Alkenyl functionalized polyarylene ether as well as preparation method and application thereof

Abstract

The invention provides alkenyl functionalized polyarylene ether as well as a preparation method and application thereof, the preparation method of the alkenyl functionalized polyarylene ether comprises the following steps: washing a dihydroxy-terminated polyarylene ether reaction solution with an alcohol-water solution, taking an organic phase, mixing the organic phase with a catalyst and an end-capping modifier for reaction, and obtaining the alkenyl functionalized polyarylene ether. And preparing the alkenyl functionalized polyarylene ether. Compared with the prior art, the alkenyl-modified polyarylene ether has the advantages that terminal group modification is directly carried out on the double-terminal hydroxyl polyarylene ether reaction liquid washed by alcohol water, the prepared alkenyl-modified polyarylene ether has better performance, the content of active groups (double bonds) is higher and reaches 1.8-2.1 mmol / g, the residual quantity of polar small molecular substances such as monohydric phenol, dihydric phenol, quinone and amine is lower, the curing and crosslinking density with other resins is higher, and the curing and crosslinking performance is better. And the prepared copper-clad plate has better thermal performance and electrical performance.

Description

Technical Field

[0001] The invention relates to the technical field of resin materials, and in particular to an alkenyl functionalized polyarylene ether and a preparation method and application thereof. Background Art

[0002] Polyarylene ether (also known as polyphenylene ether) is one of the five major general-purpose engineering plastics and is widely used in electronic appliances, automobiles, household appliances, office equipment, industrial machinery, etc. In recent years, with the rapid development of communication technology, the fifth generation (5G) communication technology has been promoted and used worldwide. 5G communication is a high-frequency communication technology, and 5G has very high requirements on the electrical and thermal properties of materials.

[0003] With the deepening of 5G communications, the requirements for sheet performance are getting higher and higher, and thus the performance requirements for the raw material resin polyarylene ether are also higher. Ordinary double-terminated hydroxyl polyarylene ether can no longer meet the increasingly stringent performance requirements. To this end, it is necessary to improve the thermosetting properties of double-terminated hydroxyl polyarylene ether. At present, the main methods for improving the thermosetting properties of polyarylene ethers include methacrylate functionalization, vinyl benzyl functionalization, and allylation. The introduction of alkenyl groups can increase the curing crosslinking density of polyarylene ether resins and other resins (epoxy, cyanate ester, etc.) and improve the thermal properties of the sheet.

[0004] The currently disclosed preparation methods of alkenyl functionalized polyarylene ether mostly use double-terminated hydroxyl polyarylene ether resin powder as raw material for end group modification. The modified resin prepared by this method has low active group content and curing crosslinking density. CN109836575A discloses a preparation process of thermosetting methacrylate functionalized polyphenylene ether, wherein the methacrylate functionalized polyphenylene ether resin is synthesized using double-terminated hydroxyl polyarylene ether powder as raw material, and the allyl content is only 2%-4%. Summary of the invention

[0005] The present invention provides an alkenyl functionalized polyarylene ether and a preparation method and application thereof, which are used to solve the defects of low active group content and low curing crosslinking density of modified products in the prior art.

[0006] In a first aspect, the present invention provides a method for preparing alkenyl functionalized polyarylene ether, comprising: washing a double-terminated hydroxyl polyarylene ether reaction liquid with an alcohol aqueous solution, taking an organic phase, mixing the organic phase with a catalyst and a capping modifier for reaction, and preparing alkenyl functionalized polyarylene ether.

[0007] The alkenyl functionalized polyarylene ether resin may also be referred to as alkenyl modified polyarylene ether or alkenyl modified polyphenylene ether.

[0008] As described in the background technology, the preparation of alkenyl functionalized polyarylene ether is currently carried out with commercially available double-terminated hydroxyl polyarylene ether resin powder as raw material for end group modification. The present invention has found that the double-terminated hydroxyl polyarylene ether reaction solution is washed with alcohol water and then end-modified, and the resulting modified resin product has a higher content of active groups (double bonds), a lower residual amount of polar small molecules such as monophenol, diphenol, quinone, and amine, and a higher curing crosslinking density with other resins, and the thermal and electrical properties of the prepared copper-clad laminate are better. In addition, the preparation method of the alkenyl-modified polyphenylene ether in the present invention eliminates the energy-consuming sections such as devolatilization, extrusion or precipitation drying, solvent recovery, etc. when preparing double-terminated hydroxyl polyarylene ether resin powder, reduces process costs, reduces the generation of hazardous waste, and conforms to the production concept of green environmental protection.

[0009] According to the preparation method provided by the present invention, the alcohol aqueous solution is a mixed solution of fatty alcohol and water, and the mass proportion of fatty alcohol in the alcohol aqueous solution is 10-30%.

[0010] Preferably, the fatty alcohol is methanol or ethanol, and more preferably, the alcohol aqueous solution is a 20% methanol aqueous solution.

[0011] According to the preparation method provided by the present invention, the amount of the alcohol aqueous solution is 10-20% of the reaction solution.

[0012] According to the preparation method provided by the present invention, the washing temperature is 30-55°C, preferably 40-50°C.

[0013] According to the preparation method provided by the present invention, the double-terminated hydroxyl polyarylene ether has the following structure:

[0014]

[0015] Wherein, m and p are both integers greater than or equal to 0, and the range of m+p is 5 to 50; n is 0 or 1, and n cannot be 0 alone;

[0016] R1-R8 are each independently selected from hydrogen, halogen, C1-C6 alkyl, halogenated alkyl or alkoxy;

[0017] Y has the following structure:

[0018]

[0019] Among them, X1-X8 are each independently selected from a hydrogen atom or a C1-8 saturated or unsaturated hydrocarbon group such as methyl, ethyl, allyl, etc.; W represents a single bond or a C1-4 alkylene group such as ethylene, isopropylene, methylene, etc.

[0020] In the present invention, the dihydroxy-terminated polyarylene ether reaction liquid refers to a reaction liquid containing dihydroxy-terminated polyarylene ether obtained by polymerization of phenol monomers, that is, a dihydroxy-terminated polyarylene ether solid material has not been obtained by post-treatment.

[0021] Specifically, the preparation of the double-terminated hydroxyl polyarylene ether reaction liquid includes: in the presence of an oxidant and a copper amine catalyst, phenol monomers undergo oxidative polymerization in a polyarylene ether good solvent to obtain a reaction liquid.

[0022] The phenol monomer is a monophenol, a polyphenol or a mixture thereof, which is selected according to the target structural formula of the double-terminated hydroxyl polyarylene ether.

[0023] Preferably, the phenol monomer is a mixture of monohydric phenol and dihydric phenol, wherein the monohydric phenol is more preferably 2,6-dimethylphenol, and the dihydric phenol is more preferably tetramethyl bisphenol. That is, the double-terminated hydroxyl polyarylene ether has the following structure:

[0024]

[0025] Wherein, m, p and W have the same meaning as above.

[0026] Furthermore, the oxidant is preferably oxygen.

[0027] Further, the copper amine catalyst is a composite catalyst of a copper salt and an amine compound, wherein the copper salt is one or more selected from cuprous chloride, cuprous bromide, cuprous sulfate, cuprous sulfate tetraamine, cuprous acetate, cupric chloride, cupric bromide, cupric sulfate, cupric sulfate tetraamine and cupric acetate; the amine compound is an amine compound, for example, a primary amine, a tertiary amine, a secondary amine, etc., a diamine compound, or a mixture thereof; further preferably, the amine compound is one or more selected from n-propylamine, isopropylamine, n-butylamine, sec-butylamine, tert-butylamine, n-pentylamine, n-hexylamine, cyclohexylamine, di-n-propylamine, di-n-butylamine, di-tert-butylamine, n-butyl-n-pentylamine, di-n-hexylamine, triethylamine, tri-n-propylamine, tri-n-butylamine, dimethyl-n-butylamine, dimethyl-n-pentylamine, N,N,N',N'-tetramethyl-1,3-diaminopropane and N,N'-di-tert-butylethylenediamine.

[0028] Furthermore, the molar ratio of the copper salt to the phenol monomer is 0.004-1.7:100; the molar ratio of the amine compound to the copper salt is 10-100:1, preferably 20-60:1.

[0029] Furthermore, the polyarylene ether good solvent can be selected conventionally in the art, for example, one or more organic solvents selected from benzene, toluene, xylene, chloroform, tetrahydrofuran, etc., preferably toluene.

[0030] Furthermore, the reaction temperature of the oxidative polymerization is 35-45°C.

[0031] Furthermore, after the polymerization is completed, the reaction solution is treated with an aqueous solution containing a copper ion chelating agent to remove copper ions, and then washed with an alcohol aqueous solution. Wherein, the copper ion chelating agent is one or more selected from EDTA, EDTA-2Na, EDTA-3Na, EDTA-4Na, sodium citrate and trisodium nitrilotriacetate.

[0032] In a specific embodiment of the present invention, the preparation method comprises the following steps:

[0033] Step 1, washing the dihydroxy-terminated polyarylene ether reaction solution with an alcohol aqueous solution;

[0034] Step 2, taking the organic phase, adding a catalyst and an end-capping modifier to react;

[0035] Step 3: After the reaction is completed, the reaction solution is washed with hot water, and the organic phase is concentrated under negative pressure to obtain a concentrated solution with a solid content of 65-70wt%;

[0036] Step 4: using a poor solvent for polyarylene ether to precipitate the concentrated solution, filter and dry it to obtain alkenyl functionalized polyarylene ether.

[0037] According to the preparation method provided by the present invention, the catalyst is one or more of 4-dimethylaminopyridine, triethylamine, and dicyclohexylcarbodiimide, preferably 4-dimethylaminopyridine, and the mass of the catalyst is 1-10%, preferably 3-5%, of the polyarylene ether.

[0038] According to the preparation method provided by the present invention, the end-capping modifier is a methacrylic acid compound, such as methacrylic anhydride, methacrylic acid, methacrylic acid chloride, etc., preferably methacrylic anhydride. Further, the molar ratio of the end-capping modifier to the hydroxyl content of the polyarylene ether is (1-3):1, preferably (1-1.5):1.

[0039] After the methacrylic acid end-capping modification, the obtained alkenyl functionalized polyarylene ether has the following structure:

[0040]

[0041] In the formula, each letter refers to the same as above.

[0042] Typically or preferably, the alkenyl functionalized poly(arylene ether) has the following structure:

[0043]

[0044] Wherein, m, p and W have the same meaning as above.

[0045] According to the preparation method provided by the present invention, the reaction temperature is 50-100° C. and the reaction time is 4-10 h; preferably, the reaction temperature is 70-90° C. and the reaction time is 5-8 h.

[0046] According to the preparation method provided by the present invention, in step 3, the temperature of the hot water is 40-60° C., preferably 50° C. The pressure of the negative pressure concentration is -70 to -90 kPa, preferably -80 kPa.

[0047] According to the preparation method provided by the present invention, in step 4, the polyarylene ether poor solvent can be selected from conventional ones in the art, for example, C1-C5 alcohol or a mixed solvent thereof, wherein methanol is preferred.

[0048] In a second aspect, the present invention provides an alkenyl functionalized polyarylene ether prepared by any of the above preparation methods, and having a double bond content of 1.8-2.1 mmol / g.

[0049] The present invention abandons the existing method of using double-terminal hydroxyl polyarylene ether resin powder as raw material for end group modification, and uses double-terminal hydroxyl polyarylene ether reaction liquid washed with alcohol water for end group modification, and the double bond content (i.e., active group content) of the obtained alkenyl functionalized polyarylene ether can be increased to 1.8-2.1mmol / g. Moreover, the residual content of polar small molecular substances such as monophenol, diphenol, quinone, amine, etc. in the obtained alkenyl functionalized polyarylene ether product is lower.

[0050] In a third aspect, the present invention provides a resin composition comprising the alkenyl-functionalized poly(arylene ether).

[0051] The alkenyl functionalized polyarylene ether product obtained by the present invention has a higher curing crosslinking density with other resins. Therefore, a resin composition comprising the alkenyl functionalized polyarylene ether and other resins such as epoxy and cyanate ester can be provided for use in the preparation of copper clad laminates.

[0052] It is understandable that the resin composition includes not only a resin matrix but also other auxiliary materials known in the art such as a hardener.

[0053] In a fourth aspect, the present invention provides a copper-clad laminate comprising a substrate and a copper material loaded on the substrate, wherein the substrate comprises a base fabric and the above-mentioned resin composition coated on the base fabric.

[0054] Preferably, the base fabric is glass fiber cloth, woven fabric or non-woven fabric, more preferably glass fiber cloth.

[0055] Since the resin composition contains alkenyl-functionalized polyarylene ether with a higher curing crosslinking density with other resins and a higher active group content, the thermal and electrical properties of the copper-clad laminate prepared by applying the resin composition to the copper-clad laminate are better.

[0056] The present invention provides an alkenyl functionalized polyarylene ether and a preparation method and application thereof. The end groups of the double-terminated hydroxyl polyarylene ether reaction liquid after washing with alcohol water are directly modified to prepare an alkenyl modified polyarylene ether with better performance, a higher content of active groups (double bonds) of 1.8-2.1 mmol / g, a lower residual amount of polar small molecular substances such as monophenol, diphenol, quinone, amine, etc., a higher curing crosslinking density with other resins, and a prepared copper clad laminate with better thermal and electrical properties. In addition, the preparation method can effectively save energy-consuming processes such as devolatilization, extrusion or precipitation drying, and solvent recovery in the post-treatment of the double-terminated hydroxyl polyarylene ether. Compared with the traditional preparation method of alkenyl functionalized polyarylene ether, the present invention reduces the production process flow, reduces the generation of hazardous waste, and conforms to the green and environmentally friendly production concept. BRIEF DESCRIPTION OF THE DRAWINGS

[0057] Figure 1 GC-MS test spectra of Example 1 (bottom) and Comparative Example 4 (top);

[0058] Figure 2 It is the nuclear magnetic hydrogen spectrum of the double bond content determined by the internal standard method in Example 2. DETAILED DESCRIPTION

[0059] In order to make the purpose, technical solution and advantages of the present invention clearer, the technical solution of the present invention will be described clearly and completely below. Obviously, the described embodiments are part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0060] If no specific technology or conditions are specified in the examples, the technology or conditions described in the literature in the field or the product instructions are used. The reagents or instruments used without indicating the manufacturer are all conventional products that can be purchased through regular channels.

[0061] The test instruments and methods involved in the following examples and comparative examples are as follows:

[0062] Test equipment:

[0063] (1) Nuclear magnetic resonance analyzer: AVANCE III 400M NMR, Bruker, Switzerland;

[0064] (2) Differential scanning calorimeter: TA company, DSC25;

[0065] (3) Thermogravimetric analyzer: NETZSCH Instrument Manufacturing Co., Ltd., Germany, TG 209F1 Libra;

[0066] (4) Fourier transform infrared spectrometer: Thermo Fisher Scientific, NICOLET iS20;

[0067] (5) UV-visible spectrophotometer: Shimadzu, UV-2450;

[0068] (6) TMA tester: Hitachi High-Tech Analytical Science Co., Ltd., TMA7300;

[0069] (7) GC-MS: Agilent Technologies, 8890.

[0070] Test method:

[0071] 1. Test method for active group (double bond) content

[0072] Preparation of internal standard solution: Separately measure 0.15 g (± 0.001 g) of DMF and 6.00 g of DCCl3, mix well to make DMF internal standard solution, and store in a sealed container.

[0073] Preparation of the sample solution to be tested: 0.35 g (±0.001 g) of olefin-modified polyarylene ether resin and 6.00 g of DCCl3 were measured respectively, mixed to form an olefin-modified polyphenylene ether DCCl3 solution, and stored in a sealed container.

[0074] Preparation of sample solution: Use a microsyringe to accurately transfer 200 μL of DMF internal standard solution and 100 μL of the sample solution to be tested into an NMR tube, accurately weigh its mass to 0.100 mg, and finally add 200 μL of DDCl3 and mix well, and measure with an NMR analyzer.

[0075] Calculation method:

[0076]

[0077] W——Ratio of the molar number of double bonds in polyphenylene ether to the mass of the added internal standard substance;

[0078] A β ——The average value of the integrated area of ​​hydrogen on the double bond in the H NMR spectrum;

[0079] A D ——Protons in internal standard 1 The integrated area of ​​H;

[0080] M D ——molar mass of the internal standard, g / mol;

[0081] X D ——As a reference in the molecular structure of the internal standard 1 The number of H;

[0082]

[0083] C——double bond content of polyphenylene ether, mol / g;

[0084] m D ——Mass of internal standard, mg;

[0085] m p ——Mass of polyphenylene ether sample, mg.

[0086] 2. Test method for residual impurities

[0087] GC-MS scanning program: initial temperature 40 °C, heating rate 20 °C / min, heating to 300 °C, and keeping constant temperature for 5 min.

[0088] 3. Delamination time (T300) test method

[0089] The sample size is approximately 6.35 mm × 6.35 mm × sample thickness.

[0090] Sample preparation: Use sandpaper or other effective tools to smooth the edges of the sample (make sure the sample is completely flat on the test platform). Pre-bake at 105±2℃ [221±3.6℉] for two hours, then cool to room temperature in a drying dish.

[0091] Measurement: Take the sample out of the desiccator and place it in the middle of the TMA platform, making sure that the sample is flat. Press the TMA probe and place it on the sample, applying a load of 0.005N [5g]. The initial temperature is 35℃ [95℉], the heating rate is 10℃ / min, and after heating to a constant temperature of 300℃, keep it for 10 minutes, and determine the time it takes for the sample to undergo an irreversible thickness change, i.e., delamination.

[0092] 4. Test method for thermal decomposition temperature of laminate materials

[0093] Place the sample in a thermogravimetric analyzer and weigh it. Heat the sample at a rate of 20°C / min from room temperature (not exceeding 50°C) to 400°C. Record the temperature at which the sample weight decreases by 2% compared to the weight measured at 50°C, i.e., Td(2%).

[0094] 5. Test method for glass transition temperature of plate

[0095] The test was carried out using a differential scanning calorimeter, in which the scanning procedure was as follows: initial temperature 40°C, heating rate of 10°C / min, heating to 180°C, and keeping constant temperature for 5 minutes; cooling rate of 20°C / min, cooling to 75°C, and keeping constant temperature for 5 minutes; heating rate of 10°C / min, heating to 200°C.

[0096] Example 1

[0097] This embodiment provides a thermosetting alkenyl-functionalized polyarylene ether, and the preparation method thereof is as follows:

[0098] (I) Synthesis of double-terminated hydroxyl polyarylene ether

[0099] 1) 2,6-dimethylphenol (DMP) 6.5kg, tetramethylbisphenol F (TMBPF) 1.1

[0100] kg and 22.4 kg of toluene were stirred and dissolved to obtain a monomer solution.

[0101] 2) Pre-add 10 kg of monomer solution, 400 kg of toluene and 0.4 kg of copper amine catalyst into the polymerization kettle and stir evenly.

[0102] 3) Continuously add the remaining monomer solution, introduce oxygen into the bottom of the kettle, introduce nitrogen into the upper gas phase space, and control the temperature in the kettle at 35-45°C.

[0103] 4) After the polymerization is completed, 0.3 kg of chelating agent sodium ethylenediaminetetraacetate (10% aqueous solution) is added.

[0104] 5) Add 50 kg of 20% wt methanol aqueous solution and stir at 45° C. for 15 min at a rotation speed of 80 rpm.

[0105] 6) After standing, take the upper organic phase, ie, the toluene solution of the double-terminated hydroxyl polyarylene ether.

[0106] (II) Synthesis of olefin-functionalized polyphenylene ether from synthesized double-terminated hydroxyl polyarylene ether

[0107] 1) The synthesized double-terminated hydroxyl polyarylene ether toluene solution, 1 kg of 4-dimethylaminopyridine and 5 kg of methacrylic anhydride were placed in a reaction kettle, the temperature was raised to 90° C., and the reaction was completed after 6 hours.

[0108] 2) Wash the reaction solution with hot water at 50°C, and concentrate the organic phase under negative pressure to a solid content of 65-70 wt%.

[0109] 3) Methanol is used as the precipitation solvent, and the precipitation ratio, i.e. the mass ratio of methanol to the concentrated liquid, is 1:8.

[0110] 4) The precipitated slurry is sent into a filtering device to separate the precipitated filtrate, and the filter cake is dried to obtain the alkenyl functionalized polyarylene ether.

[0111] The yield of the product in this example is 87% (based on the theoretical yield of complete monomer reaction, the same below), the quinone content is 27ppm, and the double bond content is 1.85mmol / g. Figure 1From the GC-MS spectrum shown, it can be observed that the contents of monophenol and diphenol with peak times of 6.24min and 7.59min are significantly reduced, and the contents of organic amines with peak times of 9.98min and 14.45min are also significantly reduced.

[0112] Example 2

[0113] According to the preparation method of Example 1, tetramethyl bisphenol F was replaced by tetramethyl bisphenol A, and other operating conditions remained unchanged to prepare low molecular weight polyarylene ether.

[0114] The product yield of this example is 87%, the quinone content is 25 ppm, and the double bond content is 1.9 mmol / g.

[0115] Among them, the nuclear magnetic hydrogen spectrum for testing the double bond content is as follows Figure 2 As shown, according to the calculation formula:

[0116]

[0117]

[0118] Example 3

[0119] According to the preparation method of Example 1, the concentration of the alcohol aqueous solution was adjusted to 30 wt % and the other operating conditions remained unchanged to prepare low molecular weight polyarylene ether.

[0120] 1) 6.5 kg of 2,6-dimethylphenol (DMP), 1.1 kg of tetramethylbisphenol F (TMBPF), and 22.4 kg of toluene were stirred and dissolved to obtain a monomer solution.

[0121] 2) Pre-add 10 kg of monomer solution, 400 kg of toluene and 0.4 kg of copper amine catalyst into the polymerization kettle and stir evenly.

[0122] 3) Continuously add the remaining monomer solution, introduce oxygen into the bottom of the kettle, introduce nitrogen into the upper gas phase space, and control the temperature in the kettle at 35-45°C.

[0123] 4) After the polymerization is completed, 0.3 kg of chelating agent sodium ethylenediaminetetraacetate (10% aqueous solution) is added.

[0124] 5) Add 50 kg of 30% wt methanol aqueous solution and stir at 45° C. for 15 min at a rotation speed of 80 rpm.

[0125] 6) After standing, take the upper organic phase, ie, the toluene solution of the double-terminated hydroxyl polyarylene ether.

[0126] 7) The synthesized double-terminated hydroxyl polyarylene ether toluene solution, 1 kg of 4-dimethylaminopyridine and 5 kg of methacrylic anhydride were placed in a reaction kettle, the temperature was raised to 90° C., and the reaction was completed after 6 hours.

[0127] 8) Wash the reaction solution with hot water at 40°C, and concentrate the organic phase under negative pressure to a solid content of 65-70 wt%.

[0128] 9) Methanol is used as the precipitation solvent, and the precipitation ratio, i.e. the mass ratio of methanol to the concentrated liquid, is 1:8.

[0129] 10) The precipitated slurry is pumped into a filtering device to separate the filtrate, and the filter cake is dried to obtain the alkenyl-functionalized polyarylene ether.

[0130] The product yield of this example is 80%, the quinone content is 40 ppm, and the double bond content is 1.79 mmol / l.

[0131] Comparative Example 1

[0132] According to the preparation method of Example 1, conventional double-terminated hydroxyl polyarylene ether powder is used as a raw material for end group modification. The preparation method is as follows:

[0133] (I) Synthesis of double-terminated hydroxyl polyarylene ether powder

[0134] 1) 6.5 kg of 2,6-dimethylphenol (DMP), 1.1 kg of tetramethylbisphenol F (TMBPF), and 22.4 kg of toluene were stirred and dissolved to obtain a monomer solution.

[0135] 2) Pre-add 10 kg of monomer mixed solution, 400 kg of toluene solvent and 0.4 kg of copper amine catalyst into the polymerization kettle and stir evenly.

[0136] 3) Continuously add the remaining monomer mixed solution, introduce oxygen into the bottom of the kettle, introduce nitrogen into the upper gas phase space, and control the temperature in the kettle at 35-45°C.

[0137] 4) After the polymerization is completed, 0.3 kg of chelating agent sodium ethylenediaminetetraacetate (10% aqueous solution) is added.

[0138] 5) Add 50 kg of deionized water and stir at 45°C for 15 min at a rotation speed of 80 rpm.

[0139] 6) The upper organic phase was taken, heated under negative pressure to remove toluene, and concentrated to a solid content of 65-70 wt%.

[0140] 7) Methanol is used as the precipitation solvent, and the precipitation ratio, i.e. the mass ratio of methanol to the concentrated liquid, is 1:6.

[0141] 8) The precipitated slurry is pumped into a filtering device to separate the precipitated filtrate, and the filter cake is dried to obtain a double-terminated hydroxyl polyarylene ether powder.

[0142] (II) Synthesis of olefin-functionalized polyphenylene ether from double-terminated hydroxyl polyarylene ether

[0143] 1) Take the synthesized double-terminated hydroxyl polyarylene ether powder and 20 kg of toluene into a reaction kettle and stir until the powder is completely dissolved.

[0144] 2) Add 1 kg of 4-dimethylaminopyridine and 5 kg of methacrylic anhydride, raise the temperature to 90°C, and time the reaction for 6 hours.

[0145] 3) Wash the reaction solution with hot water at 50°C, and take the organic phase for negative pressure concentration to a solid content of 65-70 wt%.

[0146] 4) Methanol is used as the precipitation solvent, and the precipitation ratio, i.e. the mass ratio of methanol to the concentrated liquid, is 1:8.

[0147] 5) The precipitated slurry is pumped into a filtering device to separate the filtrate, and the filter cake is dried to obtain the alkenyl-functionalized polyarylene ether.

[0148] In the preparation process of the comparative example product, the dihydroxy-terminated polyarylene ether synthesis stage consumed 100 kg of methanol and produced 50 kg of waste water, with a yield of 81%, a quinone content of 29 ppm, and a double bond content of 1.21 mmol / g.

[0149] Comparative Example 2

[0150] According to the preparation method of Example 2, the double-terminated hydroxyl polyarylene ether powder using tetramethyl bisphenol A as an intermediate is used as a raw material for end group modification, and the preparation method is as follows:

[0151] (I) Synthesis of dihydroxy-terminated polyarylene ether powder using tetramethyl bisphenol A as an intermediate

[0152] 1) 6.5 kg of 2,6-dimethylphenol (DMP), 1.2 kg of tetramethylbisphenol A (TMBPA), and 22.4 kg of toluene were stirred and dissolved to obtain a monomer solution.

[0153] 2) Pre-add 10.0 kg of monomer mixed solution, 400 kg of toluene solvent and 0.4 kg of copper amine catalyst into the polymerization kettle and stir evenly.

[0154] 3) Continuously add the remaining monomer mixed solution, introduce oxygen into the bottom of the kettle, introduce nitrogen into the upper gas phase space, and control the temperature in the kettle at 35-45°C.

[0155] 4) After the polymerization is completed, 0.3 kg of chelating agent sodium ethylenediaminetetraacetate (10% aqueous solution) is added.

[0156] 5) Add 50 kg of deionized water and stir at 45°C for 15 min at a rotation speed of 80 rpm.

[0157] 6) The upper organic phase was taken, heated under negative pressure to remove benzene, and concentrated to a solid content of 65-70 wt%.

[0158] 7) Methanol is used as the precipitation solvent, and the precipitation ratio, i.e. the mass ratio of methanol to the concentrated liquid, is 1:6.

[0159] 8) The precipitated slurry is pumped into a filtering device to separate the precipitated filtrate, and the filter cake is dried to obtain a double-terminated hydroxyl polyarylene ether powder.

[0160] (II) Synthesis of olefin-functionalized polyphenylene ether from synthesized double-terminated hydroxyl polyphenylene ether powder

[0161] 1) Take the synthesized double-terminated hydroxyl polyarylene ether powder into a reaction kettle, add 20 kg of toluene to completely dissolve the powder.

[0162] 2) Add 1 kg of 4-dimethylaminopyridine and 5 kg of methacrylic anhydride, raise the temperature to 90°C, and time for 6 hours. The reaction is complete.

[0163] 3) Wash the reaction solution with hot water at 50°C, take the organic phase, and concentrate it under negative pressure to a solid content of 65-70 wt%.

[0164] 4) Methanol is used as the precipitation solvent, and the precipitation ratio, i.e. the mass ratio of methanol to the concentrated liquid, is 1:8.

[0165] 5) The precipitated slurry is pumped into a filtering device to separate the filtrate, and the filter cake is dried to obtain the alkenyl-functionalized polyarylene ether.

[0166] In the preparation process of this comparative example, the dihydroxy-terminated polyarylene ether synthesis section consumed 100 kg of methanol and produced 50 kg of waste water. The product yield was 83%, the quinone content was 27 ppm, and the double bond content was 1.35 mmol / g.

[0167] Comparative Example 3

[0168] According to the preparation method of Example 1, the double-terminated hydroxyl polyarylene ether powder washed with alcohol water is used as a raw material for end group modification. The preparation method is as follows:

[0169] (I) Synthesis of double-terminated hydroxyl polyarylene ether powder

[0170] 1) 6.5 kg of 2,6-dimethylphenol (DMP), 1.1 kg of tetramethylbisphenol F (TMBPF), and 22.4 kg of toluene were stirred and dissolved to obtain a monomer solution.

[0171] 2) Pre-add 10 kg of monomer mixed solution, 400 kg of toluene solvent and 0.4 kg of copper amine catalyst into the polymerization kettle and stir evenly.

[0172] 3) Continuously add the remaining monomer mixed solution, introduce oxygen into the bottom of the kettle, introduce nitrogen into the upper gas phase space, and control the temperature in the kettle at 35-45°C.

[0173] 4) After the polymerization is completed, 0.3 kg of chelating agent sodium ethylenediaminetetraacetate (10% aqueous solution) is added.

[0174] 5) Add 50 kg of 20 wt % methanol aqueous solution, and stir at 45° C. for 15 min at a rotation speed of 80 rpm.

[0175] 6) The upper organic phase was taken, heated under negative pressure to remove toluene, and concentrated to a solid content of 65-70 wt%.

[0176] 7) Methanol is used as the precipitation solvent, and the precipitation ratio, i.e. the mass ratio of methanol to the concentrated liquid, is 1:6.

[0177] 8) The precipitated slurry is pumped into a filtering device to separate the precipitated filtrate, and the filter cake is dried to obtain a double-terminated hydroxyl polyarylene ether powder.

[0178] (II) Synthesis of olefin-functionalized polyphenylene ether from double-terminated hydroxyl polyarylene ether

[0179] 1) Take the synthesized double-terminated hydroxyl polyarylene ether powder and 20 kg of toluene into a reaction kettle and stir until the powder is completely dissolved.

[0180] 2) Add 1 kg of 4-dimethylaminopyridine and 5 kg of methacrylic anhydride, raise the temperature to 90°C, and time the reaction for 6 hours.

[0181] 3) Wash the reaction solution with hot water at 50°C, and take the organic phase for negative pressure concentration to a solid content of 65-70 wt%.

[0182] 4) Methanol is used as the precipitation solvent, and the precipitation ratio, i.e. the mass ratio of methanol to the concentrated liquid, is 1:8.

[0183] 5) The precipitated slurry is pumped into a filtering device to separate the filtrate, and the filter cake is dried to obtain the alkenyl-functionalized polyarylene ether.

[0184] In the preparation process of the comparative example product, the dihydroxy-terminated polyarylene ether synthesis stage consumed 110 kg of methanol and produced 40 kg of waste water, with a yield of 82%, a quinone content of 31 ppm, and a double bond content of 1.28 mmol / g.

[0185] Comparative Example 4

[0186] According to the preparation method of Example 1, deionized water was used to wash the reaction solution, and other operating conditions remained unchanged to prepare low molecular weight polyarylene ether.

[0187] 1) 6.5 kg of 2,6-dimethylphenol (DMP), 1.1 kg of tetramethylbisphenol F (TMBPF), and 22.4 kg of toluene were stirred and dissolved to obtain a monomer solution.

[0188] 2) Pre-add 10 kg of monomer solution, 400 kg of toluene and 0.3 kg of copper amine catalyst into the polymerization kettle and stir evenly.

[0189] 3) Continuously add the remaining monomer solution, introduce oxygen into the bottom of the kettle, introduce nitrogen into the upper gas phase space, and control the temperature in the kettle at 35-45°C.

[0190] 4) After the polymerization is completed, 0.4 kg of chelating agent sodium ethylenediaminetetraacetate (10% aqueous solution) is added.

[0191] 5) Add 50 kg of deionized water and stir at 45°C for 15 min at a speed of 80 rpm.

[0192] 6) After standing, take the upper organic phase, ie, the toluene solution of the double-terminated hydroxyl polyarylene ether.

[0193] 7) The synthesized double-terminated hydroxyl polyarylene ether toluene solution, 1 kg of 4-dimethylaminopyridine and 5 kg of methacrylic anhydride were placed in a reaction kettle, the temperature was raised to 90° C., and the reaction was completed after 6 hours.

[0194] 8) Wash the reaction solution with hot water at 40°C, and concentrate the organic phase under negative pressure to a solid content of 65-70 wt%.

[0195] 9) Methanol is used as the precipitation solvent, and the precipitation ratio, i.e. the mass ratio of methanol to the concentrated liquid, is 1:8.

[0196] 10) The precipitated slurry is pumped into a filtering device to separate the filtrate, and the filter cake is dried to obtain the alkenyl-functionalized polyarylene ether.

[0197] The product yield of this comparative example is 85%, the quinone content is 68 ppm, and the double bond content is 1.82 mmol / g.

[0198] from Figure 1 The GC-MS spectrum shown shows that the alcohol-water washing step can effectively remove impurities. That is, the quinone content of Example 1 (27 ppm) is significantly lower than that of Comparative Example 4 (68 ppm).

[0199] In addition, the double bond content in this comparative example is 1.82 mmol / g, which is equivalent to that in Example 1. The inventors speculate that this is because the reaction solution is directly modified instead of precipitating a solid product and then dissolving it, and the reaction solution contains low molecular weight oligomers that are easy to accept double bonds.

[0200] Comparative Example 5

[0201] According to the preparation method of Example 1, the concentration of the alcohol aqueous solution was adjusted to 35 wt % and the other operating conditions remained unchanged to prepare low molecular weight polyarylene ether.

[0202] 1) 6.5 kg of 2,6-dimethylphenol (DMP), 1.1 kg of tetramethylbisphenol F (TMBPF), and 22.4 kg of toluene were stirred and dissolved to obtain a monomer solution.

[0203] 2) Pre-add 10 kg of monomer solution, 400 kg of toluene and 0.4 kg of copper amine catalyst into the polymerization kettle and stir evenly.

[0204] 3) Continuously add the remaining monomer solution, introduce oxygen into the bottom of the kettle, introduce nitrogen into the upper gas phase space, and control the temperature in the kettle at 35-45°C.

[0205] 4) After the polymerization is completed, 0.3 kg of chelating agent sodium ethylenediaminetetraacetate (10% aqueous solution) is added.

[0206] 5) Add 50 kg of 35% wt methanol aqueous solution and stir at 45° C. for 15 min at a rotation speed of 80 rpm.

[0207] 6) After standing, take the upper organic phase, ie, the toluene solution of the double-terminated hydroxyl polyarylene ether.

[0208] 7) The synthesized double-terminated hydroxyl polyarylene ether toluene solution, 1 kg of 4-dimethylaminopyridine and 5 kg of methacrylic anhydride were placed in a reaction kettle, the temperature was raised to 90° C., and the reaction was completed after 6 hours.

[0209] 8) Wash the reaction solution with hot water at 40°C, and concentrate the organic phase under negative pressure to a solid content of 65-70 wt%.

[0210] 9) Methanol is used as the precipitation solvent, and the precipitation ratio, i.e. the mass ratio of methanol to the concentrated liquid, is 1:8.

[0211] 10) The precipitated slurry is pumped into a filtering device to separate the filtrate, and the filter cake is dried to obtain the alkenyl-functionalized polyarylene ether.

[0212] The product yield of this comparative example is 65%, the quinone content is 52 ppm, and the double bond content is 0.95 mmol / g.

[0213] Comparative Example 6

[0214] This comparative example provides a functionalized polyphenylene ether according to the preparation method of Example 2 in CN109836575A.

[0215] (I) First synthesize double-terminated hydroxyl polyphenylene ether

[0216] 1) Take 60 kg of methanol, 50 kg of DMP, 5 kg of tetramethyl bisphenol A and 5 kg of diallyl bisphenol A, and stir until they are completely dissolved.

[0217] 2) Add 40 kg of methanol, 0.25 kg of cuprous chloride, and 20 kg of pyridine into the reactor at the same time, introduce air into the fixed gas distribution device at the bottom of the reactor while stirring, and introduce N2 into the gas phase space above the reactor at the same time, maintain the pressure of the reactor at 0.4 MPa (gauge pressure) and the temperature at 20°C; start timing for 30 minutes from the start of air introduction to allow the system in the reactor to be fully pre-oxidized;

[0218] 3) After the pre-oxidation is completed, the DMP / tetramethylbisphenol A / diallyl bisphenol A methanol solution in the dissolution kettle is added to the reaction kettle using a metering pump with a controlled time of 2 hours.

[0219] 4) After the addition is completed, the reaction is continued at 20°C for 3.5 hours. As the reaction proceeds, the generated product is continuously precipitated from methanol and dispersed in methanol.

[0220] 5) After the reaction is completed, close the air system valve and use N2 to maintain normal pressure.

[0221] 6) Vacuum filtration to obtain the dihydroxy-terminated polyphenylene ether product.

[0222] (II) Synthesis of methacrylate functionalized polyphenylene ether from synthesized double-terminated hydroxyl polyphenylene ether

[0223] 1) Add 50 kg of toluene and 16 kg of dihydroxy-terminated polyphenylene ether into a reaction kettle, heat to 40°C, and stir to completely dissolve.

[0224] 2) After complete dissolution, add 2.5 kg of triethylamine and 5 kg of methacrylic anhydride.

[0225] 3) Raise the temperature to 80°C and time the reaction for 5 hours, then the reaction is complete.

[0226] 4) The reacted solution was washed with deionized water until it became neutral.

[0227] 5) The washed solution is precipitated in methanol to obtain the methacrylate functionalized polyphenylene ether resin.

[0228] 6) Vacuum filter and dry the product to obtain the finished product.

[0229] The product yield of this comparative example is 80%, the quinone content is 26 ppm, and the double bond content is 1.27 mmol / g.

[0230] Application Examples

[0231] At room temperature, 150 parts by weight of highly brominated epoxy resin (Hexion5230), 100 parts by weight of bisphenol A cyanate (Mitsubishi Gas, Japan), 30 parts by weight of methyl methacrylate polyphenylene ether prepared in Example 1, 25 parts by weight of hardener diaminodiphenyl sulfone, 0.1 parts by weight of hardening accelerator 2-methylimidazolyl, and 200 parts by weight of cyclohexanone were added into a stirrer, and the mixture was mixed and stirred for 2-5 hours to obtain a resin composition.

[0232] The resin composition was coated on 7628 glass fiber cloth by a roller coater, with the weight ratio of the resin composition to the glass fiber cloth being 42%, and then heated and dried at 170-180°C for 2-5 minutes to prepare a semi-hardened prepreg. Eight sheets of prepreg were laminated, and a 1-ounce copper foil was laminated on the outermost layers on both sides of the prepreg. The heat was raised from 2°C / min to 200°C and 25kg / cm 2 The laminate was prepared by hot pressing at a pressure of 90 min.

[0233] The methyl methacrylate polyphenylene ether in the resin composition was replaced with the modified polyphenylene ether products of each embodiment and comparative example, and laminates were prepared in the same manner. The delamination time (T300), thermal decomposition temperature Td (2%) and glass transition temperature T g , and the results are shown in the following table.

[0234] Table 1

[0235]

[0236]

[0237] From the above results, it can be seen that compared with the comparative example, the olefin-modified resin prepared in Examples 1-3 has a higher double bond content, a higher curing crosslinking density, and the prepared copper-clad laminate has better heat resistance and electrical properties. The results show that whether the intermediate is tetramethyl bisphenol A or tetramethyl bisphenol F, the product modified with the double-terminated hydroxyl polyarylene ether reaction liquid after washing with alcohol water has a much higher active group content than the product prepared by modifying the powder. Comparing the olefin-modified resins of Example 1 with Comparative Examples 4 and 5, the test results show that the alcohol-water washing step can more effectively remove polar small molecules such as amines and quinones that affect the electrical properties of the board. However, when the proportion of methanol in the alcohol-water washing liquid is too high, part of the polymer will precipitate, forming flocs, reducing the washing effect, and increasing the product loss rate. It is preferred that the methanol aqueous solution with a mass concentration of 20wt% is used to wash the double-terminated hydroxyl polyarylene ether reaction liquid.

[0238] In addition, the preparation method of directly using the treated double-terminated polyarylene ether reaction liquid as a raw material for end group modification saves the subsequent energy-consuming steps of devolatilization, extrusion or precipitation drying, solvent recovery, etc. compared with the conventional synthesis of double-terminated hydroxyl polyarylene ether resin powder for modification.

[0239] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit it. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that they can still modify the technical solutions described in the aforementioned embodiments, or make equivalent replacements for some of the technical features therein. However, these modifications or replacements do not deviate the essence of the corresponding technical solutions from the spirit and scope of the technical solutions of the embodiments of the present invention.

Claims

1. A method for preparing an alkenyl functionalized polyarylene ether, characterized in that: include: The dihydroxy-terminated polyarylene ether reaction liquid is washed with an alcohol aqueous solution, and an organic phase is taken. The organic phase is mixed with a catalyst and an end-capping modifier to react to prepare an olefin-functionalized polyarylene ether.

2. The method for preparing alkenyl functionalized polyarylene ether according to claim 1, characterized in that: The alcohol aqueous solution is a mixed solution of fatty alcohol and water, and the fatty alcohol accounts for 10-30% by weight of the alcohol aqueous solution; Preferably, the fatty alcohol is methanol or ethanol, and more preferably, the alcohol aqueous solution is a 20% methanol aqueous solution.

3. The method for preparing alkenyl functionalized polyarylene ether according to claim 1 or 2, characterized in that: The washing temperature is 30-55°C, preferably 40-50°C; And / or, the alcohol aqueous solution is used in an amount of 10-20% of the reaction solution.

4. The method for preparing alkenyl functionalized polyarylene ether according to claim 1, characterized in that: The catalyst is one or more of 4-dimethylaminopyridine, triethylamine, and dicyclohexylcarbodiimide; And / or, the end-capping modifier is a methacrylic acid compound, preferably methacrylic anhydride.

5. The method for preparing alkenyl functionalized poly(arylene ether) according to claim 1, characterized in that: The reaction temperature is 50-100°C and the reaction time is 4-10h; Preferably, the reaction temperature is 70-90°C and the reaction time is 5-8h.

6. The method for preparing an alkenyl functionalized polyarylene ether according to any one of claims 1 to 5, characterized in that: The double-terminated hydroxyl polyarylene ether has the following structure: Wherein, m and p are both integers greater than or equal to 0, and the range of m+p is 5 to 50; n is 0 or 1, and n cannot be 0 alone; R1-R8 are each independently selected from hydrogen, halogen, C1-C6 alkyl, halogenated alkyl or alkoxy; Y has the following structure: Wherein, X1-X8 are each independently selected from a hydrogen atom or a C1-C8 saturated or unsaturated hydrocarbon group; W represents a single bond or a C1-C4 alkylene group.

7. The method for preparing alkenyl functionalized polyarylene ether according to claim 1, characterized in that: The preparation of the double-terminated hydroxyl polyarylene ether reaction solution comprises: The reaction liquid is obtained after oxidative polymerization of phenol monomer in a good solvent of polyarylene ether in the presence of an oxidant and a copper amine catalyst.

8. The method for preparing an alkenyl functionalized poly(arylene ether) according to any one of claims 1 to 7, characterized in that: The following steps are involved: Step 1, washing the dihydroxy-terminated polyarylene ether reaction solution with an alcohol aqueous solution; Step 2, taking the organic phase, adding a catalyst and an end-capping modifier to react; Step 3: After the reaction is completed, the reaction solution is washed with hot water, and the organic phase is concentrated under negative pressure to obtain a concentrated solution with a solid content of 65-70wt%; Step 4: using a poor solvent for polyarylene ether to precipitate the concentrated solution, filter and dry it to obtain alkenyl functionalized polyarylene ether.

9. An alkenyl-functionalized poly(arylene ether), characterized in that: The compound is prepared by the preparation method according to any one of claims 1 to 8, and has a double bond content of 1.8 to 2.1 mmol / g.

10. A resin composition, characterized in that The invention comprises the alkenyl-functionalized polyarylene ether according to claim 9.

11. A copper clad laminate, characterized in that: It comprises a substrate and a copper material loaded on the substrate, wherein the substrate comprises a base fabric and the resin composition as claimed in claim 10 coated on the base fabric; Preferably, the base fabric is glass fiber cloth, woven fabric or non-woven fabric, more preferably glass fiber cloth.

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