Binary free radical polymerization method

Abstract

The invention relates to a binary free radical polymerization method which comprises the following steps: S0, providing a primary free radical polymerization system for capturing free radicals and a secondary free radical polymerization system for realizing chain transfer; the preparation method comprises the following steps: S1, mixing a polymeric monomer, the primary free radical polymerization system and the secondary free radical polymerization system, and starting free radical polymerization through thermal cracking, optical excitation or electrical excitation to obtain a polymer of which the molecular weight and molecular weight distribution are independently regulated and controlled. According to the binary free radical polymerization method disclosed by the invention, the primary free radical polymerization system for capturing free radicals and the secondary free radical polymerization system for realizing chain transfer are combined to successfully realize independent regulation and control of molecular weight and molecular weight distribution in living polymerization, so that the polymerization efficiency is improved, the production cost is reduced, and the production cost is reduced. The quality of a polymer product is also obviously improved.

Description

Technical Field

[0001] The invention relates to the field of free radical polymerization, in particular to a binary free radical polymerization method. Background Art

[0002] Free radical polymerization plays a dominant role in polymer synthesis. The living radical polymerization technology based on the reversible balance between free radicals and dormant species can achieve precise control of polymer molecular weight, distribution and structure. Living radical polymerization controls the activity of free radicals so that the growth of polymer chains can proceed without chain transfer and diradical termination reactions in traditional free radical polymerization, thereby obtaining polymers with narrow molecular weight distribution.

[0003] However, in traditional living free radical polymerization, controlling the dormant species of the reaction requires controlling both the molecular weight and molecular weight distribution of the polymer, which leads to a series of practical application problems. When synthesizing low molecular weight polymers, a large amount of dormant species is required, resulting in excessively high polymerization costs; while when synthesizing high molecular weight polymers, the content of dormant species needs to be greatly reduced, which may lead to uncontrolled polymerization. The contradictory relationship between molecular weight and molecular weight distribution limits the practical application of living free radical polymerization.

[0004] In view of this, a binary free radical polymerization method is urgently needed. Summary of the invention

[0005] The object of the present invention is to provide a binary free radical polymerization method in view of the deficiencies in the prior art, the steps comprising:

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

[0007] S1, mixing the polymerization monomer, the primary free radical polymerization system, and the secondary free radical polymerization system, and initiating free radical polymerization by thermal cracking, photoexcitation, or electrical excitation to obtain a polymer with independently regulated molecular weight and molecular weight distribution;

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

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

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

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

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

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

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

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

[0016] Preferably, the polymerizable monomer is selected from any one of 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), methyl 2-bromopropionate (MClP, CAS: 17639-93-9), ethyl 2-bromo-2-methylpropionate (EtBriB, CAS: 600-00-0), methyl 2-bromopropionate (MBrP, CAS: 5445-17-0), methyl 2-bromopropionate (MBrP, CAS: 5445-17-0), methyl 2-bromopropionate (MBrP, CAS: 5445-17-0). 0), 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 cupric chloride (CuCl2, CAS: 1344-67-8), cuprous chloride (CuCl, CAS: 7758-89-6), cupric bromide (CuBr2, CAS: 7789-45-9), or cuprous bromide (CuBr, CAS: 7787-70-4);

[0020] The ligand is selected from: at least one of 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 (denoted as CTA3, CAS: 73232-07-2), methyl 2-[[(dodecylthio)thiomethyl]thio]-2-methylbenzoate (denoted as CTA5, CAS: 1088555-95-6), 2-[dodecylthio(thiocarbonyl)thio]-2-methylpropionic acid (denoted as CTA4, CAS: 461642-78-4), 2-phenyl-2-propylbenzodisulfide (denoted as CTA7, CAS: 201611-77-0), ethyl 2-methyl-2-(phenylthiocarbonylthio)propionate (denoted as CTA2, CAS: 201611-84-9), 2-cyanopropyl-2-benzodisulfide (denoted as CTA8, CAS: 201611-85-0), 2-cyanopropyl-2-benzodisulfide (denoted as CTA9, CAS: 201611-86-0), 2-cyanopropyl-2-benzodisulfide (denoted as CTA10, CAS: 201611-87-1), 2-cyanopropyl-2-benzodisulfide (denoted as CTA11, CAS: 201611-86-1), 2-cyanopropyl-2-benzodisulfide (denoted as CTA12, CAS: 201611-86-1), 2-cyanopropyl-2-benzodisulfide (denoted as CTA13, CAS: 201611-86-1), 2-cyanopropyl-2-benzodisulfide (denoted as CTA14, CAS: 201611-86-1), 2-cyanopropyl-2-benzodisulfide O-ethyl 2-thiopropanedithioacetate (denoted as CTA11, CAS: 218966-80-4), 2-cyanopropyl N-methyl-N-(4-pyridine)aminodithiocarbonate (denoted as CTA6, CAS: 1158958-96-3), 4-cyano-4-(thiobenzoyl)pentanoic acid (denoted as CTA1, CAS: 201611-92-9), 4-cyano-4-(thiobenzoyl)pentanoic acid (denoted as CTA1, CAS: 201611-92-9), At least one of [[(Dodecylthio)thiomethyl]thio]pentanoic acid (denoted as CTA10, CAS: 870196-80-8), S-(2-cyano-2-propyl)-S-dodecyl trithiocarbonyl ester (denoted as CTA9, CAS: 870196-83-1), or S-benzyl O-ethyl dithiocarbonate (denoted as 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 is selected from: iodine (I2, CAS: 12190-71-5);

[0025] The second catalyst is selected from: at least one of 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 tetrakistri(dimethylamino)ethylene (TDAE, CAS: 996-70-3).

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

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

[0028] Preferably, the TERP system comprises: a third dormant species; wherein,

[0029] The third dormant species is selected from: at least one of 1-phenylethyltellurylbenzene (Te6, CAS: 121335-32-8), 2-methyl-2-(methyltelluryl)propionitrile (Te3, CAS: 682319-76-4), 2-methyl-2-(methyltelluryl)ethyl propionate (Te2, CAS: 474094-06-9), tellurium methylbenzotellurate (Te5, CAS: 76399-11-6), dimethyl ditellurium (Te7, CAS: 20334-43-4), methyl (1-phenylethyl) tellurium (Te1, CAS: 415679-75-3), or methylbenzyl tellurium (Te4, CAS: 103680-41-7).

[0030] Preferably, the RITP system comprises: 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 tert-nonyl mercaptan (TNM, CAS: 25360-10-5), tert-dodecyl mercaptan (TDM, CAS: 25103-58-6), n-butyl mercaptan (NBM, CAS: 109-79-5), n-dodecyl mercaptan (NDM, CAS: 112-55-0), or n-octyl mercaptan (NOM, CAS: 111-88-6).

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

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

[0036] Furthermore, when the polymerization monomer is mixed with the ATRP / RITP, the molar ratio of the polymerization 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 polymerization monomer is mixed with the ATRP / RAFT, the molar ratio of the polymerization 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 polymerization monomer is mixed with the RAFT / RAFT, the molar ratio of the polymerization monomer, the second chain transfer agent (denoted as CTA-1) in the primary free radical polymerization system, the second chain transfer agent (denoted as CTA-2) in the secondary free radical polymerization system, and the thermal initiator is (100-500):(1-2):(2-9):0.1.

[0039] Furthermore, when the polymerized monomer is mixed with the RAFT / Thiol, the molar ratio of the polymerized 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 polymerized monomer is mixed with the RCMP / RAFT, the molar ratio of the polymerized 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 polymerizable monomer is mixed with the NMP / RAFT, the molar ratio of the polymerizable 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 polymerizable monomer is mixed with the NMP / Thiol, the molar ratio of the polymerizable 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 polymerizable monomer is mixed with the TERP / RAFT, the molar ratio of the polymerizable 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°C-90°C.

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

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

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

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

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

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

[0051] Furthermore, the reaction temperature of the TERP / RAFT is 65°C-100°C.

[0052] Preferably, the polymerization monomer, the primary free radical polymerization system, and the secondary free 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 free radical polymerization method of the present invention successfully realizes the independent regulation of molecular weight and molecular weight distribution in active polymerization by combining a primary free radical polymerization system for capturing free radicals with a secondary free radical polymerization system for achieving chain transfer. This not only improves polymerization efficiency and reduces production costs, but also significantly improves the quality of polymer products. Since the molecular weight and molecular weight distribution of the polymer can be accurately controlled, the present invention can be widely used in various scenarios involving active controllable free radical polymerization reactions, including materials science, medicine, chemical industry and other fields, and applications with special requirements for polymer properties also benefit from it. BRIEF DESCRIPTION OF THE DRAWINGS

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

[0057] Figure 2 It is the gel permeation chromatogram of comparative example 1-2 of the present invention;

[0058] Figure 3 is the 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 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 It is the gel permeation chromatogram of comparative example 3-2 of the present invention;

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

[0064] Fig. 9 It is the gel permeation chromatogram of comparative example 4-1 of the present invention;

[0065] Fig.10 It is the gel permeation chromatogram of comparative example 4-2 of the present invention;

[0066] Fig.11 is the gel permeation chromatogram of Example 4 of the present invention;

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

[0068] Fig.13 It is the gel permeation chromatogram of comparative example 5-2 of the present invention;

[0069] Fig.14 is the gel permeation chromatogram of Example 5 of the present invention;

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

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

[0072] Fig.17 is the gel permeation chromatogram of Example 6 of the present invention;

[0073] Fig.18 It is the gel permeation chromatogram of comparative example 7-1 of the present invention;

[0074] Fig.19 It is the gel permeation chromatogram of comparative example 7-2 of the present invention;

[0075] Fig. 20 is the gel permeation chromatogram of Example 7 of the present invention;

[0076] Fig.21 It is the gel permeation chromatogram of comparative example 8-1 of the present invention;

[0077] Fig. 22 It is the gel permeation chromatogram of comparative example 8-2 of the present invention;

[0078] Fig.23 is the gel permeation chromatogram of Example 8 of the present invention;

[0079] Fig.24 It is the gel permeation chromatogram of Comparative Example 9-1 of the present invention;

[0080] Fig.25 It is the gel permeation chromatogram of comparative example 9-2 of the present invention;

[0081] Fig.26 is the gel permeation chromatogram of Example 9 of the present invention;

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

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

[0084] Fig.29 is the gel permeation chromatogram of Example 10 of the present invention;

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

[0086] Fig.31This is the gel permeation chromatogram of Comparative Example 11-2 of the present invention;

[0087] Fig.32 is the gel permeation chromatogram of Example 11 of the present invention;

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

[0089] Fig.34 is the gel permeation chromatogram of Example 12 of the present invention;

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

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

[0092] Fig.37 is the gel permeation chromatogram of Example 13 of the present invention;

[0093] Fig.38 It is the gel permeation chromatogram of comparative example 14-1 of the present invention;

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

[0095] Fig.40 is the gel permeation chromatogram of Example 14 of the present invention;

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

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

[0098] Fig.43 is the gel permeation chromatogram of Example 15 of the present invention;

[0099] Fig.44 It is the gel permeation chromatogram of comparative example 16-2 of the present invention;

[0100] Fig.45 is the gel permeation chromatogram of Example 16 of the present invention;

[0101] Fig.46 It is the gel permeation chromatogram of comparative example 17-1 of the present invention;

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

[0103] Fig.48is the gel permeation chromatogram of Example 17 of the present invention;

[0104] Fig.49 It is the gel permeation chromatogram of comparative example 18-1 of the present invention;

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

[0106] Fig.51 is the gel permeation chromatogram of Example 18 of the present invention;

[0107] Fig.52 It is the gel permeation chromatogram of Comparative Example 19-1 of the present invention;

[0108] Fig.53 It is the gel permeation chromatogram of comparative example 19-2 of the present invention;

[0109] Fig.54 is the gel permeation chromatogram of Example 19 of the present invention;

[0110] Fig.55 It is the gel permeation chromatogram of comparative example 20-1 of the present invention;

[0111] Fig.56 It is the gel permeation chromatogram of comparative example 20-2 of the present invention;

[0112] Fig.57 is the gel permeation chromatogram of Example 20 of the present invention;

[0113] Fig.58 It is the gel permeation chromatogram of comparative example 21-2 of the present invention;

[0114] Fig.59 is the gel permeation chromatogram of Example 21 of the present invention;

[0115] Fig.60 It is the gel permeation chromatogram of comparative example 22-2 of the present invention;

[0116] Fig.61 This is the gel permeation chromatogram of Example 22 of the present invention. DETAILED DESCRIPTION

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

[0118] Unless otherwise defined, technical or scientific terms used in the claims and the specification shall have the common meanings understood by persons having ordinary skills in the technical field to which the present invention belongs.

[0119] The words "include", "selected from" and the like used in the patent application specification and claims of the present invention mean that the items before the words include the items listed after the words or their equivalents, and do not exclude other items.

[0120] The numerical values ​​mentioned in the patent application specification and claims of the present invention include all numerical values ​​that increase from low to high by one unit, and it is assumed here that there are at least two units between any lower value and the higher value. For example, if a component or a physical quantity is from 1 to 100, 10 to 90 is better, and 20 to 80 is the most optimal, it is intended to express that values ​​such as 5 to 95, 14 to 76, 23 to 67, 32 to 58, 41 to 49 have been clearly listed in this specification; for values ​​less than 1, 0.0001, 0.001, 0.01 or 0.1 are considered to be a more appropriate unit. The above examples are for illustrative purposes only. In fact, all numerical combinations between the lowest value and the highest value listed are deemed to be clearly listed in this specification in a similar manner.

[0121] The free radical polymerization reactions involved in the patent application specification and claims of the present 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 polymerization monomers and / or organic solvents used in the free radical polymerization reaction are pre-purified by a neutral alumina column to remove the inhibitors therein, and are subjected to three freeze-pump-thaw cycles to remove the oxygen dissolved in the liquid.

[0122] Comparative Example 1-1 (ATRP)

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

[0124] 300 mg (3 mmol, 200 equiv) of MMA (polymerization 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 first solution (containing 0.0015 mmol, 0.1 equiv of CuBr2 and 0.003 mmol, 0.1 equiv of PMDETA) were added to a 2 mL sample bottle, and then toluene (organic solvent) was added to make the liquid volume 1 mL, so that the concentration of the polymerization monomer was 3 mol / L;

[0125] The mixture was heated in a metal bath at 75°C with continuous stirring.

[0126] In order to monitor the reaction progress, nuclear magnetic resonance technology is used to track the conversion rate of the polymerization monomer; at the same time, gel permeation chromatography technology is 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 is 59.7%, M n =12.9 kDa, M w =15.4 kDa, PDI=1.19.

[0127] Comparative Example 1-2 (RAFT)

[0128] In a 2 mL sample bottle, 300 mg (3 mmol, 200 equiv) of MMA (polymerization 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) were added, and then toluene (organic solvent) was added to make the liquid volume 1 mL, so that the concentration of the above-mentioned polymerization monomers was 3 mol / L;

[0129] The mixture was heated in a metal bath at 75°C with continuous stirring.

[0130] In order to monitor the reaction progress, nuclear magnetic resonance technology is used to track the conversion rate of the polymerization monomer; at the same time, gel permeation chromatography technology is 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 is 66.1%, M n =9.1 kDa, M w =13.1 kDa, PDI=1.43.

[0131] Example 1 (ATRP / RAFT)

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

[0133] 300 mg (3 mmol, 200 equiv) of MMA (polymerization 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 first solution (containing 0.0015 mmol, 0.1 equiv of CuBr2 and 0.003 mmol, 0.1 equiv of PMDETA) were added to a 2 mL sample bottle, and then toluene (organic solvent) was added to make the liquid volume 1 mL, so that the concentration of the polymerization monomer was 3 mol / L;

[0134] The mixture was heated in a metal bath at 75°C with continuous stirring.

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

[0136] Triggering process:

[0137]

[0138] Primary ATRP reinitiation process:

[0139]

[0140] First-order ATRP equilibrium process:

[0141]

[0142] Secondary RAFT reinitiation process:

[0143]

[0144] Secondary RAFT chain transfer process:

[0145]

[0146] In order to monitor the reaction progress, nuclear magnetic resonance technology is used to track the conversion rate of the polymerization monomer; at the same time, gel permeation chromatography technology is 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 is 62.5%, M n =6.6 kDa, M w =8.5kDa, PDI=1.28.

[0147] It can be seen that under similar monomer conversion rates, the molecular weight of the polymer obtained in Example 1 is lower than the molecular weight of the polymer obtained in Comparative Example 1-1 or Comparative Example 1-2, proving that the secondary free radical polymerization system achieves chain transfer, while the polymerization control remains within the active range, proving that the primary free radical polymerization system achieves the capture of free radicals.

[0148] Comparative Example 2-1 (ATRP)

[0149] Same as comparative example 1-1

[0150] Comparative Example 2-2 (RAFT)

[0151] In a 2 mL sample bottle, 300 mg (3 mmol, 200 equiv) of MMA (polymerization 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) were added, and then toluene (organic solvent) was added to make the liquid volume 1 mL, so that the concentration of the above-mentioned polymerization monomers was 3 mol / L;

[0152] The mixture was heated in a metal bath at 75°C with continuous stirring.

[0153] In order to monitor the reaction progress, nuclear magnetic resonance technology is used to track the conversion rate of the polymerization monomer; at the same time, gel permeation chromatography technology is 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 is 59.7%, M n =10.2 kDa, M w =16.0 kDa, PDI=1.57.

[0154] Example 2 (ATRP / RAFT)

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

[0156] In a 2 mL sample bottle, 300 mg (3 mmol, 200 equiv) of MMA (polymerization 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 first solution (containing 0.0015 mmol, 0.1 equiv of CuBr2 and 0.003 mmol, 0.1 equiv of PMDETA) were added, and then toluene (organic solvent) was added to make the liquid volume 1 mL, so that the concentration of the polymerization monomer was 3 mol / L;

[0157] The mixture was heated in a metal bath at 75°C with continuous stirring.

[0158] In order to monitor the reaction progress, nuclear magnetic resonance technology is used to track the conversion rate of the polymerization monomer; at the same time, gel permeation chromatography technology is 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 is 65.1%, M n =7.6 kDa, M w =9.9 kDa, PDI = 1.29.

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

[0160] Comparative Example 3-1 (ATRP)

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

[0162] 300 mg (3 mmol, 200 equiv) of MMA (polymerization 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 first solution (containing 0.0015 mmol, 0.1 equiv of CuBr2 and 0.003 mmol, 0.1 equiv of PMDETA) were added to a 2 mL sample bottle, and then toluene (organic solvent) was added to make the liquid volume 1 mL, so that the concentration of the polymerization monomer was 3 mol / L;

[0163] The mixture was heated in a metal bath at 75°C with continuous stirring.

[0164] In order to monitor the reaction progress, nuclear magnetic resonance technology is used to track the conversion rate of the polymerization monomer; at the same time, gel permeation chromatography technology is 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 is 51.2%, M n =10.4 kDa, M w =11.7 kDa, PDI=1.19.

[0165] Comparative Example 3-2 (RAFT)

[0166] In a 2 mL sample bottle, 300 mg (3 mmol, 200 equiv) of MMA (polymerization 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) were added, and then toluene (organic solvent) was added to make the liquid volume 1 mL, so that the concentration of the above-mentioned polymerization monomers was 3 mol / L;

[0167] The mixture was heated in a metal bath at 75°C with continuous stirring.

[0168] In order to monitor the reaction progress, nuclear magnetic resonance technology is used to track the conversion rate of the polymerization monomer; at the same time, gel permeation chromatography technology is 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 is 60.4%, M n =31.1 kDa, M w =61.8 kDa, PDI=1.99.

[0169] Example 3 (ATRP / RAFT)

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

[0171] 300 mg (3 mmol, 200 equiv) of MMA (polymerization 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 first solution (containing 0.0015 mmol, 0.1 equiv of CuBr2 and 0.003 mmol, 0.1 equiv of PMDETA) were added to a 2 mL sample bottle, and then toluene (organic solvent) was added to make the liquid volume 1 mL, so that the concentration of the polymerization monomer was 3 mol / L;

[0172] The mixture was heated in a metal bath at 75°C with continuous stirring.

[0173] In order to monitor the reaction progress, nuclear magnetic resonance technology is used to track the conversion rate of the polymerization monomer; at the same time, gel permeation chromatography technology is 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 is 47.6%, M n =8.7 kDa, M w =11.4 kDa, PDI=1.31.

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

[0175] Comparative Example 4-1 (ATRP)

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

[0177] 300 mg (3 mmol, 200 equiv) of MMA (polymerization 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 first solution (containing 0.0015 mmol, 0.1 equiv of CuBr2 and 0.003 mmol, 0.1 equiv of PMDETA) were added to a 2 mL sample bottle, and then toluene (organic solvent) was added to make the liquid volume 1 mL, so that the concentration of the polymerization monomer was 3 mol / L;

[0178] The mixture was heated in a metal bath at 75°C with continuous stirring.

[0179] In order to monitor the reaction progress, nuclear magnetic resonance technology is used to track the conversion rate of the polymerization monomer; at the same time, gel permeation chromatography technology is used to track the molecular weight and molecular weight distribution of the polymer; the relevant measurement data and results are as follows Fig. 9 As shown, the monomer conversion rate is 51.2%, M n =11.7 kDa, M w =14.0 kDa, PDI=1.19.

[0180] Comparative Example 4-2 (RAFT)

[0181] In a 2 mL sample bottle, 300 mg (3 mmol, 200 equiv) of MMA (polymerization 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) were added, and then toluene (organic solvent) was added to make the liquid volume 1 mL, so that the concentration of the above-mentioned polymerization monomers was 3 mol / L;

[0182] The mixture was heated in a metal bath at 75°C with continuous stirring.

[0183] In order to monitor the reaction progress, nuclear magnetic resonance technology is used to track the conversion rate of the polymerization monomer; at the same time, gel permeation chromatography technology is used to track the molecular weight and molecular weight distribution of the polymer; the relevant measurement data and results are as follows Fig.10 As shown, the monomer conversion rate is 58.3%, M n =22.6 kDa, M w =44.7 kDa, PDI = 1.98.

[0184] Example 4 (ATRP / RAFT)

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

[0186] In a 2 mL sample bottle, 300 mg (3 mmol, 200 equiv) of MMA (polymerization 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 first solution (containing 0.0015 mmol, 0.1 equiv of CuBr2 and 0.003 mmol, 0.1 equiv of PMDETA) were added, and then toluene (organic solvent) was added to make the liquid volume 1 mL, so that the concentration of the polymerization monomer was 3 mol / L;

[0187] The mixture was heated in a metal bath at 75°C with continuous stirring.

[0188] In order to monitor the reaction progress, nuclear magnetic resonance technology is used to track the conversion rate of the polymerization monomer; at the same time, gel permeation chromatography technology is used to track the molecular weight and molecular weight distribution of the polymer; the relevant measurement data and results are as follows Fig.11 As shown, the monomer conversion rate is 44.3%, M n =7.0 kDa, M w =9.9 kDa, PDI = 1.41.

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

[0190] Comparative Example 5-1 (ATRP)

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

[0192] 300 mg (3 mmol, 200 equiv) of MMA (polymerization 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 first solution (containing 0.0015 mmol, 0.1 equiv of CuBr2 and 0.003 mmol, 0.1 equiv of PMDETA) were added to a 2 mL sample bottle, and then toluene (organic solvent) was added to make the liquid volume 1 mL, so that the concentration of the polymerization monomer was 3 mol / L;

[0193] The mixture was heated in a metal bath at 75°C with continuous stirring.

[0194] In order to monitor the reaction progress, nuclear magnetic resonance technology is used to track the conversion rate of the polymerization monomer; at the same time, gel permeation chromatography technology is used to track the molecular weight and molecular weight distribution of the polymer; the relevant measurement data and results are as follows Fig.12 As shown, the monomer conversion rate is 49.8%, M n =18.1 kDa, M w =21.1 kDa, PDI=1.16.

[0195] Comparative Example 5-2 (RAFT)

[0196] In a 2 mL sample bottle, 300 mg (3 mmol, 200 equiv) of MMA (polymerization 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) were added, and then toluene (organic solvent) was added to make the liquid volume 1 mL, so that the concentration of the above-mentioned polymerization monomers was 3 mol / L;

[0197] The mixture was heated in a metal bath at 75°C with continuous stirring.

[0198] In order to monitor the reaction progress, nuclear magnetic resonance technology is used to track the conversion rate of the polymerization monomer; at the same time, gel permeation chromatography technology is used to track the molecular weight and molecular weight distribution of the polymer; the relevant measurement data and results are as follows Fig.13 As shown, the monomer conversion rate is 59.5%, M n =18.9 kDa, M w =38.3 kDa, PDI =2.02.

[0199] Example 5 (ATRP / RAFT)

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

[0201] In a 2 mL sample bottle, 300 mg (3 mmol, 200 equiv) of MMA (polymerization 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 first solution (containing 0.0015 mmol, 0.1 equiv of CuBr2 and 0.003 mmol, 0.1 equiv of PMDETA) were added, and then toluene (organic solvent) was added to make the liquid volume 1 mL, so that the concentration of the polymerization monomer was 3 mol / L;

[0202] The mixture was heated in a metal bath at 75°C with continuous stirring.

[0203] In order to monitor the reaction progress, nuclear magnetic resonance technology is used to track the conversion rate of the polymerization monomer; at the same time, gel permeation chromatography technology is used to track the molecular weight and molecular weight distribution of the polymer; the relevant measurement data and results are as follows Fig.14 As shown, the monomer conversion rate is 42.8%, M n =7.7 kDa, M w =11.5 kDa, PDI=1.49.

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

[0205] Comparative Example 6-1 (ATRP)

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

[0207] 300 mg (3 mmol, 200 equiv) of MMA (polymerization 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 first solution (containing 0.0015 mmol, 0.1 equiv of CuBr2 and 0.003 mmol, 0.1 equiv of PMDETA) were added to a 2 mL sample bottle, and then toluene (organic solvent) was added to make the liquid volume 1 mL, so that the concentration of the polymerization monomer was 3 mol / L;

[0208] The mixture was heated in a metal bath at 75°C with continuous stirring.

[0209] In order to monitor the reaction progress, nuclear magnetic resonance technology is used to track the conversion rate of the polymerization monomer; at the same time, gel permeation chromatography technology is used to track the molecular weight and molecular weight distribution of the polymer; the relevant measurement data and results are as follows Fig.15 As shown, the monomer conversion rate is 64.8%, M n =14.1 kDa, M w =17.0 kDa, PDI=1.21.

[0210] Comparative Example 6-2 (RAFT)

[0211] In a 2 mL sample bottle, 300 mg (3 mmol, 200 equiv) of MMA (polymerization 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) were added, and then toluene (organic solvent) was added to make the liquid volume 1 mL, so that the concentration of the above-mentioned polymerization monomers was 3 mol / L;

[0212] The mixture was heated in a metal bath at 75°C with continuous stirring.

[0213] In order to monitor the reaction progress, nuclear magnetic resonance technology is used to track the conversion rate of the polymerization monomer; at the same time, gel permeation chromatography technology is used to track the molecular weight and molecular weight distribution of the polymer; the relevant measurement data and results are as follows Fig.16 As shown, the monomer conversion rate is 59.9%, M n =5.6 kDa, M w =7.4 kDa, PDI=1.34.

[0214] Example 6 (ATRP / RAFT)

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

[0216] In a 2 mL sample bottle, 300 mg (3 mmol, 200 equiv) of MMA (polymerization 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 first solution (containing 0.0015 mmol, 0.1 equiv of CuBr2 and 0.003 mmol, 0.1 equiv of PMDETA) were added, and then toluene (organic solvent) was added to make the liquid volume 1 mL, so that the concentration of the polymerization monomer was 3 mol / L;

[0217] The mixture was heated in a metal bath at 75°C with continuous stirring.

[0218] In order to monitor the reaction progress, nuclear magnetic resonance technology is used to track the conversion rate of the polymerization monomer; at the same time, gel permeation chromatography technology is used to track the molecular weight and molecular weight distribution of the polymer; the relevant measurement data and results are as follows Fig.17 As shown, the monomer conversion rate is 63.2%, M n =5.3 kDa, M w =6.6kDa, PDI=1.25.

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

[0220] Comparative Example 7-1 (ATRP)

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

[0222] 300 mg (3 mmol, 200 equiv) of MMA (polymerization 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 first solution (containing 0.0015 mmol, 0.1 equiv of CuBr2 and 0.003 mmol, 0.1 equiv of PMDETA) were added to a 2 mL sample bottle, and then toluene (organic solvent) was added to make the liquid volume 1 mL, so that the concentration of the polymerization monomer was 3 mol / L;

[0223] The mixture was heated in a metal bath at 75°C with continuous stirring.

[0224] In order to monitor the reaction progress, nuclear magnetic resonance technology is used to track the conversion rate of the polymerization monomer; at the same time, gel permeation chromatography technology is used to track the molecular weight and molecular weight distribution of the polymer; the relevant measurement data and results are as follows Fig.18 As shown, the monomer conversion rate is 46.8%, M n =12.4 kDa, M w =13.9 kDa, PDI=1.12.

[0225] Comparative Example 7-2 (RAFT)

[0226] In a 2 mL sample bottle, 300 mg (3 mmol, 200 equiv) of MMA (polymerization 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) were added, and then toluene (organic solvent) was added to make the liquid volume 1 mL, so that the concentration of the above-mentioned polymerization monomers was 3 mol / L;

[0227] The mixture was heated in a metal bath at 75°C with continuous stirring.

[0228] In order to monitor the reaction progress, nuclear magnetic resonance technology is used to track the conversion rate of the polymerization monomer; at the same time, gel permeation chromatography technology is used to track the molecular weight and molecular weight distribution of the polymer; the relevant measurement data and results are as follows Fig.19 As shown, the monomer conversion rate is 51.5%, M n =7.0 kDa, M w =10.5 kDa, PDI=1.50.

[0229] Example 7 (ATRP / RAFT)

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

[0231] In a 2 mL sample bottle, 300 mg (3 mmol, 200 equiv) of MMA (polymerization 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 first solution (containing 0.0015 mmol, 0.1 equiv of CuBr2 and 0.003 mmol, 0.1 equiv of PMDETA) were added, and then toluene (organic solvent) was added to make the liquid volume 1 mL, so that the concentration of the polymerization monomer was 3 mol / L;

[0232] The mixture was heated in a metal bath at 75°C with continuous stirring.

[0233] In order to monitor the reaction progress, nuclear magnetic resonance technology is used to track the conversion rate of the polymerization monomer; at the same time, gel permeation chromatography technology is used to track the molecular weight and molecular weight distribution of the polymer; the relevant measurement data and results are as follows Fig. 20 As shown, the monomer conversion rate is 46.9%, M n =6.4 kDa, M w =7.78 kDa, PDI=1.21.

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

[0235] Comparative Example 8-1 (ATRP)

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

[0237] 300 mg (3 mmol, 100 equiv) of MMA (polymerization 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 first solution (containing 0.003 mmol, 0.1 equiv of CuBr2 and 0.006 mmol, 0.2 equiv of PMDETA) were added to a 2 mL sample bottle, and then toluene (organic solvent) was added to make the liquid volume 1 mL, so that the concentration of the polymerization monomer was 3 mol / L;

[0238] The mixture was heated in a metal bath at 75°C with continuous stirring.

[0239] In order to monitor the reaction progress, nuclear magnetic resonance technology is used to track the conversion rate of the polymerization monomer; at the same time, gel permeation chromatography technology is used to track the molecular weight and molecular weight distribution of the polymer; the relevant measurement data and results are as follows Fig.21 As shown, the monomer conversion rate is 41.6%, M n =6.3 kDa, M w =8.3 kDa, PDI=1.31.

[0240] Comparative Example 8-2 (RITP)

[0241] In a 2 mL sample bottle, 300 mg (3 mmol, 100 equiv) of MMA (polymerization 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) were added, and then toluene (organic solvent) was added to make the liquid volume 1 mL, so that the concentration of the above-mentioned polymerization monomers was 3 mol / L;

[0242] The mixture was heated in a metal bath at 75°C with continuous stirring.

[0243] In order to monitor the reaction progress, nuclear magnetic resonance technology is used to track the conversion rate of the polymerization monomer; at the same time, gel permeation chromatography technology is used to track the molecular weight and molecular weight distribution of the polymer; the relevant measurement data and results are as follows Fig. 22 As shown, the monomer conversion rate is 30.7%, M n =14.2 kDa, M w =27.0 kDa, PDI = 1.89.

[0244] Example 8 (ATRP / RITP)

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

[0246] 300 mg (3 mmol, 100 equiv) of MMA (polymerization 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 first solution (containing 0.003 mmol, 0.1 equiv of CuBr2 and 0.006 mmol, 0.2 equiv of PMDETA) were added to a 2 mL sample bottle, and then toluene (organic solvent) was added to make the liquid volume 1 mL, so that the concentration of the polymerization monomer was 3 mol / L;

[0247] The mixture was heated in a metal bath at 75°C with continuous stirring.

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

[0249] Triggering process:

[0250]

[0251] Primary ATRP reinitiation process:

[0252]

[0253] First-order ATRP equilibrium process:

[0254]

[0255] Secondary RITP chain transfer agent generation:

[0256]

[0257] Secondary RITP chain transfer process:

[0258]

[0259] In order to monitor the reaction progress, nuclear magnetic resonance technology is used to track the conversion rate of the polymerization monomer; at the same time, gel permeation chromatography technology is used to track the molecular weight and molecular weight distribution of the polymer; the relevant measurement data and results are as follows Fig.23 As shown, the monomer conversion rate is 42.1%, M n =5.52 kDa, M w =6.6kDa, PDI=1.26.

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

[0261] Comparative Example 9-1 (ATRP)

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

[0263] 300 mg (3 mmol, 100 equiv) of MMA (polymerization 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) were added to a 2 mL sample bottle, and then toluene (organic solvent) was added to make the liquid volume 1 mL, so that the concentration of the aforementioned polymerization monomer was 3 mol / L;

[0264] The mixture was heated in a metal bath at 75°C with continuous stirring.

[0265] In order to monitor the reaction progress, nuclear magnetic resonance technology is used to track the conversion rate of the polymerization monomer; at the same time, gel permeation chromatography technology is used to track the molecular weight and molecular weight distribution of the polymer; the relevant measurement data and results are as follows Fig.24 As shown, the monomer conversion rate is 83.2%, M n =16.4 kDa, M w =27.9 kDa, PDI=1.71.

[0266] Comparative Example 9-2 (RITP)

[0267] In a 2 mL sample bottle, 300 mg (3 mmol, 100 equiv) of MMA (polymerization 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) were added, and then toluene (organic solvent) was added to make the liquid volume 1 mL, so that the concentration of the above-mentioned polymerization monomers was 3 mol / L;

[0268] The mixture was heated in a metal bath at 75°C with continuous stirring.

[0269] In order to monitor the reaction progress, nuclear magnetic resonance technology is used to track the conversion rate of the polymerization monomer; at the same time, gel permeation chromatography technology is used to track the molecular weight and molecular weight distribution of the polymer; the relevant measurement data and results are as follows Fig.25 As shown, the monomer conversion rate is 79.3%, M n =11.9 kDa, M w =21.5 kDa, PDI=1.81.

[0270] Example 9 (ATRP / RITP)

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

[0272] 300 mg (3 mmol, 100 equiv) of MMA (polymerization 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 first solution (containing 0.003 mmol, 0.1 equiv of CuBr2 and 0.006 mmol, 0.2 equiv of PMDETA) were added to a 2 mL sample bottle, and then toluene (organic solvent) was added to make the liquid volume 1 mL, so that the concentration of the polymerization monomer was 3 mol / L;

[0273] The mixture was heated in a metal bath at 75°C with continuous stirring.

[0274] In order to monitor the reaction progress, nuclear magnetic resonance technology is used to track the conversion rate of the polymerization monomer; at the same time, gel permeation chromatography technology is used to track the molecular weight and molecular weight distribution of the polymer; the relevant measurement data and results are as follows Fig.26 As shown, the monomer conversion rate is 77.2%, M n =9.4 kDa, M w =13.0 kDa, PDI=1.37.

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

[0276] Comparative Example 10-1 (ATRP)

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

[0278] In a 2 mL sample bottle, 300 mg (3 mmol, 100 equiv) of MMA (polymerization 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 first solution (containing 0.003 mmol, 0.1 equiv of CuBr2 and 0.006 mmol, 0.2 equiv of PMDETA) were added, and then toluene (organic solvent) was added to make the liquid volume 1 mL, so that the concentration of the polymerization monomer was 3 mol / L;

[0279] The mixture was heated in a metal bath at 75°C with continuous stirring.

[0280] In order to monitor the reaction progress, nuclear magnetic resonance technology is used to track the conversion rate of the polymerization monomer; at the same time, gel permeation chromatography technology is used to track the molecular weight and molecular weight distribution of the polymer; the relevant measurement data and results are as follows Fig. 27 As shown, the monomer conversion rate is 40.2%, M n =14.2 kDa, M w =21.0 kDa, PDI=1.47.

[0281] Comparative Example 10-2 (RITP)

[0282] In a 2 mL sample bottle, 300 mg (3 mmol, 100 equiv) of MMA (polymerization 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) were added, and then toluene (organic solvent) was added to make the liquid volume 1 mL, so that the concentration of the above-mentioned polymerization monomers was 3 mol / L;

[0283] The mixture was heated in a metal bath at 75°C with continuous stirring.

[0284] In order to monitor the reaction progress, nuclear magnetic resonance technology is used to track the conversion rate of the polymerization monomer; at the same time, gel permeation chromatography technology is used to track the molecular weight and molecular weight distribution of the polymer; the relevant measurement data and results are as follows Fig.28As shown, the monomer conversion rate is 34.1%, M n =10.3 kDa, M w =20.3 kDa, PDI=1.97.

[0285] Example 10 (ATRP / RITP)

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

[0287] In a 2 mL sample bottle, 300 mg (3 mmol, 100 equiv) of MMA (polymerization 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 first solution (containing 0.003 mmol, 0.1 equiv of CuBr2 and 0.006 mmol, 0.2 equiv of PMDETA) were added, and then toluene (organic solvent) was added to make the liquid volume 1 mL, so that the concentration of the polymerization monomer was 3 mol / L;

[0288] The mixture was heated in a metal bath at 75°C with continuous stirring.

[0289] In order to monitor the reaction progress, nuclear magnetic resonance technology is used to track the conversion rate of the polymerization monomer; at the same time, gel permeation chromatography technology is used to track the molecular weight and molecular weight distribution of the polymer; the relevant measurement data and results are as follows Fig.29 As shown, the monomer conversion rate is 36.9%, M n =4.6 kDa, M w =5.54kDa, PDI=1.16.

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

[0291] Comparative Example 11-1 (RAFT)

[0292] In a 2 mL sample bottle, 300 mg (3 mmol, 200 equiv) of MMA (polymerization monomer), 4.19 mg (0.015 mmol, 1 equiv) of CTA1 (the second chain transfer agent in the primary free radical polymerization system), and 0.25 mg (0.0015 mmol, 0.1 equiv) of AIBN (thermal initiator) were added, and toluene (organic solvent) was added to make the liquid volume 1 mL, so that the concentration of the above-mentioned polymerization monomers was 3 mol / L;

[0293] The mixture was heated in a metal bath at 75°C with continuous stirring.

[0294] In order to monitor the reaction progress, nuclear magnetic resonance technology is used to track the conversion rate of the polymerization monomer; at the same time, gel permeation chromatography technology is used to track the molecular weight and molecular weight distribution of the polymer; the relevant measurement data and results are as follows Fig.30 As shown, the monomer conversion rate is 54.3%, M n =12.4 kDa, M w =13.8 kDa, PDI=1.11.

[0295] Comparative Example 11-2 (RAFT)

[0296] In a 2 mL sample bottle, 300 mg (3 mmol, 200 equiv) of MMA (polymerization monomer), 16.10 mg (0.06 mmol, 4 equiv) of CTA2 (the second chain transfer agent in the secondary free radical polymerization system), and 0.25 mg (0.0015 mmol, 0.1 equiv) of AIBN (thermal initiator) were added, and toluene (organic solvent) was added to make the liquid volume 1 mL, so that the concentration of the above-mentioned polymerization monomers was 3 mol / L;

[0297] The mixture was heated in a metal bath at 75°C with continuous stirring.

[0298] In order to monitor the reaction progress, nuclear magnetic resonance technology is used to track the conversion rate of the polymerization monomer; at the same time, gel permeation chromatography technology is used to track the molecular weight and molecular weight distribution of the polymer; the relevant measurement data and results are as follows Fig.31 As shown, the monomer conversion rate is 55.8%, M n =8.7 kDa, M w =12.5 kDa, PDI=1.45.

[0299] Example 11 (RAFT / RAFT)

[0300] In a 2 mL sample bottle, 300 mg (3 mmol, 200 equiv) of MMA (polymerization monomer), 4.19 mg (0.015 mmol, 1 equiv) of CTA1 (the second chain transfer agent in the primary free radical polymerization system), 16.10 mg (0.06 mmol, 4 equiv) of CTA2 (the second chain transfer agent in the secondary free radical polymerization system), and 0.25 mg (0.0015 mmol, 0.1 equiv) of AIBN (thermal initiator) were added, and then toluene (organic solvent) was added to make the liquid volume 1 mL, so that the concentration of the aforementioned polymerization monomers was 3 mol / L;

[0301] The mixture was heated in a metal bath at 75°C with continuous stirring.

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

[0303] Triggering process:

[0304]

[0305] Primary RAFT reinitiation process:

[0306]

[0307] Primary RAFT chain transfer process:

[0308]

[0309] Secondary RAFT reinitiation process:

[0310]

[0311] Secondary RAFT chain transfer process:

[0312]

[0313] In order to monitor the reaction progress, nuclear magnetic resonance technology is used to track the conversion rate of the polymerization monomer; at the same time, gel permeation chromatography technology is used to track the molecular weight and molecular weight distribution of the polymer; the relevant measurement data and results are as follows Fig.32 As shown, the monomer conversion rate is 57.4%, M n =6.5 kDa, M w =8.0 kDa, PDI = 1.22.

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

[0315] Comparative Example 12-1 (RAFT)

[0316] Same as comparative example 11-1

[0317] Comparative Example 12-2 (RAFT)

[0318] In a 2 mL sample bottle, 300 mg (3 mmol, 200 equiv) of MMA (polymerization monomer), 22.72 mg (0.06 mmol, 4 equiv) of CTA5 (second chain transfer agent in the secondary free radical polymerization system), and 0.25 mg (0.0015 mmol, 0.1 equiv) of AIBN (thermal initiator) were added, and toluene (organic solvent) was added to make the liquid volume 1 mL, so that the concentration of the above-mentioned polymerization monomers was 3 mol / L;

[0319] The mixture was heated in a metal bath at 75°C with continuous stirring.

[0320] In order to monitor the reaction progress, nuclear magnetic resonance technology is used to track the conversion rate of the polymerization monomer; at the same time, gel permeation chromatography technology is used to track the molecular weight and molecular weight distribution of the polymer; the relevant measurement data and results are as follows Fig.33 As shown, the monomer conversion rate is 60.0%, M n =10.2 kDa, M w =16.0 kDa, PDI=1.57.

[0321] Example 12 (RAFT / RAFT)

[0322] In a 2 mL sample bottle, 300 mg (3 mmol, 200 equiv) of MMA (polymerization monomer), 4.19 mg (0.015 mmol, 1 equiv) of CTA1 (the second chain transfer agent in the primary free radical polymerization system), 22.72 mg (0.06 mmol, 4 equiv) of CTA5 (the second chain transfer agent in the secondary free radical polymerization system), and 0.25 mg (0.0015 mmol, 0.1 equiv) of AIBN (thermal initiator) were added, and then toluene (organic solvent) was added to make the liquid volume 1 mL, so that the concentration of the aforementioned polymerization monomers was 3 mol / L;

[0323] The mixture was heated in a metal bath at 75°C with continuous stirring.

[0324] In order to monitor the reaction progress, nuclear magnetic resonance technology is used to track the conversion rate of the polymerization monomer; at the same time, gel permeation chromatography technology is used to track the molecular weight and molecular weight distribution of the polymer; the relevant measurement data and results are as follows Fig.34 As shown, the monomer conversion rate is 57.1%, Mn =7.3 kDa, M w =9.0 kDa, PDI = 1.23.

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

[0326] Comparative Example 13-1 (RAFT)

[0327] In a 2 mL sample bottle, 300 mg (3 mmol, 200 equiv) of MMA (polymerization monomer), 4.19 mg (0.015 mmol, 1 equiv) of CTA1 (the second chain transfer agent in the primary free radical polymerization system), and 0.25 mg (0.0015 mmol, 0.1 equiv) of AIBN (thermal initiator) were added, and toluene (organic solvent) was added to make the liquid volume 1 mL, so that the concentration of the above-mentioned polymerization monomers was 3 mol / L;

[0328] The mixture was heated in a metal bath at 75°C with continuous stirring.

[0329] In order to monitor the reaction progress, nuclear magnetic resonance technology is used to track the conversion rate of the polymerization monomer; at the same time, gel permeation chromatography technology is used to track the molecular weight and molecular weight distribution of the polymer; the relevant measurement data and results are as follows Fig.35 As shown, the monomer conversion rate is 64.6%, M n =14.8 kDa, M w =16.3 kDa, PDI=1.10.

[0330] Comparative Example 13-2 (RAFT)

[0331] In a 2 mL sample bottle, 300 mg (3 mmol, 200 equiv) of MMA (polymerization monomer), 21.88 mg (0.06 mmol, 4 equiv) of CTA4 (the second chain transfer agent in the secondary free radical polymerization system), and 0.25 mg (0.0015 mmol, 0.1 equiv) of AIBN (thermal initiator) were added, and toluene (organic solvent) was added to make the liquid volume 1 mL, so that the concentration of the above-mentioned polymerization monomers was 3 mol / L;

[0332] The mixture was heated in a metal bath at 75°C with continuous stirring.

[0333] In order to monitor the reaction progress, nuclear magnetic resonance technology is used to track the conversion rate of the polymerization monomer; at the same time, gel permeation chromatography technology is used to track the molecular weight and molecular weight distribution of the polymer; the relevant measurement data and results are as follows Fig.36 As shown, the monomer conversion rate is 63.0%, M n =11.8 kDa, M w =19.1 kDa, PDI =1.62.

[0334] Example 13 (RAFT / RAFT)

[0335] In a 2 mL sample bottle, 300 mg (3 mmol, 200 equiv) of MMA (polymerization monomer), 4.19 mg (0.015 mmol, 1 equiv) of CTA1 (the second chain transfer agent in the primary free radical polymerization system), 21.88 mg (0.06 mmol, 4 equiv) of CTA4 (the second chain transfer agent in the secondary free radical polymerization system), and 0.25 mg (0.0015 mmol, 0.1 equiv) of AIBN (thermal initiator) were added, and then toluene (organic solvent) was added to make the liquid volume 1 mL, so that the concentration of the aforementioned polymerization monomers was 3 mol / L;

[0336] The mixture was heated in a metal bath at 75°C with continuous stirring.

[0337] In order to monitor the reaction progress, nuclear magnetic resonance technology is used to track the conversion rate of the polymerization monomer; at the same time, gel permeation chromatography technology is used to track the molecular weight and molecular weight distribution of the polymer; the relevant measurement data and results are as follows Fig.37 As shown, the monomer conversion rate is 57.1%, M n =7.3 kDa, M w =9.0 kDa, PDI = 1.23.

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

[0339] Comparative Example 14-1 (RAFT)

[0340] In a 2 mL sample bottle, 300 mg (3 mmol, 200 equiv) of MMA (polymerization 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) were added, and toluene (organic solvent) was added to make the liquid volume 1 mL, so that the concentration of the above-mentioned polymerization monomers was 3 mol / L;

[0341] The mixture was heated in a metal bath at 75°C with continuous stirring.

[0342] In order to monitor the reaction progress, nuclear magnetic resonance technology is used to track the conversion rate of the polymerization monomer; at the same time, gel permeation chromatography technology is used to track the molecular weight and molecular weight distribution of the polymer; the relevant measurement data and results are as follows Fig.38 As shown, the monomer conversion rate is 29.4%, M n =7.2 kDa, M w =8.1 kDa, PDI=1.13.

[0343] Comparative Example 14-2 (Thiol)

[0344] In a 2 mL sample bottle, 300 mg (3 mmol, 200 equiv) of MMA (polymerization 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) were added, and toluene (organic solvent) was added to make the liquid volume 1 mL, so that the concentration of the above-mentioned polymerization monomers was 3 mol / L;

[0345] The mixture was heated in a metal bath at 75°C with continuous stirring.

[0346] In order to monitor the reaction progress, nuclear magnetic resonance technology is used to track the conversion rate of the polymerization monomer; at the same time, gel permeation chromatography technology is used to track the molecular weight and molecular weight distribution of the polymer; the relevant measurement data and results are as follows Fig.39 As shown, the monomer conversion rate is 36.1%, M n =8.8 kDa, M w =14.5 kDa, PDI=1.64.

[0347] Example 14 (RAFT / Thiol)

[0348] In a 2 mL sample bottle, 300 mg (3 mmol, 200 equiv) of MMA (polymerization 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) were added, and toluene (organic solvent) was added to make the liquid volume 1 mL, so that the concentration of the above-mentioned polymerization monomers was 3 mol / L;

[0349] The mixture was heated in a metal bath at 75°C with continuous stirring.

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

[0351] Triggering process:

[0352]

[0353] Primary RAFT reinitiation process:

[0354]

[0355] Primary RAFT chain transfer process:

[0356]

[0357] Secondary Thiol chain transfer process:

[0358]

[0359] In order to monitor the reaction progress, nuclear magnetic resonance technology is used to track the conversion rate of the polymerization monomer; at the same time, gel permeation chromatography technology is used to track the molecular weight and molecular weight distribution of the polymer; the relevant measurement data and results are as follows Fig.40 As shown, the monomer conversion rate is 34.9%, M n =5.2 kDa, M w =7.0 kDa, PDI = 1.32.

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

[0361] Comparative Example 15-1 (RCMP)

[0362] In a 2 mL sample bottle, 300 mg (3 mmol, 200 equiv) of MMA (polymerization 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) were added, and toluene (organic solvent) was added to a liquid volume of 1 mL, so that the concentration of the aforementioned polymerization monomers was 3 mol / L;

[0363] The mixture was heated in a metal bath at 65°C with continuous stirring.

[0364] In order to monitor the reaction progress, nuclear magnetic resonance technology is used to track the conversion rate of the polymerization monomer; at the same time, gel permeation chromatography technology is used to track the molecular weight and molecular weight distribution of the polymer; the relevant measurement data and results are as follows Fig.41 As shown, the monomer conversion rate is 78.7%, M n =9.8 kDa, M w =11.2 kDa, PDI=1.13.

[0365] Comparative Example 15-2 (RAFT)

[0366] In a 2 mL sample bottle, 300 mg (3 mmol, 200 equiv) of MMA (polymerization 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) were added, and toluene (organic solvent) was added to make the liquid volume 1 mL, so that the concentration of the above-mentioned polymerization monomers was 3 mol / L;

[0367] The mixture was heated in a metal bath at 65°C with continuous stirring.

[0368] In order to monitor the reaction progress, nuclear magnetic resonance technology is used to track the conversion rate of the polymerization monomer; at the same time, gel permeation chromatography technology is used to track the molecular weight and molecular weight distribution of the polymer; the relevant measurement data and results are as follows Fig.42 As shown, the monomer conversion rate is 78.6%, M n =7.5 kDa, M w =11.7 kDa, PDI=1.57.

[0369] Example 15 (RCMP / RAFT)

[0370] In a 2 mL sample bottle, 300 mg (3 mmol, 200 equiv) of MMA (polymerization 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) were added, and then toluene (organic solvent) was added to make the liquid volume 1 mL, so that the concentration of the above-mentioned polymerization monomers was 3 mol / L;

[0371] The mixture was heated in a metal bath at 65°C with continuous stirring.

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

[0373] Triggering process:

[0374]

[0375] First Level RCMP Reinitiation Process:

[0376]

[0377] First Class RCMP Balancing Process:

[0378]

[0379] Secondary RAFT reinitiation process:

[0380]

[0381] Secondary RAFT chain transfer process:

[0382]

[0383] In order to monitor the reaction progress, nuclear magnetic resonance technology is used to track the conversion rate of the polymerization monomer; at the same time, gel permeation chromatography technology is used to track the molecular weight and molecular weight distribution of the polymer; the relevant measurement data and results are as follows Fig.43 As shown, the monomer conversion rate is 71.5%, M n =5.3 kDa, M w =6.10 kDa, PDI=1.16.

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

[0385] Comparative Example 16-1 (RCMP)

[0386] Same as comparative example 15-1

[0387] Comparative Example 16-2 (RAFT)

[0388] In a 2 mL sample bottle, 300 mg (3 mmol, 200 equiv) of MMA (polymerization 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) were added, and toluene (organic solvent) was added to make the liquid volume 1 mL, so that the concentration of the above-mentioned polymerization monomers was 3 mol / L;

[0389] The mixture was heated in a metal bath at 65°C with continuous stirring.

[0390] In order to monitor the reaction progress, nuclear magnetic resonance technology is used to track the conversion rate of the polymerization monomer; at the same time, gel permeation chromatography technology is used to track the molecular weight and molecular weight distribution of the polymer; the relevant measurement data and results are as follows Fig.44 As shown, the monomer conversion rate is 79.4%, M n =8.0 kDa, M w =12.8 kDa, PDI=1.60.

[0391] Example 16 (RCMP / RAFT)

[0392] In a 2 mL sample bottle, 300 mg (3 mmol, 200 equiv) of MMA (polymerization 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) were added, and then toluene (organic solvent) was added to make the liquid volume 1 mL, so that the concentration of the above-mentioned polymerization monomers was 3 mol / L;

[0393] The mixture was heated in a metal bath at 65°C with continuous stirring.

[0394] In order to monitor the reaction progress, nuclear magnetic resonance technology is used to track the conversion rate of the polymerization monomer; at the same time, gel permeation chromatography technology is used to track the molecular weight and molecular weight distribution of the polymer; the relevant measurement data and results are as follows Fig.45 As shown, the monomer conversion rate is 75.9%, M n =5.6 kDa, M w =6.8kDa, PDI=1.22.

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

[0396] Comparative Example 17-1 (RCMP)

[0397] In a 2 mL sample bottle, 300 mg (3 mmol, 200 equiv) of MMA (polymerization 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) were added, and toluene (organic solvent) was added to a liquid volume of 1 mL, so that the concentration of the aforementioned polymerization monomers was 3 mol / L;

[0398] The mixture was heated in a metal bath at 65°C with continuous stirring.

[0399] In order to monitor the reaction progress, nuclear magnetic resonance technology is used to track the conversion rate of the polymerization monomer; at the same time, gel permeation chromatography technology is used to track the molecular weight and molecular weight distribution of the polymer; the relevant measurement data and results are as follows Fig.46 As shown, the monomer conversion rate is 69.4%, M n =7.7 kDa, M w =8.6kDa, PDI=1.11.

[0400] Comparative Example 17-2 (RAFT)

[0401] In a 2 mL sample bottle, 300 mg (3 mmol, 200 equiv) of MMA (polymerization 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) were added, and toluene (organic solvent) was added to make the liquid volume 1 mL, so that the concentration of the above-mentioned polymerization monomers was 3 mol / L;

[0402] The mixture was heated in a metal bath at 65°C with continuous stirring.

[0403] In order to monitor the reaction progress, nuclear magnetic resonance technology is used to track the conversion rate of the polymerization monomer; at the same time, gel permeation chromatography technology is used to track the molecular weight and molecular weight distribution of the polymer; the relevant measurement data and results are as follows Fig.47 As shown, the monomer conversion rate is 64.3%, M n =6.3 kDa, M w =8.9 kDa, PDI=1.41.

[0404] Example 17 (RCMP / RAFT)

[0405] In a 2 mL sample bottle, 300 mg (3 mmol, 200 equiv) of MMA (polymerization 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) were added, and then toluene (organic solvent) was added to make the liquid volume 1 mL, so that the concentration of the above-mentioned polymerization monomers was 3 mol / L;

[0406] The mixture was heated in a metal bath at 65°C with continuous stirring.

[0407] In order to monitor the reaction progress, nuclear magnetic resonance technology is used to track the conversion rate of the polymerization monomer; at the same time, gel permeation chromatography technology is used to track the molecular weight and molecular weight distribution of the polymer; the relevant measurement data and results are as follows Fig.48 As shown, the monomer conversion rate is 63.0%, M n =5.8 kDa, M w =6.7 kDa, PDI=1.15.

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

[0409] Comparative Example 18-1 (NMP)

[0410] In a 2 mL sample bottle, 625 mg (6 mmol, 200 equiv) of St (polymerized 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) were added respectively;

[0411] Stir and heat in a metal bath at 95°C, and after reacting for 3 hours, raise the temperature to 123°C.

[0412] In order to monitor the reaction progress, nuclear magnetic resonance technology is used to track the conversion rate of the polymerization monomer; at the same time, gel permeation chromatography technology is used to track the molecular weight and molecular weight distribution of the polymer; the relevant measurement data and results are as follows Fig.49 As shown, the monomer conversion rate is 71.5%, M n =13.1 kDa, M w =15.7 kDa, PDI=1.20.

[0413] Comparative Example 18-2 (Thiol)

[0414] 625 mg (6 mmol, 200 equiv) of St (polymerized 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) were added to a 2 mL sample bottle;

[0415] Stir and heat in a metal bath at 95°C, and after reacting for 3 hours, raise the temperature to 123°C.

[0416] In order to monitor the reaction progress, nuclear magnetic resonance technology is used to track the conversion rate of the polymerization monomer; at the same time, gel permeation chromatography technology is used to track the molecular weight and molecular weight distribution of the polymer; the relevant measurement data and results are as follows Fig.50 As shown, the monomer conversion rate is 67.1%, M n =6.5 kDa, M w =42.4 kDa, PDI=6.48.

[0417] Example 18 (NMP / Thiol)

[0418] In a 2 mL sample bottle, 625 mg (6 mmol, 200 equiv) of St (polymerized 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) were added respectively;

[0419] Stir and heat in a metal bath at 95°C, and after reacting for 3 hours, raise the temperature to 123°C.

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

[0421] Triggering process:

[0422]

[0423] Primary NMP balancing process:

[0424]

[0425] Secondary Thiol chain transfer process:

[0426]

[0427] In order to monitor the reaction progress, nuclear magnetic resonance technology is used to track the conversion rate of the polymerization monomer; at the same time, gel permeation chromatography technology is used to track the molecular weight and molecular weight distribution of the polymer; the relevant measurement data and results are as follows Fig.51 As shown, the monomer conversion rate is 70.4%, M n =10.5 kDa, M w =13.2 kDa, PDI=1.26.

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

[0429] Comparative Example 19-1 (NMP)

[0430] In a 2 mL sample bottle, 625 mg (6 mmol, 200 equiv) of St (polymerized 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) were added respectively;

[0431] Stir and heat in a metal bath at 95°C, and after reacting for 3 hours, raise the temperature to 123°C.

[0432] In order to monitor the reaction progress, nuclear magnetic resonance technology is used to track the conversion rate of the polymerization monomer; at the same time, gel permeation chromatography technology is used to track the molecular weight and molecular weight distribution of the polymer; the relevant measurement data and results are as follows Fig.52 As shown, the monomer conversion rate is 54.6%, M n =10.0 kDa, M w =11.4 kDa, PDI=1.14.

[0433] Comparative Example 19-2 (RAFT)

[0434] In a 2 mL sample bottle, 625 mg (6 mmol, 200 equiv) of St (polymerized 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) were added respectively;

[0435] Stir and heat in a metal bath at 95°C, and after reacting for 3 hours, raise the temperature to 123°C.

[0436] In order to monitor the reaction progress, nuclear magnetic resonance technology is used to track the conversion rate of the polymerization monomer; at the same time, gel permeation chromatography technology is used to track the molecular weight and molecular weight distribution of the polymer; the relevant measurement data and results are as follows Fig.53 As shown, the monomer conversion rate is 48.7%, M n =5.7 kDa, M w =9.6kDa, PDI=1.67.

[0437] Example 19 (NMP / RAFT)

[0438] In a 2 mL sample bottle, 625 mg (6 mmol, 200 equiv) of St (polymerized 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) were added respectively;

[0439] Stir and heat in a metal bath at 95°C, and after reacting for 3 hours, raise the temperature to 123°C.

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

[0441] Triggering process:

[0442]

[0443] Primary NMP balancing process:

[0444]

[0445] Secondary RAFT reinitiation process:

[0446]

[0447] Secondary RAFT chain transfer process:

[0448]

[0449] In order to monitor the reaction progress, nuclear magnetic resonance technology is used to track the conversion rate of the polymerization monomer; at the same time, gel permeation chromatography technology is used to track the molecular weight and molecular weight distribution of the polymer; the relevant measurement data and results are as follows Fig.54 As shown, the monomer conversion rate is 47.7%, M n =3.7 kDa, M w =5.8kDa, PDI=1.56.

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

[0451] Comparative Example 20-1 (TERP)

[0452] In a 2 mL sample bottle, 600 mg (6 mmol, 200 equiv) of MMA (polymerized 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) were added respectively;

[0453] The mixture was heated in a metal bath at 65°C with continuous stirring.

[0454] In order to monitor the reaction progress, nuclear magnetic resonance technology is used to track the conversion rate of the polymerization monomer; at the same time, gel permeation chromatography technology is used to track the molecular weight and molecular weight distribution of the polymer; the relevant measurement data and results are as follows Fig.55 As shown, the monomer conversion rate is 60.2%, M n =11.3 kDa, Mw =13.7 kDa, PDI=1.22.

[0455] Comparative Example 20-2 (RAFT)

[0456] In a 2 mL sample bottle, 600 mg (6 mmol, 200 equiv) of MMA (polymerization 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) were added respectively;

[0457] The mixture was heated in a metal bath at 65°C with continuous stirring.

[0458] In order to monitor the reaction progress, nuclear magnetic resonance technology is used to track the conversion rate of the polymerization monomer; at the same time, gel permeation chromatography technology is used to track the molecular weight and molecular weight distribution of the polymer; the relevant measurement data and results are as follows Fig.56 As shown, the monomer conversion rate is 56.4%, M n =9.0 kDa, M w =12.7 kDa, PDI=1.41.

[0459] Example 20 (TERP / RAFT)

[0460] In a 2 mL sample bottle, 600 mg (6 mmol, 200 equiv) of MMA (polymerized 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) were added respectively;

[0461] The mixture was heated in a metal bath at 65°C with continuous stirring.

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

[0463] Triggering process:

[0464]

[0465] Primary TERP re-priming process:

[0466]

[0467] Primary TERP balance process:

[0468]

[0469] Secondary RAFT reinitiation process:

[0470]

[0471] Secondary RAFT chain transfer process:

[0472]

[0473] In order to monitor the reaction progress, nuclear magnetic resonance technology is used to track the conversion rate of the polymerization monomer; at the same time, gel permeation chromatography technology is used to track the molecular weight and molecular weight distribution of the polymer; the relevant measurement data and results are as follows Fig.57 As shown, the monomer conversion rate is 54.4%, M n =7.1 kDa, M w =9.4kDa, PDI=1.33.

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

[0475] Comparative Example 21-1 (TERP)

[0476] Same as comparative example 20-1

[0477] Comparative Example 21-2 (RAFT)

[0478] In a 2 mL sample bottle, 600 mg (6 mmol, 200 equiv) of MMA (polymerization 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) were added respectively;

[0479] The mixture was heated in a metal bath at 65°C with continuous stirring.

[0480] In order to monitor the reaction progress, nuclear magnetic resonance technology is used to track the conversion rate of the polymerization monomer; at the same time, gel permeation chromatography technology is used to track the molecular weight and molecular weight distribution of the polymer; the relevant measurement data and results are as follows Fig.58 As shown, the monomer conversion rate is 64.3%, M n =8.3 kDa, M w =11.8 kDa, PDI=1.43.

[0481] Example 21 (TERP / RAFT)

[0482] In a 2 mL sample bottle, 600 mg (6 mmol, 200 equiv) of MMA (polymerized 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) were added respectively;

[0483] The mixture was heated in a metal bath at 65°C with continuous stirring.

[0484] In order to monitor the reaction progress, nuclear magnetic resonance technology is used to track the conversion rate of the polymerization monomer; at the same time, gel permeation chromatography technology is used to track the molecular weight and molecular weight distribution of the polymer; the relevant measurement data and results are as follows Fig.59 As shown, the monomer conversion rate is 54.4%, M n =7.1 kDa, M w =9.4kDa, PDI=1.33.

[0485] It can be seen that at a similar monomer conversion rate, the molecular weight of the polymer obtained in Example 21 is lower than the molecular weight of the polymer obtained in Comparative Example 21-1 or Comparative Example 21-2, proving that the secondary free radical polymerization system achieves chain transfer, while the polymerization control remains within the active range, proving that the primary free radical polymerization system achieves the capture of free radicals.

[0486] Comparative Example 22-1 (TERP)

[0487] Same as comparative example 20-1

[0488] Comparative Example 22-2 (RAFT)

[0489] 600 mg (6 mmol, 200 equiv) of MMA (polymerization 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) were added to a 2 mL sample bottle;

[0490] The mixture was heated in a metal bath at 65°C with continuous stirring.

[0491] In order to monitor the reaction progress, nuclear magnetic resonance technology is used to track the conversion rate of the polymerization monomer; at the same time, gel permeation chromatography technology is used to track the molecular weight and molecular weight distribution of the polymer; the relevant measurement data and results are as follows Fig.60 As shown, the monomer conversion rate is 65.8%, Mn =10.7 kDa, M w =15.6 kDa, PDI=1.47.

[0492] Example 21 (TERP / RAFT)

[0493] In a 2 mL sample bottle, 600 mg (6 mmol, 200 equiv) of MMA (polymerized 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) were added respectively;

[0494] The mixture was heated in a metal bath at 65°C with continuous stirring.

[0495] In order to monitor the reaction progress, nuclear magnetic resonance technology is used to track the conversion rate of the polymerization monomer; at the same time, gel permeation chromatography technology is used to track the molecular weight and molecular weight distribution of the polymer; the relevant measurement data and results are as follows Fig.61 As shown, the monomer conversion rate is 64.9%, M n =7.6 kDa, M w =9.6kDa, PDI=1.26.

[0496] It can be seen that at a similar monomer conversion rate, the molecular weight of the polymer obtained in Example 22 is lower than the molecular weight of the polymer obtained in Comparative Example 22-1 or Comparative Example 22-2, proving that the secondary free radical polymerization system achieves chain transfer, while the polymerization control remains within the active range, proving that the primary free radical polymerization system achieves the capture of free radicals.

[0497] The binary free radical polymerization method of the present invention successfully realizes the independent regulation of molecular weight and molecular weight distribution in active polymerization by combining a primary free radical polymerization system for capturing free radicals with a secondary free radical polymerization system for achieving chain transfer. This not only improves polymerization efficiency and reduces production costs, but also significantly improves the quality of polymer products. Since the molecular weight and molecular weight distribution of the polymer can be accurately controlled, the present invention can be widely used in various scenarios involving active controllable free radical polymerization reactions, including materials science, medicine, chemical industry and other fields, and applications with special requirements for polymer properties also benefit from it.

[0498] The above description is only a preferred embodiment of the present invention, and does not limit the implementation mode and protection scope of the present invention. For those skilled in the art, it should be aware that all solutions obtained by equivalent substitutions and obvious changes made using the description and illustrations of the present invention should be included in the protection scope of the present invention.

Claims

1. A binary free radical polymerization method, characterized in that the steps include: S0, providing a primary free radical polymerization system for capturing free radicals, and a secondary free radical polymerization system for achieving chain transfer; S1, mixing the polymerization monomer, the primary free radical polymerization system, and the secondary free radical polymerization system, and initiating free radical polymerization by thermal cracking, photoexcitation, or electrical excitation to obtain a polymer with independently regulated molecular weight and molecular weight distribution; Wherein, the primary free radical polymerization system is an atom transfer radical polymerization system, and the secondary free radical polymerization system is a reverse iodine atom transfer radical polymerization system; or, The primary free radical polymerization system is an atom transfer radical polymerization system, and the secondary free radical polymerization system is a reversible addition-fragmentation chain transfer polymerization system; or, The primary free radical polymerization system is a reversible addition-fragmentation chain transfer polymerization system, and the secondary free radical polymerization system is a reversible addition-fragmentation chain transfer polymerization system; or, The primary free radical polymerization system is a reversible addition-fragmentation chain transfer polymerization system, and the secondary free radical polymerization system is a free radical polymerization system using mercaptan as a chain transfer agent; or, The primary free radical polymerization system is a reversible complexation mediated polymerization system, and the secondary free radical polymerization system is a reversible addition-fragmentation chain transfer polymerization system; or, The primary free radical polymerization system is a nitroxide-mediated polymerization system, and the secondary free radical polymerization system is a reversible addition-fragmentation chain transfer polymerization system; or, The primary free radical polymerization system is a nitrogen oxide mediated polymerization system, and the secondary free radical polymerization system is a free radical polymerization system using mercaptan as a chain transfer agent; or, The primary free radical polymerization system is an organic tellurium-mediated active free radical polymerization system, and the secondary free radical polymerization system is a reversible addition-fragmentation chain transfer polymerization system.

2. The binary free radical polymerization method according to claim 1, characterized in that: The polymerizable 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.

3. The binary free radical polymerization method according to claim 1, characterized in that: At least one of the primary free radical polymerization system or the secondary free radical polymerization system comprises: a thermal initiator; wherein, The thermal initiator is selected from at least one of 2,2-azobis(4-methoxy-2,4-dimethylvaleronitrile), dibenzoyl peroxide, azobisisobutyronitrile, and azobisisoheptylonitrile.

4. The binary free radical polymerization method according to claim 3, characterized in that: The atom transfer radical polymerization system comprises: a first initiator, a first catalyst, and a ligand; wherein, The first initiator is selected from at least one of 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, methyl chloroacetate, benzyl bromide, bromoacetonitrile, or methyl bromoacetate; The first catalyst 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, and pentamethyldiethylenetriamine.

5. The binary free radical polymerization method according to claim 3, characterized in that: The reversible complexation mediated polymerization system comprises: a first dormant species and a second catalyst; wherein, 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.

6. The binary free radical polymerization method according to claim 3, characterized in that: The nitrogen oxide mediated polymerization system comprises: a second dormant species; wherein, The second dormant species is selected from: at least one of 2,2,6,6-tetramethylpiperidine-1-oxyl free radical, 2,2,5-trimethyl-4-phenyl-3-azahexane-3-nitroxide, 1-hydroxy-N,2,2-triphenylindole-3-imine, or N-tert-butyl-N-[1-diethylphosphonyl-(2,2-dimethylpropyl)].

7. The binary free radical polymerization method according to claim 3, characterized in that: The organic tellurium-mediated active free radical polymerization system comprises: a third dormant species; wherein, The third dormant species is selected from at least one of 1-phenylethyltellurylbenzene, 2-methyl-2-(methyltelluryl)propionitrile, ethyl 2-methyl-2-(methyltelluryl)propionate, tellurium methylbenzotellurate, dimethyl ditellurium, methyl (1-phenylethyl) tellurium, or methylbenzyl tellurium.

8. The binary free radical polymerization method according to claim 4, characterized in that: The reverse iodine atom transfer free radical polymerization system comprises: a fourth dormant species; wherein, The fourth dormant species is selected from: elemental iodine.

9. The binary free radical polymerization method according to claim 6, characterized in that: The free radical polymerization system using mercaptan as a chain transfer agent comprises: a first chain transfer agent; wherein, The first chain transfer agent is selected from at least one of tert-nonyl mercaptan, tert-dodecyl mercaptan, n-butyl mercaptan, n-dodecyl mercaptan, and n-octyl mercaptan.

10. The binary free radical polymerization method according to any one of claims 3, 4-7, or 9, characterized in that: The reversible addition-fragmentation chain transfer polymerization system comprises: a second chain transfer agent; wherein, The second chain transfer agent is selected from the group consisting of 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-cyanopropyl-2-benzodisulfide, 2- At least one of cyanopropyl-2-thiocarboxylic acid O-ethyl ester, 2-cyanopropyl N-methyl-N-(4-pyridyl)aminodithiocarbonate, 4-cyano-4-(thiobenzoyl)pentanoic acid, 4-cyano-4-[[(dodecylthio)thioketonemethyl]thio]pentanoic acid, S-(2-cyano-2-propyl)-S-dodecyltrithiocarbonyl ester, or S-benzyl O-ethyldithiocarbonate.

11. The binary free radical polymerization method according to claim 8, characterized in that: When the primary free radical polymerization system is an atom transfer radical polymerization system, and the secondary free radical polymerization system is a reverse iodine atom transfer radical polymerization system, the molar ratio of the polymerization 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.

12. The binary free radical polymerization method according to claim 10, characterized in that: When the primary free radical polymerization system is an atom transfer radical polymerization system, and the secondary free radical polymerization system is a reversible addition-fragmentation chain transfer polymerization system, the molar ratio of the polymerization 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).

13. The binary free radical polymerization method according to claim 10, characterized in that: When the primary free radical polymerization system is a reversible addition-fragmentation chain transfer polymerization system, and the secondary free radical polymerization system is a reversible addition-fragmentation chain transfer polymerization system, the molar ratio of the polymerization monomer, the second chain transfer agent in the primary free radical polymerization system, the second chain transfer agent in the secondary free radical polymerization system, and the thermal initiator during mixing is (100-500):(1-2):(2-9):0.

1.

14. The binary free radical polymerization method according to claim 10, characterized in that: When the primary free radical polymerization system is a reversible addition-fragmentation chain transfer polymerization system, and the secondary free radical polymerization system is a free radical polymerization system with thiol as a chain transfer agent, the molar ratio of the polymerization 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.

15. The binary free radical polymerization method according to claim 10, characterized in that: When the primary free radical polymerization system is a reversible complexation mediated polymerization system, and the secondary free radical polymerization system is a reversible addition-fragmentation chain transfer polymerization system, the molar ratio of the polymerization 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).

16. The binary free radical polymerization method according to claim 10, characterized in that: When the primary free radical polymerization system is a nitrogen oxide mediated polymerization system, and the secondary free radical polymerization system is a reversible addition-fragmentation chain transfer polymerization system, the molar ratio of the polymerization 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).

17. The binary free radical polymerization method according to claim 9, characterized in that: When the primary free radical polymerization system is a nitrogen oxide-mediated polymerization system, and the secondary free radical polymerization system is a free radical polymerization system with thiol as a chain transfer agent, the molar ratio of the polymerization 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).

18. The binary free radical polymerization method according to claim 10, characterized in that: When the primary free radical polymerization system is an organic tellurium-mediated active free radical polymerization system, and the secondary free radical polymerization system is a reversible addition-fragmentation chain transfer polymerization system, the molar ratio of the polymerization monomer, the third dormant species, the second chain transfer agent, and the thermal initiator during mixing is (100-500):(1-2):(2-9):

1.

19. The binary free radical polymerization method according to claim 1, characterized in that: The reaction temperature of the free radical polymerization is 60°C-125°C.

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

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