CN114854017B - A kind of macromolecule with main chain containing thioether group and its synthesis method - Google Patents

Abstract

The invention discloses a polymer containing thioether groups in the main chain and a synthesis method thereof. The general structural formulas of the polymers containing thioether groups in the main chain are shown in the following formulas (I) to (IV). The synthesis method includes using two double-bond monomers, sulfur-containing carbon-one monomers and water as raw materials, using alkali as a catalyst, and polymerizing under autogenous pressure; the two double-bond monomers are selected from diacrylate monomers, bisacrylamide One or more of monomers, bisvinyl sulfone monomers, and bismaleimide monomers; the sulfur-containing carbon monomer is selected from COS and/or CS ₂ . The polymer containing thioether groups in the main chain has a clear structure, the repeating unit of the main chain has a thioether structure, and contains different functional groups, and the end groups are double bonds; the main chain contains thioether groups The polymer also has a high molecular weight, has excellent mechanical properties, and has broad application prospects in the fields of food packaging, coatings, biology and electronics.

Description

A kind of macromolecule with main chain containing thioether group and its synthesis method

technical field

The invention relates to the technical field of polymer materials, in particular to a polymer with a main chain containing thioether groups and a synthesis method thereof.

Background technique

Due to the introduction of sulfur atoms, sulfur-containing polymers generally have excellent mechanical properties, thermal stability, optical functions, biocompatibility, and strong ion-binding ability, and are widely used in general, engineering, and functional materials. For example, vulcanized rubber has become the main raw material of tires since its discovery in 1839, and still plays an irreplaceable role in the modern society on wheels. Another example is polyphenylene sulfide, as a special engineering plastic with excellent comprehensive performance, it is widely used in the fields of electronic appliances, aerospace and other cutting-edge materials. As an important sulfur-containing polymer species, polymers containing thioether groups in the main chain are not only widely used in drug delivery systems, artificial tissues, and commodity materials, but also have broad applications in degradable materials, new liquid crystals, and precision optics. application prospects.

However, how to controlly introduce sulfur in a simple way is still a challenging problem in the field of synthesis, especially the synthesis of polymers containing thioether groups in the main chain is less studied.

The Chinese patent literature with the application publication number CN 113278149 A discloses a method for producing polysulfide compounds. The technical route is to make ring-opening polymerization of alicyclic episulfide compounds under the catalysis of bases, thereby obtaining polysulfide compounds effectively and economically. Thioether compounds. However, this ring-opening polymerization method is limited by the small number of reactive monomers, and the preparation, storage and transportation of alicyclic episulfide compounds are relatively difficult, resulting in a relatively single structure and type of polythioether prepared, and it is difficult to introduce other functional groups. group.

The Chinese patent document whose application publication number is CN 110139884 A discloses a polyurethane product with sulfur-containing polyester polyol and a preparation method thereof. The technical route for obtaining sulfur-containing polyester polyol is to combine sulfur-containing polyol or sulfur-containing polyol At least one sulfur-containing component of carboxylic acid, at least one aromatic component of aromatic polyfunctional ester, aromatic polyfunctional carboxylic acid and aromatic anhydride, excluding sulfur and different from said sulfur-containing polyol At least one simple polyhydric alcohol is reacted under the action of a catalyst to obtain various sulfur-containing polyesters. However, since the technical solution adopts the polycondensation method, the reaction system needs to be heated or decompressed to separate the small molecules generated in the reaction process. The reaction process is difficult to control and is a process with high energy consumption.

The research group of the inventor of the present invention has long-term research accumulation in the field of sulfur-containing polymers. In the Chinese patent literature with the application publication number CN 109180937 A, a method for preparing aliphatic polysulfides is disclosed. The technical route is as follows: Using sulfur-carbon compounds and oxygen-containing monomers as raw materials and using Lewis base as a catalyst, aliphatic polysulfides are obtained through polymerization; the polymerization is carried out at 80-180°C under autogenous pressure. However, the aliphatic polythioether obtained by this process route is entirely composed of thioether chains and lacks other functional groups.

Contents of the invention

Aiming at the problems existing in the prior art, the present invention discloses a polymer containing a thioether group in the main chain and a synthesis method thereof. The polymer containing a thioether group in the main chain has a clear structure, and the repeating unit of the main chain has The structure of thioether contains different functional groups at the same time, and the end groups are all double bonds, which has further reactivity; the polymer containing thioether group also has a higher molecular weight and excellent mechanical properties. It has broad application prospects in food packaging, coatings, biology and electronics. The synthesis process of the present invention only needs one step, the raw materials are cheap and easy to obtain, the time consumption is short, and cumbersome post-treatment and purification steps are not required, which is beneficial to the realization of industrial production.

The specific technical scheme is as follows:

A polymer with a main chain containing a thioether group, the general structure of which is shown in the following formulas (I) to (IV):

In the formula, n is selected from 1 to 200;

R ₁ is selected from C ₂ -C ₁₈ alkylene, p-xylylene, 2,5-furandimethylene, 1,4-cyclohexylene, (CH ₂ CH ₂ O) _m CH ₂ CH ₂ , m=1~3;

R ₂ is selected from H or methyl;

R ₃ is selected from C ₁ -C ₁₂ alkylene;

R ₄ is selected from C ₁ -C ₂ alkylene groups;

R ₅ is selected from C ₁ ~ C ₁₀ alkylene, 1,4-phenylene, 1,3-phenylene, 1,2-phenylene, 4,4'-methylene diphenyl, 4,4'-methylenebis(3-ethyl-5-methylphenyl), (CH ₂ CH ₂ O) _p CH ₂ CH ₂ , p=1-3.

The present invention also discloses a method for synthesizing the above-mentioned macromolecule containing a thioether group in the main chain. The raw materials include two double bond monomers, a sulfur-containing carbon monomer and water, and the alkali is used as a catalyst to carry out polymerization under autogenous pressure;

The two double bond monomers are selected from one or more of diacrylate monomers, bisacrylamide monomers, bisvinyl sulfone monomers, and bismaleimide monomers;

The sulfur-containing carbon monomer is selected from carbon oxysulfide (COS) and/or carbon disulfide (CS ₂ ).

On the basis of a large number of experimental studies, the inventor discovered the phenomenon that sulfur anions and double bond compounds can be rapidly added, and thus developed a new reaction of two double bond monomers, sulfur-containing carbon monomers and water one-step polymerization . The addition reaction of sulfide anions to double bond compounds is an anionic mechanism, which is different from the free radical addition based sulfhydryl-double bond addition reactions reported in the literature. The latter easily leads to the occurrence of cross-linking reaction.

First, COS (or CS ₂ ) and water undergo an oxygen-sulfur exchange reaction under the action of a catalyst to generate hydrogen sulfide and carbon dioxide. Hydrogen sulfide can undergo addition reaction with double bond compounds to form a sulfhydryl group. In the presence of conditions, the sulfhydryl group is quickly converted into a sulfide anion; secondly, the sulfide anion undergoes an addition reaction with another double bond compound molecule. Experimental studies have shown that such anions preferentially react with double-bonded compounds with electron-withdrawing groups. This is because the electron-withdrawing group is conducive to the electrophilic reaction of the double bond; finally, the carbon dioxide generated by COS (CS ₂ ) and water is inert, so that the reaction system is always under high pressure, and the carbon dioxide is equivalent to a solvent, which reduces the pressure of the system. The viscosity increases the mobility of the end group, which is conducive to the increase of the molecular weight of the polymer. This is significantly different from traditional stepwise polymerizations, some of which are often carried out under high temperature and high vacuum (or normal pressure) conditions. Therefore, completely different from the previous C1 polymerization system, the present invention obtains high-molecular-weight polymerization products through a gradual polymerization mechanism. On the basis of the above mechanism discovery, the present invention has been formed through experimental research.

In this synthesis method, it has better universality to two double bond monomers.

The diacrylate monomer is selected from ethylene glycol diacrylate, 1,3-propanediol diacrylate, 1,4-butanediol diacrylate, 1,5-pentanediol diacrylate, neopentyl Diol diacrylate, 1,6-hexanediol diacrylate, 1,9-nonanediol diacrylate, 1,10-decanediol diacrylate, 1,12-dodecanediol diacrylate Esters, 1,14-tetradecanediol diacrylate, 1,16-hexadecanediol diacrylate, 1,18-octadecanediol diacrylate, terephthalene dimethanol diacrylate, 2 ,5-furandimethanol diacrylate, 1,4-cyclohexanediol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, ethylene glycol Dimethacrylate, 1,3-Propanediol Dimethacrylate, 1,4-Butanediol Dimethacrylate, 1,5-Pentanediol Dimethacrylate, Neopentyl Glycol Dimethacrylate Acrylates, 1,6-hexanediol dimethacrylate, 1,9-nonanediol dimethacrylate, 1,10-decanediol dimethacrylate, 1,12-dodecane dimethacrylate One or more of alcohol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate;

The bisacrylamide monomer is selected from N,N'-methylenebisacrylamide, N,N'-ethylenebisacrylamide, N,N'-trimethylenebisacrylamide, N,N' -tetramethylenebisacrylamide, N,N'-pentamethylenebisacrylamide, N,N'-hexamethylenebisacrylamide, N,N'-heptamethylenebisacrylamide, N, N'-octamethylenebisacrylamide, N,N'-nonamethylenebisacrylamide, N,N'-decamethylenebisacrylamide, N,N'-undecamethylenebisacrylamide , one or more of N,N'-dodecamethylenebisacrylamide;

The divinylsulfone monomer is selected from divinylsulfone methane and/or divinylsulfone ethane;

The bismaleimide monomer is selected from bismaleimide methane, 1,2-bismaleimide ethane, 1,3-bismaleimide propane, 1 ,4-Bismaleimidobutane, 1,5-Bismaleimidopentane, 1,6-Bismaleimidohexane, 1,7-Bismaleimideheptane alkane, 1,8-bismaleimide octane, 1,9-bismaleimide nonane, 1,10-bismaleimide decane, N,N'-(1,4 -phenylene)bismaleimide, N,N'-(1,3-phenylene)bismaleimide, N,N'-(1,2-phenylene)bismaleimide imide, N,N'-(4,4'-methylenediphenyl)bismaleimide, bis(3-ethyl-5-methyl-4-maleimidobenzene base) methane, 1,5-bismaleimide diethylene glycol, 1,8-bismaleimide triethylene glycol, 1,11-bismaleimide tetraethylene glycol one or more of .

Preferred:

The diacrylate monomer is selected from diethylene glycol diacrylate, triethylene glycol diacrylate (TEGDA), tetraethylene glycol diacrylate, 1,2-ethylene glycol diacrylate (EGDA) , 1,4-butanediol diacrylate (BGDA), 1,5-pentanediol diacrylate (PGDA), neopentyl glycol diacrylate (NPGDA), 1,6-hexanediol diacrylate (HGDA), 1,9-nonanediol diacrylate (NGDA), 1,10-decanediol diacrylate (DGDA), 1,12-dodecanediol diacrylate (DDGDA), 1, One or more of 12-dodecanediol dimethacrylate (DDGDMA) and terephthalate dimethacrylate (BDMDA);

The bisacrylamide monomer is selected from N,N'-methylenebisacrylamide;

The bisvinyl sulfone monomer is selected from bisvinyl sulfone methane;

The bismaleimide monomer is selected from N,N'-(4,4'-methylenediphenyl)bismaleimide and/or N,N'-1,4- Phenyl bismaleimide.

The above preferred monomers with two double bonds are all cheap and easy-to-obtain industrial products, and are convenient for storage and transportation; especially important, the preferred monomers with two double bonds have good reactivity and excellent effect.

Further preferred:

The two double bond monomers are selected from diacrylate monomers, such as one or more of TEGDA, EGDA, NPGDA, HGDA, NGDA, DGDA, BDMDA, DDGDA; using the above-mentioned further preferred diacrylate monomers Polymers with higher number average molecular weight can be prepared

Still further preferably, the monomer with two double bonds is selected from TEGDA, EGDA, DGDA or DDGDA; more preferably TEGDA, DDGDA or DGDA, most preferably DGDA. With the continuous optimization of the types of the above-mentioned double bond monomers, a polymer product with a higher number average molecular weight, up to 200 kg/mol, can be prepared.

Preferably, the sulfur-containing carbon-monomer is selected from COS. It is found through experiments that compared with CS ₂ , COS has higher reactivity, and the prepared polymer has higher number-average molecular weight.

The base is selected from one or more of quaternary ammonium salts, quaternary phosphonium salts, amines, phosphazenes, guanidines, amidines, alkali metal alkoxides, and inorganic bases;

The quaternary ammonium salt is selected from one of bis(triphenylphosphoryl)ammonium chloride, tetrabutylammonium chloride, tetrabutylammonium bromide, tetraoctylammonium bromide, and p-nitrophenol tetrabutylammonium one or more kinds;

The quaternary phosphonium salt is selected from tetraphenylphosphonium chloride and/or methyltriphenylphosphonium bromide;

The amine is selected from one or more of n-hexylamine, tetramethylmethylenediamine, N,N'-dimethylethylenediamine, tetramethylethylenediamine;

Phosphazenes are selected from tert-butylimino-tris(dimethylamino)phosphorane, 1-tert-butyl-2,2,4,4,4-penta(dimethylamino)-2λ ⁵ ,4λ ⁵ -dipheno (Phosphorus nitrogen-based compounds), 1-tert-butyl-4,4,4-tris(dimethylamino)-2,2-bis[tris(dimethylamino)-phosphinylideneamino]-2λ ⁵ , One or more of 4λ ⁵ -bis(phosphorus nitrogen-based compounds);

The amidine is selected from one or more of 1,8-diazabicyclo[5.4.0]undec-7-ene and 1,5-diazabicyclo[4.3.0]non-5-ene;

Guanidine is selected from 1,5,7-triazabicyclo[4.4.0]dec-5-ene, 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene, One or more of tetramethylguanidine;

The alkali metal alkoxide is selected from one or more of sodium methoxide, potassium methoxide, sodium ethoxide, potassium tert-butoxide, lithium tert-butoxide, sodium tert-butoxide, potassium tert-butoxide;

The inorganic base is selected from one or more of sodium hydroxide, potassium hydroxide, sodium carbonate and potassium carbonate.

Preferably, the base is selected from 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), bis(triphenylphosphoryl)ammonium chloride ([PPN]Cl, The structural formula is denoted as 1), p-nitrophenol tetrabutylammonium (the structural formula is denoted as 2), methyltriphenylphosphine bromide, 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD, the structural formula is marked as 3), 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene (MTBD, the structural formula is marked as 4), 4-dimethylaminopyridine ( One or more of DMAP, whose structural formula is marked as 5), potassium tert-butoxide (t-BuOK, whose structural formula is marked as 6), and potassium carbonate. The above preferred bases are cheap and readily available and have relatively high catalytic activity.

More preferably, the catalyst is selected from TBD, MTBD, DMAP or t-BuOK; still more preferably TBD or MTBD, most preferably MTBD. With the continuous optimization of the above-mentioned catalyst types, the catalytic activity continues to increase, and the number average molecular weight of the polymerization product prepared under the same polymerization conditions is higher.

In the present invention, the molar ratio of two double-bond monomers, sulfur-containing carbon-monomers and water is 1:0.1-5.0:0.1-5.0; the molar ratio of alkali to two-double-bond monomers is 1:5-1000.

Preferably, the molar ratio of the double bond monomer to the sulfur-containing carbon monomer is 1:1.0-2.0, more preferably 1:1.1-1.8.

Preferably, the molar ratio of the two double bond monomers to water is 1:0.5-5.0, more preferably 1:1.0-1.5; more preferably 1:1.0-1.1.

Preferably, the molar ratio of the base to the double bond monomer is 1:50-100, more preferably 1:50.

With the continuous optimization of the ratio of the above raw materials, the number average molecular weight of the prepared polymer product can be higher.

In the present invention, the polymerization is bulk polymerization or solution polymerization, the polymerization temperature is 25-160°C, and the time is 0.5-120h; preferably, the polymerization temperature is 40-100°C, more preferably 60-80°C, Most preferably 60°C.

In the solution polymerization, the solvent used is selected from one or more of dichloromethane, chloroform, tetrahydrofuran, toluene, trichlorobenzene, o-dichlorobenzene, m-dichlorobenzene, p-dichlorobenzene, and dimethylformamide. species; more preferably dichloromethane or tetrahydrofuran.

The polymer containing thioether groups in the main chain prepared by the above synthesis method has a number average molecular weight of 1-200 kg/mol and a molecular weight distribution of 1.1-4.0. The number average molecular weight of the prepared polymer product can be regulated within a wide range by regulating the types and proportions of raw materials and process conditions in the synthesis method.

Preferably, the polymer containing thioether groups in the main chain has the following structural formula:

Further preferably, the polymer containing thioether groups in the main chain has the following structural formula:

Compared with the prior art, the present invention has the following beneficial effects:

(1) On the basis of a large number of experimental studies, the present invention proposes for the first time a one-step reaction of two double bond compounds containing electron-withdrawing groups, a sulfur-containing carbon monomer, and water to obtain a main chain sulfur-containing compound whose end group is a double bond. Ether-based polymers, cheap and easy-to-obtain raw materials, and simple reaction conditions;

(2) The catalytic system adopted in the present invention is commercially cheap and easy to obtain. It has a clear structure, no metal residue and colorless, the repeating unit of the main chain contains a thioether group and an ester bond structure, and the end group structure is clear, and it does not need to be complicated. The post-processing purification step;

(3) The polymer prepared by the present invention has a high molecular weight, does not contain metal ions, has excellent mechanical properties, and has broad application prospects in the fields of food packaging, coatings, biology and electronics.

Description of drawings

Fig. 1 is the ¹ H NMR spectrogram of the copolymerization polymer product prepared in embodiment 34;

Fig. 2 is the ¹³ C NMR spectrogram of the copolymerization product prepared in Example 34;

Fig. 3 is the ¹ H NMR spectrogram of the copolymerization product prepared in Example 38;

Fig. 4 is the ¹³ C NMR spectrogram of the copolymerization product prepared in Example 38;

Fig. 5 is the ¹ H NMR spectrogram of the copolymerization polymer product prepared in embodiment 39;

Fig. 6 is the ¹³ C NMR spectrogram of the copolymerization product prepared in Example 39;

Fig. 7 is the ¹ H NMR spectrogram of the copolymerization product prepared in embodiment 40;

Fig. 8 is the ¹³ C NMR spectrogram of the copolymerization product prepared in Example 40;

Fig. 9 is the ¹ H NMR spectrogram of the copolymerization product prepared in Example 41;

Figure 10 is the ¹³ C NMR spectrogram of the copolymerization product prepared in Example 41;

Fig. 11 is the ¹ H NMR spectrogram of the copolymerization product prepared in Example 42;

Figure 12 is the ¹³ C NMR spectrogram of the copolymerization product prepared in Example 42;

Fig. 13 is the ¹ H NMR spectrogram of the copolymerization product prepared in Example 43;

Figure 14 is the ¹³ C NMR spectrogram of the copolymerization product prepared in Example 43;

Fig. 15 is the ¹ H NMR spectrogram of the copolymerization product prepared in Example 44;

Figure 16 is the ¹³ C NMR spectrogram of the copolymerization product prepared in Example 44;

Fig. 17 is the ¹ H NMR spectrogram of the copolymerization product prepared in Example 45;

Fig. 18 is the ¹³ C NMR spectrum of the copolymerization product prepared in Example 45.

Fig. 19 is the ¹ H NMR spectrogram of the copolymerization product prepared in Example 47;

Fig. 20 is the ¹³ C NMR spectrum of the copolymerization product prepared in Example 47.

Detailed ways

The present invention will be further described in detail below in conjunction with examples and comparative examples, but the embodiments of the present invention are not limited thereto.

In the following examples, 1,12-dodecanediol diacrylate and terephthalamide diacrylate are self-made as raw material monomers. Taking 1,12-dodecanediol diacrylate as an example, the preparation steps as follows:

Dissolve 1,12-dodecanediol in anhydrous dichloromethane, add triethylamine, and slowly add acryloyl chloride dropwise at 0°C in a nitrogen atmosphere, then slowly rise to room temperature, and react for 12-24 hours . After washing with saturated aqueous NaHCO ₃ , saturated NaCl solution and drying, the dichloromethane was removed in vacuo.

Example 1 Reaction of triethylene glycol diacrylate/COS/H ₂ O to produce polymers containing thioether groups in the main chain repeating unit

Before the polymerization reaction, the 10mL reactor was dehydrated at 110°C for about 2 hours and cooled to room temperature; several masses of base 1,8-diazabicyclo[5.4.0]undec- 7-ene, 0.8609g triethylene glycol diacrylate and 0.066g _H2O , after which 0.22g COS was charged. The molar ratio of triethylene glycol diacrylate, water, COS and alkali is 50/55/55/1. Placed at 25°C and reacted under high pressure for 48h. After the reaction was completed, the crude product was first dissolved with dichloromethane, and then the polymer was precipitated in a mixture of 200 mL ethanol/hydrochloric acid (the molar concentration of hydrochloric acid was 5%), washed three times repeatedly, and vacuum-dried to constant weight. The molecular weight and molecular weight distribution of the polymer were determined by gel chromatography, and the test results are shown in Table 1.

Example 2-Example 7 Reaction of triethylene glycol diacrylate/COS/H ₂ O to produce polymers containing thioether groups in the main chain repeating unit

The preparation process is basically the same as in Example 1, except that the temperature of the polymerization reaction is replaced by 40°C, 60°C, 80°C, 100°C, 120°C, and 160°C in sequence, and the polymerization time is 48 hours. The molecular weight and molecular weight distribution of the polymers prepared in each embodiment were determined by gel chromatography, and the test results are shown in Table 1.

Example 8-Example 11 Reaction of triethylene glycol diacrylate/COS/H ₂ O to produce polymers containing thioether groups in the main chain repeating unit

The preparation process is basically the same as in Example 3, the only difference being that the quality of the alkali added is different, and the molar ratios of triethylene glycol diacrylate, water, COS and alkali are adjusted to be 1000/1100/1100/1, 100/110/ 110/1, 10/11/11/1, 5/5.5/5.5/1. The molecular weight and molecular weight distribution of the polymers prepared in each embodiment were determined by gel chromatography, and the test results are shown in Table 1.

Example 12-Example 17 Reaction of triethylene glycol diacrylate/COS/H ₂ O to produce polymers containing thioether groups in the main chain repeating unit

The preparation process is basically the same as in Example 3, the only difference is that the quality of the water added is different, and the molar ratios of triethylene glycol diacrylate, water, COS and alkali are adjusted to be 50/25/55/1, 50/50/ 55/1, 50/52.5/55/1, 50/75/55/1, 50/100/55/1, 50/150/55/1. The molecular weight and molecular weight distribution of the polymers prepared in each embodiment were determined by gel chromatography, and the test results are shown in Table 1.

Example 18 Reaction of Triethylene Glycol Diacrylate/COS/H ₂ O to Generate Polymers Containing Thioether Groups in Main Chain Repeating Units

Before the polymerization reaction, the 10mL reactor was dehydrated at 110°C for about 2 hours and cooled to room temperature; several masses of base 1,8-diazabicyclo[5.4.0]undec- 7-ene, 0.8609g triethylene glycol diacrylate and 0.24g _H2O , after which 0.22g COS was charged. The molar ratio of triethylene glycol diacrylate, water, COS and alkali is 50/200/55/1. Placed at 60°C for 72h under high pressure. After the reaction was completed, the crude product was first dissolved with dichloromethane, and then the polymer was precipitated in a mixture of 200 mL ethanol/hydrochloric acid (the molar concentration of hydrochloric acid was 5%), washed three times repeatedly, and vacuum-dried to constant weight. The molecular weight and molecular weight distribution of the polymer were determined by gel chromatography, and the test results are shown in Table 1.

Example 19 Reaction of triethylene glycol diacrylate/COS/H ₂ O to produce polymers containing thioether groups in the main chain repeating unit

Before the polymerization reaction, the 10mL reactor was dehydrated at 110°C for about 2 hours and cooled to room temperature; several masses of base 1,8-diazabicyclo[5.4.0]undec- 7-ene, 0.8609 g triethylene glycol diacrylate and 0.30 g H ₂ O, after which 0.22 g COS was charged. The molar ratio of triethylene glycol diacrylate, water, COS and alkali is 50/250/55/1. Placed at 60°C and reacted under high pressure for 120h. After the reaction was completed, the crude product was first dissolved with dichloromethane, and then the polymer was precipitated in a mixture of 200 mL ethanol/hydrochloric acid (the molar concentration of hydrochloric acid was 5%), washed three times repeatedly, and vacuum-dried to constant weight. The molecular weight and molecular weight distribution of the polymer were determined by gel chromatography, and the test results are shown in Table 1.

Example 20 Reaction of triethylene glycol diacrylate/COS/H ₂ O to produce polymers containing thioether groups in the main chain repeating unit

Before the polymerization reaction, the 10mL reactor was dehydrated at 110°C for about 2 hours and cooled to room temperature; several masses of base 1,8-diazabicyclo[5.4.0]undec- 7-ene, 0.8609g triethylene glycol diacrylate and 0.66g _H2O , after which 0.02g COS was charged. The molar ratio of triethylene glycol diacrylate, water, COS and alkali is 50/55/5/1. Placed at 60°C and reacted under high pressure for 120h. After the reaction was completed, the crude product was first dissolved with dichloromethane, and then the polymer was precipitated in a mixture of 200 mL ethanol/hydrochloric acid (the molar concentration of hydrochloric acid was 5%), washed three times repeatedly, and vacuum-dried to constant weight. The molecular weight and molecular weight distribution of the polymer were determined by gel chromatography, and the test results are shown in Table 1.

Example 21 Reaction of triethylene glycol diacrylate/COS/H ₂ O to produce polymers containing thioether groups in the main chain repeating unit

Before the polymerization reaction, the 10mL reactor was dehydrated at 110°C for about 2 hours and cooled to room temperature; several masses of base 1,8-diazabicyclo[5.4.0]undec- 7-ene, 0.8609 g triethylene glycol diacrylate and 0.66 g H ₂ O, after which 0.10 g COS was charged. The molar ratio of triethylene glycol diacrylate, water, COS and alkali is 50/55/25/1. Placed at 60°C for 72h under high pressure. After the reaction was completed, the crude product was first dissolved with dichloromethane, and then the polymer was precipitated in a mixture of 200 mL ethanol/hydrochloric acid (the molar concentration of hydrochloric acid was 5%), washed three times repeatedly, and vacuum-dried to constant weight. The molecular weight and molecular weight distribution of the polymer were determined by gel chromatography, and the test results are shown in Table 1.

Example 22-Example 29 Reaction of triethylene glycol diacrylate/COS/H ₂ O to produce polymers containing thioether groups in the main chain repeating unit

The preparation process is basically the same as in Example 3, the only difference being that the quality of COS added is different, and the molar ratios of triethylene glycol diacrylate, water, COS and alkali are adjusted to be 50/55/50/1, 50/55/ 65/1, 50/55/75/1, 50/55/90/1, 50/55/100/1, 50/55/150/1, 50/55/200/1, 50/55/250/ 1. The molecular weight and molecular weight distribution of the polymers prepared in each embodiment were determined by gel chromatography, and the test results are shown in Table 1.

Example 30 Reaction of Triethylene Glycol Diacrylate/COS/H ₂ O to Generate Polymers Containing Thioether Groups in Main Chain Repeating Units

Before the polymerization reaction, the 10mL reactor was dehydrated at 110°C for about 2 hours and cooled to room temperature; several masses of base bis(triphenylphosphoryl)ammonium chloride ([PPN]Cl ), 0.8609g triethylene glycol diacrylate and 0.063g H ₂ O, and then charged with 0.26g of COS. The molar ratio of triethylene glycol diacrylate, water, COS and alkali is 50/52.5/65/1. Placed at 60°C for 4h under high pressure. After the reaction was completed, the crude product was first dissolved with dichloromethane, and then the polymer was precipitated in a mixture of 200 mL ethanol/hydrochloric acid (the molar concentration of hydrochloric acid was 5%), washed three times repeatedly, and vacuum-dried to constant weight. The molecular weight and molecular weight distribution of the polymer were determined by gel chromatography, and the test results are shown in Table 1.

Example 31-Example 37 Triethylene glycol diacrylate/COS/H ₂ O reaction synthesis of polymers containing thioether group in the main chain repeating unit

The preparation process is basically the same as in Example 30, except that the types of bases to be replaced are tetrabutylammonium p-nitrophenolate, methyltriphenylphosphine bromide, 1,5,7-triazabicyclo[4.4.0 ]dec-5-ene (TBD), 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene (MTBD), 4-dimethylaminopyridine (DMAP), tert Potassium butoxide (t-BuOK), alkali potassium carbonate. The molecular weight and molecular weight distribution of the polymers prepared in each embodiment were determined by gel chromatography, and the test results are shown in Table 1.

Wherein, the ¹ H NMR spectrum of the product prepared in Example 34 is shown in FIG. 1 , and ^{the 13} C NMR spectrum is shown in FIG. 2 . Observation of Figure 1 and Figure 2 shows that the general structural formula of the product is as follows:

Example 38 Reaction of 1,2-Ethylene Glycol Diacrylate/COS/H ₂ O to Generate Sulfur-Containing Polyester with Main Chain Repeating Unit

Before the polymerization reaction, the 10mL reactor was dehydrated at 110°C for about 2 hours and cooled to room temperature; several masses of base 7-methyl-1,5,7-triazabicyclo[4.4 .0] Dec-5-ene, 0.5672 g 1,2-ethylene glycol diacrylate and 0.066 g H ₂ O, after which 0.32 g of COS was charged. The molar ratio of 1,2-ethylene glycol diacrylate, water, COS and base is 50/55/80/1. Placed at 60°C for 4h under high pressure. After the reaction was completed, the crude product was first dissolved with dichloromethane, and then the polymer was precipitated in a mixture of 200 mL ethanol/hydrochloric acid (the molar concentration of hydrochloric acid was 5%), washed three times repeatedly, and vacuum-dried to constant weight. The molecular weight and molecular weight distribution of the polymer were determined by gel chromatography, and the test results are shown in Table 1.

The ¹ H NMR spectrum of the main chain sulfur-containing polyester prepared in this embodiment is shown in FIG. 3 , and ^{the 13} C NMR spectrum is shown in FIG. 4 . Observation of Figure 3 and Figure 4 shows that the general structural formula of the product is as follows:

Example 39 Reaction of 1,4-butanediol diacrylate/COS/H ₂ O to produce main chain repeat unit sulfur-containing polyester

Before the polymerization reaction, the 10mL reactor was dehydrated at 110°C for about 2 hours and cooled to room temperature; several masses of base 7-methyl-1,5,7-triazabicyclo[4.4 .0] Dec-5-ene, 0.6607 g 1,4-butanediol diacrylate and 0.063 g H ₂ O, after which 0.26 g of COS was charged. The molar ratio of 1,4-butanediol diacrylate, water, COS and alkali is 50/52.5/65/1. Placed at 60°C for 4h under high pressure. After the reaction was completed, the crude product was first dissolved with dichloromethane, and then the polymer was precipitated in a mixture of 200 mL ethanol/hydrochloric acid (the molar concentration of hydrochloric acid was 5%), washed three times repeatedly, and vacuum-dried to constant weight. The molecular weight and molecular weight distribution of the polymer were determined by gel chromatography, and the test results are shown in Table 1.

The ¹ H NMR spectrum of the main chain sulfur-containing polyester prepared in this embodiment is shown in FIG. 5 , and ^{the 13} C NMR spectrum is shown in FIG. 6 . Observation of Figure 5 and Figure 6 shows that the general structural formula of the product is as follows:

Example 40 Reaction of 1,5-pentanediol diacrylate/COS/H ₂ O to produce main chain repeating unit sulfur-containing polyester

Before the polymerization reaction, the 10mL reactor was dehydrated at 110°C for about 2 hours and cooled to room temperature; several masses of base 7-methyl-1,5,7-triazabicyclo[4.4 .0] Dec-5-ene, 0.7075 g 1,5-pentanediol diacrylate and 0.062 g H ₂ O, after which 0.30 g of COS was charged. The molar ratio of 1,5-pentanediol diacrylate, water, COS and base is 50/52/75/1. Placed at 60°C for 4h under high pressure. After the reaction was completed, the crude product was first dissolved with dichloromethane, and then the polymer was precipitated in a mixture of 200 mL ethanol/hydrochloric acid (the molar concentration of hydrochloric acid was 5%), washed three times repeatedly, and vacuum-dried to constant weight. The molecular weight and molecular weight distribution of the polymer were determined by gel chromatography, and the test results are shown in Table 1.

The ¹ H NMR spectrum of the main chain sulfur-containing polyester prepared in this embodiment is shown in FIG. 7 , and ^{the 13} C NMR spectrum is shown in FIG. 8 . Observation of Figure 7 and Figure 8 shows that the general structural formula of the product is as follows:

Example 41 Reaction of Neopentyl Glycol Diacrylate/COS/H ₂ O to Generate Sulfur-Containing Polyester with Main Chain Repeating Unit

Before the polymerization reaction, the 10mL reactor was dehydrated at 110°C for about 2 hours and cooled to room temperature; several masses of base 7-methyl-1,5,7-triazabicyclo[4.4 .0] Dec-5-ene, 0.7075 g neopentyl glycol diacrylate and 0.064 g _H2O , after which more than 0.23 g COS was charged. The molar ratio of neopentyl glycol diacrylate, water, COS and alkali is 50/53/65/1. Placed at 60°C for 4h under high pressure. After the reaction was completed, the crude product was first dissolved with dichloromethane, and then the polymer was precipitated in a mixture of 200 mL ethanol/hydrochloric acid (the molar concentration of hydrochloric acid was 5%), washed three times repeatedly, and vacuum-dried to constant weight. The molecular weight and molecular weight distribution of the polymer were determined by gel chromatography, and the test results are shown in Table 1.

The ¹ H NMR spectrum of the main chain sulfur-containing polyester prepared in this embodiment is shown in FIG. 9 , and ^{the 13} C NMR spectrum is shown in FIG. 10 . Observe Fig. 9 and Fig. 10 as can be known, the general structural formula of product is as follows:

Example 42 Reaction of 1,6-hexanediol diacrylate/COS/H ₂ O to generate sulfur-containing polyester with main chain repeating unit

Before the polymerization reaction, the 10mL reactor was dehydrated at 110°C for about 2 hours and cooled to room temperature; several masses of base 7-methyl-1,5,7-triazabicyclo[4.4 .0] Dec-5-ene, 0.7542 g 1,6-hexanediol diacrylate and 0.063 g H ₂ O, after which more than 0.30 g COS was charged. The molar ratio of 1,6-hexanediol diacrylate, water, COS and alkali is 50/52.5/75/1. Placed at 60°C for 4h under high pressure. After the reaction was completed, the crude product was first dissolved with dichloromethane, and then the polymer was precipitated in a mixture of 200 mL ethanol/hydrochloric acid (the molar concentration of hydrochloric acid was 5%), washed three times repeatedly, and vacuum-dried to constant weight. The molecular weight and molecular weight distribution of the polymer were determined by gel chromatography, and the test results are shown in Table 1.

The ¹ H NMR spectrum of the main chain sulfur-containing polyester prepared in this example is shown in FIG. 11 , and ^{the 13} C NMR spectrum is shown in FIG. 12 . Observation of Figure 11 and Figure 12 shows that the general structural formula of the product is as follows:

Example 43 Reaction of 1,9-nonanediol diacrylate/COS/H ₂ O to produce main chain repeating unit sulfur-containing polyester

Before the polymerization reaction, the 10mL reactor was dehydrated at 110°C for about 2 hours and cooled to room temperature; several masses of base 7-methyl-1,5,7-triazabicyclo[4.4 .0] Dec-5-ene, 0.9012 g 1,9-nonanediol diacrylate and 0.064 g H ₂ O, after which 0.28 g of COS was charged. The molar ratio of 1,9-nonanediol diacrylate, water, COS and alkali is 50/53/70/1. Placed at 60°C for 4h under high pressure. After the reaction was completed, the crude product was first dissolved with dichloromethane, and then the polymer was precipitated in a mixture of 200 mL ethanol/hydrochloric acid (the molar concentration of hydrochloric acid was 5%), washed three times repeatedly, and vacuum-dried to constant weight. The molecular weight and molecular weight distribution of the polymer were determined by gel chromatography, and the test results are shown in Table 1.

The ¹ H NMR spectrum of the main chain sulfur-containing polyester prepared in this example is shown in FIG. 13 , and ^{the 13} C NMR spectrum is shown in FIG. 14 . Observation of Figure 13 and Figure 14 shows that the general structural formula of the product is as follows:

Example 44 Reaction of 1,10-decanediol diacrylate/COS/H ₂ O to produce main chain repeat unit sulfur-containing polyester

Before the polymerization reaction, the 10mL reactor was dehydrated at 110°C for about 2 hours and cooled to room temperature; several masses of base 7-methyl-1,5,7-triazabicyclo[4.4 .0] Dec-5-ene, 0.9413 g 1,10-decanediol diacrylate and 0.064 g H ₂ O, after which 0.26 g of COS was charged. The molar ratio of 1,10-decanediol diacrylate, water, COS and base is 50/53.5/65/1. Placed at 60°C for 4h under high pressure. After the reaction was completed, the crude product was first dissolved with dichloromethane, and then the polymer was precipitated in a mixture of 200 mL ethanol/hydrochloric acid (the molar concentration of hydrochloric acid was 5%), washed three times repeatedly, and vacuum-dried to constant weight. The molecular weight and molecular weight distribution of the polymer were determined by gel chromatography, and the test results are shown in Table 1.

The ¹ H NMR spectrum of the main chain sulfur-containing polyester prepared in this example is shown in FIG. 15 , and ^{the 13} C NMR spectrum is shown in FIG. 16 . Observation of Figure 15 and Figure 16 shows that the general structural formula of the product is as follows:

Example 45 Reaction of 1,12-dodecanediol diacrylate/COS/H ₂ O to produce main chain repeating unit sulfur-containing polyester

Before the polymerization reaction, the 10mL reactor was dehydrated at 110°C for about 2 hours and cooled to room temperature; several masses of base 7-methyl-1,5,7-triazabicyclo[4.4 .0] Dec-5-ene, 1.0348 g 1,12-dodecanediol diacrylate and 0.064 g H ₂ O, after which 0.26 g of COS was charged. The molar ratio of 1,12-dodecanediol diacrylate, water, COS and alkali is 50/53.5/65/1. Placed at 60°C for 4h under high pressure. After the reaction was completed, the crude product was first dissolved with dichloromethane, and then the polymer was precipitated in a mixture of 200 mL ethanol/hydrochloric acid (the molar concentration of hydrochloric acid was 5%), washed three times repeatedly, and vacuum-dried to constant weight. The molecular weight and molecular weight distribution of the polymer were determined by gel chromatography, and the test results are shown in Table 1.

The ¹ H NMR spectrum of the main chain sulfur-containing polyester prepared in this example is shown in FIG. 17 , and ^{the 13} CNMR spectrum is shown in FIG. 18 . Observation of Figure 17 and Figure 18 shows that the general structural formula of the product is as follows:

Example 46 Reaction of Tere-Phenylenedimethanol Diacrylate/COS/H ₂ O to Generate Sulfur-Containing Polyester with Main Chain Repeating Unit

Before the polymerization reaction, the 10mL reactor was dehydrated at 110°C for about 2 hours and cooled to room temperature; several masses of base 7-methyl-1,5,7-triazabicyclo[4.4 .0] Dec-5-ene, 0.8209 g terephthalate diacrylate and 0.064 g H ₂ O, after which 0.26 g COS was charged. The molar ratio of terephthalyl dimethacrylate, water, COS and alkali is 50/53.5/65/1. Placed at 60°C for 4h under high pressure. After the reaction was completed, the crude product was first dissolved with dichloromethane, and then the polymer was precipitated in a mixture of 200 mL ethanol/hydrochloric acid (the molar concentration of hydrochloric acid was 5%), washed three times repeatedly, and vacuum-dried to constant weight. The molecular weight and molecular weight distribution of the polymer were determined by gel chromatography, and the test results are shown in Table 1.

Example 47 Reaction of 1,12-dodecanediol dimethacrylate/COS/H ₂ O to produce main chain repeating unit sulfur-containing polyester

Before the polymerization reaction, the 10mL reactor was dehydrated at 110°C for about 2 hours and cooled to room temperature; several masses of base 7-methyl-1,5,7-triazabicyclo[4.4 .0] Dec-5-ene, 1.1283 g 1,12-dodecanediol dimethacrylate and 0.066 g H ₂ O, after which 0.36 g COS was charged. The molar ratio of 1,12-dodecanediol dimethacrylate, water, COS and alkali is 50/55/90/1. Placed at 60°C for 18h under high pressure. After the reaction was completed, the crude product was first dissolved with dichloromethane, and then the polymer was precipitated in a mixture of 200 mL ethanol/hydrochloric acid (the molar concentration of hydrochloric acid was 5%), washed three times repeatedly, and vacuum-dried to constant weight. The molecular weight and molecular weight distribution of the polymer were determined by gel chromatography, and the test results are shown in Table 1.

The ¹ H NMR spectrum of the main chain sulfur-containing polyester prepared in this embodiment is shown in FIG. 19 , and ^{the 13} C NMR spectrum is shown in FIG. 20 . Observation of Figure 19 and Figure 20 shows that the general structural formula of the product is as follows:

Example 48 Reaction of N,N'-methylenebisacrylamide/COS/H ² O to form main chain repeating unit sulfur-containing polyester

Before the polymerization reaction, the 10mL reactor was dehydrated at 110°C for about 2 hours and cooled to room temperature; several masses of base 7-methyl-1,5,7-triazabicyclo[4.4 .0] dec-5-ene, 0.9413g N,N'-methylenebisacrylamide and 0.066g H ₂ O, then add 1mL dichloromethane to dissolve the monomer, and then charge 0.34g COS. The molar ratio of N,N'-methylenebisacrylamide, water, COS and alkali is 50/55/85/1. Placed at 60°C for 24h under high pressure. After the reaction was completed, the crude product was first dissolved with dichloromethane, and then the polymer was precipitated in a mixture of 200 mL ethanol/hydrochloric acid (the molar concentration of hydrochloric acid was 5%), washed three times repeatedly, and vacuum-dried to constant weight. The molecular weight and molecular weight distribution of the polymer were determined by gel chromatography, and the test results are shown in Table 1. The general structural formula of the product is as follows:

Example 49 Reaction of Divinylsulfone Methane/COS/H ₂ O to Generate Sulfur-Containing Polyester with Main Chain Repeating Unit

Before the polymerization reaction, the 10mL reactor was dehydrated at 110°C for about 2 hours and cooled to room temperature; several masses of base 7-methyl-1,5,7-triazabicyclo[4.4 .0] Dec-5-ene, 0.6541 g divinylsulfonylmethane and 0.066 g _H2O , after which 0.26 g COS was charged. The molar ratio of bisvinylsulfone methane, water, COS and alkali is 50/55/65/1. Placed at 60°C for 4h under high pressure. After the reaction was completed, the crude product was first dissolved with dichloromethane, and then the polymer was precipitated in a mixture of 200 mL ethanol/hydrochloric acid (the molar concentration of hydrochloric acid was 5%), washed three times repeatedly, and vacuum-dried to constant weight. The molecular weight and molecular weight distribution of the polymer were determined by gel chromatography, and the test results are shown in Table 1. The general structural formula of the product is as follows:

Example 50 Reaction of N,N'-(4,4'-methylenediphenyl)bismaleimide/COS/H ₂ O to produce main chain repeat unit sulfur-containing polyester

Before the polymerization reaction, the 10mL reactor was dehydrated at 110°C for about 2 hours and cooled to room temperature; several masses of base 7-methyl-1,5,7-triazabicyclo[4.4 .0] Dec-5-ene, 1.1945 g N,N'-(4,4'-methylenediphenyl)bismaleimide and 0.066 g H ₂ O, after which 0.26 g COS was charged. The molar ratio of N,N'-(4,4'-methylenediphenyl)bismaleimide, water, COS and base is 50/55/65/1. Placed at 60°C for 4h under high pressure. After the reaction was completed, the crude product was first dissolved with dichloromethane, and then the polymer was precipitated in a mixture of 200 mL ethanol/hydrochloric acid (the molar concentration of hydrochloric acid was 5%), washed three times repeatedly, and vacuum-dried to constant weight. The molecular weight and molecular weight distribution of the polymer were determined by gel chromatography, and the test results are shown in Table 1.

The general structural formula of the product is as follows:

Example 51 Reaction of 1,10-decanediol diacrylate/CS ₂ /H ₂ O to produce main chain repeat unit sulfur-containing polyester

Before the polymerization reaction, the 10mL reactor was dehydrated at 110°C for about 2 hours and cooled to room temperature; several masses of base 7-methyl-1,5,7-triazabicyclo[4.4 .0] Dec-5-ene, 0.9413 g 1,10-decanediol diacrylate and 0.066 g H ₂ O, after which 0.18 g CS ₂ was charged. The molar ratio of 1,10-decanediol diacrylate, water, CS ₂ to base is 50/55/35/1. Placed at 140°C and reacted under high pressure for 120h. After the reaction was completed, the crude product was first dissolved with dichloromethane, and then the polymer was precipitated in a mixture of 200 mL ethanol/hydrochloric acid (the molar concentration of hydrochloric acid was 5%), washed three times repeatedly, and vacuum-dried to constant weight. The molecular weight and molecular weight distribution of the polymer were determined by gel chromatography, and the test results are shown in Table 2.

Table 1

Note: ^1. Types of double bond monomers: TEGDA is triethylene glycol diacrylate, BGDA is 1,4-butanediol diacrylate, PGDA is 1,5-pentanediol diacrylate, NPGDA is Neopentyl glycol diacrylate, HGDA is 1,6-hexanediol diacrylate, NGDA is 1,9-nonanediol diacrylate, DGDA is 1,10-decanediol diacrylate, DDGDA is 1 , 12-Dodecanediol Diacrylate, TDGDA is 1,14-Tetradecanediol Diacrylate, BDMDA is Terephthalene Dimethacrylate, DDGDMA is 1,12-Dodecanediol Dimethyl Acrylate, MBA is N,N'-methylenebisacrylamide, BVSM is bisvinylsulfonylmethane, BMI is N,N'-(4,4'-methylenediphenyl)bismaleimide amine. ² base types: 1 is 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), 2 is bis(triphenylphosphoryl)ammonium chloride ([PPN]Cl) , 3 p-nitrophenol tetrabutylammonium, 4 is methyltriphenylphosphine bromide, 5 is 1,5,7-triazabicyclo[4.4.0]dec-5-ene, 6 is 7-methyl Base-1,5,7-triazabicyclo[4.4.0]dec-5-ene (MTBD), 7 is 4-dimethylaminopyridine (DMAP), 8 is potassium tert-butoxide (t-BuOK), 9 is potassium carbonate. ³ The molar ratio of two double-bond monomers to water; ⁴ The molar ratio of COS to two double-bond monomers; ⁵ The molar ratio of base to two double-bond monomers; ⁶ M _n : number average molecular weight, determined by gel permeation chromatography Determination; ⁷ PDI: molecular weight distribution, determined by gel permeation chromatography.

Table 2

Note: ^1. Two double bond monomer monomer type: DGDA is 1,10-decanediol diacrylate. ² Base species: 6 is 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene (MTBD). ³ The molar ^ratio of two double-bond monomers to water; ⁴ CS The molar ratio of ₂ to two double-bond monomers; ⁵ The molar ratio of alkali to two double-bond monomers _; ⁷ PDI: molecular weight distribution, determined by gel permeation chromatography.

Examples 1-51 are the results of the copolymerization of base-catalyzed monomers with two double bonds, carbon oxysulfide (or carbon disulfide) and water. It can be seen that such systems have excellent catalytic activity and universal applicability.

The above descriptions are only some specific implementations of the present invention, and it should be pointed out that many variations and improvements can be made by those skilled in the art, and all variations or improvements that do not exceed the claims described should be considered as Be the protection scope of the present invention.

Claims (10)

1. a kind of macromolecule that main chain contains thioether group, it is characterized in that, general structural formula is as shown in following formula (I)～(IV):

In the formula, n is selected from 1 to 200; R ₁ is selected from C ₂ -C ₁₈ alkylene, p-xylylene, 2,5-furandimethylene, 1,4-cyclohexylene, (CH ₂ CH ₂ O) _m CH ₂ CH ₂ , m=1~3; R ₂ is selected from H or methyl; R ₃ is selected from C ₁ -C ₁₂ alkylene; R ₄ is selected from C ₁ -C ₂ alkylene groups; R ₅ is selected from C ₁ ~ C ₁₀ alkylene, 1,4-phenylene, 1,3-phenylene, 1,2-phenylene, 4,4'-methylene diphenyl, 4,4'-methylenebis(3-ethyl-5-methylphenyl), (CH ₂ CH ₂ O) _p CH ₂ CH ₂ , p=1-3. 2. The polymer having a thioether group in the main chain according to claim 1, characterized in that the number average molecular weight is 1-200 kg/mol, and the molecular weight distribution is 1.1-4.0. 3. the macromolecule of main chain containing thioether group according to claim 1 or 2, is characterized in that, has following structural formula:

4. a kind of synthetic method according to the macromolecule of main chain thioether group according to any one of claim 1～3, is characterized in that, raw material comprises two double bond monomers, sulfur-containing carbon monomer and water , using alkali as a catalyst to carry out polymerization under autogenous pressure; The two double bond monomers are selected from one or more of diacrylate monomers, bisacrylamide monomers, bisvinyl sulfone monomers, and bismaleimide monomers; The sulfur-containing carbon monomer is selected from COS and/or CS ₂ . 5. the synthetic method of the macromolecule that main chain contains thioether group according to claim 4 is characterized in that: The diacrylate monomer is selected from ethylene glycol diacrylate, 1,3-propanediol diacrylate, 1,4-butanediol diacrylate, 1,5-pentanediol diacrylate, neopentyl Diol diacrylate, 1,6-hexanediol diacrylate, 1,9-nonanediol diacrylate, 1,10-decanediol diacrylate, 1,12-dodecanediol diacrylate Esters, 1,14-tetradecanediol diacrylate, 1,16-hexadecanediol diacrylate, 1,18-octadecanediol diacrylate, terephthalene dimethanol diacrylate, 2 ,5-furandimethanol diacrylate, 1,4-cyclohexanediol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, ethylene glycol Dimethacrylate, 1,3-Propanediol Dimethacrylate, 1,4-Butanediol Dimethacrylate, 1,5-Pentanediol Dimethacrylate, Neopentyl Glycol Dimethacrylate Acrylates, 1,6-hexanediol dimethacrylate, 1,9-nonanediol dimethacrylate, 1,10-decanediol dimethacrylate, 1,12-dodecane dimethacrylate One or more of alcohol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate; The bisacrylamide monomer is selected from N,N'-methylenebisacrylamide, N,N'-ethylenebisacrylamide, N,N'-trimethylenebisacrylamide, N,N' -tetramethylenebisacrylamide, N,N'-pentamethylenebisacrylamide, N,N'-hexamethylenebisacrylamide, N,N'-heptamethylenebisacrylamide, N, N'-octamethylenebisacrylamide, N,N'-nonamethylenebisacrylamide, N,N'-decamethylenebisacrylamide, N,N'-undecamethylenebisacrylamide , one or more of N,N'-dodecamethylenebisacrylamide; The divinylsulfone monomer is selected from divinylsulfone methane and/or divinylsulfone ethane; The bismaleimide monomer is selected from bismaleimide methane, 1,2-bismaleimide ethane, 1,3-bismaleimide propane, 1 ,4-Bismaleimidobutane, 1,5-Bismaleimidopentane, 1,6-Bismaleimidohexane, 1,7-Bismaleimideheptane alkane, 1,8-bismaleimide octane, 1,9-bismaleimide nonane, 1,10-bismaleimide decane, N,N'-(1,4 -phenylene)bismaleimide, N,N'-(1,3-phenylene)bismaleimide, N,N'-(1,2-phenylene)bismaleimide imide, N,N'-(4,4'-methylenediphenyl)bismaleimide, bis(3-ethyl-5-methyl-4-maleimidobenzene base) methane, 1,5-bismaleimide diethylene glycol, 1,8-bismaleimide triethylene glycol, 1,11-bismaleimide tetraethylene glycol one or more of The molar ratio of two double-bond monomers, one sulfur-containing carbon monomer and water is 1:0.1-5.0:0.1-5.0. 6. the synthetic method of the polymer of main chain sulfide group according to claim 4, is characterized in that: The base is selected from one or more of quaternary ammonium salts, quaternary phosphonium salts, amines, phosphazenes, guanidines, amidines, alkali metal alkoxides, and inorganic bases; The quaternary ammonium salt is selected from one of bis(triphenylphosphoryl)ammonium chloride, tetrabutylammonium chloride, tetrabutylammonium bromide, tetraoctylammonium bromide, and p-nitrophenol tetrabutylammonium one or more kinds; The quaternary phosphonium salt is selected from tetraphenylphosphonium chloride and/or methyltriphenylphosphonium bromide; The amine is selected from one or more of n-hexylamine, tetramethylmethylenediamine, N,N'-dimethylethylenediamine, tetramethylethylenediamine, and 4-dimethylaminopyridine; Phosphazenes are selected from tert-butylimino-tris(dimethylamino)phosphorane, 1-tert-butyl-2,2,4,4,4-penta(dimethylamino)-2λ ⁵ ,4λ ⁵ -dipheno (Phosphorus nitrogen-based compounds), 1-tert-butyl-4,4,4-tris(dimethylamino)-2,2-bis[tris(dimethylamino)-phosphinylideneamino]-2λ ⁵ , One or more of 4λ ⁵ -bis(phosphorus nitrogen-based compounds); The amidine is selected from 1,8-diazabicyclo[5.4.0]undec-7-ene and/or 1,5-diazabicyclo[4.3.0]non-5-ene; Guanidine is selected from 1,5,7-triazabicyclo[4.4.0]dec-5-ene, 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene, One or more of tetramethylguanidine; The alkali metal alkoxide is selected from one or more of sodium methoxide, potassium methoxide, sodium ethoxide, potassium tert-butoxide, lithium tert-butoxide, and sodium tert-butoxide; The inorganic base is selected from one or more of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate; The molar ratio of the base to the double-bond monomer is 1:5-1000. 7. the synthetic method of the polymer of main chain thioether group according to claim 4, is characterized in that: The polymerization is bulk polymerization or solution polymerization, the polymerization temperature is 25-160°C, and the time is 0.5-120h; In the solution polymerization, the solvent used is selected from one or more of dichloromethane, chloroform, tetrahydrofuran, toluene, trichlorobenzene, o-dichlorobenzene, m-dichlorobenzene, p-dichlorobenzene, and dimethylformamide. kind. 8. according to the synthetic method of the main chain thioether group macromolecule described in any one of claim 4～7, it is characterized in that: The diacrylate monomer is selected from diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, 1,2-ethylene glycol diacrylate, 1,4-butyl Diol diacrylate, 1,5-pentanediol diacrylate, neopentyl glycol diacrylate, 1,6-hexanediol diacrylate, 1,9-nonanediol diacrylate, 1,10 - One or more of decanediol diacrylate, 1,12-dodecanediol diacrylate, 1,12-dodecanediol dimethacrylate, tere-xylylenediol diacrylate ; The bisacrylamide monomer is selected from N,N'-methylenebisacrylamide; The bisvinyl sulfone monomer is selected from bisvinyl sulfone methane; The bismaleimide monomer is selected from N,N'-(4,4'-methylenediphenyl)bismaleimide and/or N,N'-1,4- Phenyl bismaleimide; The base is selected from 1,8-diazabicyclo[5.4.0]undec-7-ene, bis(triphenylphosphoryl)ammonium chloride, tetrabutylammonium p-nitrophenolate, methyl Triphenylphosphine bromide, 1,5,7-triazabicyclo[4.4.0]dec-5-ene, 7-methyl-1,5,7-triazabicyclo[4.4.0]dec- One or more of 5-ene, 4-dimethylaminopyridine, potassium tert-butoxide, and potassium carbonate; The molar ratio of two double bond monomers, one sulfur-containing carbon monomer and water is 1:1.0～2.0:1.0～1.5; The molar ratio of the base to the double-bond monomer is 1:50-100. 9. the synthetic method of main chain thioether group polymer according to claim 8, is characterized in that: The two double bond monomers are selected from triethylene glycol diacrylate, 1,2-ethylene glycol diacrylate, neopentyl glycol diacrylate, 1,6-hexanediol diacrylate, 1,9 - One or more of nonanediol diacrylate, 1,10-decanediol diacrylate, 1,12-dodecanediol diacrylate, and terephthalenediol diacrylate; The base is selected from 1,5,7-triazabicyclo[4.4.0]dec-5-ene, 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5- One or more of alkenes, 4-dimethylaminopyridine, potassium tert-butoxide; The molar ratio of the two double bond monomers, carbon oxysulfide and water is 1:1.1-1.8:1.0-1.1; The molar ratio of base to double bond monomer is 1:50. 10. the synthetic method of main chain thioether group polymer according to claim 9, is characterized in that: The two double bond monomers are selected from one or more of triethylene glycol diacrylate, 1,10-decanediol diacrylate, and 1,12-dodecanediol diacrylate; The base is selected from 1,5,7-triazabicyclo[4.4.0]dec-5-ene and/or 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5- 5-ene.

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