CN114854017B - Polymer with main chain containing thioether group and synthesis method thereof - Google Patents
Polymer with main chain containing thioether group and synthesis method thereof Download PDFInfo
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Abstract
The invention discloses a high polymer with a main chain containing thioether groups and a synthesis method thereof, wherein the structural general formula of the high polymer with the main chain containing thioether groups is shown in the following formulas (I) to (IV). The synthesis method comprises the steps of taking a double-bond monomer, a sulfur-containing carbon-monomer and water as raw materials, taking alkali as a catalyst, and polymerizing under autogenous pressure; the double-bond monomer is selected from one or more of diacrylate monomers, bisacrylamide monomers, divinyl sulfone monomers and bismaleimide monomers; the sulfur-containing carbon-monomer is selected from COS and/or CS 2 . The polymer with the main chain containing thioether groups has a definite structure, the main chain repeating unit has a thioether structure, and simultaneously contains different functional groups, and the end groups are double bonds; the polymer with the main chain containing thioether groups also has higher molecular mass and excellent mechanical property, and has wide application prospect in the fields of food packaging, coatings, biology and electronics.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a high polymer with a main chain containing thioether groups and a synthesis method thereof.
Background
The sulfur-containing polymer has the characteristics of excellent mechanical property, thermal stability, optical function, biocompatibility, strong ion binding capacity and the like due to the introduction of sulfur atoms, and has wide application in the aspects of general, engineering, functional materials and the like. Such as vulcanized rubber, has become the main raw material of tires since its discovery in 1839, and still plays an irreplaceable role in modern society on wheels. And polyphenylene sulfide is used as a special engineering plastic with excellent comprehensive performance and is widely applied to the field of advanced materials of electronic appliances, aerospace and the like. The main chain sulfur-containing ether group polymer is an important sulfur-containing polymer variety, is widely applied to drug delivery systems, artificial tissues and commodity materials, and also has wide application prospects in the fields of degradable materials, novel liquid crystals, precise optics and the like.
However, how to controllably introduce sulfur element by a simple way still remains a challenging problem in the field of synthesis, and especially the synthesis of macromolecules containing sulfide groups on the main chain is less studied.
Chinese patent application publication No. CN 113278149A discloses a method for producing a polythioether compound, and a technical route thereof is to efficiently and economically obtain a polythioether compound by ring-opening polymerization of an alicyclic episulfide compound under the catalysis of a base. However, the ring-opening polymerization method is limited by the fact that the types of reaction monomers are few, and the preparation, storage and transportation of alicyclic episulfide compounds are difficult, so that the prepared polythioether has a single structure and type, and other functional groups are difficult to introduce.
Chinese patent application publication No. CN 110139884A discloses a polyurethane product having a sulfur-containing polyester polyol and a process for producing the same, wherein a technical route for obtaining the sulfur-containing polyester polyol is to react at least one sulfur-containing component of sulfur-containing polyol or sulfur-containing polycarboxylic acid, at least one aromatic component of aromatic polyfunctional ester, aromatic polyfunctional carboxylic acid and aromatic anhydride, and at least one simple polyol which does not include sulfur and is different from the sulfur-containing polyol, with the action of a catalyst to obtain a plurality of sulfur-containing polyesters. However, because the technical scheme adopts a polycondensation method, the small molecules generated in the reaction process need to be separated out by heating or decompressing a reaction system, the reaction process is difficult to control, and the method is a process with high energy consumption.
The subject group of the inventor of the invention has long-term research and accumulation in the field of sulfur-containing polymers, and Chinese patent document with application publication No. CN 109180937A discloses a method for preparing aliphatic polythioether, wherein the technical route is that a sulfur-carbon-containing compound and an oxygen-containing monomer are used as raw materials, lewis base is used as a catalyst, and aliphatic polythioether is obtained through polymerization reaction; the polymerization is carried out at 80 to 180 ℃ under autogenous pressure. However, the aliphatic polythioether obtained by the process route is composed of thioether chain links, and lacks other functional groups.
Disclosure of Invention
Aiming at the problems in the prior art, the invention discloses a main chain thioether group-containing macromolecule and a synthesis method thereof, wherein the main chain thioether group-containing macromolecule has a definite structure, a main chain repeating unit has a thioether structure, and simultaneously contains different functional groups, and terminal groups are double bonds and have further reactivity; the polymer containing thioether groups also has high molecular weight, excellent mechanical property and wide application prospect in the fields of food packaging, coatings, biology and electronics. The synthesis process only needs one step, the raw materials are cheap and easy to obtain, the time consumption is short, and complicated post-treatment purification steps are not needed, so that the method is favorable for realizing industrial production.
The specific technical scheme is as follows:
a macromolecule with a main chain containing thioether groups has a general structural formula shown in formulas (I) to (IV):
wherein n is selected from 1 to 200;
R 1 is selected from C 2 ～C 18 Alkylene of (A), p-xylylene, 2, 5-furandimethylene, 1, 4-cyclohexaalkylene, (CH) 2 CH 2 O) m CH 2 CH 2 ，m＝1～3；
R 2 Selected from H or methyl;
R 3 is selected from C 1 ～C 12 An alkylene group of (a);
R 4 is selected from C 1 ～C 2 An alkylene group of (a);
R 5 is selected from C 1 ～C 10 Alkylene of (a), 1, 4-phenylene, 1, 3-phenylene, 1, 2-phenylene, 4 '-methylenediphenyl, 4' -methylenebis (3-ethyl-5-methylphenyl), (CH) 2 CH 2 O) p CH 2 CH 2 ，p＝1～3。
The invention also discloses a method for synthesizing the high molecule with the main chain containing thioether groups, wherein the raw materials comprise double-bond monomers, sulfur-containing carbon-containing monomers and water, and alkali is used as a catalyst to carry out polymerization under the autogenous pressure;
the double-bond monomer is selected from one or more of diacrylate monomers, bisacrylamide monomers, bisvinyl sulfone monomers and bismaleimide monomers;
the sulfur-containing carbon-monomer is selected from carbonyl sulfide (COS) and/or carbon disulfide (CS) 2 )。
Based on a great deal of experimental research, the inventor discovers the phenomenon that the sulfur anion and the double-bond compound can be subjected to rapid addition reaction, and therefore develops a new reaction for polymerizing the double-bond monomer, the sulfur-containing carbon-monomer and water in one step. The addition reaction of the sulfur anion with the double bond compound is an anionic mechanism, unlike the mercapto-double bond addition reaction based on free radical addition reported in the literature. The latter easily causes a crosslinking reaction to occur.
First, COS (or CS) 2 ) The hydrogen sulfide and a double-bond compound undergo an addition reaction to form a sulfydryl, and the sulfydryl is quickly converted into sulfur anions in the presence of alkali; secondly, the sulfur anion is subjected to 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 electron-withdrawing groups favor electrophilic double bonds; finally, COS (CS) 2 ) The carbon dioxide generated by the water is inert, so that the reaction system is always in a high-pressure environment, the carbon dioxide is equivalent to a solvent, the viscosity of the system is reduced, the mobility of the end group is improved, and the reaction system hasIs beneficial to the increase of the molecular weight of the polymer. This is a way that is significantly different from conventional step-wise polymerizations, some of which are often conducted under conditions of high temperature and high vacuum (or atmospheric pressure). Thus, the present invention obtains a polymerization product of high molecular weight by a mechanism of stepwise polymerization, completely different from the previous C1 polymerization system. On the basis of the above-described mechanism findings, the present invention was formed through experimental studies.
The synthesis method has better universality to double-bond monomers.
The diacrylate monomer is selected from one or more of ethylene glycol diacrylate, 1, 3-propanediol diacrylate, 1, 4-butanediol diacrylate, 1, 5-pentanediol diacrylate, neopentyl glycol diacrylate, 1, 6-hexanediol diacrylate, 1, 9-nonanediol diacrylate, 1, 10-decanediol diacrylate, 1, 12-dodecanediol diacrylate, 1, 14-tetradecanediol diacrylate, 1, 16-hexadecanediol diacrylate, 1, 18-octadecanediol diacrylate, p-xylylene glycol 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, 1, 6-hexanediol dimethacrylate, 1, 9-nonanediol dimethacrylate, 1, 10-decanediol dimethacrylate, 1, 12-dodecanediol dimethacrylate, diethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate;
the bisacrylamide monomer is selected from N, N '-methylene bisacrylamide, N' -ethylene bisacrylamide, N '-trimethylene bisacrylamide, N' -tetramethylene bisacrylamide, N '-pentamethylene bisacrylamide, N' -hexamethylene bisacrylamide and N, one or more of N '-heptamethylene bisacrylamide, N' -octamethylene bisacrylamide, N '-nonamethylene bisacrylamide, N' -decamethylene bisacrylamide, N '-undecamethylene bisacrylamide and N, N' -dodecamethylene bisacrylamide;
the divinyl sulfone monomers are selected from divinyl sulfone methane and/or divinyl sulfone ethane;
the bismaleimide monomer is selected from one or more of bismaleimide methane, 1, 2-bismaleimide ethane, 1, 3-bismaleimide propane, 1, 4-bismaleimide butane, 1, 5-bismaleimide pentane, 1, 6-bismaleimide hexane, 1, 7-bismaleimide heptane, 1, 8-bismaleimide octane, 1, 9-bismaleimide nonane, 1, 10-bismaleimide decane, N ' - (1, 4-phenylene) bismaleimide, N ' - (1, 3-phenylene) bismaleimide, N ' - (1, 2-phenylene) bismaleimide, N ' - (4, 4' -methylenediphenyl) bismaleimide, bis (3-ethyl-5-methyl-4-maleimidophenyl) methane, 1, 5-bismaleimide diethylene glycol, 1, 8-bismaleimide triethylene glycol, and 1, 11-bismaleimide tetraethylene glycol.
Preferably:
the diacrylate monomer is selected from one or more of 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, 12-dodecanediol dimethacrylate (DDGDMA), and terephthalyl alcohol diacrylate (BDMDA);
the bisacrylamide monomer is selected from N, N' -methylene bisacrylamide;
the divinyl sulfone monomers are selected from divinyl sulfone methane;
the bismaleimide monomer is selected from N, N ' - (4, 4' -methylene diphenyl) bismaleimide and/or N, N ' -1, 4-phenylene bismaleimide.
The preferable double-bond monomers are cheap and easily-obtained industrial products and are convenient to store and transport; it is particularly important that the preferred double-bonded monomers have good reactivity and excellent effects.
Further preferably:
the double-bond monomer is selected from diacrylate monomers, such as one or more of TEGDA, EGDA, NPGDA, HGDA, NGDA, DGDA, BDMDA and DDGDA; with the further preferred diacrylate monomers mentioned above, a higher number average molecular weight polymer may be prepared
Still further preferably, the double bond monomer is selected from TEGDA, EGDA, DGDA or DDGDA; more preferably TEGDA, DDGDA or DGDA, most preferably DGDA. With the above-mentioned preference for the types of double-bonded monomers, it is possible to prepare polymerization products having a higher number-average molecular weight, up to 200kg/mol.
Preferably, the sulfur-containing carbon-monomer is selected from COS and test results show that 2 Compared with COS, 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 salt, quaternary phosphonium salt, amine, phosphazene, guanidine, amidine, alkali metal alkoxide and inorganic base;
the quaternary ammonium salt is one or more of bis (triphenyl phosphorane) ammonium chloride, tetrabutyl ammonium bromide, tetraoctyl ammonium bromide and tetrabutyl ammonium paranitrophenol;
the quaternary phosphonium salt is selected from tetraphenylphosphonium chloride and/or methyltriphenylphosphonium bromide;
the amine is selected from one or more of N-hexylamine, tetramethyl-methane diamine, N' -dimethyl ethylene diamine and tetramethyl ethylene diamine;
the phosphazene is selected from the group consisting of t-butylimino-tris (dimethylamino) phosphorane, 1-t-butyl-2, 4-pentakis (dimethylamino) -2 lambda 5 ,4λ 5 Bis (phosphazene), 1-tert-butyl-4, 4-tris (dimethylamino) -2, 2-bis [ tris (dimethylamino) -phosphinideneamino]-2λ 5 ，4λ 5 -one or more of vicinal bis (phosphazene compounds);
the amidine is selected from one or more of 1, 8-diazabicyclo [5.4.0] undec-7-ene, 1, 5-diazabicyclo [4.3.0] non-5-ene;
guanidine is selected from one or more of 1,5, 7-triazabicyclo [4.4.0] dec-5-ene, 7-methyl-1, 5, 7-triazabicyclo [4.4.0] dec-5-ene and tetramethyl guanidine;
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 and 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 one or more of 1, 8-diazabicyclo [5.4.0] undec-7-ene (DBU), bis (triphenylphosphoranylidene) ammonium chloride ([ PPN ] Cl, structure 1), tetrabutylammonium p-nitrophenol (structure 2), methyltriphenylphosphonium bromide, 1,5, 7-triazabicyclo [4.4.0] dec-5-ene (TBD, structure 3), 7-methyl-1, 5, 7-triazabicyclo [4.4.0] dec-5-ene (MTBD, structure 4), 4-dimethylaminopyridine (DMAP, structure 5), potassium tert-butoxide (t-BuOK, structure 6), potassium carbonate. The preferred bases are inexpensive and readily available and have high catalytic activity.
Further 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 types of the catalysts, the catalytic activity is continuously increased, and the number average molecular weight of a polymerization product prepared under the same polymerization condition is higher.
In the present invention, the molar ratio of the double-bond monomer, the sulfur-containing carbon-monomer and water is 1:0.1 to 5.0:0.1 to 5.0; the molar ratio of base to double-bond monomer is 1:5 to 1000.
Preferably, the molar ratio of the double-bond monomer to the sulfur-containing carbon-monomer is 1:1.0 to 2.0, more preferably 1:1.1 to 1.8.
Preferably, the molar ratio of the double-bond monomer to water is 1:0.5 to 5.0, more preferably 1:1.0 to 1.5; more preferably 1:1.0 to 1.1.
Preferably, the molar ratio of base to double-bonded monomer is 1:50 to 100, more preferably 1:50.
with the continuous optimization of the raw material proportion, the number average molecular weight of the prepared polymerization product can be higher.
In the invention, the polymerization is bulk polymerization or solution polymerization, the polymerization temperature is 25-160 ℃, and the polymerization time is 0.5-120 h; preferably, the polymerization temperature is from 40 to 100 ℃, more preferably from 60 to 80 ℃, most preferably 60 ℃.
The solution polymerization is carried out by adopting a solvent selected from one or more of dichloromethane, chloroform, tetrahydrofuran, toluene, trichlorobenzene, o-dichlorobenzene, m-dichlorobenzene, p-dichlorobenzene and dimethylformamide; further preferred is dichloromethane or tetrahydrofuran.
The number average molecular weight of the polymer with the main chain containing thioether groups prepared by the synthesis method is 1-200 kg/mol, and the molecular weight distribution is 1.1-4.0. The number average molecular weight of the prepared high molecular product can be regulated and controlled within a large range by regulating and controlling the types and the proportions of the raw materials and the process conditions in the synthesis method.
Preferably, the main chain thioether group-containing polymer has the following structural formula:
further preferably, the main chain thioether group-containing polymer has the following structural formula:
compared with the prior art, the invention has the following beneficial effects:
(1) On the basis of a large number of experimental researches, the invention firstly proposes that the main chain containing thioether group polymer with double bonds as end groups is obtained through one-step reaction of a double-bond compound containing electron-withdrawing groups, a sulfur-containing carbon-monomer and water, and the raw materials are cheap and easy to obtain and the reaction conditions are simple;
(2) The catalytic system adopted in the invention is commercially available, cheap and colorless, and the prepared catalyst has a definite structure, no metal residue, a main chain repeating unit containing thioether groups and ester bond structures, a definite end group structure and no need of complicated post-treatment purification steps;
(3) The polymer prepared by the method has high molecular weight, does not contain metal ions, has excellent mechanical property, and has wide application prospect in the fields of food packaging, coating, biology and electronics.
Drawings
FIG. 1 is a drawing of a copolymeric polymer product prepared in example 34 1 H NMR spectrum;
FIG. 2 is a diagram of a copolymeric polymer product prepared in example 34 13 C NMR spectrum;
FIG. 3 is a diagram of a copolymeric polymer produced in example 38 1 H NMR spectrum;
FIG. 4 is a photograph of a copolymeric polymer product prepared in example 38 13 C NMR spectrum;
FIG. 5 is a photograph of a copolymeric polymer product prepared in example 39 1 H NMR spectrum;
FIG. 6 is a photograph of a copolymeric polymer product prepared in example 39 13 C NMR spectrum;
FIG. 7 is a diagram showing a copolymerized polymer product prepared in example 40 1 H NMR spectrum;
FIG. 8 is a photograph of a copolymeric polymer product prepared in example 40 13 C NMR spectrogram;
FIG. 9 is a photograph of a copolymeric polymer product prepared in example 41 1 H NMR spectrum;
FIG. 10 is a copolymeric polymer made in example 41Of an object 13 C NMR spectrogram;
FIG. 11 is a diagram of a copolymeric polymer produced in example 42 1 H NMR spectrum;
FIG. 12 is a photograph of a copolymeric polymer product prepared in example 42 13 C NMR spectrum;
FIG. 13 is a photograph of a copolymeric polymer product prepared in example 43 1 H NMR spectrum;
FIG. 14 is a photograph of a copolymeric polymer product prepared in example 43 13 C NMR spectrogram;
FIG. 15 is a diagram of a copolymeric polymer product prepared in example 44 1 H NMR spectrum;
FIG. 16 is a photograph of a copolymeric polymer product prepared in example 44 13 C NMR spectrum;
FIG. 17 is a depiction of a copolymeric polymer product prepared in example 45 1 H NMR spectrum;
FIG. 18 is a photograph of a copolymeric polymerization product prepared in example 45 13 C NMR spectrum.
FIG. 19 is a photograph of a copolymeric polymer product prepared in example 47 1 H NMR spectrum;
FIG. 20 is a photograph of a copolymeric polymer product prepared in example 47 13 C NMR spectrum.
Detailed Description
The present invention will be described in further detail below with reference to examples and comparative examples, but the embodiments of the present invention are not limited thereto.
The 1, 12-dodecanediol diacrylate and the terephthalyl alcohol diacrylate as raw material monomers in the following examples are prepared by the following steps:
dissolving 1, 12-dodecanediol in anhydrous dichloromethane, adding triethylamine, slowly dropwise adding acryloyl chloride at 0 ℃ in a nitrogen atmosphere, slowly raising the temperature to room temperature, and reacting for 12-24 hours. With saturated NaHCO 3 After washing the aqueous solution with saturated NaCl solution and drying, the dichloromethane was removed in vacuo.
Example 1 triethylene glycol diacrylate/COS/H 2 O reaction to generate high polymer containing thioether group in main chain repeating unit
Before the polymerization reaction, a 10mL reaction kettle is firstly subjected to water removal at 110 ℃ for about 2 hours and is cooled to room temperature; sequentially adding a plurality of masses of alkali 1, 8-diazabicyclo [5.4.0] into a reaction kettle]Undec-7-ene, 0.8609g triethylene glycol diacrylate and 0.066g H 2 O, then charged with COS 0.22 g. The molar ratio of triethylene glycol diacrylate, water, COS and base is 50/55/55/1. The reaction was carried out at 25 ℃ under high pressure for 48h. After the reaction, the crude product was dissolved in dichloromethane, and the polymer was precipitated in 200mL of an ethanol/hydrochloric acid mixture (5% by mole hydrochloric acid), washed three times and dried under vacuum to constant weight. The molecular weight and molecular weight distribution of the polymer were determined by gel chromatography and the results are shown in Table 1.
Examples 2 to 7 triethylene glycol diacrylate/COS/H 2 O reaction to generate high polymer containing thioether group in main chain repeating unit
The preparation process is basically the same as that of example 1, except that the polymerization temperature is replaced by 40 ℃, 60 ℃, 80 ℃, 100 ℃, 120 ℃ and 160 ℃ in sequence, and the polymerization time is 48 hours. The molecular weight and molecular weight distribution of the polymer prepared in each example were measured by gel chromatography, and the results are shown in table 1.
Examples 8 to 11 triethylene glycol diacrylate/COS/H 2 O reaction to produce high molecular weight with main chain repeating unit containing thioether group
The preparation process is basically the same as that of example 3, except that the mass of the added base is different, and the molar ratios of triethylene glycol diacrylate, water, COS and the base are respectively adjusted to be 1000/1100/1100/1, 100/110/110/1, 10/11/11/1 and 5/5.5/5.5/1. The molecular weight and molecular weight distribution of the polymers prepared in each example were determined by gel chromatography, and the results are shown in Table 1.
Examples 12-17 triethylene glycol diacrylate/COS/H 2 O reaction to produce high molecular weight with main chain repeating unit containing thioether group
The preparation process is basically the same as that of example 3, except that the mass of the added water is different, and the molar ratios of triethylene glycol diacrylate, water and COS to the base are respectively adjusted to 50/25/55/1, 50/50/55/1, 50/52.5/55/1, 50/75/55/1, 50/100/55/1 and 50/150/55/1. The molecular weight and molecular weight distribution of the polymer prepared in each example were measured by gel chromatography, and the results are shown in table 1.
EXAMPLE 18 triethylene glycol diacrylate/COS/H 2 O reaction to generate high polymer containing thioether group in main chain repeating unit
Before the polymerization reaction, a 10mL reaction kettle is firstly dehydrated at 110 ℃ for about 2 hours and then cooled to room temperature; sequentially adding a plurality of masses of alkali 1, 8-diazabicyclo [5.4.0] into a reaction kettle]Undec-7-ene, 0.8609g triethylene glycol diacrylate and 0.24g H 2 O, then charged with COS 0.22 g. The molar ratio of triethylene glycol diacrylate, water, COS and base is 50/200/55/1. The reaction was carried out at 60 ℃ under high pressure for 72h. After the reaction, the crude product was dissolved in dichloromethane, and the polymer was precipitated in 200mL of an ethanol/hydrochloric acid mixture (5% by mole hydrochloric acid), washed three times and dried under vacuum to constant weight. The molecular weight and molecular weight distribution of the polymer were determined by gel chromatography and the results are shown in Table 1.
Example 19 triethylene glycol diacrylate/COS/H 2 O reaction to generate high polymer containing thioether group in main chain repeating unit
Before the polymerization reaction, a 10mL reaction kettle is firstly subjected to water removal at 110 ℃ for about 2 hours and is cooled to room temperature; sequentially adding a plurality of masses of alkali 1, 8-diazabicyclo [5.4.0] into a reaction kettle]Undec-7-ene, 0.8609g triethylene glycol diacrylate and 0.30g H 2 O, then charged with COS 0.22 g. The molar ratio of triethylene glycol diacrylate, water, COS and base is 50/250/55/1. The reaction is carried out for 120h at 60 ℃ under high pressure. After the reaction, the crude product was dissolved in dichloromethane, and the polymer was precipitated in 200mL of an ethanol/hydrochloric acid mixture (5% by mol hydrochloric acid), washed three times again, and dried under vacuum to constant weight. The molecular weight and molecular weight distribution of the polymer were determined by gel chromatography and the results are shown in Table 1.
Example 20 triethylene glycol diacrylate/COS/H 2 O reaction to generate high polymer containing thioether group in main chain repeating unit
Before the polymerization reactionRemoving water from a 10mL reaction kettle at 110 ℃ for about 2 hours and cooling to room temperature; sequentially adding a plurality of masses of alkali 1, 8-diazabicyclo [5.4.0] into a reaction kettle]Undec-7-ene, 0.8609g triethylene glycol diacrylate and 0.66g H 2 O, then charged with COS 0.02 g. The molar ratio of triethylene glycol diacrylate, water, COS and base is 50/55/5/1. The mixture is placed at 60 ℃ and reacted for 120 hours under high pressure. After the reaction, the crude product was dissolved in dichloromethane, and the polymer was precipitated in 200mL of an ethanol/hydrochloric acid mixture (5% by mole hydrochloric acid), washed three times and dried under vacuum to constant weight. The molecular weight and molecular weight distribution of the polymer were determined by gel chromatography and the results are shown in Table 1.
Example 21 triethylene glycol diacrylate/COS/H 2 O reaction to produce high molecular weight with main chain repeating unit containing thioether group
Before the polymerization reaction, a 10mL reaction kettle is firstly dehydrated at 110 ℃ for about 2 hours and then cooled to room temperature; sequentially adding a plurality of masses of alkali 1, 8-diazabicyclo [5.4.0] into a reaction kettle]Undec-7-ene, 0.8609g triethylene glycol diacrylate and 0.66g H 2 O, then charged with COS 0.10 g. The molar ratio of triethylene glycol diacrylate, water, COS and base is 50/55/25/1. The reaction was carried out at 60 ℃ under high pressure for 72h. After the reaction, the crude product was dissolved in dichloromethane, and the polymer was precipitated in 200mL of an ethanol/hydrochloric acid mixture (5% by mol hydrochloric acid), washed three times again, and dried under vacuum to constant weight. The molecular weight and molecular weight distribution of the polymer were determined by gel chromatography and the results are shown in Table 1.
Example 22 example 29 triethylene glycol diacrylate/COS/H 2 O reaction to generate high polymer containing thioether group in main chain repeating unit
The preparation process is substantially the same as that of example 3 except that the added COS is different in mass, and the molar ratios of triethylene glycol diacrylate, water, COS and base are adjusted to 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 and 50/55/250/1, respectively. The molecular weight and molecular weight distribution of the polymers prepared in each example were determined by gel chromatography, and the results are shown in Table 1.
Example 30 triethylene glycol diacrylate/COS/H 2 O reaction to generate high polymer containing thioether group in main chain repeating unit
Before the polymerization reaction, a 10mL reaction kettle is firstly subjected to water removal at 110 ℃ for about 2 hours and is cooled to room temperature; sequentially adding a plurality of masses of alkali bis (triphenyl phosphorane) ammonium chloride ([ PPN ] into a reaction kettle]Cl), 0.8609g of triethylene glycol diacrylate and 0.063g of H 2 O, then charged with COS 0.26 g. The molar ratio of triethylene glycol diacrylate, water, COS and base is 50/52.5/65/1. The reaction was carried out at 60 ℃ under high pressure for 4h. After the reaction, the crude product was dissolved in dichloromethane, and the polymer was precipitated in 200mL of an ethanol/hydrochloric acid mixture (5% by mole hydrochloric acid), washed three times and dried under vacuum to constant weight. The molecular weight and molecular weight distribution of the polymer were determined by gel chromatography and the results are shown in Table 1.
Examples 31 to 37 triethylene glycol diacrylate/COS/H 2 O reaction for synthesizing high polymer containing thioether group in main chain repeating unit
The procedure is essentially the same as in example 30, except that the alternative bases are tetrabutylammonium p-nitrophenol, methyltriphenylphosphonium 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), potassium tert-butoxide (t-BuOK) and potassium carbonate as bases, in that order. The molecular weight and molecular weight distribution of the polymers prepared in each example were determined by gel chromatography, and the results are shown in Table 1.
Of the products prepared in example 34 1 The H NMR spectrum is shown in figure 1, 13 the C NMR spectrum is shown in FIG. 2. As can be seen from the observation of FIGS. 1 and 2, the general structural formula of the product is as follows:
example 38, 2-ethylene glycol diacrylate/COS/H 2 O reaction to produce sulfur-containing polyester with main chain repeating unit
Before the polymerization reaction, a 10mL reaction kettle is firstly placed in a 110Removing water at the temperature of about 2 hours and cooling to room temperature; sequentially adding a plurality of masses of alkali 7-methyl-1, 5, 7-triazabicyclo [4.4.0] into a reaction kettle]Dec-5-ene, 0.5672g 1, 2-ethanediol diacrylate and 0.066g H 2 O, then charged with COS 0.32 g. The molar ratio of 1, 2-ethylene glycol diacrylate, water, COS and base is 50/55/80/1. The reaction was carried out at 60 ℃ under high pressure for 4h. After the reaction, the crude product was dissolved in dichloromethane, and the polymer was precipitated in 200mL of an ethanol/hydrochloric acid mixture (5% by mol hydrochloric acid), washed three times again, and dried under vacuum to constant weight. The molecular weight and molecular weight distribution of the polymer were determined by gel chromatography and the results are shown in Table 1.
Process for preparing the Main chain Sulfur-containing polyester prepared in this example 1 The H NMR spectrum is shown in FIG. 3, 13 the C NMR spectrum is shown in FIG. 4. As can be seen from FIGS. 3 and 4, the general structural formula of the product is as follows:
example 39 1, 4-butanediol diacrylate/COS/H 2 O reaction to produce sulfur-containing polyester with main chain repeating unit
Before the polymerization reaction, a 10mL reaction kettle is firstly subjected to water removal at 110 ℃ for about 2 hours and is cooled to room temperature; sequentially adding a plurality of masses of alkali 7-methyl-1, 5, 7-triazabicyclo [4.4.0] into a reaction kettle]Dec-5-ene, 0.6607g 1, 4-butanediol diacrylate and 0.063g H 2 O, then charged with COS 0.26 g. The molar ratio of 1, 4-butanediol diacrylate, water, COS and base is 50/52.5/65/1. The reaction was carried out at 60 ℃ under high pressure for 4h. After the reaction, the crude product was dissolved in dichloromethane, and the polymer was precipitated in 200mL of an ethanol/hydrochloric acid mixture (5% by mole hydrochloric acid), washed three times and dried under vacuum to constant weight. The molecular weight and molecular weight distribution of the polymer were determined by gel chromatography and the results are shown in Table 1.
The preparation of the backbone sulfur-containing polyester 1 The H NMR spectrum is shown in FIG. 5, 13 the C NMR spectrum is shown in FIG. 6. As can be seen from FIGS. 5 and 6, the productThe structural general formula is as follows:
example 40, 5-Pentanediol diacrylate/COS/H 2 O reaction to produce sulfur-containing polyester with main chain repeating unit
Before the polymerization reaction, a 10mL reaction kettle is firstly dehydrated at 110 ℃ for about 2 hours and then cooled to room temperature; sequentially adding a plurality of masses of alkali 7-methyl-1, 5, 7-triazabicyclo [4.4.0] into a reaction kettle]Dec-5-ene, 0.7075g 1, 5-pentanediol diacrylate and 0.062g H 2 O, then charged with COS 0.30 g. The molar ratio of 1, 5-pentanediol diacrylate, water, COS and base is 50/52/75/1. The reaction was carried out at 60 ℃ under high pressure for 4h. After the reaction, the crude product was dissolved in dichloromethane, and the polymer was precipitated in 200mL of an ethanol/hydrochloric acid mixture (5% by mole hydrochloric acid), washed three times and dried under vacuum to constant weight. The molecular weight and molecular weight distribution of the polymer were determined by gel chromatography and the results are shown in Table 1.
Process for preparing the Main chain Sulfur-containing polyester prepared in this example 1 The H NMR spectrum is shown in FIG. 7, 13 the C NMR spectrum is shown in FIG. 8. As can be seen from the observation of FIGS. 7 and 8, the general structural formula of the product is as follows:
example 41 neopentyl glycol diacrylate/COS/H 2 O reaction to produce sulfur-containing polyester with main chain repeating unit
Before the polymerization reaction, a 10mL reaction kettle is firstly dehydrated at 110 ℃ for about 2 hours and then cooled to room temperature; sequentially adding a plurality of masses of alkali 7-methyl-1, 5, 7-triazabicyclo [4.4.0] into a reaction kettle]Dec-5-ene, 0.7075g neopentyl glycol diacrylate and 0.064g H 2 O, then charged with COS greater than 0.23 g. The molar ratio of neopentyl glycol diacrylate, water, COS and base was 50/53/65/1. The reaction was carried out at 60 ℃ under high pressure for 4h. After the reaction is finished, dichloromethane is firstly usedThe crude product was dissolved and the polymer precipitated out again in 200mL of an ethanol/hydrochloric acid mixture (5% molar hydrochloric acid), washed three times and dried in vacuo to constant weight. The molecular weight and molecular weight distribution of the polymer were determined by gel chromatography and the results are shown in Table 1.
The preparation of the backbone sulfur-containing polyester 1 The H NMR spectrum is shown in FIG. 9, 13 the C NMR spectrum is shown in FIG. 10. As can be seen from FIGS. 9 and 10, the general structural formula of the product is as follows:
example 42, 6-hexanediol diacrylate/COS/H 2 O reaction to produce sulfur-containing polyester with main chain repeating unit
Before the polymerization reaction, a 10mL reaction kettle is firstly dehydrated at 110 ℃ for about 2 hours and then cooled to room temperature; sequentially adding a plurality of masses of alkali 7-methyl-1, 5, 7-triazabicyclo [4.4.0] into a reaction kettle]Dec-5-ene, 0.7542g 1, 6-hexanediol diacrylate and 0.063g H 2 O, then charged with COS greater than 0.30 g. The molar ratio of 1, 6-hexanediol diacrylate, water, COS and base was 50/52.5/75/1. The reaction was carried out at 60 ℃ under high pressure for 4h. After the reaction, the crude product was dissolved in dichloromethane, and the polymer was precipitated in 200mL of an ethanol/hydrochloric acid mixture (5% by mole hydrochloric acid), washed three times and dried under vacuum to constant weight. The molecular weight and molecular weight distribution of the polymer were determined by gel chromatography and the results are shown in Table 1.
Process for preparing the Main chain Sulfur-containing polyester prepared in this example 1 The H NMR spectrum is shown in FIG. 11, 13 the C NMR spectrum is shown in FIG. 12. As can be seen from FIGS. 11 and 12, the general structural formula of the product is as follows:
example 43, 9-nonanediol diacrylate/COS/H 2 O reaction to produce sulfur-containing polyester with main chain repeating unit
Before the polymerization reaction, a 10mL reaction kettle is firstly dehydrated at 110 ℃ for about 2 hours and then cooled to room temperature; sequentially adding a plurality of masses of alkali 7-methyl-1, 5, 7-triazabicyclo [4.4.0] into a reaction kettle]Dec-5-ene, 0.9012g 1, 9-nonanediol diacrylate and 0.064g H 2 O, then charged with COS 0.28 g. The molar ratio of 1, 9-nonanediol diacrylate, water, COS and base was 50/53/70/1. The reaction was carried out at 60 ℃ under high pressure for 4h. After the reaction, the crude product was dissolved in dichloromethane, and the polymer was precipitated in 200mL of an ethanol/hydrochloric acid mixture (5% by mole hydrochloric acid), washed three times and dried under vacuum to constant weight. The molecular weight and molecular weight distribution of the polymer were determined by gel chromatography and the results are shown in Table 1.
Process for preparing the Main chain Sulfur-containing polyester prepared in this example 1 The H NMR spectrum is shown in FIG. 13, 13 the C NMR spectrum is shown in FIG. 14. As can be seen from FIGS. 13 and 14, the general structural formula of the product is as follows:
example 44, 1, 10-decanedioldiacrylate/COS/H 2 O reaction to produce sulfur-containing polyester with main chain repeating unit
Before the polymerization reaction, a 10mL reaction kettle is firstly subjected to water removal at 110 ℃ for about 2 hours and is cooled to room temperature; sequentially adding a plurality of masses of alkali 7-methyl-1, 5, 7-triazabicyclo [4.4.0] into a reaction kettle]Dec-5-ene, 0.9413g 1, 10-decanediol diacrylate and 0.064g H 2 O, then charged with COS 0.26 g. The molar ratio of 1, 10-decanedioldiacrylate, water, COS and base was 50/53.5/65/1. The reaction was carried out at 60 ℃ under high pressure for 4h. After the reaction, the crude product was dissolved in dichloromethane, and the polymer was precipitated in 200mL of an ethanol/hydrochloric acid mixture (5% by mole hydrochloric acid), washed three times and dried under vacuum to constant weight. The molecular weight and molecular weight distribution of the polymer were determined by gel chromatography and the results are shown in Table 1.
Process for preparing the Main chain Sulfur-containing polyester prepared in this example 1 The H NMR spectrum is shown in FIG. 15， 13 The C NMR spectrum is shown in FIG. 16. As can be seen from fig. 15 and 16, the structural formula of the product is as follows:
example 45, 12-dodecanediol diacrylate/COS/H 2 O reaction to produce sulfur-containing polyester with main chain repeating unit
Before the polymerization reaction, a 10mL reaction kettle is firstly subjected to water removal at 110 ℃ for about 2 hours and is cooled to room temperature; sequentially adding a plurality of masses of alkali 7-methyl-1, 5, 7-triazabicyclo [4.4.0] into a reaction kettle]Dec-5-ene, 1.0348g 1, 12-dodecanediol diacrylate and 0.064g H 2 O, then charged with COS 0.26 g. The molar ratio of 1, 12-dodecanediol diacrylate, water, COS and base was 50/53.5/65/1. The reaction was carried out at 60 ℃ under high pressure for 4h. After the reaction, the crude product was dissolved in dichloromethane, and the polymer was precipitated in 200mL of an ethanol/hydrochloric acid mixture (5% by mol hydrochloric acid), washed three times again, and dried under vacuum to constant weight. The molecular weight and molecular weight distribution of the polymer were determined by gel chromatography and the results are shown in Table 1.
Process for preparing the Main chain Sulfur-containing polyester prepared in this example 1 The H NMR spectrum is shown in FIG. 17, 13 the CNMR spectrum is shown in FIG. 18. As can be seen from fig. 17 and 18, the structural formula of the product is as follows:
example 46 Paradimethanol diacrylate/COS/H 2 O reaction to produce sulfur-containing polyester with main chain repeating unit
Before the polymerization reaction, a 10mL reaction kettle is firstly dehydrated at 110 ℃ for about 2 hours and then cooled to room temperature; sequentially adding a plurality of masses of alkali 7-methyl-1, 5, 7-triazabicyclo [4.4.0] into a reaction kettle]Dec-5-ene, 0.8209g p-xylylene glycol diacrylate and 0.064g H 2 O, then charged with COS 0.26 g. P-xylene glycol diacrylate and waterAnd the molar ratio of COS to the base is 50/53.5/65/1. The reaction was carried out at 60 ℃ under high pressure for 4h. After the reaction, the crude product was dissolved in dichloromethane, and the polymer was precipitated in 200mL of an ethanol/hydrochloric acid mixture (5% by mole hydrochloric acid), washed three times and dried under vacuum to constant weight. The molecular weight and molecular weight distribution of the polymer were determined by gel chromatography and the results are shown in Table 1.
Example 47, 12-dodecanediol dimethacrylate/COS/H 2 O reaction to produce sulfur-containing polyester with main chain repeating unit
Before the polymerization reaction, a 10mL reaction kettle is firstly subjected to water removal at 110 ℃ for about 2 hours and is cooled to room temperature; sequentially adding a plurality of masses of alkali 7-methyl-1, 5, 7-triazabicyclo [4.4.0] into a reaction kettle]Dec-5-ene, 1.1283g 1, 12-dodecanediol dimethacrylate and 0.066g H 2 O, then charged with COS 0.36 g. The molar ratio of 1, 12-dodecanediol dimethacrylate, water, COS and base was 50/55/90/1. The reaction was carried out at 60 ℃ under high pressure for 18h. After the reaction, the crude product was dissolved in dichloromethane, and the polymer was precipitated in 200mL of an ethanol/hydrochloric acid mixture (5% by mol hydrochloric acid), washed three times again, and dried under vacuum to constant weight. The molecular weight and molecular weight distribution of the polymer were determined by gel chromatography and the results are shown in Table 1.
Process for preparing the Main chain Sulfur-containing polyester prepared in this example 1 The H NMR spectrum is shown in FIG. 19, 13 the C NMR spectrum is shown in FIG. 20. As can be seen from FIGS. 19 and 20, the general structural formula of the product is as follows:
example 48N, N' -Methylenebisacrylamide/COS/H 2 O reaction to produce sulfur-containing polyester with main chain repeating unit
Before the polymerization reaction, a 10mL reaction kettle is firstly subjected to water removal at 110 ℃ for about 2 hours and is cooled to room temperature; sequentially adding a plurality of masses of alkali 7-methyl-1, 5, 7-triazabicyclo [4.4.0] into a reaction kettle]Dec-5-ene, 0.9413g N, N' -methylenebisacrylamide and 0.066g H 2 O, 1mL of methylene chloride was added to dissolve the monomers, and then 0.34g of COS was charged. The molar ratio of N, N' -methylene-bisacrylamide, water, COS and base is 50/55/85/1. The reaction was carried out at 60 ℃ under high pressure for 24h. After the reaction, the crude product was dissolved in dichloromethane, and the polymer was precipitated in 200mL of an ethanol/hydrochloric acid mixture (5% by mole hydrochloric acid), washed three times and dried under vacuum to constant weight. The molecular weight and molecular weight distribution of the polymer were determined by gel chromatography and the results are shown in Table 1. The structural general formula of the product is as follows:
example 49 bis-vinyl sulfone based methane/COS/H 2 O reaction to produce sulfur-containing polyester with main chain repeating unit
Before the polymerization reaction, a 10mL reaction kettle is firstly subjected to water removal at 110 ℃ for about 2 hours and is cooled to room temperature; sequentially adding a plurality of masses of alkali 7-methyl-1, 5, 7-triazabicyclo [4.4.0] into a reaction kettle]Dec-5-ene, 0.6541g bisvinylsulfonylmethane and 0.066g H 2 O, then charged with COS 0.26 g. The molar ratio of the bis-vinylsulfonyl methane to the water to the COS to the base is 50/55/65/1. The reaction was carried out at 60 ℃ under high pressure for 4h. After the reaction, the crude product was dissolved in dichloromethane, and the polymer was precipitated in 200mL of an ethanol/hydrochloric acid mixture (5% by mole hydrochloric acid), washed three times and dried under vacuum to constant weight. The molecular weight and molecular weight distribution of the polymer were determined by gel chromatography and the results are shown in Table 1. The structural general formula of the product is as follows:
example 50N, N '- (4, 4' -methylenediphenyl) bismaleimide/COS/H 2 O reaction to produce sulfur-containing polyester with main chain repeating unit
Before the polymerization reaction, a 10mL reaction kettle is firstly dehydrated at 110 ℃ for about 2 hours and then cooled to room temperature; sequentially adding a plurality of alkali 7-methyl-1 with certain mass into a reaction kettle,5, 7-triazabicyclo [4.4.0]Dec-5-ene, 1.1945g N, N '- (4, 4' -methylenediphenyl) bismaleimide and 0.066g H 2 O, then charged with COS 0.26 g. The molar ratio of N, N '- (4, 4' -methylenediphenyl) bismaleimide, water, COS and base is 50/55/65/1. The reaction was carried out at 60 ℃ under high pressure for 4h. After the reaction, the crude product was dissolved in dichloromethane, and the polymer was precipitated in 200mL of an ethanol/hydrochloric acid mixture (5% by mole hydrochloric acid), washed three times and dried under vacuum to constant weight. The molecular weight and molecular weight distribution of the polymer were determined by gel chromatography and the results are shown in Table 1.
The structural general formula of the product is as follows:
example 51, 10-decanedioldiacrylate/CS 2 /H 2 O reaction to produce sulfur-containing polyester with main chain repeating unit
Before the polymerization reaction, a 10mL reaction kettle is firstly subjected to water removal at 110 ℃ for about 2 hours and is cooled to room temperature; sequentially adding a plurality of masses of alkali 7-methyl-1, 5, 7-triazabicyclo [4.4.0] into a reaction kettle]Dec-5-ene, 0.9413g 1, 10-decanediol diacrylate and 0.066g H 2 O, then charged with 0.18g of CS 2 .1, 10-decanediol diacrylate, water, CS 2 The molar ratio to the base was 50/55/35/1. The reaction was carried out at 140 ℃ under high pressure for 120h. After the reaction, the crude product was dissolved in dichloromethane, and the polymer was precipitated in 200mL of an ethanol/hydrochloric acid mixture (5% by mol hydrochloric acid), washed three times again, and dried under vacuum to constant weight. The molecular weight and molecular weight distribution of the polymer were determined by gel chromatography and the results are shown in Table 2.
TABLE 1
Note: 1 double-bond monomer species: 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, BDP-xylylene glycol diacrylate, DDGDMA is 1, 12-dodecanediol dimethacrylate, MBA is N, N ' -methylene bisacrylamide, BVSM is bis-vinylsulfonylmethane, BMI is N, N ' - (4, 4' -methylene diphenyl) bismaleimide. 2 Kind of base: 1 is 1, 8-diazabicyclo [5.4.0]]Undec-7-ene (DBU), 2 is bis (triphenylphosphoranylidene) ammonium chloride ([ PPN)]Cl), tetrabutylammonium 3-p-nitrophenol, 4 methyltriphenylphosphine bromide, 51, 5, 7-triazabicyclo [4.4.0]Dec-5-ene, 6 is 7-methyl-1, 5, 7-triazabicyclo [4.4.0]Dec-5-ene (MTBD), 7 4-Dimethylaminopyridine (DMAP), 8 potassium tert-butoxide (t-BuOK), 9 potassium carbonate. 3 The molar ratio of the double-bond monomer to water; 4 the molar ratio of COS to the double bond monomer; 5 the molar ratio of base to double-bonded monomer; 6 M n : number average molecular weight, as determined by gel permeation chromatography; 7 PDI: molecular weight distribution, determined by gel permeation chromatography.
TABLE 2
Note: 1 double-bond monomer species: DGDA is 1, 10-decanediol diacrylate. 2 Kind of base: 6 is 7-methyl-1, 5, 7-triazabicyclo [4.4.0]Dec-5-ene (MTBD). 3 The molar ratio of the double-bond monomer to water; 4 CS 2 a molar ratio to the double-bonded monomer; 5 the molar ratio of base to double-bonded monomer; 6 M n : number average molecular weight, as determined by gel permeation chromatography; 7 PDI: molecular weight distribution, determined by gel permeation chromatography.
Examples 1-51 are the results of base-catalyzed copolymerization of a double-bond monomer, carbon oxysulfide (or carbon disulfide) and water, and it can be seen that such systems have excellent catalytic activity and universality.
The above description is only a few specific embodiments of the present invention, and it should be noted that many modifications and improvements may be made by those skilled in the art, and all modifications and improvements not beyond the scope of the claims should be considered as the protection scope of the present invention.
Claims (10)
1. A polymer with a main chain containing thioether groups is characterized in that the structural general formulas are shown as the following formulas (I) to (IV):
wherein n is selected from 1 to 200;
R 1 is selected from C 2 ～C 18 Alkylene of (A), p-xylylene, 2, 5-furandimethylene, 1, 4-cyclohexylene, (CH) 2 CH 2 O) m CH 2 CH 2 ，m＝1～3；
R 2 Selected from H or methyl;
R 3 is selected from C 1 ～C 12 An alkylene group of (a);
R 4 is selected from C 1 ～C 2 An alkylene group of (a);
R 5 is selected from C 1 ～C 10 Alkylene, 1, 4-phenylene, 1, 3-phenylene, 1, 2-phenylene, 4 '-methylenediphenyl, 4' -methylenebis (3-ethyl-5-methylphenyl), (CH) 2 CH 2 O) p CH 2 CH 2 ，p＝1～3。
2. The main chain thioether group-containing polymer according to claim 1, wherein the polymer has a number average molecular weight of 1 to 200kg/mol and a molecular weight distribution of 1.1 to 4.0.
3. The main chain thioether group-containing polymer according to claim 1 or 2, which has the following structural formula:
4. a method for synthesizing a main chain thioether group-containing polymer according to any one of claims 1 to 3, wherein a raw material comprising a double bond monomer, a sulfur-containing carbon monomer and water is polymerized under autogenous pressure using an alkali as a catalyst;
the double-bond monomer is 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 method for synthesizing a polymer having a sulfide group-containing main chain according to claim 4, wherein:
the diacrylate monomer is selected from one or more of ethylene glycol diacrylate, 1, 3-propanediol diacrylate, 1, 4-butanediol diacrylate, 1, 5-pentanediol diacrylate, neopentyl glycol diacrylate, 1, 6-hexanediol diacrylate, 1, 9-nonanediol diacrylate, 1, 10-decanediol diacrylate, 1, 12-dodecanediol diacrylate, 1, 14-tetradecanediol diacrylate, 1, 16-hexadecanediol diacrylate, 1, 18-octadecanediol diacrylate, p-xylylene glycol 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, 1, 6-hexanediol dimethacrylate, 1, 9-nonanediol dimethacrylate, 1, 10-decanediol dimethacrylate, 1, 12-dodecanediol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, neopentyl glycol dimethacrylate;
the bisacrylamide monomer is selected from N, N '-methylene bisacrylamide, N' -ethylene bisacrylamide, N '-trimethylene bisacrylamide, N' -tetramethylene bisacrylamide, N '-pentamethylene bisacrylamide, N' -hexamethylene bisacrylamide and N, one or more of N '-heptamethylene bisacrylamide, N' -octamethylene bisacrylamide, N '-nonamethylene bisacrylamide, N' -decamethylene bisacrylamide, N '-undecamethylene bisacrylamide and N, N' -dodecamethylene bisacrylamide;
the divinyl sulfone monomers are selected from divinyl sulfone methane and/or divinyl sulfone ethane;
the bismaleimide monomer is selected from one or more of bismaleimide methane, 1, 2-bismaleimide ethane, 1, 3-bismaleimide propane, 1, 4-bismaleimide butane, 1, 5-bismaleimide pentane, 1, 6-bismaleimide hexane, 1, 7-bismaleimide heptane, 1, 8-bismaleimide octane, 1, 9-bismaleimide nonane, 1, 10-bismaleimide decane, N ' - (1, 4-phenylene) bismaleimide, N ' - (1, 3-phenylene) bismaleimide, N ' - (1, 2-phenylene) bismaleimide, N ' - (4, 4' -methylenediphenyl) bismaleimide, bis (3-ethyl-5-methyl-4-maleimidophenyl) methane, 1, 5-bismaleimide diethylene glycol, 1, 8-bismaleimide triethylene glycol, and 1, 11-bismaleimide tetraethylene glycol;
the molar ratio of the double-bond monomer to the sulfur-containing carbon-monomer to the water is 1:0.1 to 5.0:0.1 to 5.0.
6. The method for synthesizing a polymer having a sulfide group-containing main chain according to claim 4, wherein:
the base is selected from one or more of quaternary ammonium salt, quaternary phosphonium salt, amine, phosphazene, guanidine, amidine, alkali metal alkoxide and inorganic base;
the quaternary ammonium salt is one or more of bis (triphenyl phosphorane) ammonium chloride, tetrabutyl ammonium bromide, tetraoctyl ammonium bromide and tetrabutyl ammonium paranitrophenol;
the quaternary phosphonium salt is selected from tetraphenylphosphonium chloride and/or methyltriphenylphosphonium bromide;
the amine is selected from one or more of N-hexylamine, tetramethyl-methane diamine, N' -dimethyl ethylene diamine, tetramethyl ethylene diamine and 4-dimethylamino pyridine;
the phosphazene is selected from the group consisting of t-butylimino-tris (dimethylamino) phosphorane, 1-t-butyl-2, 4-pentakis (dimethylamino) -2 lambda 5 ,4λ 5 Bis (phosphazene), 1-tert-butyl-4, 4-tris (dimethylamino) -2, 2-bis [ tris (dimethylamino) -phosphinideneamino]-2λ 5 ，4λ 5 -one or more of a bis (phosphazene compound);
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 one or more of 1,5, 7-triazabicyclo [4.4.0] dec-5-ene, 7-methyl-1, 5, 7-triazabicyclo [4.4.0] dec-5-ene and tetramethyl guanidine;
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 and potassium carbonate;
the molar ratio of base to double-bond monomer is 1:5 to 1000.
7. The method for synthesizing a polymer having a sulfide group-containing main chain according to claim 4, wherein:
the polymerization is bulk polymerization or solution polymerization, the polymerization temperature is 25-160 ℃, and the polymerization time is 0.5-120 h;
the solvent adopted in the solution polymerization is one or more selected from dichloromethane, chloroform, tetrahydrofuran, toluene, trichlorobenzene, o-dichlorobenzene, m-dichlorobenzene, p-dichlorobenzene and dimethylformamide.
8. The method for synthesizing a polymer having a sulfide group-containing main chain according to any one of claims 4 to 7, wherein:
the diacrylate monomer is selected from one or more of diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, 1, 2-ethylene glycol diacrylate, 1, 4-butanediol diacrylate, 1, 5-pentanediol diacrylate, neopentyl glycol diacrylate, 1, 6-hexanediol diacrylate, 1, 9-nonanediol diacrylate, 1, 10-decanediol diacrylate, 1, 12-dodecanediol dimethacrylate and p-xylylene glycol diacrylate;
the bisacrylamide monomer is selected from N, N' -methylene bisacrylamide;
the divinyl sulfone monomers are selected from divinyl sulfone methane;
the bismaleimide monomer is selected from N, N ' - (4, 4' -methylene diphenyl) bismaleimide and/or N, N ' -1, 4-phenylene bismaleimide;
the base is selected from one or more of 1, 8-diazabicyclo [5.4.0] undec-7-ene, bis (triphenylphosphoranylidene) ammonium chloride, tetrabutylammonium p-nitrophenol, methyl triphenyl phosphonium bromide, 1,5, 7-triazabicyclo [4.4.0] dec-5-ene, 7-methyl-1, 5, 7-triazabicyclo [4.4.0] dec-5-ene, 4-dimethylaminopyridine, potassium tert-butoxide, potassium carbonate;
the molar ratio of the double-bond monomer to the sulfur-containing carbon-monomer to water is 1: 1.0-2.0: 1.0 to 1.5;
the molar ratio of base to doubly-bound monomer is 1:50 to 100.
9. The method for synthesizing a polymer having a sulfide group-containing main chain according to claim 8, wherein:
the double-bond monomer is selected from one or more of triethylene glycol diacrylate, 1, 2-ethylene glycol diacrylate, neopentyl glycol diacrylate, 1, 6-hexanediol diacrylate, 1, 9-nonanediol diacrylate, 1, 10-decanediol diacrylate, 1, 12-dodecanediol diacrylate and p-xylylene glycol diacrylate;
the alkali is selected from one or more of 1,5, 7-triazabicyclo [4.4.0] dec-5-ene, 7-methyl-1, 5, 7-triazabicyclo [4.4.0] dec-5-ene, 4-dimethylaminopyridine and potassium tert-butoxide;
the molar ratio of the double-bond monomer to the carbonyl sulfide to the water is 1:1.1 to 1.8:1.0 to 1.1;
the molar ratio of base to doubly-bound monomer is 1:50.
10. the method for synthesizing a polymer having a sulfide group-containing main chain according to claim 9, wherein:
the double-bond monomer is 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-ene.
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