Vinyl-terminated polyphenylene ether and method for preparing and use thereof

Abstract

The present application relates to a kind of end vinyl polyphenyl ether and its preparation method and application, the preparation method includes the following steps: (1) aromatic phenolic monomer is prepared under the catalysis of copper-based catalyst system, using precipitation method to prepare end hydroxyl polyphenyl ether;(2) end hydroxyl polyphenyl ether solution and vinyl end-capping agent solution are reacted in the tubular reactor under the catalysis of iodine-based catalyst system, obtain the end vinyl polyphenyl ether;The copper-based catalyst system includes copper-based catalyst, ligand and adjuvant, and the ligand is amine polymer compound.The end vinyl polyphenyl ether prepared by the preparation method provided by the present application has the characteristics of controllable molecular weight, narrow molecular weight distribution, continuous production, low content of colored impurities and high whiteness.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of high polymer materials, and in particular to a terminal vinyl polyphenyl ether, a preparation method and application thereof. BACKGROUND

[0002] In the field of electronic circuit boards, polyphenyl ether is suitable for future high-frequency and high-speed communication technical requirements due to its low dielectric constant and dielectric loss factor, and can be applied to electronic circuit board substrate materials, signal receiver housings, structural parts of electronic signal transmitters or receivers, etc.

[0003] Due to the limitations of its own structure, polyphenyl ether has defects such as large melt viscosity of the product and difficulty in compatibility with most other resins, so it needs to be functionally modified. Functional modified polyphenyl ether can react with many resins due to its high active functionality, increasing the compatibility of mixed resins and the crosslinking density of the material after curing, which is beneficial to improve the electrical properties, thermal mechanical properties, etc. of the product material.

[0004] Low molecular weight polyphenyl ether with active divinylbenzene structure in the terminal group is an important high-frequency and high-speed copper-clad plate substrate resin developed in recent years. Since the molecular structure does not contain polar groups, it has relatively low dielectric constant, dielectric loss and water absorption after being crosslinked and cured during use. The synthesis and preparation process of this type of resin is complex and difficult to purify, and currently only a few foreign enterprises such as SABIC, Mitsubishi Gas, Asahi Kasei, etc. produce it in large quantities.

[0005] Currently, low molecular weight polyphenyl ether with active divinylbenzene structure in the terminal group is mainly prepared by functionalizing the terminal hydroxyl group of low molecular weight polyphenyl ether to introduce crosslinkable active double bonds. When modifying polyphenyl ether, the generated impurities will affect the color of the polyphenyl ether product to some extent, making the product yellow and black, and the process yield is low and the product quality is poor. The reasons for the deepening of the color of the product during the modification of polyphenyl ether are mainly two, one is polymerization: high temperature easily initiates polymerization, and further the formation of chromophores due to the conjugation and crosslinking structure of the molecular chain of the polymer, resulting in yellow or brown color; the other is oxidation reaction: the double bond (C=C) in the raw material is oxidized at high temperature, thereby generating impurities such as peroxide and quinone compounds and showing color.

[0006] Therefore, it is necessary to develop a preparation method of terminal vinyl polyphenyl ether with low content of colored impurities, high whiteness of the product, and suitable for being used for high-frequency electronic circuit board substrate materials. SUMMARY

[0007] To solve the above technical problems, the application provides an end-vinyl polyphenyl ether and a preparation method and application thereof. The end-vinyl polyphenyl ether prepared by the preparation method has the characteristics of controllable molecular weight, narrow molecular weight distribution, continuous production, low content of colored impurities and high whiteness.

[0008] To achieve the above purpose, the application adopts the following technical solutions.

[0009] In the first aspect, the application provides a preparation method of an end-vinyl polyphenyl ether, which comprises the following steps: (1) preparing an end-hydroxyl polyphenyl ether by using a precipitation method under the catalysis of a copper-based catalyst system; and (2) reacting an end-hydroxyl polyphenyl ether solution and a vinyl end-capping agent solution in a tubular reactor under the catalysis of an iodine-based catalyst system to obtain the end-vinyl polyphenyl ether. The copper-based catalyst system comprises a copper-based catalyst, a ligand and an auxiliary agent, and the ligand is an amine-based polymer compound.

[0010] The precipitation method is a polyphenyl ether preparation process using a poor solvent as a reaction solvent. The generated polyphenyl ether has low solubility in the poor solvent and is gradually precipitated. The poor solvent can dissolve the aromatic phenolic monomer but cannot dissolve the end-hydroxyl polyphenyl ether. The product is directly precipitated during the reaction, which can be quickly separated by filtration or centrifugation. The solvent has low boiling point and low recovery cost. In the application, the end-hydroxyl polyphenyl ether with low molecular weight is continuously prepared by the precipitation method, and then the end-hydroxyl polyphenyl ether is capped by using an alkenyl compound as the vinyl end-capping agent to obtain the end-vinyl polyphenyl ether. In the preparation method, the amine-based polymer compound is used as the ligand of the catalyst in the preparation of the end-hydroxyl polyphenyl ether, so that the catalyst can be used for a long time. The poor solvent is used to precipitate the end-hydroxyl polyphenyl ether by the precipitation method, and the solvent and the catalyst can be recycled, which can realize continuous production and is suitable for industrial production.

[0011] In the application, the end-hydroxyl polyphenyl ether solution and the vinyl end-capping agent solution are reacted in the tubular reactor under the catalysis of the iodine-based catalyst system to prepare the end-vinyl polyphenyl ether. The use of the tubular reactor controls the residence time of the materials, which can avoid long-time overheating of the product. The addition of the iodine-based catalyst system helps to accelerate the substitution reaction. The preparation method is simple, and the end-vinyl polyphenyl ether prepared by the preparation method has the characteristics of controllable molecular weight, narrow molecular weight distribution, continuous production, low content of colored impurities and high whiteness, and is suitable for being used as a high-frequency electronic circuit board substrate material.

[0012] Preferably, the aromatic phenolic monomer comprises a phenolic monomer and an aromatic diphenol monomer.

[0013] Preferably, the phenolic monomer comprises 2,6-dimethylphenol and / or 2,3,6-trimethylphenol.

[0014] Preferably, the aromatic diol monomer comprises any one of tetramethyl bisphenol F, tetramethyl bisphenol A, or 2,2',3,3',5,5'-hexamethyl-4,4'-dihydroxybiphenyl, or a combination of at least two thereof.

[0015] Preferably, the molar ratio of the phenolic monomer and the aromatic diol monomer is (13-29): 1, such as 15:1, 17:1, 19:1, 21:1, 23:1, 25:1, or 27:1, etc.

[0016] Preferably, the solvent employed in the precipitation method comprises a poor solvent.

[0017] Preferably, the poor solvent comprises any one of methanol, ethanol, isopropanol, or tert-butanol, or a combination of at least two thereof, further preferably methanol.

[0018] Preferably, the solvent employed in the precipitation method further comprises a good solvent.

[0019] Preferably, the good solvent comprises any one of benzene, toluene, ethylbenzene, xylene, chloroform, dichloroethane, trichloroethane, or chlorobenzene, or a combination of at least two thereof, further preferably toluene.

[0020] Preferably, the mass of the good solvent is 0-15%, such as 2%, 4%, 6%, 8%, 10%, 12%, or 14%, etc., based on 100% of the total mass of the solvent employed in the precipitation method.

[0021] Preferably, the mass ratio of the solvent employed in the precipitation method and the aromatic phenolic monomer is (2-5): 1, such as 2.5:1, 3:1, 3.5:1, 4:1, or 4.5:1, etc., further preferably (2.5-3.5): 1.

[0022] Preferably, the number average molecular weight of the hydroxyl-terminated polyphenylene ether is 1000-3500 g / mol, such as 1400 g / mol, 1800 g / mol, 2200 g / mol, 2600 g / mol, 3000 g / mol, or 3400 g / mol, etc.

[0023] Preferably, the molecular weight distribution of the hydroxyl-terminated polyphenylene ether is ≤2.2, such as 1.7, 1.8, 1.9, 2.0, or 2.1, etc.

[0024] Preferably, the average hydroxyl functionality of the hydroxyl-terminated polyphenylene ether is ≥1.75 mgKOH / g, such as 1.76 mgKOH / g, 1.77 mgKOH / g, 1.78 mgKOH / g, 1.79 mgKOH / g, or 1.8 mgKOH / g, etc.

[0025] Preferably, the copper-based catalyst comprises a cuprous compound and / or a copper compound.

[0026] Preferably, the cuprous compound comprises any one or a combination of at least two of cuprous chloride, cuprous bromide, cuprous nitrate or cuprous sulfate.

[0027] Preferably, the copper compound comprises any one or a combination of at least two of copper chloride, copper bromide, copper nitrate or copper sulfate.

[0028] In the present application, the copper-based catalyst can be a copper salt obtained by reacting copper oxide and / or cuprous oxide with a hydrogen halide acid.

[0029] Preferably, the molar ratio of the copper-based catalyst to the aromatic diphenol monomer is (0.004-0.015):1, such as 0.006:1, 0.008:1, 0.01:1, 0.012:1 or 0.014:1, and further preferably (0.007-0.009):1.

[0030] Preferably, the amine-based polymer compound comprises a polyether amine.

[0031] Preferably, the molar ratio of the ligand to the copper-based catalyst is (0.5-5):1, such as 1:1, 1.5:1, 2:1, 2.5:1, 3:1, 3.5:1, 4:1 or 4.5:1, and further preferably (1-2):1.

[0032] Preferably, the auxiliary agent comprises an azodicarboxylate.

[0033] In the present application, the auxiliary agent is preferably an azodicarboxylate, which is a rich-electric structure. After participating in the coordination structure of the copper-based catalyst and the ligand, it forms a hydrazine radical stabilized by copper coordination, thereby increasing the overall activity of the copper-based catalyst system.

[0034] Preferably, the azodicarboxylate comprises any one or a combination of at least two of diethyl azodicarboxylate (DEAD), diisopropyl azodicarboxylate (DIAD) or tert-butyl azodicarboxylate (DBAD), and further preferably diisopropyl azodicarboxylate.

[0035] In the present application, the azodicarboxylate is preferably diisopropyl azodicarboxylate, which has the advantages of high activity and low price.

[0036] Preferably, the molar ratio of the auxiliary agent to the copper-based catalyst is (0.05-2):1, such as 0.1:1, 0.3:1, 0.5:1, 0.7:1, 0.9:1, 1.1:1, 1.3:1, 1.5:1, 1.7:1 or 1.9:1, and further preferably 0.5:1.

[0037] Preferably, the precipitation method is performed under conditions of passing a gas containing oxygen.

[0038] Preferably, the volume concentration of oxygen in the gas containing oxygen is 21% to 100%, such as 30%, 40%, 50%, 60%, 70%, or 80%, and the like, further preferably 90% to 100%.

[0039] Preferably, the molar ratio of oxygen to phenolic monomer is (0.6 to 3): 1, such as 0.9: 1, 1.2: 1, 1.5: 1, 1.8: 1, 2.1: 1, 2.4: 1, or 2.7: 1, and the like, further preferably (1 to 1.4): 1.

[0040] Preferably, the reaction temperature of the precipitation method is 30 to 70°C, such as 35°C, 40°C, 45°C, 50°C, 55°C, 60°C, or 65°C, and the like, further preferably 45 to 55°C.

[0041] Preferably, the reaction time of the precipitation method is 45 to 90 min, such as 50 min, 60 min, 65 min, 70 min, 75 min, 80 min, or 85 min, and the like, further preferably 40 to 50 min.

[0042] Preferably, the reaction of the precipitation method is performed under a pressure of 0.8 to 1.25 bar (such as 0.85 bar, 0.9 bar, 0.95 bar, 1 bar, 1.05 bar, 1.1 bar, 1.15 bar, or 1.2 bar, and the like), further preferably under 1 bar.

[0043] Preferably, the hydroxyl-terminated polyphenylene ether solution of step (2) comprises the hydroxyl-terminated polyphenylene ether prepared in step (1) and a good solvent.

[0044] Preferably, the mass concentration of the hydroxyl-terminated polyphenylene ether in the hydroxyl-terminated polyphenylene ether solution is 30% to 50%, such as 32%, 34%, 36%, 38%, 40%, 42%, 44%, 46%, or 48%, and the like.

[0045] Preferably, the vinyl end-capping agent solution comprises a vinyl end-capping agent, a base, and a good solvent.

[0046] Preferably, the vinyl end-capping agent comprises p-chloromethylstyrene.

[0047] Preferably, the base comprises any one or a combination of at least two of pyridine, diethylamine, or triethylamine, further preferably triethylamine.

[0048] Preferably, the molar ratio of the base to the vinyl capping agent is (0.8-1.5):1, such as 0.9:1, 1:1, 1.1:1, 1.2:1, 1.3:1, or 1.4:1, and the like, further preferably (0.9-1.1):1.

[0049] Preferably, the mass ratio of the good solvent in the vinyl capping agent solution to the total mass of the vinyl capping agent and the base is (0.8-1.2):1, such as 0.85:1, 0.9:1, 0.95:1, 1:1, 1.05:1, 1.1:1, or 1.15:1, and the like.

[0050] Preferably, the molar amount of the vinyl capping agent satisfies the following formula: M=(n x HV x m) / 56000, wherein M represents the molar amount of the vinyl capping agent, n is 0.95-1.1 (such as 0.97, 0.99, 1.01, 1.03, 1.05, 1.07, or 1.09, and the like), HV represents the hydroxyl value of the hydroxyl-terminated polyphenyl ether, and m represents the mass of the hydroxyl-terminated polyphenyl ether.

[0051] Preferably, the n is 0.95-1.

[0052] Preferably, the iodine-based catalyst system comprises an iodine salt and a cosolvent.

[0053] Preferably, the iodine salt comprises potassium iodide or sodium iodide, further preferably potassium iodide.

[0054] Preferably, the mass of the iodine salt is 0.5%-5% of the mass of the vinyl capping agent, such as 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, or 4.5%, and the like, further preferably 0.8%-1.2%.

[0055] Preferably, the cosolvent comprises dimethyl sulfoxide (DMSO) and / or dimethyl formamide (DMF), preferably dimethyl formamide.

[0056] Preferably, the mass ratio of the cosolvent to the iodine salt is (0.5-5):1, such as 1:1, 1.5:1, 2:1, 2.5:1, 3:1, 3.5:1, 4:1, or 4.5:1, and the like.

[0057] Preferably, the length-diameter ratio of the tubular reactor is ≥100, such as 150, 200, 250, 300, 350, 400, 450, 500, or 550, and the like, further preferably ≥400.

[0058] Preferably, the temperature of the reaction in the tubular reactor is 40-65°C, such as 43°C, 46°C, 49°C, 52°C, 55°C, 58°C, 61°C, or 64°C, and the like.

[0059] Preferably, the residence time of the material in the tubular reactor is 20-45 min, such as 23 min, 26 min, 29 min, 32 min, 35 min, 38 min, 41 min or 44 min, etc.

[0060] In the present application, a tubular reactor and high temperature are used for the end-capping reaction, the equivalent of the vinyl end-capping agent is low, the residence time of the reaction is short, the content of the colored impurities introduced by the polymerization of the vinyl end-capping agent is low, and the whiteness of the product is high, thus overcoming the problem of excessively long reaction time in the end-capping step in the conventional process due to the reduction of the reaction temperature to avoid the deterioration of chloromethyl styrene.

[0061] Preferably, the reaction of step (2) further comprises the steps of washing, precipitation and drying.

[0062] Preferably, the washing comprises washing with an aqueous hydrochloric acid solution and an aqueous ethylenediaminetetraacetic acid (EDTA) solution.

[0063] Preferably, the mass concentration of the aqueous hydrochloric acid solution is 0.5%-3%, such as 0.8%, 1.1%, 1.4%, 1.7%, 2%, 2.3%, 2.6% or 2.9%, etc., and further preferably 1%-2%.

[0064] Preferably, the mass concentration of the aqueous ethylenediaminetetraacetic acid solution is 1%-5%, such as 1.5%, 2%, 2.5%, 3%, 3.5%, 4% or 4.5%, etc., and further preferably 2%-3%.

[0065] Preferably, the mass of the aqueous hydrochloric acid solution is 20%-40% of the total mass of the hydroxy-terminated polyphenyl ether solution and the vinyl end-capping agent solution, such as 22%, 24%, 26%, 28%, 30%, 32%, 34%, 36% or 38%, etc.

[0066] Preferably, the mass of the aqueous ethylenediaminetetraacetic acid solution is 20%-40% of the total mass of the hydroxy-terminated polyphenyl ether solution and the vinyl end-capping agent solution, such as 22%, 24%, 26%, 28%, 30%, 32%, 34%, 36% or 38%, etc.

[0067] Preferably, the precipitation comprises precipitation in a poor solvent.

[0068] Preferably, the precipitation comprises the following steps: adding 1-1.5 times the mass of the poor solvent to preliminarily precipitate the vinyl-terminated polyphenyl ether, centrifuging, and washing the residual good solvent with 1-1.5 times the mass of the poor solvent and centrifuging.

[0069] Preferably, the drying comprises vacuum drying to a product volatile matter of less than 0.5 wt%, such as 0.05 wt%, 0.1 wt%, 0.2 wt%, 0.3 wt% or 0.4 wt% etc.

[0070] Preferably, the vacuum drying is at a pressure of 0.3-0.7 atm, such as 0.35 atm, 0.4 atm, 0.45 atm, 0.5 atm, 0.55 atm, 0.6 atm or 0.65 atm etc.

[0071] Preferably, the vacuum drying is at a temperature of 50-70℃, such as 53℃, 56℃, 59℃, 62℃, 65℃ or 68℃ etc.

[0072] In the present application, the post-reaction washing enables the combination of the two steps of removing copper-based catalyst and removing vinyl end-capping agent, thus simplifying the reaction steps.

[0073] Preferably, after the prepared hydroxyl-terminated polyphenyl ether is separated by the precipitation method, the aromatic phenolic monomer is added to the remaining system and the reaction is repeated.

[0074] In a second aspect, the present application provides a vinyl-terminated polyphenyl ether, which is prepared by the preparation method as described in the first aspect.

[0075] Preferably, the vinyl-terminated polyphenyl ether has an unsaturation of >1.5, such as 1.6, 1.7, 1.8, 1.9 or 2.0 etc.

[0076] Preferably, the vinyl-terminated polyphenyl ether has a number average molecular weight of 1500-3500 g / mol, such as 1700 g / mol, 1900 g / mol, 2100 g / mol, 2300 g / mol, 2500 g / mol, 2700 g / mol, 2900 g / mol, 3100 g / mol or 3300 g / mol etc.

[0077] Preferably, the vinyl-terminated polyphenyl ether has a molecular weight distribution of ≤2.25, such as 2.03, 2.06, 2.09, 2.12, 2.15, 2.18, 2.21 or 2.24 etc.

[0078] Preferably, the vinyl-terminated polyphenyl ether has a yellowness index of ≤10, such as 1, 2, 3, 4, 5, 6, 7, 8 or 9 etc., and further preferably 2-5.

[0079] In a third aspect, the present application provides the use of the vinyl-terminated polyphenyl ether as described in the second aspect in the preparation of high-frequency electronic circuit board substrates.

[0080] Compared with the prior art, the present application has at least the following beneficial effects:

[0081] The present application prepares the terminal vinyl polyphenyl ether by the reaction of the terminal hydroxyl polyphenyl ether solution and the vinyl end-capping agent solution in the catalysis of the iodine catalyst system in the tubular reactor, the preparation method has simple process and can be continuously produced, the prepared terminal vinyl polyphenyl ether has the characteristics of controllable molecular weight, low molecular weight distribution, low content of colored impurities and high whiteness, and is suitable for being used as the high-frequency electronic circuit board substrate material. BRIEF DESCRIPTION OF DRAWINGS

[0082] Figure 1 is the reaction flow schematic diagram of the preparation of the terminal vinyl polyphenyl ether in Example 1. DETAILED DESCRIPTION

[0083] The technical solutions of the present application are further illustrated by the specific embodiments in combination with the drawings. However, the following examples are only simple examples of the present application, and do not represent or limit the protection scope of the present application, and the protection scope of the present application is subject to the claims.

[0084] Some raw materials used in the following examples and comparative examples are as follows:

[0085] Polyether amine: polyether amine D230, amine value is 470 mg KOH / g, standard Q / 320116 BSNJ 013-2017.

[0086] Example 1

[0087] This example provides a terminal vinyl polyphenyl ether and a preparation method thereof, the reaction flow of the preparation method is as shown in Figure 1 The preparation method comprises the following steps:

[0088] (1) Into a beaker, 200 g of methanol, 12.7 g (0.008 eq, 0.128 mol, 99 da) of cuprous chloride, 44.2 g (0.012 eq, 0.192 mol, 230 da) of polyether amine and 12.9 g (0.004 eq, 0.064 mol, 202.2 da) of diisopropyl azodicarboxylate were added, stirred for 15 min to obtain a catalyst solution, and the catalyst solution was added to a 150 L polymerization kettle; then 90.0 kg of methanol, 4.55 kg (1 eq, 16 mol, 284.4 da) of tetramethyl bisphenol A, 25.4 kg (13 eq, 208 mol, 122 da) of 2,6-dimethyl phenol were added, stirred for 5 min to dissolve the materials, the external circulation heat exchanger of the polymerization kettle was started to control the temperature of the materials in the kettle to 45°C, the oxygen inlet was started, and oxygen was introduced into the polymerization kettle at a rate of 7.9 kg / h, the reaction was timed from the start of oxygen introduction, and the oxygen rate and the temperature in the kettle were kept stable during the polymerization reaction. After 45 min, the reaction was stopped, the oxygen gas path and the external circulation heating were closed, the materials in the kettle were pumped into a centrifugal separator for centrifugation, the reaction solution obtained by separation was recovered and returned to the polymerization kettle, and the solid filter cake obtained by centrifugal separation was dried to obtain a hydroxyl-terminated polyphenyl ether, which was denoted as hydroxyl-terminated polyphenyl ether A.

[0089] The hydroxyl-terminated polyphenyl ether A was sent into a dissolving kettle, toluene was added and heated to dissolve, and a hydroxyl-terminated polyphenyl ether solution with a mass concentration of 50% was obtained.

[0090] (2) 5.6 kg (1.77 eq, 36.8 mol, 152.6 da) of p-chloromethylstyrene, 3.7 kg (1.77 eq, 36.8 mol, 101.2 da) of triethylamine, toluene, potassium iodide and dimethylformamide were stirred and dissolved to obtain a vinyl end-capping agent solution, wherein the mass ratio of toluene to the total mass of p-chloromethylstyrene and triethylamine was 1:1, the mass of potassium iodide was 1% of the mass of p-chloromethylstyrene, and the mass ratio of potassium iodide to dimethylformamide was 1:1.

[0091] (3) using a metering pump to pass the hydroxyl-terminated polyphenyl ether solution prepared in step (1) and the vinyl-terminating agent solution prepared in step (2) into a tubular reactor (tube length 20 m, inner diameter 50 mm, length-diameter ratio 400) to react, wherein the rate of the hydroxyl-terminated polyphenyl ether solution is 1.12 kg / min, and the rate of the vinyl-terminating agent solution is 353.4 g / min (the ratio of the hydroxyl-terminated polyphenyl ether and the vinyl-terminating agent passed in per unit time satisfies: M = (n x HV x m) / 56000, wherein M represents the molar mass of the vinyl-terminating agent, n = 1, HV represents the hydroxyl value of the hydroxyl-terminated polyphenyl ether, and m represents the mass of the hydroxyl-terminated polyphenyl ether); the tubular reactor is set to a constant temperature of 50°C, and the residence time of the material in the tubular reactor is 25 min; after 53 min, the metering pump is turned off and the residual material in the tubular reactor is discharged, to obtain a product.

[0092] (4) placing the product prepared in step (3) into a washing kettle and cooling to 10°C, then adding 25 kg of hydrochloric acid aqueous solution (mass concentration 1.5%) to mix, stirring for 15 min, then standing to separate the layers, removing the water phase, then adding 25 kg of ethylenediaminetetraacetic acid aqueous solution (mass concentration 2.5 wt%) to mix, stirring to dissolve for 30 min, then standing to separate the layers, removing the water phase, and pumping the obtained 80 kg of polymer dispersion phase into a precipitation kettle; the precipitation kettle is also maintained at a temperature of 10°C by a heat exchanger, 80 kg of methanol is added to the precipitation kettle, and stirring is maintained during the addition, so that the vinyl-terminated polyphenyl ether is precipitated; after stirring for 30 min and standing for 15 min, the vinyl-terminated polyphenyl ether solid is precipitated, the supernatant is removed using a pump, then 35 kg of methanol is added to the precipitation kettle again, and stirring is performed for 30 min to make the solid precipitate completely; centrifugal separation is performed, and drying is performed in a vacuum drum dryer until the volatile matter of the product is reduced to less than or equal to 0.5 wt%, to obtain the vinyl-terminated polyphenyl ether polyphenyl ether.

[0093] Example 2

[0094] The present embodiment provides a kind of end vinyl polyphenyl ether and its preparation method, which is different from the embodiment 1, it is adjusted to step (1) as follows: after the reaction solution separated in the embodiment 1 step (1) is returned to polymerization kettle, 4.55kg (1eq, 16mol, 284.4da) tetramethyl bisphenol A and 25.4kg (13eq, 208mol, 122da) 2,6-dimethyl phenol are added to polymerization kettle again, stir 5min to make material dissolve, open the external circulation heat exchanger of polymerization kettle to control the temperature of material in kettle to 45 DEG C, open oxygen inlet, according to the rate of 7.9 kg / h, oxygen is imported into polymerization kettle, from the beginning of the timing reaction of importing oxygen, keep continuous stirring in kettle and maintain oxygen rate and stable temperature in kettle during polymerization reaction, after 45 min of reaction, end, close oxygen gas path and external circulation heating, pump the material in kettle into centrifugal separator, the reaction solution separated is returned to polymerization kettle, the solid filter cake separated by centrifugation is dried, and end hydroxyl polyphenyl ether is obtained, which is recorded as end hydroxyl polyphenyl ether B;

[0095] After the reaction solution separated in the above reaction is returned to polymerization kettle, 4.55kg (1eq, 16mol, 284.4da) tetramethyl bisphenol A and 25.4kg (13eq, 208mol, 122da) 2,6-dimethyl phenol are added to polymerization kettle again, stir 5min to make material dissolve, open the external circulation heat exchanger of polymerization kettle to control the temperature of material in kettle to 45 DEG C, open oxygen inlet, according to the rate of 7.9 kg / h, oxygen is imported into polymerization kettle, from the beginning of the timing reaction of importing oxygen, keep continuous stirring in kettle and maintain oxygen rate and stable temperature in kettle during polymerization reaction, after 45 min of reaction, end, close oxygen gas path and external circulation heating, pump the material in kettle into centrifugal separator, the reaction solution separated is returned to polymerization kettle, the solid filter cake separated by centrifugation is dried, and end hydroxyl polyphenyl ether is obtained, which is recorded as end hydroxyl polyphenyl ether B;

[0096] After the reaction solution separated in the above reaction is returned to polymerization kettle, 4.55kg (1eq, 16mol, 284.4da) tetramethyl bisphenol A and 25.4kg (13eq, 208mol, 122da) 2,6-dimethyl phenol are added to polymerization kettle again, stir 5min to make material dissolve, open the external circulation heat exchanger of polymerization kettle to control the temperature of material in kettle to 45 DEG C, open oxygen inlet, according to the rate of 7.9 kg / h, oxygen is imported into polymerization kettle, from the beginning of the timing reaction of importing oxygen, keep continuous stirring in kettle and maintain oxygen rate and stable temperature in kettle during polymerization reaction, after 45 min of reaction, end, close oxygen gas path and external circulation heating, pump the material in kettle into centrifugal separator, the reaction solution separated is returned to polymerization kettle, the solid filter cake separated by centrifugation is dried, and end hydroxyl polyphenyl ether is obtained, which is recorded as end hydroxyl polyphenyl ether B;

[0097] After the reaction solution separated is returned to the polymerizer, 4.55 kg (1 eq, 16 mol, 284.4 da) of tetramethyl bisphenol A and 25.4 kg (13 eq, 208 mol, 122 da) of 2,6-dimethyl phenol are added to the polymerizer, the material is stirred for 5 min to dissolve, the external circulation heat exchanger of the polymerizer is turned on to control the temperature of the material in the polymerizer to 45°C, the oxygen inlet is turned on, and oxygen is introduced into the polymerizer at a rate of 7.9 kg / h. The reaction is timed from the start of oxygen introduction. During the polymerization reaction, the oxygen rate and the temperature in the polymerizer are kept stable, and the material in the polymerizer is continuously stirred. After 45 min, the reaction is stopped, the oxygen path and the external circulation heating are turned off, the material in the polymerizer is pumped into a centrifugal separator, the reaction solution separated is returned to the polymerizer, and the solid filter cake separated by centrifugation is dried to obtain a hydroxyl-terminated polyphenyl ether, which is denoted as hydroxyl-terminated polyphenyl ether E.

[0098] The prepared hydroxyl-terminated polyphenyl ethers B, C, D, and E are added to a dissolving kettle, toluene is added and heated to dissolve, and a hydroxyl-terminated polyphenyl ether solution is prepared. The mass concentration of the hydroxyl-terminated polyphenyl ether solution is 50%, and the hydroxyl-terminated polyphenyl ether in the hydroxyl-terminated polyphenyl ether solution is denoted as F.

[0099] In step (3), the rate of the hydroxyl-terminated polyphenyl ether solution is adjusted to 1.09 kg / min, and the rate of the vinyl end-capping agent solution is adjusted to 376.0 g / min (the ratio of the hydroxyl-terminated polyphenyl ether and the vinyl end-capping agent introduced per unit time satisfies: M = (n x HV x m) / 56000, where M represents the molar mass of the vinyl end-capping agent, n is 1.1, HV represents the hydroxyl value of the hydroxyl-terminated polyphenyl ether, and m represents the mass of the hydroxyl-terminated polyphenyl ether), and the other conditions are the same as in Example 1.

[0100] Example 3

[0101] The difference between the present example and Example 2 is that in step (3), the rate of the hydroxyl-terminated polyphenyl ether solution is adjusted to 1.13 kg / min, and the rate of the vinyl end-capping agent solution is adjusted to 336.7 g / min (the ratio of the hydroxyl-terminated polyphenyl ether and the vinyl end-capping agent introduced per unit time satisfies: M = (n x HV x m) / 56000, where M represents the molar mass of the vinyl end-capping agent, n is 0.95, HV represents the hydroxyl value of the hydroxyl-terminated polyphenyl ether, and m represents the mass of the hydroxyl-terminated polyphenyl ether), and the other conditions are the same as in Example 2.

[0102] Example 4

[0103] The embodiment provides an end-vinyl polyphenyl ether and a preparation method thereof, which are different from those of the embodiment 2 in that the rate of the end-hydroxyl polyphenyl ether solution in step (3) is adjusted to 1.42 kg / min, the rate of the vinyl end-capping agent solution is adjusted to 445.3 g / min (the ratio of the end-hydroxyl polyphenyl ether and the vinyl end-capping agent in a unit time satisfies: M=(n*HV*m) / 56000, wherein M represents the molar mass of the vinyl end-capping agent, n=1, HV represents the hydroxyl value of the end-hydroxyl polyphenyl ether, and m represents the mass of the end-hydroxyl polyphenyl ether), the tubular reactor is set to a constant temperature of 65 DEG C, the residence time of the material in the tubular reactor is 20 min, the metering pump is closed and the residual material in the tubular reactor is discharged after 42 min, and other conditions are the same as those of the embodiment 2.

[0104] Embodiment 5

[0105] The embodiment provides an end-vinyl polyphenyl ether and a preparation method thereof, which are different from those of the embodiment 2 in that the rate of the end-hydroxyl polyphenyl ether solution in step (3) is adjusted to 1.42 kg / min, the rate of the vinyl end-capping agent solution is adjusted to 445.3 g / min (the ratio of the end-hydroxyl polyphenyl ether and the vinyl end-capping agent in a unit time satisfies: M=(n*HV*m) / 56000, wherein M represents the molar mass of the vinyl end-capping agent, n=1, HV represents the hydroxyl value of the end-hydroxyl polyphenyl ether, and m represents the mass of the end-hydroxyl polyphenyl ether), the tubular reactor is set to a constant temperature of 65 DEG C, the residence time of the material in the tubular reactor is 20 min, the metering pump is closed and the residual material in the tubular reactor is discharged after 42 min, and other conditions are the same as those of the embodiment 2.

[0106] Embodiment 6

[0107] The present embodiment provides a terminal vinyl polyphenyl ether and a preparation method thereof, the preparation method comprising the following steps: (1) adding 200 g of methanol, 12.7 g (0.008 eq, 0.128 mol, 99 da) of cuprous chloride, 44.2 g (0.012 eq, 0.192 mol, 230 da) of polyether amine, and 12.9 g (0.004 eq, 0.064 mol, 202.2 da) of diisopropyl azodicarboxylate into a beaker, stirring for 15 min to obtain a catalyst solution, and adding the catalyst solution into a 150 L polymerization kettle; then adding 82.9 kg of methanol, 14.6 kg of toluene, 2.18 kg (1 eq, 8.5 mol, 256.3 da) of tetramethyl bisphenol F, 30.1 kg (26.0 eq, 221.0 mol, 136.2 da) of 2,3,6-trimethylphenol, stirring for 5 min to dissolve the materials, opening the external circulation heat exchanger of the polymerization kettle to control the temperature of the materials in the kettle to 45°C, opening the oxygen inlet, and introducing oxygen into the polymerization kettle at a rate of 7.9 kg / h, timing the reaction from the start of oxygen introduction, maintaining continuous stirring in the kettle and stabilizing the oxygen rate and the temperature in the kettle during the polymerization reaction, and ending the reaction after 45 min, closing the oxygen path and the external circulation heating, pumping the materials in the kettle into a centrifugal separator for centrifugation, recovering the reaction solution obtained by separation, and returning it to the polymerization kettle, and drying the solid filter cake obtained by centrifugal separation to obtain a terminal hydroxyl polyphenyl ether, which is denoted as terminal hydroxyl polyphenyl ether G.

[0108] The terminal hydroxyl polyphenyl ether G is sent into a dissolving kettle, toluene is added and heated to dissolve, to obtain a terminal hydroxyl polyphenyl ether solution with a mass concentration of 50%.

[0109] (2) 5.6 kg (1.77 eq, 36.8 mol, 152.6 da) of p-chloromethylstyrene, 3.7 kg (1.77 eq, 36.8 mol, 101.2 da) of triethylamine, toluene, potassium iodide, and dimethylformamide are stirred and dissolved to mix uniformly, the mass ratio of toluene to the total mass of p-chloromethylstyrene and triethylamine is 1:1, the mass of potassium iodide is 1% of the mass of p-chloromethylstyrene, and the mass ratio of potassium iodide to dimethylformamide is 1:1, to obtain a vinyl end-capping agent solution.

[0110] (3) using a metering pump to pass the hydroxyl-terminated polyphenyl ether solution prepared in step (1) and the vinyl-terminating agent solution prepared in step (2) into a tubular reactor (tube length 20 m, inner diameter 50 mm, length-diameter ratio 400) to react, wherein the rate of the hydroxyl-terminated polyphenyl ether solution is 1.28 kg / min, and the rate of the vinyl-terminating agent solution is 191.6 g / min (the ratio of the hydroxyl-terminated polyphenyl ether and the vinyl-terminating agent passed in per unit time satisfies: M = (n x HV x m) / 56000, wherein M represents the molar mass of the vinyl-terminating agent, n = 1, HV represents the hydroxyl value of the hydroxyl-terminated polyphenyl ether, and m represents the mass of the hydroxyl-terminated polyphenyl ether); the tubular reactor is set to a constant temperature of 50°C, and the residence time of the material in the tubular reactor is 25 min; after 53 min, the metering pump is turned off and the residual material in the tubular reactor is discharged, to obtain a product.

[0111] (4) placing the product prepared in step (3) into a washing kettle and cooling to 10°C, then adding 25 kg of hydrochloric acid aqueous solution (mass concentration 1.5%) and mixing, stirring for 15 min, then standing and separating the layers, removing the water phase, then adding 25 kg of ethylenediaminetetraacetic acid aqueous solution (mass concentration 2.5 wt%), stirring and dissolving for 30 min, then standing and separating the layers, removing the water phase, and pumping the obtained 80 kg of polymer dispersion phase into a precipitation kettle, also maintaining the temperature at 10°C by using a heat exchanger, adding 80 kg of methanol to the precipitation kettle, and maintaining stirring during the process, so that the vinyl-terminated polyphenyl ether is precipitated, stirring for 30 min, then standing for 15 min, so that the vinyl-terminated polyphenyl ether solid precipitates, removing the supernatant liquid using a pump, then adding 35 kg of methanol to the precipitation kettle again, stirring vigorously for 30 min, so that the solid is completely precipitated, centrifuging and drying in a vacuum drum dryer until the volatile matter of the product is reduced to less than or equal to 0.5 wt%, to obtain the vinyl-terminated polyphenyl ether polyphenyl ether.

[0112] Example 7

[0113] The present embodiment provides a kind of end vinyl polyphenyl ether and its preparation method, the preparation method includes the following steps: (1) 200 g methanol, 12.7 g (0.008 eq, 0.128 mol, 99 da) cuprous chloride, 44.2g (0.012 eq, 0.192 mol, 230 da) polyetheramine and 12.9 g (0.004 eq, 0.064 mol, 202.2 da) diisopropyl azodicarboxylate are added to beaker, stirring 15 min, catalyst solution is obtained, and catalyst solution is added to 150L polymerization kettle;82.9kg methanol, 14.6kg toluene, 2.30kg (1 eq, 8.5 mol, 270.4.da) 2,2',3,3',5,5'-hexamethyl-4,4'-dihydroxydiphenyl, 15.8kg (13.7 eq, 116.5 mol, 136.2 da) 2,3,6-trimethylphenol, 14.3kg (13.7 eq, 116.5 mol, 122.2 da) 2,6-dimethylphenol are added, stirring 5 min to dissolve material, open the outer loop heat exchanger of polymerization kettle to control the temperature of material in kettle to 45℃, open oxygen inlet, and oxygen is imported into polymerization kettle at the rate of 7.9 kg / h, and the reaction is timed from the beginning of oxygen import, keeps constant stirring in kettle and maintains oxygen rate and kettle temperature stable during polymerization reaction, and the reaction is ended after 45 min, and oxygen gas path and outer loop heating are closed, material in kettle is pumped into centrifugal separator for centrifugation, and the reaction solution separated is recovered and returned to polymerization kettle, and the solid filter cake separated by centrifugation is dried to obtain hydroxyl-terminated polyphenyl ether, which is denoted as hydroxyl-terminated polyphenyl ether H.

[0114] The hydroxyl-terminated polyphenyl ether H is sent into dissolving kettle, toluene is added and heated to dissolve, to obtain hydroxyl-terminated polyphenyl ether solution with mass concentration of 50%.

[0115] (2) 5.6kg (1.77 eq, 36.8 mol, 152.6 da) p-chloromethylstyrene, 3.7kg (1.77 eq, 36.8 mol, 101.2 da) triethylamine, toluene, potassium iodide and dimethylformamide are stirred and dissolved to mix uniformly, the mass ratio of toluene to the total mass of p-chloromethylstyrene and triethylamine is 1:1, the mass of potassium iodide is 1% of the mass of p-chloromethylstyrene, and the mass ratio of potassium iodide to dimethylformamide is 1:1, to obtain a vinyl end-capping agent solution.

[0116] (3) using a metering pump to pass the hydroxyl-terminated polyphenyl ether solution prepared in step (1) and the vinyl-terminating agent solution prepared in step (2) into a tubular reactor (tube length 20 m, inner diameter 50 mm, length-diameter ratio 400) to react, wherein the rate of the hydroxyl-terminated polyphenyl ether solution is 1.28 kg / min, the rate of the vinyl-terminating agent solution is 194.2 g / min (the ratio of the hydroxyl-terminated polyphenyl ether and the vinyl-terminating agent passed in per unit time satisfies: M = (n x HV x m) / 56000, wherein M represents the molar mass of the vinyl-terminating agent, n = 1, HV represents the hydroxyl value of the hydroxyl-terminated polyphenyl ether, and m represents the mass of the hydroxyl-terminated polyphenyl ether), the tubular reactor is set to a constant temperature of 50°C, the residence time of the material in the tubular reactor is 25 min, the metering pump is turned off after 53 min, and the residual material in the tubular reactor is discharged to obtain a product.

[0117] (4) placing the product prepared in step (3) into a washing kettle and cooling to 10°C, then adding 25 kg of hydrochloric acid aqueous solution (mass concentration 1.5%) to mix, stirring for 15 min, then standing to separate layers, removing the water phase, then adding 25 kg of ethylenediaminetetraacetic acid aqueous solution (mass concentration 2.5 wt%) to stir and dissolve for 30 min, then standing to separate layers, removing the water phase, pumping the obtained 80 kg of polymer dispersion phase into a precipitation kettle, also maintaining the temperature at 10°C by using a heat exchanger, adding 80 kg of methanol to the precipitation kettle, and keeping stirring during the period, so that the vinyl-terminated polyphenyl ether is precipitated, stirring for 30 min, then standing for 15 min to make the vinyl-terminated polyphenyl ether solid precipitate, then removing the supernatant using a pump, then adding 35 kg of methanol to the precipitation kettle again, and stirring vigorously for 30 min to make the solid precipitate completely, then centrifugally separating, and drying in a vacuum drum dryer until the volatile matter of the product is reduced to less than or equal to 0.5 wt% to obtain the vinyl-terminated polyphenyl ether polyphenyl ether.

[0118] Comparative Example 1

[0119] This comparative example provides a vinyl-terminated polyphenyl ether and a preparation method thereof, which is different from Example 1 in that no potassium iodide and dimethylformamide are added in step (2), the rate of the hydroxyl-terminated polyphenyl ether solution in step (3) is adjusted to 1.12 kg / min, the rate of the vinyl-terminating agent solution is adjusted to 341.5 g / min (the ratio of the hydroxyl-terminated polyphenyl ether and the vinyl-terminating agent passed in per unit time satisfies: M = (n x HV x m) / 56000, wherein M represents the molar mass of the vinyl-terminating agent, n = 1, HV represents the hydroxyl value of the hydroxyl-terminated polyphenyl ether, and m represents the mass of the hydroxyl-terminated polyphenyl ether), and other conditions are the same as those in Example 1.

[0120] Comparative Example 2

[0121] The comparative example provides a terminal vinyl polyphenyl ether and a preparation method thereof, which is different from example 1 in that step (3) is adjusted to add the terminal hydroxyl polyphenyl ether solution prepared in step (1) into a 100 L polymerization kettle, start stirring and heating of the reaction kettle, and heat the materials in the kettle to 50°C; the vinyl capping agent solution prepared in step (2) is added into the polymerization kettle within 26 min; after the addition of the vinyl capping agent solution is completed, the reaction is kept and the materials in the kettle are sampled; the residual amount of p-chloromethylstyrene in the materials is monitored by HPLC; after the reaction continues for 22.5 min, the amount of p-chloromethylstyrene in the materials is reduced to less than 1% of the amount at the beginning of the reaction; the heating of the reactor is stopped; the product is obtained; and other conditions are the same as in example 1.

[0122] Comparative example 3

[0123] The comparative example provides a terminal vinyl polyphenyl ether and a preparation method thereof, which is different from example 1 in that no azobisdimethylvalerate is added in step (1), and the terminal hydroxyl polyphenyl ether prepared is denoted as terminal hydroxyl polyphenyl ether I.

[0124] In step (3), the rate of the terminal hydroxyl polyphenyl ether solution is adjusted to 1.12 kg / min, and the rate of the vinyl capping agent solution is adjusted to 319.3 g / min (the proportion relationship of the terminal hydroxyl polyphenyl ether and the vinyl capping agent added per unit time satisfies: M=(n×HV×m) / 56000, wherein M represents the molar mass of the vinyl capping agent, n=1, HV represents the hydroxyl value of the terminal hydroxyl polyphenyl ether, and m represents the mass of the terminal hydroxyl polyphenyl ether); and other conditions are the same as in example 1.

[0125] Comparative example 4

[0126] The present comparative example provides a hydroxyl-terminated polyphenyl ether and a preparation method thereof, the preparation method comprising the following steps: adding 200 g of methanol, 12.7 g (0.008 eq, 0.128 mol, 99 da) of cuprous chloride, 28.1 g (0.024 eq, 0.384 mol, 73.1 da) of diethylamine and 12.9 g (0.004 eq, 0.064 mol, 202.2 da) of diisopropyl azodicarboxylate into a beaker, stirring for 15 min to obtain a catalyst solution, and adding the catalyst solution into a 150 L polymerization kettle; then adding 90.0 kg of methanol, 4.55 kg (1 eq, 16 mol, 284.4 da) of tetramethyl bisphenol A, 25.4 kg (13 eq, 208 mol, 122 da) of 2,6-dimethylphenol, stirring for 5 min to dissolve the materials, opening the external circulation heat exchanger of the polymerization kettle to control the temperature of the materials in the kettle to 45°C, opening the oxygen inlet, and introducing oxygen into the polymerization kettle at a rate of 7.9 kg / h, timing the reaction from the start of oxygen introduction, maintaining continuous stirring in the kettle and stabilizing the oxygen rate and the temperature in the kettle during the polymerization reaction, ending the reaction after 45 min, closing the oxygen path and the external circulation heating, pumping the materials in the kettle into a centrifugal separator for centrifugation, recovering the separated reaction solution and returning it to the polymerization kettle, and drying the solid filter cake obtained by centrifugal separation to obtain a hydroxyl-terminated polyphenyl ether, which is denoted as hydroxyl-terminated polyphenyl ether J.

[0127] Comparative Example 5

[0128] The present comparative example provides a hydroxyl-terminated polyphenyl ether and a preparation method thereof, the preparation method comprising the following steps: after returning the separated reaction solution to the polymerization kettle in Comparative Example 4, adding 4.55 kg (1 eq, 16 mol, 284.4 da) of tetramethyl bisphenol A and 25.4 kg (13 eq, 208 mol, 122 da) of 2,6-dimethylphenol into the polymerization kettle, stirring for 5 min to dissolve the materials, opening the external circulation heat exchanger of the polymerization kettle to control the temperature of the materials in the kettle to 45°C, opening the oxygen inlet, and introducing oxygen into the polymerization kettle at a rate of 7.9 kg / h, timing the reaction from the start of oxygen introduction, maintaining continuous stirring in the kettle and stabilizing the oxygen rate and the temperature in the kettle during the polymerization reaction, ending the reaction after 45 min, closing the oxygen path and the external circulation heating, pumping the materials in the kettle into a centrifugal separator, returning the separated reaction solution to the polymerization kettle, and drying the solid filter cake obtained by centrifugal separation to obtain a hydroxyl-terminated polyphenyl ether, which is denoted as hydroxyl-terminated polyphenyl ether K.

[0129] After the reaction solution separated was returned to the polymerization kettle, 4.55 kg (1 eq, 16 mol, 284.4 da) of tetramethyl bisphenol A and 25.4 kg (13 eq, 208 mol, 122 da) of 2,6-dimethyl phenol were added to the polymerization kettle, the material was dissolved by stirring for 5 min, the external circulation heat exchanger of the polymerization kettle was started to control the temperature of the material in the kettle to 45°C, the oxygen inlet was started, and oxygen was introduced into the polymerization kettle at a rate of 7.9 kg / h, the reaction was timed from the start of the introduction of oxygen, the polymerization reaction was maintained by continuously stirring the material in the kettle and maintaining the oxygen rate and the temperature in the kettle stable, the reaction was continued for 45 min, and then ended, the oxygen line and the external circulation heating were closed, the material in the kettle was pumped into a centrifugal separator, the reaction solution separated was returned to the polymerization kettle, and the solid filter cake separated by centrifugation was dried to obtain a hydroxyl-terminated polyphenyl ether, which was recorded as hydroxyl-terminated polyphenyl ether L.

[0130] After the reaction solution separated was returned to the polymerization kettle, 4.55 kg (1 eq, 16 mol, 284.4 da) of tetramethyl bisphenol A and 25.4 kg (13 eq, 208 mol, 122 da) of 2,6-dimethyl phenol were added to the polymerization kettle, the material was dissolved by stirring for 5 min, the external circulation heat exchanger of the polymerization kettle was started to control the temperature of the material in the kettle to 45°C, the oxygen inlet was started, and oxygen was introduced into the polymerization kettle at a rate of 7.9 kg / h, the reaction was timed from the start of the introduction of oxygen, the polymerization reaction was maintained by continuously stirring the material in the kettle and maintaining the oxygen rate and the temperature in the kettle stable, the reaction was continued for 45 min, and then ended, the oxygen line and the external circulation heating were closed, the material in the kettle was pumped into a centrifugal separator, the reaction solution separated was returned to the polymerization kettle, and the solid filter cake separated by centrifugation was dried to obtain a hydroxyl-terminated polyphenyl ether, which was recorded as hydroxyl-terminated polyphenyl ether M.

[0131] After the reaction solution separated was returned to the polymerization kettle, 4.55 kg (1 eq, 16 mol, 284.4 da) of tetramethyl bisphenol A and 25.4 kg (13 eq, 208 mol, 122 da) of 2,6-dimethyl phenol were added to the polymerization kettle, the material was dissolved by stirring for 5 min, the external circulation heat exchanger of the polymerization kettle was started to control the temperature of the material in the kettle to 45°C, the oxygen inlet was started, and oxygen was introduced into the polymerization kettle at a rate of 7.9 kg / h, the reaction was timed from the start of the introduction of oxygen, the polymerization reaction was maintained by continuously stirring the material in the kettle and maintaining the oxygen rate and the temperature in the kettle stable, the reaction was continued for 45 min, and then ended, the oxygen line and the external circulation heating were closed, the material in the kettle was pumped into a centrifugal separator, the reaction solution separated was returned to the polymerization kettle, and the solid filter cake separated by centrifugation was dried to obtain a hydroxyl-terminated polyphenyl ether, which was recorded as hydroxyl-terminated polyphenyl ether N.

[0132] Comparative Example 6

[0133] The comparative example provides a terminal hydroxyl polyphenyl ether and a preparation method thereof, which is different from step (1) in Example 1 in that methanol is replaced by the same mass of toluene;

[0134] The reaction time is adjusted to 25 min, after the reaction is completed, the oxygen gas path and the external circulation heating are closed, the materials in the kettle are pumped into a precipitation kettle containing 250 kg of methanol, stirring is performed, the polymer solids are precipitated, pumping into a centrifugal separator is performed, the solid filter cake obtained by centrifugal separation is dried, and a terminal hydroxyl polyphenyl ether is obtained, which is recorded as terminal hydroxyl polyphenyl ether O.

[0135] The terminal hydroxyl polyphenyl ethers provided by Examples 1 to 7 and Comparative Examples 1 to 6 are tested as follows.

[0136] (1) Number average molecular weight (Mn) and molecular weight distribution (D): The number average molecular weight and the molecular weight distribution of the terminal hydroxyl polyphenyl ether are determined by using gel chromatography according to GB / T 27843-2011.

[0137] (2) Hydroxyl value (HV): The hydroxyl value is determined by using chemical titration (acylation reaction) according to ASTM D4274-05, and the average hydroxyl functionality of the terminal hydroxyl polyphenyl ether product is calculated.

[0138] The test results are shown in Table 1 below.

[0139] The terminal vinyl polyphenyl ethers provided by Examples 1 to 7 and Comparative Examples 1 to 3 are tested for the following performances.

[0140] (1) Number average molecular weight and molecular weight distribution: The number average molecular weight and the molecular weight distribution of the terminal vinyl polyphenyl ether are determined by using gel chromatography according to GB / T 27843-2011.

[0141] (2) Unsaturation (U): The unsaturation is measured by using iodometric method according to GB / T 34247.1-2017.

[0142] (3) Yellowness (YI): The yellowness is determined by using a spectrophotometer according to ASTM D1925-70.

[0143] The test results are shown in Table 2 below.

[0144] Table 1 Test results of terminal hydroxyl polyphenyl ether

[0145]

[0146] Table 2 Test results of terminal vinyl polyphenyl ether

[0147]

[0148] It can be seen from the test results that the preparation method of the end-vinyl polyphenyl ether provided in embodiments 1-7 has simple process, the prepared end-vinyl polyphenyl ether has controllable molecular weight, molecular weight distribution ≤2.25, low molecular weight distribution, low content of colored impurities, high unsaturation, yellow index ≤10, and high whiteness.

[0149] Compared with embodiments 1-3, if the amount of the vinyl blocking agent is too high (embodiment 2), the unsaturation of the prepared end-vinyl polyphenyl ether does not increase significantly, but the yellow index increases; if the amount of the vinyl blocking agent is too low (embodiment 3), the unsaturation of the prepared end-vinyl polyphenyl ether decreases.

[0150] Compared with embodiment 2, if the temperature is raised to shorten the residence time in step (4) to obtain similar unsaturation (embodiment 4), the yellow index of the prepared end-vinyl polyphenyl ether increases.

[0151] Compared with embodiment 1, if potassium iodide and dimethylformamide are not added (comparative example 1), the unsaturation of the prepared end-vinyl polyphenyl ether decreases, and the yellow index increases.

[0152] Compared with embodiment 1, if the reaction in step (3) is carried out in a polymerization kettle (comparative example 2), the molecular weight distribution of the prepared end-vinyl polyphenyl ether is wide, and the yellow index increases.

[0153] Compared with embodiment 1, if no additive is added in the preparation method of the end-hydroxyl polyphenyl ether in step (1) (comparative example 3), the molecular weight distribution of the prepared end-hydroxyl polyphenyl ether is wide, the hydroxyl value is low, the molecular weight distribution of the end-vinyl polyphenyl ether prepared by using the end-hydroxyl polyphenyl ether is wide, the unsaturation is low, and the yellow index is high.

[0154] As can be seen from the comparison of embodiments 1 and 2 and comparative examples 4 and 5, it is preferred to use an amine-based high molecular compound as a ligand in the preparation of the end-hydroxyl polyphenyl ether, which can realize continuous production and has good stability, and the number average molecular weight, the molecular weight distribution, the hydroxyl value and the average hydroxyl functionality of the end-hydroxyl polyphenyl ether prepared by recycling the reaction solution for multiple times remain basically unchanged. This is because when the ligand is a small molecule amine compound such as diethylamine in the preparation of the end-hydroxyl polyphenyl ether, the ligand is easy to flow out, and after multiple cycles, the ligand is lost and dispersed, and the catalytic activity of the catalytic system will decrease significantly after long-term and multiple uses. Under the condition of lower activity, the proportion of monohydroxyl polyphenyl ether obtained by self-polymerization of 2,6-dimethylphenol in the polymerization product increases, resulting in a decrease in the hydroxyl functionality of the end group of the product and a decrease in the hydroxyl value of the product. In comparison, the amine-based high molecular compound (polyether amine) has better solubility in methanol, and the amine-based high molecular compound will not be lost in large amounts during repeated use, and can maintain high catalytic activity during multiple recycling and reuse of the solvent and the catalytic system.

[0155] From the comparison of Example 1 and Comparative Example 6, it can be seen that when methanol is replaced by the same mass of toluene, and a hydroxyl-terminated polyphenyl ether with a molecular weight similar to that of Example 1 is prepared by controlling the reaction time using the homogeneous method, the product contains a large amount of oligomers, the molecular weight distribution of the polymer is increased, the oligomers are mainly toluenediol self-polymerization, the average functionality of the hydroxyl groups in the product is low, and the hydroxyl value is low. Therefore, it can be seen that the hydroxyl-terminated polyphenyl ether prepared by the precipitation method has low molecular weight distribution and high hydroxyl value.

[0156] The applicant declares that the above is only a specific embodiment of the present application, but the protection scope of the present application is not limited thereto. It should be understood by those skilled in the art that any changes or replacements within the technical scope disclosed by the present application can be easily thought of by any person skilled in the art, and falls within the protection scope and disclosure scope of the present application.

Claims

1. A method for preparing vinyl-terminated polyphenylene ether, characterized in that, The preparation method includes the following steps: (1) Aromatic phenolic monomers are used to prepare hydroxyl-terminated polyphenylene ethers by precipitation under the catalysis of a copper-based catalyst system; (2) The terminal hydroxyl polyphenylene ether solution and the vinyl end-capping agent solution are reacted in a tubular reactor under the catalysis of an iodine-based catalyst system to obtain the terminal vinyl polyphenylene ether; The copper-based catalyst system includes a copper-based catalyst, a ligand, and an auxiliary agent, wherein the ligand is an amine polymer compound.

2. The preparation method according to claim 1, characterized in that, The aromatic phenolic monomers include phenolic monomers and aromatic diphenol monomers; The phenolic monomers include 2,6-dimethylphenol and / or 2,3,6-trimethylphenol; The aromatic diphenol monomer includes any one or a combination of at least two of tetramethylbisphenol F, tetramethylbisphenol A, or 2,2',3,3',5,5'-hexamethyl-4,4'-dihydroxybiphenyl. The molar ratio of the phenolic monomer to the aromatic diphenol monomer is (13~29):1; The solvents used in the precipitation method include both poor solvents and good solvents; The undesirable solvents include any one or a combination of at least two of methanol, ethanol, isopropanol or tert-butanol. The good solvent includes any one or a combination of at least two of benzene, toluene, ethylbenzene, xylene, chloroform, dichloroethane, trichloroethane, or chlorobenzene; With the total mass of the solvent used in the precipitation method being 100%, the mass of the good solvent is 0-15%. The mass ratio of solvent to aromatic phenolic monomer used in the precipitation method is (2~5):1; The number-average molecular weight of the terminal hydroxyl polyphenylene ether is 1000~3500 g / mol; The molecular weight distribution of the terminal hydroxyl polyphenylene ether is ≤2.2; The average hydroxyl functionality of the terminal hydroxyl polyphenylene ether is ≥1.75 mgKOH / g.

3. The preparation method according to claim 2, characterized in that, The copper-based catalyst includes cuprous compounds and / or copper compounds; The cuprous compound includes any one or a combination of at least two of cuprous chloride, cuprous bromide, cuprous nitrate or cuprous sulfate; The copper compound includes any one or a combination of at least two of copper chloride, copper bromide, copper nitrate or copper sulfate; The molar ratio of the copper-based catalyst to the aromatic diphenol monomer is (0.004~0.015):1; The amine polymers include polyetheramines; The molar ratio of the ligand to the copper-based catalyst is (0.5~5):1; The additives include azodicarbonate; The azodicarbonate includes any one or a combination of at least two of diethyl azodicarbonate, diisopropyl azodicarbonate, or tert-butyl azodicarbonate. The molar ratio of the additive to the copper-based catalyst is (0.05~2):

1.

4. The preparation method according to claim 2, characterized in that, The precipitation method described in step (1) is carried out under conditions of passing an oxygen-containing gas; The volume concentration of oxygen in the oxygen-containing gas is 21% to 100%. The molar ratio of oxygen to phenol monomers is (0.6~3):1; The reaction temperature for the precipitation method is 30~70℃; The reaction time for the precipitation method is 45-90 min; The precipitation reaction was carried out at a pressure of 0.8 to 1.25 bar.

5. The preparation method according to claim 1, characterized in that, The hydroxyl-terminated polyphenylene ether solution in step (2) comprises the hydroxyl-terminated polyphenylene ether obtained in step (1) and a good solvent; The mass concentration of hydroxyl-terminated polyphenylene ether in the hydroxyl-terminated polyphenylene ether solution is 30%~50%; The vinyl end-capping agent solution comprises a vinyl end-capping agent, an alkali, and a good solvent; The vinyl end-capping agent includes p-chloromethylstyrene; The base includes any one or a combination of at least two of pyridine, diethylamine, or triethylamine; The molar ratio of the alkali to the vinyl end-capping agent is (0.8~1.5):1; The mass ratio of the good solvent to the total mass of the vinyl end-capping agent and alkali in the vinyl end-capping agent solution is (0.8~1.2):1; The molar amount of the vinyl end-capping agent satisfies the following formula: M = (n × HV × m) / 56000, where M represents the molar amount of the vinyl end-capping agent, n is 0.95~1.1, HV represents the hydroxyl value of the hydroxyl-terminated polyphenylene ether, and m represents the mass of the hydroxyl-terminated polyphenylene ether. The iodine-based catalyst system includes iodine salts and a co-solvent; The iodized salt includes potassium iodide or sodium iodide; The mass of the iodized salt is 0.5% to 5% of the mass of the vinyl end-capping agent; The co-solvent includes dimethyl sulfoxide and / or dimethylformamide; The mass ratio of the co-solvent to the iodized salt is (0.5~5):

1.

6. The preparation method according to claim 1, characterized in that, The length-to-diameter ratio of the tubular reactor is ≥100; The reaction temperature in the tubular reactor is 40~65℃; The residence time of the material in the tubular reactor is 20-45 min.

7. The preparation method according to claim 1, characterized in that, Step (2) further includes washing, precipitation and drying steps after the reaction; The washing process includes washing with an aqueous hydrochloric acid solution and an aqueous ethylenediaminetetraacetic acid solution. The mass concentration of the hydrochloric acid aqueous solution is 0.5%~3%; The mass concentration of the ethylenediaminetetraacetic acid aqueous solution is 1%~5%; The mass of the hydrochloric acid aqueous solution is 20% to 40% of the total mass of the hydroxyl-terminated polyphenylene ether solution and the vinyl end-capping agent solution; The mass of the ethylenediaminetetraacetic acid aqueous solution is 20% to 40% of the total mass of the hydroxyl-terminated polyphenylene ether solution and the vinyl end-capping agent solution; The precipitation includes precipitation in unsuitable solvents.

8. A vinyl-terminated polyphenylene ether, characterized in that, The terminal vinyl polyphenylene ether is prepared by the preparation method according to any one of claims 1 to 7.

9. The vinyl-terminated polyphenylene ether according to claim 8, characterized in that, The degree of unsaturation of the terminal vinyl polyphenylene ether is >1.5; The number-average molecular weight of the terminal vinyl polyphenylene ether is 1500~3500 g / mol; The molecular weight distribution of the terminal vinyl polyphenylene ether is ≤2.25; The yellowness index of the terminal vinyl polyphenylene ether is ≤10.

10. The application of the terminal vinyl polyphenylene ether as described in claim 8 or 9 in the fabrication of high-frequency electronic circuit board substrates.

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