A method for preparing sulfur-containing polymers based on isomerization-driven irreversible ring-opening polymerization

Abstract

This invention discloses a method for preparing sulfur-containing polymers based on isomerization-driven irreversible ring-opening polymerization. The method includes: in an organic solvent, in the presence of a main catalyst, carrying out a polymerization reaction of one or more monomers; wherein the main catalyst is an anionic or cationic catalyst; the anionic catalyst is a phosphononitrile base, guanidine organic base, amidine organic base, N-heterocyclic carbene organic base, N-heterocyclic olefin organic base, carboxylate, or thiocarboxylate; the cationic catalyst is a zwitterionic catalyst, a neutral Lewis acid catalyst, or a protic acid (ester) catalyst; and the monomer is a five-membered ring skeleton compound as shown in Formula I. This method provides convenience for the industrial production of environmentally friendly sulfur-containing polymer materials. The synthesized sulfur-containing polymer has advantages such as high molecular weight, wide-range tunable physical properties, and excellent degradability, and can be used as plastics, rubber, elastomers, fibers, and other products.

Description

Technical Field

[0001] This invention relates to a sulfur-containing polymer and a method for preparing the sulfur-containing polymer based on isomerization-driven irreversible ring-opening polymerization. Background Technology

[0002] Unstrained five-membered ring monomers are a class of highly promising renewable monomers, widely found in natural products and capable of large-scale production from starch, lignocellulose, or carbon dioxide. However, ring-opening polymerization (ROP) of unstrained five-membered ring monomers at room temperature is generally thermodynamically forbidden. These compounds are often referred to as "non-polymerizable" monomers in literature and textbooks because their unstrained five-membered rings cannot provide sufficient ring strain to drive ROP. Furthermore, since ring-opening polymerization is a typical thermodynamic equilibrium of polymerization / depolymerization, thermodynamically stable five-membered ring lactones are prone to depolymerization during polymerization. In 2016, Hong and Chen pioneered a new strategy for the ring-opening polymerization of unstrained five-membered ring lactones (Nat. Chem. 2016, 8, 42-49), which disrupts the polymerization-depolymerization equilibrium by controlling the reaction temperature below the upper limit of polymerization and causing polymer precipitation. However, the extremely low polymerization temperature severely hinders its applicability to industrial production.

[0003] In a previously disclosed polymerization reaction catalyzed by an anionic catalyst, a five-membered ring thiocarbonyl lactone monomer, after being dehydrogenated by a basic anionic catalyst, can undergo nucleophilic attack on the γ-methylene (methoxy) group of the monomer to undergo isomerization and ring-opening polymerization, or it can undergo nucleophilic attack on the thiocarbonyl group of another monomer molecule to lose a molecule of hydrogen sulfide and undergo an ester condensation reaction, generating a dimer product rather than a polymer (as shown below). How to limit the latter ester condensation reaction is the key to whether the polymerization can proceed efficiently.

[0004]

[0005] To date, there is still a lack of a universal method for efficiently polymerizing stress-free five-membered ring monomers under mild conditions to prepare sustainable polysulfide materials with varying properties. Summary of the Invention

[0006] The technical problem this invention aims to solve is to overcome the shortcomings of existing non-strained five-membered ring monomers, which are difficult to ring-open polymerize under mild conditions, and to provide a new method for irreversible ring-opening polymerization. The preparation method of this invention facilitates the industrial production of environmentally friendly sulfur-containing polymer materials. The synthesized sulfur-containing polymers have advantages such as high molecular weight, wide-range tunable physical properties, and excellent degradability, and can be used as plastics, rubbers, elastomers, fibers, and other products.

[0007] This invention provides a method for preparing a sulfur-containing polymer, comprising the following steps: in an organic solvent, in the presence of a main catalyst, performing a polymerization reaction on one or more polymeric monomers;

[0008] The main catalyst is either an anionic or a cationic catalyst; the anionic catalyst is one or more of the following: phosphononitrile base, guanidine organic base, amidine organic base, N-heterocyclic carbene organic base, N-heterocyclic olefin organic base, carboxylates, and thiocarboxylates; the cationic catalyst is one or more of the following: zwitterion-pair catalyst, neutral Lewis acid catalyst, and proton acid (ester) catalyst.

[0009] The polymeric monomers are independently compounds as shown in formula (I):

[0010]

[0011] in, for

[0012] R 11 R 12 R 13 R 14 R 21 R 22 R 23 R 31 R 32 R 33 R 41 R 42 R 43 R 51 R 52 R 53 and R 54 Independently, H, halogen (e.g., fluorine, chlorine, bromine, or iodine, or again, fluorine or chlorine), hydroxyl group, C 1-10 Alkyl (e.g., C10) 1-8 Alkyl groups, such as methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-nonyl), C 6-10 Aryl (e.g., phenyl) or C 1-10 alkenyl (e.g., C) 1-8 alkenyl, for example C 1-4 Alkenyl, or for example vinyl); the C 1-10 Alkyl groups are optionally surrounded by halogens (e.g., fluorine, chlorine, bromine, or iodine, or again, fluorine or chlorine), hydroxyl groups, and C. 6-10 One or more substitutions in an aryl group (e.g., phenyl);

[0013] Or, R 12 and R 13 R 13 and R14 R 22 and R 23 R 32 and R 33 R 42 and R 41 、or R 52 and R 53 Together with the atoms that connect them, they form C 3-10 Cycloalkyl (e.g., cyclopentyl, cyclohexyl, or cycloheptyl), C 3-10 Cycloalkenyl (e.g., cyclohexenyl) or C 6-10 Aryl (e.g., phenyl);

[0014] When the main catalyst is an anionic main catalyst, then R 11 R 12 R 21 R 22 R 31 R 32 and R 41 All are H;

[0015] When the main catalyst is an anionic catalyst, and the polymer monomer is of one type, then the polymer monomer is not...

[0016] In some implementation schemes, R 11 R 12 R 13 R 14 R 21 R 22 R 23 R 31 R 32 R 33 R 41 R 42 R 43 R 51 R 52 R 53 and R 54 Independently, H, halogen (e.g., fluorine, chlorine, bromine, or iodine, or again, fluorine or chlorine), hydroxyl group, C 1-10 Alkyl (e.g., C10) 1-8 Alkyl groups, such as methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-nonyl) or C 1-10 alkenyl (e.g., C) 1-8 alkenyl, for example C 1-4 Alkenyl, or for example vinyl); the C 1-10 Alkyl groups are optionally surrounded by halogens (e.g., fluorine, chlorine, bromine, or iodine, or again, fluorine or chlorine), hydroxyl groups, and C. 6-10 One or more substitutions in aryl (e.g., phenyl).

[0017] In some embodiments, the compound represented by formula (I) has any of the following structures:

[0018]

[0019]

[0020] In some implementation schemes, for

[0021] Preferably, R 11 R 12 R 13 and R 14 Independently for H and C 1-10 Alkyl or C 1-10 alkenyl; or, R 13 and R 14 Together with the atoms that connect them, they form C 3-10 cycloalkyl;

[0022] More preferably, R 11 R 12 R 13 and R 14 It has the following definition:

[0023] (1)R 11 R 12 and R 13 For H, R 14 C 1-10 alkyl;

[0024] (2)R 11 R 12 and R 14 For H, R 13 C 1-10 Alkyl or C 1-10 alkenyl;

[0025] (3)R 12 R 13 and R 14 For H, R 11 C 1-10 alkyl;

[0026] (4)R 13 and R 14 For H, R 11 and R 12 Independently for C 1-10 alkyl;

[0027] (5)R 12 and R 14For H, R 11 and R 13 Independently for C 1-10 alkyl;

[0028] (6)R 11 and R 12 For H, R 13 and R 14 Together with the atoms that connect them, they form C 3-10 cycloalkyl;

[0029] (7)R 11 R 12 R 13 and R 14 For H;

[0030] In some implementation schemes, for

[0031] Preferably, R 12 and R 13 Together with the atoms that connect them, they form C 3-10 cycloalkyl;

[0032] More preferably, R 11 and R 14 For H, R 12 and R 13 Together with the atoms that connect them, they form C 3-10 Cycloalkyl.

[0033] In some implementation schemes, for

[0034] Preferably, R 51 R 52 R 53 and R 54 Independent of H, halogen, C 1-10 Alkyl, C 6-10 Aryl or C 1-10 alkenyl; the C 1-10 Alkyl groups are optionally coated with halogens, hydroxyl groups, and C. 6-10 One or more substitutions in the aryl group.

[0035] More preferably, R 51 Halogens (e.g., fluorine), C 1-10 Alkyl (e.g., methyl, ethyl), C 6-10 Aryl (e.g., phenyl) or C 1-10 Alkenyl (e.g., vinyl); the C 1-10 Alkyl groups may optionally be substituted with chlorine, hydroxyl, or phenyl; R 52 R 53 and R54 For H.

[0036] In some implementation schemes, for

[0037] Preferably, R 51 R 52 R 53 and R 54 Independently H or C 1-10 alkyl.

[0038] More preferably, R 51 C 1-10 Alkyl, R 52 R 53 and R 54 For H.

[0039] In some preferred embodiments, the compound represented by formula (I) has any of the following structures:

[0040]

[0041] In some embodiments, the polymerization reaction is preferably carried out under a protective gas atmosphere, which can be a conventional protective gas in the art, such as nitrogen and / or argon. The protective gas described in this invention is an inert gas as described in the art.

[0042] In some embodiments, the molar volume ratio of the polymeric monomer to the organic solvent may be a conventional molar volume ratio in the art, preferably 0.2 mol / L-10 mol / L, more preferably 2.0 mol / L-7.0 mol / L, for example 2.0 mol / L or 5.0 mol / L.

[0043] In some embodiments, the organic solvent may be a conventional organic solvent in the art.

[0044] Preferably, the organic solvent is one or more of straight-chain hydrocarbon solvents, halogenated hydrocarbon solvents, cyclic ether solvents, aromatic hydrocarbon solvents, halogenated aromatic hydrocarbon solvents, and amide solvents, such as aromatic hydrocarbon solvents and / or amide solvents, and for example, toluene and / or N,N-dimethylformamide. The straight-chain hydrocarbon solvent is preferably one or more of n-hexane, n-heptane, and n-pentane. The halogenated hydrocarbon solvent is preferably one or more of dichloromethane, trichloromethane, 1,2-dichloroethane, and tetrachloroethane. The cyclic ether solvent is preferably tetrahydrofuran and / or dioxane. The aromatic hydrocarbon solvent is preferably one or more of toluene, benzene, and xylene, more preferably toluene. The halogenated aromatic hydrocarbon solvent is preferably one or more of o-dichlorobenzene, o-difluorobenzene, o-dibromobenzene, chlorobenzene, fluorobenzene, bromobenzene, and mesitylene, more preferably o-dichlorobenzene. The amide solvent is preferably N,N-dimethylformamide.

[0045] In some embodiments, the molar ratio of the polymerizable monomer to the main catalyst can be a conventional molar ratio in the art, preferably 20:1-1600:1, more preferably 100:1-1600:1, and even more preferably 400:1-1600:1, such as 400:1, 1200:1 or 1600:1.

[0046] In some embodiments, the phosphononitrile base in the anionic main catalyst can be a conventional phosphononitrile base in the art. Preferably, the phosphononitrile base has the following structure:

[0047]

[0048] Wherein, R and R' are independently C1-C4 alkyl groups (e.g., methyl, ethyl, propyl, isopropyl, or tert-butyl); n1 is 0, 1, 2, or 3; and y is 0, 1, 2, or 3.

[0049] More preferably, the phosphononitrile base is 1-tert-butyl-4,4,4-tris(dimethylamino)-2,2-bis[tris(dimethylamino)-n-phosphine-imideamino]-2λ 5 ,4λ 5 -Bis(phosphorus nitrogen compounds) t Bu-P4), its structure is shown below:

[0050]

[0051] More preferably, the phosphononitrile base may also be tert-butylimino-tris(dimethylamino)phosphonium ( t Bu-P1), whose structure is shown below:

[0052]

[0053] In some embodiments, the guanidine organic base in the anionic main catalyst may be a conventional guanidine organic base in the art. Preferably, the guanidine organic base is 1,5,7-triazidobicyclo(4.4.0)dec-5-ene (TBD) and / or 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene (MTBD), the structure of which is shown below:

[0054]

[0055] In some embodiments, the amidine organic base in the anionic main catalyst may be a conventional amidine organic base in the art. Preferably, the amidine organic base is 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), whose structure is shown below:

[0056]

[0057] In some embodiments, the N-heterocyclic carbene organic base in the anionic main catalyst can be a conventional N-heterocyclic carbene organic base in the art. Preferably, the N-heterocyclic carbene organic base has the following structure:

[0058]

[0059] Among them, R 1a and R 2a Independently hydrogen, alkyl (e.g., C10) 1-4 alkyl) or aryl (e.g., C) 6-10 Aryl); R 3a and R 4a Independently alkyl (e.g., C10) 1-4 alkyl) or aryl (e.g., C) 6-10 Aryl).

[0060] More preferably, the N-heterocyclic carbene organic base is 1,3-di-tert-butylimidazolium-2-ylene(I t Bu), whose structure is shown below:

[0061]

[0062] In some embodiments, the N-heterocyclic olefin organic base in the anionic main catalyst may be a conventional N-heterocyclic olefin organic base in the art. Preferably, the N-heterocyclic olefin organic base has the following structure:

[0063]

[0064] Among them, R 1b and R 2b Independently hydrogen, alkyl (e.g., C10)1-4 alkyl) or aryl (e.g., C) 6-10 Aryl); R 3b and R 4b Independently alkyl (e.g., C10) 1-4 alkyl) or aryl (e.g., C) 6-10 Aryl); R 5b It is hydrogen or alkyl (e.g., C10) 1-4 alkyl).

[0065] More preferably, the N-heterocyclic olefinic organic base is 1,3,4-trimethyl-2-(isopropenyl)-imidazolium (NHO), whose structure is shown below:

[0066]

[0067] In some embodiments, the carboxylate in the anionic main catalyst may be a metal carboxylate or an organic carboxylate.

[0068] Preferably, the anions in the metal carboxylate and organic carboxylate independently have the following structures:

[0069]

[0070] Among them, R 1c Alkyl (e.g., C10) 1-4 Alkyl groups, such as methyl groups, or aryl groups, such as C4 groups, are used to form alkyl groups. 6-10 Aryl).

[0071] More preferably, the anion in the metal carboxylate and the organic carboxylate is independently an acetate anion.

[0072] Preferably, the cation in the metal carboxylate is an alkali metal cation (e.g., lithium, sodium, potassium, rubidium, or cesium, or potassium).

[0073] Preferably, the cation in the organic carboxylate is a quaternary ammonium cation, an imidazolium cation, a phosphononitrile cation, a bis(triphenylphosphine)ammonium cation, or an amidon cation.

[0074] More preferably, the cation in the organic carboxylate has any of the following structures:

[0075]

[0076] Among them, R 1d R 2d R 3d R 4d R 5d and R 6d Independently hydrogen, alkyl or aryl, n2 is 0, 1, 2 or 3; y2 is 0, 1, 2 or 3.

[0077] In some embodiments, the thiocarboxylate in the anionic main catalyst may be a metal thiocarboxylate.

[0078] Preferably, the anion in the thiocarboxylate has the following structure:

[0079]

[0080] Among them, R 1e Alkyl (e.g., C10) 1-4 Alkyl groups, such as methyl groups, or aryl groups, such as C4 groups, are used to form alkyl groups. 6-10 (Aryl). Preferably, the anion is a thioacetic acid anion.

[0081] Preferably, the cation in the thiocarboxylate is an alkali metal cation (e.g., lithium, sodium, potassium, rubidium, or cesium, or potassium, for example).

[0082] More preferably, the thiocarboxylate is potassium thioacetate.

[0083] In some preferred embodiments, the anionic main catalyst may be a phosphononitrile base and / or a thiocarboxylate, such as 1-tert-butyl-4,4,4-tris(dimethylamino)-2,2-bis[tris(dimethylamino)-n-phosphinemylidene]-2λ 5 ,4λ 5 -Bis(phosphorus nitrogen compounds) t Bu-P4) and / or potassium thioacetate.

[0084] In some embodiments, the zwitterionic catalyst in the cationic main catalyst may be a conventional zwitterionic catalyst in the art.

[0085] Preferably, the zwitterionic catalyst has the following structure:

[0086] [R] + [X] -

[0087] (VIII)

[0088] Wherein, the [R] + The [X]- is a carbocation, silicon cation, oxonium ion, thioonium ion, thioonium ion, chloride ion, bromium ion, or iodonium ion, and the [X]- is a borate anion, aluminate anion, phosphate anion, sulfonic acid anion, sulfonylimide anion, antimony anion, or arsenate anion.

[0089] More preferably, the carbocation has the following structure:

[0090]

[0091] Among them, R 1f R 2f R 3f It is independently phenyl, 2,4,6-trimethylphenyl, 2,6-dimethylphenyl, 2,3,5,6-tetramethylphenyl or 2,6-diisopropylphenyl.

[0092] More preferably, the silicon positive ion has the following structure:

[0093]

[0094] Among them, R 1g R 2g and R 3g Each of the following can be independently hydrogen, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, phenyl, 2,4,6-trimethylphenyl, 2,6-dimethylphenyl, 2,3,5,6-tetramethylphenyl, or 2,6-diisopropylphenyl.

[0095] More preferably, the silicon positive ion may also have the following structure:

[0096]

[0097] Among them, R 1g R 2g and R 3g Each of the following can be independently hydrogen, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, phenyl, 2,4,6-trimethylphenyl, 2,6-dimethylphenyl, 2,3,5,6-tetramethylphenyl, or 2,6-diisopropylphenyl.

[0098] More preferably, the oxonium ion and the thionium ion each have the following structures:

[0099]

[0100] Among them, R 1h R 2h and R 3h Each of the following can be independently hydrogen, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, phenyl, 2,4,6-trimethylphenyl, 2,6-dimethylphenyl, 2,3,5,6-tetramethylphenyl, or 2,6-diisopropylphenyl.

[0101] More preferably, the chloride ion and the bromide ion have the following structures respectively:

[0102]

[0103] Among them, R 1iand R 2i It is independently phenyl, 2,4,6-trimethylphenyl, 2,6-dimethylphenyl, 2,3,5,6-tetramethylphenyl or 2,6-diisopropylphenyl.

[0104] More preferably, the iodine ion has the following structure:

[0105]

[0106] Among them, R 1j and R 2j Each of the following can be independently methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, phenyl, 2,4,6-trimethylphenyl, 2,6-dimethylphenyl, 2,3,5,6-tetramethylphenyl, or 2,6-diisopropylphenyl.

[0107] More preferably, the zeolite ion has the following structure:

[0108]

[0109] More preferably, the borate anion and the aluminate anion have the following structures:

[0110]

[0111] Among them, X 1 X 2 X 3 and X 4 Each of these can be independently fluorine, chlorine, phenyl, pentafluorophenyl, 3,5-di(trifluoromethyl)phenyl, pentafluorophenoxy, or 3,5-di(trifluoromethyl)phenoxy.

[0112] More preferably, the phosphate anion has any of the following structures:

[0113]

[0114] More preferably, the sulfonic acid anion and the sulfonyl imide anion each have the following structures:

[0115]

[0116] Among them, X 1a and X 2a It can be fluorine, methyl, phenyl, trifluoromethyl, pentafluoroethyl, pentafluorophenyl or 3,5-bis(trifluoromethyl)phenyl, respectively.

[0117] More preferably, the antimonyate anion and the arsenate anion have the following structures respectively:

[0118]

[0119] Among them, X 1c X 2c X 3c X 4c X 5c and X 6c Each can be fluorine, chlorine, or bromine, independently.

[0120] More preferably, the [R] + [X] is a carbocation. - The amphoteric catalyst is [Ph3C][B(C6F5)4], for example, the zwitterionic catalyst is [Ph3C][B(C6F5)4].

[0121] More preferably, the [R] + The [X] is an oxonium ion. - The catalyst is a borate anion, for example, the zwitterionic catalyst is [Et3O][B(C6F5)4] or Me3OBF4.

[0122] More preferably, the [R] + The [X] is a zotonium ion. - The amphoteric catalyst is a borate anion, for example, C7H7BF4.

[0123] More preferably, the [R] + The [X] is a silicon positive ion. - The amphoteric catalyst is a borate anion, for example, [Et3Si-H-SiEt3][B(C6F5)4].

[0124] In some embodiments, the neutral Lewis acid catalyst in the cationic main catalyst may be a conventional neutral Lewis acid catalyst in the art.

[0125] Preferably, the neutral Lewis acid catalyst is a boron complex or an aluminum complex.

[0126] More preferably, the boron complex is a trialkylboron or a triarylboron.

[0127] More preferably, the aluminum complex is a trialkylaluminum, a triarylaluminum, an alkylbisphenolaluminum, an alkylaluminum dichloride, or a dialkylaluminum chloride.

[0128] More preferably, the trialkylboron and the trialkylaluminum each have the following structures:

[0129]

[0130] Among them, R 1k R2k and R 3k Each of the following can be independently methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, cyclohexyl, or n-octyl.

[0131] More preferably, the triarylboron and the triarylaluminum each have the following structures:

[0132]

[0133] Among them, R 1n R 2n R 3n R 4n and R 5n Each of the following can be independently hydrogen, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, cyclohexyl, fluorine, chlorine, trifluoromethyl, pentafluorophenyl, or trimethylsilyl.

[0134] More preferably, the alkylbisphenol aluminum has the following structure:

[0135]

[0136] Among them, R 1m R 2m R 3m R 4m R 5m R 6m R 7m R 8m R 9m R 10m and R 11m Each of the following can be independently hydrogen, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, cyclohexyl, fluorine, chlorine, trifluoromethyl, pentafluorophenyl, or trimethylsilyl.

[0137] More preferably, the alkyl aluminum chloride and the dialkyl aluminum chloride each have the following structures:

[0138]

[0139] Among them, R 1o and R 2o Each of the following can be independently methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, cyclohexyl, or n-octyl.

[0140] More preferably, the neutral Lewis acid catalyst is a boron complex (e.g., triarylboron, or B(C6F5)3).

[0141] More preferably, the neutral Lewis acid catalyst is a triarylborane compound, more preferably a fluorinated triarylborane compound; for example, B(C6F5)3.

[0142] More preferably, the neutral Lewis acid catalyst is an aluminum complex (e.g., triarylaluminum, or Al(C6F5)3).

[0143] More preferably, the neutral Lewis acid catalyst is a triaryl aluminum compound, more preferably a fluorinated triaryl aluminum compound; for example, Al(C6F5)3.

[0144] In some embodiments, the protonic acid (ester) type catalyst in the cationic main catalyst may be a conventional protonic acid (ester) type catalyst in the art.

[0145] Preferably, the protic acid (ester) type catalyst is a sulfonic acid, a sulfonate ester, a sulfonyl imide, an N-substituted sulfonyl imide, an oxonium protic acid, or a thionium protic acid.

[0146] Preferably, the protic acid (ester) type catalyst is a bisphosphonium imide ester.

[0147] Preferably, the protic acid (ester) type catalyst is a sulfonic acid, a sulfonate ester, a sulfonyl imide, an N-substituted sulfonyl imide, an oxonium protic acid, or a thioonium protic acid.

[0148] More preferably, the sulfonic acid, sulfonate, sulfonyl imide, and N-substituted sulfonyl imide each have the following structures:

[0149]

[0150] Among them, X 1d and X 2d Each of these can be independently fluorine, methyl, phenyl, trifluoromethyl, pentafluoroethyl, pentafluorophenyl, or 3,5-di(trifluoromethyl)phenyl; R xd It can be methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, cyclohexyl, trimethylsilyl, triethylsilyl, tripropylsilyl, triisopropylsilyl, tributylsilyl, or tert-butyldimethylsilyl.

[0151] More preferably, the oxonium protonic acid and the thionium protonic acid have the following structures:

[0152]

[0153] Among them, R 1p and R 2pEach of the following can be independently methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, phenyl, 2,4,6-trimethylphenyl, 2,6-dimethylphenyl, 2,3,5,6-tetramethylphenyl, or 2,6-diisopropylphenyl; [X] – The aforementioned borate anion, aluminate anion, phosphate anion, sulfonic acid anion, sulfonamide anion, antimony anion, or arsenate anion.

[0154] More preferably, the bisphosphonium imide ester has the following structure:

[0155]

[0156] Among them, R 1q C 6-10 Aryl (e.g., 3,5-dimethylphenyl), the C 6-10 The aryl group is optionally substituted with one or more halogens (e.g., fluorine); R 2q The methanesulfonyl group is optionally substituted with one or more halogens (e.g., fluorine).

[0157] More preferably, the protonic acid (ester) catalyst is a bisphosphonium imide ester, such as IDPi-CF3, with the following structure:

[0158]

[0159] More preferably, the protonic acid (ester) type catalyst is an oxonium protonic acid, such as [H(Et2O)2][B(C6F5)4].

[0160] In some preferred embodiments, the cationic main catalyst is one or more of [Ph3C][B(C6F5)4], Me3OBF4, [Et3O][B(C6F5)4], C7H7BF4, B(C6F5)3, Al(C6F5)3, IDPi-CF3, [Et3Si-H-SiEt3][B(C6F5)4], and [H(Et2O)2][B(C6F5)4].

[0161] In some preferred embodiments, the cationic main catalyst is one or more of [Ph3C][B(C6F5)4], B(C6F5)3 and [H(Et2O)2][B(C6F5)4].

[0162] In some embodiments, the polymerization reaction may also be carried out in the presence of a cocatalyst, which is one or more of a hydrogen bond donor, a hydrogen bond acceptor, and a Lewis acid.

[0163] In some preferred embodiments, the molar ratio of the main catalyst to the co-catalyst can be a conventional molar ratio in the art, preferably 1:1 to 1:10, more preferably 1:1 to 1:5, such as 1:1, 1:2 or 1:3.

[0164] In some preferred embodiments, the hydrogen bond donor in the cocatalyst can be a conventional hydrogen bond donor in the art.

[0165] Preferably, the hydrogen bond donor is one or more of alcohols, thiols, carboxylic acids, ureas, and thioureas, such as one or more of alcohols, thiols, and thioureas, and for example, one or more of diphenylmethanol, benzyl alcohol, 1-octylthiol, and N,N'-diisopropylthiourea. The alcohol is preferably diphenylmethanol and / or benzyl alcohol. The thiol is preferably 1-octylthiol. The carboxylic acid is preferably phenylacetic acid. The urea is preferably diethylurea. The thiourea is preferably N,N'-diisopropylthiourea or 1-[3,5-bis(trifluoromethyl)phenyl]-3-cyclohexylthiourea. The thiourea is more preferably N,N'-diisopropylthiourea.

[0166] In some preferred embodiments, the hydrogen bond acceptor in the cocatalyst may be a conventional hydrogen bond acceptor in the art.

[0167] Preferably, the hydrogen bond acceptor is one or more of crown ethers, polyethylene glycol dimethyl ether, cyclodextrin, calixarenes, and azacyclic cryptanes, such as one or more of crown ethers and polyethylene glycol dimethyl ethers, or, for example, 18-crown-6 ether. The cyclodextrin is preferably methyl β-cyclodextrin. The calixarenes are preferably O(1),O(2),O(3),O(4)-tetramethyl-p-tert-butylcalixarenes. The polyethylene glycol dimethyl ether is preferably tetraethylene glycol dimethyl ether. The azacyclic cryptane is preferably 4,7,13,16,21-pentaoxa-1,10-diazabicyclo[8.8.5]tetracosane.

[0168] In some preferred embodiments, the Lewis acid in the co-catalyst may be a Lewis acid conventional in the art.

[0169] Preferably, the Lewis acid is one or more of an alkali metal compound, an alkaline earth metal compound, a zinc compound, a boron compound, an aluminum compound, and a rare earth compound, such as a zinc compound, for example, di(pentafluorophenyl)zinc. The alkali metal compound is preferably lithium chloride. The alkaline earth metal compound is preferably magnesium chloride. The zinc compound is preferably diethylzinc and / or di(pentafluorophenyl)zinc. The boron compound is preferably tri(pentafluorophenyl)boron. The aluminum compound is preferably tri(pentafluorophenyl)aluminum. The rare earth compound is preferably tris[bis(trimethylsilyl)amino]lanthanum.

[0170] In some embodiments, the polymerization reaction may also be carried out in the presence of an initiator, which is a carboxylic acid and / or a thiocarboxylic acid.

[0171] In some preferred embodiments, the molar ratio of the main catalyst to the initiator can be a conventional molar ratio in the art, preferably 1:1 to 1:10, more preferably 1:1 to 1:5, such as 1:1, 1:2 or 1:3.

[0172] In some preferred embodiments, the carboxylic acid in the initiator is acetic acid, benzoic acid, or phenylpropionic acid.

[0173] In some preferred embodiments, the thiocarboxylic acid in the initiator is thioacetic acid or thiobenzoic acid.

[0174] In some embodiments, the polymerization temperature of the polymerization reaction can be a conventional polymerization temperature in the art, preferably 0-120 degrees Celsius, more preferably 40-80 degrees Celsius.

[0175] In some implementations, the progress of the polymerization reaction can be monitored by means conventional in the art (e.g., by means of...). 1 The conversion rate is monitored by 1H NMR (the hydrogen fraction of the generated polymer to the remaining monomer is monitored). The polymerization reaction time is preferably 5-720 minutes, more preferably 30-240 minutes, for example 30 minutes, 120 minutes, 180 minutes or 240 minutes.

[0176] In some preferred embodiments, the preparation method includes the following steps: in an organic solvent, in the presence of a main catalyst, the polymeric monomer is subjected to a polymerization reaction; the molar ratio of the polymeric monomer to the main catalyst is 100:1-1600:1.

[0177] In some preferred embodiments, the preparation method includes the following steps: in an organic solvent, in the presence of a main catalyst and a co-catalyst, the polymeric monomer is subjected to a polymerization reaction; the molar ratio of the polymeric monomer to the main catalyst is 100:1-1600:1, and the molar ratio of the main catalyst to the co-catalyst is 1:1-1:10.

[0178] In some preferred embodiments, the preparation method includes the following steps: in an organic solvent, in the presence of a main catalyst and an initiator, the polymeric monomer is subjected to a polymerization reaction; the molar ratio of the polymeric monomer to the main catalyst is 100:1-1600:1, and the molar ratio of the main catalyst to the initiator is 1:1-1:10.

[0179] In some preferred embodiments, the polymerization reaction includes the following steps: in an organic solvent, in the presence of a main catalyst, or a main catalyst and a co-catalyst, or a main catalyst and an initiator, the monomer is subjected to a polymerization reaction.

[0180] In some preferred embodiments, the polymerization reaction includes the following steps: adding the polymerizable monomer into a reaction vessel, connecting the reaction vessel to a vacuum line protected by an inert gas, adding an organic solvent, a main catalyst, or a main catalyst and a co-catalyst, or a main catalyst and an initiator, reacting at room temperature, or heating to the polymerization temperature, and waiting for the polymerization reaction to complete.

[0181] In some preferred embodiments, the polymerization reaction includes the following steps: adding the polymerizable monomer to the reaction flask in a glove box, removing the glove box, connecting the reaction flask to a vacuum line protected by an inert gas, heating it to the corresponding polymerization temperature, and then adding the main catalyst, or a solution of the main catalyst and a co-catalyst in an organic solvent to the solution, and waiting for the polymerization reaction to complete.

[0182] In some embodiments, the raw materials for the polymerization reaction are the polymerizing monomer, the cationic main catalyst, and the solvent.

[0183] In some embodiments, the raw materials for the polymerization reaction are the polymerizing monomer, the anionic catalyst, and the solvent.

[0184] In some embodiments, the raw materials for the polymerization reaction are the polymerization monomer, the anionic main catalyst, the solvent, and the co-catalyst.

[0185] In some embodiments, the raw materials for the polymerization reaction are the polymerizing monomer, the anionic main catalyst, the solvent, and the initiator.

[0186] In some embodiments, the raw materials for the polymerization reaction are the polymerization monomer, the anionic main catalyst, the solvent, the initiator, and the co-catalyst.

[0187] In some preferred embodiments, after the polymerization reaction is completed, a post-treatment may be further included. This post-treatment may include the following steps: mixing the reaction solution with one or more of an aqueous solution, an allyl chloride solution, and a benzoic acid solution, then mixing with ethanol, centrifuging or filtering, and drying. The aqueous solution is preferably a tetrahydrofuran solution of water, wherein the volume ratio of the tetrahydrofuran solution to water is preferably 1 / 20 or 1 / 30; the allyl chloride solution is preferably a toluene solution of allyl chloride, wherein the volume ratio of the toluene solution to allyl chloride is preferably 1 / 2; the benzoic acid is preferably a chloroform solution of benzoic acid, wherein the mass-volume ratio of the chloroform solution of benzoic acid is preferably 10 mg / mL. The addition of the tetrahydrofuran solution of water, the toluene solution of allyl chloride, and the chloroform solution of benzoic acid is to terminate the growth of the polymerization chain. Mixing with ethanol causes the polymer to precipitate and solidify. The filtration or centrifugation is preferably followed by a washing step, wherein the washing solvent is preferably ethanol. The number of washings is preferably 2-5 times (e.g., 3 times). The drying is preferably vacuum drying. The drying temperature is preferably 25-60 degrees Celsius. The drying time is preferably 20-100 hours, for example, 24 hours.

[0188] In some preferred embodiments, the polymeric monomer is The main catalyst is a cationic main catalyst (e.g., a zwitterionic catalyst, such as [Ph3C][B(C6F5)4]).

[0189] In some preferred embodiments, the polymeric monomer is The main catalyst is a cationic main catalyst (e.g., a zwitterionic catalyst, such as [Ph3C][B(C6F5)4]).

[0190] In some preferred embodiments, the polymeric monomer is The main catalyst is a cationic main catalyst (e.g., a zwitterionic catalyst, such as [Ph3C][B(C6F5)4]).

[0191] In some preferred embodiments, the polymeric monomer is The main catalyst is a cationic main catalyst (e.g., a zwitterionic catalyst, such as [Ph3C][B(C6F5)4]).

[0192] In some preferred embodiments, the polymeric monomer is The main catalyst is a cationic main catalyst (e.g., a zwitterionic catalyst, such as [Ph3C][B(C6F5)4]).

[0193] In some preferred embodiments, the polymeric monomer is The main catalyst is a cationic main catalyst (e.g., a zwitterionic catalyst, such as [Ph3C][B(C6F5)4]).

[0194] In some preferred embodiments, the polymeric monomer is The main catalyst is a cationic main catalyst (e.g., a zwitterionic catalyst, such as [Ph3C][B(C6F5)4]).

[0195] In some preferred embodiments, the polymeric monomer is The main catalyst is a cationic main catalyst (e.g., a zwitterionic catalyst, such as [Ph3C][B(C6F5)4]).

[0196] In some preferred embodiments, the polymeric monomer is The main catalyst is a cationic main catalyst (e.g., a zwitterionic catalyst, such as [Ph3C][B(C6F5)4]).

[0197] In some preferred embodiments, the polymeric monomer is The main catalyst is a cationic main catalyst (e.g., a zwitterionic catalyst, such as [Ph3C][B(C6F5)4]).

[0198] In some preferred embodiments, the polymeric monomer is The main catalyst is an anionic catalyst (e.g., thiocarboxylate, or potassium thioacetate).

[0199] In some preferred embodiments, the polymeric monomer is The main catalyst is an anionic catalyst (e.g., phosphononitrile base, or for example...). t Bu-P4, wherein the cocatalyst is a hydrogen bond donor (e.g., an alcohol, or more specifically, diphenylmethanol).

[0200] In some preferred embodiments, the polymeric monomer is The main catalyst is an anionic catalyst (e.g., phosphononitrile base, or for example...). t Bu-P4), wherein the cocatalyst is a hydrogen bond donor (e.g., an alcohol, or, for example, diphenylmethanol).

[0201] In some preferred embodiments, the polymeric monomer is The main catalyst is an anionic catalyst (e.g., thiocarboxylate, or potassium thioacetate), and the co-catalyst is a hydrogen bond acceptor (e.g., crown ether, or 18-crown-6 ether).

[0202] In some preferred embodiments, the polymeric monomer is The main catalyst is an anionic catalyst (e.g., thiocarboxylate, or potassium thioacetate), and the co-catalyst is a hydrogen bond acceptor (e.g., crown ether, or 18-crown-6 ether).

[0203] In some preferred embodiments, the polymeric monomer is The main catalyst is an anionic catalyst (e.g., phosphononitrile base, or for example...). t Bu-P4), wherein the initiator is a carboxylic acid (e.g., benzoic acid).

[0204] In some preferred embodiments, the polymeric monomer is The main catalyst is a cationic main catalyst (e.g., a zwitterionic catalyst, such as [Ph3C][B(C6F5)4]).

[0205] In some preferred embodiments, the polymeric monomer is The main catalyst is a cationic main catalyst (e.g., a neutral Lewis acid catalyst, or B(C6F5)3).

[0206] In some preferred embodiments, the polymeric monomer is The main catalyst is a cationic main catalyst (e.g., a protic acid (ester) type catalyst, such as an oxonium protic acid, such as [H(Et2O)2][B(C6F5)4]).

[0207] In some preferred embodiments, the polymeric monomer is The main catalyst is an anionic catalyst (e.g., thiocarboxylate, or potassium thioacetate).

[0208] In some preferred embodiments, the polymeric monomer is The main catalyst is an anionic catalyst (e.g., thiocarboxylate, or potassium thioacetate).

[0209] In some preferred embodiments, the polymeric monomer is The main catalyst is a cationic main catalyst (e.g., a zwitterionic catalyst, such as [Ph3C][B(C6F5)4]).

[0210] In some preferred embodiments, the polymeric monomer is The main catalyst is an anionic catalyst (e.g., guanidine organic base catalyst, or TBD). The initiator is a carboxylic acid (e.g., benzoic acid).

[0211] In some preferred embodiments, the polymeric monomer is The main catalyst is an anionic catalyst (e.g., amidine-based organic base catalysts, or DBU). The initiator is a thiocarboxylic acid (e.g., thiobenzoic acid).

[0212] In some preferred embodiments, the polymeric monomer is The main catalyst is an anionic catalyst (e.g., N-heterocyclic carbene organic base catalyst, or, for example, I...). t Bu: ).

[0213] In some preferred embodiments, the polymeric monomer is The main catalyst is an anionic catalyst (e.g., N-heterocyclic olefin organic base catalyst, such as NHO: ).

[0214] In some preferred embodiments, the polymeric monomer is The main catalyst is an anionic main catalyst (e.g., phosphononitrile base catalyst, or, for example...). t Bu-P1: ).

[0215] In some preferred embodiments, the polymeric monomer is The main catalyst is a cationic main catalyst (e.g., zwitterionic pair catalyst, such as [Et3Si-H-SiEt3][B(C6F5)4).

[0216] In some preferred embodiments, the polymeric monomer is The main catalyst is a cationic main catalyst (e.g., a zwitterion-pair catalyst, or Ph3CB(C6F5)4 / Et3SiH).

[0217] In some preferred embodiments, the polymeric monomer is The main catalyst is a cationic main catalyst (e.g., a zwitterion-pair catalyst, or Me3OBF4).

[0218] In some preferred embodiments, the polymeric monomer is The main catalyst is a cationic main catalyst (e.g., a zwitterion catalyst, such as [Et3O][B(C6F5)4]).

[0219] In some preferred embodiments, the polymeric monomer is The main catalyst is a cationic main catalyst (e.g., a zwitterion catalyst, such as C7H7BF4).

[0220] In some preferred embodiments, the polymeric monomer is The main catalyst is a cationic main catalyst (e.g., a neutral Lewis acid catalyst, or Al(C6F5)3).

[0221] In some preferred embodiments, the polymeric monomer is The main catalyst is a cationic main catalyst (e.g., a protic acid (ester) type catalyst, such as IDPi-CF3). ).

[0222] In some preferred embodiments, the polymeric monomer is The main catalyst is a cationic main catalyst (e.g., a zwitterion catalyst, such as [Et3O][B(C6F5)4]).

[0223] In some preferred embodiments, the polymeric monomer is The main catalyst is a cationic main catalyst (e.g., a zwitterion catalyst, such as [Et3O][B(C6F5)4]).

[0224] In some preferred embodiments, the polymeric monomer is The main catalyst is a cationic main catalyst (e.g., a zwitterion catalyst, such as [Et3O][B(C6F5)4]).

[0225] In some preferred embodiments, the polymeric monomer is The main catalyst is a cationic main catalyst (e.g., a zwitterion catalyst, such as [Et3O][B(C6F5)4]).

[0226] In some preferred embodiments, the polymeric monomer is The main catalyst is a cationic main catalyst (e.g., a zwitterion catalyst, such as [Et3O][B(C6F5)4]).

[0227] In some preferred embodiments, the polymeric monomer is The main catalyst is a cationic main catalyst (e.g., a zwitterion catalyst, such as [Et3O][B(C6F5)4]).

[0228] In some preferred embodiments, the polymeric monomer is The main catalyst is a cationic main catalyst (e.g., a zwitterion catalyst, such as [Et3O][B(C6F5)4]).

[0229] In some preferred embodiments, the polymeric monomer is The main catalyst is a cationic main catalyst (e.g., a zwitterion catalyst, such as [Et3O][B(C6F5)4]).

[0230] In some preferred embodiments, the polymeric monomer is The main catalyst is a cationic main catalyst (e.g., a zwitterion catalyst, such as [Et3O][B(C6F5)4]).

[0231] In some preferred embodiments, the polymeric monomer is The main catalyst is an anionic catalyst (e.g., amidine-based organic base catalysts, or DBU). The co-catalyst is benzyl alcohol.

[0232] In some preferred embodiments, the polymeric monomer is The main catalyst is an anionic catalyst (e.g., amidine-based organic base catalysts, or DBU). The co-catalyst is benzyl alcohol and 1-[3,5-bis(trifluoromethyl)phenyl]-3-cyclohexylthiourea.

[0233] In some preferred embodiments, the polymeric monomer is The main catalyst is a cationic main catalyst (e.g., a zwitterion catalyst, such as [Et3O][B(C6F5)4]).

[0234] In some preferred embodiments, the polymeric monomer is The main catalyst is a cationic main catalyst (e.g., a zwitterion catalyst, such as [Et3O][B(C6F5)4]).

[0235] The present invention also provides a sulfur-containing polymer, which is prepared according to the method for preparing sulfur-containing polymers described herein.

[0236] The present invention also provides a sulfur-containing polymer, wherein the main chain of the sulfur-containing polymer is composed of one or more of the following structural units:

[0237]

[0238] Wherein, the degree of polymerization of the sulfur-containing polymer is greater than or equal to 50, and the definitions of each group are as described in any embodiment of the present invention.

[0239] In the structure of the sulfur-containing polymer, each structure within “()” represents a structural unit, and each structural unit is independent of the others.

[0240] In some embodiments, the degree of polymerization of the sulfur-containing polymer is 50-4900, preferably 190-2450, and more preferably 840-1600.

[0241] In some embodiments, the number-average molecular weight of the sulfur-containing polymer is greater than or equal to 3 kg / mol, preferably greater than or equal to 5 kg / mol, more preferably 10-500 kg / mol, even more preferably 20-250 kg / mol, and even more preferably 80-250 kg / mol.

[0242] In some embodiments, the sulfur-containing polymer has a molecular weight distribution of 1.0-3.0, preferably 1.0-1.5.

[0243] In some embodiments, the sulfur-containing polymer is a homopolymer or a multi-component copolymer.

[0244] Preferably, the multi-component copolymer is a random copolymer or a block copolymer.

[0245] Preferably, the multi-component copolymer is a ternary copolymer, and the molar percentage of each structural unit is 5-90%.

[0246] In some embodiments, the glass transition temperature T of the sulfur-containing polymer is... g The temperature ranges from -57.0 to 59.5℃.

[0247] In some embodiments, the tensile strength at break of the sulfur-containing polymer is 638%-1451.30%.

[0248] In some embodiments, the yield stress of the sulfur-containing polymer is 9.05 MPa.

[0249] In some embodiments, the sulfur-containing polymer has a fracture stress of 16.62-24.27 MPa.

[0250] In some embodiments, the elastic recovery rate of the sulfur-containing polymer is 72.3%.

[0251] In this invention, unless otherwise specified, "℃" refers to degrees Celsius; "h" refers to hours; and "min" refers to minutes.

[0252] Borate anion: According to the naming rules for boron-containing compounds, "boron-containing anions are all indicated by borate ions" (Inorganic Chemistry Nomenclature Rules, 1982 edition, p. 2194). The borate anion mentioned in the text refers to (pentafluorophenyl)borate anion [B(C6F5)4]. - wait.

[0253] Without violating common sense in the field, the above-mentioned preferred conditions can be combined arbitrarily to obtain various preferred embodiments of the present invention.

[0254] The reagents and raw materials used in this invention are all commercially available.

[0255] The positive and progressive effects of this invention are as follows:

[0256] The preparation method of this invention uses isomerization as the thermodynamic driving force, rather than the traditional ring strain, and is not limited by the upper limit of polymerization temperature. It can promote the irreversible ring-opening polymerization of a series of non-strained five-membered ring monomers (including five-membered ring thiocarbonyl lactones and five-membered ring thiocarbonyl carbonates) at temperatures ranging from 25 to 120°C at room temperature to high temperatures. Because a concerted isomerization reaction accompanies the ring-opening process, the generated sulfur-containing polymer does not depolymerize into the initial monomer, thus promoting the polymerization reaction to proceed in the forward direction until the initial monomer is completely consumed. This exhibits irreversible ring-opening polymerization, achieving efficient and quantitative monomer conversion. This invention can suppress the occurrence of bite-back side reactions, successfully controlling the content of bite-back byproducts to below 1%, and achieving a maximum yield of sulfur-containing polymers of up to 99%.

[0257] The polysulfides prepared by this invention have a number-average molecular weight of 3.2 kg / mol to 431.1 kg / mol and a molecular weight distribution index of 1.01 to 2.05. The number-average molecular weight increases linearly with the increase of the monomer-to-catalyst ratio, exhibiting good molecular weight control. The glass transition temperature To of the polysulfides provided by this invention is... g The temperature range is approximately -57.0 to 59.5℃. The polysulfide esters prepared by this invention exhibit highly adjustable properties to meet various application scenarios. For example, the poly-(S)-(γ-thiovalactone) obtained by this invention has an elongation at break of 638%, a yield stress of 9.05 MPa, and a breaking stress of 24.27 MPa, making it a strong and tough polymer material. Its mechanical tensile test properties are superior to those of low-density polyethylene (elongation at break 430%, breaking stress 10.6 MPa) and isotactic polypropylene (elongation at break 420%, breaking stress 26.0 MPa), and approach the tensile properties of high-density polypropylene (elongation at break 420%, breaking stress 26.0 MPa). The ternary random copolymer obtained by copolymerization in this invention has an elongation at break of 1451.30%, a breaking stress of 16.62 MPa, and an elastic recovery rate of 72.3%, making it a strong and tough elastomeric polymer material. All mechanical tensile test indicators are superior to those of commercial ethylene propylene rubber (elongation at break is 275.0%, and breaking stress is 5.70 MPa).

[0258] The sulfur-containing homopolymers and copolymers obtained by this invention provide convenience for the industrial production of environmentally friendly sulfur-containing polymer materials. The synthesized sulfur-containing polymers have advantages such as high molecular weight, wide range of tunable physical properties, and excellent degradability, and can be used as plastics, rubbers, elastomers, fibers, and other products. Attached Figure Description

[0259] Figure 1 The poly(γ-thiovalactone) obtained in Example 2 1 H NMR spectrum.

[0260] Figure 2 The poly(γ-thiovalactone) obtained in Example 2 13 C10 NMR spectrum.

[0261] Figure 3 The poly(γ-thiocaprolactone) obtained in Example 3 1 H NMR spectrum.

[0262] Figure 4 The poly(γ-thiocaprolactone) obtained in Example 3 13 C10 NMR spectrum.

[0263] Figure 5 The poly(γ-thioheptane lactone) obtained in Example 4 1 H NMR spectrum.

[0264] Figure 6 The poly(γ-thioheptane lactone) obtained in Example 4 13 C10 NMR spectrum.

[0265] Figure 7 The poly(γ-thiooctyl lactone) obtained in Example 5 1 H NMR spectrum.

[0266] Figure 8 The poly(γ-thiooctyl lactone) obtained in Example 5 13 C10 NMR spectrum.

[0267] Figure 9 The poly(γ-thiononolactone) obtained in Example 6 1 H NMR spectrum.

[0268] Figure 10 The poly(γ-thiononolactone) obtained in Example 6 13 C10 NMR spectrum.

[0269] Figure 11 The poly(γ-thiodecyl lactone) obtained in Example 7 1 H NMR spectrum.

[0270] Figure 12 The poly(γ-thiodecyl lactone) obtained in Example 7 13 C10 NMR spectrum.

[0271] Figure 13The poly(γ-thioundecyl lactone) obtained in Example 8 1 H NMR spectrum.

[0272] Figure 14 The poly(γ-thioundecyl lactone) obtained in Example 8 13 C10 NMR spectrum.

[0273] Figure 15 The poly(γ-thiodododecyl lactone) obtained in Example 9 1 H NMR spectrum.

[0274] Figure 16 The poly(γ-thiodododecyl lactone) obtained in Example 9 13 C10 NMR spectrum.

[0275] Figure 17 The poly(γ-methyl-γ-thiodecyl lactone) obtained in Example 10 1 H NMR spectrum.

[0276] Figure 18 The poly(γ-methyl-γ-thiodecyl lactone) obtained in Example 10 13 C10 NMR spectrum.

[0277] Figure 19 The poly(β-methyl-γ-thiooctyl lactone) obtained in Example 11 1 H NMR spectrum.

[0278] Figure 20 The poly(β-methyl-γ-thiooctyl lactone) obtained in Example 11 13 C10 NMR spectrum.

[0279] Figure 21 The poly(α-methylγ-thiobutyrolactone) obtained in Example 12 1 H NMR spectrum.

[0280] Figure 22 The poly(α-methylγ-thiobutyrolactone) obtained in Example 12 13 C10 NMR spectrum.

[0281] Figure 23 The poly(β-methylγ-thiobutyrolactone) obtained in Example 13 1 H NMR spectrum.

[0282] Figure 24 The poly(β-methylγ-thiobutyrolactone) obtained in Example 13 13 C10 NMR spectrum.

[0283] Figure 25The random copolymer obtained in Example 14 1 H NMR spectrum.

[0284] Figure 26 The poly(cis-hexahydroisobenzothiophene-1-one) obtained in Example 15 1 H NMR spectrum.

[0285] Figure 27 The poly(cis-hexahydroisobenzothiophene-1-one) obtained in Example 15 13 C10 NMR spectrum.

[0286] Figure 28 The block copolymer obtained in Example 21 1 H NMR spectrum.

[0287] Figure 29 The poly(propylene monothiocarbonate) obtained in Example 22 1 H NMR spectrum.

[0288] Figure 30 The poly(propylene monothiocarbonate) obtained in Example 22 13 C10 NMR spectrum.

[0289] Figure 31 M is poly(γ-thiovalactone) n Linear graph of monomer / catalyst ratio.

[0290] Figure 32 The TGA curve of poly(γ-thiovalerate) obtained in Example 2 is shown.

[0291] Figure 33 The DSC curves are for the poly(γ-thiocaprolactone) (abbreviation: PTGCL), poly(γ-thioheptanelactone) (abbreviation: PTGHL), poly(γ-thiooctanelactone) (abbreviation: PTGOL), poly(γ-thiononalactone) (abbreviation: PTGNL), poly(γ-thiodecylactone) (abbreviation: PTGDL), poly(γ-thioundecaprolactone) (abbreviation: PTGUDL), poly(γ-thiododecylactone) (abbreviation: PTGDDL), and poly(γ-methyl-γ-thiodecylactone) (abbreviation: PTGGMDL) obtained in Examples 3-10.

[0292] Figure 34The DSC curves are for poly(γ-thiovalactone) (PTGVL) obtained in Example 2, poly(α-methyl-γ-thiobutyrolactone) (PαMeTBL) and poly(β-methyl-γ-thiobutyrolactone) (PβMeTBL) obtained in Examples 12-13, poly(β-methyl-γ-thiooctylactone) (PTWL) obtained in Example 11, and poly(cis-hexahydroisobenzofuran-1-one) (P3,4-S6TBL) obtained in Example 15.

[0293] Figure 35 The degradation diagram of poly(γ-thiobutyl terephthalate) obtained in Example 2 under the catalysis of 1,5,7-triazidobiscyclic (4.4.0)dec-5-ene.

[0294] Figure 36 The γ-thiocarbonyl valerate obtained in Example 1 1 H NMR spectrum.

[0295] Figure 37 The poly-(S)-4-methyl-1,3-dioxolane-2-thione obtained in Example 36 1 H NMR spectrum.

[0296] Figure 38 The poly-(S)-4-methyl-1,3-dioxolane-2-thione obtained in Example 36 13 C10 NMR spectrum.

[0297] Figure 39 The poly-(rac)-4-chloromethyl-1,3-dioxolane-2-thione obtained in Example 38 1 H NMR spectrum.

[0298] Figure 40 The poly(R)-4-chloromethyl-1,3-dioxolane-2-thione obtained in Example 39 1 H NMR spectrum.

[0299] Figure 41 The poly-4-phenyl-1,3-dioxolane-2-thione obtained in Example 41 1 H NMR spectrum.

[0300] Figure 42 The poly-4-phenyl-1,3-dioxolane-2-thione obtained in Example 41 13 C10 NMR spectrum.

[0301] Figure 43This is a superimposed DSC curve of poly-1,3-dioxolane-2-thione (PEMTC) obtained in Example 35, poly-(S)-4-methyl-1,3-dioxolane-2-thione (S-PPMTC) obtained in Example 36, poly-(R)-4-methyl-1,3-dioxolane-2-thione (R-PPMTC) obtained in Example 37, poly-4-chloromethyl-1,3-dioxolane-2-thione (PCMMTC) obtained in Example 38, and poly-4-phenyl-1,3-dioxolane-2-thione (PBMTC) obtained in Example 41.

[0302] Figure 44 The DSC curve of poly(R)-4-chloromethyl-1,3-dioxolane-2-thione (abbreviation: R-PCMMTC) obtained in Example 39 is shown.

[0303] Figure 45 The image shows the DSC curve of poly(S)-4-chloromethyl-1,3-dioxolane-2-thione (abbreviation: S-PCMMTC) obtained in Example 40.

[0304] Figure 46 The mechanical tensile test diagram is shown for the terpolymer obtained in Example 14.

[0305] Figure 47 This is a cyclic tensile test diagram of the terpolymer obtained in Example 14.

[0306] Figure 48 The image shows the DSC curve of poly-(S)-(γ-thiovalactone) (abbreviation: S-PTNGVL) obtained in Example 44.

[0307] Figure 49 The mechanical tensile test diagram of poly-(S)-(γ-thiovalerate) (abbreviation: S-PTNGVL) obtained in Example 44 is shown. Detailed Implementation

[0308] The present invention is further illustrated below by way of embodiments, but the invention is not limited to the scope of the embodiments described herein. Experimental methods in the following embodiments that do not specify specific conditions were performed according to conventional methods and conditions, or as selected according to the product instructions.

[0309] Example 1

[0310] The polymer monomers described in this invention are self-made products, with commercially available five-membered ring lactones and cyclic carbonates as initial raw materials, prepared through a one-step reaction. There are no special restrictions on the preparation method, but it is preferred to prepare them according to the method described in the following scientific paper: Matsumoto Y, Nakatake D, Yazaki R, Ohshima T. Chemistry–A European Journal, 2018, 24(23):6062-6066. The synthesis steps of all compounds are similar; the synthesis of γ-thiocarbonyl valerate lactone is used as an example:

[0311] 121.3 g (0.3 mol) of Lawson's reagent was added to a 1 L round-bottom flask, followed by 500 mL of anhydrous toluene and stirring to form a yellow suspension. Then, 50.1 g of γ-valerolactone (0.5 mol) was added, and the mixture was refluxed and stirred for 5 h. After the reaction was complete and the temperature had cooled to room temperature, 200 mL of saturated potassium carbonate solution was added and stirred for 30 min. The mixture was separated, and the aqueous phase was extracted three times with anhydrous toluene. The organic phases were then combined. After drying with anhydrous sodium sulfate and filtration, the organic phase was collected by column chromatography with a petroleum ether / diethyl ether gradient elution (40:1–5:1). The monomer was then dried with calcium hydride for 3 days, distilled under reduced pressure at 100 mTorr and 60 °C, and stored in a glove box for later use.

[0312] The γ-thiocarbonyl valerate monomer obtained by this invention is a pale yellow liquid. The mass of the obtained γ-thiocarbonyl valerate monomer is 48.3 g, and the calculated yield is 83.2%.

[0313] The synthesized γ-thiocarbonyl valerate monomer was characterized by nuclear magnetic resonance (NMR). 1 The 1H NMR spectrum is consistent with literature reports, confirming that the γ-thiocarbonylpentanolide monomer prepared in this invention has the following structure. 1 H NMR spectrum as follows Figure 36 As shown.

[0314]

[0315] Example 2

[0316] In an argon-atmospheric glove box at room temperature, 0.005 mmol of [Ph3C][B(C6F5)4] was dissolved in 0.4 mL of toluene in a dry 5 mL glass vial. Then, 1 mmol (116.2 mg, 0.1 mL) of γ-thiocarbonylpentanolide monomer was added. The initial monomer concentration was 2 mol / L, and the catalyst concentration of [Ph3C][B(C6F5)4] was 10 mmol / L. The molar ratio of monomer to [Ph3C][B(C6F5)4] was 200:1. The reaction was maintained at room temperature and stirred for 120 minutes. A small sample was dissolved in deuterated chloroform and analyzed... 1 The conversion rate was monitored by ¹H NMR and found to be 98.1%, with a γ-thiovalactone byproduct:poly(γ-thiovalactone) ratio of 2:98. The reaction was then quenched by adding 2 mL of a water / tetrahydrofuran mixture (volume ratio 1:20). The reaction solution was added dropwise to ethanol to allow the polymer to precipitate. After centrifugation, the supernatant was discarded. This process of dissolving in dichloromethane, adding dropwise to ethanol for precipitation, centrifugation, and discarding the supernatant was repeated twice. The product was then dried at room temperature in a vacuum oven for three days to obtain colorless poly(γ-thiovalactone). Nuclear magnetic resonance (NMR) analysis was performed on poly(γ-thiovalactone). 1 H NMR spectrum and 13 The C NMR spectra are as follows: Figure 1 and Figure 2 As shown.

[0317]

[0318] The present invention uses differential scanning calorimetry (DSC) to detect the melting temperature and glass transition temperature of poly(γ-thiovalactone). The results show that the glass transition temperature of poly(γ-thiovalactone) prepared in this embodiment is -15.4℃.

[0319] This invention uses gel permeation chromatography (GPC) to determine the molecular weight and molecular weight distribution of poly(γ-thiovalactone), with tetrahydrofuran as the eluent and a flow rate of 1.0 mL / min. A standard curve is prepared using polymethyl methacrylate as the standard. The results show that the poly(γ-thiovalactone) prepared in this example has a number-average molecular weight of 27.5 kg / mol and a molecular weight distribution of 1.16.

[0320] Example 3

[0321] In an argon-atmospheric glove box at room temperature, 0.005 mmol of [Ph3C][B(C6F5)4] was dissolved in 0.4 mL of toluene in a dry 5 mL glass bottle. Then, 1 mmol (130.2 mg, 0.11 mL) of γ-thiocarbonylcaprolactone monomer was added. The initial concentration of the monomer was 2 mol / L, the concentration of the catalyst [Ph3C][B(C6F5)4] was 10 mmol / L, and the molar ratio of monomer to [Ph3C][B(C6F5)4] was 200:1.

[0322] Maintain the reaction temperature at room temperature and stir for 2.5 hours. Then, take a small amount of sample and dissolve it in deuterated chloroform. 1 The conversion rate was monitored by ¹H NMR, and was greater than 99%. The ratio of γ-thiocaprolactone byproduct to poly(γ-thiocaprolactone) was 3:97. Then, 2 mL of a water / tetrahydrofuran mixture (volume ratio 1:20) was added to quench the reaction. The reaction solution was then added dropwise to ethanol to allow the polymer to precipitate. After centrifugation, the supernatant was discarded. This process of dissolving in dichloromethane, adding dropwise to ethanol for precipitation, centrifugation, and discarding the supernatant was repeated twice. The product was then dried at room temperature in a vacuum oven for three days to obtain colorless poly(γ-thiocaprolactone). Nuclear magnetic resonance (NMR) analysis was performed on the poly(γ-thiocaprolactone). 1 H NMR spectrum and 13 The C NMR spectra are as follows: Figure 3 and Figure 4 As shown.

[0323]

[0324] The present invention uses differential scanning calorimetry (DSC) to detect the melting temperature and glass transition temperature of poly(γ-thiocaprolactone). The results show that the glass transition temperature of poly(γ-thiocaprolactone) prepared in this embodiment is -20.8℃.

[0325] This invention employs gel permeation chromatography (GPC) to determine the molecular weight and molecular weight distribution of poly(γ-thiocaprolactone), using tetrahydrofuran as the eluent at a flow rate of 1.0 mL / min. A standard curve is constructed using polymethyl methacrylate as the standard. The results show that the poly(γ-thiocaprolactone) prepared in this embodiment has a number-average molecular weight of 33.6 kg / mol and a molecular weight distribution of 1.33.

[0326] Example 4

[0327] In an argon-atmospheric glove box at room temperature in a dry glass bottle, 0.005 mmol of [Ph3C][B(C6F5)4] was dissolved in 0.36 mL of toluene, and then 1 mmol (144.2 mg, 0.14 mL) of γ-thiocarbonylheptanolone monomer was added. The initial concentration of the monomer was 2 mol / L, the concentration of the catalyst [Ph3C][B(C6F5)4] was 10 mmol / L, and the molar ratio of monomer to [Ph3C][B(C6F5)4] was 200:1.

[0328] Maintain the reaction temperature at room temperature and stir for 2.5 hours. Then, take a small sample and dissolve it in deuterated chloroform. 1 The conversion rate was monitored by ¹H NMR, and was greater than 99%. The ratio of γ-thioheptanol byproduct to poly(γ-thioheptanol) was 1:99. The reaction was then quenched by adding 2 mL of a water / tetrahydrofuran mixture (volume ratio 1:20). The reaction solution was added dropwise to ethanol to allow the polymer to precipitate. After centrifugation, the supernatant was discarded. This process of dissolving in dichloromethane, adding dropwise to ethanol for precipitation, centrifugation, and discarding the supernatant was repeated twice. The product was then dried at room temperature in a vacuum oven for three days to obtain colorless poly(γ-thioheptanol). Nuclear magnetic resonance (NMR) analysis was performed on poly(γ-thioheptanol). 1 H NMR spectrum and 13 The C NMR spectra are as follows: Figure 5 and Figure 6 As shown.

[0329]

[0330] The present invention uses differential scanning calorimetry (DSC) to detect the melting temperature and glass transition temperature of poly(γ-thioheptanol). The results show that the glass transition temperature of poly(γ-thioheptanol) prepared in this embodiment is -21.5℃.

[0331] This invention employs gel permeation chromatography (GPC) to determine the molecular weight and molecular weight distribution of poly(γ-thioheptanolactone), using tetrahydrofuran as the eluent at a flow rate of 1.0 mL / min. A standard curve is constructed using polymethyl methacrylate as the standard. The results show that the poly(γ-thioheptanolactone) prepared in this embodiment has a number-average molecular weight of 38.1 kg / mol and a molecular weight distribution of 1.36.

[0332] Example 5

[0333] In an argon-atmospheric glove box at room temperature in a dry glass bottle, 0.005 mmol of [Ph3C][B(C6F5)4] was dissolved in 0.35 mL of toluene, and then 1 mmol (158.3 mg, 0.15 mL) of γ-thiocarbonyloctyl lactone monomer was added. The initial concentration of the monomer was 2 mol / L, the concentration of the catalyst [Ph3C][B(C6F5)4] was 10 mmol / L, and the molar ratio of monomer to [Ph3C][B(C6F5)4] was 200:1.

[0334] Maintain the reaction temperature at room temperature and stir for 2.5 hours. Take a small amount of sample and dissolve it in deuterated chloroform. 1 The conversion rate was monitored by ¹H NMR, and was greater than 99%. The ratio of γ-thiooctyl lactone byproduct to poly(γ-thiooctyl lactone) was 3:97. Then, 2 mL of a water / tetrahydrofuran mixture (volume ratio 1:20) was added to quench the reaction. The reaction solution was then added dropwise to ethanol to allow the polymer to precipitate. After centrifugation, the supernatant was discarded. This process of dissolving in dichloromethane, adding dropwise to ethanol for precipitation, centrifugation, and discarding the supernatant was repeated twice. The product was then dried at room temperature in a vacuum oven for three days to obtain colorless poly(γ-thiooctyl lactone). Nuclear magnetic resonance (NMR) analysis was performed on the poly(γ-thiooctyl lactone). 1 H NMR spectrum and 13 The C NMR spectra are as follows: Figure 7 and Figure 8 As shown.

[0335]

[0336] The present invention uses differential scanning calorimetry (DSC) to detect the melting temperature and glass transition temperature of poly(γ-thiooctanolactone). The results show that the glass transition temperature of poly(γ-thiooctanolactone) prepared in this embodiment is -32.3℃.

[0337] This invention employs gel permeation chromatography (GPC) to determine the molecular weight and molecular weight distribution of poly(γ-thiooctanolide), using tetrahydrofuran as the eluent at a flow rate of 1.0 mL / min. A standard curve is constructed using polymethyl methacrylate as the standard. The results show that the poly(γ-thiooctanolide) prepared in this embodiment has a number-average molecular weight of 34.5 kg / mol and a molecular weight distribution of 1.33.

[0338] Example 6

[0339] In an argon-atmospheric glove box at room temperature, 0.005 mmol of [Ph3C][B(C6F5)4] was dissolved in 0.35 mL of toluene in a dry 5 mL glass bottle. Then, 1 mmol (172.3 mg, 0.16 mL) of γ-thiocarbonyl nonyl lactone monomer was added. The initial concentration of the monomer was 2 mol / L, the concentration of the catalyst [Ph3C][B(C6F5)4] was 10 mmol / L, and the molar ratio of monomer to [Ph3C][B(C6F5)4] was 200:1.

[0340] Maintain the reaction temperature at room temperature and stir for 2.5 hours. Then, take a small amount of sample and dissolve it in deuterated chloroform. 1 The conversion rate was monitored by ¹H NMR and found to be 97.4%, with a γ-thiononolactone byproduct to poly(γ-thiononolactone) ratio of 3:97. The reaction was then quenched by adding 2 mL of a water / tetrahydrofuran mixture (1:20 v / v). The reaction solution was then added dropwise to ethanol to allow the polymer to precipitate. After centrifugation, the supernatant was discarded. This process of dissolving in dichloromethane, adding dropwise to ethanol for precipitation, centrifugation, and discarding the supernatant was repeated twice. The product was then dried at room temperature in a vacuum oven for three days to obtain colorless poly(γ-thiononolactone). Nuclear magnetic resonance (NMR) analysis was performed on the poly(γ-thiononolactone). 1 H NMR spectrum and 13 The C NMR spectra are as follows: Figure 9 and Figure 10 As shown.

[0341]

[0342] The present invention uses differential scanning calorimetry (DSC) to detect the melting temperature and glass transition temperature of poly(γ-thiononolactone). The results show that the glass transition temperature of poly(γ-thiononolactone) prepared in this embodiment is -38.8℃.

[0343] This invention employs gel permeation chromatography (GPC) to determine the molecular weight and molecular weight distribution of poly(γ-thiononolactone), using tetrahydrofuran as the eluent at a flow rate of 1.0 mL / min. A standard curve is constructed using polymethyl methacrylate as the standard. The results show that the poly(γ-thiononolactone) prepared in this embodiment has a number-average molecular weight of 46.4 kg / mol and a molecular weight distribution of 1.26.

[0344] Example 7

[0345] In an argon-atmospheric glove box, 0.005 mmol of [Ph3C][B(C6F5)4] was dissolved in 0.32 mL of toluene in a dry 5 mL glass bottle. Then, 1 mmol (186.3 mg, 0.18 mL) of γ-thiocarbonyldecyl lactone monomer was added. The initial concentration of the monomer was 2 mol / L, the concentration of the catalyst [Ph3C][B(C6F5)4] was 10 mmol / L, and the molar ratio of monomer to [Ph3C][B(C6F5)4] was 200:1.

[0346] Maintain the reaction temperature at room temperature and stir for 2.5 hours. Then, take a small amount of sample and dissolve it in deuterated chloroform. 1 The conversion rate was monitored by ¹H NMR, and was greater than 99%. The ratio of γ-thiodecyl lactone byproduct to poly(γ-thiodecyl lactone) was 3:97. The reaction was then quenched by adding 2 mL of a water / tetrahydrofuran mixture (volume ratio 1:20). The reaction solution was added dropwise to ethanol to allow the polymer to precipitate. After centrifugation, the supernatant was discarded. This process of dissolving in dichloromethane, adding dropwise to ethanol for precipitation, centrifugation, and discarding the supernatant was repeated twice. The product was then dried at room temperature in a vacuum oven for three days to obtain colorless poly(γ-thiodecyl lactone). Nuclear magnetic resonance (NMR) analysis was performed on the poly(γ-thiodecyl lactone). 1 H NMR spectrum and 13 The C NMR spectra are as follows: Figure 11 and Figure 12 As shown.

[0347]

[0348] The present invention uses differential scanning calorimetry (DSC) to detect the melting temperature and glass transition temperature of poly(γ-thiodecyl lactone). The results show that the glass transition temperature of poly(γ-thiodecyl lactone) prepared in this embodiment is -44.8℃.

[0349] This invention uses gel permeation chromatography (GPC) to determine the molecular weight and molecular weight distribution of poly(γ-thiodecyl lactone), with tetrahydrofuran as the eluent and a flow rate of 1.0 mL / min. A standard curve is prepared using polymethyl methacrylate as the standard. The results show that the poly(γ-thiodecyl lactone) prepared in this example has a number-average molecular weight of 43.3 kg / mol and a molecular weight distribution of 1.31.

[0350] Example 8

[0351] In an argon-atmospheric glove box, 0.005 mmol of [Ph3C][B(C6F5)4] was dissolved in 0.3 mL of toluene in a dry 5 mL glass bottle. Then, 1 mmol (200.3 mg, 0.19 mL) of γ-thiocarbonyl undecyl lactone monomer was added. The initial concentration of the monomer was 2 mol / L, the concentration of the catalyst [Ph3C][B(C6F5)4] was 10 mmol / L, and the molar ratio of monomer to [Ph3C][B(C6F5)4] was 200:1.

[0352] Maintain the reaction temperature at room temperature and stir for 2.5 hours. Take a small amount of sample and dissolve it in deuterated chloroform. 1 The conversion rate was monitored by ¹H NMR, and was 97.4%. The ratio of γ-thioundecyl lactone byproduct to poly(γ-thioundecyl lactone) was 2:98. The reaction was then quenched by adding 2 mL of a water / tetrahydrofuran mixture (volume ratio 1:20). The reaction solution was added dropwise to ethanol to allow the polymer to precipitate. After centrifugation, the supernatant was discarded. This process of dissolving in dichloromethane, adding dropwise to ethanol for precipitation, centrifugation, and discarding the supernatant was repeated twice. The product was then dried at room temperature in a vacuum oven for three days to obtain colorless poly(γ-thioundecyl lactone). Nuclear magnetic resonance (NMR) analysis was performed on poly(γ-thioundecyl lactone). 1 H NMR spectrum and 13 The C NMR spectra are as follows: Figure 13 and Figure 14 As shown.

[0353]

[0354] The present invention uses differential scanning calorimetry (DSC) to detect the melting temperature and glass transition temperature of poly(γ-thioundecyl lactone). The results show that the glass transition temperature of poly(γ-thioundecyl lactone) prepared in this embodiment is -50.0℃.

[0355] This invention employs gel permeation chromatography (GPC) to determine the molecular weight and molecular weight distribution of poly(γ-thioundecyl lactone), using tetrahydrofuran as the eluent at a flow rate of 1.0 mL / min. A standard curve is constructed using polymethyl methacrylate as the standard. The results show that the poly(γ-thioundecyl lactone) prepared in this embodiment has a number-average molecular weight of 37.1 kg / mol and a molecular weight distribution of 1.37.

[0356] Example 9

[0357] In an argon-atmospheric glove box, 0.005 mmol of [Ph3C][B(C6F5)4] was dissolved in 0.3 mL of toluene in a dry 5 mL glass bottle. Then, 1 mmol (214.4 mg, 0.2 mL) of γ-thiocarbonyl dodecyl lactone monomer was added. The initial concentration of the monomer was 2 mol / L, the concentration of the catalyst [Ph3C][B(C6F5)4] was 10 mmol / L, and the molar ratio of monomer to [Ph3C][B(C6F5)4] was 200:1.

[0358] Maintain the reaction temperature at room temperature and stir for 2.5 hours. Take a small amount of sample and dissolve it in deuterated chloroform. 1 The conversion rate was monitored by ¹H NMR, and was greater than 99%. The ratio of γ-thiodododecyl lactone byproduct to poly(γ-thiodododecyl lactone) was 4:96. The reaction was then quenched by adding 2 mL of a water / tetrahydrofuran mixture (volume ratio 1:20). The reaction solution was added dropwise to ethanol to allow the polymer to precipitate. After centrifugation, the supernatant was discarded. This process of dissolving in dichloromethane, adding dropwise to ethanol for precipitation, centrifugation, and discarding the supernatant was repeated twice. The product was then dried at room temperature in a vacuum oven for three days to obtain colorless poly(γ-thiodododecyl lactone). Nuclear magnetic resonance (NMR) analysis was performed on poly(γ-thiodododecyl lactone). 1 H NMR spectrum and 13 The C NMR spectra are as follows: Figure 15 and Figure 16 As shown.

[0359]

[0360] The present invention uses differential scanning calorimetry (DSC) to detect the melting temperature and glass transition temperature of poly(γ-thiodododecyl lactone). The results show that the glass transition temperature of poly(γ-thiodododecyl lactone) prepared in this embodiment is -56.7℃.

[0361] This invention employs gel permeation chromatography (GPC) to determine the molecular weight and molecular weight distribution of poly(γ-thiodododecyl lactone), using tetrahydrofuran as the eluent at a flow rate of 1.0 mL / min. A standard curve is constructed using polymethyl methacrylate as the standard. The results show that the poly(γ-thiodododecyl lactone) prepared in this embodiment has a number-average molecular weight of 56.2 kg / mol and a molecular weight distribution of 1.58.

[0362] Example 10

[0363] In an argon-atmospheric glove box, 0.005 mmol of [Ph3C][B(C6F5)4] was dissolved in 0.3 mL of toluene in a dry 5 mL glass bottle. Then, 1 mmol (200.3 mg, 0.2 mL) of γ-methyl-γ-thiocarbonyldecyl lactone monomer was added. The initial concentration of the monomer was 2 mol / L, the concentration of the catalyst [Ph3C][B(C6F5)4] was 10 mmol / L, and the molar ratio of monomer to [Ph3C][B(C6F5)4] was 200:1.

[0364] After maintaining the reaction temperature at room temperature and stirring for 48 hours, a small sample was dissolved in deuterated chloroform and analyzed. 1 The conversion rate was monitored by H NMR and reached 97.7%. The ratio of γ-methyl-γ-thiodecyl lactone to poly(γ-methyl-γ-thiodecyl lactone) in the product was 28:72. The reaction was then quenched by adding 2 mL of a water / tetrahydrofuran mixture (1:20 v / v). The reaction solution was added dropwise to ethanol to allow the polymer to settle. After centrifugation, the supernatant was discarded. This process of dissolving in dichloromethane, adding dropwise to ethanol for sedimentation, centrifugation, and discarding the supernatant was repeated twice. The product was then dried at room temperature in a vacuum oven for three days to obtain colorless poly(γ-methyl-γ-thiodecyl lactone). Nuclear magnetic resonance (NMR) analysis was performed on poly(γ-methyl-γ-thiodecyl lactone). 1 H NMR spectrum and 13 CNMR spectra are as follows: Figure 17 and Figure 18 As shown.

[0365]

[0366] The present invention uses differential scanning calorimetry (DSC) to detect the melting temperature and glass transition temperature of poly(γ-methyl-γ-thiodecyl lactone). The results show that the glass transition temperature of poly(γ-methyl-γ-thiodecyl lactone) prepared in this embodiment is -34.8℃.

[0367] This invention employs gel permeation chromatography (GPC) to determine the molecular weight and molecular weight distribution of poly(γ-methyl-γ-thiodecyl lactone), using tetrahydrofuran as the eluent at a flow rate of 1.0 mL / min. A standard curve is constructed using polymethyl methacrylate as the standard. The results show that the poly(γ-methyl-γ-thiodecyl lactone) prepared in this embodiment has a number-average molecular weight of 12.8 kg / mol and a molecular weight distribution of 1.42.

[0368] Example 11

[0369] In an argon-atmospheric glove box, 0.005 mmol of [Ph3C][B(C6F5)4] was dissolved in 0.35 mL of toluene in a dry 5 mL glass bottle. Then, 1 mmol (172.3 mg, 0.16 mL) of β-methyl-γ-thiocarbonyloctyl lactone monomer was added. The initial concentration of the monomer was 2 mol / L, the concentration of the catalyst [Ph3C][B(C6F5)4] was 10 mmol / L, and the molar ratio of monomer to [Ph3C][B(C6F5)4] was 200:1.

[0370] Maintaining the reaction temperature at room temperature and stirring for 5 hours, a small sample was dissolved in deuterated chloroform and analyzed. 1 The conversion rate was monitored by H NMR, reaching 85.9%, with a β-methyl-γ-thiooctanolide:poly(β-methyl-γ-thiooctanolide) ratio of 1:99 in the product. The reaction was then quenched by adding 2 mL of a water / tetrahydrofuran mixture (1:20 v / v). The reaction solution was added dropwise to ethanol to allow the polymer to settle, centrifuged, and the supernatant was discarded. This process was repeated twice, involving dissolution with dichloromethane, precipitation in ethanol, centrifugation, and discarding of the supernatant. The product was then dried at room temperature in a vacuum oven for three days to obtain colorless poly(β-methyl-γ-thiooctanolide). Nuclear magnetic resonance (NMR) analysis was performed on poly(β-methyl-γ-thiooctanolide). 1 H NMR spectrum and 13 The C NMR spectra are as follows: Figure 19 and Figure 20 As shown.

[0371]

[0372] The present invention uses differential scanning calorimetry (DSC) to detect the melting temperature and glass transition temperature of poly(β-methyl-γ-thiooctanolide). The results show that the glass transition temperature of poly(β-methyl-γ-thiooctanolide) prepared in this embodiment is 3.4℃.

[0373] This invention employs gel permeation chromatography (GPC) to determine the molecular weight and molecular weight distribution of poly(β-methyl-γ-thiooctanolide), using tetrahydrofuran as the eluent at a flow rate of 1.0 mL / min. A standard curve is constructed using polymethyl methacrylate as the standard. The results show that the poly(β-methyl-γ-thiooctanolide) prepared in this embodiment has a number-average molecular weight of 38.6 kg / mol and a molecular weight distribution of 1.29.

[0374] Example 12

[0375] In an argon-atmospheric glove box, 0.02 mmol of potassium thioacetate and 0.2 mL of N,N-dimethylformamide were added to a dry Schlenk flask, followed by 2 mmol (232 mg, 0.2 mL) of α-methyl-γ-thiocarbonylbutyrolactone monomer. The initial concentration of the monomer was 5 mol / L, the concentration of the potassium thioacetate catalyst was 50 mmol / L, and the molar ratio of monomer to potassium thioacetate was 100:1.

[0376] Remove the flask from the glove box and connect the Schlenk flask to an argon-protected vacuum line. Stir the reaction at 80°C for 2 hours. After polymerization, add 0.15 mL of a toluene solution containing 0.05 mL of allyl chloride to terminate the reaction. Take a small amount of the solution for further processing. 1 ¹H NMR analysis was used to determine the conversion rate, which was greater than 99%. The ratio of α-methyl-γ-thiobutyrolactone byproduct to poly(α-methyl-γ-thiobutyrolactone) was 3:97. The remaining reaction solution was poured into ethanol to allow the polymer to precipitate. The precipitated solid was centrifuged, and the supernatant was discarded. This process of dissolving in dichloromethane, adding dropwise to ethanol for precipitation, centrifuging, and discarding the supernatant was repeated twice. The product was then dried in a vacuum oven at room temperature for three days to obtain colorless poly(α-methyl-γ-thiobutyrolactone). Nuclear magnetic resonance (NMR) analysis was performed on poly(α-methyl-γ-thiobutyrolactone). 1 H NMR spectrum and 13 The C NMR spectra are as follows: Figure 21 and Figure 22 As shown.

[0377]

[0378] The present invention uses differential scanning calorimetry (DSC) to detect the melting temperature and glass transition temperature of poly(α-methyl-γ-thiobutyrolactone). The results show that the glass transition temperature of poly(α-methyl-γ-thiobutyrolactone) prepared in this embodiment is -30.2℃.

[0379] This invention employs gel permeation chromatography (GPC) to determine the molecular weight and molecular weight distribution of poly(α-methyl-γ-thiobutyrolactone), using tetrahydrofuran as the eluent at a flow rate of 1.0 mL / min. A standard curve is constructed using polymethyl methacrylate as the standard. The results show that the poly(α-methyl-γ-thiobutyrolactone) prepared in this embodiment has a number-average molecular weight of 8.6 kg / mol and a molecular weight distribution of 1.03.

[0380] Example 13

[0381] In an argon-atmospheric glove box, 0.928 g (8 mmol, 0.8 mL) of β-methyl-γ-thiocarbonylbutyrolactone monomer was added to a dry Schlenk flask. The flask was then removed from the glove box and connected to a vacuum line under argon protection. After stirring at 80 °C for 10 minutes, 0.005 mmol of the monomer was dissolved in 0.8 mL of toluene. t Bu-P4 and 0.005 mmol of diphenylmethanol were added separately to the Schlenk flasks mentioned above. Polymerization began with a total volume of 1.6 mL and an initial monomer concentration of 5 mol / L. The catalyst... t The concentration of Bu-P4 was 3.1 mmol / L, the concentration of the co-catalyst diphenylmethanol was 3.1 mmol / L, and the monomer and t The molar ratio of Bu-P4 was 1600:1. The reaction temperature was maintained at 80℃, and the polymerization reaction was carried out for 4 hours. After the polymerization reaction was complete, a chloroform solution with a mass concentration of 10 mg / mL benzoic acid was added to dissolve the product, and a small amount of the solution was taken for further processing. 1 ¹H NMR analysis was used to determine the conversion rate. The remaining reaction solution was poured into ethanol to allow the polymer to precipitate. The precipitated solid was filtered, washed three times with ethanol, and then dried in a vacuum drying oven at 40°C for 24 hours to obtain white poly(β-methyl-γ-thiobutyrolactone). Nuclear magnetic resonance (NMR) analysis was then performed on poly(β-methyl-γ-thiobutyrolactone). 1 H NMR spectrum and 13 The C NMR spectra are as follows: Figure 23 and Figure 24 As shown.

[0382]

[0383] The present invention detected the hydrogen nuclear magnetic resonance spectrum of the obtained reaction solution, and the results showed that the conversion rate of monomer was 99.8% and the ratio of β-methyl-γ-thiobutyrolactone byproduct to poly(β-methyl-γ-thiobutyrolactone) was 3:97.

[0384] The present invention uses differential scanning calorimetry (DSC) to detect the melting temperature and glass transition temperature of poly(β-methyl-γ-thiobutyrolactone). The results show that the glass transition temperature of poly(β-methyl-γ-thiobutyrolactone) prepared in this embodiment is -30.4℃.

[0385] The present invention uses gel permeation chromatography (GPC) to detect the molecular weight and molecular weight distribution of poly(β-methyl-γ-thiobutyrolactone). The results show that the number-average molecular weight of poly(β-methyl-γ-thiobutyrolactone) prepared in this embodiment is 251.0 kg / mol and the molecular weight distribution is 1.56.

[0386] Example 14

[0387] In an argon-atmospheric glove box, 0.327 g (3.2 mmol, 280 μL) of γ-thiocarbonylbutyrolactone and 0.022 g (0.17 mmol, 20 μL) of β-vinyl-γ-thiocarbonylbutyrolactone monomer were added to a dry Schlenk flask. The flask was then removed from the glove box and connected to an argon-protected vacuum line. After stirring at 80 °C for 10 minutes, 0.01 mmol of the monomer was dissolved in 0.4 mL of toluene. t A mixture of Bu-P4 and 0.01 mmol of Ph2CHOH and 0.093 g (0.8 mmol, 83 μL) of α-methyl-γ-thiocarbonylbutyrolactone was added to the Schlenk flask described above. Polymerization began with a total volume of 0.78 mL. The initial concentrations of monomers were: γ-thiocarbonylbutyrolactone 4.1 mol / L, β-vinyl-γ-thiocarbonylbutyrolactone 0.2 mol / L, and α-methyl-γ-thiocarbonylbutyrolactone 1.0 mol / L. The catalyst... t The concentration of Bu-P4 was 12.8 mmol / L, the concentration of the co-catalyst Ph2CHOH was 12.8 mmol / L, and the three monomers and t The molar ratio of Bu-P4 was 320:80:17:1. The reaction temperature was maintained at 80℃, and the polymerization reaction was carried out for 1 hour. After the polymerization reaction was completed, a chloroform solution with a mass concentration of 10 mg / mL benzoic acid was added to dissolve the product, and a small amount of the solution was taken for further processing. 1 ¹H NMR analysis was used to determine the conversion rate. The remaining reaction solution was poured into ethanol to allow the polymer to precipitate. The precipitated solid was filtered, washed three times with ethanol, and then dried in a vacuum drying oven at 40°C for 24 hours to obtain a white terpolymer. Nuclear magnetic resonance (NMR) analysis was performed on the copolymer. 1 H NMR spectrum as follows Figure 25 As shown.

[0388]

[0389] The present invention detected the hydrogen nuclear magnetic resonance spectrum of the obtained reaction solution, and the results showed that the conversion rate of monomer was 99.9% and the ratio of backbite byproduct to copolymer in the generated product was 5:95.

[0390] The present invention uses differential scanning calorimetry (DSC) to detect the melting temperature and glass transition temperature of the copolymer. The results show that the glass transition temperature of the terpolymer prepared in this embodiment is -47.89℃ and the melting temperature is 59.51℃.

[0391] The present invention uses gel permeation chromatography (GPC) to detect the molecular weight and molecular weight distribution of the terpolymer. The results show that the number-average molecular weight of the terpolymer prepared in this embodiment is 65.0 kg / mol and the molecular weight distribution is 1.73.

[0392] The mechanical properties of the obtained ternary random copolymer were tested: the tensile test showed that the elongation at break of the ternary random copolymer was 1451.30% and the breaking stress was 16.62 MPa; in addition, the cyclic tensile test showed that the elastic recovery rate of the ternary random copolymer was 72.3%.

[0393] Example 15

[0394] In an argon-atmospheric glove box, 0.1 mL of toluene, 0.01 mL of mesitylene, and 1 mmol (156 mg, 0.14 mL) of cis-hexahydroisobenzofuran-1-thione monomer were placed in a dry Schlenk flask. 0.01 mL of the solution was then used for… 1 ¹H NMR analysis determined the ratio of monomer to internal standard thiomethylbenzene in the initial reaction solution; then 0.01 mol of potassium thioacetate and 0.01 mmol of 18-crown-6 ether were added. The initial concentration of monomer was 4 mol / L, the concentration of potassium thioacetate catalyst was 4 mmol / L, and the molar ratio of monomer to potassium thioacetate and 18-crown-6 ether was 100:1:1.

[0395] Remove the flask from the glove box and connect the Schlenk flask to an argon-protected vacuum line. Stir the reaction at 80°C for 4 hours. After polymerization, add 0.15 mL of a toluene solution containing 0.05 mL of allyl chloride to terminate the reaction. Take a small amount of the solution for further processing. 1 The conversion rate was determined by ¹H NMR analysis and by analyzing the change in the integral ratio of monomer to internal standard methylbenzylene. The conversion rate was greater than 99%, and the ratio of cis-hexahydroisobenzothiophene-1-one byproduct to poly(cis-hexahydroisobenzothiophene-1-one) was 12:88. The remaining reaction solution was poured into ice-cold methanol to allow the polymer to precipitate. The precipitated solid was centrifuged, the supernatant was discarded, and the process of dissolving in dichloromethane, precipitating in methanol, centrifuging, and discarding the supernatant was repeated twice. Then, it was dried at room temperature in a vacuum drying oven for three days to obtain a white solid of poly(cis-hexahydroisobenzothiophene-1-one), which was then detected by nuclear magnetic resonance (NMR). 1 H NMR spectrum and 13 CNMR spectra are as follows: Figure 26 and Figure 27 As shown.

[0396]

[0397] The present invention uses differential scanning calorimetry (DSC) to detect the melting temperature and glass transition of poly(cis-hexahydroisobenzothiophene-1-one). The results show that the glass transition temperature of poly(cis-hexahydroisobenzothiophene-1-one) prepared in this embodiment is 65.1℃.

[0398] The thermal stability of the poly(cis-hexahydroisobenzothiophene-1-one) prepared in this embodiment was determined using a thermogravimetric analyzer (TGA). The initial decomposition temperature (T) of the polymer was obtained. d The temperature at which 5% weight loss occurs is 255.3℃, exhibiting good thermal stability.

[0399] This invention employs gel permeation chromatography (GPC) to determine the molecular weight and molecular weight distribution of poly(cis-hexahydroisobenzothiophene-1-one), using tetrahydrofuran as the eluent at a flow rate of 1.0 mL / min. A standard curve is constructed using polymethyl methacrylate as the standard. The results show that the poly(cis-hexahydroisobenzothiophene-1-one) prepared in this embodiment has a number-average molecular weight of 22.6 kg / mol and a molecular weight distribution of 1.23.

[0400] Example 16

[0401] In an argon-atmospheric glove box, 0.02 mmol of potassium thioacetate, 0.02 mmol of 18-crown-6 ether, and 0.2 mL of toluene were added to a dry Schlenk flask. Then, 2 mmol (232 mg, 0.2 mL) of α-methyl-γ-thiocarbonylbutyrolactone monomer was added. The initial concentration of the monomer was 5 mol / L, the concentration of the catalyst potassium thioacetate was 50 mmol / L, and the molar ratio of monomer to potassium thioacetate and 18-crown-6 ether was 100:1:1.

[0402] Remove the flask from the glove box and connect the Schlenk flask to an argon-protected vacuum line. Stir the reaction at 80°C for 5 hours. After polymerization, add 0.15 mL of a toluene solution containing 0.05 mL of allyl chloride to terminate the reaction. Take a small amount of the solution for further processing. 1 ¹H NMR analysis was used to determine the conversion rate, which was greater than 99%. The ratio of α-methyl-γ-thiobutyrolactone byproduct to poly(α-methyl-γ-thiobutyrolactone) was 6:94. The remaining reaction solution was poured into ethanol to allow the polymer to precipitate. The precipitated solid was centrifuged, and the supernatant was discarded. The process of dissolving in dichloromethane, adding dropwise to ethanol for precipitation, centrifuging, and discarding the supernatant was repeated twice. The product was then dried in a vacuum drying oven at room temperature for three days to obtain colorless poly(α-methyl-γ-thiobutyrolactone).

[0403]

[0404] The present invention uses differential scanning calorimetry (DSC) to detect the melting temperature and glass transition of poly(α-methyl-γ-thiobutyrolactone). The results show that the glass transition temperature of poly(α-methyl-γ-thiobutyrolactone) prepared in this embodiment is -30.2℃.

[0405] This invention employs gel permeation chromatography (GPC) to determine the molecular weight and molecular weight distribution of poly(α-methyl-γ-thiobutyrolactone), using tetrahydrofuran as the eluent at a flow rate of 1.0 mL / min. A standard curve is constructed using polymethyl methacrylate as the standard. The results show that the poly(α-methyl-γ-thiobutyrolactone) prepared in this embodiment has a number-average molecular weight of 11.4 kg / mol and a molecular weight distribution of 1.02.

[0406] Example 17

[0407] In an argon-atmospheric glove box, 0.01 mol of benzoic acid and 0.01 mmol of [unspecified substance] were added to a dry Schlenk flask. t Bu-P4 and 0.2 mL of toluene were added, followed by 2 mmol (232 mg, 0.2 mL) of α-methyl-γ-thiocarbonylbutyrolactone monomer at an initial concentration of 5 mol / L, and catalyst. t The concentration of Bu-P4 was 25 mmol / L, and the monomer and t The molar ratio of Bu-P4 to benzoic acid is 200:1:1.

[0408] Remove the flask from the glove box and connect the Schlenk flask to an argon-protected vacuum line. Stir the reaction at 80°C for 1 hour. After polymerization, add 0.15 mL of a toluene solution containing 0.05 mL of allyl chloride to terminate the reaction. Take a small amount of the solution for further processing. 1 ¹H NMR analysis was used to determine the conversion rate, which was greater than 99%. The ratio of α-methyl-γ-thiobutyrolactone byproduct to poly(α-methyl-γ-thiobutyrolactone) was 5:95. The remaining reaction solution was poured into ethanol to allow the polymer to precipitate. The precipitated solid was centrifuged, and the supernatant was discarded. The process of dissolving in dichloromethane, precipitating in ethanol, centrifuging, and discarding the supernatant was repeated twice. The product was then dried at room temperature in a vacuum drying oven for three days to obtain colorless poly(α-methyl-γ-thiobutyrolactone).

[0409]

[0410] The present invention uses differential scanning calorimetry (DSC) to detect the melting temperature and glass transition of poly(α-methyl-γ-thiobutyrolactone). The results show that the glass transition temperature of poly(α-methyl-γ-thiobutyrolactone) prepared in this embodiment is -30.2℃.

[0411] This invention employs gel permeation chromatography (GPC) to determine the molecular weight and molecular weight distribution of poly(α-methyl-γ-thiobutyrolactone), using tetrahydrofuran as the eluent at a flow rate of 1.0 mL / min. A standard curve is constructed using polymethyl methacrylate as the standard. The results show that the poly(α-methyl-γ-thiobutyrolactone) prepared in this embodiment has a number-average molecular weight of 20.0 kg / mol and a molecular weight distribution of 1.05.

[0412] Example 18

[0413] In an argon-atmospheric glove box at room temperature, 0.005 mmol of [Ph3C][B(C6F5)4] was dissolved in 0.8 mL of toluene in a dry 5 mL glass bottle. Then, 8 mmol (929.4 mg, 0.86 mL) of γ-thiocarbonyl valerate monomer was added. The initial concentration of the monomer was 5 mol / L, the concentration of the catalyst [Ph3C][B(C6F5)4] was 3.1 mmol / L, and the molar ratio of monomer to [Ph3C][B(C6F5)4] was 1600:1.

[0414] After maintaining the reaction temperature at room temperature and stirring for 18 hours, a small sample was dissolved in deuterated chloroform and analyzed. 1 The conversion rate was monitored by ¹H NMR and found to be 94.3%, with a γ-thiovalactone byproduct to poly(γ-thiovalactone) ratio of 1:99. The reaction was then quenched by adding 12 mL of a water / tetrahydrofuran mixture (volume ratio 1:30). The reaction solution was then added dropwise to ethanol to allow the polymer to precipitate. After centrifugation, the supernatant was discarded. This process of dissolving in dichloromethane, adding dropwise to ethanol for precipitation, centrifugation, and discarding the supernatant was repeated twice. Finally, the product was dried at room temperature in a vacuum oven for three days to obtain colorless poly(γ-thiovalactone).

[0415]

[0416] The present invention uses differential scanning calorimetry (DSC) to detect the melting temperature and glass transition of poly(γ-thiovalactone). The results show that the glass transition temperature of poly(γ-thiovalactone) prepared in this embodiment is -9.8℃.

[0417] This invention employs gel permeation chromatography (GPC) to determine the molecular weight and molecular weight distribution of poly(γ-thiovalactone), using tetrahydrofuran as the eluent at a flow rate of 1.0 mL / min. A standard curve is constructed using polymethyl methacrylate as the standard. The results show that the poly(γ-thiovalactone) prepared in this embodiment has a number-average molecular weight of 133.2 kg / mol and a molecular weight distribution of 1.76.

[0418] Example 19

[0419] In an argon-atmospheric glove box, 0.01 mmol of [H(Et2O)2][B(C6F5)4] and 0.4 mL of toluene were added to a dry glass bottle. Then, 1 mmol (116.2 mg, 0.10 mL) of γ-thiocarbonyl valerate monomer was added. The initial concentration of the monomer was 2 mol / L, the concentration of the catalyst [H(Et2O)2][B(C6F5)4] was 20 mmol / L, and the molar ratio of monomer to [H(Et2O)2][B(C6F5)4] was 100:1.

[0420] Maintain the reaction temperature at room temperature, and during the polymerization process, dissolve a small amount of sample in deuterated chloroform. 1 The conversion rate was monitored by ¹H NMR. The conversion rate reached 98.4% after 2 hours of polymerization. The ratio of γ-thiovalactone to poly(γ-thiovalactone) in the product was 10:90. Then, 2 mL of water / tetrahydrofuran mixture (volume ratio 1:30) was added to quench the reaction. The reaction solution was then added dropwise to ethanol to allow the polymer to settle. After centrifugation, the supernatant was discarded. The process of dissolving in dichloromethane, adding dropwise to ethanol to allow precipitation, centrifugation, and discarding the supernatant was repeated twice. Finally, the product was dried at room temperature in a vacuum drying oven for three days to obtain colorless poly(γ-thiovalactone).

[0421]

[0422] This invention employs gel permeation chromatography (GPC) to determine the molecular weight and molecular weight distribution of poly(γ-thiovalactone), using tetrahydrofuran as the eluent at a flow rate of 1.0 mL / min. A standard curve is constructed using polymethyl methacrylate as the standard. The results show that the poly(γ-thiovalactone) prepared in this embodiment has a number-average molecular weight of 32.9 kg / mol and a molecular weight distribution of 1.46.

[0423] Example 20

[0424] In an argon-atmospheric glove box, 0.01 mmol of B(C6F5)3 and 0.1 mL of toluene were added to a dry Schlenk flask, followed by 1 mmol (116.2 mg, 0.10 mL) of γ-thiocarbonyl valerate monomer. The initial monomer concentration was 5 mol / L, the catalyst concentration of B(C6F5)3 was 50 mmol / L, and the molar ratio of monomer to B(C6F5)3 was 100:1.

[0425] Remove the flask from the glove box and connect it to an argon-protected vacuum line. Stir the reaction at 80°C for 1.5 hours. After polymerization, add 2 mL of a water / tetrahydrofuran mixture (1:30 v / v) to quench the reaction. Dissolve a small amount of sample in deuterated chloroform. 1The conversion rate was monitored by ¹H NMR, and the polymerization conversion rate reached 94.8%. The ratio of γ-thiovalactone to poly(γ-thiovalactone) in the product was 66:34. The reaction solution was added dropwise to ethanol to allow the polymer to settle. After centrifugation, the supernatant was discarded. The process of dissolving in dichloromethane, adding dropwise to ethanol to allow precipitation, centrifugation, and discarding the supernatant was repeated twice. The product was then dried at room temperature in a vacuum drying oven for three days to obtain colorless poly(γ-thiovalactone).

[0426]

[0427] This invention employs gel permeation chromatography (GPC) to determine the molecular weight and molecular weight distribution of poly(γ-thiovalactone), using tetrahydrofuran as the eluent at a flow rate of 1.0 mL / min. A standard curve is constructed using polymethyl methacrylate as the standard. The results show that the poly(γ-thiovalactone) prepared in this embodiment has a number-average molecular weight of 74.0 kg / mol and a molecular weight distribution of 1.65.

[0428] Example 21

[0429] In an argon-atmospheric glove box, 0.232 g (2.0 mmol, 200 μL) of α-methyl-γ-thiocarbonylbutyrolactone and 0.40 mL of N,N-dimethylformamide solution containing 2.3 mg (0.02 mmol) of potassium thioacetate were added to a dry Schlenk flask. The glove box was removed and the Schlenk flask was connected to an argon-protected vacuum line. The reaction was stirred at 80 °C for 2.5 h until the α-methyl-γ-thiocarbonylbutyrolactone had completely reacted. Then, 0.204 g (2.0 mmol, 175 μL) of γ-thiocarbonylbutyrolactone monomer was added using a syringe, and the reaction was continued for 1 h. The initial concentrations of α-methyl-γ-thiocarbonylbutyrolactone monomer were 3.3 mol / L and γ-thiocarbonylbutyrolactone monomer were 2.6 mol / L. The concentration of the catalyst potassium thioacetate was 66.7 mmol / L, and the molar ratio of α-methyl-γ-thiocarbonylbutyrolactone to γ-thiocarbonylbutyrolactone and potassium thioacetate was 100:100:1.

[0430] After the polymerization reaction was completed, 0.15 mL of a toluene solution containing 0.05 mL of allyl chloride was added to terminate the reaction. A small amount of the solution was then taken for further processing. 1 ¹H NMR analysis was used to determine the conversion rate. The conversion rate of α-methyl-γ-thiocarbonylbutyrolactone was 97.7%, and that of γ-thiocarbonylbutyrolactone was 77.7%. The ratio of byproduct to copolymer in the product was 6.2:93.8. The remaining reaction solution was poured into ethanol to allow the polymer to settle. The precipitated solid was filtered, washed three times with ethanol, and then dried in a vacuum drying oven at 40°C for 24 hours to obtain a white block copolymer. Nuclear magnetic resonance (NMR) analysis was performed on the copolymer. 1 H NMR spectrum as follows Figure 28 As shown.

[0431]

[0432] The present invention uses differential scanning calorimetry (DSC) to detect the melting temperature and glass transition temperature of the copolymer. The results show that the glass transition temperature of the terpolymer prepared in this embodiment is -32.90℃ and the melting temperature is 92.74℃.

[0433] The present invention uses gel permeation chromatography (GPC) to detect the molecular weight and molecular weight distribution of the terpolymer. The results show that the number-average molecular weight of the terpolymer prepared in this embodiment is 32.2 kg / mol and the molecular weight distribution is 1.09.

[0434] Example 22

[0435] In an argon-atmospheric glove box, 0.236 g (2.0 mmol, 200 μL) of propylene thiocarbonate and 0.20 mL of N,N-dimethylformamide solution containing 2.3 mg (0.02 mmol) of potassium thioacetate were added to a dry Schlenk flask. The flask was removed from the glove box and connected to an argon-protected vacuum line. The concentration of potassium thioacetate catalyst was 50 mmol / L, the initial concentration of propylene thiocarbonate monomer was 5 mol / L, and the molar ratio of propylene thiocarbonate to potassium thioacetate was 100:1.

[0436] After the polymerization reaction was completed, 0.15 mL of a toluene solution containing 0.05 mL of allyl chloride was added to terminate the reaction. A small amount of the solution was then taken for further processing. 1 ¹H NMR analysis was used to determine the conversion rate, which was 99% for poly(propylene monothiocarbonate). The remaining reaction solution was poured into ethanol to allow the polymer to settle. The precipitated solid was filtered, washed three times with ethanol, and then dried in a vacuum drying oven at 40°C for 24 hours to obtain white poly(propylene monothiocarbonate). Nuclear magnetic resonance (NMR) analysis was then performed on the polymer. 1 H NMR spectrum and 13 The C NMR spectra are as follows: Figure 29 and Figure 30 As shown.

[0437]

[0438] The present invention uses gel permeation chromatography (GPC) to detect the molecular weight and molecular weight distribution of poly(propylene monothiocarboxylate). The results show that the number-average molecular weight of the poly(propylene monothiocarboxylate) prepared in this embodiment is 9.2 kg / mol and the molecular weight distribution is 1.53.

[0439] Example 23

[0440] In an argon-atmospheric glove box, 0.005 mmol of [Ph3C][B(C6F5)4] was dissolved in 0.32 mL of toluene in a dry 5 mL glass bottle. Then, 1 mmol (186.3 mg, 0.18 mL) of thiocarbonyl carbonate monomer was added. The initial concentration of the monomer was 2 mol / L, the concentration of the catalyst [Ph3C][B(C6F5)4] was 10 mmol / L, and the molar ratio of monomer to [Ph3C][B(C6F5)4] was 200:1.

[0441] Maintain the reaction temperature at room temperature and stir for 1.0 h. Then, take a small amount of sample and dissolve it in deuterated chloroform. 1 The conversion rate was monitored by H NMR and was greater than 99%. Then, 2 mL of water / tetrahydrofuran mixture (volume ratio 1:20) was added to quench the reaction. The reaction solution was added dropwise to ethanol to allow the polymer to settle. After centrifugation, the supernatant was discarded. The process of dissolving in dichloromethane, adding dropwise to ethanol to settle, centrifuging, and discarding the supernatant was repeated twice. The product was then dried at room temperature in a vacuum drying oven for three days to obtain colorless poly(monothiopropylene carbonate).

[0442]

[0443] This invention uses gel permeation chromatography (GPC) to determine the molecular weight and molecular weight distribution of poly(propylene monothiocarboxylate), with tetrahydrofuran as the eluent and a flow rate of 1.0 mL / min. A standard curve is prepared using polymethyl methacrylate as the standard. The results show that the poly(propylene monothiocarboxylate) prepared in this embodiment has a number-average molecular weight of 10.2 kg / mol and a molecular weight distribution of 1.65.

[0444] Example 24

[0445] In an argon-atmospheric glove box, 4 mmol (464.5 mg, 0.43 mL) of α-methylγ-thiocarbonylbutyrolactone monomer was added to a dry Schlenk flask. The flask was then removed from the glove box and connected to an argon-protected vacuum line. The mixture was stirred at 80 °C for 10 minutes. 0.01 mmol of TBD and 0.01 mmol of PhCOOH were dissolved in 0.43 mL of toluene, and this solution was added to the aforementioned Schlenk flask. The initial monomer concentration was 5 mol / L, and the concentrations of the catalyst TBD and initiator PhCOOH were 12.5 mmol / L. The molar ratio of monomer to TBD / PHCOOH was 400:1:1.

[0446] After maintaining the reaction temperature at 80℃ and polymerizing for 17 hours, a chloroform solution with a mass concentration of 10 mg / mL benzoic acid was added to dissolve the product. A small amount of the solution was then taken for further processing. 1¹H NMR analysis was used to determine the conversion rate, which was 82.4%. The ratio of α-methyl-γ-thiobutyrolactone byproduct to poly(α-methyl-γ-thiobutyrolactone) in the product was 16:84. The remaining reaction solution was poured into ethanol to allow the polymer to precipitate. The precipitated solid was centrifuged, and the supernatant was discarded. The process of dissolving in dichloromethane, adding dropwise to ethanol for precipitation, centrifuging, and discarding the supernatant was repeated twice. The product was then dried in a vacuum drying oven at room temperature for three days to obtain colorless poly(α-methyl-γ-thiobutyrolactone).

[0447]

[0448] This invention employs gel permeation chromatography (GPC) to determine the molecular weight and molecular weight distribution of poly(α-methyl-γ-thiobutyrolactone), using tetrahydrofuran as the eluent at a flow rate of 1.0 mL / min. A standard curve is constructed using polymethyl methacrylate as the standard. The results show that the poly(α-methyl-γ-thiobutyrolactone) prepared in this embodiment has a number-average molecular weight of 22.6 kg / mol and a molecular weight distribution of 1.20.

[0449] Example 25

[0450] In an argon-atmospheric glove box, 2 mmol (232.5 mg, 0.22 mL) of α-methylγ-thiocarbonylbutyrolactone monomer was added to a dry Schlenk flask. The flask was then removed from the glove box and connected to an argon-protected vacuum line. The mixture was stirred at 80 °C for 10 minutes. 0.02 mmol of DBU and 0.02 mmol of PhCOSH were dissolved in 0.22 mL of toluene, and this solution was added to the aforementioned Schlenk flask. The initial monomer concentration was 5 mol / L, and the concentrations of the catalyst DBU and initiator PhCOSH were 50 mmol / L. The molar ratio of monomer to DBU / PHCOSH was 100:1:1.

[0451] After maintaining the reaction temperature at 80℃ and polymerizing for 5 hours, a chloroform solution with a mass concentration of 10 mg / mL benzoic acid was added to dissolve the product. A small amount of the solution was then taken for further processing. 1 ¹H NMR analysis was used to determine the conversion rate, which reached 96.8%. The ratio of α-methyl-γ-thiobutyrolactone byproduct to poly(α-methyl-γ-thiobutyrolactone) in the product was 11:89. The remaining reaction solution was poured into ethanol to allow the polymer to precipitate. The precipitated solid was centrifuged, and the supernatant was discarded. The process of dissolving in dichloromethane, precipitating in ethanol, centrifuging, and discarding the supernatant was repeated twice. The product was then dried at room temperature in a vacuum drying oven for three days to obtain colorless poly(α-methyl-γ-thiobutyrolactone).

[0452]

[0453] This invention employs gel permeation chromatography (GPC) to determine the molecular weight and molecular weight distribution of poly(α-methyl-γ-thiobutyrolactone), using tetrahydrofuran as the eluent at a flow rate of 1.0 mL / min. A standard curve is constructed using polymethyl methacrylate as the standard. The results show that the poly(α-methyl-γ-thiobutyrolactone) prepared in this embodiment has a number-average molecular weight of 9.9 kg / mol and a molecular weight distribution of 1.02.

[0454] Example 26

[0455] In an argon-atmospheric glove box, 2 mmol (232.5 mg, 0.22 mL) of α-methylγ-thiocarbonylbutyrolactone monomer was added to a dry Schlenk flask. The flask was then removed from the glove box and connected to an argon-protected vacuum line. The mixture was stirred at 80 °C for 10 minutes. 0.01 mmol of I was dissolved in 0.22 mL of toluene. t Bu N-heterocyclic carbene catalyst, and the toluene solution was added to the above-mentioned Schlenk flask, with an initial monomer concentration of 5 mol / L, catalyst I t The concentration of Bu was 50 mmol / L, and the monomer and I t The molar ratio of Bu is 100:1.

[0456] After maintaining the reaction temperature at 80℃ and polymerizing for 1 hour, a chloroform solution with a mass concentration of 10 mg / mL benzoic acid was added to dissolve the product. A small amount of the solution was then taken for further processing. 1 ¹H NMR analysis was used to determine the conversion rate, which was 95.7%. The ratio of α-methyl-γ-thiobutyrolactone byproduct to poly(α-methyl-γ-thiobutyrolactone) in the product was 2:98. The remaining reaction solution was poured into ethanol to allow the polymer to precipitate. The precipitated solid was centrifuged, and the supernatant was discarded. The process of dissolving in dichloromethane, precipitating in ethanol, centrifuging, and discarding the supernatant was repeated twice. The product was then dried in a vacuum drying oven at room temperature for three days to obtain colorless poly(α-methyl-γ-thiobutyrolactone).

[0457]

[0458] This invention employs gel permeation chromatography (GPC) to determine the molecular weight and molecular weight distribution of poly(α-methyl-γ-thiobutyrolactone), using tetrahydrofuran as the eluent at a flow rate of 1.0 mL / min. A standard curve is constructed using polymethyl methacrylate as the standard. The results show that the poly(α-methyl-γ-thiobutyrolactone) prepared in this embodiment has a number-average molecular weight of 9.39 kg / mol and a molecular weight distribution of 1.01.

[0459] Example 27

[0460] In an argon-atmospheric glove box, 4 mmol (464.5 mg, 0.43 mL) of α-methylγ-thiocarbonylbutyrolactone monomer was added to a dry Schlenk flask. The flask was then removed from the glove box and connected to an argon-protected vacuum line. The mixture was stirred at 80 °C for 10 minutes. 0.01 mmol of NHO N-heterocyclic olefin catalyst was dissolved in 0.43 mL of toluene, and this solution was added to the aforementioned Schlenk flask. The initial monomer concentration was 5 mol / L, the NHO catalyst concentration was 12.5 mmol / L, and the molar ratio of monomer to NHO was 400:1.

[0461] After maintaining the reaction temperature at 80℃ and polymerizing for 2 hours, a chloroform solution with a mass concentration of 10 mg / mL benzoic acid was added to dissolve the product. A small amount of the solution was then taken for further processing. 1 ¹H NMR analysis was used to determine the conversion rate, which was 87.8%. The ratio of α-methyl-γ-thiobutyrolactone byproduct to poly(α-methyl-γ-thiobutyrolactone) in the product was 3:97. The remaining reaction solution was poured into ethanol to allow the polymer to precipitate. The precipitated solid was centrifuged, and the supernatant was discarded. The process of dissolving in dichloromethane, precipitating in ethanol, centrifuging, and discarding the supernatant was repeated twice. The product was then dried in a vacuum drying oven at room temperature for three days to obtain colorless poly(α-methyl-γ-thiobutyrolactone).

[0462]

[0463] This invention employs gel permeation chromatography (GPC) to determine the molecular weight and molecular weight distribution of poly(α-methyl-γ-thiobutyrolactone), using tetrahydrofuran as the eluent at a flow rate of 1.0 mL / min. A standard curve is constructed using polymethyl methacrylate as the standard. The results show that the poly(α-methyl-γ-thiobutyrolactone) prepared in this embodiment has a number-average molecular weight of 43.6 kg / mol and a molecular weight distribution of 1.08.

[0464] Example 28

[0465] In an argon-atmospheric glove box, 4 mmol (464.5 mg, 0.43 mL) of α-methylγ-thiocarbonylbutyrolactone monomer was added to a dry Schlenk flask. The flask was then removed from the glove box and connected to an argon-protected vacuum line. The mixture was stirred at 80 °C for 10 minutes. 0.01 mmol of the monomer was dissolved in 0.43 mL of toluene. t BuP1 phosphononitrile base catalyst, and this solution was added to the aforementioned Schlenk flask, with an initial monomer concentration of 5 mol / L, catalyst t The concentration of BuP1 was 12.5 mmol / L, and the monomer and t The molar ratio of BuP1 is 400:1.

[0466] After maintaining the reaction temperature at 80℃ and polymerizing for 1 hour, a chloroform solution with a mass concentration of 10 mg / mL benzoic acid was added to dissolve the product. A small amount of the solution was then taken for further processing. 1 ¹H NMR analysis was used to determine the conversion rate, which was 87.8%. The ratio of α-methyl-γ-thiobutyrolactone byproduct to poly(α-methyl-γ-thiobutyrolactone) in the product was 5:99. The remaining reaction solution was poured into ethanol to allow the polymer to precipitate. The precipitated solid was centrifuged, and the supernatant was discarded. The process of dissolving in dichloromethane, precipitating in ethanol, centrifuging, and discarding the supernatant was repeated twice. The product was then dried in a vacuum drying oven at room temperature for three days to obtain colorless poly(α-methyl-γ-thiobutyrolactone).

[0467]

[0468] This invention employs gel permeation chromatography (GPC) to determine the molecular weight and molecular weight distribution of poly(α-methyl-γ-thiobutyrolactone), using tetrahydrofuran as the eluent at a flow rate of 1.0 mL / min. A standard curve is constructed using polymethyl methacrylate as the standard. The results show that the poly(α-methyl-γ-thiobutyrolactone) prepared in this embodiment has a number-average molecular weight of 20.0 kg / mol and a molecular weight distribution of 1.05.

[0469] Example 29

[0470] In an argon-atmospheric glove box at room temperature, 0.01 mmol of [Et3Si-H-SiEt3][B(C6F5)4] was dissolved in 0.4 mL of toluene in a dry 5 mL glass bottle. Then, 1 mmol (116.2 mg, 0.10 mL) of γ-thiocarbonyl valerate monomer was added. The initial concentration of the monomer was 2 mol / L, the concentration of the catalyst [Et3Si-H-SiEt3][B(C6F5)4] was 20 mmol / L, and the molar ratio of monomer to [Et3Si-H-SiEt3][B(C6F5)4] was 100:1.

[0471] Maintain the reaction temperature at room temperature, stir the reaction for 1 hour, then dissolve a small amount of sample in deuterated chloroform and analyze the reaction mixture. 1 The conversion rate was monitored by ¹H NMR and found to be 99.0%. The ratio of γ-thiovalactone byproduct to poly(γ-thiovalactone) was 6:94. The reaction was then quenched by adding 12 mL of a water / tetrahydrofuran mixture (volume ratio 1:30). The reaction solution was added dropwise to ethanol to allow the polymer to precipitate. After centrifugation, the supernatant was discarded. This process of dissolving in dichloromethane, adding dropwise to ethanol for precipitation, centrifugation, and discarding the supernatant was repeated twice. Finally, the product was dried at room temperature in a vacuum oven for three days to obtain colorless poly(γ-thiovalactone).

[0472]

[0473] This invention uses gel permeation chromatography (GPC) to determine the molecular weight and molecular weight distribution of poly(γ-thiovalactone), with tetrahydrofuran as the eluent and a flow rate of 1.0 mL / min. A standard curve is prepared using polymethyl methacrylate as the standard. The results show that the poly(γ-thiovalactone) prepared in this example has a number-average molecular weight of 10.2 kg / mol and a molecular weight distribution of 1.47.

[0474] Example 30

[0475] In an argon-atmospheric glove box, 0.01 mmol of Ph3CB(C6F5)4, 0.01 mmol of Et3SiH, and 0.4 mL of toluene were added to a dry glass bottle. Then, 1 mmol (116.2 mg, 0.10 mL) of γ-thiocarbonyl valerate monomer was added. The initial concentration of the monomer was 2 mol / L, the concentration of the catalyst Ph3CB(C6F5)4 / Et3SiH was 20 mmol / L, and the molar ratio of monomer to Ph3CB(C6F5)4 / Et3SiH was 100:1:1.

[0476] Maintain the reaction temperature at room temperature, and during the polymerization process, dissolve a small amount of sample in deuterated chloroform. 1 The conversion rate was monitored by ¹H NMR. The conversion rate reached 99.0% after 1 hour of polymerization. The ratio of γ-thiovalactone to poly(γ-thiovalactone) in the product was 9:91. Then, 2 mL of water / tetrahydrofuran mixture (volume ratio 1:30) was added to quench the reaction. The reaction solution was added dropwise to ethanol to allow the polymer to settle. After centrifugation, the supernatant was discarded. The process of dissolving in dichloromethane, adding dropwise to ethanol to settle, centrifugation, and discarding the supernatant was repeated twice. Finally, the product was dried at room temperature in a vacuum drying oven for three days to obtain colorless poly(γ-thiovalactone).

[0477]

[0478] This invention uses gel permeation chromatography (GPC) to determine the molecular weight and molecular weight distribution of poly(γ-thiovalactone), with tetrahydrofuran as the eluent and a flow rate of 1.0 mL / min. A standard curve is prepared using polymethyl methacrylate as the standard. The results show that the poly(γ-thiovalactone) prepared in this example has a number-average molecular weight of 8.4 kg / mol and a molecular weight distribution of 1.35.

[0479] Example 31

[0480] In an argon-atmospheric glove box, 0.01 mmol of Me3OBF4 and 0.4 mL of toluene were added to a dry glass bottle, followed by 1 mmol (116.2 mg, 0.10 mL) of γ-thiocarbonyl valerate monomer. The initial concentration of the monomer was 2 mol / L, the concentration of the catalyst Me3OBF4 was 20 mmol / L, and the molar ratio of monomer to Me3OBF4 was 100:1.

[0481] Maintain the reaction temperature at room temperature, and during the polymerization process, dissolve a small amount of sample in deuterated chloroform. 1 The conversion rate was monitored by ¹H NMR. The conversion rate reached 96.5% after 9 hours of polymerization. The ratio of γ-thiovalactone to poly(γ-thiovalactone) in the product was 1:99. Then, 2 mL of water / tetrahydrofuran mixture (volume ratio 1:30) was added to quench the reaction. The reaction solution was added dropwise to ethanol to allow the polymer to settle. After centrifugation, the supernatant was discarded. The process of dissolving in dichloromethane, adding dropwise to ethanol to settle, centrifugation, and discarding the supernatant was repeated twice. Finally, the product was dried at room temperature in a vacuum drying oven for three days to obtain colorless poly(γ-thiovalactone).

[0482]

[0483] This invention uses gel permeation chromatography (GPC) to determine the molecular weight and molecular weight distribution of poly(γ-thiovalactone), with tetrahydrofuran as the eluent and a flow rate of 1.0 mL / min. A standard curve is prepared using polymethyl methacrylate as the standard. The results show that the poly(γ-thiovalactone) prepared in this example has a number-average molecular weight of 6.8 kg / mol and a molecular weight distribution of 1.26.

[0484] Example 32

[0485] In an argon-atmospheric glove box, 0.01 mmol of [Et3O][B(C6F5)4] and 0.4 mL of toluene were added to a dry glass bottle, followed by 1 mmol (116.2 mg, 0.10 mL) of γ-thiocarbonylpentyl lactone monomer. The initial monomer concentration was 2 mol / L, the catalyst concentration of [Et3O][B(C6F5)4] was 20 mmol / L, and the molar ratio of monomer to [Et3O][B(C6F5)4] was 100:1.

[0486] Maintain the reaction temperature at room temperature, and during the polymerization process, dissolve a small amount of sample in deuterated chloroform. 1The conversion rate was monitored by ¹H NMR. The conversion rate reached 99.0% after 1 hour of polymerization. The ratio of γ-thiovalactone to poly(γ-thiovalactone) in the product was 1:99. Then, 2 mL of water / tetrahydrofuran mixture (volume ratio 1:30) was added to quench the reaction. The reaction solution was added dropwise to ethanol to allow the polymer to settle. After centrifugation, the supernatant was discarded. The process of dissolving in dichloromethane, adding dropwise to ethanol to settle, centrifugation, and discarding the supernatant was repeated twice. Finally, the product was dried at room temperature in a vacuum drying oven for three days to obtain colorless poly(γ-thiovalactone).

[0487]

[0488] This invention employs gel permeation chromatography (GPC) to determine the molecular weight and molecular weight distribution of poly(γ-thiovalactone), using tetrahydrofuran as the eluent at a flow rate of 1.0 mL / min. A standard curve is constructed using polymethyl methacrylate as the standard. The results show that the poly(γ-thiovalactone) prepared in this embodiment has a number-average molecular weight of 20.5 kg / mol and a molecular weight distribution of 1.06.

[0489] Example 33

[0490] In an argon-atmospheric glove box, 0.01 mmol of C7H7BF4 and 0.4 mL of toluene were added to a dry glass bottle, followed by 1 mmol (116.2 mg, 0.10 mL) of γ-thiocarbonyl valerate monomer. The initial concentration of the monomer was 2 mol / L, the concentration of the catalyst C7H7BF4 was 20 mmol / L, and the molar ratio of monomer to C7H7BF4 was 100:1.

[0491] Maintain the reaction temperature at room temperature, and during the polymerization process, dissolve a small amount of sample in deuterated chloroform. 1 The conversion rate was monitored by ¹H NMR. After 72 h of polymerization, the conversion rate reached 61.4%, and the ratio of γ-thiovalactone to poly(γ-thiovalactone) in the product was 9:91. Then, 2 mL of water / tetrahydrofuran mixture (volume ratio 1:30) was added to quench the reaction. The reaction solution was then added dropwise to ethanol to allow the polymer to settle. After centrifugation, the supernatant was discarded. The process of dissolving in dichloromethane, adding dropwise to ethanol to settle, centrifugation, and discarding the supernatant was repeated twice. Finally, the product was dried at room temperature in a vacuum drying oven for three days to obtain colorless poly(γ-thiovalactone).

[0492]

[0493] This invention employs gel permeation chromatography (GPC) to determine the molecular weight and molecular weight distribution of poly(γ-thiovalactone), using tetrahydrofuran as the eluent at a flow rate of 1.0 mL / min. A standard curve is constructed using polymethyl methacrylate as the standard. The results show that the poly(γ-thiovalactone) prepared in this embodiment has a number-average molecular weight of 32.3 kg / mol and a molecular weight distribution of 1.88.

[0494] Example 34

[0495] In an argon-atmospheric glove box, 0.01 mmol of Al(C6F5)3 was added to a dry glass bottle, followed by 1 mmol (116.2 mg, 0.10 mL) of α-methyl-γ-thiobutyrolactone monomer. The initial concentration of the monomer was 10 mol / L, the concentration of the catalyst Al(C6F5)3 was 100 mmol / L, and the molar ratio of monomer to Al(C6F5)3 was 100:1.

[0496] Maintain the reaction temperature at room temperature, and during the polymerization process, dissolve a small amount of sample in deuterated chloroform. 1 The conversion rate was monitored by ¹H NMR. The conversion rate reached 89.3% after 5 hours of polymerization. The ratio of α-methyl-γ-thiobutyrolactone byproduct to poly(α-methyl-γ-thiobutyrolactone) in the product was 2:98. Then, 2 mL of water / tetrahydrofuran mixture (volume ratio 1:30) was added to quench the reaction. The reaction solution was added dropwise to ethanol to allow the polymer to settle. After centrifugation, the supernatant was discarded. The process of dissolving in dichloromethane, adding dropwise to ethanol to settle, centrifugation, and discarding the supernatant was repeated twice. Finally, the product was dried at room temperature in a vacuum drying oven for three days to obtain colorless poly(α-methyl-γ-thiobutyrolactone).

[0497]

[0498] This invention employs gel permeation chromatography (GPC) to determine the molecular weight and molecular weight distribution of poly(α-methyl-γ-thiobutyrolactone), using tetrahydrofuran as the eluent at a flow rate of 1.0 mL / min. A standard curve is constructed using polymethyl methacrylate as the standard. The results show that the poly(α-methyl-γ-thiobutyrolactone) prepared in this embodiment has a number-average molecular weight of 431.1 kg / mol and a molecular weight distribution of 1.80.

[0499] Example 35

[0500] In an argon-atmospheric glove box, 0.01 mmol of [Et3O][B(C6F5)4] was weighed into a dry 10 mL Shrek flask, and 0.4 mL of toluene was added. The mixture was then taken out of the glove box and connected to a vacuum line, and pre-cooled at 0 °C for 10 min. Next, 1 mmol (104.1 mg) of 1,3-dioxolane-2-thione was weighed into a 5 mL glass bottle in the glove box, and 1.0 mL of toluene was added to dissolve the monomer. This solution was then taken out of the glove box and added to the previously pre-cooled Shrek flask, and the reaction was carried out at 0 °C. The initial monomer concentration was 0.7 mol / L, the catalyst [Et3O][B(C6F5)4] concentration was 7.0 mmol / L, and the molar ratio of monomer to [Et3O][B(C6F5)4] was 100:1.

[0501] Maintain the reaction temperature at 0℃, stir the reaction for 10 minutes, then take a small amount of the supernatant and dissolve it in deuterated chloroform. 1 The conversion rate was monitored by HNMR and was greater than 99%. Then, 2 mL of water / tetrahydrofuran mixture (volume ratio 1:20) was added to quench the reaction. The reaction solution was then added dropwise to ethanol to allow the polymer to settle. After centrifugation, the supernatant was discarded. The process of dissolving in dichloromethane, adding dropwise to ethanol to settle, centrifuging, and discarding the supernatant was repeated twice. Finally, the mixture was dried at room temperature in a vacuum drying oven for three days to obtain white polymonothiocarbonate.

[0502]

[0503] The present invention uses differential scanning calorimetry (DSC) to detect the melting temperature and glass transition temperature of poly(1,3-dioxolane-2-thione). The results show that the glass transition temperature of poly(1,3-dioxolane-2-thione) prepared in this embodiment is 24.5℃.

[0504] Example 36

[0505] In an argon-atmospheric glove box, 0.01 mmol of [Et3O][B(C6F5)4] was weighed into a dry 10 mL Shrek flask, and 0.30 mL of toluene was added. The mixture was then removed from the glove box and connected to a vacuum line, and pre-cooled at 0 °C for 10 min. Next, 4 mmol (472.6 mg, 0.38 mL) of (S)-4-methyl-1,3-dioxolane-2-thione monomer was weighed into a 5 mL glass bottle in the glove box, dissolved in 0.40 mL of toluene, and added to the pre-cooled Shrek flask. The reaction was carried out at 0 °C. The initial monomer concentration was 3.7 mol / L, the catalyst [Et3O][B(C6F5)4] concentration was 9.2 mmol / L, and the molar ratio of monomer to [Et3O][B(C6F5)4] was 400:1.

[0506] Maintain the reaction temperature at 0℃, stir the reaction for 120 min, then take a small amount of sample and dissolve it in deuterated chloroform. 1 The conversion rate was monitored by H NMR and was greater than 99%. Then, 2 mL of water / tetrahydrofuran mixture (volume ratio 1:20) was added to quench the reaction. The reaction solution was then added dropwise to ethanol to allow the polymer to settle. After centrifugation, the supernatant was discarded. The process of dissolving in dichloromethane, adding dropwise to ethanol to settle, centrifuging, and discarding the supernatant was repeated twice. Finally, the mixture was dried at room temperature in a vacuum drying oven for three days to obtain colorless and transparent polymonothiocarbonate.

[0507] The polymer was subjected to nuclear magnetic resonance (NMR) detection. 1 H NMR spectrum and 13 The C NMR spectra are as follows: Figure 37 and Figure 38 As shown.

[0508]

[0509] The present invention uses differential scanning calorimetry (DSC) to detect the melting temperature and glass transition temperature of poly(S)-4-methyl-1,3-dioxolane-2-thione. The results show that the glass transition temperature of poly(S)-4-methyl-1,3-dioxolane-2-thione prepared in this embodiment is 17.2℃.

[0510] This invention employs gel permeation chromatography (GPC) to determine the molecular weight and molecular weight distribution of poly(S)-4-methyl-1,3-dioxolane-2-thione. Tetrahydrofuran was used as the mobile phase at a flow rate of 1.0 mL / min. A standard curve was constructed using polymethyl methacrylate as the standard. The results show that the number-average molecular weight of poly(S)-4-methyl-1,3-dioxolane-2-thione prepared in this embodiment is 38.9 kg / mol, and the molecular weight distribution is 1.26.

[0511] Example 37

[0512] In an argon-atmospheric glove box, 0.01 mmol of [Et3O][B(C6F5)4] was weighed into a dry 10 mL Shrek flask, and 0.30 mL of toluene was added. The mixture was then removed from the glove box and connected to a vacuum line, and pre-cooled at 0 °C for 10 min. Next, 4 mmol (472.6 mg, 0.38 mL) of (R)-4-methyl-1,3-dioxolane-2-thione monomer was weighed into a 5 mL glass bottle in the glove box, dissolved in 0.40 mL of toluene, and added to the pre-cooled Shrek flask. The reaction was carried out at 0 °C. The initial monomer concentration was 3.7 mol / L, the catalyst [Et3O][B(C6F5)4] concentration was 9.2 mmol / L, and the molar ratio of monomer to [Et3O][B(C6F5)4] was 400:1.

[0513] Maintain the reaction temperature at 0℃, stir the reaction for 50 min, then take a small amount of sample and dissolve it in deuterated chloroform. 1 The conversion rate was monitored by H NMR and was greater than 99%. Then, 2 mL of water / tetrahydrofuran mixture (volume ratio 1:20) was added to quench the reaction. The reaction solution was then added dropwise to ethanol to allow the polymer to settle. After centrifugation, the supernatant was discarded. The process of dissolving in dichloromethane, adding dropwise to ethanol to settle, centrifuging, and discarding the supernatant was repeated twice. Finally, the mixture was dried at room temperature in a vacuum drying oven for three days to obtain colorless and transparent polymonothiocarbonate.

[0514]

[0515] This invention employs gel permeation chromatography (GPC) to determine the molecular weight and molecular weight distribution of poly(R)-4-methyl-1,3-dioxolane-2-thione. Tetrahydrofuran was used as the mobile phase at a flow rate of 1.0 mL / min. A standard curve was constructed using polymethyl methacrylate as the standard. The results show that the number-average molecular weight of poly(R)-4-methyl-1,3-dioxolane-2-thione prepared in this embodiment is 45.3 kg / mol, and the molecular weight distribution is 1.04.

[0516] This invention employs differential scanning calorimetry (DSC) to determine the melting temperature and glass transition temperature of poly(R)-4-methyl-1,3-dioxolane-2-thione. The results show that the glass transition temperature of the poly(R)-4-methyl-1,3-dioxolane-2-thione prepared in this embodiment is 18.2℃.

[0517] Example 38

[0518] In an argon-atmospheric glove box, 0.01 mmol of [Et3O][B(C6F5)4] was weighed into a dry 10 mL Shrek flask, and 0.4 mL of toluene was added. The mixture was then removed from the glove box and connected to a vacuum line, and pre-cooled at 0 °C for 10 min. Next, 1 mmol (152.6 mg) of 4-(chloromethyl)-1,3-dioxolane-2-thione monomer was weighed into a 5 mL glass bottle in the glove box, dissolved in 1.0 mL of toluene, and added to the pre-cooled Shrek flask. The reaction was carried out at 0 °C. The initial monomer concentration was 0.7 mol / L, the catalyst [Et3O][B(C6F5)4] concentration was 7.0 mmol / L, and the molar ratio of monomer to [Et3O][B(C6F5)4] was 100:1.

[0519] Maintain the reaction temperature at 0℃, stir the reaction for 10 min, then take a small amount of sample and dissolve it in deuterated chloroform. 1The conversion rate was monitored by ¹H NMR and was greater than 99%. Then, 2 mL of a water / tetrahydrofuran mixture (volume ratio 1:20) was added to quench the reaction. The reaction solution was then added dropwise to ethanol to allow the polymer to settle. After centrifugation, the supernatant was discarded. This process of dissolving in dichloromethane, adding dropwise to ethanol for sedimentation, centrifugation, and discarding the supernatant was repeated twice. The mixture was then dried at room temperature in a vacuum oven for three days to obtain white polymonothiocarbonate. Nuclear magnetic resonance (NMR) analysis was performed. 1 H NMR spectrum as follows Figure 39 .

[0520]

[0521] The present invention uses differential scanning calorimetry (DSC) to detect the melting temperature and glass transition temperature of poly(4-(chloromethyl)-1,3-dioxolane-2-thione). The results show that the glass transition temperature of poly(4-(chloromethyl)-1,3-dioxolane-2-thione) prepared in this embodiment is 41.6℃.

[0522] This invention employs gel permeation chromatography (GPC) to determine the molecular weight and molecular weight distribution of poly(4-(chloromethyl)-1,3-dioxolane-2-thione), using tetrahydrofuran as the mobile phase at a flow rate of 1.0 mL / min. A standard curve is constructed using polymethyl methacrylate as the standard. The results show that the number-average molecular weight of poly(4-(chloromethyl)-1,3-dioxolane-2-thione) prepared in this embodiment is 25.8 kg / mol, and the molecular weight distribution is 1.37.

[0523] Example 39

[0524] In an argon-atmospheric glove box, 0.01 mmol of [Et3O][B(C6F5)4] was weighed into a dry 10 mL Shrek flask, and 0.4 mL of toluene was added. The mixture was then removed from the glove box and pre-cooled at 0 °C for 10 min via a vacuum line. Next, 1 mmol (152.6 mg) of (R)-4-(chloromethyl)-1,3-dioxolane-2-thione monomer was weighed into a 5 mL glass bottle in the glove box, dissolved in 1.0 mL of toluene, and added to the pre-cooled Shrek flask. The reaction was carried out at 0 °C. The initial monomer concentration was 0.7 mol / L, the catalyst [Et3O][B(C6F5)4] concentration was 7.0 mmol / L, and the molar ratio of monomer to [Et3O][B(C6F5)4] was 100:1.

[0525] Maintain the reaction temperature at 0℃, stir the reaction for 10 minutes, then take a small amount of the supernatant and dissolve it in deuterated chloroform. 1The conversion rate was monitored by HNMR and was greater than 99%. Then, 2 mL of water / tetrahydrofuran mixture (volume ratio 1:20) was added to quench the reaction. The reaction solution was then added dropwise to ethanol to allow the polymer to settle. After centrifugation, the supernatant was discarded. The process of dissolving in dichloromethane, adding dropwise to ethanol to settle, centrifuging, and discarding the supernatant was repeated twice. Finally, the mixture was dried at room temperature in a vacuum drying oven for three days to obtain white polymonothiocarbonate. 1 H NMR spectrum as follows Figure 40 As shown.

[0526]

[0527] The present invention uses differential scanning calorimetry (DSC) to detect the melting temperature and glass transition temperature of poly(R)-4-(chloromethyl)-1,3-dioxolane-2-thione. The results show that the glass transition temperature of poly(R)-4-(chloromethyl)-1,3-dioxolane-2-thione prepared in this embodiment is 39.8℃ and the melting temperature is 162.8℃.

[0528] This invention employs gel permeation chromatography (GPC) to determine the molecular weight and molecular weight distribution of poly(R)-4-(chloromethyl)-1,3-dioxolane-2-thione. Tetrahydrofuran was used as the mobile phase at a flow rate of 1.0 mL / min. A standard curve was constructed using polymethyl methacrylate as the standard. The results show that the number-average molecular weight of poly(R)-4-(chloromethyl)-1,3-dioxolane-2-thione prepared in this embodiment is 24.5 kg / mol, and the molecular weight distribution is 1.35.

[0529] Example 40

[0530] In an argon-atmospheric glove box, 0.01 mmol of [Et3O][B(C6F5)4] was weighed into a dry 10 mL Shrek flask, and 0.4 mL of toluene was added. The mixture was then removed from the glove box and pre-cooled at 0 °C for 10 min via a vacuum line. Next, 1 mmol (152.6 mg) of the thiocarbonyl carbonate monomer (S)-4-(chloromethyl)-1,3-dioxolane-2-thione was weighed into a 5 mL glass bottle in the glove box, dissolved in 1.0 mL of toluene, and added to the pre-cooled Shrek flask. The reaction was carried out at 0 °C. The initial monomer concentration was 0.7 mol / L, the catalyst concentration of [Et3O][B(C6F5)4] was 7.0 mmol / L, and the molar ratio of monomer to [Et3O][B(C6F5)4] was 100:1.

[0531] Maintain the reaction temperature at 0℃, stir the reaction for 10 minutes, then take a small amount of the supernatant and dissolve it in deuterated chloroform. 1The conversion rate was monitored by HNMR and was greater than 99%. Then, 2 mL of water / tetrahydrofuran mixture (volume ratio 1:20) was added to quench the reaction. The reaction solution was then added dropwise to ethanol to allow the polymer to settle. After centrifugation, the supernatant was discarded. The process of dissolving in dichloromethane, adding dropwise to ethanol to settle, centrifuging, and discarding the supernatant was repeated twice. Finally, the mixture was dried at room temperature in a vacuum drying oven for three days to obtain white polymonothiocarbonate.

[0532]

[0533] The present invention uses differential scanning calorimetry (DSC) to detect the melting temperature and glass transition temperature of poly(S)-4-(chloromethyl)-1,3-dioxolane-2-thione. The results show that the glass transition temperature of poly(S)-4-(chloromethyl)-1,3-dioxolane-2-thione prepared in this embodiment is 39.0℃ and the melting temperature is 163.0℃.

[0534] This invention employs gel permeation chromatography (GPC) to determine the molecular weight and molecular weight distribution of poly(S)-4-(chloromethyl)-1,3-dioxolane-2-thione. Tetrahydrofuran was used as the mobile phase at a flow rate of 1.0 mL / min. A standard curve was constructed using polymethyl methacrylate as the standard. The results show that the number-average molecular weight of poly(S)-4-(chloromethyl)-1,3-dioxolane-2-thione prepared in this embodiment is 19.3 kg / mol, and the molecular weight distribution is 1.43.

[0535] Example 41

[0536] In an argon-atmospheric glove box, 0.01 mmol of [Et3O][B(C6F5)4] was weighed into a dry 10 mL Shrek flask, and 0.4 mL of toluene was added. The mixture was then removed from the glove box and connected to a vacuum line, and pre-cooled at 0 °C for 10 min. Next, 1 mmol (180.2 mg) of 4-phenyl-1,3-dioxolane-2-thione monomer was weighed into a 5 mL glass bottle in the glove box, dissolved in 1.0 mL of toluene, and added to the pre-cooled Shrek flask. The reaction was carried out at 0 °C. The initial monomer concentration was 0.7 mol / L, the catalyst [Et3O][B(C6F5)4] concentration was 7.0 mmol / L, and the molar ratio of monomer to [Et3O][B(C6F5)4] was 100:1.

[0537] Maintain the reaction temperature at 0℃, stir the reaction for 10 min, then take a small amount of sample and dissolve it in deuterated chloroform. 1The conversion rate was monitored by ¹H NMR and was greater than 99%. Then, 2 mL of a water / tetrahydrofuran mixture (volume ratio 1:20) was added to quench the reaction. The reaction solution was then added dropwise to ethanol to allow the polymer to settle. After centrifugation, the supernatant was discarded. This process of dissolving in dichloromethane, adding dropwise to ethanol for sedimentation, centrifugation, and discarding the supernatant was repeated twice. The polymer was then dried in a vacuum oven at room temperature for three days to obtain a white polymonothiocarbonate. The polymer was then analyzed by nuclear magnetic resonance (NMR). 1 H NMR spectrum and 13 The C NMR spectra are as follows: Figure 41 and Figure 42 As shown.

[0538]

[0539] The present invention uses differential scanning calorimetry (DSC) to detect the melting temperature and glass transition temperature of poly(4-phenyl-1,3-dioxolane-2-thione). The results show that the glass transition temperature of poly(4-phenyl-1,3-dioxolane-2-thione) prepared in this embodiment is 59.5℃.

[0540] This invention employs gel permeation chromatography (GPC) to determine the molecular weight and molecular weight distribution of poly(4-phenyl-1,3-dioxolane-2-thione). Tetrahydrofuran was used as the mobile phase at a flow rate of 1.0 mL / min. A standard curve was prepared using poly(4-phenyl-1,3-dioxolane-2-thione) as a standard. The results show that the polymonothiocarbonate prepared in this embodiment has a number-average molecular weight of 19.7 kg / mol and a molecular weight distribution of 2.05.

[0541] Example 42

[0542] In an argon-atmospheric glove box, 0.05 mmol (7.6 mg, 0.0074 mL) of DBU and 0.05 mmol (5.4 mg, 0.0052 mL) of benzyl alcohol were weighed into a dry 5 mL glass bottle and mixed. 1.0 mL of toluene was added until completely dissolved. Then, 5 mmol (590.7 mg, 0.47 mL) of the thiocarbonyl carbonate monomer (R)-4-methyl-1,3-dioxolane-2-thione was added to the 5 mL glass bottle, and the reaction was carried out at 25 °C. The initial monomer concentration was 3.7 mol / L, the DBU catalyst concentration was 37 mmol / L, and the molar ratio of monomer to DBU was 100:1.

[0543] After maintaining the reaction temperature at 25℃ and stirring for 60 hours, a small sample was dissolved in deuterated chloroform and analyzed. 1The conversion rate was monitored by H NMR and was greater than 99%. Then, 2 mL of benzoic acid / dichloromethane mixture (concentration of 10 mg / mL) was added to quench the reaction. The reaction solution was then added dropwise to ethanol to allow the polymer to settle. After centrifugation, the supernatant was discarded. The process of dissolving in dichloromethane, adding dropwise to ethanol to settle, centrifugation, and discarding the supernatant was repeated twice. Finally, the mixture was dried at room temperature in a vacuum drying oven for three days to obtain colorless and transparent polymonothiocarbonate.

[0544]

[0545] This invention uses gel permeation chromatography (GPC) to determine the molecular weight and molecular weight distribution of polymonothiocarbonate. Tetrahydrofuran is used as the mobile phase at a flow rate of 1.0 mL / min. A standard curve is prepared using polymethyl methacrylate as the standard. The results show that the polymonothiocarbonate prepared in this example has a number-average molecular weight of 4.9 kg / mol and a molecular weight distribution of 1.38.

[0546] Example 43

[0547] In an argon-atmospheric glove box, 0.05 mmol (7.6 mg, 0.0074 mL) of DBU and 0.05 mmol (5.4 mg, 0.0052 mL) of benzyl alcohol were weighed into a dry 5 mL glass bottle and mixed. 0.5 mL of toluene was added until completely dissolved. In another 5 mL glass bottle, 0.05 mmol (18.5 mg) of 1-[3,5-bis(trifluoromethyl)phenyl]-3-cyclohexylthiourea and 5 mmol (590.7 mg, 0.47 mL) of the thiocarbonyl carbonate monomer (R)-4-methyl-1,3-dioxolane-2-thione were weighed into a mixture. 0.5 mL of toluene was added until completely dissolved. The solutions in both bottles were thoroughly mixed and reacted at 25 °C. The initial monomer concentration was 3.7 mol / L, the DBU catalyst concentration was 37 mmol / L, and the molar ratio of monomer to DBU was 100:1.

[0548] After maintaining the reaction temperature at 25℃ and stirring for 120 hours, a small sample was dissolved in deuterated chloroform and analyzed. 1 The conversion rate was monitored by H NMR and was greater than 99%. Then, 2 mL of benzoic acid / dichloromethane mixture (concentration of 10 mg / mL) was added to quench the reaction. The reaction solution was then added dropwise to ethanol to allow the polymer to settle. After centrifugation, the supernatant was discarded. The process of dissolving in dichloromethane, adding dropwise to ethanol to settle, centrifugation, and discarding the supernatant was repeated twice. Finally, the mixture was dried at room temperature in a vacuum drying oven for three days to obtain colorless and transparent polymonothiocarbonate.

[0549]

[0550] This invention uses gel permeation chromatography (GPC) to determine the molecular weight and molecular weight distribution of polymonothiocarbonate. Tetrahydrofuran is used as the mobile phase at a flow rate of 1.0 mL / min. A standard curve is prepared using polymethyl methacrylate as the standard. The results show that the polymonothiocarbonate prepared in this example has a number-average molecular weight of 3.2 kg / mol and a molecular weight distribution of 1.49.

[0551] Example 44

[0552] In an argon-atmospheric glove box at room temperature, 0.005 mmol of [Et3O][B(C6F5)4] was dispersed in 4.8 mL of toluene in a dry 20 mL glass bottle. Then, 12 mmol (1394.2 mg, 1.2 mL) of (R)-γ-thiocarbonylpentanolide monomer was added. The initial concentration of the monomer was 2 mol / L, the concentration of the catalyst [Et3O][B(C6F5)4] was 1.67 mmol / L, and the molar ratio of monomer to [Et3O][B(C6F5)4] was 1200:1.

[0553] After maintaining the reaction temperature at room temperature and stirring for 18 hours, a small sample was dissolved in deuterated chloroform and analyzed. 1 The conversion rate was monitored by ¹H NMR and was 93.6%. The ratio of γ-thiovalactone byproduct to poly-(S)-(γ-thiovalactone) was less than 1:99. Then, 10 mL of water / tetrahydrofuran mixture (volume ratio 1:20) was added to quench the reaction. The reaction solution was added dropwise to ethanol to allow the polymer to precipitate. The mixture was filtered, washed with ethanol, and then dried at room temperature in a vacuum drying oven for three days to obtain white poly-(S)-(γ-thiovalactone).

[0554]

[0555] The present invention uses differential scanning calorimetry (DSC) to detect the melting temperature and glass transition temperature of poly(S)-(γ-thiovalactone). The results show that the glass transition temperature of poly(S)-(γ-thiovalactone) prepared in this embodiment is about -8.8℃ and the melting point is about 82.3℃.

[0556] This invention uses thermogravimetric analysis (TGA) to determine the thermal stability of poly(S)-(γ-thiovalactone). The results show that the initial decomposition temperature (T0) of poly(S)-(γ-thiovalactone) prepared in this embodiment is [missing information]. d The temperature at which 5% weight loss occurs is 235.5℃.

[0557] This invention employs gel permeation chromatography (GPC) to determine the molecular weight and molecular weight distribution of poly(S)-(γ-thiovalactone), using tetrahydrofuran as the eluent at a flow rate of 1.0 mL / min. A standard curve is constructed using polymethyl methacrylate as the standard. The results show that the poly(S)-(γ-thiovalactone) prepared in this embodiment has a number-average molecular weight of 106.1 kg / mol and a molecular weight distribution of 1.40.

[0558] Mechanical tensile tests were conducted on the poly(S)-(γ-thiovalerate) prepared in this invention. The results showed that the (S)-poly(γ-thiovalerate) prepared in this embodiment had an elongation at break of 638%, a yield stress of 9.05 MPa, and a fracture stress of 24.27 MPa.

[0559] Example 45

[0560] In an argon-atmospheric glove box at room temperature, 0.005 mmol of [Et3O][B(C6F5)4] was dispersed in 4.8 mL of toluene in a dry 20 mL glass bottle. Then, 12 mmol (1394.2 mg, 1.2 mL) of (S)-γ-thiocarbonylpentanolide monomer was added. The initial concentration of the monomer was 2 mol / L, the concentration of the catalyst [Et3O][B(C6F5)4] was 1.67 mmol / L, and the molar ratio of monomer to [Et3O][B(C6F5)4] was 1200:1.

[0561] After maintaining the reaction temperature at room temperature and stirring for 18 hours, a small sample was dissolved in deuterated chloroform and analyzed. 1 The conversion rate was monitored by ¹H NMR and was 98.5%. The ratio of γ-thiovalactone byproduct to poly(R)-(γ-thiovalactone) was 1:99. Then, 10 mL of water / tetrahydrofuran mixture (volume ratio 1:20) was added to quench the reaction. The reaction solution was added dropwise to ethanol to allow the polymer to precipitate. The mixture was filtered, washed with ethanol, and then dried in a vacuum drying oven at room temperature for three days to obtain white (R)-poly(γ-thiovalactone).

[0562]

[0563] The present invention uses differential scanning calorimetry (DSC) to detect the melting temperature and glass transition temperature of poly(R)-(γ-thiovalactone). The results show that the glass transition temperature of poly(R)-(γ-thiovalactone) prepared in this embodiment is about -8.9℃ and the melting point is about 81.0℃.

[0564] This invention employs gel permeation chromatography (GPC) to determine the molecular weight and molecular weight distribution of poly(R)-(γ-thiovalactone), using tetrahydrofuran as the eluent at a flow rate of 1.0 mL / min. A standard curve is constructed using polymethyl methacrylate as the standard. The results show that the poly(R)-(γ-thiovalactone) prepared in this embodiment has a number-average molecular weight of 101.2 kg / mol and a molecular weight distribution of 1.68.

[0565] Comparative Example 1

[0566] In an argon-atmospheric glove box, 0.02 mmol of potassium thioacetate, 0.02 mmol of 18-crown-6 ether, and 0.2 mL of N,N-dimethylformamide were added to a dry Schlenk flask. Then, 2 mmol (232 mg, 0.2 mL) of γ-thiocarbonyl valerate monomer was added. The initial concentration of the monomer was 5 mol / L, the concentration of the catalyst potassium thioacetate was 50 mmol / L, and the molar ratio of monomer to potassium thioacetate and 18-crown-6 ether was 100:1:1.

[0567] Remove the flask from the glove box and connect the Schlenk flask to a vacuum line protected by argon. After stirring the reaction at 80°C for 48 hours, add 0.15 mL of toluene solution containing 0.05 mL of allyl chloride to terminate the reaction. Take a small amount of the solution for further processing. 1 ¹H NMR analysis was used to determine the conversion rate. The monomer conversion rate was 66.5%, and the ratio of dimer:γ-thiovalactone:poly(γ-thiovalactone) in the product was 15.0:64.4:20.6. The remaining reaction solution was poured into ethanol, and since oligomers were formed, no polymer precipitated.

[0568]

[0569] Example 1: Performance Parameter Measurement

[0570] 1.1 Molecular weight control

[0571] This invention uses a Waters E2695 gel permeation chromatograph to determine the number-average molecular weight (Mn) of polysulfides. n ) and molecular weight distribution (D=M w / M n The chromatographic column was an Agilent Plgel 5μm, and the differential detector was a Wyatt. T-Rex was used as the eluent, tetrahydrofuran was used, the column temperature was 40℃, and the flow rate was 1.0 mL / min. A standard curve was prepared using polymethyl methacrylate as a standard. The results showed that the number-average molecular weight of the polysulfide prepared in the examples of this invention was 3.2 kg / mol to 431.1 kg / mol, and the molecular weight distribution index was 1.01 to 2.05.

[0572] Under the reaction conditions with [Ph3C][B(C6F5)4] as the main catalyst, the amount of catalyst was varied, and polymerization reactions were carried out at monomer-to-catalyst ratios of 100:1, 200:1, 400:1, 800:1, and 1200:1. The number-average molecular weights of the resulting polymers were 16.3, 27.5, 55.0, 95.9, and 122.0 kg / mol, respectively, with corresponding molecular weight distribution indices of 1.22, 1.16, 1.25, 1.43, and 1.51. The number-average molecular weight increased linearly with the increase of the monomer-to-catalyst ratio, as shown in the figure. Figure 31 As shown (the catalyst here refers to the main catalyst), Figure 31 In the figure, the horizontal axis represents the molar ratio of monomer γ-thiovalactone to catalyst, "■" represents the number-average molecular weight of polymer, and "◆" represents the molecular weight distribution of polymer, which has good molecular weight controllability.

[0573] 1.2 Thermal Performance Analysis

[0574] Thermogravimetric analysis (TGA) of the polymer was performed using a TGA 550 thermogravimetric analyzer from TA Instruments to obtain the thermal decomposition temperature of the polymer. The TGA tests were conducted under a nitrogen atmosphere, with a temperature range of 25–700 °C and a heating rate of 15 °C / min. The initial decomposition temperature (T0.05) of the poly(γ-thiovalactone) prepared in Example 2 was also determined. d (The temperature at which 5% weight loss occurs) is at 251℃, such as Figure 32 As shown; the initial decomposition temperature (T) of poly(γ-thiocaprolactone) prepared in Example 3. d The initial decomposition temperature (T5) of the poly(γ-thioheptanolactone) prepared in Example 4 was 287°C. d The initial decomposition temperature (T5) of the poly(γ-thiooctyl lactone) prepared in Example 5 was 282°C. d The initial decomposition temperature (T5) of poly(γ-thiononolactone) prepared in Example 6 was 268°C. d The initial decomposition temperature (T5) of poly(γ-thiodecyl lactone) prepared in Example 7 was 245°C. d The initial decomposition temperature (T5) of the poly(γ-thioundecyl lactone) prepared in Example 8 was 253°C. d The initial decomposition temperature (T5) of poly(γ-thiodododecyl lactone) prepared in Example 9 was 248°C. d The initial decomposition temperature (T5) of poly(γ-methyl-γ-thiodecyl lactone) prepared in Example 10 was 273°C. dThe initial decomposition temperature (T5) of poly(β-methyl-γ-thiooctanolide) prepared in Example 11 was 268°C. d The initial decomposition temperature (T5) of poly(α-methylγ-thiobutyrolactone) prepared in Example 12 was 290°C. d The initial decomposition temperature (T5) of the poly(β-methyl-γ-thiobutyrolactone) prepared in Example 13 was 259.1 °C. d The initial decomposition temperature (T5) of poly(γ-thiovalerate) prepared in Example 15 was 260°C. d The initial decomposition temperature (T5) of poly4-(chloromethyl)-1,3-dioxolane-2-thione prepared in Example 38 was 255°C. d The initial decomposition temperature (T5) of poly-(S)-(γ-thiovalerate) prepared in Example 44 was 270°C. d The temperature at which 5% weight loss occurs is 235.5℃; it exhibits good thermal stability.

[0575] This invention utilizes a differential scanning calorimeter (DSC 2000) from TA Instruments to analyze the polysulfide prepared in the above examples using differential scanning calorimetry (DSC). Representative curves are shown below. Figure 33 and 34 As shown. Test results indicate that the glass transition temperature T of the polysulfide provided by this invention is... g It is within the range of -57.0 to 59.5℃, offering great adjustability to meet different usage scenarios.

[0576] The DSC curves of poly(γ-thiocaprolactone) (PTGCL), poly(γ-thioheptanolactone) (PTGHL), poly(γ-thiooctanolactone) (PTGOL), poly(γ-thiononanolactone) (PTGNL), poly(γ-thiodecanolactone) (PTGDL), poly(γ-thioundecanolactone) (PTGUDL), poly(γ-thiododecalactone) (PTGDDL), and poly(γ-methyl-γ-thiodecanolactone) (PTGMDL) obtained in Examples 3-10 are shown below. Figure 33 As shown.

[0577] The DSC curves of poly(γ-thiovalactone) (PTGVL) obtained in Example 2, poly(α-methyl-γ-thiobutyrolactone) (PαMeTBL) and poly(β-methyl-γ-thiobutyrolactone) (PβMeTBL) obtained in Examples 12-13, poly(β-methyl-γ-thiooctylactone) (PTWL) obtained in Example 11, and poly(cis-hexahydroisobenzofuran-1-one) (P3,4-S6TBL) obtained in Example 15 are shown below. Figure 34 As shown.

[0578] The DSC curve overlay plots of the poly-1,3-dioxolane-2-thione (PEMTC) obtained in Example 35, the poly-(S)-4-methyl-1,3-dioxolane-2-thione (S-PPMTC) obtained in Example 36, the poly-(R)-4-methyl-1,3-dioxolane-2-thione (R-PPMTC) obtained in Example 37, the poly-4-chloromethyl-1,3-dioxolane-2-thione (PCMMTC) obtained in Example 38, and the poly-4-phenyl-1,3-dioxolane-2-thione (PBMTC) obtained in Example 41 are shown below. Figure 43 As shown.

[0579] The DSC curve of poly(R)-4-chloromethyl-1,3-dioxolane-2-thione (abbreviation: R-PCMMTC) obtained in Example 39 is shown in the figure below. Figure 44 As shown.

[0580] The DSC curve of poly-(S)-4-chloromethyl-1,3-dioxolane-2-thione (abbreviation: S-PCMMTC) obtained in Example 40 is shown in the figure below. Figure 45 As shown.

[0581] The DSC curve of poly-(S)-poly(γ-thiovalactone) (abbreviation: S-PTGVL) obtained in Example 44 is shown in the figure. Figure 48 As shown.

[0582] 1.3 Mechanical property testing

[0583] The mechanical properties of the polymers prepared in the examples of this invention were tested. First, the polymer was hot-pressed into a polymer film using a tetrafluoroethylene template and then cut into dumbbell-shaped tensile strips. The effective tensile dimensions were 10×5×1mm. 3 Subsequently, the data was tested using a Linkam TST350 tensile testing machine, with ASTM as the standard, at 30°C and a tensile rate of 5 mm / min. The final data was the average of five experiments.

[0584] The tensile test results of poly-(S)-(γ-thiovalactone) prepared in Example 44 are as follows: Figure 49 As shown, mechanical tensile test (such as Figure 49 The experiments shown indicate that the prepared (S)-poly(γ-thiovalactone) has an elongation at break of 638%, a yield stress of 9.05 MPa, and a fracture stress of 24.27 MPa. This demonstrates that the poly(γ-thiovalactone) provided by this invention is a strong and tough polymer material, with all mechanical tensile test indicators superior to low-density polyethylene (elongation at break 430%, fracture stress 10.6 MPa) and isotactic polypropylene (elongation at break 420%, fracture stress 26.0 MPa), and approaching the tensile properties of high-density polypropylene (elongation at break 420%, fracture stress 26.0 MPa). In terms of elongation at break, poly(S)-(γ-thiovalactone) is 1.5 times that of commercially available low-density polyethylene and isotactic polypropylene, indicating that its toughness is significantly superior to that of commercially available low-density polyethylene and isotactic polypropylene.

[0585] The mechanical properties of the ternary random copolymer prepared in Example 14 were tested: tensile testing (e.g.) Figure 46 As shown, the elongation at break was 1451.30%, and the breaking stress was 16.62 MPa; additionally, cyclic tensile testing (such as...) Figure 47 As shown in the figure, the experiment shows that the elastic recovery rate of this ternary random copolymer is 72.3%, which indicates that the ternary random copolymer provided by the present invention is a strong and tough elastomer polymer material. All mechanical tensile test indicators are superior to commercial ethylene propylene rubber (elongation at break 275.0%, breaking stress 5.70 MPa, recovery rate 50-80%).

[0586] 1.4 Degradability Analysis

[0587] The polysulfides and polymonothiocarbonates described in this invention possess biodegradability unmatched by commercially available polyolefins. Taking poly(γ-thiovalactone) as an example, rapid and controllable degradation can occur under specific conditions: at room temperature, when 1,5,7-triazidobicyclo(4.4.0)dec-5-ene (TBD) is added as a degradation catalyst, the poly(γ-thiovalactone) obtained in Example 4 can be rapidly and quantitatively degraded into γ-thiovalactone within 1 minute. Figure 35 As shown. The specific reaction process is as follows: 232.4 mg of dried poly(γ-thiovalactone) was dissolved in 2.5 mL of anhydrous dichloromethane. 0.5 mL of TBD (0.02 mol / L) dichloromethane solution was added to the resulting transparent solution. After stirring for 1 min, it was found that the polymer had been completely degraded into γ-thiovalactone.

[0588] The performance analysis of the polymers obtained in this invention demonstrates that the sulfur-containing homopolymers and copolymers prepared in this invention provide convenience for the industrial production of environmentally friendly sulfur-containing polymer materials. The synthesized sulfur-containing polymers possess advantages such as high molecular weight, good molecular weight controllability, a wide range of tunable physical properties, and excellent degradability, making them suitable for use in plastics, rubber, elastomers, fibers, and other products, with broad applications.

Claims

1. A process for the preparation of a sulfur-containing polymer, characterized in that, It comprises the following steps: polymerizing one or more polymerization monomers in an organic solvent in the presence of a main catalyst; The main catalyst is a cationic main catalyst; The cationic main catalyst is a zwitterion pair type catalyst; the zwitterion pair type catalyst is shown by the following structure: ； wherein [R] + is a carbocation, sili cation, oxonium ion or yl cation, [X] - is a borate anion; The carbocation is shown by the following structure: ； wherein R 1f , R 2f , R 3f are each independently phenyl, 2,4,6-trimethylphenyl, 2,6-dimethylphenyl, 2,3,5,6-tetramethylphenyl, or 2,6-diisopropylphenyl; The silyl cation is shown by the following structure: ； wherein R 1g , R 2g , and R 3g are each independently methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, or t-butyl; The oxonium ion is shown by the following structure: ； wherein R 1h , R 2h , and R 3h are each independently methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, or t-butyl; The uronium ion is shown by the following structure: ； The borate anion is shown by the following structure: ； wherein X 1 , X 2 , X 3 , and X 4 are each independently fluorine, pentafluorophenyl, or 3,5-di(trifluoromethyl)phenyl; The polymerization monomer is independently a five-membered ring skeleton compound as shown in formula (I): ； wherein is , , , or ; R 11 , R 12 , R 13 , R 14 , R 21 , R 22 , R 23 , R 31 , R 32 , R 33 , R 41 , R 42 , R 43 , R 51 , R 52 , R 53 and R 54 are independently H, halogen, hydroxyl, C 6-10 aryl, C 1-10 alkyl or C 1-10 alkenyl; said C 1-10 alkyl is optionally substituted with one or more of halogen, hydroxyl and C 6-10 aryl; or R 12 and R 13 , R 13 and R 14 , R 22 and R 23 , R 32 and R 33 , R 42 and R 41 , or R 52 and R 53 together with the atoms linking them form a C 3-10 cycloalkyl, C 3-10 cycloalkenyl or C 6-10 aryl group; Alternatively, the polymerized monomer is , and the procatalyst is Ph3CB(C6F5)4 / Et3SiH.

2. The production method according to claim 1, wherein It meets one or more of the following conditions: (1) In the compound shown in formula (I), the halogen is independently fluorine, chlorine, bromine or iodine; (2), the compound shown in formula (I), the C 1-10 alkyl is independently C 1-8 alkyl; (3), the compound shown in formula (I), the C 1-10 alkenyl is independently C 1-8 alkenyl; (4) In the compound of formula (I), C 6-10 aryl is independently phenyl; (5) In the compound of formula (I), C 3-10 Cycloalkyl is independently cyclopentyl, cyclohexyl or cycloheptyl. (6) In the compound of formula (I), C 3-10 Cycloalkenyl is independently cyclohexenyl. (7) The polymerization reaction is carried out in a protective gas atmosphere, and the protective gas is nitrogen and / or argon; (8) The molar volume ratio of the polymerization monomer to the organic solvent is 0.2 mol / L-10 mol / L; (9) The organic solvent is one or more of linear hydrocarbon solvents, halogenated hydrocarbon solvents, cyclic ether solvents, aromatic hydrocarbon solvents and amide solvents; (10) The molar ratio of the polymerization monomer to the main catalyst is 20:1-1600:1; (11) The polymerization temperature of the polymerization reaction is 0-120 degrees Celsius; (12) The polymerization reaction time is 5-720 minutes.

3. The production method according to claim 2, wherein It meets one or more of the following conditions: (1) In the compound shown in formula (I), the halogen is independently fluorine or chlorine; (2), the compound shown in formula (I), the C 1-10 alkyl is independently methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl or n-heptyl; (3), the compound shown in formula (I), the C 1-10 alkenyl is independently C 1-4 alkenyl.

4. The production method according to claim 3, wherein In the compound of formula (I), C 1-10 Alkene is independently vinyl.

5. The production method according to claim 2, wherein It meets one or more of the following conditions: (1) The compound as shown in formula (I) is shown by any one of the following structures: ； ； (2) The molar volume ratio of the polymerization monomer to the organic solvent is 2.0 mol / L-7.0 mol / L; (3) In the organic solvent, the linear hydrocarbon solvent is one or more of n-hexane, n-heptane and n-pentane; (4) In the organic solvent, the halogenated hydrocarbon solvent is one or more of halogenated aromatic hydrocarbon solvents, dichloromethane, trichloromethane, 1,2-dichloroethane and tetrachloroethane; (5) In the organic solvent, the cyclic ether solvent is tetrahydrofuran and / or dioxane; (6) In the organic solvent, the aromatic hydrocarbon solvent is one or more of toluene, benzene and xylene; (7) In the organic solvent, the amide solvent is N,N-dimethylformamide; (8) The molar ratio of the polymerization monomer to the main catalyst is 100:1-1600:1; (9) The polymerization temperature of the polymerization reaction is 40-80 degrees Celsius; (10) The polymerization reaction time is 30-240 minutes.

6. The production method according to claim 5, wherein The halogenated aromatic hydrocarbon solvent is one or more of o-dichlorobenzene, o-difluorobenzene, o-dibromobenzene, chlorobenzene, fluorobenzene, bromobenzene and meso-trichlorobenzene.

7. The production method according to claim 1, wherein It meets one or more of the following conditions: (1) the compound of formula (I) wherein is or ; R 11 , R 12 , R 13 and R 14 are independently H, C 1-10 alkyl or C 1-10 alkenyl; or, R 13 and R 14 together with the atoms to which they are attached form a C 3-10 cycloalkyl group; R 51 , R 52 , R 53 and R 54 are independently H or C 1-10 alkyl; (2) The organic solvent is an aromatic hydrocarbon solvent and / or an amide solvent; (3) the cationic procatalyst is one or more of [Ph3C][B(C6F5)4], Me3OBF4, [Et3O][B(C6F5)4], C7H7BF4 and [Et3Si-H-SiEt3][B(C6F5)4].

8. The production method according to claim 7, wherein It meets one or both of the following conditions: (1) the compound as shown in formula (I) is shown by any of the following structures: ； ； (2) the organic solvent is toluene and / or N, N-dimethylformamide.

9. The production method according to any one of claims 1 to 8, wherein It is any of the following schemes, Scheme 1, the polymerized monomer is , and the procatalyst is [Ph3C][B(C6F5)4]. Scheme 2, the polymerized monomer is , and the procatalyst is [Ph3C][B(C6F5)4]. Scheme 3, the polymerization monomer is , and the main catalyst is [Ph3C][B(C6F5)4]. Scheme 4, the polymerized monomer is , and the procatalyst is [Ph3C][B(C6F5)4]. Scheme 5, the polymerized monomer is , and the procatalyst is [Ph3C][B(C6F5)4]. Scheme 6, the polymerized monomer is , and the procatalyst is [Ph3C][B(C6F5)4]. Scheme 7, the polymerized monomer is , and the procatalyst is [Ph3C][B(C6F5)4]. Scheme 8, the polymerized monomer is , and the procatalyst is [Ph3C][B(C6F5)4]. Scheme 9, the polymerized monomer is , and the procatalyst is [Ph3C][B(C6F5)4]. Scheme 10, the polymerized monomer is , and the procatalyst is [Ph3C][B(C6F5)4]. Scheme 17, the polymerized monomer is , and the procatalyst is [Ph3C][B(C6F5)4]. Scheme 22, the polymerized monomer is , and the procatalyst is [Ph3C][B(C6F5)4]. Scheme 28, the polymerized monomer is , and the procatalyst is [Et3Si-H-SiEt3][B(C6F5)4]. Scheme 30, the polymerized monomer is , and the procatalyst is Me3OBF4. Scheme 31, the polymerized monomer is , and the procatalyst is [Et3O][B(C6F5)4]. Scheme 32, the polymerized monomer is , and the procatalyst is C7H7BF4. Scheme 35, the polymerized monomer is , and the procatalyst is [Et3O][B(C6F5)4]. Scheme 36, the polymerized monomer is , and the procatalyst is [Et3O][B(C6F5)4]. Scheme 37, the polymerized monomer is , and the procatalyst is [Et3O][B(C6F5)4]. Scheme 38, the polymerized monomer is , and the procatalyst is [Et3O][B(C6F5)4]. Scheme 39, the polymerized monomer is , and the procatalyst is [Et3O][B(C6F5)4]. Scheme 40, the polymerized monomer is , and the procatalyst is [Et3O][B(C6F5)4]. Scheme 41, the polymerized monomer is , and the procatalyst is [Et3O][B(C6F5)4]. Scheme 44, the polymerized monomer is , and the procatalyst is [Et3O][B(C6F5)4]. Scheme 45, the polymerized monomer is , and the procatalyst is [Et3O][B(C6F5)4].

10. A sulfur-containing polymer characterized in that, which is prepared according to the preparation method according to any one of claims 1 to 9; the polymeric monomer is 、 、 、 、 、 、 ; or , and in combination.

11. A sulfur-containing polymer characterized in that, the main chain of the sulfur-containing polymer is composed of one or more of the following structural units, 、 ， wherein the degree of polymerization of the sulfur-containing polymer is greater than or equal to 50, The polymerization monomer of the structural unit (A) is , , , , or ; or , and in combination; The polymerization monomer of the structural unit (E) is .

12. The sulfur-containing polymer of claim 11, characterized in that, It meets one or more of the following conditions: (1) the degree of polymerization of the sulfur-containing polymer is 50-4900; (2) the number average molecular weight of the sulfur-containing polymer is greater than or equal to 5 kg / mol; (3) the molecular weight distribution of the sulfur-containing polymer is 1.0-3.0; (4) the sulfur-containing polymer is a homopolymer or a multi-component copolymer; (5) the tensile elongation at break of the sulfur-containing polymer is 638%-1451.30%; (6) the yield stress of the sulfur-containing polymer is 9.05 MPa; (7) the breaking stress of the sulfur-containing polymer is 16.62-24.27 MPa; (8) the elastic recovery rate of the sulfur-containing polymer is 72.3%; (9) The glass transition temperature Tg of the sulfur-containing polymer is -57.0 to 59.5 °C. g -57.0~59.5 ℃。 13. The sulfur-containing polymer of claim 12, characterized in that, It meets one or more of the following conditions: (1) the degree of polymerization of the sulfur-containing polymer is 190-2450; (2) the number average molecular weight of the sulfur-containing polymer is 5-500 kg / mol; (3) the molecular weight distribution of the sulfur-containing polymer is 1.0-1.5; (4) the multi-component copolymer is a random copolymer or a block copolymer; (5) the multi-component copolymer is a terpolymer, wherein the molar percentage of each structural unit is 5-90%.

14. The sulfur-containing polymer of claim 13, characterized in that, It meets one or both of the following conditions: (1) the degree of polymerization of the sulfur-containing polymer is 840-1600; (2) the number average molecular weight of the sulfur-containing polymer is 20-250 kg / mol.

15. The sulfur-containing polymer of claim 14, characterized in that, The number average molecular weight of the sulfur-containing polymer is 80-250 kg / mol.

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