Copolymer of vinylpyridine monomer, styrene monomer and acrylate monomer and preparation method thereof

Abstract

The invention discloses a vinyl pyridine monomer, styrene monomer and acrylate monomer copolymer and a preparation method thereof, the method comprises the following steps: 1) mixing a small molecule RAFT reagent, a vinyl pyridine monomer, a first initiator and a first solvent for polymerization reaction to obtain a CTA-terminated polyvinyl pyridine polymer; 2) mixing the CTA-terminated polyvinyl pyridine polymer, a styrene monomer, a second initiator, an emulsifier, a buffering agent and a second solvent for polymerization reaction to obtain a CTA-terminated poly (vinyl pyridine-b-styrene) polymer; and 3) mixing the CTA-terminated poly (vinylpyridine-b-styrene) polymer, an acrylate monomer, a third initiator and a third solvent, and carrying out a polymerization reaction to obtain the (vinylpyridine-b-styrene-b-acrylate) copolymer. According to the invention, the prepared product has a narrow polymer dispersity index (lt; 1.2), and the conversion rates of the three monomers are all increased to 95% or above.

Description

Technical Field

[0001] This invention relates to the field of polymer preparation technology, and more specifically, to a copolymer of vinylpyridine monomers, styrene monomers and acrylate monomers, and a method for preparing the same. Background Technology

[0002] Poly(vinylpyridine-b-styrene-b-acrylate) and similar polymers are a class of functional copolymers with wide applications in various fields due to their unique chemical structure and properties. The following are their main applications and functions:

[0003] 1. Functional coating materials

[0004] Adhesion and Chemical Resistance Coatings: The hydroxyl groups of hydroxyethyl acrylate provide strong adhesion, the basic structure of vinylpyridine enhances adhesion to metal surfaces, and styrene provides rigidity and weather resistance, making the copolymer suitable for metal anti-corrosion coatings and functional coatings.

[0005] Smart responsive coatings: Copolymers containing vinylpyridine are sensitive to pH and can be used as environmentally responsive coating materials, with certain applications in water treatment and environmental protection.

[0006] 2. Adhesive

[0007] High-performance adhesives: Because the hydroxyl groups of hydroxyethyl acrylate can form hydrogen bonds or chemical reactions with a variety of substrates (such as glass, metal, and plastic), this copolymer can be used to prepare adhesives with high adhesion, especially in high-temperature, humid, or corrosive environments.

[0008] 3. Biomedical materials

[0009] Drug carrier: The vinylpyridine group in the copolymer can be used to load drugs, especially in pH-responsive drug release systems, with targeting and controlled release properties.

[0010] Tissue engineering and repair materials: The hydroxyl groups provided by hydroxyethyl esters help improve biocompatibility and can be used as coatings for synthetic artificial bone repair materials or other implantable devices.

[0011] 4. Catalytic and separation materials

[0012] Ion exchange resin or catalyst support: The basic sites provided by vinylpyridine are beneficial for capturing acidic substances or loading metal ions, so the copolymer can be used as a catalyst support or ion exchange material for industrial catalysis or water treatment.

[0013] Membrane material: As a separation membrane material, this copolymer can be used for desalination or separation of specific substances, especially in the chemical and environmental protection industries.

[0014] 5. Functional textile treatment agents

[0015] Antibacterial and antistatic treatment: Copolymers containing vinylpyridine have antibacterial properties and can be used for the functionalization of textiles, while the crosslinking provided by hydroxyl groups improves the durability of the coating.

[0016] 6. Other special applications

[0017] Optoelectronic materials: Styrene units endow the copolymer with excellent optical and electronic properties. Combined with other functional groups, this copolymer may be used in optical components or electronic packaging materials.

[0018] Self-healing materials: By designing copolymers with crosslinkable or reversible chemical bonds, certain self-healing functions may be achieved.

[0019] Current synthesis techniques mostly focus on diblock polymers and random polymers. There are currently no reports on triblock copolymerization methods for vinylpyridine, styrene and acrylates, and the polymer dispersibility index of multiblock polymers is often difficult to control well. Summary of the Invention

[0020] To address the aforementioned problems in the background art, the main objective of this invention is to provide a copolymer of vinylpyridine monomers, styrene monomers, and acrylate monomers, and a method for preparing the copolymer thereof, resulting in a triblock polymer with a narrow polymer dispersibility index (<1.2), and the conversion rates of the three monomers are all increased to over 95%.

[0021] To achieve one aspect of the above objectives, the present invention employs the following technical solution:

[0022] A copolymer of vinylpyridine monomers, styrene monomers, and acrylate monomers, comprising polymers of the general chemical formula shown in Formula I and their substituent derivatives:

[0023]

[0024] Wherein, the values ​​of m, n, and o are all in the range of 1-500, depending on the required monomer molar ratio; substituent R1 is selected from one of chlorine atom, bromine atom, chloromethyl, bromomethyl, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, and tert-butyl; R2 is selected from one of chlorine atom, bromine atom, chloromethyl, bromomethyl, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, and tert-butyl; R3 is selected from one of hydrogen atom, methyl, ethyl, n-propyl, and n-butyl; R4 is selected from one of hydroxymethyl, hydroxyethyl, hydroxyn-propyl, and hydroxyn-butyl.

[0025] In this invention, the specific positions of R1 and R2 on the ring are not limited.

[0026] A second aspect of the present invention provides a method for preparing a copolymer of vinylpyridine monomers, styrene monomers, and acrylate monomers, comprising the following steps:

[0027] 1) A small molecule RAFT reagent, vinylpyridine monomer, first initiator and first solvent are mixed and polymerized to obtain CTA-terminated polyvinylpyridine polymer reagent;

[0028] 2) A CTA-terminated polyvinylpyridine polymer reagent, a styrene monomer, a second initiator, an emulsifier, a buffer, and a second solvent are mixed and polymerized to obtain a CTA-terminated poly(vinylpyridine-b-styrene) polymer reagent;

[0029] 3) Mix CTA-terminated poly(vinylpyridine-b-styrene) polymer reagent, acrylate monomer, third initiator and third solvent to carry out polymerization reaction to obtain (vinylpyridine-b-styrene-b-acrylate) copolymer.

[0030] In some embodiments, the small molecule RAFT reagent in step 1) is one or more of 1-cyano-1-methylethyl butyl ester, 2-[n-butyltrithiocarbonate]propionic acid, 2-cyano-2-butylphenyl dithioester, 2,2'-[thiocarbonyl(sulfur)]bis[2-methylpropionic acid], methyl 2-((ethoxythiocarbonyl)thio)propionate, and 4-cyano-4-(thiobenzoyl)valerate, and the amount used is calculated from the desired number-average molecular weight, as exemplarily shown in the following formula: Wherein: m(CTA1) is the mass of the small molecule RAFT reagent described in step 1), m(VP) is the mass of the vinylpyridine monomer described in step 1), M(CTA1) is the molecular weight of the small molecule RAFT reagent described in step 1), and Mn1(cal) is the desired number-average molecular weight in step 1).

[0031] In some embodiments, the vinylpyridine monomer in step 1) is one of n1-R1-n2-vinylpyridine; wherein: R1 is selected from one of chlorine atom, bromine atom, chloromethyl, bromomethyl, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl; n1≠n2; n1, n2∈[2,4], and are exemplary 2-vinylpyridine, 3-vinylpyridine or 4-vinylpyridine, the amount of which is calculated from the desired number-average molecular weight.

[0032] In some embodiments, the first initiator in step 1) is one or more of azobisisobutyronitrile, azobisisoheptanenitrile, dimethyl azobisisobutyrate, benzoyl peroxide, and dicumyl peroxide, and its molar amount is 50% to 200% of the molar amount of the small molecule RAFT reagent, exemplarily 60%, 70%, 80%, 90%, 100%, 110%, 120%, 130%, 140%, 150%, 160%, 170%, 180%, 190%, etc.

[0033] In some embodiments, the first solvent in step 1) is one of acetonitrile, toluene, and dimethyl sulfoxide, and its mass is 2-10 times that of the vinylpyridine monomer.

[0034] In some embodiments, the reaction temperature in step 1) is 70-110°C, exemplarily 75°C, 80°C, 85°C, 90°C, 95°C, 100°C, 105°C, etc.; the reaction time t is 2-48 hours; and the number average molecular weight of the obtained CTA-terminated polyvinylpyridine polymer reagent is 1-100 kg / mol.

[0035] In some embodiments, the amount of the CTA-terminated polyvinylpyridine polymer reagent in step 2) is calculated based on the desired number-average molecular weight, as exemplarily shown in the following formula: Wherein: m(CTA2) is the mass of the macromolecular RAFT reagent described in step 2), m(St) is the mass of the styrene monomer described in step 2), M(CTA2) is the number-average molecular weight of the macromolecular RAFT reagent described in step 2), Mn1(exp) is the actual number-average molecular weight in step 1), and Mn2(cal) is the required number-average molecular weight in step 2).

[0036] In some embodiments, the styrene monomer in step 2) is one of n3-R2-n4-styrene; wherein: R2 is selected from one of chlorine atom, bromine atom, chloromethyl, bromomethyl, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl; n3≠n4; n3, n4∈[3,4], and are exemplary styrene, 4-halostyrene or 4-halomethylstyrene, the amount of which is calculated from the desired number-average molecular weight.

[0037] In some embodiments, the second initiator in step 2) is one or more of azobisisobutyronitrile, azobisisoheptanenitrile, dimethyl azobisisobutyrate, benzoyl peroxide, dicumyl peroxide, potassium persulfate, and sodium persulfate, and its molar amount is 50% to 200% of the molar amount of CTA-terminated polyvinylpyridine polymer reagent, exemplarily 60%, 70%, 80%, 90%, 100%, 110%, 120%, 130%, 140%, 150%, 160%, 170%, 180%, 190%, etc.

[0038] In some embodiments, the emulsifier in step 2) is one or more of sodium stearate, sodium dodecyl sulfate, bubbly powder, sodium rosin soap, and potassium dehydrorosinate, and its dosage is 0.05-0.2 mol / L.

[0039] In some embodiments, the buffer in step 2) is one or more of anhydrous sodium carbonate, anhydrous sodium bicarbonate, anhydrous sodium monohydrogen phosphate, and sodium phosphate dodecahydrate, and its dosage is 0.05-0.2 mol / L.

[0040] In some embodiments, the second solvent in step 2) is deionized water, and its mass is 2-10 times that of the styrene monomer.

[0041] In some embodiments, the reaction temperature in step 2) is 30-50°C, exemplarily 35°C, 40°C, 45°C, etc.; the reaction time is 24-72 hours; and the number average molecular weight of the obtained CTA-terminated poly(vinylpyridine-b-styrene) polymer reagent is 2-1000 kg / mol.

[0042] In some embodiments, the amount of the CTA-terminated poly(vinylpyridine-b-styrene) polymer reagent in step 3) is calculated based on the desired number-average molecular weight, as exemplarily shown in the following formula: m(CTA3) is the mass of the macromolecular RAFT reagent described in step 3), m(MA) is the mass of the acrylate monomer described in step 3), M(CTA3) is the number-average molecular weight of the macromolecular RAFT reagent described in step 3), Mn2(exp) is the actual number-average molecular weight in step 2), and Mn3(cal) is the desired number-average molecular weight in step 3).

[0043] In some embodiments, the acrylate monomer in step 3) is one of R3-acrylate-R4-ester; wherein: R3 is selected from one of hydrogen atom, methyl, ethyl, n-propyl, and n-butyl; R4 is selected from one of hydroxymethyl, hydroxyethyl, hydroxyn-propyl, and hydroxyn-butyl, and is exemplary to be the water-soluble monomer hydroxyethyl acrylate or hydroxyethyl methacrylate, for the convenience of the application end, and its amount is calculated from the desired number average molecular weight.

[0044] In some embodiments, the third initiator in step 3) is one or more of azobisisobutyronitrile, azobisisoheptanenitrile, dimethyl azobisisobutyrate, benzoyl peroxide, and dicumyl peroxide, and its molar amount is 50% to 200% of the molar amount of CTA-terminated poly(vinylpyridine-b-styrene) polymer reagent, exemplarily 60%, 70%, 80%, 90%, 100%, 110%, 120%, 130%, 140%, 150%, 160%, 170%, 180%, 190%, etc.

[0045] In some embodiments, the third solvent in step 3) is one of acetonitrile, toluene, and dimethyl sulfoxide, and its mass is 2-10 times that of the hydroxyethyl acrylate monomer.

[0046] In some embodiments, the reaction temperature in step 3) is 70-110°C, exemplarily 75°C, 80°C, 85°C, 90°C, 95°C, 100°C, 105°C, etc.; the reaction time is 2-48 hours; and the number average molecular weight of the resulting (vinylpyridine-b-styrene-b-acrylate) copolymer is 2-1000 kg / mol.

[0047] In some embodiments, the reactions in steps 1)-3) are all carried out under an inert atmosphere, exemplarily argon.

[0048] A third aspect of the present invention provides copolymers of vinylpyridine monomers, styrene monomers and acrylate monomers prepared by the above method.

[0049] Compared with the prior art, the present invention has the following advantages:

[0050] This invention uses vinylpyridine, styrene, and acrylate compounds as monomers to prepare (vinylpyridine-b-styrene-b-acrylate) triblock copolymers via solution polymerization, emulsion polymerization, and solution polymerization in sequence. This method has the advantages of simple operation, no need for catalysts, no by-products generated in the reaction process, high product purity, high conversion rate, and suitability for industrial production.

[0051] Furthermore, by selecting chain transfer agents (CTAs) suitable for the three monomers, the present invention enables the product to obtain a good polymer dispersibility index (<1.2); and by optimizing the molar ratio of CTA reagent to initiator in the first step of the reaction, the total conversion rate of the reaction is as high as 86-97%.

[0052] The copolymers prepared by this invention can be applied to functional coating materials, adhesives, biomedical materials, catalytic and separation materials, and functional textile treatment agents.

[0053] Other features and advantages of the present invention will be described in detail through the following specific embodiments. Attached Figure Description

[0054] Figure 1a The above is the 1H NMR spectrum of the copolymer prepared in Example 1. Figure 1b The image shows the GPC test report of the copolymer prepared in Example 1.

[0055] Figure 2a The above is the 1H NMR spectrum of the copolymer prepared in Example 2. Figure 2b The image shows the GPC test report of the copolymer prepared in Example 2.

[0056] Figure 3a The above is the 1H NMR spectrum of the copolymer prepared in Example 3. Figure 3b The image shows the GPC test report of the copolymer prepared in Example 3.

[0057] Figure 4a The above is the 1H NMR spectrum of the copolymer prepared in Example 4. Figure 4b The image shows the GPC test report of the copolymer prepared in Example 4.

[0058] Figure 5a The above is the 1H NMR spectrum of the copolymer prepared in Example 5. Figure 5b This is a GPC test report image of the copolymer prepared in Example 5. Detailed Implementation

[0059] The specific embodiments of the present invention will be described in detail below. It should be understood that the following embodiments are only used to more clearly illustrate the technical solutions of the present invention, and are not intended to limit the scope of protection of the present invention. Various changes, modifications, substitutions, and variations made by those skilled in the art to these embodiments without departing from the principles and spirit of the present invention should be included within the scope of protection of the present invention.

[0060] The endpoints and any values ​​of the ranges disclosed herein are not limited to the precise ranges or values, and should be understood to include those approximate. For numerical ranges, the endpoint values ​​of the ranges, the endpoint values ​​of the ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein.

[0061] Unless otherwise specified, all reagents and materials used in the following examples are commercially available.

[0062] This invention uses an Agilent Technologies 1260 Infinity II liquid nuclear magnetic resonance spectrometer to detect the product. 1 1H NMR spectra, with deuterated DMSO and deuterated MeOH as solvents, and tetramethylsilane (TMS) as an internal standard.

[0063] This invention uses a Varian 400M gel permeation chromatograph to detect the number-average molecular weight, weight-average molecular weight, and PDI of the product.

[0064] Example 1

[0065] (1) Synthesis of CTA-terminated poly(4-vinylpyridine)

[0066] 0.5 g of 4-cyano-4-(thiobenzoyl)valeric acid, 25.22 g of 4-vinylpyridine, 0.147 g of azobisisobutyronitrile, and 50.44 mL of toluene were added to a three-necked flask and stirred to dissolve. The mixture was then evacuated under argon gas for three cycles. The reaction was carried out at 100 °C for 24 hours. Samples were taken to measure the conversion rate. The reaction was stopped when the conversion rate reached 95% or higher. The reaction solution was precipitated into 500 mL of methanol, filtered, and dried under vacuum to obtain 24.6 g of a yellow powder. The single-step yield was 97.4%. The number average molecular weight of the synthesized polymer was approximately 13517, and the PDI was 1.07, as determined by gel permeation chromatography.

[0067] (2) Synthesis of CTA-terminated poly(4-vinylpyridine-b-styrene)

[0068] 18g of CTA-terminated poly(4-vinylpyridine), 2.36g of styrene, 0.36g of potassium persulfate, 1.87g of sodium stearate, 2.31g of sodium phosphate dodecahydrate, and 61mL of deionized water were added to a three-necked flask and stirred to dissolve. The mixture was then evacuated under argon gas for three cycles, and the temperature was raised to 40℃ for 48 hours. Samples were taken to measure the conversion rate. The reaction was stopped when the conversion rate reached above 95%. The product was filtered, frozen, and pulverized to obtain 19.46g of a light yellow powder. The single-step yield was 95.6%. The number average molecular weight of the synthesized polymer was approximately 15213, and the PDI was 1.14, as determined by gel permeation chromatography.

[0069] (3) Synthesis of poly(4-vinylpyridine-b-styrene-b-hydroxyethyl acrylate)

[0070] 10 g of CTA-terminated poly(4-vinylpyridine-b-styrene), 2.37 g of hydroxyethyl acrylate, 0.054 g of azobisisobutyronitrile (AIOBR), and 26 mL of toluene were added to a three-necked flask and stirred to dissolve. The mixture was evacuated under argon gas for three cycles. After heating to 70 °C, the conversion rate was measured. The reaction was stopped when the conversion rate reached 95% or higher. The reaction solution was then deposited into 260 mL of ice-cold methanol, filtered, and vacuum dried to obtain 11.8 g of a yellow powder. The single-step yield was 95.6%. The number-average molecular weight of the synthesized polymer was approximately 19326, and the PDI was 1.19, as determined by gel permeation chromatography.

[0071] By nuclear magnetic resonance hydrogen spectrum Figure 1a It can be proven that the synthesized polymer is poly(4-vinylpyridine-b-styrene-b-hydroxyethyl acrylate), and it passes the GPC test report. Figure 1b The molecular weight information of the synthesized polymer can be determined; the structural formula of the polymer is shown below:

[0072]

[0073] Example 2

[0074] (1) Synthesis of CTA-terminated poly(2-vinylpyridine)

[0075] 0.745 g of methyl 2-((ethoxythiocarbonyl)thio)propionate, 33.12 g of 2-vinylpyridine, 0.294 g of azobisisobutyronitrile, and 99 mL of toluene were added to a three-necked flask and stirred to dissolve. The mixture was then evacuated under argon gas for three cycles and the reaction was carried out at 100 °C for 24 hours. Samples were taken to measure the conversion rate. The reaction was stopped when the conversion rate reached 95% or higher. The reaction solution was precipitated into 990 mL of methanol, filtered, and dried under vacuum to obtain 31.43 g of a yellow powder. The single-step yield was 95%. The number-average molecular weight of the synthesized polymer was approximately 8905, and the PDI was 1.07, as determined by gel permeation chromatography.

[0076] (2) Synthesis of CTA-terminated poly(2-vinylpyridine-b-styrene)

[0077] 18g of CTA-terminated poly(2-vinylpyridine), 1.89g of styrene, 0.546g of potassium persulfate, 2.02g of sodium stearate, 2.51g of sodium phosphate dodecahydrate, and 66mL of deionized water were added to a three-necked flask and stirred to dissolve. The mixture was then evacuated under argon gas for three cycles, and the temperature was raised to 40℃ for 48 hours. Samples were taken to measure the conversion rate. The reaction was stopped when the conversion rate reached above 95%. The product was filtered, frozen, and pulverized to obtain 19.84g of a light yellow powder. The single-step yield was 97.6%. The number-average molecular weight of the synthesized polymer was approximately 9908, and the PDI was 1.15, as determined by gel permeation chromatography.

[0078] (3) Synthesis of poly(2-vinylpyridine-b-styrene-b-hydroxyethyl acrylate)

[0079] 10 g of CTA-terminated poly(2-vinylpyridine-b-styrene), 1.52 g of hydroxyethyl acrylate, 0.083 g of azobisisobutyronitrile (AIB), and 34.5 mL of toluene were added to a three-necked flask and stirred to dissolve. The mixture was evacuated under argon gas for three cycles. After heating to 70 °C, the conversion rate was measured. The reaction was stopped when the conversion rate reached 95% or higher. The reaction solution was then deposited into 345 mL of ice-cold methanol, filtered, and vacuum dried to obtain 11.45 g of yellow powder. The single-step yield was 95.7%. The number-average molecular weight of the synthesized polymer was approximately 11506, and the PDI was 1.19, as determined by gel permeation chromatography.

[0080] By nuclear magnetic resonance hydrogen spectrum Figure 2a It can be proven that the synthesized polymer is poly(2-vinylpyridine-b-styrene-b-hydroxyethyl acrylate), and it passes the GPC test report. Figure 2b The molecular weight information of the synthesized polymer can be determined; the structural formula of the polymer is shown below:

[0081]

[0082] Example 3

[0083] (1) Synthesis of CTA-terminated poly(4-vinylpyridine)

[0084] 0.505 g of 2,2'-[thiocarbonyl(sulfur)]bis[2-methylpropionic acid], 37.26 g of 4-vinylpyridine, 0.147 g of azobisisobutyronitrile, and 75 mL of toluene were added to a three-necked flask and stirred to dissolve. The mixture was then evacuated under argon gas for three cycles and heated to 100 °C for 24 hours. Samples were taken to measure the conversion rate. The reaction was stopped when the conversion rate reached 95% or higher. The reaction solution was precipitated into 750 mL of methanol, filtered, and vacuum dried to obtain 35.43 g of a yellow powder. The single-step yield was 95.1%. The number-average molecular weight of the synthesized polymer was approximately 19965, and the PDI was 1.07, as determined by gel permeation chromatography.

[0085] (2) Synthesis of CTA-terminated poly(4-vinylpyridine-b-4-chlorostyrene)

[0086] 18g of CTA-terminated poly(4-vinylpyridine), 3.37g of 4-chlorostyrene, 0.244g of potassium persulfate, 2.02g of sodium stearate, 2.51g of sodium phosphate dodecahydrate, and 66mL of deionized water were added to a three-necked flask and stirred to dissolve. The mixture was then evacuated under argon gas for three cycles, and the temperature was raised to 40℃ for 48 hours. Samples were taken to measure the conversion rate. The reaction was stopped when the conversion rate reached above 95%. The mixture was filtered, frozen, and pulverized to obtain 21.24g of a light yellow powder. The single-step yield was 96.2%. The number-average molecular weight of the synthesized polymer was approximately 23584, and the PDI was 1.12, as determined by gel permeation chromatography.

[0087] (3) Synthesis of poly(4-vinylpyridine-b-4-chlorostyrene-b-hydroxyethyl acrylate)

[0088] 10 g of CTA-terminated poly(4-vinylpyridine-b-4-chlorostyrene), 3.15 g of hydroxyethyl acrylate, 0.035 g of azobisisobutyronitrile, and 39 mL of toluene were added to a three-necked flask and stirred to dissolve. The mixture was evacuated under argon gas for three cycles. After heating to 70 °C, a sample was taken to measure the conversion rate. The reaction was stopped when the conversion rate reached above 95%. The reaction solution was precipitated into 390 mL of ice-cold methanol, filtered, and vacuum dried to obtain 13.0 g of yellow powder. The single-step yield was 95.3%. The number-average molecular weight of the synthesized polymer was approximately 31893, and the PDI was 1.18, as determined by gel permeation chromatography.

[0089] By nuclear magnetic resonance hydrogen spectrum Figure 3a It can be proven that the synthesized polymer is poly(4-vinylpyridine-b-4-chlorostyrene-b-hydroxyethyl acrylate), and it passes the GPC test report. Figure 3b The molecular weight information of the synthesized polymer can be determined; the structural formula of the polymer is shown below:

[0090]

[0091] Example 4

[0092] (1) Synthesis of CTA-terminated poly(4-vinylpyridine)

[0093] 0.842 g of 2-cyano-2-butylphenyl dithioester, 38.01 g of 4-vinylpyridine, 0.294 g of azobisisobutyronitrile, and 76 mL of toluene were added to a three-necked flask and stirred to dissolve. The mixture was then evacuated under argon gas for three cycles. The reaction was carried out at 100 °C for 24 hours. Samples were taken to measure the conversion rate. The reaction was stopped when the conversion rate reached 95% or higher. The reaction solution was precipitated into 760 mL of methanol, filtered, and dried under vacuum to obtain 37 g of yellow powder. The single-step yield was 97.3%. The number-average molecular weight of the synthesized polymer was approximately 10516, and the PDI was 1.08, as determined by gel permeation chromatography.

[0094] (2) Synthesis of CTA-terminated poly(4-vinylpyridine-b-4-chloromethylstyrene)

[0095] 30g of CTA-terminated poly(4-vinylpyridine), 7.4g of 4-chloromethylstyrene, 0.771g of potassium persulfate, 2.32g of sodium stearate, 2.89g of sodium phosphate dodecahydrate, and 76mL of deionized water were added to a three-necked flask and stirred to dissolve. The mixture was then evacuated under argon gas for three cycles, and the temperature was raised to 40℃ for 48 hours. Samples were taken to measure the conversion rate. The reaction was stopped when the conversion rate reached above 95%. The product was filtered, frozen, and pulverized to obtain 37.03g of a light yellow powder. The single-step yield was 95.0%. The number-average molecular weight of the synthesized polymer was approximately 14281, and the PDI was 1.16, as determined by gel permeation chromatography.

[0096] (3) Synthesis of poly(4-vinylpyridine-b-4-chloromethylstyrene-b-hydroxyethyl acrylate)

[0097] 10 g of CTA-terminated poly(4-vinylpyridine-b-4-chloromethylstyrene), 12.28 g of hydroxyethyl acrylate, 0.057 g of azobisisobutyronitrile (AIBN), and 46 mL of toluene were added to a three-necked flask and stirred to dissolve. The mixture was evacuated under argon gas for three cycles. After heating to 70 °C, the conversion rate was measured. The reaction was stopped when the conversion rate reached 95% or higher. The reaction solution was then deposited into 460 mL of ice-cold methanol, filtered, and vacuum dried to obtain 22 g of yellow powder. The single-step yield was 97.9%. The number-average molecular weight of the synthesized polymer was approximately 30931, and the PDI was 1.18, as determined by gel permeation chromatography.

[0098] By nuclear magnetic resonance hydrogen spectrum Figure 4a It can be proven that the synthesized polymer is poly(4-vinylpyridine-b-4-chloromethylstyrene-b-hydroxyethyl acrylate), and it passes the GPC test report. Figure 4b The molecular weight information of the synthesized polymer can be determined; the structural formula of the polymer is shown below:

[0099]

[0100] Example 5

[0101] (1) Synthesis of CTA-terminated poly(4-vinylpyridine)

[0102] 2.56 g of 2-[n-butyltrithiocarbonate]propionic acid, 37.26 g of 4-vinylpyridine, 0.881 g of azobisisobutyronitrile, and 80 mL of toluene were added to a three-necked flask and stirred to dissolve. The mixture was then evacuated under argon gas for three cycles. The reaction was carried out at 100 °C for 24 hours. Samples were taken to measure the conversion rate. The reaction was stopped when the conversion rate reached 95% or higher. The reaction solution was precipitated into 800 mL of methanol, filtered, and dried under vacuum to obtain 36.3 g of a yellow powder. The single-step yield was 97.4%. The number-average molecular weight of the synthesized polymer was approximately 3413, and the PDI was 1.08, as determined by gel permeation chromatography.

[0103] (2) Synthesis of CTA-terminated poly(4-vinylpyridine-b-styrene)

[0104] 30g of CTA-terminated poly(4-vinylpyridine), 2.75g of styrene, 2.38g of potassium persulfate, 2.02g of sodium stearate, 2.51g of sodium phosphate dodecahydrate, and 66mL of deionized water were added to a three-necked flask and stirred to dissolve. The mixture was then evacuated under argon gas for three cycles, and the temperature was raised to 40℃ for 48 hours. Samples were taken to measure the conversion rate. The reaction was stopped when the conversion rate reached above 95%. The product was filtered, frozen, and pulverized to obtain 32.5g of a light yellow powder. The single-step yield was 95.6%. The number-average molecular weight of the synthesized polymer was approximately 3843, and the PDI was 1.14, as determined by gel permeation chromatography.

[0105] (3) Synthesis of poly(4-vinylpyridine-b-styrene-b-hydroxyethyl methacrylate)

[0106] 10 g of CTA-terminated poly(4-vinylpyridine-b-4-styrene), 9.48 g of hydroxyethyl methacrylate, 0.213 g of azobisisobutyronitrile, and 40 mL of toluene were added to a three-necked flask and stirred to dissolve. The mixture was evacuated under argon gas for three cycles. After heating to 70 °C, the conversion rate was measured. The reaction was stopped when the conversion rate reached 95% or higher. The reaction solution was then deposited into 400 mL of ice-cold methanol, filtered, and vacuum dried to obtain 18.95 g of yellow powder. The single-step yield was 94.5%. The number-average molecular weight of the synthesized polymer was approximately 6796, and the PDI was 1.19, as determined by gel permeation chromatography.

[0107] By nuclear magnetic resonance hydrogen spectrum Figure 5a It can be proven that the synthesized polymer is poly(4-vinylpyridine-b-styrene-b-hydroxyethyl methacrylate), and it passes the GPC test report. Figure 5b The molecular weight information of the synthesized polymer can be determined; the structural formula of the polymer is shown below:

[0108]

[0109] Comparative Example 1

[0110] The difference from Example 5 is that the chain transfer agent is methyl cyanomethyl (phenyl)aminodithiocarbamate, as detailed below:

[0111] Synthesis of CTA-terminated poly(4-vinylpyridine)

[0112] 3g of methyl cyanomethyl methyl (phenyl)aminodithiocarbamate, 46.82g of 4-vinylpyridine, 1.11g of azobisisobutyronitrile, and 100mL of toluene were added to a three-necked flask and stirred to dissolve. The mixture was evacuated under argon gas for three cycles, and then heated to 100℃ for 24 hours. The conversion rate was measured to be 37.8%. The reaction was stopped, and the reaction solution was precipitated into 1000mL of methanol, filtered, and dried under vacuum to obtain 16.49g of yellow powder. The single-step yield was 35.2%. Gel permeation chromatography showed that the number average molecular weight of the synthesized polymer was approximately 4000, and the PDI was 1.81.

[0113] Synthesis of CTA-terminated poly(4-vinylpyridine-b-styrene)

[0114] 15g of CTA-terminated poly(4-vinylpyridine), 1.17g of styrene, 1.01g of potassium persulfate, 1.01g of sodium stearate, 1.25g of sodium phosphate dodecahydrate, and 33mL of deionized water were added to a three-necked flask and stirred to dissolve. The mixture was then evacuated under argon gas for three cycles, and the temperature was raised to 40℃ for 48 hours. A sample was taken to measure the conversion rate, which was found to be 69.9%. The reaction was stopped, filtered, frozen, and pulverized to obtain 15.7g of a light yellow powder. The single-step yield was 60.8%. Gel permeation chromatography showed that the number-average molecular weight of the synthesized polymer was approximately 7403, and the PDI was 2.99.

[0115] Synthesis of poly(4-vinylpyridine-b-styrene-b-hydroxyethyl methacrylate)

[0116] 10g of CTA-terminated poly(4-vinylpyridine-b-4-styrene), 1.68g of hydroxyethyl methacrylate, 0.042g of azobisisobutyronitrile, and 24mL of toluene were added to a three-necked flask and stirred to dissolve. The mixture was then evacuated and purged with argon gas for three cycles. After the reaction was carried out at 70℃, a sample was taken to measure the conversion rate. The conversion rate was found to be 0%, indicating that the reaction could not proceed.

[0117] Comparative Example 2

[0118] The difference from Example 5 is that the molar ratio of CTA reagent to initiator in step (1) is set to 0.5, in step (2) it is 0.25, and in step (3) it is 0.25; specifically as follows:

[0119] (1) Synthesis of CTA-terminated poly(4-vinylpyridine)

[0120] 3 g of 4-cyano-4-(thiobenzoyl)valeric acid, 37.26 g of 4-vinylpyridine, 3.53 g of azobisisobutyronitrile, and 80 mL of toluene were added to a three-necked flask and stirred to dissolve. The mixture was then evacuated under argon gas for three cycles. The reaction was carried out at 100 °C for 24 hours. Samples were taken to measure the conversion rate. The reaction was stopped when the conversion rate reached 95% or higher. The reaction solution was precipitated into 800 mL of methanol, filtered, and dried under vacuum to obtain 36.7 g of a yellow powder. The single-step yield was 98.4%. The number-average molecular weight of the synthesized polymer was approximately 3805, and the PDI was 1.54, as determined by gel permeation chromatography.

[0121] (2) Synthesis of CTA-terminated poly(4-vinylpyridine-b-styrene)

[0122] 30g of CTA-terminated poly(4-vinylpyridine), 2.46g of styrene, 8.52g of potassium persulfate, 2.02g of sodium stearate, 2.51g of sodium phosphate dodecahydrate, and 66mL of deionized water were added to a three-necked flask and stirred to dissolve. The mixture was then evacuated under argon gas for three cycles, and the temperature was raised to 40℃ for 48 hours. Samples were taken to measure the conversion rate. The reaction was stopped when the conversion rate reached above 95%. The product was filtered, frozen, and pulverized to obtain 32.43g of a light yellow powder. The single-step yield was 99.1%. The number average molecular weight of the synthesized polymer was approximately 6050, and the PDI was 2.88, as determined by gel permeation chromatography.

[0123] (3) Synthesis of poly(4-vinylpyridine-b-styrene-b-hydroxyethyl methacrylate)

[0124] 10 g of CTA-terminated poly(4-vinylpyridine-b-4-styrene), 5.37 g of hydroxyethyl methacrylate, 1.09 g of azobisisobutyronitrile (AIB), and 32 mL of toluene were added to a three-necked flask and stirred to dissolve. The mixture was evacuated under argon gas for three cycles. After heating to 70 °C, the conversion rate was measured. The reaction was stopped when the conversion rate reached 95% or higher. The reaction solution was then deposited into 320 mL of ice-cold methanol, filtered, and vacuum dried to obtain 15.36 g of yellow powder. The single-step yield was 99.8%. The number-average molecular weight of the synthesized polymer was approximately 13945, and the PDI was 3.14, as determined by gel permeation chromatography.

[0125] The following conclusions can be drawn from the comparison between Example 5 and Comparative Examples 1-2:

[0126] By selecting a chain transfer agent (CTA) that is compatible with the three monomers, the product can obtain a good polymer dispersibility index (<1.2). In Comparative Example 1, the chain transfer agent selected was methyl cyanomethyl methyl (phenyl)aminodithiocarbamate, which resulted in a large difference between the actual molecular weight and the designed molecular weight, a wide PDI, and an extremely low conversion rate.

[0127] By optimizing the molar ratio of CTA reagent to initiator (in Example 5, the molar ratio of CTA reagent to initiator in step (1) is 2.0, in step (2) it is 1.0, and in step (3) it is 2.0), the overall conversion rate of the reaction can be improved. In Comparative Example 2, the molar ratio of CTA reagent to initiator in step (1) is 0.5, in step (2) it is 0.25, and in step (3) it is 0.25, which leads to a large difference between the actual molecular weight and the designed molecular weight and a wide PDI.

[0128] Although the present invention has been described in detail through the preferred embodiments described above, it should be understood that the above description should not be considered as a limitation of the present invention. Those skilled in the art will understand that modifications or adjustments can be made to the present invention based on the teachings of this specification. These modifications or adjustments should also be within the scope defined by the claims of the present invention.

Claims

1. A copolymer of vinylpyridine monomers, styrene monomers, and acrylate monomers, characterized in that, It includes polymers with the general chemical structure shown in Formula I and their substituent derivatives: Wherein, the values ​​of m, n, and o are all in the range of 1-500; substituent R1 is selected from one of chlorine atom, bromine atom, chloromethyl, bromomethyl, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, and tert-butyl; R2 is selected from one of chlorine atom, bromine atom, chloromethyl, bromomethyl, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, and tert-butyl; R3 is selected from one of hydrogen atom, methyl, ethyl, n-propyl, and n-butyl; and R4 is selected from one of hydroxymethyl, hydroxyethyl, hydroxyn-propyl, and hydroxyn-butyl.

2. A method for preparing a copolymer of vinylpyridine monomers, styrene monomers, and acrylate monomers, characterized in that, Includes the following steps: 1) A small molecule RAFT reagent, vinylpyridine monomer, first initiator and first solvent are mixed and polymerized to obtain CTA-terminated polyvinylpyridine polymer reagent; 2) A CTA-terminated polyvinylpyridine polymer reagent, a styrene monomer, a second initiator, an emulsifier, a buffer, and a second solvent are mixed and polymerized to obtain a CTA-terminated poly(vinylpyridine-b-styrene) polymer reagent; 3) Mix CTA-terminated poly(vinylpyridine-b-styrene) polymer reagent, acrylate monomer, third initiator and third solvent to carry out polymerization reaction to obtain (vinylpyridine-b-styrene-b-acrylate) copolymer.

3. The method for preparing the copolymer of vinylpyridine monomers, styrene monomers, and acrylate monomers according to claim 2, characterized in that, The small molecule RAFT reagent mentioned in step 1) is one or more of the following: 1-cyano-1-methylacetate, 2-[n-butyltrithiocarbonate]propionic acid, 2-cyano-2-butylbenzene dithioester, 2,2'-[thiocarbonyl(sulfur)]bis[2-methylpropionic acid], methyl 2-((ethoxythiocarbonyl)thio)propionate, and 4-cyano-4-(thiobenzoyl)valerate. Step 1) The vinylpyridine monomer is one of n1-R1-n2-vinylpyridine; wherein: R1 is selected from one of chlorine atom, bromine atom, chloromethyl, bromomethyl, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl; n1≠n2; n1, n2∈[2,4]; The first initiator mentioned in step 1) is one or more of azobisisobutyronitrile, azobisisoheptanenitrile, dimethyl azobisisobutyrate, benzoyl peroxide, and dicumyl peroxide, and its molar amount is 50% to 200% of the molar amount of the small molecule RAFT reagent. The first solvent mentioned in step 1) is one of acetonitrile, toluene, and dimethyl sulfoxide, and its mass is 2-10 times that of the vinylpyridine monomer.

4. The method for preparing the copolymer of vinylpyridine monomers, styrene monomers, and acrylate monomers according to claim 2, characterized in that, The reaction temperature in step 1) is 70-110℃; the reaction time is 2-48 hours; and the number average molecular weight of the obtained CTA-terminated polyvinylpyridine polymer reagent is 1-100 kg / mol.

5. The method for preparing the copolymer of vinylpyridine monomers, styrene monomers, and acrylate monomers according to claim 2, characterized in that, Step 2) The styrene monomer is one of n3-R2-n4-styrene; wherein: R2 is selected from one of chlorine atom, bromine atom, chloromethyl, bromomethyl, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl; n3≠n4; n3, n4∈[3,4]; The second initiator mentioned in step 2) is one or more of azobisisobutyronitrile, azobisisoheptanenitrile, dimethyl azobisisobutyrate, benzoyl peroxide, dicumyl peroxide, potassium persulfate, and sodium persulfate, and its molar amount is 50% to 200% of the molar amount of CTA-terminated polyvinylpyridine polymer reagent. The emulsifier mentioned in step 2) is one or more of sodium stearate, sodium dodecyl sulfate, bubbly powder, sodium rosin soap, and potassium dehydrorosinate, and its dosage is 0.05-0.2 mol / L; The buffer in step 2) is one or more of anhydrous sodium carbonate, anhydrous sodium bicarbonate, anhydrous sodium monohydrogen phosphate, and sodium phosphate dodecahydrate, and its dosage is 0.05-0.2 mol / L. The second solvent mentioned in step 2) is deionized water, and its mass is 2-10 times that of styrene monomers.

6. The method for preparing the copolymer of vinylpyridine monomers, styrene monomers, and acrylate monomers according to claim 2, characterized in that, The reaction temperature in step 2) is 30-50℃; the reaction time is 24-72 hours; and the number average molecular weight of the obtained CTA-terminated poly(vinylpyridine-b-styrene) polymer reagent is 2-1000 kg / mol.

7. The method for preparing the copolymer of vinylpyridine monomers, styrene monomers, and acrylate monomers according to claim 2, characterized in that, Step 3) The acrylate monomer is one of R3-acrylate-R4-ester; wherein: R3 is selected from one of hydrogen atom, methyl, ethyl, n-propyl, and n-butyl; R4 is selected from one of hydroxymethyl, hydroxyethyl, hydroxyn-propyl, and hydroxyn-butyl. The third initiator mentioned in step 3) is one or more of azobisisobutyronitrile, azobisisoheptanenitrile, dimethyl azobisisobutyrate, benzoyl peroxide, and dicumyl peroxide, and its molar amount is 50% to 200% of the molar amount of CTA-terminated poly(vinylpyridine-b-styrene) polymer reagent. The third solvent mentioned in step 3) is one of acetonitrile, toluene, and dimethyl sulfoxide, and its mass is 2-10 times that of the hydroxyethyl acrylate monomer.

8. The method for preparing the copolymer of vinylpyridine monomers, styrene monomers, and acrylate monomers according to claim 2, characterized in that, The reaction temperature in step 3) is 70-110℃; the reaction time is 2-48 hours; and the number average molecular weight of the resulting (vinylpyridine-b-styrene-b-acrylate) copolymer is 2-1000 kg / mol.

9. The method for preparing copolymers of vinylpyridine monomers, styrene monomers and acrylate monomers according to any one of claims 2-8, wherein the reactions in steps 1)-3) are all carried out under an inert atmosphere.

10. A copolymer of vinylpyridine monomers, styrene monomers and acrylate monomers prepared by the method of any one of claims 2-9.

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