CN114479045A - Carbon dioxide-based elastomer and preparation method thereof - Google Patents
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Abstract
The invention provides a carbon dioxide-based elastomer, wherein an epoxy compound with a saturated long-chain branch is introduced into a carbon dioxide-allyl glycidyl ether system for ternary random copolymerization, and the density of double bonds in the copolymer elastomer is regulated and controlled by changing the monomer ratio and reaction conditions, so that controllable crosslinking is realized, the mechanical property of the prepared carbon dioxide-based elastomer is improved, and the prepared carbon dioxide-based elastomer has higher value as an environment-friendly green material.
Description
Technical Field
The invention belongs to the field of high polymer materials, and particularly relates to a carbon dioxide-based elastomer and a preparation method thereof.
Background
At present, in the field of fixation and utilization of carbon dioxide, major research is also focused on carbon dioxide-based plastics, and development and application of carbon dioxide-based elastomers are hardly reported. Carbon dioxide-based elastomers are a new class of bio-based elastomers, which contain polycarbonate linkages which determine their biodegradability. Therefore, the development and application of the carbon dioxide-based elastomer not only meet the requirement of green chemistry, but also can make up the blank of the research of carbon dioxide in the field of elastomers. However, in the research process of carbon dioxide-based elastomers at present, only a rare earth three-way catalyst is used for catalyzing the copolymerization of carbon dioxide and allyl glycidyl ether to generate a bio-based elastomer meeting the conditions of elastomer materials, but the density of double bonds carried in the copolymer is too high, and controllable crosslinking cannot be realized, which becomes an important problem for hindering further research on the performance of the copolymer.
Since the mechanical strength of carbon dioxide copolymers is inherently low, the range of applications of carbon dioxide-based elastomers is limited. Chinese patent CN109485842A proposes that a random copolymer meeting the conditions of elastomer materials is prepared by anion coordination polymerization and rare earth three-way catalyst catalysis carbon dioxide and allyl glycidol, and the copolymer has uncontrollable crosslinking, large brittleness after vulcanization and poor mechanical properties.
Disclosure of Invention
In order to solve the problems in the prior art, the invention introduces an epoxy compound with a saturated long-chain branch into a carbon dioxide-allyl glycidyl ether system for ternary random copolymerization, and realizes the purpose that the copolymer carries more proper double bond content by changing the monomer proportion and reaction conditions, so that the controllable crosslinking is realized by vulcanization, and the carbon dioxide-based elastomer has the mechanical property meeting the application requirements by doping nano reinforcing fillers with different formulas.
One of the purposes of the invention is to provide a carbon dioxide-based elastomer, which is characterized in that the repeating unit structural formula in the elastomer is as follows:
wherein a is an integer of 1-5.
The molecular weight of the elastomer is 30000-200000, preferably 50000-150000.
The carbon dioxide-based elastomer is a random copolymer of carbon dioxide, a glycidyl ether compound and an epoxy compound. Wherein, the glycidyl ether compound is at least one selected from allyl glycidyl ether and glycidyl methacrylate, preferably selected from allyl glycidyl ether; the epoxy compound is selected from saturated alkyl epoxy compounds with 3-12 carbon atoms, preferably at least one selected from 1, 2-epoxybutane, 1, 2-epoxypentane, 1, 2-epoxyhexane, 1, 2-epoxyheptane, 1, 2-epoxyoctane, 1, 2-epoxydodecane, epichlorohydrin and epoxy 10-methyl undecylenate, and preferably selected from 1, 2-epoxyhexane.
The second object of the present invention is to provide a method for preparing the carbon dioxide-based elastomer, which comprises mixing the carbon dioxide, the glycidyl ether compound, and the epoxy compound, and then carrying out a polymerization reaction to obtain the carbon dioxide-based elastomer, and specifically comprises the following steps:
and 2, cooling the crude product of the carbon dioxide-based elastomer obtained in the step 1, dissolving the crude product in a solvent S1, adding a solvent S2, precipitating and drying to obtain the carbon dioxide-based elastomer.
Specifically, in the step 1,
the volume ratio of the epoxy compound to the glycidyl ether compound is 1: 1-5: 1, preferably 1: 1-3: 1;
the total volume of the epoxy compound and the glycidyl ether compound is 1/3-4/5 of the volume of the reaction kettle, preferably 1/2-2/3;
the epoxy compound and the glycidyl ether compound are dried before reaction, and the drying is carried out by adopting a common drying process;
the polymerization reaction temperature is 60-90 ℃, and preferably 70-85 ℃;
the polymerization reaction time is 5-25 h, preferably 10-20 h;
the polymerization pressure is 2-6 MPa, preferably 3-5 MPa;
the polymerization reaction is carried out under the anhydrous and oxygen-free conditions;
a catalyst is also added in the polymerization reaction; the catalyst is selected from at least one of metalloporphyrin catalyst, bimetallic catalyst, rare earth metal catalyst and chelating schiff base catalyst (salen catalyst), preferably selected from bimetallic catalyst, more preferably selected from bimetallic cyanide complex catalyst, and most preferably selected from zinc cobalt cyanide complex (Zn-Co DMC catalyst); the dosage of the catalyst is 0.01-0.2% of the dosage of the epoxy compound, and preferably 0.03-0.05%.
Specifically, in the step 2,
the solvent S1 is at least one selected from dichloromethane, toluene and tetrahydrofuran, preferably dichloromethane;
the solvent S2 is selected from at least one of methanol and ethanol, preferably methanol;
the volume ratio of the solvent S1 to the solvent S2 is 1: 5-1: 20, preferably 1: 8-1: 10; wherein, the adding amount of the solvent S1 in the step 2 is only required to be capable of dissolving the added crude product of the carbon dioxide-based elastomer;
the drying temperature is 50-80 ℃, and preferably 60-70 ℃.
In the invention, a bimetallic Zn-Co DMC catalyst is utilized to introduce an epoxy compound into a carbon dioxide-glycidyl ether system to carry out ternary random copolymerization in a random copolymerization mode, and the density of double bonds in the copolymer elastomer is regulated and controlled by the design of the feeding ratio, so that controllable crosslinking is realized, and the mechanical property of the prepared carbon dioxide-based elastomer is improved. According to the invention, the carbon dioxide-based elastomer composite material is vulcanized and then is subjected to tensile test, and the result shows that the composite material has excellent mechanical properties.
The invention effectively reduces the double bond content in the carbon dioxide elastomer, thereby effectively regulating and controlling the crosslinking density and obviously improving the mechanical strength of the carbon dioxide-based elastomer. Meanwhile, the elongation at break of the carbon dioxide elastomer is obviously improved, and the brittleness of the carbon dioxide elastomer is reduced, so that the carbon dioxide-based elastomer has higher value as an environment-friendly green material.
Compared with the prior art, the invention has the following beneficial effects:
1. according to the invention, by introducing the epoxy compound and adjusting the dosage ratio of the epoxy compound to the glycidyl ether compound, the double bond content in the carbon dioxide-based elastomer can be effectively reduced, so that controllable crosslinking can be realized, the brittleness is reduced, and the mechanical property is obviously improved;
2. the Zn-Co DMC catalyst used in the invention has better catalytic activity and better selectivity, not only improves the conversion rate of the monomer, but also ensures that the proper polycarbonate chain segment accounts for the ratio, and the content of byproducts is very low;
3. the preparation method of the carbon dioxide-based elastomer provided by the invention is simple in process, green and environment-friendly, and has a wide application prospect.
Drawings
FIG. 1 is a graph comparing the IR spectra of ternary and binary carbon dioxide-based elastomers obtained in example 1 (curve a) and comparative example 1 (curve b). In FIG. 1, 1750.47cm-1Corresponds to a characteristic absorption peak of C ═ O in the carbonate group, 1247.72cm-1Corresponds to the C-O-C stretching vibration peak in the carbonate group, 2867.65cm-1At a peak corresponding to methylene group on ether bond of 1646.09cm-1Corresponds to a characteristic absorption peak of C ═ C, 3078.21cm-1And 997.75cm-1The positions are respectively corresponding to the stretching vibration peak and the out-of-plane bending vibration peak of the double bond C-H. It can be seen that the binary carbon dioxide-based elastomer prepared without the introduction of 1, 2-epoxyhexane contained no methyl groups at 2960.71cm-1The C-H stretching vibration peak of methyl does not appear, and in the carbon dioxide-allyl glycidyl ether-1, 2-epoxy hexane ternary carbon dioxide-based elastomer, the vibration peak is 2960.71cm-1The obvious C-H stretching vibration peak of the methyl appears because the branched chain containing one methyl of the 1, 2-epoxy hexane does not participate in the reaction and is reserved as a side chain, so the obvious C-H stretching vibration peak of the methyl appears in the infrared spectrum of the ternary product. Meanwhile, before and after 1, 2-epoxy hexane is introduced in a contrast manner, the double bond absorption peak intensity of the ternary product is obviously reduced compared with that of the binary product.
FIG. 2 is a tensile property test curve of the ternary carbon dioxide-based elastomer obtained in example 1. As can be seen from FIG. 2, the carbon dioxide-based elastomer synthesized by the invention has the advantages of obvious increase of tensile strength, great increase of elongation at break and reduced brittleness.
FIG. 3 shows ternary and binary carbon dioxide-based elastomers from example 1 (curve b) and comparative example 1 (curve a)1HNMR comparison. The peak areas are obtained by integrating the peaks of the characteristic hydrogen on the double bonds corresponding to the chemical shifts of 5.95-5.78 ppm and 5.29-5.13 ppm, and the peak areas of the curve a and the curve b are respectively 19.38 and 8.92, so that the double bond density of the ternary carbon dioxide-based elastomer obtained in example 1 is reduced by 117.26% after the 1, 2-epoxyhexane is introduced.
Detailed Description
While the present invention will be described in detail with reference to the following examples, it should be understood that the following examples are illustrative of the present invention and are not to be construed as limiting the scope of the present invention.
The test instruments and test conditions used in the examples were as follows:
fourier Infrared tester (model: TENSOR 27; manufacturer: BRUKER, Germany);
differential Scanning Calorimeter (DSC) (model: DSC822 e; manufacturer: Mettler-Toledo company);
gel permeation chromatography (model: 5151 HPLC; manufacturer: Waters, USA);
a plate vulcanizing machine (model: XQLB-350X 350; manufacturer: Shanghai rubber machinery manufacturer);
a high-speed rail universal tensile machine (model: AI-7000S 1; manufacturer: high-speed rail testing apparatus (Dongguan) Co., Ltd.).
Nuclear magnetic testing: the model is as follows: AV300-400 MHZ; the manufacturer: BRUKER, Germany
The raw materials and sources used in the examples are as follows:
carbon dioxide, Yongsheng gas;
allyl glycidyl ether, kyo enoki technologies ltd;
1, 2-epoxyhexane, shanghai meirui chemical technology ltd;
methanol, Beijing chemical plant;
dichloromethane, beijing enokay technologies ltd.
Preparation of Zn-Co DMC catalyst:
potassium hexacyanocobaltate was dissolved in 10ml of deionized water, and zinc dichloride was dissolved in a mixed solution of 10ml of deionized water and 10ml of t-butanol (the molar ratio of the amounts of potassium hexacyanocobaltate and zinc dichloride was 1: 3). Then, slowly dropping a potassium hexacyanocobaltate solution into a zinc dichloride solution under strong stirring, then, vigorously stirring at 75 ℃ for 3 hours, filtering and separating under pressure to obtain a white precipitate, pouring the white precipitate into a mixed solution of deionized water and tert-butyl alcohol (volume ratio is 1:1) for repulping, separating the precipitate after stirring for 3 hours, pouring the precipitate into a mixed solution of ethanol and deionized water (volume ratio is 1:1) for repulping, then separating the precipitate, pouring the precipitate into a mixed solution of tert-butyl alcohol and deionized water (volume ratio is 3:1), washing to remove potassium ions in the precipitate, finally, slurrying in a pure tert-butyl alcohol solution, separating and drying at 75 ℃ under vacuum to constant weight.
Example 1
Preparation of carbon dioxide-based elastomers
Under the anhydrous and oxygen-free atmosphere, respectively weighing a Zn-Co DMC catalyst according to a proportion, pouring and sucking dried allyl glycidyl ether and 1, 2-epoxyhexane, injecting into a dried hydrothermal reaction kettle with a stirrer, and locking the kettle; adjusting the stirring speed to 350r/min at the temperature of 75 ℃, opening an air inlet valve of the reaction kettle, filling carbon dioxide with the purity higher than 99.95% into the kettle, stabilizing the pressure in the kettle at 4MPa, continuously reacting for 13h, taking out the reaction kettle from the heating device, cooling the reaction kettle to room temperature, opening an air outlet valve of the reaction kettle to release the residual carbon dioxide to 0MPa, and taking out a crude product of the carbon dioxide-based elastomer; the crude product was dissolved in dichloromethane solution and poured into a large amount of methanol solution to precipitate the copolymer, which was then repeated three times with stirring. And drying the obtained carbon dioxide-allyl glycidyl ether-1, 2-epoxy hexane ternary random copolymer at 60 ℃ for 48 hours in vacuum. The glass transition temperature of the polymer is-32.60 ℃, and the number average molecular weight is 76766.
In example 1, the total amount of allyl glycidyl ether and 1, 2-epoxyhexane used was strictly controlled to 3/5 based on the pot volume, and the volume ratio of the amount of allyl glycidyl ether to 1, 2-epoxyhexane used was 1: the amount of 1, Zn-Co DMC catalyst used was 0.04% (based on the total mass of epoxy compound added).
0.05 part of DCP (based on 100 parts by weight of the carbon dioxide-based elastomer) is added into the obtained ternary carbon dioxide-based elastomer to promote crosslinking, and the mechanical properties of the ternary carbon dioxide-based elastomer are tested. Vulcanized by a flat vulcanizing machine at 160 ℃ for 15min and then taken out, and the tensile strength is measured to be 0.62MPa, and the elongation at break is 300.39%.
Example 2
Preparation of carbon dioxide-based elastomer products
Under the anhydrous and oxygen-free atmosphere, respectively weighing a Zn-Co DMC catalyst according to a proportion, pouring and sucking dried allyl glycidyl ether and 1, 2-epoxyhexane, injecting into a dried hydrothermal reaction kettle with a stirrer, and locking the kettle; adjusting the stirring speed to 250r/min at the temperature of 70 ℃, opening an air inlet valve of the reaction kettle, filling carbon dioxide with the purity higher than 99.95% into the kettle, stabilizing the pressure in the kettle at 5MPa, continuously reacting for 18h, taking out the reaction kettle from the heating device, cooling the reaction kettle to room temperature, opening an air outlet valve of the reaction kettle to release the residual carbon dioxide to 0MPa, and taking out a crude product of the carbon dioxide-based elastomer; the crude product was dissolved in dichloromethane solution and poured into a large amount of methanol solution to precipitate the copolymer, which was then repeated three times with stirring. And drying the obtained carbon dioxide-allyl glycidyl ether-1, 2-epoxy hexane ternary random copolymer at 60 ℃ for 48 hours in vacuum. The polymer had a glass transition temperature of-39.28 ℃ and a number average molecular weight of 69877.
In example 2, the total amount of allyl glycidyl ether and 1, 2-epoxyhexane used was strictly controlled to 3/5 based on the pot volume, and the volume ratio of the amount of allyl glycidyl ether to 1, 2-epoxyhexane used was 1: the amount of 2, Zn-Co DMC catalyst used was 0.04% (based on the total mass of epoxy compound added).
Example 3
Preparation of carbon dioxide-based elastomer products
Under the anhydrous and oxygen-free atmosphere, respectively weighing a Zn-Co DMC catalyst according to a proportion, pouring and sucking dried allyl glycidyl ether and 1, 2-epoxyhexane, injecting into a dried hydrothermal reaction kettle with a stirrer, and locking the kettle; adjusting the stirring speed to 300r/min at the temperature of 80 ℃, opening an air inlet valve of the reaction kettle, filling carbon dioxide with the purity higher than 99.95% into the kettle, stabilizing the pressure in the kettle at 3MPa, continuously reacting for 15h, taking out the reaction kettle from the heating device, cooling the reaction kettle to room temperature, opening an air outlet valve of the reaction kettle to release the residual carbon dioxide to 0MPa, and taking out a crude product of the carbon dioxide-based elastomer; the crude product was dissolved in dichloromethane solution and poured into a large amount of methanol solution to precipitate the copolymer, which was then repeated three times with stirring. And drying the obtained carbon dioxide-allyl glycidyl ether-1, 2-epoxy hexane ternary random copolymer at 60 ℃ for 48 hours in vacuum. The polymer had a glass transition temperature of-42.36 ℃ and a number average molecular weight of 57335.
In example 3, the total amount of allyl glycidyl ether and 1, 2-epoxyhexane used was strictly controlled to 3/5 based on the pot volume, and the volume ratio of the amount of allyl glycidyl ether to 1, 2-epoxyhexane used was 1: the amount of 3, Zn-Co DMC catalyst used was 0.04% (based on the total mass of epoxy compound added).
Comparative example 1
Preparation of binary carbon dioxide-based elastomers
Under the anhydrous and oxygen-free atmosphere, respectively weighing a Zn-Co DMC catalyst in proportion, pouring and sucking dried allyl glycidyl ether, injecting the allyl glycidyl ether into a dried hydrothermal reaction kettle with a stirrer, and locking the kettle; adjusting the stirring speed to 350r/min at the temperature of 75 ℃, opening an air inlet valve of the reaction kettle, filling carbon dioxide with the purity higher than 99.95% into the kettle, stabilizing the pressure in the kettle at 4MPa, continuously reacting for 13h, taking out the reaction kettle from the heating device, cooling the reaction kettle to room temperature, opening an air outlet valve of the reaction kettle to release the residual carbon dioxide to 0MPa, and taking out a crude product of the carbon dioxide-based elastomer; the crude product was dissolved in dichloromethane solution and poured into a large amount of methanol solution to precipitate the copolymer, which was then repeated three times with stirring. The obtained carbon dioxide-allyl glycidyl ether binary random copolymer is dried for 48 hours at the temperature of 60 ℃ under vacuum. The glass transition temperature of the polymer was-41.57 ℃ and the number average molecular weight was 98449.
In comparative example 1, the total allyl glycidyl amount is strictly controlled to 3/5 for the pot volume and the amount of Zn-Co DMC catalyst is 0.04% (based on the total mass of added epoxy compound).
0.05 part of DCP (based on 100 parts by weight of the carbon dioxide-based elastomer) is added into the obtained ternary carbon dioxide-based elastomer to promote crosslinking, and the mechanical properties of the ternary carbon dioxide-based elastomer are tested. Vulcanized by a flat vulcanizing machine at 160 ℃ for 15min and then taken out, and the tensile strength is measured to be 0.1MPa, and the elongation at break is 61.55%. The tensile strength of the ternary carbon dioxide-based elastomer introduced with 1, 2-epoxyhexane in the example 1 is 0.62MPa, the elongation at break is 300.29%, compared with the tensile strength of the example 1, the tensile strength is increased by 520%, the elongation at break is increased by 387.88%, and the performance is remarkably improved.
Claims (10)
1. A carbon dioxide-based elastomer, characterized in that the repeating unit of the elastomer has the following structural formula:
wherein a is an integer of 1-5.
2. An elastomer as claimed in claim 1, wherein said elastomer has a number average molecular weight in the range of 30000 to 200000, preferably 50000 to 150000.
3. An elastomer as claimed in claim 1 or claim 2 wherein said elastomer is a random copolymer of carbon dioxide, glycidyl ether compounds, epoxy compounds.
4. An elastomeric body according to claim 3,
the glycidyl ether compound is at least one of allyl glycidyl ether and glycidyl methacrylate; and/or the presence of a gas in the gas,
the epoxy compound is selected from saturated alkyl epoxy compounds with 3-12 carbon atoms, and preferably is at least one selected from 1, 2-epoxybutane, 1, 2-epoxypentane, 1, 2-epoxyhexane, 1, 2-epoxyheptane, 1, 2-epoxyoctane, 1, 2-epoxydodecane, epichlorohydrin and epoxy 10-methyl undecylenate.
5. An elastomeric body according to claim 4,
the glycidyl ether compound is selected from allyl glycidyl ether; and/or the presence of a gas in the gas,
the epoxy compound is selected from 1, 2-epoxy hexane.
6. A method for preparing the carbon dioxide-based elastomer according to any one of claims 1 to 5, comprising mixing the carbon dioxide, the glycidyl ether compound and the epoxy compound, and carrying out a polymerization reaction to obtain the carbon dioxide-based elastomer.
7. The preparation method according to claim 6, wherein the preparation method specifically comprises the following steps:
step 1, weighing an epoxy compound and a glycidyl ether compound, adding the epoxy compound and the glycidyl ether compound into a reaction container, heating, introducing carbon dioxide gas, and heating for polymerization reaction to obtain a carbon dioxide-based elastomer crude product;
and 2, cooling the crude product of the carbon dioxide-based elastomer obtained in the step 1, dissolving the crude product in a solvent S1, adding a solvent S2, precipitating and drying to obtain the carbon dioxide-based elastomer.
8. The method according to claim 7, wherein, in step 1,
the volume ratio of the epoxy compound to the glycidyl ether compound is 1: 1-5: 1, preferably 1: 1-3: 1; and/or the presence of a gas in the gas,
the total volume of the epoxy compound and the glycidyl ether compound is 1/3-4/5 of the volume of the reaction kettle, preferably 1/2-2/3; and/or the presence of a gas in the gas,
the epoxy compound and the glycidyl ether compound are dried before reaction; and/or the presence of a gas in the gas,
the polymerization reaction temperature is 60-90 ℃, and preferably 70-85 ℃; and/or the presence of a gas in the gas,
the polymerization reaction time is 5-25 h, preferably 10-20 h; and/or the presence of a gas in the gas,
the polymerization pressure is 2-6 MPa, preferably 3-5 MPa; and/or the presence of a gas in the gas,
the polymerization reaction is carried out under the anhydrous and oxygen-free conditions; and/or the presence of a gas in the gas,
and a catalyst is also added in the polymerization reaction.
9. The method according to claim 8,
the catalyst is selected from at least one of metalloporphyrin catalyst, bimetallic catalyst, rare earth metal catalyst and chelating Schiff base catalyst, preferably from bimetallic catalyst, more preferably from zinc cobalt cyanide complex; and/or the presence of a gas in the gas,
the amount of the catalyst is 0.01-0.2% of the amount of the epoxy compound, preferably 0.03-0.05% by mass.
10. The production method according to claim 7, wherein, in the step 2,
the solvent S1 is at least one selected from dichloromethane, toluene and tetrahydrofuran, preferably dichloromethane; and/or the presence of a gas in the gas,
the solvent S2 is selected from at least one of methanol and ethanol, preferably methanol; and/or the presence of a gas in the gas,
the volume ratio of the solvent S1 to the solvent S2 is 1: 5-1: 20, preferably 1: 8-1: 10; and/or the presence of a gas in the gas,
the drying temperature is 50-80 ℃, and preferably 60-70 ℃.
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| WO2024070798A1 (en) * | 2022-09-30 | 2024-04-04 | リンテック株式会社 | Aliphatic polycarbonate resin, crosslinked aliphatic polycarbonate resin, methods for producing same, and adhesive sheet |
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