength DMP toluene solution was quantitatively prepared in a compounding tank, 1835g of dipropenyl bisphenol A was added to the compounding tank, and stirred until dissolved. Closing the outlet valve V1 of the reaction kettle, and adding the ingredients into the reaction kettle from a feed inlet. 3. And 4, opening a charging hole of the reaction kettle, pouring 2250ml of catalyst liquid into the reaction kettle, and closing the charging hole. Slowly opening an air supply valve to be fully opened, then starting a circulating pump, rapidly opening a pump outlet valve V4 in about 2 seconds, observing that a liquid flowmeter starts to indicate the upper amount and shows that the flow is stable, controlling the flow of tail gas of a condenser to be 13L/min at the pump flow of 2.3 cubic/hour. The remaining steps are the same as those of example 1. The test data are shown in Table 1.
Example 4
The embodiment discloses a method for preparing small-molecular-weight double-end hydroxyl polyphenyl ether by a microchannel reactor, wherein a reaction device adopts three static mixers which are parallelly connected to form a static mixer unit, inlets and outlets of the three static mixers are respectively connected in parallel, and the microchannel reactor and a 100 liter reaction kettle are used as main reaction equipment. The reaction raw materials are DMP and TBA, the formula of the generated product is as follows,
the method comprises the following steps:
1. preparation of synthesis: the procedure was the same as in example 1. 2. Feeding: a60 liter 15% strength DMP toluene solution was quantitatively prepared in a compounding tank, 2095g of tetrapropenyl bisphenol A was added to the compounding tank, and stirred until dissolved. Closing the outlet valve V1 of the reaction kettle, and adding the ingredients into the reaction kettle from a feed inlet. 3. And 4, opening a charging hole of the reaction kettle, pouring 2250ml of catalyst liquid into the reaction kettle, and closing the charging hole. Slowly opening an air supply valve to be fully opened, then starting a circulating pump, rapidly opening a pump outlet valve V4 in about 2 seconds, observing that a liquid flowmeter starts to indicate the upper amount and shows that the flow is stable, controlling the flow of tail gas of a condenser to be 13L/min at the pump flow of 2.3 cubic/hour. The remaining steps are the same as those of example 1. The test data are shown in Table 1.
Example 5
The embodiment discloses a method for preparing small-molecular-weight double-end hydroxyl polyphenyl ether by a micro-channel reactor, wherein a reaction device adopts an AFR gas-liquid phase micro-channel reactor of corning company and a 100 liter reaction kettle as main reaction equipment. The reaction raw materials are DMP and DBA bisphenol A, the reaction equation of the generated product is shown in the reaction equation of the example 3, and the operation steps are as follows:
1. preparation of synthesis: the procedure is the same as in example 1,2, charging: 30 liters of a 15% strength DMP toluene solution was quantitatively prepared in a compounding tank, 917g of dipropenyl bisphenol A was added to the compounding tank, and stirred until dissolved. Closing the outlet valve V1 of the reaction kettle, and adding the ingredients into the reaction kettle from a feed inlet. 3. The procedure is the same as in example 1; 4. the reaction kettle feed hole was opened, 1120ml of catalyst liquid was poured into the reaction kettle, and the feed hole was closed. Slowly opening an air supply valve to be fully opened, then starting a circulating pump, rapidly opening a pump outlet valve V4 in about 2 seconds, observing that a liquid flowmeter starts to indicate the upper amount and shows that the flow is stable, wherein the pump flow is 1.6 cubic/hour, and regulating the flow of tail gas of a condenser to be 6L/min. The remaining steps are the same as those of example 1. The test data are shown in Table 1.
Example 6
The embodiment discloses a method for preparing small-molecular-weight double-end hydroxyl polyphenyl ether by a microchannel reactor, wherein a reaction device adopts an MF-X microchannel static mixer of Michauchoi micro (microflu) company and a 100 liter reaction kettle as main reaction equipment. The reaction raw materials are DMP and TMBPA. The reaction equation is the same as that of example 1.
The method comprises the following steps:
1. preparation of synthesis: the procedure is the same as in example 1,2, charging: 30 liters of a 15% strength DMP toluene solution was dosed in a dosing tank, 800g TMBPA was added to the dosing tank and stirred until dissolved. Closing the outlet valve V1 of the reaction kettle, and adding the ingredients into the reaction kettle from a feed inlet. 3. The procedure is the same as in example 1; 4. the reaction kettle feed hole was opened, 1120ml of catalyst liquid was poured into the reaction kettle, and the feed hole was closed. Slowly opening an air supply valve to be fully opened, then starting a circulating pump, rapidly opening a pump outlet valve V4 in about 2 seconds, observing that a liquid flowmeter starts to indicate the upper amount and shows that the flow is stable, wherein the pump flow is 1.6 cubic/hour, and regulating the flow of tail gas of a condenser to be 6L/min. The remaining steps are the same as those of example 1. The test data are shown in Table 1.
Example 7
The embodiment discloses a method for preparing small-molecular-weight double-end hydroxyl polyphenyl ether by a microchannel reactor, wherein a reaction device adopts three static mixers which are parallelly connected to form a static mixer unit, inlets and outlets of the three static mixers are respectively connected in parallel, and the microchannel reactor and a 100 liter reaction kettle are used as main reaction equipment. The reaction gas is a mixture of air and oxygen, wherein the air accounts for 80% (v/v), and the oxygen accounts for 20% (v/v). The reaction raw materials are DMP and TMBPA. The reaction equation is the same as in example 1.
The operation steps are as follows:
step 1 is the same as the corresponding step in the embodiment 1, steps 2 and 3 are the same as the corresponding step in the embodiment 2, 4, opening an air and oxygen valve, adjusting a gas mixer, adjusting the volume flow of oxygen to be 1/5 of the air flow, then slowly opening a gas supply valve V5 to be fully opened, then starting a circulating pump, rapidly opening a pump outlet valve V4 for about 2 seconds, observing that a liquid flowmeter starts to indicate the upper amount and shows that the flow is stable, adjusting the flow of tail gas of a condenser to be 7L/min, wherein the flow of the pump is 2.3 cubic/hour. The remaining steps are the same as those of example 1. The test data are shown in Table 1.
Example 8
The embodiment discloses a method for preparing small-molecular-weight double-end hydroxyl polyphenyl ether by a microchannel reactor, wherein a reaction device adopts three static mixers which are parallelly connected to form a static mixer unit, inlets and outlets of the three static mixers are respectively connected in parallel, and the microchannel reactor and a 100 liter reaction kettle are used as main reaction equipment. The reaction raw materials are DMP and BPA, and the following equation is generated:
the operation steps are as follows:
1. preparation of synthesis: the procedure is the same as in example 1; 2. feeding: 60 liters of a 15% strength DMP toluene solution was quantitatively prepared in a compounding tank, 1285g of bisphenol A was added to the compounding tank, and stirred until dissolved. Closing an outlet valve V1 of the reaction kettle, and adding the ingredients into the reaction kettle from a feed inlet; the remaining steps are the same as the corresponding steps in example 2; the test data are shown in Table 1.
Table 1 table of test data for the synthesis of double-ended hydroxyl polyphenylene ether
Note that: the yield is calculated by the weight of the reaction product after chelating purification and drying divided by the sum of the weights of 2, 6-dimethylphenol and bisphenol in the reaction mass.
As can be seen from the table, the molecular weight of the synthesized dihydroxy polyphenyl ether is relatively stable, the molecular weight is distributed between 1.43 and 1.76, the hydroxyl value of the product is reduced along with the increase of the molecular weight, and the yield of the purified product is more than 82 percent; after the partial formula product of the invention is chemically modified by methacrylic anhydride, the prepared high-frequency high-speed board is tested by a test, and the comprehensive performance of the board reaches or exceeds the standard of related products, so that the technical scheme of the invention is proved to be feasible.
The foregoing examples are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the foregoing examples, and any other changes, substitutions, combinations, and modifications that do not depart from the technical principles of the present invention should be equivalent to the above examples, and are included in the scope of the present invention.
Claims (9)
1. A method for preparing small molecular weight double-end hydroxyl polyphenyl ether by a micro-channel reactor is characterized by comprising the following steps:
the reaction system adopted by the method is as follows: the system comprises a circulating system consisting of a reaction kettle and a micro-channel reactor unit; a tubular distributor is arranged from the outlet of the microchannel reactor unit to the inside of the reaction kettle, is positioned at a position which is far from the center of the height of the reaction kettle and is submerged in the material filled in the reaction kettle;
the method comprises the following steps:
step 1, preparation: starting an air compressor and adjusting the outlet pressure of the pressure regulating valve to 0.3-0.8 Mpa; starting a steam tracing or circulating hot water tracing system to heat a jacket of the reaction kettle; a cooling system connected with the microchannel reactor; starting the reaction kettle to empty a tail gas condenser cold source;
step 2, feeding: quantitatively preparing a toluene solution of monophenol with the mass concentration of 15% in a preparation tank, adding the toluene solution into the preparation tank according to the molar ratio of monophenol to bisphenol of 11:1, and stirring until the toluene solution is dissolved; closing an outlet valve of the reaction kettle, and pumping the ingredients into the reaction kettle;
step 3, starting the reaction kettle for stirring, when the temperature of materials in the reaction kettle reaches 37-40 ℃, then starting a discharge valve of the reaction kettle, starting a circulating pump, keeping circulating until the temperature of the reaction kettle and the outlet temperature of the microchannel reactor reach 37-40 ℃, after the temperature reaches the temperature, closing the circulating pump and the outlet valve of the pump, keeping the reaction kettle for stirring operation, opening a charging hole cover of the reaction kettle, and pouring catalyst liquid into the reaction kettle and closing the charging hole or pumping the catalyst liquid into the reaction kettle by using a metering pump;
step 4, slowly opening an air supply valve to be fully opened, then starting a circulating pump, rapidly opening a pump outlet valve after 2 seconds, observing that a flowmeter starts to indicate the upper amount and display the stable flow, and regulating the flow of tail gas of a condenser to calculate the required gas flow according to the flow value of the reaction gas required by each mole of monophenol reactant;
step 5, observing an oxygen analyzer, recording reaction time when the oxygen content value begins to decline after stabilizing, adjusting the temperature of a hot water system in the reaction process, and intermittently introducing cooling water into the microchannel reactor to control the reaction temperature; the reaction temperature of the reaction kettle and the micro-channel reactor is kept at 39-42 ℃;
step 6, the real-time database system collects the oxygen content in real time and calculates the total oxygen consumption, and when the total oxygen consumption reaches the theoretical total oxygen consumption and the reaction time is 3.5-4.5 hours, the device stops to run and the reaction is ended; after the reaction is finished, closing the air supply system, closing the circulating pump and stirring the reaction kettle, opening a discharge valve at an outlet of the reaction kettle for discharging after the gas of the system is discharged, and purging the residual materials in the system by adopting nitrogen after the discharging is finished;
and 7, discharging the reaction product from the system, pouring the reaction product into a conical bottom tank, standing for more than 10 hours, settling the catalyst from the reaction product liquid, discharging the catalyst from the bottom, collecting and then carrying out additional treatment, enabling the oily liquid at the upper part to enter a chelating procedure, separating out the purified reaction product after chelation by adopting methanol, and drying the separated solid to obtain the dihydroxypolyphenyl ether product.
2. The method according to claim 1, characterized in that: the microchannel reactor comprises one or more microchannel reactor units, each microchannel reactor unit is formed by connecting one or two or more microchannel reactor units in parallel, and the microchannel reactor is one of the following three types: 1 or more AFR gas-liquid phase micro-channel reactors are combined in parallel; b, combining 1 or more MF-X microchannel static mixer type reactors in parallel; a combination of 1 or more parallel static mixers. Any of the above microchannel reactors must have only one material inlet and material outlet.
3. The method according to claim 1, characterized in that: the catalyst is a coordination compound formed by copper ions and ethylenediamine organic amine or propylenediamine organic amine; the molar ratio of the organic amine to the copper ions in the catalyst is in the range of: (2-20) 1) wherein the compound containing copper ions is cuprous chloride or one of cupric chloride, cupric chloride hydrate, cupric sulfate and cupric nitrate;
the ethylenediamine organic amine is one of the following:
N，N , -dimethylethylenediamine, N , -trimethylethylenediamine, N , ,N , -tetramethyl ethylenediamine, N ’ -diethyl ethylenediamine, N ’ Triethylethylenediamine, N ’ ,N ’ -tetraethyl ethylenediamine, N-propylethylenediamine, N-diisopropylethylenediamine, N ， -di-tert-butylethylenediamine
The propylenediamine organic amine is one of the following:
1, 2-propanediamine, 1, 3-propanediamine or 2, 2-dimethyl 1, 3-propanediamine.
4. A method according to claim 3, characterized in that: the organic amine is as follows: 1, 2-propanediamine, 1, 3-propanediamine, 2-dimethyl 1, 3-propanediamine, N , -dimethylethylenediamine, N , -trimethylethylenediamine, N , ,N , -tetramethyl ethylenediamine, N ’ -diethyl ethylenediamine, N ’ Triethylethylenediamine, N ’ ,N ’ -tetraethyl ethylenediamine, N-propylethylenediamine, N-diisopropylethylenediamine, N ， -one of di-tert-butylethylenediamine;
the monophenol is as follows: one of 2, 6-dimethylphenol, o-methylphenol, m-methylphenol; the bisphenol raw material is one of tetramethyl bisphenol A, dipropenyl bisphenol A, tetrapropenyl bisphenol A and bisphenol A.
5. A method according to claim 3, characterized in that: the solvent prepared from the reaction raw materials is toluene or dimethylbenzene, and the mass concentration of the monophenol raw material is 10% -30%; the molar ratio of monophenol to bisphenol is in the range of n Monophenol :n Bisphenol A =7:1—19:1。
6. The method according to claim 1, characterized in that: the molar ratio of the copper ions added to the catalyst in the reaction to the monophenol compound in the reaction mass is: n is n Cu :n Monophenol =0.003:1—0.021:1。
7. The method according to claim 1, characterized in that: the reaction gas is air or the mixture of air and oxygen, and the pressure range of the introduced gas is as follows: 0.3Mpa-0.7Mpa; the temperature of the reaction kettle is 34-45 ℃; the outlet temperature of the microchannel reactor is 34-47 ℃.
8. The method according to claim 1, characterized in that: the reaction system comprises one or more groups of micro-channel reactors.
9. The method according to claim 1, characterized in that: a tubular distributor is arranged from the outlet of the microchannel reactor unit to the inside of the reaction kettle, is positioned at a position which is far from the center of the height of the reaction kettle and is submerged in the material filled in the reaction kettle; the tube distributor has one or more.
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| CN108371932A (en) * | 2017-12-29 | 2018-08-07 | 安丽华 | A kind of reaction system and method preparing small-molecular-weight polyphenylene oxide |
| CN110156982A (en) * | 2019-06-21 | 2019-08-23 | 常州中英新材料有限公司 | A kind of liquid liquid homogeneous method using continuous flow micro passage reaction synthesis polyarylether |
| CN110156983A (en) * | 2019-06-21 | 2019-08-23 | 常州中英新材料有限公司 | Liquid-liquid heterogeneous method for synthesizing polyarylether by using continuous flow microchannel reactor |
| CN110483762A (en) * | 2019-08-07 | 2019-11-22 | 常州中英新材料有限公司 | A method of heat curing type polyarylether resin is synthesized using continuous flow micro passage reaction |
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| CN114605629A (en) * | 2022-03-23 | 2022-06-10 | 张静 | Preparation system and preparation method of dihydroxy polyphenyl ether |
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| CN116023650A (en) * | 2022-12-09 | 2023-04-28 | 中国科学院大连化学物理研究所 | Process for producing polyphenyl ether by using tubular reactor |
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