CN115960355A

CN115960355A - Method for preparing sulfur-containing polymer based on isomerization-driven irreversible ring-opening polymerization

Info

Publication number: CN115960355A
Application number: CN202211243132.8A
Authority: CN
Inventors: 洪缪; 孙洋洋; 夏永亮; 袁鹏俊
Original assignee: Shanghai Institute of Organic Chemistry of CAS
Current assignee: Shanghai Institute of Organic Chemistry of CAS
Priority date: 2021-10-11
Filing date: 2022-10-11
Publication date: 2023-04-14
Also published as: WO2023061379A2; WO2023061379A3

Abstract

The invention discloses a method for preparing a sulfur-containing polymer based on isomerization-driven irreversible ring-opening polymerization. The method comprises the following steps: in an organic solvent, in the presence of a main catalyst, carrying out polymerization reaction on one or more than one polymerization monomer; wherein the main catalyst is an anion main catalyst or a cation main catalyst; the anion main catalyst is phosphazene base, guanidine organic base, amidine organic base, N-heterocyclic carbene organic base, N-heterocyclic olefin organic base, carboxylate and thiocarboxylate; the cation main catalyst is amphoteric ion pair catalyst, neutral Lewis acid catalyst or protonic acid (ester) catalyst; the polymeric monomer is a five-membered ring framework compound shown in formula I. The method provides convenience for industrial production of the environment-friendly sulfur-containing high polymer material. The synthesized sulfur-containing polymer has the advantages of high molecular weight, wide-range adjustable physical properties, excellent degradability and the like, and can be used as a catalystPlastic, rubber, elastomer, fiber, etc.

Description

Method for preparing sulfur-containing polymer based on isomerization-driven irreversible ring-opening polymerization

Technical Field

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

Background

The non-tension five-membered ring monomer is a very potential renewable monomer, is commonly present in natural products in the nature, and can also be produced on a large scale by taking starch, lignocellulose or carbon dioxide as raw materials. However, ring-opening polymerization (ROP) of non-strained five-membered ring monomers at room temperature conditions is generally thermodynamically forbidden, and such compounds are generally referred to in the literature and texts as "non-polymerizable" monomers because their non-strained five-membered rings do not provide sufficient ring tension to drive the ring-opening polymerization (ROP), while the thermodynamically stable five-membered ring lactones are susceptible to depolymerization during polymerization, since ring-opening polymerization is a typical thermodynamic equilibrium of polymerization/depolymerization. In 2016, hongmuir and Chen pioneered the development of a new strategy for non-strained five-membered ring lactone ring-opening polymerization (nat. Chem.2016,8, 42-49), i.e., breaking the polymerization-depolymerization balance by controlling the reaction temperature below the upper polymerization limit temperature and precipitating the polymer, but the extremely low polymerization temperature seriously hinders the applicability of industrial production.

In the disclosed polymerization reaction catalyzed by an anionic catalyst, after the five-membered ring thiocarbonyl lactone monomer is subjected to hydrogen extraction by the basic anionic catalyst, the five-membered ring thiocarbonyl lactone monomer can be nucleophilically attacked by a gamma-position methylene (methine) of the monomer to perform isomerization ring-opening polymerization, and also can be nucleophilically attacked by a thiocarbonyl of another monomer molecule to lose one molecule of hydrogen sulfide to perform ester condensation reaction to generate a dimerization product rather than a polymer (shown as below), and how to limit the latter ester condensation reaction is the key to efficient polymerization.

So far, a universal method for preparing sustainable polythioester materials with various properties by efficiently polymerizing non-tension five-membered ring monomers under mild conditions is still lacked.

Disclosure of Invention

The invention aims to overcome the defect that the existing non-tension five-membered ring monomer is difficult to be subjected to ring-opening polymerization under mild conditions, and provides a novel method for irreversible ring-opening polymerization. The preparation method of the invention provides convenience for industrial production of environment-friendly sulfur-containing high polymer materials. The synthesized sulfur-containing polymer has the advantages of high molecular weight, wide-range adjustable physical properties, excellent degradability and the like, and can be used as products such as plastics, rubber, elastomers, fibers and the like.

The invention provides a preparation method of a sulfur-containing polymer, which comprises the following steps: in an organic solvent, in the presence of a main catalyst, carrying out polymerization reaction on one or more than one polymerization monomer;

wherein the main catalyst is an anionic main catalyst or a cationic main catalyst; the anion main catalyst is one or more of phosphazene base, guanidine organic base, amidine organic base, N-heterocyclic carbene organic base, N-heterocyclic olefin organic base, carboxylate and thiocarboxylate; the cation main catalyst is one or more of zwitterion-pair catalyst, neutral Lewis acid catalyst and protonic acid (ester) catalyst;

the polymerized monomer is independently a compound shown as the formula (I):

wherein the content of the first and second substances,

is->

R ₁₁ 、R ₁₂ 、R ₁₃ 、R ₁₄ 、R ₂₁ 、R ₂₂ 、R ₂₃ 、R ₃₁ 、R ₃₂ 、R ₃₃ 、R ₄₁ 、R ₄₂ 、R ₄₃ 、R ₅₁ 、R ₅₂ 、R ₅₃ And R ₅₄ Independently H, halogen (e.g. fluorine, chlorine, bromine or iodine, again e.g. fluorine or chlorine), hydroxy, C _1-10 Alkyl (e.g. C) _1-8 Alkyl radicals such as, in turn, methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-nonyl), C _6-10 Aryl radicals (e.g. phenyl) or C _1-10 Alkenyl (e.g. C) _1-8 Alkenyl radicals, further e.g. C _1-4 Alkenyl, such as vinyl); said C _1-10 Alkyl is optionally substituted by halogen (e.g. fluorine, chlorine, bromine or iodine, further e.g. fluorine or chlorine), hydroxy and C _6-10 One or more substitutions in aryl (e.g., phenyl);

or, R ₁₂ And R ₁₃ 、R ₁₃ And R ₁₄ 、R ₂₂ And R ₂₃ 、R ₃₂ And R ₃₃ 、R ₄₂ And R ₄₁ Or R ₅₂ And R ₅₃ Together with the atoms linking them form C _3-10 Cycloalkyl (e.g. cyclopentyl, cyclohexyl or cycloheptyl), C _3-10 Cycloalkenyl (e.g. cyclohexenyl) or C _6-10 Aryl (e.g., phenyl);

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 polymerized monomer is one, the polymerized 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 Independently H, halogen (e.g. fluorine, chlorine, bromine or iodine, again e.g. fluorine or chlorine), hydroxy, C _1-10 Alkyl (e.g. C) _1-8 Alkyl, such as, in turn, methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-nonyl) or C _1-10 Alkenyl (e.g. C) _1-8 Alkenyl radicals, further e.g. C _1-4 Alkenyl, such as vinyl); said C _1-10 Alkyl is optionally substituted by halogen (e.g. fluorine, chlorine, bromine or iodine, further e.g. fluorine or chlorine), hydroxy and C _6-10 One or more of the aryl groups (e.g., phenyl) are substituted.

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

/>

in some embodiments of the present invention, the substrate is,

is->

Preferably, R ₁₁ 、R ₁₂ 、R ₁₃ And R ₁₄ Independently H, C _1-10 Alkyl or C _1-10 An alkenyl group; or, R ₁₃ And R ₁₄ Together with the atoms linking them form C _3-10 A cycloalkyl group;

further preferably, R ₁₁ 、R ₁₂ 、R ₁₃ And R ₁₄ Has the following definitions:

(1)R ₁₁ 、R ₁₂ and R ₁₃ Is H, R ₁₄ Is C _1-10 An alkyl group;

(2)R ₁₁ 、R ₁₂ and R ₁₄ Is H, R ₁₃ Is C _1-10 Alkyl or C _1-10 An alkenyl group;

(3)R ₁₂ 、R ₁₃ and R ₁₄ Is H, R ₁₁ Is C _1-10 An alkyl group;

(4)R ₁₃ and R ₁₄ Is H, R ₁₁ And R ₁₂ Independently is C _1-10 An alkyl group;

(5)R ₁₂ and R ₁₄ Is H, R ₁₁ And R ₁₃ Independently is C _1-10 An alkyl group;

(6)R ₁₁ and R ₁₂ Is H, R ₁₃ And R ₁₄ Together with the atom to which they are attached form C _3-10 A cycloalkyl group;

(7)R ₁₁ 、R ₁₂ 、R ₁₃ and R ₁₄ Is H;

in some embodiments of the present invention, the substrate is,

is->

Preferably, R ₁₂ And R ₁₃ Together with the atoms linking them form C _3-10 A cycloalkyl group;

further preferably, R ₁₁ And R ₁₄ Is H, R ₁₂ And R ₁₃ Together with the atoms linking them form C _3-10 A cycloalkyl group.

In some embodiments of the present invention, the substrate is,

is->

Preferably, R ₅₁ 、R ₅₂ 、R ₅₃ And R ₅₄ Independently of one another H, halogen, C _1-10 Alkyl radical, C _6-10 Aryl or C _1-10 An alkenyl group; said C _1-10 Alkyl optionally substituted by halogen, hydroxy and C _6-10 One or more of the aryl groups.

Further preferably, R ₅₁ Is halogen (e.g. fluorine), C _1-10 Alkyl (e.g. methyl, ethyl), C _6-10 Aryl radicals (e.g. phenyl) or C _1-10 Alkenyl (e.g., vinyl); said C _1-10 Alkyl optionally substituted with chloro, hydroxy or phenyl; r ₅₂ 、R ₅₃ And R ₅₄ Is H.

In some embodiments of the present invention, the substrate is,

is->

Preferably, R ₅₁ 、R ₅₂ 、R ₅₃ And R ₅₄ Independently is H or C _1-10 An alkyl group.

Further preferably, R ₅₁ Is C _1-10 Alkyl radical, R ₅₂ 、R ₅₃ And R ₅₄ Is H.

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

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

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

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

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

In some embodiments, the molar ratio of the polymerized monomer to the procatalyst may be from 20.

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

wherein R and R' are independently C ₁ -C ₄ Alkyl (e.g., methyl, ethyl, propyl, isopropyl, or tert-butyl); n1 is 0, 1,2 or3; y is 0, 1,2 or 3.

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

more preferably, the phosphazene base can also be tert-butylimino-tris (dimethylamino) phosphorane(s) (II) ^t Bu-P ₁ ) The structure is as follows:

in some embodiments, the guanidine organic base in the anionic procatalyst can be a guanidine organic base as is conventional in the art. Preferably, the guanidine organic base is 1,5, 7-triazabicyclo (4.4.0) dec-5-ene (TBD) and/or 7-methyl-1, 5, 7-triazabicyclo [4.4.0] dec-5-ene (MTBD), and the structure is shown as follows:

in some embodiments, the anionic procatalyst, the amidine organic base may be one conventional in the art. Preferably, the amidine organic base is 1, 8-diazabicyclo [5.4.0] undec-7-ene (DBU), the structure of which is shown below:

in some embodiments, the anionic procatalyst, the N-heterocyclic carbene organic base may be an N-heterocyclic carbene organic base as is conventional in the art. Preferably, the N-heterocyclic carbene organic base is represented by the following structure:

wherein R is _1a And R _2a Independently hydrogen, alkyl (e.g. C) _1-4 Alkyl) or aryl (e.g. C) _6-10 Aryl); r is _3a And R _4a Independently is alkyl (e.g. C) _1-4 Alkyl) or aryl (e.g. C) _6-10 Aryl).

More preferably, the N-heterocyclic carbene organic base is 1, 3-di-tert-butyl imidazole-2-subunit (I) ^t Bu), the structure of which is shown below:

in some embodiments, the anionic procatalyst, the N-heterocyclic olefin organic base may be an N-heterocyclic olefin organic base conventional in the art. Preferably, the N-heterocyclic olefinic organic base is represented by the following structure:

wherein R is _1b And R _2b Independently hydrogen, alkyl (e.g. C) _1-4 Alkyl) or aryl (e.g. C) _6-10 Aryl groups); r is _3b And R _4b Independently is alkyl (e.g. C) _1-4 Alkyl) or aryl (e.g. C) _6-10 Aryl groups); r is _5b Is hydrogen or alkyl (e.g. C) _1-4 Alkyl groups).

More preferably, the N-heterocyclic olefinic organic base is 1,3, 4-trimethyl-2- (isopropenylidene) -imidazole (NHO), which has the following structure:

in some embodiments, the carboxylate salt of the anionic procatalyst can be a metal carboxylate salt or an organic carboxylate salt.

Preferably, the anions of the metal carboxylate and the organic carboxylate are independently represented by the following structures:

wherein R is _1c Is alkyl (e.g. C) _1-4 Alkyl radicals, such as methyl, or aryl radicals (e.g. C) _6-10 Aryl).

More preferably, the anions in the metal carboxylate and the organic carboxylate are independently acetate anions.

Preferably, the cation in the metal carboxylate is an alkali metal (e.g., lithium, sodium, potassium, rubidium, or cesium, and further, for example, potassium) cation.

Preferably, the cation in the organic carboxylate is a quaternary ammonium cation, an imidazolium cation, a phosphazenium cation, a bis (triphenylphosphine) ammonium cation, or an amidinium cation.

More preferably, the cation in the organic carboxylate salt is represented by any one of the following structures:

wherein R is _1d 、R _2d 、R _3d 、R _4d 、R _5d And R _6d Independently hydrogen, alkyl or aryl, n2 is 0, 1,2 or 3; y2 is 0, 1,2 or 3.

In some embodiments, the anionic procatalyst, the thiocarboxylate salt can be a metal thiocarboxylate salt.

Preferably, the anion in the thiocarboxylate salt is represented by the structure:

wherein R is _1e Is alkyl (e.g. C) _1-4 Alkyl radicals, further e.g. methyl) or aryl radicals (e.g. C) _6-10 Aryl). Preferably, the anion is a thioacetate anion.

Preferably, the cation in the thiocarboxylate salt is an alkali metal (e.g., lithium, sodium, potassium, rubidium, or cesium, and further, for example, potassium) cation.

More preferably, the thiocarboxylate salt is potassium thioacetate.

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

In some embodiments, the cationic procatalyst, the zwitterionic geminate catalyst can be a zwitterionic geminate catalyst as is conventional in the art.

Preferably, the zwitterionic pair catalyst is represented by the following structure:

[R] ⁺ [X] ^-

(VIII)

wherein, the [ R ] is] ⁺ Is a carbenium ion, a silanium ion, an oxonium ion, a sulfonium ion, a phosphonium ion, a chloronium ion, a bromonium ion or an iodonium ion, [ X ] is]-is a borate anion, an aluminate anion, a phosphate anion, a sulfonate anion, a sulfonimide anion, an antimonate anion or an arsenate anion.

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

/>

wherein R is ^1f 、R ^2f 、R ^3f Each independently is phenyl, 2,4, 6-trimethylbenzeneA 2, 6-dimethylphenyl group, a 2,3,5, 6-tetramethylphenyl group or a 2, 6-diisopropylphenyl group.

More preferably, the positive silicon ion is represented by the following structure:

wherein R is ^1g 、R ^2g And R ^3g Each 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 positive silicon ion 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 is ^1h 、R ^2h And R ^3h Each 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 chloride ion and the bromide ion are represented by the following structures:

wherein R is ¹ⁱ And R ²ⁱ Each independently is 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 is ^1j And R ^2j Each independently a methyl group, an ethyl group, a propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a tert-butyl group, a phenyl group, a 2,4, 6-trimethylphenyl group, a 2, 6-dimethylphenyl group, a 2,3,5, 6-tetramethylphenyl group or a 2, 6-diisopropylphenyl group.

More preferably, said phosphonium ion is represented by the following structure:

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

wherein, X ¹ 、X ² 、X ³ And X ⁴ Each 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 one of the following structures:

more preferably, said sulfonic acid anion and said sulfonimide anion are represented by the following structures, respectively:

wherein, X ^1a And X ^2a Each independently being fluoro, methyl, phenyl, trifluoromethyl, pentafluoroethyl, pentafluorophenyl or 3, 5-bis (trifluoromethyl) phenyl.

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

wherein X ^1c 、X ^2c 、X ^3c 、X ^4c 、X ^5c And X ^6c Each independently fluorine, chlorine or bromine.

Further preferably, [ R ] is] ⁺ Is a carbocation, said [ X ] being] ^- Being a borate anion, e.g. the zwitterion-pair type catalyst is [ Ph ₃ C][B(C ₆ F ₅ ) ₄ ]。

Further preferably, [ R ] mentioned] ⁺ Is an oxonium ion, [ X ] of] ^- Is a borate anion, e.g. the zwitterion-pair catalyst is [ Et ] ₃ O][B(C ₆ F ₅ ) ₄ ]、Me ₃ OBF ₄ 。

Further preferably, [ R ] mentioned] ⁺ Is a phosphonium ion, [ X ] of] ^- Being borate anions, e.g. said zwitterionic geminate catalyst being C ₇ H ₇ BF ₄ 。

Further preferably, [ R ] mentioned] ⁺ Is silicon cation, [ X ] described] ^- Is a borate anion, e.g. the zwitterion-pair catalyst is [ Et ] ₃ Si-H-SiEt ₃ ][B(C ₆ F ₅ ) ₄ ]。

In some embodiments, the cationic procatalyst, the neutral lewis acid-type catalyst may be one conventional in the art.

Preferably, the neutral lewis acid-type catalyst is a boron complex or an aluminum complex.

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

More preferably, the aluminum complex is trialkylaluminum, triarylaluminum, alkyl bisphenol aluminum, alkyl aluminum dichloride or dialkyl aluminum chloride.

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

wherein R is ^1k 、R ^2k And R ^3k Each independently is methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, cyclohexyl or n-octyl.

Further preferably, the triarylboron and the triarylaluminum are each represented by the following structure:

wherein R is ¹ⁿ 、R ²ⁿ 、R ³ⁿ 、R ⁴ⁿ And R ⁵ⁿ Each independently hydrogen, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, cyclohexyl, fluoro, chloro, trifluoromethyl, pentafluorophenyl or trimethylsilyl.

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

wherein R is ^1m 、R ^2m 、R ^3m 、R ^4m 、R ^5m 、R ^6m 、R ^7m 、R ^8m 、R ^9m 、R ^10m And R ^11m Each independently hydrogen, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, cyclohexyl, fluoro, chloro, trifluoromethyl, pentafluorophenyl or trimethylsilyl.

Further preferably, said alkyl aluminum dichloride and said dialkyl aluminum chloride are represented by the following structures, respectively:

wherein R is ^1o And R ^2o Each independently is methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, cyclohexyl or n-octyl.

Further preferably, the neutral Lewis acid type catalyst is a boron complex (e.g., triarylboron, such as B (C) ₆ F ₅ ) ₃ )。

Still more preferably, said neutral lewis acid type catalyst is a triarylboron based compound, preferably a fluorinated triarylboron based compound; for example B (C) ₆ F ₅ ) ₃ 。

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

Still more preferably, the neutral lewis acid type catalyst is a triarylaluminum-based compound, preferably a fluorinated triarylaluminum-based compound; for example Al (C) ₆ F ₅ ) ₃ 。

In some embodiments, the cationic procatalyst, the protonic acid (ester) type catalyst may be one conventional in the art.

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

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

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

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

wherein X ^1d And X ^2d Each independently is fluoro, methyl, phenyl, trifluoromethyl, pentafluoroethyl, pentafluorophenyl or 3, 5-bis (trifluoromethyl) phenyl; r ^xd Is methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, cyclohexyl, trimethylsilyl, triethylsilyl, tripropylsilyl, triisopropylsilyl, tributylsilyl or tert-butyldimethylsilyl.

Still more preferably, the oxonium protonic acid and the sulfonium protonic acid are represented by the following structures:

wherein R is ^1p And R ^2p Each independently is methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, phenyl, 2,4, 6-trimethylphenyl, 2, 6-dimethylphenyl, 2,3,5, 6-tetramethylphenyl or 2, 6-diisopropylphenyl; [ X ]] ^– The aforementioned borate anion, aluminate anion, phosphate anion, sulfonate anion, sulfonimide anion, antimonate anion or arsenate anion.

Still more preferably, the bis-phosphonimide esters are represented by the following structure:

wherein R is ^1q Is C _6-10 Aryl (e.g. 3, 5-dimethylphenyl), said C _6-10 Aryl is optionally substituted with one or more of halo (e.g., fluoro); r is ^2q Is methylsulfonyl, optionally substituted with one or more of halo (e.g., fluoro).

Even more preferably, the protonic acid (ester) -type catalyst is a bis (phosphinimide) ester, such as IDPi-CF ₃ The structure is as follows:

still more preferably, the protonic 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 [ H (Et) ₂ O) ₂ ][B(C ₆ F ₅ ) ₄ ]One or more of (a).

In some preferred embodiments, the cationic procatalyst is [ Ph ₃ C][B(C ₆ F ₅ ) ₄ ]、B(C ₆ F ₅ ) ₃ And [ H (Et) ₂ O) ₂ ][B(C ₆ F ₅ ) ₄ ]One ofOne or more of them.

In some embodiments, the polymerization reaction may also be carried out in the presence of a co-catalyst that 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 procatalyst to the cocatalyst may be from 1.

In some preferred embodiments, the hydrogen bond donor in the co-catalyst may be a hydrogen bond donor conventional in the art.

Preferably, the hydrogen bond donor is one or more of an alcohol, a thiol, a carboxylic acid, a urea and a thiourea, such as one or more of an alcohol, a thiol and a thiourea, and further such as one or more of benzhydrol, benzyl alcohol, 1-octanethiol and N, N' -diisopropylthiourea. The alcohol is preferably benzhydryl alcohol and/or benzyl alcohol. The thiol is preferably 1-octanethiol. The carboxylic acid is preferably phenylacetic acid. The urea is preferably diethyl urea. 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, the hydrogen bond acceptor in the co-catalyst may be a hydrogen bond acceptor conventional in the art.

Preferably, the hydrogen bond acceptor is one or more of crown ether, polyethylene glycol dimethyl ether, cyclodextrin, calixarene and azetidine ether, such as one or more of crown ether and polyethylene glycol dimethyl ether, and further such as 18 crown 6 ether. The cyclodextrin is preferably methyl beta-cyclodextrin. The calixarene is preferably O (1), O (2), O (3), O (4) -tetramethyl-p-tert-butyl calixarene. The polyethylene glycol dimethyl ether is preferably tetraethylene glycol dimethyl ether. The N-heterocyclic cryptand ether is preferably 4,7,13,16, 21-pentaoxa-1, 10-diazabicyclo [8.8.5] trioxane.

In some preferred embodiments, the lewis acid of the co-catalyst may be a lewis acid conventional in the art.

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

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

In some preferred embodiments, the molar ratio of the procatalyst to the initiator may be from 1.

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

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

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

In some embodiments, the progress of the polymerization reaction can be monitored by means conventional in the art (e.g., by ¹ H NMR monitors the hydrogen integral ratio of the polymer formed to the remaining monomer to monitor the conversion), the polymerization time is preferably 5 to 720 minutes, more preferably 30 to 240 minutes, for example 30 minutes, 120 minutes, 180 minutes or 240 minutes.

In some preferred embodiments, the preparation method comprises the following steps: in an organic solvent, in the presence of a main catalyst, carrying out polymerization reaction on the polymerization monomer; the molar ratio of the polymerization monomer to the main catalyst is (100).

In some preferred embodiments, the preparation method comprises the steps of: in an organic solvent, carrying out polymerization reaction on the polymerized monomer in the presence of a main catalyst and a cocatalyst; the molar ratio of the polymerized monomer to the main catalyst is 100-1600, and the molar ratio of the main catalyst to the cocatalyst is 1-1.

In some preferred embodiments, the preparation method comprises the following steps: in an organic solvent, in the presence of a main catalyst and an initiator, carrying out polymerization reaction on the polymerized monomer; the molar ratio of the polymerization monomer to the main catalyst is from 100 to 1600.

In some preferred embodiments, the polymerization reaction comprises the steps of: and (2) in an organic solvent, carrying out polymerization reaction on the polymerized monomer in the presence of a main catalyst, or the main catalyst and a cocatalyst, or the main catalyst and an initiator.

In some preferred embodiments, the polymerization reaction comprises the steps of: adding the polymerization monomer into a reaction vessel, connecting the reaction vessel to a vacuum line protected by inert gas, adding an organic solvent, a main catalyst, or the main catalyst and a cocatalyst, or the main catalyst and an initiator, reacting at room temperature, or heating to a polymerization temperature, and finishing the polymerization reaction.

In some preferred embodiments, the polymerization reaction comprises the steps of: and adding the polymerization monomer into a reaction bottle in a glove box, removing the glove box, connecting the reaction bottle to a vacuum line protected by inert gas, heating to a corresponding polymerization temperature, adding a solution of a main catalyst or an organic solvent of the main catalyst and a cocatalyst into the solution, and finishing the polymerization reaction.

In some embodiments, the polymerization starting materials are the polymerized monomer, the cationic procatalyst, and the solvent.

In some embodiments, the polymerization starting materials are the polymerized monomer, the anionic procatalyst, and the solvent.

In some embodiments, the polymerization reaction is carried out using the polymerized monomers, the anionic procatalyst, the solvent and the cocatalyst.

In some embodiments, the polymerization starting materials are the polymerized monomer, the anionic procatalyst, the solvent, and the initiator.

In some embodiments, the polymerization reaction is carried out using the polymerized monomers, the anionic procatalyst, the solvent, the initiator and the cocatalyst.

In some preferred embodiments, after the polymerization reaction is finished, the method may further comprise a post-treatment, and the post-treatment may comprise the following steps: mixing the reaction solution with one or more of water solution, allyl chloride solution and benzoic acid solution, mixing with ethanol, centrifuging or filtering, and drying. The water 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; the allyl chloride solution is preferably a toluene solution of allyl chloride, and the volume ratio of the toluene solution of the allyl chloride is preferably 1/2; the benzoic acid is preferably a chloroform solution of benzoic acid, and the mass-to-volume ratio of the chloroform solution of benzoic acid is preferably 10mg/mL. The addition of water in tetrahydrofuran, allyl chloride in toluene and benzoic acid in chloroform was done to terminate the propagation of the polymeric chain. Mixing with ethanol is to settle the polymer and precipitate it for fixation. Said filtration or centrifugation preferably followed by a washing step, said washed solvent preferably being ethanol. The number of washing is preferably 2 to 5 (e.g., 3). The drying is preferably vacuum drying. The drying temperature is preferably 25-60 ℃. The drying time is preferably 20 to 100 hours, for example 24 hours.

In some preferred embodiments, the polymerizable monomer is

The procatalyst is a cationic procatalyst (e.g., a zwitterionic pair catalyst, such as [ Ph ] ₃ C][B(C ₆ F ₅ ) ₄ ])。

In some preferred embodiments, the polymerizable monomer is

In some preferred embodiments, the polymerizable monomer is

The procatalyst is a cationic procatalyst (e.g., a zwitterionic pair-type catalyst, again, e.g., [ Ph ] ₃ C][B(C ₆ F ₅ ) ₄ ])。

In some preferred embodiments, the polymerizable monomer is

The procatalyst is a cationic procatalyst (e.g., a zwitterionic pair-type catalyst, again, e.g., [ Ph ] ₃ C][B(C ₆ F ₅ ) ₄ ])。/>

In some preferred embodiments, the polymerizable monomer is

In some preferred embodiments, the polymerizable monomer is

The masterThe catalyst is a cationic procatalyst (e.g., a zwitterionic pair catalyst, e.g., [ Ph ] ₃ C][B(C ₆ F ₅ ) ₄ ])。

In some preferred embodiments, the polymerizable monomer is

In some preferred embodiments, the polymerizable monomer is

In some preferred embodiments, the polymerizable monomer is

In some preferred embodiments, the polymerizable monomer is

In some preferred embodiments, the polymerizable monomer is

The procatalyst is an anionic procatalyst (e.g., a thiocarboxylate salt, such as potassium thioacetate).

In some casesIn a preferred embodiment, the polymerizable monomer is

The procatalyst is an anionic procatalyst (e.g., a phosphazene base, as well as, for example, a phosphazene base) ^t Bu-P ₄ The co-catalyst is a hydrogen bond donor (e.g., an alcohol, such as benzhydrol).

In some preferred embodiments, the polymerizable monomer is

The procatalyst is an anionic procatalyst (e.g., a phosphazene base, as well as, for example, a phosphazene base) ^t Bu-P ₄ ) The co-catalyst is a hydrogen bond donor (e.g., an alcohol, such as benzhydrol).

In some preferred embodiments, the polymerizable monomer is

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

In some preferred embodiments, the polymerizable monomer is

The procatalyst is an anionic procatalyst (e.g., a thiocarboxylate salt, such as potassium thioacetate, for example) and the cocatalyst is a hydrogen bond acceptor (e.g., a crown ether, such as 18 crown 6 ether, for example).

In some preferred embodiments, the polymerizable monomer is

The procatalyst is an anionic procatalyst (e.g., a phosphazene base, as well as ^t Bu-P ₄ ) The initiator is a carboxylic acid (e.g., benzoic acid).

In some preferred embodiments, the polymerizable monomer is

In some preferred embodiments, the polymerizable monomer is

The procatalyst is a cationic procatalyst (e.g., a neutral Lewis acid type catalyst, such as B (C) ₆ F ₅ ) ₃ )。

In some preferred embodiments, the polymerizable monomer is

The procatalyst is a cationic procatalyst (e.g., a protonic acid (ester) type catalyst, such as an oxonium protonic acid, such as [ H (Et) or ₂ O) ₂ ][B(C ₆ F ₅ ) ₄ ])。

In some preferred embodiments, the polymerizable monomer is

In some preferred embodiments, the polymerizable monomer is

In some preferred embodiments, the polymerizable monomer is

In some preferred embodiments, the polymerizable monomer is

The main catalyst is an anionic main catalyst (such as guanidine organic base catalyst, such as TBD: (Beckmann-Schwerk): (Beckmann-Straussler & Schwerk))>

) The initiator is a carboxylic acid (e.g., benzoic acid).

In some preferred embodiments, the polymerizable monomer is

The procatalyst is an anionic procatalyst (e.g., amidine based organo-base catalyst, such as DBU: device for selecting or keeping>

) The initiator is a thiocarboxylic acid (e.g., thiobenzoic acid).

In some preferred embodiments, the polymerizable monomer is

The procatalyst is an anionic procatalyst (e.g., an N-heterocyclic carbene organic base catalyst, e.g., I) ^t Bu:/>

)。

In some preferred embodiments, the polymerizable monomer is

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

)。

In some preferred embodiments, the polymerizable monomer is

The procatalyst is an anionic procatalyst (e.g., a phosphazene base catalyst, as well as ^t Bu-P ₁ :/>

)。

In some preferred embodiments, the polymerizable monomer is

The procatalyst is a cationic procatalyst (e.g., a zwitterionic gemini catalyst, such as [ Et ] ₃ Si-H-SiEt ₃ ][B(C ₆ F ₅ ) ₄ ]。

In some preferred embodiments, the polymerizable monomer is

The procatalyst is a cationic procatalyst (e.g., a zwitterionic pair catalyst, e.g., ph ₃ CB(C ₆ F ₅ ) ₄ /Et ₃ SiH)。

In some preferred embodiments, the polymerizable monomer is

The procatalyst is a cationic procatalyst (e.g., a zwitterionic gemini catalyst, such as Me) ₃ OBF ₄ )。

In some preferred embodiments, the polymerizable monomer is

The procatalyst is a cationic procatalyst (e.g., a zwitterionic gemini catalyst, such as [ Et ] ₃ O][B(C ₆ F ₅ ) ₄ ])。

In some preferred embodiments, the polymerizable monomer is

The procatalyst is a cationic procatalyst (e.g., a zwitterionic gemini catalyst, such as C) ₇ H ₇ BF ₄ )。

In some preferred embodiments, the polymerizable monomer is

The procatalyst is a cationic procatalyst (e.g., a neutral Lewis acid type catalyst, such as Al (C) ₆ F ₅ ) ₃ )。

In some preferred embodiments, the polymerizable monomer is

The procatalyst is a cationic procatalyst (e.g., a protonic acid (ester) type catalyst, such as IDPi-CF ₃ />

)。

In some preferred embodiments, the polymerizable monomer is

In some preferred embodiments, the polymerizable monomer is

In some preferred embodiments, the polymerizable monomer is

The procatalyst is a cationic procatalyst (e.g., a zwitterionic gemini catalyst, such as [ Et ] ₃ O][B(C ₆ F ₅ ) ₄ ])。/>

In some preferred embodiments, the polymerizable monomer is

In some preferred embodiments, the polymerizable monomer is

In some preferred embodiments, the polymerizable monomer is

In some preferred embodiments, the polymerizable monomer is

In some preferred embodiments, the polymerizable monomer is

In some preferred embodiments, the polymerizable monomer is

In some preferred embodiments, the polymerizable monomer is

) The cocatalyst is benzyl alcohol.

In some preferred embodiments, the polymerizable monomer is

The cocatalyst is benzyl alcohol and 1- [3, 5-bis (trifluoromethyl) phenyl group]-3-cyclohexylthiourea).

In some preferred embodiments, the polymerizable monomer is

In some preferred embodiments, theThe polymerized monomer is

The present invention also provides a sulfur-containing polymer prepared according to the method for preparing a sulfur-containing polymer described herein.

The 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 polymerization degree of the sulfur-containing polymer is greater than or equal to 50, and each group is defined as any one of the embodiments of the 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 from 50 to 4900, preferably from 190 to 2450, and more preferably from 840 to 1600.

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

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

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

Preferably, the multipolymer is a random copolymer or a block copolymer.

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

In some embodiments, the sulfur-containing polymer has a glass transition temperature T _g Is-57.0 to 59.5 ℃.

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

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

In some embodiments, the sulfur-containing polymer has a stress at break of 16.62 to 24.27MPa.

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

In the present invention, "° c" means degrees celsius, unless otherwise specified; "h" means hours; "min" means minutes.

The anion of boric acid: according to the nomenclature of boron-containing compounds, "boron-containing anions" are indicated by borate "(" nomenclature of inorganic chemistry ", 1982, p.2194), the term" borate anion "in this context means the anion of a (pentafluorophenyl) borate [ B (C) ₆ F ₅ ) ₄ ] ^- And the like.

The above preferred conditions may be combined arbitrarily to obtain preferred embodiments of the present invention without departing from the general knowledge in the art.

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

The positive progress effects of the invention are as follows:

the preparation method of the invention uses isomerization as a thermodynamic driving force, does not use the traditional ring tension, is not limited by the upper limit temperature of polymerization, and can promote a series of non-tension five-membered ring monomers (including five-membered ring thiocarbonyl lactone and five-membered ring thiocarbonyl carbonate) to carry out irreversible ring opening polymerization at room temperature to high temperature at the temperature of 25-120 ℃. As the ring opening process is accompanied by the synergistic isomerization reaction, the generated sulfur-containing polymer can not be depolymerized into the initial monomer, thereby promoting the polymerization reaction to be carried out forward until the initial monomer is completely consumed, showing irreversible ring opening polymerization and realizing the high-efficiency quantitative monomer conversion. The invention can inhibit the occurrence of the back-biting side reaction, successfully control the content of the back-biting by-products to be less than 1 percent, and the yield of the sulfur-containing polymer can reach 99 percent at most.

The polythioester prepared by the invention has the number average molecular weight of 3.2 kg/mol-431.1 kg/mol and the molecular weight distribution index of 1.01-2.05. The number average molecular weight linearly increases along with the ratio of the monomer to the catalyst, and the polythioester provided by the invention has good molecular weight control performance and glass transition temperature T _g Approximately in the range of-57.0 to 59.5 deg.c. The polythioester prepared by the invention has great adjustability in performance and can meet different use scenes. For example, the poly- (S) - (gamma-thioglycollate) prepared by the invention has the elongation at break of 638%, the yield stress of 9.05MPa and the breaking stress of 24.27MPa, is a strong and tough polymer material, and has various indexes superior to those of low-density polyethylene (the elongation at break is 430% and the breaking stress is 10.6 MPa) and isotactic polypropylene (the elongation at break is 420% and the breaking stress is 26.0 MPa) in a mechanical tensile test, and is close to the tensile properties of high-density polypropylene (the elongation at break is 420% and the breaking stress is 26.0 MPa). The breaking elongation of the ternary random copolymer prepared by copolymerization is 1451.30%, and the breaking stress is 16.62MPa; the elastic recovery rate is 72.3%, and the elastic polymer material is a strong and tough elastomer polymer material. All indexes of the mechanical tensile test are superior to those of commercial ethylene propylene rubber (the elongation at break is 275.0 percent, and the stress at break is 5.70 MPa).

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

Drawings

FIG. 1 is a drawing showing the preparation of poly (. Gamma. -thioglycollate) obtained in example 2 ¹ H NMR spectrum.

FIG. 2 is a photograph of the poly (. Gamma. -thioglycollate) obtained in example 2 ¹³ C NMR spectrum.

FIG. 3 is a drawing showing the preparation of poly (. Gamma. -thiocaprolactone) obtained in example 3 ¹ H NMR spectrum.

FIG. 4 is the poly (. Gamma. -thiohexane) obtained in example 3Of lactones) ¹³ C NMR spectrum.

FIG. 5 shows the preparation of poly (. Gamma. -thioheptalactone) obtained in example 4 ¹ H NMR spectrum.

FIG. 6 shows the poly (. Gamma. -thio-heptolactone) obtained in example 4 ¹³ C NMR spectrum.

FIG. 7 shows the poly (. Gamma. -thio-octanolactone) obtained in example 5 ¹ H NMR spectrum.

FIG. 8 is a photograph of the poly (. Gamma. -thio-octalactone) obtained in example 5 ¹³ C NMR spectrum.

FIG. 9 is a photograph of the poly (. Gamma. -thiononalactone) obtained in example 6 ¹ H NMR spectrum.

FIG. 10 is a photograph of the poly (. Gamma. -thiononalactone) obtained in example 6 ¹³ C NMR spectrum.

FIG. 11 is a photograph of poly (. Gamma. -thio-decalactone) obtained in example 7 ¹ H NMR spectrum.

FIG. 12 is a photograph of the poly (. Gamma. -thio-decalactone) obtained in example 7 ¹³ C NMR spectrum.

FIG. 13 is a photograph of the poly (. Gamma. -thiaundecanolide) obtained in example 8 ¹ H NMR spectrum.

FIG. 14 is a photograph of the poly (. Gamma. -thiaundecanolide) obtained in example 8 ¹³ C NMR spectrum.

FIG. 15 is a photograph of the poly (. Gamma. -thiododecalactone) obtained in example 9 ¹ H NMR spectrum.

FIG. 16 is a photograph of the poly (. Gamma. -thiododecalactone) obtained in example 9 ¹³ C NMR spectrum.

FIG. 17 is a photograph of poly (. Gamma. -methyl-. Gamma. -thio-decalactone) obtained in example 10 ¹ H NMR spectrum.

FIG. 18 is a photograph of poly (. Gamma. -methyl-. Gamma. -thio-decalactone) obtained in example 10 ¹³ C NMR spectrum.

FIG. 19 is a photograph of the poly (. Beta. -methyl-. Gamma. -thio-octanolactone) obtained in example 11 ¹ H NMR spectrum.

FIG. 20 is a photograph of the poly (. Beta. -methyl-. Gamma. -thio-octanolactone) obtained in example 11 ¹³ C NMR spectrum.

FIG. 21 is a photograph of poly (. Alpha. -methylgamma. -thiobutyrolactone) obtained in example 12 ¹ H NMR spectrum.

FIG. 22 shows poly (. Alpha. -methyl-. Gamma. -thiobutyrolactone) obtained in example 12 ¹³ C NMR spectrum.

FIG. 23 is a photograph of poly (. Beta. -methyly-. Gamma. -thiobutyrolactone) obtained in example 13 ¹ H NMR spectrum.

FIG. 24 shows the poly (. Beta. -methyl-. Gamma. -thiobutyrolactone) obtained in example 13 ¹³ C NMR spectrum.

FIG. 25 shows a random copolymer obtained in example 14 ¹ H NMR spectrum.

FIG. 26 is a photograph of poly (cis-hexahydroisobenzothiophen-1-one) obtained in example 15 ¹ H NMR spectrum.

FIG. 27 is a photograph of poly (cis-hexahydroisobenzothiophen-1-one) obtained in example 15 ¹³ C NMR spectrum.

FIG. 28 shows a block copolymer obtained in example 21 ¹ H NMR spectrum.

FIG. 29 is a graph showing poly (propylene monothiocarbonate) s obtained in example 22 ¹ H NMR spectrum.

FIG. 30 shows poly (propylene monothiocarbonate) s obtained in example 22 ¹³ C NMR spectrum.

FIG. 31 shows M of poly (. Gamma. -thioglutaryl lactone) _n Linear plot with monomer/catalyst ratio.

FIG. 32 is a TGA curve of poly (γ -thioglycollate) obtained from example 2.

FIG. 33 is a DSC curve of poly (γ -thiacaprolactone) (abbreviation: PTGCL), poly (γ -thiapimelactone) (abbreviation: PTGHL), poly (γ -thiaoctanolide) (abbreviation: PTGOL), poly (γ -thianonalactone) (abbreviation: PTGNL), poly (γ -thiadecalactone) (abbreviation: PTGDL), poly (γ -thiaundecanolactone) (abbreviation: PTGUDL), poly (γ -thiadodecalactone) (abbreviation: PTGDDL), and poly (γ -methyl- γ -thiadecanolactone) (abbreviation: PTGMDL) obtained in examples 3-10.

FIG. 34 is a DSC curve of poly (. Gamma. -thiogalactone) (abbreviation: PTGVL) obtained in example 2, DSC curves of poly (. Alpha. -methyl-. Gamma. -thiobutyrolactone) (abbreviation: P. Alpha. -MeTBL) and poly (. Beta. -methyl-. Gamma. -thiobutyrolactone) (abbreviation: P. Beta. -MeTBL) obtained in examples 12 to 13, DSC curves of poly (. Beta. -methyl-. Gamma. -thiooctanolide) (abbreviation: PTWL) obtained in example 11 and poly (cis-hexahydroisobenzofuran-1-one) (abbreviation: P3,4-S6 TBL) obtained in example 15.

FIG. 35 is a graph showing the catalyzed degradation of poly (. Gamma. -thiobutyl) ester obtained in example 2 by 1,5, 7-triazabicyclo (4.4.0) dec-5-ene.

FIG. 36 shows the preparation of gamma-thiocarbonylvalerolactone obtained in example 1 ¹ H NMR spectrum.

FIG. 37 is a drawing showing the preparation of poly- (S) -4-methyl-1, 3-dioxolan-2-thione obtained in example 36 ¹ H NMR spectrum.

FIG. 38 shows the preparation of poly- (S) -4-methyl-1, 3-dioxolane-2-thione obtained in example 36 ¹³ C NMR spectrum.

FIG. 39 shows the preparation of poly- (rac) -4-chloromethyl-1, 3-dioxolan-2-thione obtained in example 38 ¹ H NMR spectrum.

FIG. 40 is the preparation of poly- (R) -4-chloromethyl-1, 3-dioxolane-2-thione obtained in example 39 ¹ H NMR spectrum.

FIG. 41 is a drawing showing the preparation of poly-4-phenyl-1, 3-dioxolane-2-thione obtained in example 41 ¹ H NMR spectrum.

FIG. 42 is a drawing showing the preparation of poly-4-phenyl-1, 3-dioxolane-2-thione obtained in example 41 ¹³ C NMR spectrum.

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

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

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

FIG. 46 is a mechanical tensile test chart of the terpolymer obtained in example 14.

FIG. 47 is a graph showing a cyclic tensile test of the terpolymer obtained in example 14.

FIG. 48 is a DSC chart of poly- (S) - (γ -thiogalactone) (abbreviation: S-PTNGVL) obtained in example 44.

FIG. 49 is a graph showing the mechanical tensile test of poly- (S) - (gamma-thioglycollate) (abbreviation: S-PTNGVL) obtained in example 44.

Detailed Description

The invention is further illustrated by the following examples, which are not intended to limit the scope of the invention. The experimental methods without specifying specific conditions in the following examples were selected according to the conventional methods and conditions, or according to the commercial instructions.

Example 1

The polymeric monomer is a self-made product, the initial raw materials of the polymeric monomer are commercialized five-membered ring lactone and cyclic carbonate, and the polymeric monomer is prepared by one-step reaction, the preparation method is not particularly limited, and the polymeric monomer is preferably prepared according to the method described in the following scientific and technological paper: matsumoto Y, nakatake D, yazaki R, ohshima T.chemistry-A European Journal,2018,24 (23): 6062-6066. The synthetic procedure for all compounds is similar and is now illustrated by the synthesis of gamma-thiolactone:

121.3g (0.3 mol) of Lawson's reagent was put into a 1L eggplant-shaped bottle, 500mL of anhydrous toluene was added thereto and stirred to form a yellow suspension, and then 50.1g of gamma-valerolactone (0.5 mol) was added thereto and stirred under reflux for 5 hours. After the reaction is finished, after the reaction temperature is reduced to normal temperature, 200mL of saturated potassium carbonate solution is added, the mixture is stirred for 30min, liquid is separated, the water phase is extracted for three times by using anhydrous toluene, and then the organic phases are combined. After drying over anhydrous sodium sulfate, filtration and spin-drying, the second fraction was collected by column chromatography using a petroleum ether/ether gradient (40. The monomers were then dried for 3 days by adding calcium hydride, distilled at 100mTorr at 60 ℃ under reduced pressure and stored in a glove box until use.

The gamma-thionocyclopentanolide monomer obtained by the method is light yellow liquid, the mass of the obtained gamma-thionocyclopentanolide monomer is 48.3g, and the calculated yield is 83.2%.

The invention is toPerforming Nuclear Magnetic Resonance (NMR) characterization on the synthesized gamma-thiocarbonylvalerolactone monomer, ¹ the H NMR spectrum is consistent with the report in the literature, and the gamma-thiocarbonylvalerolactone monomer prepared by the invention is proved to have the following structure, ¹ the H NMR spectrum is shown in FIG. 36.

Example 2

In a glove box under argon atmosphere, 0.005mmol of [ Ph ] was charged into a dry 5mL glass bottle at room temperature ₃ C][B(C ₆ F ₅ ) ₄ ]Dissolved in 0.4mL of toluene, then 1mmol (116.2 mg, 0.1mL) of gamma-thionopentanolide monomer was added, the initial concentration of monomer was 2mol/L, catalyst [ Ph ₃ C][B(C ₆ F ₅ ) ₄ ]In a concentration of 10mmol/L, monomers with [ Ph ] ₃ C][B(C ₆ F ₅ ) ₄ ]In a molar ratio of 200. Maintaining the reaction temperature at room temperature, stirring the mixture to react for 120 minutes, taking a small amount of sample, dissolving the sample in deuterated chloroform, and passing the solution through ¹ H NMR monitored the conversion to 98.1%, the ratio of γ -thiogalactone by-product to poly (γ -thiogalactone) was 2. Then 2mL of a water/tetrahydrofuran mixture (volume ratio 1: 20) was added to quench the reaction, the reaction solution was dropped into ethanol to precipitate the polymer, centrifuged, and the supernatant was discarded, followed by repeated dissolution with methylene chloride, dropping into ethanol to precipitate, centrifuging, and discarding the supernatant twice, and then drying in a vacuum oven at room temperature for three days to obtain colorless poly (γ -thiovalerolactone). Detecting poly (gamma-thiovalerolactone) by Nuclear Magnetic Resonance (NMR), ¹ h NMR spectrum and ¹³ the C NMR spectra are shown in FIGS. 1 and 2, respectively.

The melting temperature and the glass transition temperature of poly (gamma-thioglycollate) are detected by a Differential Scanning Calorimetry (DSC), and the result shows that the glass transition temperature of the poly (gamma-thioglycollate) prepared in the example is-15.4 ℃.

The invention adopts Gel Permeation Chromatography (GPC) to detect the molecular weight and the molecular weight distribution of poly (gamma-thioglutamyl lactone), takes tetrahydrofuran as an eluent, has the flow rate of 1.0mL/min, takes polymethyl methacrylate as a standard substance to make a standard curve, and the result shows that the number average molecular weight of the poly (gamma-thiogmyl lactone) prepared in the embodiment is 27.5kg/mol, and the molecular weight distribution is 1.16.

Example 3

In a glove box under argon atmosphere, 0.005mmol of [ Ph ] was charged at room temperature in a dry 5mL glass bottle ₃ C][B(C ₆ F ₅ ) ₄ ]Dissolved in 0.4mL of toluene and then 1mmol (130.2mg, 0.11mL) of gamma-thiocarbonylcaprolactone monomer was added, the initial concentration of monomer was 2mol/L, catalyst [ Ph ₃ C][B(C ₆ F ₅ ) ₄ ]In a concentration of 10mmol/L, monomer with [ Ph ] ₃ C][B(C ₆ F ₅ ) ₄ ]In a molar ratio of 200.

Keeping the reaction temperature at room temperature, stirring for 2.5h, dissolving a small amount of sample in deuterated chloroform, and purifying by ¹ H NMR monitored the conversion, which was greater than 99%, with a ratio of γ -thiacaprolactone byproduct to poly (γ -thiacaprolactone) of 3. Then 2mL of a water/tetrahydrofuran mixture (volume ratio: 1: 20) was added to quench the reaction, the reaction solution was dropped into ethanol to precipitate the polymer, centrifuged, and the supernatant was discarded, followed by repeated dissolution with methylene chloride, dropping into ethanol to precipitate, centrifuging, and discarding the supernatant twice, followed by drying in a vacuum oven at room temperature for three days to obtain colorless poly (γ -thiacaprolactone). Detecting poly (gamma-thio caprolactone) by Nuclear Magnetic Resonance (NMR), ¹ h NMR spectrum of ¹³ The C NMR spectra are shown in FIGS. 3 and 4, respectively.

The melting temperature and the glass transition temperature of poly (gamma-thio caprolactone) are detected by a Differential Scanning Calorimetry (DSC), and the result shows that the glass transition temperature of the poly (gamma-thio caprolactone) prepared by the embodiment is-20.8 ℃.

The invention adopts Gel Permeation Chromatography (GPC) to detect the molecular weight and the molecular weight distribution of poly (gamma-thio caprolactone), uses tetrahydrofuran as an eluent, has the flow rate of 1.0mL/min, uses polymethyl methacrylate as a standard substance to make a standard curve, and shows that the number average molecular weight of the poly (gamma-thio caprolactone) prepared in the embodiment is 33.6kg/mol, and the molecular weight distribution is 1.33.

Example 4

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

Keeping the reaction temperature at room temperature, stirring for 2.5h, dissolving a small amount of sample in deuterated chloroform, and purifying by ¹ H NMR monitors the conversion rate, the conversion rate is more than 99%, and the ratio of the gamma-sulfo-heptalactone byproduct to poly (gamma-sulfo-heptalactone) is 1. Then 2mL of a water/tetrahydrofuran mixture (volume ratio 1: 20) was added to quench the reaction, the reaction solution was dropped into ethanol to precipitate the polymer, centrifuged, and the supernatant was discarded, followed by repeated dissolution with methylene chloride, dropping into ethanol to precipitate, centrifuging, and discarding the supernatant twice, and then drying in a vacuum oven at room temperature for three days to obtain colorless poly (γ -thio-heptolactone). Detecting the poly (gamma-sulfo-heptalactone) by Nuclear Magnetic Resonance (NMR), ¹ h NMR spectrum of ¹³ The C NMR spectra are shown in FIGS. 5 and 6, respectively.

The melting temperature and the glass transition temperature of poly (gamma-thio-heptalactone) are detected by adopting a Differential Scanning Calorimetry (DSC), and the result shows that the glass transition temperature of the poly (gamma-thio-heptalactone) prepared by the embodiment is-21.5 ℃.

The invention adopts Gel Permeation Chromatography (GPC) to detect the molecular weight and the molecular weight distribution of poly (gamma-thio-heptalactone), uses tetrahydrofuran as an eluent, has the flow rate of 1.0mL/min, uses polymethyl methacrylate as a standard substance to make a standard curve, and the result shows that the number average molecular weight of the poly (gamma-thio-heptalactone) prepared in the embodiment is 38.1kg/mol, and the molecular weight distribution is 1.36.

Example 5

In a glove box under argon atmosphere, 0.005mmol of [ Ph ] was added at room temperature in a dry glass bottle ₃ C][B(C ₆ F ₅ ) ₄ ]Dissolved in 0.35mL of toluene and then 1mmol (158.3 mg, 0.15mL) of gamma-thionocaprylolactone monomer was added, the initial concentration of monomer was 2mol/L, catalyst [ Ph ₃ C][B(C ₆ F ₅ ) ₄ ]In a concentration of 10mmol/L, monomers with [ Ph ] ₃ C][B(C ₆ F ₅ ) ₄ ]In a molar ratio of 200.

Keeping the reaction temperature at room temperature, stirring for 2.5h, taking a small amount of sample, dissolving in deuterated chloroform, and passing ¹ H NMR monitors the conversion rate, the conversion rate is more than 99%, and the ratio of the gamma-thio-octalactone byproduct to poly (gamma-thio-octalactone) is 3. Then 2mL of a water/tetrahydrofuran mixture (volume ratio: 1: 20) was added to quench the reaction, the reaction solution was dropped into ethanol to precipitate the polymer, centrifuged, and the supernatant was discarded, followed by repeated dissolution with methylene chloride, dropping into ethanol to precipitate, centrifuging, and discarding the supernatant twice, followed by drying in a vacuum oven at room temperature for three days to obtain colorless poly (γ -thiocoractone). Detecting poly (gamma-thio-octalactone) by Nuclear Magnetic Resonance (NMR), ¹ h NMR spectrum and ¹³ the C NMR spectra are shown in FIGS. 7 and 8, respectively.

The melting temperature and the glass transition temperature of poly (gamma-thio-octalactone) are detected by adopting a Differential Scanning Calorimetry (DSC), and the result shows that the glass transition temperature of the poly (gamma-thio-octalactone) prepared by the embodiment is-32.3 ℃.

The invention adopts Gel Permeation Chromatography (GPC) to detect the molecular weight and the molecular weight distribution of poly (gamma-thio-octalactone), uses tetrahydrofuran as an eluent, has the flow rate of 1.0mL/min, uses polymethyl methacrylate as a standard substance to make a standard curve, and the result shows that the number average molecular weight of the poly (gamma-thio-octalactone) prepared in the embodiment is 34.5kg/mol, and the molecular weight distribution is 1.33.

Example 6

In a glove box under argon atmosphere, 0.005mmol of [ Ph ] was added at room temperature in a dry 5mL glass bottle ₃ C][B(C ₆ F ₅ ) ₄ ]Dissolved in 0.35mL of toluene and then 1mmol (172.3 mg, 0.16mL) of gamma-thiononalactone monomer was added, the initial concentration of monomer was 2mol/L, catalyst [ Ph ₃ C][B(C ₆ F ₅ ) ₄ ]In a concentration of 10mmol/L, monomers with [ Ph ] ₃ C][B(C ₆ F ₅ ) ₄ ]In a molar ratio of 200.

Keeping the reaction temperature at room temperature, stirring for 2.5h, dissolving a small amount of sample in deuterated chloroform, and purifying by ¹ The conversion was monitored by H NMR and was 97.4%, the ratio of γ -thiononalactone by-product to poly (γ -thiononalactone) was 3. Then 2mL of a water/tetrahydrofuran mixture (volume ratio: 1: 20) was added to quench the reaction, the reaction solution was dropped into ethanol to precipitate the polymer, centrifuged, and the supernatant was discarded, followed by repeated dissolution with methylene chloride, dropping into ethanol to precipitate, centrifuging, discarding the supernatant twice, and then drying in a vacuum oven at room temperature for three days to obtain colorless poly (γ -thiononalactone). Detecting poly (gamma-thio-nonalactone) by Nuclear Magnetic Resonance (NMR), ¹ h NMR spectrum of ¹³ The C NMR spectra are shown in FIGS. 9 and 10, respectively.

The melting temperature and the glass transition temperature of poly (gamma-thio-nonalactone) are detected by a Differential Scanning Calorimetry (DSC), and the result shows that the glass transition temperature of the poly (gamma-thio-nonalactone) prepared in the embodiment is-38.8 ℃.

The invention adopts Gel Permeation Chromatography (GPC) to detect the molecular weight and molecular weight distribution of poly (gamma-thio-nonalactone), uses tetrahydrofuran as an eluent, has the flow rate of 1.0mL/min, and uses polymethyl methacrylate as a standard substance to make a standard curve, and the result shows that the number average molecular weight of the poly (gamma-thio-nonalactone) prepared in the embodiment is 46.4kg/mol, and the molecular weight distribution is 1.26.

Example 7

In a glove box under argon atmosphere, in a dry 5mL glass bottle, 0.005mmol of [ Ph ₃ C][B(C ₆ F ₅ ) ₄ ]Dissolved in 0.32mL of toluene, then 1mmol (186.3 mg, 0.18mL) of gamma-thionocebactone monomer was added, the initial concentration of monomer was 2mol/L, catalyst [ Ph ₃ C][B(C ₆ F ₅ ) ₄ ]In a concentration of 10mmol/L, monomers with [ Ph ] ₃ C][B(C ₆ F ₅ ) ₄ ]In a molar ratio of 200.

Keeping the reaction temperature at room temperature, stirring for 2.5h, taking a small amount of sample, dissolving in deuterated chloroform, and reacting ¹ H NMR monitored the conversion, which was greater than 99%, and the ratio of γ -thio-decalactone byproduct to poly (γ -thio-decalactone) was 97. Then 2mL of a water/tetrahydrofuran mixture (volume ratio 1: 20) was added to quench the reaction, the reaction solution was dropped into ethanol to precipitate the polymer, centrifuged, and the supernatant was discarded, followed by repeated dissolution with methylene chloride, dropping into ethanol to precipitate, centrifuging, and discarding the supernatant twice, and then dried in a vacuum oven at room temperature for three days to obtain colorless poly (γ -thio-decalactone). Detecting poly (gamma-thio-decalactone) by Nuclear Magnetic Resonance (NMR), ¹ h NMR spectrum and ¹³ the C NMR spectra are shown in FIGS. 11 and 12, respectively.

The melting temperature and the glass transition temperature of the poly (gamma-thio-decalactone) are detected by a Differential Scanning Calorimetry (DSC), and the result shows that the glass transition temperature of the poly (gamma-thio-decalactone) prepared in the embodiment is-44.8 ℃.

The invention adopts Gel Permeation Chromatography (GPC) to detect the molecular weight and molecular weight distribution of poly (gamma-thio-decalactone), tetrahydrofuran is taken as an eluent, the flow rate is 1.0mL/min, polymethyl methacrylate is taken as a standard substance to make a standard curve, and the result shows that the number average molecular weight of the poly (gamma-thio-decalactone) prepared in the embodiment is 43.3kg/mol, and the molecular weight distribution is 1.31.

Example 8

In a glove box under argon atmosphere, in a dry 5mL glass bottle, 0.005mmol of [ Ph ] ₃ C][B(C ₆ F ₅ ) ₄ ]Dissolved in 0.3mL of toluene, and then 1mmol (200.3 mg, 0.19mL) of gamma-thiocarbonyl undecanolactone monomer was added, the initial concentration of monomer was 2mol/L, and the catalyst [ Ph ₃ C][B(C ₆ F ₅ ) ₄ ]In a concentration of 10mmol/L, monomers with [ Ph ] ₃ C][B(C ₆ F ₅ ) ₄ ]In a molar ratio of 200.

Keeping the reaction temperature at room temperature, stirring for 2.5h, taking a small amount of sample, dissolving in deuterated chloroform, and passing ¹ H NMR monitored the conversion to 97.4%, and the ratio of γ -thiaundecanolactone by-product to poly (γ -thiaundecanolactone) was 2. Then 2mL of a water/tetrahydrofuran mixture (volume ratio: 1: 20) was added to quench the reaction, the reaction solution was dropped into ethanol to precipitate the polymer, centrifuged, and the supernatant was discarded, followed by repeated dissolution with methylene chloride, dropping into ethanol to precipitate, centrifuging, and discarding the supernatant twice, followed by drying in a vacuum oven at room temperature for three days to obtain colorless poly (γ -thiaundecanolide). Detecting poly (gamma-thio undecalactone) by Nuclear Magnetic Resonance (NMR), ¹ h NMR spectrum and ¹³ the C NMR spectra are shown in FIGS. 13 and 14, respectively.

The melting temperature and the glass transition temperature of poly (gamma-thio-undecalactone) are detected by a Differential Scanning Calorimetry (DSC), and the result shows that the glass transition temperature of the poly (gamma-thio-undecalactone) prepared in the example is-50.0 ℃.

The invention adopts Gel Permeation Chromatography (GPC) to detect the molecular weight and the molecular weight distribution of poly (gamma-thio undecalactone), uses tetrahydrofuran as an eluent, has the flow rate of 1.0mL/min, uses polymethyl methacrylate as a standard substance to make a standard curve, and shows that the number average molecular weight of the poly (gamma-thio undecalactone) prepared in the embodiment is 37.1kg/mol, and the molecular weight distribution is 1.37.

Example 9

In a glove box under argon atmosphere, in a dry 5mL glass bottle, 0.005mmol of [ Ph ] ₃ C][B(C ₆ F ₅ ) ₄ ]Dissolved in 0.3mL of toluene, and then 1mmol (214.4 mg, 0.2mL) of gamma-thionocodecanolide monomer was added, initial concentration of monomer 2mol/L, catalyst [ Ph ₃ C][B(C ₆ F ₅ ) ₄ ]In a concentration of 10mmol/L, monomers with [ Ph ] ₃ C][B(C ₆ F ₅ ) ₄ ]In a molar ratio of 200.

Maintaining the reaction temperature at room temperature, stirring for 2.5h, taking a small amount of sample, dissolving in deuterated chloroform, passing ¹ H NMR monitored the conversion, which was greater than 99%, with a ratio of γ -thiadodecalactone by-product to poly (γ -thiadodecalactone) of 4. Then 2mL of a water/tetrahydrofuran mixture (volume ratio: 1: 20) was added to quench the reaction, the reaction solution was dropped into ethanol to precipitate the polymer, centrifuged, and the supernatant was discarded, followed by repeated dissolution with methylene chloride, dropping into ethanol to precipitate, centrifuging, and discarding the supernatant twice, followed by drying in a vacuum oven at room temperature for three days to obtain colorless poly (γ -thiododecalactone). Detecting poly (gamma-thio dodecalactone) by Nuclear Magnetic Resonance (NMR), ¹ h NMR spectrum and ¹³ the C NMR spectra are shown in FIGS. 15 and 16, respectively.

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The melting temperature and the glass transition temperature of poly (gamma-thio-dodecalactone) are detected by a Differential Scanning Calorimetry (DSC), and the result shows that the glass transition temperature of the poly (gamma-thio-dodecalactone) prepared in the example is-56.7 ℃.

The invention adopts Gel Permeation Chromatography (GPC) to detect the molecular weight and molecular weight distribution of poly (gamma-thio-dodecalactone), tetrahydrofuran is taken as an eluent, the flow rate is 1.0mL/min, polymethyl methacrylate is taken as a standard substance to make a standard curve, and the result shows that the number average molecular weight of the poly (gamma-thio-dodecalactone) prepared in the embodiment is 56.2kg/mol, and the molecular weight distribution is 1.58.

Example 10

In a glove box under argon atmosphere, in a dry 5mL glass bottle, 0.005mmol of [ Ph ] ₃ C][B(C ₆ F ₅ ) ₄ ]Dissolved in 0.3mL of toluene, and then 1mmol (200.3 mg,0.2 mL) of gamma-methyl-gamma-thionocebactone monomer was added, the initial concentration of monomer was 2mol/L, catalyst [ Ph ₃ C][B(C ₆ F ₅ ) ₄ ]In a concentration of 10mmol/L, monomers with [ Ph ] ₃ C][B(C ₆ F ₅ ) ₄ ]In a molar ratio of 200.

Keeping the reaction temperature at room temperature, stirring for 48h, dissolving a small amount of sample in deuterated chloroform, and reacting ¹ H NMR monitors the conversion rate, the conversion rate reaches 97.7 percent, and the gamma-methyl-gamma-sulfo-decalactone in the generated product: the ratio of poly (γ -methyl- γ -thio-decalactone) was 28. Then 2mL of a water/tetrahydrofuran mixture (volume ratio: 1: 20) was added to quench the reaction, the reaction solution was dropped into ethanol to precipitate the polymer, centrifuged, the supernatant was discarded, and then the dissolution with methylene chloride, the dropping into ethanol to precipitate, centrifuged, the supernatant was discarded twice, and then dried in a vacuum oven at room temperature for three days to obtain colorless poly (γ -methyl- γ -thio-decalactone). Detecting poly (gamma-methyl-gamma-thio-decalactone) by Nuclear Magnetic Resonance (NMR), ¹ h NMR spectrum and ¹³ the C NMR spectra are shown in FIGS. 17 and 18, respectively.

The melting temperature and the glass transition temperature of the poly (gamma-methyl-gamma-thio-decalactone) are detected by a Differential Scanning Calorimetry (DSC), and the result shows that the glass transition temperature of the poly (gamma-methyl-gamma-thio-decalactone) prepared in the embodiment is-34.8 ℃.

The invention adopts Gel Permeation Chromatography (GPC) to detect the molecular weight and molecular weight distribution of poly (gamma-methyl-gamma-thio-decalactone), tetrahydrofuran is taken as an eluent, the flow rate is 1.0mL/min, polymethyl methacrylate is taken as a standard substance to make a standard curve, and the result shows that the number average molecular weight of the poly (gamma-methyl-gamma-thio-decalactone) prepared in the embodiment is 12.8kg/mol, and the molecular weight distribution is 1.42.

Example 11

In a glove box under argon atmosphere, in a dry 5mL glass bottle, 0.005mmol of [ Ph ] ₃ C][B(C ₆ F ₅ ) ₄ ]Dissolved in 0.35mL of toluene, then 1mmol (172.3 mg, 0.16mL) of the beta-methyl-gamma-thionocaprylolactone monomer was added, the initial concentration of the monomer was 2mol/L, catalyst [ Ph ₃ C][B(C ₆ F ₅ ) ₄ ]In a concentration of 10mmol/L, monomers with [ Ph ] ₃ C][B(C ₆ F ₅ ) ₄ ]In a molar ratio of 200.

Keeping the reaction temperature at room temperature, stirring for 5h, dissolving a small amount of sample in deuterated chloroform, and reacting ¹ H NMR monitors the conversion rate, the conversion rate reaches 85.9 percent, and the beta-methyl-gamma-thio-octalactone in the product is generated: the ratio of poly (β -methyl- γ -thio-octalactone) was 1. Then 2mL of a water/tetrahydrofuran mixed solution (volume ratio 1: 20) was added to quench the reaction, the reaction solution was dropped into ethanol to precipitate the polymer, centrifuged, the supernatant was discarded, and then the dissolution with methylene chloride, the dropping into ethanol to precipitate, centrifuged, and the supernatant was discarded twice, followed by drying in a vacuum oven at room temperature for three days to obtain colorless poly (β -methyl- γ -thiooctanolactone). Detecting poly (beta-methyl-gamma-thio-octalactone) by Nuclear Magnetic Resonance (NMR), ¹ h NMR spectrum and ¹³ the C NMR spectra are shown in FIGS. 19 and 20, respectively.

The melting temperature and the glass transition temperature of the poly (beta-methyl-gamma-thio-octalactone) are detected by a Differential Scanning Calorimetry (DSC), and the result shows that the glass transition temperature of the poly (beta-methyl-gamma-thio-octalactone) prepared in the embodiment is 3.4 ℃.

The invention adopts Gel Permeation Chromatography (GPC) to detect the molecular weight and the molecular weight distribution of poly (beta-methyl-gamma-thio-octalactone), uses tetrahydrofuran as an eluent, has the flow rate of 1.0mL/min, uses polymethyl methacrylate as a standard substance to make a standard curve, and shows that the number average molecular weight of the poly (beta-methyl-gamma-thio-octalactone) prepared in the embodiment is 38.6kg/mol, and the molecular weight distribution is 1.29.

Example 12

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

The glovebox was removed and a Schlenk flask was connected to a vacuum line with argon protection and the reaction stirred at 80 ℃ for 2h. After completion of the polymerization, 0.15mL of a toluene solution containing 0.05mL of allyl chloride was added to terminate the reaction, and a small amount of the solution was taken out ¹ H NMR analysis to determine conversion, greater than 99%, with a ratio of α -methyl- γ -thiobutyrolactone byproduct to poly (α -methyl γ -thiobutyrolactone) of 3. And pouring the residual reaction liquid into ethanol to settle the polymer, centrifuging the precipitated solid, discarding the supernatant, repeatedly dissolving with dichloromethane, dripping into the ethanol to settle, centrifuging, discarding the supernatant twice, and drying in a vacuum drying oven at room temperature for three days to obtain the colorless poly (alpha-methyl-gamma-thiobutyrolactone). Nuclear Magnetic Resonance (NMR) detection is carried out on the poly (alpha-methyl-gamma-thiobutyrolactone), ¹ h NMR spectrum and ¹³ the C NMR spectra are shown in FIGS. 21 and 22, respectively.

The melting temperature and the glass transition temperature of poly (alpha-methyl-gamma-thiobutyrolactone) are detected by a Differential Scanning Calorimetry (DSC), and the result shows that the glass transition temperature of the poly (alpha-methyl-gamma-thiobutyrolactone) prepared in the embodiment is-30.2 ℃.

The invention adopts Gel Permeation Chromatography (GPC) to detect the molecular weight and molecular weight distribution of poly (alpha-methyl-gamma-thiobutyrolactone), uses tetrahydrofuran as an eluent, has a flow rate of 1.0mL/min, and uses polymethyl methacrylate as a standard substance to make a standard curve, and the result shows that the poly (alpha-methyl-gamma-thiobutyrolactone) prepared in the embodiment has a number average molecular weight of 8.6kg/mol and a molecular weight distribution of 1.03.

Example 13

In an argon atmosphere glove box, 0.928g (8mmol, 0.8mL) of beta-methyl-gamma-thiobutyrolactone monomer was charged into a dry Schlenk bottle, the glove box was removed, the Schlenk bottle was connected to a vacuum line under argon atmosphere, and after stirring at 80 ℃ for 10 minutes, 0.005mmol of toluene was dissolved in each case ^t Bu-P ₄ And 0.005mmol of benzhydrol, and the two solutions were charged into the above-mentioned Schlenk flask, respectively, and polymerization was started with a total volume of 1.6mL, an initial concentration of the monomer of 5mol/L, and a catalyst ^t Bu-P ₄ Has a concentration of 3.1mmol/L and a concentration of 3.1mmol/L of cocatalyst benzhydrol, monomers and ^t Bu-P ₄ the molar ratio of (a) to (b) is 1600. The reaction temperature was kept at 80 ℃ and the polymerization was carried out for 4h. After the polymerization reaction is finished, adding a chloroform solution with the mass concentration of 10mg/mL of benzoic acid to dissolve the product, and taking a small amount of solution to carry out ¹ H NMR analysis is carried out to determine the conversion rate, the residual reaction solution is poured into ethanol to settle the polymer, and the precipitated solid is filtered and washed with ethanol for three times and then dried in a vacuum drying oven at 40 ℃ for 24H to obtain white poly (beta-methyl-gamma-thiobutyrolactone). Nuclear Magnetic Resonance (NMR) detection is carried out on the poly (beta-methyl-gamma-thiobutyrolactone), ¹ h NMR spectrum and ¹³ the C NMR spectra are shown in FIGS. 23 and 24, respectively.

The results of the nuclear magnetic resonance hydrogen spectrum detection of the obtained reaction liquid show that the conversion rate of the monomer is 99.8 percent, and the proportion of the beta-methyl-gamma-thiobutyrolactone byproduct to poly (beta-methyl-gamma-thiobutyrolactone) is 3.

The melting temperature and the glass transition temperature of the poly (beta-methyl-gamma-thiobutyrolactone) are detected by adopting a Differential Scanning Calorimetry (DSC), and the result shows that the glass transition temperature of the poly (beta-methyl-gamma-thiobutyrolactone) prepared in the embodiment is-30.4 ℃.

The present inventors examined the molecular weight and molecular weight distribution of poly (. Beta. -methyl-. Gamma. -thiobutyrolactone) by Gel Permeation Chromatography (GPC), and as a result, it was revealed that poly (. Beta. -methyl-. Gamma. -thiobutyrolactone) prepared in this example had a number average molecular weight of 251.0kg/mol and a molecular weight distribution of 1.56.

Example 14

In an argon atmosphere glove box, 0.327g (3.2mmol, 280. Mu.L) of gamma-thiobutyrolactone and 0.022g (0.17mmol, 20. Mu.L) of beta-vinyl-gamma-thiobutyrolactone monomers were charged into a dried Schlenk bottle, the glove box was removed and the Schlenk bottle was connected to a vacuum line protected with argon, and after stirring at 80 ℃ for 10 minutes, 0.01mmol of toluene was dissolved therein ^t Bu-P ₄ And 0.01mmol of Ph ₂ A mixture of CHOH and 0.093g (0.8mmol, 83. Mu.L) of α -methyl- γ -thiobutyrolactones, and this solution was charged into the above-mentioned Schlenk bottle, and polymerization was started with a total volume of 0.78mL, an initial concentration of monomer γ -thiobutyrolactones of 4.1mol/L, an initial concentration of monomer β -vinyl- γ -thiobutyrolactones of 0.2mol/L, an initial concentration of monomer α -methyl- γ -thiobutyrolactones of 1.0mol/L, and a catalyst of 1.0mol/L ^t Bu-P ₄ Has a concentration of 12.8mmol/L and a cocatalyst Ph ₂ CHOH concentration of 12.8mmol/L, three monomers and ^t Bu-P ₄ the molar ratio of (a). The reaction temperature was kept at 80 ℃ and the polymerization was carried out for 1h. After the polymerization reaction is finished, adding a chloroform solution with the mass concentration of 10mg/mL of benzoic acid to dissolve the product, and taking a small amount of solution to carry out ¹ H NMR analysis is carried out to determine the conversion rate, the residual reaction solution is poured into ethanol to settle the polymer, and the precipitated solid is filtered and washed with ethanol for three times and then dried in a vacuum drying oven at 40 ℃ for 24 hours to obtain the white terpolymer. Nuclear Magnetic Resonance (NMR) detection of the copolymer, ¹ the H NMR spectrum is shown in FIG. 25.

The nuclear magnetic resonance hydrogen spectrum detection of the obtained reaction liquid shows that the conversion rate of the monomer is 99.9 percent, and the back-biting by-product in the generated product is as follows: the proportion of copolymer was 5.

The melting temperature and the glass transition temperature of the copolymer are detected by a Differential Scanning Calorimetry (DSC), and the result shows that the terpolymer prepared by the embodiment has the glass transition temperature of-47.89 ℃ and the melting temperature of 59.51 ℃.

The molecular weight and molecular weight distribution of the terpolymer were measured by Gel Permeation Chromatography (GPC) according to the present invention, and the number average molecular weight of the terpolymer prepared in this example was 65.0kg/mol and the molecular weight distribution was 1.73.

The mechanical properties of the prepared ternary random copolymer are tested by the invention: the mechanical tensile test experiment shows that the breaking elongation of the ternary random copolymer is 1451.30 percent, and the breaking stress is 16.62MPa; the cyclic tensile test experiment showed that the elastic recovery of the ternary random copolymer was 72.3%.

Example 15

In a glove box under an argon atmosphere, 0.1mL of toluene, 0.01mL of mesitylene and 1mmol (156mg, 0.14mL) of cis-hexahydroisobenzofuran-1-thione monomer were put into a dry Schlenk flask, and 0.01mL of the solution was taken ¹ H NMR analysis is carried out to determine the proportion of the monomer and the internal standard mesitylene in the initial reaction liquid; then 0.01mol of potassium thioacetate, 0.01mmol of 18 crown 6 ether were added. The initial concentration of the monomer is 4mol/L, the concentration of the catalyst potassium thioacetate is 4mmol/L, and the molar ratio of the monomer to the potassium thioacetate and the 18-crown-6 is 100。

The glovebox was removed and the Schlenk flask was connected to a vacuum line with argon protection and the reaction stirred at 80 ℃ for 4h. After completion of the polymerization, 0.15mL of a toluene solution containing 0.05mL of allyl chloride was added to terminate the reaction, and a small amount of the solution was taken out ¹ H NMR analysis and determination of conversion by analysis of integral ratio change of monomer and internal standard mesitylene, the conversion rate is more than 99%, cis-hexahydroisobenzothiophene-1-one by-product: the ratio of poly (cis-hexahydroisobenzothiophen-1-one) was 12. Pouring the residual reaction solution into ice methanol to allow the polymer to settle, centrifuging the precipitated solid, discarding the supernatant, repeatedly dissolving with dichloromethane, dripping into methanol to settle, centrifuging, discarding the supernatant twice, drying in a vacuum drying oven at room temperature for three days to obtain white solid poly (cis-hexahydro-isobenzothiophene-1-one), detecting by Nuclear Magnetic Resonance (NMR), ¹ h NMR spectrum of ¹³ The C NMR spectra are shown in FIGS. 26 and 27, respectively.

The melting temperature and the glass transition of the poly (cis-hexahydro-isobenzothiophene-1-ketone) are detected by a Differential Scanning Calorimetry (DSC), and the result shows that the glass transition temperature of the poly (cis-hexahydro-isobenzothiophene-1-ketone) prepared in the embodiment is 65.1 ℃.

The present invention measured the thermal stability of the poly (cis-hexahydroisobenzothiophen-1-one) obtained in this example using a Thermal Gravimetric Analyzer (TGA) and the initial decomposition temperature (T) of the resulting polymer _d And the temperature at 5% weight loss) is 255.3 ℃, and the thermal stability is better.

The invention adopts Gel Permeation Chromatography (GPC) to detect the molecular weight and the molecular weight distribution of poly (cis-hexahydro-isobenzothiophene-1-ketone), tetrahydrofuran is taken as an eluent, the flow rate is 1.0mL/min, polymethyl methacrylate is taken as a standard substance to make a standard curve, and the result shows that the number average molecular weight of the poly (cis-hexahydro-isobenzothiophene-1-ketone) prepared in the embodiment is 22.6kg/mol, and the molecular weight distribution is 1.23.

Example 16

In a glove box under argon atmosphere, a dry Schlenk bottle was charged with 0.02mmol of potassium thioacetate, 0.02mmol of 18 crown 6 ether and 0.2mL of toluene, followed by 2mmol (232mg, 0.2 mL) of α -methyl- γ -thiobutyrolactone monomer at an initial concentration of 5mol/L, a concentration of catalyst potassium thioacetate of 50mmol/L and a molar ratio of monomer to potassium thioacetate and 18 crown 6 ether of 100.

The glovebox was removed and a Schlenk flask was connected to a vacuum line with argon protection and the reaction was stirred at 80 ℃ for 5h. After completion of the polymerization, 0.15mL of a toluene solution containing 0.05mL of allyl chloride was added to terminate the reaction, and a small amount of the solution was taken out ¹ H NMR analysis to determine conversion, up to greater than 99%, with a ratio of α -methyl- γ -thiobutyrolactone by-product to poly (α -methyl- γ -thiobutyrolactone) of 6. And pouring the residual reaction liquid into ethanol to settle the polymer, centrifuging the precipitated solid, discarding the supernatant, repeatedly dissolving with dichloromethane, dripping into ethanol for settling, centrifuging, discarding the supernatant twice, and drying in a vacuum drying oven at room temperature for three days to obtain colorless poly (alpha-methyl-gamma-thiobutyrolactone).

The melting temperature and the glass transition of poly (alpha-methyl-gamma-thiobutyrolactone) are detected by adopting a Differential Scanning Calorimetry (DSC), and the result shows that the glass transition temperature of the poly (alpha-methyl-gamma-thiobutyrolactone) prepared in the embodiment is-30.2 ℃.

The invention adopts Gel Permeation Chromatography (GPC) to detect the molecular weight and molecular weight distribution of poly (alpha-methyl-gamma-thiobutyrolactone), uses tetrahydrofuran as an eluent, has a flow rate of 1.0mL/min, and uses polymethyl methacrylate as a standard substance to make a standard curve, and the result shows that the poly (alpha-methyl-gamma-thiobutyrolactone) prepared in the embodiment has a number average molecular weight of 11.4kg/mol and a molecular weight distribution of 1.02.

Example 17

Hand in argon atmosphereIn a box, 0.01mol of benzoic acid and 0.01mmol of benzoic acid were added to a dry Schlenk flask ^t Bu-P ₄ And 0.2mL of toluene, followed by 2mmol (232mg, 0.2mL) of α -methyl- γ -thiobutyrolactone monomer at an initial concentration of 5mol/L, catalyst ^t Bu-P ₄ In a concentration of 25mmol/L, monomers and ^t Bu-P ₄ and benzoic acid at a molar ratio of 200.

The glovebox was removed and a Schlenk flask was connected to a vacuum line with argon protection and the reaction stirred at 80 ℃ for 1h. After completion of the polymerization, 0.15mL of a toluene solution containing 0.05mL of allyl chloride was added to terminate the reaction, and a small amount of the solution was taken out ¹ H NMR analysis to determine conversion, up to greater than 99%, with a ratio of α -methyl- γ -thiobutyrolactone by-product to poly (α -methyl- γ -thiobutyrolactone) of 5. And pouring the residual reaction liquid into ethanol to settle the polymer, centrifuging the precipitated solid, discarding the supernatant, repeatedly dissolving with dichloromethane, dripping into ethanol for settling, centrifuging, discarding the supernatant twice, and drying in a vacuum drying oven at room temperature for three days to obtain colorless poly (alpha-methyl-gamma-thiobutyrolactone).

The invention adopts Gel Permeation Chromatography (GPC) to detect the molecular weight and molecular weight distribution of poly (alpha-methyl-gamma-thiobutyrolactone), uses tetrahydrofuran as an eluent, has a flow rate of 1.0mL/min, and uses polymethyl methacrylate as a standard substance to make a standard curve, and the result shows that the poly (alpha-methyl-gamma-thiobutyrolactone) prepared in the embodiment has a number average molecular weight of 20.0kg/mol and a molecular weight distribution of 1.05.

Example 18

In a glove box under argon atmosphere, 5mL of dry argon gas was used at room temperatureIn a glass bottle, 0.005mmol of [ Ph ] ₃ C][B(C ₆ F ₅ ) ₄ ]Dissolved in 0.8mL of toluene and then charged with 8mmol (929.4 mg, 0.86mL) of gamma-thionopentanolide monomer at an initial concentration of 5mol/L, catalyst [ Ph ₃ C][B(C ₆ F ₅ ) ₄ ]In a concentration of 3.1mmol/L, monomer and [ Ph ₃ C][B(C ₆ F ₅ ) ₄ ]The molar ratio of (a) to (b) is 1600.

Keeping the reaction temperature at room temperature, stirring for 18h, taking a small amount of sample, dissolving in deuterated chloroform, and reacting by ¹ H NMR monitored the conversion to 94.3% and the ratio of gamma-thioglycollate byproduct to poly (gamma-thioglycollate) was 1. Then, the reaction was quenched by adding 12mL of a water/tetrahydrofuran mixture (volume ratio 1: 30), the reaction solution was dropped into ethanol to settle the polymer, centrifuged, and the supernatant was discarded, followed by repeated dissolution with methylene chloride, dropping into ethanol to settle, centrifuging, and discarding the supernatant twice, and then dried in a vacuum oven at room temperature for three days to obtain colorless poly (γ -thiovalerolactone).

The melting temperature and the glass transition of poly (gamma-thioglycollate) are detected by a Differential Scanning Calorimetry (DSC), and the result shows that the glass transition temperature of the poly (gamma-thioglycollate) prepared in the embodiment is-9.8 ℃.

The invention adopts Gel Permeation Chromatography (GPC) to detect the molecular weight and the molecular weight distribution of poly (gamma-thioglutamyl lactone), takes tetrahydrofuran as an eluent, has the flow rate of 1.0mL/min, takes polymethyl methacrylate as a standard substance to make a standard curve, and the result shows that the number average molecular weight of the poly (gamma-thiogmyl lactone) prepared in the embodiment is 133.2kg/mol, and the molecular weight distribution is 1.76.

Example 19

In a glove box under argon atmosphere, 0.01mmol of [ H (Et) was added to a dry glass bottle ₂ O) ₂ ][B(C ₆ F ₅ ) ₄ ]0.4mL of toluene, then 1mmol of (C)116.2mg, 0.10mL) of gamma-thiolactonic monomer, initial concentration of the monomer was 2mol/L, catalyst [ H (Et) ₂ O) ₂ ][B(C ₆ F ₅ ) ₄ ]In a concentration of 20mmol/L, monomer and [ H (Et) ₂ O) ₂ ][B(C ₆ F ₅ ) ₄ ]In a molar ratio of 100.

Keeping the reaction temperature at room temperature, and dissolving a small amount of sample in deuterated chloroform during the polymerization process ¹ The conversion rate is monitored by H NMR, the conversion rate reaches 98.4% when the polymerization reaction is carried out for 2H, and the gamma-thiovalerolactone in the product is generated: the ratio of poly (gamma-thioglycollate) is 10. Then 2mL of a water/tetrahydrofuran mixture (volume ratio 1: 30) was added to quench the reaction, the reaction solution was dropped into ethanol to precipitate the polymer, centrifuged, and the supernatant was discarded, followed by repeated dissolution with methylene chloride, dropping into ethanol to precipitate, centrifuging, and discarding the supernatant twice, and then drying in a vacuum oven at room temperature for three days to obtain colorless poly (γ -thiovalerolactone).

The invention adopts Gel Permeation Chromatography (GPC) to detect the molecular weight and the molecular weight distribution of poly (gamma-thioglutamyl lactone), takes tetrahydrofuran as an eluent, has the flow rate of 1.0mL/min, takes polymethyl methacrylate as a standard substance to make a standard curve, and the result shows that the number average molecular weight of the poly (gamma-thiogmyl lactone) prepared in the embodiment is 32.9kg/mol, and the molecular weight distribution is 1.46.

Example 20

In a glove box under argon atmosphere, 0.01mmol of B (C) was added to a dried Schlenk bottle ₆ F ₅ ) ₃ 0.1mL of toluene, then 1mmol (116.2mg, 0.10 mL) of gamma-thiovalerolactone monomer was added at an initial concentration of 5mol/L, catalyst B (C) ₆ F ₅ ) ₃ In a concentration of 50mmol/L, monomer and B (C) ₆ F ₅ ) ₃ The molar ratio of (a) to (b) is 100.

Remove the glovebox and connect the Schlenk flask to a vacuum line with argon protection at 80 deg.CThe reaction was stirred for 1.5h. After the polymerization was completed, the reaction was quenched by adding 2mL of a water/tetrahydrofuran mixture (volume ratio 1. Dissolving a small amount of sample in deuterated chloroform for ¹ And (3) monitoring the conversion rate by H NMR, wherein the conversion rate of the polymerization reaction reaches 94.8 percent, and the gamma-thiovalerolactone in the product is generated: the ratio of poly (gamma-thiogalactone) was 66. Dropping the reaction liquid into ethanol to settle the polymer, centrifuging, discarding supernatant, dissolving with dichloromethane repeatedly, dropping into ethanol to settle, centrifuging, discarding supernatant twice, and drying in vacuum drying oven at room temperature for three days to obtain colorless poly (gamma-thioglycollate).

The invention adopts Gel Permeation Chromatography (GPC) to detect the molecular weight and the molecular weight distribution of poly (gamma-thioglutamyl lactone), takes tetrahydrofuran as an eluent, has the flow rate of 1.0mL/min, takes polymethyl methacrylate as a standard substance to make a standard curve, and the result shows that the number average molecular weight of the poly (gamma-thiogmyl lactone) prepared in the embodiment is 74.0kg/mol, and the molecular weight distribution is 1.65.

Example 21

In a dry Schlenk bottle, 0.232g (2.0 mmol, 200. Mu.L) of α -methyl- γ -thiobutyrolactone and 0.40mL of a solution of 2.3mg (0.02 mmol) of potassium thioacetate in N, N-dimethylformamide were charged in an argon atmosphere glove box. The glovebox was removed and a Schlenk flask was attached to a vacuum line with argon protection, and the reaction was stirred at 80 ℃ for 2.5 hours until the α -methyl- γ -thionocarbonyl butyrolactone had reacted. Then 0.204g (2.0 mmol, 175. Mu.L) of gamma-thiobutyrolacton monomer was added by syringe and the reaction was continued for 1 hour. The initial concentration of the monomer alpha-methyl-gamma-thiobutyrolactones was 3.3mol/L, and the initial concentration of gamma-thiobutyrolactones was 2.6mol/L. The concentration of the catalyst potassium thioacetate is 66.7mmol/L, and the molar ratio of the alpha-methyl gamma-thiobutyrolactone to the potassium thioacetate is 100.

After the polymerization was completed, 0.15mL of a toluene solution containing 0.05mL of allyl chloride was added to terminate the reaction, and a small amount of the solution was takenLiquid process ¹ H NMR analysis to determine conversion, α -methyl γ -butyrolactone conversion was 97.7%, γ -butyrolactone conversion was 77.7%, back-biting by-products in the product were generated: the proportion of copolymer was 6.2. And pouring the residual reaction liquid into ethanol to settle the polymer, filtering and washing the precipitated solid with ethanol for three times, and drying in a vacuum drying oven at 40 ℃ for 24 hours to obtain the white block copolymer. Nuclear Magnetic Resonance (NMR) detection of the copolymer, ¹ the H NMR spectrum is shown in FIG. 28.

The melting temperature and the glass transition temperature of the copolymer are detected by adopting a Differential Scanning Calorimetry (DSC), and the result shows that the glass transition temperature of the terpolymer prepared by the embodiment is-32.90 ℃ and the melting temperature is 92.74 ℃.

The molecular weight and molecular weight distribution of the terpolymer are detected by Gel Permeation Chromatography (GPC), and the number average molecular weight of the terpolymer prepared in the embodiment is 32.2kg/mol, and the molecular weight distribution is 1.09.

Example 22

In a dry Schlenk bottle, 0.236g (2.0 mmol, 200. Mu.L) of propylene thiocarbonylcarbonate and 0.20mL of a solution of 2.3mg (0.02 mmol) of potassium thioacetate in N, N-dimethylformamide were added in an argon atmosphere glove box. The glovebox was removed and a Schlenk flask was attached to a vacuum line with argon protection, the concentration of the catalyst potassium thioacetate was 50mmol/L, the initial concentration of the monomeric propylene thiocarbonate was 5mol/L, and the molar ratio of propylene thiocarbonate to potassium thioacetate was 100.

After completion of the polymerization, 0.15mL of a toluene solution containing 0.05mL of allyl chloride was added to terminate the reaction, and a small amount of the solution was taken out ¹ H NMR analysis to determine conversion, the thionocarbonate conversion was 99%. Pouring the rest reaction solution into ethanol to settle the polymer, filtering the precipitated solid, washing with ethanol for three times, and drying in a vacuum drying oven at 40 deg.C for 24 hr to obtain whitePoly propylene monothiocarbonate. Subjecting the polymer to Nuclear Magnetic Resonance (NMR) detection, ¹ h NMR spectrum and ¹³ the C NMR spectra are shown in FIGS. 29 and 30, respectively.

According to the invention, the molecular weight and the molecular weight distribution of the polypropylene monothiocarbonate are detected by adopting Gel Permeation Chromatography (GPC), and the result shows that the polypropylene monothiocarbonate prepared in the embodiment has the number average molecular weight of 9.2kg/mol and the molecular weight distribution of 1.53.

Example 23

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

Keeping the reaction temperature at room temperature, stirring for 1.0h, dissolving a small amount of sample in deuterated chloroform, and purifying by ¹ H NMR monitored the conversion, which was greater than 99%. Then 2mL of water/tetrahydrofuran mixed solution (volume ratio 1: 20) is added to quench the reaction, the reaction solution is dripped into ethanol to settle the polymer, the mixture is centrifuged, the supernatant is discarded, then the dissolution with dichloromethane is repeated, the mixture is dripped into ethanol to settle and is centrifuged, the supernatant is discarded twice, and the mixture is dried in a vacuum drying oven at room temperature for three days to obtain colorless polypropylene monothiocarbonate.

The invention adopts Gel Permeation Chromatography (GPC) to detect the molecular weight and the molecular weight distribution of the polypropylene monothiocarbonate, tetrahydrofuran is taken as an eluent, the flow rate is 1.0mL/min, and polymethyl methacrylate is taken as a standard substance to make a standard curve, and the result shows that the polypropylene monothiocarbonate prepared in the embodiment has the number average molecular weight of 10.2kg/mol and the molecular weight distribution of 1.65.

Example 24

In an argon atmosphere glove box, 4mmol (464.5 mg, 0.43mL) of α -methyl γ -thiocarbonylbutyrolactone monomer was added to a dry Schlenk bottle, the glove box was removed and the Schlenk bottle was connected to a vacuum line with argon protection and stirred at 80 ℃ for 10 minutes. 0.01mmol of TBD and 0.01mmol of PhCOOH were dissolved in 0.43mL of toluene and the solution was charged to the above-described Schlenk flask at an initial monomer concentration of 5mol/L, a catalyst TBD and initiator PhCOOH concentration of 12.5mmol/L and a monomer to TBD/PHCOOH molar ratio of 400.

Keeping the reaction temperature at 80 ℃, after the polymerization reaction is carried out for 17 hours, adding a chloroform solution with the mass concentration of 10mg/mL benzoic acid to dissolve the product, and taking a small amount of solution to carry out ¹ H NMR analysis to determine conversion, 82.4%, the product produced a by-product of α -methyl- γ -thiobutyrolactone to poly (α -methyl γ -thiobutyrolactone) ratio of 16. And pouring the residual reaction liquid into ethanol to settle the polymer, centrifuging the precipitated solid, discarding the supernatant, repeatedly dissolving with dichloromethane, dripping into ethanol for settling, centrifuging, discarding the supernatant twice, and drying in a vacuum drying oven at room temperature for three days to obtain colorless poly (alpha-methyl-gamma-thiobutyrolactone).

The invention adopts Gel Permeation Chromatography (GPC) to detect the molecular weight and molecular weight distribution of poly (alpha-methyl-gamma-thiobutyrolactone), uses tetrahydrofuran as an eluent, has a flow rate of 1.0mL/min, and uses polymethyl methacrylate as a standard substance to make a standard curve, and the result shows that the poly (alpha-methyl-gamma-thiobutyrolactone) prepared in the embodiment has a number average molecular weight of 22.6kg/mol and a molecular weight distribution of 1.20.

Example 25

In an argon atmosphere glove box, 2mmol (232.5 mg, 0.22ml) of α -methyl γ -thiocarbonylbutyrolactone monomer was added to a dry Schlenk bottle, the glove box was removed and the Schlenk bottle was connected to a vacuum line with argon protection and stirred at 80 ℃ for 10 minutes. 0.02mmol of DBU and 0.02mmol of PhCOSH are dissolved in 0.22mL of toluene and the solution is introduced into the above-mentioned Schlenk flask, the initial concentration of the monomers is 5mol/L, the concentrations of catalyst DBU and initiator PhCOSH are 50mmol/L, the molar ratio of monomers to DBU/PHCOSH is 100.

Keeping the reaction temperature at 80 ℃, after 5 hours of polymerization reaction, adding a chloroform solution with the mass concentration of 10mg/mL benzoic acid to dissolve the product, and taking a small amount of solution to carry out ¹ H NMR analysis is carried out to determine the conversion rate, the conversion rate reaches 96.8%, and the proportion of the alpha-methyl-gamma-thiobutyrolactone byproduct to the poly (alpha-methyl-gamma-thiobutyrolactone) in the generated product is 11. And pouring the residual reaction liquid into ethanol to settle the polymer, centrifuging the precipitated solid, discarding the supernatant, repeatedly dissolving with dichloromethane, dripping into the ethanol to settle, centrifuging, discarding the supernatant twice, and drying in a vacuum drying oven at room temperature for three days to obtain the colorless poly (alpha-methyl-gamma-thiobutyrolactone).

The invention adopts Gel Permeation Chromatography (GPC) to detect the molecular weight and molecular weight distribution of poly (alpha-methyl-gamma-thiobutyrolactone), uses tetrahydrofuran as an eluent, has a flow rate of 1.0mL/min, and uses polymethyl methacrylate as a standard substance to make a standard curve, and the result shows that the poly (alpha-methyl-gamma-thiobutyrolactone) prepared in the embodiment has a number average molecular weight of 9.9kg/mol and a molecular weight distribution of 1.02.

Example 26

In an argon atmosphere glove box, 2mmol (232.5 mg, 0.22ml) of α -methyl γ -thiocarbonylbutyrolactone monomer was added to a dry Schlenk bottle, the glove box was removed and the Schlenk bottle was connected to a vacuum line with argon protection and stirred at 80 ℃ for 10 minutes. 0.01mmol of I was dissolved in 0.22mL of toluene ^t Bu N-heterocyclic carbene catalystsReagent, and the toluene solution was added to the above Schlenk flask, the initial concentration of the monomer was 5mol/L, and the catalyst I was added ^t Bu concentration of 50mmol/L, monomer and I ^t The molar ratio of Bu is 100.

Keeping the reaction temperature at 80 ℃, after 1h of polymerization reaction, adding a chloroform solution with the mass concentration of 10mg/mL of benzoic acid to dissolve the product, and taking a small amount of solution to carry out ¹ H NMR analysis to determine conversion, 95.7%, the ratio of α -methyl- γ -thiobutyrolactone byproduct to poly (α -methyl γ -thiobutyrolactone) in the product was 2. And pouring the residual reaction liquid into ethanol to settle the polymer, centrifuging the precipitated solid, discarding the supernatant, repeatedly dissolving with dichloromethane, dripping into the ethanol to settle, centrifuging, discarding the supernatant twice, and drying in a vacuum drying oven at room temperature for three days to obtain the colorless poly (alpha-methyl-gamma-thiobutyrolactone).

The invention adopts Gel Permeation Chromatography (GPC) to detect the molecular weight and molecular weight distribution of poly (alpha-methyl-gamma-thiobutyrolactone), uses tetrahydrofuran as an eluent, has a flow rate of 1.0mL/min, and uses polymethyl methacrylate as a standard substance to make a standard curve, and the result shows that the poly (alpha-methyl-gamma-thiobutyrolactone) prepared in the embodiment has a number average molecular weight of 9.39kg/mol and a molecular weight distribution of 1.01.

Example 27

In an argon atmosphere glove box, 4mmol (464.5 mg, 0.43mL) of α -methyl γ -thiocarbonylbutyrolactone monomer was added to a dry Schlenk bottle, the glove box was removed and the Schlenk bottle was connected to a vacuum line with argon protection and stirred at 80 ℃ for 10 minutes. 0.01mmol of NHO N-heterocylic olefin catalyst was dissolved in 0.43mL of toluene and the solution was added to the above Schlenk flask with an initial monomer concentration of 5mol/L, catalyst NHO concentration of 12.5mmol/L and monomer to NHO molar ratio of 400.

Keeping the reaction temperature at 80 ℃, adding 10mg of the mixture after 2 hours of polymerization reactionThe product is dissolved in chloroform in a small volume of benzoic acid ¹ H NMR analysis to determine the conversion, 87.8%, the ratio of α -methyl- γ -thiobutyrolactone byproduct to poly (α -methyl γ -thiobutyrolactone) in the product was 3. And pouring the residual reaction liquid into ethanol to settle the polymer, centrifuging the precipitated solid, discarding the supernatant, repeatedly dissolving with dichloromethane, dripping into ethanol for settling, centrifuging, discarding the supernatant twice, and drying in a vacuum drying oven at room temperature for three days to obtain colorless poly (alpha-methyl-gamma-thiobutyrolactone).

The invention adopts Gel Permeation Chromatography (GPC) to detect the molecular weight and molecular weight distribution of poly (alpha-methyl-gamma-thiobutyrolactone), uses tetrahydrofuran as an eluent, has a flow rate of 1.0mL/min, and uses polymethyl methacrylate as a standard substance to make a standard curve, and the result shows that the poly (alpha-methyl-gamma-thiobutyrolactone) prepared in the embodiment has a number average molecular weight of 43.6kg/mol and a molecular weight distribution of 1.08.

Example 28

In a glove box under argon atmosphere, 4mmol (464.5mg, 0.43mL) of α -methyl γ -thionocarbonylbutyrolactone monomer was added to a dry Schlenk bottle, the glove box was removed and the Schlenk bottle was connected to a vacuum line with argon protection and stirred at 80 ℃ for 10 minutes. 0.01mmol of toluene was dissolved in 0.43mL of toluene ^t BuP ₁ Phosphazene base catalyst, and this solution was charged into the above-mentioned Schlenk flask, the initial concentration of the monomer was 5mol/L, and the catalyst was added ^t BuP ₁ In a concentration of 12.5mmol/L, monomers and ^t BuP ₁ the molar ratio of (1) is 400.

Keeping the reaction temperature at 80 ℃, adding a chloroform solution with the mass concentration of 10mg/mL to dissolve the product after 1h of polymerization reaction, and taking a small amount of solution to carry out ¹ H NMR analysis to determine the conversion, 87.8%, the ratio of α -methyl- γ -thiobutyrolactone byproduct to poly (α -methyl γ -thiobutyrolactone) in the product was 5. Remains ofThe reaction solution is poured into ethanol to settle the polymer, the precipitated solid is centrifuged, the supernatant is discarded, then the dichloromethane dissolution is repeated, the solid is dripped into the ethanol for settlement, the centrifugation and the supernatant discarding are carried out twice, and then the solid is dried in a vacuum drying oven at room temperature for three days to obtain colorless poly (alpha-methyl-gamma-thiobutyrolactone).

Example 29

In a glove box under argon atmosphere, 0.01mmol of [ Et ] was added at room temperature in a dry 5mL glass bottle ₃ Si-H-SiEt ₃ ][B(C ₆ F ₅ ) ₄ ]Dissolved in 0.4mL of toluene, and then 1mmol (116.2mg, 0.10 mL) of gamma-thionopentanolide monomer was added, the initial concentration of monomer being 2mol/L, catalyst [ Et ₃ Si-H-SiEt ₃ ][B(C ₆ F ₅ ) ₄ ]In a concentration of 20mmol/L, monomer with [ Et ] ₃ Si-H-SiEt ₃ ][B(C ₆ F ₅ ) ₄ ]In a molar ratio of 100.

Keeping the reaction temperature at room temperature, stirring for 1h, taking a small amount of sample, dissolving in deuterated chloroform, and passing ¹ H NMR monitored the conversion to 99.0% and the ratio of gamma-thioglycollate byproduct to poly (gamma-thioglycollate) was 6. Then, the reaction was quenched by adding 12mL of a water/tetrahydrofuran mixture (volume ratio 1: 30), the reaction solution was dropped into ethanol to settle the polymer, centrifuged, and the supernatant was discarded, followed by repeated dissolution with methylene chloride, dropping into ethanol to settle, centrifuging, and discarding the supernatant twice, and then dried in a vacuum oven at room temperature for three days to obtain colorless poly (γ -thiovalerolactone).

The invention adopts Gel Permeation Chromatography (GPC) to detect the molecular weight and the molecular weight distribution of poly (gamma-thioglutamyl lactone), takes tetrahydrofuran as an eluent, has the flow rate of 1.0mL/min, takes polymethyl methacrylate as a standard substance to make a standard curve, and the result shows that the number average molecular weight of the poly (gamma-thiogmyl lactone) prepared in the embodiment is 10.2kg/mol, and the molecular weight distribution is 1.47.

Example 30

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

Maintaining the reaction temperature at room temperature, and dissolving a small amount of sample in deuterated chloroform during the polymerization process ¹ The conversion rate is monitored by H NMR, the conversion rate reaches 99.0% after 1H of polymerization reaction, and the gamma-thioglycollate in the product is generated: the ratio of poly (gamma-thiogalactone) was 9. Then 2mL of a water/tetrahydrofuran mixture (volume ratio: 1: 30) was added to quench the reaction, the reaction solution was dropped into ethanol to precipitate the polymer, centrifuged, and the supernatant was discarded, followed by repeated dissolution with methylene chloride, dropping into ethanol to precipitate, centrifuging, and discarding the supernatant twice, followed by drying in a vacuum oven at room temperature for three days to obtain colorless poly (γ -thioglycollate).

The invention adopts Gel Permeation Chromatography (GPC) to detect the molecular weight and molecular weight distribution of poly (gamma-thio valerolactone), tetrahydrofuran is taken as an eluent, the flow rate is 1.0mL/min, polymethyl methacrylate is taken as a standard substance to make a standard curve, and the result shows that the number average molecular weight of the poly (gamma-thio valerolactone) prepared by the embodiment is 8.4kg/mol, and the molecular weight distribution is 1.35.

Example 31

In a glove box under argon atmosphere, 0.01mmol of Me was added to the dried glass bottle ₃ OBF ₄ And 0.4mL of toluene, followed by 1mmol (116.2 mg,0.10 mL) of gamma-thionopentanolide monomer at an initial concentration of 2mol/L, catalyst Me ₃ OBF ₄ In a concentration of 20mmol/L, monomer and Me ₃ OBF ₄ In a molar ratio of 100.

Keeping the reaction temperature at room temperature, and dissolving a small amount of sample in deuterated chloroform during the polymerization process ¹ The conversion rate is monitored by H NMR, the conversion rate reaches 96.5% when the polymerization reaction is carried out for 9 hours, and the gamma-thiovalerolactone in the product is generated: the ratio of poly (gamma-thioglycollate) is 1. Then 2mL of a water/tetrahydrofuran mixture (volume ratio: 1: 30) was added to quench the reaction, the reaction solution was dropped into ethanol to precipitate the polymer, centrifuged, and the supernatant was discarded, followed by repeated dissolution with methylene chloride, dropping into ethanol to precipitate, centrifuging, and discarding the supernatant twice, followed by drying in a vacuum oven at room temperature for three days to obtain colorless poly (γ -thioglycollate).

The invention adopts Gel Permeation Chromatography (GPC) to detect the molecular weight and molecular weight distribution of poly (gamma-thiovalerolactone), tetrahydrofuran is taken as an eluent, the flow rate is 1.0mL/min, polymethyl methacrylate is taken as a standard substance to make a standard curve, and the result shows that the number average molecular weight of the poly (gamma-thiovalerolactone) prepared by the embodiment is 6.8kg/mol, and the molecular weight distribution is 1.26.

Example 32

In a glove box under argon atmosphere, 0.01mmol of [ Et ] was added to a dry glass bottle ₃ O][B(C ₆ F ₅ ) ₄ ]And 0.4mL of toluene, followed by 1mmol (116.2mg, 0.10mL) of gamma-thionopentanolide monomer at an initial concentration of 2mol/L, catalyst [ Et ₃ O][B(C ₆ F ₅ ) ₄ ]In a concentration of 20mmol/L, monomer with [ Et ] ₃ O][B(C ₆ F ₅ ) ₄ ]In a molar ratio of 100.

Maintaining the reaction temperature at room temperature, and dissolving a small amount of sample in deuterated chloroform during the polymerization process ¹ The conversion rate is monitored by H NMR, the conversion rate reaches 99.0% after 1H of polymerization reaction, and the gamma-thioglycollate in the product is generated: the ratio of poly (gamma-thioglycollate) is 1. Then 2mL of a water/tetrahydrofuran mixture (volume ratio: 1: 30) was added to quench the reaction, the reaction solution was dropped into ethanol to precipitate the polymer, centrifuged, and the supernatant was discarded, followed by repeated dissolution with methylene chloride, dropping into ethanol to precipitate, centrifuging, and discarding the supernatant twice, followed by drying in a vacuum oven at room temperature for three days to obtain colorless poly (γ -thioglycollate).

The invention adopts Gel Permeation Chromatography (GPC) to detect the molecular weight and the molecular weight distribution of poly (gamma-thioglutamyl lactone), takes tetrahydrofuran as an eluent, has the flow rate of 1.0mL/min, takes polymethyl methacrylate as a standard substance to make a standard curve, and the result shows that the number average molecular weight of the poly (gamma-thiogmyl lactone) prepared in the embodiment is 20.5kg/mol, and the molecular weight distribution is 1.06.

Example 33

In a glove box under argon atmosphere, 0.01mmol of C was added to a dry glass bottle ₇ H ₇ BF ₄ And 0.4mL of toluene, followed by 1mmol (116.2mg, 0.10mL) of gamma-thionopentanolide monomer at an initial concentration of 2mol/L, catalyst C ₇ H ₇ BF ₄ In a concentration of 20mmol/L, monomer and C ₇ H ₇ BF ₄ The molar ratio of (a) to (b) is 100.

The reaction temperature was maintained at room temperature and a small sample was taken during the polymerizationDissolving in deuterated chloroform ¹ The conversion rate is monitored by H NMR, the conversion rate reaches 61.4% when the polymerization reaction is carried out for 72H, and the gamma-thiovalerolactone in the product is generated: the ratio of poly (γ -thioglycollate) was 9. Then 2mL of a water/tetrahydrofuran mixture (volume ratio: 1: 30) was added to quench the reaction, the reaction solution was dropped into ethanol to precipitate the polymer, centrifuged, and the supernatant was discarded, followed by repeated dissolution with methylene chloride, dropping into ethanol to precipitate, centrifuging, and discarding the supernatant twice, followed by drying in a vacuum oven at room temperature for three days to obtain colorless poly (γ -thioglycollate).

The invention adopts Gel Permeation Chromatography (GPC) to detect the molecular weight and molecular weight distribution of poly (gamma-thio valerolactone), tetrahydrofuran is taken as an eluent, the flow rate is 1.0mL/min, polymethyl methacrylate is taken as a standard substance to make a standard curve, and the result shows that the number average molecular weight of the poly (gamma-thio valerolactone) prepared by the embodiment is 32.3kg/mol, and the molecular weight distribution is 1.88.

Example 34

In a glove box under argon atmosphere, 0.01mmol of Al (C) was added to a dried glass bottle ₆ F ₅ ) ₃ Then 1mmol (116.2mg, 0.10mL) of alpha-methyl gamma-thiobutyrolactone monomer with an initial concentration of 10mol/L and Al (C) as catalyst ₆ F ₅ ) ₃ In a concentration of 100mmol/L, monomer and Al (C) ₆ F ₅ ) ₃ In a molar ratio of 100.

Keeping the reaction temperature at room temperature, and dissolving a small amount of sample in deuterated chloroform during the polymerization process ¹ The conversion rate is monitored by H NMR, the conversion rate reaches 89.3 percent when the polymerization reaction is carried out for 5 hours, and the proportion of the by-product of the alpha-methyl-gamma-thiobutyrolactone to the poly (alpha-methyl-gamma-thiobutyrolactone) in the generated product is 2. Then 2mL of a water/tetrahydrofuran mixture (volume ratio: 1The supernatant was removed twice and then dried in a vacuum oven at room temperature for three days to give colorless poly (. Alpha. -methyl-. Gamma. -thiobutyrolactone).

The invention adopts Gel Permeation Chromatography (GPC) to detect the molecular weight and molecular weight distribution of poly (alpha-methyl-gamma-thiobutyrolactone), tetrahydrofuran is taken as an eluent, the flow rate is 1.0mL/min, and a standard curve is made by taking polymethyl methacrylate as a standard substance, and the result shows that the number average molecular weight of the poly (alpha-methyl-gamma-thiobutyrolactone) prepared in the embodiment is 431.1kg/mol, and the molecular weight distribution is 1.80.

Example 35

In a glove box under argon atmosphere, 0.01mmol of [ Et ] was weighed in a dry 10mL Schlenk bottle ₃ O][B(C ₆ F ₅ ) ₄ ]0.4mL of toluene was added, taken out of the glove box and pre-cooled at 0 ℃ for 10min with a vacuum line. Then 1mmol (104.1 mg) of 1, 3-dioxolane-2-thione was weighed into a 5mL glass bottle in a glove box, 1.0mL of toluene was added to dissolve the monomers, taken out of the glove box and added to a previously precooled Schlenk bottle to react at 0 ℃. Initial concentration of monomer 0.7mol/L, catalyst [ Et ] ₃ O][B(C ₆ F ₅ ) ₄ ]In a concentration of 7.0mmol/L, monomer with [ Et ] ₃ O][B(C ₆ F ₅ ) ₄ ]In a molar ratio of 100.

Keeping the reaction temperature at 0 deg.C, stirring for 10min, collecting a small amount of supernatant, dissolving in deuterated chloroform, and passing ¹ H NMR monitored the conversion, which was greater than 99%. Then 2mL of a water/tetrahydrofuran mixture (volume ratio: 1: 20) was added to quench the reaction, the reaction solution was dropped into ethanol to precipitate the polymer, the polymer was centrifuged, the supernatant was discarded, the dissolution with methylene chloride was repeated, the solution was dropped into ethanol to precipitate, the supernatant was centrifuged and discarded twice, and the solution was dried in a vacuum oven at room temperature for three days to obtain white polythiocarbonate.

The melting temperature and the glass transition temperature of the poly (1, 3-dioxolane-2-thione) are detected by a Differential Scanning Calorimetry (DSC), and the result shows that the glass transition temperature of the poly (1, 3-dioxolane-2-thione) prepared in the embodiment is 24.5 ℃.

Example 36

In a glove box under argon atmosphere, 0.01mmol of [ Et ] was weighed in a dry 10mL Schlenk bottle ₃ O][B(C ₆ F ₅ ) ₄ ]0.30mL of toluene was added, taken out of the glove box and pre-cooled at 0 ℃ for 10min with a vacuum line. Then 4mmol (472.6mg, 0.38mL) of (S) -4-methyl-1, 3-dioxolane-2-thione monomer was weighed into a 5mL glass bottle in a glove box, dissolved by adding 0.40mL of toluene, taken out of the glove box, added to a previously precooled Schlenk bottle, and reacted at 0 ℃. Initial concentration of monomer 3.7mol/L, catalyst [ Et ] ₃ O][B(C ₆ F ₅ ) ₄ ]In a concentration of 9.2mmol/L, monomer and [ Et ] ₃ O][B(C ₆ F ₅ ) ₄ ]The molar ratio of (1) is 400.

Keeping the reaction temperature at 0 deg.C, stirring for reaction for 120min, dissolving a small amount of sample in deuterated chloroform, and passing through ¹ H NMR monitored the conversion, which was greater than 99%. Then 2mL of a water/tetrahydrofuran mixture (volume ratio: 1: 20) was added to quench the reaction, the reaction solution was dropped into ethanol to precipitate the polymer, the polymer was centrifuged, the supernatant was discarded, the dissolution with methylene chloride was repeated, the solution was dropped into ethanol to precipitate, the supernatant was centrifuged and discarded twice, and the solution was dried in a vacuum oven at room temperature for three days to obtain a colorless transparent polythiocarbonate.

Subjecting the polymer to Nuclear Magnetic Resonance (NMR) detection, ¹ h NMR spectrum and ¹³ the C NMR spectra are shown in FIGS. 37 and 38, respectively.

The melting temperature and the glass transition temperature of the poly- (S) -4-methyl-1, 3-dioxolane-2-thione are detected by a Differential Scanning Calorimetry (DSC), and the result shows that the glass transition temperature of the poly (S) -4-methyl-1, 3-dioxolane-2-thione prepared in the embodiment is 17.2 ℃.

The invention adopts Gel Permeation Chromatography (GPC) to detect the molecular weight and the molecular weight distribution of poly- (S) -4-methyl-1, 3-dioxolane-2-thione, tetrahydrofuran is taken as a mobile phase, the flow rate is 1.0mL/min, and a standard curve is made by taking polymethyl methacrylate as a standard substance, and the result shows that the number average molecular weight of the poly- (S) -4-methyl-1, 3-dioxolane-2-thione prepared by the embodiment is 38.9kg/mol, and the molecular weight distribution is 1.26.

Example 37

In a glove box under argon atmosphere, 0.01mmol of [ Et ] was weighed in a dry 10mL Schlenk bottle ₃ O][B(C ₆ F ₅ ) ₄ ]0.30mL of toluene was added, taken out of the glove box and pre-cooled at 0 ℃ for 10min with a vacuum line. Then 4mmol (472.6mg, 0.38mL) of (R) -4-methyl-1, 3-dioxolane-2-thione monomer was weighed into a 5mL glass bottle in a glove box, dissolved by adding 0.40mL of toluene, taken out of the glove box, added to a previously precooled Schlenk bottle, and reacted at 0 ℃. Initial concentration of monomer 3.7mol/L, catalyst [ Et ] ₃ O][B(C ₆ F ₅ ) ₄ ]In a concentration of 9.2mmol/L, monomer and [ Et ] ₃ O][B(C ₆ F ₅ ) ₄ ]The molar ratio of (1) is 400.

Keeping the reaction temperature at 0 deg.C, stirring for 50min, dissolving a small amount of sample in deuterated chloroform, and allowing reaction to pass ¹ H NMR monitored the conversion, which was greater than 99%. Then 2mL of a water/tetrahydrofuran mixture (volume ratio: 1: 20) was added to quench the reaction, the reaction solution was dropped into ethanol to precipitate the polymer, the polymer was centrifuged, the supernatant was discarded, the dissolution with methylene chloride, the dropping into ethanol to precipitate, the centrifugation and the discarding of the supernatant were repeated twice, and then the reaction solution was dried in a vacuum oven at room temperature for three days to obtain colorless transparent poly (monothiocarbonate).

The invention adopts Gel Permeation Chromatography (GPC) to detect the molecular weight and the molecular weight distribution of poly- (R) -4-methyl-1, 3-dioxolane-2-thione, tetrahydrofuran is taken as a mobile phase, the flow rate is 1.0mL/min, and a standard curve is made by taking polymethyl methacrylate as a standard substance, and the result shows that the number average molecular weight of the poly- (R) -4-methyl-1, 3-dioxolane-2-thione prepared by the embodiment is 45.3kg/mol, and the molecular weight distribution is 1.04.

The melting temperature and the glass transition temperature of the poly- (R) -4-methyl-1, 3-dioxolane-2-thione are detected by a Differential Scanning Calorimetry (DSC), and the result shows that the glass transition temperature of the poly- (R) -4-methyl-1, 3-dioxolane-2-thione prepared by the embodiment is 18.2 DEG C

Example 38

In a glove box under argon atmosphere, 0.01mmol of [ Et ] was weighed in a dry 10mL Schlenk bottle ₃ O][B(C ₆ F ₅ ) ₄ ]0.4mL of toluene was added, taken out of the glove box and connected to a vacuum line for precooling at 0 ℃ for 10min. Then 1mmol (152.6 mg) of 4- (chloromethyl) -1, 3-dioxolane-2-thione monomer was weighed into a 5mL glass bottle in a glove box, dissolved by adding 1.0mL of toluene, taken out of the glove box, added to a previously precooled Schlenk bottle, and reacted at 0 ℃. Initial concentration of monomer 0.7mol/L, catalyst [ Et ] ₃ O][B(C ₆ F ₅ ) ₄ ]In a concentration of 7.0mmol/L, monomer with [ Et ] ₃ O][B(C ₆ F ₅ ) ₄ ]In a molar ratio of 100.

Keeping the reaction temperature at 0 deg.C, stirring for 10min, dissolving a small amount of sample in deuterated chloroform, and allowing reaction to pass ¹ H NMR monitored the conversion, which was greater than 99%. Then 2mL of a water/tetrahydrofuran mixture (volume ratio: 1: 20) was added to quench the reaction, the reaction solution was dropped into ethanol to precipitate the polymer, the polymer was centrifuged, the supernatant was discarded, the dissolution with methylene chloride, the dropping into ethanol to precipitate, the centrifugation and the discarding of the supernatant were repeated twice, and then the reaction solution was dried in a vacuum oven at room temperature for three days to obtain white poly (monothiocarbonate). Performing Nuclear Magnetic Resonance (NMR) detection to obtain a sample, ¹ the H NMR spectrum is shown in FIG. 39.

The melting temperature and the glass transition temperature of the poly-4- (chloromethyl) -1, 3-dioxolane-2-thione are detected by a Differential Scanning Calorimetry (DSC), and the result shows that the glass transition temperature of the poly-4- (chloromethyl) -1, 3-dioxolane-2-thione prepared in the embodiment is 41.6 ℃.

The invention adopts Gel Permeation Chromatography (GPC) to detect the molecular weight and the molecular weight distribution of poly 4- (chloromethyl) -1, 3-dioxolane-2-thione, tetrahydrofuran is taken as a mobile phase, the flow rate is 1.0mL/min, and a standard curve is drawn by taking polymethyl methacrylate as a standard substance, and the result shows that the number average molecular weight of the poly 4- (chloromethyl) -1, 3-dioxolane-2-thione prepared in the embodiment is 25.8kg/mol, and the molecular weight distribution is 1.37.

Example 39

In a glove box under argon atmosphere, 0.01mmol of [ Et ] was weighed in a dry 10mL Schlenk bottle ₃ O][B(C ₆ F ₅ ) ₄ ]0.4mL of toluene was added, taken out of the glove box and pre-cooled at 0 ℃ for 10min with a vacuum line. Then 1mmol (152.6 mg) of (R) -4- (chloromethyl) -1, 3-dioxolane-2-thione monomer was weighed into a 5mL glass bottle in a glove box, dissolved by adding 1.0mL of toluene, taken out of the glove box, added to a previously precooled Schlenk bottle, and reacted at 0 ℃. Initial concentration of monomer 0.7mol/L, catalyst [ Et ] ₃ O][B(C ₆ F ₅ ) ₄ ]In a concentration of 7.0mmol/L, monomer with [ Et ] ₃ O][B(C ₆ F ₅ ) ₄ ]The molar ratio of (a) to (b) is 100.

Keeping the reaction temperature at 0 deg.C, stirring for 10min, collecting a small amount of supernatant, dissolving in deuterated chloroform, and passing ¹ H NMR monitored the conversion, which was greater than 99%. Then 2mL of a water/tetrahydrofuran mixture (volume ratio: 1: 20) was added to quench the reaction, the reaction solution was dropped into ethanol to precipitate the polymer, the polymer was centrifuged, the supernatant was discarded, the dissolution with methylene chloride was repeated, the solution was dropped into ethanol to precipitate, the supernatant was centrifuged and discarded twice, and the solution was dried in a vacuum oven at room temperature for three days to obtain white polythiocarbonate. ¹ The H NMR spectrum is shown in FIG. 40.

The melting temperature and the glass transition temperature of the poly- (R) -4- (chloromethyl) -1, 3-dioxolane-2-thione are detected by adopting a Differential Scanning Calorimetry (DSC), and the result shows that the glass transition temperature of the poly (R) -4- (chloromethyl) -1, 3-dioxolane-2-thione prepared by the embodiment is 39.8 ℃ and the melting temperature is 162.8 ℃.

The invention adopts Gel Permeation Chromatography (GPC) to detect the molecular weight and the molecular weight distribution of poly- (R) -4- (chloromethyl) -1, 3-dioxolane-2-thione, tetrahydrofuran is taken as a mobile phase, the flow rate is 1.0mL/min, and polymethyl methacrylate is taken as a standard substance to make a standard curve, and the result shows that the number average molecular weight of the poly- (R) -4- (chloromethyl) -1, 3-dioxolane-2-thione prepared in the embodiment is 24.5kg/mol, and the molecular weight distribution is 1.35.

Example 40

In a glove box under argon atmosphere, 0.01mmol of [ Et ] was weighed in a dry 10mL Schlenk bottle ₃ O][B(C ₆ F ₅ ) ₄ ]0.4mL of toluene was added, taken out of the glove box and connected to a vacuum line for precooling at 0 ℃ for 10min. Then 1mmol (152.6 mg) of the thiocarbonate monomer (S) -4- (chloromethyl) -1, 3-dioxolane-2-thione was weighed out into a 5mL glass bottle in a glove box, dissolved by adding 1.0mL of toluene, taken out of the glove box, added to a previously precooled Schlenk bottle, and reacted at 0 ℃. Initial concentration of monomer 0.7mol/L, catalyst [ Et ] ₃ O][B(C ₆ F ₅ ) ₄ ]In a concentration of 7.0mmol/L, monomer with [ Et ] ₃ O][B(C ₆ F ₅ ) ₄ ]In a molar ratio of 100.

Keeping the reaction temperature at 0 deg.C, stirring for 10min, collecting a small amount of supernatant, dissolving in deuterated chloroform, and passing ¹ H NMR monitored the conversion, which was greater than 99%. The reaction was then quenched by addition of 2mL of a water/tetrahydrofuran mixture (volume ratio 1And dissolving by using dichloromethane repeatedly, dropping into ethanol for settling, centrifuging, removing supernatant twice, and then drying in a vacuum drying oven at room temperature for three days to obtain white poly (monothiocarbonate).

The melting temperature and the glass transition temperature of the poly- (S) -4- (chloromethyl) -1, 3-dioxolane-2-thione are detected by a Differential Scanning Calorimetry (DSC), and the result shows that the glass transition temperature and the melting temperature of the poly- (S) -4- (chloromethyl) -1, 3-dioxolane-2-thione prepared in the example are 39.0 ℃ and 163.0 ℃.

The invention adopts Gel Permeation Chromatography (GPC) to detect the molecular weight and the molecular weight distribution of poly- (S) -4- (chloromethyl) -1, 3-dioxolane-2-thione, uses tetrahydrofuran as a mobile phase, has the flow rate of 1.0mL/min, uses polymethyl methacrylate as a standard substance to make a standard curve, and the result shows that the number average molecular weight of the poly- (S) -4- (chloromethyl) -1, 3-dioxolane-2-thione prepared in the example is 19.3kg/mol, and the molecular weight distribution is 1.43.

EXAMPLE 41

In a glove box under argon atmosphere, 0.01mmol of [ Et ] was weighed in a dry 10mL Schlenk bottle ₃ O][B(C ₆ F ₅ ) ₄ ]0.4mL of toluene was added, taken out of the glove box and connected to a vacuum line for precooling at 0 ℃ for 10min. Then 1mmol (180.2 mg) of 4-phenyl-1, 3-dioxolane-2-thione monomer was weighed in a 5mL glass bottle in a glove box, dissolved by adding 1.0mL of toluene, taken out of the glove box and added to a previously precooled Schlenk bottle to react at 0 ℃. Initial concentration of monomer 0.7mol/L, catalyst [ Et ] ₃ O][B(C ₆ F ₅ ) ₄ ]In a concentration of 7.0mmol/L, monomer with [ Et ] ₃ O][B(C ₆ F ₅ ) ₄ ]In a molar ratio of 100.

Keeping the reaction temperature at 0 deg.C, stirring for 10min, dissolving a small amount of sample in deuterated chloroform, and allowing reaction to pass ¹ H NMR monitored the conversion, which was greater than 99%. Then 2mL of a water/tetrahydrofuran mixture was addedVolume ratio of 1. Subjecting the polymer to Nuclear Magnetic Resonance (NMR) detection, ¹ h NMR spectrum and ¹³ the C NMR spectra are shown in FIGS. 41 and 42, respectively.

The melting temperature and the glass transition temperature of the poly 4-phenyl-1, 3-dioxolane-2-thione are detected by a Differential Scanning Calorimetry (DSC), and the result shows that the glass transition temperature of the poly 4-phenyl-1, 3-dioxolane-2-thione prepared in the embodiment is 59.5 ℃.

The invention adopts Gel Permeation Chromatography (GPC) to detect the molecular weight and molecular weight distribution of poly 4-phenyl-1, 3-dioxolane-2-thione, tetrahydrofuran is taken as a mobile phase, the flow rate is 1.0mL/min, and a standard curve is made by taking poly 4-phenyl-1, 3-dioxolane-2-thione as a standard substance, and the result shows that the number average molecular weight of the poly monothiocarbonate prepared in the embodiment is 19.7kg/mol, and the molecular weight distribution is 2.05.

Example 42

In a glove box under an argon atmosphere, 0.05mmol (7.6mg, 0.0074mL) of DBU and 0.05mmol (5.4mg, 0.0052mL) of benzyl alcohol were weighed out into a dry 5mL glass bottle and mixed, and 1.0mL of toluene was added until sufficiently dissolved. Then, 5mmol (590.7mg, 0.47mL) of the thiocarbonate monomer (R) -4-methyl-1, 3-dioxolan-2-thione was charged into a 5mL glass bottle and reacted at 25 ℃. The initial concentration of monomer was 3.7mol/L, the concentration of catalyst DBU was 37mmol/L, and the molar ratio of monomer to DBU was 100.

Keeping the reaction temperature at 25 ℃, stirring and reacting for 60 hours, taking a small amount of sample, dissolving in deuterated chloroform, and passing through ¹ H NMR monitored the conversion, which was greater than 99%. Then, 2mL of a mixture of benzoic acid and methylene chloride (10 mg/mL) was added thereto to quench the reaction, and the reaction mixture was quenchedDropping into ethanol to settle the polymer, centrifuging, discarding the supernatant, repeatedly dissolving with dichloromethane, dropping into ethanol to settle, centrifuging, discarding the supernatant twice, and drying in a vacuum drying oven at room temperature for three days to obtain colorless transparent poly (monothiocarbonate).

The invention adopts Gel Permeation Chromatography (GPC) to detect the molecular weight and molecular weight distribution of the poly (monothiocarbonate), tetrahydrofuran is taken as a mobile phase, the flow rate is 1.0mL/min, and polymethyl methacrylate is taken as a standard substance to make a standard curve, and the result shows that the number average molecular weight of the poly (monothiocarbonate) prepared by the embodiment is 4.9kg/mol, and the molecular weight distribution is 1.38.

Example 43

In a glove box under an argon atmosphere, 0.05mmol (7.6 mg, 0.0074mL) of DBU and 0.05mmol (5.4 mg, 0.0052mL) of benzyl alcohol were weighed out into a dry 5mL glass bottle and mixed, and 0.5mL of toluene was added thereto until sufficiently dissolved. In another 5mL glass vial, 0.05mmol (18.5 mg) of 1- [3, 5-bis (trifluoromethyl) phenyl ] -3-cyclohexylthiourea and 5mmol (590.7mg, 0.47mL) of the thiocarbonate monomer (R) -4-methyl-1, 3-dioxolane-2-thione were weighed out and mixed, and 0.5mL of toluene was added to dissolve sufficiently. The solutions in the two vials were mixed well and reacted at 25 ℃. The initial concentration of monomer was 3.7mol/L, the concentration of catalyst DBU was 37mmol/L, and the molar ratio of monomer to DBU was 100.

Keeping the reaction temperature at 25 ℃, stirring and reacting for 120h, taking a small amount of sample, dissolving in deuterated chloroform, and passing ¹ H NMR monitored the conversion, which was greater than 99%. Then 2mL of benzoic acid/dichloromethane mixed solution (with the concentration of 10 mg/mL) is added to quench the reaction, the reaction solution is dripped into ethanol to settle the polymer, the centrifugation is carried out, the supernatant fluid is discarded, then the dissolution by dichloromethane, the dripping into ethanol to settle, the centrifugation and the supernatant fluid discarding are repeated twice, and the drying is carried out in a vacuum drying oven at room temperature for three days to obtain the colorless and transparent poly monothiocarbonate.

The invention adopts Gel Permeation Chromatography (GPC) to detect the molecular weight and molecular weight distribution of the poly (monothiocarbonate), tetrahydrofuran is taken as a mobile phase, the flow rate is 1.0mL/min, and polymethyl methacrylate is taken as a standard substance to make a standard curve, and the result shows that the number average molecular weight of the poly (monothiocarbonate) prepared by the embodiment is 3.2kg/mol, and the molecular weight distribution is 1.49.

Example 44

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

Keeping the reaction temperature at room temperature, stirring for 18h, taking a small amount of sample, dissolving in deuterated chloroform, and reacting by ¹ H NMR monitors the conversion rate, the conversion rate is 93.6%, and the proportion of gamma-thiovalerolactone byproduct, namely poly- (S) - (gamma-thiovalerolactone) is less than 1. The reaction was then quenched by the addition of 10mL of a water/tetrahydrofuran mixture (volume ratio 1: 20), the reaction was dropped into ethanol to allow the polymer to settle, filtered, and washed with ethanol, and then dried in a vacuum oven at room temperature for three days to give poly- (S) - (γ -thioglycollactone) as a white solid.

The melting temperature and the glass transition temperature of the poly- (S) - (gamma-thioglycollactone) are detected by Differential Scanning Calorimetry (DSC), and the result shows that the glass transition temperature of the poly- (S) - (gamma-thioglycollactone) prepared in the example is about-8.8 ℃ and the melting point is about 82.3 ℃.

The thermal stability of poly- (S) - (gamma-thiovalerolactone) was measured by thermogravimetric analysis (TGA) according to the present invention, and the results show that poly- (S) - (gamma-thiovalerolactone) prepared in this example has an initial decomposition temperature (T) _d Temperature at 5% weight loss) at 235.5 ℃.

The invention adopts Gel Permeation Chromatography (GPC) to detect the molecular weight and molecular weight distribution of poly- (S) - (gamma-thiovalerolactone), tetrahydrofuran is taken as an eluent, the flow rate is 1.0mL/min, and polymethyl methacrylate is taken as a standard substance to make a standard curve, and the result shows that the number average molecular weight of the poly- (S) - (gamma-thiovalerolactone) prepared in the embodiment is 106.1kg/mol, and the molecular weight distribution is 1.40.

The poly- (S) - (gamma-thio-valerolactone) prepared by the invention is subjected to mechanical tensile test, and the result shows that the (S) -poly- (gamma-thio-valerolactone) prepared in the example has the elongation at break of 638%, the yield stress of 9.05MPa and the breaking stress of 24.27MPa.

Example 45

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

Keeping the reaction temperature at room temperature, stirring for 18h, taking a small amount of sample, dissolving in deuterated chloroform, and reacting ¹ H NMR monitored the conversion of 98.5%, with a ratio of gamma-thioglycollate by-product to poly- (R) - (gamma-thioglycollate) of 1. The reaction was then quenched by the addition of 10mL of a water/tetrahydrofuran mixture (volume ratio 1: 20), the reaction was dropped into ethanol to allow the polymer to settle, filtered, and washed with ethanol, and then dried in a vacuum oven at room temperature for three days to give white (R) -poly (γ -thioglycollate).

The melting temperature and the glass transition temperature of the poly- (R) - (gamma-thioglycollactone) are detected by Differential Scanning Calorimetry (DSC), and the result shows that the glass transition temperature of the poly- (R) - (gamma-thioglycollactone) prepared in the example is about-8.9 ℃ and the melting point is about 81.0 ℃.

The invention adopts Gel Permeation Chromatography (GPC) to detect the molecular weight and molecular weight distribution of poly- (R) - (gamma-thio-valerolactone), tetrahydrofuran is taken as an eluent, the flow rate is 1.0mL/min, and polymethyl methacrylate is taken as a standard substance to make a standard curve, and the result shows that the number average molecular weight of the poly- (R) - (gamma-thio-valerolactone) prepared by the embodiment is 101.2kg/mol, and the molecular weight distribution is 1.68.

Comparative example 1

In a dry Schlenk flask under argon atmosphere, 0.02mmol of potassium thioacetate, 0.02mmol of 18 crown 6 ether and 0.2mL of N, N-dimethylformamide were added, followed by 2mmol (232mg, 0.2mL) of gamma-thiovalerolactone monomer at an initial concentration of 5mol/L and a concentration of catalyst potassium thioacetate of 50mmol/L in a molar ratio of monomer to potassium thioacetate and 18 crown 6 ether of 100.

The glovebox was removed and a Schlenk flask was connected to a vacuum line with argon protection, and after stirring the reaction at 80 ℃ for 48 hours, 0.15mL of a toluene solution containing 0.05mL of allyl chloride was added to terminate the reaction, and a small amount of the solution was taken out ¹ H NMR analysis to determine conversion, monomer conversion 66.5%, dimer in product: gamma-thiovalerolactone: the ratio of poly (gamma-thiogalactone) is 15.0. The remaining reaction solution was poured into ethanol, and no polymer precipitated since an oligomer was produced.

Effect example 1: performance parameter determination:

1.1 molecular weight control Property

Hair brushMin number average molecular weight (M) of polythioesters determined by gel permeation chromatography, model Waters E2695 _n ) And molecular weight distribution (D = M) _w /M _n ) Wherein the model of the chromatographic column is Agilent Plgel 5 μm, and the model of the differential detector is Wyatt

T-Rex, eluent tetrahydrofuran, column temperature 40 deg.C, and flow rate 1.0mL/min. A standard curve is made by taking polymethyl methacrylate as a standard substance, and the result shows that: the polythioester prepared by the embodiment of the invention has the number average molecular weight of 3.2 kg/mol-431.1 kg/mol and the molecular weight distribution index of 1.01-2.05.

In [ Ph ₃ C][B(C ₆ F ₅ ) ₄ ]Under the reaction conditions of the main catalyst, the amount of the catalyst was changed, and polymerization reactions were carried out at monomer-to-catalyst ratios of 100, 200, 1, 400, 1, 800, and 1200. The number average molecular weight linearly increases with the monomer to catalyst ratio, as shown in FIG. 31 (the catalyst here refers to the main catalyst, and the abscissa in FIG. 31 is the molar ratio of the monomer gamma-thiovalerolactone to the catalyst, "\9632;" is the number average molecular weight of the polymer, ". Diamond. -like" is the molecular weight distribution of the polymer), and has good molecular weight control.

1.2 thermal Performance analysis

The thermal decomposition temperature of the polymer is obtained by performing Thermal Gravimetric Analysis (TGA) through a TGA 550 thermogravimetric analyzer of TA company, and the test of the thermogravimetric analysis is carried out in N ₂ The test is carried out in the atmosphere, the test temperature range is 25-700 ℃, and the heating rate is 15 ℃/min. Example 2 initial decomposition temperature (T) of Poly (. Gamma. -thioglutamyl lactone) Polymer _d Temperature at 5% weight loss) at 251 ℃, as shown in fig. 32; initial decomposition temperature (T) of Poly (. Gamma. -thio-caprolactone) prepared in example 3 _d Temperature at 5% weight loss) at 287 ℃; initial decomposition temperature (T) of Poly (. Gamma. -thio-heptolactone) prepared in example 4 _d Temperature at 5% weight loss) at 282 deg.C(ii) a Initial decomposition temperature (T) of Poly (. Gamma. -thio-octanolides) prepared in example 5 _d Temperature at 5% weight loss) at 268 ℃; initial decomposition temperature (T) of Poly (. Gamma. -thiononalactone) prepared in example 6 _d Temperature at 5% weight loss) at 245 ℃; initial decomposition temperature (T) of Poly (. Gamma. -thio-decalactone) prepared in example 7 _d Temperature at 5% weight loss) at 253 ℃; initial decomposition temperature (T) of Poly (. Gamma. -thiaundecanolide) prepared in example 8 _d Temperature at 5% weight loss) at 248 ℃; initial decomposition temperature (T) of Poly (. Gamma. -thiododecalactone) prepared in example 9 _d Temperature at 5% weight loss) at 273 ℃; initial decomposition temperature (T) of Poly (gamma-methyl-gamma-thio-decalactone) prepared in example 10 _d Temperature at 5% weight loss) at 268 ℃; initial decomposition temperature (T) of Poly (. Beta. -methyl-. Gamma. -thio-octanolactone) prepared in example 11 _d Temperature at 5% weight loss) at 290 ℃; initial decomposition temperature (T) of Poly (. Alpha. -methylgamma. -thiobutyrolactone) prepared in example 12 _d Temperature at 5% weight loss) at 259.1 ℃; initial decomposition temperature (T) of Poly (. Beta. -methyl-. Gamma. -thiobutyrolactone) prepared in example 13 _d Temperature at 5% weight loss) at 260 ℃; initial decomposition temperature (T) of Poly (. Gamma. -thioglycolide) obtained in example 15 _d Temperature at 5% weight loss) at 255 ℃; initial decomposition temperature (T) of Poly-4- (chloromethyl) -1, 3-dioxolan-2-thione prepared in example 38 _d Temperature at 5% weight loss) at 270 ℃; initial decomposition temperature (T) of Poly- (S) - (gamma-thioglutamyl lactone) prepared in example 44 _d Temperature at 5% weight loss) at 235.5 ℃; has better thermal stability.

Polythioesters prepared in the above examples were analyzed by Differential Scanning Calorimetry (DSC) using a differential scanning calorimeter model DSC 2000, model TA, inc., and representative curves are shown in FIGS. 33 and 34. The test result shows that the glass transition temperature T of the polythioester provided by the invention _g Is positioned in the range of-57.0 to 59.5 ℃, has great adjustability and can meet different use scenes.

Among them, DSC curves of poly (γ -thiacaprolactone) (abbreviation: PTGCL), poly (γ -thiapimelactone) (abbreviation: PTGHL), poly (γ -thiaoctanolide) (abbreviation: PTGOL), poly (γ -thianonalactone) (abbreviation: PTGNL), poly (γ -thiadecalactone) (abbreviation: PTGDL), poly (γ -thiaundecanolactone) (abbreviation: PTGUDL), poly (γ -thiadodecalactone) (abbreviation: PTGDDL), and poly (γ -methyl- γ -thiadecanolactone) (abbreviation: PTGMDL) obtained in examples 3 to 10 are shown in FIG. 33.

DSC curves of poly (. Gamma. -thiogalactone) (abbreviation: PTGVL) obtained in example 2, poly (. Alpha. -methyl-. Gamma. -thiobutyrolactone) (abbreviation: P. Alpha. -MeTBL) and poly (. Beta. -methyl-. Gamma. -thiobutyrolactone) (abbreviation: P. Beta. -MeTBL) obtained in examples 12 to 13, poly (. Beta. -methyl-. Gamma. -thiooctanolide) (abbreviation: PTWL) obtained in example 11 and poly (cis-hexahydroisobenzofuran-1-one) (abbreviation: P3,4-S6 TBL) obtained in example 15 are shown in FIG. 34.

The DSC curves of poly-1, 3-dioxolan-2-thione (abbreviation: PEMTC) obtained in example 35, poly- (S) -4-methyl-1, 3-dioxolan-2-thione (abbreviation: S-PPMTC) obtained in example 36, poly- (R) -4-methyl-1, 3-dioxolan-2-thione (abbreviation: R-PPMTC) obtained in example 37, poly-4-chloromethyl-1, 3-dioxolan-2-thione (abbreviation: PCMMTC) obtained in example 38, and poly-4-phenyl-1, 3-dioxolan-2-thione (abbreviation: PBPBMTC) obtained in example 41 were superimposed as shown in FIG. 43.

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

The DSC chart 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 (. Gamma. -thioglycollate) (abbreviation: S-PTGVL) obtained in example 44 is shown in FIG. 48.

1.3 mechanical Property testing

The polymer prepared in the examples is first hot pressed with tetrafluoroethylene template to prepare polymer film and cut into dumbbell-shaped tensile sample strips with effective tensile size of 10X 5X 1mm ³ Then, the resultant was subjected to stretching at 30 ℃ and a stretching rate of 5mm/min by a LinkamTST350 tensile tester in accordance with ASTM standards, and the final data was averaged over five experiments.

The results of the mechanical tensile test of poly- (S) - (gamma-thioglutaryl lactone) prepared in example 44 are shown in FIG. 49, and the experiments of the mechanical tensile test (shown in FIG. 49) show that the prepared poly- (S) -gamma-thioglutaryl lactone) has the elongation at break of 638%, the yield stress of 9.05MPa and the breaking stress of 24.27MPa. The poly (gamma-thiobutyrolactone) provided by the invention is a strong and tough polymer material, and all indexes of a mechanical tensile test are superior to those of low-density polyethylene (elongation at break is 430% and stress at break is 10.6 MPa) and isotactic polypropylene (elongation at break is 420% and stress at break is 26.0 MP), and the tensile property of the poly (gamma-thiobutyrolactone) is close to that of high-density polypropylene (elongation at break is 420% and stress at break is 26.0 MP). In terms of elongation at break, poly- (S) - (gamma-thiovalerolactone) is 1.5 times that of the commercial low density polyethylene and isotactic polypropylene, which shows that the toughness is obviously better than that of the commercial low density polyethylene and isotactic polypropylene.

The mechanical properties of the ternary random copolymer obtained in example 14 were tested: the mechanical tensile test (as shown in fig. 46) has an elongation at break of 1451.30% and a stress at break of 16.62MPa; in addition, the cyclic tensile test (as shown in FIG. 47) shows that the elastic recovery rate of the ternary random copolymer is 72.3%, which indicates that the ternary random copolymer provided by the invention is a strong and tough elastomeric polymer material. All indexes of a mechanical tensile test are superior to those of 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 degradation analysis

Polythioesters and polymonosulfocarbonates of the present invention have degradability incomparable to commercial polyolefins. Taking poly (gamma-thioglycollate) as an example, rapid and controlled degradation can occur under specific conditions: at room temperature, when 1,5, 7-triazabicyclo (4.4.0) dec-5-ene (TBD) was added as a degradation catalyst, poly (. Gamma. -thioglutaryl lactone) obtained in example 4 was rapidly and quantitatively degraded into. Gamma. -thioglutaryl lactone within 1min, as shown in FIG. 35. The specific reaction process is as follows: 232.4mg of poly (gamma-thioglycollate) after drying was dissolved in 2.5mL of anhydrous dichloromethane, 0.5mL of a dichloromethane solution of TBD (0.02 mol/L) was added to the resulting clear solution, and the reaction was stirred for 1min to find that the polymer had been completely degraded into gamma-thioglycollate.

Through the performance analysis of the polymer obtained by the invention, the sulfur-containing homopolymer and copolymer prepared by the invention provide convenience for industrial production of environment-friendly sulfur-containing high molecular materials. The synthesized sulfur-containing polymer has the advantages of high molecular weight, good molecular weight control, large-range adjustable physical properties, excellent degradability and the like, can be used as products such as plastics, rubber, elastomers, fibers and the like, and has wide application.

Claims

1. A process for the preparation of a sulfur-containing polymer, comprising the steps of: in an organic solvent, in the presence of a main catalyst, carrying out polymerization reaction on one or more than one polymerization monomer;

wherein the main catalyst is an anionic main catalyst or a cationic main catalyst;

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

the cation main catalyst is one or more of zwitterion-pair catalyst, neutral Lewis acid catalyst and protonic acid (ester) catalyst;

the polymerized monomer is independently a five-membered ring framework compound shown as the formula (I):

wherein, the first and the second end of the pipe are connected with each other,

is->

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, hydroxy, C _6-10 Aryl radical, C _1-10 Alkyl or C _1-10 An alkenyl group; said C _1-10 Alkyl optionally substituted by halogen, hydroxy and C _6-10 One or more substitutions in aryl;

or, R ₁₂ And R ₁₃ 、R ₁₃ And R ₁₄ 、R ₂₂ And R ₂₃ 、R ₃₂ And R ₃₃ 、R ₄₂ And R ₄₁ Or R ₅₂ And R ₅₃ Together with the atoms linking them form C _3-10 Cycloalkyl, C _3-10 Cycloalkenyl or C _6-10 An aryl group;

when the main catalyst is an anionic main catalyst and the polymeric monomer is one, the polymeric monomer is not

2. The method of claim 1, wherein one or more of the following conditions are satisfied:

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

(2) In the compound of the formula (I), C _1-10 Alkyl is independently C _1-8 Alkyl groups 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), C _1-10 Alkenyl is independentGround is C _1-8 Alkenyl radicals, e.g. C _1-4 Alkenyl, such as vinyl;

(4) In the compound of the formula (I), C _6-10 Aryl is independently phenyl;

(5) In the compound represented by the formula (I), C _3-10 Cycloalkyl is independently cyclopentyl, cyclohexyl, or cycloheptyl;

(6) In the compound of the formula (I), C _3-10 Cycloalkenyl is independently cyclohexenyl;

(7) The polymerization reaction is carried out in the atmosphere of protective gas, and the protective gas is nitrogen and/or argon;

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

(9) The organic solvent is one or more of straight-chain hydrocarbon solvent, halogenated hydrocarbon solvent, cyclic ether solvent, aromatic hydrocarbon solvent, halogenated aromatic hydrocarbon solvent and amide solvent;

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

(11) In the anion main catalyst, the phosphazene base is shown by the following structure:

wherein R and R' are independently C ₁ -C ₄ Alkyl groups of (a); n1 is 0, 1,2 or 3; y is 0, 1,2 or 3;

(12) In the anionic main catalyst, the guanidine organic alkali is 1,5, 7-triazabicyclo (4.4.0) deca-5-ene and/or 7-methyl-1, 5, 7-triazabicyclo [4.4.0] deca-5-ene;

(13) In the anionic main catalyst, the amidine organic base is 1, 8-diazabicyclo [5.4.0] undec-7-ene;

(14) In the anionic main catalyst, the N-heterocyclic carbene organic base is represented by the following structure:

wherein R is _1a And R _2a Independently hydrogen, alkyl or aryl; r _3a And R _4a Independently is an alkyl or aryl group;

(15) In the anionic main catalyst, the N-heterocyclic olefin organic base is represented by the following structure:

wherein R is _1b And R _2b Independently hydrogen, alkyl or aryl; r is _3b And R _4b Independently is an alkyl or aryl group; r is _5b Is hydrogen or alkyl;

(16) In the anion main catalyst, the carboxylate is metal carboxylate or organic carboxylate; wherein the cation in the metal carboxylate is an alkali metal cation; the cation in the organic carboxylate is quaternary ammonium cation, imidazolium cation, phosphazenium cation, bis (triphenylphosphine) ammonium cation or amidinium cation; the anions in the metal carboxylate and the organic carboxylate are independently represented by the following structures:

wherein R is _1c Is alkyl or aryl;

(17) In the anion main catalyst, the thiocarboxylate is metal thiocarboxylate; wherein the cation in the thiocarboxylate is an alkali metal cation; the anion in the thiocarboxylate salt is represented by the structure:

wherein R is _1e Is alkyl or aryl;

(18) In the cationic main catalyst, the zwitter-ion pair catalyst is represented by the following structure:

[R] ⁺ [X] ^-

(VIII)

wherein, the [ R ] is] ⁺ Is a carbenium ion, a silylium ion, an oxonium ion, a sulfonium ion, a phosphonium ion, a chloronium ion, a bromonium ion or an iodonium ion, [ X ] is]-is a borate, aluminate, phosphate, sulfonate, sulfonimide, antimonate or arsenate anion;

(19) In the cation main catalyst, the neutral Lewis acid type catalyst is a boron complex or an aluminum complex;

(20) In the cation main catalyst, the protonic acid (ester) type catalyst is sulfonic acid, sulfonic ester, sulfimide, N-substituted sulfimide, oxonium protonic acid, sulfonium protonic acid or diphosphonimide ester;

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

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

(23) The polymerization temperature of the polymerization reaction is 0-120 ℃;

(24) And the time of the polymerization reaction is 5 to 720 minutes.

3. The method of claim 2, wherein one or more of the following conditions are satisfied:

(1) The compound shown in the formula (I) is shown by any one of the following structures:

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

(3) In the organic solvent, the straight-chain hydrocarbon solvent is one or more of n-hexane, n-heptane and n-pentane;

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

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

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

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

(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 100-1600;

(10) In the anion main catalyst, the phosphazene base is 1-tert-butyl-4, 4-tri (dimethylamino) -2, 2-di [ tri (dimethylamino) -phosphoranylideneamino]-2λ ⁵ ,4λ ⁵ -a vicinal bis (phosphazene compound);

(11) In the anion main catalyst, the anions in the metal carboxylate and the organic carboxylate are independently acetic acid anions;

(12) In the anion main catalyst, the positive ions in the metal carboxylate are lithium ions, sodium ions, potassium ions, rubidium ions or cesium ions;

(13) In the anionic procatalyst, the cation of the organic carboxylate is represented by any one of the following structures:

wherein R is _1d 、R _2d 、R _3d 、R _4d 、R _5d And R _6d Independently hydrogen, alkyl or aryl, n2 is 0, 1,2 or 3; y2 is 0, 1,2 or 3;

(14) In the anionic main catalyst, the anion in the thiocarboxylate is thioacetate anion;

(15) In the anion main catalyst, cations in the thiocarboxylate are lithium ions, sodium ions, potassium ions, rubidium ions or cesium ions;

(16) In the cation main catalyst, in the zwitterion pair type catalyst, the carbocation is represented by the following structure:

wherein R is ^1f 、R ^2f 、R ^3f Each independently is phenyl, 2,4, 6-trimethylphenyl, 2, 6-dimethylphenyl, 2,3,5, 6-tetramethylphenyl or 2, 6-diisopropylphenyl;

(17) In the cationic main catalyst, in the zwitterion pair catalyst, the silicon positive ions are represented by the following structures:

wherein R is ^1g 、R ^2g And R ^3g Each 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 main catalyst, the onium ion and the sulfonium ion in the zwitterionic geminate catalyst are represented by the following structures:

wherein R is ^1h 、R ^2h And R ^3h Each 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, the zwitterion pair catalyst may be one in which the chloride ion and the bromide ion are each represented by the following structure:

wherein R is ¹ⁱ And R ²ⁱ Each independently is phenyl, 2,4, 6-trimethylphenyl, 2, 6-dimethylphenyl, 2,3,5, 6-tetramethylphenyl or 2, 6-diisopropylphenyl;

(20) In the cationic main catalyst, the iodonium ion in the zwitterionic geminate catalyst is represented by the following structure:

wherein R is ^1j And R ^2j Each independently is 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 main catalyst and the zwitterion pair type catalyst, the phosphonium ion is shown by the following structure:

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

wherein X ¹ 、X ² 、X ³ And X ⁴ Each independently is fluoro, chloro, phenyl, pentafluorophenyl, 3, 5-bis (trifluoromethyl) phenyl, pentafluorophenoxy, or 3, 5-bis (trifluoromethyl) phenoxy;

(23) In the cationic procatalyst, the zwitterion pair type catalyst has a structure in which the phosphate anion is represented by any one of the following structures:

(24) In the cationic procatalyst, the zwitterionic gemini catalyst, the sulfonic acid anion and the sulfonimide anion are respectively represented by the following structures:

wherein, X ^1a And X ^2a Each independently is fluoro, methyl, phenyl, trifluoromethyl, pentafluoroethyl, pentafluorophenyl or 3, 5-bis (trifluoromethyl) phenyl;

(25) In the cationic main catalyst and the zwitterionic geminate catalyst, the antimonic acid anions and the arsenic acid anions are respectively shown by the following structures:

wherein X ^1c 、X ^2c 、X ^3c 、X ^4c 、X ^5c And X ^6c Each independently is fluorine, chlorine or bromine;

(26) In the cation main catalyst, in the neutral Lewis acid catalyst, the boron complex is trialkylboron or triarylboron;

(27) In the cation main catalyst, in the neutral Lewis acid catalyst, the aluminum complex is trialkyl aluminum, triaryl aluminum, alkyl bisphenol aluminum, alkyl aluminum dichloride or dialkyl aluminum chloride;

(28) In the cationic main catalyst, in the protonic acid (ester) type catalyst, the sulfonic acid ester, the sulfonimide and the N-substituted sulfonimide are respectively represented by the following structures:

/>

wherein, X ^1d And X ^2d Each independently is fluoro, methyl, phenyl, trifluoromethyl, pentafluoroethyl, pentafluorophenyl or 3, 5-bis (trifluoromethyl) phenyl; r ^xd Is methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, cyclohexyl, trimethylsilyl, triethylsilyl, tripropylsilyl, triisopropylsilyl, tributylsilyl or tert-butyldimethylsilyl;

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

wherein R is ^1p And R ^2p Each independently a methyl group, an ethyl group, a propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a tert-butyl group, a phenyl group, a 2,4, 6-trimethylphenyl group, a 2, 6-dimethylphenyl group, a 2,3,5, 6-tetramethylphenyl group or a 2, 6-diisopropylphenyl group; [ X ]] ^– Is a borate anion, an aluminate anion, a phosphate anion, a sulfonate anion, a sulfonimide anion, an antimonate anion or an arsenate anion of the foregoing;

(30) The molar ratio of the main catalyst to the cocatalyst is 1-1;

(31) In the catalyst promoter, 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 azacyclo-crypt ether;

(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;

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

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

(37) The polymerization temperature of the polymerization reaction is 40-80 ℃;

(38) The time of the polymerization reaction is 30 to 240 minutes;

(39) In the anion main catalyst, the phosphazene base is tert-butylimino-tris (dimethylamino) phosphorane;

(40) In the anion main catalyst, the N-heterocyclic carbene organic base is 1, 3-di-tert-butyl imidazole-2-subunit;

(41) In the anionic main catalyst, the N-heterocyclic olefin organic base is

(42) In the cationic main catalyst, in the protonic acid (ester) type catalyst, the diphosphonimidate is represented by the following structure:

wherein R is ^1q Is C _6-10 Aryl radical, said C _6-10 Aryl being optionally substituted by one or more of halogen, R ^2q Is methylsulfonyl, optionally substituted with one or more of halogens;

preferably, R ^1q Is 3, 5-dimethylphenyl, said R ^1q C in (1) _6-10 Aryl being substituted by one or more fluoro, said R ^2q The methylsulfonyl group in (a) is substituted with one or more fluoro;

further preferably, in the protonic acid (ester) -type catalyst, the diphosphonimides are IDPi-CF ₃ The structure is as follows:

4. the method of claim 1, wherein one or more of the following conditions are satisfied:

(1) In the compound shown in the formula (I),

is->

R ₁₁ 、R ₁₂ 、R ₁₃ And R ₁₄ Independently H, C _1-10 Alkyl or C _1-10 An alkenyl group; or, R ₁₃ And R ₁₄ Together with the atoms linking them form C _3-10 A cycloalkyl group; r ₅₁ 、R ₅₂ 、R ₅₃ And R ₅₄ Independently is H or C _1-10 An alkyl group;

(2) The organic solvent is an aromatic hydrocarbon solvent and/or an amide solvent;

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

(4) The cation 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 [ H (Et) ₂ O) ₂ ][B(C ₆ F ₅ ) ₄ ]One or more of;

(5) The polymerization reaction is carried out in the presence of a cocatalyst, wherein the cocatalyst 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 carboxylic acid.

5. The method of claim 4, wherein one or more of the following conditions are satisfied:

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

(3) The anion main catalyst is 1-tert-butyl-4, 4-tri (dimethylamino) -2, 2-di [ tri (dimethylamino)) -phosphoranylideneamino]-2λ ⁵ ,4λ ⁵ -bis (phosphazene) and/or potassium thioacetate;

(4) The polymerization is carried out in the presence of a cocatalyst which is an alcohol and/or a crown ether, such as dibenzol and/or 18 crown 6 ether;

(5) The polymerization reaction is carried out in the presence of an initiator, and the initiator is benzoic acid.

6. The process according to any one of claims 1 to 5, wherein it is any one of the following embodiments,

scheme 1 the polymerized monomer is

The main catalyst is [ Ph ₃ C][B(C ₆ F ₅ ) ₄ ]；

Scheme 2 the polymerized monomer is

The main catalyst is [ Ph ₃ C][B(C ₆ F ₅ ) ₄ ]；

Scheme 3 the polymerized monomer is

The main catalyst is [ Ph ₃ C][B(C ₆ F ₅ ) ₄ ]；

Scheme 4 the polymerized monomer is

The main catalyst is [ Ph ₃ C][B(C ₆ F ₅ ) ₄ ]；

Scheme 5 the polymerized monomers are

The main catalyst is [ Ph ₃ C][B(C ₆ F ₅ ) ₄ ]；

Scheme 6 the polymerized monomers are

The main catalyst is [ Ph ₃ C][B(C ₆ F ₅ ) ₄ ]；

Scheme 7, the polymerized monomers are

The main catalyst is [ Ph ₃ C][B(C ₆ F ₅ ) ₄ ]；

Scheme 8 the polymerizable monomer is

The main catalyst is [ Ph ₃ C][B(C ₆ F ₅ ) ₄ ]；

Scheme 9, the polymerized monomers are

The main catalyst is [ Ph ₃ C][B(C ₆ F ₅ ) ₄ ]；/>

Scheme 10, the polymerized monomer is

The main catalyst is [ Ph ₃ C][B(C ₆ F ₅ ) ₄ ]；

Scheme 11, the polymerized monomers are

The main catalyst is potassium thioacetate;

scheme 12, the polymerized monomers are

SaidThe main catalyst is ^t Bu-P ₄ The cocatalyst is benzhydrol;

scheme 13 the polymerized monomers are

The main catalyst is ^t Bu-P ₄ The cocatalyst is benzhydrol;

scheme 14, the polymerized monomers are

The main catalyst is potassium thioacetate, and the cocatalyst is 18 crown 6 ether;

scheme 15, the polymerized monomers are

scheme 16, the polymerizable monomer is

The main catalyst is ^t Bu-P ₄ The initiator is benzoic acid;

scheme 17, the polymerized monomers are

The main catalyst is [ Ph ₃ C][B(C ₆ F ₅ ) ₄ ]；

Scheme 18, the polymerized monomers are

The main catalyst is [ H (Et) ₂ O) ₂ ][B(C ₆ F ₅ ) ₄ ]；

Scheme 19 the polymerized monomers are

The main catalyst is B (C) ₆ F ₅ ) ₃ ；

Scheme 20, the polymerized monomers are

The main catalyst is potassium thioacetate;

scheme 21, the polymerized monomers are

The main catalyst is potassium thioacetate;

scheme 22 the polymerizable monomer is

The main catalyst is [ Ph ₃ C][B(C ₆ F ₅ ) ₄ ]；

Scheme 23 the polymerizable monomer is

The main catalyst is TBD:>

scheme 24, the polymerizable monomer is

The main catalyst is DBU>

Scheme 25, the polymerized monomers are

The main catalyst is I ^t Bu:/>

Scheme 26, the polymerized monomers are

The main catalyst is NHO: device for selecting or keeping>

/>

Scheme 27, the polymerizable monomer is

The main catalyst is ^t Bu-P ₁ :/>

Scheme 28 the polymerizable monomer is

The main catalyst is [ Et ] ₃ Si-H-SiEt ₃ ][B(C ₆ F ₅ ) ₄ ]；

Scheme 29, the polymerizable monomer is

The main catalyst is Ph ₃ CB(C ₆ F ₅ ) ₄ /Et ₃ SiH；

Scheme 30, the polymerized monomers are

The main catalyst is Me ₃ OBF ₄ ；

Scheme 31 the polymerizable monomer is

SaidThe main catalyst is [ Et ] ₃ O][B(C ₆ F ₅ ) ₄ ]；

Scheme 32, the polymerizable monomer is

The main catalyst is C ₇ H ₇ BF ₄ ；

Scheme 33, the polymerized monomers are

The main catalyst is Al (C) ₆ F ₅ ) ₃ ；

Scheme 34 the polymerizable monomer is

The main catalyst is IDPi-CF ₃ />

Scheme 35, the polymerizable monomer is

The main catalyst is [ Et ] ₃ O][B(C ₆ F ₅ ) ₄ ]；

Scheme 36, the polymerized monomers are

The main catalyst is [ Et ] ₃ O][B(C ₆ F ₅ ) ₄ ]；

Scheme 37, the polymerizable monomer is

The main catalyst is [ Et ] ₃ O][B(C ₆ F ₅ ) ₄ ]；

Scheme 38, the polymerizable monomer is

The main catalyst is [ Et ] ₃ O][B(C ₆ F ₅ ) ₄ ]；

Scheme 39 the polymerizable monomer is

The main catalyst is [ Et ] ₃ O][B(C ₆ F ₅ ) ₄ ]；

Scheme 40 the polymerizable monomer is

The main catalyst is [ Et ] ₃ O][B(C ₆ F ₅ ) ₄ ]；

Scheme 41, the polymerized monomers are

The main catalyst is [ Et ] ₃ O][B(C ₆ F ₅ ) ₄ ]；

Scheme 42 the polymerizable monomer is

The main catalyst is->

(DBU)；/>

Scheme 43 the polymerizable monomer is

The main catalyst is>

(DBU)；

Scheme 44 the polymerizable monomer is

The main catalyst is [ Et ] ₃ O][B(C ₆ F ₅ ) ₄ ])；

Scheme 45, the polymerizable monomer is

The main catalyst is [ Et ] ₃ O][B(C ₆ F ₅ ) ₄ ])。

7. A sulfur-containing polymer produced by the method according to any one of claims 1 to 6.

8. A sulfur-containing polymer characterized in that the main chain of said sulfur-containing polymer is composed of one or more of the following structural units,

wherein the polymerization degree of the sulfur-containing polymer is 50 or more,

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 Is as defined in claim 1 or 2.

9. The sulfur-containing polymer of claim 8, wherein one or more of the following conditions is satisfied:

(1) The polymerization degree of the sulfur-containing polymer is 50-4900;

(2) The number average molecular weight of the sulfur-containing polymer is more than or equal to 5kg/mol;

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

(4) The sulfur-containing polymer is a homopolymer or a multipolymer;

(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 breaking stress of the sulfur-containing polymer is 16.62-24.27MPa;

(8) The elastic recovery rate of the sulfur-containing polymer is 72.3 percent;

(9) The glass transition temperature T of the sulfur-containing polymer _g Is-57.0 to 59.5 ℃.

10. The sulfur-containing polymer of claim 9, wherein one or more of the following conditions is satisfied:

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

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

(3) The molecular weight distribution of the sulfur-containing polymer is 1.0-1.5;

(4) The multipolymer is a random copolymer or a block copolymer;

(5) The multipolymer is a terpolymer, wherein the mol percentage of each structural unit is 5-90%.