CN1314758C - Polymrization method of preparing polyphonyl ether/phenylethylene kind polymer alloy in reactor - Google Patents
Polymrization method of preparing polyphonyl ether/phenylethylene kind polymer alloy in reactor Download PDFInfo
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- CN1314758C CN1314758C CNB2005100507445A CN200510050744A CN1314758C CN 1314758 C CN1314758 C CN 1314758C CN B2005100507445 A CNB2005100507445 A CN B2005100507445A CN 200510050744 A CN200510050744 A CN 200510050744A CN 1314758 C CN1314758 C CN 1314758C
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Abstract
The present invention relates to a polymerization method for preparing polymer alloy of classes of polyphenylether/styrene in a reactor. A phenol compound and oxidant are reacted in a full aqueous medium by an oxidative polymerization way under the existence of a styrene class monomer, catalyst, surfactant and an alkaline compound; then, the styrene class monomer can generate free radical polymerization reaction by adding an evocating agent or by heat initiation, and the styrene class monomer is centrifugally filtered or agglomerated in a shearing way, centrifugally filtered and dried after the reaction is finished. The method of the present invention introduces the styrene class monomer into a reaction medium which comprises the phenol compound, the styrene class monomer is used as a swelling agent of the oxidative polymerization reaction of the phenol compound to promote oxidative coupling reaction, and the molecular weight of the polyphenylether is increased. Because organic solvent is not used to produce the polymer alloy of the classes of the polyphenylether/styrene, the polymer alloy of the classes of the polyphenylether/styrene is reacted and prepared in the full aqueous medium, and the present invention almost has no pollution to environment. Therefore, the present invention is friendly to the environment, decreases melt blending steps in a screw rod extrusion machine, and can prevent fusion degradation and discoloration of the polymer.
Description
Technical field
The present invention relates to prepare the method for polyphenylene oxide/styrenic polymer alloy, especially about preparing the method for polyphenylene oxide/styrenic polymer alloy in the reactor.
Background technology
Polyphenylene oxide is because of its excellent physical strength, thermotolerance, electrical insulating property, dimensional stability etc., has application widely in fields such as electric, automotive industry, machinofacture, but because the polyphenylene oxide melt viscosity is big, mobile poor, make its forming process difficulty, so it uses after usually making alloy with the styrene resin melt blending.
United States Patent (USP) 3,306,874; 3,306,875; 3,257,357; 3,257,358 grades have been announced the production method that the oxybenzene compound oxidative coupling is produced polyphenylene oxide in the organic solvent, mainly be in the polymerization system that good solvent, metal-salt, amine compound by oxybenzene compound, polyphenylene oxide constitute, to feed oxygen-containing gas to make oxybenzene compound oxypolymerization, the poor solvent that adds polyphenylene oxide then in the polyphenylene oxide solution that obtains at separating metal salt, water, separate out the polyphenylene oxide particle, at last its filtration is prepared polyphenylene oxide.This method uses a large amount of organic solvents as reaction medium, therefore needs solvent recuperation and high temperature devolatilization device, and environmental pollution is serious.
Polyphenylene oxide/styrenic polymer alloy often adopts the melt-blending process preparation.Blending method is with polyphenylene oxide and styrenic polymer or other properties-correcting agent melt blending, extruding pelletization and make polyphenylene oxide alloy in screw extrusion press.United States Patent (USP) 3,373,226 and 3,383,435 disclose the method for preparing polyphenyl ether/styrene base polymer alloy with blending method.United States Patent (USP) 4,360,618,4,277,575,4,684,695,4,196,116,4,309,514 disclose with polyphenylene oxide with contain the method that the unitary styrenic superpolymer of rubber-like structure melt blending prepares the impact polyphenyl ether/styrene alloy, but the method for this production polyphenylene oxide alloy needs polyphenylene oxide and styrenic polymer melt blending at high temperature, easily makes the polymer degradation variable color.
Summary of the invention
The purpose of this invention is to provide that a kind of environmental friendliness, technology are simple, the products obtained therefrom excellent property in full water medium in the reactor polymerization prepare the method for polyphenylene oxide/styrenic polymer alloy.
Polyphenylene oxide of the present invention/styrenic polymer alloy is made up of the polyphenylene oxide of 10～90 weight % and the styrenic polymer of 90～10 weight %.The limiting viscosity of polyphenylene oxide is between 3.5-23 in this alloy, and the limiting viscosity of styrenic polymer is between 8.0-80.
Polymerization prepares the method for polyphenylene oxide/styrenic polymer alloy in the reactor, may further comprise the steps: at styrene monomer, catalyzer, tensio-active agent, basic cpd exists down, the oxybenzene compound of use formula (1) representative and oxygenant carry out oxidative polymerization under 1～80 ℃ in full water medium, the amount ratio of styrene monomer and oxybenzene compound is 1: 9～9: 1, the weight ratio of oxybenzene compound and styrene monomer total amount and reaction medium is 1: 1～1: 90, the molar ratio of catalyzer and oxybenzene compound is 0.01～0.5, the molar ratio of tensio-active agent and oxybenzene compound is 0.001～0.1, oxidative polymerization 0.5～30 hour
R in the formula
1And R
2Representative has alkyl or the replacement or the unsubstituted phenyl of 1～4 carbon atom, R
3Represent hydrogen or halogen atom, after treating that oxidative polymerization finishes, add initiator and under 100～200 ℃, make styrene monomer generation Raolical polymerizable 0.5～20 hour down or by thermal initiation in 60～110 ℃, the amount of initiator is between 0.01～2wt% of styrene monomer consumption, above-mentioned oxidative polymerization and Raolical polymerizable carry out under agitation condition, after reaction finishes, centrifuging or by shearing centrifuging again after the cohesion, drying gets polyphenylene oxide/styrenic polymer alloy.
Among the present invention, said oxygenant is the gas that contains oxygen, can be oxygen, air or oxygen and the rare gas element gas with various mixed.Said full water medium is deionized water or distilled water.
Among the present invention, said tensio-active agent comprises aniorfic surfactant and nonionic surface active agent.Wherein aniorfic surfactant is including, but not limited to carboxylate surface active agent, alkyl sulfate surfactant, alkyl sulfonate surfactants and alkyl benzene sulfonate surfactant, the general formula that is used for carboxylate surface active agent of the present invention is RCOOM, wherein R is alkyl (C
12-C
18), M is a metal ion, for example the dodecyl carboxylic acid sodium.The general formula that is used for alkyl sulfate surfactant of the present invention is ROSO
3M, wherein R is alkyl (C
8-C
18), M is a metal ion, sodium lauryl sulphate for example, sodium stearyl sulfate etc.The general formula that is used for alkylsulfonate of the present invention is R-SO
3M, R is alkyl (C in the formula
12-C
16), M is a metal ion, sodium sulfosuccinate for example, sodium cetanesulfonate etc.The general formula that is used for alkylbenzene sulfonate of the present invention is R-C
6H
4-SO
3M, R is alkyl (C in the formula
12-C
16), M is a metal ion, Sodium dodecylbenzene sulfonate for example, hexadecyl benzene sulfonic acid sodium salt etc.And nonionic surface active agent is including, but not limited to fatty alcohol-polyoxyethylene ether, polyoxyethylene alkylphenol ether and polyvalent alcohol alkyl esters tensio-active agent, for example dodecyl glyceryl ester etc.
Among the present invention, said catalyzer is a potassium ferricyanate, or the copper-amine complex of copper compound and amine compound complexing, the molar ratio of nitrogen-atoms and copper compound is at least 2 in the aminated compounds, or the complex compound of manganic compound and amine compound or α-Qiang Jiwo, the molar ratio of nitrogen-atoms and manganic compound is at least 2 in the aminated compounds.
Be used for copper compound of the present invention including, but not limited to water-soluble cupric salt, cuprous salt or its mixture.Can select cuprous chloride, cuprous bromide, cuprous sulfate, cuprous nitrate, cupric chloride, cupric bromide, copper sulfate or cupric nitrate etc. for use.Wherein preferred cuprous chloride, cuprous bromide, cupric chloride or cupric bromide.With the amine compound of copper compound complexing be N-substituting group imidazoles, N, N, N ', N '-four substituting group-1,2-two amido ethane, N, N, N ', N '-four substituting group-1,3-two amido propane and N, N, N ', N '-four substituting group-1, one or more mixtures in 3-two amidos-1-substituting group propane.The N-substituted imidazole can be selected imidazoles, N-Methylimidazole or N-ethyl imidazol(e) for use; N, N, N ', N '-four substituting group-1,2-two amido ethane can be selected N for use, N, N ', N '-tetraethyl--1,2-two amido ethane, N, N, N ', N '-tetraacethyl-1,2-two amido ethane or N, N, N ', N '-tetramethyl--1,2-two amido ethane; N, N, N ', N '-four substituting group-1,3-two amido propane can be selected N for use, N, N ', N '-tetramethyl--1,3-two amido propane, N, N, N ', N '-tetraethyl--1,3-two amido propane or N, N, N ', N '-tetraacethyl-1,3-two amido propane; N, N, N ', N '-four substituting group-1,3-two amidos-1-substituting group propane can be selected N, N for use, N ', N '-tetramethyl--1,3-two amidos-1-methylpropane, N, N, N ', N '-tetramethyl--1,3-two amidos-1-ethyl propane, N, N, N ', N '-tetraethyl--1,3-two amidos-1-methylpropane, N, N, N ', N '-tetraethyl--1,3-two amidos-1-ethyl propane, N, N, N ', N '-tetraacethyl-1,3-two amidos-1-methylpropane or N, N, N ', N '-tetraacethyl-1,3-two amidos-1-ethyl propane etc.
Be used for manganic compound of the present invention including, but not limited to Manganous chloride tetrahydrate, Manganese dibromide, manganese iodide, manganous carbonate, manganese acetate, manganous nitrate, manganous sulfate or manganous phosphate etc.With the amine compound of manganic compound complexing can be 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, the diamines yl diphenyl ether, 3,3 '-tolidine and 3, in 3 '-dimethoxy benzidine one or more, have following formula structure, wherein R with the α-Qiang Jiwo of manganic compound complexing
a, R
b, R
c, R
dBe hydrogen or ring-type or straight-chain paraffin, n is the integer of 1-5.
Among the present invention, said styrene monomer can be selected vinylbenzene for use, 2, the 4-dichlorostyrene, to methoxy styrene, p-nitrophenyl ethene, p-methylstyrene, 3, the 4-dimethyl styrene, between t-butyl styrene, to dodecyl vinylbenzene, to styryl phenyl, to acetoxy-styrene, Vinylstyrene, p-aminophenyl ethene, to (chloromethyl) vinylbenzene, between cyano-styrene, o-hydroxy ethene, to vinyl benzoic acid, alpha-methyl styrene, α-propylstyrene, α-undecyl vinylbenzene, adjacent methyl-alpha-methyl styrene, between methyl-alpha-methyl styrene, to methyl-alpha-methyl styrene, to methoxyl group-alpha-methyl styrene, to cyano group-alpha-methyl styrene, between the bromo-alpha-methyl styrene, to chloro-alpha-methyl styrene or a chloro-alpha-methyl styrene or their mixture.
The monomer that is used to prepare polyphenylene oxide is the oxybenzene compound with following formula structure:
R in the formula
1And R
2Representative has alkyl or the replacement or the unsubstituted phenyl of 1～4 carbon atom, R
3Represent hydrogen or halogen atom.
Can be used for specific oxybenzene compound of the present invention includes, but are not limited to:
2, the 6-xylenol, 2, the 6-diethyl phenol, 2-methyl-6-ethylphenol, 2,6-dipropyl phenol, 2-methyl-6-propylphenol, 2-ethyl-6-propylphenol, 2,6-phenylbenzene phenol, 2-methyl-6-phenylphenol, 2-ethyl-6-phenylphenol, 2-propyl group-6-phenylphenol, 2,6-dimethyl-4-bromophenol, 2,6-diethyl-4-bromophenol, 2-methyl-6-ethyl-4-bromophenol, 2,6-dipropyl-4-bromophenol, 2-methyl-6-propyl group-4-bromophenol, 2-ethyl-6-propyl group-4-bromophenol, 2,6-phenylbenzene-4-bromophenol, 2-methyl-6-phenyl-4-bromophenol, 2-ethyl-6-phenyl-4-bromophenol, 2-propyl group-6-phenyl-4-bromophenol, 2,6-dimethyl-4-chlorophenol, 2,6-diethyl-4-chlorophenol, 2-methyl-6-ethyl-4-chlorophenol, 2,6-dipropyl-4-chlorophenol, 2-methyl-6-propyl group-4-chlorophenol, 2-ethyl-6-propyl group-4-chlorophenol, 2,6-phenylbenzene-4-chlorophenol, 2-methyl-6-phenyl-4-chlorophenol, 2-ethyl-6-phenyl-4-chlorophenol or 2-propyl group-6-phenyl-4-chlorophenol.Preferred oxybenzene compound is 2, the 6-xylenol.
Oxidative polymerization and Raolical polymerizable carry out under agitation condition, and stir speed (S.S.) is usually between 10rpm～2000rpm.
Among the present invention, said initiator comprises azo class, peroxide initiator.Wherein the azo class can be selected for use but be not limited to a kind of or its mixture in Diisopropyl azodicarboxylate and the 2,2'-Azobis(2,4-dimethylvaleronitrile); Peroxide can be selected for use but be not limited to Potassium Persulphate, ammonium persulphate, dibenzoyl peroxide, dilauroyl peroxide, peroxide tert pivalate ester, the special butyl ester of peroxidation phenylformic acid, di-isopropyl peroxydicarbonate, di-cyclohexylperoxy dicarbonate, 2; 5 dimethyl-2; two (peroxidation of the ethyl hexanoyl base) hexanes of 5-, di-t-butyl peroxide, dicumyl peroxide and 2; 5 dimethyl-2, one or more in two (benzoyl peroxidation) hexanes of 5-.
Basic cpd among the present invention one or more in potassium hydroxide, sodium hydroxide, lithium hydroxide, sodium methylate, yellow soda ash, salt of wormwood, saleratus or the sodium bicarbonate etc.Adding certain basic cpd reaches more than 10 the pH value of reaction medium.
During oxybenzene compound oxypolymerization, if temperature of reaction is too low, then speed of reaction is slower; If temperature is too high, catalyst deactivation then is so temperature of reaction is between 1～80 ℃, preferably between 40～60 ℃.Add initiator and cause in the styrene monomer radical polymerization process, temperature of reaction is elevated to 60～110 ℃.If adopt thermopolymerization, can not add initiator, directly temperature of reaction is elevated to 100～200 ℃.
The inventive method will have reactive styrene monomer introducing and comprise in the reaction medium of oxybenzene compound, swelling agent as the oxybenzene compound oxidative polymerization, the carrying out of promotes oxidn coupled reaction, improve the molecular weight of polyphenylene oxide, the limiting viscosity that makes polyphenylene oxide in the alloy is between 3.5～23.Owing to produce polyphenylene oxide/styrenic polymer alloy not with an organic solvent, in full water medium, prepare in the reactor, almost environment is not polluted, therefore very friendly to environment, and reduced the operation of melt blending in the screw extrusion press, can prevent that polymkeric substance is in pyritous fusion degraded, variable color.
Embodiment
Following embodiment further describes the present invention, but described embodiment only is used to illustrate the present invention rather than restriction the present invention.
Embodiment 1
Use a 500mL reactor that has gas inlet and outlet, stirring rake, thermometer and constant temperature jacket, carry out the preparation of polyphenyl ether/styrene alloy as follows.
The 250mL distilled water that will contain 10 gram sodium hydroxide is added in the reactor, and the temperature of reactor is controlled at 40 ℃, stirs sodium hydroxide is dissolved fully.Then with 2 of 2.44g, the 6-xylenol adds and is stirred to dissolving fully, bubbling air simultaneously in this aqueous solution.Preparation contains the mixing solutions of the cuprous 0.50g of chlorination, quadrol 1.2g, water 10mL separately.This mixing solutions is joined in the reactor, add the 145mg sodium lauryl sulphate again.Treat that stirring reaction is after 1 hour, add 2.44g vinylbenzene, stir speed (S.S.) is increased to 1500rpm, react after 18 hours, add the 0.00244g dibenzoyl peroxide, with airtight behind the air in the nitrogen venting aforesaid reaction vessel, and temperature of reaction is elevated to 85 ℃, continues reaction and stop after 4 hours stirring.With polymkeric substance washing and the drying that filtration obtains, and the limiting viscosity of polyphenylene oxide and polystyrene in the polymer alloy that obtains thus (η]) be respectively 5.5 and 40.
Embodiment 2～7
The basic embodiment 1 described operation that repeats, different is copper compound and amine compound, sees Table 1.
Table 1
| Embodiment | Copper compound (mmol) | Amine compound (mmol) | The limiting viscosity of polymkeric substance | |
| Polyphenylene oxide (η]) | Polystyrene (η]) | |||
| 2 3 4 5 6 7 | Copper chloride (10) copper chloride (5) copper chloride (5) copper chloride (5) stannous chloride (5) stannous chloride (5) | N, N, N ', N '-tetramethyl--1,3-two amidos-1-ethyl propane (20) N, N, N ', N '-tetraethyl--1,3-two amidos-1-methylpropane (10) 1,3-two amido propane (10) N-Methylimidazole (10) N, N, N ', N-EDTA (10) N, N, N ', N-tetramethyl--1,3-two amido propane (10) | 4.8 5.2 4.3 4.6 3.9 6.2 | 39 35 40 39 41 34 |
Embodiment 8
Use a 500mL reactor that has gas inlet and outlet, stirring rake, thermometer and constant temperature jacket, carry out the preparation of polyphenyl ether/styrene alloy as follows.
The 250mL distilled water that will contain 10 gram potassium hydroxide is added in the reactor, and the temperature of reactor is controlled at 50 ℃, stirs potassium hydroxide is dissolved fully.Then 2-methyl-6-phenylphenol of 21.2g is added and be stirred to dissolving fully in this aqueous solution, aerating oxygen simultaneously, keeping the oxygen pressure in the reactor is 1atm.Add 1.316g potassium ferricyanate and 1.45g sodium lauryl sulphate again.Treat stirring reaction after 1 hour, add 10.6g vinylbenzene and 0.6g alpha-methyl styrene, stir speed (S.S.) is increased to 1000rpm.React after 18 hours, add the 0.053g Diisopropyl azodicarboxylate,, and temperature of reaction is elevated to 95 ℃, continue reaction and stop after 12 hours stirring with airtight behind the air in the nitrogen venting aforesaid reaction vessel.With polymkeric substance washing and drying that filtration obtains, the limiting viscosity of polyphenylene oxide and styrol copolymer in the polymer alloy that obtains thus ([η]) is respectively 4.4 and 30.
Embodiment 9
Use a reactor that has the 500mL of gas inlet and outlet, agitator, thermometer and constant temperature jacket, carry out the preparation of polyphenyl ether/styrene alloy as follows.
The 250mL distilled water that will contain the 12g lithium hydroxide is added in the reactor, and the temperature of reactor is controlled at 50 ℃, and continuously stirring is dissolved lithium hydroxide fully.2-methyl-6-ethyl-4-chlorophenol with 3.43g joins in this aqueous solution then, is stirred to dissolving fully, the while aerating oxygen, and keeping the oxygen pressure in the reactor is 1atm.Preparation contains the mixing solutions of manganous nitrate 0.358g, EDTA 1.17g, water 10mL separately.This mixing solutions is joined in the reactor, add the 0.496g Sodium dodecylbenzene sulfonate again.Behind the question response 1 hour, add 30.9g, stir speed (S.S.) is increased to 2000rpm methoxy styrene.React after 4 hours, add the 0.00309g dicumyl peroxide,, and temperature of reaction is elevated to 110 ℃, continue reaction and stop after 10 hours stirring with airtight behind the air in the nitrogen venting aforesaid reaction vessel.Also dry by the polymkeric substance that filtration obtains through washing, and the limiting viscosity of polyphenylene oxide and styrenic polymer in the polymer alloy that obtains thus (η]) be respectively 4.0 and 30.
Embodiment 10～16
The basic embodiment 1 described operation that repeats, the different catalyzer that is to use is the manganese amine complex, wherein manganic compound and amine compound or α-Qiang Jiwo and molar mass thereof see Table 2.
Table 2
| Embodiment | Manganic compound (mmol) | Amine compound or α-Qiang Jiwo (mmol) | The limiting viscosity of polymkeric substance | |
| Polyphenylene oxide ([η]) | Polystyrene (η]) | |||
| 10 11 12 13 14 15 16 | Manganous chloride tetrahydrate, (5) Manganous chloride tetrahydrate, (5) Manganous chloride tetrahydrate, (5) Manganese dibromide, (5) Manganese dibromide, (5) Manganese dibromide, (5) Manganese dibromide, (5) | Acetaldoxime (10) 2 hydroxy ethylamine (10) 2-methylamino ethamine (10) 2 hydroxy ethylamine (10) 2-methylamino ethamine (10) n-propylamine (20) Putriscine (10) | 4.1 15 10 3.8 4.8 11 19 | 31 30 32 34 29 33 25 |
Embodiment 17
Use a pressure reaction still that has the 500mL of gas inlet and outlet, agitator, thermometer and constant temperature jacket, carry out the preparation of polyphenyl ether/styrene alloy as follows.
The distilled water that will contain the 250mL of 10 gram sodium hydroxide is added in the reactor, and the temperature of reactor is controlled at 60 ℃.Continuously stirring is dissolved sodium hydroxide fully.With 2 of 52.6g, 6-dimethyl-4-bromophenol joins in this aqueous solution then, is stirred to dissolving fully, the while aerating oxygen, and keeping the oxygen pressure in the reactor is 1atm.Add 6.58g potassium ferricyanate and 5.44g dodecyl glyceryl ester again, question response added 5.85g vinylbenzene after 1 hour, with airtight behind the air in the nitrogen venting aforesaid reaction vessel, stir speed (S.S.) was increased to 1200rpm.React after 40 hours, temperature of reaction is elevated to 150 ℃, continue reaction and stop after 3 hours stirring.The polymkeric substance that filtration obtains is also dry through washing, and the limiting viscosity of polyphenylene oxide and polystyrene in the polymer alloy that obtains thus (η]) be respectively 6.5 and 24.
Embodiment 18～22
The basic embodiment 17 described operations that repeat, different is the temperature difference of Raolical polymerizable, gained the results are shown in Table 3.
Table 3
| Embodiment | The Raolical polymerizable temperature (℃) | The limiting viscosity of polymkeric substance | |
| Polyphenylene oxide ([η]) | Polystyrene (η]) | ||
| 18 19 20 21 22 | 110 130 160 180 200 | 6.7 6.6 6.1 6.2 6.0 | 27 25 21 22 20 |
Claims (10)
1. the interior polymerization of reactor prepares the method for polyphenylene oxide/styrenic polymer alloy, it is characterized in that this method may further comprise the steps: at styrene monomer, catalyzer, tensio-active agent, basic cpd exists down, the oxybenzene compound of use formula (1) representative and oxygenant carry out oxidative polymerization under 1～80 ℃ in full water medium, the weight ratio of styrene monomer and oxybenzene compound is 1: 9～9: 1, the weight ratio of oxybenzene compound and styrene monomer total amount and reaction medium is 1: 1～1: 90, the molar ratio of catalyzer and oxybenzene compound is 0.01～0.5, the molar ratio of tensio-active agent and oxybenzene compound is 0.001～0.1, oxidative polymerization 0.5～30 hour
Formula (1)
R in the formula
1And R
2Representative has alkyl or the replacement or the unsubstituted phenyl of 1～4 carbon atom, R
3Represent hydrogen or halogen atom, after treating that oxidative polymerization finishes, add initiator and under 100～200 ℃, make styrene monomer generation Raolical polymerizable 0.5～20 hour down or by thermal initiation in 60～110 ℃, the amount of initiator is between 0.01～2wt% of styrene monomer consumption, above-mentioned oxidative polymerization and Raolical polymerizable carry out under agitation condition, after reaction finishes, centrifuging or by shearing centrifuging again after the cohesion, drying gets polyphenylene oxide/styrenic polymer alloy.
2. polymerization prepares the method for polyphenylene oxide/styrenic polymer alloy in the reactor according to claim 1, it is characterized in that said catalyzer is a potassium ferricyanate, or the copper-amine complex of copper compound and amine compound complexing, the molar ratio of nitrogen-atoms and copper compound is at least 2 in the aminated compounds, or the complex compound of manganic compound and amine compound or α-Qiang Jiwo, the molar ratio of nitrogen-atoms and manganic compound is at least 2 in the aminated compounds.
3. polymerization prepares the method for polyphenylene oxide/styrenic polymer alloy in the reactor according to claim 2, it is characterized in that copper compound selects cuprous chloride, cuprous bromide, cuprous sulfate, cuprous nitrate, cupric chloride, cupric bromide, copper sulfate or cupric nitrate for use, with the amine compound of copper compound complexing be N-substituting group imidazoles, N, N, N ', N '-four substituting group-1,2-two amido ethane, N, N, N ', N '-four substituting group-1,3-two amido propane and N, N, N ', N '-four substituting group-1, one or more mixtures in 3-two amidos-1-substituting group propane.
4. polymerization prepares the method for polyphenylene oxide/styrenic polymer alloy in the reactor according to claim 2, it is characterized in that manganic compound is selected from Manganous chloride tetrahydrate, Manganese dibromide, manganese iodide, manganous carbonate, manganese acetate, manganous nitrate, manganous sulfate or manganous phosphate, with the amine compound of manganic compound complexing be 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, the diamines yl diphenyl ether, 3,3 '-tolidine and 3, in 3 '-dimethoxy benzidine one or more, have following formula structure, wherein R with the α-Qiang Jiwo of manganic compound complexing
a, R
b, R
c, R
dBe hydrogen or ring-type or straight-chain paraffin, n is the integer of 1-5.
5. polymerization prepares the method for polyphenylene oxide/styrenic polymer alloy in the reactor according to claim 1, it is characterized in that said styrene monomer is selected from vinylbenzene, 2, the 4-dichlorostyrene, to methoxy styrene, p-nitrophenyl ethene, p-methylstyrene, 3, the 4-dimethyl styrene, between t-butyl styrene, to dodecyl vinylbenzene, to styryl phenyl, to acetoxy-styrene, Vinylstyrene, p-aminophenyl ethene, to (chloromethyl) vinylbenzene, between cyano-styrene, o-hydroxy ethene, to vinyl benzoic acid, alpha-methyl styrene, α-propylstyrene, α-undecyl vinylbenzene, adjacent methyl-alpha-methyl styrene, between methyl-alpha-methyl styrene, to methyl-alpha-methyl styrene, to methoxyl group-alpha-methyl styrene, to cyano group-alpha-methyl styrene, between the bromo-alpha-methyl styrene, to chloro-alpha-methyl styrene or a chloro-alpha-methyl styrene or their mixture.
6. polymerization prepares the method for polyphenylene oxide/styrenic polymer alloy in the reactor according to claim 1, it is characterized in that said tensio-active agent comprises aniorfic surfactant and nonionic surface active agent.
7. polymerization prepares the method for polyphenylene oxide/styrenic polymer alloy in the reactor according to claim 6, it is characterized in that aniorfic surfactant comprises carboxylate surface active agent, alkyl sulfate surfactant, alkyl sulfonate surfactants and alkyl benzene sulfonate surfactant, said nonionic surface active agent comprises fatty alcohol-polyoxyethylene ether, polyoxyethylene alkylphenol ether and polyvalent alcohol alkyl esters tensio-active agent.
8. polymerization prepares the method for polyphenylene oxide/styrenic polymer alloy in the reactor according to claim 1, it is characterized in that said initiator comprises azo class, peroxide initiator.
9. polymerization prepares the method for polyphenylene oxide/styrenic polymer alloy in the reactor according to claim 1, it is characterized in that said full water medium is deionized water or distilled water.
10. polymerization prepares the method for polyphenylene oxide/styrenic polymer alloy in the reactor according to claim 1, it is characterized in that said oxygenant is oxygen, air or oxygen and the rare gas element gas with various mixed.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104508005B (en) * | 2012-08-29 | 2017-03-08 | 松下知识产权经营株式会社 | Noryl, its manufacture method, polyphenyl ether resin composition, resin varnish, prepreg, metal-clad laminate and printed wiring board |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3257358A (en) * | 1963-07-02 | 1966-06-21 | Du Pont | 2, 6-dichloro-1, 4-polyphenylene ether |
| US3383435A (en) * | 1965-01-06 | 1968-05-14 | Gen Eiectric Company | Blend of a polyphenylene ether and a styrene resin |
| US4684695A (en) * | 1983-09-29 | 1987-08-04 | Takeda Chemical Industries, Ltd. | Flame-retardant, unsaturated polyester resin and composition therefor |
-
2005
- 2005-07-15 CN CNB2005100507445A patent/CN1314758C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3257358A (en) * | 1963-07-02 | 1966-06-21 | Du Pont | 2, 6-dichloro-1, 4-polyphenylene ether |
| US3383435A (en) * | 1965-01-06 | 1968-05-14 | Gen Eiectric Company | Blend of a polyphenylene ether and a styrene resin |
| US4684695A (en) * | 1983-09-29 | 1987-08-04 | Takeda Chemical Industries, Ltd. | Flame-retardant, unsaturated polyester resin and composition therefor |
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| Publication number | Publication date |
|---|---|
| CN1718634A (en) | 2006-01-11 |
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