A method of binary free radical polymerization

Abstract

This invention relates to a binary radical polymerization method, comprising the steps of: S0, providing a primary radical polymerization system for capturing free radicals and a secondary radical polymerization system for achieving chain transfer; S1, mixing the polymerizing monomer, the primary radical polymerization system, and the secondary radical polymerization system, and initiating radical polymerization by thermal decomposition, photoexcitation, or electroexcitation to obtain a polymer with independently controllable molecular weight and molecular weight distribution. The binary radical polymerization method of this invention, by combining the primary radical polymerization system for capturing free radicals and the secondary radical polymerization system for achieving chain transfer, successfully achieves independent control of molecular weight and molecular weight distribution in living polymerization. This not only improves polymerization efficiency and reduces production costs but also significantly enhances the quality of the polymer product.

Description

Technical Field

[0001] This invention relates to the field of free radical polymerization, and more particularly to a binary free radical polymerization method. Background Technology

[0002] Free radical polymerization plays a dominant role in polymer synthesis. Living radical polymerization, based on the reversible equilibrium between free radicals and dormant species, enables precise control over the molecular weight, distribution, and structure of polymers. By controlling the activity of free radicals, living radical polymerization allows polymer chain growth to occur without chain transfer and bimolecular termination reactions present in traditional free radical polymerization, thus yielding polymers with narrower molecular weight distributions.

[0003] However, in traditional living radical polymerization, controlling the dormant species required to process the reaction necessitates simultaneous control of the polymer's molecular weight and molecular weight distribution, leading to a series of practical application problems. Synthesizing low-molecular-weight polymers requires a large amount of dormant species, resulting in excessively high polymerization costs; conversely, synthesizing high-molecular-weight polymers requires a significant reduction in the dormant species content, which can lead to runaway polymerization. This contradictory relationship between molecular weight and molecular weight distribution limits the practical application of living radical polymerization.

[0004] Therefore, there is an urgent need for a binary radical polymerization method. Summary of the Invention

[0005] The purpose of this invention is to address the shortcomings of existing technologies by providing a binary radical polymerization method, the steps of which include:

[0006] S0, providing a primary radical polymerization system for capturing free radicals and a secondary radical polymerization system for achieving chain transfer;

[0007] S1. Mix the polymerizable monomer, the primary radical polymerization system, and the secondary radical polymerization system, and initiate radical polymerization by thermal decomposition, photoexcitation, or electroexcitation to obtain a polymer with independently regulated molecular weight and molecular weight distribution.

[0008] Wherein, the primary radical polymerization system is an atom transfer radical polymerization (ATRP) system, and the secondary radical polymerization system is a reverse iodine atom transfer radical polymerization (RITP) system, denoted as ATRP / RITP; or,

[0009] The primary radical polymerization system is an atom transfer radical polymerization system, and the secondary radical polymerization system is a reversible addition-fragmentation chain transfer polymerization (RAFT) system, denoted as ATRP / RAFT; or,

[0010] The primary radical polymerization system is a reversible addition-fracture chain transfer polymerization system, and the secondary radical polymerization system is also a reversible addition-fracture chain transfer polymerization system, denoted as RAFT / RAFT; or,

[0011] The primary radical polymerization system is a reversible addition-fragmentation chain transfer polymerization system, and the secondary radical polymerization system is a thiol-based radical polymerization system, denoted as RAFT / Thiol; or,

[0012] The primary radical polymerization system is a reversible complexation-mediated polymerization (RCMP) system, and the secondary radical polymerization system is a reversible addition-fragmentation chain transfer polymerization system, denoted as RCMP / RAFT; or,

[0013] The primary radical polymerization system is a nitrogen oxide-mediated polymerization (NMP) system, and the secondary radical polymerization system is a reversible addition-fragmentation chain transfer polymerization system, denoted as NMP / RAFT; or,

[0014] The primary radical polymerization system is a nitrogen oxide-mediated polymerization system, and the secondary radical polymerization system is a radical polymerization system using thiol as a chain transfer agent, denoted as NMP / Thiol; or,

[0015] The primary radical polymerization system is an organotellurium-mediated living radical polymerization (TERP) system, and the secondary radical polymerization system is a reversible addition-fragmentation chain transfer polymerization system, denoted as TEP / RAFT.

[0016] Preferably, the polymeric monomer is selected from any one of the following: styrene (St, CAS: 100-42-5), methyl acrylate (MA, CAS: 292638-85-8), ethyl acrylate (EA, CAS: 140-88-5), n-butyl acrylate (IBA, CAS: 106-63-8), isobutyl acrylate (BA, CAS: 141-32-2), methyl methacrylate (MMA, CAS: 80-62-6), ethyl methacrylate (EMA, CAS: 97-63-2), isopropyl methacrylate (IPMA, CAS: 4655-34-9), or n-butyl methacrylate (BMA, CAS: 97-88-1).

[0017] Preferably, the ATRP system comprises: a first initiator, a first catalyst, and a ligand; wherein,

[0018] The first initiator is selected from: 1-chloro-1-phenylethane (PECl, CAS: 672-65-1), 1-bromophenylethane (PEBr, CAS: 38661-81-3), ethyl 2-chloro-2-methylpropionate (EtCliB, CAS: 62554-44-3), 2-chloropropionitrile (ClPN, CAS: 1617-17-0), methyl 2-chloropropionate (MClP, CAS: 17639-93-9), ethyl 2-bromo-2-methylpropionate (EtBriB, CAS: 600-00-0), 2-bromopropionitrile (BrPN, CAS: 19481-82-4), methyl 2-bromopropionate (MBrP, CAS: 5445-17- 0), at least one of the following: tert-butyl 2-bromopropionate (tBBrP, CAS: 39149-80-9), methyl 2-bromoisobutyrate (MBriB, CAS: 23426-63-3), ethyl α-bromophenylacetate (EBPA, CAS: 2882-19-1), benzyl chloride (BzCl, CAS: 100-44-7), chloroacetonitrile (ClAN, CAS: 107-14-2), methyl chloroacetate (MClAc, CAS: 96-34-4), benzyl bromide (BzBr, CAS: 100-39-0), bromoacetonitrile (BrAN, CAS: 590-17-0), or methyl bromoacetate (MBrAc, CAS: 96-32-2);

[0019] The first catalyst is selected from at least one of: copper chloride (CuCl2, CAS: 1344-67-8), cuprous chloride (CuCl, CAS: 7758-89-6), copper bromide (CuBr2, CAS: 7789-45-9), or cuprous bromide (CuBr, CAS: 7787-70-4);

[0020] The ligand is selected from at least one of the following: 2,2'-bipyridine (bpy, CAS: 366-88-6), 4,4'-bis(1-butylpentyl)-2,2'-bipyridine (dNpy, CAS: 72230-93-4), tris(2-pyridylmethyl)amine (TPMA, CAS: 16858-01-8), tris(2-dimethylaminoethyl)amine (Me6TREN, CAS: 33527-91-2), tris(2-diethylaminoethyl)amine (Et6TREN, CAS: 4432-88-6), tetramethylethylenediamine (TMEDA, CAS: 110-18-9), or pentamethyldiethylenetriamine (PMDETA, CAS: 3030-47-5).

[0021] Preferably, the RAFT system comprises: a second chain transfer agent; wherein,

[0022] The second chain transfer agent is selected from: ethyl 2-[(ethoxythiocarbonyl)thio]propionate (CTA3, CAS: 73232-07-2), methyl 2-[[(dodecylmercapto)thiomethyl]thio]-2-methylbenzoate (CTA5, CAS: 1088555-95-6), methyl 2-[dodecylthio(thiocarbonyl)thio]-2-methylpropionic acid (CTA4, CAS: 461642-78-4), 2-phenyl-2-propylbenzodisulfide (CTA7, CAS: 201611-77-0), ethyl 2-methyl-2-(phenylthiocarbonylthio)propionate (CTA2, CAS: 201611-84-9), 2-cyanopropyl-2-ylbenzodisulfide (CTA8, CAS: 201611-85-0), 2-cyanopropyl-2-ylbenzodisulfide, etc. O-ethyl propyl-2-thiomethylacetic acid (CTA11, CAS: 218966-80-4), 2-cyanopropyl N-methyl-N-(4-pyridine)aminodithiocarbonate (CTA6, CAS: 1158958-96-3), 4-cyano-4-(thiobenzoyl)valerate (CTA1, CAS: 201611-92-9), 4-cyano-4- At least one of [[(dodecylthio)thionylmethyl]thio]valerate (CTA10, CAS: 870196-80-8), S-(2-cyano-2-propyl)-S-dodecyl trithiocarbonyl ester (CTA9, CAS: 870196-83-1), or S-benzyl O-ethyl dithiocarbonate (CTA12, CAS: 2943-26-2).

[0023] Preferably, the RCMP system comprises: a first dormant species and a second catalyst; wherein,

[0024] The first dormant species was selected from: elemental iodine (I2, CAS: 12190-71-5);

[0025] The second catalyst is selected from at least one of the following: 1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane (TMTAC, CAS: 102-82-9), tributylmethylphosphine iodide (BMPI, CAS: 1702-42-7), triethylamine (TEA, CAS: 121-44-8), tri-n-butylamine (TBA, CAS: 102-82-9), tetrabutylammonium iodide (BNI, CAS: 311-28-4), tetramethylethylenediamine (TMEDA, CAS: 110-18-9), or tetratris(dimethylamino)ethylene (TDAE, CAS: 996-70-3).

[0026] Preferably, the NMP system includes: a second dormant species; wherein,

[0027] The second dormant species is selected from at least one of the following: 2,2,6,6-tetramethylpiperidine-1-oxygen radical (TEMPO, CAS: 2564-83-2), 2,2,5-trimethyl-4-phenyl-3-azahexane-3-nitrooxy (TIPNO, CAS: 61015-94-9), 1-hydroxy-N,2,2-triphenylindole-3-imine (DPAIO, CAS: 57309-20-3), or N-tert-butyl-N-[1-diethylphosphono-(2,2-dimethylpropyl)] (SG-1, CAS: 188526-94-5).

[0028] Preferably, the TEP system includes: a third dormant species; wherein,

[0029] The third dormant species is selected from at least one of the following: 1-phenylethyl tellurylbenzene (Te6, CAS: 121335-32-8), 2-methyl-2-(methyltelluryl)propionitrile (Te3, CAS: 682319-76-4), ethyl 2-methyl-2-(methyltelluryl)propionate (Te2, CAS: 474094-06-9), methyltelluride benzo[a]tellurate (Te5, CAS: 76399-11-6), dimethyl ditelluride (Te7, CAS: 20334-43-4), methyl(1-phenylethyl)telluride (Te1, CAS: 415679-75-3), or methylbenzyltelluride (Te4, CAS: 103680-41-7).

[0030] Preferably, the RITP system includes: a fourth dormant species; wherein,

[0031] The fourth dormant species is selected from: elemental iodine (I2, CAS: 12190-71-5).

[0032] Preferably, the Thiol system comprises: a first chain transfer agent; wherein,

[0033] The first chain transfer agent is selected from at least one of the following: tert-nonylthiol (TNM, CAS: 25360-10-5), tert-dodecylthiol (TDM, CAS: 25103-58-6), n-butanethiol (NBM, CAS: 109-79-5), n-dodecylthiol (NDM, CAS: 112-55-0), or n-octylthiol (NOM, CAS: 111-88-6).

[0034] Preferably, at most one of the primary radical polymerization system or the secondary radical polymerization system includes: a thermal initiator; wherein,

[0035] The thermal initiator is selected from at least one of the following: 2,2-azobis(4-methoxy-2,4-dimethylpentanonitrile) (V-70, CAS: 15545-97-8), benzoyl peroxide (BPO, CAS: 94-36-0), azobisisobutyronitrile (AIBN, CAS: 78-67-1), or azobisisoheptanenitrile (ABVN, CAS: 4419-11-8).

[0036] Furthermore, when the polymeric monomer is mixed with the ATRP / RITP, the molar ratio of the polymeric monomer, the first initiator, the first catalyst, the ligand, the fourth dormant species, and the thermal initiator is (100-500):(0.05-0.5):(0.1-1):(0.2-2):(0.25-0.475):1.

[0037] Furthermore, when the polymer monomer is mixed with the ATRP / RAFT, the molar ratio of the polymer monomer, the first initiator, the first catalyst, the ligand, the second chain transfer agent, and the thermal initiator is (100-500):(1-2):(0.01-1):(0.02-2):(2-9):(0-0.1).

[0038] Furthermore, when the polymeric monomer is mixed with the RAFT / RAFT, the molar ratio of the polymeric monomer, the second chain transfer agent (denoted as CTA-1) in the primary radical polymerization system, the second chain transfer agent (denoted as CTA-2) in the secondary radical polymerization system, and the thermal initiator is (100-500):(1-2):(2-9):0.1.

[0039] Furthermore, when the polymeric monomer is mixed with the RAFT / Thiol, the molar ratio of the polymeric monomer, the second chain transfer agent, the first chain transfer agent, and the thermal initiator is (100-500):(1-2):(2-9):0.1.

[0040] Furthermore, when the polymer monomer is mixed with the RCMP / RAFT, the molar ratio of the polymer monomer, the first dormant species, the second catalyst, the second chain transfer agent, and the thermal initiator is (100-500):(1-2):(2-9):(1.5-4).

[0041] Furthermore, when the polymeric monomer is mixed with the NMP / RAFT, the molar ratio of the polymeric monomer, the second dormant species, the second chain transfer agent, and the thermal initiator is (100-500):(1-2):(2-9):(1.2-3).

[0042] Furthermore, when the polymeric monomer is mixed with the NMP / Thiol, the molar ratio of the polymeric monomer, the second dormant species, the first chain transfer agent, and the thermal initiator is (100-500):(1-2):(2-4):(1.2-3).

[0043] Furthermore, when the polymeric monomer is mixed with the TEP / RAFT, the molar ratio of the polymeric monomer, the third dormant species, the second chain transfer agent, and the thermal initiator is (100-500):(1-2):(2-9):1.

[0044] Furthermore, the reaction temperature of the ATRP / RITP is 60℃-90℃.

[0045] Furthermore, the reaction temperature of the ATRP / RAFT is 60℃-90℃.

[0046] Furthermore, the reaction temperature of the RAFT / RAFT is 60℃-90℃.

[0047] Furthermore, the reaction temperature of the RAFT / Thiol is 60℃-90℃.

[0048] Furthermore, the reaction temperature of the RCMP / RAFT is 65℃-100℃.

[0049] Furthermore, the reaction temperature of the NMP / RAFT is 80℃-125℃.

[0050] Furthermore, the reaction temperature of the NMP / Thiol is 80℃-125℃.

[0051] Furthermore, the reaction temperature of the TEP / RAFT is 65℃-100℃.

[0052] Preferably, the polymerizing monomer, the primary radical polymerization system, and the secondary radical polymerization system are mixed in an organic solvent; wherein,

[0053] The organic solvent is selected from at least one of benzene (CAS: 71-43-2), dimethylformamide (DMF, CAS: 6976-91-6), dimethyl sulfoxide (DMSO, CAS: 67-68-5), or toluene (CAS: 108-88-3).

[0054] The present invention adopts the above technical solution and has the following technical effects compared with the prior art:

[0055] The binary radical polymerization method of this invention, by combining a primary radical polymerization system for capturing free radicals with a secondary radical polymerization system for achieving chain transfer, successfully achieves independent control of molecular weight and molecular weight distribution in living polymerization. This not only improves polymerization efficiency and reduces production costs, but also significantly enhances the quality of polymer products. Because it can precisely control the molecular weight and molecular weight distribution of polymers, this invention can be widely applied to various scenarios involving living and controllable radical polymerization reactions, including materials science, medicine, chemical engineering, and other fields. Applications with special requirements for polymer performance will also benefit from this. Attached Figure Description

[0056] Figure 1 This is the gel permeation chromatogram of Comparative Example 1-1 of the present invention;

[0057] Figure 2 These are the gel permeation chromatograms of Comparative Examples 1-2 of this invention;

[0058] Figure 3 This is a gel permeation chromatogram of Example 1 of the present invention;

[0059] Figure 4 This is the gel permeation chromatogram of Comparative Example 2-2 of the present invention;

[0060] Figure 5 This is the gel permeation chromatogram of Example 2 of the present invention;

[0061] Figure 6 This is the gel permeation chromatogram of Comparative Example 3-1 of the present invention;

[0062] Figure 7 This is the gel permeation chromatogram of Comparative Example 3-2 of the present invention;

[0063] Figure 8 This is the gel permeation chromatogram of Example 3 of the present invention;

[0064] Figure 9 This is the gel permeation chromatogram of Comparative Example 4-1 of the present invention;

[0065] Figure 10 This is the gel permeation chromatogram of Comparative Example 4-2 of the present invention;

[0066] Figure 11 This is the gel permeation chromatogram of Example 4 of the present invention;

[0067] Figure 12 This is the gel permeation chromatogram of Comparative Example 5-1 of the present invention;

[0068] Figure 13 This is the gel permeation chromatogram of Comparative Example 5-2 of the present invention;

[0069] Figure 14 This is the gel permeation chromatogram of Example 5 of the present invention;

[0070] Figure 15 This is the gel permeation chromatogram of Comparative Example 6-1 of the present invention;

[0071] Figure 16 This is the gel permeation chromatogram of Comparative Example 6-2 of the present invention;

[0072] Figure 17 This is the gel permeation chromatogram of Example 6 of the present invention;

[0073] Figure 18 This is the gel permeation chromatogram of Comparative Example 7-1 of the present invention;

[0074] Figure 19 This is the gel permeation chromatogram of Comparative Example 7-2 of the present invention;

[0075] Figure 20 This is the gel permeation chromatogram of Example 7 of the present invention;

[0076] Figure 21 This is the gel permeation chromatogram of Comparative Example 8-1 of the present invention;

[0077] Figure 22 This is the gel permeation chromatogram of Comparative Example 8-2 of the present invention;

[0078] Figure 23 This is the gel permeation chromatogram of Example 8 of the present invention;

[0079] Figure 24 This is the gel permeation chromatogram of Comparative Example 9-1 of the present invention;

[0080] Figure 25 This is the gel permeation chromatogram of Comparative Example 9-2 of the present invention;

[0081] Figure 26 This is the gel permeation chromatogram of Example 9 of the present invention;

[0082] Figure 27 This is the gel permeation chromatogram of Comparative Example 10-1 of the present invention;

[0083] Figure 28 This is the gel permeation chromatogram of Comparative Example 10-2 of the present invention;

[0084] Figure 29 This is the gel permeation chromatogram of Example 10 of the present invention;

[0085] Figure 30 This is the gel permeation chromatogram of Comparative Example 11-1 of the present invention;

[0086] Figure 31This is a gel permeation chromatogram of Comparative Examples 11-2 of the present invention;

[0087] Figure 32 This is the gel permeation chromatogram of Example 11 of the present invention;

[0088] Figure 33 This is a gel permeation chromatogram of Comparative Example 12-2 of the present invention;

[0089] Figure 34 This is the gel permeation chromatogram of Example 12 of the present invention;

[0090] Figure 35 This is the gel permeation chromatogram of Comparative Example 13-1 of the present invention;

[0091] Figure 36 This is the gel permeation chromatogram of Comparative Example 13-2 of the present invention;

[0092] Figure 37 This is the gel permeation chromatogram of Example 13 of the present invention;

[0093] Figure 38 This is the gel permeation chromatogram of Comparative Example 14-1 of the present invention;

[0094] Figure 39 This is the gel permeation chromatogram of Comparative Example 14-2 of the present invention;

[0095] Figure 40 This is the gel permeation chromatogram of Example 14 of the present invention;

[0096] Figure 41 This is the gel permeation chromatogram of Comparative Example 15-1 of the present invention;

[0097] Figure 42 This is the gel permeation chromatogram of Comparative Example 15-2 of the present invention;

[0098] Figure 43 This is the gel permeation chromatogram of Example 15 of the present invention;

[0099] Figure 44 This is the gel permeation chromatogram of Comparative Example 16-2 of the present invention;

[0100] Figure 45 This is the gel permeation chromatogram of Example 16 of the present invention;

[0101] Figure 46 This is the gel permeation chromatogram of Comparative Example 17-1 of the present invention;

[0102] Figure 47 This is the gel permeation chromatogram of Comparative Example 17-2 of the present invention;

[0103] Figure 48This is the gel permeation chromatogram of Example 17 of the present invention;

[0104] Figure 49 This is the gel permeation chromatogram of Comparative Example 18-1 of the present invention;

[0105] Figure 50 This is the gel permeation chromatogram of Comparative Example 18-2 of the present invention;

[0106] Figure 51 This is the gel permeation chromatogram of Example 18 of the present invention;

[0107] Figure 52 This is the gel permeation chromatogram of Comparative Example 19-1 of the present invention;

[0108] Figure 53 This is a gel permeation chromatogram of Comparative Example 19-2 of the present invention;

[0109] Figure 54 This is the gel permeation chromatogram of Example 19 of the present invention;

[0110] Figure 55 This is the gel permeation chromatogram of Comparative Example 20-1 of the present invention;

[0111] Figure 56 This is the gel permeation chromatogram of Comparative Example 20-2 of the present invention;

[0112] Figure 57 This is the gel permeation chromatogram of Example 20 of the present invention;

[0113] Figure 58 This is a gel permeation chromatogram of Comparative Example 21-2 of the present invention;

[0114] Figure 59 This is the gel permeation chromatogram of Example 21 of the present invention;

[0115] Figure 60 This is the gel permeation chromatogram of Comparative Example 22-2 of the present invention;

[0116] Figure 61 This is a gel permeation chromatogram of Example 22 of the present invention. Detailed Implementation

[0117] The specific embodiments of the present invention will be described in detail below.

[0118] Unless otherwise defined, the technical or scientific terms used in the claims and description shall have the ordinary meaning as understood by one of ordinary skill in the art to which this invention pertains.

[0119] The words “comprising” or “selected from” or similar terms used in the patent application specification and claims of this invention mean that the objects preceding the word include the objects listed after the word or their equivalents, but do not exclude other objects.

[0120] The numerical values ​​mentioned in this patent application specification and claims include all values ​​increasing one unit at a time from low to high, assuming that there is at least a two-unit interval between any lower and higher value. For example, if a component quantity or a physical quantity is said to be better from 1 to 100, 10 to 90, and 20 to 80, it means that values ​​such as 5 to 95, 14 to 76, 23 to 67, 32 to 58, and 41 to 49 are clearly listed in this specification; for values ​​less than 1, 0.0001, 0.001, 0.01, or 0.1 are considered suitable units. The foregoing examples are for illustrative purposes only; in practice, all combinations of values ​​between the lowest and highest listed values ​​are considered to be clearly listed in this specification in a similar manner.

[0121] The free radical polymerization reactions described in the patent application specification and claims of this invention are all carried out in a glove box to ensure that the entire process is carried out under anaerobic conditions; at the same time, the monomers and / or organic solvents used in the free radical polymerization reaction are purified in advance by passing them through a neutral alumina column to remove the polymerization inhibitors, and are subjected to three freeze-evacuation-thawing cycles to remove dissolved oxygen in the liquid.

[0122] Comparative Example 1-1 (ATRP)

[0123] 6.69 mg of CuBr2 (first catalyst) and 10.4 mg of PMDETA (ligand) were dissolved in 1 mL of DMF (organic solvent) to obtain the first solution;

[0124] Add 300 mg (3 mmol, 200 equiv) of MMA (polymer monomer), 2.93 mg (0.015 mmol, 1 equiv) of EtBriB (first initiator), 0.25 mg (0.0015 mmol, 0.1 equiv) of AIBN (thermal initiator), and 50 μL of the aforementioned first solution (containing 0.0015 mmol, 0.1 equiv of CuBr2 and 0.003 mmol, 0.1 equiv of PMDETA) to a 2 mL sample vial. Then add toluene (organic solvent) to a liquid volume of 1 mL to make the concentration of the aforementioned polymer monomer 3 mol / L.

[0125] It is continuously stirred and heated in a metal bath at 75°C.

[0126] To monitor the reaction progress, nuclear magnetic resonance (NMR) technology was used to track the conversion rate of the monomers; simultaneously, gel permeation chromatography (GPC) was used to track the molecular weight and molecular weight distribution of the polymer; the relevant measurement data and results are as follows: Figure 1 As shown, the monomer conversion rate was 59.7%, M n =12.9kDa, M w =15.4kDa, PDI=1.19.

[0127] Comparative Examples 1-2 (RAFT)

[0128] Add 300 mg (3 mmol, 200 equiv) of MMA (polymer monomer), 16.10 mg (0.06 mmol, 4 equiv) of CTA2 (second chain transfer agent), 0.25 mg (0.0015 mmol, 0.1 equiv) of AIBN (thermal initiator), and 50 μL of DMF (organic solvent) to a 2 mL sample vial. Then add toluene (organic solvent) to make the liquid volume 1 mL, so that the concentration of the aforementioned polymer monomer is 3 mol / L.

[0129] It is continuously stirred and heated in a metal bath at 75°C.

[0130] To monitor the reaction progress, nuclear magnetic resonance (NMR) technology was used to track the conversion rate of the monomers; simultaneously, gel permeation chromatography (GPC) was used to track the molecular weight and molecular weight distribution of the polymer; the relevant measurement data and results are as follows: Figure 2 As shown, the monomer conversion rate was 66.1%, M n =9.1kDa, M w =13.1kDa, PDI=1.43.

[0131] Example 1 (ATRP / RAFT)

[0132] 6.69 mg of CuBr2 (first catalyst) and 10.4 mg of PMDETA (ligand) were dissolved in 1 mL of DMF (organic solvent) to obtain the first solution;

[0133] Add 300 mg (3 mmol, 200 equiv) of MMA (polymerizable monomer), 2.93 mg (0.015 mmol, 1 equiv) of EtBriB (first initiator), 16.10 mg (0.06 mmol, 4 equiv) of CTA2 (second chain transfer agent), 0.25 mg (0.0015 mmol, 0.1 equiv) of AIBN (thermal initiator), and 50 μL of the aforementioned first solution (containing 0.0015 mmol, 0.1 equiv of CuBr2 and 0.003 mmol, 0.1 equiv of PMDETA) to a 2 mL sample vial. Then add toluene (organic solvent) to a liquid volume of 1 mL to make the concentration of the aforementioned polymerizable monomer 3 mol / L.

[0134] It is continuously stirred and heated in a metal bath at 75°C.

[0135] The reaction mechanism in this embodiment is as follows:

[0136] Triggering process:

[0137]

[0138] Level 1 ATRP re-triggering process:

[0139]

[0140] First-level ATRP balancing process:

[0141]

[0142] Second-level RAFT re-triggered process:

[0143]

[0144] Second-level RAFT chain transfer process:

[0145]

[0146] To monitor the reaction progress, nuclear magnetic resonance (NMR) technology was used to track the conversion rate of the monomers; simultaneously, gel permeation chromatography (GPC) was used to track the molecular weight and molecular weight distribution of the polymer; the relevant measurement data and results are as follows: Figure 3 As shown, the monomer conversion rate was 62.5%, M n =6.6kDa, M w =8.5kDa, PDI=1.28.

[0147] It is evident that, under similar monomer conversion rates, the molecular weight of the polymer obtained in Example 1 is lower than that of the polymers obtained in Comparative Examples 1-1 or 1-2, demonstrating that the secondary radical polymerization system achieved chain transfer, while the polymerization control remained within the active range, demonstrating that the primary radical polymerization system achieved free radical capture.

[0148] Comparative Example 2-1 (ATRP)

[0149] Same as Comparative Example 1-1

[0150] Comparative Example 2-2 (RAFT)

[0151] Add 300 mg (3 mmol, 200 equiv) of MMA (polymerizable monomer), 22.72 mg (0.06 mmol, 4 equiv) of CTA5 (second chain transfer agent), 0.25 mg (0.0015 mmol, 0.1 equiv) of AIBN (thermal initiator), and 50 μL of DMF (organic solvent) to a 2 mL sample vial. Then add toluene (organic solvent) to make the liquid volume 1 mL, so that the concentration of the aforementioned polymerizable monomer is 3 mol / L.

[0152] It is continuously stirred and heated in a metal bath at 75°C.

[0153] To monitor the reaction progress, nuclear magnetic resonance (NMR) technology was used to track the conversion rate of the monomers; simultaneously, gel permeation chromatography (GPC) was used to track the molecular weight and molecular weight distribution of the polymer; the relevant measurement data and results are as follows: Figure 4 As shown, the monomer conversion rate was 59.7%, M n =10.2kDa, M w =16.0kDa, PDI=1.57.

[0154] Example 2 (ATRP / RAFT)

[0155] 6.69 mg of CuBr2 (first catalyst) and 10.4 mg of PMDETA (ligand) were dissolved in 1 mL of DMF (organic solvent) to obtain the first solution;

[0156] Add 300 mg (3 mmol, 200 equiv) of MMA (polymerizable monomer), 2.93 mg (0.015 mmol, 1 equiv) of EtBriB (first initiator), 22.72 mg (0.06 mmol, 4 equiv) of CTA5 (second chain transfer agent), 0.25 mg (0.0015 mmol, 0.1 equiv) of AIBN (thermal initiator), and 50 μL of the aforementioned first solution (containing 0.0015 mmol, 0.1 equiv of CuBr2 and 0.003 mmol, 0.1 equiv of PMDETA) to a 2 mL sample vial. Then add toluene (organic solvent) to a liquid volume of 1 mL to make the concentration of the aforementioned polymerizable monomer 3 mol / L.

[0157] It is continuously stirred and heated in a metal bath at 75°C.

[0158] To monitor the reaction progress, nuclear magnetic resonance (NMR) technology was used to track the conversion rate of the monomers; simultaneously, gel permeation chromatography (GPC) was used to track the molecular weight and molecular weight distribution of the polymer; the relevant measurement data and results are as follows: Figure 5 As shown, the monomer conversion rate was 65.1%, M n =7.6kDa, M w =9.9kDa, PDI=1.29.

[0159] As can be seen, under similar monomer conversion rates, the molecular weight of the polymer obtained in Example 2 is lower than that of the polymers obtained in Comparative Example 2-1 or Comparative Example 2-2, proving that the secondary radical polymerization system achieved chain transfer, while the polymerization control remained within the active range, proving that the primary radical polymerization system achieved free radical capture.

[0160] Comparative Example 3-1 (ATRP)

[0161] 6.69 mg of CuBr2 (first catalyst) and 10.4 mg of PMDETA (ligand) were dissolved in 1 mL of DMF (organic solvent) to obtain the first solution;

[0162] Add 300 mg (3 mmol, 200 equiv) of MMA (polymer monomer), 2.93 mg (0.015 mmol, 1 equiv) of EtBriB (first initiator), 0.25 mg (0.0015 mmol, 0.1 equiv) of AIBN (thermal initiator), and 50 μL of the aforementioned first solution (containing 0.0015 mmol, 0.1 equiv of CuBr2 and 0.003 mmol, 0.1 equiv of PMDETA) to a 2 mL sample vial. Then add toluene (organic solvent) to a liquid volume of 1 mL to make the concentration of the aforementioned polymer monomer 3 mol / L.

[0163] It is continuously stirred and heated in a metal bath at 75°C.

[0164] To monitor the reaction progress, nuclear magnetic resonance (NMR) technology was used to track the conversion rate of the monomers; simultaneously, gel permeation chromatography (GPC) was used to track the molecular weight and molecular weight distribution of the polymer; the relevant measurement data and results are as follows: Figure 6 As shown, the monomer conversion rate was 51.2%, M n =10.4kDa, M w =11.7kDa, PDI=1.19.

[0165] Comparative Example 3-2 (RAFT)

[0166] Add 300 mg (3 mmol, 200 equiv) of MMA (polymer monomer), 15.08 mg (0.06 mmol, 4 equiv) of CTA6 (second chain transfer agent), 0.25 mg (0.0015 mmol, 0.1 equiv) of AIBN (thermal initiator), and 50 μL of DMF (organic solvent) to a 2 mL sample vial. Then add toluene (organic solvent) to make the liquid volume 1 mL, so that the concentration of the aforementioned polymer monomer is 3 mol / L.

[0167] It is continuously stirred and heated in a metal bath at 75°C.

[0168] To monitor the reaction progress, nuclear magnetic resonance (NMR) technology was used to track the conversion rate of the monomers; simultaneously, gel permeation chromatography (GPC) was used to track the molecular weight and molecular weight distribution of the polymer; the relevant measurement data and results are as follows: Figure 7 As shown, the monomer conversion rate was 60.4%, M n =31.1kDa, M w =61.8kDa, PDI=1.99.

[0169] Example 3 (ATRP / RAFT)

[0170] 6.69 mg of CuBr2 (first catalyst) and 10.4 mg of PMDETA (ligand) were dissolved in 1 mL of DMF (organic solvent) to obtain the first solution;

[0171] Add 300 mg (3 mmol, 200 equiv) of MMA (polymerizable monomer), 2.93 mg (0.015 mmol, 1 equiv) of EtBriB (first initiator), 15.08 mg (0.06 mmol, 4 equiv) of CTA6 (second chain transfer agent), 0.25 mg (0.0015 mmol, 0.1 equiv) of AIBN (thermal initiator), and 50 μL of the aforementioned first solution (containing 0.0015 mmol, 0.1 equiv of CuBr2 and 0.003 mmol, 0.1 equiv of PMDETA) to a 2 mL sample vial. Then add toluene (organic solvent) to a liquid volume of 1 mL to make the concentration of the aforementioned polymerizable monomer 3 mol / L.

[0172] It is continuously stirred and heated in a metal bath at 75°C.

[0173] To monitor the reaction progress, nuclear magnetic resonance (NMR) technology was used to track the conversion rate of the monomers; simultaneously, gel permeation chromatography (GPC) was used to track the molecular weight and molecular weight distribution of the polymer; the relevant measurement data and results are as follows: Figure 8 As shown, the monomer conversion rate was 47.6%, M n =8.7kDa, M w =11.4kDa, PDI=1.31.

[0174] As can be seen, under similar monomer conversion rates, the molecular weight of the polymer obtained in Example 3 is lower than that of the polymers obtained in Comparative Example 3-1 or Comparative Example 3-2, proving that the secondary radical polymerization system achieved chain transfer, while the polymerization control remained within the active range, proving that the primary radical polymerization system achieved free radical capture.

[0175] Comparative Example 4-1 (ATRP)

[0176] 6.69 mg of CuBr2 (first catalyst) and 10.4 mg of PMDETA (ligand) were dissolved in 1 mL of DMF (organic solvent) to obtain the first solution;

[0177] Add 300 mg (3 mmol, 200 equiv) of MMA (polymer monomer), 2.93 mg (0.015 mmol, 1 equiv) of EtBriB (first initiator), 0.25 mg (0.0015 mmol, 0.1 equiv) of AIBN (thermal initiator), and 50 μL of the aforementioned first solution (containing 0.0015 mmol, 0.1 equiv of CuBr2 and 0.003 mmol, 0.1 equiv of PMDETA) to a 2 mL sample vial. Then add toluene (organic solvent) to a liquid volume of 1 mL to make the concentration of the aforementioned polymer monomer 3 mol / L.

[0178] It is continuously stirred and heated in a metal bath at 75°C.

[0179] To monitor the reaction progress, nuclear magnetic resonance (NMR) technology was used to track the conversion rate of the monomers; simultaneously, gel permeation chromatography (GPC) was used to track the molecular weight and molecular weight distribution of the polymer; the relevant measurement data and results are as follows: Figure 9 As shown, the monomer conversion rate was 51.2%, M n =11.7kDa, M w =14.0kDa, PDI=1.19.

[0180] Comparative Example 4-2 (RAFT)

[0181] Add 300 mg (3 mmol, 200 equiv) of MMA (polymer monomer), 33.93 mg (0.135 mmol, 9 equiv) of CTA6 (second chain transfer agent), 0.25 mg (0.0015 mmol, 0.1 equiv) of AIBN (thermal initiator), and 50 μL of DMF (organic solvent) to a 2 mL sample vial. Then add toluene (organic solvent) to make the liquid volume 1 mL, so that the concentration of the aforementioned polymer monomer is 3 mol / L.

[0182] It is continuously stirred and heated in a metal bath at 75°C.

[0183] To monitor the reaction progress, nuclear magnetic resonance (NMR) technology was used to track the conversion rate of the monomers; simultaneously, gel permeation chromatography (GPC) was used to track the molecular weight and molecular weight distribution of the polymer; the relevant measurement data and results are as follows: Figure 10 As shown, the monomer conversion rate was 58.3%, M n =22.6kDa, M w =44.7kDa, PDI=1.98.

[0184] Example 4 (ATRP / RAFT)

[0185] 6.69 mg of CuBr2 (first catalyst) and 10.4 mg of PMDETA (ligand) were dissolved in 1 mL of DMF (organic solvent) to obtain the first solution;

[0186] Add 300 mg (3 mmol, 200 equiv) of MMA (polymerizable monomer), 2.93 mg (0.015 mmol, 1 equiv) of EtBriB (first initiator), 33.93 mg (0.135 mmol, 9 equiv) of CTA6 (second chain transfer agent), 0.25 mg (0.0015 mmol, 0.1 equiv) of AIBN (thermal initiator), and 50 μL of the aforementioned first solution (containing 0.0015 mmol, 0.1 equiv of CuBr2 and 0.003 mmol, 0.1 equiv of PMDETA) to a 2 mL sample vial. Then add toluene (organic solvent) to a liquid volume of 1 mL to make the concentration of the aforementioned polymerizable monomer 3 mol / L.

[0187] It is continuously stirred and heated in a metal bath at 75°C.

[0188] To monitor the reaction progress, nuclear magnetic resonance (NMR) technology was used to track the conversion rate of the monomers; simultaneously, gel permeation chromatography (GPC) was used to track the molecular weight and molecular weight distribution of the polymer; the relevant measurement data and results are as follows: Figure 11 As shown, the monomer conversion rate was 44.3%, M n =7.0kDa, M w =9.9kDa, PDI=1.41.

[0189] As can be seen, under similar monomer conversion rates, the molecular weight of the polymer obtained in Example 4 is lower than that of the polymers obtained in Comparative Example 4-1 or Comparative Example 4-2, proving that the secondary radical polymerization system achieved chain transfer, while the polymerization control remained within the active range, proving that the primary radical polymerization system achieved free radical capture.

[0190] Comparative Example 5-1 (ATRP)

[0191] 6.69 mg of CuBr2 (first catalyst) and 10.4 mg of PMDETA (ligand) were dissolved in 1 mL of DMF (organic solvent) to obtain the first solution;

[0192] Add 300 mg (3 mmol, 200 equiv) of MMA (polymer monomer), 1.46 mg (0.0075 mmol, 0.5 equiv) of EtBriB (first initiator), 0.25 mg (0.0015 mmol, 0.1 equiv) of AIBN (thermal initiator), and 50 μL of the aforementioned first solution (containing 0.0015 mmol, 0.1 equiv of CuBr2 and 0.003 mmol, 0.1 equiv of PMDETA) to a 2 mL sample vial. Then add toluene (organic solvent) to a liquid volume of 1 mL to make the concentration of the aforementioned polymer monomer 3 mol / L.

[0193] It is continuously stirred and heated in a metal bath at 75°C.

[0194] To monitor the reaction progress, nuclear magnetic resonance (NMR) technology was used to track the conversion rate of the monomers; simultaneously, gel permeation chromatography (GPC) was used to track the molecular weight and molecular weight distribution of the polymer; the relevant measurement data and results are as follows: Figure 12 As shown, the monomer conversion rate was 49.8%, M n =18.1kDa, M w =21.1kDa, PDI=1.16.

[0195] Comparative Example 5-2 (RAFT)

[0196] Add 300 mg (3 mmol, 200 equiv) of MMA (polymer monomer), 35.82 mg (0.1425 mmol, 9.5 equiv) of CTA6 (second chain transfer agent), 0.25 mg (0.0015 mmol, 0.1 equiv) of AIBN (thermal initiator), and 50 μL of DMF (organic solvent) to a 2 mL sample vial. Then add toluene (organic solvent) to make the liquid volume 1 mL, so that the concentration of the aforementioned polymer monomer is 3 mol / L.

[0197] It is continuously stirred and heated in a metal bath at 75°C.

[0198] To monitor the reaction progress, nuclear magnetic resonance (NMR) technology was used to track the conversion rate of the monomers; simultaneously, gel permeation chromatography (GPC) was used to track the molecular weight and molecular weight distribution of the polymer; the relevant measurement data and results are as follows: Figure 13 As shown, the monomer conversion rate was 59.5%, M n =18.9kDa, M w =38.3kDa, PDI=2.02.

[0199] Example 5 (ATRP / RAFT)

[0200] 6.69 mg of CuBr2 (first catalyst) and 10.4 mg of PMDETA (ligand) were dissolved in 1 mL of DMF (organic solvent) to obtain the first solution;

[0201] Add 300 mg (3 mmol, 200 equiv) of MMA (polymerizable monomer), 1.46 mg (0.0075 mmol, 0.5 equiv) of EtBriB (first initiator), 35.82 mg (0.1425 mmol, 9.5 equiv) of CTA6 (second chain transfer agent), 0.25 mg (0.0015 mmol, 0.1 equiv) of AIBN (thermal initiator), and 50 μL of the aforementioned first solution (containing 0.0015 mmol, 0.1 equiv of CuBr2 and 0.003 mmol, 0.1 equiv of PMDETA) to a 2 mL sample vial. Then add toluene (organic solvent) to a volume of 1 mL to make the concentration of the aforementioned polymerizable monomer 3 mol / L.

[0202] It is continuously stirred and heated in a metal bath at 75°C.

[0203] To monitor the reaction progress, nuclear magnetic resonance (NMR) technology was used to track the conversion rate of the monomers; simultaneously, gel permeation chromatography (GPC) was used to track the molecular weight and molecular weight distribution of the polymer; the relevant measurement data and results are as follows: Figure 14 As shown, the monomer conversion rate was 42.8%, M n =7.7kDa, M w =11.5kDa, PDI=1.49.

[0204] As can be seen, under similar monomer conversion rates, the molecular weight of the polymer obtained in Example 5 is lower than that of the polymers obtained in Comparative Example 5-1 or Comparative Example 5-2, proving that the secondary radical polymerization system achieved chain transfer, while the polymerization control remained within the active range, proving that the primary radical polymerization system achieved free radical capture.

[0205] Comparative Example 6-1 (ATRP)

[0206] 6.69 mg of CuBr2 (first catalyst) and 10.4 mg of PMDETA (ligand) were dissolved in 1 mL of DMF (organic solvent) to obtain the first solution;

[0207] Add 300 mg (3 mmol, 200 equiv) of MMA (polymer monomer), 2.93 mg (0.015 mmol, 1 equiv) of EtBriB (first initiator), 0.25 mg (0.0015 mmol, 0.1 equiv) of AIBN (thermal initiator), and 50 μL of the aforementioned first solution (containing 0.0015 mmol, 0.1 equiv of CuBr2 and 0.003 mmol, 0.1 equiv of PMDETA) to a 2 mL sample vial. Then add toluene (organic solvent) to a liquid volume of 1 mL to make the concentration of the aforementioned polymer monomer 3 mol / L.

[0208] It is continuously stirred and heated in a metal bath at 75°C.

[0209] To monitor the reaction progress, nuclear magnetic resonance (NMR) technology was used to track the conversion rate of the monomers; simultaneously, gel permeation chromatography (GPC) was used to track the molecular weight and molecular weight distribution of the polymer; the relevant measurement data and results are as follows: Figure 15 As shown, the monomer conversion rate was 64.8%, M n =14.1kDa, M w =17.0kDa, PDI=1.21.

[0210] Comparative Example 6-2 (RAFT)

[0211] Add 300 mg (3 mmol, 200 equiv) of MMA (polymer monomer), 36.23 mg (0.135 mmol, 9 equiv) of CTA2 (second chain transfer agent), 0.25 mg (0.0015 mmol, 0.1 equiv) of AIBN (thermal initiator), and 50 μL of DMF (organic solvent) to a 2 mL sample vial. Then add toluene (organic solvent) to make the liquid volume 1 mL, so that the concentration of the aforementioned polymer monomer is 3 mol / L.

[0212] It is continuously stirred and heated in a metal bath at 75°C.

[0213] To monitor the reaction progress, nuclear magnetic resonance (NMR) technology was used to track the conversion rate of the monomers; simultaneously, gel permeation chromatography (GPC) was used to track the molecular weight and molecular weight distribution of the polymer; the relevant measurement data and results are as follows: Figure 16 As shown, the monomer conversion rate was 59.9%, M n =5.6kDa, M w =7.4kDa, PDI=1.34.

[0214] Example 6 (ATRP / RAFT)

[0215] 6.69 mg of CuBr2 (first catalyst) and 10.4 mg of PMDETA (ligand) were dissolved in 1 mL of DMF (organic solvent) to obtain the first solution;

[0216] Add 300 mg (3 mmol, 200 equiv) of MMA (polymerizable monomer), 2.93 mg (0.015 mmol, 1 equiv) of EtBriB (first initiator), 36.23 mg (0.135 mmol, 9 equiv) of CTA2 (second chain transfer agent), 0.25 mg (0.0015 mmol, 0.1 equiv) of AIBN (thermal initiator), and 50 μL of the aforementioned first solution (containing 0.0015 mmol, 0.1 equiv of CuBr2 and 0.003 mmol, 0.1 equiv of PMDETA) to a 2 mL sample vial. Then add toluene (organic solvent) to a liquid volume of 1 mL to make the concentration of the aforementioned polymerizable monomer 3 mol / L.

[0217] It is continuously stirred and heated in a metal bath at 75°C.

[0218] To monitor the reaction progress, nuclear magnetic resonance (NMR) technology was used to track the conversion rate of the monomers; simultaneously, gel permeation chromatography (GPC) was used to track the molecular weight and molecular weight distribution of the polymer; the relevant measurement data and results are as follows: Figure 17 As shown, the monomer conversion rate was 63.2%, M n =5.3kDa, M w =6.6kDa, PDI=1.25.

[0219] As can be seen, under similar monomer conversion rates, the molecular weight of the polymer obtained in Example 6 is lower than that of the polymers obtained in Comparative Example 6-1 or Comparative Example 6-2, proving that the secondary radical polymerization system achieved chain transfer, while the polymerization control remained within the active range, proving that the primary radical polymerization system achieved free radical capture.

[0220] Comparative Example 7-1 (ATRP)

[0221] 6.69 mg of CuBr2 (first catalyst) and 10.4 mg of PMDETA (ligand) were dissolved in 1 mL of DMF (organic solvent) to obtain the first solution;

[0222] Add 300 mg (3 mmol, 200 equiv) of MMA (polymer monomer), 2.93 mg (0.015 mmol, 1 equiv) of EtBriB (first initiator), 0.25 mg (0.0015 mmol, 0.1 equiv) of AIBN (thermal initiator), and 50 μL of the aforementioned first solution (containing 0.0015 mmol, 0.1 equiv of CuBr2 and 0.003 mmol, 0.1 equiv of PMDETA) to a 2 mL sample vial. Then add toluene (organic solvent) to a liquid volume of 1 mL to make the concentration of the aforementioned polymer monomer 3 mol / L.

[0223] It is continuously stirred and heated in a metal bath at 75°C.

[0224] To monitor the reaction progress, nuclear magnetic resonance (NMR) technology was used to track the conversion rate of the monomers; simultaneously, gel permeation chromatography (GPC) was used to track the molecular weight and molecular weight distribution of the polymer; the relevant measurement data and results are as follows: Figure 18 As shown, the monomer conversion rate was 46.8%, M n =12.4kDa, M w =13.9kDa, PDI=1.12.

[0225] Comparative Example 7-2 (RAFT)

[0226] Add 300 mg (3 mmol, 200 equiv) of MMA (polymer monomer), 51.12 mg (0.135 mmol, 9 equiv) of CTA5 (second chain transfer agent), 0.25 mg (0.0015 mmol, 0.1 equiv) of AIBN (thermal initiator), and 50 μL of DMF (organic solvent) to a 2 mL sample vial. Then add toluene (organic solvent) to make the liquid volume 1 mL, so that the concentration of the aforementioned polymer monomer is 3 mol / L.

[0227] It is continuously stirred and heated in a metal bath at 75°C.

[0228] To monitor the reaction progress, nuclear magnetic resonance (NMR) technology was used to track the conversion rate of the monomers; simultaneously, gel permeation chromatography (GPC) was used to track the molecular weight and molecular weight distribution of the polymer; the relevant measurement data and results are as follows: Figure 19 As shown, the monomer conversion rate was 51.5%, M n =7.0kDa, M w =10.5kDa, PDI=1.50.

[0229] Example 7 (ATRP / RAFT)

[0230] 6.69 mg of CuBr2 (first catalyst) and 10.4 mg of PMDETA (ligand) were dissolved in 1 mL of DMF (organic solvent) to obtain the first solution;

[0231] Add 300 mg (3 mmol, 200 equiv) of MMA (polymerizable monomer), 2.93 mg (0.015 mmol, 1 equiv) of EtBriB (first initiator), 51.12 mg (0.135 mmol, 9 equiv) of CTA5 (second chain transfer agent), 0.25 mg (0.0015 mmol, 0.1 equiv) of AIBN (thermal initiator), and 50 μL of the aforementioned first solution (containing 0.0015 mmol, 0.1 equiv of CuBr2 and 0.003 mmol, 0.1 equiv of PMDETA) to a 2 mL sample vial. Then add toluene (organic solvent) to a liquid volume of 1 mL to make the concentration of the aforementioned polymerizable monomer 3 mol / L.

[0232] It is continuously stirred and heated in a metal bath at 75°C.

[0233] To monitor the reaction progress, nuclear magnetic resonance (NMR) technology was used to track the conversion rate of the monomers; simultaneously, gel permeation chromatography (GPC) was used to track the molecular weight and molecular weight distribution of the polymer; the relevant measurement data and results are as follows: Figure 20 As shown, the monomer conversion rate was 46.9%, M n =6.4kDa, M w =7.78kDa, PDI=1.21.

[0234] As can be seen, under similar monomer conversion rates, the molecular weight of the polymer obtained in Example 7 is lower than that of the polymers obtained in Comparative Example 7-1 or Comparative Example 7-2, proving that the secondary radical polymerization system achieved chain transfer, while the polymerization control remained within the active range, proving that the primary radical polymerization system achieved free radical capture.

[0235] Comparative Example 8-1 (ATRP)

[0236] 13.38 mg of CuBr2 (first catalyst) and 20.80 mg of PMDETA (ligand) were dissolved in 1 mL of DMF (organic solvent) to obtain the first solution;

[0237] Add 300 mg (3 mmol, 100 equiv) of MMA (polymer monomer), 2.93 mg (0.015 mmol, 0.5 equiv) of EtBriB (first initiator), 4.92 mg (0.03 mmol, 1 equiv) of AIBN (thermal initiator), and 50 μL of the aforementioned first solution (containing 0.003 mmol, 0.1 equiv of CuBr2 and 0.006 mmol, 0.2 equiv of PMDETA) to a 2 mL sample vial. Then add toluene (organic solvent) to a liquid volume of 1 mL to make the concentration of the aforementioned polymer monomer 3 mol / L.

[0238] It is continuously stirred and heated in a metal bath at 75°C.

[0239] To monitor the reaction progress, nuclear magnetic resonance (NMR) technology was used to track the conversion rate of the monomers; simultaneously, gel permeation chromatography (GPC) was used to track the molecular weight and molecular weight distribution of the polymer; the relevant measurement data and results are as follows: Figure 21 As shown, the monomer conversion rate was 41.6%, M n =6.3kDa, M w =8.3kDa, PDI=1.31.

[0240] Comparative Example 8-2 (RITP)

[0241] Add 300 mg (3 mmol, 100 equiv) of MMA (polymer monomer), 1.91 mg (0.0075 mmol, 0.25 equiv) of I2 (fourth dormant species), 4.92 mg (0.03 mmol, 1 equiv) of AIBN (thermal initiator), and 50 μL of DMF (organic solvent) to a 2 mL sample vial. Then add toluene (organic solvent) to make the liquid volume 1 mL, so that the concentration of the aforementioned polymer monomer is 3 mol / L.

[0242] It is continuously stirred and heated in a metal bath at 75°C.

[0243] To monitor the reaction progress, nuclear magnetic resonance (NMR) technology was used to track the conversion rate of the monomers; simultaneously, gel permeation chromatography (GPC) was used to track the molecular weight and molecular weight distribution of the polymer; the relevant measurement data and results are as follows: Figure 22 As shown, the monomer conversion rate was 30.7%, M n =14.2kDa, M w =27.0kDa, PDI=1.89.

[0244] Example 8 (ATRP / RITP)

[0245] 13.38 mg of CuBr2 (first catalyst) and 20.80 mg of PMDETA (ligand) were dissolved in 1 mL of DMF (organic solvent) to obtain the first solution;

[0246] Add 300 mg (3 mmol, 100 equiv) of MMA (polymer monomer), 2.93 mg (0.015 mmol, 0.5 equiv) of EtBriB (first initiator), 1.91 mg (0.0075 mmol, 0.25 equiv) of I2 (fourth dormant species), 4.92 mg (0.03 mmol, 1 equiv) of AIBN (thermal initiator), and 50 μL of the aforementioned first solution (containing 0.003 mmol, 0.1 equiv of CuBr2 and 0.006 mmol, 0.2 equiv of PMDETA) to a 2 mL sample vial. Then add toluene (organic solvent) to a liquid volume of 1 mL to make the concentration of the aforementioned polymer monomer 3 mol / L.

[0247] It is continuously stirred and heated in a metal bath at 75°C.

[0248] The reaction mechanism in this embodiment is as follows:

[0249] Triggering process:

[0250]

[0251] Level 1 ATRP re-triggering process:

[0252]

[0253] First-level ATRP balancing process:

[0254]

[0255] Secondary RITP chain transfer agent generation:

[0256]

[0257] Secondary RITP chain transfer process:

[0258]

[0259] To monitor the reaction progress, nuclear magnetic resonance (NMR) technology was used to track the conversion rate of the monomers; simultaneously, gel permeation chromatography (GPC) was used to track the molecular weight and molecular weight distribution of the polymer; the relevant measurement data and results are as follows: Figure 23 As shown, the monomer conversion rate was 42.1%, M n = 5.52kDa, M w =6.6kDa, PDI=1.26.

[0260] As can be seen, under similar monomer conversion rates, the molecular weight of the polymer obtained in Example 8 is lower than that of the polymers obtained in Comparative Example 8-1 or Comparative Example 8-2, proving that the secondary radical polymerization system achieved chain transfer, while the polymerization control remained within the active range, proving that the primary radical polymerization system achieved free radical capture.

[0261] Comparative Example 9-1 (ATRP)

[0262] 13.38 mg of CuBr2 (first catalyst) and 20.80 mg of PMDETA (ligand) were dissolved in 1 mL of DMF (organic solvent) to obtain the first solution;

[0263] Add 300 mg (3 mmol, 100 equiv) of MMA (polymer monomer), 0.59 mg (0.003 mmol, 0.1 equiv) of EtBriB (first initiator), 4.92 mg (0.03 mmol, 1 equiv) of AIBN (thermal initiator), and 50 μL of the aforementioned first solution (containing 0.003 mmol, 0.1 equiv of CuBr2 and 0.006 mmol, 0.2 equiv of PMDETA) to a 2 mL sample vial. Then add toluene (organic solvent) to a liquid volume of 1 mL to make the concentration of the aforementioned polymer monomer 3 mol / L.

[0264] It is continuously stirred and heated in a metal bath at 75°C.

[0265] To monitor the reaction progress, nuclear magnetic resonance (NMR) technology was used to track the conversion rate of the monomers; simultaneously, gel permeation chromatography (GPC) was used to track the molecular weight and molecular weight distribution of the polymer; the relevant measurement data and results are as follows: Figure 24 As shown, the monomer conversion rate was 83.2%, M n =16.4kDa, M w =27.9kDa, PDI=1.71.

[0266] Comparative Example 9-2 (RITP)

[0267] Add 300 mg (3 mmol, 100 equiv) of MMA (polymer monomer), 3.43 mg (0.0135 mmol, 0.45 equiv) of I2 (fourth dormant species), 4.92 mg (0.03 mmol, 1 equiv) of AIBN (thermal initiator), and 50 μL of DMF (organic solvent) to a 2 mL sample vial. Then add toluene (organic solvent) to make the liquid volume 1 mL, so that the concentration of the aforementioned polymer monomer is 3 mol / L.

[0268] It is continuously stirred and heated in a metal bath at 75°C.

[0269] To monitor the reaction progress, nuclear magnetic resonance (NMR) technology was used to track the conversion rate of the monomers; simultaneously, gel permeation chromatography (GPC) was used to track the molecular weight and molecular weight distribution of the polymer; the relevant measurement data and results are as follows: Figure 25 As shown, the monomer conversion rate was 79.3%, M n =11.9kDa, M w =21.5kDa, PDI=1.81.

[0270] Example 9 (ATRP / RITP)

[0271] 13.38 mg of CuBr2 (first catalyst) and 20.80 mg of PMDETA (ligand) were dissolved in 1 mL of DMF (organic solvent) to obtain the first solution;

[0272] Add 300 mg (3 mmol, 100 equiv) of MMA (monomer), 0.59 mg (0.003 mmol, 0.1 equiv) of EtBriB (first initiator), 3.43 mg (0.0135 mmol, 0.45 equiv) of I2 (fourth dormant species), 4.92 mg (0.03 mmol, 1 equiv) of AIBN (thermal initiator), and 50 μL of the aforementioned first solution (containing 0.003 mmol, 0.1 equiv of CuBr2 and 0.006 mmol, 0.2 equiv of PMDETA) to a 2 mL sample vial. Then add toluene (organic solvent) to a liquid volume of 1 mL to make the concentration of the aforementioned monomer 3 mol / L.

[0273] It is continuously stirred and heated in a metal bath at 75°C.

[0274] To monitor the reaction progress, nuclear magnetic resonance (NMR) technology was used to track the conversion rate of the monomers; simultaneously, gel permeation chromatography (GPC) was used to track the molecular weight and molecular weight distribution of the polymer; the relevant measurement data and results are as follows: Figure 26 As shown, the monomer conversion rate was 77.2%, M n = 9.4kDa, M w =13.0kDa, PDI=1.37.

[0275] As can be seen, under similar monomer conversion rates, the molecular weight of the polymer obtained in Example 9 is lower than that of the polymers obtained in Comparative Examples 9-1 or 9-2, proving that the secondary radical polymerization system achieved chain transfer, while the polymerization control remained within the active range, proving that the primary radical polymerization system achieved free radical capture.

[0276] Comparative Example 10-1 (ATRP)

[0277] 13.38 mg of CuBr2 (first catalyst) and 20.80 mg of PMDETA (ligand) were dissolved in 1 mL of DMF (organic solvent) to obtain the first solution;

[0278] Add 300 mg (3 mmol, 100 equiv) of MMA (polymer monomer), 0.29 mg (0.0015 mmol, 0.05 equiv) of EtBriB (first initiator), 4.92 mg (0.03 mmol, 1 equiv) of AIBN (thermal initiator), and 50 μL of the aforementioned first solution (containing 0.003 mmol, 0.1 equiv of CuBr2 and 0.006 mmol, 0.2 equiv of PMDETA) to a 2 mL sample vial. Then add toluene (organic solvent) to a liquid volume of 1 mL to make the concentration of the aforementioned polymer monomer 3 mol / L.

[0279] It is continuously stirred and heated in a metal bath at 75°C.

[0280] To monitor the reaction progress, nuclear magnetic resonance (NMR) technology was used to track the conversion rate of the monomers; simultaneously, gel permeation chromatography (GPC) was used to track the molecular weight and molecular weight distribution of the polymer; the relevant measurement data and results are as follows: Figure 27 As shown, the monomer conversion rate was 40.2%, M n =14.2kDa, M w =21.0kDa, PDI=1.47.

[0281] Comparative Example 10-2 (RITP)

[0282] Add 300 mg (3 mmol, 100 equiv) of MMA (polymer monomer), 3.62 mg (0.01425 mmol, 0.475 equiv) of I2 (fourth dormant species), 4.92 mg (0.03 mmol, 1 equiv) of AIBN (thermal initiator), and 50 μL of DMF (organic solvent) to a 2 mL sample vial. Then add toluene (organic solvent) to make the liquid volume 1 mL, so that the concentration of the aforementioned polymer monomer is 3 mol / L.

[0283] It is continuously stirred and heated in a metal bath at 75°C.

[0284] To monitor the reaction progress, nuclear magnetic resonance (NMR) technology was used to track the conversion rate of the monomers; simultaneously, gel permeation chromatography (GPC) was used to track the molecular weight and molecular weight distribution of the polymer; the relevant measurement data and results are as follows: Figure 28As shown, the monomer conversion rate was 34.1%, M n =10.3kDa, M w =20.3kDa, PDI=1.97.

[0285] Example 10 (ATRP / RITP)

[0286] 13.38 mg of CuBr2 (first catalyst) and 20.80 mg of PMDETA (ligand) were dissolved in 1 mL of DMF (organic solvent) to obtain the first solution;

[0287] Add 300 mg (3 mmol, 100 equiv) of MMA (monomer), 0.29 mg (0.0015 mmol, 0.05 equiv) of EtBriB (first initiator), 3.62 mg (0.01425 mmol, 0.475 equiv) of I2 (fourth dormant species), 4.92 mg (0.03 mmol, 1 equiv) of AIBN (thermal initiator), and 50 μL of the aforementioned first solution (containing 0.003 mmol, 0.1 equiv of CuBr2 and 0.006 mmol, 0.2 equiv of PMDETA) to a 2 mL sample vial. Then add toluene (organic solvent) to a volume of 1 mL to make the concentration of the aforementioned monomer 3 mol / L.

[0288] It is continuously stirred and heated in a metal bath at 75°C.

[0289] To monitor the reaction progress, nuclear magnetic resonance (NMR) technology was used to track the conversion rate of the monomers; simultaneously, gel permeation chromatography (GPC) was used to track the molecular weight and molecular weight distribution of the polymer; the relevant measurement data and results are as follows: Figure 29 As shown, the monomer conversion rate was 36.9%, M n =4.6kDa, M w =5.54kDa, PDI=1.16.

[0290] As can be seen, under similar monomer conversion rates, the molecular weight of the polymer obtained in Example 10 is lower than that of the polymers obtained in Comparative Example 10-1 or Comparative Example 10-2, proving that the secondary radical polymerization system achieved chain transfer, while the polymerization control remained within the active range, proving that the primary radical polymerization system achieved free radical capture.

[0291] Comparative Example 11-1 (RAFT)

[0292] Add 300 mg (3 mmol, 200 equiv) of MMA (polymerizable monomer), 4.19 mg (0.015 mmol, 1 equiv) of CTA1 (second chain transfer agent in primary radical polymerization system), and 0.25 mg (0.0015 mmol, 0.1 equiv) of AIBN (thermal initiator) to a 2 mL sample vial, and then add toluene (organic solvent) to a liquid volume of 1 mL, so that the concentration of the aforementioned polymerizable monomer is 3 mol / L;

[0293] It is continuously stirred and heated in a metal bath at 75°C.

[0294] To monitor the reaction progress, nuclear magnetic resonance (NMR) technology was used to track the conversion rate of the monomers; simultaneously, gel permeation chromatography (GPC) was used to track the molecular weight and molecular weight distribution of the polymer; the relevant measurement data and results are as follows: Figure 30 As shown, the monomer conversion rate was 54.3%, M n =12.4kDa, M w =13.8kDa, PDI=1.11.

[0295] Comparative Example 11-2 (RAFT)

[0296] Add 300 mg (3 mmol, 200 equiv) of MMA (polymerizable monomer), 16.10 mg (0.06 mmol, 4 equiv) of CTA2 (second chain transfer agent in the secondary radical polymerization system), and 0.25 mg (0.0015 mmol, 0.1 equiv) of AIBN (thermal initiator) to a 2 mL sample vial, and then add toluene (organic solvent) to a liquid volume of 1 mL, so that the concentration of the aforementioned polymerizable monomer is 3 mol / L;

[0297] It is continuously stirred and heated in a metal bath at 75°C.

[0298] To monitor the reaction progress, nuclear magnetic resonance (NMR) technology was used to track the conversion rate of the monomers; simultaneously, gel permeation chromatography (GPC) was used to track the molecular weight and molecular weight distribution of the polymer; the relevant measurement data and results are as follows: Figure 31 As shown, the monomer conversion rate was 55.8%, M n =8.7kDa, M w =12.5kDa, PDI=1.45.

[0299] Example 11 (RAFT / RAFT)

[0300] Add 300 mg (3 mmol, 200 equiv) of MMA (polymerizable monomer), 4.19 mg (0.015 mmol, 1 equiv) of CTA1 (second chain transfer agent in primary radical polymerization system), 16.10 mg (0.06 mmol, 4 equiv) of CTA2 (second chain transfer agent in secondary radical polymerization system), and 0.25 mg (0.0015 mmol, 0.1 equiv) of AIBN (thermal initiator) to a 2 mL sample vial, then add toluene (organic solvent) to a liquid volume of 1 mL, so that the concentration of the aforementioned polymerizable monomer is 3 mol / L.

[0301] It is continuously stirred and heated in a metal bath at 75°C.

[0302] The reaction mechanism in this embodiment is as follows:

[0303] Triggering process:

[0304]

[0305] Level 1 RAFT re-triggered process:

[0306]

[0307] First-level RAFT chain transfer process:

[0308]

[0309] Second-level RAFT re-triggered process:

[0310]

[0311] Second-level RAFT chain transfer process:

[0312]

[0313] To monitor the reaction progress, nuclear magnetic resonance (NMR) technology was used to track the conversion rate of the monomers; simultaneously, gel permeation chromatography (GPC) was used to track the molecular weight and molecular weight distribution of the polymer; the relevant measurement data and results are as follows: Figure 32 As shown, the monomer conversion rate was 57.4%, M n =6.5kDa, M w =8.0kDa, PDI=1.22.

[0314] As can be seen, under similar monomer conversion rates, the molecular weight of the polymer obtained in Example 11 is lower than that of the polymers obtained in Comparative Example 11-1 or Comparative Example 11-2, proving that the secondary radical polymerization system achieved chain transfer, while the polymerization control remained within the active range, proving that the primary radical polymerization system achieved free radical capture.

[0315] Comparative Example 12-1 (RAFT)

[0316] Same as Comparative Example 11-1

[0317] Comparative Example 12-2 (RAFT)

[0318] Add 300 mg (3 mmol, 200 equiv) of MMA (polymerizable monomer), 22.72 mg (0.06 mmol, 4 equiv) of CTA5 (second chain transfer agent in the secondary radical polymerization system), and 0.25 mg (0.0015 mmol, 0.1 equiv) of AIBN (thermal initiator) to a 2 mL sample vial, and then add toluene (organic solvent) to a liquid volume of 1 mL, so that the concentration of the aforementioned polymerizable monomer is 3 mol / L;

[0319] It is continuously stirred and heated in a metal bath at 75°C.

[0320] To monitor the reaction progress, nuclear magnetic resonance (NMR) technology was used to track the conversion rate of the monomers; simultaneously, gel permeation chromatography (GPC) was used to track the molecular weight and molecular weight distribution of the polymer; the relevant measurement data and results are as follows: Figure 33 As shown, the monomer conversion rate was 60.0%, M n =10.2kDa, M w =16.0kDa, PDI=1.57.

[0321] Example 12 (RAFT / RAFT)

[0322] Add 300 mg (3 mmol, 200 equiv) of MMA (polymerizable monomer), 4.19 mg (0.015 mmol, 1 equiv) of CTA1 (second chain transfer agent in primary radical polymerization system), 22.72 mg (0.06 mmol, 4 equiv) of CTA5 (second chain transfer agent in secondary radical polymerization system), and 0.25 mg (0.0015 mmol, 0.1 equiv) of AIBN (thermal initiator) to a 2 mL sample vial, then add toluene (organic solvent) to a liquid volume of 1 mL, so that the concentration of the aforementioned polymerizable monomer is 3 mol / L.

[0323] It is continuously stirred and heated in a metal bath at 75°C.

[0324] To monitor the reaction progress, nuclear magnetic resonance (NMR) technology was used to track the conversion rate of the monomers; simultaneously, gel permeation chromatography (GPC) was used to track the molecular weight and molecular weight distribution of the polymer; the relevant measurement data and results are as follows: Figure 34 As shown, the monomer conversion rate was 57.1%, Mn =7.3kDa, M w =9.0kDa, PDI=1.23.

[0325] As can be seen, under similar monomer conversion rates, the molecular weight of the polymer obtained in Example 12 is lower than that of the polymers obtained in Comparative Example 12-1 or Comparative Example 12-2, proving that the secondary radical polymerization system achieved chain transfer, while the polymerization control remained within the active range, proving that the primary radical polymerization system achieved free radical capture.

[0326] Comparative Example 13-1 (RAFT)

[0327] Add 300 mg (3 mmol, 200 equiv) of MMA (polymerizable monomer), 4.19 mg (0.015 mmol, 1 equiv) of CTA1 (second chain transfer agent in primary radical polymerization system), and 0.25 mg (0.0015 mmol, 0.1 equiv) of AIBN (thermal initiator) to a 2 mL sample vial, and then add toluene (organic solvent) to a liquid volume of 1 mL, so that the concentration of the aforementioned polymerizable monomer is 3 mol / L;

[0328] It is continuously stirred and heated in a metal bath at 75°C.

[0329] To monitor the reaction progress, nuclear magnetic resonance (NMR) technology was used to track the conversion rate of the monomers; simultaneously, gel permeation chromatography (GPC) was used to track the molecular weight and molecular weight distribution of the polymer; the relevant measurement data and results are as follows: Figure 35 As shown, the monomer conversion rate was 64.6%, M n =14.8kDa, M w =16.3kDa, PDI=1.10.

[0330] Comparative Example 13-2 (RAFT)

[0331] Add 300 mg (3 mmol, 200 equiv) of MMA (polymerizable monomer), 21.88 mg (0.06 mmol, 4 equiv) of CTA4 (second chain transfer agent in the secondary radical polymerization system), and 0.25 mg (0.0015 mmol, 0.1 equiv) of AIBN (thermal initiator) to a 2 mL sample vial, and then add toluene (organic solvent) to a liquid volume of 1 mL, so that the concentration of the aforementioned polymerizable monomer is 3 mol / L;

[0332] It is continuously stirred and heated in a metal bath at 75°C.

[0333] To monitor the reaction progress, nuclear magnetic resonance (NMR) technology was used to track the conversion rate of the monomers; simultaneously, gel permeation chromatography (GPC) was used to track the molecular weight and molecular weight distribution of the polymer; the relevant measurement data and results are as follows: Figure 36 As shown, the monomer conversion rate was 63.0%, M n =11.8kDa, M w =19.1kDa, PDI=1.62.

[0334] Example 13 (RAFT / RAFT)

[0335] Add 300 mg (3 mmol, 200 equiv) of MMA (polymerizable monomer), 4.19 mg (0.015 mmol, 1 equiv) of CTA1 (second chain transfer agent in primary radical polymerization system), 21.88 mg (0.06 mmol, 4 equiv) of CTA4 (second chain transfer agent in secondary radical polymerization system), and 0.25 mg (0.0015 mmol, 0.1 equiv) of AIBN (thermal initiator) to a 2 mL sample vial, then add toluene (organic solvent) to a volume of 1 mL, so that the concentration of the aforementioned polymerizable monomer is 3 mol / L.

[0336] It is continuously stirred and heated in a metal bath at 75°C.

[0337] To monitor the reaction progress, nuclear magnetic resonance (NMR) technology was used to track the conversion rate of the monomers; simultaneously, gel permeation chromatography (GPC) was used to track the molecular weight and molecular weight distribution of the polymer; the relevant measurement data and results are as follows: Figure 37 As shown, the monomer conversion rate was 57.1%, M n =7.3kDa, M w =9.0kDa, PDI=1.23.

[0338] As can be seen, under similar monomer conversion rates, the molecular weight of the polymer obtained in Example 13 is lower than that of the polymers obtained in Comparative Example 13-1 or Comparative Example 13-2, proving that the secondary radical polymerization system achieved chain transfer, while the polymerization control remained within the active range, proving that the primary radical polymerization system achieved free radical capture.

[0339] Comparative Example 14-1 (RAFT)

[0340] Add 300 mg (3 mmol, 200 equiv) of MMA (polymer monomer), 4.19 mg (0.015 mmol, 1 equiv) of CTA1 (second chain transfer agent), and 0.25 mg (0.0015 mmol, 0.1 equiv) of AIBN (thermal initiator) to a 2 mL sample vial, and then add toluene (organic solvent) to a liquid volume of 1 mL, so that the concentration of the aforementioned polymer monomer is 3 mol / L.

[0341] It is continuously stirred and heated in a metal bath at 75°C.

[0342] To monitor the reaction progress, nuclear magnetic resonance (NMR) technology was used to track the conversion rate of the monomers; simultaneously, gel permeation chromatography (GPC) was used to track the molecular weight and molecular weight distribution of the polymer; the relevant measurement data and results are as follows: Figure 38 As shown, the monomer conversion rate was 29.4%, M n =7.2kDa, M w =8.1kDa, PDI=1.13.

[0343] Comparative Example 14-2 (Thiol)

[0344] Add 300 mg (3 mmol, 200 equiv) of MMA (polymer monomer), 12.14 mg (0.06 mmol, 4 equiv) of NDM (first chain transfer agent), and 0.25 mg (0.0015 mmol, 0.1 equiv) of AIBN (thermal initiator) to a 2 mL sample vial, and then add toluene (organic solvent) to a liquid volume of 1 mL, so that the concentration of the aforementioned polymer monomer is 3 mol / L;

[0345] It is continuously stirred and heated in a metal bath at 75°C.

[0346] To monitor the reaction progress, nuclear magnetic resonance (NMR) technology was used to track the conversion rate of the monomers; simultaneously, gel permeation chromatography (GPC) was used to track the molecular weight and molecular weight distribution of the polymer; the relevant measurement data and results are as follows: Figure 39 As shown, the monomer conversion rate was 36.1%, M n =8.8kDa, M w =14.5kDa, PDI=1.64.

[0347] Example 14 (RAFT / Thiol)

[0348] Add 300 mg (3 mmol, 200 equiv) of MMA (polymerizable monomer), 4.19 mg (0.015 mmol, 1 equiv) of CTA1 (second chain transfer agent), 12.14 mg (0.06 mmol, 4 equiv) of NDM (first chain transfer agent), and 0.25 mg (0.0015 mmol, 0.1 equiv) of AIBN (thermal initiator) to a 2 mL sample vial, then add toluene (organic solvent) to a volume of 1 mL, so that the concentration of the aforementioned polymerizable monomer is 3 mol / L.

[0349] It is continuously stirred and heated in a metal bath at 75°C.

[0350] The reaction mechanism in this embodiment is as follows:

[0351] Triggering process:

[0352]

[0353] Level 1 RAFT re-triggered process:

[0354]

[0355] First-level RAFT chain transfer process:

[0356]

[0357] Second-level Thiol chain transfer process:

[0358]

[0359] To monitor the reaction progress, nuclear magnetic resonance (NMR) technology was used to track the conversion rate of the monomers; simultaneously, gel permeation chromatography (GPC) was used to track the molecular weight and molecular weight distribution of the polymer; the relevant measurement data and results are as follows: Figure 40 As shown, the monomer conversion rate was 34.9%, M n =5.2kDa, M w =7.0kDa, PDI=1.32.

[0360] As can be seen, under similar monomer conversion rates, the molecular weight of the polymer obtained in Example 14 is lower than that of the polymers obtained in Comparative Example 14-1 or Comparative Example 14-2, proving that the secondary radical polymerization system achieved chain transfer, while the polymerization control remained within the active range, proving that the primary radical polymerization system achieved free radical capture.

[0361] Comparative Example 15-1 (RCMP)

[0362] Add 300 mg (3 mmol, 200 equiv) of MMA (polymer monomer), 3.81 mg (0.015 mmol, 1 equiv) of I2 (first dormant species), 11.08 mg (0.03 mmol, 2 equiv) of BNI (second catalyst), and 6.33 mg (0.0255 mmol, 1.7 equiv) of ABVN (thermal initiator) to a 2 mL sample vial, then add toluene (organic solvent) to a liquid volume of 1 mL, so that the concentration of the aforementioned polymer monomer is 3 mol / L;

[0363] It is continuously stirred and heated in a metal bath at 65°C.

[0364] To monitor the reaction progress, nuclear magnetic resonance (NMR) technology was used to track the conversion rate of the monomers; simultaneously, gel permeation chromatography (GPC) was used to track the molecular weight and molecular weight distribution of the polymer; the relevant measurement data and results are as follows: Figure 41 As shown, the monomer conversion rate was 78.7%, M n = 9.8kDa, M w =11.2kDa, PDI=1.13.

[0365] Comparative Example 15-2 (RAFT)

[0366] Add 300 mg (3 mmol, 200 equiv) of MMA (polymer monomer), 16.10 mg (0.06 mmol, 4 equiv) of CTA2 (second chain transfer agent), and 6.33 mg (0.0255 mmol, 1.7 equiv) of ABVN (thermal initiator) to a 2 mL sample vial, and then add toluene (organic solvent) to a liquid volume of 1 mL, so that the concentration of the aforementioned polymer monomer is 3 mol / L.

[0367] It is continuously stirred and heated in a metal bath at 65°C.

[0368] To monitor the reaction progress, nuclear magnetic resonance (NMR) technology was used to track the conversion rate of the monomers; simultaneously, gel permeation chromatography (GPC) was used to track the molecular weight and molecular weight distribution of the polymer; the relevant measurement data and results are as follows: Figure 42 As shown, the monomer conversion rate was 78.6%, M n =7.5kDa, M w =11.7kDa, PDI=1.57.

[0369] Example 15 (RCMP / RAFT)

[0370] Add 300 mg (3 mmol, 200 equiv) of MMA (polymer monomer), 3.81 mg (0.015 mmol, 1 equiv) of I2 (first dormant species), 11.08 mg (0.03 mmol, 2 equiv) of BNI (second catalyst), 16.10 mg (0.06 mmol, 4 equiv) of CTA2 (second chain transfer agent), and 6.33 mg (0.0255 mmol, 1.7 equiv) of ABVN (thermal initiator) to a 2 mL sample vial, then add toluene (organic solvent) to a liquid volume of 1 mL, so that the concentration of the aforementioned polymer monomer is 3 mol / L.

[0371] It is continuously stirred and heated in a metal bath at 65°C.

[0372] The reaction mechanism in this embodiment is as follows:

[0373] Triggering process:

[0374]

[0375] First-level RCMP re-triggering process:

[0376]

[0377] First-order RCMP equilibration process:

[0378]

[0379] Second-level RAFT re-triggered process:

[0380]

[0381] Second-level RAFT chain transfer process:

[0382]

[0383] To monitor the reaction progress, nuclear magnetic resonance (NMR) technology was used to track the conversion rate of the monomers; simultaneously, gel permeation chromatography (GPC) was used to track the molecular weight and molecular weight distribution of the polymer; the relevant measurement data and results are as follows: Figure 43 As shown, the monomer conversion rate was 71.5%, M n =5.3kDa, M w =6.10kDa, PDI=1.16.

[0384] As can be seen, under similar monomer conversion rates, the molecular weight of the polymer obtained in Example 15 is lower than that of the polymers obtained in Comparative Example 15-1 or Comparative Example 15-2, proving that the secondary radical polymerization system achieved chain transfer, while the polymerization control remained within the active range, proving that the primary radical polymerization system achieved free radical capture.

[0385] Comparative Example 16-1 (RCMP)

[0386] Same as Comparative Example 15-1

[0387] Comparative Example 16-2 (RAFT)

[0388] Add 300 mg (3 mmol, 200 equiv) of MMA (polymer monomer), 22.72 mg (0.06 mmol, 4 equiv) of CTA5 (second chain transfer agent), and 6.33 mg (0.0255 mmol, 1.7 equiv) of ABVN (thermal initiator) to a 2 mL sample vial, and then add toluene (organic solvent) to a liquid volume of 1 mL, so that the concentration of the aforementioned polymer monomer is 3 mol / L.

[0389] It is continuously stirred and heated in a metal bath at 65°C.

[0390] To monitor the reaction progress, nuclear magnetic resonance (NMR) technology was used to track the conversion rate of the monomers; simultaneously, gel permeation chromatography (GPC) was used to track the molecular weight and molecular weight distribution of the polymer; the relevant measurement data and results are as follows: Figure 44 As shown, the monomer conversion rate was 79.4%, M n =8.0kDa, M w =12.8kDa, PDI=1.60.

[0391] Example 16 (RCMP / RAFT)

[0392] Add 300 mg (3 mmol, 200 equiv) of MMA (polymer monomer), 3.81 mg (0.015 mmol, 1 equiv) of I2 (first dormant species), 11.08 mg (0.03 mmol, 2 equiv) of BNI (second catalyst), 22.72 mg (0.06 mmol, 4 equiv) of CTA5 (second chain transfer agent), and 6.33 mg (0.0255 mmol, 1.7 equiv) of ABVN (thermal initiator) to a 2 mL sample vial, then add toluene (organic solvent) to a liquid volume of 1 mL, so that the concentration of the aforementioned polymer monomer is 3 mol / L.

[0393] It is continuously stirred and heated in a metal bath at 65°C.

[0394] To monitor the reaction progress, nuclear magnetic resonance (NMR) technology was used to track the conversion rate of the monomers; simultaneously, gel permeation chromatography (GPC) was used to track the molecular weight and molecular weight distribution of the polymer; the relevant measurement data and results are as follows: Figure 45 As shown, the monomer conversion rate was 75.9%, M n =5.6kDa, M w =6.8kDa, PDI=1.22.

[0395] As can be seen, under similar monomer conversion rates, the molecular weight of the polymer obtained in Example 16 is lower than that of the polymers obtained in Comparative Example 16-1 or Comparative Example 16-2, proving that the secondary radical polymerization system achieved chain transfer, while the polymerization control remained within the active range, proving that the primary radical polymerization system achieved free radical capture.

[0396] Comparative Example 17-1 (RCMP)

[0397] Add 300 mg (3 mmol, 200 equiv) of MMA (polymer monomer), 3.81 mg (0.015 mmol, 1 equiv) of I2 (first dormant species), 11.08 mg (0.03 mmol, 2 equiv) of BNI (second catalyst), and 6.33 mg (0.0255 mmol, 1.7 equiv) of ABVN (thermal initiator) to a 2 mL sample vial, then add toluene (organic solvent) to a liquid volume of 1 mL, so that the concentration of the aforementioned polymer monomer is 3 mol / L;

[0398] It is continuously stirred and heated in a metal bath at 65°C.

[0399] To monitor the reaction progress, nuclear magnetic resonance (NMR) technology was used to track the conversion rate of the monomers; simultaneously, gel permeation chromatography (GPC) was used to track the molecular weight and molecular weight distribution of the polymer; the relevant measurement data and results are as follows: Figure 46 As shown, the monomer conversion rate was 69.4%, M n =7.7kDa, M w =8.6kDa, PDI=1.11.

[0400] Comparative Example 17-2 (RAFT)

[0401] Add 300 mg (3 mmol, 200 equiv) of MMA (polymer monomer), 21.88 mg (0.06 mmol, 4 equiv) of CTA4 (second chain transfer agent), and 6.33 mg (0.0255 mmol, 1.7 equiv) of ABVN (thermal initiator) to a 2 mL sample vial, and then add toluene (organic solvent) to a liquid volume of 1 mL, so that the concentration of the aforementioned polymer monomer is 3 mol / L.

[0402] It is continuously stirred and heated in a metal bath at 65°C.

[0403] To monitor the reaction progress, nuclear magnetic resonance (NMR) technology was used to track the conversion rate of the monomers; simultaneously, gel permeation chromatography (GPC) was used to track the molecular weight and molecular weight distribution of the polymer; the relevant measurement data and results are as follows: Figure 47 As shown, the monomer conversion rate was 64.3%, M n =6.3kDa, M w =8.9kDa, PDI=1.41.

[0404] Example 17 (RCMP / RAFT)

[0405] Add 300 mg (3 mmol, 200 equiv) of MMA (polymer monomer), 3.81 mg (0.015 mmol, 1 equiv) of I2 (first dormant species), 11.08 mg (0.03 mmol, 2 equiv) of BNI (second catalyst), 21.88 mg (0.06 mmol, 4 equiv) of CTA4 (second chain transfer agent), and 6.33 mg (0.0255 mmol, 1.7 equiv) of ABVN (thermal initiator) to a 2 mL sample vial, then add toluene (organic solvent) to a liquid volume of 1 mL, so that the concentration of the aforementioned polymer monomer is 3 mol / L.

[0406] It is continuously stirred and heated in a metal bath at 65°C.

[0407] To monitor the reaction progress, nuclear magnetic resonance (NMR) technology was used to track the conversion rate of the monomers; simultaneously, gel permeation chromatography (GPC) was used to track the molecular weight and molecular weight distribution of the polymer; the relevant measurement data and results are as follows: Figure 48 As shown, the monomer conversion rate was 63.0%, M n =5.8kDa, M w =6.7kDa, PDI=1.15.

[0408] As can be seen, under similar monomer conversion rates, the molecular weight of the polymer obtained in Example 17 is lower than that of the polymers obtained in Comparative Example 17-1 or Comparative Example 17-2, proving that the secondary radical polymerization system achieved chain transfer, while the polymerization control remained within the active range, proving that the primary radical polymerization system achieved free radical capture.

[0409] Comparative Example 18-1 (NMP)

[0410] Add 625 mg (6 mmol, 200 equiv) of St (polymer monomer), 5.63 mg (0.036 mmol, 1.2 equiv) of TEMPO (second dormant species), and 4.92 mg (0.03 mmol, 1 equiv) of AIBN (thermal initiator) to a 2 mL sample vial.

[0411] The mixture was stirred and heated in a metal bath at 95°C, and after reacting for 3 hours, the temperature was raised to 123°C.

[0412] To monitor the reaction progress, nuclear magnetic resonance (NMR) technology was used to track the conversion rate of the monomers; simultaneously, gel permeation chromatography (GPC) was used to track the molecular weight and molecular weight distribution of the polymer; the relevant measurement data and results are as follows: Figure 49 As shown, the monomer conversion rate was 71.5%, M n =13.1kDa, M w =15.7kDa, PDI=1.20.

[0413] Comparative Example 18-2 (Thiol)

[0414] Add 625 mg (6 mmol, 200 equiv) of St (polymer monomer), 12.14 mg (0.06 mmol, 4 equiv) of NDM (first chain transfer agent), and 4.92 mg (0.03 mmol, 1 equiv) of AIBN (thermal initiator) to a 2 mL sample vial.

[0415] The mixture was stirred and heated in a metal bath at 95°C, and after reacting for 3 hours, the temperature was raised to 123°C.

[0416] To monitor the reaction progress, nuclear magnetic resonance (NMR) technology was used to track the conversion rate of the monomers; simultaneously, gel permeation chromatography (GPC) was used to track the molecular weight and molecular weight distribution of the polymer; the relevant measurement data and results are as follows: Figure 50 As shown, the monomer conversion rate was 67.1%, M n =6.5kDa, M w =42.4kDa, PDI=6.48.

[0417] Example 18 (NMP / Thiol)

[0418] Add 625 mg (6 mmol, 200 equiv) of St (polymer monomer), 5.63 mg (0.036 mmol, 1.2 equiv) of TEMPO (second dormant species), 12.14 mg (0.06 mmol, 4 equiv) of NDM (first chain transfer agent), and 4.92 mg (0.03 mmol, 1 equiv) of AIBN (thermal initiator) to a 2 mL sample vial.

[0419] The mixture was stirred and heated in a metal bath at 95°C, and after reacting for 3 hours, the temperature was raised to 123°C.

[0420] The reaction mechanism in this embodiment is as follows:

[0421] Triggering process:

[0422]

[0423] First-order NMP equilibrium process:

[0424]

[0425] Second-level Thiol chain transfer process:

[0426]

[0427] To monitor the reaction progress, nuclear magnetic resonance (NMR) technology was used to track the conversion rate of the monomers; simultaneously, gel permeation chromatography (GPC) was used to track the molecular weight and molecular weight distribution of the polymer; the relevant measurement data and results are as follows: Figure 51 As shown, the monomer conversion rate was 70.4%, M n =10.5kDa, M w =13.2kDa, PDI=1.26.

[0428] As can be seen, under similar monomer conversion rates, the molecular weight of the polymer obtained in Example 18 is lower than that of the polymers obtained in Comparative Example 18-1 or Comparative Example 18-2, proving that the secondary radical polymerization system achieved chain transfer, while the polymerization control remained within the active range, proving that the primary radical polymerization system achieved free radical capture.

[0429] Comparative Example 19-1 (NMP)

[0430] Add 625 mg (6 mmol, 200 equiv) of St (polymer monomer), 5.63 mg (0.036 mmol, 1.2 equiv) of TEMPO (second dormant species), and 4.92 mg (0.03 mmol, 1 equiv) of AIBN (thermal initiator) to a 2 mL sample vial.

[0431] The mixture was stirred and heated in a metal bath at 95°C, and after reacting for 3 hours, the temperature was raised to 123°C.

[0432] To monitor the reaction progress, nuclear magnetic resonance (NMR) technology was used to track the conversion rate of the monomers; simultaneously, gel permeation chromatography (GPC) was used to track the molecular weight and molecular weight distribution of the polymer; the relevant measurement data and results are as follows: Figure 52 As shown, the monomer conversion rate was 54.6%, M n =10.0kDa, M w =11.4kDa, PDI=1.14.

[0433] Comparative Example 19-2 (RAFT)

[0434] Add 625 mg (6 mmol, 200 equiv) of St (polymer monomer), 26.68 mg (0.12 mmol, 4 equiv) of CTA6 (second chain transfer agent), and 4.92 mg (0.03 mmol, 1 equiv) of AIBN (thermal initiator) to a 2 mL sample vial.

[0435] The mixture was stirred and heated in a metal bath at 95°C, and after reacting for 3 hours, the temperature was raised to 123°C.

[0436] To monitor the reaction progress, nuclear magnetic resonance (NMR) technology was used to track the conversion rate of the monomers; simultaneously, gel permeation chromatography (GPC) was used to track the molecular weight and molecular weight distribution of the polymer; the relevant measurement data and results are as follows: Figure 53 As shown, the monomer conversion rate was 48.7%, M n =5.7kDa, M w =9.6kDa, PDI=1.67.

[0437] Example 19 (NMP / RAFT)

[0438] Add 625 mg (6 mmol, 200 equiv) of St (polymer monomer), 5.63 mg (0.036 mmol, 1.2 equiv) of TEMPO (second dormant species), 26.68 mg (0.12 mmol, 4 equiv) of CTA6 (second chain transfer agent), and 4.92 mg (0.03 mmol, 1 equiv) of AIBN (thermal initiator) to a 2 mL sample vial.

[0439] The mixture was stirred and heated in a metal bath at 95°C, and after reacting for 3 hours, the temperature was raised to 123°C.

[0440] The reaction mechanism in this embodiment is as follows:

[0441] Triggering process:

[0442]

[0443] First-order NMP equilibrium process:

[0444]

[0445] Second-level RAFT re-triggered process:

[0446]

[0447] Second-level RAFT chain transfer process:

[0448]

[0449] To monitor the reaction progress, nuclear magnetic resonance (NMR) technology was used to track the conversion rate of the monomers; simultaneously, gel permeation chromatography (GPC) was used to track the molecular weight and molecular weight distribution of the polymer; the relevant measurement data and results are as follows: Figure 54 As shown, the monomer conversion rate was 47.7%, M n =3.7kDa, M w =5.8kDa, PDI=1.56.

[0450] As can be seen, under similar monomer conversion rates, the molecular weight of the polymer obtained in Example 19 is lower than that of the polymers obtained in Comparative Example 19-1 or Comparative Example 19-2, proving that the secondary radical polymerization system achieved chain transfer, while the polymerization control remained within the active range, proving that the primary radical polymerization system achieved free radical capture.

[0451] Comparative Example 20-1 (TERP)

[0452] Add 600 mg (6 mmol, 200 equiv) of MMA (polymer monomer), 7.43 mg (0.03 mmol, 1 equiv) of Te1 (third dormant species), 8.56 mg (0.03 mmol, 1 equiv) of Te7 (third dormant species), and 4.92 mg (0.03 mmol, 1 equiv) of AIBN (thermal initiator) to a 2 mL sample vial, respectively.

[0453] It is continuously stirred and heated in a metal bath at 65°C.

[0454] To monitor the reaction progress, nuclear magnetic resonance (NMR) technology was used to track the conversion rate of the monomers; simultaneously, gel permeation chromatography (GPC) was used to track the molecular weight and molecular weight distribution of the polymer; the relevant measurement data and results are as follows: Figure 55 As shown, the monomer conversion rate was 60.2%, M n =11.3kDa, Mw =13.7kDa, PDI=1.22.

[0455] Comparative Example 20-2 (RAFT)

[0456] Add 600 mg (6 mmol, 200 equiv) of MMA (polymer monomer), 32.21 mg (0.12 mmol, 4 equiv) of CTA2 (second chain transfer agent), and 4.92 mg (0.03 mmol, 1 equiv) of AIBN (thermal initiator) to a 2 mL sample vial.

[0457] It is continuously stirred and heated in a metal bath at 65°C.

[0458] To monitor the reaction progress, nuclear magnetic resonance (NMR) technology was used to track the conversion rate of the monomers; simultaneously, gel permeation chromatography (GPC) was used to track the molecular weight and molecular weight distribution of the polymer; the relevant measurement data and results are as follows: Figure 56 As shown, the monomer conversion rate was 56.4%, M n =9.0kDa, M w =12.7kDa, PDI=1.41.

[0459] Example 20 (TERP / RAFT)

[0460] Add 600 mg (6 mmol, 200 equiv) of MMA (polymer monomer), 7.43 mg (0.03 mmol, 1 equiv) of Te1 (third dormant species), 8.56 mg (0.03 mmol, 1 equiv) of Te7 (third dormant species), 32.21 mg (0.12 mmol, 4 equiv) of CTA2 (second chain transfer agent), and 4.92 mg (0.03 mmol, 1 equiv) of AIBN (thermal initiator) to a 2 mL sample vial.

[0461] It is continuously stirred and heated in a metal bath at 65°C.

[0462] The reaction mechanism in this embodiment is as follows:

[0463] Triggering process:

[0464]

[0465] Level 1 TEP re-triggering process:

[0466]

[0467] First-level TEP equilibration process:

[0468]

[0469] Second-level RAFT re-triggered process:

[0470]

[0471] Second-level RAFT chain transfer process:

[0472]

[0473] To monitor the reaction progress, nuclear magnetic resonance (NMR) technology was used to track the conversion rate of the monomers; simultaneously, gel permeation chromatography (GPC) was used to track the molecular weight and molecular weight distribution of the polymer; the relevant measurement data and results are as follows: Figure 57 As shown, the monomer conversion rate was 54.4%, M n =7.1kDa, M w =9.4kDa, PDI=1.33.

[0474] As can be seen, under similar monomer conversion rates, the molecular weight of the polymer obtained in Example 20 is lower than that of the polymers obtained in Comparative Example 20-1 or Comparative Example 20-2, proving that the secondary radical polymerization system achieved chain transfer, while the polymerization control remained within the active range, proving that the primary radical polymerization system achieved free radical capture.

[0475] Comparative Example 21-1 (TERP)

[0476] Same comparison 20-1

[0477] Comparative Example 21-2 (RAFT)

[0478] Add 600 mg (6 mmol, 200 equiv) of MMA (polymer monomer), 43.76 mg (0.12 mmol, 4 equiv) of CTA4 (second chain transfer agent), and 4.92 mg (0.03 mmol, 1 equiv) of AIBN (thermal initiator) to a 2 mL sample vial.

[0479] It is continuously stirred and heated in a metal bath at 65°C.

[0480] To monitor the reaction progress, nuclear magnetic resonance (NMR) technology was used to track the conversion rate of the monomers; simultaneously, gel permeation chromatography (GPC) was used to track the molecular weight and molecular weight distribution of the polymer; the relevant measurement data and results are as follows: Figure 58 As shown, the monomer conversion rate was 64.3%, M n =8.3kDa, M w =11.8kDa, PDI=1.43.

[0481] Example 21 (TERP / RAFT)

[0482] Add 600 mg (6 mmol, 200 equiv) of MMA (polymer monomer), 7.43 mg (0.03 mmol, 1 equiv) of Te1 (third dormant species), 8.56 mg (0.03 mmol, 1 equiv) of Te7 (third dormant species), 43.76 mg (0.12 mmol, 4 equiv) of CTA4 (second chain transfer agent), and 4.92 mg (0.03 mmol, 1 equiv) of AIBN (thermal initiator) to a 2 mL sample vial.

[0483] It is continuously stirred and heated in a metal bath at 65°C.

[0484] To monitor the reaction progress, nuclear magnetic resonance (NMR) technology was used to track the conversion rate of the monomers; simultaneously, gel permeation chromatography (GPC) was used to track the molecular weight and molecular weight distribution of the polymer; the relevant measurement data and results are as follows: Figure 59 As shown, the monomer conversion rate was 54.4%, M n =7.1kDa, M w =9.4kDa, PDI=1.33.

[0485] As can be seen, under similar monomer conversion rates, the molecular weight of the polymer obtained in Example 21 is lower than that of the polymers obtained in Comparative Example 21-1 or Comparative Example 21-2, proving that the secondary radical polymerization system achieved chain transfer, while the polymerization control remained within the active range, proving that the primary radical polymerization system achieved free radical capture.

[0486] Comparative Example 22-1 (TERP)

[0487] Same comparison 20-1

[0488] Comparative Example 22-2 (RAFT)

[0489] Add 600 mg (6 mmol, 200 equiv) of MMA (polymer monomer), 45.44 mg (0.12 mmol, 4 equiv) of CTA5 (second chain transfer agent), and 4.92 mg (0.03 mmol, 1 equiv) of AIBN (thermal initiator) to a 2 mL sample vial.

[0490] It is continuously stirred and heated in a metal bath at 65°C.

[0491] To monitor the reaction progress, nuclear magnetic resonance (NMR) technology was used to track the conversion rate of the monomers; simultaneously, gel permeation chromatography (GPC) was used to track the molecular weight and molecular weight distribution of the polymer; the relevant measurement data and results are as follows: Figure 60 As shown, the monomer conversion rate was 65.8%, Mn =10.7kDa, M w =15.6kDa, PDI=1.47.

[0492] Example 21 (TERP / RAFT)

[0493] Add 600 mg (6 mmol, 200 equiv) of MMA (polymer monomer), 7.43 mg (0.03 mmol, 1 equiv) of Te1 (third dormant species), 8.56 mg (0.03 mmol, 1 equiv) of Te7 (third dormant species), 45.44 mg (0.12 mmol, 4 equiv) of CTA5 (second chain transfer agent), and 4.92 mg (0.03 mmol, 1 equiv) of AIBN (thermal initiator) to a 2 mL sample vial.

[0494] It is continuously stirred and heated in a metal bath at 65°C.

[0495] To monitor the reaction progress, nuclear magnetic resonance (NMR) technology was used to track the conversion rate of the monomers; simultaneously, gel permeation chromatography (GPC) was used to track the molecular weight and molecular weight distribution of the polymer; the relevant measurement data and results are as follows: Figure 61 As shown, the monomer conversion rate was 64.9%, M n =7.6kDa, M w =9.6kDa, PDI=1.26.

[0496] As can be seen, under similar monomer conversion rates, the molecular weight of the polymer obtained in Example 22 is lower than that of the polymers obtained in Comparative Example 22-1 or Comparative Example 22-2, proving that the secondary radical polymerization system achieved chain transfer, while the polymerization control remained within the active range, proving that the primary radical polymerization system achieved free radical capture.

[0497] The binary radical polymerization method of this invention, by combining a primary radical polymerization system for capturing free radicals with a secondary radical polymerization system for achieving chain transfer, successfully achieves independent control of molecular weight and molecular weight distribution in living polymerization. This not only improves polymerization efficiency and reduces production costs, but also significantly enhances the quality of polymer products. Because it can precisely control the molecular weight and molecular weight distribution of polymers, this invention can be widely applied to various scenarios involving living and controllable radical polymerization reactions, including materials science, medicine, chemical engineering, and other fields. Applications with special requirements for polymer performance will also benefit from this.

[0498] The above description is merely a preferred embodiment of the present invention and does not limit the implementation and protection scope of the present invention. Those skilled in the art should realize that any equivalent substitutions and obvious changes made based on the description and illustrations of the present invention should be included within the protection scope of the present invention.

Claims

1. A binary radical polymerization method, characterized in that the steps include... include: S0, providing a primary radical polymerization system for capturing free radicals and a secondary radical polymerization system for achieving chain transfer; S1. Mix the polymerizable monomer, the primary radical polymerization system, and the secondary radical polymerization system, and initiate radical polymerization by thermal decomposition to obtain a polymer with independently regulated molecular weight and molecular weight distribution; The primary radical polymerization system is a nitrogen oxide-mediated polymerization system, and the secondary radical polymerization system is a radical polymerization system in which thiols are used as chain transfer agents. The polymeric monomer is selected from any one of styrene, methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, or n-butyl methacrylate. Wherein, at most one of the primary radical polymerization system or the secondary radical polymerization system includes: a thermal initiator; the thermal initiator is selected from at least one of: 2,2-azobis(4-methoxy-2,4-dimethylpentanonitrile), benzoyl peroxide, azobisisobutyronitrile, or azobisisoheptanenitrile; The oxynitride-mediated polymerization system includes a second dormant species; the second dormant species is selected from at least one of the following: 2,2,6,6-tetramethylpiperidine-1-oxy radical, 2,2,5-trimethyl-4-phenyl-3-azahexane-3-nitrooxy, 1-hydroxy-N,2,2-triphenylindole-3-imine, or N-tert-butyl-N-[1-diethylphosphono-(2,2-dimethylpropyl)]. The free radical polymerization system in which the thiol is used as a chain transfer agent includes: a first chain transfer agent; the first chain transfer agent is selected from at least one of: tert-nonylthiol, tert-dodecylthiol, n-butanethiol, n-dodecylthiol, or n-octylthiol; The molar ratio of the polymeric monomer, the second dormant species, the first chain transfer agent, and the thermal initiator during mixing is (100-500):(1-2):(2-4):(1.2-3). The reaction temperature for free radical polymerization is 80℃-125℃; Alternatively, the primary radical polymerization system is an organic tellurium-mediated living radical polymerization system, and the secondary radical polymerization system is a reversible addition-fragmentation chain transfer polymerization system; The polymeric monomer is selected from any one of styrene, methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, or n-butyl methacrylate. Wherein, at most one of the primary radical polymerization system or the secondary radical polymerization system includes: a thermal initiator; the thermal initiator is selected from at least one of: 2,2-azobis(4-methoxy-2,4-dimethylpentanonitrile), benzoyl peroxide, azobisisobutyronitrile, or azobisisoheptanenitrile; The organic tellurium-mediated living radical polymerization system includes a third dormant species; the third dormant species is selected from at least one of: 1-phenylethyl tellurylbenzene, 2-methyl-2-(methyltelluryl)propionitrile, ethyl 2-methyl-2-(methyltelluryl)propionate, tellurium methylbenzotellurate, dimethyl ditellurium, methyl (1-phenylethyl)tellurium, or methylbenzyl tellurium; The reversible addition-fragmentation chain transfer polymerization system includes a second chain transfer agent; the second chain transfer agent is selected from: ethyl 2-[(ethoxythiocarbonyl)thio]propionate, methyl 2-[[(dodecylmercapto)thiomethyl]thio]-2-methylbenzoate, 2-[dodecylthio(thiocarbonyl)thio]-2-methylpropionic acid, 2-phenyl-2-propylbenzodisulfide, ethyl 2-methyl-2-(phenylthiocarbonylthio)propionate, 2 At least one of the following: cyanopropyl-2-ylbenzodisulfide, 2-cyanopropyl-2-thiomethylacetic acid O-ethyl ester, 2-cyanopropyl N-methyl-N-(4-pyridine)aminodithiocarbonate, 4-cyano-4-(thiobenzoyl)valeric acid, 4-cyano-4-[[(dodecylthio)thionylmethyl]thio]valeric acid, S-(2-cyano-2-propyl)-S-dodecyl trithiocarbonyl ester, or S-benzyl O-ethyl dithiocarbonate; The molar ratio of the polymeric monomer, the third dormant species, the second chain transfer agent, and the thermal initiator during mixing is (100-500):(1-2):(2-9):

1. The reaction temperature for free radical polymerization is 65℃-100℃.

2. The binary radical polymerization method according to claim 1, characterized in that, The polymerizing monomer, the primary radical polymerization system, and the secondary radical polymerization system are mixed in an organic solvent; wherein, The organic solvent is selected from at least one of benzene, dimethylformamide, dimethyl sulfoxide, or toluene.

3. A binary radical polymerization method, characterized in that the steps include... include: S0, providing a primary radical polymerization system for capturing free radicals and a secondary radical polymerization system for achieving chain transfer; S1. Mix the polymerizable monomer, the primary radical polymerization system, and the secondary radical polymerization system, and initiate radical polymerization by thermal decomposition to obtain a polymer with independently regulated molecular weight and molecular weight distribution; Wherein, the primary radical polymerization system is an atom transfer radical polymerization system, and the secondary radical polymerization system is a reverse iodine atom transfer radical polymerization system; The polymeric monomer is selected from any one of styrene, methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, or n-butyl methacrylate. Wherein, at most one of the primary radical polymerization system or the secondary radical polymerization system includes: a thermal initiator; the thermal initiator is selected from at least one of: 2,2-azobis(4-methoxy-2,4-dimethylpentanonitrile), benzoyl peroxide, azobisisobutyronitrile, or azobisisoheptanenitrile; The atom transfer radical polymerization system comprises: a first initiator, a first catalyst, and a ligand; the first initiator is selected from: 1-chloro-1-phenylethane, 1-bromophenylethane, ethyl 2-chloro-2-methylpropionate, 2-chloropropionitrile, methyl 2-chloropropionate, ethyl 2-bromo-2-methylpropionate, 2-bromopropionitrile, methyl 2-bromopropionate, tert-butyl 2-bromopropionate, methyl 2-bromoisobutyrate, ethyl α-bromophenylacetate, benzyl chloride, chloroacetonitrile, and methyl chloroacetate. The first catalyst is selected from at least one of benzyl bromide, bromoacetonitrile, or methyl bromoacetate; the ligand is selected from at least one of cupric chloride, cuprous chloride, cupric bromide, or cuprous bromide; the ligand is selected from at least one of 2,2'-bipyridine, 4,4'-bis(1-butylpentyl)-2,2'-bipyridine, tris(2-pyridylmethyl)amine, tris(2-dimethylaminoethyl)amine, tris(2-diethylaminoethyl)amine, tetramethylethylenediamine, or pentamethyldiethylenetriamine. The reverse iodine atom transfer radical polymerization system includes a fourth dormant species; the fourth dormant species is selected from elemental iodine. The molar ratio of the polymerizing monomer, the first initiator, the first catalyst, the ligand, the fourth dormant species, and the thermal initiator during mixing is (100-500):(0.05-0.5):(0.1-1):(0.2-2):(0.25-0.475):1; The reaction temperature for free radical polymerization is 60℃-90℃.

4. The binary radical polymerization method according to claim 3, characterized in that, The polymerizing monomer, the primary radical polymerization system, and the secondary radical polymerization system are mixed in an organic solvent; wherein, The organic solvent is selected from at least one of benzene, dimethylformamide, dimethyl sulfoxide, or toluene.

5. A binary radical polymerization method, characterized in that the steps include... include: S0, providing a primary radical polymerization system for capturing free radicals and a secondary radical polymerization system for achieving chain transfer; S1. Mix the polymerizable monomer, the primary radical polymerization system, and the secondary radical polymerization system, and initiate radical polymerization by thermal decomposition to obtain a polymer with independently regulated molecular weight and molecular weight distribution; Wherein, the primary radical polymerization system is an atom transfer radical polymerization system, and the secondary radical polymerization system is a reversible addition-fragmentation chain transfer polymerization system; The polymeric monomer is selected from any one of styrene, methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, or n-butyl methacrylate. Wherein, at most one of the primary radical polymerization system or the secondary radical polymerization system includes: a thermal initiator; the thermal initiator is selected from at least one of: 2,2-azobis(4-methoxy-2,4-dimethylpentanonitrile), benzoyl peroxide, azobisisobutyronitrile, or azobisisoheptanenitrile; The atom transfer radical polymerization system comprises: a first initiator, a first catalyst, and a ligand; the first initiator is selected from: 1-chloro-1-phenylethane, 1-bromophenylethane, ethyl 2-chloro-2-methylpropionate, 2-chloropropionitrile, methyl 2-chloropropionate, ethyl 2-bromo-2-methylpropionate, 2-bromopropionitrile, methyl 2-bromopropionate, tert-butyl 2-bromopropionate, methyl 2-bromoisobutyrate, ethyl α-bromophenylacetate, benzyl chloride, chloroacetonitrile, and methyl chloroacetate. The first catalyst is selected from at least one of benzyl bromide, bromoacetonitrile, or methyl bromoacetate; the ligand is selected from at least one of cupric chloride, cuprous chloride, cupric bromide, or cuprous bromide; the ligand is selected from at least one of 2,2'-bipyridine, 4,4'-bis(1-butylpentyl)-2,2'-bipyridine, tris(2-pyridylmethyl)amine, tris(2-dimethylaminoethyl)amine, tris(2-diethylaminoethyl)amine, tetramethylethylenediamine, or pentamethyldiethylenetriamine. The reversible addition-fragmentation chain transfer polymerization system includes a second chain transfer agent; the second chain transfer agent is selected from: ethyl 2-[(ethoxythiocarbonyl)thio]propionate, methyl 2-[[(dodecylmercapto)thiomethyl]thio]-2-methylbenzoate, 2-[dodecylthio(thiocarbonyl)thio]-2-methylpropionic acid, 2-phenyl-2-propylbenzodisulfide, ethyl 2-methyl-2-(phenylthiocarbonylthio)propionate, 2 At least one of the following: cyanopropyl-2-ylbenzodisulfide, 2-cyanopropyl-2-thiomethylacetic acid O-ethyl ester, 2-cyanopropyl N-methyl-N-(4-pyridine)aminodithiocarbonate, 4-cyano-4-(thiobenzoyl)valeric acid, 4-cyano-4-[[(dodecylthio)thionylmethyl]thio]valeric acid, S-(2-cyano-2-propyl)-S-dodecyl trithiocarbonyl ester, or S-benzyl O-ethyl dithiocarbonate; The molar ratio of the polymerizing monomer, the first initiator, the first catalyst, the ligand, the second chain transfer agent, and the thermal initiator during mixing is (100-500):(1-2):(0.01-1):(0.02-2):(2-9):(0-0.1). The reaction temperature for free radical polymerization is 60℃-90℃.

6. The binary radical polymerization method according to claim 5, characterized in that, The polymerizing monomer, the primary radical polymerization system, and the secondary radical polymerization system are mixed in an organic solvent; wherein, The organic solvent is selected from at least one of benzene, dimethylformamide, dimethyl sulfoxide, or toluene.

7. A binary radical polymerization method, characterized in that the steps include... include: S0, providing a primary radical polymerization system for capturing free radicals and a secondary radical polymerization system for achieving chain transfer; S1. Mix the polymerizable monomer, the primary radical polymerization system, and the secondary radical polymerization system, and initiate radical polymerization by thermal decomposition to obtain a polymer with independently regulated molecular weight and molecular weight distribution; Wherein, the primary radical polymerization system is a reversible addition-fracture chain transfer polymerization system, and the secondary radical polymerization system is a reversible addition-fracture chain transfer polymerization system; The polymeric monomer is selected from any one of styrene, methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, or n-butyl methacrylate. Wherein, at most one of the primary radical polymerization system or the secondary radical polymerization system includes: a thermal initiator; the thermal initiator is selected from at least one of: 2,2-azobis(4-methoxy-2,4-dimethylpentanonitrile), benzoyl peroxide, azobisisobutyronitrile, or azobisisoheptanenitrile; The reversible addition-fragmentation chain transfer polymerization system includes a second chain transfer agent; the second chain transfer agent is selected from: ethyl 2-[(ethoxythiocarbonyl)thio]propionate, methyl 2-[[(dodecylmercapto)thiomethyl]thio]-2-methylbenzoate, 2-[dodecylthio(thiocarbonyl)thio]-2-methylpropionic acid, 2-phenyl-2-propylbenzodisulfide, ethyl 2-methyl-2-(phenylthiocarbonylthio)propionate, 2 At least one of the following: cyanopropyl-2-ylbenzodisulfide, 2-cyanopropyl-2-thiomethylacetic acid O-ethyl ester, 2-cyanopropyl N-methyl-N-(4-pyridine)aminodithiocarbonate, 4-cyano-4-(thiobenzoyl)valeric acid, 4-cyano-4-[[(dodecylthio)thionylmethyl]thio]valeric acid, S-(2-cyano-2-propyl)-S-dodecyl trithiocarbonyl ester, or S-benzyl O-ethyl dithiocarbonate; The molar ratio of the polymerizing monomer, the second chain transfer agent in the primary radical polymerization system, the second chain transfer agent in the secondary radical polymerization system, and the thermal initiator during mixing is (100-500):(1-2):(2-9):0.

1. The reaction temperature for free radical polymerization is 60℃-90℃.

8. The binary radical polymerization method according to claim 7, characterized in that, The polymerizing monomer, the primary radical polymerization system, and the secondary radical polymerization system are mixed in an organic solvent; wherein, The organic solvent is selected from at least one of benzene, dimethylformamide, dimethyl sulfoxide, or toluene.

9. A binary free radical polymerization method, characterized in that the steps include... include: S0, providing a primary radical polymerization system for capturing free radicals and a secondary radical polymerization system for achieving chain transfer; S1. Mix the polymerizable monomer, the primary radical polymerization system, and the secondary radical polymerization system, and initiate radical polymerization by thermal decomposition to obtain a polymer with independently regulated molecular weight and molecular weight distribution; The primary radical polymerization system is a reversible addition-fragmentation chain transfer polymerization system, and the secondary radical polymerization system is a radical polymerization system in which thiols are used as chain transfer agents. The polymeric monomer is selected from any one of styrene, methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, or n-butyl methacrylate. Wherein, at most one of the primary radical polymerization system or the secondary radical polymerization system includes: a thermal initiator; the thermal initiator is selected from at least one of: 2,2-azobis(4-methoxy-2,4-dimethylpentanonitrile), benzoyl peroxide, azobisisobutyronitrile, or azobisisoheptanenitrile; The reversible addition-fragmentation chain transfer polymerization system includes a second chain transfer agent; the second chain transfer agent is selected from: ethyl 2-[(ethoxythiocarbonyl)thio]propionate, methyl 2-[[(dodecylmercapto)thiomethyl]thio]-2-methylbenzoate, 2-[dodecylthio(thiocarbonyl)thio]-2-methylpropionic acid, 2-phenyl-2-propylbenzodisulfide, ethyl 2-methyl-2-(phenylthiocarbonylthio)propionate, 2 At least one of the following: cyanopropyl-2-ylbenzodisulfide, 2-cyanopropyl-2-thiomethylacetic acid O-ethyl ester, 2-cyanopropyl N-methyl-N-(4-pyridine)aminodithiocarbonate, 4-cyano-4-(thiobenzoyl)valeric acid, 4-cyano-4-[[(dodecylthio)thionylmethyl]thio]valeric acid, S-(2-cyano-2-propyl)-S-dodecyl trithiocarbonyl ester, or S-benzyl O-ethyl dithiocarbonate; The free radical polymerization system in which the thiol is used as a chain transfer agent includes: a first chain transfer agent; the first chain transfer agent is selected from at least one of: tert-nonylthiol, tert-dodecylthiol, n-butanethiol, n-dodecylthiol, or n-octylthiol; The molar ratio of the polymerizing monomer, the second chain transfer agent, the first chain transfer agent, and the thermal initiator during mixing is (100-500):(1-2):(2-9):0.1; The reaction temperature for free radical polymerization is 60℃-90℃.

10. The binary radical polymerization method according to claim 9, characterized in that, The polymerizing monomer, the primary radical polymerization system, and the secondary radical polymerization system are mixed in an organic solvent; wherein, The organic solvent is selected from at least one of benzene, dimethylformamide, dimethyl sulfoxide, or toluene.

11. A binary radical polymerization method, characterized in that the steps include... include: S0, providing a primary radical polymerization system for capturing free radicals and a secondary radical polymerization system for achieving chain transfer; S1. Mix the polymerizable monomer, the primary radical polymerization system, and the secondary radical polymerization system, and initiate radical polymerization by thermal decomposition to obtain a polymer with independently regulated molecular weight and molecular weight distribution; Wherein, the primary radical polymerization system is a reversible complexation-mediated polymerization system, and the secondary radical polymerization system is a reversible addition-fracture chain transfer polymerization system; The polymeric monomer is selected from any one of styrene, methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, or n-butyl methacrylate. Wherein, at most one of the primary radical polymerization system or the secondary radical polymerization system includes: a thermal initiator; the thermal initiator is selected from at least one of: 2,2-azobis(4-methoxy-2,4-dimethylpentanonitrile), benzoyl peroxide, azobisisobutyronitrile, or azobisisoheptanenitrile; The reversible complexation-mediated polymerization system comprises: a first dormant species and a second catalyst; the first dormant species is selected from: elemental iodine; the second catalyst is selected from: at least one of: 1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane, tributylmethylphosphine iodide, triethylamine, tri-n-butylamine, tetrabutylammonium iodide, tetramethylethylenediamine, or tetratris(dimethylamino)ethylene; The reversible addition-fragmentation chain transfer polymerization system includes a second chain transfer agent; the second chain transfer agent is selected from: ethyl 2-[(ethoxythiocarbonyl)thio]propionate, methyl 2-[[(dodecylmercapto)thiomethyl]thio]-2-methylbenzoate, 2-[dodecylthio(thiocarbonyl)thio]-2-methylpropionic acid, 2-phenyl-2-propylbenzodisulfide, ethyl 2-methyl-2-(phenylthiocarbonylthio)propionate, 2 At least one of the following: cyanopropyl-2-ylbenzodisulfide, 2-cyanopropyl-2-thiomethylacetic acid O-ethyl ester, 2-cyanopropyl N-methyl-N-(4-pyridine)aminodithiocarbonate, 4-cyano-4-(thiobenzoyl)valeric acid, 4-cyano-4-[[(dodecylthio)thionylmethyl]thio]valeric acid, S-(2-cyano-2-propyl)-S-dodecyl trithiocarbonyl ester, or S-benzyl O-ethyl dithiocarbonate; The molar ratio of the polymer monomer, the first dormant species, the second catalyst, the second chain transfer agent, and the thermal initiator during mixing is (100-500):(1-2):(2-9):(1.5-4). The reaction temperature for free radical polymerization is 65℃-100℃.

12. The binary radical polymerization method according to claim 11, characterized in that, The polymerizing monomer, the primary radical polymerization system, and the secondary radical polymerization system are mixed in an organic solvent; wherein, The organic solvent is selected from at least one of benzene, dimethylformamide, dimethyl sulfoxide, or toluene.

13. A binary radical polymerization method, characterized in that the steps include... include: S0, providing a primary radical polymerization system for capturing free radicals and a secondary radical polymerization system for achieving chain transfer; S1. Mix the polymerizable monomer, the primary radical polymerization system, and the secondary radical polymerization system, and initiate radical polymerization by thermal decomposition to obtain a polymer with independently regulated molecular weight and molecular weight distribution; The primary radical polymerization system is a nitrogen oxide-mediated polymerization system, and the secondary radical polymerization system is a reversible addition-fracture chain transfer polymerization system. The polymeric monomer is selected from any one of styrene, methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, or n-butyl methacrylate. Wherein, at most one of the primary radical polymerization system or the secondary radical polymerization system includes: a thermal initiator; the thermal initiator is selected from at least one of: 2,2-azobis(4-methoxy-2,4-dimethylpentanonitrile), benzoyl peroxide, azobisisobutyronitrile, or azobisisoheptanenitrile; The oxynitride-mediated polymerization system includes a second dormant species; the second dormant species is selected from at least one of the following: 2,2,6,6-tetramethylpiperidine-1-oxy radical, 2,2,5-trimethyl-4-phenyl-3-azahexane-3-nitrooxy, 1-hydroxy-N,2,2-triphenylindole-3-imine, or N-tert-butyl-N-[1-diethylphosphono-(2,2-dimethylpropyl)]. The reversible addition-fragmentation chain transfer polymerization system includes a second chain transfer agent; the second chain transfer agent is selected from: ethyl 2-[(ethoxythiocarbonyl)thio]propionate, methyl 2-[[(dodecylmercapto)thiomethyl]thio]-2-methylbenzoate, 2-[dodecylthio(thiocarbonyl)thio]-2-methylpropionic acid, 2-phenyl-2-propylbenzodisulfide, ethyl 2-methyl-2-(phenylthiocarbonylthio)propionate, 2 At least one of the following: cyanopropyl-2-ylbenzodisulfide, 2-cyanopropyl-2-thiomethylacetic acid O-ethyl ester, 2-cyanopropyl N-methyl-N-(4-pyridine)aminodithiocarbonate, 4-cyano-4-(thiobenzoyl)valeric acid, 4-cyano-4-[[(dodecylthio)thionylmethyl]thio]valeric acid, S-(2-cyano-2-propyl)-S-dodecyl trithiocarbonyl ester, or S-benzyl O-ethyl dithiocarbonate; The molar ratio of the polymeric monomer, the second dormant species, the second chain transfer agent, and the thermal initiator during mixing is (100-500):(1-2):(2-9):(1.2-3). The reaction temperature for free radical polymerization is 80℃-125℃.

14. The binary radical polymerization method according to claim 13, characterized in that, The polymerizing monomer, the primary radical polymerization system, and the secondary radical polymerization system are mixed in an organic solvent; wherein, The organic solvent is selected from at least one of benzene, dimethylformamide, dimethyl sulfoxide, or toluene.

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