CN103145975A - Method for preparing polyphenyl ether with side chain containing unsaturated carbon-carbon double bond in water medium - Google Patents
Method for preparing polyphenyl ether with side chain containing unsaturated carbon-carbon double bond in water medium Download PDFInfo
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Abstract
The invention discloses a method for preparing polyphenyl ether with a side chain containing an unsaturated carbon-carbon double bond in a water medium. The method comprises the following steps of: carrying out oxidative copolymerization reaction on a common phenol monomer and a phenol monomer containing the unsaturated carbon-carbon double bond in the water medium at 30-60 DEG C for 4-24 hours in the presence of a catalyst, a surfactant, an alkali compound and an oxidant; and after the oxidative copolymerization reaction is finished, carrying out demulsification, filtering and washing to obtain the polyphenyl ether with the side chain containing the unsaturated carbon-carbon double bond. The polyphenyl ether containing the unsaturated carbon-carbon double bond prepared in the water medium according to the method disclosed by the invention has the characteristics of low residual metal catalyst content, low dielectric constant, low medium loss, organic solvent resistance, high temperature resistance, good processing performance and the like; and the preparation process is green, environment-friendly, simple, convenient, and easy to implement, safe and nontoxic, has wide development space and great market application value, and is in line with the requirements of sustainable development.
Description
Technical field
The present invention relates to the macromolecule chemical industry technical field, be specifically related to a kind of method that side chain contains the polyphenylene oxide of unsaturated carbon-to-carbon double bond for preparing in water medium.
Background technology
Poly-2,6-dimethyl phenylate is called for short polyphenylene oxide (PPO), the engineering plastics of excellent combination property, not only has good mechanical property, also has the outstanding performance such as low-k, low dielectric loss, high glass-transition temperature, acid-alkali-corrosive-resisting, especially very excellent (ε=2.5-2.6, tan δ=0.0015-0.0019) of electrical property.But PPO is a kind of thermoplastic resin, can not bear the requirement of welding under high temperature, and is soluble in aromatic hydrocarbons or chlorinated aliphatic hydrocarbon, and anti-solvent is relatively poor, and film-forming properties is also bad, therefore must polyphenylene ether carry out modification, expands its use range.A method is to introduce unsaturated carbon-to-carbon double bond in PPO, its advantage is: (1) shared ratio is seldom in whole PPO due to unsaturated carbon-to-carbon double bond, thereby can substantially keep the excellent specific property of former thermoplasticity PPO resin, as low-k, high glass-transition temperature, agent of low hygroscopicity etc.(2) the PPO resin after crosslinking curing improves a lot on solvent resistance.(3) undersaturated carbon-to-carbon double bond is non-polar group, and it has good, the suitable solidification value of dielectric properties, the advantage such as non-volatile thing when solidifying.The PPO that side chain is introduced unsaturated carbon-to-carbon double bond is applied in the manufacturing of copper-clad plate, not only can keep its good electrical property, can also be in the welding property that significantly improves after curing under its solvent resistance and high temperature, simple for process, more can adapt to the requirement of high frequency printed circuit board.
sheet is posted according to male at document (Yoshiyuki ISHII, Masakatsu KURPKI, Hirozi ODA, Takeshi ARAI, and Teruo KATAYOSE.Novel Thermosettable Poly (phenylene ether) .Synthesis, Blend, the allylation polyphenylene oxide (Allyl-PPO) of Japanese Asahi Kasei Corporation exploitation has been described and Application to Copper Clad Laminates.), its synthetic route comprises PPO is dissolved in tetrahydrofuran (THF), use butyllithium and PPO to react, hydrogen on the lithium substituent methyl, above-mentioned product and allyl halide react subsequently, thereby obtain containing allylic PPO, technique is loaded down with trivial details, dangerous high, and the structure of the allylation PPO that obtains is clear and definite not, reason is may allylation reaction repeatedly occur in a plurality of sites or with a site in a structural unit.
Traditional PPO synthetic method is carried out in as organic solvents such as toluene, benzene, chloroform, pyridines, a large amount of organic solvents are not only used in reaction, need the high and explosion-proof reactor of stopping property, can be to environment, in addition, PPO molecular weight synthetic in organic solvent is large, its second-order transition temperature high and be not easy to processing, and due to the cause of homogeneous reaction, catalyst metal ion content residual in product is higher, has reduced to a certain extent its electrical property.with water as reaction medium, not only meet the requirement of Green Chemistry, molecular weight of product synthetic product in the organic solvent, and product is water insoluble, be easy to separate, lower (the Catalyzed oxidative polymerization to form poly (2 of content of copper ion residual in product, 6-dimethyl-1, 6-phenylene oxide) in water using water-soluble copper complex.Saito K, Kuwashiro N, Nishide H.Polymer2006, 47, 6581.), in water medium, synthetic PPO content of copper ion is about the 1ppm left and right.And aspect the research of synthesizing polyphenylene oxide with water as medium, at present only to 2, the homopolymerization of 6-xylenol is studied, and has synthesized common PPO, and side chain is contained the synthetic report that there is not yet of the polyphenylene oxide of unsaturated carbon-to-carbon double bond.
Summary of the invention
The invention provides a kind of in water medium the preparation side chain contain the method for the polyphenylene oxide of unsaturated carbon-to-carbon double bond, realized adopting as medium with water the phenol monomer that contains unsaturated carbon-to-carbon double bond and the copolymerization of common phenol monomer to synthesize the polyphenylene oxide that side chain contains unsaturated carbon-to-carbon double bond.
the present invention finds: if can use the phenol monomer that contains unsaturated carbon-to-carbon double bond and the phenol monomer of routine to carry out copolyreaction in water medium, can solve simultaneously exist in prior art " in organic solvent, synthetic PPO molecular weight is large, its second-order transition temperature high and be not easy to processing, and the cause due to homogeneous reaction, catalyst metal ion content residual in product is higher, reduced to a certain extent its electrical property " and " introduce easily unsaturated carbon-to-carbon double bond and carry out modification with polyphenylene ether in PPO, expand its use range " problem, and PPO molecular weight synthetic in water medium is little, be convenient to processing.Yet the phenol monomer can have different reactive behavioies because its substituent difference makes phenolic hydroxyl group, and substituent size also can cause sterically hindered difference in reaction process, thus the carrying out of impact reaction; In water medium, the research of the copolymerization aspect of phenol monomer still belongs to blank, has important theory significance and using value with water as the polyphenylene oxide that the synthetic side chain of medium contains unsaturated carbon-to-carbon double bond.
In water medium provided by the invention, to contain the mechanism of polyphenylene oxide of unsaturated carbon-to-carbon double bond as follows for the preparation side chain: the benzene oxygen anion that initial reaction stage all kinds phenol monomer is water-soluble with basic cpd reaction generation.The benzene oxygen anion is the benzene oxyradical by catalyst oxidation, and the divalent-metal ion in catalyzer is reduced to monovalence simultaneously.Under oxygenant existed, the metal ion of monovalence was oxidized, again obtains the metal ion of divalence, and between the benzene oxygen anion, oxidative coupling constantly increases the molecular weight of product, and catalyzed oxidation polymerization thus circulates.Carrying out with polyreaction, oligopolymer is insoluble to alkaline aqueous solution and Precipitation becomes nonhomogeneous system, forms stable polymer particle by tensio-active agent, make the oxidative coupling polymerization reaction continue to carry out, finally obtain the polyphenylene oxide that side chain contains unsaturated carbon-to-carbon double bond.
a kind of in water medium the preparation side chain contain the method for the polyphenylene oxide of unsaturated carbon-to-carbon double bond, specifically comprise following scheme: at catalyzer, tensio-active agent, under the condition that basic cpd and oxygenant exist, the phenol monomer that contains unsaturated carbon-to-carbon double bond shown in phenol monomer shown in the formula I structure and formula II structure is carried out oxidation copolymerization and close reaction 4 hours～24 hours in water medium under 30 ℃～60 ℃, after oxidation copolymerization is closed the reaction end, through breakdown of emulsion, filter and wash and obtain the polyphenylene oxide that the side chain shown in the formula III structure contains unsaturated carbon-to-carbon double bond,
R in formula I
1And R
2Identical or different, R
1Be 1 to 4 alkyl, haloalkyl, aminoalkyl group or alkoxyl group for hydrogen, carbonatoms, R
2Be 1 to 4 alkyl, haloalkyl, aminoalkyl group or alkoxyl group for hydrogen, carbonatoms, R
3Be hydrogen or halogen;
R in formula II
4And R
5Identical or different, R
4Be 1 to 4 alkyl, haloalkyl, aminoalkyl group or alkoxyl group for carbonatoms be 2-4 the group that contains unsaturated carbon-to-carbon double bond, hydrogen, carbonatoms, R
5Be 1 to 4 alkyl, haloalkyl, aminoalkyl group or alkoxyl group for carbonatoms be 2-4 the group that contains unsaturated carbon-to-carbon double bond, hydrogen, carbonatoms, and R
4And R
5Both have at least one to be the group that contains unsaturated carbon-to-carbon double bond of 2-4 for carbonatoms, R
6Be hydrogen or halogen;
R in formula III
1, R
2Respectively with formula I in R
1, R
2Has identical implication, the R in formula III
4, R
5Respectively with formula II in R
4, R
5Has identical implication; M is that 15～50, n is 2～17; The weight-average molecular weight of described polyphenylene oxide is 4000～16000.For example, described m can be 2～7 for 15～22, n; The weight-average molecular weight of described polyphenylene oxide is 4100～7400.
As preferably, the alkyl in described haloalkyl, aminoalkyl group or alkoxyl group is all that carbonatoms is 1 to 4 alkyl independently of one another, is more conducive to the carrying out that oxidation copolymerization is closed reaction.
As preferably, described carbonatoms is that the group that contains unsaturated carbon-to-carbon double bond of 2-4 is vinyl, allyl group, propenyl, butenyl or alkene butyl, is more conducive to the carrying out that oxidation copolymerization is closed reaction.
Described halogen is selected the general halogen in this area, a kind of as in F, Cl, Br, I etc.
Described oxidation copolymerization closes that in reaction, the mol ratio of each raw material consists of:
Phenol monomer 1 shown in the formula I structure;
The phenol monomer 0.1～0.45 that contains unsaturated carbon-to-carbon double bond shown in the formula II structure;
Basic cpd 0.055～100;
Tensio-active agent 0.001～0.15;
Catalyzer 0.001～0.75;
Oxygenant is appropriate.
As preferably, described oxidation copolymerization closes that in reaction, the mol ratio of each raw material consists of:
Phenol monomer 1 shown in the formula I structure;
The phenol monomer 0.1～0.43 that contains unsaturated carbon-to-carbon double bond shown in the formula II structure;
Basic cpd 0.055～1.3;
Tensio-active agent 0.0055～0.15;
Catalyzer 0.001～0.75;
Oxygenant is appropriate.
Described basic cpd is selected one or more in potassium hydroxide, sodium hydroxide, lithium hydroxide, sodium methylate, sodium carbonate, salt of wormwood, saleratus, sodium bicarbonate.
Described tensio-active agent is selected aniorfic surfactant, specifically can select one or more in carboxylate surface active agent, alkyl sulfate surfactant, alkyl sulfonate surfactants, alkyl benzene sulfonate surfactant.
Described catalyzer is selected the copper-amine complex of copper compound and amine compound complexing, is perhaps the manganese amine complex of manganic compound and amine compound.In described copper-amine complex, the molar ratio of nitrogen-atoms and cupric ion is preferably 2～8, and more preferably 2～4, perhaps in described manganese amine complex, the molar ratio of nitrogen-atoms and mn ion is preferably 2～8, and more preferably 2～4.
Described copper compound is selected cupric compound, one or more in preferred cupric chloride, cupric bromide, copper sulfate, cupric nitrate; Perhaps, described manganic compound is selected manganous compound, one or more in preferred Manganous chloride tetrahydrate, Manganese dibromide, manganese iodide, manganous carbonate, manganese acetate, manganous nitrate, manganous sulfate, manganous phosphate.
described amine compound is selected methylamine, ethamine, 2 hydroxy ethylamine, 2-methylamino ethamine, Tri N-Propyl Amine, the ring butylamine, TERTIARY BUTYL AMINE, 1, the 4-butanediamine, 1-hydroxyl butylamine, n-amylamine, 1, the 5-pentamethylene diamine, the ring pentamethylene diamine, normal hexyl Amine, 4-sec.-propyl hexahydroaniline, 1, the 4-cyclohexane diamine, 3-methoxyl group hexanediamine, benzyl amine, 1, the 6-hexanediamine, 1, the 8-octamethylenediamine, 4-sec.-propyl-1, the 3-phenylenediamine, two amido sulfobenzides, diaminodiphenyl ether, 3, the 3-tolidine, 3, the 3-dimethoxy benzidine, ethylenediamine tetraacetic acid (EDTA), N-substituting group imidazoles, N, N, N ', N '-tetramethyl--1, 3-two amidos-1-ethyl propane, N, N, N ', N '-tetraethyl--1, 3-two amidos-1-methylpropane, 1, 3-two amido propane, N, N, N ', N '-tetramethyl--1, one or more in 3-two amido propane.
Described oxygenant is oxygen, air or mixes by oxygen and rare gas element the mixed gas that forms.In described mixed gas, oxygen and rare gas element can mix with various ratios (oxygen proportion can not be 0).
The product that the present invention is synthesized is taked the method for temperature programming or UV-irradiation under peroxide initiator or light trigger effect, crosslinking reaction can occur the unsaturated carbon-to-carbon double bond on side chain, the Noryl that obtains solidifying.
Raw material of the present invention, reagent all can adopt the commercially available prod.
Compared with prior art, the present invention has following marked improvement:
The residual metal ion content of the polyphenylene oxide that contains unsaturated carbon-to-carbon double bond that the present invention prepares in water medium is few, and specific inductivity is low, dielectric loss is low, good processability, anti-solvent after product solidifies,
Temperature tolerance is good; Simultaneously, synthetic method of the present invention is more simple and easy to do, environmental protection, and safety non-toxic has wide development space and great market using value, more meets the requirement of Sustainable development.
Embodiment
In embodiment 1 water medium, the preparation side chain contains the polyphenylene oxide of unsaturated carbon-to-carbon double bond
with stirring rake, in the reactor of thermometer, add sodium hydroxide (0.2g, 5mmol), sodium lauryl sulphate (0.1694g, 0.5mmol), 2, 6-xylenol (DMP, 0.4930g, 4mmol), 2-allyl group-6-methylphenol (AMP, 0.15ml, 1mmol) and distilled water 100mL, the temperature to 50 ℃ of rear rising reactor stirs, add again cupric chloride (0.0086g, 0.05mmol)/ethylenediamine tetraacetic acid (EDTA) (EDTA, 0.05mmol) complex compound, pass into oxygen, at 600rotor/min(rev/min) stirring velocity under, reacted 24 hours.Add the sodium-chlor breakdown of emulsion after reaction finishes, then filter, washing, vacuum-drying to the constant weight solid product, i.e. double bond containing polyphenylene oxide, productive rate 78.35%, weight-average molecular weight 6000, molecular weight distribution 2.2, m=17, n=4, remaining copper ion content 0.80ppm.
Embodiment 2～3
Method according to embodiment 1 prepares the polyphenylene oxide that side chain contains unsaturated carbon-to-carbon double bond in water medium, different is the ratio that changes two kinds of phenol monomers, and polymerization result sees Table 1:
Table 1
Embodiment 4
Method according to embodiment 1 prepares the polyphenylene oxide that side chain contains unsaturated carbon-to-carbon double bond in water medium, different is to use 0.52g(5.2mmol) saleratus replacement sodium hydroxide, productive rate 76.57%, product weight-average molecular weight 5900, molecular weight distribution 2.1, m=18, n=4, remaining copper ion content 0.76ppm.
Embodiment 5
Method according to embodiment 1 prepares the polyphenylene oxide that side chain contains unsaturated carbon-to-carbon double bond in water medium, different is that oxygenant is air, productive rate 76.78%, molecular weight of product 5800, molecular weight distribution 2.2, m=17, n=4, remaining copper ion content 0.81ppm.
Embodiment 6
Method according to embodiment 1 prepares the polyphenylene oxide that side chain contains unsaturated carbon-to-carbon double bond in water medium, different is with 2,6-diethyl phenol (0.5053g, 4mmol) replaces 2,6-xylenol, productive rate 77.28%, product weight-average molecular weight 6200, molecular weight distribution 2.3, m=17, n=4, remaining copper ion content 0.79ppm.
Embodiment 7
Method according to embodiment 1 prepares the polyphenylene oxide that side chain contains unsaturated carbon-to-carbon double bond in water medium, different is with 2-alkene butyl-6-methylphenol (0.15ml, 1mmol) replace 2-allyl group-6-methylphenol, productive rate 79.35%, product weight-average molecular weight 6300, molecular weight distribution 2.3, m=18, n=5, remaining copper ion content 0.78ppm.
Embodiment 8
Method according to embodiment 1 prepares the polyphenylene oxide that side chain contains unsaturated carbon-to-carbon double bond in water medium, different is that temperature of reaction is 30 ℃, and the reaction times is 8 hours, productive rate 70.32%, product weight-average molecular weight 4900, molecular weight distribution 2.0, m=16, n=4, remaining copper ion content 0.80ppm.
Embodiment 9～13
Method according to embodiment 1 prepares the polyphenylene oxide that side chain contains unsaturated carbon-to-carbon double bond in water medium, different is the copper-amine complex that uses different concns, and polymerization result sees Table 2:
Table 2
Embodiment 14～18
Method according to embodiment 1 prepares the polyphenylene oxide that side chain contains unsaturated carbon-to-carbon double bond in water medium, different is to use different copper-amine complex, and polymerization result sees Table 3:
Table 3
Embodiment 19～23
Method according to embodiment 1 prepares the polyphenylene oxide that side chain contains unsaturated carbon-to-carbon double bond in water medium, different is to use different manganese amine complexes, and polymerization result sees Table 4:
Table 4
Embodiment 24
Product 1g and initiator isopropyl benzene hydroperoxide (CHPO) 10mg synthetic in embodiment 1 are dissolved in 5ml toluene; under nitrogen or protection of inert gas; under 80 ℃, heating is 1 hour; then be warming up to the Noryl that 180 ℃ of heating obtained solidifying in 1 hour; product gel content 98.6%; 5% decomposition temperature is 383 ℃, and the polymerization after crosslinked no longer is dissolved in the organic solvents such as toluene, chloroform.
Embodiment 25
With product 1g and light trigger TPO(2 synthetic in embodiment 1; 4; 6-trimethylbenzoyl-diphenyl phosphine oxide) 10mg is dissolved in 5ml toluene; under nitrogen or protection of inert gas; the lower 10s of irradiation under the UV-light of 200nm; product gel content 99.1%, 5% decomposition temperature is 392 ℃, and the polymerization after crosslinked no longer is dissolved in the organic solvents such as toluene, chloroform.
Claims (10)
1. one kind prepares the method that side chain contains the polyphenylene oxide of unsaturated carbon-to-carbon double bond in water medium, it is characterized in that, at catalyzer, tensio-active agent, under basic cpd and oxygenant exist, the phenol monomer that contains unsaturated carbon-to-carbon double bond shown in the phenol monomer shown in the formula I structure and formula II structure is carried out oxidation copolymerization and close reaction 4 hours～24 hours in water medium under 30 ℃～60 ℃, after oxidation copolymerization is closed the reaction end, through breakdown of emulsion, filter and wash and obtain the polyphenylene oxide that the side chain shown in the formula III structure contains unsaturated carbon-to-carbon double bond,
R in formula I
1And R
2Identical or different, R
1Be 1 to 4 alkyl, haloalkyl, aminoalkyl group or alkoxyl group for hydrogen, carbonatoms, R
2Be 1 to 4 alkyl, haloalkyl, aminoalkyl group or alkoxyl group for hydrogen, carbonatoms, R
3Be hydrogen or halogen;
R in formula II
4And R
5Identical or different, R
4Be 1 to 4 alkyl, haloalkyl, aminoalkyl group or alkoxyl group for carbonatoms be 2-4 the group that contains unsaturated carbon-to-carbon double bond, hydrogen, carbonatoms, R
5Be 1 to 4 alkyl, haloalkyl, aminoalkyl group or alkoxyl group for carbonatoms be 2-4 the group that contains unsaturated carbon-to-carbon double bond, hydrogen, carbonatoms, and R
4And R
5Both have at least one to be the group that contains unsaturated carbon-to-carbon double bond of 2-4 for carbonatoms, R
6Be hydrogen or halogen;
R in formula III
1, R
2Respectively with formula I in R
1, R
2Has identical implication, formula
R in (III)
4, R
5Respectively with formula II in R
4, R
5Has identical implication; M is that 15～50, n is 2～17; The weight-average molecular weight of described polyphenylene oxide is 4000～16000.
2. method according to claim 1, is characterized in that, the alkyl in described haloalkyl, aminoalkyl group or alkoxyl group is all that carbonatoms is 1 to 4 alkyl independently of one another.
3. method according to claim 1, is characterized in that, described carbonatoms is that the group that contains unsaturated carbon-to-carbon double bond of 2-4 is vinyl, allyl group, propenyl, butenyl or alkene butyl.
4. method according to claim 1, is characterized in that, described oxidation copolymerization closes that in reaction, the mol ratio of each raw material consists of:
Phenol monomer 1 shown in the formula I structure;
The phenol monomer 0.1～0.45 that contains unsaturated carbon-to-carbon double bond shown in the formula II structure;
Basic cpd 0.055～100;
Tensio-active agent 0.001～0.15;
Catalyzer 0.001～0.75;
Oxygenant is appropriate.
5. according to claim 1 or 4 described methods, is characterized in that, described basic cpd is one or more in potassium hydroxide, sodium hydroxide, lithium hydroxide, sodium methylate, sodium carbonate, salt of wormwood, saleratus, sodium bicarbonate;
Described tensio-active agent is aniorfic surfactant;
Described catalyzer is the copper-amine complex of copper compound and amine compound complexing, is perhaps the manganese amine complex of manganic compound and amine compound.
6. method according to claim 5, is characterized in that, described tensio-active agent is one or more in carboxylate surface active agent, alkyl sulfate surfactant, alkyl sulfonate surfactants, alkyl benzene sulfonate surfactant.
7. method according to claim 5, is characterized in that, in described copper-amine complex, the molar ratio of nitrogen-atoms and cupric ion is 2～8, and perhaps in described manganese amine complex, the molar ratio of nitrogen-atoms and mn ion is 2～8.
8. method according to claim 5, is characterized in that, described copper compound is selected one or more in cupric chloride, cupric bromide, copper sulfate, cupric nitrate; Perhaps, described manganic compound is selected one or more in Manganous chloride tetrahydrate, Manganese dibromide, manganese iodide, manganous carbonate, manganese acetate, manganous nitrate, manganous sulfate, manganous phosphate.
9. method according to claim 5, it is characterized in that, described amine compound is selected methylamine, ethamine, 2 hydroxy ethylamine, 2-methylamino ethamine, Tri N-Propyl Amine, the ring butylamine, TERTIARY BUTYL AMINE, 1, the 4-butanediamine, 1-hydroxyl butylamine, n-amylamine, 1, the 5-pentamethylene diamine, the ring pentamethylene diamine, normal hexyl Amine, 4-sec.-propyl hexahydroaniline, 1, the 4-cyclohexane diamine, 3-methoxyl group hexanediamine, benzyl amine, 1, the 6-hexanediamine, 1, the 8-octamethylenediamine, 4-sec.-propyl-1, the 3-phenylenediamine, two amido sulfobenzides, diaminodiphenyl ether, 3, the 3-tolidine, 3, the 3-dimethoxy benzidine, ethylenediamine tetraacetic acid (EDTA), N-substituting group imidazoles, N, N, N ', N '-tetramethyl--1, 3-two amidos-1-ethyl propane, N, N, N ', N '-tetraethyl--1, 3-two amidos-1-methylpropane, 1, 3-two amido propane, N, N, N ', N '-tetramethyl--1, one or more in 3-two amido propane.
10. according to claim 1 or 4 described methods, is characterized in that, described oxygenant is oxygen, air or mixes by oxygen and rare gas element the mixed gas that forms.
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| CN108148195A (en) * | 2018-01-29 | 2018-06-12 | 四川大学 | The application in polyphenylene oxide is prepared is used in combination with emulsifier in catalyst |
| CN109776790A (en) * | 2017-11-10 | 2019-05-21 | 中国科学院大连化学物理研究所 | A kind of method of oxidative coupling polymerization synthesis polyphenylene oxide |
| CN109836568A (en) * | 2017-11-29 | 2019-06-04 | 中国科学院大连化学物理研究所 | A method of polyphenylene ether copolymer is prepared in oil/water two-phase medium |
| 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 |
| CN110387037A (en) * | 2018-04-19 | 2019-10-29 | 旭化成株式会社 | Polyphenylene oxide and its manufacturing method |
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| CN110387037B (en) * | 2018-04-19 | 2022-05-13 | 旭化成株式会社 | Polyphenylene ether and process for producing the same |
| 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 |
| CN110156982B (en) * | 2019-06-21 | 2022-02-08 | 常州中英新材料有限公司 | Liquid-liquid homogeneous phase method for synthesizing polyarylether by using continuous flow microchannel reactor |
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