End group functionalized polyphenyl ether modified polyurethane and preparation method thereof

Abstract

The invention discloses end group functionalized polyphenyl ether modified polyurethane and a preparation method thereof. The method comprises the following steps: preparing hydroxyethyl or amino-terminated polyphenyl ether by taking polyphenyl ether as a raw material; the hydroxyethyl or amino-terminated polyphenyl ether modified polyurethane is prepared by mixing hydroxyethyl or amino-terminated polyphenyl ether with a chain extender according to different proportions to obtain a mixed chain extender, and then carrying out chain extension reaction on the mixed chain extender and different polyurethane prepolymers. The preparation process is simple and easy to operate, and the obtained end group functionalized polyphenyl ether modified polyurethane has good dielectric property and hardness, is stable in property, and has great application potential in the fields of tires, pistons, electronics and the like.

Description

Technical Field

[0001] The invention belongs to the field of modified polyurethane, and particularly relates to terminal functionalized polyphenylene ether modified polyurethane and a preparation method thereof. Background Art

[0002] Polyurethane is a high-performance thermoplastic elastomer with the characteristics of rich synthetic raw materials, good chemical stability, strong designability and excellent resilience. After decades of development, it has been widely used in various fields of the national economy and military.

[0003] However, polyurethane also faces some unresolved issues in practical applications, such as poor dynamic mechanical properties and high-temperature resistance. Polyphenylene ether, on the other hand, possesses excellent physical and chemical properties, such as good heat resistance and a high glass transition temperature. Furthermore, polyphenylene ether has a low dielectric constant and dielectric loss, is virtually unaffected by temperature and humidity, and can be used in low, medium, and high-frequency electric fields. Therefore, its introduction into polyurethane systems is expected to yield even better performance.

[0004] Currently, there are few reports on methods for modifying polyphenylene ether to prepare polyurethanes. Previously, Shabit introduced polyphenylene ether (PPE-M) into EO / PO block polyethers and then reacted it with MDI under the catalysis of dibutyltin dilaurate to produce a new type of polyurethane. However, due to the phenolic hydroxyl groups at both ends of the polyphenylene ether, the urethane bonds formed by its reaction with isocyanate have poor thermal stability, resulting in a low thermal decomposition temperature and still poor performance. Furthermore, there are no literature or patent reports on methods for preparing modified polyurethanes using hydroxyethyl and amino-terminated polyphenylene ethers.

[0005] Therefore, it is urgent to propose a method that can solve the problems of poor dielectric properties, poor high temperature resistance, low hardness, etc. of traditional polyurethane materials, and improve the application ability of modified polyurethane in extreme environments. Summary of the Invention

[0006] In response to the above-mentioned problems in the prior art, the present inventors conducted intensive research and developed a polyurethane modified with end-group functionalized polyphenylene ether and a preparation method thereof. The modified polyurethane not only has the properties of general polyphenylene ether, such as high temperature resistance, low expansion coefficient, and low dielectric loss, but also has great rigidity due to the presence of a large number of benzene ring structures. In addition, its end-group functionalization provides the possibility of introducing engineering plastics in the preparation of polyurethane, giving polyurethane some properties of polyphenylene ether, thereby improving its application ability in extreme environments; the modified polyurethane also has good dielectric properties, which can also broaden the application of traditional polyurethane in the electronics field, such as electronic packaging, cable insulation and other fields. By introducing hydroxyethyl and amino-terminated polyphenylene ether into the polyurethane system to prepare the modified polyurethane, the problems of poor dielectric properties, poor high temperature resistance, low hardness and the like existing in traditional polyurethane materials are solved, and the application ability of the modified polyurethane in extreme environments is improved, thereby completing the present invention.

[0007] Therefore, one of the objects of the present invention is to provide a method for preparing end-functionalized polyphenylene ether modified polyurethane, which is prepared using hydroxyethyl terminated polyphenylene ether or amino terminated polyphenylene ether, a polyurethane prepolymer and a chain extender as raw materials.

[0008] The preparation method according to the present invention comprises the following steps: Step 1: Modifying polyphenylene ether to obtain hydroxyethyl and / or amino terminated polyphenylene ether; Step 2: mixing the modified polyphenylene ether terminated with hydroxyethyl and / or amino groups with a chain extender to obtain a mixed chain extender; Step 3: reacting the mixed chain extender with the polyurethane prepolymer, and aging the mixture to prepare a hydroxyethyl and / or amino-terminated polyphenylene ether modified polyurethane.

[0009] The hydroxyethyl terminated polyphenylene ether polyol (PPOD) can be represented by the following formula: Where, The value of x+y is 5 to 100, preferably 8 to 50, more preferably 10 to 20; The value of m+n is 1 to 50, preferably 2 to 20, more preferably 2 to 10; R is selected from one of hydrogen, alkyl and cycloalkyl, preferably selected from one of hydrogen and alkyl.

[0010] The amino-terminated polyphenylene ether diamine (APPO) can be represented by the following formula: In the formula, the value of x+y is 5 to 100, preferably 8 to 50, and more preferably 10 to 20.

[0011] The hydroxyethyl terminated polyphenylene ether polyol is prepared by reacting bihydroxy-terminated polyphenylene ether (PPO) with alkylene carbonate or epoxide in the presence of an alkaline catalyst. The amino-terminated polyphenylene ether polyol is prepared by reacting dihydroxylated polyphenylene ether (PPO) with halogenated nitrobenzene in the presence of an alkaline catalyst to prepare a nitroaromatic compound, which is then further hydrogenated under the action of a palladium-carbon catalyst to prepare an amino-terminated polyphenylene ether. Preferably, the double-terminated hydroxyl polyphenylene ether (PPO) is as shown below: The p-halogen nitrobenzene is selected from one or two of p-fluoronitrobenzene, p-chloronitrobenzene, p-iodine nitrobenzene and p-bromonitrobenzene.

[0012] In step 2 of the present invention, the chain extender is selected from one or more of 4,4'-methylenebis(2-chloroaniline) (MOCA), 1,4-bis(2-hydroxyethoxy)benzene (HQEE), 1,4-butanediol (BDO), diethyltoluenediamine (DETDA), dimethylthiotoluenediamine (DMTDA), and 4,4'-methylenebis(3-chloro-2,6-diethylaniline) (MCDEA).

[0013] In step 2, the temperature is 40-180° C., preferably 50-140° C., more preferably 60-120° C., and the equivalent ratio of the terminal functionalized polyphenylene ether in the mixed chain extender to the active hydrogen group of the chain extender is 1-500.

[0014] In step 3 of the present invention, the polyether or polyester diol in the prepolymer is selected from one or more of polyethylene glycol (PEG), polypropylene glycol (PPG), polytetramethylene ether (PTMEG), polycaprolactone diol (PCL), polycarbonate diol (PCD), polyethylene terephthalate (PET), polytrimethylene terephthalate (PTT), and polybutylene terephthalate (PBT), and / or The isocyanate in the prepolymer is selected from one or more of diphenylmethane diisocyanate (MDI), toluene diisocyanate (TDI), p-phenylene diisocyanate (PPDI), hexamethylene diisocyanate (HDI), m-phenylenediisocyanate (XDI), cyclohexane dimethylene diisocyanate (HXDI), cyclohexane-1,4-diisocyanate (CHDI) or dicyclohexylmethane diisocyanate (HMDI). Preferably, the prepolymer is selected from one or more prepolymers prepared from the polyether or polyester diol and the isocyanate.

[0015] In step 3, the chain extension reaction is carried out using a high-speed disperser with a stirring speed of 1000~3000r / min, a chain extension reaction temperature of 40~160°C, preferably 60~150°C, a chain extension time of 1~60min, preferably 1~30min, a aging temperature of 80~150°C, preferably 90~130°C, and a aging time of 10~30h, preferably 15~25h.

[0016] Another object of the present invention is to provide a terminal functionalized polyphenylene ether modified polyurethane, which is preferably prepared according to the above method. BRIEF DESCRIPTION OF THE DRAWINGS

[0017] Figure 1 This is the H NMR spectrum of the hydroxyethyl terminated polyphenylene ether prepared in Example 1; Figure 2 This is the H NMR spectrum of the nitro- and amino-terminated polyphenylene ether prepared in Example 2; Figure 3 IR spectra of the modified polyurethane strips prepared in Comparative Example 1 and Example 1; Figure 4 IR spectra of the modified polyurethane strips prepared in Comparative Example 2 and Example 6; Figure 5 IR spectra of the modified polyurethane strips prepared in Comparative Example 3 and Example 11; Figure 6 IR spectra of the modified polyurethane strips prepared in Comparative Example 4 and Example 16.

[0018] Figure 7 1 is the H-NMR spectrum of the modified polyurethane strips prepared in Comparative Example 3 and Example 11. DETAILED DESCRIPTION

[0019] The present invention will be described in further detail below with reference to preferred embodiments. The embodiments of the present invention include but are not limited to the scope represented by the following embodiments.

[0020] According to the present invention, a terminal functionalized polyphenylene ether modified polyurethane is provided. The modified polyurethane is prepared using hydroxyethyl terminated polyphenylene ether or amino terminated polyphenylene ether, a polyurethane prepolymer and a chain extender as raw materials.

[0021] According to the present invention, the hydroxyethyl terminated polyphenylene ether polyol (PPOD) can be represented by the following formula: Where, The value of x+y is 5 to 100, preferably 8 to 50, more preferably 10 to 20; The value of m+n is 1 to 50, preferably 2 to 20, more preferably 2 to 10; R is selected from one of hydrogen, alkyl and cycloalkyl, preferably selected from one of hydrogen and alkyl, more preferably selected from hydrogen or methyl.

[0022] According to the present invention, the amino-terminated polyphenylene ether diamine (APPO) can be represented by the following formula: Where, The value of x+y is 5-100, preferably 8-50, and more preferably 10-20.

[0023] Preferably, the average molecular weight of the hydroxyethyl or amino terminated polyphenylene ether is 1000-3000.

[0024] According to the present invention, the polyether or polyester diol in the prepolymer is selected from one or more of polyethylene glycol (PEG), polypropylene glycol (PPG), polytetramethylene glycol ether (PTMEG), polycaprolactone diol (PCL), polycarbonate diol (PCD), polyethylene terephthalate (PET), polytrimethylene terephthalate (PTT), and polybutylene terephthalate (PBT), preferably, selected from one or more of polyethylene glycol, polypropylene glycol, polytetramethylene glycol ether, polycaprolactone and polycarbonate diol, more preferably, selected from one or two of polypropylene glycol and polytetramethylene glycol ether.

[0025] The isocyanate in the prepolymer is selected from one or more of diphenylmethane diisocyanate (MDI), toluene diisocyanate (TDI), p-phenylene diisocyanate (PPDI), hexamethylene diisocyanate (HDI), meta-phenylenediisocyanate (XDI), cyclohexane dimethylene diisocyanate (HXDI), cyclohexane-1,4-diisocyanate (CHDI) or dicyclohexylmethane diisocyanate (HMDI), preferably selected from one or more of diphenylmethane diisocyanate, toluene diisocyanate, meta-phenylenediisocyanate and cyclohexane-1,4-diisocyanate, more preferably toluene diisocyanate.

[0026] The prepolymer is selected from one or more of the prepolymers prepared from the above-mentioned diols and diisocyanates, such as polypropylene glycol-toluene diisocyanate prepolymer (pre-PPG-TDI), polypropylene glycol-p-phenylene diisocyanate prepolymer (pre-PPG-PPDI), polypropylene glycol-diphenylmethane diisocyanate prepolymer (pre-PPG-MDI), polytetramethylene ether-diphenylmethane diisocyanate prepolymer (pre-PTMEG-MDI), polytetramethylene ether-toluene diisocyanate prepolymer (pre-PTMEG-TDI), polytetramethylene ether-p-phenylene diisocyanate prepolymer (pre-PTMEG-PPDI), polytetramethylene ether-m-phenylenediisocyanate prepolymer (pre-PTMEG-XDI), polycarbonate-diphenylmethane ... The invention further comprises one or more polyurethane prepolymers which can be prepared, such as polypropylene glycol-toluene diisocyanate (pre-PCD-MDI), polycarbonate-toluene diisocyanate (pre-PCD-TDI), polycaprolactone-diphenylmethane diisocyanate (pre-PCL-MDI), polycaprolactone-toluene diisocyanate (pre-PCL-TDI), polycaprolactone-p-phenylene diisocyanate (pre-PCL-PPDI), preferably one or more polypropylene glycol-p-phenylene diisocyanate prepolymer, polypropylene glycol-toluene diisocyanate prepolymer, polytetramethylene ether-p-phenylene diisocyanate prepolymer and polytetramethylene ether-toluene diisocyanate prepolymer, more preferably one or two polypropylene glycol-toluene diisocyanate prepolymer and polytetramethylene ether-toluene diisocyanate prepolymer.

[0027] The chain extender is selected from one or more of 4,4'-methylenebis(2-chloroaniline) (MOCA), 1,4-bis(2-hydroxyethoxy)benzene (HQEE), 1,4-butanediol (BDO), diethyltoluenediamine (DETDA), dimethylthiotoluenediamine (DMTDA), and 4,4'-methylenebis(3-chloro-2,6-diethylaniline) (MCDEA), preferably selected from one or more of 4,4'-methylenebis(2-chloroaniline), 1,4-butanediol, and 1,4-bis(2-hydroxyethoxy)benzene, and more preferably 4,4'-methylenebis(2-chloroaniline).

[0028] According to the present invention, the terminal functionalized polyphenylene ether modified polyurethane has a structure shown in the following formula (3) or (4): Formula (3) in, R1 is a PPOD providing unit; R2 is a diol providing unit; R3 is a diisocyanate providing unit; R4 is a chain extender providing unit; Formula (4) in, R1 is an APPO providing unit; R2 is a diol providing unit; R3 is a diisocyanate providing unit; and R4 is a chain extender providing unit.

[0029] According to the present invention, a method for preparing the terminal functionalized polyphenylene ether modified polyurethane is also provided, which is prepared using hydroxyethyl terminated polyphenylene ether or amino terminated polyphenylene ether, a polyurethane prepolymer and a chain extender.

[0030] According to a preferred embodiment of the present invention, the hydroxyethyl or amino-terminated polyphenylene ether is prepared using polyphenylene ether as a raw material, which is mixed with a chain extender in different ratios to obtain a mixed chain extender, which is then chain extended and aged with different polyurethane prepolymers to prepare a hydroxyethyl or amino-terminated polyphenylene ether modified polyurethane.

[0031] Specifically, the preparation method comprises the following steps: Step 1, modifying polyphenylene ether to obtain hydroxyethyl-terminated and amino-terminated polyphenylene ether; Step 2: mixing the modified polyphenylene ether terminated with hydroxyethyl and amino groups with a chain extender to obtain a mixed chain extender; Step 3: reacting the mixed chain extender with the polyurethane prepolymer, and preparing a polyurethane modified with hydroxyethyl and amino terminated polyphenylene ether through aging.

[0032] In step 1 of the present invention, hydroxyethyl-terminated polyphenylene ether, also known as hydroxyethyl-terminated polyphenylene ether polyol, is prepared by reacting dihydroxy-terminated polyphenylene ether (PPO) with alkylene carbonate or epoxide in the presence of a basic catalyst.

[0033] Preferably, the preparation is carried out by the following steps: Step a, reacting a dihydroxy-terminated polyphenylene ether and an alkylene carbonate or an epoxide in a solvent in the presence of a basic catalyst to obtain a reaction mixture; In step a, the alkaline catalyst is selected from one or more of an organic base, an alkali metal hydride, an alkali metal hydroxide, an alkali metal carbonate compound and an alkali metal bicarbonate compound.

[0034] The solvent is an organic solvent, preferably one or more selected from the group consisting of benzene, toluene, xylene, dichloromethane, chloroform, tetrahydrofuran, and N,N-dimethylformamide.

[0035] The alkylene carbonate is selected from one or more of ethylene carbonate (EC), propylene carbonate (PC), and butylene carbonate (BC), and is preferably selected from one or two of ethylene carbonate and propylene carbonate.

[0036] The epoxide is selected from one or more of ethylene oxide (EO), propylene oxide (PO), and butylene oxide (BO), and is preferably selected from one or two of ethylene oxide and propylene oxide.

[0037] The molar ratio of alkylene carbonate or epoxide to dihydroxy-terminated polyphenylene ether is (1-1000):1, preferably (1-500):1, and more preferably (2-100):1.

[0038] The molar ratio of the alkaline catalyst to the dihydroxy-terminated polyphenylene ether is (0.5-100):1, preferably (0.5-80):1, and more preferably (1-50):1.

[0039] The reaction temperature is 50-200°C, preferably 70-180°C, more preferably 90-150°C.

[0040] The reaction time is 1 to 100 hours, preferably 2 to 70 hours, and more preferably 2 to 50 hours.

[0041] Step b: The reaction mixture is precipitated, washed, filtered and dried to obtain a hydroxyethyl-terminated polyphenylene ether.

[0042] In step b, after stopping the reaction, a precipitant is added to the supernatant of the reaction mixture for precipitation, and the precipitant is preferably methanol.

[0043] A detergent is added to the precipitate for washing, and the detergent is preferably methanol.

[0044] Repeat the above washing and filtering steps multiple times, preferably 2 to 3 times, until no reaction solvent is left in the product, and finally vacuum dry it.

[0045] The drying temperature is 60-90° C., and the drying time is 15-30 hours.

[0046] In step 1 of the present invention, the amino-terminated polyphenylene ether is also called amino-terminated polyphenylene ether polyol, which uses dihydroxy-terminated polyphenylene ether (PPO) as a raw material, reacts with p-halogen nitrobenzene in the presence of an alkaline catalyst to prepare a nitroaromatic compound, and then further hydrogenates under the action of a palladium-carbon catalyst to prepare the amino-terminated polyphenylene ether.

[0047] Preferably, the preparation is carried out by the following steps: Step a: In the presence of a basic catalyst, a dihydroxy-terminated polyphenylene ether and a p-halogen nitrobenzene compound react in a solvent to obtain a nitrated polyphenylene ether.

[0048] In step a, the double-terminated hydroxyl polyphenylene ether (PPO) is as shown below: Where, The value of x+y is 5-100, preferably 8-50, and more preferably 10-20.

[0049] The p-halogen nitrobenzene is selected from one or two of p-fluoronitrobenzene, p-chloronitrobenzene, p-iodine nitrobenzene and p-bromonitrobenzene.

[0050] The molar ratio of p-halogen nitrobenzene to dihydroxy-terminated polyphenylene ether is (1-100):1, preferably (1-50):1, and more preferably (1-20):1.

[0051] The alkaline catalyst is selected from one or more of organic bases, alkali metal hydrides, alkali metal hydroxides, alkali metal carbonate compounds and alkali metal bicarbonate compounds.

[0052] The molar ratio of the alkaline catalyst to the dihydroxy-terminated polyphenylene ether is (0.5-100):1, preferably (1-60):1, and more preferably (1-20):1.

[0053] The solvent is an organic solvent, preferably one or more selected from the group consisting of benzene, toluene, xylene, dichloromethane, chloroform, tetrahydrofuran, N,N-dimethylformamide, and N,N-dimethylacetamide.

[0054] The reaction temperature is 20-200°C, preferably 40-160°C, more preferably 60-120°C.

[0055] The reaction time is 1 to 100 hours, preferably 2 to 50 hours, and more preferably 2 to 30 hours.

[0056] Step b: The reaction mixture is precipitated, washed, filtered and dried to obtain nitrated polyphenylene ether.

[0057] In step b, after stopping the reaction, a precipitant is added to the supernatant of the reaction mixture for precipitation, and the precipitant is preferably methanol.

[0058] A detergent is added to the precipitate for washing, and the detergent is preferably methanol.

[0059] Repeat the above washing and filtering steps multiple times, preferably 2 to 3 times, until no reaction solvent is left in the product, and finally vacuum dry it.

[0060] The drying temperature is 60-90° C., and the drying time is 15-30 h.

[0061] Step c: In the presence of a palladium-carbon catalyst, the nitrated polyphenylene ether is subjected to a hydrogenation reaction in a solvent in a high-temperature and high-pressure reactor to obtain an amino-terminated polyphenylene ether.

[0062] In step c, the solvent is an organic solvent, preferably one or more selected from tetrahydrofuran, chloroform, ethanol, water, toluene, xylene, dichloromethane, N,N-dimethylformamide, and N,N-dimethylacetamide.

[0063] The mass ratio of the palladium-carbon catalyst to the nitrated polyphenylene ether is 1:(10-500), preferably 1:(50-200), and more preferably 1:(80-150). The drying temperature is 60-90° C., and the drying time is 15-30 h. The pressure after hydrogenation is 0.05-5 MPa, preferably 0.4-2 MPa.

[0064] The reaction temperature is 40-180°C, preferably 60-140°C, more preferably 80-120°C.

[0065] The reaction time is 1 to 50 hours, preferably 2 to 30 hours, more preferably 2 to 15 hours.

[0066] Step d: The reaction mixture is precipitated, washed, filtered and dried to obtain amino-terminated polyphenylene ether.

[0067] In step d, after stopping the reaction, a precipitant is added to the supernatant of the reaction mixture for precipitation, and the precipitant is preferably methanol.

[0068] A detergent is added to the precipitate for washing, and the detergent is preferably methanol.

[0069] Repeat the above washing and filtering steps multiple times, preferably 2 to 3 times, until no reaction solvent is left in the product, and finally vacuum dry it.

[0070] The drying temperature is 60-90° C., and the drying time is 15-30 hours.

[0071] In step 2 of the present invention, the chain extender is selected from one or more of 4,4'-methylenebis(2-chloroaniline) (MOCA), 1,4-bis(2-hydroxyethoxy)benzene (HQEE), 1,4-butanediol (BDO), diethyltoluenediamine (DETDA), dimethylthiotoluenediamine (DMTDA), and 4,4'-methylenebis(3-chloro-2,6-diethylaniline) (MCDEA), preferably one or more of 4,4'-methylenebis(2-chloroaniline), 1,4-butanediol, and 1,4-bis(2-hydroxyethoxy)benzene, and more preferably 4,4'-methylenebis(2-chloroaniline).

[0072] Preferably, the mixed chain extender is prepared by melting the selected conventional chain extender into a liquid, and then adding the end-group functionalized polyphenylene ether in a specified equivalent ratio to fully mix and dissolve the mixture.

[0073] The preparation temperature is 40-180°C, preferably 50-140°C, more preferably 60-120°C.

[0074] The equivalent ratio of the terminal functionalized polyphenylene ether in the mixed chain extender to the active hydrogen groups of the selected chain extender is 1-500, preferably 1-300, and more preferably 1-100.

[0075] The equivalent ratio of the active hydrogen groups of the mixed chain extender to the isocyanate groups of the prepolymer is 0.9 to 1.5, preferably 1 to 1.2, and more preferably 1.02 to 1.05.

[0076] As the amount of end-functionalized polyphenylene ether added increases, the viscosity of the mixed chain extender also increases. In order to ensure that the two can be fully mixed and at the same time have a certain fluidity for subsequent chain extension, the mixed chain extender is prepared within the above temperature range.

[0077] In step 3 of the present invention, the prepolymer is selected from one or more of the prepolymers prepared from the above-mentioned diols and diisocyanates, such as polypropylene glycol-toluene diisocyanate prepolymer (pre-PPG-TDI), polypropylene glycol-p-phenylene diisocyanate prepolymer (pre-PPG-PPDI), polypropylene glycol-diphenylmethane diisocyanate prepolymer (pre-PPG-MDI), polytetramethylene ether-diphenylmethane diisocyanate prepolymer (pre-PTMEG-MDI), polytetramethylene ether-toluene diisocyanate prepolymer (pre-PTMEG-TDI), polytetramethylene ether-p-phenylene diisocyanate prepolymer (pre-PTMEG-PPDI), polytetramethylene ether-m-phenylenediisocyanate prepolymer (pre-PTMEG-XDI), polycarbonate-di ... The polyurethane prepolymer may be one or more of other preparable polyurethane prepolymers such as phenylmethane diisocyanate (pre-PCD-MDI), polycarbonate-toluene diisocyanate (pre-PCD-TDI), polycaprolactone-diphenylmethane diisocyanate (pre-PCL-MDI), polycaprolactone-toluene diisocyanate (pre-PCL-TDI), and polycaprolactone-p-phenylene diisocyanate (pre-PCL-PPDI), preferably one or more of polypropylene glycol-p-phenylene diisocyanate prepolymer, polypropylene glycol-toluene diisocyanate prepolymer, polytetramethylene ether-p-phenylene diisocyanate prepolymer, and polytetramethylene ether-toluene diisocyanate prepolymer, more preferably one or two of polypropylene glycol-toluene diisocyanate prepolymer and polytetramethylene ether-toluene diisocyanate prepolymer.

[0078] The equivalent ratio of the isocyanate groups of the prepolymer to the active hydrogen groups of the mixed chain extender is 0.9 to 1.5, preferably 1 to 1.2, and more preferably 1.02 to 1.05.

[0079] The chain extension reaction is carried out using a high-speed disperser, and the stirring speed is preferably 1000-3000 r / min.

[0080] The chain extension reaction temperature is 60 to 160°C, preferably 60 to 130°C, and more preferably 70 to 110°C.

[0081] The chain extension time is 1 to 60 minutes, preferably 1 to 30 minutes, and more preferably 1 to 10 minutes. Since the chain extension speed increases with increasing temperature, different chain extension times are selected.

[0082] The aging temperature is 80-150°C, preferably 90-130°C, and more preferably 100-120°C.

[0083] Aging can make the polymerization reaction more complete and the polymer molecular weight further increase, thereby making the polyurethane have higher mechanical strength.

[0084] The aging time is 10 to 30 hours, preferably 15 to 25 hours, and more preferably 20 to 25 hours.

[0085] The present inventors have found that adding end-group functionalized polyphenylene ether to the reaction system can improve the dielectric properties of the modified polyurethane, and as the amount of end-group functionalized polyphenylene ether added increases, the dielectric constant and dielectric loss of the modified polyurethane gradually decrease.

[0086] According to the present invention, the dielectric constant of the terminal functionalized polyphenylene ether modified polyurethane at 10 GHz is less than 2.22, and the dielectric loss is less than 0.05.

[0087] The beneficial effects of the present invention are: (1) The modified polyurethane of the present invention has excellent performance, good storage stability, dielectric properties, and high hardness.

[0088] (2) The hydroxyethyl and amino-terminated polyphenylene ether modified polyurethane prepared by the present invention provides a new idea for the modification of polyurethane materials, solving the problems of low hardness and poor dielectric properties of traditional polyurethane materials. It is expected to enhance the application capability of polyurethane materials in extreme environments, such as aerospace, automobiles, coatings, automobile pistons, etc. In addition, the polyurethane with improved dielectric properties can also be used in electronic packaging, cable insulation and other fields, broadening the application range of modified polyurethane.

[0089] (3) The modified polyurethane preparation method of the present invention does not require a catalyst, has a simple process flow, and can reduce production costs. Example

[0090] The present invention is further described below through specific examples. These examples are only intended to illustrate the present invention and are not intended to limit the scope of the present invention.

[0091] Preliminary Example 1 In a three-necked round-bottom flask equipped with a reflux condenser, 5.00 g (about 3.13 mmol) of double-terminated hydroxyl polyphenylene ether (PPO, purchased from Saudi Basic Industries (China) Co., Ltd., model No. Noryl SA90, molecular weight 1600, x+y=10), 0.55 g (about 6.25 mmol) of ethylene carbonate (EC) and 0.44 g (about 3.13 mmol) of K2CO3 were added to 25 mL of N,N-dimethylformamide (DMF), and the mixture was stirred and refluxed at 145 ° C for 3 h to stop the reaction.

[0092] The supernatant of the reaction mixture was dropped into anhydrous methanol for precipitation. The resulting off-white precipitate was further obtained by suction filtration, and the filter cake was washed with anhydrous methanol. Repeat the above vacuum filtration step and wash with anhydrous methanol 2 to 3 times until there is no reaction solvent in the product. Finally, the product was dried in a vacuum oven at 80 ° C for 24 hours. 4.59g of hydroxyethyl-terminated polyphenylene ether was obtained and named PPOD. The nuclear magnetic hydrogen spectrum is as follows Figure 1 As shown, it is verified that m+n=2.

[0093] Preliminary Example 2 In a three-necked round-bottom flask equipped with a reflux condenser, 40.00 g (about 25.00 mmol) of dihydroxy-terminated polyphenylene ether (PPO, purchased from Saudi Basic Industries (China) Co., Ltd., model No. Noryl SA90, molecular weight 1600, x+y=10), 11.76 g (about 75.00 mmol) of p-chloronitrobenzene and 10.32 g (74.50 mmol) of K2CO3 were added to 120 mL of N,N-dimethylformamide (DMF), and the mixture was stirred and refluxed at 70°C for 24 h to stop the reaction.

[0094] The supernatant from the reaction mixture was added dropwise to anhydrous methanol for precipitation. The resulting off-white precipitate was further filtered and the filter cake was washed with anhydrous methanol. The vacuum filtration step was repeated 2–3 times, followed by washing with anhydrous methanol, until the product was free of reaction solvent. Finally, the product was dried in a vacuum oven at 80°C for 24 h. This yielded 35.96 g of nitroated polyphenylene ether, designated NPPO.

[0095] In a 500 mL high-temperature autoclave, 30.00 g (18.80 mmol) of nitropolyphenylene ether (NPPO) and 0.24 g (about 0.226 mmol) of Pd / C were added to 110 mL of tetrahydrofuran (THF) and 60 mL of anhydrous ethanol (EtOH). The mixture was reacted at 100°C and a hydrogen pressure of 1.11 MPa for 10 h, and the reaction was stopped.

[0096] The supernatant of the reaction mixture was dropped into anhydrous methanol for precipitation. The resulting off-white precipitate was further obtained by suction filtration and the filter cake was washed with anhydrous methanol. Repeat the above vacuum filtration step and wash with anhydrous methanol 2 to 3 times until there is no reaction solvent in the product. Finally, the product was dried in a vacuum oven at 80°C for 24 hours. 27.82g of amino-terminated polyphenylene ether was obtained and named APPO. The H NMR spectrum is as follows Figure 2 As shown, it proves that its structure is correct.

[0097] Comparative Example 1 A high-speed disperser was used for chain extension. 100 g of polypropylene glycol-toluene diisocyanate polyurethane prepolymer (pre-PPG-TDI) with an NCO value (isocyanate content) of 6.14% was weighed and added to a tetrafluoroethylene beaker. Under high-speed stirring at 2000 r / min, 19.21 g (about 71.91 mmol) of MOCA (4,4'-methylenebis(2-chloroaniline)) was added at 70 ° C for chain extension reaction. The reaction was stirred for 3 minutes, and then the product was transferred to a 110 ° C oven for aging for 24 hours to obtain 118.42 g of polyurethane with an Mn of about 17900 and an Mw of about 42500. The infrared spectrum is shown as follows: Figure 3 As shown, 3263cm -1 The characteristic peak of -NH is at 1720cm -1 The peak is the characteristic peak of C=O.

[0098] After vulcanization and pressing, the Shore hardness was 60A and the dielectric constant D f is 2.24, dielectric loss D f It is 0.026.

[0099] Example 1 25 g (about 93.58 mmol) of MOCA (4,4'-methylenebis(2-chloroaniline)) was weighed and melted at 60°C, and 2.99 g (about 1.87 mmol) of PPOD was added and dissolved to obtain a mixed chain extender.

[0100] A high-speed disperser was used for chain extension. 100 g of polypropylene glycol-toluene diisocyanate polyurethane prepolymer (pre-PPG-TDI) with an NCO value (isocyanate group content) of 6.14% was weighed and added to a tetrafluoroethylene beaker. Under high-speed stirring at 2000 r / min, 21.09 g of a mixed chain extender was added at 70 ° C for chain extension reaction. The reaction was stirred for 3 minutes, and then the product was transferred to a 110 ° C oven for aging for 24 hours to obtain 119.82 g of polyurethane with an Mn of about 18500 and an Mw of about 50000. The infrared spectrum is shown as follows: Figure 3 As shown, 3263cm -1The characteristic peak of -NH is at 1720cm -1 The peak is the characteristic peak of C=O.

[0101] Example 2 The modified polyurethane was prepared in a manner similar to Example 1, except that the amount of PPOD added to the mixed chain extender was 5.99 g and the preparation temperature was 65°C.

[0102] The amount of mixed chain extender added was 22.89 g, the chain extension reaction temperature was 75° C., and the reaction time was 2 min.

[0103] Example 3 The modified polyurethane was prepared in a manner similar to Example 1, except that the amount of PPOD added to the mixed chain extender was 8.98 g and the preparation temperature was 75°C.

[0104] The amount of the mixed chain extender added was 24.63 g, the chain extension reaction temperature was 85° C., and the reaction time was 2 min.

[0105] Example 4 The modified polyurethane was prepared in a manner similar to Example 1, except that the amount of PPOD added to the mixed chain extender was 11.98 g and the preparation temperature was 85°C.

[0106] The amount of the mixed chain extender added was 26.31 g, the chain extension reaction temperature was 90° C., and the reaction time was 2 min.

[0107] Example 5 The modified polyurethane was prepared in a manner similar to Example 1, except that the amount of PPOD added to the mixed chain extender was 14.97 g and the preparation temperature was 90°C.

[0108] The amount of the mixed chain extender added was 27.92 g, the chain extension reaction temperature was 95° C., and the reaction time was 2 min.

[0109] The modified polyurethanes obtained in Examples 1-5 were subjected to hardness and dielectric tests after vulcanization and tableting. The test results are shown in Table 1: Table 1 Example Shore hardness (A) <![CDATA[Dielectric constant D k > <![CDATA[Dielectric loss D f > 1 61 2.22 0.023 2 65 2.13 0.022 3 67 2.07 0.021 4 71 2.00 0.020 5 72 1.94 0.020 Comparative Example 2 A high-speed disperser was used for chain extension. 100 g of polytetramethylene ether-toluene diisocyanate polyurethane prepolymer (pre-PTMEG-TDI) with an NCO value (isocyanate content) of 6.08% was weighed and added to a tetrafluoroethylene beaker. Under high-speed stirring at 2000 r / min, 18.96 g (about 70.97 mmol) of MOCA (4,4'-methylenebis(2-chloroaniline)) was added at 70 ° C for chain extension reaction. The reaction was stirred for 3 minutes, and then the product was transferred to a 110 ° C oven for aging for 24 hours to obtain 117.65 g of polyurethane with an Mn of about 19500 and an Mw of about 44900. The infrared spectrum is shown as follows: Figure 4 As shown, 3263cm -1 The characteristic peak of -NH is at 1720cm -1 The peak is the characteristic peak of C=O.

[0110] After vulcanization and pressing, the Shore hardness was 75A and the dielectric constant D f is 2.18, dielectric loss D f It is 0.059.

[0111] Example 6 25 g (about 93.58 mmol) of MOCA (4,4'-methylenebis(2-chloroaniline)) was weighed and melted at 60°C, and 2.99 g (about 1.87 mmol) of PPOD was added and dissolved to obtain a mixed chain extender.

[0112] A high-speed disperser was used for chain extension. 100 g of polytetramethylene ether-toluene diisocyanate polyurethane prepolymer (pre-PTMEG-TDI) with an NCO value (isocyanate content) of 6.08% was weighed and added to a PTFE beaker. Under high-speed stirring at 2000 r / min, 20.81 g of a mixed chain extender was added at 70°C for chain extension reaction. The reaction was stirred for 3 minutes, and then the product was transferred to a 110°C oven for aging for 24 hours to obtain 119.20 g of polyurethane with an Mn of approximately 19700 and an Mw of approximately 51100. The infrared spectrum is shown in FIG. Figure 4 As shown, 3263cm -1 The characteristic peak of -NH is at 1720cm -1 The peak is the characteristic peak of C=O.

[0113] Example 7 The modified polyurethane was prepared in a manner similar to Example 6, except that the amount of PPOD added to the mixed chain extender was 5.99 g and the preparation temperature was 65°C.

[0114] The amount of the mixed chain extender added was 22.60 g, the chain extension reaction temperature was 75° C., and the reaction time was 2 min.

[0115] Example 8 The modified polyurethane was prepared in a manner similar to Example 6, except that the amount of PPOD added to the mixed chain extender was 8.98 g and the preparation temperature was 75°C.

[0116] The amount of the mixed chain extender added was 24.31 g, the chain extension reaction temperature was 85° C., and the reaction time was 2 min.

[0117] Example 9 The modified polyurethane was prepared in a manner similar to Example 6, except that the amount of PPOD added to the mixed chain extender was 11.98 g and the preparation temperature was 85°C.

[0118] The amount of the mixed chain extender added was 25.96 g, the chain extension reaction temperature was 90° C., and the reaction time was 2 min.

[0119] Example 10 The modified polyurethane was prepared in a manner similar to Example 6, except that the amount of PPOD added to the mixed chain extender was 14.97 g and the preparation temperature was 90°C.

[0120] The amount of the mixed chain extender added was 27.56 g, the chain extension reaction temperature was 95° C., and the reaction time was 2 min.

[0121] The modified polyurethanes obtained in Examples 6-10 were subjected to hardness and dielectric tests after vulcanization and tableting. The test results are shown in Table 2: Table 2 Example Shore hardness (A) <![CDATA[Dielectric constant D k > <![CDATA[Dielectric loss D f > 6 77 2.16 0.050 7 78 2.10 0.051 8 79 2.02 0.050 9 79 1.98 0.048 10 83 1.94 0.046 Comparative Example 3 A high-speed disperser was used for chain extension. 100 g of polypropylene glycol-toluene diisocyanate polyurethane prepolymer (pre-PPG-TDI) with an NCO value (isocyanate content) of 6.14% was weighed and added to a tetrafluoroethylene beaker. Under high-speed stirring at 2000 r / min, 19.21 g (about 71.91 mmol) of MOCA (4,4'-methylenebis(2-chloroaniline)) was added at 70 ° C for chain extension reaction. The reaction was stirred for 3 minutes, and then the product was transferred to a 110 ° C oven for aging for 24 hours to obtain 118.42 g of polyurethane with an Mn of about 17900 and an Mw of about 42500. The infrared spectrum is shown as follows: Figure 3 As shown, 3284cm -1 The characteristic peak of -NH is at 1717cm -1 The peak is C=O. Figure 7As shown, the peak at 9.63 ppm is the NH proton peak of the urea bond, the peak at 8.21 ppm is the proton peak of the o-chlorine-substituted benzene ring of MOCA, the peak at 5.43 ppm is the NH proton peak in carbamate, and the peak at 2.93 ppm is the methylene −CH2− proton in MOCA.

[0122] After vulcanization and pressing, the Shore hardness was 60A and the dielectric constant D f is 2.24, dielectric loss D f It is 0.026.

[0123] Example 11 25 g (about 93.58 mmol) of MOCA (4,4'-methylenebis(2-chloroaniline)) was weighed and melted at 80°C, and 3.34 g (about 1.87 mmol) of APPO was added thereto and dissolved to obtain a mixed chain extender.

[0124] A high-speed disperser was used for chain extension. 100 g of polypropylene glycol-toluene diisocyanate polyurethane prepolymer (pre-PPG-TDI) with an NCO value (isocyanate content) of 6.14% was weighed and added to a PTFE beaker. Under high-speed stirring at 2000 r / min, 21.32 g of a mixed chain extender was added at 80°C for chain extension reaction. The reaction was stirred for 3 minutes, and then the product was transferred to a 110°C oven for aging for 24 hours to obtain 119.14 g of polyurethane with an Mn of approximately 25600 and an Mw of approximately 51700. The infrared spectrum is shown in FIG. Figure 5 As shown, 3284cm -1 The characteristic peak of -NH is at 1717cm -1 The peak is C=O. Figure 7 As shown, the peak at 9.63 ppm is the NH proton peak of the urea bond, the peak at 8.21 ppm is the proton peak of the o-chlorine-substituted benzene ring in MOCA, the peak at 6.78 ppm is the proton peak of the benzene ring in APPO, the peak at 5.43 ppm is the NH proton peak in carbamate, and the peak at 2.93 ppm is the methylene −CH2− proton in MOCA.

[0125] Example 12 The modified polyurethane was prepared in a manner similar to Example 11, except that the amount of APPO added to the mixed chain extender was 6.67 g and the preparation temperature was 85°C.

[0126] The amount of the mixed chain extender added was 23.49 g, the chain extension reaction temperature was 85° C., and the reaction time was 2 min.

[0127] Example 13 The modified polyurethane was prepared in a manner similar to Example 11, except that the amount of APPO added to the mixed chain extender was 10.00 g and the preparation temperature was 95°C.

[0128] The amount of the mixed chain extender added was 25.66 g, the chain extension reaction temperature was 95° C., and the reaction time was 2 min.

[0129] Example 14 The modified polyurethane was prepared in a manner similar to Example 11, except that the amount of APPO added to the mixed chain extender was 13.34 g and the preparation temperature was 95°C.

[0130] The amount of mixed chain extender added was 27.83 g, the chain extension reaction temperature was 95° C., and the reaction time was 1.5 min.

[0131] Example 15 The modified polyurethane was prepared in a manner similar to Example 11, except that the amount of APPO added to the mixed chain extender was 16.68 g and the preparation temperature was 100°C.

[0132] The amount of the mixed chain extender added was 30.00 g, the chain extension reaction temperature was 105° C., and the reaction time was 1 min.

[0133] The modified polyurethanes obtained in Examples 11-15 were subjected to hardness and dielectric tests after vulcanization and tableting. The test results are shown in Table 3: Table 3 Example Shore hardness (A) <![CDATA[Dielectric constant D k > <![CDATA[Dielectric loss D f > 11 68 2.20 0.024 12 75 2.10 0.023 13 78 2.03 0.022 14 80 2.03 0.022 15 78 1.97 0.020 Comparative Example 4 A high-speed disperser was used for chain extension. 100 g of polytetramethylene ether-toluene diisocyanate polyurethane prepolymer (pre-PTMEG-TDI) with an NCO value (isocyanate content) of 6.08% was weighed and added to a tetrafluoroethylene beaker. Under high-speed stirring at 2000 r / min, 18.96 g (about 70.97 mmol) of MOCA (4,4'-methylenebis(2-chloroaniline)) was added at 70 ° C for chain extension reaction. The reaction was stirred for 3 minutes, and then the product was transferred to a 110 ° C oven for aging for 24 hours to obtain 117.65 g of polyurethane with an Mn of about 19500 and an Mw of about 44900. The infrared spectrum is shown as follows: Figure 6 As shown, 3279cm -1 The characteristic peak of -NH is at 1726cm -1 The peak is the characteristic peak of C=O.

[0134] After vulcanization and pressing, the Shore hardness was tested to be 75A and the dielectric constant D f is 2.18, dielectric loss Df It is 0.059.

[0135] Example 16 25 g (about 93.58 mmol) of MOCA (4,4'-methylenebis(2-chloroaniline)) was weighed and melted at 80°C, and 3.34 g (about 1.87 mmol) of APPO was added thereto and dissolved to obtain a mixed chain extender.

[0136] A high-speed disperser was used for chain extension. 100 g of polytetramethylene ether-toluene diisocyanate polyurethane prepolymer (pre-PTMEG-TDI) with an NCO value (isocyanate content) of 6.08% was weighed and added to a PTFE beaker. Under high-speed stirring at 2000 r / min, 21.11 g of a mixed chain extender was added at 70°C for chain extension reaction. The reaction was stirred for 3 minutes, and then the product was transferred to a 110°C oven for aging for 24 hours to obtain 120.25 g of polyurethane with an Mn of approximately 31300 and an Mw of approximately 88900. The infrared spectrum is shown in FIG. Figure 6 As shown, 3279cm -1 The characteristic peak of -NH is at 1726cm -1 The peak is the characteristic peak of C=O.

[0137] Example 17 The modified polyurethane was prepared in a manner similar to Example 16, except that the amount of APPO added to the mixed chain extender was 6.67 g and the preparation temperature was 85°C.

[0138] The amount of the mixed chain extender added was 23.26 g, the chain extension reaction temperature was 85° C., and the reaction time was 2 min.

[0139] Example 18 The modified polyurethane was prepared in a manner similar to Example 16, except that the amount of APPO added to the mixed chain extender was 10.00 g and the preparation temperature was 95°C.

[0140] The amount of the mixed chain extender added was 25.41 g, the chain extension reaction temperature was 5° C., and the reaction time was 2 min.

[0141] Example 19 The modified polyurethane was prepared in a manner similar to Example 16, except that the amount of APPO added to the mixed chain extender was 13.34 g and the preparation temperature was 95°C.

[0142] The amount of the mixed chain extender added was 27.56 g, the chain extension reaction temperature was 95° C., and the reaction time was 1.5 min.

[0143] Example 20 The modified polyurethane was prepared in a manner similar to Example 16, except that the amount of APPO added to the mixed chain extender was 16.68 g and the preparation temperature was 100°C.

[0144] The amount of the mixed chain extender added was 29.71 g, the chain extension reaction temperature was 105° C., and the reaction time was 1 min.

[0145] The modified polyurethanes obtained in Examples 16-20 were subjected to hardness and dielectric tests after vulcanization and tableting. The test results are shown in Table 4: Table 4 Example Shore hardness (A) <![CDATA[Dielectric constant D k > <![CDATA[Dielectric loss D f > 16 78 2.08 0.050 17 81 2.05 0.047 18 84 2.01 0.047 19 88 1.98 0.045 20 89 1.96 0.043 Although the embodiments disclosed herein are as described above, the contents described herein are merely embodiments for facilitating understanding of the present invention and are not intended to limit the present invention. Any person skilled in the art may make any modifications and variations in the form and details of the embodiments without departing from the spirit and scope of the present invention. However, the scope of patent protection of the present invention shall remain subject to the scope defined by the appended claims.

Claims

1. A method for preparing end-group functionalized polyphenylene ether modified polyurethane, characterized in that: The polyphenylene ether is prepared from hydroxyethyl-terminated polyphenylene ether or amino-terminated polyphenylene ether, polyurethane prepolymer and chain extender as raw materials.

2. The preparation method according to claim 1, characterized in that The following steps are involved: Step 1: Modifying polyphenylene ether to obtain hydroxyethyl and / or amino terminated polyphenylene ether; Step 2: mixing the modified polyphenylene ether terminated with hydroxyethyl and / or amino groups with a chain extender to obtain a mixed chain extender; Step 3: reacting the mixed chain extender with the polyurethane prepolymer, and aging the mixture to prepare a hydroxyethyl and / or amino-terminated polyphenylene ether modified polyurethane.

3. The preparation method according to claim 1 or 2, characterized in that The hydroxyethyl terminated polyphenylene ether polyol (PPOD) can be represented by the following formula: ； Where, The value of x+y is 5 to 100, preferably 8 to 50, more preferably 10 to 20; The value of m+n is 1 to 50, preferably 2 to 20, more preferably 2 to 10; R is selected from one of hydrogen, alkyl and cycloalkyl, preferably selected from one of hydrogen and alkyl.

4. The preparation method according to claim 1 or 2, characterized in that The amino-terminated polyphenylene ether diamine (APPO) can be represented by the following formula: ； In the formula, the value of x+y is 5 to 100, preferably 8 to 50, and more preferably 10 to 20.

5. The preparation method according to any one of claims 2 to 4, characterized in that The hydroxyethyl terminated polyphenylene ether polyol is prepared by reacting bihydroxy-terminated polyphenylene ether (PPO) with alkylene carbonate or epoxide in the presence of an alkaline catalyst. The amino-terminated polyphenylene ether polyol is prepared by reacting dihydroxylated polyphenylene ether (PPO) with halogenated nitrobenzene in the presence of an alkaline catalyst to prepare a nitroaromatic compound, which is then further hydrogenated under the action of a palladium-carbon catalyst to prepare an amino-terminated polyphenylene ether. Preferably, the double-terminated hydroxyl polyphenylene ether (PPO) is as shown below: ； The p-halogen nitrobenzene is selected from one or two of p-fluoronitrobenzene, p-chloronitrobenzene, p-iodine nitrobenzene and p-bromonitrobenzene.

6. The preparation method according to any one of claims 2 to 5, characterized in that In step 2, The chain extender is selected from one or more of 4,4'-methylenebis(2-chloroaniline) (MOCA), 1,4-bis(2-hydroxyethoxy)benzene (HQEE), 1,4-butanediol (BDO), diethyltoluenediamine (DETDA), dimethylthiotoluenediamine (DMTDA), and 4,4'-methylenebis(3-chloro-2,6-diethylaniline) (MCDEA).

7. The preparation method according to any one of claims 2 to 6, characterized in that In step 2, The temperature is 40 to 180°C, preferably 50 to 140°C, more preferably 60 to 120°C, The equivalent ratio of the terminal functionalized polyphenylene ether in the mixed chain extender to the active hydrogen groups of the chain extender is 1-500.

8. The preparation method according to any one of claims 2 to 7, characterized in that In step 3, The polyether or polyester diol in the prepolymer is selected from one or more of polyethylene glycol (PEG), polypropylene glycol (PPG), polytetramethylene ether (PTMEG), polycaprolactone diol (PCL), polycarbonate diol (PCD), polyethylene terephthalate (PET), polytrimethylene terephthalate (PTT), polybutylene terephthalate (PBT), and / or The isocyanate in the prepolymer is selected from one or more of diphenylmethane diisocyanate (MDI), toluene diisocyanate (TDI), p-phenylene diisocyanate (PPDI), hexamethylene diisocyanate (HDI), m-phenylenediisocyanate (XDI), cyclohexane dimethylene diisocyanate (HXDI), cyclohexane-1,4-diisocyanate (CHDI) or dicyclohexylmethane diisocyanate (HMDI). Preferably, the prepolymer is selected from one or more prepolymers prepared from the polyether or polyester diol and the isocyanate.

9. The preparation method according to any one of claims 2 to 8, characterized in that: In step 3, The chain extension reaction is carried out using a high-speed disperser with a stirring speed of 1000~3000r / min. The chain extension reaction temperature is 40-160°C, preferably 60-150°C, and the chain extension time is 1-60 min, preferably 1-30 min. The aging temperature is 80 to 150° C., preferably 90 to 130° C., and the aging time is 10 to 30 hours, preferably 15 to 25 hours.

10. End-group functionalized polyphenylene ether modified polyurethane, prepared according to the method of any one of claims 1 to 9.

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