TWI238166B - Thiocarbonylthio compound and free radical polymerization using the same - Google Patents

Abstract

The present invention provides a thiocarbonylthio compound used in free radical polymerization and represented by the formula (I), wherein when R is CR1R2SO2R3, Z is independently perfluoroalkyl, alkyl, haloalkyl, aryl, alkylaryl, haloalkylaryl, arylalkyl, aminoalkyl, alkylamino, alkoxy, alkoxyaryl, (R')2P(=O) or (R')2P(=S); wherein R1, R2 and R3 is independently alkyl, aryl, aminoalkyl, alkylamino, alkoxy or alkoxyaryl; R' is independently alkyl, aryl, alkylaryl, arylalkyl, alkoxy or alkoxyaryl; and when R is independently alkyl, aryl, alkylaryl, arylalkyl, aminoalkyl, alkylamino, alkoxy, alkylsilyl alkylsulfide or substituent containing CN, COOR4 or heterocyclic moieties, Z is perfluoroalkyl, wherein R4 is H or methyl. The thiocarbonylthio compound can be used as a reversible chain transfer agent in a free radical polymerization to obtain a polymer with a predetermined molecular weight and narrow molecular weight distribution.

Description

1238166 发明 Description of the invention: [Technical power to which the invention belongs] The present invention relates to thiocarbonylthio compounds, and in particular, to the control of free radical polymerization in the presence of this thiothiothio compound to produce a narrow molecular weight Distribution and predeterminable molecular weight of at least one vinyl monomer polymer. [Previous technology] Traditional free radical polymerization is the most widely used polymerization method in the industry, and the most polymerizable monomers are the most widely used, such as Benben Shaobuo, acrylates, and methyl acryl si (mma) or propionitrile. More than 50% of commercial polymers are prepared this way. The reaction conditions of the radical polymerization are also less severe, and they can be carried out even in water as long as oxygen is removed. However, ‘traditional radical polymerization technology is difficult to control the degree of polymerization arbitrarily and the molecular weight distribution is wide (PDI > 1 · 5)’ The polymer structure and functional group distribution cannot be effectively controlled ’, which leads to the inability to accurately control the material properties. Traditional active cation and living anion polymerization techniques can only effectively polymerize a small number of monomers to a degree similar to living polymerization (pDI < 1.5) ', and the reaction conditions are severe, and most of them need to be carried out in an anhydrous, anaerobic or low temperature environment 'Less widely applicable. Living free radical polymerization (Living free radical polymerization) — is the focus of related research, because it is expected to control vinyl monomers under less severe reaction conditions than living anionic or cationic polymerization techniques. ) 'S aggregation. Control of polymer structure, backbone composition and functional group distribution, as well as control of molecular weight and molecular weight distribution. WO98 / 01478 discloses a living radical polymerization method called a reversible addition-fragmentation chain transfer process (RAFT polymerization method for short). The RAFT polymerization method is to add a certain amount of thiocarbonylthio compound (S = C (Z) SR) specially designed by the patent inventor to the traditional radical polymerization method to obtain a polymer with a narrow molecular weight distribution, and the polymer The chain length can also be controlled in advance. However, for some monomers such as acrylates 1238166, if a narrow molecular weight distribution polymer is to be obtained, the polymerization reaction must be performed in a very dilute solution. Otherwise, at high monomer concentration and high monomer conversion rate, the molecular weight distribution of the obtained polymer tends to widen; or because of some side reactions, there are very high molecular weight polymers, forming a bimodal distribution of molecular weight (bimodal distribution) . In addition, the polymerization reaction in a very diluted solution is very slow, which is not economical. Therefore, the development of a novel reversible addition cleavage chain transfer reagent, in a solution with relatively high monomer concentration, can still have a high degree of control over the polymerization of vinyl monomers is a topic worthy of research. The present invention relates to a novel thiocarbonylthio compound system, and has a faster polymerization reaction rate for vinyl monomers, while still controlling the molecular weight and molecular weight distribution. The novel reversible addition cleavage chain transfer agent developed by the present invention can actively polymerize acrylate monomers at a relatively fast reaction rate under relatively high concentration reaction conditions, and still can obtain a high conversion rate and a narrow molecular weight distribution. Polymer. [Summary of the Invention] An object of the present invention is to provide a sulfur thiocarbonyl compound capable of living radical polymerization, as shown in Chemical Formula (I):

Wherein when R is CRiRjC ^ Rs, Z is independently a fluorocarbon group, an alkyl group, a haloalkyl group, an aromatic group, an aryl group, a halogenated aryl group, an aryl group, an aminoalkyl group, :): Alkylamino (alkylamino), :): oxyl, oxyloxy, thiol, :): thiol, (R ') 2P (= 0) or (R') 2P (= S), its center, only 2 and R3 are independently alkyl, aromatic 1238166, amine, langyl, silk, or silk aryl, and R, independently are courtyard, aromatic, alkylaryl, alkyl Oxy, alkoxyaryl; and when R is independently alkynyl, aryl, aryl, aryl, amine, aminoaky, alkoxy (aikylamin), alkoxy When it is alkylsilyl, or CN, C00R4 (where & is H or alkyl), or a substituent of a heterocyclic group, Z is independently a fluorocarbon group. Another object of the present invention is to provide a thiol sulfur-based compound capable of living radical polymerization, as shown in chemical formula (II):

S (7 c / (CR6R7) ns〇4r5 厶 s Jm (II) where z is rabbit fluoro nicotinyl, :): cumyl, haloalkyl, aromatic, aryl, alkaryl, aralkyl , Amine alkyl, alkylamino, alkoxy, alkoxyaryl, alkylthio, alkylthioaryl, (R ') 2P (= 〇) or (R') 2P (= S), where R, independently alkyl, aryl, aryl, alkoxy, alkoxy, alkoxyaryl; Rs is alkyl, aryl, alkaryl, aryl, :): endoxy, calcite Ethyl, sulfanyl, or substituents containing CN, C = 0, COOR4, CRii ^ SC ^ R3, or heterocyclic groups, wherein are independently alkyl, aromatic, amine alkyl, alkylamino, and alkoxy R6 and R7 are independently fluorene, alkyl, aryl, alkaryl, aralkyl; ^ is 0 or 1; and m is any greater than zero Integer, the best is an integer from 1 to 10. Another object of the present invention is to provide a thiocarbonylthio compound capable of living radical polymerization, as shown in chemical formula (III): 1238166

/

y F2n + lC (III) where

Ru is independently alkyl, aryl, alkaryl, aralkyl, aminealkyl, alkoxy or alkylsilyl, or contains C = 0, COOR4 (R4 is fluorene or alkyl), CRil ^ SC ^ Rs or a substituent of a heterocyclic group, wherein Rr R2 and R3 are independently an alkyl group, an aromatic group, an amine alkyl group, an alkylamino group, an alkoxy group, or an alkoxyaryl group; η is 1 to 10 An integer; and m is any integer greater than zero, and the best is an integer from 1 to 10. Another object of the present invention is to provide a radical polymerization method, comprising: polymerizing at least one ethylenic monomer in the presence of a thiocarbonylthio compound represented by formula (I), (II) or (ΠΙ).体 (vinyl monomer). The aforementioned mono- or copolymerizable vinyl monomer system includes acrylic acid and its salts, acrylates, fluoracrylic acid and its salts, methacrylates, acrylonitrile, styrene, Acrylamide, vinyl acetate, butadiene, isoprene, norbornene and its derivatives, vinyl chloride, olefins (a- oleHn) such as ethylene, 1-hexene, etc. or a mixture thereof. [Embodiment] The thiocarbonylthio compound capable of living radical polymerization provided by the present invention is as shown in chemical formula (I):

S z 10 (I) 1238166 Wherein when R is CRiUC ^ R3, z is independently a fluorocarbon group, an alkyl group, a haloalkyl group, a hydrocarbyl group, a haloyl group, a haloyl group, a halo group, and an amine group. (Aminoalkyl), :): alkylamino, alkoxy, alkoxyaryl, alkylthio, alkylthioaryl, (R ') 2P (= 〇) or (R') 2P (= S), wherein R1, R2, and I are independently alkyl, aromatic, aminealkyl, alkylamino, alkoxy, or alkoxyaryl; R is independently alkyl, aromatic, alkane Aryl, alkoxy, alkoxyaryl; and when R is independently alkyl, aryl, alkaryl, aralkyl, aminoalkyl, alkylamin, alkyl When an oxy group or an alkylsilyl group, or a substituent containing Cn, C00r4 (where 取代 is η or an alkyl group), or a heterocyclic group, Z is independently a fluorocarbon group. The alkyl group referred to in this specification may be a branched or unbranched bond, and may contain 1 to 18 ', preferably 1 to 1 carbon atom, such as methyl, ethyl, propyl, or butyl. The alkyl group may be a branched chain or an unbranched chain, and may contain 1 to 18, preferably 1 to 10 carbon atoms, such as a gas methyl group (_CH2C1). Aromatic groups may contain 6 to 10 carbon atoms, such as phenyl. Burned aryl or aralkyl may contain 7 to 20, preferably 7 to 15 carbon atoms; an example of burned aryl is methylbenzyl (C0H4-CH3), an example of arylalkyl is benzyl Fluorenyl (1-CH2-CeHs) ° The halogenated aryl group may contain 7 to 20, preferably 7 to 15 carbon atoms, such as trifluoromethylphenyl. Each of the alkyl groups on the aminoalkyl group may contain 1 to is, preferably 1 to 10 carbon atoms. This amine alkyl can be primary, secondary, or tertiary. Specific examples include aminoamido (monoCH2-NH2), methylamidomethyl (monoCH2-NH (CH3)), and diamidoaminomethyl (monoCH2-N (CH3) 2). The alkyl group on the alkylamino group may each contain 1 to 18, preferably 丄 to 10 carbon atoms. This alkylamino group can be secondary or tertiary. Specific examples include a methylamine η 1238166 group (mono-NH-CH3) and a dimethylamino group (mono-N (CH3) 2). The alkoxy group may contain 1 to 18, preferably 1 to 10 carbon atoms. Specific examples include fluorenyloxy and ethoxy. The alkoxyaryl group may have 7 to 24, preferably 7 to 16 carbon atoms. For example, methoxyphenyl. The alkylsilyl group may contain 1 to 20, preferably 1 to 10 carbon atoms. Specific examples include trimethylsilyl (Si (CH3) 3), dimethylsilyl (SiH (CH3) 2), and dimethylethylsilyl; --Si (CH3 ) 2 (C2H5)) 〇 One preferred embodiment of the thiocarbonylthio compound of the present invention is shown by the chemical formula (la):

Where Z is a fluorocarbon group, an alkyl group, a haloalkyl group, an aromatic group, an alkaryl group, a haloalkaryl group, an aryl group, an aminoalkyl group, an alkylamino group, :) , Alkoxyaryl, alkylthio or alkylthioaryl; R8 is fluorene, alkyl, alkoxy, haloalkyl, haloalkyl or alkylthio. A preferred embodiment of the thiocarbonylthio compound of the present invention is shown by the chemical formula (lb):

ch2so2

12 1238166 wherein R9 and R9 are independently Η, CH3, 0CH3 or CF3. Another preferred embodiment of the sulfur% sulfur-based compound of the present invention is shown in Chemical Formula (Ic):

S T7 n \ / R10 ^ 2n + l ^ n S (Ic) where R1 () is independently alkyl, aromatic, alkaryl, aralkyl, amine alkyl, alkylamino, alkoxy, alkane Thio or alkyhilyl, or substituents containing CN, C = 0, COOR4, OU ^ ShR3 or heterocyclic group, wherein & and R ^ 〇R3 are independently alkyl, aryl «, amine An alkyl group, an alkylamino group, an alkyloxy group, or an alkyloxyaryl group, as fluorene or an alkyl group; and η is an integer from 1 to 10. Another preferred embodiment of the sulfur number sulfur-based compound of the present invention is shown by the chemical formula (Id):

S

(Id) Another preferred embodiment of the thiosulfanyl compound of the present invention is shown by the chemical formula (Ie):

(Ie) 13 1238166 Another preferred embodiment of the sulfur thiothio compound of formula T

S f3ct (If) / CH3c \ cnh: Another invention-purpose, provide-a sulfur-based compound capable of living radical polymerization, as shown in chemical formula (u):

S

T / (CR6R7) nS〇2 | R5 m (Π) where ^ is a fluorocarbon group, a xyl group, a sintered group, an aromatic group, a material group, a fluorenyl group, an aviation group, a test group, a silk group, and oxygen Aryl, fluorenyl, and thiol = "(= 〇) or (R,) 2p (= s), where R is independently a city group, an aromatic group, an aryl group, a thiol group, and an oxyaryl group R5 is a substituent of xyl, aryl, aryl, aryl, aryl, oxo, thio, thio, or 纟 CN, C_-0, C00R4, postal or heterocyclic substituent, where &, R2, and R3 are independently a alkynyl group, a aryl radical, a kynyl group, a alkynyl group, an alkoxy group, or an alkoxyaryl group, and the alkoxy group; 1, and in are any vocal child greater than zero f / +., ^, ^ 7 The positive number is preferably an integer from 1 to 10. Among them, each substituent is as defined above. t Another aspect of the invention—the purpose and the provision—can be used for living radical polymerization. The thiocarbonylthio compound is as shown in Chemical Formula ⑴ 丨): 14 1238166

Rll (III) where

Rl 1 is independently :): aryl, aryl, :): aryl, aryl, amine: (: aryl, fluorenyl or alkylsilyl, or containing C = 0, COOR4 (R4 is fluorenyl or alkynyl), CRiR2S02R3 or a heterocyclic substituent, wherein R, R2 and R3 are independently alkynyl, aromatic, amine alkyl, alkylamino, alkoxy or alkane Oxyaryl; n is an integer from 1 to 10; and m is any integer greater than zero, and the most preferred is an integer from 1 to 10. wherein each substituent is as defined above. Another object of the present invention Provided is a radical polymerization method, comprising: polymerizing at least one vinyl monomer in the presence of a thiocarbonylthio compound represented by formula (I), (II), or (III), or compounding one or more Polymerizable vinyl monomers. The aforementioned mono- or copolymerizable vinyl monomer systems include acrylic acid and its salts | members, acrylates, methacrylic acid and its salts, methacrylates, Acrylonitriles, Styrene, Acrylamides, Gf Vinyl Acetate, Butadiene, Isoprene Rene), norbornene and its derivatives, vinyl chloride, alpha-olefins such as ethylene, 1-hexene, etc. or mixtures thereof. For example : Styrene, p-fluorenylstyrene, ethyl acrylate (including all isomers), butyl acrylic acid (including all isomers), 2-hydroxyethyl acrylate (2-hydroxyethyl acrylate), Isobornyl acrylate, acrylic acid, benzyl acrylate, phenyl acryl, N, N-dimethylamino ethyl methacrylate Ester (N, N-dimethylaminoethyl methacrylate), methacrylic acid 15 1238166 methyl methacrylate, borneol, acetonitrile, butadiene and ethene etc. In the formula (I), (Π) or ( III) The molecular weight of the obtained polymer can be controlled in the presence of the thiocarbonylthio compound and a free radical initiator shown in the figure. The molecular weight distribution of the obtained polymer is usually in the range of 1.05 to 2.5, and the preferred one can be reduced to In the range of 1.05 to 1.5, the better can be reduced to the range of 1.05 to 1.3. The free radical compounds or free radical initiators are not necessarily limited, and can be any suitable for traditional free radical polymerization. Taking thermally initiated homolytic compounds as examples include peroxides, peroxyesters, or azos. Compounds, such as 2,2'-azobis (isobutyronitrile) (AIbis), 2,2'-azobis (cyclohexanenitrile), 4,4'-azobis (4-cyano Valeric acid), diacyl peroxides and di-tert-butyl peroxide. Either free radicals are generated by the monomers themselves, such as styrene, or free radicals are generated by methods such as reduction oxidation and photochemistry. Generally speaking, the molar ratio of free radical initiator and chain transfer (RAFT) reagent is usually in the range of 10/1 to 1/10, and the better can be reduced to the range of 5/1 to 1/5. The better can fall to the range of 2/1 to 1/5. The polymer obtained by the present invention may be a monopolymer or a copolymer. Various copolymers with clear structure can be obtained, including (1) block copolymers with narrow molecular weight distribution (two or more blocks), (2) graft copolymers with narrow molecular weight distribution, and (3) ladder. ) Copolymers, (4) star copolymers, and (5) hyperbranched copolymers; various polymers with terminal functional groups can also be prepared. The preparation of various novel polymers can provide new materials with novel physical properties for industrial application. This will not only enhance the properties of current products, but also accelerate the development of new products. The polymer materials developed by the present invention can be applied in many fields, including dispersants (such as pigment dispersants in inks), photoresists, surfactants, surface treatment agents, adhesives, and rheology controllers. , Coatings, and thermoplastic elastomers. In the following, the method, features and advantages of the present invention will be further explained through several examples. However, it is not intended to limit the scope of the present invention. The scope of the present invention shall be based on the scope of the attached patent application. Example 1 Preparation of a chain transfer reagent (Ib-1) In a mixture of methanol (15 ml), sulfur (0.06 mol, 1.92 g), and a sodium methoxide methanol solution (30%; 12ML), in P-methoxybenzyl chloride (0.03 mol, 3.8 g) was added dropwise over 1 hour. The reaction mixture was stirred vigorously at 70 t for 3 hours. After the reaction solution was cooled to room temperature, it was transferred to a solution (acetonitrile) containing bromomethylphenyl sulfone, and refluxed with a force σ for 6 hours. After the solution was cooled to room temperature, the insoluble matter was filtered off, and the volatiles were vacuum-dried, and the crude product was separated by column chromatography (ethyl acetate / hexane: 2/3). Acetone / Hex :): After recrystallization at low temperature, an orange-red oil (lb-1) was obtained.

Example 2 Preparation of low molecular weight distribution poly (t-butyl acrylate) using a chain transfer reagent (Ib-1) t-butyl acrylate (5 ml), toluene (2.5 ml), AIBN (6.2 mg), and chain transfer Reagent (Ib-1) (26 mg) was placed in a Schlenk tube. Degassing of the solution was performed by four cold-gas-exhaust-thaw cycles. Then, it was heated at 60 ° C for 15 hours to obtain poly (butyl acrylate). The conversion of the obtained polymer was 17 1238166 70%, its Mn = 39814 and Mw / Mn = 1.18. Example 3 compares the effect of the chain transfer reagent of Example 2 The procedure is the same as that of Example 2, except that the compound (lb-1) is replaced by the compound (IV). The compound (II) is a chain transfer agent used in WO 98/01478. The obtained polymer had Mn = 24600 and Mw / Mn = 1.33. The conversion rate of the obtained polymer was 42%, and the GPC spectrum of this polymer showed a small peak of high molecular weight in addition to the main peak. This small peak of high molecular weight did not exist in the RAFT agent (lb-1) polymer. GPC spectrum. From this, it can be seen that the compounds of the present invention can be used to obtain polymers with a low molecular weight distribution (Mw / Mn) at high monomer conversion.

Example 4 Preparation of low molecular weight distribution poly (styrene) using a chain transfer reagent (Ib-1) Styrene (5 ml), toluene (2.5 ml), AIBN (7.2 mg), and a chain transfer reagent (Ic-1 ) (30 mg) in a Schlenk tube. Four cold-knock-pump-thaw cycles were performed to complete the degassing of the solution. Then, it was heated at 60 ° C for 45 hours to obtain poly (styrene). Its conversion rate was 60%, Mn = 35715, Mw / Mn = 1.26. Example 5 was prepared using a chain transfer reagent (Ib-1). Poly (methyl methacrylate) with low molecular weight distribution Put methacrylate (5ml), toluene (2.5ml), AIBN (7.8mg), and chain transfer reagent (Ic-1) (26mg) in a Schlenk In the tube. Four freeze 18 1238166-pump-thaw cycles were performed to complete the degassing of the solution. Then, heated at 60 ° C for 15 hours, poly (methyl methacrylate) was obtained. The conversion rate was 92%, Mn = 59886, and Mw / Mn = 1.19. Example 6 Preparation of a chain transfer reagent (Id)

f3c. (Id) Take a solution of sulfur oxychloride (S02C12) in methane (0.02 mol, 10ML) and slowly add phenyl (2,2,2-trifluoroethyl) sulfide (benzyl (2,2,2_trifluoroethyl) ) sulfide) in dichloroarsine (0.01 mol, 20ML) solution. After vigorously stirring at room temperature for 3 hours, the solvent was removed under vacuum (0.2 torr) at room temperature. A yellow transparent liquid was obtained, which was benzyl (1,1-dichloro-2,2,2-trifluoroethyl) sulfide. . iHNMR ^ CDCb, ppm): 4.21; 7.30 〇 Take the aforementioned phenyl (1,1-digas · 2,2,2-trifluoroethyl) sulfide (0.008 mol) and ZnS (0.16 mol) (ZnS reference Bull · Soc. Chim · Fr (1997) 134, 697) was placed in a round bottom flask of acetonitrile (16 ML) and heated to reflux for 12 hours. After cooling to room temperature, the precipitate was filtered. The obtained filtrate was first distilled off the solvent under atmospheric pressure, and then subjected to fractional distillation under reduced pressure to obtain a red liquid, namely benzyl trifluorodithioacetate (If). iHNMR (CDCh, ppm): 4.42; 7.30. Example 7 Preparation of low molecular weight poly (19-1238166 t-butyl acrylate) using a chain transfer reagent (Id) t-butyl acrylate (3 ml), toluene (1 ml), AIBN (4.29 mg), and a chain transfer reagent (Id) (l2.5 mg) was placed in a Schlenk tube. Defreeze the solution by performing four freeze-pump-thaw cycles. Then, at 60. Poly (butyl methacrylate) can be obtained by heating for MH at 0 ° C, Mn = _〇, Mw paper = ι · 3. As described above on bismuth, the present invention provides a new thiocarbonylthio compound, the synthesis and purification steps are relatively simple, and the polymerization of acrylate ㈣ has a faster polymerization rate and high conversion rate, and for molecular weight and molecular weight The distribution can still have a high degree of clarity. This has been disclosed in the example of the car and the above. However, it is not intended to limit what is defined in this hairline. Ｍ 月 之 保 si_ Please attach a patent in the attached text [Simplified illustration of the drawing] None 20

Claims (1)

Volume 12381 No. 634827 Patentable scope: Thiocarbonylthio compounds that can undergo living radical polymerization, such as the chemical s / R z / (I) where R is CRil ^ SC ^ I ^, Z is independently a fluorocarbon, alkane Group, haloalkyl group, aromatic group, aryl group, aromatic group, square group, square group, aminoalkyl group, alkylamino group, alkoxy group, alkoxy group, thio group, Thiothioaryl, (R ') 2P (= 〇) or (R') 2P (= S), where 112 and R3 are independently alkyl, aromatic, amine alkyl, alkylamino, alkoxy Or alkoxyaryl, R ′ is independently alkyl, aryl, aryl, aryl, aryl, or aryl; and when R— is independently aryl, aryl, or aryl, Aryl, aminoalkyl, alkylamino, oxy or alkylsilyl, or CN, COOR4 or CN, CQOR4 (where R4 is Η or alkyl), When substituted as a heterocyclic group, Z is independently a fluorocarbon group. 2. The thiocarbonylthio compound according to item 1 of the application scope, wherein the compound is represented by the chemical formula (la): Z ch2s〇2 r8 (la) where Z is a fluorocarbon fluoro group, xyl group, haloxyl group, aromatic group, aryl group, halogen aryl group, aryl group, aminoalkyl group, :): alkylamino group ), :): Endoxy, alkoxyaryl, alkylthio or alkylthioaryl; R8 is fluorene, alkyl, alkoxy, haloalkyl 12 1238166, haloalkyl or alkylthio. 3. The thiocarbonylthio compound according to item 1 of the scope of application, wherein the compound is represented by the chemical formula (lb): S R9 r9 (lb) where R9 and R9 'are independently Η, CH3, OCH3, or CF3. 4. The thiocarbonylthio compound according to item 1 of the application scope, wherein the compound is represented by the chemical formula (Ic): S Wherein Rio is independently an alkyl group, an aromatic group, an aromatic group, an aromatic group, an amine group, an amine group, an alkoxy group, an alkylthio group, or an alkylsilyl group, or CN, 00, or C. 〇R4, 〇1128〇2113 or heterocyclic substituents, wherein Ri, 112 and R3 are independently alkyl, aromatic, amine alkyl, alkylamino, alkoxy or alkoxyaryl, r4 Is fluorene or alkyl; and η is an integer from 1 to 10. 5. The thiocarbonylthio compound according to item 4 of the application scope, wherein the compound is represented by the chemical formula (Id): 22 1238166 S f3c (Id) wherein the compound is represented by the chemical formula (Ie) of a thiocarbonylthio compound as described in item 1 of the scope of application: s ch3 / / = c2F5 ^ s ^ CH V, (Ie) wherein the compound is as 7. The chemical formula (If) of the thiocarbonylthio compound as described in item 1 of the scope of application: • The thiocarbonylthio compound as described in item 3 of the scope of application is represented by the chemical formula (Ib-1): wherein the compound is as S s / CH2S〇2 (Ib-1) 23 1238166 9. A thiocarbonylthio compound capable of living radical polymerization, as shown in chemical formula (Π): S (z ^ \ s / (CR6R7) nS〇2 + R5 (II) where z is the reason Fluorotinyl, alkynyl, alkynyl, aryl, aryl, aryl, aralkyl, amine alkyl, alkylamino, alkoxy, alkoxyaryl, alkylthio, alkyl Thioaryl, (R ') 2P (= 〇) or (R') 2P (= S), where R is independently alkyl, aryl, alkaryl, alkoxy, alkoxyaryl ; R5 is alkyl, aryl, alkaryl, aryl: ^, alkoxy, sulfuryl, thiol, or substituted with CN, C = 0, COOR4, CRiR2S02R3 or heterocyclic group Group, wherein Ri, R2 * r3 are independently alkyl, aromatic, amine alkyl, alkylamino, alkoxy or alkoxyaryl, and fluorene is alkyl; R6 and R7 are independently fluorene and alkyl , Aromatic group, alkaryl group, aralkyl group; n is 0 or 1; and m is any integer greater than zero. 10 · The sulfur thiosulfide compound described in the scope of item 9 of Shenqiao Patent, wherein the chemical formula ( I!) M is an integer from 1 to 10. 11. An active self Thion radical polymerization reactions of sulfur compounds, such as the Department of Chemical Formula (III) below: F2n + 1 Rll 24 (III) 1238166 wherein Ru is independently alkyl, aromatic, alkaryl, aralkyl, amine alkyl, alkoxy, or alkylsilyl, or containing 〇, 〇〇〇4 R4 & H or alkyl), cr! R2S02R3 or heterocyclic substituents, wherein Ri, r2 * are independently alkyl, aromatic, amine alkyl, alkylamino, alkoxy or alkoxy Aryl; integers from 1 to 10; and m is any integer greater than zero. 12. The thiocarbonylthio compound according to item 11 of the scope of patent application, wherein ㈤ is an integer from 10 to 10. 13. · A type of free radical polymerization method includes: polymerizing at least one vinyl monomer in the presence of a sulfur thiosulfide compound as described in items i, 9 and 11 of the scope of patent application, wherein The structure of the aforementioned thiocarbonylthio compound is as shown in Chemical Formula VII, (II) or (III), wherein all substituents are as defined above. (III) 'wherein the aforementioned ethylene methacrylic acid and its salt 14. The radical polymerization method according to item 13 of the application scope includes acrylic acid and its salts, acrylates, 25 1238166, and Acrylic acids, acrylics, acrylonitriles, acrylonitriles, aCi7lamides, vinyl acetate (batch), butadiene, isoprene, etc. , Norbomene and its derivatives, ethylene, a'efm, or mixtures thereof. 1 5. The radical polymerization method as described in item 13 of the scope of claim, wherein the method comprises a thiocarbonylthio compound represented by one of the chemical formula (), (II) or (III) and a free radical starting In the presence of an initiator, at least one vinyl monomer is polymerized or one or more polymerizable vinyl co-monomers are blended. 16. The free-radical polymerization method according to item 15 of the claim, wherein the aforementioned free radical initiator may be a peroxide, a peroxyester, or an azo compound. W. The free-radical polymerization method according to item 15 of the application, wherein the aforementioned free-radical initiator is a monomer which can be cleaved by itself, or a radical is generated by a reduction oxidation or photochemical method as an initiator. 18_ The free-radical polymerization method according to claim 13, wherein the molecular weight distribution of the obtained polymer is in the range of 1.05 to 2.5. 19. The free-radical polymerization method as described in item 18 of Shen Yan's scope, wherein the knife of the obtained polymer is distributed in the range of 1.05 to 1.5. 20. The free-radical polymerization method according to item 19 of the scope of application, wherein the molecular weight distribution is in the range of ... to ". The radical polymerization method according to item 18 of the claim, wherein the molar ratio of the aforementioned radical initiator and thiocarbonylthio compound is in the range of 10/1 to 1/10. A radical polymerization method according to claim 19, wherein the molar ratio of the aforementioned free radicals and thiocarbonylthio compounds is in the range of 5/1 to 1/5. 2. The radical polymerization method according to claim 20, wherein the molar ratio of the aforementioned radical 26 1238166 initiator to the thiothio compound is in the range of 2/1 to 1/5. 27