CN110540529A - Dihydric alcohol-based carbonate polymerizable monomer and polymer thereof - Google Patents

Abstract

The invention discloses a dihydric alcohol base carbonic ester polymerizable monomer and a polymer thereof, wherein the monomer is prepared by taking dihydric alcohol, monohaloalkane and CO2 as raw materials. The polymer is prepared by the following method: (1) dissolving a monomer in an organic solvent, adding a photoinitiator and a dimercapto compound, and irradiating under ultraviolet light; (2) adding the product into an organic solvent, then adding the organic solvent into an anti-solvent for regeneration, washing and purifying to obtain the dihydric alcohol based polycarbonate. Or prepared by the following method: (1) adding the monomer into a Schlenk bottle, carrying out oil bath, and then adding a catalyst and an anti-isomerization reagent; (2) and (2) adding the product obtained in the step (1) into an organic solvent and ethyl vinyl ether, then dropwise adding the product into an anti-solvent for regeneration, washing and purifying to obtain the dihydric alcohol-based polycarbonate. The polymerizable monomer and the polymer thereof have the characteristics of simple preparation, low cost, easy implementation and strong operability, and are a sustainable and environment-friendly new technology.

Description

dihydric alcohol-based carbonate polymerizable monomer and polymer thereof

Technical Field

The invention relates to a carbonate polymerizable monomer and a polymer thereof, in particular to a dihydric alcohol-based carbonate polymerizable monomer and a polymer thereof.

Background

With the continuous depletion of fossil resources and the increasing awareness of the finite nature of fossil resources, there is an increasing interest in the production of chemicals from renewable and sustainable carbon resources. Carbon dioxide, among the major gases responsible for the greenhouse effect, is an environmentally problematic and particularly attractive gas due to its availability, low cost, abundance and nontoxicity, and is also a waste product produced in many industrial processes, and a long-term goal of synthetic chemistry is to develop and utilize it, thereby consuming it, which is, however, very difficult to accomplish. Carbon dioxide, the final oxidation form of carbon, is the lowest energy of all carbon-containing neutral species and requires a large amount of energy to utilize it.

The bio-based resource is a typical renewable resource, has high research heat in recent years and has the highest potential to replace petroleum-based resources, and as for the traditional thermoplastic engineering plastic bisphenol A polycarbonate, the application range is very wide due to good chemical and physical properties, and in the biomass resource, the furan-based compound which can replace the bisphenol A polycarbonate is the most possible, and as for the structural characteristics of the furan-based compound, the furan-based compound also has chemical properties similar to benzene rings, has high rigidity, and has rich sources, can be obtained from renewable resources such as glucose, fructose and cellulose, can form fructose through the isomerization of the glucose, and then obtains the platform compound of 5-hydroxymethyl furfural through the dehydration reaction of the fructose [ see ACS Catalysis,2012,2,930-.

based on previous researches, the most industrialized process for synthesizing polycarbonate is to synthesize polycarbonate by using bisphenol A and phosgene [ see Chemical Engineering Science 1986, 41, 2939-. Michael R.Kember [ see Chemical communications 2011,47,141-163 ] et al, have studied the synthesis of polycarbonate by copolymerizing carbon dioxide and epoxide with a catalyst, and although the synthesis of polycarbonate was successful, the molecular weight of the synthesized polycarbonate was very limited, and since cyclic carbonate is produced in addition to the synthesis of polycarbonate during the polymerization process, a polymer with high molecular weight cannot be synthesized. Then, ring-opening polymerization of cyclic carbonate monomers is developed, a variety of ring-opening processes are developed through research on the ring-opening polymerization reaction induced by trimethyl carbonate heat, according to different mechanisms such as anion polymerization, cation polymerization and coordination polymerization, and Sarah Tempelar [ see chem.Soc.Rev 2013,42,1312-1336 ], and the like, research on the ring-opening polymerization for preparing polycarbonate, wherein a plurality of cyclic carbonate monomers with different functions are synthesized firstly, and then the monomers are subjected to ring-opening polymerization to synthesize different polycarbonates. Ji Hae Park (see Macromolecules 2013,46, 3301-3308.) et al, studied the synthesis of polycarbonate using dimethyl carbonate and aliphatic diol, successfully synthesized high molecular weight polycarbonate, but required a relatively precise ratio of diol to dimethyl carbonate of 1, otherwise resulted in the synthesis of many unwanted byproducts, thereby reducing the yield of the desired product, and required a reduced pressure treatment to reduce the production of methanol, which is one of the byproducts, and required a reaction at a high temperature of 180 ℃, so that the reaction conditions were relatively harsh and energy consumption required for the reaction was high. Shen (see Green chem.,2017,19, 4930-4938) et al propose a new strategy to prepare furan dicarboxylic acid based polyesters by melt polycondensation using dimethyl 2, 5-furandicarboxylate and a diol having a long alkyl chain, which strategy produces a byproduct of volatile methanol rather than a diol having a high boiling point.

at present, through patent and literature search, no reports of constructing unsaturated bond-containing carbonate structure polymerizable monomers by using diol monomers and capturing carbon dioxide through organic function catalysis and preparing corresponding polymers are found.

Disclosure of Invention

the invention aims to provide a diol-based carbonate polymerizable monomer and a polymer thereof. The polymerizable monomer and the polymer thereof have the characteristics of simple preparation, low cost, easy implementation and strong operability, and are a sustainable and environment-friendly new technology.

The technical scheme of the invention is as follows: a dihydric alcohol-based carbonate polymerizable monomer is prepared from dihydric alcohol, monohaloalkane and CO 2.

the preparation method of the dihydric alcohol carbonate polymerizable monomer comprises the following steps:

(1) Adding a mixed solution of dihydric alcohol, an organic solvent and a catalyst into a high-pressure reaction kettle, covering the reaction kettle, introducing 0.1-10MPa CO2, and reacting at 0-80 ℃ for 1-10 hours to obtain a monocarbonate ionic compound intermediate solution A;

(2) Adding monohaloalkane containing carbon-carbon double bond or carbon-carbon triple bond into the solution A, maintaining the pressure of CO2 in a high-pressure reaction kettle at 0.1-10MPa, and reacting at 0-80 ℃ for 1-72 hours to obtain a dihydric alcohol-based carbonic acid ester polymerizable monomer solution B;

(3) and separating and purifying the solution B to obtain the dihydric alcohol base carbonic ester polymerizable monomer.

the diol-based carbonate polymerizable monomer is one of the following structures:

(1) Aliphatic:

(2) Aromatic:

the mass concentration of the dihydric alcohol in the mixed solution in the step (1) is 5-50%;

the organic solvent is one or a mixture of two or more of N, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, acetonitrile, 1, 3-dimethyl-2-imidazolidinone or dimethyl sulfoxide;

The catalyst is one or two of cesium carbonate, potassium carbonate, sodium carbonate, lithium carbonate, sodium hydroxide, potassium hydroxide, triethylamine, tributylamine, pyridine, tetramethylguanidine, 1,5, 7-triazabicyclo [4,4,0] dec-5-ene, 7-methyl-1, 5, 7-triazabicyclo [4,4,0] dec-5-ene, 1, 8-diazabicycloundec-7-ene or 1, 5-diazabicyclo [4,3,0] non-5-ene; the dosage of the catalyst is 1 to 3 times of the mole number of the dihydric alcohol.

the above diol-based carbonate polymerizable monomer, the monohaloalkane containing a carbon-carbon double bond or a carbon-carbon triple bond is one of the following structures:

(a) Aliphatic alkyl halides: CnH2n-1X or CmH2m-3X, wherein n is more than or equal to 3 and less than or equal to 10, and m is more than or equal to 3 and less than or equal to 5; wherein X is halogen Cl, Br or I, the position of X is not limited, and the position of unsaturated bond is not limited;

(b) aromatic alkyl halides: C2H3ArCH2X, wherein X is a halogen Cl, Br or I, wherein the position of CH2X is not limited;

wherein the amount of the monohaloalkane substance added is 1 to 6 times of the amount of the glycol substance.

the polymer prepared from the diol carbonate polymerizable monomer has the following structural formula:

wherein R1 is one of the following groups:

(1) Contains aliphatic carbon-carbon saturated groups and has the following structural general formula: -CnH2n-, wherein 3. ltoreq. n.ltoreq.10;

(2) An aromatic saturated group, -C2H4ArCH 2-;

the R2 group is one of the following structural formulas:

(1) Aliphatic:

(2) Aromatic:

the R3 group is one of the following structural formulas:

(1) Aliphatic: (x is more than or equal to 1 and less than or equal to 8),

(2) aromatic:

The polymer prepared from the diol carbonate polymerizable monomer is prepared by the following method:

(1) dissolving a dihydric alcohol carbonate polymerizable monomer in an organic solvent, adding a photoinitiator and a dimercapto compound, placing the mixture in an ultraviolet crosslinking instrument, and irradiating for 1-24 hours under the ultraviolet light of 190-400 nm;

(2) And (2) adding the product obtained in the step (1) into an organic solvent for dissolving, then adding the product into an anti-solvent for regeneration, washing and purifying to obtain the dihydric alcohol-based polycarbonate.

A polymer made from the foregoing diol based carbonate polymerizable monomer, said process comprising:

the initiator is as follows: one of 2-hydroxy-methylphenylpropane-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- (4-methylthiophenyl) -2-morpholinyl-1-propanone, benzoin dimethyl ether, 2,4, 6-trimethylbenzoyldiphenylphosphine oxide, ethyl 4- (N, N-dimethylamino) benzoate, benzophenone or 4-chlorobenzophenone; the amount of the initiator is 0.5 to 30 percent of the mole number of the dihydric alcohol carbonate monomer;

the dimercapto compound is: one of biphenyl-4, 4 '-dithiol, 1, 5-dimercaptonaphthalene, bis (2-mercaptoethyl) ether, dimercaptoethyl sulfide, 2, 5-dimercaptothiadiazole, ethanedithiol, propanedithiol, butanedithiol, pentanedithiol, hexanedithiol, heptanedithiol, nonanedithiol, decanedithiol, dimercaprol, 3, 6-dioxa-1, 8-octanedithiol, 2, 3-butanedithiol, 1, 2-benzenedithiol, toluene-3, 4-dithiol, terephthal thiol, isophthal thiol, p-xylylene thiol, m-xylylene thiol, or 4,4' -dithiodiphenyl; the amount of the mercapto compound is 1 time of the mole number of the diol carbonate monomer.

The polymer prepared from the diol carbonate polymerizable monomer has the following structural formula:

Wherein the R1 group is as follows:

(2) Contains aliphatic carbon-carbon saturated groups and has the following structural general formula: -CnH2n-, wherein 1. ltoreq. n.ltoreq.8;

(2) An aromatic saturated group, -CHARCH 2-;

The R2 group is one of the following structural formulas:

(1) aliphatic:

(2) aromatic:

the polymer prepared from the diol carbonate polymerizable monomer is prepared by the following method:

(1) adding a dihydric alcohol carbonate monomer into a reaction bottle, putting the reaction bottle into an oil bath kettle at the temperature of 30-150 ℃, reacting for 1-10 hours, then adding a catalyst and an anti-isomerization reagent, and reacting for 1-48 hours;

(2) Adding the product obtained in the step (1) into an organic solvent and ethyl vinyl ether, reacting for 1-10 hours at room temperature, then dropwise adding into an anti-solvent for regeneration, washing and purifying to obtain the dihydric alcohol-based polycarbonate.

the polymer prepared by the diol carbonate polymerizable monomer,

the catalyst is one of Grubbs1st, Grubbs2nd, Hoveyda-Grubbs 1st or Hoveyda-Grubbs 2 nd; the dosage of the catalyst is 0.5 to 30 percent of the mole number of the dihydric alcohol carbonate monomer;

The anti-isomerization reagent is benzoquinone, naphthoquinone, phenanthrenequinone or anthraquinone; the dosage of the isomerization-preventing reagent is 0.5 to 30 percent of the mole number of the dihydric alcohol carbonate monomer.

the invention has the advantages of

(1) The invention can efficiently capture carbon dioxide by organic functional catalysis, and can efficiently construct a carbonate ester intermediate containing carbonate bonds by using a bio-based platform compound furan dimethanol. The preparation method is simple and easy to implement and operate.

(2) The invention introduces functional groups capable of being polymerized again by adding alkyl halide containing unsaturated bonds, thereby efficiently constructing the polymerizable carbonate monomer. Lays a foundation for the polymerization application of the carbonate intermediate.

(3) the invention can select different dihydric alcohol and alkyl halide, thereby obtaining the dihydric alcohol group carbonic ester polymerizable monomer with various structures, the preparation method is simple, the reaction condition is mild, and abundant raw materials are provided for the preparation of novel polycarbonate.

drawings

FIG. 1 is a nuclear magnetic hydrogen spectrum of a polymerizable monomer prepared in example 1;

FIG. 2 is a nuclear magnetic carbon spectrum of the polymerizable monomer obtained in example 1;

FIG. 3 is an infrared image of the polymerizable monomer prepared in example 1;

FIG. 4 is a hydrogen spectrum of the polymer obtained in example 9;

FIG. 5 is a carbon spectrum of the polymer obtained in example 9;

FIG. 6 is an infrared image of the polymer obtained in example 9;

FIG. 7 is a thermogram of the polymer obtained in example 9;

FIG. 8 is a DSC of the polymer obtained in example 9;

FIG. 9 is a thermogram of the polymer obtained in example 12;

FIG. 10 is a DSC of the polymer obtained in example 12;

FIG. 11 is a GPC chart of the polymer obtained in example 12;

FIG. 12 is a nuclear magnetic hydrogen spectrum of the polymer obtained in example 14;

FIG. 13 is a nuclear magnetic carbon spectrum of the polymer obtained in example 14;

FIG. 14 is an infrared image of the polymer obtained in example 14;

FIG. 15 is a thermogram of the polymer obtained in example 14;

FIG. 16 is a DSC of the polymer obtained in example 14;

FIG. 17 is an XRD pattern of the polymer obtained in example 14;

FIG. 18 is a thermogram of the polymer obtained in example 17;

FIG. 19 is a DSC of the polymer obtained in example 17.

Detailed Description

the present invention is further illustrated by the following examples, which are not to be construed as limiting the invention.

examples of the invention

example 1: dihydric alcohol-based carbonate polymerizable monomer

Weighing furandimethanol (1 mmol), DMF (3 ml) and TMG (2 mmol) in a high-pressure reaction kettle, stirring uniformly at room temperature, combining the reaction kettles, charging and discharging CO2 for three times, charging CO2 to 1-2 MPa, stirring uniformly at room temperature, discharging gas and pressing to 1MPa, and moving to 30 ℃ for reaction for 1 hour. After the reaction is finished, charging air into bromopropylene (6 millimole) and pumping into a reaction kettle, stirring at room temperature until the air pressure is stable, placing the air pressure to 1MPa, and transferring into an oil bath at 30 ℃ for reaction for 48 hours. The reaction was stopped and the autoclave was cooled to room temperature. And opening the high-pressure reaction kettle, pouring out the sample, and performing suction filtration. The filtrate was poured into 3 ml of water, extracted with ethyl acetate (3 ml × 3 times), the combined ethyl acetate phases were washed twice with water (3 ml × 2 times), once with saturated brine, and dried over anhydrous sodium sulfate. The dried solution was rotary evaporated to remove the excess solvent, and the remaining product was subjected to column separation (eluent petroleum ether: ethyl acetate 10:1) to purify the product. Obtained as a light yellow liquid, yield: product a, 46.7%, product b, 17.0%. 1H NMR (400MHz,) Δ 6.42(d, J-3 Hz,2H),5.92(ddt, J-22.2, 10.6,5.8Hz,2H), 5.39-5.23 (m,5H),5.09(s,4H),4.63 (dt, J-5.8, 1.3Hz,4H), 13C NMR (100MHz, CDCl 3). delta 155.5,139.6, 132.1,118.2,107.8,68.4,63.2.IR: upsilon max3133,3089,3017 and 2889,1747, 1241649, 1560,1450 and 1385, 5,1077,949,790 cm-1.

The influence of the kind of solvent and the concentration of the reactive monomers on the preparation of the polymerizable monomers is illustrated by the following comparative examples.

Example 2: dihydric alcohol-based carbonate polymerizable monomer

weighing furan dimethanol (1 mmol), organic solvent (3 ml) and TMG (2 mmol) in a high-pressure reaction kettle, uniformly stirring at room temperature, combining the reaction kettles, charging and discharging CO2 for three times, charging CO2 to 1-2 MPa, uniformly stirring at room temperature, discharging gas and pressing to 1MPa, and moving to 30 ℃ for reaction for 1 hour. And (3) after the reaction is finished, inflating bromopropylene (6 millimoles) into the reaction kettle, stirring at room temperature until the air pressure is stable, placing the air pressure to 1MPa, and transferring the mixture into an oil bath at the temperature of 30 ℃ for reaction for 48 hours. The reaction was stopped and the autoclave was cooled to room temperature. And opening the high-pressure reaction kettle, pouring out the sample, and performing suction filtration. The filtrate was poured into 3 ml of water, extracted with ethyl acetate (3 ml × 3 times), the combined ethyl acetate phases were washed twice with water (3 ml × 2 times), once with saturated brine and dried over anhydrous sodium sulfate. The dried solution was rotary evaporated to remove the excess solvent, and the remaining product was subjected to column separation (eluent petroleum ether: ethyl acetate 10:1) to purify the product. The specific results are as follows:

TABLE 1 Synthesis of carbonate monomer yields c with different solvent and monomer concentrations

c: the pressure is 1 MPa; the temperature is 30 ℃; the time is 48 hours; the organic base is TMG; the alkyl halide is bromopropene; the amount of the alkyl halide used is 3 times the mole number of the diol.

The type of catalyst has an important effect on the synthesis of glycol based carbonate monomers and we will illustrate by the following comparative examples.

Example 3: dihydric alcohol-based carbonate polymerizable monomer

Weighing furandimethanol (1 mmol), DMF (3 ml), organic base (2 mmol) or inorganic base (3 mmol) in a high-pressure reaction kettle, stirring uniformly at room temperature, combining the reaction kettles, charging and discharging CO2 for three times, charging CO2 to 1-2 MPa, stirring uniformly at room temperature, discharging gas and pressing to 1MPa, and moving to 30 ℃ for reaction for 1 hour. After the reaction is finished, charging air into bromopropylene (6 millimole) and pumping into a reaction kettle, stirring at room temperature until the air pressure is stable, placing the air pressure to 1MPa, and transferring into an oil bath at 30 ℃ for reaction for 48 hours. The reaction was stopped and the autoclave was cooled to room temperature. And opening the high-pressure reaction kettle, pouring out the sample, and performing suction filtration. The filtrate was poured into 3 ml of water, extracted with ethyl acetate (3 ml × 3 times), the combined ethyl acetate phases were washed twice with water (3 ml × 2 times), once with saturated brine and dried over anhydrous sodium sulfate. The dried solution was rotary evaporated to remove the excess solvent, and the remaining product was subjected to column separation (eluent petroleum ether: ethyl acetate 10:1) to purify the product. The specific results are as follows:

TABLE 2 Synthesis of carbonate monomer yields d from different bases

d: the pressure is 1 MPa; the temperature is 30 ℃; the time is 48 hours; the alkyl halide is bromopropene; the amount of the halogenated alkane is 3 times of the mole number of the dihydric alcohol.

To investigate the effect of different pressure, temperature and time selections on the yield of the same polymerizable carbonate monomer obtained under different conditions, we illustrate by the following comparative examples.

example 4: dihydric alcohol-based carbonate polymerizable monomer

weighing furandimethanol (1 mmol), DMF (3 ml) and TMG (2 mmol) in a high-pressure reaction kettle, stirring uniformly at room temperature, combining the reaction kettles, charging and discharging CO2 for three times, charging CO2 to a certain MPa, stirring uniformly at room temperature, discharging gas until the gas pressure is stable, and moving to a certain temperature for reaction for 1 hour. And (3) after the reaction is finished, inflating bromopropylene (6 millimoles) into the reaction kettle, stirring at room temperature until the air pressure is stable, placing the air pressure to a certain MPa, and moving the reaction kettle to an oil bath at a certain temperature for reaction for a period of time. The reaction was stopped and the autoclave was cooled to room temperature. And opening the high-pressure reaction kettle, pouring out the sample, and performing suction filtration. The filtrate was poured into 3 ml of water, extracted with ethyl acetate (3 ml × 3 times), the combined ethyl acetate phases were washed twice with water (3 ml × 2 times), once with saturated brine, and dried over anhydrous sodium sulfate. The dried solution was rotary evaporated to remove the excess solvent, and the remaining product was subjected to column separation (eluent petroleum ether: ethyl acetate 10:1) to purify the product. The specific results are as follows:

TABLE 3 Synthesis of carbonate monomer yield e under different reaction conditions

e: the dihydric alcohol is furan dimethanol; the strong base is TMG; the alkyl halide is bromopropene; the amount of the alkyl halide used is 3 times of the mole number of the dihydric alcohol

By selecting the dihydric alcohols with different structures, the invention has certain universality and can construct various glycol-based carbonate polymerizable monomers.

Example 5: dihydric alcohol-based carbonate polymerizable monomer

Weighing dihydric alcohol (1 mmol), DMF (3 ml) and TMG (2 mmol) in a high-pressure reaction kettle, stirring uniformly at room temperature, combining the reaction kettles, charging and discharging CO2 for three times, charging CO2 to 1-2 MPa, stirring uniformly at room temperature, discharging gas and pressing to 1MPa, and moving to 30 ℃ for reaction for 1 hour. After the reaction is finished, charging air into bromopropylene (6 millimole) and pumping into the reaction kettle, stirring at room temperature until the air pressure is stable, placing the air pressure to 1 mega Pa, and transferring into an oil bath at 30 ℃ for reaction for 48 hours. The reaction was stopped and the autoclave was cooled to room temperature. And opening the high-pressure reaction kettle, pouring out the sample, and performing suction filtration. The filtrate was poured into 3 ml of water, extracted with ethyl acetate (3 ml × 3 times), the combined ethyl acetate phases were washed twice with water (3 ml × 2 times), once with saturated brine and dried over anhydrous sodium sulfate. The dried solution was rotary evaporated to remove the excess solvent, and the remaining product was subjected to column separation (eluent petroleum ether: ethyl acetate 10:1) to purify the product. The specific results are as follows:

TABLE 4 preparation of diol based polymerizable carbonate monomer yields f with different diols

The invention has certain universality through selecting the alkyl halides with different carbon chain lengths, and the structure of the polymerizable carbonate monomer can be regulated and controlled through selecting different structures, which is illustrated by the following examples.

Example 6: dihydric alcohol-based carbonate polymerizable monomer

weighing furandimethanol (1 mmol), DMF (3 ml) and TMG (2 mmol) in a high-pressure reaction kettle, stirring uniformly at room temperature, combining the reaction kettles, charging and discharging CO2 for three times, charging CO2 to 1-2 MPa, stirring uniformly at room temperature, discharging gas and pressing to 1MPa, and moving to 30 ℃ for reaction for 1 hour. After the reaction is finished, 6-bromine-1-hexene (6 millimoles) is charged into a reaction kettle, stirred at room temperature until the air pressure is stable, put under the pressure of 1MPa, and moved into an oil bath at 30 ℃ for reaction for 48 hours. The reaction was stopped and the autoclave was cooled to room temperature. And opening the high-pressure reaction kettle, pouring out the sample, and performing suction filtration. The filtrate was poured into 4 ml of water, extracted with ethyl acetate (4 ml × 3 times), the combined ethyl acetate phases were washed twice with water (4 ml × 2 times), once with saturated brine and dried over anhydrous sodium sulfate. The dried solution was rotary evaporated to remove the excess solvent, and the remaining product was subjected to column separation (eluent petroleum ether: ethyl acetate 10:1) to purify the product. A pale yellow liquid was obtained. 1H NMR (400MHz, CDCl3): delta 6.37(s,2H),5.77-5.82(m,2H),5.17(s,4H),4.98-5.13(m,2H), 4.83-4.88(m,2H),4.23(t, J ═ 8.8Hz,4H),2.13(d, J ═ 7.4Hz,4H), 1.57-1.61(m,8H).13C NMR (100MHz, CDCl3): delta 155.0,149.8,138.3, 115.0,112.2,77.2,68.4,61.2,33.3,28.1,25.0.IR: upsilon 3138,3078, 2934-.

example 7: dihydric alcohol-based carbonate polymerizable monomer

Weighing furandimethanol (1 mmol), DMF (3 ml) and TMG (2 mmol) in a high-pressure reaction kettle, stirring uniformly at room temperature, combining the reaction kettles, charging and discharging CO2 for three times, charging CO2 to 1-2 MPa, stirring uniformly at room temperature, discharging gas and pressing to 1MPa, and moving to 30 ℃ for reaction for 1 hour. After the reaction is finished, charging 10-bromo-1-decene (6 mmol) into a reaction kettle, stirring at room temperature until the air pressure is stable, placing the air pressure to 1MPa, and transferring to an oil bath at 30 ℃ for reaction for 48 hours. The reaction was stopped and the autoclave was cooled to room temperature. And opening the high-pressure reaction kettle, pouring out the sample, and performing suction filtration. The filtrate was poured into 4 ml of water, extracted with ethyl acetate (4 ml × 3 times), the combined ethyl acetate phases were washed twice with water (4 ml × 2 times), once with saturated brine and dried over anhydrous sodium sulfate. The dried solution was rotary evaporated to remove the excess solvent, and the remaining product was subjected to column separation (eluent petroleum ether: ethyl acetate 10:1) to purify the product. A pale yellow liquid was obtained. 1H NMR (400MHz, CDCl3) < delta > 6.38(s,4H),5.77-5.83(m,2H),5.17(s,4H),5.09-5.13(m,2H), 4.88-5.01(m,2H),4.13(t, J ═ 8Hz,4H),2.02-2.04(m,4H),1.60-1.66 (m,4H),1.28-1.36(m,10H) < 13C NMR (100MHz, CDCl3) < delta > 155.0,149.9, 139.2,114.3,112.2,77.2,68.6,61.2,33.9,29.4,29.2,29.1,29.0, 28.7,25.8.IR: upsilon 3135,3076, 2927-.

example 8: a method for preparing dihydric alcohol-based polycarbonate based on non-cyclic diene metathesis polymerization is as follows:

(1) Adding the diol-based carbonate monomer (1 mmol) obtained in any one of examples 1 to 7 into a reaction flask, putting the flask into an oil bath kettle at a certain temperature (60-120 ℃), reacting for 1 hour, then adding a catalyst (1 mol%) and an anti-isomerization reagent (2 mol%), and reacting for a period of time (12-36 hours);

(2) Adding tetrahydrofuran (3-5 ml) and ethyl vinyl ether (3-5 ml) into the product obtained in the step (1), reacting for 1 hour at room temperature, then dropwise adding into cold methanol (20 ml) for regeneration, washing and purifying to obtain the dihydric alcohol based polycarbonate.

the following examples are helpful in understanding this patent and are specific to the procedure used to prepare the same.

Example 9: preparation of dihydric alcohol-based polycarbonate based on non-cyclic diene metathesis polymerization

Weighing terephthalyl alcohol (1 mmol), DMF (3 ml) and tetramethylguanidine (2 mmol) in a high-pressure reaction kettle, stirring uniformly at room temperature, combining the reaction kettles, charging and discharging CO2 for three times, charging CO2 to 1-2 Mpa, stirring uniformly at room temperature, discharging gas and pressing to 1MPa, and moving to 30 ℃ for reaction for 1 hour. After the reaction is finished, charging air into bromopropylene (6 millimole) and pumping into a reaction kettle, stirring at room temperature until the air pressure is stable, placing the air pressure to 1MPa, and transferring into an oil bath at 30 ℃ for reaction for 48 hours. The reaction was stopped and the autoclave was cooled to room temperature. And opening the high-pressure reaction kettle, pouring out the sample, and performing suction filtration. The filtrate was poured into 4 ml of water, extracted with ethyl acetate (4 ml. times.3 times), the combined ethyl acetate phases were washed twice with water (4 ml. times.2 times), once with saturated brine, and dried over anhydrous sodium sulfate. The dried solution was rotary evaporated to remove the excess solvent, and the remaining product was subjected to column separation (eluent petroleum ether: ethyl acetate 10:1) to purify the product. A pale yellow liquid was obtained. Yield: a 44.6% of product.

Weighing 3-p-xylylene carbonate monomer (1 mmol) and adding into a 50 ml reaction bottle, adding a magnetic rotor, putting into oil at 80 ℃ in a pot, vacuumizing, stirring for 1 hour, and completely dissolving the monomer. After dissolution, the reaction flask was taken out, cooled to room temperature, added with Hoveyda-Grubbs catalyst (1 mol%) and p-benzoquinone (2 mol%), evacuated, put in a pot with oil at 80 ℃ and reacted for 24 h. After the reaction was completed, the reaction flask was taken out, cooled to room temperature, and then 3 ml of THF and 3 ml of ethyl vinyl ether were added to terminate the reaction. After the product was dissolved, it was added to 20 ml of cold methanol to precipitate, washed, and then the precipitate was dissolved with tetrahydrofuran and then added to cold methanol to wash the precipitate three times. And (4) drying the washed product in a vacuum drying oven at 40 ℃ for 24 h. A dark green solid was obtained. Yield: 78.6 percent. 1H NMR (400MHz, CDCl3, ppm). delta.7.38 (s,4H),5.89(s,2H),5.15(s, 4H),4.63(s,4H).13C NMR (100MHz, CDCl3, ppm). delta. 154.8,135.6,131.5, 128.6,77.5,77.2,76.8,69.4,67.2.IR: upsilonmax 2960,1740,1450,1391, 1235,1081,931,891,837,790,757cm-1.

the patent of the present invention has certain universality and can prepare various polycarbonate compounds through the selection of different diol carbonate monomers, and the details are shown in the following examples.

example 10: preparation of dihydric alcohol-based polycarbonate based on non-cyclic diene metathesis polymerization

Weighing dihydric alcohol carbonate monomer (1 mmol) and adding into a 50 ml reaction bottle, adding magnetic rotor, putting into 80 ℃ oil in a pot, vacuumizing, stirring for 1 hour, and completely dissolving the monomer. After dissolution, the reaction flask was taken out, cooled to room temperature, added with Hoveyda-Grubbs catalyst (1 mol%) and p-benzoquinone (2 mol%), evacuated, put in a pot with oil at 80 ℃ and reacted for 24 h. After the reaction was completed, the reaction flask was taken out, cooled to room temperature, and then 3 ml of THF and 3 ml of ethyl vinyl ether were added to terminate the reaction. After the product was dissolved, it was added to 20 ml of cold methanol to precipitate, washed, and then the precipitate was dissolved with tetrahydrofuran and then added to cold methanol to wash the precipitate three times. And (4) drying the washed product in a vacuum drying oven at 40 ℃ for 24 h.

TABLE 5 preparation of diol based polycarbonate from different diol based carbonate monomers yield a

In order to investigate the effect of the choice of different temperatures and reaction times on the yield of the same polycarbonate obtained under different conditions, we illustrate by means of the following comparative examples.

Example 11: preparation of dihydric alcohol-based polycarbonate based on non-cyclic diene metathesis polymerization

weighing 6-p-xylylene carbonate monomer (1 mmol) and adding into a 50 ml reaction bottle, adding a magnetic rotor, putting into 80 ℃ oil in a pot, vacuumizing, stirring for 1 hour, and completely dissolving the monomer. After dissolution, the reaction flask was taken out, cooled to room temperature, added with Hoveyda-Grubbs catalyst (1 mol%) and p-benzoquinone (2 mol%), evacuated, put in a pot with oil at 80 ℃ and reacted for 24 h. After the reaction was completed, the reaction flask was taken out, cooled to room temperature, and then 3 ml of THF and 3 ml of ethyl vinyl ether were added to terminate the reaction. After the product was dissolved, it was added to 20 ml of cold methanol to precipitate, washed, and then the precipitate was dissolved with tetrahydrofuran and then added to cold methanol to wash the precipitate three times. And (4) drying the washed product in a vacuum drying oven at 40 ℃ for 24 h. A dark green solid was obtained. Yield: 81.6 percent

TABLE 6 polycarbonate synthesis yields b at different temperatures

numbering	Reaction temperature (. degree.C.)	yield (%)	Catalyst and process for preparing same
				1	60	54.2	H.G
2	70	76.3	H.G
				3	80	81.6	H.G
4	90	77.8	H.G
				5	100	65.2	H.G
6	120	44.8	H.G

b: the diol-based carbonate monomer is 6-p-xylylene glycol-based carbonate monomer; the chain terminator is ethyl vinyl ether when the reaction time is 24 hours.

example 12: preparation of dihydric alcohol-based polycarbonate based on non-cyclic diene metathesis polymerization

Weighing 10-p-xylylene carbonate monomer (1 mmol) and adding into a 50 ml reaction bottle, adding a magnetic rotor, putting into oil at 80 ℃ in a pot, vacuumizing, stirring for 1 hour, and completely dissolving the monomer. After dissolution, the reaction flask was taken out, cooled to room temperature, added with Hoveyda-Grubbs catalyst (1 mol%) and p-benzoquinone (2 mol%), evacuated, put in a pot with 80 ℃ oil, and reacted for 24 hours. After the reaction was completed, the reaction flask was taken out, cooled to room temperature, and then 3 ml of THF and 3 ml of ethyl vinyl ether were added to terminate the reaction. After the product was dissolved, it was added to 20 ml of cold methanol to precipitate, washed, and then the precipitate was dissolved with tetrahydrofuran and then added to cold methanol to wash the precipitate three times. And (4) drying the washed product in a vacuum drying oven at 40 ℃ for 24 h. A dark green solid was obtained. Yield: 87.4 percent

TABLE 7 polycarbonate synthesis yields at different temperatures c

numbering	reaction time (hours)	Yield (%)	Catalyst and process for preparing same
				1	12	69.3	H.G
2	18	78.1	H.G
				3	24	87.4	H.G
4	30	89.3	H.G
				5	36	89.9	H.G

b: the diol-based carbonate monomer is 6-p-xylylene glycol-based carbonate monomer; the reaction time was 24 hours and the chain terminator was ethyl vinyl ether.

example 13: a click chemistry-based glycol-based polycarbonate prepared comprising the steps of:

(1) The diol based carbonate monomer (1 mmol) obtained in any one of examples 1 to 7 was dissolved in tetrahydrofuran (1 ml), and benzoin dimethyl ether (5 mol%) and a dimercapto compound (1 mmol) were added, and the mixture was placed in an ultraviolet crosslinking apparatus and irradiated under ultraviolet light (256nm to 365nm) for 1 to 10 hours.

(2) and (2) adding tetrahydrofuran (1-2 ml) into the product obtained in the step (1) for dissolving, then dropwise adding the product into cold methanol (20 ml) for regeneration, and washing and purifying to obtain the diol-based polycarbonate.

the following examples are helpful in understanding this patent and are specific to the procedure used to prepare the same.

example 14: dihydric alcohol-based polycarbonate prepared based on click chemistry

weighing terephthalyl alcohol (1 mmol), DMF (3 ml) and tetramethylguanidine (2 mmol) in a high-pressure reaction kettle, stirring uniformly at room temperature, combining the reaction kettles, charging and discharging CO2 for three times, charging CO2 to 1-2 Mpa, stirring uniformly at room temperature, discharging gas and pressing to 1MPa, and moving to 30 ℃ for reaction for 1 hour. After the reaction is finished, charging air into bromopropylene (6 millimole) and pumping into a reaction kettle, stirring at room temperature until the air pressure is stable, placing the air pressure to 1MPa, and transferring into an oil bath at 30 ℃ for reaction for 48 hours. The reaction was stopped and the autoclave was cooled to room temperature. And opening the high-pressure reaction kettle, pouring out the sample, and performing suction filtration. The filtrate was poured into 4 ml of water, extracted with ethyl acetate (4 ml. times.3 times), the combined ethyl acetate phases were washed twice with water (4 ml. times.2 times), once with saturated brine, and dried over anhydrous sodium sulfate. The dried solution was rotary evaporated to remove the excess solvent, and the remaining product was subjected to column separation (eluent petroleum ether: ethyl acetate 10:1) to purify the product. A pale yellow liquid was obtained. Yield: a 44.6% of product.

propanedithiol (1 mmol), 3-terephthaloyl carbonate monomer (1 mmol), benzoin dimethyl ether (DMPA, 5 mol%) were weighed out, dissolved with THF (1 ml) and placed in a vial. The vial was placed in a pre-set uv cross-linker and irradiated at 365nm for 2 hours. And (3) taking out the small bottle after the reaction is finished, dissolving the reacted product by using 1-2ml of tetrahydrofuran, separating out a precipitate by using 20 ml of cold methanol, washing for 3 times, and drying for 24 hours in vacuum at 40 ℃. A white solid was obtained. Yield: 98.2 percent. 1H NMR (400MHz, CDCl3, ppm): delta 7.38(s,4H),5.14(s,4H),4.24(t, J ═ 6.8Hz,4H),2.56-2.63(m,8H),1.81-1.95(m,4H),1.60(s,2H), 1.25(s,2H).13C NMR (100MHz, CDCl3, ppm): delta 155.0,135.6,128.6, 77.5,77.2,76.8,69.2,66.7,30.8,29.0,28.6,28.2.IR: upsilon max2957-2849, 5,1517,1453,1393,1253,1085-849,789cm-1.

The patent of the present invention has certain universality and can prepare various polycarbonate compounds through the selection of different diol carbonate monomers, and the details are shown in the following examples.

example 15: dihydric alcohol-based polycarbonate prepared based on click chemistry

Propanedithiol (1 mmol), diol-based carbonate monomer (1 mmol), benzoin dimethyl ether (DMPA, 5 mol%) were weighed out, dissolved with THF (1 ml) and placed in a vial. The vial was placed in a pre-set uv cross-linker and irradiated at 365nm for 2 hours. After the reaction is finished, the small bottle is taken out, the reacted product is dissolved by 1-2ml of tetrahydrofuran, precipitated by 20 ml of cold methanol, washed for 3 times and dried for 24 hours in vacuum at 40 ℃.

TABLE 8 preparation of diol based polycarbonate from different diol based carbonate monomers yield a

The universality of the preparation method and the regulation and control of the structure of the polycarbonate are proved to be certain feasibility by selecting different dimercapto compounds, and the polycarbonate compounds with different structural characteristics can be prepared. We illustrate by way of comparative examples as follows.

example 16: dihydric alcohol-based polycarbonate prepared based on click chemistry

1, 6-hexanedithiol (1 mmol), 3-terephthaloyl carbonate monomer (1 mmol), benzoin dimethyl ether (DMPA, 5 mol%) were weighed out and dissolved in THF (1 mL) in a vial. The vial was placed in a pre-set uv cross-linker and irradiated at 365nm for 2 hours. And (3) taking out the small bottle after the reaction is finished, dissolving the reacted product by using 1-2ml of tetrahydrofuran, precipitating by using 20 ml of cold methanol, washing for 3 times, and drying for 24 hours in vacuum at 40 ℃. A white solid was obtained, yield: 88.5 percent.

example 17: dihydric alcohol-based polycarbonate prepared based on click chemistry

1, 10-decanedithiol (1 mmol), 3-terephthaloyl carbonate monomer (1 mmol), benzoin dimethyl ether (DMPA, 5 mol%) were weighed out and dissolved in THF (1 ml) in a vial. The vial was placed in a pre-set uv cross-linker and irradiated at 365nm for 2 hours. And (3) taking out the small bottle after the reaction is finished, dissolving the reacted product by using 1-2ml of tetrahydrofuran, precipitating by using 20 ml of cold methanol, washing for 3 times, and drying for 24 hours in vacuum at 40 ℃. A white solid was obtained, yield: 84.7 percent.

In order to investigate the effect of the choice of different UV wavelengths and irradiation times on the yield of the same polycarbonate obtained under different conditions, we illustrate the following comparative examples.

Example 18: dihydric alcohol-based polycarbonate prepared based on click chemistry

propanedithiol (1 mmol), 3-terephthaloyl carbonate monomer (1 mmol), benzoin dimethyl ether (DMPA, 5 mol%) were weighed out, dissolved in THF (1 ml) and placed in a vial. The vial was placed in a pre-set uv cross-linker and irradiated under uv light for a period of time. And (3) taking out the bottle after the reaction is finished, dissolving the reacted product by using 1-2ml of tetrahydrofuran, precipitating the precipitate by using 20 ml of cold methanol, washing for 3 times, and drying for 24 hours in vacuum at 40 ℃.

TABLE 9 polycarbonate synthesis yields a under different reaction conditions

a: the diol-based carbonate monomer is a terephthalyl alcohol-based carbonate monomer; the dimercapto compound is propanedithiol.

Claims (10)

1. a diol-based carbonate polymerizable monomer, characterized in that: is prepared by taking dihydric alcohol, monohalogenated alkane and CO2 as raw materials.

2. The diol carbonate polymerizable monomer according to claim 1, wherein: the preparation method comprises the following steps:

(1) Adding the mixed solution of dihydric alcohol, an organic solvent and a catalyst into a high-pressure reaction kettle, covering the reaction kettle, introducing CO2 with the pressure of 0.1-10MPa, and reacting for 1-10 hours at the temperature of 0-80 ℃ to obtain a monocarbonate ionic compound intermediate solution A;

(2) Adding monohaloalkane containing carbon-carbon double bond or carbon-carbon triple bond into the solution A, maintaining the pressure of CO2 in a high-pressure reaction kettle at 0.1-10MPa, and reacting at 0-80 ℃ for 1-72 hours to obtain dihydric alcohol group carbonic ester polymerizable monomer solution B;

(3) and separating and purifying the solution B to obtain the dihydric alcohol base carbonic ester polymerizable monomer.

3. the diol carbonate polymerizable monomer according to claim 1 or 2, wherein: the diol is one of the following structures:

(1) aliphatic:

(2) Aromatic:

The mass concentration of the dihydric alcohol in the mixed solution in the step (1) is 5-50%;

The organic solvent is one or a mixture of two or more of N, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, acetonitrile, 1, 3-dimethyl-2-imidazolidinone or dimethyl sulfoxide;

the catalyst is one or two of cesium carbonate, potassium carbonate, sodium carbonate, lithium carbonate, sodium hydroxide, potassium hydroxide, triethylamine, tributylamine, pyridine, tetramethylguanidine, 1,5, 7-triazabicyclo [4,4,0] dec-5-ene, 7-methyl-1, 5, 7-triazabicyclo [4,4,0] dec-5-ene, 1, 8-diazabicycloundec-7-ene or 1, 5-diazabicyclo [4,3,0] non-5-ene; the dosage of the catalyst is 1 to 3 times of the mole number of the dihydric alcohol.

4. The diol carbonate polymerizable monomer according to claim 2, wherein the monohaloalkane containing a carbon-carbon double bond or a carbon-carbon triple bond is one of the following structures:

(a) Aliphatic alkyl halides: CnH2n-1X or CmH2m-3X, wherein n is more than or equal to 3 and less than or equal to 10, and m is more than or equal to 3 and less than or equal to 5; wherein X is halogen Cl, Br or I, the position of X is not limited, and the position of unsaturated bond is not limited;

(b) aromatic alkyl halides: C2H3ArCH2X, wherein X is a halogen Cl, Br or I, wherein the position of CH2X is not limited;

wherein the amount of the monohaloalkane substance added is 1 to 6 times the mole number of the diol.

5. A polymer prepared using the diol carbonate polymerizable monomer of any one of claims 1 to 4, having the formula:

wherein R1 is one of the following groups:

(1) Contains aliphatic carbon-carbon saturated groups and has the following structural general formula: -CnH2n-, wherein 3. ltoreq. n.ltoreq.10;

(2) An aromatic saturated group, -C2H4ArCH 2-;

the R2 group is one of the following structural formulas:

(1) Aliphatic:

(2) Aromatic:

The R3 group is one of the following structural formulas:

(1) Aliphatic: (x is more than or equal to 1 and less than or equal to 8),

(2) Aromatic:

6. the polymer prepared from the diol carbonate polymerizable monomer according to claim 5, wherein the polymer is prepared by:

(1) dissolving a dihydric alcohol carbonate polymerizable monomer in an organic solvent, adding a photoinitiator and a dimercapto compound, placing the mixture in an ultraviolet crosslinking instrument, and irradiating for 1-24 hours under the ultraviolet light of 190-400 nm;

(2) and (2) adding the product obtained in the step (1) into an organic solvent for dissolving, then adding the product into an anti-solvent for regeneration, washing and purifying to obtain the dihydric alcohol-based polycarbonate.

7. The polymer made from diol carbonate polymerizable monomer according to claim 6, wherein in said process:

The initiator is as follows: one of 2-hydroxy-methylphenylpropane-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- (4-methylthiophenyl) -2-morpholinyl-1-propanone, benzoin dimethyl ether, 2,4, 6-trimethylbenzoyldiphenylphosphine oxide, 4- (N, N-dimethylamino) ethyl benzoate, benzophenone or 4-chlorobenzophenone; the amount of the initiator is 0.5 to 30 percent of the mole number of the dihydric alcohol carbonate monomer;

The dimercapto compound is: one of biphenyl-4, 4 '-dithiol, 1, 5-dimercaptonaphthalene, bis (2-mercaptoethyl) ether, dimercaptoethyl sulfide, 2, 5-dimercaptothiadiazole, ethanedithiol, propanedithiol, butanedithiol, pentanedithiol, hexanedithiol, heptanedithiol, nonanedithiol, decanedithiol, dimercaprol, 3, 6-dioxa-1, 8-octanedithiol, 2, 3-butanedithiol, 1, 2-benzenedithiol, toluene-3, 4-dithiol, terephthal thiol, isophthal thiol, terephthal thiol, m-benzenedimethylthiol, or 4,4' -dithiodiphenyl; the mercapto compound is used in an amount of 1 time the moles of the diol-based carbonate polymerizable monomer.

8. a polymer prepared using the diol carbonate polymerizable monomer of any one of claims 1 to 4, having the formula:

wherein the R1 group is as follows:

(2) contains aliphatic carbon-carbon saturated groups and has the following structural general formula: -CnH2n-, wherein 1. ltoreq. n.ltoreq.8;

(2) An aromatic saturated group, -CHARCH 2-;

the R2 group is one of the following structural formulas:

(1) Aliphatic:

(2) aromatic:

9. The polymer prepared from the diol carbonate polymerizable monomer according to claim 8, wherein the polymer is prepared by:

(1) adding a dihydric alcohol carbonate monomer into a reaction bottle, putting the reaction bottle into an oil bath kettle at the temperature of 30-150 ℃, reacting for 1-10 hours, then adding a catalyst and an anti-isomerization reagent, and reacting for 1-48 hours;

(2) and (2) adding the product obtained in the step (1) into an organic solvent and ethyl vinyl ether, reacting for 1-10 hours at room temperature, then dropwise adding the product into an anti-solvent for regeneration, washing and purifying to obtain the dihydric alcohol-based polycarbonate.

10. a polymer made from a diol carbonate polymerizable monomer according to claim 9, wherein:

The catalyst is one of Grubbs1st, Grubbs2nd, Hoveyda-Grubbs 1st or Hoveyda-Grubbs 2 nd; the dosage of the catalyst is 0.5 to 30 percent of the mole number of the dihydric alcohol carbonate monomer;

The anti-isomerization reagent is benzoquinone, naphthoquinone, phenanthrenequinone or anthraquinone; the dosage of the isomerization-preventing reagent is 0.5 to 30 percent of the mole number of the dihydric alcohol carbonate monomer.