WO2023061379A2

WO2023061379A2 - Method for preparing sulphur-containing polymer based on isomerisation-driven irreversible ring-opening polymerisation

Info

Publication number: WO2023061379A2
Application number: PCT/CN2022/124703
Authority: WO
Inventors: 洪缪; 孙洋洋; 夏永亮; 袁鹏俊
Original assignee: 中国科学院上海有机化学研究所
Priority date: 2021-10-11
Filing date: 2022-10-11
Publication date: 2023-04-20
Also published as: WO2023061379A3; CN115960355A

Abstract

Disclosed in the present invention is a method for preparing a sulphur-containing polymer based on isomerisation-driven irreversible ring-opening polymerisation. The method comprises: in an organic solvent and in the presence of a main catalyst, implementing a polymerisation reaction of one or more polymerisable monomers, wherein the main catalyst is an anionic main catalyst or a cationic main catalyst; the anionic main catalyst is a phosphazene base, guanidine organic base, amidine organic base, N-heterocyclic carbene organic base, N-heterocyclic olefin organic base, carboxylate, or thiocarboxylate; and the cationic main catalyst is a zwitterionic pair catalyst, a neutral Lewis acid type catalyst, or a proton acid (ester) type catalyst; and the polymerisable monomer is a five-membered ring skeleton compound as shown in formula I. The present method provides convenience for the industrial production of environmentally-friendly sulphur-containing polymer materials. The synthesised sulphur-containing polymer has the advantages of high molecular weight, a wide range of adjustable physical properties, and excellent degradability, and can be used for plastic, rubber, elastomer, and fibre products.

Description

A method for the preparation of sulfur-containing polymers based on isomerization-driven irreversible ring-opening polymerization

This application claims the priority of Chinese patent application 2021111810407 with a filing date of October 11, 2021. This application cites the full text of the above-mentioned Chinese patent application.

technical field

The invention relates to a sulfur-containing polymer and a method for preparing the sulfur-containing polymer based on irreversible ring-opening polymerization driven by isomerization.

Background technique

Non-strained five-membered ring monomers are a class of renewable monomers with great potential. They are commonly found in natural products in nature, and can also be produced on a large scale from starch, lignocellulose, or carbon dioxide. However, the ring-opening polymerization (ROP) of unstrained five-membered ring monomers at room temperature is usually thermodynamically forbidden, and such compounds are usually referred to as "non-polymerizable" monomers in literature and textbooks, which is Because their non-strained five-membered rings cannot provide sufficient ring tension to drive ring-opening polymerization (ROP), meanwhile, since ring-opening polymerization is a typical polymerization/depolymerization thermodynamic equilibrium, thermodynamically stable five-membered ring lactones Depolymerization reactions are prone to occur during the polymerization process. In 2016, Hong Miao and Chen pioneered the development of a new strategy for the ring-opening polymerization of non-tensioned five-membered ring lactones (Nat.Chem.2016, 8, 42-49), that is, by controlling the reaction temperature below the upper limit temperature of the polymerization and Precipitation of polymers breaks the polymerization-depolymerization equilibrium, but the extremely low polymerization temperature seriously hinders the applicability of industrial production.

In a disclosed polymerization reaction catalyzed by an anionic catalyst, after the five-membered ring thionolactone monomer is hydrogen-extracted by a basic anionic catalyst, it can nucleophilically attack the monomer γ-position methylene (methine) Isomerization ring-opening polymerization can also nucleophilically attack the thiocarbonyl group of another monomer molecule and then lose a molecule of hydrogen sulfide to undergo ester condensation reaction, resulting in dimerization products instead of polymers (as shown below), how to limit the latter The ester condensation reaction is the key to whether the polymerization can be carried out efficiently.

So far, there is still a lack of a universal method that can efficiently polymerize non-strained five-membered ring monomers under mild conditions to prepare sustainable polythioester materials with various properties.

Contents of the invention

The technical problem to be solved by the present invention is to overcome the defect that existing non-tensioned five-membered ring monomers are difficult to ring-opening polymerization under mild conditions, and provide a new method for irreversible ring-opening polymerization. The preparation method of the invention provides convenience for the industrialized production of environmentally friendly sulfur-containing polymer materials. The synthesized sulfur-containing polymer has the advantages of high molecular weight, wide range of adjustable physical properties, excellent degradability, etc., and can be used as plastics, rubber, elastomers, fibers and other products.

The invention provides a method for preparing a sulfur-containing polymer, which comprises the following steps: in an organic solvent, in the presence of a main catalyst, one or more polymerizable monomers are polymerized;

Wherein, the main catalyst is an anion main catalyst or a cationic main catalyst; the anion main catalyst is a phosphazene base, a guanidine organic base, an amidine organic base, an N-heterocyclic carbene organic base, an N-heterocyclic One or more of olefinic organic bases, carboxylates and thiocarboxylates; the cationic main catalyst is zwitterion pair catalyst, neutral Lewis acid catalyst and protonic acid (ester) catalyst one or more of

The polymerized monomer is independently a compound shown in formula (I):

in,

for

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 (such as fluorine, chlorine, bromine or iodine, and such as fluorine or chlorine), hydroxyl, C _1-10 alkyl (such as C _1-8 alkyl, and such as methyl, ethyl, n-propyl base, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-nonyl), C _6-10 aryl (such as phenyl) or C _1-10 alkenyl (such as C _1-8 alkenyl, and Such as C _1-4 alkenyl, such as vinyl); said C _1-10 alkyl is optionally replaced by halogen (such as fluorine, chlorine, bromine or iodine, such as fluorine or chlorine), hydroxyl and C _6- One or more substitutions in ₁₀ aryl (such as phenyl);

Alternatively, 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 connecting them form a C _3-10 ring Alkyl (such as cyclopentyl, cyclohexyl or cycloheptyl), C _3-10 cycloalkenyl (such as cyclohexenyl) or C _6-10 aryl (such as phenyl);

When the main catalyst is an anionic main catalyst, then R ₁₁ , R ₁₂ , R ₂₁ , R ₂₂ , R ₃₁ , R ₃₂ and R4 ₁ are all H;

When the main catalyst is an anionic main catalyst, and the polymer monomer is one, then the polymer monomer is not

In some embodiments, 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 (such as fluorine, chlorine, bromine or iodine, such as fluorine or chlorine), hydroxyl, C _1-10 alkyl (such as C _1-8 alkyl, and such as methyl , ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-nonyl) or C _1-10 alkenyl (such as C _1-8 alkenyl, and for example C _1-4 alkenyl group, such as vinyl); the C _1-10 alkyl group is optionally replaced by halogen (such as fluorine, chlorine, bromine or iodine, such as fluorine or chlorine), hydroxyl and C _6-10 aryl (such as benzene One or more substitutions in group).

In some embodiments, the compound represented by formula (I) is represented by any of the following structures:

In some embodiments,

for

Preferably, 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 connecting them form C _{3- 10} cycloalkyl;

Further preferably, R ₁₁ , R ₁₂ , R ₁₃ and R ₁₄ have the following definitions:

(1) R ₁₁ , R ₁₂ and R ₁₃ are H, and R ₁₄ is C _1-10 alkyl;

(2) R ₁₁ , R ₁₂ and R ₁₄ are H, and R ₁₃ is C _1-10 alkyl or C _1-10 alkenyl;

(3) R ₁₂ , R ₁₃ and R ₁₄ are H, and R ₁₁ is C _1-10 alkyl;

(4) R ₁₃ and R ₁₄ are H, R ₁₁ and R ₁₂ are independently C _1-10 alkyl;

(5) R ₁₂ and R ₁₄ are H, R ₁₁ and R ₁₃ are independently C _1-10 alkyl;

(6) R ₁₁ and R ₁₂ are H, R ₁₃ and R ₁₄ form a C _3-10 cycloalkyl group together with the atoms connecting them;

(7) R ₁₁ , R ₁₂ , R ₁₃ and R ₁₄ are H;

In some embodiments,

for

Preferably, R ₁₂ and R ₁₃ together with the atoms connecting them form a C _3-10 cycloalkyl;

Further preferably, R ₁₁ and R ₁₄ are H, and R ₁₂ and R ₁₃ together with the atoms connecting them form a C _3-10 cycloalkyl group.

In some embodiments,

for

Preferably, R ₅₁ , R ₅₂ , R ₅₃ and R ₅₄ are independently H, halogen, C _1-10 alkyl, C _6-10 aryl or C _1-10 alkenyl; said C _1-10 alkane The radical is optionally substituted by one or more of halogen, hydroxyl and C _6-10 aryl.

Further preferably, R ₅₁ is halogen (such as fluorine), C _1-10 alkyl (such as methyl, ethyl), C _6-10 aryl (such as phenyl) or C _1-10 alkenyl (such as vinyl ); the C _1-10 alkyl is optionally substituted by chlorine, hydroxyl or phenyl; R ₅₂ , R ₅₃ and R ₅₄ are H.

In some embodiments,

for

Preferably, R ₅₁ , R ₅₂ , R ₅₃ and R ₅₄ are independently H or C _1-10 alkyl.

Further preferably, R ₅₁ is a C _1-10 alkyl group, and R ₅₂ , R ₅₃ and R ₅₄ are H.

In some preferred embodiments, the compound shown in formula (I) is represented by any of the following structures:

In some embodiments, the polymerization reaction is preferably performed under a protective gas atmosphere, and the protective gas may be a conventional protective gas in the art, such as nitrogen and/or argon. The protective gas described in the present invention is the inert gas described in the art.

In some embodiments, the molar volume ratio of the polymerized monomer to the organic solvent can be a conventional molar volume ratio in the art, preferably 0.2mol/L-10mol/L, more preferably 2.0mol/L-7.0 mol/L, such as 2.0mol/L or 5.0mol/L.

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

Preferably, the organic solvent is one or more of linear hydrocarbon solvents, halogenated hydrocarbon solvents, cyclic ether solvents, aromatic hydrocarbon solvents, halogenated aromatic hydrocarbon solvents and amide solvents, such as aromatic hydrocarbons solvents and/or amide solvents, such as toluene and/or N,N-dimethylformamide. The linear 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, chloroform, 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 solvent is preferably one or more of o-dichlorobenzene, o-difluorobenzene, o-dibromobenzene, chlorobenzene, fluorobenzene, bromobenzene and trichlorobenzene, more preferably o-dichlorobenzene benzene. The amide solvent is preferably N,N-dimethylformamide.

In some embodiments, the molar ratio of the polymerized monomer to the procatalyst can be a conventional molar ratio in the art, preferably 20:1-1600:1, more preferably 100:1-1600:1, further Preferably 400:1 to 1600:1, eg 400:1, 1200:1 or 1600:1.

In some embodiments, in the anionic procatalyst, the phosphazene base may be a conventional phosphazene base in the art. Preferably, the phosphazene base is represented by the following structure:

Wherein, R and R' are independently C1-C4 alkyl (such as methyl, ethyl, propyl, isopropyl or tert-butyl); n1 is 0, 1, 2 or 3; y is 0, 1 , 2 or 3.

More preferably, the phosphazene base is 1-tert-butyl-4,4,4-tris(dimethylamino)-2,2-bis[tris(dimethylamino)-phosphoranylideneamino]- 2λ ⁵ , 4λ ⁵ -bis(phosphorus nitrogen-based compound) ( ^t Bu-P ₄ ), its structure is as follows:

More preferably, the phosphazene base can also be tert-butylimino-tris(dimethylamino)phosphorane ( ^tBu -P ₁ ), whose structure is as follows:

In some embodiments, in the anion procatalyst, the guanidine organic base may be a conventional guanidine organic base in the art. Preferably, the guanidine organic base is 1,5,7-triazidebicyclo(4.4.0)dec-5-ene (TBD) and/or 7-methyl-1,5,7-triazol Heterobicyclo[4.4.0]dec-5-ene (MTBD), the structure of which is shown below:

In some embodiments, in the anion procatalyst, the amidine organic base 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 as follows:

In some embodiments, in the anion procatalyst, the N-heterocyclic carbene organic base can be a conventional N-heterocyclic carbene organic base in the art. Preferably, the N-heterocyclic carbene organic base is represented by the following structure:

Wherein, R _1a and R _2a are independently hydrogen, alkyl (such as C _1-4 alkyl) or aryl (such as C _6-10 aryl); R _3a and R _4a are independently alkyl (such as C _{1 -4} alkyl) or aryl (eg C _6-10 aryl).

More preferably, the N-heterocyclic carbene organic base is 1,3-di-tert-butylimidazol-2-ylidene (ItBu), its structure is as follows:

In some embodiments, in the anion procatalyst, the N-heterocyclic olefinic organic base can be a conventional N-heterocyclic olefinic organic base in the art. Preferably, the N-heterocyclic olefinic organic base is represented by the following structure:

Wherein, R _1b and R _2b are independently hydrogen, alkyl (such as C _1-4 alkyl) or aryl (such as C _6-10 aryl); R _3b and R _4b are independently alkyl (such as C _{1 -4} alkyl) or aryl (such as C _6-10 aryl); R _5b is hydrogen or alkyl (such as C _1-4 alkyl).

More preferably, the N-heterocyclic olefinic organic base is 1,3,4-trimethyl-2-(isopropenylene)-imidazole (NHO), whose structure is as follows:

In some embodiments, in the anionic procatalyst, the carboxylate may be a metal carboxylate or an organic carboxylate.

Preferably, the anion in the metal carboxylate and organic carboxylate is independently represented by the following structure:

Wherein, R _1c is an alkyl group (such as a C _1-4 alkyl group, such as a methyl group) or an aryl group (such as a C _6-10 aryl group).

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

Preferably, the cations in the metal carboxylate are alkali metal (such as lithium, sodium, potassium, rubidium or cesium, and also such as potassium) cations.

Preferably, the cations in the organic carboxylate are quaternary ammonium cations, imidazolium cations, phosphazenium cations, bis(triphenylphosphine)ammonium cations or amidinium cations.

More preferably, the cation in the described organic carboxylate is shown by any of the following structures:

Wherein, R _1d , R _2d , R _3d , R _4d , R _5d and R _6d are independently hydrogen, alkyl or aryl, n2 is 0, 1, 2 or 3; y2 is 0, 1, 2 or 3.

In some embodiments, in the anionic procatalyst, the thiocarboxylate may be a metal thiocarboxylate.

Preferably, the anion in the described thiocarboxylate is represented by the following structure:

Wherein, R _1e is an alkyl group (such as a C _1-4 alkyl group, such as a methyl group) or an aryl group (such as a C _6-10 aryl group). Preferably, the anion is a thioacetate anion.

Preferably, the cations in the thiocarboxylate are alkali metal (such as lithium, sodium, potassium, rubidium or cesium, and such as potassium) cations.

More preferably, the thiocarboxylate is potassium thioacetate.

In some preferred embodiments, the anionic procatalyst may be a phosphazene base and/or a thiocarboxylate, such as 1-tert-butyl-4,4,4-tris(dimethylamino)-2,2 - Bis[tris(dimethylamino)-phosphoranylideneamino]-2λ ⁵ , 4λ ⁵ -bis(phosphoryl nitrogen) ( ^t Bu-P ₄ ) and/or potassium thioacetate.

In some embodiments, in the cationic procatalyst, the zwitterion pair catalyst may be a conventional zwitterion pair catalyst in the art.

Preferably, the zwitterion-pair catalyst is represented by the following structure:

[R] ⁺ [X] ^-

(VIII)

Wherein, the [R] ⁺ is carbocation, silicon cation, oxonium ion, sulfonium ion, azonium ion, chloride onium ion, bromium ion or iodonium ion, and the [X] ^- is Borate anion, aluminate anion, phosphate anion, sulfonate anion, sulfonimide anion, antimonate anion or arsenate anion.

More preferably, the carbocation is represented by the following structure:

Among them, R ^1f , R ^2f , and R ^3f are independently phenyl, 2,4,6-trimethylphenyl, 2,6-dimethylphenyl, 2,3,5,6-tetramethyl Phenyl or 2,6-diisopropylphenyl.

More preferably, the silicon cation is represented by the following structure:

Wherein, R ^1g , R ^2g and R ^3g are 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.

More preferably, the silicon cation can also be represented by the following structure:

More preferably, the oxonium ion and the sulfonium ion are represented by the following structures respectively:

Wherein, R ^1h , R ^2h and R ^3h are 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.

More preferably, said chloride ion and said bromium ion are represented by the following structures respectively:

Wherein, R ¹ⁱ and R ²ⁱ are independently phenyl, 2,4,6-trimethylphenyl, 2,6-dimethylphenyl, 2,3,5,6-tetramethylphenyl or 2,6-Diisopropylphenyl.

More preferably, the iodonium ion is represented by the following structure:

Wherein, R ^1j and R ^2j are 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.

More preferably, the zolium ion is shown by the following structure:

More preferably, the borate anion and the aluminate anion are represented by the following structures:

Wherein, X ¹ , X ² , X ³ and X ⁴ are independently fluorine, chlorine, phenyl, pentafluorophenyl, 3,5-bis(trifluoromethyl)phenyl, pentafluorophenoxy or 3 , 5-bis(trifluoromethyl)phenoxy.

More preferably, the phosphate anion is represented by any of the following structures:

More preferably, the sulfonate anion and the sulfonimide anion are represented by the following structures respectively:

Wherein, X ^1a and X ^2a are each independently fluorine, methyl, phenyl, trifluoromethyl, pentafluoroethyl, pentafluorophenyl or 3,5-bis(trifluoromethyl)phenyl.

More preferably, the antimonate anion and the arsenate anion are represented by the following structures respectively:

Wherein, X ^1c , X ^2c , X ^3c , X ^4c , X ^5c and X ^6c are each independently fluorine, chlorine or bromine.

Further preferably, the [R] ⁺ is a carbocation, and the [X] ^- is a borate anion, for example, the zwitterion pair catalyst is [Ph ₃ C][B(C ₆ F ₅ ) ₄ ].

Further preferably, the [R] ⁺ is an oxonium ion, and the [X] ^- is a borate anion, for example, the zwitterion pair catalyst is [Et ₃ O][B(C ₆ F ₅ ) ₄ ], Me ₃ OBF ₄ .

Further preferably, the [R] ⁺ is a zwitterium ion, and the [X] ^- is a borate anion, for example, the zwitterion pair catalyst is C ₇ H ₇ BF ₄ .

Further preferably, the [R] ⁺ is a silicon cation, and the [X] ^- is a borate anion, for example, the zwitterion pair catalyst is [Et ₃ Si-H-SiEt ₃ ][B (C ₆ F ₅ ) ₄ ].

In some embodiments, in the cationic procatalyst, the neutral Lewis acid catalyst may be a conventional neutral Lewis acid catalyst in the art.

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

More preferably, the boron complex is trialkylboron or triarylboron.

More preferably, the aluminum complex is trialkylaluminum, triarylaluminum, alkylbisphenolaluminum, alkylaluminum dichloride or dialkylaluminum chloride.

Further preferably, the trialkylboron and the trialkylaluminum are respectively represented by the following structures:

Wherein, R ^1k , R ^2k and R ^3k are independently methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, cyclohexyl or n-octyl base.

Further preferably, the triarylboron and the triarylaluminum are represented by the following structures respectively:

Wherein, R ¹ⁿ , R ²ⁿ , R ³ⁿ , R ⁴ⁿ and R ⁵ⁿ are independently hydrogen, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, cyclohexyl, fluorine, chlorine, trifluoromethyl, pentafluorophenyl or trimethylsilyl.

Further preferably, said aluminum alkyl bisphenolate is represented by the following structure:

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 are independently hydrogen, methyl, ^ethyl , propyl, iso Propyl, butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, cyclohexyl, fluorine, chlorine, trifluoromethyl, pentafluorophenyl or trimethylsilyl.

Further preferably, the alkylaluminum dichloride and the bisalkylaluminum chloride are represented by the following structures respectively:

Wherein, R ^1o and R ^2o are independently methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, cyclohexyl or n-octyl.

Further preferably, the neutral Lewis acid catalyst is a boron complex (such as triaryl boron, such as B(C ₆ F ₅ ) ₃ ).

Still more preferably, the neutral Lewis acid catalyst is a triaryl boron compound, preferably a fluorinated triaryl boron compound; for example B(C ₆ F ₅ ) ₃ .

Further preferably, the neutral Lewis acid catalyst is an aluminum complex (such as triarylaluminum, such as Al(C ₆ F ₅ ) ₃ ).

Still more preferably, the neutral Lewis acid catalyst is a triaryl aluminum compound, preferably a fluorinated triaryl aluminum compound; for example Al(C ₆ F ₅ ) ₃ .

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

Preferably, the protonic acid (ester) type catalyst is sulfonic acid, sulfonic acid ester, sulfonimide, N-substituted sulfonimide, oxonium protonic acid, sulfonium protonic acid.

Preferably, the protonic acid (ester) type catalyst is a bisphosphonimide ester.

Preferably, the protic acid (ester) type catalyst is sulfonic acid, sulfonic acid ester, sulfonimide, N-substituted sulfonimide, oxonium type protonic acid or sulfonium type protonic acid.

Further preferably, the sulfonic acid, sulfonic acid ester, sulfonimide and N-substituted sulfonimide are respectively represented by the following structures:

Wherein, X ^1d and X ^2d are independently fluorine, methyl, phenyl, trifluoromethyl, pentafluoroethyl, pentafluorophenyl or 3,5-bis(trifluoromethyl)phenyl; R ^xd Methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, cyclohexyl, trimethylsilyl, triethylsilyl, tripropyl Silyl, Triisopropylsilyl, Tributylsilyl or tert-butyldimethylsilyl.

Further preferably, the oxonium protonic acid and the sulfonium protonic acid are shown by the following structures respectively:

Wherein, R ^1p and R ^2p are 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] ^- is the aforementioned borate anion, aluminate anion, Phosphate anion, sulfonate anion, sulfonimide anion, antimonate anion or arsenate anion.

More preferably, the bisphosphonimide esters are represented by the following structure:

Wherein, R ^1q is a C _6-10 aryl group (such as 3,5-dimethylphenyl), and the C _6-10 aryl group is optionally substituted by one or more of halogens (such as fluorine); R ^2q is methylsulfonyl optionally substituted with one or more of halogen (eg, fluorine).

More preferably, the protic acid (ester) type catalyst is a bisphosphonimide ester, such as IDPi-CF ₃ , the structure of which is as follows:

Still more preferably, the protic acid (ester) type catalyst is an oxonium protonic acid, such as [H(Et ₂ O) ₂ ][B(C ₆ F ₅ ) ₄ ].

In some preferred embodiments, the cationic procatalyst is [Ph ₃ C][B(C ₆ F ₅ ) ₄ ], Me ₃ OBF ₄ , [Et ₃ O][B(C ₆ F ₅ ) ₄ ] , C ₇ H ₇ BF ₄ , B(C ₆ F ₅ ) ₃ , Al(C ₆ F ₅ ) ₃ , IDPi-CF ₃ , [Et ₃ Si-H-SiEt ₃ ][B(C ₆ F ₅ ) ₄ ] and one or more of [H(Et ₂ O) ₂ ][B(C ₆ F ₅ ) ₄ ].

In some preferred embodiments, the cationic procatalysts are [Ph ₃ C][B(C ₆ F ₅ ) ₄ ], B(C ₆ F ₅ ) ₃ and [H(Et ₂ O) ₂ ][B One or more of (C ₆ F ₅ ) ₄ ].

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

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 1:1-1:10, more preferably 1:1-1:5, for example 1:1, 1:2 or 1:3.

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

Preferably, the hydrogen bond donor is one or more of alcohol, thiol, carboxylic acid, urea and thiourea, such as one or more of alcohol, thiol, and thiourea, and for example One or more of diphenylmethanol, benzylmethanol, 1-octylthiol, and N,N'-diisopropylthiourea. The alcohol is preferably benzhydryl alcohol and/or benzyl alcohol. The mercaptan is preferably 1-octanethiol. Described 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.

In some preferred embodiments, in the cocatalyst, the hydrogen bond acceptor can be a conventional hydrogen bond acceptor in the art.

Preferably, the hydrogen bond acceptor is one or more of crown ether, polyethylene glycol dimethyl ether, cyclodextrin, calixarene and azacyclic cryptate, such as crown ether, polyethylene glycol One or more of dimethyl ethers, such as 18-crown 6 ether. Said cyclodextrin is preferably methyl β-cyclodextrin. The calixarene is preferably O(1), O(2), O(3), O(4)-tetramethyl-tert-butyl calixarene. The polyethylene glycol dimethyl ether is preferably tetraethylene glycol dimethyl ether. The azacyclic cryptate is preferably 4,7,13,16,21-pentoxa-1,10-diazabicyclo[8.8.5]tricosane.

In some preferred embodiments, in the cocatalyst, the Lewis acid can be a conventional Lewis acid in the art.

Preferably, the Lewis acid is one or more of alkali metal compounds, alkaline earth metal compounds, zinc compounds, boron compounds, aluminum compounds and rare earth compounds, such as zinc compounds, and bis(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 bis(pentafluorophenyl)zinc. The boron compound is preferably tris(pentafluorophenyl)boron. The aluminum compound is preferably tris(pentafluorophenyl)aluminum. The rare earth compound is preferably tris[bis(trimethylsilyl)amino]lanthanum.

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

In some preferred embodiments, the molar ratio of the main catalyst to the initiator can be a conventional molar ratio in the art, preferably 1:1-1:10, more preferably 1:1-1:5, for example 1:1, 1:2 or 1:3.

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

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

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

In some embodiments, the progress of the polymerization reaction can be monitored by conventional means in the art (for example, the conversion rate can be monitored by monitoring the hydrogen integral ratio of the generated polymer to the remaining monomer by ¹ H NMR), and the The time of the polymerization reaction is preferably 5-720 minutes, more preferably 30-240 minutes, such as 30 minutes, 120 minutes, 180 minutes or 240 minutes.

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

In some preferred embodiments, the preparation method includes the following steps: in an organic solvent, in the presence of a main catalyst and a cocatalyst, the polymerization monomer is subjected to a polymerization reaction, that is, the polymerization monomer The molar ratio of the main catalyst 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.

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 polymerized monomer is polymerized, that is, the polymerized monomer The molar ratio of the main catalyst 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.

In some preferred embodiments, the polymerization reaction comprises the following steps: in an organic solvent, in the presence of a main catalyst, or a main catalyst and a cocatalyst, or a main catalyst and an initiator, the polymerization monomer carry out the polymerization reaction.

In some preferred embodiments, the polymerization reaction comprises the following steps: adding the polymerized 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, the main catalyst and the co-catalyst, or, the main catalyst and the initiator, react at room temperature, or heat to the polymerization temperature, and wait until the polymerization reaction is completed.

In some preferred embodiments, the polymerization reaction comprises the following steps: adding the polymerized monomer to the reaction bottle in a glove box, removing the glove box, and connecting the reaction bottle to a vacuum line protected by an inert gas , and heated to the corresponding polymerization temperature, then add the main catalyst, or the solution of the organic solvent of the main catalyst and the co-catalyst to the solution, and wait until the polymerization reaction is completed.

In some embodiments, the raw materials of the polymerization reaction are the polymerized monomer, the cationic procatalyst and the solvent.

In some embodiments, the raw materials of the polymerization reaction are the polymerized monomers, the anion procatalyst and the solvent.

In some embodiments, the raw materials of the polymerization reaction are the polymerized monomer, the anionic procatalyst, the solvent and the cocatalyst.

In some embodiments, the raw materials of the polymerization reaction are the polymerized monomers, the anion procatalyst, the solvent and the initiator.

In some embodiments, the raw materials of the polymerization reaction are the polymerized monomer, the anionic procatalyst, the solvent, the initiator and the cocatalyst.

In some preferred embodiments, after the end of the polymerization reaction, post-treatment may be further included, and the post-treatment may include the following steps: mixing the reaction solution with one of aqueous solution, allyl chloride solution and benzoic acid solution Mix one or more kinds, then mix with ethanol, centrifuge or filter, and dry. Said aqueous solution is preferably a tetrahydrofuran solution of water, wherein the volume ratio of the tetrahydrofuran solution of water is preferably 1/20 or 1/30; said allyl chloride solution is preferably a toluene solution of allyl chloride, and said allyl chloride The volume ratio of the toluene solution is preferably 1/2; the preferred benzoic acid chloroform solution of the benzoic acid, the chloroform solution mass volume ratio of the benzoic acid is preferably 10mg/mL. Water in tetrahydrofuran, allyl chloride in toluene, and benzoic acid in chloroform were added to terminate polymeric chain growth. Mixing with ethanol is to make the polymer sedimentation, precipitation and fixation. A washing step is preferably included after the filtering or centrifuging, and the washing solvent is preferably ethanol. The number of times of said washing is preferably 2-5 times (for example 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, such as 24 hours.

In some preferred embodiments, the polymerized monomer is

The main catalyst is a cationic main catalyst (for example, a zwitterion pair catalyst, such as [Ph ₃ C][B(C ₆ F ₅ ) ₄ ]).

In some preferred embodiments, the polymerized monomer is

The main catalyst is an anion main catalyst (such as thiocarboxylate, such as potassium thioacetate).

In some preferred embodiments, the polymerized monomer is

The main catalyst is an anionic main catalyst (such as phosphazene base, such as ^tBu -P ₄ ), and the cocatalyst is a hydrogen bond donor (such as alcohol, such as benzhydryl alcohol).

In some preferred embodiments, the polymerized monomer is

The main catalyst is an anionic main catalyst (such as thiocarboxylate, such as potassium thioacetate), and the cocatalyst is a hydrogen bond acceptor (such as crown ether, such as 18 crown 6 ether).

In some preferred embodiments, the polymerized monomer is

The main catalyst is an anionic main catalyst (such as phosphazene base, such as ^tBu -P ₄ ), and the initiator is a carboxylic acid (such as benzoic acid).

In some preferred embodiments, the polymerized monomer is

The main catalyst is a cationic main catalyst (for example, a neutral Lewis acid catalyst, such as B(C ₆ F ₅ ) ₃ ).

In some preferred embodiments, the polymerized monomer is

The main catalyst is a cationic main catalyst (for example, a protonic acid (ester) type catalyst, such as an oxonium protonic acid, and such as [H(Et ₂ O) ₂ ][B(C ₆ F ₅ ) ₄ ]) .

In some preferred embodiments, the polymerized monomer is

and

In some preferred embodiments, the polymerized monomer is

Described main catalyst is anion main catalyst (for example, guanidine organic base catalyst, and for example TBD again:

), the initiator is a carboxylic acid (such as benzoic acid).

In some preferred embodiments, the polymerized monomer is

Described main catalyst is anion main catalyst (for example, amidine organic base catalyst, and for example DBU again:

), the initiator is a thiocarboxylic acid (such as thiobenzoic acid).

In some preferred embodiments, the polymerized monomer is

Described procatalyst is anionic procatalyst (for example, N-heterocyclic carbene organic base catalyst, and for example ^It Bu:

).

In some preferred embodiments, the polymerized monomer is

The main catalyst is an anionic main catalyst (for example, N-heterocyclic olefin organic base catalyst, such as NHO:

).

In some preferred embodiments, the polymerized monomer is

The main catalyst is an anionic main catalyst (for example, a phosphazene base catalyst, such as ^tBu -P ₁ :

).

In some preferred embodiments, the polymerized monomer is

The main catalyst is a cationic main catalyst (for example, a zwitterion pair catalyst, such as [Et ₃ Si-H-SiEt ₃ ][B(C ₆ F ₅ ) ₄ ].

In some preferred embodiments, the polymerized monomer is

The main catalyst is a cationic main catalyst (for example, a zwitterion pair catalyst, such as Ph ₃ CB(C ₆ F ₅ ) ₄ /Et ₃ SiH).

In some preferred embodiments, the polymerized monomer is

The main catalyst is a cationic main catalyst (for example, a zwitterion pair catalyst, such as Me ₃ OBF ₄ ).

In some preferred embodiments, the polymerized monomer is

The main catalyst is a cationic main catalyst (for example, a zwitterion pair catalyst, such as [Et ₃ O][B(C ₆ F ₅ ) ₄ ]).

In some preferred embodiments, the polymerized monomer is

The main catalyst is a cationic main catalyst (for example, a zwitterion pair catalyst, such as C ₇ H ₇ BF ₄ ).

In some preferred embodiments, the polymerized monomer is

The main catalyst is a cationic main catalyst (for example, a neutral Lewis acid catalyst, such as Al(C ₆ F ₅ ) ₃ ).

In some preferred embodiments, the polymerized monomer is

Described main catalyst is cationic main catalyst (for example, protonic acid (ester) type catalyst, and for example IDPi-CF ₃

).

In some preferred embodiments, the polymerized monomer is

), the cocatalyst is benzyl alcohol.

In some preferred embodiments, the polymerized monomer is

The cocatalysts are benzyl alcohol and 1-[3,5-bis(trifluoromethyl)phenyl]-3-cyclohexylthiourea).

In some preferred embodiments, the polymerized monomer is

The present invention also provides a sulfur-containing polymer, which is prepared according to the preparation method of the sulfur-containing polymer described herein.

The present invention also provides a sulfur-containing polymer, the main chain of which 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, and the definition of each group is as described in any solution of the present invention.

In the structure of the sulfur-containing polymer, each structure in "()" represents a structural unit, and each structural unit is independent of each other.

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

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, further preferably 20-250 kg/mol, and even more preferably 80-250kg/mol.

In some embodiments, the molecular weight distribution of the sulfur-containing polymer is 1.0-3.0, preferably 1.0-1.5.

In some embodiments, the sulfur-containing polymer is a homopolymer or a multi-polymer.

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

Preferably, the multi-component copolymer is a terpolymer, and the mole percentage of each structural unit is 5-90%.

In some embodiments, the glass transition temperature T _g of the sulfur-containing polymer is -57.0-59.5°C.

In some embodiments, the sulfur-containing polymer has an elongation at break of 638%-1451.30%.

In some embodiments, the sulfur-containing polymer has a yield stress of 9.05 MPa.

In some embodiments, the fracture stress of the sulfur-containing polymer is 16.62-24.27 MPa.

In some embodiments, the sulfur-containing polymer has an elastic recovery of 72.3%.

In the present invention, unless otherwise specified, "°C" refers to degrees Celsius; "h" refers to hours; and "min" refers to minutes.

Borate anion: According to the naming rules of boron-containing compounds, "boron-containing anions are represented by borate radicals"("Inorganic Chemistry Nomenclature Rules", 1982 edition, page 2194), the borate anion in the text refers to (pentafluorophenyl) borate anion[ B(C ₆ F ₅ ) ₄ ] ^- etc.

On the basis of not violating common knowledge in the field, the above-mentioned preferred conditions can be combined arbitrarily to obtain preferred examples of the present invention.

The reagents and raw materials used in the present invention are all commercially available.

The positive progress effect of the present invention is:

The preparation method of the present invention uses isomerization as the thermodynamic driving force, rather than traditional ring tension, and is not limited by the upper limit temperature of polymerization, and can promote a series of non-tensioned five-membered ring monomers (including Five-membered ring thionolactone and five-membered ring thionocarbonate) undergo irreversible ring-opening polymerization at room temperature to high temperature. Due to the synergistic isomerization reaction during the ring-opening process, the generated sulfur-containing polymers will not be depolymerized into initial monomers, thereby promoting the forward polymerization until the initial monomers are consumed, which is an irreversible ring-opening polymerization. Achieve efficient and quantitative monomer conversion. The invention can suppress the occurrence of biting-back side reactions, successfully control the content of biting-back by-products to less than 1%, and the yield of sulfur-containing polymers can reach up to 99%.

The number-average molecular weight of the polythioester prepared by the invention is 3.2kg/mol-431.1kg/mol, and the molecular weight distribution index is 1.01-2.05. The number average molecular weight increases linearly with the increase of the ratio of the monomer to the catalyst, and the polythioester provided by the invention has a glass transition temperature T _g in the range of about -57.0 to 59.5° C. with good molecular weight controllability. The performance of the polythioester prepared by the invention has great adjustability, and can meet different use scenarios. For example the elongation at break of poly-(S)-(γ-thiovalerolactone) that the present invention makes is 638%, and yield stress is 9.05MPa, and breaking stress is 24.27MPa, is a kind of strong and tough high Molecular materials, all indicators of mechanical tensile test are better than low-density polyethylene (elongation at break 430%, stress at break 10.6MPa) and isotactic polypropylene (elongation at break 420%, stress at break 26.0 MPa), close to the tensile properties of high-density polypropylene (the elongation at break is 420%, and the stress at break is 26.0MPa). The elongation at break of the ternary random copolymer prepared by copolymerization in the present invention is 1451.30%, the stress at break is 16.62MPa, and the elastic recovery rate is 72.3%, which is a strong and tough elastic polymer material. All indexes of the mechanical tensile test are better than commercial ethylene-propylene rubber (the elongation at break is 275.0%, and the stress at break is 5.70Mpa).

The sulfur-containing homopolymer and copolymer prepared by the invention provide convenience for the industrialized production of environment-friendly sulfur-containing polymer materials. The synthesized sulfur-containing polymer has the advantages of high molecular weight, wide range of adjustable physical properties, excellent degradability, etc., and can be used as plastics, rubber, elastomers, fibers and other products.

Description of drawings

Fig. 1 is the ¹ H NMR spectrum of poly(γ-thiovalerolactone) obtained in Example 2.

Fig. 2 is the ¹³ C NMR spectrum of poly(γ-thiovalerolactone) obtained in Example 2.

Fig. 3 is the ¹ H NMR spectrum of poly(γ-thiocaprolactone) obtained in Example 3.

Fig. 4 is the ¹³ C NMR spectrum of poly(γ-thiocaprolactone) obtained in Example 3.

FIG. 5 is the ¹ H NMR spectrum of poly(γ-thioenantholactone) obtained in Example 4. FIG.

FIG. 6 is the ¹³ C NMR spectrum of poly(γ-thioenantholactone) obtained in Example 4. FIG.

Fig. 7 is the ¹ H NMR spectrum of poly(γ-thiooctrolactone) obtained in Example 5.

FIG. 8 is the ¹³ C NMR spectrum of poly(γ-thiooctrolactone) obtained in Example 5. FIG.

FIG. 9 is the ¹ H NMR spectrum of poly(γ-thiononanolide) obtained in Example 6. FIG.

Fig. 10 is the ¹³ C NMR spectrum of poly(γ-thiononanolide) obtained in Example 6.

Fig. 11 is the ¹ H NMR spectrum of poly(γ-thiodecalactone) obtained in Example 7.

Fig. 12 is the ¹³ C NMR spectrum of poly(γ-thiodecalactone) obtained in Example 7.

FIG. 13 is the ¹ H NMR spectrum of poly(γ-thioundecalactone) obtained in Example 8. FIG.

Fig. 14 is the ¹³ C NMR spectrum of poly(γ-thioundecalactone) obtained in Example 8.

FIG. 15 is a ¹ H NMR spectrum of poly(γ-thiolaurolactone) obtained in Example 9. FIG.

FIG. 16 is a ¹³ C NMR spectrum of poly(γ-thiododecalactone) obtained in Example 9. FIG.

17 is a ¹ H NMR spectrum of poly(γ-methyl-γ-thiodecalactone) obtained in Example 10. FIG.

18 is a ¹³ C NMR spectrum of poly(γ-methyl-γ-thiodecalactone) obtained in Example 10.

FIG. 19 is a ¹ H NMR spectrum chart of poly(β-methyl-γ-thiooctrolactone) obtained in Example 11. FIG.

20 is a ¹³ C NMR spectrum of poly(β-methyl-γ-thiooctanolide) obtained in Example 11.

21 is a ¹ H NMR spectrum chart of poly(α-methylγ-thiobutyrolactone) obtained in Example 12. FIG.

22 is a ¹³ C NMR spectrum of poly(α-methylγ-thiobutyrolactone) obtained in Example 12.

FIG. 23 is a ¹ H NMR spectrum of poly(β-methylγ-thiobutyrolactone) obtained in Example 13. FIG.

24 is a ¹³ C NMR spectrum of poly(β-methylγ-thiobutyrolactone) obtained in Example 13.

Fig. 25 is the ¹ H NMR spectrum of the random copolymer obtained in Example 14.

Fig. 26 is the ¹ H NMR spectrum of poly(cis-hexahydroisobenzothiophen-1-one) obtained in Example 15.

Fig. 27 is the ¹³ C NMR spectrum of poly(cis-hexahydroisobenzothiophen-1-one) obtained in Example 15.

28 is a ¹ H NMR spectrum of the block copolymer obtained in Example 21.

FIG. 29 is a ¹ H NMR spectrum chart of poly(propylene monothiocarbonate) obtained in Example 22. FIG.

30 is a ¹³ C NMR spectrum of poly(propylene monothiocarbonate) obtained in Example 22.

Figure 31 is a linear plot of _Mn for poly(γ-thiovalerolactone) versus monomer/catalyst ratio.

32 is a TGA curve of poly(γ-thiovalerolactone) obtained in Example 2.

Figure 33 shows the poly(γ-thiocaprolactone) (abbreviation: PTGCL), poly(γ-thioencaprolactone) (abbreviation: PTGHL), poly(γ-thiocaprolactone) obtained in Example 3-10 ester) (abbreviation: PTGOL), poly(γ-thiononanolide) (abbreviation: PTGNL), poly(γ-thiodecalactone) (abbreviation: PTGDL), poly(γ-thioundecalactone) ) (abbreviation: PTGUDL), poly(γ-thiododecalactone) (abbreviation: PTGDDL) and poly(γ-methyl-γ-thiodecalactone) (abbreviation: PTGMDL) DSC curves.

Figure 34 is the DSC curve of the poly(γ-thiovalerolactone) (abbreviation: PTGVL) obtained in Example 2, and the poly(α-methyl-γ-thiobutyrolactone) obtained in Examples 12-13 ( Abbreviation: DSC curve of PαMeTBL) and poly(β-methyl-γ-thiobutyrolactone) (abbreviation: PβMeTBL), poly(β-methyl-γ-thiooctrolactone) obtained in Example 11 ( Abbreviation: PTWL) and the DSC curves of poly(cis-hexahydroisobenzofuran-1-one) (abbreviation: P3,4-S6TBL) obtained in Example 15.

Fig. 35 is a degradation diagram of poly(γ-butylpentyl thioester) obtained in Example 2 under the catalysis of 1,5,7-triazidebicyclo(4.4.0)dec-5-ene.

36 is a ¹ H NMR spectrum chart of γ-thionovalerolactone obtained in Example 1. FIG.

37 is a ¹ H NMR spectrum of poly-(S)-4-methyl-1,3-dioxolane-2-thione obtained in Example 36.

38 is a ¹³ C NMR spectrum of poly-(S)-4-methyl-1,3-dioxolane-2-thione obtained in Example 36.

39 is a ¹ H NMR spectrum of poly-(rac)-4-chloromethyl-1,3-dioxolane-2-thione obtained in Example 38. FIG.

40 is a ¹ H NMR spectrum of poly-(R)-4-chloromethyl-1,3-dioxolane-2-thione obtained in Example 39.

41 is a ¹ H NMR spectrum of poly-4-phenyl-1,3-dioxolane-2-thione obtained in Example 41.

42 is a ¹³ C NMR spectrum of poly-4-phenyl-1,3-dioxolane-2-thione obtained in Example 41.

Figure 43 shows the poly-1,3-dioxolane-2-thione (abbreviation: PEMTC) obtained in Example 35 and the poly-(S)-4-methyl-1,3-bis obtained in Example 36. Oxolane-2-thione (abbreviation: S-PPMTC), poly-(R)-4-methyl-1,3-dioxolane-2-thione (abbreviation: R- PPMTC), the poly-4-chloromethyl-1,3-dioxolane-2-thione (abbreviation: PCMMTC) obtained in Example 38 and the poly-4-phenyl-1,3- Overlay of DSC curves of dioxolane-2-thione (abbreviation: PBMTC).

44 is a DSC curve of poly-(R)-4-chloromethyl-1,3-dioxolane-2-thione (abbreviation: R-PCMMTC) obtained in Example 39. FIG.

45 is a DSC graph of poly-(S)-4-chloromethyl-1,3-dioxolane-2-thione (abbreviation: S-PCMMTC) obtained in Example 40. FIG.

Fig. 46 is a mechanical tensile test diagram of the terpolymer obtained in Example 14.

Figure 47 is a graph of the cyclic tensile test of the terpolymer obtained in Example 14.

48 is a DSC graph of poly-(S)-(γ-thiovalerolactone) (abbreviation: S-PTNGVL) obtained in Example 44. FIG.

49 is a mechanical tensile test diagram of poly-(S)-(γ-thiovalerolactone) (abbreviation: S-PTNGVL) obtained in Example 44.

Detailed ways

The present invention is further illustrated below by means of examples, but the present invention is not limited to the scope of the examples. For the experimental methods that do not specify specific conditions in the following examples, select according to conventional methods and conditions, or according to the product instructions.

Example 1

The polymerized monomer of the present invention is a self-made product, and its initial raw material is a commercialized five-membered ring lactone and a cyclocarbonate, which are prepared through a one-step reaction. The preparation method has no special restrictions, preferably according to the following scientific papers. Methods for preparation: Matsumoto Y, Nakatake D, Yazaki R, Ohshima T. Chemistry-A European Journal, 2018, 24(23): 6062-6066. The synthetic steps of all compounds are similar, and the synthesis of γ-thionovalerolactone is taken as an example to illustrate:

Add 121.3g (0.3mol) of Lawson's reagent in a 1L eggplant-shaped bottle, add 500mL of anhydrous toluene and stir to form a yellow suspension, then add 50.1g of γ-valerolactone (0.5mol) therein, Stir at reflux for 5h. After the reaction was completed, after the reaction temperature dropped to normal temperature, 200 mL of saturated potassium carbonate solution was added and stirred for 30 min, and the liquids were separated. After the aqueous phase was extracted three times with anhydrous toluene, the organic phases were combined. After drying with anhydrous sodium sulfate, filtration and spin-drying, the second fraction was collected by column chromatography with petroleum ether/diethyl ether gradient elution (40:1-5:1). Subsequently, the monomer was added to calcium hydride and dried for 3 days, then distilled under reduced pressure at 100 mTorr and 60° C., and then stored in a glove box until use.

The gamma-thionovalerolactone monomer obtained in the present invention is a light yellow liquid, the mass of the obtained gamma-thionovalerolactone monomer is 48.3 g, and the calculated yield is 83.2%.

The present invention carries out nuclear magnetic resonance (NMR) characterization of the γ-thionovalerolactone monomer synthesized, and the ¹ H NMR spectrum is consistent with the literature report, proving that the γ-thionovalerolactone monomer prepared by the present invention has the following The structure, ¹ H NMR spectrum is shown in FIG. 36 .

Example 2

In a glove box under an argon atmosphere, into a dry 5 mL glass bottle at room temperature, 0.005 mmol of [Ph ₃ C][B(C ₆ F ₅ ) ₄ ] was dissolved in 0.4 mL of toluene, and then 1 mmol (116.2 mg, 0.1mL) of γ-thionovalerolactone monomer, the initial concentration of the monomer is 2mol/L, the concentration of the catalyst [Ph ₃ C][B(C ₆ F ₅ ) ₄ ] is 10mmol/L, The molar ratio of monomer to [Ph ₃ C][B(C ₆ F ₅ ) ₄ ] was 200:1. Keep the reaction temperature at room temperature, stir the reaction for 120 minutes, take a small amount of sample and dissolve it in deuterated chloroform, monitor the conversion rate by ¹ H NMR, the conversion rate is 98.1%, the by-product of γ-thiovalerolactone: poly(γ-thiovalerolactone valerolactone) in a ratio of 2:98. Then add 2 mL of water/tetrahydrofuran mixed solution (volume ratio 1:20) to quench the reaction, drop the reaction solution into ethanol to settle the polymer, centrifuge, discard the supernatant, then repeatedly dissolve with dichloromethane and drop into ethanol Settling, centrifuging, discarding the supernatant twice, and then drying at room temperature in a vacuum oven for three days to obtain colorless poly(γ-thiovalerolactone). The poly(γ-thiovalerolactone) was detected by nuclear magnetic resonance (NMR), and ^{the 1} H NMR spectrum and ^{the 13} C NMR spectrum are shown in Figure 1 and Figure 2, respectively.

The present invention adopts differential scanning calorimetry (DSC) to detect the melting temperature and the glass transition temperature of poly(γ-thiovalerolactone), and the result shows that the glass of poly(γ-thiovalerolactone) prepared in the present embodiment The transition temperature is -15.4°C.

The present invention adopts gel permeation chromatography (GPC) to detect the molecular weight and molecular weight distribution of poly(γ-thiovalerolactone), using tetrahydrofuran as eluent, flow rate is 1.0mL/min, and polymethyl methacrylate is used as A standard curve was made with standard products, and the results showed that the poly(γ-thiovalerolactone) prepared in this example had a number average molecular weight of 27.5 kg/mol and a molecular weight distribution of 1.16.

Example 3

In a glove box under an argon atmosphere, in a dry 5 mL glass bottle at room temperature, 0.005 mmol of [Ph ₃ C][B(C ₆ F ₅ ) ₄ ] was dissolved in 0.4 mL of toluene, and then 1 mmol (130.2 mg, 0.11mL) of γ-thionocaprolactone monomer, the initial concentration of the monomer is 2mol/L, the concentration of the catalyst [Ph ₃ C][B(C ₆ F ₅ ) ₄ ] is 10mmol/L, The molar ratio of monomer to [Ph ₃ C][B(C ₆ F ₅ ) ₄ ] was 200:1.

Keep the reaction temperature at room temperature, stir and react for 2.5h, take a small amount of sample and dissolve it in deuterated chloroform, monitor the conversion rate by ¹ H NMR, the conversion rate is greater than 99%, the by-product of γ-thiocaprolactone: poly(γ-sulfur Caprolactone) ratio is 3:97. Then add 2 mL of water/tetrahydrofuran mixed solution (volume ratio 1:20) to quench the reaction, drop the reaction solution into ethanol to settle the polymer, centrifuge, discard the supernatant, then repeatedly dissolve with dichloromethane and drop into ethanol Settling in medium, centrifuging, discarding the supernatant twice, and then drying at room temperature in a vacuum oven for three days to obtain colorless poly(γ-thiocaprolactone). The poly(γ-thiocaprolactone) was detected by nuclear magnetic resonance (NMR), and ^{the 1} H NMR spectrum and ^{the 13} C NMR spectrum are shown in Figure 3 and Figure 4, respectively.

The present invention adopts differential scanning calorimetry (DSC) to detect the melting temperature and glass transition temperature of poly(γ-thiocaprolactone), and the results show that the glass of poly(γ-thiocaprolactone) prepared in the present embodiment The transition temperature is -20.8°C.

The present invention adopts gel permeation chromatography (GPC) to detect the molecular weight and molecular weight distribution of poly(γ-thiocaprolactone), using tetrahydrofuran as eluent, flow rate is 1.0mL/min, and polymethyl methacrylate is used as A calibration curve was made with standard products, and the results showed that the number average molecular weight of the poly(γ-thiocaprolactone) prepared in this example was 33.6 kg/mol, and the molecular weight distribution was 1.33.

Example 4

In a glove box under an argon atmosphere, in a dry glass bottle at room temperature, 0.005 mmol of [Ph ₃ C][B(C ₆ F ₅ ) ₄ ] was dissolved in 0.36 mL of toluene, and then 1 mmol (144.2 mg, 0.14mL) of γ-thionoenantholactone monomer, the initial concentration of the monomer is 2mol/L, the concentration of the catalyst [Ph ₃ C][B(C ₆ F ₅ ) ₄ ] is 10mmol/L, the monomer The molar ratio of [Ph ₃ C][B(C ₆ F ₅ ) ₄ ] to [Ph 3 C][B(C 6 F 5 ) 4 ] is 200:1.

Keep the reaction temperature at room temperature, stir and react after 2.5h, take a small amount of sample and dissolve it in deuterated chloroform, monitor the conversion rate by ¹ H NMR, the conversion rate is greater than 99%, γ-thioenantholactone by-product: poly(γ- Thioenantholactone) in a ratio of 1:99. Then add 2 mL of water/tetrahydrofuran mixed solution (volume ratio 1:20) to quench the reaction, drop the reaction solution into ethanol to settle the polymer, centrifuge, discard the supernatant, then repeatedly dissolve with dichloromethane and drop into ethanol Settling, centrifuging, discarding the supernatant twice, and then drying at room temperature in a vacuum oven for three days to obtain colorless poly(γ-thioenantholactone). The poly(γ-thioenantholactone) was detected by nuclear magnetic resonance (NMR), and ^{the 1} H NMR spectrum and ^{the 13} C NMR spectrum are shown in Figure 5 and Figure 6, respectively.

The present invention adopts differential scanning calorimetry (DSC) to detect the melting temperature and the glass transition temperature of poly(γ-thioenantholactone), and the results show that the glass of poly(γ-thioenantholactone) prepared in the present embodiment The transition temperature is -21.5°C.

The present invention adopts gel permeation chromatography (GPC) to detect the molecular weight and molecular weight distribution of poly(γ-thioenantholactone), using tetrahydrofuran as eluent, flow rate is 1.0mL/min, and polymethylmethacrylate is used as A calibration curve was made with standard products, and the results showed that the poly(γ-thioenantholactone) prepared in this example had a number average molecular weight of 38.1 kg/mol and a molecular weight distribution of 1.36.

Example 5

In a glove box under an argon atmosphere, in a dry glass bottle at room temperature, 0.005 mmol of [Ph ₃ C][B(C ₆ F ₅ ) ₄ ] was dissolved in 0.35 mL of toluene, and then 1 mmol (158.3 mg, 0.15mL) of γ-thionocaprolactone monomer, the initial concentration of the monomer is 2mol/L, the concentration of the catalyst [Ph ₃ C][B(C ₆ F ₅ ) ₄ ] is 10mmol/L, the monomer The molar ratio of [Ph ₃ C][B(C ₆ F ₅ ) ₄ ] to [Ph 3 C][B(C 6 F 5 ) 4 ] is 200:1.

Keep the reaction temperature at room temperature, stir the reaction for 2.5h, take a small amount of sample and dissolve it in deuterated chloroform, monitor the conversion rate by ¹ H NMR, the conversion rate is greater than 99%, the by-product of γ-thiooctanolide: poly(γ-thiocaprolactone Caprylactone) ratio is 3:97. Then add 2 mL of water/tetrahydrofuran mixed solution (volume ratio 1:20) to quench the reaction, drop the reaction solution into ethanol to settle the polymer, centrifuge, discard the supernatant, then repeatedly dissolve with dichloromethane and drop into ethanol Settling in medium, centrifuging, discarding the supernatant twice, and then drying at room temperature in a vacuum oven for three days to obtain colorless poly(γ-thiooctanolide). The poly(γ-thiooctanolide) was detected by nuclear magnetic resonance (NMR), and ^{the 1} H NMR spectrum and ^{the 13} C NMR spectrum are shown in Figure 7 and Figure 8, respectively.

The present invention adopts differential scanning calorimetry (DSC) to detect the melting temperature and the glass transition temperature of poly(γ-thiooctanolide), and the result shows that the glass of poly(γ-thiooctanolide) prepared by the present embodiment The transition temperature is -32.3°C.

The present invention adopts gel permeation chromatography (GPC) to detect the molecular weight and molecular weight distribution of poly(γ-thiooctyl lactone), using tetrahydrofuran as eluent, flow rate is 1.0mL/min, and polymethyl methacrylate is used as A standard curve was made with standard products, and the results showed that the number average molecular weight of the poly(γ-thiooctolactone) prepared in this example was 34.5 kg/mol, and the molecular weight distribution was 1.33.

Example 6

In a glove box under an argon atmosphere, in a dry 5 mL glass bottle at room temperature, 0.005 mmol of [Ph ₃ C][B(C ₆ F ₅ ) ₄ ] was dissolved in 0.35 mL of toluene, and then 1 mmol (172.3 mg , 0.16mL) of γ-thionolactone monomer, the initial concentration of monomer is 2mol/L, the concentration of catalyst [Ph ₃ C][B(C ₆ F ₅ ) ₄ ] is 10mmol/L, single The molar ratio of body to [Ph ₃ C][B(C ₆ F ₅ ) ₄ ] is 200:1.

Keep the reaction temperature at room temperature, stir and react for 2.5h, take a small amount of sample and dissolve it in deuterated chloroform, monitor the conversion rate by ¹ H NMR, the conversion rate is 97.4%, the by-product of γ-thiononanolide: poly(γ-sulfur Substitute nonalactone) ratio is 3:97. Then add 2 mL of water/tetrahydrofuran mixed solution (volume ratio 1:20) to quench the reaction, drop the reaction solution into ethanol to settle the polymer, centrifuge, discard the supernatant, then repeatedly dissolve with dichloromethane and drop into ethanol Settling in medium, centrifuging, discarding the supernatant twice, and then drying at room temperature in a vacuum oven for three days to obtain colorless poly(γ-thiononanolide). The poly(γ-thiononanolide) was detected by nuclear magnetic resonance (NMR), and ^{the 1} H NMR spectrum and ^{the 13} C NMR spectrum are shown in Figure 9 and Figure 10 , respectively.

The present invention adopts differential scanning calorimetry (DSC) to detect the melting temperature and the glass transition temperature of poly(γ-thiononalactone), and the result shows that the glass of poly(γ-thiononalactone) prepared in the present embodiment The transition temperature is -38.8°C.

The present invention adopts gel permeation chromatography (GPC) to detect the molecular weight and molecular weight distribution of poly(γ-thiononanolide), using tetrahydrofuran as eluent, flow rate is 1.0mL/min, polymethyl methacrylate is used as A calibration curve was made with standard products, and the results showed that the number average molecular weight of the poly(γ-thiononanolide) prepared in this example was 46.4 kg/mol, and the molecular weight distribution was 1.26.

Example 7

In a glove box under an argon atmosphere, in a dry 5 mL glass bottle, 0.005 mmol of [Ph ₃ C][B(C ₆ F ₅ ) ₄ ] was dissolved in 0.32 mL of toluene, and then 1 mmol (186.3 mg, 0.18 mL) of the γ-thionodecalactone monomer, the initial concentration of the monomer is 2mol/L, the concentration of the catalyst [Ph ₃ C][B(C ₆ F ₅ ) ₄ ] is 10mmol/L, the monomer and The molar ratio of [Ph ₃ C][B(C ₆ F ₅ ) ₄ ] was 200:1.

Keep the reaction temperature at room temperature, stir and react for 2.5h, take a small amount of sample and dissolve it in deuterated chloroform, monitor the conversion rate by ¹ H NMR, the conversion rate is greater than 99%, the by-product of γ-thiodecalactone: poly(γ-sulfur The ratio of dedecalactone) is 3:97. Then add 2 mL of water/tetrahydrofuran mixed solution (volume ratio 1:20) to quench the reaction, drop the reaction solution into ethanol to settle the polymer, centrifuge, discard the supernatant, then repeatedly dissolve with dichloromethane and drop into ethanol Settling, centrifuging, discarding the supernatant twice, and then drying at room temperature in a vacuum oven for three days to obtain colorless poly(γ-thiodecalactone). The poly(γ-thiodecalactone) was detected by nuclear magnetic resonance (NMR), and ^{the 1} H NMR spectrum and ^{the 13} C NMR spectrum are shown in Figure 11 and Figure 12 respectively.

The present invention adopts differential scanning calorimetry (DSC) to detect the melting temperature and the glass transition temperature of poly(γ-thiodecalactone), and the result shows that the glass of poly(γ-thiodecalactone) prepared in the present embodiment The transition temperature is -44.8°C.

The present invention adopts gel permeation chromatography (GPC) to detect the molecular weight and molecular weight distribution of poly(γ-thiodecalactone), using tetrahydrofuran as eluent, flow rate is 1.0mL/min, and polymethylmethacrylate is used as A standard curve was made with standard products, and the results showed that the number average molecular weight of the poly(γ-thiodecalactone) prepared in this example was 43.3 kg/mol, and the molecular weight distribution was 1.31.

Example 8

In a glove box under an argon atmosphere, in a dry 5 mL glass bottle, 0.005 mmol of [Ph ₃ C][B(C ₆ F ₅ ) ₄ ] was dissolved in 0.3 mL of toluene, and then 1 mmol (200.3 mg, 0.19 mL) of γ-thionoundecalactone monomer, the initial concentration of the monomer is 2mol/L, the concentration of the catalyst [Ph ₃ C][B(C ₆ F ₅ ) ₄ ] is 10mmol/L, the monomer The molar ratio of [Ph ₃ C][B(C ₆ F ₅ ) ₄ ] to [Ph 3 C][B(C 6 F 5 ) 4 ] is 200:1.

Keep the reaction temperature at room temperature, stir the reaction for 2.5h, take a small amount of sample and dissolve it in deuterated chloroform, monitor the conversion rate by ¹ H NMR, the conversion rate is 97.4%, the by-product of γ-thioundecalactone: poly(γ-sulfur Undecalactone) ratio is 2:98. Then add 2 mL of water/tetrahydrofuran mixed solution (volume ratio 1:20) to quench the reaction, drop the reaction solution into ethanol to settle the polymer, centrifuge, discard the supernatant, then repeatedly dissolve with dichloromethane and drop into ethanol Settling in medium, centrifuging, discarding the supernatant twice, and then drying at room temperature in a vacuum oven for three days to obtain colorless poly(γ-thioundecalactone). The poly(γ-thioundecalactone) was detected by nuclear magnetic resonance (NMR), and ^{the 1} H NMR spectrum and ^{the 13} C NMR spectrum are shown in Figure 13 and Figure 14 respectively.

The present invention adopts differential scanning calorimetry (DSC) to detect the melting temperature and the glass transition temperature of poly(γ-thioundecalactone), and the results show that the poly(γ-thioundecalactone) prepared in the present embodiment Its glass transition temperature is -50.0°C.

The present invention adopts gel permeation chromatography (GPC) to detect the molecular weight and molecular weight distribution of poly(γ-thioundecalactone), using tetrahydrofuran as eluent, flow rate is 1.0mL/min, polymethyl methacrylate A calibration curve was made for the standard product, and the results showed that the poly(γ-thioundecalactone) prepared in this example had a number average molecular weight of 37.1 kg/mol and a molecular weight distribution of 1.37.

Example 9

In a glove box under an argon atmosphere, in a dry 5 mL glass bottle, dissolve 0.005 mmol of [Ph ₃ C][B(C ₆ F ₅ ) ₄ ] in 0.3 mL of toluene, then add 1 mmol (214.4 mg, 0.2 mL) of γ-thionododecanolide monomer, the initial concentration of the monomer is 2mol/L, the concentration of the catalyst [Ph ₃ C][B(C ₆ F ₅ ) ₄ ] is 10mmol/L, the monomer The molar ratio of [Ph ₃ C][B(C ₆ F ₅ ) ₄ ] to [Ph 3 C][B(C 6 F 5 ) 4 ] is 200:1.

Keep the reaction temperature at room temperature, stir the reaction for 2.5h, take a small amount of sample and dissolve it in deuterated chloroform, monitor the conversion rate by ¹ H NMR, the conversion rate is greater than 99%, the by-product of γ-thiolaurolactone: poly(γ-sulfur The ratio of laurelactone) is 4:96. Then add 2 mL of water/tetrahydrofuran mixed solution (volume ratio 1:20) to quench the reaction, drop the reaction solution into ethanol to settle the polymer, centrifuge, discard the supernatant, and then repeatedly dissolve with dichloromethane, drop into Settling in ethanol, centrifuging, discarding the supernatant twice, and then drying in a vacuum oven at room temperature for three days to obtain colorless poly(γ-thiododecanolactone). Nuclear magnetic resonance (NMR) detection was performed on poly(γ-thiolaurolactone), and ^{the 1} H NMR spectrum and ¹³ C NMR spectrum are shown in Figure 15 and Figure 16 respectively.

The present invention adopts differential scanning calorimetry (DSC) to detect the melting temperature and the glass transition temperature of poly(γ-thiolaurolactone), and the results show that the poly(γ-thiolaurolactone) prepared in the present embodiment Its glass transition temperature is -56.7°C.

The present invention adopts gel permeation chromatography (GPC) to detect the molecular weight and molecular weight distribution of poly(γ-thiolaurolactone), using tetrahydrofuran as eluent, flow rate is 1.0mL/min, polymethyl methacrylate A calibration curve was made for the standard product, and the results showed that the poly(γ-thiolaurolactone) prepared in this example had a number average molecular weight of 56.2 kg/mol and a molecular weight distribution of 1.58.

Example 10

In a glove box under an argon atmosphere, in a dry 5 mL glass bottle, dissolve 0.005 mmol of [Ph ₃ C][B(C ₆ F ₅ ) ₄ ] in 0.3 mL of toluene, then add 1 mmol (200.3 mg, 0.2 mL) of the γ-methyl-γ-thionodecalactone monomer, the initial concentration of the monomer is 2mol/L, and the concentration of the catalyst [Ph ₃ C][B(C ₆ F ₅ ) ₄ ] is 10mmol/L L, the molar ratio of monomer to [Ph ₃ C][B(C ₆ F ₅ ) ₄ ] is 200:1.

Keep the reaction temperature at room temperature, stir and react for 48 hours, take a small amount of sample and dissolve it in deuterated chloroform, monitor the conversion rate by ¹ H NMR, the conversion rate reaches 97.7%, and the γ-methyl-γ-thiodecalactone in the product is generated: The ratio of poly(γ-methyl-γ-thiodecalactone) was 28:72. Then add 2 mL of water/tetrahydrofuran mixed solution (volume ratio 1:20) to quench the reaction, drop the reaction solution into ethanol to settle the polymer, centrifuge, discard the supernatant, then repeatedly dissolve with dichloromethane and drop into ethanol Settling in medium, centrifuging, discarding the supernatant twice, and then drying at room temperature in a vacuum oven for three days to obtain colorless poly(γ-methyl-γ-thiodecalactone). The poly(γ-methyl-γ-thiodecalactone) was detected by nuclear magnetic resonance (NMR), and ^{the 1} H NMR spectrum and ^{the 13} C NMR spectrum are shown in Figure 17 and Figure 18 respectively.

The present invention adopts differential scanning calorimetry (DSC) to detect the melting temperature and the glass transition temperature of poly(γ-methyl-γ-thiodecalactone), and the results show that the poly(γ-methyl-thiodecalactone) prepared in the present embodiment γ-thiodecalactone) has a glass transition temperature of -34.8°C.

The present invention adopts gel permeation chromatography (GPC) to detect the molecular weight and molecular weight distribution of poly(γ-methyl-γ-thiodecalactone), using tetrahydrofuran as eluent, and the flow rate is 1.0mL/min, using polyformaldehyde Methyl acrylate was used as a standard product to make a calibration curve, and the results showed that the number average molecular weight of the poly(γ-methyl-γ-thiodecalactone) prepared in this embodiment was 12.8kg/mol, and the molecular weight distribution was 1.42.

Example 11

In a glove box under an argon atmosphere, in a dry 5 mL glass bottle, 0.005 mmol of [Ph ₃ C][B(C ₆ F ₅ ) ₄ ] was dissolved in 0.35 mL of toluene, and then 1 mmol (172.3 mg, 0.16 mL) of the β-methyl-γ-thionooctylactone monomer, the initial concentration of the monomer is 2mol/L, and the concentration of the catalyst [Ph ₃ C][B(C ₆ F ₅ ) ₄ ] is 10mmol/L L, the molar ratio of monomer to [Ph ₃ C][B(C ₆ F ₅ ) ₄ ] is 200:1.

Keep the reaction temperature at room temperature, stir and react for 5 hours, take a small amount of sample and dissolve it in deuterated chloroform, monitor the conversion rate by ¹ H NMR, the conversion rate reaches 85.9%, and the β-methyl-γ-thiooctrolactone in the product is generated: The ratio of poly(β-methyl-γ-thiooctanolide) was 1:99. Then add 2 mL of water/tetrahydrofuran mixed solution (volume ratio 1:20) to quench the reaction, drop the reaction solution into ethanol to settle the polymer, centrifuge, discard the supernatant, then repeatedly dissolve with dichloromethane and drop into ethanol Settling in medium, centrifuging, discarding the supernatant twice, and then drying at room temperature in a vacuum oven for three days to obtain colorless poly(β-methyl-γ-thiooctanolide). The poly(β-methyl-γ-thiooctanolide) was detected by nuclear magnetic resonance (NMR), and ^{the 1} H NMR spectrum and ^{the 13} C NMR spectrum are shown in Figure 19 and Figure 20 respectively.

The present invention adopts differential scanning calorimetry (DSC) to detect the melting temperature and the glass transition temperature of poly(β-methyl-γ-thiooctrolactone), and the results show that the poly(β-methyl-thiolactone prepared in the present embodiment) γ-thiooctyl lactone) has a glass transition temperature of 3.4°C.

The present invention adopts gel permeation chromatography (GPC) to detect the molecular weight and molecular weight distribution of poly(β-methyl-γ-thiooctyl lactone), using tetrahydrofuran as eluent, flow rate is 1.0mL/min, polyformaldehyde Methyl acrylate was used as a standard to make a calibration curve, and the results showed that the number average molecular weight of the poly(β-methyl-γ-thiooctolactone) prepared in this embodiment was 38.6kg/mol, and the molecular weight distribution was 1.29.

Example 12

In a glove box under an argon atmosphere, add 0.02 mmol of potassium thioacetate and 0.2 mL of N,N-dimethylformamide to a dry Schlenk bottle, followed by 2 mmol (232 mg, 0.2 mL) of α-methyl -γ-thionobutyrolactone monomer, the initial concentration of the monomer is 5mol/L, the concentration of the catalyst potassium thioacetate is 50mmol/L, and the molar ratio of the monomer to potassium thioacetate is 100:1.

The glove box was removed and the Schlenk bottle was connected to a vacuum line protected by argon, and the reaction was stirred at 80° C. for 2 h. After the polymerization reaction was completed, 0.15 mL of toluene solution containing 0.05 mL of allyl chloride was added to terminate the reaction, and a small amount of solution was taken for ¹ H NMR analysis to measure the conversion rate. The conversion rate was greater than 99%. The ratio of lactone by-product:poly(α-methylγ-thiobutyrolactone) is 3:97. The remaining reaction solution was poured into ethanol to settle the polymer, the precipitated solid was centrifuged, and the supernatant was discarded, then dissolved in dichloromethane repeatedly, dropped into ethanol to settle, centrifuged, and the supernatant was discarded twice, and then Dry in a vacuum oven at room temperature for three days to obtain colorless poly(α-methyl-γ-thiobutyrolactone). The poly(α-methyl-γ-thiobutyrolactone) was detected by nuclear magnetic resonance (NMR), and ^{the 1} H NMR spectrum and ^{the 13} C NMR spectrum are shown in Figure 21 and Figure 22 respectively.

The present invention adopts differential scanning calorimetry (DSC) to detect the melting temperature and the glass transition temperature of poly(α-methyl-γ-thiobutyrolactone), and the results show that the poly(α-methyl-thiobutyrolactone) prepared in the present embodiment γ-thiobutyrolactone) has a glass transition temperature of -30.2°C.

The present invention adopts gel permeation chromatography (GPC) to detect the molecular weight and molecular weight distribution of poly(alpha-methyl-gamma-thiobutyrolactone), using tetrahydrofuran as eluent, flow rate is 1.0mL/min, polyformaldehyde Methyl acrylate was used as a standard to make a calibration curve, and the results showed that the number average molecular weight of the poly(α-methyl-γ-thiobutyrolactone) prepared in this embodiment was 8.6kg/mol, and the molecular weight distribution was 1.03.

Example 13

In the argon atmosphere glove box, add 0.928g (8mmol, 0.8mL) β-methyl-γ-thionobutyrolactone monomer into the dry Schlenk bottle, remove the glove box and connect the Schlenk bottle to an argon After stirring at 80°C for 10 minutes on a vacuum line protected by air, dissolve 0.005 mmol of ^tBu - _P4 and 0.005 mmol of benzylmethanol in 0.8 mL of toluene, respectively, and add these two solutions to the above In the Schlenk bottle, the polymerization starts, the total volume of the polymerization is 1.6mL, the initial concentration of the monomer is 5mol/L, the concentration of the catalyst ^tBu - _P4 is 3.1mmol/L, and the concentration of the cocatalyst benzylcarbinol is 3.1 mmol/L, the molar ratio of monomer to ^tBu - _P4 is 1600:1. Keeping the reaction temperature at 80°C, the polymerization reaction was carried out for 4 hours. After the polymerization reaction was completed, adding a mass concentration of 10 mg/mL benzoic acid in chloroform solution dissolved the product, got a small amount of solution and carried out ¹ H NMR analysis to measure the conversion rate, and the remaining reaction solution was poured into ethanol to allow the polymer to settle. After filtering and washing with ethanol three times, it was dried in a vacuum oven at 40° C. for 24 hours to obtain white poly(β-methyl-γ-thiobutyrolactone). The poly(β-methyl-γ-thiobutyrolactone) was detected by nuclear magnetic resonance (NMR), and ^{the 1} H NMR spectrum and ^{the 13} C NMR spectrum are shown in Figure 23 and Figure 24 respectively.

The present invention detects the obtained reaction liquid proton nuclear magnetic resonance spectrum, and the result shows that the conversion rate of the monomer is 99.8%, and the by-product of β-methyl-γ-thiobutyrolactone: poly(β-methyl-γ-thiobutyrolactone Butyrolactone) ratio is 3:97.

The present invention adopts differential scanning calorimetry (DSC) to detect the melting temperature and the glass transition temperature of poly(β-methyl-γ-thiobutyrolactone), and the results show that the poly(β-methyl-thiobutyrolactone) prepared by the present embodiment γ-thiobutyrolactone) has a glass transition temperature of -30.4°C.

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

Example 14

In an argon atmosphere glove box, add 0.327 g (3.2 mmol, 280 μL) of γ-thionobutyrolactone and 0.022 g (0.17 mmol, 20 μL) of β-vinyl-γ-thionobutyrolactone into a dry Schlenk bottle Butyrolactone monomer, remove the glove box and connect the Schlenk bottle to the vacuum line protected by argon, after stirring at 80 °C for 10 minutes, dissolve 0.01 mmol of ^tBu - _P4 and 0.01 mmol of A mixture of Ph ₂ CHOH and 0.093g (0.8mmol, 83μL) α-methyl-γ-thionobutyrolactone, and this solution was added to the above-mentioned Schlenk bottle, the polymerization started, and the total volume of the polymerization was 0.78 mL, the initial concentration of the monomer γ-thionobutyrolactone is 4.1mol/L, the initial concentration of the monomer β-vinyl-γ-thionobutyrolactone is 0.2mol/L, and the monomer α-formazol The initial concentration of the base-γ-thionobutyrolactone is 1.0mol/L, the concentration of the catalyst ^tBu - _P4 is 12.8mmol/L, the concentration of the cocatalyst _Ph2CHOH is 12.8mmol/L, and the three monomers The molar ratios to ^tBu - _P4 are 320:80:17:1, respectively. Keeping the reaction temperature at 80°C, the polymerization reaction was carried out for 1 hour. After the completion of the polymerization reaction, adding a mass concentration of 10 mg/mL benzoic acid chloroform solution to dissolve the product, get a small amount of solution for ¹ H NMR analysis to measure the conversion rate, and the remaining reaction solution is poured into ethanol to allow the polymer to settle. After filtering and washing with ethanol three times, it was dried in a vacuum oven at 40° C. for 24 hours to obtain a white terpolymer. The copolymer was detected by nuclear magnetic resonance (NMR), and ^{the 1} H NMR spectrum is shown in FIG. 25 .

The present invention detects the obtained reaction liquid by proton nuclear magnetic resonance spectrum, and the result shows that the conversion rate of the monomer is 99.9%, and the ratio of biting by-products in the generated product to the copolymer is 5:95.

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 example is -47.89°C, and the melting temperature is 59.51°C.

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 65.0kg/mol, and the molecular weight distribution is 1.73.

The present invention carries out the test of mechanical properties to the prepared ternary random copolymer: the mechanical tensile test experiment shows that the elongation at break of the ternary random copolymer is 1451.30%, and the breaking stress is 16.62MPa; in addition, the cyclic tensile test Experiments show that the elastic recovery rate of the terpolymer is 72.3%.

Example 15

0.1 mL of toluene, 0.01 mL of mesitylene, and 1 mmol (156 mg, 0.14 mL) of cis-hexahydroisobenzofuran-1-thione monomer in a dry Schlenk bottle in an argon atmosphere glove box , take 0.01 mL of the solution for ¹ H NMR analysis to determine the ratio of the monomer in the initial reaction solution to the internal standard mesitylene; then add 0.01 mol of potassium thioacetate and 0.01 mmol of 18-crown 6 ether. The initial concentration of the monomer is 4 mol/L, the concentration of the catalyst potassium thioacetate is 4 mmol/L, and the molar ratio of the monomer to the potassium thioacetate and 18-crown-6 is 100:1:1.

The glove box was removed and the Schlenk bottle was connected to a vacuum line protected by argon, and the reaction was stirred at 80° C. for 4 h. After the polymerization reaction is completed, add 0.15mL toluene solution containing 0.05mL allyl chloride to terminate the reaction, take a small amount of solution for ¹ H NMR analysis and determine the conversion rate by analyzing the integral ratio change of the monomer and the internal standard mesitylene, the conversion rate Achieving greater than 99%, the ratio of cis-hexahydroisobenzothiophen-1-one by-product:poly(cis-hexahydroisobenzothiophen-1-one) was 12:88. The remaining reaction solution was poured into ice methanol to settle the polymer, the precipitated solid was centrifuged, and the supernatant was discarded, then dissolved in dichloromethane, dropped into methanol to settle, centrifuged, and the supernatant was discarded twice. Then dry at room temperature in a vacuum oven for three days to obtain poly(cis-hexahydroisobenzothiophene-1-one) as a white solid, which is detected by nuclear magnetic resonance (NMR). ^{The 1} H NMR spectrum and ^{the 13} C NMR spectrum are respectively as follows Figure 26 and Figure 27.

The present invention adopts differential scanning calorimetry (DSC) to detect the melting temperature and glass transition of poly(cis-hexahydroisobenzothiophene-1-one), and the results show that the poly(cis-hexahydroisobenzothiophene) prepared in this embodiment Thiophene-1-one) has a glass transition temperature of 65.1°C.

The present invention uses a thermogravimetric analyzer (TGA) to measure the thermal stability of the poly(cis-hexahydroisobenzothiophene-1-one) obtained in this implementation, and the initial decomposition temperature of the obtained polymer (T _d , 5% weight loss When the temperature) at 255.3 ℃, has good thermal stability.

The present invention adopts gel permeation chromatography (GPC) to detect the molecular weight and molecular weight distribution of poly(cis-hexahydroisobenzothiophene-1-one), using tetrahydrofuran as eluent, and the flow rate is 1.0mL/min, using polyformaldehyde Methyl acrylate was used as a standard to make a calibration curve, and the results showed that the number average molecular weight of the poly(cis-hexahydroisobenzothiophene-1-one) prepared in this example was 22.6 kg/mol, and the molecular weight distribution was 1.23.

Example 16

In a glove box under an argon atmosphere, add 0.02 mmol of potassium thioacetate, 0.02 mmol of 18-crown 6 ether and 0.2 mL of toluene to a dry Schlenk bottle, and then add 2 mmol (232 mg, 0.2 mL) of α-methyl -γ-thionobutyrolactone monomer, the initial concentration of the monomer is 5mol/L, the concentration of the catalyst potassium thioacetate is 50mmol/L, and the molar ratio of the monomer to potassium thioacetate and 18 crown 6 ether is 100:1:1.

The glove box was removed and the Schlenk bottle was connected to a vacuum line protected by argon, and the reaction was stirred at 80° C. for 5 h. After the polymerization reaction was completed, 0.15 mL of toluene solution containing 0.05 mL of allyl chloride was added to terminate the reaction, and a small amount of solution was taken for ¹ H NMR analysis to measure the conversion rate. The conversion rate reached more than 99%, and α-methyl-γ-thio The ratio of butyrolactone by-product:poly(α-methyl-γ-thiobutyrolactone) was 6:94. The remaining reaction solution was poured into ethanol to settle the polymer, the precipitated solid was centrifuged, and the supernatant was discarded, then dissolved in dichloromethane repeatedly, dropped into ethanol to settle, centrifuged, and the supernatant was discarded twice, and then Dry in a vacuum oven at room temperature for three days to obtain colorless poly(α-methyl-γ-thiobutyrolactone).

The present invention adopts differential scanning calorimetry (DSC) to detect the melting temperature and glass transition of poly(alpha-methyl-gamma-thiobutyrolactone), and the results show that poly(alpha-methyl-gamma) prepared by the present embodiment -thiobutyrolactone) has a glass transition temperature of -30.2°C.

The present invention adopts gel permeation chromatography (GPC) to detect the molecular weight and molecular weight distribution of poly(alpha-methyl-gamma-thiobutyrolactone), using tetrahydrofuran as eluent, flow rate is 1.0mL/min, polyformaldehyde Methyl acrylate was used as a standard to make a calibration curve, and the results showed that the number average molecular weight of the poly(α-methyl-γ-thiobutyrolactone) prepared in this embodiment was 11.4kg/mol, and the molecular weight distribution was 1.02.

Example 17

In a glove box under an argon atmosphere, add 0.01 mol of benzoic acid, 0.01 mmol of tBu-P4, and 0.2 mL of toluene to a dry Schlenk bottle, followed by 2 mmol (232 mg, 0.2 mL) of α-methyl-γ - Thiobutyrolactone monomer, the initial concentration of the monomer is 5mol/L, the concentration of the catalyst tBu-P4 is 25mmol/L, and the molar ratio of the monomer to tBu-P4 and benzoic acid is 200:1:1.

The glove box was removed and the Schlenk bottle was connected to a vacuum line protected by argon, and the reaction was stirred at 80° C. for 1 h. After the polymerization reaction was completed, 0.15 mL of toluene solution containing 0.05 mL of allyl chloride was added to terminate the reaction, and a small amount of solution was taken for ¹ H NMR analysis to measure the conversion rate. The conversion rate reached more than 99%, and α-methyl-γ-thio The ratio of butyrolactone by-product:poly(α-methyl-γ-thiobutyrolactone) is 5:95. The remaining reaction solution was poured into ethanol to settle the polymer, the precipitated solid was centrifuged, and the supernatant was discarded, then dissolved in dichloromethane repeatedly, dropped into ethanol to settle, centrifuged, and the supernatant was discarded twice, and then Dry in a vacuum oven at room temperature for three days to obtain colorless poly(α-methyl-γ-thiobutyrolactone).

The present invention adopts gel permeation chromatography (GPC) to detect the molecular weight and molecular weight distribution of poly(alpha-methyl-gamma-thiobutyrolactone), using tetrahydrofuran as eluent, flow rate is 1.0mL/min, polyformaldehyde Methyl acrylate was used as a standard to make a calibration curve, and the results showed that the number average molecular weight of the poly(α-methyl-γ-thiobutyrolactone) prepared in this example was 20.0kg/mol, and the molecular weight distribution was 1.05.

Example 18

In a glove box under an argon atmosphere, in a dry 5 mL glass bottle at room temperature, 0.005 mmol of [Ph ₃ C][B(C ₆ F ₅ ) ₄ ] was dissolved in 0.8 mL of toluene, and then 8 mmol (929.4 mg, 0.86mL) of γ-thionovalerolactone monomer, the initial concentration of the monomer is 5mol/L, and the concentration of the catalyst [Ph ₃ C][B(C ₆ F ₅ ) ₄ ] is 3.1mmol/L , the molar ratio of monomer to [Ph ₃ C][B(C ₆ F ₅ ) ₄ ] was 1600:1.

Keep the reaction temperature at room temperature, stir and react for 18 hours, take a small amount of sample and dissolve it in deuterated chloroform, monitor the conversion rate by ¹ H NMR, the conversion rate is 94.3%, the by-product of γ-thiovalerolactone: poly(γ-thiovalerolactone valerolactone) in a ratio of 1:99. Then add 12mL of water/tetrahydrofuran mixed solution (volume ratio 1:30) to quench the reaction, drop the reaction solution into ethanol to settle the polymer, centrifuge, discard the supernatant, then repeatedly dissolve with dichloromethane, drop into ethanol Settling, centrifuging, discarding the supernatant twice, and then drying at room temperature in a vacuum oven for three days to obtain colorless poly(γ-thiovalerolactone).

The present invention adopts differential scanning calorimetry (DSC) to detect the melting temperature and glass transition of poly(γ-thiovalerolactone), and the results show that the glass transition of poly(γ-thiovalerolactone) prepared by the present embodiment is The transition temperature is -9.8°C.

The present invention adopts gel permeation chromatography (GPC) to detect the molecular weight and molecular weight distribution of poly(γ-thiovalerolactone), using tetrahydrofuran as eluent, flow rate is 1.0mL/min, and polymethyl methacrylate is used as A calibration curve was made with standard products, and the results showed that the poly(γ-thiovalerolactone) prepared in this example had a number average molecular weight of 133.2 kg/mol and a molecular weight distribution of 1.76.

Example 19

In a glove box under an argon atmosphere, add 0.01 mmol of [H(Et ₂ O) ₂ ][B(C ₆ F ₅ ) ₄ ], 0.4 mL of toluene, and then add 1 mmol (116.2 mg, 0.10mL) of γ-thionovalerolactone monomer, the initial concentration of the monomer is 2mol/L, and the concentration of the catalyst [H(Et ₂ O) ₂ ][B(C ₆ F ₅ ) ₄ ] is 20mmol/L L, the molar ratio of monomer to [H(Et ₂ O) ₂ ][B(C ₆ F ₅ ) ₄ ] is 100:1.

Keep reaction temperature at room temperature, get a small amount of sample to be dissolved in deuterated chloroform and carry out ¹ H NMR to monitor conversion rate in polymerization process, conversion rate reaches 98.4% in the time of polymerization reaction 2h, γ-thiovalerolactone in the generation product: poly(γ -thiovalerolactone) in a ratio of 10:90. Then add 2 mL of water/tetrahydrofuran mixed solution (volume ratio 1:30) to quench the reaction, drop the reaction solution into ethanol to settle the polymer, centrifuge, discard the supernatant, then repeat dissolving with dichloromethane, drop into ethanol Settling, centrifuging, discarding the supernatant twice, and then drying at room temperature in a vacuum oven for three days to obtain colorless poly(γ-thiovalerolactone).

The present invention adopts gel permeation chromatography (GPC) to detect the molecular weight and molecular weight distribution of poly(γ-thiovalerolactone), using tetrahydrofuran as eluent, flow rate is 1.0mL/min, and polymethyl methacrylate is used as A calibration curve was made with standard products, and the results showed that the poly(γ-thiovalerolactone) prepared in this example had a number average molecular weight of 32.9 kg/mol and a molecular weight distribution of 1.46.

Example 20

In a glove box under an argon atmosphere, add 0.01 mmol of B(C ₆ F ₅ ) ₃ , 0.1 mL of toluene, and then 1 mmol (116.2 mg, 0.10 mL) of γ-thiocarbopentane in a dry Schlenk bottle For the ester monomer, the initial concentration of the monomer is 5 mol/L, the concentration of the catalyst B(C ₆ F ₅ ) ₃ is 50 mmol/L, and the molar ratio of the monomer to B(C ₆ F ₅ ) ₃ is 100:1.

The glove box was removed and the Schlenk bottle was connected to a vacuum line protected by argon, and the reaction was stirred at 80° C. for 1.5 h. After the polymerization reaction was completed, 2 mL of water/tetrahydrofuran mixed solution (volume ratio 1:30) was added to quench the reaction. A small amount of sample was dissolved in deuterated chloroform for ¹ H NMR to monitor the conversion rate, the polymerization conversion rate reached 94.8%, and the ratio of γ-thiovalerolactone in the generated product: poly(γ-thiovalerolactone) was 66: 34. Drop the reaction solution into ethanol to settle the polymer, centrifuge, discard the supernatant, then repeat the dissolution with dichloromethane, drop into ethanol to settle, centrifuge, discard the supernatant twice, and then place in a vacuum drying oven After drying at room temperature for three days, colorless poly(γ-thiovalerolactone) was obtained.

The present invention adopts gel permeation chromatography (GPC) to detect the molecular weight and molecular weight distribution of poly(γ-thiovalerolactone), using tetrahydrofuran as eluent, flow rate is 1.0mL/min, and polymethyl methacrylate is used as A calibration curve was made with standard products, and the results showed that the poly(γ-thiovalerolactone) prepared in this example had a number average molecular weight of 74.0 kg/mol and a molecular weight distribution of 1.65.

Example 21

In an argon atmosphere glove box, add 0.232 g (2.0 mmol, 200 μL) of α-methyl-γ-thionobutyrolactone and 0.40 mL of 2.3 mg (0.02 mmol) of thioacetic acid in a dry Schlenk bottle Potassium in N,N-dimethylformamide. Remove the glove box and connect the Schlenk bottle to a vacuum line protected by argon, and stir the reaction at 80° C. for 2.5 hours until the reaction of α-methyl-γ-thionobutyrolactone is complete. Subsequently, 0.204 g (2.0 mmol, 175 μL) of γ-thionobutyrolactone monomer was added by syringe, and the reaction was continued for 1 hour. The initial concentration of monomer α-methyl-γ-thionobutyrolactone was 3.3 mol/L, and that of γ-thionobutyrolactone was 2.6 mol/L. The concentration of the catalyst potassium thioacetate is 66.7 mmol/L, and the molar ratio of α-methyl γ-thionobutyrolactone to γ-thionobutyrolactone and potassium thioacetate is 100:100:1.

After the polymerization reaction was completed, 0.15 mL of toluene solution containing 0.05 mL of allyl chloride was added to terminate the reaction, and a small amount of solution was taken for ¹ H NMR analysis to determine the conversion rate. The conversion rate of α-methyl γ-thionobutyrolactone was 97.7 %, the conversion rate of γ-thionobutyrolactone was 77.7%, and the biting by-product in the generated product: the ratio of the copolymer was 6.2:93.8. The remaining reaction liquid was poured into ethanol to make the polymer settle, and the precipitated solid was filtered and washed three times with ethanol, and then dried in a vacuum oven at 40° C. for 24 hours to obtain a white block copolymer. The copolymer was detected by nuclear magnetic resonance (NMR), and ^{the 1} H NMR spectrum is shown in FIG. 28 .

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°C, and the melting temperature is 92.74°C.

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 32.2kg/mol, and the molecular weight distribution is 1.09.

Example 22

In an argon atmosphere glove box, add 0.236 g (2.0 mmol, 200 μL) of propylene thiocarbonate and 0.20 mL of N,N-dicarbonate dissolved in 2.3 mg (0.02 mmol) of potassium thioacetate into a dry Schlenk bottle. Methylformamide solution. Remove the glove box and connect the Schlenk bottle to the vacuum line protected by argon, the concentration of the catalyst potassium thioacetate is 50mmol/L, the initial concentration of the monomer propylene thiocarbonate is 5mol/L, and the concentration of thiocarbonic acid The molar ratio of propylene ester and potassium thioacetate is 100:1.

After the polymerization reaction was completed, 0.15 mL of toluene solution containing 0.05 mL of allyl chloride was added to terminate the reaction, and a small amount of the solution was taken for ¹ H NMR analysis to determine the conversion rate, and the conversion rate of propylene thiocarbonate was 99%. The remaining reaction liquid was poured into ethanol to make the polymer settle, and the precipitated solid was filtered and washed three times with ethanol, and then dried in a vacuum oven at 40°C for 24 hours to obtain white polypropylene monothiocarbonate. The polymer was tested by nuclear magnetic resonance (NMR), and ^{the 1} H NMR spectrum and ^{the 13} C NMR spectrum are shown in Figure 29 and Figure 30 respectively.

The present invention adopts gel permeation chromatography (GPC) to detect the molecular weight and the molecular weight distribution of polypropylene monothiocarbonate, and the result shows that its number-average molecular weight of polypropylene monothiocarbonate prepared in the present embodiment is 9.2kg/mol, The molecular weight distribution was 1.53.

Example 23

In a glove box under an argon atmosphere, in a dry 5 mL glass bottle, 0.005 mmol of [Ph ₃ C][B(C ₆ F ₅ ) ₄ ] was dissolved in 0.32 mL of toluene, and then 1 mmol (186.3 mg, 0.18 mL) of propylene thiocarbonate monomer, the initial concentration of the monomer is 2mol/L, the concentration of the catalyst [Ph ₃ C][B(C ₆ F ₅ ) ₄ ] is 10mmol/L, the monomer and [Ph The molar ratio of ₃ C][B(C ₆ F ₅ ) ₄ ] is 200:1.

Keep the reaction temperature at room temperature, stir the reaction for 1.0 h, take a small amount of sample and dissolve it in deuterated chloroform, and monitor the conversion rate by ¹ H NMR, and the conversion rate is greater than 99%. Then add 2 mL of water/tetrahydrofuran mixed solution (volume ratio 1:20) to quench the reaction, drop the reaction solution into ethanol to settle the polymer, centrifuge, discard the supernatant, then repeatedly dissolve with dichloromethane and drop into ethanol Settling, centrifuging, discarding the supernatant twice, and then drying in a vacuum oven at room temperature for three days to obtain colorless polypropylene monothiocarbonate.

The present invention adopts gel permeation chromatography (GPC) to detect the molecular weight and molecular weight distribution of polypropylene monothiocarbonate, with tetrahydrofuran as eluent, flow rate is 1.0mL/min, with polymethyl methacrylate as standard product Standard curve, the results show that the number average molecular weight of the polypropylene monothiocarbonate prepared in this embodiment is 10.2kg/mol, and the molecular weight distribution is 1.65.

Example 24

In an argon atmosphere glove box, add 4 mmol (464.5 mg, 0.43 mL) of α-methyl γ-thionobutyrolactone monomer to a dry Schlenk bottle, remove the glove box and connect the Schlenk bottle to an argon Stir at 80°C for 10 minutes on an air-protected vacuum line. Dissolve 0.01mmol of TBD and 0.01mmol of PhCOOH with 0.43mL of toluene, and add the solution to the above-mentioned Schlenk bottle. The initial concentration of the monomer is 5mol/L, and the concentration of the catalyst TBD and the initiator PhCOOH is 12.5mmol/L. L, the molar ratio of monomer to TBD/PHCOOH is 400:1:1.

Keep the reaction temperature at 80°C, after 17 hours of polymerization, add a chloroform solution with a mass concentration of 10 mg/mL benzoic acid to dissolve the product, take a small amount of the solution for ¹ H NMR analysis to determine the conversion rate, the conversion rate is 82.4%, and the α - The ratio of methyl-γ-thiobutyrolactone by-product:poly(α-methylγ-thiobutyrolactone) was 16:84. The remaining reaction solution was poured into ethanol to settle the polymer, the precipitated solid was centrifuged, and the supernatant was discarded, then dissolved in dichloromethane repeatedly, dropped into ethanol to settle, centrifuged, and the supernatant was discarded twice, and then Dry in a vacuum oven at room temperature for three days to obtain colorless poly(α-methyl-γ-thiobutyrolactone).

The present invention adopts gel permeation chromatography (GPC) to detect the molecular weight and molecular weight distribution of poly(alpha-methyl-gamma-thiobutyrolactone), using tetrahydrofuran as eluent, flow rate is 1.0mL/min, polyformaldehyde Methyl acrylate was used as a standard to make a calibration curve, and the results showed that the number average molecular weight of the poly(α-methyl-γ-thiobutyrolactone) prepared in this example was 22.6kg/mol, and the molecular weight distribution was 1.20.

Example 25

In an argon atmosphere glove box, add 2 mmol (232.5 mg, 0.22 mL) of α-methyl γ-thionobutyrolactone monomer to a dry Schlenk bottle, remove the glove box and connect the Schlenk bottle to an argon Stir at 80°C for 10 minutes on an air-protected vacuum line. Dissolve 0.02mmol of DBU and 0.02mmol of PhCOSH in 0.22mL of toluene, and add the solution to the above-mentioned Schlenk bottle. The initial concentration of the monomer is 5mol/L, and the concentration of the catalyst DBU and the initiator PhCOSH is 50mmol/L , the molar ratio of monomer to DBU/PHCOSH is 100:1:1.

Keep the reaction temperature at 80°C, after 5 hours of polymerization, add a chloroform solution with a mass concentration of 10 mg/mL benzoic acid to dissolve the product, take a small amount of the solution for ¹ H NMR analysis to measure the conversion rate, the conversion rate reaches 96.8%, and the α - The ratio of methyl-γ-thiobutyrolactone by-product:poly(α-methylγ-thiobutyrolactone) was 11:89. The remaining reaction solution was poured into ethanol to settle the polymer, the precipitated solid was centrifuged, and the supernatant was discarded, then dissolved in dichloromethane repeatedly, dropped into ethanol to settle, centrifuged, and the supernatant was discarded twice, and then Dry in a vacuum oven at room temperature for three days to obtain colorless poly(α-methyl-γ-thiobutyrolactone).

The present invention adopts gel permeation chromatography (GPC) to detect the molecular weight and molecular weight distribution of poly(alpha-methyl-gamma-thiobutyrolactone), using tetrahydrofuran as eluent, flow rate is 1.0mL/min, polyformaldehyde Methyl acrylate was used as a standard to make a calibration curve, and the results showed that the number-average molecular weight of the poly(α-methyl-γ-thiobutyrolactone) prepared in this embodiment was 9.9kg/mol, and the molecular weight distribution was 1.02.

Example 26

In an argon atmosphere glove box, add 2 mmol (232.5 mg, 0.22 mL) of α-methyl γ-thionobutyrolactone monomer to a dry Schlenk bottle, remove the glove box and connect the Schlenk bottle to an argon Stir at 80°C for 10 minutes on an air-protected vacuum line. The It ^BuN- heterocyclic carbene catalyst of 0.01mmol is dissolved with the toluene of 0.22mL, and this toluene solution is added in the above-mentioned Schlenk bottle, and the initial concentration of monomer is 5mol/L, and the concentration of catalyst ItBu is 50mmol/L, The molar ratio of monomer to ^ItBu was 100:1.

Keep the reaction temperature at 80°C. After the polymerization reaction for 1 hour, add a chloroform solution with a mass concentration of 10 mg/mL benzoic acid to dissolve the product, and take a small amount of the solution for ¹ H NMR analysis to determine the conversion rate. The conversion rate is 95.7%, and the α - The ratio of methyl-γ-thiobutyrolactone by-product:poly(α-methylγ-thiobutyrolactone) was 2:98. The remaining reaction solution was poured into ethanol to settle the polymer, the precipitated solid was centrifuged, and the supernatant was discarded, then dissolved in dichloromethane repeatedly, dropped into ethanol to settle, centrifuged, and the supernatant was discarded twice, and then Dry in a vacuum oven at room temperature for three days to obtain colorless poly(α-methyl-γ-thiobutyrolactone).

The present invention adopts gel permeation chromatography (GPC) to detect the molecular weight and molecular weight distribution of poly(alpha-methyl-gamma-thiobutyrolactone), using tetrahydrofuran as eluent, flow rate is 1.0mL/min, polyformaldehyde Methyl acrylate was used as a standard to make a calibration curve, and the results showed that the number-average molecular weight of the poly(α-methyl-γ-thiobutyrolactone) prepared in this example was 9.39kg/mol, and the molecular weight distribution was 1.01.

Example 27

In an argon atmosphere glove box, add 4 mmol (464.5 mg, 0.43 mL) of α-methyl γ-thionobutyrolactone monomer to a dry Schlenk bottle, remove the glove box and connect the Schlenk bottle to an argon Stir at 80°C for 10 minutes on an air-protected vacuum line. Use 0.43mL of toluene to dissolve 0.01mmol of the NHO N-heterocyclic olefin catalyst, and add the solution to the above-mentioned Schlenk bottle. The initial concentration of the monomer is 5mol/L, and the concentration of the catalyst NHO is 12.5mmol/L. The molar ratio of body to NHO is 400:1.

Keep the reaction temperature at 80°C, after 2 hours of polymerization, add a chloroform solution with a mass concentration of 10 mg/mL benzoic acid to dissolve the product, take a small amount of the solution for ¹ H NMR analysis to determine the conversion rate, the conversion rate is 87.8%, and the α - The ratio of methyl-γ-thiobutyrolactone by-product:poly(α-methylγ-thiobutyrolactone) was 3:97. The remaining reaction solution was poured into ethanol to settle the polymer, the precipitated solid was centrifuged, and the supernatant was discarded, then dissolved in dichloromethane repeatedly, dropped into ethanol to settle, centrifuged, and the supernatant was discarded twice, and then Dry in a vacuum oven at room temperature for three days to obtain colorless poly(α-methyl-γ-thiobutyrolactone).

The present invention adopts gel permeation chromatography (GPC) to detect the molecular weight and molecular weight distribution of poly(alpha-methyl-gamma-thiobutyrolactone), using tetrahydrofuran as eluent, flow rate is 1.0mL/min, polyformaldehyde Methyl acrylate was used as a standard to make a calibration curve, and the results showed that the number-average molecular weight of the poly(α-methyl-γ-thiobutyrolactone) prepared in this example was 43.6kg/mol, and the molecular weight distribution was 1.08.

Example 28

In an argon atmosphere glove box, add 4 mmol (464.5 mg, 0.43 mL) of α-methyl γ-thionobutyrolactone monomer to a dry Schlenk bottle, remove the glove box and connect the Schlenk bottle to an argon Stir at 80°C for 10 minutes on an air-protected vacuum line. Dissolve 0.01 mmol of ^tBuP ₁ phosphazene base catalyst with 0.43 mL of toluene, and add this solution into the above-mentioned Schlenk bottle, the initial concentration of monomer is 5 mol/L, and the concentration of catalyst ^tBuP ₁ is 12.5 mmol/L , the molar ratio of monomer to ^tBuP ₁ was 400:1.

Keep the reaction temperature at 80°C. After 1 hour of polymerization, add a chloroform solution with a mass concentration of 10 mg/mL benzoic acid to dissolve the product, and take a small amount of the solution for ¹ H NMR analysis to determine the conversion rate. The conversion rate is 87.8%, and the α - The ratio of methyl-γ-thiobutyrolactone by-product:poly(α-methylγ-thiobutyrolactone) was 5:99. The remaining reaction solution was poured into ethanol to settle the polymer, the precipitated solid was centrifuged, and the supernatant was discarded, then dissolved in dichloromethane repeatedly, dropped into ethanol to settle, centrifuged, and the supernatant was discarded twice, and then Dry in a vacuum oven at room temperature for three days to obtain colorless poly(α-methyl-γ-thiobutyrolactone).

Example 29

Dissolve 0.01 mmol of [Et ₃ Si-H-SiEt ₃ ][B(C ₆ F ₅ ) ₄ ] in 0.4 mL of toluene at room temperature in a glove box under an argon atmosphere in a dry 5 mL glass bottle, Then add 1mmol (116.2mg, 0.10mL) of γ-thionovalerolactone monomer, the initial concentration of the monomer is 2mol/L, the catalyst [Et ₃ Si-H-SiEt ₃ ][B(C ₆ F ₅ ) ₄ ] at a concentration of 20mmol/L, and the molar ratio of monomer to [Et ₃ Si-H-SiEt ₃ ][B(C ₆ F ₅ ) ₄ ] was 100:1.

Keep the reaction temperature at room temperature, stir and react for 1h, take a small amount of sample and dissolve it in deuterated chloroform, monitor the conversion rate by ¹ H NMR, the conversion rate is 99.0%, the by-product of γ-thiovalerolactone: poly(γ-thiovalerolactone valerolactone) ratio of 6:94. Then add 12mL of water/tetrahydrofuran mixed solution (volume ratio 1:30) to quench the reaction, drop the reaction solution into ethanol to settle the polymer, centrifuge, discard the supernatant, then repeatedly dissolve with dichloromethane, drop into ethanol Settling, centrifuging, discarding the supernatant twice, and then drying at room temperature in a vacuum oven for three days to obtain colorless poly(γ-thiovalerolactone).

The present invention adopts gel permeation chromatography (GPC) to detect the molecular weight and molecular weight distribution of poly(γ-thiovalerolactone), using tetrahydrofuran as eluent, flow rate is 1.0mL/min, and polymethyl methacrylate is used as A standard curve was made with standard products, and the results showed that the poly(γ-thiovalerolactone) prepared in this example had a number average molecular weight of 10.2 kg/mol and a molecular weight distribution of 1.47.

Example 30

In a glove box under an argon atmosphere, add 0.01 mmol of Ph ₃ CB (C ₆ F ₅ ) ₄ and 0.01 mmol of Et ₃ SiH and 0.4 mL of toluene to a dry glass bottle, then add 1 mmol (116.2 mg, 0.10 mL ) γ-thionovalerolactone monomer, the initial concentration of the monomer is 2mol/L, the concentration of the catalyst Ph ₃ CB(C ₆ F ₅ ) ₄ /Et ₃ SiH is 20mmol/L, the monomer and Ph ₃ The molar ratio of CB(C ₆ F ₅ ) ₄ /Et ₃ SiH is 100:1:1.

Keep reaction temperature at room temperature, get a small amount of sample to be dissolved in deuterated chloroform and carry out ¹ H NMR to monitor conversion rate during the polymerization process, conversion rate reaches 99.0% in the time of polymerization reaction 1h, γ-thiovalerolactone in the generation product: poly(γ -thiovalerolactone) in a ratio of 9:91. Then add 2 mL of water/tetrahydrofuran mixed solution (volume ratio 1:30) to quench the reaction, drop the reaction solution into ethanol to settle the polymer, centrifuge, discard the supernatant, then repeat dissolving with dichloromethane, drop into ethanol Settling, centrifuging, discarding the supernatant twice, and then drying at room temperature in a vacuum oven for three days to obtain colorless poly(γ-thiovalerolactone).

The present invention adopts gel permeation chromatography (GPC) to detect the molecular weight and molecular weight distribution of poly(γ-thiovalerolactone), using tetrahydrofuran as eluent, flow rate is 1.0mL/min, and polymethyl methacrylate is used as A standard curve was made with standard products, and the results showed that the poly(γ-thiovalerolactone) prepared in this example had a number average molecular weight of 8.4 kg/mol and a molecular weight distribution of 1.35.

Example 31

In a glove box under an argon atmosphere, add 0.01 mmol of Me ₃ OBF ₄ and 0.4 mL of toluene to a dry glass bottle, then add 1 mmol (116.2 mg, 0.10 mL) of γ-thionovalerolactone monomer, The initial concentration of the monomer is 2 mol/L, the concentration of the catalyst Me ₃ OBF ₄ is 20 mmol/L, and the molar ratio of the monomer to Me ₃ OBF ₄ is 100:1.

Keep reaction temperature at room temperature, get a small amount of sample to be dissolved in deuterated chloroform and carry out ¹ H NMR to monitor conversion rate during the polymerization process, conversion rate reaches 96.5% when polymerization reaction 9h, generates gamma-thiovalerolactone in the product: poly(γ -thiovalerolactone) in a ratio of 1:99. Then add 2 mL of water/tetrahydrofuran mixed solution (volume ratio 1:30) to quench the reaction, drop the reaction solution into ethanol to settle the polymer, centrifuge, discard the supernatant, then repeat dissolving with dichloromethane, drop into ethanol Settling, centrifuging, discarding the supernatant twice, and then drying at room temperature in a vacuum oven for three days to obtain colorless poly(γ-thiovalerolactone).

The present invention adopts gel permeation chromatography (GPC) to detect the molecular weight and molecular weight distribution of poly(γ-thiovalerolactone), using tetrahydrofuran as eluent, flow rate is 1.0mL/min, and polymethyl methacrylate is used as A calibration curve was made with standard products, and the results showed that the poly(γ-thiovalerolactone) prepared in this example had a number average molecular weight of 6.8 kg/mol and a molecular weight distribution of 1.26.

Example 32

In a glove box under an argon atmosphere, add 0.01 mmol of [Et ₃ O][B(C ₆ F ₅ ) ₄ ] and 0.4 mL of toluene to a dry glass bottle, and then add 1 mmol (116.2 mg, 0.10 mL) of γ-thionovalerolactone monomer, the initial concentration of the monomer is 2mol/L, the concentration of the catalyst [Et ₃ O][B(C ₆ F ₅ ) ₄ ] is 20mmol/L, the monomer and [Et ₃ The molar ratio of O][B(C ₆ F ₅ ) ₄ ] is 100:1.

Keep reaction temperature at room temperature, get a small amount of sample to be dissolved in deuterated chloroform and carry out ¹ H NMR to monitor conversion rate during the polymerization process, conversion rate reaches 99.0% in the time of polymerization reaction 1h, γ-thiovalerolactone in the generation product: poly(γ -thiovalerolactone) in a ratio of 1:99. Then add 2 mL of water/tetrahydrofuran mixed solution (volume ratio 1:30) to quench the reaction, drop the reaction solution into ethanol to settle the polymer, centrifuge, discard the supernatant, then repeat dissolving with dichloromethane, drop into ethanol Settling, centrifuging, discarding the supernatant twice, and then drying at room temperature in a vacuum oven for three days to obtain colorless poly(γ-thiovalerolactone).

The present invention adopts gel permeation chromatography (GPC) to detect the molecular weight and molecular weight distribution of poly(γ-thiovalerolactone), using tetrahydrofuran as eluent, flow rate is 1.0mL/min, and polymethyl methacrylate is used as A standard curve was made with standard products, and the results showed that the number average molecular weight of the poly(γ-thiovalerolactone) prepared in this example was 20.5 kg/mol, and the molecular weight distribution was 1.06.

Example 33

In a glove box under an argon atmosphere, add 0.01 mmol of C ₇ H ₇ BF ₄ and 0.4 mL of toluene to a dry glass bottle, and then add 1 mmol (116.2 mg, 0.10 mL) of γ-thionovalerolactone mono The initial concentration of the monomer is 2 mol/L, the concentration of the catalyst C ₇ H ₇ BF ₄ is 20 mmol/L, and the molar ratio of the monomer to C ₇ H ₇ BF ₄ is 100:1.

Keep reaction temperature at room temperature, get a small amount of sample to be dissolved in deuterated chloroform and carry out ¹ H NMR to monitor conversion rate during the polymerization process, conversion rate reaches 61.4% when polymerization reaction 72h, generates gamma-thiovalerolactone in the product: poly(γ -thiovalerolactone) in a ratio of 9:91. Then add 2 mL of water/tetrahydrofuran mixed solution (volume ratio 1:30) to quench the reaction, drop the reaction solution into ethanol to settle the polymer, centrifuge, discard the supernatant, then repeat dissolving with dichloromethane, drop into ethanol Settling, centrifuging, discarding the supernatant twice, and then drying at room temperature in a vacuum oven for three days to obtain colorless poly(γ-thiovalerolactone).

The present invention adopts gel permeation chromatography (GPC) to detect the molecular weight and molecular weight distribution of poly(γ-thiovalerolactone), using tetrahydrofuran as eluent, flow rate is 1.0mL/min, and polymethyl methacrylate is used as A calibration curve was made with standard products, and the results showed that the poly(γ-thiovalerolactone) prepared in this example had a number average molecular weight of 32.3 kg/mol and a molecular weight distribution of 1.88.

Example 34

In a glove box under an argon atmosphere, add 0.01 mmol of Al(C ₆ F ₅ ) ₃ 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 monomer is 10mol/L, the concentration of catalyst Al(C ₆ F ₅ ) ₃ is 100mmol/L, and the molar ratio of monomer to Al(C ₆ F ₅ ) ₃ is 100:1.

Keep the reaction temperature at room temperature, take a small amount of sample and dissolve it in deuterated chloroform to monitor the conversion rate by ¹ H NMR during the polymerization process. The conversion rate reaches 89.3% in 5 hours of polymerization reaction, and the α-methyl-γ-thiobutane in the generated product is The ratio of ester by-product:poly(α-methyl-γ-thiobutyrolactone) was 2:98. Then add 2 mL of water/tetrahydrofuran mixed solution (volume ratio 1:30) to quench the reaction, drop the reaction solution into ethanol to settle the polymer, centrifuge, discard the supernatant, then repeat dissolving with dichloromethane, drop into ethanol Settling in medium, centrifuging, discarding the supernatant twice, and then drying at room temperature in a vacuum oven for three days to obtain colorless poly(α-methyl-γ-thiobutyrolactone).

The present invention adopts gel permeation chromatography (GPC) to detect the molecular weight and molecular weight distribution of poly(alpha-methyl-gamma-thiobutyrolactone), using tetrahydrofuran as eluent, flow rate is 1.0mL/min, polyformaldehyde Methyl acrylate was used as a standard product to make a calibration curve, and the results showed that the number average molecular weight of the poly(α-methyl-γ-thiobutyrolactone) prepared in this example was 431.1kg/mol, and the molecular weight distribution was 1.80.

Example 35

In a glove box with an argon atmosphere, weigh 0.01 mmol of [Et ₃ O][B(C ₆ F ₅ ) ₄ ] in a dry 10 mL Shrek bottle, add 0.4 mL of toluene, take out the glove box and connect to the vacuum line Pre-cool at 0°C for 10 minutes. Then weigh 1 mmol (104.1 mg) of 1,3-dioxolane-2-thione in a 5 mL glass bottle in the glove box, add 1.0 mL of toluene to dissolve the monomer, take it out of the glove box and add it to the pre-cooled Shrek In the bottle, react at 0°C. The initial concentration of the monomer is 0.7mol/L, the concentration of the catalyst [Et ₃ O][B(C ₆ F ₅ ) ₄ ] is 7.0mmol/L, the monomer and [Et ₃ O][B(C ₆ F _{5 )} ) ₄ ] in a molar ratio of 100:1.

Keep the reaction temperature at 0° C., stir and react for 10 minutes, take a small amount of supernatant and dissolve it in deuterated chloroform, and monitor the conversion rate by 1H NMR, and the conversion rate is greater than 99%. Then add 2 mL of water/tetrahydrofuran mixed solution (volume ratio 1:20) to quench the reaction, drop the reaction solution into ethanol to settle the polymer, centrifuge, discard the supernatant, then repeatedly dissolve with dichloromethane and drop into ethanol Settling, centrifuging, discarding the supernatant twice, and then drying in a vacuum oven at room temperature for three days to obtain white polymonothiocarbonate.

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 poly(1,3-thione) prepared in this embodiment Dioxolane-2-thione) has a glass transition temperature of 24.5°C.

Example 36

In a glove box with an argon atmosphere, weigh 0.01 mmol of [Et ₃ O][B(C ₆ F ₅ ) ₄ ] in a dry 10 mL Shrek bottle, add 0.30 mL of toluene, take it out of the glove box and connect it to the vacuum line Pre-cool at 0°C for 10 minutes. Then weigh 4 mmol (472.6 mg, 0.38 mL) of (S)-4-methyl-1,3-dioxolane-2-thione monomer in a 5 mL glass bottle in the glove box, add 0.40 mL of toluene to dissolve, Take it out of the glove box and add it to the pre-cooled Shrek bottle, and react at 0°C. The initial concentration of the monomer is 3.7mol/L, the concentration of the catalyst [Et ₃ O][B(C ₆ F ₅ ) ₄ ] is 9.2mmol/L, the monomer and [Et ₃ O][B(C ₆ F _{5 )} ) ₄ ] in a molar ratio of 400:1.

Keep the reaction temperature at 0° C., stir and react for 120 minutes, take a small amount of sample and dissolve it in deuterated chloroform, and monitor the conversion rate by ¹ H NMR, and the conversion rate is greater than 99%. Then add 2 mL of water/tetrahydrofuran mixed solution (volume ratio 1:20) to quench the reaction, drop the reaction solution into ethanol to settle the polymer, centrifuge, discard the supernatant, then repeatedly dissolve with dichloromethane and drop into ethanol Settling in medium, centrifuging, discarding the supernatant twice, and then drying at room temperature in a vacuum oven for three days to obtain colorless and transparent polymonothiocarbonate. The polymer was detected by nuclear magnetic resonance (NMR), and ^{the 1} H NMR spectrum and ^{the 13} C NMR spectrum are shown in Figure 37 and Figure 38 respectively.

The present invention adopts differential scanning calorimetry (DSC) to detect the melting temperature and the glass transition temperature of poly-(S)-4-methyl-1,3-dioxolane-2-thione, and the results show that the present embodiment The prepared poly(S)-4-methyl-1,3-dioxolane-2-thione has a glass transition temperature of 17.2°C.

The present invention adopts gel permeation chromatography (GPC) to detect the molecular weight and molecular weight distribution of poly-(S)-4-methyl-1,3-dioxolane-2-thione, with tetrahydrofuran as mobile phase, flow velocity is 1.0mL/min, take polymethyl methacrylate as standard substance to do calibration curve, the results show that the poly-(S)-4-methyl-1,3-dioxolane-2-sulfur prepared in the present embodiment The number average molecular weight of the ketone was 38.9 kg/mol, and the molecular weight distribution was 1.26.

Example 37

In a glove box with an argon atmosphere, weigh 0.01 mmol of [Et ₃ O][B(C ₆ F ₅ ) ₄ ] in a dry 10 mL Shrek bottle, add 0.30 mL of toluene, take it out of the glove box and connect it to the vacuum line Pre-cool at 0°C for 10 minutes. Then weigh 4 mmol (472.6 mg, 0.38 mL) of (R)-4-methyl-1,3-dioxolane-2-thione monomer in a 5 mL glass bottle in the glove box, add 0.40 mL of toluene to dissolve, Take it out of the glove box and add it to the pre-cooled Shrek bottle, and react at 0°C. The initial concentration of the monomer is 3.7mol/L, the concentration of the catalyst [Et ₃ O][B(C ₆ F ₅ ) ₄ ] is 9.2mmol/L, the monomer and [Et ₃ O][B(C ₆ F _{5 )} ) ₄ ] in a molar ratio of 400:1.

Keep the reaction temperature at 0° C., stir and react for 50 minutes, take a small amount of sample and dissolve it in deuterated chloroform, and monitor the conversion rate by ¹ H NMR, and the conversion rate is greater than 99%. Then add 2 mL of water/tetrahydrofuran mixed solution (volume ratio 1:20) to quench the reaction, drop the reaction solution into ethanol to settle the polymer, centrifuge, discard the supernatant, then repeatedly dissolve with dichloromethane and drop into ethanol Settling in medium, centrifuging, discarding the supernatant twice, and then drying at room temperature in a vacuum oven for three days to obtain colorless and transparent polymonothiocarbonate.

The present invention adopts gel permeation chromatography (GPC) to detect the molecular weight and molecular weight distribution of poly-(R)-4-methyl-1,3-dioxolane-2-thione, with tetrahydrofuran as mobile phase, flow velocity is 1.0mL/min, take polymethyl methacrylate as standard substance to do calibration curve, the results show that the poly-(R)-4-methyl-1,3-dioxolane-2-sulfur prepared in the present embodiment The number average molecular weight of the ketone was 45.3 kg/mol, and the molecular weight distribution was 1.04.

The present invention adopts differential scanning calorimetry (DSC) to detect the melting temperature and the glass transition temperature of poly-(R)-4-methyl-1,3-dioxolane-2-thione, and the results show that the present embodiment The prepared poly-(R)-4-methyl-1,3-dioxolane-2-thione has a glass transition temperature of 18.2°C

Example 38

In a glove box with an argon atmosphere, weigh 0.01 mmol of [Et ₃ O][B(C ₆ F ₅ ) ₄ ] in a dry 10 mL Shrek bottle, add 0.4 mL of toluene, take out the glove box and connect to the vacuum line Pre-cool at 0°C for 10 minutes. Then weigh 1mmol (152.6mg) of 4-(chloromethyl)-1,3-dioxolane-2-thione monomer in a 5mL glass bottle in the glove box, add 1.0mL toluene to dissolve it, and take it out of the glove box Add it to the pre-cooled Shrek bottle and react at 0°C. The initial concentration of the monomer is 0.7mol/L, the concentration of the catalyst [Et ₃ O][B(C ₆ F ₅ ) ₄ ] is 7.0mmol/L, the monomer and [Et ₃ O][B(C ₆ F _{5 )} ) ₄ ] in a molar ratio of 100:1.

Keep the reaction temperature at 0° C., stir and react for 10 minutes, take a small amount of sample and dissolve it in deuterated chloroform, and monitor the conversion rate by ¹ H NMR, and the conversion rate is greater than 99%. Then add 2 mL of water/tetrahydrofuran mixed solution (volume ratio 1:20) to quench the reaction, drop the reaction solution into ethanol to settle the polymer, centrifuge, discard the supernatant, then repeatedly dissolve with dichloromethane and drop into ethanol Settling, centrifuging, discarding the supernatant twice, and then drying in a vacuum oven at room temperature for three days to obtain white polymonothiocarbonate. Nuclear magnetic resonance (NMR) detection was performed, and ^{the 1} H NMR spectrum is shown in Figure 39.

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, and the results show that the prepared The glass transition temperature of poly 4-(chloromethyl)-1,3-dioxolane-2-thione is 41.6°C.

The present invention adopts gel permeation chromatography (GPC) to detect the molecular weight and molecular weight distribution of poly-4-(chloromethyl)-1,3-dioxolane-2-thione, using tetrahydrofuran as mobile phase, and the flow rate is 1.0mL /min, with polymethyl methacrylate as a standard product to do a calibration curve, the results show that the poly 4-(chloromethyl)-1,3-dioxolane-2-thione number average molecular weight prepared by the present embodiment It is 25.8kg/mol, and the molecular weight distribution is 1.37.

Example 39

In a glove box with an argon atmosphere, weigh 0.01 mmol of [Et ₃ O][B(C ₆ F ₅ ) ₄ ] in a dry 10 mL Shrek bottle, add 0.4 mL of toluene, take out the glove box and connect to the vacuum line Pre-cool at 0°C for 10 minutes. Then weigh 1 mmol (152.6 mg) of (R)-4-(chloromethyl)-1,3-dioxolane-2-thione monomer in a 5 mL glass bottle in the glove box, add 1.0 mL of toluene to dissolve, Take it out of the glove box and add it to the pre-cooled Shrek bottle, and react at 0°C. The initial concentration of the monomer is 0.7mol/L, the concentration of the catalyst [Et ₃ O][B(C ₆ F ₅ ) ₄ ] is 7.0mmol/L, the monomer and [Et ₃ O][B(C ₆ F _{5 )} ) ₄ ] in a molar ratio of 100:1.

Keep the reaction temperature at 0° C., stir and react for 10 minutes, take a small amount of supernatant and dissolve it in deuterated chloroform, and monitor the conversion rate by ¹ H NMR, and the conversion rate is greater than 99%. Then add 2 mL of water/tetrahydrofuran mixed solution (volume ratio 1:20) to quench the reaction, drop the reaction solution into ethanol to settle the polymer, centrifuge, discard the supernatant, then repeatedly dissolve with dichloromethane and drop into ethanol Settling, centrifuging, discarding the supernatant twice, and then drying in a vacuum oven at room temperature for three days to obtain white polymonothiocarbonate. ^{The 1} H NMR spectrum is shown in FIG. 40 .

The present invention adopts differential scanning calorimetry (DSC) to detect the melting temperature and the glass transition temperature of poly-(R)-4-(chloromethyl)-1,3-dioxolane-2-thione, and the results show that, The poly(R)-4-(chloromethyl)-1,3-dioxolane-2-thione prepared in this example has a glass transition temperature of 39.8°C and a melting temperature of 162.8°C.

The present invention adopts gel permeation chromatography (GPC) to detect the molecular weight and molecular weight distribution of poly-(R)-4-(chloromethyl)-1,3-dioxolane-2-thione, using tetrahydrofuran as mobile phase , the flow rate is 1.0mL/min, and polymethyl methacrylate is used as a standard to make a standard curve. The results show that the poly-(R)-4-(chloromethyl)-1,3-diox Pentacycline-2-thione has a number average molecular weight of 24.5 kg/mol and a molecular weight distribution of 1.35.

Example 40

In a glove box with an argon atmosphere, weigh 0.01 mmol of [Et ₃ O][B(C ₆ F ₅ ) ₄ ] in a dry 10 mL Shrek bottle, add 0.4 mL of toluene, take out the glove box and connect to the vacuum line Pre-cool at 0°C for 10 minutes. Then weigh 1mmol (152.6mg) of thiocarbonate monomer (S)-4-(chloromethyl)-1,3-dioxolane-2-thione in a 5mL glass bottle in the glove box, add Dissolve 1.0mL of toluene, take it out of the glove box and add it to the previously pre-cooled Shrek bottle, and react at 0°C. The initial concentration of the monomer is 0.7mol/L, the concentration of the catalyst [Et ₃ O][B(C ₆ F ₅ ) ₄ ] is 7.0mmol/L, the monomer and [Et ₃ O][B(C ₆ F _{5 )} ) ₄ ] in a molar ratio of 100:1.

Keep the reaction temperature at 0° C., stir and react for 10 minutes, take a small amount of supernatant and dissolve it in deuterated chloroform, and monitor the conversion rate by ¹ H NMR, and the conversion rate is greater than 99%. Then add 2 mL of water/tetrahydrofuran mixed solution (volume ratio 1:20) to quench the reaction, drop the reaction solution into ethanol to settle the polymer, centrifuge, discard the supernatant, then repeatedly dissolve with dichloromethane and drop into ethanol Settling, centrifuging, discarding the supernatant twice, and then drying in a vacuum oven at room temperature for three days to obtain white polymonothiocarbonate.

The present invention adopts differential scanning calorimetry (DSC) to detect the melting temperature and the glass transition temperature of poly-(S)-4-(chloromethyl)-1,3-dioxolane-2-thione, and the results show that, The poly-(S)-4-(chloromethyl)-1,3-dioxolane-2-thione prepared in this example has a glass transition temperature of 39.0°C and a melting temperature of 163.0°C.

The present invention adopts gel permeation chromatography (GPC) to detect the molecular weight and molecular weight distribution of poly-(S)-4-(chloromethyl)-1,3-dioxolane-2-thione, using tetrahydrofuran as mobile phase , the flow rate is 1.0mL/min, and polymethyl methacrylate is used as a standard to make a standard curve. The results show that the poly-(S)-4-(chloromethyl)-1,3-diox Pentacycline-2-thione has a number average molecular weight of 19.3 kg/mol and a molecular weight distribution of 1.43.

Example 41

In a glove box with an argon atmosphere, weigh 0.01 mmol of [Et ₃ O][B(C ₆ F ₅ ) ₄ ] in a dry 10 mL Shrek bottle, add 0.4 mL of toluene, take out the glove box and connect to the vacuum line Pre-cool at 0°C for 10 minutes. Then weigh 1mmol (180.2mg) of 4-phenyl-1,3-dioxolane-2-thione monomer in a 5mL glass bottle in the glove box, add 1.0mL toluene to dissolve it, take it out of the glove box and add it to the In a pre-cooled Shrek bottle, react at 0°C. The initial concentration of the monomer is 0.7mol/L, the concentration of the catalyst [Et ₃ O][B(C ₆ F ₅ ) ₄ ] is 7.0mmol/L, the monomer and [Et ₃ O][B(C ₆ F _{5 )} ) ₄ ] in a molar ratio of 100:1.

Keep the reaction temperature at 0° C., stir and react for 10 minutes, take a small amount of sample and dissolve it in deuterated chloroform, and monitor the conversion rate by ¹ H NMR, and the conversion rate is greater than 99%. Then add 2 mL of water/tetrahydrofuran mixed solution (volume ratio 1:20) to quench the reaction, drop the reaction solution into ethanol to settle the polymer, centrifuge, discard the supernatant, then repeatedly dissolve with dichloromethane and drop into ethanol Settling, centrifuging, discarding the supernatant twice, and then drying in a vacuum oven at room temperature for three days to obtain white polymonothiocarbonate. The polymer was detected by nuclear magnetic resonance (NMR), and ^{the 1} H NMR spectrum and ^{the 13} C NMR spectrum are shown in Figure 41 and Figure 42, respectively.

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, and the results show that the poly-4- The glass transition temperature of phenyl-1,3-dioxolane-2-thione is 59.5°C.

The present invention adopts gel permeation chromatography (GPC) to detect the molecular weight and molecular weight distribution of poly-4-phenyl-1,3-dioxolane-2-thione, using tetrahydrofuran as the mobile phase, and the flow rate is 1.0mL/min, Taking poly-4-phenyl-1,3-dioxolane-2-thione as standard substance to do standard curve, the result shows that its number-average molecular weight of the polymonothiocarbonate prepared in the present embodiment is 19.7kg/mol , the molecular weight distribution is 2.05.

Example 42

In a glove box under an argon atmosphere, weigh 0.05mmol (7.6mg, 0.0074mL) of DBU and 0.05mmol (5.4mg, 0.0052mL) of benzyl alcohol in a dry 5mL glass bottle and mix them, add 1.0mL of toluene to Fully dissolve. Then add 5mmol (590.7mg, 0.47mL) of thionocarbonate monomer (R)-4-methyl-1,3-dioxolane-2-thione to a 5mL glass bottle, at 25°C reaction. The initial concentration of monomer is 3.7mol/L, the concentration of catalyst DBU is 37mmol/L, and the molar ratio of monomer to DBU is 100:1.

Keep the reaction temperature at 25° C., stir and react for 60 h, take a small amount of sample and dissolve it in deuterated chloroform, and monitor the conversion rate by ¹ H NMR, and the conversion rate is greater than 99%. Then add 2 mL of benzoic acid/dichloromethane mixed solution (concentration is 10 mg/mL) to quench the reaction, drop the reaction solution into ethanol to settle the polymer, centrifuge, discard the supernatant, and then repeat the dissolution with dichloromethane, Drop into ethanol for sedimentation, centrifuge, discard the supernatant twice, and then dry in a vacuum oven at room temperature for three days to obtain colorless and transparent polymonothiocarbonate.

The present invention adopts gel permeation chromatography (GPC) to detect the molecular weight and the molecular weight distribution of polymonothiocarbonate, with tetrahydrofuran as mobile phase, flow velocity is 1.0mL/min, take polymethyl methacrylate as standard product to do standard curve , The results show that the number average molecular weight of the polymonothiocarbonate prepared in this embodiment is 4.9kg/mol, and the molecular weight distribution is 1.38.

Example 43

In a glove box under an argon atmosphere, weigh 0.05mmol (7.6mg, 0.0074mL) of DBU and 0.05mmol (5.4mg, 0.0052mL) of benzyl alcohol in a dry 5mL glass bottle and mix them, add 0.5mL of toluene to Fully dissolve. Weigh 0.05mmol (18.5mg) of 1-[3,5-bis(trifluoromethyl)phenyl]-3-cyclohexylthiourea and 5mmol (590.7mg, 0.47mL) of Thiocarbonate monomer (R)-4-methyl-1,3-dioxolane-2-thione was mixed, and 0.5 mL of toluene was added until fully dissolved. The solutions in the two glass bottles were fully mixed and reacted at 25°C. The initial concentration of monomer is 3.7mol/L, the concentration of catalyst DBU is 37mmol/L, and the molar ratio of monomer to DBU is 100:1.

Keeping the reaction temperature at 25° C., stirring for 120 h, a small amount of sample was dissolved in deuterated chloroform, and the conversion rate was monitored by ¹ H NMR, and the conversion rate was greater than 99%. Then add 2 mL of benzoic acid/dichloromethane mixed solution (concentration is 10 mg/mL) to quench the reaction, drop the reaction solution into ethanol to settle the polymer, centrifuge, discard the supernatant, and then repeat the dissolution with dichloromethane, Drop into ethanol for sedimentation, centrifuge, discard the supernatant twice, and then dry in a vacuum oven at room temperature for three days to obtain colorless and transparent polymonothiocarbonate.

The present invention adopts gel permeation chromatography (GPC) to detect the molecular weight and the molecular weight distribution of polymonothiocarbonate, with tetrahydrofuran as mobile phase, flow velocity is 1.0mL/min, take polymethyl methacrylate as standard product to do standard curve , The results show that the number average molecular weight of the polymonothiocarbonate prepared in this example is 3.2kg/mol, and the molecular weight distribution is 1.49.

Example 44

In a glove box under an argon atmosphere, in a dry 20 mL glass bottle at room temperature, 0.005 mmol of [Et ₃ O][B(C ₆ F ₅ ) ₄ ] was dispersed in 4.8 mL of toluene, and then 12 mmol ( 1394.2mg, 1.2mL) of (R)-γ-thionovalerolactone monomer, the initial concentration of the monomer is 2mol/L, the concentration of the catalyst [Et ₃ O][B(C ₆ F ₅ ) ₄ ] The molar ratio of monomer to [Et ₃ O][B(C ₆ F ₅ ) ₄ ] is 1.67mmol/L, 1200:1.

Keep the reaction temperature at room temperature, stir and react for 18 hours, take a small amount of sample and dissolve it in deuterated chloroform, monitor the conversion rate by ¹ H NMR, the conversion rate is 93.6%, the by-product of γ-thiovalerolactone: poly-(S)- The ratio of (γ-thiovalerolactone) is less than 1:99. Then add 10mL of water/tetrahydrofuran mixed solution (volume ratio 1:20) to quench the reaction, drop the reaction solution into ethanol to settle the polymer, filter, and wash with ethanol, then dry at room temperature in a vacuum oven for three days to obtain a white poly-(S)-(γ-thiovalerolactone).

The present invention uses differential scanning calorimetry (DSC) to detect the melting temperature and glass transition temperature of poly-(S)-(γ-thiovalerolactone), and the results show that the poly-(S)- (γ-thiovalerolactone) has a glass transition temperature of about -8.8°C and a melting point of about 82.3°C.

The present invention adopts thermogravimetric analyzer (TGA) to measure and detect the thermal stability of poly-(S)-(γ-thiovalerolactone), and the result shows that the poly-(S)-(γ-sulfide prepared in this embodiment Valerolactone) has an initial decomposition temperature (T _d , temperature at 5% weight loss) of 235.5°C.

The present invention adopts gel permeation chromatography (GPC) to detect the molecular weight and molecular weight distribution of poly-(S)-(γ-thiovalerolactone), using tetrahydrofuran as eluent, flow rate is 1.0mL/min, polyformaldehyde Methyl acrylate was used as a standard to make a calibration curve, and the results showed that the number-average molecular weight of the poly-(S)-(γ-thiovalerolactone) prepared in this example was 106.1kg/mol, and the molecular weight distribution was 1.40.

The poly-(S)-(γ-thiovalerolactone) prepared in the present invention was subjected to a mechanical tensile test, and the results showed that the fracture of the (S)-poly(γ-thiovalerolactone) prepared in this example The elongation is 638%, the yield stress is 9.05MPa, and the breaking stress is 24.27MPa.

Example 45

In a glove box under an argon atmosphere, in a dry 20 mL glass bottle at room temperature, 0.005 mmol of [Et ₃ O][B(C ₆ F ₅ ) ₄ ] was dispersed in 4.8 mL of toluene, and then 12 mmol ( 1394.2mg, 1.2mL) of (S)-γ-thionovalerolactone monomer, the initial concentration of the monomer is 2mol/L, the concentration of the catalyst [Et ₃ O][B(C ₆ F ₅ ) ₄ ] The molar ratio of monomer to [Et ₃ O][B(C ₆ F ₅ ) ₄ ] is 1.67mmol/L, 1200:1.

Keep the reaction temperature at room temperature, stir and react for 18 hours, take a small amount of sample and dissolve it in deuterated chloroform, monitor the conversion rate by ¹ H NMR, the conversion rate is 98.5%, the by-product of γ-thiovalerolactone: poly-(R)- The ratio of (γ-thiovalerolactone) was 1:99. Then add 10mL of water/tetrahydrofuran mixed solution (volume ratio 1:20) to quench the reaction, drop the reaction solution into ethanol to settle the polymer, filter, and wash with ethanol, then dry at room temperature in a vacuum oven for three days to obtain a white (R)-poly(γ-thiovalerolactone).

The present invention uses differential scanning calorimetry (DSC) to detect the melting temperature and glass transition temperature of poly-(R)-(γ-thiovalerolactone), and the results show that the poly-(R)- (γ-thiovalerolactone) has a glass transition temperature of about -8.9°C and a melting point of about 81.0°C.

The present invention adopts gel permeation chromatography (GPC) to detect the molecular weight and molecular weight distribution of poly-(R)-(γ-thiovalerolactone), using tetrahydrofuran as eluent, flow rate is 1.0mL/min, polyformaldehyde Methyl acrylate was used as a standard to make a calibration curve, and the results showed that the number average molecular weight of the poly-(R)-(γ-thiovalerolactone) prepared in this example was 101.2kg/mol, and the molecular weight distribution was 1.68.

Comparative example 1

In a glove box under an argon atmosphere, add 0.02 mmol of potassium thioacetate, 0.02 mmol of 18-crown 6 ether and 0.2 mL of N, N-dimethylformamide to a dry Schlenk bottle, and then add 2 mmol (232 mg, 0.2 mL) of γ-thionovalerolactone monomer, the initial concentration of monomer is 5mol/L, the concentration of catalyst potassium thioacetate is 50mmol/L, the mole of monomer and potassium thioacetate and 18 crown 6 ether The ratio is 100:1:1.

Remove the glove box and connect the Schlenk bottle to a vacuum line protected by argon. After stirring the reaction at 80 ° C for 48 h, add 0.15 mL of toluene solution containing 0.05 mL of allyl chloride to terminate the reaction, and take a small amount of the solution for ¹ H NMR Analyzed to determine the conversion, the monomer conversion was 66.5%, and the ratio of dimer:γ-thiovalerolactone:poly(γ-thiovalerolactone) in the product was 15.0:64.4:20.6. The remaining reaction solution was poured into ethanol, and no polymer was precipitated because oligomers were generated.

Effect embodiment 1: performance parameter determination:

1.1 Molecular weight control

The present invention measures the number average molecular weight (M _n ) and the molecular weight distribution of polythioester by the gel permeation chromatograph of Waters E2695 by model

Among them, the model of the chromatographic column is Agilent Plgel 5μm, and the model of the differential detector is Wyatt

For T-Rex, the eluent is tetrahydrofuran, the column temperature is 40°C, and the flow rate is 1.0 mL/min. Using polymethyl methacrylate as a standard product to make a calibration curve, the results show that the number average molecular weight of the polythioester prepared in the embodiment of the present invention is 3.2kg/mol-431.1kg/mol, and the molecular weight distribution index is 1.01-2.05.

Under the reaction conditions of [Ph ₃ C][B(C ₆ F ₅ ) ₄ ] as the main catalyst, change the amount of catalyst, and the ratio of monomer to catalyst is 100:1, 200:1, 400:1, 800: 1 and 1200:1, carry out polymerization reaction, the number average molecular weight of gained polymer is respectively 16.3, 27.5, 55.0, 95.9 and 122.0kg/mol, and corresponding molecular weight distribution index is respectively 1.22, 1.16, 1.25, 1.43 and 1.51. The number-average molecular weight increases linearly with the ratio increase of the monomer and the catalyst, as shown in Figure 31 (the catalyst here refers to the main catalyst, and in Figure 31, the abscissa is the ratio of the monomer γ-thiovalerolactone and the catalyst. molar ratio, "■" is the number average molecular weight of the polymer, "◆" is the molecular weight distribution of the polymer), and has good molecular weight controllability.

1.2 Thermal performance analysis

The present invention carries out thermogravimetric analysis (TGA) through TGA 550 thermogravimetric analyzer of TA Company, obtains the thermal decomposition temperature of polymer, and thermogravimetric analysis test is carried out under _N2 atmosphere, and test temperature range is 25～700 ℃, and heating rate 15°C/min. The initial decomposition temperature (T _d , temperature at 5% weight loss) of the poly(γ-thiovalerolactone) prepared in Example 2 is 251°C, as shown in Figure 32; the poly(γ-thiovalerolactone) prepared in Example 3 The initial decomposition temperature (T _d , temperature at 5% weight loss) of (γ-thiocaprolactone) is at 287°C; the initial decomposition temperature (T _d , the temperature at 5% weight loss) at 282°C; the initial decomposition temperature (T _d , the temperature at 5% weight loss) of the poly(γ-thiooctolactone) prepared in Example 5 was at 268°C; Example The initial decomposition temperature (T _d , temperature at 5% weight loss) of the poly(γ-thiodecalactone) prepared in 6 is at 245°C; the poly(γ-thiodecalactone) obtained in Example 7 is The initial decomposition temperature (T _d , the temperature at 5% weight loss) is at 253°C; the initial decomposition temperature (T _d , the temperature at 5% weight loss) of the poly(γ-thioundecalactone) prepared in Example 8 At 248°C; the initial decomposition temperature (T _d , temperature at 5% weight loss) of the poly(γ-thiododecanolactone) obtained in Example 9 was at 273°C; the poly(γ-thiododecalactone) obtained in Example 10 The initial decomposition temperature (T _d , temperature at 5% weight loss) of methyl-γ-thiodecalactone) is at 268°C; the poly(β-methyl-γ-thiooctrolactone prepared in Example 11 ) initial decomposition temperature (T _d , temperature at 5% weight loss) at 290°C; the initial decomposition temperature (T _d , 5% The temperature at the time of weight loss) is at 259.1°C; the initial decomposition temperature (T _d , the temperature at 5% weight loss) of the poly(β-methyl-γ-thiobutyrolactone) prepared in Example 13 is at 260°C; The initial decomposition temperature (T _d , temperature at 5% weight loss) of the poly(γ-thiovalerolactone) obtained in Example 15 was 255° C.; the poly-4-(chloromethyl)-1 obtained in Example 38 , the initial decomposition temperature (T _d , temperature at 5% weight loss) of 3-dioxolane-2-thione is at 270°C; the poly-(S)-(γ-thiovalerolide prepared in Example 44 The initial decomposition temperature (T _d , temperature at 5% weight loss) of ester) is 235.5°C; it has good thermal stability.

In the present invention, a differential scanning calorimeter (DSC 2000) of TA Company is used to conduct differential scanning calorimetry (DSC) analysis on the polythioester prepared in the above examples, and representative curves are shown in Figures 33 and 34. The test results show that the polythioester provided by the invention has a glass transition temperature T _g in the range of -57.0°C to 59.5°C, which is highly adjustable and can meet different application scenarios.

Among them, the poly(γ-thiocaprolactone) (abbreviation: PTGCL), poly(γ-thioenantrolactone) (abbreviation: PTGHL) and poly(γ-thiocaprolactone) obtained in Examples 3-10 ) (abbreviation: PTGOL), poly(γ-thiononanolide) (abbreviation: PTGNL), poly(γ-thiodecalactone) (abbreviation: PTGDL), poly(γ-thioundecalactone) (abbreviation: PTGUDL), poly(γ-thiododecalactone) (abbreviation: PTGDDL) and poly(γ-methyl-γ-thiodecalactone) (abbreviation: PTGMDL) DSC curves are shown in Figure 33 Show.

The DSC curve of the poly(γ-thiovalerolactone) (abbreviation: PTGVL) obtained in Example 2, the poly(α-methyl-γ-thiobutyrolactone) obtained in Examples 12-13 (abbreviation: PαMeTBL ) and poly(β-methyl-γ-thiobutyrolactone) (abbreviation: PβMeTBL), the poly(β-methyl-γ-thiobutyrolactone) obtained in Example 11 (abbreviation: PTWL ) and the DSC curves of poly(cis-hexahydroisobenzofuran-1-one) (abbreviation: P3,4-S6TBL) obtained in Example 15 are shown in Figure 34.

Poly-1,3-dioxolane-2-thione (abbreviation: PEMTC) obtained in Example 35, poly-(S)-4-methyl-1,3-dioxolane obtained in Example 36 -2-thione (abbreviation: S-PPMTC), poly-(R)-4-methyl-1,3-dioxolane-2-thione (abbreviation: R-PPMTC) obtained in Example 37, The poly-4-chloromethyl-1,3-dioxolane-2-thione (abbreviation: PCMMTC) obtained in Example 38 and the poly-4-phenyl-1,3-dioxolane obtained in Example 41 The overlay of the DSC curve of cyclo-2-thione (abbreviation: PBMTC) is shown in FIG. 43 .

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

The DSC curve of poly-(S)-4-chloromethyl-1,3-dioxolane-2-thione (abbreviation: S-PCMMTC) obtained in Example 40 is shown in FIG. 45 .

The DSC curve of poly-(S)-poly(γ-thiovalerolactone) (abbreviation: S-PTGVL) obtained in Example 44 is shown in FIG. 48 .

1.3 Mechanical property test

The present invention tests the mechanical properties of the polymer obtained in the examples. First, the polymer is prepared into a polymer film by hot pressing with a tetrafluoroethylene template and cut into a dumbbell-shaped stretched spline. The effective size of the stretch is 10 ×5×1mm ³ , then passed through a LinkamTST350 tensile tester, with ASTM as the standard, stretched at 30°C, with a tensile rate of 5mm/min, and the final data was the average of five experiments.

The result of the mechanical tensile test of the poly-(S)-(γ-thiovalerolactone) prepared in Example 44 is shown in Figure 49, and the mechanical tensile test (as shown in Figure 49) experiment shows that the prepared (S) - Poly(γ-thiovalerolactone) has an elongation at break of 638%, a yield stress of 9.05 MPa, and a break stress of 24.27 MPa. This shows that poly(gamma-thiobutyrolactone) provided by the invention is a kind of strong and tough macromolecule material, and every index of mechanical tensile test is all better than low-density polyethylene (elongation at break is 430%, Stress at break is 10.6MPa) and isotactic polypropylene (elongation at break is 420%, stress at break is 26.0MP), close to the tensile properties of high-density polypropylene (elongation at break is 420%, stress at break is 26.0MP ). In terms of elongation at break, poly-(S)-(γ-thiovalerolactone) is 1.5 times that of commercial low-density polyethylene and isotactic polypropylene, indicating that its toughness is significantly better than that of commercial low-density polyethylene. Ethylene and isotactic polypropylene.

The ternary random copolymer that embodiment 14 is made carries out the test of mechanical properties: mechanical tensile test (as shown in Figure 46) elongation at break is 1451.30%, and breaking stress is 16.62MPa; In addition cyclic tensile test ( As shown in Figure 47) experiments show that the elastic recovery rate of the ternary random copolymer is 72.3%, which shows that the ternary random copolymer provided by the present invention is a strong and tough elastomer polymer material. All the indicators of the mechanical tensile test are better than commercial ethylene-propylene rubber (the elongation at break is 275.0%, the stress at break is 5.70Mpa, and the recovery rate is 50-80%).

1.4 Degradability analysis

The polythioester and polymonothiocarbonate described in the present invention have degradability unmatched by commercial polyolefins. Taking poly(γ-thiovalerolactone) as an example, rapid and controllable degradation can occur under specific conditions: at room temperature, when 1,5,7-triazidebicyclo(4.4.0)decane-5- When ene (TBD) is used as the degradation catalyst, the poly(γ-thiovalerolactone) obtained in Example 4 can be rapidly and quantitatively degraded into γ-thiovalerolactone within 1 minute, as shown in FIG. 35 . The specific reaction process is as follows: 232.4 mg of dried poly(γ-thiovalerolactone) is dissolved in 2.5 mL of anhydrous dichloromethane, and 0.5 mL of TBD (0.02 mol/L) is added to the obtained transparent solution. dichloromethane solution, stirred for 1 min to find that the polymer had been completely degraded into γ-thiovalerolactone.

Through the above performance analysis of the polymer obtained in the present invention, it can be seen that the sulfur-containing homopolymer and copolymer prepared in the present invention provide convenience for industrial production of environmentally friendly sulfur-containing polymer materials. The synthesized sulfur-containing polymer has the advantages of high molecular weight, good molecular weight controllability, wide-range adjustable physical properties, and excellent degradability. It can be used as plastic, rubber, elastomer, fiber and other products, and has a wide range of applications.

Claims

A method for preparing a sulfur-containing polymer, characterized in that it comprises the following steps: in an organic solvent, in the presence of a main catalyst, one or more polymerizable monomers are polymerized;

Wherein, the main catalyst is an anionic main catalyst or a cationic main catalyst;

The anionic main catalyst is phosphazene base, guanidine organic base, amidine organic base, N-heterocyclic carbene organic base, N-heterocyclic olefin organic base, carboxylate and thiocarboxylate one or more;

The cationic main catalyst is one or more of zwitterion pair catalysts, neutral Lewis acid catalysts and protic acid (ester) catalysts;

The polymerized monomer is independently a five-membered ring skeleton compound as shown in formula (I):

in,
for

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, hydroxyl, C 6-10 aryl, C 1-10 alkyl or C 1-10 alkenyl; said C 1-10 alkyl is optionally replaced by halogen, hydroxyl and C 6- One or more substitutions in 10 aryl groups;

Alternatively, 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 connecting them form a C 3-10 ring Alkyl, C 3-10 cycloalkenyl or C 6-10 aryl;

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 are all H;

When the main catalyst is an anionic main catalyst, and the polymer monomer is one, then the polymer monomer is not
The preparation method according to claim 1, wherein it satisfies one or more of the following conditions:

(1), in the compound represented by the formula (I), the halogen is independently fluorine, chlorine, bromine or iodine, such as fluorine or chlorine;

(2), in the compound represented by the formula (I), the C 1-10 alkyl group is independently a C 1-8 alkyl group, such as methyl, ethyl, n-propyl, n-butyl , n-pentyl, n-hexyl, n-heptyl, n-nonyl;

(3), in the compound represented by the formula (I), the C 1-10 alkenyl is independently a C 1-8 alkenyl, such as a C 1-4 alkenyl, or vinyl;

(4), in the compound represented by the formula (I), the C 6-10 aryl groups are independently phenyl;

(5), in the compound represented by the formula (I), the C 3-10 cycloalkyl is independently cyclopentyl, cyclohexyl or cycloheptyl;

(6), in the compound represented by the formula (I), the C 3-10 cycloalkenyl is independently cyclohexenyl;

(7), the polymerization reaction is carried out under a protective gas atmosphere, and the protective gas is nitrogen and/or argon;

(8), the molar volume ratio of the polymerized monomer to the organic solvent is 0.2mol/L-10mol/L;

(9), the organic solvent is one or more of linear hydrocarbon solvents, halogenated hydrocarbon solvents, cyclic ether solvents, aromatic hydrocarbon solvents, halogenated aromatic hydrocarbon solvents and amide solvents;

(10), the molar ratio of the polymerized monomer to the main catalyst is 20:1-1600:1;

(11), in the described anion procatalyst, the described phosphazene base is represented by the following structure:

Wherein, R and R' are independently C 1 -C 4 alkyl; n1 is 0, 1, 2 or 3; y is 0, 1, 2 or 3;

(12), in the anion procatalyst, the guanidine organic base is 1,5,7-triazidebicyclo(4.4.0)dec-5-ene and/or 7-methyl-1, 5,7-Triazabicyclo[4.4.0]dec-5-ene;

(13), in the anion procatalyst, the amidine organic base is 1,8-diazabicyclo[5.4.0]undec-7-ene;

(14), in the described anion procatalyst, the described N-heterocyclic carbene organic base is shown by the following structure:

Wherein, R 1a and R 2a are independently hydrogen, alkyl or aryl; R 3a and R 4a are independently alkyl or aryl;

(15), in the anion procatalyst, the N-heterocyclic olefinic organic base is shown by the following structure:

Wherein, R 1b and R 2b are independently hydrogen, alkyl or aryl; R 3b and R 4b are independently alkyl or aryl; R 5b is hydrogen or alkyl;

(16), in the anion procatalyst, the carboxylate is a metal carboxylate or an organic carboxylate; wherein, the cation in the metal carboxylate is an alkali metal cation; the organic The cation in the carboxylate is quaternary ammonium cation, imidazolium cation, phosphazenium cation, bis(triphenylphosphine) ammonium cation or amidinium cation; the anion in the described metal carboxylate and organic carboxylate is independent ground is shown by the following structure:

Wherein, R 1c is alkyl or aryl;

(17), in the anion procatalyst, the thiocarboxylate is a metal thiocarboxylate; wherein, the cation in the thiocarboxylate is an alkali metal cation; the sulfur The anion in carboxylate is represented by the following structure:

Wherein, R 1e is alkyl or aryl;

(18), in the cationic procatalyst, the zwitterion pair catalyst is represented by the following structure:

[R] + [X] -

(VIII)

Wherein, the [R] + is carbocation, silicon cation, oxonium ion, sulfonium ion, azonium ion, chloride onium ion, bromium ion or iodonium ion, and the [X] - is Borate, aluminate, phosphate, sulfonate, sulfonimide, antimonate, or arsenate anions;

(19), in the cationic procatalyst, the neutral Lewis acid catalyst is a boron complex or an aluminum complex;

(20), in the cationic main catalyst, the protic acid (ester) type catalyst is sulfonic acid, sulfonic acid ester, sulfonimide, N-substituted sulfonimide, oxonium protonic acid, sulfur Onium protic acids or bisphosphonimide esters;

(21), the polymerization reaction is carried out in the presence of a co-catalyst, and the co-catalyst is one or more of a hydrogen bond donor, a hydrogen bond acceptor and a Lewis acid;

(22), the polymerization reaction is carried out in the presence of an initiator, and the initiator is a carboxylic acid and/or a thiocarboxylic acid;

(23), the polymerization temperature of the polymerization reaction is 0-120 degrees Celsius;

(24), the time of the polymerization reaction is 5-720 minutes.
The preparation method according to claim 2, characterized in that it satisfies one or more of the following conditions:

(1), the described compound shown in formula (I) is represented by any of the following structures:

(2), the molar volume ratio of the polymerized monomer to the organic solvent is 2.0mol/L-7.0mol/L;

(3), in the described organic solvent, the described linear hydrocarbon solvent is one or more in n-hexane, n-heptane and n-pentane;

(4), in the organic solvent, the halogenated hydrocarbon solvent is one or more of dichloromethane, chloroform, 1,2-dichloroethane and tetrachloroethane;

(5), in the described organic solvent, the described cyclic ether solvent is tetrahydrofuran and/or dioxane;

(6), in the organic solvent, the aromatic solvent is one or more of toluene, benzene and xylene;

(7), in the organic solvent, the halogenated aromatic hydrocarbon solvent is o-dichlorobenzene, o-difluorobenzene, o-dibromobenzene, chlorobenzene, fluorobenzene, bromobenzene and trichlorobenzene one or more;

(8), in the organic solvent, the amide solvent is N,N-dimethylformamide;

(9), the molar ratio of the polymerized monomer to the main catalyst is 100:1-1600:1;

(10), in the anion procatalyst, the phosphazene base is 1-tert-butyl-4,4,4-tris(dimethylamino)-2,2-bis[tris(dimethylamino) -Phosphoranylidene amino]-2λ 5 , 4λ 5 -bis(phosphoryl nitrogen-based compounds);

(11), in the anion procatalyst, the anion in the metal carboxylate and the organic carboxylate is independently an acetate anion;

(12), in the anion procatalyst, the cation in the metal carboxylate is lithium ion, sodium ion, potassium ion, rubidium ion or cesium ion;

(13), in the described anion procatalyst, the cation in the described organic carboxylate is shown by any of the following structures:

Wherein, R 1d , R 2d , R 3d , R 4d , R 5d and R 6d are independently hydrogen, alkyl or aryl, n2 is 0, 1, 2 or 3; y2 is 0, 1, 2 or 3;

(14), in the described anion procatalyst, the anion in the described thiocarboxylate is thioacetate anion;

(15), in the anion procatalyst, the cation in the thiocarboxylate is lithium ion, sodium ion, potassium ion, rubidium ion or cesium ion;

(16), in the cationic procatalyst, in the zwitterion pair catalyst, the carbocation is represented by the following structure:

Among them, R 1f , R 2f , and R 3f are independently phenyl, 2,4,6-trimethylphenyl, 2,6-dimethylphenyl, 2,3,5,6-tetramethyl Phenyl or 2,6-diisopropylphenyl;

(17), in the cationic procatalyst, in the zwitterion pair catalyst, the silicon cation is represented by the following structure:

Wherein, R 1g , R 2g and R 3g are 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;

(18), in the cationic procatalyst, in the zwitterion pair catalyst, the oxonium ion and the sulfonium ion are represented by the following structures respectively:

Wherein, R 1h , R 2h and R 3h are 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;

(19), in the cationic procatalyst, in the zwitterion-pair catalyst, the chloride onium ion and the bromide onium ion are represented by the following structures respectively:

Wherein, R 1i and R 2i are independently phenyl, 2,4,6-trimethylphenyl, 2,6-dimethylphenyl, 2,3,5,6-tetramethylphenyl or 2,6-diisopropylphenyl;

(20), in the cationic procatalyst, in the zwitterion pair catalyst, the iodonium ion is represented by the following structure:

Wherein, R 1j and R 2j are 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;

(21), in the cationic procatalyst, in the zwitterion-pair catalyst, the zwitterium ion is represented by the following structure:

(22) In the cationic procatalyst, in the zwitterion pair catalyst, the borate anion and the aluminate anion are represented by the following structure:

Wherein, X 1 , X 2 , X 3 and X 4 are independently fluorine, chlorine, phenyl, pentafluorophenyl, 3,5-bis(trifluoromethyl)phenyl, pentafluorophenoxy or 3 , 5-bis(trifluoromethyl)phenoxy;

(23) In the cationic procatalyst, in the zwitterion pair catalyst, the phosphate anion is represented by any of the following structures:

(24) In the cationic procatalyst, in the zwitterion pair catalyst, the sulfonic acid anion and the sulfonylimide anion are respectively represented by the following structures:

Wherein, X 1a and X 2a are independently fluorine, methyl, phenyl, trifluoromethyl, pentafluoroethyl, pentafluorophenyl or 3,5-bis(trifluoromethyl)phenyl;

(25) In the cationic main catalyst, in the zwitterion pair catalyst, the antimonate anion and the arsenic acid anion are represented by the following structures respectively:

Wherein, X 1c , X 2c , X 3c , X 4c , X 5c and X 6c are independently fluorine, chlorine or bromine;

(26), in the cationic procatalyst, in the neutral Lewis acid type catalyst, the boron complex is trialkylboron or triarylboron;

(27), in the cationic procatalyst, in the neutral Lewis acid type catalyst, the aluminum complex is trialkylaluminum, triarylaluminum, alkylbisphenolaluminum, alkyldichloride aluminum chloride or bisalkylaluminum chloride;

(28), in the cationic procatalyst, in the protic acid (ester) type catalyst, the sulfonic acid, sulfonate, sulfonimide and N-substituted sulfonimide respectively have the following structure Shown:

Wherein, X 1d and X 2d are independently fluorine, methyl, phenyl, trifluoromethyl, pentafluoroethyl, pentafluorophenyl or 3,5-bis(trifluoromethyl)phenyl; R xd Methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, cyclohexyl, trimethylsilyl, triethylsilyl, tripropyl Silyl, triisopropylsilyl, tributylsilyl or tert-butyldimethylsilyl;

(29), in the cationic main catalyst, in the protic acid (ester) type catalyst, the oxonium protic acid and the sulfonium protic acid are represented by the following structures respectively:

Wherein, R 1p and R 2p are 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] - is the aforementioned borate anion, aluminate anion, Phosphate, sulfonate, sulfonimide, antimonate, or arsenate anions;

(30), the molar ratio of the main catalyst to the co-catalyst is 1:1-1:10;

(31), in the cocatalyst, the hydrogen bond donor is one or more of alcohol, mercaptan, carboxylic acid, urea and thiourea;

(32), in the cocatalyst, the hydrogen bond acceptor is one or more of crown ether, polyethylene glycol dimethyl ether, cyclodextrin, calixarene and cryptate;

(33) In the cocatalyst, the Lewis acid is one or more of alkali metal compounds, alkaline earth metal compounds, zinc compounds, boron compounds, aluminum compounds and rare earth compounds;

(34), the molar ratio of the main catalyst to the initiator is 1:1-1:10;

(35), in the described initiator, the described carboxylic acid is acetic acid, benzoic acid or phenylpropionic acid;

(36), in the described initiator, the described thiocarboxylic acid is thioacetic acid or thiobenzoic acid;

(37), the polymerization temperature of described polymerization reaction is 40-80 degree Celsius;

(38), the time of the polymerization reaction is 30-240 minutes;

(39), in the anion procatalyst, the phosphazene base is tert-butylimino-tris(dimethylamino)phosphorane;

(40), in the anion procatalyst, the N-heterocyclic carbene organic base is 1,3-di-tert-butylimidazol-2-ylidene;

(41), in the anion procatalyst, the N-heterocyclic olefinic organic base is

(42), in the cationic procatalyst, in the protic acid (ester) type catalyst, the bisphosphonimide ester is represented by the following structure:

Wherein, R 1q is C 6-10 aryl, said C 6-10 aryl is optionally substituted by one or more of halogen, R 2q is methylsulfonyl, said methylsulfonyl is any is optionally substituted by one or more of halogen;

Preferably, R 1q is 3,5-dimethylphenyl, the C 6-10 aryl in said R 1q is substituted by one or more fluorines, and the methylsulfonyl group in said R 2q is substituted by one or more a fluorine substitution;

Further preferably, in the protic acid (ester) type catalyst, the bisphosphonimide ester is IDPi-CF 3 , and its structure is as follows:
The preparation method according to claim 1, wherein it satisfies one or more of the following conditions:

(1), in the described compound shown in formula (I),
for
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 form a C 3-10 cycloalkane together with the atoms connecting them R 51 , R 52 , R 53 and R 54 are independently H or C 1-10 alkyl;

(2), described organic solvent is aromatic hydrocarbon solvent and/or amide solvent;

(3), described anion main catalyst is phosphazene base and/or thiocarboxylate;

(4), the cationic main catalyst is [Ph 3 C][B(C 6 F 5 ) 4 ], Me 3 OBF 4 , [Et 3 O][B(C 6 F 5 ) 4 ], C 7 H 7 BF 4 , B(C 6 F 5 ) 3 , Al(C 6 F 5 ) 3 , IDPi-CF 3 , [Et 3 Si-H-SiEt 3 ][B(C 6 F 5 ) 4 ] and [ One or more of H(Et 2 O) 2 ][B(C 6 F 5 ) 4 ];

(5), the polymerization reaction is carried out in the presence of a co-catalyst, and the co-catalyst is a hydrogen bond donor and/or a hydrogen bond acceptor;

(6), the polymerization reaction is carried out in the presence of an initiator, and the initiator is a carboxylic acid.
The preparation method according to claim 4, characterized in that it satisfies one or more of the following conditions:

(1), the described compound shown in formula (I) is represented by any of the following structures:

(2), described organic solvent is toluene and/or N,N-dimethylformamide;

(3), the anionic main catalyst is 1-tert-butyl-4,4,4-tris(dimethylamino)-2,2-bis[tris(dimethylamino)-phosphoranylideneamino]- 2λ 5 , 4λ 5 -bis(phosphorus nitrogen compounds) and/or potassium thioacetate;

(4), described polymerization reaction is carried out in the presence of co-catalyst, and described co-catalyst is alcohol and/or crown ether, for example benzhydryl alcohol and/or 18 crown 6 ether;

(5), described polymerization reaction is carried out under the existence of initiator, and described initiator is benzoic acid.
The preparation method according to any one of claims 1 to 5, characterized in that it is any of the following schemes,

Scheme 1, the described polymerization monomer is
The main catalyst is [Ph 3 C][B(C 6 F 5 ) 4 ];

Scheme 2, described polymerization monomer is
The main catalyst is [Ph 3 C][B(C 6 F 5 ) 4 ];

Scheme 3, the described polymerization monomer is
The main catalyst is [Ph 3 C][B(C 6 F 5 ) 4 ];

Scheme 4, described polymerization monomer is
The main catalyst is [Ph 3 C][B(C 6 F 5 ) 4 ];

Scheme 5, the described polymerization monomer is
The main catalyst is [Ph 3 C][B(C 6 F 5 ) 4 ];

Scheme 6, the described polymerization monomer is
The main catalyst is [Ph 3 C][B(C 6 F 5 ) 4 ];

Scheme 7, the described polymerization monomer is
The main catalyst is [Ph 3 C][B(C 6 F 5 ) 4 ];

Scheme 8, the described polymerization monomer is
The main catalyst is [Ph 3 C][B(C 6 F 5 ) 4 ];

Scheme 9, the described polymerization monomer is
The main catalyst is [Ph 3 C][B(C 6 F 5 ) 4 ];

Scheme 10, described polymerization monomer is
The main catalyst is [Ph 3 C][B(C 6 F 5 ) 4 ];

Scheme 11, described polymerization monomer is
Described main catalyst is potassium thioacetate;

Scheme 12, the described polymerization monomer is
Described procatalyst is tBu -P4, and described cocatalyst is diphenylmethanol;

Scheme 13, the described polymerization monomer is
The main catalyst is tBu -P 4 , and the cocatalyst is diphenylmethanol;

Scheme 14, the described polymerization monomer is
Described main catalyst is potassium thioacetate, and described cocatalyst is 18 crown 6 ethers;

Scheme 15, the described polymerization monomer is
Described main catalyst is potassium thioacetate, and described cocatalyst is 18 crown 6 ethers;

Scheme 16, the described polymerization monomer is
The main catalyst is tBu - P4 , and the initiator is benzoic acid;

Scheme 17, the described polymerization monomer is
The main catalyst is [Ph 3 C][B(C 6 F 5 ) 4 ];

Scheme 18, the described polymerization monomer is
The main catalyst is [H(Et 2 O) 2 ][B(C 6 F 5 ) 4 ];

Scheme 19, the described polymerization monomer is
The main catalyst is B(C 6 F 5 ) 3 ;

Scheme 20, the described polymerization monomer is
Described main catalyst is potassium thioacetate;

Scheme 21, the described polymerized monomer is
Described main catalyst is potassium thioacetate;

Scheme 22, the described polymerized monomer is
The main catalyst is [Ph 3 C][B(C 6 F 5 ) 4 ];

Scheme 23, the described polymerized monomer is
Described main catalyst is TBD:

Scheme 24, the polymerized monomer is
The main catalyst is DBU:

Scheme 25, the described polymerized monomer is
Described main catalyst is It Bu:

Scheme 26, the polymerized monomer is
Described main catalyst is NHO:

Scheme 27, the described polymerized monomer is
The main catalyst is t Bu-P 1 :

Scheme 28, the polymerized monomer is
The main catalyst is [Et 3 Si-H-SiEt 3 ][B(C 6 F 5 ) 4 ];

Scheme 29, the polymerized monomer is
The main catalyst is Ph 3 CB(C 6 F 5 ) 4 /Et 3 SiH;

Scheme 30, the polymerized monomer is
The main catalyst is Me 3 OBF 4 ;

Scheme 31, the polymerized monomer is
The main catalyst is [Et 3 O][B(C 6 F 5 ) 4 ];

Scheme 32, the polymerized monomer is
The main catalyst is C 7 H 7 BF 4 ;

Scheme 33, the polymerized monomer is
The main catalyst is Al(C 6 F 5 ) 3 ;

Scheme 34, the polymerized monomer is
The main catalyst is IDPi-CF 3

Scheme 35, the polymerized monomer is
The main catalyst is [Et 3 O][B(C 6 F 5 ) 4 ];

Scheme 36, the polymerized monomer is
The main catalyst is [Et 3 O][B(C 6 F 5 ) 4 ];

Scheme 37, the polymerized monomer is
The main catalyst is [Et 3 O][B(C 6 F 5 ) 4 ];

Scheme 38, the polymerized monomer is
The main catalyst is [Et 3 O][B(C 6 F 5 ) 4 ];

Scheme 39, the polymerized monomer is
The main catalyst is [Et 3 O][B(C 6 F 5 ) 4 ];

Scheme 40, the polymerized monomer is
The main catalyst is [Et 3 O][B(C 6 F 5 ) 4 ];

Scheme 41, the polymerized monomer is
The main catalyst is [Et 3 O][B(C 6 F 5 ) 4 ];

Scheme 42, the polymerized monomer is
The main catalyst is

Scheme 43, the polymerized monomer is
The main catalyst is

Scheme 44, the polymerized monomer is
The main catalyst is [Et 3 O][B(C 6 F 5 ) 4 ]);

Scheme 45, the polymerized monomer is
The main catalyst is [Et 3 O][B(C 6 F 5 ) 4 ]).
A sulfur-containing polymer, characterized in that it is prepared according to the method described in any one of claims 1-6.
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,

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 The definition is as described in claim 1 or 2.
The sulfur-containing polymer according to claim 8, wherein it satisfies 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 5kg/mol;

(3), the molecular weight distribution of described sulfur-containing polymer is 1.0-3.0;

(4), the sulfur-containing polymer is a homopolymer or multi-polymer;

(5), the elongation at break of the sulfur-containing polymer is 638%-1451.30%;

(6), the yield stress of the sulfur-containing polymer is 9.05MPa;

(7), the fracture stress of the sulfur-containing polymer is 16.62-24.27MPa;

(8), the elastic recovery rate of described sulfur-containing polymer is 72.3%;

(9) The glass transition temperature T g of the sulfur-containing polymer is -57.0-59.5°C.
The sulfur-containing polymer according to claim 9, wherein it satisfies one or more of the following conditions:

(1), the degree of polymerization of the sulfur-containing polymer is 190-2450, more preferably 840-1600;

(2), the number average molecular weight of the sulfur-containing polymer is 3-500kg/mol, more preferably 20-250kg/mol, further preferably 80-250kg/mol;

(3), the molecular weight distribution of described 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 mole percentage of each structural unit is 5-90%.