CN110540529B - Dihydric alcohol-based carbonate polymerizable monomer and polymer thereof - Google Patents
Dihydric alcohol-based carbonate polymerizable monomer and polymer thereof Download PDFInfo
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- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
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- C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
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- C08G64/30—General preparatory processes using carbonates
Abstract
The invention discloses a dihydric alcohol group carbonic ester polymerizable monomer and a polymer thereof, wherein the monomer is prepared from dihydric alcohol, monohaloalkane and CO 2 Is prepared by taking the raw materials 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) And adding the product into an organic solvent, then adding the product into an anti-solvent for regeneration, washing and purifying to obtain the diol-based polycarbonate. Or prepared by the following method: (1) Adding the monomer into a Schlenk bottle, performing 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
Technical Field
The invention relates to a carbonate polymerizable monomer and a polymer thereof, in particular to a diol carbonate polymerizable monomer and a polymer thereof.
Background
With the increasing consumption of fossil resources and the growing awareness that fossil resources are finite, there is an increasing interest in producing chemicals from renewable and sustainable carbon resources. Of which carbon dioxide is one of the main gases causing the greenhouse effect, causing environmental problems that are becoming more and more serious, and which is particularly attractive due to its availability, low cost, abundance and non-toxicity, and also being a waste product produced in many industrial processes, 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 biomass-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 due to the structural characteristics of the furan-based compound, the chemical property similar to that of a benzene ring is also provided, the rigidity is high, the source of the furan-based compound is rich, the furan-based compound can be obtained from renewable resources such as glucose, fructose and cellulose, fructose can be formed through isomerization of glucose, then the fructose is subjected to dehydration reaction to obtain the platform compound of 5-hydroxymethylfurfural [ see ACS Catalysis,2012,2,930-934 ], and then the platform compound is subjected to reaction with sodium borohydride in an ice bath to obtain the target product of 2, 5-furandimethanol [ see RSC Advances,2016,6, 83470-466 ].
Based on previous researches, one of the most industrialized processes for synthesizing polycarbonate is to synthesize polycarbonate by using bisphenol A and phosgene [ see Chemical Engineering Science 1986, 41,2939-2952 ], however, phosgene is a toxic gas, the source of phosgene is also a toxic gas, hydrogen chloride gas is released during the synthesis of polycarbonate, and the environment is polluted, so that a non-toxic and green synthetic route is required for synthesizing polycarbonate. Michael R.Kember [ see Chemical communications 2011,47,141-163 ] et al, have studied the copolymerization of carbon dioxide and epoxide using a catalyst to synthesize polycarbonate, and although the polycarbonate is successfully synthesized, the molecular weight of the synthesized polycarbonate is very limited, and since cyclic carbonate is generated during the polymerization process, a high molecular weight polymer cannot be synthesized. Then, ring-opening polymerization of cyclic carbonate monomers is developed, and through research on the ring-opening polymerization reaction induced by heat of trimethyl carbonate, a variety of ring-opening processes are developed according to different mechanisms such as anion polymerization, cation polymerization and coordination polymerization, and Sarah Tempeaar [ see chem.Soc.Rev 2013,42,1312-1336 ], et al, study on the preparation of polycarbonates by ring-opening polymerization, firstly, a plurality of cyclic carbonate monomers with different functionalities are synthesized, 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, which 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 high reaction conditions of 180 ℃ at high temperature, so that the reaction conditions were severe and energy consumption required for the reaction was high. Shen et al (see Green chem.,2017,19, 4930-4938) proposed a new strategy to prepare furan dicarboxylic acid based polyesters by melt polycondensation using dimethyl 2, 5-furan dicarboxylate and a diol containing a long alkyl chain, which strategy by-product is volatile methanol rather than a diol with 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 thereof exist.
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 which is prepared from dihydric alcohol, monohaloalkane and CO 2 As a raw material preparationAnd (4) obtaining the finished product.
The diol carbonate polymerizable monomer is prepared by the following specific method:
(1) Adding the mixed solution of dihydric alcohol, organic solvent and catalyst into a high-pressure reaction kettle, covering the reaction kettle, and introducing 0.1-10MPa CO 2 Reacting for 1-10 hours at 0-80 ℃ to obtain monocarbonate ionic compound intermediate solution A;
(2) Adding monohaloalkane containing carbon-carbon double bond or carbon-carbon triple bond into the solution A, and maintaining CO in the high-pressure reaction kettle 2 Reacting for 1-72 hours at 0-80 ℃ under the pressure of 0.1-10MPa to obtain dihydric alcohol base carbonic 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 compounds:
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, 0] dec-5-ene, 7-methyl-1, 5, 7-triazabicyclo [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: c n H 2n-1 X or C m H 2m-3 X, wherein n is more than or equal to 3 and less than or equal to 10, 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: c 2 H 3 ArCH 2 X, wherein X is halogen Cl, br or I, wherein CH 2 The position of X 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 R is 1 Is one of the following groups:
(1) Contains aliphatic carbon-carbon saturated groups and has the following structural general formula: -C n H 2n -n is greater than or equal to 3 and less than or equal to 10;
(2) Aromatic saturated radical, -C 2 H 4 ArCH 2 -；
R 2 The group is one of the following structural formulas:
(1) Aliphatic:
(2) Aromatic:
R 3 the group is one of the following structural formulas:
(1) Aliphatic:
(1≤x≤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, octanedithiol, nonanedithiol, decanedithiol, dimercaprol, 3, 6-dioxa-1, 8-octanedithiol, 2, 3-butanedithiol, 1, 2-benzenedithiol, toluene-3, 4-dithiol, terephthalenethiol, isophthalylthiol, terephthalenethiol, m-benzenedimethylthiol, or 4,4' -dithiodiphenyl; the mercapto compound is used in an amount of 1 time the moles of the diol-based carbonate monomer.
The polymer prepared from the diol carbonate polymerizable monomer has the following structural formula:
wherein R is 1 The groups are as follows:
(2) Contains aliphatic carbon-carbon saturated groups and has the following structural general formula: -C n H 2n -n is greater than or equal to 1 and less than or equal to 8;
(2) Aromatic saturated group, -CHARCH 2 -；
R 2 The 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) 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.
The polymer prepared by the diol based carbonate polymerizable monomer,
the catalyst is one of Grubbs 1st, grubbs 2nd, 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 isomerization-preventing 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 function catalysis, and can efficiently construct a carbonate ester intermediate containing carbonate ester bonds by a bio-based platform compound furandimethanol. 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 dihydric alcohol group carbonate polymerizable monomers with various structures, has simple preparation method and mild reaction conditions, and provides abundant raw materials 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 CO 2 Three times, charging CO 2 Stirring the mixture evenly at room temperature to 1-2 MPa, discharging gas and pressing the mixture to 1MPa, and moving the mixture to 30 ℃ for reaction for 1 hour. After the reaction is finished, charging bromopropylene (6 millimole) into a reaction kettle by air inflation, stirring at room temperature until the air pressure is stable, placing the air pressure to 1MPa, and transferring the air pressure 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 excess solvent, and then the remaining product was subjected to column separation (eluent petroleum ether: ethyl acetate = 10. Obtained as a light yellow liquid, yield: product a, 46.7%, product b, 17.0%. 1 H NMR(400MHz,)δ6.42(d,J＝3.3Hz,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). 13 C NMR(100MHz,CDCl 3 ):δ155.5,139.6, 132.1,118.2,107.8,68.4,63.2.IR:υ max 3133,3089,3017-2889,1747, 1649,1560,1450-1385,1245,1077,949,790cm -1 。
The influence of the type 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 furandimethanol (1 mmol), organic solvent (3 ml) and TMG (2 mmol) in a high-pressure reaction kettle, stirring uniformly at room temperature, combining the reaction kettles, charging and discharging CO 2 Three times, charging CO 2 Stirring to 1-2 MPa, discharging gas to 1MPa, and reacting at 30 deg.C for 1 hr. After the reaction is finished, charging bromopropene (6 mmol) into the reactorStirring at room temperature in a kettle until the air pressure is stable, placing the air pressure to 1MPa, and transferring the kettle 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 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 excess solvent and the remaining product was subjected to column separation (eluent petroleum ether: ethyl acetate = 10). The specific results are as follows:
TABLE 1 Synthesis of carbonate monomer yields at different solvent and monomer concentrations c
c: the pressure is 1MPa; the temperature is 30 ℃; the time is 48 hours; the organic base is TMG; the alkyl halide is bromopropylene; the amount of the alkyl halide used is 3 times of the mole number of the dihydric alcohol.
The type of catalyst has an important effect on the synthesis of glycol based carbonate monomers and we will illustrate it 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 CO 2 Three times, filling with CO 2 Stirring to 1-2 MPa, discharging gas to 1MPa, and reacting at 30 deg.C for 1 hr. 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. Times.3 times), the combined ethyl acetate phases were washed twice with water(3 ml. Times.2 times), washed once with saturated brine, and dried over anhydrous sodium sulfate. The dried solution was rotary evaporated to remove excess solvent, and then the remaining product was subjected to column separation (eluent petroleum ether: ethyl acetate = 10. The specific results are shown in the following table:
TABLE 2 Synthesis of carbonate monomer yield from different bases d
d: the pressure is 1MPa; the temperature is 30 ℃; the time is 48 hours; the alkyl halide is bromopropylene; the amount of the alkyl halide used is 3 times the mole number of the diol.
In order 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 CO 2 Three times, charging CO 2 Stirring at room temperature under certain MPa, releasing gas until the pressure is stable, and moving to a certain temperature for reaction for 1 hour. After the reaction is finished, charging 6 millimole of bromopropylene into a reaction kettle, stirring at room temperature until the air pressure is stable, placing the air pressure to a certain megapascal, and transferring the mixture into 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 excess solvent and the remaining product was subjected to column separation (eluent petroleum ether: ethyl acetate = 10). The specific results are shown in the following table:
TABLE 3 different reaction stripsYield of under-part synthesized carbonate monomer e
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 CO 2 Three times, charging CO 2 Stirring to 1-2 MPa, discharging gas to 1MPa, and reacting at 30 deg.C for 1 hr. 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 excess solvent, and then the remaining product was subjected to column separation (eluent petroleum ether: ethyl acetate = 10. The specific results are as follows:
TABLE 4 differencesYield of diol-based polymerizable carbonate monomer prepared from dihydric alcohol f
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 CO 2 Three times, filling with CO 2 Stirring the mixture evenly at room temperature to 1-2 MPa, discharging gas and pressing the mixture to 1MPa, and moving the mixture 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, and then the air pressure is increased to 1MPa, and the mixture is 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 excess solvent and the remaining product was subjected to column separation (eluent petroleum ether: ethyl acetate = 10). A pale yellow liquid was obtained. 1 H NMR(400MHz,CDCl 3 ): δ6.37(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). 13 C NMR(100MHz,CDCl 3 ):δ155.0,149.8,138.3, 115.0,112.2,77.2,68.4,61.2,33.3,28.1,25.0.IR:υ max 3138,3078, 2934-2860,1748,1640,1565,1455-1370,1248,995-914,791cm -1 .
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 CO 2 Three times, charging CO 2 Stirring the mixture evenly at room temperature to 1-2 MPa, discharging gas and pressing the mixture to 1MPa, and moving the mixture to 30 ℃ for reaction for 1 hour. After the reaction is finished, charging 10-bromo-1-decene (6 mmol) into a reaction kettle by inflation, stirring at room temperature until the air pressure is stable, placing the air pressure to 1MPa, and moving 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 excess solvent, and then the remaining product was subjected to column separation (eluent petroleum ether: ethyl acetate = 10. A pale yellow liquid was obtained. 1 H NMR(400MHz,CDCl 3 ): δ6.38(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). 13 C NMR(100MHz,CDCl 3 ):δ155.0,149.9, 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:υ max 3135,3076,2927-2855,1747,1640,1565, 1455-1369,1249,996-910,791cm -1 。
Example 8: a method for preparing dihydric alcohol-based polycarbonate based on acyclic 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 bottle, putting the reaction bottle 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 agent (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 at room temperature for 1 hour, then dropwise adding into cold methanol (20 ml) for regeneration, washing and purifying to obtain the diol-based polycarbonate.
The following examples are helpful in understanding this patent and specify the procedures for the preparation.
Example 9: preparation of dihydric alcohol-based polycarbonate based on non-cyclic diene metathesis polymerization
Weighing terephthalyl alcohol (1 mmol), DMF (3 mL), tetramethylguanidine (2 mmol) in a high-pressure reaction kettle, stirring uniformly at room temperature, combining the reaction kettle, charging and discharging CO 2 Three times, charging CO 2 Stirring to 1-2 MPa, discharging gas to 1MPa, and reacting at 30 deg.C for 1 hr. 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 × 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 excess solvent and the remaining product was subjected to column separation (eluent petroleum ether: ethyl acetate = 10). 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 oil at 80 ℃ into the 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 24h. 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 is dissolved, it is added to 20 ml of cold methanol for precipitation, washed, and then the precipitate is dissolved with tetrahydrofuran and added to cold methanol for washing the precipitate three times. The washed product was dried in a vacuum oven at 40 ℃ for 24h. A greenish black solid was obtained. Yield: 78.6 percent. 1 H NMR(400MHz,CDCl 3 ,ppm):δ7.38(s,4H),5.89(s,2H),5.15(s, 4H),4.63(s,4H). 13 C NMR(100MHz,CDCl 3 ,ppm):δ154.8,135.6,131.5, 128.6,77.5,77.2,76.8,69.4,67.2.IR:υ max 2960,1740,1450,1391, 1235,1081,931,891,837,790,757cm -1 .
The patent of the present invention has certain universality through the selection of different diol-based carbonate monomers, and can prepare various polycarbonate compounds, which is specifically illustrated by the following examples.
Example 10: preparation of dihydric alcohol-based polycarbonate based on non-cyclic diene metathesis polymerization
Weighing dihydric alcohol based carbonate monomer (1 mmol) and adding into a 50 ml reaction bottle, adding a magnetic rotor, putting into oil with the temperature of 80 ℃ in a pot, vacuumizing, stirring for 1 hour, and completely dissolving the monomer. After the catalyst is dissolved, the reaction bottle is taken out, cooled to room temperature, added with Hoveyda-Grubbs catalyst (1 mol%) and p-benzoquinone (2 mol%), vacuumized, put into oil at 80 ℃ 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 is dissolved, it is added to 20 ml of cold methanol for precipitation, washed, and then the precipitate is dissolved with tetrahydrofuran and added to cold methanol for washing the precipitate three times. And (4) drying the washed product in a vacuum drying oven at 40 ℃ for 24h.
TABLE 5 yield of diol based polycarbonate prepared from different diol based carbonate monomers 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 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 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 24h. 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 24h. A greenish black solid was obtained. Yield: 81.6 percent
TABLE 6 polycarbonate synthesis yields at different temperatures b
| Number of | 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 a 6-p-xylylene glycol-based carbonate monomer; the reaction time was 24 hours and the chain terminator was ethyl vinyl ether.
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 oil at 80 ℃ and reacted for 24h. 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. The washed product was dried in a vacuum oven at 40 ℃ for 24h. A greenish black solid was obtained. Yield: 87.4 percent
TABLE 7 polycarbonate synthesis yields at different temperatures c
| Number of | Reaction time (hours) | Yield (%) | Catalyst and process for producing the 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 a 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), followed by addition of benzoin dimethyl ether (5 mol%) and a dimercapto compound (1 mmol), and the resulting solution was placed in an ultraviolet crosslinking apparatus and irradiated under ultraviolet light (256 nm to 365 nm) 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 for understanding this patent and are specific to the procedure detailed.
Example 14: dihydric alcohol-based polycarbonate prepared based on click chemistry
Weighing terephthalyl alcohol (1 mmol), DMF (3 mL), tetramethylguanidine (2 mmol) in a high-pressure reaction kettle, stirring uniformly at room temperature, combining the reaction kettle, charging and discharging CO 2 Three times, filling with CO 2 Stirring the mixture evenly at room temperature to 1-2 MPa, discharging gas and pressing the mixture to 1MPa, and moving the mixture 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 × 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 excess solvent and the remaining product was subjected to column separation (eluent petroleum ether: ethyl acetate = 10). 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. After the reaction is finished, the small bottle is taken out, the reacted product is dissolved by 1-2ml of tetrahydrofuran, 20 ml of cold methanol is used for separating out a precipitate, the precipitate is washed for 3 times, and the vacuum drying is carried out for 24 hours at the temperature of 40 ℃. A white solid was obtained. Yield: 98.2 percent. 1 H NMR(400MHz,CDCl 3 ,ppm):δ7.38(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). 13 C NMR(100MHz,CDCl 3 ,ppm):δ155.0,135.6,128.6, 77.5,77.2,76.8,69.2,66.7,30.8,29.0,28.6,28.2.IR:υ max 2957-2849,1745,1517,1453,1393,1253,1085-849,789cm -1 .
The selection of different diol-based carbonate monomers can show that the invention has certain universality and can prepare various polycarbonate compounds, and the preparation method is specifically illustrated by 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 in 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, 20 ml of cold methanol is used for separating out a precipitate, the precipitate is washed for 3 times, and the vacuum drying is carried out for 24 hours at the temperature of 40 ℃.
TABLE 8 yield of diol based polycarbonate prepared from different diol based carbonate monomers a
The universality of the preparation method and the regulation and control of the structure of the polycarbonate are demonstrated by the selection of 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%) was 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. After the reaction is finished, taking out the small bottle, dissolving the reacted product by 1-2ml of tetrahydrofuran, precipitating by 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. After the reaction is finished, the small bottle is taken out, the reacted product is dissolved by 1-2ml of tetrahydrofuran, 20 ml of cold methanol is used for separating out a precipitate, the precipitate is washed for 3 times, and the vacuum drying is carried out for 24 hours at the temperature of 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 with 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. After the reaction is finished, the small bottle is taken out, the reacted product is dissolved by 1-2ml of tetrahydrofuran, 20 ml of cold methanol is used for separating out a precipitate, the precipitate is washed for 3 times, and the vacuum drying is carried out for 24 hours at the temperature of 40 ℃.
TABLE 9 polycarbonate synthesis yields under different reaction conditions a
a: the diol-based carbonate monomer is a terephthalyl alcohol-based carbonate monomer; the dimercapto compound is propanedithiol.
Claims (3)
1. A polymer prepared from a diol based carbonate polymerizable monomer, wherein the polymer has the following structural formula:
wherein R is 1 Is one of the following groups; contains aliphatic carbon-carbon saturated groups and has the following structural general formula: -C m H 2m -m is more than or equal to 3 and less than or equal to 10;
R 2 the group is one of the following structural formulas:
(1) Aliphatic:
(2) Aromatic:
；
R 3 the group is one of the following structural formulas:
aliphatic:
(1≤x≤8)、
2. the polymer prepared from glycol based carbonate polymerizable monomers according to claim 1, wherein the polymer is prepared by the following method:
(1) Adding the mixed solution of the dihydric alcohol, the organic solvent and the catalyst into a high-pressure reaction kettle, covering the reaction kettle, and introducing 0.1-10MPa of CO 2 In the range of 0 to 80 o C, reacting for 1-10 hours to obtain monocarbonate ionic compound intermediate solution A;
the diol is one of the following structures:
(a) Aliphatic:
(b) Aromatic:
the mass concentration of the dihydric alcohol 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, 0] dec-5-ene, 7-methyl-1, 5, 7-triazabicyclo [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;
(2) Adding monohaloalkane containing carbon-carbon double bond into the solution A, and maintaining CO in the high-pressure reaction kettle 2 The pressure is 0.1-10MPa and 0-80 o C, reacting for 1-72 hours to obtain a dihydric alcohol base carbonic ester polymerizable monomer solution B;
the monohaloalkane containing carbon-carbon double bonds is one of the following structures:
C m H 2m-1 x, wherein m is more than or equal to 3 and less than or equal to 10; wherein X is halogen Cl, br or I, the position of X is not limited, and the position of unsaturated bond is not limited;
wherein the amount of the monohalogenated alkane added is 1 to 6 times of the mole number of the dihydric alcohol;
(3) Separating and purifying the solution B to obtain a dihydric alcohol base carbonic ester polymerizable monomer;
(4) 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;
(5) And (5) adding the product obtained in the step (4) 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.
3. The polymer prepared from glycol based carbonate polymerizable monomers according to claim 2, wherein in the method:
the photoinitiator 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 using amount of the photoinitiator is 0.5 to 30 percent of the mole number of the dihydric alcohol carbonate monomer;
the dimercapto compound is: one of dimercaptoethyl sulfide, ethanedithiol, propanedithiol, butanedithiol, pentanedithiol, hexanedithiol, heptanedithiol, octanedithiol, dimercaptopropanol, 3, 6-dioxa-1, 8-octanedithiol, and 2, 3-butanedithiol; the amount of the dimercapto compound is 1 time of the mole number of the dihydric alcohol based carbonate polymerizable monomer.
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