CN112724403B - Poly (gamma-thiobutyrolactone) and preparation method thereof - Google Patents
Poly (gamma-thiobutyrolactone) and preparation method thereof Download PDFInfo
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Abstract
The invention relates to poly (gamma-thiobutyrolactone) and a preparation method thereof. The invention discloses a compound shown as a formula (I). The invention also discloses a preparation method of the high molecular compound, which comprises the following steps: in an organic solvent, carrying out a polymerization reaction on a compound shown as a formula (II) in the presence of a main catalyst; the main catalyst is one or more of phosphazene base, guanidine organic base, amidine organic base, N-heterocyclic carbene organic base and N-heterocyclic olefin organic base. The poly (gamma-thiobutyrolactone) prepared by the preparation method provided by the invention has the advantages that the number average molecular weight and the purity are obviously improved, the poly (gamma-thiobutyrolactone) has stronger solvent corrosion resistance, excellent mechanical properties, surface properties and the like, and excellent degradability is realized.
Description
Technical Field
The invention relates to the technical field of polymer synthesis, in particular to poly (gamma-thiobutyrolactone) and a preparation method thereof.
Background
The synthetic polymer material is an important material essential to national economic construction and daily life of people, the annual output of the synthetic polymer material reaches 3.35 hundred million tons in 2016 years, and the annual output is predicted to increase to 11.2 hundred million tons in 2050 years. Unfortunately, most synthetic polymers are made from non-renewable petrochemical resources, and the contradiction between the shortage of raw materials and the demand increase is increasingly prominent, which leads to the serious unsustainability of the synthesis of the current polymer materials, and the development of bio-based polymer materials for replacing petroleum-based polymer materials has urgent practical significance. On the other hand, the application performance and tolerance of the traditional polymer materials are usually only considered during design and synthesis, which causes that most polymer materials are difficult to degrade, causes white pollution and brings great harm to the ecological environment. Aliphatic polyester (such as polylactic acid) based on biomass sources is considered as a potential green substitute of petroleum-based high polymer materials due to unique degradability, and has certain application in the fields of biological medicine, tissue engineering, packaging and the like at present. Nevertheless, bio-based aliphatic polyesters currently commercialized or reported in the literature generally suffer from the problems of high price and difficulty in competing physical properties with petroleum-based polymers (e.g., polyolefin materials).
The five-membered ring gamma-thiocarbonyl butyrolactone can be used as a polymerization monomer, and has the following properties: (1) The gamma-thiocarbonyl butyrolactone has a renewable green source and is low in price, and the upstream product succinic acid is recently listed as one of ten compounds which are most suitable for replacing petrochemical products by the United states department of energy; (2) The main chain of the polymer obtained by ring-opening polymerization has thioester or thiono ester functional group, so that the degradability of the polymer is ensured; (3) The introduction of sulfur atoms into the polymer can improve the optical, mechanical and mechanical properties of the material, and endow the material with chemical and biological corrosion resistance and heavy metal recognition capability, so that the polymer obtained by the ring-opening polymerization of gamma-thiocarbonyl butyrolactone has potentially superior properties. However, because of the small ring tension of the five-membered ring structure of gamma-thiocarbonylbutyrolactone and the great challenges of ring-opening polymerization, only one example of the ring-opening polymerization of gamma-thiocarbonylbutyrolactone is reported (Hirofumi, K.; norio, T.; takeshi, E.chem.Lett.2005,34, 376-377), and the polymer obtained by the method is low in molecular weight (number-average molecular weight M) by using a trifluoromethanesulfonic acid rare earth compound as a catalytic system n 3.4-6.3 kg/mol), broad molecular weight distribution
And the reaction is accompanied by 20-40% of unknown byproducts, so the method has no application value.
Disclosure of Invention
The invention aims to overcome the defects of low molecular weight, low purity and the like of the existing poly (gamma-thiobutyrolactone) (PTBL) and provides the poly (gamma-thiobutyrolactone) and the preparation method thereof. The poly (gamma-thiobutyrolactone) prepared by the preparation method provided by the invention has the advantages that the number average molecular weight and the purity are obviously improved, the poly (gamma-thiobutyrolactone) has stronger solvent corrosion resistance, excellent mechanical properties, surface properties and the like, and excellent degradability is realized.
The present invention solves the above-mentioned problems by the following means.
The invention provides a compound as shown in formula (I), the structure of which is shown as follows,
wherein n is 65 or more.
According to the common knowledge in the art, in the compound shown in the formula (I), each structure in the "[ ]" represents a structural unit; and n is polymerization degree, and also is number average polymerization degree or average polymerization degree.
Said n is preferably 65 to 4900, more preferably 190 to 2450, still more preferably 840 to 2450.
The number average molecular weight of the compound shown as the formula (I) is preferably more than or equal to 7kg/mol, and more preferably 7-500kg/mol; more preferably 20 to 250kg/mol, still more preferably 80 to 250kg/mol, for example 85.8kg/mol, 99.9kg/mol, 101.1kg/mol, 103.4kg/mol, 129.5kg/mol, 195.0kg/mol or 248.8kg/mol.
The molecular weight distribution of the compound of formula (I) is preferably 1.0-2.5, more preferably 1.5-2.0, such as 1.50, 1.60, 1.74, 1.76, 1.77, 1.82 or 1.87.
The invention provides a preparation method of a high molecular compound, which comprises the following steps: in an organic solvent, carrying out a polymerization reaction on a compound shown as a formula (II) in the presence of a main catalyst;
the main catalyst is one or more of phosphazene base, guanidine organic base, amidine organic base, N-heterocyclic carbene organic base and N-heterocyclic olefin organic base.
In the preparation method of the compound shown in the formula (I), the high molecular compound is preferably the compound shown in the formula (I),
wherein n is 10 or more, preferably 65 or more, more preferably 65 to 4900, more preferably 190 to 2450, further preferably 840 to 2450;
in the preparation method of the compound shown in the formula (I), the number average molecular weight of the compound shown in the formula (I) is preferably more than or equal to 1kg/mol, preferably more than or equal to 7kg/mol, more preferably 7-500kg/mol, more preferably 20-250kg/mol, and even more preferably 80-250kg/mol.
In the preparation method of the compound shown in the formula (I), the molecular weight distribution of the compound shown in the formula (I) is preferably 1.0-2.5, and more preferably 1.5-2.0.
In the preparation method of the compound shown in the formula (I), the polymerization reaction is preferably performed under a protective gas atmosphere, and the protective gas may be a protective gas conventional in the art, such as nitrogen and/or argon. The protective gas in the present invention is an inert gas as described in the art.
In the preparation method of the compound shown in the formula (I), the organic solvent may be an organic solvent which is conventional in the art, preferably one or more of a straight-chain hydrocarbon solvent, a halogenated hydrocarbon solvent, a cyclic ether solvent, an aromatic hydrocarbon solvent and a halogenated aromatic hydrocarbon solvent, more preferably an aromatic hydrocarbon solvent and/or a halogenated aromatic hydrocarbon solvent, and more preferably toluene and/or o-dichlorobenzene. The straight-chain hydrocarbon solvent is preferably one or more of n-hexane, n-heptane and n-pentane. The halogenated hydrocarbon solvent is preferably one or more of dichloromethane, trichloromethane, 1, 2-dichloroethane and tetrachloroethane. The cyclic ether solvent is preferably tetrahydrofuran and/or dioxane. The aromatic hydrocarbon solvent is preferably one or more of toluene, benzene and xylene, and more preferably toluene. The halogenated aromatic hydrocarbon solvent is preferably one or more of o-dichlorobenzene, o-difluorobenzene, o-dibromobenzene, chlorobenzene, fluorobenzene, bromobenzene and trichlorobenzene, and more preferably o-dichlorobenzene.
In the preparation method of the compound shown in the formula (I), the main catalyst is preferably phosphazene base.
In the preparation method of the compound shown in the formula (I), the phosphazene base can be a phosphazene base which is conventional in the field, preferably a compound shown in the formula (III), and the structure of the compound is shown as follows,
wherein R and R' are independently C 1 -C 4 Alkyl (e.g., methyl, ethyl, propyl, isopropyl, or tert-butyl); n1 is 0, 1,2 or 3; y is 0, 1,2 or 3;
more preferably 1-tert-butyl-4, 4-tris (dimethylamino) -2, 2-bis [ tris (dimethylamino) -phosphoranylideneamino]-2 Λ 5( t Bu-P 4 ) The structure of the composite material is shown as follows,
in the preparation method of the compound shown as the formula (I), the guanidine organic base can be conventional guanidine organic base in the field, preferably 1,5, 7-triazabicyclo (4.4.0) deca-5-ene (TBD) and/or 7-methyl-1, 5, 7-triazabicyclo [4.4.0] deca-5-ene (MTBD) with the structure shown as follows,
in the preparation method of the compound shown in the formula (I), the amidine organic base can be conventional amidine organic base in the field, preferably 1, 8-diazabicyclo [5.4.0] undec-7-ene (DBU), the structure of which is shown in the specification,
in the preparation method of the compound shown in the formula (I), the N-heterocyclic carbene organic base can be a conventional N-heterocyclic carbene organic base in the field, preferably a compound shown in the formula (IV), and the structure of the compound is shown as follows,
wherein R is 1a And R 2a Independently hydrogen, alkyl or aryl (e.g., methyl, ethyl or phenyl);
R 3a and R 4a Independently an alkyl or aryl group (e.g., methyl, ethyl, isopropyl, t-butyl, phenyl, 2, 6-diisopropylphenyl or 2,4, 6-trimethylphenyl).
In the preparation method of the compound shown in the formula (I), the N-heterocyclic olefin organic base can be a conventional N-heterocyclic olefin organic base in the field, preferably a compound shown in the formula (V), and the structure of the compound is shown in the specification,
wherein R is 1b And R 2b Independently hydrogen, methyl or phenyl;
R 3b and R 4b Independently an alkyl or aryl group (e.g., methyl, ethyl, isopropyl, t-butyl, phenyl, 2, 6-diisopropylphenyl or 2,4, 6-trimethylphenyl);
R 5b is hydrogen, methyl or ethyl.
In the preparation method of the compound shown in the formula (I), the molar concentration of the compound shown in the formula (II) in the organic solvent can be the molar concentration which is conventional in the field, preferably 0.2mol/L-10mol/L, more preferably 2.0mol/L-7.0mol/L, such as 1.69mol/L or 6.78mol/L.
In the preparation method of the compound shown in the formula (I), the molar ratio of the compound shown in the formula (II) to the main catalyst can be a molar ratio of 20.
In the preparation method of the compound shown in the formula (I), the polymerization reaction temperature is preferably 0-120 ℃, and more preferably 40-80 ℃.
In the process for the preparation of the compound of formula (I), the progress of the polymerization reaction can be monitored by means conventional in the art (e.g.by monitoring the progress of the polymerization reaction 1 H NMR monitors the hydrogen integral ratio of the polymer formed to the remaining monomer to monitor the conversion), the time of the polymerization reaction is preferably 5 to 720 minutes, more preferably 30 to 240 minutes, such as 30 minutes, 120 minutes, 180 minutes or 240 minutes.
In the preparation method of the compound shown in the formula (I), the polymerization reaction can be carried out in the presence of a cocatalyst, wherein the cocatalyst is a hydrogen bond donor and/or Lewis acid.
The hydrogen bond donor may be a hydrogen bond donor generally used in the art, preferably one or more of alcohol, thiol, carboxylic acid, urea and thiourea, more preferably one or more of alcohol, thiol and thiourea, and further preferably one or more of benzhydrol, benzyl alcohol, 1-octanethiol and N, N' -diisopropylthiourea. The alcohol is preferably benzhydryl alcohol and/or benzyl alcohol. The thiol is preferably 1-octanethiol. The carboxylic acid is preferably phenylacetic acid. The urea is preferably diethyl urea. The thiourea is preferably N, N' -diisopropyl thiourea.
The lewis acid may be any one or more of lewis acids conventional in the art, preferably one or more of alkali metal compounds, alkaline earth metal compounds, zinc compounds, boron compounds, aluminum compounds, and rare earth compounds, more preferably zinc compounds, and further preferably bis (pentafluorophenyl) zinc. The alkali metal compound is preferably lithium chloride. The alkaline earth metal compound is preferably magnesium chloride. The zinc compound is preferably diethyl zinc and/or di (pentafluorophenyl) zinc. The boron compound is preferably tris (pentafluorophenyl) boron. The aluminum compound is preferably tris (pentafluorophenyl) aluminum. The rare earth compound is preferably tri [ bis (trimethylsilyl) amino ] lanthanum.
In the preparation method of the compound shown in the formula (I), the molar ratio of the main catalyst to the cocatalyst can be a molar ratio which is conventional in the art, preferably 1.
In certain preferred embodiments of the present invention, the preparation method comprises the steps of: in an organic solvent, carrying out a polymerization reaction on a compound shown as a formula (II) in the presence of a main catalyst; the molar ratio of the compound shown in the formula (II) to the main catalyst is 400-1600.
In certain preferred embodiments of the present invention, the preparation method comprises the steps of: in an organic solvent, in the presence of a main catalyst and a cocatalyst, carrying out a polymerization reaction on a compound shown as a formula (II); the molar ratio of the compound shown in the formula (II) to the main catalyst is (100-1600).
In certain preferred embodiments of the present invention, the polymerization reaction comprises the steps of: under the atmosphere of protective gas, in an organic solvent, in the presence of a main catalyst or the main catalyst and a cocatalyst, carrying out a polymerization reaction on the compound shown as the formula (II) at a polymerization temperature, and finishing the polymerization reaction.
In certain preferred embodiments of the present invention, the polymerization reaction comprises the steps of: adding the compound shown as the formula (II) into a reaction container, connecting the reaction container to a vacuum line protected by inert gas, adding an organic solvent, a main catalyst or the main catalyst and a cocatalyst, heating to a polymerization temperature, and finishing the polymerization reaction.
In certain preferred embodiments of the present invention, the polymerization reaction comprises the steps of: adding the compound shown as the formula (II) into a reaction bottle in a glove box, removing the glove box, connecting the reaction bottle to a vacuum line protected by inert gas, heating to a corresponding polymerization temperature, adding a main catalyst or a solution of the main catalyst and an organic solvent of a cocatalyst into the solution, and finishing the polymerization reaction.
In the preparation method of the compound shown in the formula (I), after the polymerization reaction is finished, the method may preferably further comprise a post-treatment, and the post-treatment may comprise the following steps: mixing the reaction solution with benzoic acid, mixing with ethanol, filtering, and drying. The benzoic acid is preferably a chloroform solution of benzoic acid, and the concentration of the chloroform solution of benzoic acid is preferably 10mg/mL. The addition of the benzoic acid in chloroform was performed to terminate the propagation of the polymeric chain. Mixing with ethanol is to settle the polymer and precipitate it for fixation. The filtration preferably followed by a washing step, the washed solvent preferably being ethanol. The number of washing is preferably 2 to 5 (e.g., 3). The drying is preferably vacuum drying. The drying temperature is preferably 40-60 ℃. The drying time is preferably 20 to 30 hours, for example 24 hours.
The invention also provides a macromolecular compound prepared according to the preparation method.
The macromolecular compound is a compound shown as a formula (I);
wherein n is greater than or equal to 65, preferably 65 to 4900, more preferably 190 to 2450, and still more preferably 840 to 2450.
The number average molecular weight of the compound represented by the formula (I) is preferably not less than 7kg/mol, preferably 7 to 500kg/mol, more preferably 20 to 250kg/mol, and still more preferably 80 to 250kg/mol.
The molecular weight distribution of the compound shown in the formula (I) is preferably 1.0-2.5, and more preferably 1.5-2.0.
The invention realizes the efficient and controllable preparation of high molecular weight poly (gamma-thiobutyrolactone) by the following three strategies:
1. the invention synthesizes poly (gamma-thiobutyrolactone) with the structure of formula (I) instead of poly (gamma-thiocarbonylbutyrolactone). Therefore, there is no depolymerization-polymerization equilibrium between the γ -thiocarbonylbutyrolactone monomer and the polymerization product poly (γ -thiobutyrolactone), i.e., there is no polymerization upper limit temperature in the polymerization reaction, thereby promoting the polymerization to proceed efficiently under normal/high temperature conditions.
2. The invention can inhibit the occurrence of dimerization side reaction (shown as the following) so as to promote the generation yield of the compound poly (gamma-thiobutyrolactone) shown as the formula (I) and realize the complete inhibition of the dimerization side reaction.
3. The invention can inhibit the occurrence of the back-biting side reaction, successfully controls the proportion of the back-biting product gamma-thiobutyrolactone to the polymerization product poly (gamma-thiobutyrolactone) to be 4.
The above preferred conditions can be arbitrarily combined to obtain preferred embodiments of the present invention without departing from the common general knowledge in the art.
In the present invention, "° c" means degrees celsius, unless otherwise specified; "h" means hours; "min" means minutes.
The reagents and starting materials used in the present invention are commercially available.
The positive progress effects of the invention are as follows:
the preparation method effectively reduces the side reaction in the polymerization process of the gamma-thiocarbonyl butyrolactone, so that the monomer can be converted into the poly (gamma-thiobutyrolactone) with high conversion rate. Compared with the method reported in the literature, the method avoids raw material waste, and simultaneously controllably obtains the high molecular weight poly (gamma-thiobutyrolactone) which can not be synthesized in the literature report, and the mechanical property of the polymer can be obviously improved by improving the molecular weight.
The poly (gamma-thiobutyrolactone) provided by the invention is a strong and tough semi-crystalline material, has stronger solvent corrosion resistance, has a melting temperature similar to that of commercialized low-density polyethylene (Yangzi petrochemical), has better mechanical properties and surface properties than the commercialized low-density polyethylene (Yangzi petrochemical), and can be rapidly and controllably degraded under specific conditions, so that the poly (gamma-thiobutyrolactone) provided by the invention is a potential green substitute for the low-density polyethylene.
Drawings
FIG. 1 is a drawing showing the preparation of poly (. Gamma. -thiobutyrolactone) obtained in example 2 1 H NMR spectrum.
FIG. 2 is a graph of poly (. Gamma. -thiobutyrolactone) obtained in example 2 13 C NMR spectrum.
FIG. 3 shows M of poly (. Gamma. -thiobutyrolactone) n Line graphs with monomer/catalyst ratio.
FIG. 4 is a DSC curve of poly (. Gamma. -thiobutyrolactone) having a number average molecular weight of 248.8kg/mol, obtained in example 4.
FIG. 5 is a wide angle X-ray powder diffraction pattern of poly (. Gamma. -thiobutyrolactone) obtained in examples 2 and 4.
FIG. 6 is a graphical TGA plot of the poly (. Gamma. -thiobutyrolactone) obtained in example 4.
FIG. 7 is a stress-strain diagram of poly (. Gamma. -thiobutyrolactone) obtained in examples 2 and 4.
FIG. 8 is a DMA curve of poly (. Gamma. -thiobutyrolactone) having a number average molecular weight of 103.4kg/mol, obtained in example 2.
FIG. 9 is a DMA curve of poly (. Gamma. -thiobutyrolactone) having a number average molecular weight of 248.8kg/mol obtained in example 4.
FIG. 10 is a graph showing the static contact angle against water of the film of poly (. Gamma. -thiobutyrolactone) obtained in example 4.
FIG. 11 is a graph showing the hydrolysis curve of poly (. Gamma. -thiobutyrolactone) obtained in example 4 under basic conditions.
FIG. 12 is a graph showing the degradation of poly (. Gamma. -thiobutyrolactone) obtained in example 4 catalyzed by 1,5, 7-triazabicyclo (4.4.0) dec-5-ene.
FIG. 13 shows the preparation of gamma-thiocarbonylbutyrolactone obtained in example 1 1 H NMR spectrum.
Detailed Description
The invention is further illustrated by the following examples, which are not intended to limit the scope of the invention. The experimental methods without specifying specific conditions in the following examples were selected according to the conventional methods and conditions, or according to the commercial instructions.
Example 1
The compound shown in the formula (II) is a self-made product, the initial raw material of the compound is commercialized gamma-butyrolactone, and the compound is prepared by one-step reaction, the preparation method is not particularly limited, and the compound is preferably prepared according to the method described in the following scientific and technological paper: matsumoto Y, nakatake D, yazaki R, ohshima T.chemistry-A European Journal,2018,24 (23): 6062-6066.
A500 mL three-necked flask was charged with 48.6g of Lawson's reagent, charged with 200mL of anhydrous toluene, stirred to dissolve, and then charged with 15.4mL of gamma-butyrolactone, and stirred under reflux for 5 hours. After the reaction is finished, after the reaction temperature is reduced to normal temperature, 200mL of saturated potassium carbonate solution is added, the mixture is stirred for 30min, liquid separation is carried out, the aqueous phase is extracted with anhydrous toluene for three times, and then the organic phases are combined. After drying over anhydrous sodium sulfate, filtration and spin-drying, the second fraction was collected by column chromatography using a petroleum ether/ether gradient (40. The monomer is then added with calcium hydride and dried for 3 days, and then is distilled under reduced pressure at 100mTorr and 60 ℃ and then is placed in a glove box for storage for later use.
The gamma-thiobutyrolactone monomer obtained by the invention is light yellow liquid, the mass of the gamma-thiocarbonyl-butyrolactone monomer is 16.3g, and the calculated yield is 80%.
The invention carries out Nuclear Magnetic Resonance (NMR) characterization on the obtained gamma-thiocarbonyl butyrolactone monomer, 1 the H NMR spectrum is shown in FIG. 13, consistent with literature reports. The gamma-thiocarbonyl butyrolactone monomer prepared by the invention is proved to have a structure shown in a formula (II).
Example 2
In a glove box under argon atmosphere, in a dry Schlenk bottleTo this was added 0.817g (8 mmol, 0.70mL) of a γ -thiocarbonylbutyrolactone monomer, the glove box was removed and a Schlenk bottle was connected to a vacuum line with argon protection, and after stirring at 80 ℃ for 10 minutes, 0.01mmol of γ -thiocarbonylbutyrolactone monomer was dissolved in 0.24mL of toluene, respectively t Bu-P 4 And 0.01mmol of benzhydrol, and the two solutions were charged into the above-mentioned Schlenk flask, respectively, and polymerization was started with a total volume of 1.18mL, an initial concentration of the monomer of 6.8mol/L, and a catalyst t Bu-P 4 Has a concentration of 8.5mmol/L, a concentration of the cocatalyst benzhydrol of 8.5mmol/L, the monomers and t Bu-P 4 the molar ratio of (1).
The reaction temperature was maintained at 80 ℃ and polymerization was carried out for 120 minutes. After the polymerization reaction is finished, adding a chloroform solution with the mass concentration of 10mg/mL of benzoic acid to dissolve the product, and taking a small amount of solution to carry out 1 H NMR analysis is carried out to determine the conversion rate, the residual reaction liquid is poured into ethanol to settle the polymer, and the precipitated solid is filtered and washed by ethanol for three times and then dried for 24 hours in a vacuum drying oven at 40 ℃ to obtain white poly (gamma-thiobutyrolactone). Nuclear Magnetic Resonance (NMR) detection is carried out on the poly (gamma-thiobutyrolactone), 1 h NMR spectrum and 13 the C NMR spectra are shown in FIGS. 1 and 2, respectively.
The invention carries out the reaction on the obtained reaction liquid 1 H NMR analysis, the test results showed 90.0% conversion of monomer, dimer in product: gamma-thiobutyrolactone: the ratio of poly (γ -thiobutyrolactone) is 0.
The melting temperature and the glass transition of poly (gamma-thiobutyrolactone) are detected by a Differential Scanning Calorimetry (DSC), and the result shows that the melting temperature of the poly (gamma-thiobutyrolactone) prepared in the embodiment is 99.3 ℃ and the glass transition temperature is-53.1 ℃.
The invention adopts Gel Permeation Chromatography (GPC) to detect the molecular weight and the molecular weight distribution of poly (gamma-thiobutyrolactone), uses dichloromethane as an eluent, has the flow rate of 1.0mL/min, uses polymethyl methacrylate as a standard substance to make a standard curve, and shows that the number average molecular weight of the poly (gamma-thiobutyrolactone) prepared in the embodiment is 103.4kg/mol, and the molecular weight distribution is 1.76.
Example 3
In an argon atmosphere glove box, 0.817g (8mmol, 0.70mL) of a γ -thiocarbonylbutyrolactone monomer was charged into a dry Schlenk bottle, the glove box was removed and the Schlenk bottle was connected to a vacuum line with an argon shield, and after stirring at 80 ℃ for 10 minutes, 0.0067mmol of γ -thiocarbonylbutyrolactone was dissolved in 0.24mL of toluene t Bu-P 4 And 0.0067mmol of diphenylmethanol, and the two solutions were separately charged into the above-mentioned Schlenk flask, and polymerization was started with a total volume of 1.18mL, an initial concentration of the monomer of 6.8mol/L, and a catalyst t Bu-P 4 Has a concentration of 5.67mmol/L and a concentration of the cocatalyst benzhydrol of 5.67mmol/L, the monomers are reacted with t Bu-P 4 The molar ratio of (1). The reaction temperature was maintained at 80 ℃ and polymerization was carried out for 180 minutes. After the polymerization reaction is finished, adding a chloroform solution with the mass concentration of 10mg/mL of benzoic acid to dissolve the product, and taking a small amount of solution to carry out 1 H NMR analysis is carried out to determine the conversion rate, the residual reaction solution is poured into ethanol to settle the polymer, and the precipitated solid is filtered and washed with ethanol for three times and then dried in a vacuum drying oven at 40 ℃ for 24H to obtain white poly (gamma-thiobutyrolactone).
The reaction solution obtained by the invention is detected by nuclear magnetic resonance hydrogen spectrum, the result shows that the conversion rate of the monomer is 97.4 percent, and the dimer in the generated product: gamma-thiobutyrolactone: the ratio of poly (γ -thiobutyrolactone) is 0.
The melting temperature and the glass transition of poly (gamma-thiobutyrolactone) are detected by a Differential Scanning Calorimetry (DSC), and the result shows that the melting temperature of the poly (gamma-thiobutyrolactone) prepared in the embodiment is 98.0 ℃ and the glass transition temperature is-54.7 ℃.
The molecular weight and molecular weight distribution of poly (gamma-thiobutyrolactone) were measured by Gel Permeation Chromatography (GPC) according to the present invention, and it was found that the poly (gamma-thiobutyrolactone) prepared in this example had a number average molecular weight of 195.0kg/mol and a molecular weight distribution of 1.77.
Example 4
In a glove box under argon atmosphere, 0.817g (8 mmol, 0.70mL) of a γ -thiocarbonylbutyrolactone monomer was charged into a dry Schlenk bottle, the glove box was removed and the Schlenk bottle was connectedStirring the mixture at 80 ℃ for 10 minutes on a vacuum line with argon protection, and dissolving 0.005mmol of toluene in 0.24mL of toluene t Bu-P 4 And 0.005mmol of benzhydrol, and the two solutions were charged into the above-mentioned Schlenk flask, respectively, and polymerization was started with a total volume of 1.18mL, an initial concentration of the monomer of 6.8mol/L, and a catalyst t Bu-P 4 Has a concentration of 4.24mmol/L and a concentration of cocatalyst benzhydrol of 4.24mmol/L, monomer and t Bu-P 4 the molar ratio of (a) to (b) is 1600. The reaction temperature was maintained at 80 ℃ and polymerization was carried out for 240 minutes. After the polymerization reaction is finished, adding a chloroform solution with the mass concentration of 10mg/mL of benzoic acid to dissolve the product, and taking a small amount of solution to carry out 1 H NMR analysis is carried out to determine the conversion rate, the residual reaction solution is poured into ethanol to settle the polymer, and the precipitated solid is filtered and washed with ethanol for three times and then dried in a vacuum drying oven at 40 ℃ for 24H to obtain white poly (gamma-thiobutyrolactone).
The reaction solution obtained by the invention is detected by nuclear magnetic resonance hydrogen spectrum, the result shows that the conversion rate of the monomer is 99.8 percent, and the dimer in the generated product: gamma-thiobutyrolactone: the ratio of poly (γ -thiobutyrolactone) was 0.
The melting temperature and the glass transition temperature of poly (gamma-thiobutyrolactone) are detected by adopting a Differential Scanning Calorimetry (DSC), and the result shows that the melting temperature of the poly (gamma-thiobutyrolactone) prepared in the embodiment is 99.4 ℃ and the glass transition temperature is-49.2 ℃.
The molecular weight and molecular weight distribution of poly (gamma-thiobutyrolactone) were measured by Gel Permeation Chromatography (GPC) according to the present invention, and the number average molecular weight and molecular weight distribution of poly (gamma-thiobutyrolactone) prepared in this example were found to be 248.8kg/mol and 1.87.
Example 5
In an argon atmosphere glove box, 0.817g (8mmol, 0.70mL) of a γ -thiocarbonylbutyrolactone monomer was charged into a dry Schlenk bottle, the glove box was removed and the Schlenk bottle was connected to a vacuum line with an argon shield, and after stirring at 80 ℃ for 10 minutes, 0.01mmol of the γ -thiocarbonylbutyrolactone monomer was dissolved in 0.24mL of toluene t Bu-P 4 And 0.01mmol of 1-octanethiol, and the two solutions were each separately mixedWas charged into the above-mentioned Schlenk flask, polymerization was started, the total volume of polymerization was 1.18mL, the initial concentration of monomer was 6.8mol/L, and the catalyst was added t Bu-P 4 The concentration of (a) is 8.5mmol/L, the concentration of the cocatalyst 1-octanethiol is 8.5mmol/L, the monomer and t Bu-P 4 the molar ratio of (1). The reaction temperature was maintained at 80 ℃ and the polymerization was carried out for 120 minutes. After the polymerization reaction is finished, adding a chloroform solution with the mass concentration of 10mg/mL of benzoic acid to dissolve the product, and taking a small amount of solution to carry out 1 H NMR analysis is carried out to determine the conversion rate, the residual reaction solution is poured into ethanol to settle the polymer, and the precipitated solid is filtered and washed with ethanol for three times and then dried in a vacuum drying oven at 40 ℃ for 24H to obtain white poly (gamma-thiobutyrolactone).
The reaction solution obtained by the invention is detected by nuclear magnetic resonance hydrogen spectrum, the result shows that the conversion rate of the monomer is 95.1 percent, and the dimer in the generated product: gamma-thiobutyrolactone: the ratio of poly (γ -thiobutyrolactone) is 0.
The melting temperature of the obtained poly (gamma-thiobutyrolactone) is detected by a Differential Scanning Calorimetry (DSC), and the result shows that the melting temperature of the poly (gamma-thiobutyrolactone) prepared in the embodiment is 98.26 ℃ and the glass transition temperature is-55.6 ℃.
The molecular weight and molecular weight distribution of poly (gamma-thiobutyrolactone) were determined by Gel Permeation Chromatography (GPC) according to the present invention, and the number average molecular weight of poly (gamma-thiobutyrolactone) prepared in this example was 129.5kg/mol, and the molecular weight distribution was 1.74.
Example 6
In an argon atmosphere glove box, 0.817g (8mmol, 0.70mL) of a γ -thiocarbonylbutyrolactone monomer was charged into a dry Schlenk bottle, the glove box was removed and the Schlenk bottle was connected to a vacuum line protected with argon, and after stirring at 80 ℃ for 10 minutes, 0.01mmol of toluene was dissolved therein t Bu-P 4 And the solution was charged into the above-mentioned Schlenk flask, polymerization was started with a total volume of 1.18mL and an initial concentration of the monomer of 6.8mol/L, t Bu-P 4 in a concentration of 8.5mmol/L, monomers and t Bu-P 4 the molar ratio of (1). Maintaining the reaction temperature atPolymerization was carried out at 80 ℃ for 120 minutes. After the polymerization reaction is finished, adding a chloroform solution with the mass concentration of 10mg/mL of benzoic acid to dissolve the product, and taking a small amount of solution to carry out 1 H NMR analysis is carried out to determine the conversion rate, the residual reaction solution is poured into ethanol to settle the polymer, and the precipitated solid is filtered and washed with ethanol for three times and then dried in a vacuum drying oven at 40 ℃ for 24H to obtain white poly (gamma-thiobutyrolactone).
The nuclear magnetic resonance hydrogen spectrum detection of the obtained reaction liquid shows that the conversion rate of the monomer is 90.4 percent, and the dimer in the generated product: gamma-thiobutyrolactone: the ratio of poly (γ -thiobutyrolactone) is 0.
The melting temperature of the poly (gamma-thiobutyrolactone) obtained by the method is detected by a Differential Scanning Calorimetry (DSC), and the result shows that the melting temperature of the poly (gamma-thiobutyrolactone) prepared in the embodiment is 98.46 ℃ and the glass transition temperature is-51.8 ℃.
The molecular weight and molecular weight distribution of poly (gamma-thiobutyrolactone) were measured by Gel Permeation Chromatography (GPC) according to the present invention, and it was shown that the poly (gamma-thiobutyrolactone) prepared in this example had a number average molecular weight of 99.9kg/mol and a molecular weight distribution of 1.77.
Example 7
In an argon atmosphere glove box, 0.817g (8mmol, 0.70mL) of a γ -thiocarbonylbutyrolactone monomer was charged into a dry Schlenk bottle, the glove box was removed and the Schlenk bottle was connected to a vacuum line with an argon shield, and after stirring at 80 ℃ for 10 minutes, 0.01mmol of o-dichlorobenzene was dissolved in 0.48mL of o-dichlorobenzene t Bu-P 4 And the solution was charged into the above-mentioned Schlenk flask, polymerization was started with a total volume of 1.18mL and an initial concentration of the monomer of 6.8mol/L, t Bu-P 4 in a concentration of 8.5mmol/L, monomers and t Bu-P 4 the molar ratio of (1). The reaction temperature was maintained at 80 ℃ and polymerization was carried out for 120 minutes. After the polymerization reaction is finished, adding a chloroform solution with the mass concentration of 10mg/mL of benzoic acid to dissolve the product, and taking a small amount of solution to carry out 1 H NMR analysis to determine conversion, the remaining reaction solution was poured into ethanol to precipitate the polymer, the precipitated solid was filtered, washed three times with ethanol, and the filtrate was filtered off and washed with ethanolDrying for 24h at 40 ℃ in a vacuum drying oven to obtain white poly (gamma-thiobutyrolactone).
The nuclear magnetic resonance hydrogen spectrum detection of the obtained reaction liquid shows that the conversion rate of the monomer is 94.7 percent, and the dimer in the generated product: gamma-thiobutyrolactone: the ratio of poly (γ -thiobutyrolactone) is 0.
The melting temperature of the poly (gamma-thiobutyrolactone) obtained by the invention is detected by Differential Scanning Calorimetry (DSC), and the result shows that the melting temperature of the poly (gamma-thiobutyrolactone) prepared in the example is 99.33 ℃ and the glass transition temperature is-51.6 ℃.
The molecular weight and molecular weight distribution of poly (gamma-thiobutyrolactone) were measured by Gel Permeation Chromatography (GPC) according to the present invention, and the number average molecular weight of poly (gamma-thiobutyrolactone) prepared in this example was 101.1kg/mol, and the molecular weight distribution was 1.82.
Example 8
In a glove box under an argon atmosphere, 0.817g (8 mmol, 0.70mL) of a γ -thiocarbonylbutyrolactone monomer and 3.2mg (0.02 mmol) of N, N' -diisopropylthiourea were charged into a dry Schlenk bottle, the glove box was removed and the Schlenk bottle was connected to a vacuum line under an argon atmosphere, and after stirring at 80 ℃ for 10 minutes, 0.01mmol of toluene was dissolved in each case t Bu-P 4 And 0.01mmol of benzyl alcohol, and the two solutions were charged into the above-mentioned Schlenk flask, respectively, and polymerization was started with a total volume of 1.18mL, an initial concentration of the monomer of 6.8mol/L, and a catalyst t Bu-P 4 The concentration of the cocatalyst N, N' -diisopropylthiourea and the benzyl alcohol is respectively 17.0 and 8.5mmol/L, and the monomer and the benzyl alcohol are mixed t Bu-P 4 The molar ratio of (1). The reaction temperature was maintained at 80 ℃ and polymerization was carried out for 180 minutes. After the polymerization reaction is finished, adding a chloroform solution with the mass concentration of 10mg/mL of benzoic acid to dissolve the product, and taking a small amount of solution to carry out 1 H NMR analysis is carried out to determine the conversion rate, the residual reaction liquid is poured into ethanol to settle the polymer, and the precipitated solid is filtered and washed by ethanol for three times and then dried for 24 hours in a vacuum drying oven at 40 ℃ to obtain white poly (gamma-thiobutyrolactone).
The nuclear magnetic resonance hydrogen spectrum detection of the obtained reaction liquid shows that the conversion rate of the monomer is 71.0 percent, and the dimer in the generated product: gamma-thiobutyrolactone: the ratio of poly (γ -thiobutyrolactone) was 0.
The melting temperature of the poly (gamma-thiobutyrolactone) obtained by the method is detected by a Differential Scanning Calorimetry (DSC), and the result shows that the melting temperature of the poly (gamma-thiobutyrolactone) prepared in the embodiment is 99.82 ℃ and the glass transition temperature is-50.8 ℃.
The poly (gamma-thiobutyrolactone) prepared in this example has a number average molecular weight of 85.8kg/mol and a molecular weight distribution of 1.60, as determined by Gel Permeation Chromatography (GPC).
Example 9
In an argon atmosphere glove box, 0.204g (2mmol, 0.18mL) of a γ -thiocarbonylbutyrolactone monomer and 8.0mg (0.02 mmol) of zinc bis (pentafluorophenyl) were charged into a dried Schlenk bottle, the glove box was removed and the Schlenk bottle was connected to a vacuum line protected with argon, and after stirring at 80 ℃ for 10 minutes, 0.02mmol of toluene was dissolved in each of the bottles t Bu-P 4 And 0.02mmol of benzyl alcohol, and the two solutions were separately charged into the above-mentioned Schlenk flask, and polymerization was started with a total volume of 1.18mL, an initial concentration of the monomer of 1.7mol/L, and a catalyst t Bu-P 4 Has a concentration of 17.0mmol/L, the concentrations of the cocatalyst bis (pentafluorophenyl) zinc and the benzyl alcohol are respectively 17.0 and 17.0mmol/L, the monomer and the benzyl alcohol are reacted with t Bu-P 4 The molar ratio of (a) to (b) is 100. The reaction temperature was maintained at 80 ℃ and the polymerization was carried out for 30 minutes. After the polymerization reaction is finished, adding a chloroform solution with the mass concentration of 10mg/mL of benzoic acid to dissolve the product, and taking a small amount of solution to carry out 1 H NMR analysis is carried out to determine the conversion rate, the residual reaction solution is poured into ethanol to settle the polymer, and the precipitated solid is filtered and washed with ethanol for three times and then dried in a vacuum drying oven at 40 ℃ for 24H to obtain white poly (gamma-thiobutyrolactone).
The nuclear magnetic resonance hydrogen spectrum detection of the obtained reaction liquid shows that the conversion rate of the monomer is 98.4 percent, and the dimer in the generated product: gamma-thiobutyrolactone: the ratio of poly (γ -thiobutyrolactone) was 2.
The melting temperature of the poly (gamma-thiobutyrolactone) obtained by the method is detected by a Differential Scanning Calorimetry (DSC), and the result shows that the melting temperature of the poly (gamma-thiobutyrolactone) prepared in the embodiment is 103.57 ℃ and the glass transition temperature is-50.0 ℃.
The poly (gamma-thiobutyrolactone) prepared in this example obtained by Gel Permeation Chromatography (GPC) detection had a number average molecular weight of 24.0kg/mol and a molecular weight distribution of 1.50.
Comparative example 1
The literature: hirofumi, k.; norio, t.; takeshi, E.chem.Lett.2005,34,376-377.
The polymerization of TnBL (catalyst Y (OTf) was repeated under literature conditions 3 ，TnBL/Y(OTf) 3 Polymerization in bulk at 100 ℃ for 2 hours, polymerization results and literature (M) = 100/1) n ＝4.5kg/mol,
Monomer conversion =84%, polymer yield = 45%) were similar: m n ＝4.8kg/mol,
Monomer conversion =84.6%, the back-biting monomer/polymer ratio is 30/70, only low molecular weight polymers can be obtained, and a large amount of back-biting monomer by-products is generated.
Performance parameter determination:
the invention uses a gel permeation chromatograph to determine the molecular weight and the molecular weight distribution of poly (gamma-thiobutyrolactone), uses dichloromethane as an eluent, has the flow rate of 1.0mL/min, uses polymethyl methacrylate as a standard substance to make a standard curve, and the result shows that: the poly (. Gamma. -thiobutyrolactone) prepared in examples 2-9 of the present invention had a number average molecular weight of 24.0kg/mol to 248.8kg/mol and a molecular weight distribution index of 1.50 to 1.87. When the amount of the catalyst is changed, the number average molecular weight linearly increases as the ratio of the monomer to the catalyst increases (the catalyst herein refers to a main catalyst), and the molecular weight control property is good (as shown in fig. 3, wherein the abscissa is the molar ratio of the monomer gamma-thiobutyrolactone to the catalyst).
The melting temperature (T) of poly (gamma-thiobutyrolactone) obtained in example 4 was measured by Differential Scanning Calorimetry (DSC) m ) The measurement is carried out, a representative curve is shown in figure 4, and the test shows that the glass transition temperature T of the poly (gamma-thiobutyrolactone) provided by the invention g About-50 ℃ and a melting temperature of 99.4 ℃, which is similar to the melting temperature of commercial Low Density Polyethylene (LDPE) (Yankee petrochemical, T) m ＝103℃)。
Wide-angle X-ray powder diffraction test shows that the poly (gamma-thiobutyrolactone) prepared in example 2 and example 4 has the crystallinity of 63.1-67.4% and the interplanar spacing of
And
although the melting temperatures of poly (. Gamma. -thiobutyrolactone) and commercial low density polyethylene are close, the crystallization patterns of the two are completely different (the crystallinity of commercial low density polyethylene is 51.1%, and the interplanar spacings are respectively 51.1%)
And
as shown in fig. 5. The test sample for wide-angle X-ray powder diffraction is a disk with a diameter of 25mm and a thickness of 1mm, and is prepared by hot pressing at 120 ℃ by a tablet press.
The thermal stability of poly (. Gamma. -thiobutyrolactone) obtained in example 4 was determined using a Thermal Gravimetric Analyzer (TGA) according to the present invention, as shown in FIG. 6, and the initial decomposition temperature (T) of the resulting polymer d Temperature at 5% weight loss) at 202 ℃, has a processing window of more than 100 ℃, and has excellent processing performance.
The invention tests the mechanical properties of the poly (gamma-thiobutyrolactone) prepared in example 2 and example 4: the mechanical tensile test (as shown in FIG. 7) shows that the poly (gamma-thiobutyrolactone) with the number average molecular weight of 103.4kg/mol has the elongation at break of 385.85 percent, the yield stress of 14.11MPa and the breaking stress of 23.03MPa; the poly (gamma-thiobutyrolactone) with the number average molecular weight of 248.8kg/mol has the elongation at break of 412.46%, the yield stress of 15.69MPa and the breaking stress of 29.78MPa, which shows that the poly (gamma-thiobutyrolactone) provided by the invention is a strong and tough polymer material, and all indexes of a mechanical tensile test are superior to those of low density polyethylene (the elongation at break is 76.36%, the yield stress is 11.40MPa and the breaking stress is 7.40 MPa), particularly in the aspect of the elongation at break, the poly (gamma-thiobutyrolactone) is 5.4 times of that of commercial low density polyethylene, which shows that the toughness is obviously superior to that of the commercial low density polyethylene.
The invention adopts Dynamic Mechanical Analysis (DMA) to further characterize the mechanical properties of the poly (gamma-thiobutyrolactone) prepared in the examples 2 and 4, as shown in figures 8 and 9, at 25 ℃, the poly (gamma-thiobutyrolactone) with the number average molecular weight of 103.4kg/mol has the storage modulus of 418.0MPa, the loss modulus of 17.4MPa and the glass transition temperature of-40.1 ℃ (as shown in figure 8); poly (. Gamma. -thiobutyrolactone) having a number-average molecular weight of 248.8kg/mol had a storage modulus of 357.4MPa, a loss modulus of 15.0MPa, and a glass transition temperature of-42.0 deg.C (see FIG. 9). DMA tests show that: at 25 ℃, the storage modulus (E 'or Young modulus) of the poly (gamma-thiobutyrolactone) is far larger than the loss modulus (E'), and the material mainly shows elastic deformation at the temperature and meets the requirements of structural materials.
The poly (gamma-thiobutyrolactone) has stronger solvent corrosion resistance, and the polymer can be dissolved in individual halogen-containing solvents such as dichloromethane, chloroform and the like, and is almost insoluble in other common organic solvents (such as toluene, o-dichlorobenzene, chlorobenzene, THF, DMF, DMSO and the like). Meanwhile, the invention also represents the surface performance of poly (gamma-thiobutyrolactone), and because the polyolefin material is a non-polar polymer and has low surface energy, the material has poor printing property, antistatic property and hydrophilicity, can only be used alone generally, and is difficult to blend and hybridize with other polar materials, and the inherent defect seriously hinders the application of the polyolefin material in many fields. Static contact Angle test of poly (. Gamma. -thiobutyrolactone) obtained in example 4 according to the present invention As shown in FIG. 10, the contact angle of poly (. Gamma. -thiobutyrolactone) was 78.4 ℃ and was significantly lower than that of low density polyethylene (96.0 ℃), since it was shown that poly (. Gamma. -thiobutyrolactone) prepared according to the present invention has a polar thiol functional group in its main chain, so that the surface properties of poly (. Gamma. -thiobutyrolactone) were much better than those of low density polyethylene.
Due to the presence of thioester functional groups in the backbone, the poly (gamma-thiobutyrolactone) of the present invention has a degradability not comparable to commercial low density polyethylene and can undergo rapid and controlled degradation under specific conditions: at room temperature, the poly (gamma-thiobutyrolactone) obtained in example 4 gradually disappeared with time in the basic aqueous solution and was completely degraded into sodium 4-mercaptobutyrate (reaction formula shown below) within 12 days, as shown in fig. 11, whereas in the acidic and neutral aqueous solutions, the hydrolysis of poly (gamma-thiobutyrolactone) was extremely slow and no hydrolysis product appeared within the monitoring period (one month);
when 1,5, 7-triazabicyclo (4.4.0) dec-5-ene (TBD) was added as a degradation catalyst, poly (. Gamma. -thiobutyrolactone) obtained in example 4 was rapidly and quantitatively degraded into. Gamma. -thiobutyrolactone within 15 seconds (reaction formula shown below), as shown in FIG. 12. The specific reaction process is as follows: 51mg of poly (. Gamma. -thiobutyrolactone) dried was dissolved in 0.9mL of anhydrous methylene chloride, and 0.1mL of a methylene chloride solution of TBD (0.05 mol/L) was added to the resulting transparent solution, and the reaction was stirred for 15 seconds to find that the polymer had been completely degraded to (. Gamma. -thiobutyrolactone).
Claims (19)
1. A method for producing a polymer compound, characterized by comprising the steps of: in an organic solvent, in the presence of a main catalyst, carrying out a polymerization reaction on a compound shown as a formula (II);
the main catalyst is one or more of phosphazene base, guanidine organic base, amidine organic base, N-heterocyclic carbene organic base and N-heterocyclic olefin organic base.
2. The process of claim 1 wherein the procatalyst is a phosphazene base.
3. The method according to claim 1, wherein the polymer compound is a compound represented by the formula (I),
wherein n is greater than or equal to 10;
and/or the polymerization reaction is carried out in a protective gas atmosphere;
and/or the organic solvent is one or more of straight-chain hydrocarbon solvent, halogenated hydrocarbon solvent, cyclic ether solvent, aromatic hydrocarbon solvent and halogenated aromatic hydrocarbon solvent;
and/or the phosphazene base is a compound shown as a formula (III), the structure of which is shown as the following,
wherein R and R' are independently C 1 -C 4 Alkyl groups of (a); n1 is 0, 1,2 or 3; y is 0, 1,2 or 3;
and/or the guanidine organic base is 1,5, 7-triazabicyclo (4.4.0) dec-5-ene and/or 7-methyl-1, 5, 7-triazabicyclo [4.4.0] dec-5-ene, the structures of which are shown as follows,
and/or the amidine organic base is 1, 8-diazabicyclo [5.4.0] undec-7-ene, the structure of which is shown as follows,
and/or the N-heterocyclic carbene organic base is a compound shown as a formula (IV), and the structure of the N-heterocyclic carbene organic base is shown as follows,
wherein R is 1a And R 2a Independently hydrogen, alkyl or aryl; r is 3a And R 4a Independently is an alkyl or aryl group;
and/or the N-heterocyclic olefin organic base is a compound shown as a formula (V) and has the structure shown as the following,
wherein R is 1b And R 2b Independently hydrogen, methyl or phenyl; r is 3b And R 4b Independently is an alkyl or aryl group; r 5b Is hydrogen, methyl or ethyl;
and/or the molar concentration of the compound shown as the formula (II) in the organic solvent is 0.2-10 mol/L;
and/or the molar ratio of the compound shown as the formula (II) to the main catalyst is 20-1600;
and/or the temperature of the polymerization reaction is 0-120 ℃;
and/or the time of the polymerization reaction is 5 to 720 minutes.
4. The method according to claim 3, wherein n is 65 or more;
and/or the organic solvent is an aromatic hydrocarbon solvent and/or a halogenated aromatic hydrocarbon solvent;
and/or, in the compound shown in the formula (III), R and R' are independently methyl, ethyl, propyl, isopropyl or tert-butyl.
5. The method of claim 4, wherein n is from 65 to 4900;
and/or the organic solvent is toluene and/or o-dichlorobenzene.
6. The method of claim 5, wherein n is 190-2450.
7. The method of claim 6, wherein n is 840-2450.
8. The method according to claim 3,
the number average molecular weight of the compound shown as the formula (I) is more than or equal to 1kg/mol;
and/or the molecular weight distribution of the compound shown in the formula (I) is 1.0-2.5;
and/or the protective gas is nitrogen and/or argon;
and/or the straight-chain hydrocarbon solvent is one or more of n-hexane, n-heptane and n-pentane;
and/or the halogenated hydrocarbon solvent is one or more of dichloromethane, trichloromethane, 1, 2-dichloroethane and tetrachloroethane;
and/or the cyclic ether solvent is tetrahydrofuran and/or dioxane;
and/or the aromatic hydrocarbon solvent is one or more of toluene, benzene and xylene;
and/or the halogenated aromatic hydrocarbon solvent is one or more of o-dichlorobenzene, o-difluorobenzene, o-dibromobenzene, chlorobenzene, fluorobenzene, bromobenzene and sym-trichlorobenzene;
and/or the phosphazene base is 1-tert-butyl-4, 4-tris (dimethylamino) -2, 2-bis [ tris (dimethylamino) -phosphoranylideneamino]-2λ 5 ,4λ 5 -a bis (phosphazene-based compound) having the structure shown below,
and/or, R of the compound shown as the formula (IV) 1a And R 2a Independently methyl, ethyl or phenyl; r 3a And R 4a Independently methyl, ethyl, isopropyl, tert-butyl, phenyl, 2, 6-diisopropylphenyl or 2,4, 6-trimethylphenyl;
and/or, R of the compound shown in the formula (V) 3b And R 4b Independently methyl, ethyl, isopropyl, tert-butyl, phenyl, 2, 6-diisopropylphenyl or 2,4, 6-trimethylphenyl;
and/or the molar concentration of the compound shown as the formula (II) in the organic solvent is 2.0-7.0 mol/L;
and/or the molar ratio of the compound shown as the formula (II) to the main catalyst is (100);
and/or the temperature of the polymerization reaction is 40-80 ℃;
and/or the time of the polymerization reaction is 30 to 240 minutes.
9. The method according to claim 8, wherein the compound of formula (I) has a number average molecular weight of 7kg/mol or more;
and/or the molecular weight distribution of the compound shown in the formula (I) is 1.5-2.0;
and/or the aromatic hydrocarbon solvent is toluene;
and/or, the halogenated aromatic hydrocarbon solvent is o-dichlorobenzene;
and/or the molar ratio of the compound shown in the formula (II) to the main catalyst is 400-1600.
10. The process according to claim 9, wherein the compound of formula (I) has a number average molecular weight of 7 to 500kg/mol.
11. The process according to claim 10, wherein the compound of formula (I) has a number average molecular weight of 20 to 250kg/mol.
12. The process according to claim 11, wherein the compound of formula (I) has a number average molecular weight of 80 to 250kg/mol.
13. The process of claim 1 wherein the polymerization is carried out in the presence of a co-catalyst which is a hydrogen bond donor and/or a lewis acid.
14. The method of claim 13, wherein the hydrogen bond donor is one or more of an alcohol, a thiol, a carboxylic acid, a urea, and a thiourea;
and/or the Lewis acid is one or more of alkali metal compounds, alkaline earth metal compounds, zinc compounds, boron compounds, aluminum compounds and rare earth compounds;
and/or the molar ratio of the main catalyst to the cocatalyst is 1.
15. The method of claim 14, wherein the hydrogen bond donor is one or more of an alcohol, a thiol, and a thiourea;
and/or the Lewis acid is a zinc compound.
16. The method of claim 15, wherein the hydrogen bond donor is one or more of benzhydrol, benzyl alcohol, 1-octanethiol, and N, N' -diisopropylthiourea;
and/or the Lewis acid is bis (pentafluorophenyl) zinc.
17. The process according to claim 14, wherein the alcohol is benzhydrol and/or benzyl alcohol;
and/or, the mercaptan is 1-octanethiol;
and/or, the carboxylic acid is phenylacetic acid;
and/or, the urea is diethyl urea;
and/or the thiourea is N, N' -diisopropyl thiourea;
and/or, the alkali metal compound is lithium chloride;
and/or, the alkaline earth metal compound is magnesium chloride;
and/or the zinc compound is diethyl zinc and/or di (pentafluorophenyl) zinc;
and/or the boron compound is tris (pentafluorophenyl) boron;
and/or the aluminum compound is tris (pentafluorophenyl) aluminum;
and/or the rare earth compound is tris [ bis (trimethylsilyl) amino ] lanthanum;
and/or the molar ratio of the main catalyst to the cocatalyst is 1.
18. The method of claim 1, comprising the steps of: in an organic solvent, carrying out a polymerization reaction on a compound shown as a formula (II) in the presence of a main catalyst; the molar ratio of the compound shown in the formula (II) to the main catalyst is 400-1600.
19. The method of claim 13, comprising the steps of: in an organic solvent, carrying out a polymerization reaction on a compound shown as a formula (II) in the presence of a main catalyst and a cocatalyst; the molar ratio of the compound shown in the formula (II) to the main catalyst is (100) - (1600).
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