Epoxy-terminated trithioester compound and preparation method and application thereof

Abstract

The present invention relates to the field of polymerization technology, and discloses a terminal epoxy trithioester compound and a preparation method and application thereof. The structure of the terminal epoxy trithioester compound of the present invention is shown in the following formula (1), wherein m, n and p respectively represent integers of 0-6. According to the present invention, a novel terminal epoxy trithioester compound can be provided, which can be used as a chain transfer agent for RAFT polymerization to prepare a double-end epoxy functionalized polymer, thereby realizing controlled radical polymerization of petroleum-based monomers.

Description

Technical Field

[0001] The invention relates to the field of polymerization technology, and in particular to a terminal epoxy trithioester compound and a preparation method and application thereof. Background Art

[0002] RAFT (Reversible Addition-Fragmentation Chain Transfer) polymerization is an important living free radical polymerization method that has developed rapidly since it was reported in the 1990s. Through RAFT polymerization, polymers with narrow molecular weight distribution can be obtained, and polymer structures such as block, star, and graft can be easily prepared, and end group functionalization can also be easily achieved. In RAFT polymerization, chain transfer agents play an important role. Only by selecting appropriate chain transfer agents can controlled polymerization be achieved, polymers with narrow molecular weight distribution can be obtained, and preset polymer structures can be achieved, thereby realizing different functions and uses of polymers.

[0003] Up to now, there is no suitable RAFT polymerization chain transfer agent that can achieve good polymerization control effect on petroleum-based monomers (styrene, butadiene, isoprene, etc.) and realize epoxy functionalization of polymer chain ends. Summary of the invention

[0004] The purpose of the present invention is to provide a novel terminal epoxy trithioester compound, which can be used as a chain transfer agent for RAFT polymerization to prepare a double-terminal epoxy functionalized polymer and realize the controlled free radical polymerization of petroleum-based monomers.

[0005] In order to achieve the above object, the present invention provides an epoxy-terminated trithioester compound, wherein the structure of the epoxy-terminated trithioester compound is as shown in the following formula (1):

[0006]

[0007] In formula (1), m, n and p each represent an integer of 0-6.

[0008] Preferably, the terminal epoxy trithioester compound is a compound having a structure represented by the following formula (1-1):

[0009]

[0010] According to a second aspect of the present invention, a method for preparing an epoxy-terminated trithioester compound is provided, wherein the method comprises the following steps:

[0011] 1) a step of subjecting a mixture containing carbon disulfide, ketone, tetrabutylammonium hydrogen sulfate and halogenated alkane to a contact reaction with a first base, and then acidifying the contact reaction product to obtain a compound having a structure represented by the following formula (2);

[0012] 2) contacting the compound represented by the formula (2) with an epoxide to obtain a compound represented by the formula (1) below,

[0013]

[0014] In the formula, m, n and p represent integers of 0-6 respectively.

[0015] Preferably, the ketone is one or more of acetone, methyl acetone, methyl isobutyl ketone and methyl isoamyl ketone.

[0016] Preferably, the halogenated alkane is one or more of chloroform, trichloroethane, trichloropropane and trichlorobutane.

[0017] Preferably, the contact reaction conditions include: a temperature of 0-30°C, and a reaction time of more than 5 hours; more preferably, the contact reaction conditions include: a temperature of 5-25°C, and a reaction time of 10-50 hours.

[0018] Preferably, the first alkali solution is added dropwise to the mixture to carry out the contact reaction.

[0019] Preferably, the alkali content in the first alkali solution is 30-70% by mass.

[0020] Preferably, the first base is sodium hydroxide and / or potassium hydroxide.

[0021] Preferably, the molar ratio of carbon disulfide to the ketone is 1:1-12.

[0022] Preferably, the molar ratio of carbon disulfide to tetrabutylammonium hydrogen sulfate is 15-150:1.

[0023] Preferably, the molar ratio of carbon disulfide to the halogenated alkane is 1:1-12.

[0024] Preferably, the molar ratio of carbon disulfide to the first base is 1:3-11.

[0025] Preferably, the mixture further contains a solvent.

[0026] Preferably, the solvent is petroleum ether.

[0027] Preferably, the amount of the solvent used is 2-6 ml, preferably 3-5 ml, relative to 1 g of carbon disulfide.

[0028] Preferably, the acid used for the acidification is one or more of hydrochloric acid, sulfuric acid and nitric acid.

[0029] Preferably, the molar ratio of carbon disulfide to the acid is 1:5-20.

[0030] Preferably, the method further comprises recrystallizing the acidified product.

[0031] Preferably, the recrystallization solvent is a mixture of toluene and acetone.

[0032] Preferably, the molar ratio of toluene to acetone in the mixed solution of toluene and acetone is 1:3-3:1.

[0033] Preferably, the step of contacting the compound of formula (2) with an epoxide comprises: contacting the compound of formula (2) with a haloalkylene oxide in the presence of a second base.

[0034] Preferably, the halogenated alkylene oxide is epichlorohydrin and / or epichlorohydrin.

[0035] Preferably, the step of contacting the compound with the structure represented by formula (2) with epoxide comprises: subjecting the compound with the structure represented by formula (2) to an esterification reaction with epoxy alcohol.

[0036] Preferably, the epoxy alcohol is one or more of glycidol, glycidol, glycidol and glycidol.

[0037] According to a third aspect of the present invention, there is provided an epoxy-terminated trithioester compound prepared by the method for preparing the epoxy-terminated trithioester compound of the present invention.

[0038] According to a fourth aspect of the present invention, there is provided use of the epoxy-terminated trithioester compound of the present invention as a chain transfer agent.

[0039] Through the above technical scheme, a new type of terminal epoxy trithioester compound can be provided, which can be used as a chain transfer agent for RAFT polymerization to prepare a double-terminal epoxy functionalized polymer, thereby realizing the controlled free radical polymerization of petroleum-based monomers. BRIEF DESCRIPTION OF THE DRAWINGS

[0040] Figure 1 This is the H-NMR spectrum of the compound with the structure represented by formula (2-1) obtained in Example 1.

[0041] Figure 2 This is the H-NMR spectrum of the compound with the structure represented by formula (1-1) obtained in Example 1.

[0042] Figure 3 This is the mass spectrum of the compound represented by formula (1-1) obtained in Example 1.

[0043] Figure 4 It is the kinetic curve of the polymerization process of styrene butadiene solution copolymerization in Example 6. DETAILED DESCRIPTION

[0044] The endpoints and any values ​​of the ranges disclosed in this article are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of each range, the endpoint values ​​of each range and the individual point values, and the individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed in this article.

[0045] In one aspect, the present invention provides an epoxy-terminated trithioester compound, wherein the structure of the epoxy-terminated trithioester compound is as shown in the following formula (1):

[0046]

[0047] In formula (1), m, n and p each represent an integer of 0-6.

[0048] According to the present invention, the terminal epoxy trithioester compound is a chemical structure with a trithioester bond in the middle of the molecule and epoxy functional groups at both ends.

[0049] As mentioned above, m, n and p can be 0, 1, 2, 3, 4, 5 and 6 respectively; preferably, m, n and p are 0, 1, 2 and 3 respectively; more preferably, m, n and p are 0, 1 and 2 respectively.

[0050] In the present invention, examples of the epoxy-terminated trithioester compound include:

[0051] A compound represented by formula (1) wherein m=0, n=p=0 (i.e., a compound represented by formula (1-1) below);

[0052]

[0053] A compound represented by formula (1) wherein m=1, n=p=0;

[0054] A compound wherein m=1, n=p=1 in the structure represented by formula (1);

[0055] A compound represented by formula (1) wherein m=1, n=p=2;

[0056] A compound represented by formula (1) wherein m=1, n=p=3;

[0057] A compound represented by formula (1) wherein m=1, n=p=4;

[0058] A compound represented by formula (1) wherein m=1, n=p=5;

[0059] A compound wherein m=1, n=p=6 in the structure represented by formula (1).

[0060] According to a second aspect of the present invention, a method for preparing an epoxy-terminated trithioester compound is provided, wherein the method comprises the following steps:

[0061] 1) a step of subjecting a mixture containing carbon disulfide, ketone, tetrabutylammonium hydrogen sulfate and halogenated alkane to a contact reaction with a first base, and then acidifying the contact reaction product to obtain a compound having a structure represented by the following formula (2);

[0062] 2) contacting the compound represented by the formula (2) with an epoxide to obtain a compound represented by the formula (1) below,

[0063]

[0064] In the formula, m, n and p represent integers of 0-6 respectively.

[0065] As mentioned above, m, n and p can be 0, 1, 2, 3, 4, 5 and 6 respectively; preferably, m, n and p are 0, 1, 2 and 3 respectively; more preferably, m, n and p are 0, 1 and 2 respectively.

[0066] According to the present invention, preferably, the ketone is one or more of acetone, methyl acetone, methyl isobutyl ketone and methyl isoamyl ketone.

[0067] According to the present invention, preferably, the halogenated alkane is one or more of chloroform, trichloroethane, trichloropropane and trichlorobutane.

[0068] According to the present invention, preferably, the epoxide is a halogenated alkylene oxide and / or an epoxy alcohol.

[0069] Preferred examples of the halogenated alkylene oxide include epichlorohydrin and / or epichlorohydrin.

[0070] The epoxy alcohol is preferably one or more of glycidol, glycidol, glycidol and glycidol; more preferably glycidol and / or glycidol.

[0071] According to the present invention, the compound having the structure represented by formula (2) includes, for example:

[0072] In formula (2), a compound in which both n and p are 0 (i.e., a compound represented by the following formula (2-1));

[0073]

[0074] In formula (2), a compound in which n and p are both 1;

[0075] In formula (2), a compound in which n and p are both 2;

[0076] In formula (2), n and p are both 3;

[0077] In formula (2), n and p are both 4;

[0078] In formula (2), the compound wherein n and p are both 5;

[0079] In the formula (2), a compound wherein n and p are both 6.

[0080] According to the present invention, in step 1), preferably, the conditions of the contact reaction include: a temperature of 0-30°C, and a reaction time of more than 5 hours; more preferably, the conditions of the contact reaction include: a temperature of 5-25°C, and a reaction time of 10-50 hours.

[0081] According to the present invention, the first base may be various inorganic bases commonly used in the art, for example, sodium hydroxide and / or potassium hydroxide, more preferably sodium hydroxide.

[0082] According to the present invention, the first alkali is preferably used in the form of a solution. When used in the form of a solution, its concentration (the alkali content in the first alkali solution) is preferably 30-70% by mass, more preferably 40-60% by mass.

[0083] According to the present invention, it is preferred that the first alkali solution is added dropwise to the mixture to carry out the contact reaction.

[0084] According to the present invention, the amount of the ketone can be appropriately determined based on carbon disulfide. Preferably, the molar ratio of carbon disulfide to the ketone is 1:1-12; more preferably, the molar ratio of carbon disulfide to the ketone is 1:2-9; further preferably, the molar ratio of carbon disulfide to the ketone is 1:2-5; further preferably, the molar ratio of carbon disulfide to the ketone is 1:2.5-4.

[0085] According to the present invention, preferably, the molar ratio of carbon disulfide to tetrabutylammonium hydrogen sulfate is 15-150:1; more preferably, the molar ratio of carbon disulfide to tetrabutylammonium hydrogen sulfate is 15-130:1; further preferably, the molar ratio of carbon disulfide to tetrabutylammonium hydrogen sulfate is 20-110:1.

[0086] According to the present invention, the amount of the halogenated alkane can be appropriately determined based on carbon disulfide. Preferably, the molar ratio of carbon disulfide to the halogenated alkane is 1:1-12; more preferably, the molar ratio of carbon disulfide to the halogenated alkane is 1:1-9; further preferably, the molar ratio of carbon disulfide to the halogenated alkane is 1:1-5; further preferably, the molar ratio of carbon disulfide to the halogenated alkane is 1:1.2-2.6.

[0087] According to the present invention, the amount of the first base can be appropriately determined according to carbon disulfide. Preferably, the molar ratio of carbon disulfide to the first base is 1:3-11; more preferably, the molar ratio of carbon disulfide to the first base is 1:3-10.

[0088] According to the present invention, preferably, the mixture further contains a solvent; preferably, the solvent is one or more of petroleum ether, dioxane and dichloromethane; more preferably, the solvent is petroleum ether.

[0089] Preferably, the amount of the solvent used is 2-6 ml, preferably 3-5 ml, relative to 1 g of carbon disulfide.

[0090] According to the present invention, in step 1), the acidification can be carried out using an acid commonly used in the art, preferably, the acid used for the acidification is one or more of hydrochloric acid, sulfuric acid and nitric acid; more preferably, the acid is hydrochloric acid. The acidification can use an acid with a higher concentration, for example, concentrated hydrochloric acid.

[0091] According to the present invention, the amount of the acid can be appropriately determined based on carbon disulfide. Preferably, the molar ratio of carbon disulfide to the acid is 1:5-20.

[0092] According to the present invention, preferably, the method further comprises recrystallizing the acidified product. The solvent used for the crystallization is preferably a mixture of toluene and acetone. In the mixture of toluene and acetone, the molar ratio of toluene to acetone in the mixture of toluene and acetone is 1:3-3:1.

[0093] According to the present invention, the method for contacting the compound represented by the formula (2) with the epoxide may be any one of the following methods 1) to 4).

[0094] Method 1)

[0095] The step of contacting the compound represented by formula (2) with an epoxide comprises: contacting the compound represented by formula (2) with the halogenated epoxyalkane in the presence of a second base.

[0096] Preferably, the compound of the structure represented by formula (2) is first reacted with the second base, and then the haloalkylene oxide is added dropwise to the reaction product to carry out the contact reaction.

[0097] The temperature for reacting the compound of formula (2) with the second base can be, for example, 30-70°C, and the reaction time can be, for example, 20-120 minutes. Preferably, the temperature for reacting the compound of formula (2) with the second base is 60-70°C, and the reaction time is 50-80 minutes.

[0098] The temperature for adding the halogenated epoxyalkane dropwise to the reaction product to carry out the contact reaction may be, for example, room temperature (5-45° C.), and the reaction time may be, for example, 5-48 hours, preferably 15-30 hours.

[0099] The second base may be any inorganic base commonly used in the art, for example, sodium hydroxide and / or potassium hydroxide, more preferably sodium hydroxide.

[0100] In method 1), the amount of the second base can be appropriately selected according to the amount of the compound of the structure represented by formula (2). Preferably, the molar ratio of the compound of the structure represented by formula (2) to the second base is 1:2-5. The molar ratio of the compound of the structure represented by formula (2) to the second base can be 1:2, 1:3, 1:4 or 1:5, etc.

[0101] In method 1), the amount of the halogenated alkylene oxide can be appropriately selected according to the amount of the compound of the structure represented by formula (2). Preferably, the molar ratio of the compound of the structure represented by formula (2) to the halogenated alkylene oxide is 1:2-5. The molar ratio of the compound of the structure represented by formula (2) to the halogenated alkylene oxide can be 1:2, 1:3, 1:4 or 1:5, etc.

[0102] Preferably, in method 1), the contact reaction is carried out in the presence of an organic solvent. The organic solvent may be an organic solvent that can dissolve the reaction raw materials and is inert to the reaction raw materials. Such an organic solvent may be, for example, dioxane.

[0103] After the reaction is completed, various methods known in the art can be used for purification, for example, the crude product can be eluted through a silica gel column for purification.

[0104] Method 2)

[0105] The step of contacting the compound of the structure represented by formula (2) with epoxide comprises: allowing the compound of the structure represented by formula (2) to undergo an esterification reaction with the epoxy alcohol.

[0106] Specifically, in method 2), in the presence of an organic solvent, the compound of the structure represented by formula (2) is contacted with dicyclohexylcarbodiimide or 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride, and 4-dimethylaminopyridine, and then esterified with the epoxy alcohol.

[0107] Preferably, in method 2), the molar ratio of the compound of the structure represented by formula (2) to dicyclohexylcarbodiimide or 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride is 1:1-5. The molar ratio of the compound of the structure represented by formula (2) to dicyclohexylcarbodiimide or 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride can be 1:1, 1:2, 1:3, 1:4 or 1:5, etc.

[0108] Preferably, in method 2), the molar ratio of the compound of formula (2) to 4-dimethylaminopyridine is 2-6: 1. The molar ratio of the compound of formula (2) to 4-dimethylaminopyridine can be 2: 1, 3: 1, 4: 1, 5: 1 or 6: 1.

[0109] Preferably, in method 2), the molar ratio of the compound of formula (2) to the organic solvent is 1:1-4. The molar ratio of the compound of formula (2) to the organic solvent can be 1:1, 1:2, 1:3 or 1:4.

[0110] The contacting may be carried out at room temperature (5-45° C.), and the contacting time may be 10-50 minutes, preferably 20-40 minutes.

[0111] The above esterification reaction can also be carried out at room temperature (5-45° C.), and the reaction time can be 10-100 hours, preferably 24-96 hours (1-4 days).

[0112] The organic solvent may be an organic solvent that can dissolve the reaction raw materials and is inert to the reaction raw materials. Examples of such an organic solvent include one or more of dichloromethane, dioxane and chloroform.

[0113] After the reaction is completed, various methods known in the art can be used for purification, for example, the crude product can be eluted through a silica gel column for purification.

[0114] Method 3)

[0115] Method 3) also includes: subjecting the compound having the structure shown in formula (2) to an esterification reaction with the epoxy alcohol.

[0116] Specifically, in method 3), the compound of the structure shown in formula (2) is first contacted with a SOCl2 solution to react to obtain an intermediate product, and then the solution containing the intermediate product is added dropwise to the epoxy alcohol solution in the presence of a third base.

[0117] The temperature for the contact reaction of the compound of formula (2) with SOCl2 solution can be, for example, 50-65°C, preferably reflux temperature, and the time for the contact reaction can be, for example, 1-5 hours, preferably 2-4 hours. In addition, the contact reaction is preferably carried out under anhydrous conditions.

[0118] Preferably, the molar ratio of the compound of formula (2) to SOCl2 is 1:2-30. The molar ratio of the compound of formula (2) to SOCl2 can be 1:2, 1:3, 1:4, 1:5, 1:6, 1:7, 1:8, 1:10, 1:12, 1:15, 1:20, 1:25 or 1:30, etc.

[0119] Preferably, method 3) further comprises, after the contact reaction is completed, continuously purging the reaction liquid with nitrogen until the reaction liquid becomes solid.

[0120] Preferably, the content of the intermediate product in the solution in which the intermediate product is dissolved is 50% by mass or more, preferably 50-95% by mass. In addition, the solvent for dissolving the intermediate product may be one or more of dichloromethane, dioxane and chloroform. In addition, the solvent is preferably an anhydrous solvent.

[0121] Preferably, in method 3), the amount of the epoxy alcohol used can be appropriately selected according to the amount of the compound of the structure shown in formula (2). Preferably, the molar ratio of the compound of the structure shown in formula (2) to the epoxy alcohol is 1:2-8. The molar ratio of the compound of the structure shown in formula (2) to the epoxy alcohol can be 1:2, 1:3, 1:4, 1:5, 1:6, 1:7 or 1:8, etc.

[0122] Preferably, in method 3), the amount of the third base can be appropriately selected according to the amount of the compound of the structure shown in formula (2). Preferably, the molar ratio of the compound of the structure shown in formula (2) to the third base is 1:1-4. The third base can be the same as the first base and the second base. The molar ratio of the compound of the structure shown in formula (2) to the third base can be 1:1, 1:2, 1:3 or 1:4, etc.

[0123] Preferably, in method 3), the content of epoxy alcohol in the epoxy alcohol solution may be 50-100% by mass. The solvent in the epoxy alcohol solution may be, for example, one or more of dichloromethane, dioxane and chloroform. From the perspective of reducing impurities, it is preferably the same as the solvent for dissolving the intermediate product.

[0124] Preferably, in method 3), the dropping speed is sufficient as long as the temperature of the reaction system is kept at 0-10° C. In addition, the reaction time after the dropping can be, for example, more than 5 hours, preferably 12-36 hours.

[0125] After the reaction is completed, various methods known in the art can be used for purification, for example, the crude product can be eluted through a silica gel column for purification.

[0126] Method 4)

[0127] Method 4) also comprises: subjecting the compound having the structure represented by formula (2) to an esterification reaction with the epoxy alcohol.

[0128] Specifically, in method 4), a diisopropyl azodicarboxylate solution is added dropwise to a solution containing the compound of formula (2), the epoxy alcohol and triphenylphosphine.

[0129] Preferably, in method 4), the molar ratio of the compound of formula (2) to the epoxy alcohol is 1:2-8. The molar ratio of the compound of formula (2) to the epoxy alcohol can be 1:2, 1:3, 1:4, 1:5, 1:6, 1:7 or 1:8, etc.

[0130] Preferably, in method 4), the molar ratio of the compound of formula (2) to triphenylphosphine is 1-5: 1. The molar ratio of the compound of formula (2) to triphenylphosphine can be 1: 1, 2: 1, 3: 1, 4: 1 or 5: 1.

[0131] Preferably, in method 4), the molar ratio of the compound of formula (2) to diisopropyl azodicarboxylate is 1:5-10. The molar ratio of the compound of formula (2) to diisopropyl azodicarboxylate can be 1:5, 1:6, 1:7, 1:8, 1:9 or 1:10, etc.

[0132] Preferably, in method 4), the solvent in the solution containing the compound of the structure shown in formula (2), the epoxy alcohol and triphenylphosphine can be, for example, one or more of tetrahydrofuran, dioxane and chloroform. The amount of the solvent used here can be appropriately selected according to the amount of the compound of the structure shown in formula (2). For example, the amount of the solvent used is 1-4 moles relative to 1 mole of the compound of the structure shown in formula (2).

[0133] Preferably, in method 4), the content of diisopropyl azodicarboxylate in the diisopropyl azodicarboxylate solution may be 50% by mass or more, preferably 50-95% by mass. The solvent in the diisopropyl azodicarboxylate solution may be, for example, one or more of tetrahydrofuran, dioxane and chloroform. From the perspective of reducing impurities, the solvent is preferably the same as the solvent for dissolving the intermediate product. In addition, the solvent is preferably an anhydrous solvent.

[0134] Preferably, in method 4), the dropping speed is sufficient as long as the temperature of the reaction system is kept at 0-10° C. In addition, the reaction time after the dropping can be, for example, more than 10 hours, preferably 20-60 hours.

[0135] After the reaction is completed, various methods known in the art can be used for purification, for example, the crude product can be eluted through a silica gel column for purification.

[0136] According to a third aspect of the present invention, there is provided an epoxy-terminated trithioester compound prepared by the method for preparing the epoxy-terminated trithioester compound of the present invention.

[0137] According to a fourth aspect of the present invention, there is provided use of the epoxy-terminated trithioester compound of the present invention as a chain transfer agent.

[0138] The present invention will be described in detail below by way of examples. In the following examples, unless otherwise specified, all reagents used are commercially available.

[0139] Example 1

[0140] 1) Add carbon disulfide (30.14g) to a 2L round-bottom flask containing 120mL petroleum ether and a magnetic stirrer, then add acetone (57.53g), tetrabutylammonium hydrogen sulfate (2.65g), chloroform (118.25g), cool in an ice bath, stir for 10 minutes, ensure that the temperature is below 20°C, and add 221.76g of a 50% sodium hydroxide aqueous solution dropwise within 90 minutes, during which the temperature must be kept below 25°C. The reaction is stirred overnight. Add 850mL of distilled water to the round-bottom flask, then directly add 115mL of concentrated hydrochloric acid, and react with magnetic stirring for 30 minutes. Filter the reaction solution, place it in a room temperature oven to dry for 48 hours, and recrystallize it in 100mL of a toluene / acetone mixture (the volume ratio of toluene to acetone is 4:6). The reaction solution was filtered and placed in a room temperature oven to dry for 48 hours. The light yellow solid was the compound represented by formula (2-1) (hereinafter also referred to as BDAAT). Its H NMR spectrum was as follows: Figure 1 shown.

[0141] 2) Take BDAAT (1.16 g) and NaOH (0.327 g) and add them to a 250 mL round-bottom flask equipped with a rotor and a thermometer, and stir at 65°C for 30 minutes. Use a constant pressure separatory funnel to drop epichlorohydrin (7.06 g), and keep the temperature at 65°C. React overnight with stirring. The reaction solution is washed with water and the organic phase is distilled under reduced pressure. The crude product is eluted through a silica gel column with hexane / ethyl acetate (the volume ratio of hexane to ethyl acetate is 1:1) to obtain a compound with the structure shown in formula (1-1) (hereinafter also referred to as BODAAT), which is a yellow-brown oil with a yield of 30%. Its nuclear magnetic resonance hydrogen spectrum is as follows Figure 2 As shown, the MS spectrum is Figure 3 shown.

[0142] Example 2

[0143] 1) Add carbon disulfide (30.14 g) to a 2L round-bottom flask containing 90 mL of petroleum ether and a magnetic stirrer, then add acetone (61 g), tetrabutylammonium bisulfate (0.75 g), chloroform (60 g), cool in an ice bath, stir for 10 minutes, ensure that the temperature is below 20°C, and add 100 g of a 50% sodium hydroxide aqueous solution dropwise within 80 minutes, during which the temperature must be kept below 25°C. The reaction is stirred overnight. Add 750 mL of distilled water to the round-bottom flask, then directly add 150 mL of concentrated hydrochloric acid, and react with magnetic stirring for 45 minutes. Filter the reaction solution, place it in a room temperature oven to dry for 48 hours, and recrystallize it in 100 mL of a toluene / acetone mixture (the volume ratio of toluene to acetone is 4:6). The reaction solution is filtered and placed in a room temperature oven to dry for 48 hours. The light yellow solid is identified by nuclear magnetic resonance as the compound (BDAAT) with the structure shown in formula (2-1).

[0144] 2) A 250 mL round-bottom flask with a rotor was placed at a constant temperature of 25°C, and BDAAT (0.53 g), dicyclohexylcarbodiimide (0.567 g), 4-dimethylaminopyridine (0.07 g) and 100 mL of dichloromethane were added, stirred at 25°C for 30 minutes, and then glycidol (0.4 g) was added. The reaction was carried out at 25°C for 72 hours. After washing with water, the liquid was separated, and the organic phase was distilled under reduced pressure. The crude product was eluted with hexane / ethyl acetate (the volume ratio of hexane to ethyl acetate was 1:1) through a silica gel column to obtain a yellow-brown oil (yield was 40%). The yellow-brown oil was confirmed to be BODAAT by nuclear magnetic resonance and mass spectrometry.

[0145] Example 3

[0146] 1) Add carbon disulfide (30.14 g) to a 2L round-bottom flask containing 150 mL of petroleum ether and a magnetic stirrer, then add acetone (90 g), tetrabutylammonium bisulfate (0.5 g), chloroform (90 g), cool in an ice bath, stir for 10 minutes, ensure that the temperature is below 20°C, and add 300 g of a 50% sodium hydroxide aqueous solution dropwise within 90 minutes, during which the temperature must be kept below 25°C. The reaction is stirred overnight. Add 900 mL of distilled water to the round-bottom flask, then directly add 450 mL of concentrated hydrochloric acid, and react with magnetic stirring for 90 minutes. Filter the reaction solution, place it in a room temperature oven to dry for 48 hours, and recrystallize it in 100 mL of a toluene / acetone mixture (the volume ratio of toluene to acetone is 4:6). The reaction solution is filtered and placed in a room temperature oven to dry for 48 hours. The light yellow solid is identified by nuclear magnetic resonance as the compound (BDAAT) with the structure shown in formula (2-1).

[0147] 2) Add BDAAT (1.41 g) in a SOCl2 solution (6 mL) to an oven-dried round-bottom flask equipped with a condenser, and stir and reflux at 60°C for 3 hours; remove the condenser, continue to purge the reaction solution with nitrogen until the reaction solution becomes solid, stop heating, and obtain an intermediate product, which is dissolved in anhydrous dichloromethane (10 mL) for standby use. Add propylene oxide (0.82 g) and NaOH (0.5 g) to another dry round-bottom flask equipped with a magnetic stirrer, ice bath to 0°C, and under continuous stirring, dropwise add the anhydrous dichloromethane solution containing the intermediate product, and stir overnight. Add 40°C distilled water to the reaction solution, and the organic phase is distilled under reduced pressure to a high concentration and then purified by flash column chromatography to obtain a yellow-brown oil (yield 70%). The yellow-brown oil obtained is confirmed to be BODAAT by nuclear magnetic resonance and mass spectrometry.

[0148] Example 4

[0149] 1) According to step 1) of Example 1, BDAAT was obtained.

[0150] 2) Add BDAAT (0.50 g), glycidol (0.28 g), triphenylphosphine (1.48 g) and 8 mL of anhydrous tetrahydrofuran to a round-bottom flask under a nitrogen atmosphere. Soak the flask in an ice bath and dropwise add diisopropyl azodicarboxylate (1.80 mL) in 5 mL of dry tetrahydrofuran. Keep the temperature of the mixture below 10°C. Stir at room temperature for 24 hours, then stir at 40°C for 24 hours. The reaction mixture is cooled to room temperature, diluted with 20 mL of dichloromethane, and washed twice with 10 mL of saturated sodium bicarbonate aqueous solution. The composite organic layer is dried over magnesium sulfate and concentrated in vacuo. Purification by flash column chromatography gives a yellow-brown oil (yield 60%), which is confirmed to be BODAAT by nuclear magnetic resonance and mass spectrometry.

[0151] Example 5

[0152] 1) According to step 1) of Example 1, BDAAT was obtained.

[0153] 2) Add BDAAT (0.50 g), butylene oxide (0.30 g), triphenylphosphine (1.48 g) and 8 mL of anhydrous tetrahydrofuran to a round-bottom flask under a nitrogen atmosphere. Soak the flask in an ice bath and dropwise add diisopropyl azodicarboxylate (1.80 mL) in 5 mL of dry tetrahydrofuran. Keep the temperature of the mixture below 10°C. Stir at room temperature for 24 hours, and then stir at 40°C for 24 hours. Cool the reaction mixture to room temperature, dilute with 20 mL of dichloromethane, and wash twice with 10 mL of saturated sodium bicarbonate aqueous solution. Dry the composite organic layer over magnesium sulfate and concentrate in vacuo. Purify by flash column chromatography to obtain a yellow-brown oil (yield 60%). The yellow-brown oil is confirmed by nuclear magnetic resonance and mass spectrometry to be the compound with m=1 and n=p=0 in the structure shown in formula (1) (hereinafter also referred to as BODAAT2).

[0154] Example 6

[0155] 1) The process was carried out in accordance with step 1) of Example 1, except that acetone was replaced by methyl isoamyl ketone and chloroform was replaced by trichlorobutane, to obtain a compound BDAAT (n=p=3) represented by formula (2).

[0156] 2) Add BDAAT (0.50 g), butylene oxide (0.30 g), triphenylphosphine (1.48 g) and 8 mL of anhydrous tetrahydrofuran to a round-bottom flask under a nitrogen atmosphere. Immerse the flask in an ice bath and dropwise add diisopropyl azodicarboxylate (1.80 mL) in 5 mL of dry tetrahydrofuran. Keep the temperature of the mixture below 10°C. Stir at room temperature for 24 hours, and then stir at 40°C for 24 hours. Cool the reaction mixture to room temperature, dilute with 20 mL of dichloromethane, and wash twice with 10 mL of saturated sodium bicarbonate aqueous solution. Dry the composite organic layer over magnesium sulfate and concentrate in vacuo. Purify by flash column chromatography to obtain a yellow-brown oil (yield 60%). The yellow-brown oil is confirmed by nuclear magnetic resonance and mass spectrometry to be the compound with m=1, n=p=3 in the structure shown in formula (1) (hereinafter also referred to as BODAAT3).

[0157] Example 7

[0158] Take dioxane (1.17 mol), styrene monomer (66.88 mmol), butadiene monomer (92.00 mmol), BODAAT prepared in Example 4 (0.84 mmol) and azobisisobutyronitrile (0.17 mmol) and add them to a stainless steel high-temperature and high-pressure reactor, wherein the molar ratio of styrene monomer to BODAAT is 80:1, and the molar ratio of BODAAT to azobisisobutyronitrile is 5:1. The reactor was flushed with nitrogen three times, then the solution was degassed, and the reactor was sealed under nitrogen. The reactor was heated at 95°C with stirring for 30 hours. The reaction solution was dripped into methanol (300 mL) solvent, and the mixed product was treated by centrifugation. The solid product was dried in a high-temperature vacuum oven (45°C, 0.7 kPa) for 48 hours to obtain a solution-polymerized styrene-butadiene rubber with epoxy functionalization at both ends.

[0159] In addition, with the same material feed ratio as above, the polymerization time was changed to obtain multiple groups of polymers with different monomer conversion rates. The number average molecular weight and polymer molecular weight distribution of each group of polymers were measured by GPC using N,N-dimethylacetamide as the mobile phase. The monomer conversion rate of each group of polymers was then calculated based on the measured number average molecular weight. Finally, the Figure 4 The kinetic curve.

[0160] Figure 4 The kinetic curve of the polymerization process was presented, which showed linear first-order kinetic behavior and a polymer molecular weight distribution of <1.50. These data were consistent with the characteristics of well-controlled reversible deactivation free radical polymerization, proving that the living free radical polymerization of styrene butadiene solution copolymerization was successfully achieved using trithioester organic matter with epoxy functional groups as chain transfer agents.

[0161] Example 8

[0162] Take dioxane (1.17 mol), styrene monomer (66.88 mmol), butadiene monomer (92.00 mmol), BODAAT2 prepared in Example 5 (m = 1, n = p = 0, 0.84 mmol) and azobisisobutyronitrile (0.17 mmol) and add them to a stainless steel high-temperature and high-pressure reactor, wherein the molar ratio of styrene monomer to BODAAT is 80:1, and the molar ratio of BODAAT2 to azobisisobutyronitrile is 5:1. The reactor is flushed with nitrogen three times, then the solution is degassed, and the reactor is sealed under nitrogen. The reactor is heated at 95°C with stirring for 30 hours. The reaction solution is dripped into methanol (300 mL) solvent, and the mixed product is treated by centrifugation. The solid product is dried in a high-temperature vacuum oven (45°C, 0.7 kPa) for 48 hours to obtain a solution-polymerized styrene-butadiene rubber with epoxy functionalization at both ends.

[0163] Example 9

[0164] Take dioxane (1.17 mol), styrene monomer (66.88 mmol), butadiene monomer (92.00 mmol), BODAAT3 prepared in Example 6 (m = 1, n = p = 3, 0.84 mmol) and azobisisobutyronitrile (0.17 mmol) and add them to a stainless steel high-temperature and high-pressure reactor, wherein the molar ratio of styrene monomer to BODAAT is 80:1, and the molar ratio of BODAAT3 to azobisisobutyronitrile is 5:1. The reactor is flushed with nitrogen three times, then the solution is degassed, and the reactor is sealed under nitrogen. The reactor is heated and stirred at 95°C for 30 hours. The reaction solution is dripped into methanol (300 mL) solvent, and the mixed product is treated by centrifugation. The solid product is dried in a high-temperature vacuum oven (45°C, 0.7 kPa) for 48 hours to obtain a solution-polymerized styrene-butadiene rubber with epoxy functionalization at both ends.

[0165] The preferred embodiments of the present invention are described in detail above, but the present invention is not limited thereto. Within the technical concept of the present invention, the technical solution of the present invention can be subjected to a variety of simple modifications, including the combination of various technical features in any other suitable manner, and these simple modifications and combinations should also be regarded as the contents disclosed by the present invention and belong to the protection scope of the present invention.

Claims

1. A terminal epoxy trithioester compound, characterized in that: The structure of the epoxy-terminated trithioester compound is shown in the following formula (1): Formula (1) In formula (1), m, n and p represent integers of 0-6 respectively.

2. The epoxy-terminated trithioester compound according to claim 1, wherein The epoxy-terminated trithioester compound is a compound having a structure represented by the following formula (1-1): Formula (1-1).

3. A method for preparing a terminal epoxy trithioester compound, characterized in that: The method comprises the following steps: 1) a step of contacting a mixture containing carbon disulfide, ketone, tetrabutylammonium hydrogen sulfate and halogenated alkane with a first base, and then acidifying the contact reaction product to obtain a compound having a structure represented by the following formula (2); 2) contacting the compound represented by the formula (2) with an epoxide to obtain a compound represented by the formula (1) below, Formula (2) Formula (1) In the formula, m, n and p represent integers of 0-6 respectively.

4. The method according to claim 3, wherein: The ketone is one or more of acetone, methyl acetone, methyl isobutyl ketone and methyl isoamyl ketone.

5. The method according to claim 3, wherein: The halogenated alkane is one or more of chloroform, trichloroethane, trichloropropane and trichlorobutane.

6. The method according to claim 3, wherein: The contact reaction conditions include: a temperature of 0-30° C. and a reaction time of more than 5 hours.

7. The method according to claim 6, wherein: The contact reaction conditions include: a temperature of 5-25° C. and a reaction time of 10-50 hours.

8. The method according to claim 3, wherein: The first alkali solution is added dropwise to the mixture to carry out the contact reaction.

9. The method according to claim 8, wherein: The alkali content in the first alkali solution is 30-70% by mass.

10. The method according to claim 3, wherein: The first alkali is sodium hydroxide and / or potassium hydroxide.

11. The method according to claim 3, wherein: The molar ratio of carbon disulfide to the ketone is 1:1-12.

12. The method according to claim 3, wherein: The molar ratio of carbon disulfide to tetrabutylammonium hydrogen sulfate is 15-150:

1.

13. The method according to claim 3, wherein: The molar ratio of carbon disulfide to the halogenated alkane is 1:1-12.

14. The method according to claim 3, wherein: The molar ratio of carbon disulfide to the first base is 1:3-11.

15. The method according to claim 3, wherein: The mixture also contains a solvent.

16. The method according to claim 15, wherein: The solvent is petroleum ether.

17. The method according to claim 15, wherein: The amount of the solvent used is 2-6 ml relative to 1 g of carbon disulfide.

18. The method according to claim 17, wherein: The amount of the solvent used is 3-5 ml relative to 1 g of carbon disulfide.

19. The method according to any one of claims 3 to 18, wherein: The acid used for the acidification is one or more of hydrochloric acid, sulfuric acid and nitric acid.

20. The method according to claim 19, wherein: The molar ratio of carbon disulfide to the acid is 1:5-20.

21. The method according to any one of claims 3 to 18, wherein: The method further comprises recrystallizing the acidified product.

22. The method according to claim 21, wherein: The solvent for the recrystallization is a mixed solution of toluene and acetone.

23. The method according to claim 22, wherein: The molar ratio of toluene to acetone in the mixed solution of toluene and acetone is 1:3-3:

1.

24. The method according to any one of claims 3 to 18, wherein: The step of contacting the compound represented by formula (2) with epoxide comprises: contacting the compound represented by formula (2) with halogenated epoxyalkylene in the presence of a second base.

25. The method according to claim 24, wherein: The halogenated alkylene oxide is epichlorohydrin and / or epichlorohydrin.

26. The method according to any one of claims 3 to 18, wherein: The step of contacting the compound represented by the formula (2) with an epoxide comprises: subjecting the compound represented by the formula (2) to an esterification reaction with an epoxy alcohol.

27. The method according to claim 26, wherein: The epoxy alcohol is one or more of glycidol, glycidol, glycidol and glycidol.

28. Use of the epoxy-terminated trithioester compound according to claim 1 or 2 as a chain transfer agent.

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