Alcohol hydroxyl terminated polyphenylene ether polyol and preparation method thereof

Abstract

The invention provides a polyphenylene ether polyol terminated with an alcohol hydroxyl group and a preparation method thereof. The polyphenylene ether polyol terminated with an alcohol hydroxyl group is prepared by reacting a double-terminated hydroxyl polyphenylene ether with an alkyl carbonate or an epoxide in the presence of an alkaline catalyst, and has alcohol hydroxyl groups at both ends. The molecular weight and degree of polymerization of the polyphenylene ether polyol terminated with an alcohol hydroxyl group are adjustable, and the property is stable. The polyphenylene ether polyol terminated with an alcohol hydroxyl group can be used not only to modify a polymer, but also as an intermediate for preparing a polymer. The addition of the polyphenylene ether polyol terminated with an alcohol hydroxyl group can give the obtained product some unique characteristics of polyphenylene ether, and improve the hardness, heat resistance and other properties of the obtained polymer. At the same time, the preparation method of the polyphenylene ether polyol terminated with an alcohol hydroxyl group is simple, the reaction selectivity is high, the yield is high, the production cost is low, and the application prospect is good.

Description

Technical Field

[0001] The invention relates to the field of alcohol hydroxyl-terminated polyphenylene ether polyols, and in particular to alcohol hydroxyl-terminated polyphenylene ether polyols with different molecular weights, that is, different chain lengths, and preparation methods thereof. Background Art

[0002] The polyphenylene ether polyol terminated with alcohol hydroxyl group is an etherified polyol of polyphenylene ether, named as PPOD. The polyphenylene ether polyol terminated with alcohol hydroxyl group is a white powder, which not only has the properties of high temperature resistance, low expansion coefficient, low dielectric loss, etc. of general polyphenylene ether, but also has great rigidity due to the presence of a large number of benzene ring structures. In addition, its two ends are terminated with alcohol hydroxyl groups, which has the properties of polyols, providing the possibility of introducing engineering plastics in the preparation of polyurethane, further giving polyurethane some properties of polyphenylene ether, and modifying it so that it can be more widely used. For example, it can be used to make corrosion-resistant parts such as automobile tires, valves, and pipes, and can also be used in aerospace, automobile and other fields, such as high-temperature resistant coatings for space shuttles, rockets, automobile pistons, etc.

[0003] At present, there is no clear report on the preparation method of alcohol hydroxyl terminated polyphenylene ether polyol. Sabit successfully prepared a NORYL AP2001G polyol for cast polyurethane, but there is no specific report. There have been many reports based on similar phenol etherification.

[0004] At present, Wang Jiaxi and others have prepared etherified polyols of bisphenol A using bisphenol A as a raw material and dibutyltin oxide as a catalyst; CN110294666A discloses a method for preparing alkylene etherified polyols from bisphenol A and alkylene carbonate, and CN110669213A discloses a method for preparing bisphenol A polyethers from bisphenol A and propylene oxide, using di-n-butyl ether, ethylene glycol diethyl ether, ethylene glycol n-propyl ether, etc. as solvents, and the solvents are relatively toxic. Summary of the invention

[0005] Based on the above technical background, the inventors have made great progress and used double-terminated hydroxyl polyphenylene ether (i.e., PPO) as the main raw material, and reacted with alkyl carbonate or epoxide in the presence of an alkaline catalyst to obtain an alcohol hydroxyl-terminated polyphenylene ether polyol. The alcohol hydroxyl-terminated polyphenylene ether polyol has alcohol hydroxyl groups at both ends, and its molecular weight and degree of polymerization are adjustable, and its properties are stable. It can not only be used to modify polymers, but also can be used as an intermediate for preparing polymers. The addition of the alcohol hydroxyl-terminated polyphenylene ether polyol can give the obtained product some properties of polyphenylene ether, effectively improving the hardness and heat resistance of the product. In addition, the preparation method of the polyol is simple, the conversion rate and yield are high, and the application prospect is good, thereby completing the present invention.

[0006] The first aspect of the present invention is to provide a polyphenylene ether polyol terminated with an alcohol hydroxyl group, wherein the polyphenylene ether polyol terminated with an alcohol hydroxyl group is represented by the following formula (1):

[0007]

[0008] In formula (1), the value of x+y is 10 to 100, the value of m+n is 1 to 1000, and R is selected from one of hydrogen, alkyl, and cycloalkyl.

[0009] The second aspect of the present invention is to provide a method for preparing the polyphenylene ether polyol terminated with an alcohol hydroxyl group according to the first aspect of the present invention, the method comprising the following steps:

[0010] Step 1, in the presence of a basic catalyst, reacting a dihydroxy-terminated polyphenylene ether and an alkylene carbonate or an epoxide in a solvent to obtain a reaction mixture;

[0011] Step 2: The reaction mixture is precipitated, washed, filtered and dried to obtain an alcoholic hydroxyl-terminated polyphenylene ether polyol.

[0012] The third aspect of the present invention is to provide an application of the polyphenylene ether polyol terminated with an alcohol hydroxyl group according to the first aspect of the present invention or the polyphenylene ether polyol terminated with an alcohol hydroxyl group prepared by the preparation method according to the second aspect of the present invention, which can be used to modify a polymer or as an intermediate for preparing a polymer. It is preferably used to modify polyurethane and polystyrene, and as an intermediate for preparing polyester and epoxy resin. BRIEF DESCRIPTION OF THE DRAWINGS

[0013] Figure 1 The polyphenylene ether polyol terminated with alcohol hydroxyl group obtained in Example 1 is shown. 1 HNMR (400 MHz, solvent: deuterated chloroform) spectrum;

[0014] Figure 2 The polyphenylene ether polyol terminated with alcohol hydroxyl group obtained in Example 12 is shown. 1 HNMR (400 MHz, solvent: deuterated chloroform) spectrum;

[0015] Figure 3 The esterification of the polyphenylene ether polyol terminated with alcohol hydroxyl group obtained in Example 1 is shown. 1 H NMR (400 MHz, solvent: deuterated chloroform) spectrum;

[0016] Figure 4 FT-IR comparison charts of double-terminated hydroxyl polyphenylene ether PPO (SA90), hydroxyl-terminated polyphenylene ether polyol PPOD prepared in Example 1, and sample MPPOD prepared by esterification in Experimental Example 1 are shown. DETAILED DESCRIPTION

[0017] The present invention will be described in detail below, and the characteristics and advantages of the present invention will become clearer and more distinct with the description.

[0018] The first aspect of the present invention is to provide a polyphenylene ether polyol terminated with an alcohol hydroxyl group, wherein the polyphenylene ether polyol terminated with an alcohol hydroxyl group is represented by the following formula (1):

[0019]

[0020] In formula (1), the value of x+y is 10 to 100, the value of m+n is 1 to 1000, and R is selected from one of hydrogen, alkyl, and cycloalkyl.

[0021] Preferably, the value of x+y is 10 to 50, the value of m+n is 1 to 500, and R is selected from hydrogen and an alkyl group.

[0022] More preferably, the value of x+y is 10 to 20, the value of m+n is 1 to 100, and R is selected from hydrogen or methyl.

[0023] The etherified groups at both ends of the alcohol hydroxyl-terminated polyphenylene ether polyol of the present invention have different polymerization degrees and stable properties. It can not only be used to modify polymers such as polyurethane and polystyrene, but also be used as an intermediate for preparing polymers such as polyester and epoxy resin, giving the prepared products some unique properties of polyphenylene ether.

[0024] The alcohol hydroxyl terminated polyphenylene ether polyol is prepared by taking dihydroxyl-terminated polyphenylene ether (ie PPO) as raw material and reacting with alkylene carbonate or epoxide in the presence of an alkaline catalyst.

[0025] The double-terminated hydroxyl polyphenylene ether is shown in the following formula:

[0026]

[0027] In the formula, the value of x+y is 10-100, preferably the value of x+y is 10-50, and more preferably the value of x+y is 10-20.

[0028] According to the present invention, the alkylene carbonate is selected from one or more of ethylene carbonate (EC), propylene carbonate (PC), and butylene carbonate (BC), preferably selected from one or two of ethylene carbonate and propylene carbonate.

[0029] 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.

[0030] The molar ratio of alkylene carbonate to dihydroxy-terminated polyphenylene ether is (1-1000):1, preferably (1-500):1, and more preferably (2-100):1.

[0031] The molar ratio of epoxide to dihydroxy-terminated polyphenylene ether is (1-1000):1, preferably (1-500):1, and more preferably (2-200):1.

[0032] 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, preferably selected from one or more of an alkali metal carbonate, an alkali metal bicarbonate and an alkali metal hydride, and more preferably selected from one or more of potassium carbonate, potassium bicarbonate and sodium hydride.

[0033] For alkene esters and epoxides, the anionic ring-opening polymerization method is generally used in the industry. However, when using cationic ring-opening polymerization, there are many side reactions, and the relative molecular mass of the generated product is low. If a protonic acid is used, it will be limited by the affinity of the acid anion and the target product cannot be obtained. Therefore, the present invention chooses to use a basic catalyst.

[0034] 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.

[0035] The alcohol hydroxyl-terminated polyphenylene ether polyol of the present invention can be used to modify polymer compounds such as polyurethane and polystyrene, effectively improving the hardness, glass transition temperature and other properties of the polymer, and as the amount of alcohol hydroxyl-terminated polyphenylene ether polyol added increases, the performance of the modified polymer continues to improve.

[0036] By using polyphenylene ether polyol terminated with alcohol hydroxyl groups to modify polyurethane, the hardness of polyurethane can be increased to above 85A and the glass transition temperature can be increased to above 72°C.

[0037] By using it to modify polystyrene, the dielectric constant of the modified polystyrene at 10GHz can be reduced to below 2.34 and the glass transition temperature can be increased to above 129°C.

[0038] The second aspect of the present invention is to provide a method for preparing the polyphenylene ether polyol terminated with an alcohol hydroxyl group according to the first aspect of the present invention, the method comprising the following steps:

[0039] Step 1, in the presence of a basic catalyst, reacting a dihydroxy-terminated polyphenylene ether and an alkylene carbonate or an epoxide in a solvent to obtain a reaction mixture;

[0040] Step 2: The reaction mixture is precipitated, washed, filtered and dried to obtain an alcoholic hydroxyl-terminated polyphenylene ether polyol.

[0041] This step is described and illustrated in detail below.

[0042] Step 1: In the presence of a basic catalyst, a dihydroxy-terminated polyphenylene ether and an alkylene carbonate or an epoxide are reacted in a solvent to obtain a reaction mixture.

[0043] 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, preferably selected from one or more of an alkali metal carbonate, an alkali metal bicarbonate and an alkali metal hydride, and more preferably selected from one or more of potassium carbonate, potassium bicarbonate and sodium hydride.

[0044] The solvent is an organic solvent, preferably one or more selected from benzene, toluene, xylene, dichloromethane, chloroform, tetrahydrofuran, N,N-dimethylformamide, preferably one or two selected from N,N-dimethylformamide and tetrahydrofuran.

[0045] The present invention does not impose any particular limitation on the amount of solvent added, as long as the dihydroxy-terminated polyphenylene ether, alkyl carbonate or epoxide, and alkaline catalyst can be completely dissolved.

[0046] If the reaction raw materials are dihydroxy-terminated polyphenylene ether and alkylene carbonate, the dihydroxy-terminated polyphenylene ether, alkylene carbonate and alkaline catalyst are placed in a solvent and subjected to reflux reaction under mechanical stirring.

[0047] 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.

[0048] The molar ratio of alkylene carbonate to dihydroxy-terminated polyphenylene ether is (1-1000):1, preferably (1-500):1, and more preferably (2-100):1.

[0049] 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.

[0050] The reaction temperature is 50-200°C, preferably 70-180°C, more preferably 90-150°C.

[0051] The reaction time is 1 to 100 h, preferably 2 to 70 h, more preferably 2 to 50 h.

[0052] If the reaction raw materials are double-terminated polyphenylene ether and epoxide, the following steps are included:

[0053] Step 1-1, adding a double-terminated polyphenylene ether and a basic catalyst into a solvent to perform a reflux reaction;

[0054] Step 1-2, after the reaction is completed, the reaction is cooled, epoxide is added to the cooled system, and the temperature is raised to perform a reflux reaction;

[0055] Optionally, in step 1-3, after the reaction of step 1-2 is completed, a basic catalyst is added to carry out a reflux reaction, and after the reaction is completed, epoxide is added after cooling, and the temperature is raised to carry out a reflux reaction.

[0056] Specifically, in step 1-1, the molar ratio of the alkaline catalyst to the double-terminated polyphenylene ether is (0.5-20):1, preferably (0.5-10):1, and more preferably (1-5):1.

[0057] The reaction temperature is 30-90°C, preferably 50-80°C, more preferably 50-70°C.

[0058] The reaction time is 1 to 10 hours, preferably 2 to 8 hours, more preferably 2 to 5 hours.

[0059] In step 1-2, the mixture is cooled in an ice-water bath to 0 to 10°C, preferably 0 to 5°C.

[0060] Since the boiling point of alkylene oxide is low, such as ethylene oxide, which is a gas at room temperature, adding it after cooling to a low temperature can not only accurately measure the amount of addition, but also reduce the difficulty of operation and prevent the reaction system from being over-pressurized.

[0061] 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.

[0062] The molar ratio of epoxide to dihydroxy-terminated polyphenylene ether is (1-200):1, preferably (1-150):1, and more preferably (2-100):1.

[0063] The temperature is raised to 30 to 90°C, preferably 50 to 80°C, more preferably 50 to 70°C for reflux reaction.

[0064] The reaction time is 1 to 10 hours, preferably 2 to 8 hours, more preferably 2 to 5 hours.

[0065] In step 1-3, step 1-3 can be repeated multiple times to increase the molecular weight and degree of polymerization of the polyphenylene ether polyol terminated with alcohol hydroxyl groups. If added once, under the same conditions, its degree of polymerization cannot be increased, and its m+n value is up to 4. Selecting multiple additional reactions is conducive to increasing the degree of polymerization of the product.

[0066] The cooling temperature and the reflux reaction temperature are the same as those in step 1-1 and step 1-2.

[0067] The molar ratio of the added alkaline catalyst to the dihydroxy-terminated polyphenylene ether is (0.5-20):1, preferably (0.5-10):1, and more preferably (1-5):1.

[0068] The molar ratio of the added epoxide to the double-terminated hydroxyl polyphenylene ether is (1-200):1, preferably (1-150):1, and more preferably (2-100):1.

[0069] Step 2: The reaction mixture is precipitated, washed, filtered and dried to obtain an alcoholic hydroxyl-terminated polyphenylene ether polyol.

[0070] After the reaction is stopped, a precipitant is added to the supernatant of the reaction mixture for precipitation, wherein the precipitant is selected from methanol and n-hexane, preferably methanol.

[0071] A detergent is added to the precipitate for washing, wherein the detergent is one or more of water, methanol, and n-hexane, preferably methanol.

[0072] The above washing and filtering steps are repeated for multiple times, preferably 2 to 3 times, until no reaction solvent is present in the product, and finally vacuum drying is performed.

[0073] The drying temperature is 60 to 90° C., preferably 70 to 80° C. The drying time is 15 to 30 hours, preferably 20 to 25 hours.

[0074] The preparation method of the invention has high yield, which is as high as more than 85%.

[0075] The third aspect of the present invention is to provide an application of the polyphenylene ether polyol terminated with an alcohol hydroxyl group according to the first aspect of the present invention or the polyphenylene ether polyol terminated with an alcohol hydroxyl group prepared by the preparation method according to the second aspect of the present invention, which can be used to modify a polymer or as an intermediate for preparing a polymer. It is preferably used to modify polyurethane and polystyrene, and as an intermediate for preparing polyester and epoxy resin.

[0076] The beneficial effects of the present invention are:

[0077] (1) The preparation method of the present invention has the advantages of fewer reaction steps, simple process flow, and reduced production cost;

[0078] (2) The catalyst used in the present invention has a wide range of sources and can be removed by filtering. The removal method is simple, and the preparation method has high reaction selectivity and high yield, which can reach more than 85%;

[0079] (3) The polyphenylene ether polyol terminated with alcohol hydroxyl groups prepared by the method of the present invention has an adjustable molecular weight and a degree of polymerization of the etherified groups at both ends, which can be adjusted according to specific needs;

[0080] (4) The polyphenylene ether polyol terminated with alcohol hydroxyl groups of the present invention has stable properties and can be used not only to modify polymers such as polyurethane and polystyrene, but also to improve the hardness of the polyurethane modified with it to above 85A and the glass transition temperature to above 72°C. It can also be used as an intermediate for preparing polymers such as polyester and epoxy resin. The addition of the polyphenylene ether polyol terminated with alcohol hydroxyl groups can give the obtained product some unique properties of polyphenylene ether, such as high temperature resistance, low dielectric loss, high rigidity, etc., so that it can be applied to the fields of aerospace, medical equipment, coatings, automobiles, etc.

[0081] Example

[0082] The present invention is further described below by means of specific examples. These embodiments are only intended to illustrate the present invention but are not intended to limit the scope of the present invention.

[0083] Example 1

[0084] In a three-necked round-bottom flask equipped with a reflux condenser, 5.00 g (3.13 mmol) of bihydroxylated polyphenylene ether (PPO, molecular weight 1600, purchased from Saudi Basic Industries (China) Co., Ltd., model NorylSA90, x+y=10), 0.55 g (6.25 mmol) of ethylene carbonate (EC) and 0.44 g (3.13 mmol) of K 2 CO 3 The mixture was added into 25 mL of N,N-dimethylformamide (DMF), and stirred under reflux at 145° C. for 3 h to stop the reaction.

[0085] The supernatant of the reaction mixture was dropped into anhydrous methanol for precipitation, and 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. The polyphenylene ether polyol terminated with alcohol hydroxyl group was obtained as an off-white solid powder with a yield of 94%.

[0086] The chemical reaction process is speculated as shown in formula (2), where R' is EC, 1 H NMR spectrum Figure 1 As shown, m+n=2, the infrared spectrum is as follows Figure 4 As shown, the infrared characteristic peak is 3450cm -1 The presence of OH at the position indicates that the obtained product contains alcoholic hydroxyl groups.

[0087]

[0088] Example 2

[0089] The preparation of polyphenylene ether polyol terminated with alcoholic hydroxyl group was carried out in a manner similar to Example 1, except that the amount of ethylene carbonate added was 2.06 g and the reaction time was 4 h.

[0090] H-NMR spectrum showed that m+n=4.

[0091] Example 3

[0092] The preparation of polyphenylene ether polyol terminated with alcohol hydroxyl group was carried out in a manner similar to that of Example 1, except that the catalyst was KHCO 3 , the added amount is 0.45g.

[0093] The H-NMR spectrum showed that m+n=2.

[0094] Example 4

[0095] In a three-necked round-bottom flask equipped with a reflux condenser, 5.00 g (3.13 mmol) of PPO (molecular weight 1600, purchased from Saudi Basic Industries (China) Co., Ltd., model NorylSA90, x+y=10), 0.64 g (6.25 mmol) of propylene carbonate (PC) and 0.50 g (3.62 mmol) of K 2 CO 3 The mixture was added into 25 mL of DMF and stirred under reflux at 145° C. for 3 h to stop the reaction.

[0096] The supernatant of the reaction mixture was dropped into anhydrous methanol for precipitation, and 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. The polyphenylene ether diol terminated with alcohol hydroxyl group was obtained as an off-white solid powder with a yield of 91%.

[0097] The chemical reaction process is speculated as shown in formula (2), where R' is PC, and the nuclear magnetic resonance spectroscopy shows that m+n=2, and the infrared characteristic peak is 3450cm -1 .

[0098] Example 5

[0099] The preparation of polyphenylene ether polyol terminated with alcoholic hydroxyl group was carried out in a manner similar to Example 4, except that the addition amount of propylene carbonate was 4.08 g and the reaction time was 4 h.

[0100] H-NMR spectrum showed that m+n=4.

[0101] Example 6

[0102] In a three-necked round-bottom flask equipped with a reflux condenser, 5.00 g (3.13 mmol) of PPO (molecular weight 1600, purchased from Saudi Basic Industries (China) Co., Ltd., model Noryl SA90, x + y = 10) and 0.44 g (3.13 mmol) of K 2 CO 3 Add to 25 mL of anhydrous tetrahydrofuran (THF), stir and reflux at 60°C for 3 h, stop the reaction, and cool to 0-5°C. Then, introduce 1.00 g (22.73 mol) of ethylene oxide (EO) into the reaction mixture at 0°C, stir and reflux at 60°C for 3 h, and stop the reaction.

[0103] The supernatant was dropped into anhydrous methanol for precipitation, and the resulting off-white precipitate was further obtained by suction filtration and the filter cake was washed with anhydrous methanol. The above vacuum filtration step was repeated and washed with anhydrous methanol 2 to 3 times until no reaction solvent was present in the product. Finally, the product was dried in a vacuum oven at 80°C for 24 hours. The polyphenylene ether polyol terminated with alcohol hydroxyl groups was obtained as an off-white solid powder with a yield of 90%.

[0104] The chemical reaction process is speculated as shown in formula (2), where R' is EO, and the nuclear magnetic resonance spectroscopy shows that m+n=2, and the infrared characteristic peak is 3450cm -1 .

[0105] Example 7

[0106] The preparation of polyphenylene ether polyol terminated with alcoholic hydroxyl group was carried out in a manner similar to Example 6, except that the amount of ethylene oxide added was 1.5 g.

[0107] H-NMR spectrum showed that m+n=4.

[0108] Example 8

[0109] In a three-necked round-bottom flask equipped with a reflux condenser, 5.00 g (3.13 mmol) of PPO (molecular weight 1600, purchased from Saudi Basic Industries (China) Co., Ltd., model Noryl SA90, x + y = 10) and 0.44 g (3.13 mmol) of K 2 CO 3 Add to 25 mL of anhydrous THF, stir and reflux at 60°C for 3 h, stop the reaction, and cool to 0-5°C. Then add 1.32 g (22.73 mol) of propylene oxide (PO) to the reaction mixture at 0°C, stir and reflux at 60°C for 3 h, and stop the reaction.

[0110] The supernatant was dropped into anhydrous methanol for precipitation, and the resulting off-white precipitate was further filtered and the filter cake was washed with anhydrous methanol. The above vacuum filtration step was repeated and washed with anhydrous methanol 2 to 3 times until no reaction solvent was present in the product. Finally, the product was dried in a vacuum oven at 80°C for 24 hours. The polyphenylene ether polyol terminated with alcohol hydroxyl groups was obtained as an off-white solid powder with a yield of 88%.

[0111] The chemical reaction process is speculated as shown in formula (2), where R' is PO, and the nuclear magnetic resonance spectroscopy shows that m+n=2, and the infrared characteristic peak is 3450cm -1 .

[0112] Example 9

[0113] The preparation of polyphenylene ether polyol terminated with alcoholic hydroxyl group was carried out in a manner similar to Example 8, except that the amount of propylene oxide added was 2.01 g.

[0114] H-NMR spectrum showed that m+n=4.

[0115] Example 10

[0116] In a three-necked round-bottom flask equipped with a reflux condenser, 5.00 g (3.13 mmol) of PPO (molecular weight 1600, purchased from Saudi Basic Industries (China) Co., Ltd., model NorylSA90, x+y=10) and 0.15 g (6.25 mmol) of NaH were added to 25 mL of anhydrous THF, and stirred at 60°C for 3 h under reflux, the reaction was stopped, and the reaction was cooled to 0-5°C. Then, 1.50 g (45.46 mol) of EO was introduced into the reaction mixture at 0°C, and stirred at 60°C for 3 h under reflux.

[0117] After stopping the reaction, the product was not separated and 0.15g (6.25mmol) NaH was added again. After reacting for 3h at 60℃, 1.50g (45.46mol) EO was added under ice bath condition, and stirred and refluxed for 3h at 60℃ to stop the reaction. The supernatant was dropped into anhydrous methanol for precipitation, and 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℃ for 24h. The polyphenylene ether polyol terminated with alcohol hydroxyl group was obtained as an off-white solid powder with a yield of 90%.

[0118] The chemical reaction process is speculated as shown in formula (2), where R' is EO, and the nuclear magnetic resonance spectroscopy shows that m+n=8, and the infrared characteristic peak is 3450cm -1 .

[0119] Embodiment 11

[0120] The preparation of polyphenylene ether polyol terminated with alcohol hydroxyl group was carried out in a manner similar to Example 10, except that NaH was added twice, 0.15 g each time, and EO was added twice, 1.5 g each time. The total reaction time was 18 h, and the yield was 89%.

[0121] H-NMR spectrum showed that m+n=12.

[0122] Example 12

[0123] The preparation of polyphenylene ether polyol terminated with alcohol hydroxyl group was carried out in a manner similar to Example 10, except that NaH was added twice, 0.15 g each time, and EO was added three times, 1.5 g each time. The total reaction time was 24 h, and the yield was 91%.

[0124] H-NMR spectrum showed that m+n=16.

[0125] Embodiment 13

[0126] The preparation of polyphenylene ether polyol terminated with alcohol hydroxyl group was carried out in a manner similar to Example 10, except that NaH was added five times, 0.15 g each time, and EO was added seven times, 1.5 g each time. The total reaction time was 36 h, and the yield was 87%.

[0127] The H-NMR spectrum showed that m+n=30.

[0128] Embodiment 14

[0129] The preparation of polyphenylene ether polyol terminated with alcohol hydroxyl group was carried out in a manner similar to Example 10, except that NaH was added seven times, 0.15 g each time, and EO was added eleven times, 1.5 g each time. The total reaction time was 48 h, and the yield was 86%.

[0130] The H-NMR spectrum showed that m+n=40.

[0131] Embodiment 15

[0132] The preparation of polyphenylene ether polyol terminated with alcoholic hydroxyl group was carried out in a manner similar to Example 10, except that EO was replaced by PO, the added amount was 2.00 g, and the yield was 92%.

[0133] H-NMR spectrum showed that m+n=8.

[0134] Example 16

[0135] The preparation of polyphenylene ether polyol terminated with alcoholic hydroxyl group was carried out in a manner similar to Example 11, except that EO was replaced by PO, and 2.00 g of PO was added each time, with a yield of 88%.

[0136] The magnetic hydrogen spectrum shows that m+n=12.

[0137] Embodiment 17

[0138] The preparation of polyphenylene ether polyol terminated with alcoholic hydroxyl group was carried out in a manner similar to Example 12, except that EO was replaced by PO, and 2.00 g of PO was added each time, with a yield of 88%.

[0139] H-NMR spectrum showed that m+n=16.

[0140] Embodiment 18

[0141] The preparation of polyphenylene ether polyol terminated with alcoholic hydroxyl group was carried out in a manner similar to Example 13, except that EO was replaced by PO, 2.00 g of PO was added each time, and the yield was 85%.

[0142] The H-NMR spectrum showed that m+n=30.

[0143] Embodiment 19

[0144] The preparation of polyphenylene ether polyol terminated with alcoholic hydroxyl group was carried out in a manner similar to Example 14, except that EO was replaced by PO, and 2.00 g of PO was added each time, with a yield of 87%.

[0145] The H-NMR spectrum showed that m+n=40.

[0146] Experimental example

[0147] Experimental Example 1

[0148] Since the product obtained in Example 1 1 The characteristic peak of alcoholic hydroxyl group was not observed in the H NMR spectrum, so methacrylic anhydride and alcoholic hydroxyl terminated polyphenylene ether diol were further used for esterification reaction to verify the correctness of its structure. The specific preparation process is as follows:

[0149] In a three-necked round-bottom flask equipped with a reflux condenser, 1.00 g (0.6 mmol) of the hydroxyl-terminated polyphenylene ether diol obtained in Example 1 and 0.28 g (1.70 mmol) of methyl methacrylate anhydride were added to 20 mL of toluene, and 0.2531 g (25 wt%) of DMAP (4-dimethylaminopyridine) was added as a catalyst, and the mixture was refluxed at 70°C for 10 h. After the reaction, the supernatant was dropped into methanol for precipitation, and filtered, and the filter cake was further washed with methanol. Finally, the product was dried in a vacuum oven at 80°C. The esterified product was an off-white solid powder with a yield of 97%. The chemical reaction process is presumably shown in Formula (3). The infrared spectrum of the product is shown in Figure 4 As shown, from Figure 4It can be seen that the infrared spectrum of the product obtained after esterification is 3450cm -1 The characteristic peak at disappeared, indicating that -OH disappeared after esterification.

[0150]

[0151] After esterification, the product MPPOD is obtained. 1 H NMR spectrum Figure 3 As shown, it is shown that the product prepared in Example 1 has alcoholic hydroxyl groups, and the alcoholic hydroxyl groups are located at both ends of the polymer, which further shows that the structural formula of the product prepared in Example 1 is shown in formula (1).

[0152] The present invention has been described in detail above in conjunction with specific implementations and exemplary examples, but these descriptions cannot be understood as limiting the present invention. Those skilled in the art understand that, without departing from the spirit and scope of the present invention, a variety of equivalent substitutions, modifications or improvements may be made to the technical solution of the present invention and its implementation methods, all of which fall within the scope of the present invention. The scope of protection of the present invention shall be subject to the attached claims.

Claims

1. A use of a polyphenylene ether polyol terminated with an alcohol hydroxyl group for modifying a polymer, wherein the polyphenylene ether polyol terminated with an alcohol hydroxyl group is represented by the following formula (1): In formula (1), the value of x+y is 10 to 50, the value of m+n is 2 to 500, and R is selected from hydrogen or methyl. The polymer is polyurethane or polystyrene, The alcoholic hydroxyl terminated polyphenylene ether polyol is prepared by a method comprising the following steps: Step 1, in the presence of a basic catalyst, reacting a dihydroxy-terminated polyphenylene ether and an epoxide in a solvent to obtain a reaction mixture; The epoxide is ethylene oxide (EO) or propylene oxide (PO), The alkaline catalyst is selected from one or more of potassium carbonate, potassium bicarbonate and sodium hydride, The solvent is one or two of N,N-dimethylformamide and tetrahydrofuran; Step 2, the reaction mixture is precipitated, washed, filtered and dried to obtain an alcohol hydroxyl terminated polyphenylene ether polyol; In step 1, the following steps are included: Step 1-1, adding a double-terminated polyphenylene ether and a basic catalyst into a solvent to perform a reflux reaction; Step 1-2, after the reaction is completed, the reaction is cooled, epoxide is added to the cooled system, and the temperature is raised to perform a reflux reaction; In step 1-1, the reaction temperature is 30 to 90° C. and the reaction time is 1 to 10 h; In step 1-2, the mixture is cooled to 0-10°C and heated to 30-90°C for reflux reaction.

2. The use according to claim 1, characterized in that In the formula (1), the value of m+n is 2 to 40.

3. The use according to claim 1, characterized in that Step 1 also includes the following steps: Step 1-3: After the reaction of step 1-2 is completed, an alkaline catalyst is added to carry out a reflux reaction. After the reaction is completed, the epoxide is added after cooling, and the temperature is raised to carry out a reflux reaction.

4. The use according to claim 1, characterized in that In step 1-1, the reaction temperature is 50-80°C and the reaction time is 2-8h; In step 1-2, the mixture is cooled to 0-5°C and heated to 50-80°C for reflux reaction.

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