CN113881030A - Low-molecular-weight carbon dioxide-cyclohexene oxide copolymer, preparation method thereof and epoxy-terminated polycyclohexene carbonate - Google Patents
Low-molecular-weight carbon dioxide-cyclohexene oxide copolymer, preparation method thereof and epoxy-terminated polycyclohexene carbonate Download PDFInfo
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
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- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
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- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
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Abstract
The invention provides a low molecular weight carbon dioxide-cyclohexene oxide copolymer, which has a structure shown in a formula (I). The invention adopts the oligomeric porphyrin aluminum catalyst and a specific preparation route to catalyze the copolymerization of carbon dioxide and cyclohexene oxide, and the low molecular weight poly (cyclohexene carbonate) with controllable molecular weight is prepared. The invention also performs epoxidation modification on the terminal group of the polycyclohexene carbonate to obtain the epoxy-terminated polycyclohexene carbonate, and obtains the carbon dioxide-based epoxy resin which is biodegradable and has excellent performance, thereby realizing high-value utilization of carbon dioxide and substitution of the traditional petroleum-based epoxy resin, and having the advantages of high-value utilization of carbon dioxide and capability of replacing the traditional petroleum-based epoxy resinAnd (4) biodegradation. And the main body of the polycyclohexene carbonate is an alicyclic structure, a carbonate group and an ether group, wherein the alicyclic structure can provide certain rigidity and toughness for the polymer and resist corrosion, the carbonate structure provides biodegradation performance of the material, and the ether bond provides flexibility of a molecular chain.
Description
Technical Field
The invention belongs to the technical field of carbon dioxide-based biodegradable coatings/adhesives, and relates to a carbon dioxide-based copolymer and a preparation method thereof, epoxy-terminated polycyclohexene carbonate and application thereof, in particular to a low-molecular-weight carbon dioxide-cyclohexene oxide copolymer and a preparation method thereof, and epoxy-terminated polycyclohexene carbonate and application thereof.
Background
The thermosetting epoxy resin has good comprehensive mechanical property, excellent insulativity, good cohesive force, small shrinkage and good stability, and can be widely used as a coating, an adhesive, a composite material resin matrix, an electronic packaging material, a pouring material and the like in the fields of chemical industry, machinery, electronics, aerospace and the like. The traditional epoxy resin takes bisphenol A and other petrochemical products as raw materials, generates huge consumption on fossil energy, is difficult to recover, causes huge waste on resources, and pollutes the environment. Therefore, the development of the biodegradable epoxy resin with renewable resources as raw materials is of great significance.
At present, bio-based epoxy resin is taken as a hotspot of current research, and an epoxy group is obtained by modifying a compound with biological origin through subsequent reaction and is used as epoxy resin to replace the traditional petroleum-based material. Although the sources of bio-based resources are wide, the purification steps of bio-based resources are often complicated, and multiple post-modifications are often needed to reach the use standard, so that the cost of the product is increased. Carbon dioxide is a greenhouse gas and is also a renewable carbon-oxygen resource, and the high-value utilization of carbon dioxide in the chemical industry is a research hotspot in recent years. Can be copolymerized with an epoxy compound under the catalysis of a proper catalyst to obtain a polymer, so that the carbon dioxide is fixed, and the polymer is endowed with economic value and environmental protection value, and at present, the copolymerization product of the carbon dioxide and the propylene oxide, namely the poly (lactide-co-carbonate) (PPC), is already taken as a biodegradable product to realize industrial production, and has wide application in the aspects of mulching films and food packaging. The copolymer of carbon dioxide and cyclohexene oxide, namely the polycyclohexene carbonate (PCHC), has high glass transition temperature and mechanical strength, but has poor elongation at break, and is difficult to directly process and utilize.
Therefore, how to obtain a high-performance PCHC material and realize the application thereof is a research focus in the field of carbon dioxide-based materials, and is one of the focuses of great concern of many prospective researchers in the field.
Disclosure of Invention
The invention provides a copolymer of low molecular weight carbon dioxide and cyclohexene oxide, which not only has better comprehensive performance, but also can obtain biodegradable carbon dioxide-based epoxy resin with excellent performance, thereby realizing the substitution of the traditional petroleum-based epoxy resin.
The invention provides a low molecular weight carbon dioxide-cyclohexene oxide copolymer, which has a structure shown in a formula (I);
wherein x is 1-70; y is 1-40; n is 2-6;
R1is selected from
Preferably, the number average molecular weight of the low molecular weight carbon dioxide-cyclohexene oxide copolymer is 500-10000;
the carbon dioxide-cyclohexene oxide copolymer is polycarbonate cyclohexene ester;
x is 1-30;
and y is 1-10.
The invention provides a preparation method of a low molecular weight carbon dioxide-cyclohexene oxide copolymer, which comprises the following steps:
1) under the atmosphere of carbon dioxide, reacting cyclohexene oxide, a catalyst, a cocatalyst and an initiator to obtain a low-molecular-weight carbon dioxide-cyclohexene oxide copolymer with a structure shown in a formula (I);
wherein x is 1-70; y is 1-40; n is 2-6;
R1is selected from
Preferably, the catalyst comprises an oligomeric porphyrin aluminum catalyst;
the cocatalyst comprises bis (triphenylphosphoranylidene) ammonium chloride;
the initiator comprises one or more of carboxylic acid compounds, alcohol compounds and phenolic compounds;
the mol ratio of cyclohexene oxide to the initiator is (10-100): 1;
the mol ratio of the cyclohexene oxide to the aluminum metal in the oligomeric porphyrin aluminum catalyst is (5000-50000): 1;
the mol ratio of the cyclohexene oxide to the cocatalyst is (5000-50000): 2.
preferably, the catalyst has a structure represented by formula (II):
wherein n is the polymerization degree of oligomeric porphyrin aluminum, and n is 4-20;
the initiator comprises terephthalic acid and/or terephthalyl alcohol;
the reaction temperature is 70-150 ℃;
the reaction time is 4-24 h;
the carbon dioxide atmosphere is under the condition that the pressure of carbon dioxide is 3-6 MPa;
after the reaction is finished, the method also comprises the steps of washing the product with methanol and heating and purifying the product under vacuum condition.
The invention provides epoxy-terminated polycyclohexene carbonate, which has a structure shown in a formula (III);
wherein x is 1-70; y is 1-40; n is 2-6;
R1is selected from
Preferably, the polycyclohexene carbonate comprises the carbon dioxide-cyclohexene oxide copolymer as described in any one of claims 1 to 2 or the carbon dioxide-cyclohexene oxide copolymer prepared by the preparation method as described in any one of claims 3 to 5;
the epoxy-terminated polycyclohexene carbonate is carbon dioxide-based epoxy resin;
the preparation process of the epoxy-terminated polycyclohexene carbonate comprises the following steps:
(1) mixing the polycyclohexene carbonate, triethylamine and an organic solvent, and then adding methacryloyl chloride to carry out a first reaction to obtain the polycyclohexene carbonate terminated by olefin;
(2) and carrying out a second reaction on the olefin-terminated polycyclohexene carbonate obtained in the step, peroxide and an organic solvent to obtain the epoxy-terminated polycyclohexene carbonate.
Preferably, the mixing temperature is-20 to 20 ℃;
the temperature of the first reaction is 25-40 ℃;
the first reaction time is 0.5-12 h;
the molar ratio of the polycyclohexene carbonate to triethylamine is 1: (2.8-4.5);
the mol ratio of the polycyclohexene carbonate to the methacrylic acid chloride is 1: (2.4-3.0).
Preferably, the organic solvent comprises one or more of dichloromethane, chloroform, ethyl acetate, tetrahydrofuran, dioxane and diethyl ether;
the peroxide comprises one or more of m-chloroperoxybenzoic acid, peroxybenzoic acid, peroxyacetic acid and trifluoroperoxyacetic acid;
the mol ratio of the olefin-terminated polycyclohexene carbonate to the peroxide is 1: (2.4-4.0);
the temperature of the second reaction is 40-50 ℃;
the time of the second reaction is 24-72 hours.
The invention also provides application of the epoxy-terminated polycyclohexene carbonate in any one of the technical schemes in the field of epoxy resin.
The invention provides a low molecular weight carbon dioxide-cyclohexene oxide copolymer, which has a structure shown in a formula (I). Compared with the prior art, the invention aims at the limitation that the existing copolymer of carbon dioxide and cyclohexene oxide, namely the polycyclohexene carbonate has higher glass transition temperature and mechanical strength, but has poorer elongation at break and is difficult to directly process and utilize.
The invention creatively adopts the oligomeric porphyrin aluminum catalyst and a specific preparation route to catalyze the copolymerization of carbon dioxide and cyclohexene oxide, and prepares the low molecular weight carbon dioxide-cyclohexene oxide copolymer with controllable molecular weight, namely the polycarbonate cyclohexene ester. Compared with high molecular weight poly (cyclohexene carbonate), the molecular weight-controllable low molecular weight carbon dioxide-cyclohexene oxide copolymer has higher end group reactivity and is easier to modify, so that epoxy-terminated poly (cyclohexene carbonate) can be obtained subsequently, and resin with a high epoxy value can be obtained after modification, thereby being more favorable for subsequent curing and use.
According to the invention, through analyzing the structure of the polycyclohexene carbonate, the alicyclic structure can provide certain rigidity and toughness for the polymer and resist corrosion, the carbonate structure provides the biodegradation performance of the material, and the ether bond provides certain flexibility for a molecular chain, so that the end group of the polycyclohexene carbonate is chemically modified, and epoxy-terminated polycyclohexene carbonate can be obtained through epoxidation modification, can be used as epoxy resin and is a biodegradable carbon dioxide-based epoxy resin with excellent performance, thereby realizing high-value utilization of carbon dioxide and substitution for the traditional petroleum-based epoxy resin.
The invention takes the carbon dioxide-based polycyclohexene carbonate as a raw material to prepare the epoxy-terminated polycyclohexene carbonate which is applied as epoxy resin, realizes the fixation and high-value utilization of carbon dioxide and has the characteristic of biodegradation. And the main body of the polycyclohexene carbonate is an alicyclic structure, a carbonate group and an ether group, wherein the alicyclic structure can provide certain rigidity and toughness for the polymer and resist corrosion, the carbonate structure provides biodegradation performance of the material, and the ether bond provides flexibility of a molecular chain.
Experimental results show that the epoxy-terminated polycyclohexene carbonate prepared by the invention has excellent mechanical properties after being cured, and can be used as a novel epoxy resin.
Drawings
FIG. 1 is a diagram of the preparation of low molecular weight polycyclohexene carbonate according to example 1 of the present invention1HNMR spectrogram;
FIG. 2 is a diagram of the preparation of low molecular weight polycyclohexene carbonate according to example 1 of the present invention13CNMR spectrogram;
FIG. 3 is a time-of-flight mass spectrum of a low molecular weight polycyclohexene carbonate prepared in example 1 of the present invention;
FIG. 4 is a diagram of the preparation of epoxy terminated polycyclohexene carbonate according to example 1 of the present invention1HNMR spectrogram.
Detailed Description
For a further understanding of the invention, reference will now be made to the preferred embodiments of the invention by way of example, and it is to be understood that the description is intended to further illustrate features and advantages of the invention, and not to limit the scope of the claims.
All of the starting materials of the present invention, without particular limitation as to their source, may be purchased commercially or prepared according to conventional methods well known to those skilled in the art.
All the raw materials of the present invention are not particularly limited in their purity, and the present invention preferably employs the purity conventionally used in the field of analytically pure or carbon dioxide based epoxy resins.
All noun expressions, acronyms and designations of the invention belong to the general noun expressions, acronyms and designations in the field, each noun expression, acronyms and designation is clear and definite in the relevant application field, and a person skilled in the art can clearly, exactly and uniquely understand the noun expression, acronyms and designations.
The invention discloses a low molecular weight carbon dioxide-cyclohexene oxide copolymer, which has a structure shown in a formula (I);
wherein x is 1-70; y is 1-40; n is 2-6;
R1is selected from
In the present invention, x and y are both the degree of polymerization.
In the invention, x is 1-70, preferably 5-60, more preferably 10-50, more preferably 15-40, and more preferably 20-30.
In the invention, y is 1-40, preferably 3-30, more preferably 5-25, more preferably 8-20, and more preferably 10-15.
Furthermore, x is preferably 1-30, more preferably 3-25, more preferably 5-20, and more preferably 8-15.
The y is preferably 1-10, more preferably 2-8, and more preferably 3-6.
In the invention, n is preferably 2-6, more preferably 2-5, more preferably 2-4, and more preferably 3-6.
In the invention, the number average molecular weight of the low molecular weight carbon dioxide-cyclohexene oxide copolymer is preferably 500-10000, more preferably 1000-8000, and more preferably 1500-6000. Specifically, the range of the specific surface area can be 500-5000, or 800-4000, or 1200-3000.
In the present invention, the carbon dioxide-cyclohexene oxide copolymer is preferably polycyclohexene carbonate. Specifically, the carbon dioxide-cyclohexene oxide copolymer is preferably obtained by copolymerizing the carbon dioxide and the cyclohexene oxide under the action of an oligomeric porphyrin aluminum catalyst. More specifically, the raw materials in the copolymerization also comprise an initiator. Further, a cocatalyst is included.
The invention also provides a preparation method of the low molecular weight carbon dioxide-cyclohexene oxide copolymer, which comprises the following steps:
1) under the atmosphere of carbon dioxide, reacting cyclohexene oxide, a catalyst, a cocatalyst and an initiator to obtain a low-molecular-weight carbon dioxide-cyclohexene oxide copolymer with a structure shown in a formula (I);
wherein x is 1-70; y is 1-40; n is 2-6;
R1is selected from
In the present invention, the catalyst preferably comprises an oligomeric aluminum porphyrin catalyst.
In the present invention, the cocatalyst preferably comprises bis (triphenylphosphoranylidene) ammonium chloride.
In the present invention, the initiator preferably includes one or more of a carboxylic acid compound, an alcohol compound and a phenol compound, and more preferably a carboxylic acid compound, an alcohol compound or a phenol compound.
In the invention, the molar ratio of cyclohexene oxide to the initiator is preferably (10-100): 1, more preferably (30 to 80): 1, more preferably (50 to 60): 1.
in the invention, the molar ratio of cyclohexene oxide to aluminum metal in the oligomeric porphyrin aluminum catalyst is preferably (5000-50000): 1, more preferably (15000 to 40000): 1, more preferably (25000 to 30000): 1.
in the invention, the molar ratio of cyclohexene oxide to the cocatalyst is preferably (5000-50000): 2, more preferably (15000 to 40000): 2, more preferably (25000 to 30000): 2.
in the present invention, the catalyst has a structure represented by formula (II):
wherein n is preferably the polymerization degree of oligomeric porphyrin aluminum, and n is preferably 4-20, more preferably 7-17, and more preferably 10-14.
In the present invention, the initiator preferably comprises terephthalic acid and/or terephthalyl alcohol, more preferably terephthalic acid or terephthalyl alcohol.
In the invention, the reaction temperature is preferably 70-150 ℃, more preferably 80-140 ℃, more preferably 90-130 ℃, and more preferably 100-120 ℃.
In the invention, the reaction time is preferably 4-24 h, more preferably 8-20 h, and more preferably 12-16 h.
In the present invention, the carbon dioxide atmosphere is preferably under a pressure of 3 to 6MPa, more preferably 3.5 to 5.5MPa, and still more preferably 4 to 5 MPa.
In the present invention, after the reaction is completed, the method preferably further comprises the steps of washing the product with methanol and purifying by heating under vacuum.
The invention is an integral and refined integral technical scheme, and better ensures the parameters, the structure and the performance of the carbon dioxide-cyclohexene oxide copolymer, such as molecular weight, and the like, and the preparation method of the carbon dioxide-cyclohexene oxide copolymer can specifically comprise the following steps:
under the inert gas atmosphere, adding metered cyclohexene oxide, a catalyst, a cocatalyst and an initiator into a high-pressure reaction kettle, sealing the reaction kettle, heating to 70-150 ℃, filling 3-6 MPa of carbon dioxide, and stirring for reacting for 4-24 hours. After the reaction is finished, cooling the reaction kettle to room temperature, slowly releasing carbon dioxide, opening the kettle, transferring the product to a vacuum condition, heating and removing unreacted monomers to obtain the copolymer with the structure (I).
In particular, the inert gas in the preparation process is preferably nitrogen and/or argon.
The invention also provides epoxy-terminated polycyclohexene carbonate, which has a structure shown in a formula (III);
wherein x is 1-70; y is 1-40; n is 2-6;
R1is selected from
In the present invention, the polycyclohexene carbonate preferably includes the carbon dioxide-cyclohexene oxide copolymer described in any one of the above technical schemes or the carbon dioxide-cyclohexene oxide copolymer prepared by the preparation method described in any one of the above technical schemes.
In the present invention, the epoxy-terminated polycyclohexene carbonate is preferably a carbon dioxide based epoxy resin.
In the present invention, the preparation process of the epoxy-terminated polycyclohexene carbonate preferably comprises the following steps:
(1) mixing the polycyclohexene carbonate, triethylamine and an organic solvent, and then adding methacryloyl chloride to carry out a first reaction to obtain the polycyclohexene carbonate terminated by olefin;
(2) and carrying out a second reaction on the olefin-terminated polycyclohexene carbonate obtained in the step, peroxide and an organic solvent to obtain the epoxy-terminated polycyclohexene carbonate.
According to the invention, the polycarbonate cyclohexene ester, the triethylamine and the organic solvent are mixed, and then the methacrylic chloride is added for the first reaction, so that the olefin-terminated polycarbonate cyclohexene ester is obtained.
In the invention, the mixing temperature is preferably-20 ℃, more preferably-15 ℃, more preferably-10 ℃, and more preferably-5 ℃.
In the invention, the temperature of the first reaction is preferably 25-40 ℃, more preferably 28-37 ℃, and more preferably 31-34 ℃.
In the invention, the time of the first reaction is preferably 0.5-12 h, more preferably 2-10 h, and more preferably 4-8 h.
In the present invention, the molar ratio of the polycyclohexene carbonate to triethylamine is preferably 1: (2.8 to 4.5), more preferably 1: (3.2 to 4.1), more preferably 1: (3.6-3.7).
In the present invention, the molar ratio of the polycyclohexene carbonate to methacryloyl chloride is preferably 1: (2.4-3.0), more preferably 1: (2.5-2.9), more preferably 1: (2.6-2.8).
In the present invention, the organic solvent preferably includes one or more of dichloromethane, chloroform, ethyl acetate, tetrahydrofuran, dioxane and diethyl ether, and more preferably dichloromethane, chloroform, ethyl acetate, tetrahydrofuran, dioxane or diethyl ether.
Finally, carrying out a second reaction on the olefin-terminated polycyclohexene carbonate obtained in the step, peroxide and an organic solvent to obtain the epoxy-terminated polycyclohexene carbonate.
In the present invention, the peroxide preferably includes one or more of m-chloroperoxybenzoic acid, perbenzoic acid, peracetic acid, and trifluoroperoxyacetic acid, and more preferably m-chloroperoxybenzoic acid, perbenzoic acid, peracetic acid, or trifluoroperoxyacetic acid.
In the present invention, the molar ratio of the olefin-terminated polycyclohexene carbonate and the peroxide is preferably 1: (2.4 to 4.0), more preferably 1: (2.7-3.7), more preferably 1: (3-3.4).
In the invention, the temperature of the second reaction is preferably 40-50 ℃, more preferably 42-48 ℃, and more preferably 44-46 ℃.
In the invention, the time of the second reaction is preferably 24-72 h, more preferably 34-62 h, and more preferably 44-52 h.
The invention is a complete and refined integral technical scheme, better ensures the parameters and the structure of the epoxy-terminated polycyclohexene carbonate, improves the comprehensive performance of the epoxy-terminated polycyclohexene carbonate, and the preparation method of the epoxy-terminated polycyclohexene carbonate can specifically comprise the following steps:
(1) dissolving the polycyclohexene carbonate of the formula (I) in an organic solvent, adding triethylamine at-20 ℃, uniformly stirring, adding methacryloyl chloride, transferring to 25-40 ℃, and reacting for 0.5-12 h to obtain the polycyclohexene carbonate terminated by olefin;
(2) and (2) dissolving the olefin-terminated polycyclohexene carbonate obtained in the step (1) in an organic solvent, heating to 40-50 ℃, adding peroxide to react, and obtaining the epoxy-terminated polycyclohexene carbonate.
And (3) further dissolving the epoxy-terminated polycyclohexene carbonate and isophorone diamine obtained in the step (2) in an organic solvent to obtain a mixed solution, then heating in vacuum, and after the solvent is volatilized, heating to 80 ℃ for curing to obtain the carbon dioxide-based epoxy resin.
Specifically, the molecular weight of the polycyclohexene carbonate in the step (1) is preferably 500-10000, and more preferably 500-3000.
The peroxide in step (2) is preferably one or more of m-chloroperoxybenzoic acid, peroxybenzoic acid, peroxyacetic acid and trifluoroperoxyacetic acid, and more preferably m-chloroperoxybenzoic acid.
Specifically, the molar ratio of the epoxy-terminated polycyclohexene carbonate to the curing agent is preferably 2: 1.
specifically, the step (1) is followed by a purification step. The method comprises the following steps of separating and purifying the obtained olefin-terminated polycyclohexene carbonate: and adding deionized water into the reacted system for extraction to remove water-soluble salt, collecting an organic phase, and performing vacuum drying to obtain the purified olefin-terminated polycyclohexene carbonate.
Specifically, the step (2) is followed by a purification step. The method comprises the following steps of separating and purifying the obtained epoxy-terminated polycyclohexene carbonate: and filtering the reacted system to remove insoluble substances, washing the filtrate with a saturated sodium thiosulfate aqueous solution, a saturated sodium bicarbonate aqueous solution and deionized water in sequence, adding a drying agent into the separated organic phase, drying to remove water, filtering, performing rotary evaporation on the filtered filtrate to remove the organic solvent, and performing vacuum drying to obtain the purified epoxy terminal polycyclohexene carbonate.
The invention provides application of the epoxy-terminated polycyclohexene carbonate in any one of the technical schemes in the field of epoxy resin.
The invention provides a low molecular weight carbon dioxide-cyclohexene oxide copolymer, a preparation method thereof, epoxy-terminated polycyclohexene carbonate and application thereof. The invention adopts the oligomeric porphyrin aluminum catalyst, the initiator and the cocatalyst as well as a specific preparation route to catalyze the copolymerization of carbon dioxide and cyclohexene oxide, and the low molecular weight carbon dioxide-cyclohexene oxide copolymer with controllable molecular weight, namely the polycarbonate cyclohexene ester, is prepared. Compared with high molecular weight poly (cyclohexene carbonate), the molecular weight-controllable low molecular weight carbon dioxide-cyclohexene oxide copolymer has higher end group reactivity and is easier to modify, so that epoxy-terminated poly (cyclohexene carbonate) can be obtained subsequently, and resin with a high epoxy value can be obtained after modification, thereby being more favorable for subsequent curing and use.
According to the invention, through analyzing the structure of the polycyclohexene carbonate, the alicyclic structure can provide certain rigidity and toughness for the polymer and resist corrosion, the carbonate structure provides the biodegradation performance of the material, and the ether bond provides certain flexibility for a molecular chain, so that the end group of the polycyclohexene carbonate is chemically modified, and epoxy-terminated polycyclohexene carbonate can be obtained through epoxidation modification, can be used as epoxy resin and is a biodegradable carbon dioxide-based epoxy resin with excellent performance, thereby realizing high-value utilization of carbon dioxide and substitution for the traditional petroleum-based epoxy resin.
The invention takes the carbon dioxide-based polycyclohexene carbonate as a raw material to prepare the epoxy-terminated polycyclohexene carbonate which is applied as epoxy resin, realizes the fixation and high-value utilization of carbon dioxide and has the characteristic of biodegradation. And the main body of the polycyclohexene carbonate is an alicyclic structure, a carbonate group and an ether group, wherein the alicyclic structure can provide certain rigidity and toughness for the polymer and resist corrosion, the carbonate structure provides biodegradation performance of the material, and the ether bond provides flexibility of a molecular chain.
Experimental results show that the epoxy-terminated polycyclohexene carbonate prepared by the invention has excellent mechanical properties after being cured, and can be used as a novel epoxy resin.
To further illustrate the present invention, a carbon dioxide-based copolymer, a method for preparing the same, an epoxy-terminated polycyclohexene carbonate, and applications thereof are described in detail with reference to the following examples, but it should be understood that the examples are carried out on the premise of the technical solution of the present invention, and that the detailed embodiments and specific procedures are given only for further illustrating the features and advantages of the present invention, but not for limiting the claims of the present invention, and the scope of the present invention is not limited to the following examples.
The reagent raw materials and apparatus used in the following examples are commercially available products.
Example 1
Preparation of carbon dioxide-based epoxy resin:
under the atmosphere of nitrogen, 40mL of cyclohexene oxide, 7.8mg of oligomeric porphyrin aluminum catalyst, 8.4mg of PPNCl and 6.56g of terephthalic acid are added into a high-pressure reaction kettle, the reaction kettle is sealed, the temperature is raised to 100 ℃, 5MPa of carbon dioxide is filled, and the mixture is stirred and reacts for 24 hours. After the reaction is finished, cooling the reaction kettle to room temperature, slowly releasing carbon dioxide, washing the product in the high-pressure reaction kettle with methanol, transferring the product to a vacuum oven, and heating and drying to obtain the carbon dioxide-cyclohexene oxide copolymer with the structure (I), namely the low molecular weight cyclohexene carbonate.
The low molecular weight polycyclohexene carbonate prepared in example 1 of the present invention was characterized.
Referring to FIG. 1, FIG. 1 shows the preparation of low molecular weight polycyclohexene carbonate according to example 1 of the present invention1HNMR spectrogram;
referring to FIG. 2, FIG. 2 shows the preparation of low molecular weight polycyclohexene carbonate according to example 1 of the present invention13C NMR spectrum;
referring to fig. 3, fig. 3 is a time-of-flight mass spectrum of the low molecular weight polycyclohexene carbonate prepared in example 1 of the present invention.
Dissolving 2.0mmol of polycyclohexene carbonate with the molecular weight of 560g/mol in 5mL of dichloromethane, cooling to 0 ℃, adding 5.6mmol of triethylamine, stirring uniformly, dropwise adding 4.8mmol of methacryloyl chloride, and transferring to the condition of 25 ℃ to stir for reaction for 4 hours; adding 5mL of deionized water into the reaction mixture, washing for 3 times, collecting a dichloromethane phase, and drying in vacuum to obtain a purified alkene terminal polycyclohexene carbonate product;
dissolving 2.0mmol of olefin-terminated polycyclohexene carbonate in 5mL of dichloromethane, adding 5.0mmol of m-chloroperoxybenzoic acid, carrying out reflux reaction at 50 ℃ for 72 hours, filtering to remove insoluble substances, washing filtrate with 5mL of saturated sodium thiosulfate solution, 5mL of saturated sodium bicarbonate solution and 5mL of deionized water in sequence, adding anhydrous sodium sulfate into the separated organic phase, drying, filtering to obtain an organic phase, removing the organic solvent by rotary evaporation, and carrying out vacuum drying to obtain the polycyclohexene carbonate at the epoxy terminal.
The epoxy-terminated polycyclohexene carbonate prepared in example 1 of the present invention was characterized.
Referring to FIG. 4, FIG. 4 is a schematic representation of the preparation of epoxy terminated polycyclohexene carbonate according to example 1 of the present invention1H NMR spectrum.
The epoxy-terminated polycyclohexene carbonate prepared in example 1 of the present invention was examined.
Referring to Table 1, Table 1 shows performance test data for epoxy terminated polycyclohexene carbonate prepared in accordance with the examples of the present invention.
TABLE 1
| Tensile Strength (MPa) | Elongation at Break (%) | |
| Example 1 | 33 | 10.3 |
| Example 2 | 38 | 9.6 |
| Example 3 | 40 | 7.2 |
Example 2
Preparation of carbon dioxide-based epoxy resin:
under the atmosphere of argon, 40mL of cyclohexene oxide, 7.8mg of oligomeric porphyrin catalyst, 8.4mg of PPNCl and 5.46g of terephthalyl alcohol are added into a high-pressure reaction kettle, the reaction kettle is sealed, the temperature is raised to 100 ℃, 6MPa of carbon dioxide is filled, and the mixture is stirred and reacts for 24 hours. After the reaction is finished, cooling the reaction kettle to room temperature, slowly releasing carbon dioxide, washing a product in the high-pressure reaction kettle with methanol, transferring the product to a vacuum oven, and heating and drying to obtain the copolymer with the structure (I);
dissolving 2.0mmol of cyclohexene carbonate with the molecular weight of 790g/mol in 5mL of ethyl acetate, adding 9.0mmol of triethylamine at the temperature of-20 ℃, uniformly stirring, dropwise adding 6.0mmol of methacryloyl chloride, and transferring to the condition of 40 ℃ for stirring reaction for 0.5 h; adding 5mL of deionized water into the reaction mixture, washing for 3 times, collecting an ethyl acetate phase, and drying in vacuum to obtain a purified alkene-terminated polycyclohexene carbonate product;
dissolving 2.0mmol of olefin-terminated polycyclohexene carbonate in 5mL of ethyl acetate, adding 8.0mmol of perbenzoic acid, carrying out reflux reaction at 40 ℃ for 48h, filtering to remove insoluble substances, washing the filtrate with 5mL of saturated sodium thiosulfate solution, 5mL of saturated sodium bicarbonate solution and 5mL of deionized water in sequence, adding anhydrous sodium sulfate into the separated organic phase, drying, filtering to obtain an organic phase, removing the organic solvent by rotary evaporation, and carrying out vacuum drying to obtain the polycyclohexene carbonate at the epoxy terminal.
The epoxy-terminated polycyclohexene carbonate prepared in example 2 of the present invention was examined.
Referring to Table 1, Table 1 shows performance test data for epoxy terminated polycyclohexene carbonate prepared in accordance with the examples of the present invention.
Example 3
Preparation of carbon dioxide-based epoxy resin:
under the nitrogen atmosphere, 40mL of cyclohexene oxide, 7.8mg of oligomeric porphyrin aluminum catalyst, 8.4mg of bis (triphenyl phosphorane) ammonium chloride and 3.28g of terephthalic acid are added into a high-pressure reaction kettle, the reaction kettle is sealed, the temperature is raised to 150 ℃, 4MPa of carbon dioxide is filled, and the mixture is stirred and reacted for 4 hours. After the reaction is finished, cooling the reaction kettle to room temperature, slowly releasing carbon dioxide, washing a product in the high-pressure reaction kettle by using methanol, transferring the product to a vacuum oven, and heating to remove unreacted monomers to obtain a copolymer with a structure (I);
dissolving 2.0mmol of cyclohexene carbonate with the molecular weight of 1200g/mol in 5mL of ethyl acetate, adding 9.0mmol of triethylamine at the temperature of-20 ℃, uniformly stirring, dropwise adding 6.0mmol of methacryloyl chloride, and transferring to the condition of 40 ℃ for stirring reaction for 0.5 h; adding 5mL of deionized water into the reaction mixture, washing for 3 times, collecting an ethyl acetate phase, and drying in vacuum to obtain a purified alkene-terminated polycyclohexene carbonate product;
dissolving 2.0mmol of olefin-terminated polycyclohexene carbonate in 5mL of ethyl acetate, adding 8.0mmol of perbenzoic acid, carrying out reflux reaction at 50 ℃ for 24 hours, filtering to remove insoluble substances, washing the filtrate with 5mL of saturated sodium thiosulfate solution, 5mL of saturated sodium bicarbonate solution and 5mL of deionized water in sequence, adding anhydrous sodium sulfate into the separated organic phase, drying, filtering to obtain an organic phase, removing the organic solvent by rotary evaporation, and carrying out vacuum drying to obtain the polycyclohexene carbonate at the epoxy terminal.
The epoxy-terminated polycyclohexene carbonate prepared in example 3 of the present invention was examined.
Referring to Table 1, Table 1 shows performance test data for epoxy terminated polycyclohexene carbonate prepared in accordance with the examples of the present invention.
While the present invention has been described in detail with respect to a low molecular weight carbon dioxide-cyclohexene oxide copolymer and method of making the same, an epoxy terminated polycyclohexene carbonate and its applications, the present invention is described herein using specific examples to illustrate the principles and embodiments of the present invention, which are included to assist in understanding the process of the present invention and its core concepts, including the best mode, and also to enable any person skilled in the art to practice the invention, including making and using any devices or systems and performing any incorporated methods. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention. The scope of the invention is defined by the claims and may include other embodiments that occur to those skilled in the art. Such other embodiments are intended to be within the scope of the claims if they have structural elements that do not differ from the literal language of the claims, or if they include equivalent structural elements with insubstantial differences from the literal languages of the claims.
Claims (10)
1. A low molecular weight carbon dioxide-cyclohexene oxide copolymer is characterized by having a structure shown in formula (I);
wherein x is 1-70; y is 1-40; n is 2-6;
R1is selected from
2. The low molecular weight carbon dioxide-cyclohexene oxide copolymer according to claim 1, wherein the low molecular weight carbon dioxide-cyclohexene oxide copolymer has a number average molecular weight of 500 to 10000;
the carbon dioxide-cyclohexene oxide copolymer is polycarbonate cyclohexene ester;
x is 1-30;
and y is 1-10.
3. A preparation method of a low molecular weight carbon dioxide-cyclohexene oxide copolymer is characterized by comprising the following steps:
1) under the atmosphere of carbon dioxide, reacting cyclohexene oxide, a catalyst, a cocatalyst and an initiator to obtain a low-molecular-weight carbon dioxide-cyclohexene oxide copolymer with a structure shown in a formula (I);
wherein x is 1-70; y is 1-40; n is 2-6;
R1is selected from
4. The method of claim 3, wherein the catalyst comprises an oligomeric aluminum porphyrin catalyst;
the cocatalyst comprises bis (triphenylphosphoranylidene) ammonium chloride;
the initiator comprises one or more of carboxylic acid compounds, alcohol compounds and phenolic compounds;
the mol ratio of cyclohexene oxide to the initiator is (10-100): 1;
the mol ratio of the cyclohexene oxide to the aluminum metal in the oligomeric porphyrin aluminum catalyst is (5000-50000): 1;
the mol ratio of the cyclohexene oxide to the cocatalyst is (5000-50000): 2.
5. the method of claim 3, wherein the catalyst has a structure represented by formula (II):
wherein n is the polymerization degree of oligomeric porphyrin aluminum, and n is 4-20;
the initiator comprises terephthalic acid and/or terephthalyl alcohol;
the reaction temperature is 70-150 ℃;
the reaction time is 4-24 h;
the carbon dioxide atmosphere is under the condition that the pressure of carbon dioxide is 3-6 MPa;
after the reaction is finished, the method also comprises the steps of washing the product with methanol and heating and purifying the product under vacuum condition.
6. An epoxy-terminated polycyclohexene carbonate having the structure of formula (III);
wherein x is 1-70; y is 1-40; n is 2-6;
R1is selected from
7. The epoxy-terminated polycyclohexene carbonate according to claim 6, wherein the polycyclohexene carbonate comprises the carbon dioxide-cyclohexene oxide copolymer according to any one of claims 1 to 2 or the carbon dioxide-cyclohexene oxide copolymer prepared by the preparation method according to any one of claims 3 to 5;
the epoxy-terminated polycyclohexene carbonate is carbon dioxide-based epoxy resin;
the preparation process of the epoxy-terminated polycyclohexene carbonate comprises the following steps:
(1) mixing the polycyclohexene carbonate, triethylamine and an organic solvent, and then adding methacryloyl chloride to carry out a first reaction to obtain the polycyclohexene carbonate terminated by olefin;
(2) and carrying out a second reaction on the olefin-terminated polycyclohexene carbonate obtained in the step, peroxide and an organic solvent to obtain the epoxy-terminated polycyclohexene carbonate.
8. The epoxy-terminated polycyclohexene carbonate according to claim 7 wherein the temperature of the mixing is-20 to 20 ℃;
the temperature of the first reaction is 25-40 ℃;
the first reaction time is 0.5-12 h;
the molar ratio of the polycyclohexene carbonate to triethylamine is 1: (2.8-4.5);
the mol ratio of the polycyclohexene carbonate to the methacrylic acid chloride is 1: (2.4-3.0).
9. The epoxy-terminated polycyclohexene carbonate according to claim 7 wherein the organic solvent includes one or more of dichloromethane, chloroform, ethyl acetate, tetrahydrofuran, dioxane and diethyl ether;
the peroxide comprises one or more of m-chloroperoxybenzoic acid, peroxybenzoic acid, peroxyacetic acid and trifluoroperoxyacetic acid;
the mol ratio of the olefin-terminated polycyclohexene carbonate to the peroxide is 1: (2.4-4.0);
the temperature of the second reaction is 40-50 ℃;
the time of the second reaction is 24-72 hours.
10. Use of the epoxy-terminated polycyclohexene carbonate according to any of claims 6 to 9 in the field of epoxy resins.
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