Low molecular weight asymmetric thermosetting polyphenylene ether resin polymer and its preparation, purification and use

Abstract

The present invention provides a low molecular weight asymmetric thermosetting polyphenylene ether resin polymer and its preparation, purification and use, which relate to the technical field of resin materials. The low molecular weight asymmetric thermosetting polyphenylene ether resin polymer provided by the present invention has excellent dielectric properties, good film-forming properties, high cost performance and excellent overall performance. The present invention completely reacts bifunctional polyphenylene ether oligomer in two steps, fully converts thermoplastic to thermosetting, has good film-forming properties and reduces costs.

Description

[Technical field]

[0001] The present invention relates to the technical field of resin materials, in particular to low molecular weight asymmetric thermosetting polyphenylene ether resin polymers and their preparation, purification and use. [Background technology]

[0002] In recent years, with the rapid development of the information industry, the increasing frequency of signal transmission, and the increasing speed of information processing, the demand for dielectric properties and heat resistance of electronic circuit boards is increasing. Polyphenylene ether resin has excellent physical and mechanical properties, heat resistance, and electrical insulation, and has low moisture absorption, high strength, excellent dimensional stability, and the best creep resistance at high temperatures among all thermoplastic engineering plastics, so it is currently widely used in electronic circuit boards.

[0003] Patent Document 1 discloses a thermosetting polyphenylene ether resin polymer having excellent dielectric properties and heat resistance, which is prepared with a pentafunctional or more than pentafunctional vinylbenzyl ether modified thermosetting polyphenylene ether resin and a vinyl resin crosslinker. However, the solution requires improving the proportion of vinylbenzyl halide used to obtain a lower dielectric constant and lower dielectric loss. The prepared substrate has a lower dielectric constant and lower dielectric loss, but the vinylbenzyl halide cannot react completely with the polyphenylene ether resin, the film forming property is rather low, and the cost is very high, which cannot meet the needs of customers. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] China Patent Publication No. 106609032 Summary of the Invention [Problem to be solved by the invention]

[0005] The object of the present invention is to provide a low molecular weight asymmetric thermosetting polyphenylene ether resin polymer, and a preparation method, purification method and use thereof. The low molecular weight asymmetric thermosetting polyphenylene ether resin polymer provided by the present invention has excellent dielectric properties, good film-forming properties, high cost performance and excellent overall performance. [Means for solving the problem]

[0006] In order to solve the above technical problems, the technical solutions adopted in the present invention are as follows:

[0007] The present invention provides low molecular weight asymmetric thermoset polyphenylene ether resin polymers having the structure shown in Formula 1:

[0008] [ka]

[0009] [ka]

[0010] R 1 , R 2 , R 7 and R 8 are independently a halogen atom, an alkyl group having 1 to 6 carbon atoms, or an aryl group; R 3 , R 4 , R 5 and R 6 are independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, or an aryl group; A is a single bond, or a linear alkylene group, a branched alkylene group, or a cyclic alkylene group having 1 to 6 carbon atoms; n and m are independently an integer of 1 to 30.

[0011] Preferably, the n is an integer of 1 to 20, and the m is an integer of 1 to 20.

[0012] [ka]

[0013] The present invention provides a method for preparing the low molecular weight asymmetric thermosetting polyphenylene ether resin polymer described in the above technical solution, comprising: A step of mixing a bifunctional polyphenylene ether oligomer, a polar aprotic solvent, an alkali metal alkoxide and a vinylbenzyl halide to carry out an etherification reaction to obtain an etherification reaction system; mixing the etherification reaction system with an acid binder and a methacryloyl halide to carry out an esterification reaction to obtain an esterification reaction system; and adjusting the pH value of the esterification reaction system to 6.0 to 8.0, and adding water or a water-alcohol mixed solution to cause precipitation, thereby obtaining a low molecular weight asymmetric thermosetting polyphenylene ether resin polymer; The difunctional polyphenylene ether oligomer has a structure shown in Formula 2.

[0014] [ka]

[0015] Preferably, the polar aprotic solvent comprises one or more of toluene, N,N-dimethylformamide, N,N-dimethylacetamide and 1-methyl-2-pyrrolidone.

[0016] Preferably, the alkali metal alkoxide comprises one or more of lithium methoxide, sodium methoxide, potassium methoxide, lithium ethoxide, sodium ethoxide and potassium ethoxide.

[0017] Preferably, the vinylbenzyl halide comprises one or more of m-vinylbenzyl chloride, p-vinylbenzyl chloride, m-vinylbenzyl bromide and p-vinylbenzyl bromide.

[0018] Preferably, the molar ratio of the alkali metal alkoxide to the phenolic hydroxyl group in the bifunctional polyphenylene ether oligomer is 0.9-4.8:1, and the molar ratio of the vinylbenzyl halide to the phenolic hydroxyl group in the bifunctional polyphenylene ether oligomer is 0.5-2.0:1.

[0019] Preferably, the temperature of the etherification reaction is 0 to 90° C., and the time of the etherification reaction is 10 minutes to 30 hours.

[0020] Preferably, the acid binding agent comprises one or more of triethylamine, pyridine, N,N-diisopropylethylamine, 4-dimethylaminopyridine, triethanolamine, tetrabutylammonium bromide, potassium carbonate, ammonium carbonate and sodium carbonate.

[0021] Preferably, the methacryloyl halide is one or two of methacryloyl chloride and methacryloyl bromide.

[0022] Preferably, the molar ratio of the acid binder to the bifunctional polyphenylene ether oligomer is 1-2:1; The molar ratio of the methacryloyl halide to the phenolic hydroxyl group in the difunctional polyphenylene ether oligomer is 0.5 to 2:1.

[0023] Preferably, the temperature of the esterification reaction is 0 to 90° C., and the time of the esterification reaction is 10 minutes to 30 hours.

[0024] The present invention provides a method for improving the purity of a low molecular weight asymmetric thermoset polyphenylene ether resin polymer, comprising the steps of: The present invention provides a method for producing a low molecular weight asymmetric thermosetting polyphenylene ether resin polymer, comprising the steps of: mixing a crude product of the low molecular weight asymmetric thermosetting polyphenylene ether resin polymer prepared by the preparation method described in the above technical solution with a polar aprotic solvent, a polymerization inhibitor and diethylamine to obtain a mixed solution; adding the mixed solution to water to perform precipitation to obtain a first solid; mixing the first solid with water and grinding to obtain a first dispersion; performing solid-liquid separation of the first dispersion to obtain a second solid; mixing the second solid with water and slurrying to obtain a second dispersion; mixing the second dispersion with acetic acid, performing a neutralization reaction, and performing solid-liquid separation to obtain a third solid; and successively slurrying the third solid in water and methanol to obtain a low molecular weight asymmetric thermosetting polyphenylene ether resin polymer.

[0025] Preferably, the polymerization inhibitor is tris(2,3-dibromopropyl)isocyanurate.

[0026] Preferably, the low molecular weight asymmetric thermosetting polyphenylene ether resin polymer has a chlorine content of less than 50 ppm, a VBC of 15 ppm or less, a NaCl content of 25 ppm or less, (C 2 H 5 ) 3 N HCl is 5 ppm or less.

[0027] The present invention provides the use of the low molecular weight asymmetric thermosetting polyphenylene ether resin polymer described in the above technical solution, or the low molecular weight asymmetric thermosetting polyphenylene ether resin polymer prepared by the preparation method described in the above technical solution, or the low molecular weight asymmetric thermosetting polyphenylene ether resin polymer prepared by the method for improving the purity of the low molecular weight asymmetric thermosetting polyphenylene ether resin polymer described in the above technical solution, in an electronic circuit board.

[0028] The present invention provides a low molecular weight asymmetric thermosetting polyphenylene ether resin polymer, in which in the polymer structure described in the present invention, the methacryl group has very low activity and is difficult to react completely, while the styrene group has high activity and is complementary to the methacryl group, and reacts quickly, so that the polymer has good film-forming property, good crosslinking effect, and significantly improved overall performance.

[0029] The low molecular weight asymmetric thermosetting polyphenylene ether resin polymer provided by the present invention has no strong polar group in its molecular structure, has good electrical insulation properties, and has stable electrical properties.Its dielectric constant and dielectric loss tangent are small among engineering plastics, and are hardly affected by temperature, humidity, etc., and its volume resistivity is also high among engineering plastics, so that its dielectric properties are excellent.

[0030] The molecular chain of the low molecular weight asymmetric thermosetting polyphenylene ether resin polymer contains an aromatic ring structure and a large amount of vinylbenzyl groups, and the methacrylate groups seal the active sites of the phenol groups, thereby increasing the rigidity of the molecules and the cohesive force between the molecules. The molecular chain sensitivity is strong, there is no polar hydrolyzable group, and the glass transition temperature is high, so that the heat resistance is good.

[0031] The low molecular weight asymmetric thermosetting polyphenylene ether resin polymer provided by the present invention has excellent dielectric properties, good film-forming properties, high cost performance, and excellent overall performance.

[0032] The present invention further provides a method for preparing the low molecular weight asymmetric thermosetting polyphenylene ether resin polymer, in which bifunctional polyphenylene ether oligomer is completely reacted in two steps to fully convert thermoplastic to thermosetting, with good film-forming properties and reduced costs. The prepared low molecular weight asymmetric thermosetting polyphenylene ether resin polymer has excellent dielectric properties and heat resistance, excellent comprehensive performance, and high cost performance. [Brief description of the drawings]

[0033] [Figure 1]FIG. 1H-NMR diagram of the low molecular weight asymmetric thermosetting polyphenylene ether resin polymer in Example 1. [Diagram 2] FIG. 2 is a GPC diagram of the low molecular weight asymmetric thermosetting polyphenylene ether resin polymer in Example 1. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0034] The present invention will now be described with reference to examples and drawings.

[0035] The present invention provides low molecular weight asymmetric thermoset polyphenylene ether resin polymers having the structure shown in Formula 1:

[0036] [ka]

[0037] [ka]

[0038] R 1 , R 2 , R 7 and R 8 are independently a halogen atom, an alkyl group having 1 to 6 carbon atoms, or an aryl group; R 3 , R 4 , R 5 and R 6 are independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, or an aryl group; A is a single bond, or a linear alkylene group, a branched alkylene group, or a cyclic alkylene group having 1 to 6 carbon atoms; n and m are independently an integer of 1 to 30.

[0039] In the present invention, the n is preferably an integer of 1 to 20, and the m is preferably an integer of 1 to 20.

[0040] In the present invention, the alkyl group having 1 to 6 carbon atoms is preferably a substituted alkyl group, and the aryl group is preferably a substituted aryl group. In the present invention, A is preferably a linear alkylene group, a branched alkylene group, or a cyclic alkylene group having 1 to 3 carbon atoms.

[0041] In the present invention, the R 1 , R 2 , R 7 and R 8 are independently chlorine, a methyl group, or a benzyl group, and R 3 , R 4 , R 5 and R 6 are independently a hydrogen atom, chlorine, a methyl group or a benzyl group. In the present invention, the linear alkylene group is preferably a methylene group, the branched alkylene group is preferably an isopropylidene group, and the cyclic alkylene group is preferably a cyclohexylisopropylidene group.

[0042] In a specific embodiment of the present invention, R 1 is a methyl group, and R 2 is a methyl group, and R 3 is a hydrogen atom or a halogen atom, and R 4 is a hydrogen atom or a halogen atom, and R 5 is a hydrogen atom or a halogen atom, and R 6 is a hydrogen atom or a halogen atom, and R 7 is a methyl group, and R 8 is a methyl group and A is an isopropylidene group.

[0043] [ka]

[0044] The present invention provides a method for preparing the low molecular weight asymmetric thermosetting polyphenylene ether resin polymer described in the above technical solution, comprising: A step of mixing a bifunctional polyphenylene ether oligomer, a polar aprotic solvent, an alkali metal alkoxide and a vinylbenzyl halide to carry out an etherification reaction to obtain an etherification reaction system; mixing the etherification reaction system with an acid binder and a methacryloyl halide to carry out an esterification reaction to obtain an esterification reaction system; adjusting the pH value of the esterification reaction system to 6.0-7.0, and adding water or a water-alcohol mixed solution to cause precipitation, thereby obtaining a low molecular weight asymmetric thermosetting polyphenylene ether resin polymer.

[0045] In the present invention, a bifunctional polyphenylene ether oligomer, a polar aprotic solvent, an alkali metal alkoxide, and a vinylbenzyl halide are mixed together to carry out an etherification reaction, thereby obtaining an etherification reaction system. In the present invention, the bifunctional polyphenylene ether oligomer has a structure represented by formula 2.

[0046] [ka]

[0047] In the present invention, the method for preparing the bifunctional polyphenylene ether oligomer preferably comprises mixing 2,6-dimethylphenol, HO-X-OH, methanol, toluene and a copper-amine catalyst, and carrying out an oxidative polymerization reaction in oxygen to obtain a bifunctional polyphenylene ether oligomer. In the present invention, the copper-amine catalyst preferably comprises cuprous chloride, di-n-butylamine and tetramethylpropanediamine.

[0048] In the present invention, mixing the 2,6-dimethylphenol, HO-X-OH, methanol, toluene and copper-amine catalyst preferably includes mixing a part of methanol, a part of toluene, cuprous chloride, a part of di-n-butylamine and a part of tetramethylpropanediamine to obtain a first mixed solution, mixing the remaining methanol, the remaining toluene, 2,6-dimethylphenol, HO-X-OH, the remaining di-n-butylamine and the remaining tetramethylpropanediamine to obtain a second mixed solution, and dropping the second mixed solution into the first mixed solution. In the present invention, the mass ratio of the part of methanol, the part of toluene, the cuprous chloride, the part of di-n-butylamine and the part of tetramethylpropanediamine is preferably 500-5000:500-5000:10-150:1-3:10-200, more preferably 1000:1000:30:1:25. In the present invention, the ratio of the remaining methanol, the remaining toluene, the 2,6-dimethylphenol, the HO-X-OH, the remaining di-n-butylamine and the remaining tetramethylpropanediamine to be used is preferably 500-5000g:500-5000g:1-15mol:1-3mol:1-5g:5-120g, more preferably 2000g:2000g:5.6mol:1.2mol:1g:30g. In the present invention, the mass ratio of the second mixed solution to the first mixed solution is preferably 1-6:1, more preferably 2:1. In the present invention, the temperature of the mixing is preferably 10-50°C, more preferably 30°C. In the present invention, the time for dropping the second mixed solution into the first mixed solution is preferably within 3 hours.

[0049] In the present invention, the flow rate of the oxygen introduced is preferably 1 to 5 L / min, and more preferably 1.5 L / min. In the present invention, it is preferable that after the second mixed solution is dropped into the first mixed solution, oxygen is then introduced for 2 hours.

[0050] In the present invention, the temperature of the oxidative polymerization reaction is preferably 20 to 80° C., more preferably 40° C., and the time of the oxidative polymerization reaction is preferably 1 to 8 hours, more preferably 3 hours.

[0051] The present invention preferably further includes, after the oxidative polymerization reaction, adding glacial acetic acid to terminate the reaction, adding water to wash the reaction solution, separating the aqueous phase from the organic phase, washing the obtained organic phase with water and concentrating to obtain a toluene solution of a difunctional phenylene ether oligomer, and pouring the toluene solution of the difunctional phenylene ether oligomer into methanol to precipitate particulate matter, followed by solid-liquid separation to obtain a difunctional polyphenylene ether oligomer having a structure represented by formula 2. In the present invention, the mass ratio of the glacial acetic acid, 2,6-dimethylphenol, HO-X-OH, methanol, toluene and copper / amine catalyst is preferably 1:2 to 24:3 to 56:15 to 200:15 to 200:0.5 to 8, more preferably 1:12:28:100:100:2.

[0052] In the present invention, the bifunctional polyphenylene ether oligomer has a number average molecular weight of 1200 g / mol and a weight average molecular weight of 2200 g / mol.

[0053] In a specific embodiment of the present invention, the chemical reaction formula of the bifunctional polyphenylene ether oligomer is:

[0054] [ka]

[0055] wherein X is the same as X in formula 1.

[0056] In the present invention, the polar aprotic solvent preferably includes one or more of toluene, N,N-dimethylformamide, N,N-dimethylacetamide, and 1-methyl-2-pyrrolidone. In a specific embodiment of the present invention, when the polar aprotic solvent is toluene and N,N-dimethylformamide, the mass ratio of the toluene to N,N-dimethylformamide is 1:1. In the present invention, the mass ratio of the polar aprotic solvent to the bifunctional polyphenylene ether oligomer is preferably 1 to 20:1, more preferably 2:1.

[0057] In the present invention, the alkali metal alkoxide preferably contains one or more of lithium methoxide, sodium methoxide, potassium methoxide, lithium ethoxide, sodium ethoxide, and potassium ethoxide. In the present invention, the molar ratio of the alkali metal alkoxide to the phenolic hydroxyl group in the bifunctional polyphenylene ether oligomer is preferably 0.9 to 4.8:1, more preferably 1.0 to 2.4:1. In the present invention, the alkali metal alkoxide is reacted with the bifunctional polyphenylene ether oligomer to form an ether, and when the alkali metal alkoxide is used in at least an equimolar amount, a bifunctional polyphenylene ether oligomer having an extremely low content of remaining unreacted substances that become ionic impurities can be produced.

[0058] In the present invention, the vinylbenzyl halide preferably includes one or more of m-vinylbenzyl chloride, p-vinylbenzyl chloride, m-vinylbenzyl bromide and p-vinylbenzyl bromide. In the present invention, the molar ratio of the vinylbenzyl halide to the phenolic hydroxyl group in the bifunctional polyphenylene ether oligomer is preferably 0.5 to 2.0:1, more preferably 1.0 to 2.0:1. In the present invention, if the amount of the vinylbenzyl halide is small, the amount of remaining unreacted phenolic hydroxyl group increases, so that the dielectric properties of the cured product are deteriorated, and if the amount of the vinylbenzyl halide is large, the amount of unreacted bifunctional polyphenylene ether oligomer increases without changing the reaction, so that the dielectric properties of the cured product are deteriorated, resulting in economical disadvantages.

[0059] In the present invention, mixing the bifunctional polyphenylene ether oligomer, the polar aprotic solvent, the alkali metal alkoxide and the vinylbenzyl halide preferably includes dissolving the bifunctional polyphenylene ether oligomer in the polar aprotic solvent, adding the alkali metal alkoxide, removing alcohol by heating and stirring, and then adding the vinylbenzyl halide. In the present invention, the dissolution temperature of the bifunctional polyphenylene ether oligomer in the polar aprotic solvent is preferably 40 to 80°C, the temperature of the heating and stirring is preferably 50 to 60°C, and the time of the heating and stirring is preferably 1 hour.

[0060] In the present invention, the temperature of the etherification reaction is preferably 0 to 90°C, more preferably 30 to 60°C, and the time of the etherification reaction is preferably 10 min to 30 h, more preferably 3 to 6 h. In the present invention, the etherification reaction preferably includes a low-temperature reaction and a high-temperature reaction carried out in sequence, the temperature of the low-temperature reaction is preferably 0 to 10°C, the time of the low-temperature reaction is preferably 1 to 6 h, more preferably 3 h, the temperature of the high-temperature reaction is preferably 50 to 60°C, and the time of the high-temperature reaction is preferably 1 to 6 h, more preferably 3 h.

[0061] In the present invention, after the etherification reaction, the obtained system is preferably cooled to 30 to 40° C. to obtain an etherification reaction system. In the present invention, one end of the main product of the etherification reaction is a hydroxysodium salt, and the other end is blocked with styryl.

[0062] In the present invention, after obtaining an etherification reaction system, the etherification reaction system is mixed with an acid binder and a methacryloyl halide to carry out an esterification reaction, thereby obtaining an esterification reaction system. In the present invention, the acid binder preferably contains one or more of triethylamine, pyridine, N,N-diisopropylethylamine, 4-dimethylaminopyridine, triethanolamine, tetrabutylammonium bromide, potassium carbonate, ammonium carbonate, and sodium carbonate. In the present invention, the molar ratio of the acid binder to the bifunctional polyphenylene ether oligomer is preferably 1 to 2:11, and more preferably 1.3:1.

[0063] In the present invention, the methacryloyl halide is preferably one or two of methacryloyl chloride and methacryloyl bromide. In the present invention, the molar ratio of the methacryloyl halide to the phenolic hydroxyl group in the bifunctional polyphenylene ether oligomer is preferably 0.5 to 2:1, more preferably 1.0 to 2.0:1. In the present invention, if the amount of the methacryloyl halide added is small, the amount of unreacted phenolic hydroxyl group remaining increases, so that the dielectric properties of the cured product deteriorates, and if the amount of the methacryloyl halide added is too large, the amount of unreacted bifunctional polyphenylene ether oligomer increases without changing the reaction, so that the dielectric properties of the cured product deteriorate, resulting in economical disadvantages.

[0064] In the present invention, mixing the etherification reaction system with an acid binder and a methacryloyl halide preferably comprises sequentially adding the acid binder and the methacryloyl halide to the etherification reaction system.

[0065] In the present invention, the temperature of the esterification reaction is preferably 0 to 90°C, more preferably 30 to 60°C, and the time of the esterification reaction is preferably 10 min to 30 h, more preferably 3 to 6 h. In the present invention, the esterification reaction preferably includes a low-temperature reaction and a high-temperature reaction carried out in sequence, the temperature of the low-temperature reaction is preferably 0 to 10°C, the time of the low-temperature reaction is preferably 1 to 6 h, more preferably 3 h, the temperature of the high-temperature reaction is preferably 50 to 60°C, and the time of the high-temperature reaction is preferably 1 to 6 h, more preferably 3 h.

[0066] In the present invention, after obtaining an esterification reaction system, the pH value of the esterification reaction system is adjusted to 6.0 to 8.0, and water or a water-alcohol mixed solution is added to cause precipitation, thereby obtaining a low molecular weight asymmetric thermosetting polyphenylene ether resin polymer. In the present invention, it is preferable to adjust the pH of the esterification reaction system to 6.0 to 8.0, more preferably 6.0 to 7.0, using an acidic substance. In the present invention, the acidic substance preferably contains one or more of phosphoric acid, sulfuric acid, hydrochloric acid, benzenesulfonic acid, and benzoic acid, and more preferably contains hydrochloric acid.

[0067] In the present invention, the alcohol in the water-alcohol mixed solution preferably contains one or more of methanol, ethanol, n-propanol, and isopropanol, and more preferably contains methanol or ethanol. In the present invention, the content of alcohol in the water-alcohol mixed solution is preferably 40 to 95 wt%, more preferably 50 to 90 wt%. In the present invention, if the alcohol content is less than 40 wt%, the obtained polyphenylene ether resin polymer becomes emulsified and difficult to handle. If the alcohol content exceeds 95 wt%, the water content is low, and the by-product salt generated by the reaction contained in the reaction solution cannot be sufficiently dissolved and removed.

[0068] In the present invention, the esterification reaction system is directly added to water or a water-alcohol mixed solution to precipitate a solid, without going through a step of washing the organic layer with pure water or the like. In general, when an organic solution in which an oligomer is dissolved is washed with water, it becomes emulsified after denaturation, and it is difficult to separate the aqueous layer from the organic layer, so the liquid-separation washing step takes a very long time. Furthermore, even if liquid-separation washing is performed using water, it is very difficult to completely remove the by-product salt generated in the reaction. The production method of the present invention can omit such a complicated liquid-separation washing step, and the by-product salt generated in the reaction can be dissolved and removed by coagulation using water or a water-alcohol mixed solution.

[0069] In the present invention, after the precipitation, the obtained precipitate is preferably washed with water and an alcohol solution in that order and dried to obtain a low molecular weight asymmetric thermosetting polyphenylene ether resin polymer. In the present invention, the water washing is preferably deionized water washing, the alcohol solution used in the alcohol washing is preferably methanol, and the method of the alcohol washing is preferably immersion. In the present invention, the drying temperature is preferably 80°C. In the present invention, by washing with water and alcohol, by-product salts generated in the reaction can be dissolved and removed.

[0070] In the present invention, after the water washing, the alcohol solution washing and the drying, a crude product of the low molecular weight asymmetric thermosetting polyphenylene ether resin polymer is obtained, and the crude product of the low molecular weight asymmetric thermosetting polyphenylene ether resin polymer is preferably purified. In the present invention, the halogen content and salt content of the product are further reduced by the purification, and the dielectric loss Df is further reduced.

[0071] The purification process will now be described in detail.

[0072] The present invention provides a method for improving the purity of a low molecular weight asymmetric thermoset polyphenylene ether resin polymer, comprising the steps of: The method includes the steps of mixing the crude product of the low molecular weight asymmetric thermosetting polyphenylene ether resin polymer prepared by the preparation method described in the above technical solution with a polar aprotic solvent, a polymerization inhibitor and diethylamine to obtain a mixed solution, adding the mixed solution to water to perform precipitation and obtain a first solid, mixing the first solid with water and grinding to obtain a first dispersion, performing solid-liquid separation of the first dispersion to obtain a second solid, mixing the second solid with water and slurrying to obtain a second dispersion, mixing the second dispersion with acetic acid to perform neutralization reaction and perform solid-liquid separation to obtain a third solid, and successively slurrying the third solid in water and methanol to obtain a low molecular weight asymmetric thermosetting polyphenylene ether resin polymer. In the present invention, the water is preferably distilled water.

[0073] In the present invention, it is preferable to mix the crude product of the low molecular weight asymmetric thermosetting polyphenylene ether resin polymer obtained by precipitation with a polar aprotic solvent, a polymerization inhibitor and diethylamine to obtain a mixed solution. In the present invention, it is preferable that the polar aprotic solvent contains N,N-dimethylformamide (DMF), dimethylacetamide, dimethylsulfoxide or 1-methyl-2-pyrrolidone. In the present invention, the mass ratio of the crude product of the low molecular weight asymmetric thermosetting polyphenylene ether resin polymer to the polar aprotic solvent is preferably 1:2 to 20, more preferably 1:2.5. In the present invention, the polymerization inhibitor is preferably tris(2,3-dibromopropyl)isocyanurate (TBC). In the present invention, the mass ratio of the crude product of the low molecular weight asymmetric thermosetting polyphenylene ether resin polymer to the polymerization inhibitor is preferably 1000 to 10000:0.1, more preferably 1000:0.4. In the present invention, the mass ratio of the crude product of the low molecular weight asymmetric thermosetting polyphenylene ether resin polymer to diethylamine is preferably 1000:10 to 500, more preferably 1000:65. In the present invention, the function of diethylamine is to react with the unreacted raw material p-chloromethylstyrene to generate hydrochloride, and the hydrochloride is easily soluble in water, thereby achieving the function of removing halogen.

[0074] In the present invention, mixing the crude product of the low molecular weight asymmetric thermosetting polyphenylene ether resin polymer, the polar aprotic solvent, the polymerization inhibitor and diethylamine preferably includes mixing the crude product of the low molecular weight asymmetric thermosetting polyphenylene ether resin polymer with the polar aprotic solvent, adding the polymerization inhibitor, dissolving by heating, and then adding diethylamine and stirring. In the present invention, the temperature of the heat dissolution is preferably 0 to 80°C, more preferably 35°C. In the present invention, the stirring speed is preferably 100 to 300 r / min, and the stirring time is preferably 2 h.

[0075] In the present invention, it is preferable to obtain a first solid by adding the mixed solution to water and carrying out precipitation after obtaining the mixed solution. In the present invention, the mass ratio of the crude product of the low molecular weight asymmetric thermosetting polyphenylene ether resin polymer to water is preferably 1:5 to 100, more preferably 1:18. In the present invention, it is preferable to obtain a first solid by carrying out suction filtration after the precipitation.

[0076] In the present invention, after obtaining the first solid, it is preferable to mix the first solid with water and pulverize to obtain a first dispersion. In the present invention, the mass ratio of the water to the crude product of the low molecular weight asymmetric thermosetting polyphenylene ether resin polymer is preferably 5 to 100:1, more preferably 18:1. In the present invention, the pulverization is preferably performed with a mixer, and the pulverization time is preferably 10 to 200 s. In the present invention, it is preferable to obtain a first dispersion by stirring for 30 s after the pulverization. In the present invention, the rotation speed of the stirring is preferably 100 to 300 r / min, and the stirring time is preferably 1 h. In the present invention, the salt in the solid is removed by pulverization.

[0077] In the present invention, after obtaining the first dispersion, it is preferable to perform solid-liquid separation of the first dispersion to obtain the second solid matter. In the present invention, the method of the solid-liquid separation is preferably suction filtration.

[0078] In the present invention, after obtaining the second solid, it is preferable to mix the second solid with water and form a slurry to obtain a second dispersion. In the present invention, the mass ratio of the water to the crude product of the low molecular weight asymmetric thermosetting polyphenylene ether resin polymer is preferably 5 to 100:1, more preferably 18:1. In the present invention, the process parameters of the slurrying are preferably 20 to 30°C and 100 to 300 r / min, and the time of the slurrying is preferably 1 h.

[0079] In the present invention, after obtaining the second dispersion, it is preferable to mix the second dispersion with acetic acid, carry out a neutralization reaction, and perform solid-liquid separation to obtain a third solid. In the present invention, there is no special requirement for the amount of acetic acid used, and it is preferable that the pH value of the system obtained after the neutralization reaction is less than 6, and more preferably the pH value is 5.5 to 6. In the present invention, the method of the solid-liquid separation is preferably suction filtration. In the present invention, acetic acid is used to neutralize the remaining diethylamine into a salt.

[0080] In the present invention, after obtaining the third solid, the third solid is preferably slurried in water and methanol in sequence to obtain a low molecular weight asymmetric thermosetting polyphenylene ether resin polymer. In the present invention, the mass ratio of the water to the crude product of the low molecular weight asymmetric thermosetting polyphenylene ether resin polymer is preferably 5 to 100:1, more preferably 18:1, and the mass ratio of the methanol to the crude product of the low molecular weight asymmetric thermosetting polyphenylene ether resin polymer is preferably 2 to 20:1, more preferably 4:1. In the present invention, the process parameters for slurrying the third solid in water are preferably 20 to 30°C, 100 to 300 r / min, and the time is 1 h, and the number of times of slurrying in methanol is preferably two times, and the process parameters for each time are preferably 20 to 30°C, 100 to 300 r / min, and the time for each time is preferably 1 h. In the present invention, it is preferable to perform solid-liquid separation after slurrying in water, and further slurry the obtained solid in methanol. In the present invention, it is preferable to add a polymerization inhibitor during the final slurrying with methanol. In the present invention, the polymerization inhibitor is preferably TBC. In the present invention, the mass ratio of the crude product of the low molecular weight asymmetric thermosetting polyphenylene ether resin polymer to the polymerization inhibitor is preferably 1000 to 10000: 0.1, more preferably 1000: 0.4. In the present invention, the mass ratio of the crude product of the low molecular weight asymmetric thermosetting polyphenylene ether resin polymer to the polymerization inhibitor is preferably 1000 to 10000: 0.1, more preferably 1000: 0.14. In the present invention, it is preferable to obtain a low molecular weight asymmetric thermosetting polyphenylene ether resin polymer by performing solid-liquid separation after the completion of the slurrying and drying the obtained solid. In the present invention, the method of the solid-liquid separation is preferably suction filtration. In the present invention, the temperature of the drying is preferably 20 to 60°C, and the time of the drying is preferably 8 to 48 hours. In the present invention, organic salts are easily dissolved in water and alcohol, and the present invention is useful for removing salts in solids by slurrying them with water and methanol.

[0081] In the present invention, the low molecular weight asymmetric thermosetting polyphenylene ether resin polymer has a chlorine content of preferably less than 50 ppm, a VBC (4-chloromethylstyrene, 3-chloromethylstyrene and 2-chloromethylstyrene) content of preferably 15 ppm or less, a NaCl (sodium chloride) content of preferably 25 ppm or less, and (C 2 H 5 ) 3 N·HCl (triethylamine hydrochloride) is preferably 5 ppm or less, and Df is preferably 0.003.

[0082] The present invention can efficiently produce a low molecular weight asymmetric thermosetting polyphenylene ether resin polymer with an extremely low content of ionic impurities and an extremely low content of residual alkali metal ions. The present invention makes the manufacturing method of the present invention more economical because the bifunctional polyphenylene ether oligomer is completely reacted in two steps and does not include a very complicated liquid washing-separation step. In addition, the cured product obtained by thermally curing the low molecular weight asymmetric thermosetting polyphenylene ether resin polymer has remarkably excellent dielectric properties and film-forming properties, and can be used as a matrix in the field of electrical and electronic materials.

[0083] The present invention also provides the use of the low molecular weight asymmetric thermosetting polyphenylene ether resin polymer described in the above technical solution, or the low molecular weight asymmetric thermosetting polyphenylene ether resin polymer prepared by the preparation method described in the above technical solution, or the low molecular weight asymmetric thermosetting polyphenylene ether resin polymer prepared by the method for improving the purity of the low molecular weight asymmetric thermosetting polyphenylene ether resin polymer described in the above technical solution, in an electronic circuit board.

[0084] The low molecular weight asymmetric thermosetting polyphenylene ether resin polymer provided by the present invention and its preparation method, purification method and use will be described in detail below with reference to examples, but they should not be understood as limiting the protection scope of the present invention.

[0085] Example 1

[0086] (1) 2000 g of methanol, 2000 g of toluene, 60 g of cuprous chloride, 2 g of di-n-butylamine and 50 g of tetramethylpropanediamine were added to a 20 L reaction flask equipped with a stirrer, a thermometer, a dropping funnel, a condenser and an oxygen inlet tube, and the components were stirred at 30°C. A mixed solution was obtained by pre-dissolving 686 g of 2,6-dimethylphenol, 288 g of 3,3',5,5'-tetramethyl-(1,1'-biphenyl)-4,4'-diol, 1 g of di-n-butylamine and 30 g of tetramethylpropanediamine in 2000 g of methanol and 2000 g of toluene, and the mixture in the reactor was added under conditions of 30°C. The mixture was added dropwise within 1 hour, and oxygen was simultaneously introduced and bubbled. After the completion of the addition, oxygen was continued to be bubbled for 2 hours. 100g of glacial acetic acid was added to terminate the reaction. 6000g of water was added to wash the reaction liquid. The aqueous phase and the organic layer were separated. The organic layer was washed with water and concentrated in an evaporator to obtain 2000g of a toluene solution of a bifunctional phenylene ether oligomer. The solution was slowly poured into 6000g of methanol to precipitate particulate matter. The solution was stirred for 0.5 hours, suction filtered, and the filter cake was dried to obtain 840g of a bifunctional polyphenylene ether oligomer (PPO) having a structure represented by Formula 2. The number average molecular weight of the PPO was 1200 and the weight average molecular weight was 2200.

[0087] The chemical reaction scheme for preparing the difunctional polyphenylene ether oligomer is as follows:

[0088] [ka]

[0089] (2) 800 g of the PPO, 800 g of toluene, and 800 g of N,N-dimethylformamide were added to a 5 L reaction flask equipped with a stirrer, a thermometer, and a condenser, and after complete dissolution at 40°C, 42 g of sodium methoxide was added in batches, the mixture was stirred at 50 to 60°C for 1 hour, the methanol was removed under reduced pressure (removed to 60°C using a mechanical pump), cooled, and 120 g of mixed grade vinylbenzyl chloride (o-vinylbenzyl chloride 76 wt%, p-vinylbenzyl chloride 17 wt%, m-vinylbenzyl chloride 5 wt%) was added dropwise at 40°C. After completion of the dropwise addition, the mixture was kept warm at 40°C for 3 hours, and then cooled to 60°C. After keeping at 30°C for 3 hours, the reaction solution was cooled to 30°C, 87g of triethylamine was added, and 83g of methacryloyl chloride was dropped at 30°C. After the dropwise addition, the reaction solution was kept at 30°C for 3 hours, and then kept at 60°C for 3 hours. After the reaction was completed, the reaction solution was dropped into a mixture of 4000g of methanol, 200g of hydrochloric acid and 500g of water (while stirring), and a solid was precipitated. The mixture was stirred for 0.5 hours, filtered by suction, and the filter cake was washed several times with 10L of deionized water. Finally, the mixture was immersed in methanol for 0.5 hours, filtered by suction, and dried at 80°C to obtain 865g of a crude product of a low molecular weight asymmetric thermosetting polyphenylene ether resin polymer. The dielectric properties of the obtained crude product of the low molecular weight asymmetric thermosetting polyphenylene ether resin polymer are shown in Table 1.

[0090] The chemical reaction formula is as follows:

[0091] [ka]

[0092] (3) 1 kg of the crude product of the low molecular weight asymmetric thermosetting polyphenylene ether resin polymer obtained by combining multiple batches prepared in step (2) is added to 2500 g of DMF, 0.4 g of TBC is added, and after dissolving at 35 ° C, 65 g of diethylamine is added, stirred for 2 hours, slowly poured into 18 kg of distilled water to precipitate, suction filtered, the filter cake is added to 18 kg of distilled water and crushed in a "mixer", stirred for 1 hour, suction filtered, the filter cake is added to 18 kg of distilled water to make a slurry for 1 hour, and then the mixture is subjected to CH3 Add 30 g of COOH to adjust the pH to less than 6 (specifically, CH 3 The mixture was filtered with suction, the filter cake was added to 18 kg of distilled water to form a slurry for 1 hour, filtered with suction, the filter cake was added to 4 kg of methanol to form a slurry twice for 1 hour each time, and 0.14 g of TBC was added to the final slurry with methanol, suction filtered, and dried to obtain 970 g of a low molecular weight asymmetric thermosetting polyphenylene ether resin polymer having the structure represented by Formula 1.

[0093] The low molecular weight asymmetric thermosetting polyphenylene ether resin polymer prepared in this example had a yield of 97 wt %, a chlorine content of 45 ppm, a salt content of 30 ppm, and a Df of 0.0028.

[0094] Example 2

[0095] (1) PPO was prepared according to the method in step (1) of Example 1.

[0096] (2) 800 g of the PPO, 800 g of toluene, and 800 g of N,N-dimethylformamide were added to a 5 L reaction flask equipped with a stirrer, a thermometer, and a condenser, and after complete dissolution at 40°C, 56 g of sodium ethoxide was added in batches, and the mixture was stirred at 50-60°C for 1 hour, and ethanol was removed under reduced pressure (removed to 60°C using a mechanical pump), cooled, and 120 g of mixed grade vinylbenzyl chloride (o-vinylbenzyl chloride 76 wt%, p-vinylbenzyl chloride 17 wt%, m-vinylbenzyl chloride 5 wt%) was added dropwise at 40°C. After completion of the dropwise addition, the mixture was kept at 40°C for 3 hours, and then kept at 60°C for 3 hours. After keeping the mixture, the reaction solution was dissolved in ethanol. Cool to 30 ° C, add 87g of triethylamine, control at 30 ° C, drop 83g of methacryloyl chloride, after completion of drop, keep at 30 ° C for 3h, keep at 60 ° C for 3h, after completion of reaction, drop the reaction liquid into a mixture of 4000g of methanol, 200g of hydrochloric acid and 500g of water (with stirring), precipitate a solid, continue stirring for 0.5h, filter with suction, wash the filter cake with 10L of deionized water several times, finally immerse in methanol for 0.5h, filter with suction, dry at 80 ° C, obtain 875g of crude product of low molecular weight asymmetric thermosetting polyphenylene ether resin polymer. The dielectric properties of the obtained crude product of low molecular weight asymmetric thermosetting polyphenylene ether resin polymer are shown in Table 1.

[0097] The chemical reaction formula is as follows:

[0098] [ka]

[0099] (3) 1 kg of the crude product of the low molecular weight asymmetric thermosetting polyphenylene ether resin polymer obtained by combining multiple batches prepared in step (2) is added to 2500 g of DMF, 0.4 g of TBC is added, and after dissolving at 35 ° C, 65 g of diethylamine is added, stirred for 2 hours, slowly poured into 18 kg of distilled water to precipitate, suction filtered, the filter cake is added to 18 kg of distilled water and crushed in a "mixer", stirred for 1 hour, suction filtered, the filter cake is added to 18 kg of distilled water to make a slurry for 1 hour, and then slurried in CH3 Add 30 g of COOH to adjust the pH to less than 6 (specifically, CH 3 The mixture was filtered with suction, the filter cake was added to 18 kg of distilled water to form a slurry for 1 hour, filtered with suction, the filter cake was added to 4 kg of methanol to form a slurry twice for 1 hour each time, and 0.14 g of TBC was added to the final slurry with methanol, suction filtered, and dried to obtain 972 g of a low molecular weight asymmetric thermosetting polyphenylene ether resin polymer having the structure represented by Formula 1.

[0100] The low molecular weight asymmetric thermosetting polyphenylene ether resin polymer prepared in this example had a yield of 97.2%, a chlorine content of 43 ppm, a salt content of 27 ppm, and a Df of 0.0030.

[0101] Example 3

[0102] (1) PPO was prepared according to the method in step (1) of Example 1.

[0103] (2) 800 g of the PPO and 1,600 g of N,N-dimethylformamide were added to a 5 L reaction flask equipped with a stirrer, a thermometer, and a condenser, and the mixture was completely dissolved at 80°C and then cooled. 56 g of sodium ethoxide was added in batches at 40°C, the mixture was stirred at 50-60°C for 1 hour, the ethanol was removed under reduced pressure (removed to 60°C using a mechanical pump), the mixture was cooled, and 120 g of mixed grade vinylbenzyl chloride (o-vinylbenzyl chloride 76 wt%, p-vinylbenzyl chloride 17 wt%, m-vinylbenzyl chloride 5 wt%) was added dropwise at 40°C. After the addition was completed, the mixture was kept at 40°C for 3 hours, and then kept at 60°C for 3 hours. After keeping the mixture, the reaction solution was cooled. Cool to 30 ° C, add 87g of triethylamine, control at 30 ° C, drop 83g of methacryloyl chloride, after completion of drop, keep at 30 ° C for 3h, keep at 60 ° C for 3h, after completion of reaction, drop the reaction liquid into a mixture of 4000g of methanol, 200g of hydrochloric acid and 500g of water (while stirring), precipitate a solid, continue stirring for 0.5h, filter with suction, wash the filter cake with 10L of deionized water several times, finally immerse in methanol for 0.5h, filter with suction, dry at 80 ° C, obtain 870g of crude product of low molecular weight asymmetric thermosetting polyphenylene ether resin polymer. The dielectric properties of the obtained crude product of low molecular weight asymmetric thermosetting polyphenylene ether resin polymer are shown in Table 1.

[0104] The chemical reaction formula is as follows:

[0105] [ka]

[0106] (3) 1 kg of the crude product of the low molecular weight asymmetric thermosetting polyphenylene ether resin polymer obtained by combining multiple batches prepared in step (2) is added to 2500 g of DMF, 0.4 g of TBC is added, stirred for 2 hours, slowly poured into 18 kg of distilled water to precipitate, suction filtered, the filter cake is added to 18 kg of distilled water and crushed in a "mixer", stirred for 1 hour, suction filtered, the filter cake is added to 18 kg of distilled water and stirred for 1 hour, and then added to CH 3Add 30 g of COOH to adjust the pH to less than 6 (specifically, CH 3 The mixture was filtered with suction, the filter cake was added to 18 kg of distilled water to form a slurry for 1 hour, filtered with suction, the filter cake was added to 4 kg of methanol to form a slurry twice for 1 hour each time, and 0.14 g of TBC was added to the final slurry with methanol, suction filtered, and dried to obtain 980 g of a low molecular weight asymmetric thermosetting polyphenylene ether resin polymer having the structure represented by Formula 1.

[0107] The low molecular weight asymmetric thermosetting polyphenylene ether resin polymer prepared in this example had a yield of 98%, a chlorine content of 39 ppm, a salt content of 25 ppm, and a Df of 0.0025.

[0108] Comparative Example 1

[0109] (1) PPO was prepared according to the method in step (1) of Example 1.

[0110] (2) 800g of the PPO, 1600g of toluene and 5g of N,N-dimethylformamide were added to a 5L reaction flask equipped with a stirrer, a thermometer and a condenser, and the mixture was cooled after being completely dissolved at 80°C. 176g of triethylamine was added at 30°C. The temperature was controlled to 30°C and 166g of methacryloyl chloride was added dropwise. After the dropwise addition was completed over 2h, the mixture was kept at 30°C for 3h and then kept at 60°C for 3h. After the reaction was completed, the reaction solution was slowly poured into 4000g of methanol and 100g of hydrochloric acid (while stirring), a solid was precipitated, the mixture was stirred for 0.5h, filtered by suction, the filter cake was washed several times with 10L of deionized water, and finally immersed in methanol for 0.5h, filtered by suction, and dried at 80°C to obtain 840g of a polyphenylene ether resin composition. The dielectric properties of the obtained polyphenylene ether resin composition are shown in Table 1.

[0111] The chemical reaction formula is as follows:

[0112] [ka]

[0113] The low molecular weight thermosetting polyphenylene ether resin polymer prepared in this comparative example had a yield of 105 wt %, a chlorine content of 44 ppm, a salt content of 44 ppm, and a Df of 0.0041.

[0114] Comparative Example 2

[0115] (1) PPO was prepared according to the method in step (1) of Example 1.

[0116] (2) Add 800 g of the PPO and 1,600 g of toluene to a 5 L reaction flask equipped with a stirrer, a thermometer, and a condenser, and completely dissolve at 80°C. Then, cool the mixture. Then, add 112 g of sodium ethoxide in batches at 40°C. Stir at 50-60°C for 1 h. Remove ethanol under reduced pressure (remove to 60°C with a mechanical pump). Cool the mixture. Drop 240 g of mixed grade vinylbenzyl chloride (o-vinylbenzyl chloride 76 wt%, p-vinylbenzyl chloride 17 wt%, m-vinylbenzyl chloride 5 wt%) at 40°C. After the dropwise addition, the mixture was kept at 40°C for 3 hours, then at 60°C for 3 hours, and cooled to 30°C. The reaction solution was dropped into a mixture of 4000g of methanol, 200g of hydrochloric acid and 500g of water (while stirring), and a solid was precipitated. The mixture was stirred for 0.5 hours, filtered by suction, and the filter cake was washed several times with 10L of deionized water. Finally, the mixture was immersed in methanol for 0.5 hours, filtered by suction, and dried at 80°C to obtain 880g of a crude product of low molecular weight thermosetting polyphenylene ether resin polymer. The dielectric properties of the obtained crude product of low molecular weight thermosetting polyphenylene ether resin polymer are shown in Table 1.

[0117] The chemical reaction formula is as follows:

[0118] [ka]

[0119] (3) 1 kg of the crude product of the low molecular weight thermosetting polyphenylene ether resin polymer obtained by combining multiple batches prepared in step (2) is added to 2500 g of DMF, 0.4 g of TBC is added, and after dissolving at 35 ° C, 65 g of diethylamine is added, stirred for 2 hours, slowly poured into 18 kg of distilled water to precipitate, suction filtered, the filter cake is added to 18 kg of distilled water and crushed in a "mixer", stirred for 1 hour, suction filtered, the filter cake is added to 18 kg of distilled water to make a slurry for 1 hour, and then the mixture is subjected to CH 3 30g of COOH was added, the pH was adjusted to less than 6, suction filtered, the filter cake was added to 18kg of distilled water to be slurried for 1 hour, suction filtered, the filter cake was added to 4kg of methanol to be slurried twice for 1 hour each time, 0.14g of TBC was added to the final slurry with methanol, suction filtered, and dried to obtain 990g of a low molecular weight thermosetting polyphenylene ether resin polymer.

[0120] The low molecular weight thermosetting polyphenylene ether resin polymer prepared in this comparative example had a yield of 99%, a chlorine content of 47 ppm, a salt content of 37 ppm, and a Df of 0.0039.

[0121] Test Example

[0122] (1) The number average molecular weight and weight average molecular weight were measured by gel permeation chromatography (GPC) (shown in Figure 2). Data processing was performed based on the GPC curve and molecular weight calibration curve of the sample. The molecular weight calibration curve was obtained by using the following equation to obtain an approximation of the relationship between the molecular weight of standard polystyrene and its dissolution time. LogM=A 0 X 3 +A 1 X 2 +A 2 X+A 3 +A 4 / X 2 Here, M represents the molecular weight, X represents the elution time, which is 19 minutes, and A 0 ~A 4 represents the coefficient.

[0123] (2) FIG. 1 shows the low molecular weight asymmetric thermosetting polyphenylene ether resin polymer in Example 1. 1 H-NMR diagram. 1 From the peaks of vinylbenzyl ether and methacryl ether in the H-NMR analysis, it was confirmed that a low molecular weight asymmetric thermosetting polyphenylene ether resin polymer was prepared according to the present invention.

[0124] (3) For pH measurements, a METTLER TLED electrode, Inpro4250SG / 225 / Pt1000, was used.

[0125] (4) The dielectric constant and dielectric tangent of the cured material were determined by the cavity resonance perturbation method.

[0126] [Table 1]

[0127] From Table 1, it was found that the difference in number average molecular weight (Mn) and weight average molecular weight (Mw) between the low molecular weight asymmetric thermosetting resin polymers prepared in Examples 1, 2, and 3 and the low molecular weight thermosetting resin polymers prepared in Comparative Examples 1 and 2 was small, and all had good solubility in toluene and methyl ethyl ketone. However, since Examples 1 to 3 use two types of terminal blocking groups, vinylbenzyl chloride and methacryl, respectively, at both ends, the dielectric constant and dielectric loss tangent of such asymmetric low molecular weight polyphenylene ether resins are all superior to Comparative Examples 1 and 2, and although the superior range is not particularly clear, the test data after the next film formation cannot be compared with Comparative Examples 1 and 2. The performance of each item is leading, and the overall performance is particularly excellent.

[0128] The above description of the embodiments is merely for understanding the method of the present invention and its core idea. However, those skilled in the art may make some improvements and modifications to the present invention without departing from the principles of the present invention, and these improvements and modifications are also included in the scope of the claims of the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the general principles defined herein may be implemented in other embodiments without departing from the spirit or scope of the present invention. Thus, the present invention is not limited to these embodiments shown in the present specification, but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

Claims

1. Formula 1 below: 【Chemistry 1】 【Chemistry 2】 R １ , R ２ , R ７ and R ８ are independently a halogen atom, an alkyl group having 1 to 6 carbon atoms, or an aryl group; R ３ , R ４ , R ５ and R ６ are independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, or an aryl group; A is a single bond, or a linear alkylene group, branched alkylene group, or cyclic alkylene group having 1 to 6 carbon atoms; n and m are independently an integer from 1 to 30. having a structure represented by A low molecular weight asymmetric thermosetting polyphenylene ether resin polymer.

2. The n is 1 to 20, and the m is 1 to 20. The low molecular weight asymmetric thermoset polyphenylene ether resin polymer of claim 1 .

3. The X is 【Chemistry 3】 is The low molecular weight asymmetric thermoset polyphenylene ether resin polymer of claim 1 .

4. A method for preparing the low molecular weight asymmetric thermosetting polyphenylene ether resin polymer of claims 1 to 3, comprising the steps of: mixing a bifunctional polyphenylene ether oligomer, a polar aprotic solvent, an alkali metal alkoxide and a vinylbenzyl halide to carry out an etherification reaction to obtain an etherification reaction system; mixing the etherification reaction system with an acid binder and a methacryloyl halide to carry out an esterification reaction to obtain an esterification reaction system; adjusting the pH value of the esterification reaction system to 6.0-8.0, and adding water or a water-alcohol mixed solution to cause precipitation, thereby obtaining a low molecular weight asymmetric thermosetting polyphenylene ether resin polymer; The difunctional polyphenylene ether oligomer has the following Formula 2: 【Chemistry 4】 having a structure represented by A method comprising:

5. The polar aprotic solvent includes one or more of toluene, N,N-dimethylformamide, N,N-dimethylacetamide, and 1-methyl-2-pyrrolidone.

5. The method of claim 4.

6. The alkali metal alkoxide includes one or more of lithium methoxide, sodium methoxide, potassium methoxide, lithium ethoxide, sodium ethoxide, and potassium ethoxide.

5. The method of claim 4.

7. The vinylbenzyl halide includes one or more of m-vinylbenzyl chloride, p-vinylbenzyl chloride, m-vinylbenzyl bromide, and p-vinylbenzyl bromide.

5. The method of claim 4.

8. The molar ratio of the alkali metal alkoxide to the phenolic hydroxyl group in the bifunctional polyphenylene ether oligomer is 0.9 to 4.8:1, and the molar ratio of the vinylbenzyl halide to the phenolic hydroxyl group in the bifunctional polyphenylene ether oligomer is 0.5 to 2.0:

1.

5. The method of claim 4.

9. The temperature of the etherification reaction is 0 to 90° C., and the time of the etherification reaction is 10 min to 30 h.

9. The preparation method according to claim 4 or 8.

10. The acid binder includes one or more of triethylamine, pyridine, N,N-diisopropylethylamine, 4-dimethylaminopyridine, triethanolamine, tetrabutylammonium bromide, potassium carbonate, ammonium carbonate, and sodium carbonate.

5. The method of claim 4.

11. The methacryloyl halide is one or more of methacryloyl chloride and methacryloyl bromide.

5. The method of claim 4.

12. the molar ratio of the acid binder to the difunctional polyphenylene ether oligomer is 1-2:1; The molar ratio of the methacryloyl halide to the phenolic hydroxyl group in the bifunctional polyphenylene ether oligomer is 0.5 to 2:

1.

5. The method of claim 4.

13. The temperature of the esterification reaction is 0 to 90° C., and the time of the esterification reaction is 10 min to 30 h.

13. The preparation method according to claim 4 or 12.

14. 1. A method for improving the purity of a low molecular weight asymmetric thermoset polyphenylene ether resin polymer, comprising: The method includes the steps of: mixing a crude product of a low molecular weight asymmetric thermosetting polyphenylene ether resin polymer prepared by the preparation method according to any one of claims 4 to 13 with a polar aprotic solvent, a polymerization inhibitor, and diethylamine to obtain a mixed solution; adding the mixed solution to water and performing precipitation to obtain a first solid; mixing the first solid with water and pulverizing to obtain a first dispersion; performing solid-liquid separation of the first dispersion to obtain a second solid; mixing the second solid with water and slurrying to obtain a second dispersion; mixing the second dispersion with acetic acid, performing a neutralization reaction, and performing solid-liquid separation to obtain a third solid; and successively slurrying the third solid in water and methanol to obtain a low molecular weight asymmetric thermosetting polyphenylene ether resin polymer.

2. A method for improving the purity of a low molecular weight asymmetric thermosetting polyphenylene ether resin polymer, comprising:

15. The polymerization inhibitor is tris(2,3-dibromopropyl)isocyanurate.

15. The method of claim 14.

16. The low molecular weight asymmetric thermosetting polyphenylene ether resin polymer has a chlorine content of less than 50 ppm, a VBC of 15 ppm or less, a NaCl content of 25 ppm or less, (C ２ H ５ ) ３ N・HCl is 5 ppm or less 15. The method of claim 14.

17. Use of the low molecular weight asymmetric thermosetting polyphenylene ether resin polymer according to any one of claims 1 to 3, or the low molecular weight asymmetric thermosetting polyphenylene ether resin polymer prepared by the preparation method according to any one of claims 4 to 13, or the low molecular weight asymmetric thermosetting polyphenylene ether resin polymer prepared by the method according to any one of claims 14 to 16, in an electronic circuit board.

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