CN114573799B - Biodegradable carbon dioxide-based copolyester-carbonate dihydric alcohol and preparation method thereof - Google Patents
Biodegradable carbon dioxide-based copolyester-carbonate dihydric alcohol and preparation method thereof Download PDFInfo
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- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 68
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 34
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 34
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 33
- 239000003054 catalyst Substances 0.000 claims abstract description 27
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000000178 monomer Substances 0.000 claims abstract description 23
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 150000002148 esters Chemical class 0.000 claims abstract description 9
- 238000007334 copolymerization reaction Methods 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims abstract description 6
- 238000004519 manufacturing process Methods 0.000 claims abstract description 5
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 claims description 12
- 125000001931 aliphatic group Chemical group 0.000 claims description 12
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 claims description 12
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 8
- -1 diol phthalate Chemical class 0.000 claims description 7
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 5
- 229910044991 metal oxide Inorganic materials 0.000 claims description 4
- 150000004706 metal oxides Chemical class 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 229910002482 Cu–Ni Inorganic materials 0.000 claims description 2
- 229910006404 SnO 2 Inorganic materials 0.000 claims description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 2
- 238000005886 esterification reaction Methods 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 150000002009 diols Chemical class 0.000 abstract description 13
- 229920000515 polycarbonate Polymers 0.000 abstract description 13
- 239000004417 polycarbonate Substances 0.000 abstract description 13
- 229920000642 polymer Polymers 0.000 abstract description 7
- 239000004721 Polyphenylene oxide Substances 0.000 abstract description 4
- 125000003118 aryl group Chemical group 0.000 abstract description 4
- 230000003647 oxidation Effects 0.000 abstract description 4
- 238000007254 oxidation reaction Methods 0.000 abstract description 4
- 229920000570 polyether Polymers 0.000 abstract description 4
- 229920001400 block copolymer Polymers 0.000 abstract description 2
- 239000012024 dehydrating agents Substances 0.000 abstract description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 abstract description 2
- 239000000376 reactant Substances 0.000 abstract description 2
- 238000010408 sweeping Methods 0.000 abstract description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 12
- 229920000728 polyester Polymers 0.000 description 5
- 238000010926 purge Methods 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 2
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- FFNVQNRYTPFDDP-UHFFFAOYSA-N 2-cyanopyridine Chemical compound N#CC1=CC=CC=N1 FFNVQNRYTPFDDP-UHFFFAOYSA-N 0.000 description 1
- 206010060800 Hot flush Diseases 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006065 biodegradation reaction Methods 0.000 description 1
- 125000005587 carbonate group Chemical group 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 150000005676 cyclic carbonates Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000005311 nuclear magnetism Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 239000002516 radical scavenger Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/64—Polyesters containing both carboxylic ester groups and carbonate groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/141—Feedstock
Abstract
The invention discloses biodegradable carbon dioxide-based copolyester-carbonic ester dihydric alcohol and a preparation method thereof. The invention reduces the cost of long chain diol monomer needed by polymer and improves the degradability of the long chain diol monomer by introducing aromatic chain segment, and adopts a reaction system with mild pressure range and no dehydrating agent to reduce equipment and production cost. The moisture generated by the reaction is taken away through the sweeping of reactant carbon dioxide, and the monomer dihydroxyaliphatic glycol phthalate and CO are catalyzed 2 The polyester-polycarbonate block copolymer obtained by copolymerization can have different sequence structures, including random structures, block structures and the like. After the reaction is finished, the catalyst and the product are easy to separate, and the carbon dioxide can be recycled. Compared with the traditional polyether glycol, the modified polyether glycol has better oxidation resistance and degradability. The carbon dioxide-based copolyester-carbonic ester dihydric alcohol synthesized by the method has low cost, and opens up a new application field of carbon dioxide as a green resource.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to biodegradable carbon dioxide-based copolyester-carbonic ester dihydric alcohol and a preparation method thereof.
Background
The petroleum-based polymer material brings convenience to life of people, and meanwhile, a large amount of nondegradable plastics also cause serious white pollution, so that plastic forbidden commands are pushed out in many ways. Therefore, the development of biodegradable materials has great significance; on the other hand, in the past century of global industrialization development, carbon dioxide produced by humans has led to a sharp rise in the concentration of carbon dioxide in the atmosphere. The increasingly serious greenhouse effect is caused, and the fixation and resource utilization of carbon dioxide have become research hotspots on the global scale. The strategic development targets of the carbon reaching peak and the carbon neutralization 3060 are further defined in China.
Since CO 2 The direct synthesis of dimethyl carbonate with methanol has been found to lead to an industry search for CO due to its simple, non-toxic reaction process 2 Hot flushes with alcohols. Tomishige et al in 2016 utilized CeO 2 CO was carried out as a catalyst and 2-cyanopyridine as a water scavenger 2 Polycondensation with a series of diols was investigated (Sci. Rep.6, 24038) to give polycarbonate diols of different molecular weights.
The polycarbonate diol has wide application, especially in the synthesis of polyurethane, can lead the oxidation resistance of the polycarbonate diol to be more excellent, and can lead the polycarbonate diol to have degradability by introducing aromatic rings and carbonate groups. Since short-chain molecular diols tend to be readily CO-compatible 2 The formation of cyclic carbonates, polycarbonate diols reported at present, often employ long carbon chain diols (C.gtoreq.4), however, the relatively high price of long chain diols makes practical production applications of polycarbonate diols limited.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides biodegradable carbon dioxide-based copolyester-carbonic ester dihydric alcohol and a preparation method thereof.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
a biodegradable carbon dioxide-based copolyester-carbonate dihydric alcohol has a structure shown in formula 1:
wherein m is more than or equal to 1, n is more than or equal to 1, and m and n are integers; r is any one or more of aliphatic hydrocarbon groups with 2-6 carbon atoms, ar represents benzene ring.
The preparation method of the biodegradable carbon dioxide-based copolyester-carbonic ester dihydric alcohol comprises the following steps: the catalyst is prepared by carrying out copolymerization reaction on first monomer dihydroxyaliphatic diol phthalate, second monomer carbon dioxide and third monomer aliphatic diol under the action of a catalyst; wherein the first monomer phthalic acid dihydroxyl fatty glycol ester is obtained by esterification reaction of phthalic acid or phthalic anhydride and aliphatic dihydric alcohol, the structural formula is shown in the formula 2,
wherein Ar represents a benzene ring, a carbonyl group connected with the benzene ring is positioned at the ortho position, the meta position or the para position of the benzene ring, and R is any one or more of aliphatic hydrocarbon groups with 2-6 carbon atoms.
Preferably, in the above production method, the aliphatic diol is selected from aliphatic diols having 2 to 6 carbon atoms.
Preferably, the above preparation method comprises the steps of: adding phthalic acid or phthalic anhydride, aliphatic dihydric alcohol and a catalyst into a reactor, introducing nitrogen and heating to react to obtain a first monomer, then switching nitrogen into carbon dioxide to serve as a second monomer, taking excessive aliphatic dihydric alcohol in a system as a third monomer, carrying out copolymerization reaction on the three monomers, and removing the catalyst through hot filtration after the reaction is finished to obtain the purified carbon dioxide-based copolyester-carbonic ester dihydric alcohol.
Preferably, in the preparation method, the catalyst is one or more of a supported Cu-Ni bimetallic catalyst or a metal oxide.
Preferably, in the above preparation method, the metal oxide is CeO 2 、SnO 2 Or ZrO(s) 2 。
Preferably, in the above preparation method, the molar ratio of the catalyst to the aliphatic diol is 1:20-3000, wherein the feeding molar ratio of the phthalic acid or phthalic anhydride to the aliphatic diol is 1:2-10, the flow rate of nitrogen is greater than 100mL/min, the flow rate of carbon dioxide is greater than 200mL/min, the whole reaction pressure is 0.01-0.1MPa, the reaction temperature is 200-300 ℃, and the reaction time is 4-96h.
Compared with the prior art, the invention has the following beneficial effects: the invention reduces the cost of long chain diol monomer needed by polymer and improves the degradability of the long chain diol monomer by introducing aromatic chain segment, and adopts a reaction system with mild pressure range and no dehydrating agent to reduce equipment and production cost. The moisture generated by the reaction is taken away through the sweeping of reactant carbon dioxide, and the monomer dihydroxyaliphatic glycol phthalate and CO are catalyzed 2 The polyester-polycarbonate block copolymer obtained by copolymerization can have different sequence structures, including random structures, block structures and the like. After the reaction is finished, the catalyst and the product are easy to separate, and the carbon dioxide can be recycled. The carbon dioxide-based copolymer dihydric alcohol can obtain different sequence structures through monomer structure design and adjustment of polyester and polycarbonate chain segments, and endows materials with various performances such as heat resistance, mechanical performance, oxidation resistance, water resistance, biodegradation and the like required by different application scenes. Compared with the traditional polyether glycol, the modified polyether glycol has better oxidation resistance and degradability. The carbon dioxide-based copolyester-carbonic ester dihydric alcohol synthesized by the method has low cost, and opens up a new application field of carbon dioxide as a green resource.
Drawings
FIG. 1 shows the nuclear magnetism of the polymer prepared in example 1 of the present invention 1 HNMR diagram.
Detailed Description
The invention may be further illustrated and described in connection with the following specific examples, which are not intended to limit the invention in any manner:
example 1
In a 50mL reaction vessel, 3.32g terephthalic acid, 3.40g ethylene glycol, 10mg Mn (Ac) 2 、100mg CeO 2 The catalyst is added sequentially. Maintaining the pressure at 0.1MPa, and introducing N 2 Purging, flowing speed is 100mL/min, and reflux reaction is carried out for 10h at 215 ℃. Subsequent switching of N 2 Is CO 2 Control of CO 2 The reaction was continued for 48h at a flow rate of 200mL/min and at a reaction temperature of 210 ℃. And after the reaction is finished, the catalyst is removed by hot filtration, and a product is obtained. Yield 88.5% (based on terephthalic acid), conversion 100% (base)In terephthalic acid), polymer selectivity 92.0%, mn=2742, polyester content 55.2%, polycarbonate content 44.8%. And carrying out a nuclear magnetic experiment on the product, wherein the result is shown in figure 1, which shows that the obtained product is the target product.
Example 2
In a 50mL reaction vessel, 2.82g of phthalic anhydride, 3.40g of ethylene glycol, 20mg of tetrabutyl titanate, 100mg of CeO 2 The catalyst is added sequentially. Maintaining the pressure at 0.08MPa, and introducing N 2 Purging, and refluxing at 200 ℃ for 5 hours at a flow rate of 100 mL/min. Subsequent switching of N 2 Is CO 2 Control of CO 2 The flow rate was 200mL/min, the reaction time was 48h, and the reaction temperature was 220 ℃. And after the reaction is finished, the catalyst is removed by hot filtration, and a product is obtained. The yield was 90.0% (based on phthalic anhydride), the conversion was 100% (based on phthalic anhydride), the polymer selectivity was 96.4%, mn=2260, the polyester content was 62.5%, and the polycarbonate content was 37.5%.
Example 3
In a 100mL reaction vessel, 3.32g of terephthalic acid, 4.15g of butanediol, 100mg of CeO 2 The catalyst is added sequentially. Maintaining the pressure at 0.05MPa, and introducing N 2 Reflux reaction was carried out at 200℃for 4h. Then from N 2 Switching N after purging for 1h 2 Is CO 2 Control of CO 2 The reaction was continued for 48h at a flow rate of 200mL/min and at a reaction temperature of 235 ℃. And after the reaction is finished, the catalyst is removed by hot filtration, and a product is obtained. Yield 86.2% (based on terephthalic acid), conversion 100% (based on terephthalic acid), polymer selectivity 94.5%, mn=3012, polyester content 60.6%, polycarbonate content 39.4%.
Example 4
In a 50mL reaction vessel, 2.82g of phthalic anhydride, 3.60g of butanediol, 20mg of tetrabutyl titanate catalyst, 100mg of CeO 2 The catalyst is added sequentially. Maintaining the pressure at 0.02MPa, and introducing N 2 Purging, and refluxing at 200 ℃ for 6 hours at a flow rate of 100 mL/min. Subsequent switching of N 2 Is CO 2 Control of CO 2 The flow rate was 200mL/min, the reaction time was 72h, and the reaction temperature was 240 ℃. After the reaction is finished, the catalyst is removed by hot filtrationAnd (3) a catalyst to obtain an aromatic ester-carbonic ester structured product. Yield 92.0% (based on phthalic anhydride), conversion 100% (based on phthalic anhydride), polymer selectivity 98.1%, mn=4249, polyester content 64.4%, polycarbonate content 35.6%.
Claims (5)
1. A preparation method of biodegradable carbon dioxide-based copolyester-carbonate diol is characterized in that the structure of the biodegradable carbon dioxide-based copolyester-carbonate diol is shown as formula 1:
wherein m is more than or equal to 1, n is more than or equal to 1, and m and n are integers; r is any one or more of aliphatic hydrocarbon groups with 2-6 carbon atoms, ar represents benzene ring;
the preparation method of the biodegradable carbon dioxide-based copolyester-carbonate dihydric alcohol comprises the following steps: the catalyst is prepared by carrying out copolymerization reaction on first monomer dihydroxyaliphatic diol phthalate, second monomer carbon dioxide and third monomer aliphatic diol under the action of a catalyst; wherein the first monomer phthalic acid dihydroxyl fatty glycol ester is obtained by esterification reaction of phthalic acid or phthalic anhydride and aliphatic dihydric alcohol, the structural formula is shown in the formula 2,
ar represents a benzene ring, a carbonyl group connected with the benzene ring is positioned at the ortho position, the meta position or the para position of the benzene ring, and R is any one or more of aliphatic hydrocarbon groups with 2-6 carbon atoms;
the method comprises the following steps: adding phthalic acid or phthalic anhydride, aliphatic dihydric alcohol and a catalyst into a reactor, introducing nitrogen and heating to react to obtain a first monomer, then switching nitrogen into carbon dioxide to serve as a second monomer, taking excessive aliphatic dihydric alcohol in a system as a third monomer, carrying out copolymerization reaction on the three monomers, and removing the catalyst through hot filtration after the reaction is finished to obtain the purified carbon dioxide-based copolyester-carbonic ester dihydric alcohol.
2. The method for producing biodegradable carbon dioxide-based copolyester-carbonate diol according to claim 1, wherein the aliphatic glycol is selected from aliphatic glycols having 2 to 4 carbon atoms.
3. The method for preparing biodegradable carbon dioxide based copolyester-carbonate diol according to claim 1, wherein the catalyst is one or more of supported Cu-Ni bimetallic catalyst or metal oxide.
4. The method for preparing biodegradable carbon dioxide based copolyester-carbonate diol according to claim 3, wherein said metal oxide is CeO 2 、SnO 2 Or ZrO(s) 2 。
5. The method for preparing biodegradable carbon dioxide-based copolyester-carbonate diol according to claim 1, characterized in that the molar ratio of catalyst to aliphatic glycol is 1:20-3000, wherein the feeding molar ratio of the phthalic acid or phthalic anhydride to the aliphatic diol is 1:2-10, the flow rate of nitrogen is greater than 100mL/min, the flow rate of carbon dioxide is greater than 200mL/min, the whole reaction pressure is 0.01-0.1MPa, the reaction temperature is 200-300 ℃, and the reaction time is 4-96h.
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| 可生物降解聚合物的现状及生物降解性研究;那天海, 宋春雷, 莫志深;功能高分子学报(第03期);第129-133页 * |
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