CN114854000A - Bio-based polycarbonate copolymer and preparation method thereof - Google Patents
Bio-based polycarbonate copolymer and preparation method thereof Download PDFInfo
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- CN114854000A CN114854000A CN202210588252.5A CN202210588252A CN114854000A CN 114854000 A CN114854000 A CN 114854000A CN 202210588252 A CN202210588252 A CN 202210588252A CN 114854000 A CN114854000 A CN 114854000A
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- 239000004417 polycarbonate Substances 0.000 title claims abstract description 79
- 229920000515 polycarbonate Polymers 0.000 title claims abstract description 78
- 238000002360 preparation method Methods 0.000 title description 7
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims abstract description 51
- 239000002994 raw material Substances 0.000 claims abstract description 38
- 239000003054 catalyst Substances 0.000 claims abstract description 29
- 229920000642 polymer Polymers 0.000 claims abstract description 27
- 150000001875 compounds Chemical class 0.000 claims abstract description 21
- 150000004650 carbonic acid diesters Chemical class 0.000 claims abstract description 13
- KLDXJTOLSGUMSJ-JGWLITMVSA-N Isosorbide Chemical compound O[C@@H]1CO[C@@H]2[C@@H](O)CO[C@@H]21 KLDXJTOLSGUMSJ-JGWLITMVSA-N 0.000 claims description 29
- 229960002479 isosorbide Drugs 0.000 claims description 28
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 22
- 238000006243 chemical reaction Methods 0.000 claims description 20
- ROORDVPLFPIABK-UHFFFAOYSA-N diphenyl carbonate Chemical compound C=1C=CC=CC=1OC(=O)OC1=CC=CC=C1 ROORDVPLFPIABK-UHFFFAOYSA-N 0.000 claims description 20
- 238000010438 heat treatment Methods 0.000 claims description 17
- 238000006068 polycondensation reaction Methods 0.000 claims description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 10
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 10
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 8
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 8
- 229910052783 alkali metal Inorganic materials 0.000 claims description 8
- 150000001340 alkali metals Chemical group 0.000 claims description 8
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 8
- 150000002148 esters Chemical group 0.000 claims description 7
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- -1 carbonate compound Chemical class 0.000 claims description 6
- PMMYEEVYMWASQN-IMJSIDKUSA-N cis-4-Hydroxy-L-proline Chemical compound O[C@@H]1CN[C@H](C(O)=O)C1 PMMYEEVYMWASQN-IMJSIDKUSA-N 0.000 claims description 6
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 claims description 6
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 claims description 5
- 229940043375 1,5-pentanediol Drugs 0.000 claims description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 4
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 claims description 4
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 4
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 claims description 4
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 4
- 239000011780 sodium chloride Substances 0.000 claims description 4
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 claims description 3
- 229940035437 1,3-propanediol Drugs 0.000 claims description 3
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 3
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 3
- QLVWOKQMDLQXNN-UHFFFAOYSA-N dibutyl carbonate Chemical compound CCCCOC(=O)OCCCC QLVWOKQMDLQXNN-UHFFFAOYSA-N 0.000 claims description 3
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 3
- VUPKGFBOKBGHFZ-UHFFFAOYSA-N dipropyl carbonate Chemical compound CCCOC(=O)OCCC VUPKGFBOKBGHFZ-UHFFFAOYSA-N 0.000 claims description 3
- 229920000166 polytrimethylene carbonate Polymers 0.000 claims description 3
- MFGOFGRYDNHJTA-UHFFFAOYSA-N 2-amino-1-(2-fluorophenyl)ethanol Chemical compound NCC(O)C1=CC=CC=C1F MFGOFGRYDNHJTA-UHFFFAOYSA-N 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- 229910001514 alkali metal chloride Inorganic materials 0.000 claims description 2
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 claims description 2
- 229910000024 caesium carbonate Inorganic materials 0.000 claims description 2
- AIYUHDOJVYHVIT-UHFFFAOYSA-M caesium chloride Chemical compound [Cl-].[Cs+] AIYUHDOJVYHVIT-UHFFFAOYSA-M 0.000 claims description 2
- HUCVOHYBFXVBRW-UHFFFAOYSA-M caesium hydroxide Inorganic materials [OH-].[Cs+] HUCVOHYBFXVBRW-UHFFFAOYSA-M 0.000 claims description 2
- PKPOVTYZGGYDIJ-UHFFFAOYSA-N dioctyl carbonate Chemical compound CCCCCCCCOC(=O)OCCCCCCCC PKPOVTYZGGYDIJ-UHFFFAOYSA-N 0.000 claims description 2
- HSNQKJVQUFYBBY-UHFFFAOYSA-N dipentyl carbonate Chemical compound CCCCCOC(=O)OCCCCC HSNQKJVQUFYBBY-UHFFFAOYSA-N 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 2
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 2
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 239000001103 potassium chloride Substances 0.000 claims description 2
- 235000011164 potassium chloride Nutrition 0.000 claims description 2
- 229940093476 ethylene glycol Drugs 0.000 claims 1
- 229920001577 copolymer Polymers 0.000 abstract description 13
- 239000000178 monomer Substances 0.000 abstract description 8
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 abstract description 3
- 229920001289 polyvinyl ether Polymers 0.000 abstract description 3
- 230000009477 glass transition Effects 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 12
- 239000007858 starting material Substances 0.000 description 11
- 238000006116 polymerization reaction Methods 0.000 description 6
- 238000005809 transesterification reaction Methods 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- KLDXJTOLSGUMSJ-UNTFVMJOSA-N (3s,3ar,6s,6ar)-2,3,3a,5,6,6a-hexahydrofuro[3,2-b]furan-3,6-diol Chemical compound O[C@H]1CO[C@@H]2[C@@H](O)CO[C@@H]21 KLDXJTOLSGUMSJ-UNTFVMJOSA-N 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- 238000007334 copolymerization reaction Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229930185605 Bisphenol Natural products 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- 150000005690 diesters Chemical class 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical group CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical group C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 101001081953 Homo sapiens Phosphoribosylaminoimidazole carboxylase Proteins 0.000 description 2
- 102100027330 Phosphoribosylaminoimidazole carboxylase Human genes 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000007859 condensation product Substances 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 2
- 229920006351 engineering plastic Polymers 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical class C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- BYWLOJPPHKPJHL-UHFFFAOYSA-N N1C=NC=C1.C(C)[N+](CC)(CC)CC Chemical compound N1C=NC=C1.C(C)[N+](CC)(CC)CC BYWLOJPPHKPJHL-UHFFFAOYSA-N 0.000 description 1
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- ZDRTUOLLFPPIKP-UHFFFAOYSA-N bis(2-acetylphenyl) carbonate Chemical compound CC(=O)C1=CC=CC=C1OC(=O)OC1=CC=CC=C1C(C)=O ZDRTUOLLFPPIKP-UHFFFAOYSA-N 0.000 description 1
- MUCRFDZUHPMASM-UHFFFAOYSA-N bis(2-chlorophenyl) carbonate Chemical compound ClC1=CC=CC=C1OC(=O)OC1=CC=CC=C1Cl MUCRFDZUHPMASM-UHFFFAOYSA-N 0.000 description 1
- QLCWLFJKMPVUQJ-UHFFFAOYSA-N bis(2-formylphenyl) carbonate Chemical compound O=CC1=CC=CC=C1OC(=O)OC1=CC=CC=C1C=O QLCWLFJKMPVUQJ-UHFFFAOYSA-N 0.000 description 1
- DQPSUGZZTADITQ-UHFFFAOYSA-N bis(2-nitrophenyl) carbonate Chemical compound [O-][N+](=O)C1=CC=CC=C1OC(=O)OC1=CC=CC=C1[N+]([O-])=O DQPSUGZZTADITQ-UHFFFAOYSA-N 0.000 description 1
- QKUZHOWQFIEVCU-UHFFFAOYSA-N bis(5-oxo-6-phenylcyclohexa-1,3-dien-1-yl) carbonate Chemical compound C(OC=1C(C(C=CC=1)=O)C1=CC=CC=C1)(OC=1C(C(C=CC=1)=O)C1=CC=CC=C1)=O QKUZHOWQFIEVCU-UHFFFAOYSA-N 0.000 description 1
- 125000005587 carbonate group Chemical group 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- ZFTFAPZRGNKQPU-UHFFFAOYSA-N dicarbonic acid Chemical compound OC(=O)OC(O)=O ZFTFAPZRGNKQPU-UHFFFAOYSA-N 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 229920006158 high molecular weight polymer Polymers 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 238000012643 polycondensation polymerization Methods 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 125000001453 quaternary ammonium group Chemical class 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 230000004580 weight loss Effects 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
- C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
- C08G64/16—Aliphatic-aromatic or araliphatic polycarbonates
- C08G64/1608—Aliphatic-aromatic or araliphatic polycarbonates saturated
-
- 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
- C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
- C08G64/20—General preparatory processes
- C08G64/30—General preparatory processes using carbonates
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
The invention discloses a copolymer of bio-based polycarbonate, which has the following structural formula:
x and y are the number of the polymer repeating units; x + y is an integer between 80 and 120; the bio-based polycarbonate copolymer is prepared by taking carbonic acid diester, dihydroxy compound and bisphenol A polyvinyl ether as raw materials and catalyzing the raw materials by a catalyst. By adopting the technical scheme of the invention, the polycarbonate copolymer contains benzene ring and flexible long-chain-CH by introducing the third monomer of hydroxyethylated bisphenol A 2 CH 2 The polycarbonate copolymer can simultaneously endow certain rigidity and toughness to the polycarbonate polymer, the rigidity and the toughness are compatible in a polycarbonate copolymer system, and the polycarbonate copolymer improves the toughness of the polymer and further improves the thermophysical property and the processability of the polymer on the premise of keeping the high molecular weight characteristic。
Description
Technical Field
The invention relates to the technical field of polycarbonate copolymerization, in particular to a copolymer of bio-based polycarbonate and a preparation method thereof.
Background
Polycarbonate, also known as PC plastic; the polymer is a high molecular polymer containing carbonate groups in the molecular chain, and can be classified into various types such as aliphatic, aromatic, aliphatic-aromatic and the like according to the structure of the ester groups. Among them, aliphatic and aliphatic-aromatic polycarbonates have limited their use as engineering plastics due to their low mechanical properties. The aromatic polycarbonate has a series of excellent performances such as impact resistance, creep resistance, electrical insulation, weather resistance, high light transmittance and the like, and is an engineering plastic with wide application.
In industrial production, polycarbonates generally use bisphenol a as a monomer for polymerization, which is derived from non-renewable petroleum resources and is biologically toxic. With the need for environmental protection and health, the development of safe and environmentally friendly polycarbonate synthesis routes has become a focus of attention in the global polycarbonate industry.
Isosorbide, which is derived from glucose, is a bio-based monomer with a dihydroxy structure, has the characteristics of high molecular rigidity, chiral structure and the like, is industrially produced, and can be used for synthesizing polycarbonate instead of bisphenol A. However, isosorbide has lower hydroxyl reactivity than bisphenol A, which is detrimental to the rapid increase in molecular weight of the polymer, and therefore, polycarbonates synthesized by this method are generally lower in molecular weight. In addition, two connected furan rings in the molecular structure of isosorbide increase the rigidity of the molecular chain of the polymer, and the polymer prepared by using the furan ring has poor processability.
In the prior art, isosorbide is used for preparing polycarbonate in two modes of solution polymerization and melt polymerization, wherein phosgene and a chlorine-containing solvent are required to be used as raw materials in the former mode, and the environmental pollution is large. However, in the process of preparing polycarbonate by melt polymerization, condensation products are generated, which results in that a high molecular weight polymer cannot be obtained, and in order to obtain a high molecular weight polycarbonate, severe reaction conditions are required to remove the condensation products, which in turn results in side reactions, and further results in degradation and coloration of the polymer.
Synthesis of Bis (hydroxy ethyl) s of Aromatic Dihydroxy Compounds and Poly (ether-carbonate) s with Bisphenol A, Polymer International, 1998, 47, 439-444 discloses the Synthesis of modified Bisphenol A type polycarbonates using Bisphenol A, hydroxyethylated Bisphenol A, diphenyl carbonate as monomers, with an intrinsic viscosity of up to 0.40dL/g, a glass transition temperature of 132 ℃, an initial decomposition temperature of 382 ℃; the molecular weight Mw ranges from 29000 to 112000 g/mol. Bisphenol diphenyl (hydroxyethyl ether) is used for melt phase polycondensation reaction with bisphenol A and diphenyl carbonate to synthesize polyester (ether-carbonate) with Tg of 62-140 deg.C, and bis (hydroxyethyl ether) of various bisphenols is used to synthesize extensive poly (ether carbonate). However, poly (ether carbonates) obtained by melt phase polycondensation in the above-mentioned manner have a low glass transition temperature and poor hardness, resulting in poor processability. A isosorbide-type polycarbonate prepared by melt transesterification using a Catalyst commonly used in a series of polycondensation reactions is disclosed in Catalyst screening for the polymerization of isosorbide-based polycarbonates, having a weight average molecular weight of up to 32,600 and a glass transition temperature of 164 ℃. Synthesis of a series of quaternary ammonium ionic liquid catalysts are disclosed in Synthesis of isosorbitol-based polycarbonates via polymerization catalysis, namely, core Journal of catalysis, 2017, 38, 908-917, and isosorbide polycarbonate is prepared by melt condensation polymerization by using isosorbide and diphenyl carbonate as monomers, wherein tetraethylammonium imidazolium (TEAI) has the best catalytic effect, the weight average molecular weight of the polymer can reach 25,600g/mol, the conversion rate of isosorbide reaches 92%, but PAICS is amorphous, and the glass transition temperature of the PAICS is 50-110 ℃. And the molecular weight range of the polymer produced in the above-mentioned method is large, and approximately, stable dimensional stability performance cannot be maintained.
Chinese patent application CN101889041A discloses an isosorbide-based polycarbonate, method of making the same, and articles formed therefrom, using a melt polymerization process using an activated carbonate source including bis (ortho-methoxycarbonyl benzene) carbonatePhenyl) carbonate, bis (o-chlorophenyl) carbonate, bis (o-nitrophenyl) carbonate, bis (o-acetylphenyl) carbonate, bis (o-phenylketophenyl) carbonate, and bis (o-formylphenyl) carbonate) to produce an isosorbide-based composition comprising isosorbide units and C 14-44 Aliphatic dicarboxylic acids, C 14-44 Polycarbonate polymers of aliphatic units of aliphatic diols or combinations thereof having molecular weights Mw of greater than 39,000g/mol and glass transition temperatures of 135 ℃ or less have good mechanical properties, but low glass transition temperatures. Chinese patent CN111138650A discloses a high molecular weight high flexibility bio-based polycarbonate copolymer and a preparation method thereof, the invention adopts carbonic acid diester, 1,4:3, 6-dianhydrohexitol and dihydroxy compound as raw materials to obtain copolycarbonate containing C-O-C-bond aliphatic diol structure, thereby improving the flexibility of the copolymer. However, the low reactivity of isosorbide, isomannide and isoidide during the reaction results in poor selectivity of copolymerization, it is difficult to obtain copolymers with molecular weight of more than 5000 in practice, and the glass transition temperature of the copolymer obtained by polycondensation is generally lower than 130 ℃ due to the influence of aliphatic diol structure.
Obviously, the problem to be solved in the prior art of synthesizing polycarbonate polymer by substituting isosorbide for bisphenol A is to increase the reactivity of hydroxyl group in isosorbide to increase the molecular weight of the polymer and to make the polymer have high glass transition temperature.
Disclosure of Invention
The invention aims to provide a copolymer of bio-based polycarbonate and a preparation method thereof, wherein the copolymer contains a rigid benzene ring structure and flexible-CH 2 CH 2 The dihydric alcohol of the unit is used for carrying out copolymerization modification on the polycarbonate so as to further improve the thermophysical property and the processing property of the polycarbonate on the premise of keeping higher molecular weight property of the polycarbonate.
In order to achieve the purpose, the invention provides the following technical scheme:
a copolymer of bio-based polycarbonate having the formula:
x and y are the number of the polymer repeating units; x + y is an integer between 80 and 120, preferably 100; further, x: y is 1:20 to 2:1, preferably 1:9 to 1: 1; the bio-based polycarbonate copolymer is prepared by taking carbonic acid diester, dihydroxy compound and bisphenol A polyvinyl ether as raw materials and catalyzing the raw materials by a catalyst.
In the technical scheme, the addition ratio of carbonic diester, dihydroxy compound and hydroxyethylated bisphenol A is 1: (1-10): (0.25-5).
In the above technical scheme, the dosage of the catalyst is 1 × 10 of the molar weight of the carbonic diester -5 -1×10 -3 。
In the above technical scheme, the catalyst is an alkali metal catalyst, and the alkali metal catalyst is at least one of hydroxide or chloride of alkali metal or carbonate compound.
Preferably, the alkali metal hydroxide is at least one of lithium hydroxide, sodium hydroxide, potassium hydroxide and cesium hydroxide; the alkali metal chloride is at least one of lithium chloride, sodium chloride, potassium chloride and cesium chloride; the carbonate of the alkali metal is at least one of lithium carbonate, sodium carbonate, potassium carbonate and cesium carbonate.
Further preferably, the catalyst is an alkali metal hydroxide.
In the above technical scheme, the dihydroxy compound is any one or a mixture of several of isosorbide, ethylene glycol, 1, 2-ethanediol, 1, 3-propanediol, 1, 4-butanediol, 1, 5-pentanediol, 1, 6-hexanediol, 1, 4-cyclohexanediol, 1, 4-cyclohexanedimethanol, and bisphenol a.
In the above technical solution, the carbonic acid diester is selected from at least one of dimethyl carbonate, diethyl carbonate, dipropyl carbonate, dibutyl carbonate, and diphenyl carbonate.
In the above technical scheme, the prepared polycarbonate copolymer has a weight average molecular weight of 3.3 × 10 4 ～4.3×10 4 g/mol。
In order to achieve the above object, the present invention also provides a method for preparing the above polycarbonate, comprising the steps of:
(1) and (3) ester exchange stage: using carbonic acid diester, dihydroxy compound and bisphenol A polyvinyl ether as raw materials, adding a catalyst, heating to 130-160 ℃ under nitrogen atmosphere and normal pressure, and continuously heating to 180-200 ℃ for reaction for 0.5-5 h after the raw materials are melted and uniformly mixed to obtain a prepolymer;
(2) a polycondensation stage: and continuously heating to 220-260 ℃, gradually reducing the pressure of the reaction system to 50-300 Pa, and reacting for 1-5 h to obtain the polycarbonate copolymer.
The present invention uses dihydroxy compounds instead to synthesize bio-based polycarbonates. The invention has better effects compared with isosorbide, isomannide or isoidide by selecting ethylene glycol, 1, 2-ethylene glycol, 1, 3-propylene glycol, 1, 4-butanediol, 1, 5-pentanediol, 1, 6-hexanediol, 1, 4-cyclohexanediol and 1, 4-cyclohexanedimethanol besides adopting isosorbide and bisphenol A.
The invention carries out copolymerization modification by introducing a third monomer, wherein the third monomer is hydroxyethylated bisphenol A, C 19 H 16 O 4 The structural formula is as follows:
when the mole percentage content of the hydroxyethylated bisphenol A in the copolymer is 30 percent, the storage modulus at 25 ℃ is 2570Mpa and is lower than 1,4:3,6 dianhydrohexitol homopolymerization type polycarbonate, and the flexibility is obviously improved. This is attributed to the presence of benzene ring and-CH in the molecule of hydroxyethylated bisphenol A 2 CH 2 The polymer can be endowed with certain rigidity and toughness, and the rigidity and the toughness are compatible in a copolymer system, so that the characteristics of high glass transition temperature and high elongation at break are embodied.
Due to the application of the technical scheme, compared with the prior art, the invention has the following advantages:
1. by adopting the technical scheme of the invention, the third monomer of hydroxyethylated bisphenol A is introduced to ensure that the polycarbonate copolymer contains the bisphenol ABenzene ring and flexible long chain-CH 2 CH 2 The polycarbonate copolymer can simultaneously endow certain rigidity and toughness to the polycarbonate polymer, the rigidity and the toughness are compatible in a polycarbonate copolymer system, and the polycarbonate copolymer improves the toughness of the polymer and further improves the thermophysical property and the processability of the polymer on the premise of keeping the characteristic of high molecular weight.
2. According to the polycarbonate copolymer provided by the invention, the hydroxyethylated bisphenol A is introduced into the copolymer, and the polycarbonate copolymer has high molecular weight and higher glass transition temperature on the premise of keeping the excellent performance of the aromatic polycarbonate copolymer, so that the processability of the bio-based polycarbonate copolymer is improved, and the thermal stability is good.
3. By adopting the technical scheme of the invention, the bio-based polycarbonate copolymer with the molecular weight in a specific range can be provided, and the dimensional stability of the copolymer can be highly maintained, so that the wide industrial application of the copolymer can be met.
4. Compared with the traditional polymer, the bio-based polycarbonate copolymer obtained by adopting the dicarbonate, the dihydroxy compound and the hydroxyethylated bisphenol A as the raw materials has higher glass transition temperature and better optical performance, and the material has no health risk in the use process, and accords with the high-quality development concept of green and environment-friendly synthetic materials from the aspects of preparation route and material performance.
Detailed Description
The technical solutions in the embodiments of the present invention are clearly and completely described below with reference to the specific contents of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments of the present invention without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides a preparation method of a bio-based polycarbonate copolymer, which comprises a transesterification stage and a polycondensation stage. The method specifically comprises the following steps:
(1) and (3) ester exchange stage: using carbonic acid diester, dihydroxy compound and hydroxyethylated bisphenol A as raw materials, adding a catalyst, heating to 130-160 ℃ under nitrogen atmosphere and normal pressure, continuing to heat to 180-200 ℃ after the raw materials are melted and uniformly mixed, and reacting for 0.5-5 h to obtain a prepolymer; wherein the addition ratio of the carbonic diester, the dihydroxy compound and the hydroxyethylated bisphenol A is 1: (1-10): (0.25-5).
The dihydroxy compound can be any one or a mixture of several of isosorbide, ethylene glycol, 1, 2-ethanediol, 1, 3-propanediol, 1, 4-butanediol, 1, 5-pentanediol, 1, 6-hexanediol, 1, 4-cyclohexanediol, 1, 4-cyclohexanedimethanol and bisphenol A.
The carbonic acid diester is selected from one or more of diphenyl carbonate, dimethyl carbonate, diethyl carbonate, dipropyl carbonate, dibutyl carbonate, dipentyl carbonate and dioctyl carbonate.
(2) A polycondensation stage: and continuously heating to 220-260 ℃, gradually reducing the pressure of the reaction system to 50-300 Pa, and reacting for 1-5 h to obtain the polycarbonate copolymer.
Example 1
Adding 42.9g of diphenyl carbonate, 29.2g of isosorbide and 61.6g of hydroxyethylated bisphenol A as raw materials into a 250mL three-neck flask, adding 0.08g of sodium hydroxide, heating to 130-160 ℃ under the atmosphere of nitrogen and normal pressure, stirring after the raw materials are molten, mixing uniformly, and then continuously heating to 180 ℃ for carrying out ester exchange reaction for 0.5h to obtain a prepolymer; and continuously heating to 220 ℃ and gradually reducing the pressure of the reaction system to 50Pa to perform polycondensation reaction to obtain the polycarbonate copolymer.
Example 2
This example differs from example 1 in that 42.9g of diphenyl carbonate, 29.2g of isosorbide and 184.8g of hydroxyethylated bisphenol A are used as starting materials.
Example 3
This example differs from example 1 in that 42.9g of diphenyl carbonate, 29.2g of isosorbide and 123.2g of hydroxyethylated bisphenol A are used as starting materials.
Example 4
This example differs from example 1 in that 42.9g of diphenyl carbonate, 29.2g of isosorbide and 30.8g of hydroxyethylated bisphenol A are used as starting materials.
Example 5
This example differs from example 1 in that 42.9g of diphenyl carbonate, 29.2g of isosorbide and 15.4g of hydroxyethylated bisphenol A are used as starting materials.
Example 6
This example differs from example 1 in that 42.9g of diphenyl carbonate, 292g of isosorbide and 61.6g of hydroxyethylated bisphenol A are used as starting materials.
Example 7
This example differs from example 1 in that 42.9g of diphenyl carbonate, 146g of isosorbide and 61.6g of hydroxyethylated bisphenol A are used as starting materials.
Example 8
This example differs from example 1 in that 42.9g of diphenyl carbonate, 12.4g of ethylene glycol and 61.6g of hydroxyethylated bisphenol A were used as starting materials.
Example 9
This example differs from example 1 in that 42.9g of diphenyl carbonate, 23.6g of 1, 6-hexanediol and 61.6g of hydroxyethylated bisphenol A are used as starting materials.
Example 10
This example differs from example 1 in that 42.9g of diphenyl carbonate, 23.2g of 1, 4-cyclohexanediol and 61.6g of hydroxyethylated bisphenol A were used as starting materials.
Example 11
This example is different from example 1 in that the amount of sodium hydroxide added as a catalyst used in this example is 0.0008 g.
Example 12
The difference between this example and example 1 is that the catalyst used in this example is sodium carbonate and the amount added is 0.212 g.
Example 13
The difference between this example and example 1 is that the catalyst used in this example is sodium chloride, and the amount added is 0.107 g.
Example 14
The difference between the embodiment and the embodiment 1 is that the raw materials and the catalyst in the embodiment are mixed and then heated to 130-160 ℃ under nitrogen atmosphere and normal pressure, after the raw materials are melted, the raw materials are stirred and mixed uniformly, and then the temperature is continuously raised to 180 ℃ for transesterification reaction for 0.5h to obtain a prepolymer; and continuously heating to 220 ℃ and gradually reducing the pressure of the reaction system to 300Pa to perform polycondensation reaction to obtain the polycarbonate copolymer.
Example 15
The difference between the embodiment and the embodiment 1 is that the raw materials and the catalyst in the embodiment are mixed and then heated to 130-160 ℃ under nitrogen atmosphere and normal pressure, after the raw materials are melted, the raw materials are stirred and mixed uniformly, and then the temperature is continuously raised to 180 ℃ for transesterification reaction for 0.5h to obtain a prepolymer; and continuously heating to 220 ℃, gradually reducing the pressure of the reaction system to 100Pa, and carrying out polycondensation reaction to obtain the polycarbonate copolymer.
Example 16
The difference between the embodiment and the embodiment 1 is that the raw materials and the catalyst in the embodiment are mixed and then heated to 130-160 ℃ under nitrogen atmosphere and normal pressure, after the raw materials are melted, the raw materials are stirred and mixed uniformly, and then the temperature is continuously raised to 180 ℃ for transesterification reaction for 0.5h to obtain a prepolymer; and continuously heating to 260 ℃ and gradually reducing the pressure of the reaction system to 50Pa to perform polycondensation reaction to obtain the polycarbonate copolymer.
Example 17
The difference between the embodiment and the embodiment 1 is that the raw materials and the catalyst in the embodiment are mixed and then heated to 130-160 ℃ under nitrogen atmosphere and normal pressure, after the raw materials are melted, the raw materials are stirred and mixed uniformly, and then the temperature is continuously raised to 200 ℃ for transesterification reaction for 0.5h to obtain a prepolymer; and continuously heating to 220 ℃ and gradually reducing the pressure of the reaction system to 50Pa to perform polycondensation reaction to obtain the polycarbonate copolymer.
Comparative example 1
The difference between the comparative example and the example 1 is that the raw materials and the catalyst are heated to 130-160 ℃ under nitrogen atmosphere and normal pressure, and after the raw materials are melted, the raw materials are stirred for ester exchange reaction for 0.5h to obtain a prepolymer; and continuously heating to 220 ℃ and gradually reducing the pressure of the reaction system to 400Pa to perform polycondensation reaction to obtain the polycarbonate copolymer.
Comparative example 2
The difference between the comparative example and the example 1 is that the raw materials and the catalyst in the comparative example are mixed and then heated to 130-160 ℃ under nitrogen atmosphere and normal pressure, after the raw materials are melted, the raw materials are stirred and mixed uniformly, and then the temperature is continuously raised to 200 ℃ for ester exchange reaction for 0.5h to obtain a prepolymer; and continuously heating to 300 ℃ and gradually reducing the pressure of the reaction system to 50Pa to perform polycondensation reaction to obtain the polycarbonate copolymer.
Comparative example 3
This comparative example differs from example 1 in that 42.9g of diphenyl carbonate, 29.2g of a dihydroxy compound and 7.7g of hydroxyethylated bisphenol A were used as starting materials.
Comparative example 4
This comparative example differs from example 1 in that 42.9g of diphenyl carbonate, 29.2g of dihydroxy compound and 246.4g of hydroxyethylated bisphenol A were used as starting materials.
The molecular weight, thermal properties and mechanical properties of the polymers prepared in the above examples were examined. The detection method comprises the following steps:
molecular weight: gel Permeation Chromatography (GPC) using N, N-Dimethylformamide (DMF) and monodisperse polystyrene as standard samples.
Thermal properties: detecting the glass transition temperature of the polymer by Differential Scanning Calorimetry (DSC); thermogravimetric analyzer (TGA) characterizes the temperature of thermal weight loss.
Tensile property: elongation at break, UTM universal tester.
Storage modulus: DMA242C detection.
TABLE 1 molecular weight and Performance parameters of the polymers prepared in the examples and comparative examples
In examples 1-5, the ratio of diphenyl carbonate to dihydroxy compound was 1: the molar percentages of hydroxyethylated bisphenol A added are 30%, 60%, 50%, 20% and 10%, respectively, and 30% is the most preferred molar percentage of hydroxyethylated bisphenol A added.
Example 1 and examples 6-7 are examples with different isosorbide contents, diphenyl carbonate, isosorbide and hydroxyethylated bisphenol a being added in proportions of 1: 1: 1. 1: 10: 1 and 1: 5: 1, example 7 is the best.
Examples 1 and 8-10 are examples of different dihydroxy compounds, and the object of the present invention was achieved using isosorbide, ethylene glycol, 1, 6-hexanediol and 1, 4-cyclohexanediol, respectively.
Example 1 and examples 11-13 are comparative experiments with different catalysts and it can be seen that the catalytic effect with sodium hydroxide and sodium carbonate is superior to that of sodium chloride.
In the comparative experiment of the reaction conditions of the embodiment 1 and the embodiments 14 to 17, in the ester exchange stage, carbonic acid diester, dihydroxy compound and hydroxyethylated bisphenol A are used as raw materials, after a catalyst is added, the raw materials are heated to 130 to 160 ℃ under nitrogen atmosphere and normal pressure, and after the raw materials are melted and uniformly mixed, the temperature is continuously raised to 180 to 200 ℃ for reaction for 0.5 to 5 hours, so as to obtain a prepolymer; and in the polycondensation stage, continuously heating to 220-260 ℃, gradually reducing the pressure of the reaction system to 50-300 Pa, and reacting for 1-5 h to obtain the polycarbonate copolymer. The molecular weight of the obtained polycarbonate copolymer is 3.3-4.3 multiplied by 10 4 g/mol. Meanwhile, the high glass transition temperature is kept, so that the polycarbonate material has high rigidity and high fracture elongation, namely, the polycarbonate copolymer system provided by the invention is compatible with dual characteristics of rigidity and toughness, the molecular weight can be kept in a certain range, and the dimensional stability of the material is highly kept.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (9)
1. A bio-based polycarbonate copolymer, wherein the bio-based polycarbonate copolymer has the following general structural formula:
x and y are the number of the polymer repeating units, and x + y is an integer between 80 and 120; x: y is 1:20-2: 1;
the bio-based polycarbonate copolymer is prepared by using carbonic acid diester, dihydroxy compound and hydroxyethylated bisphenol A as raw materials and catalyzing the raw materials by a catalyst.
2. The method for preparing a bio-based polycarbonate copolymer according to claim 1, wherein the carbonic acid diester, the dihydroxy compound and the hydroxyethylated bisphenol A are added in a ratio of 1: (1-10): (0.25-5).
3. The bio-based polycarbonate copolymer of claim 1, wherein the amount of the catalyst is 1 x 10 molar amount of the carbonic acid diester -5 ～1×10 -3 。
4. The method of claim 3, wherein the catalyst is an alkali metal catalyst, and the alkali metal catalyst is at least one of a hydroxide or a chloride of an alkali metal or a carbonate compound.
5. The method for preparing a bio-based polycarbonate copolymer according to any one of claims 1 to 4, wherein the alkali metal hydroxide is at least one of lithium hydroxide, sodium hydroxide, potassium hydroxide, and cesium hydroxide; the alkali metal chloride is at least one of lithium chloride, sodium chloride, potassium chloride and cesium chloride; the carbonate of the alkali metal is at least one of lithium carbonate, sodium carbonate, potassium carbonate and cesium carbonate.
6. The bio-based polycarbonate copolymer according to claim 1, wherein the dihydroxy compound is any one or a mixture of isosorbide, ethylene glycol, 1, 3-propanediol, 1, 4-butanediol, 1, 5-pentanediol, 1, 6-hexanediol, 1, 4-cyclohexanediol, 1, 4-cyclohexanedimethanol, or bisphenol a.
7. The bio-based polycarbonate copolymer according to claim 1, wherein the carbonic acid diester is selected from one or more of diphenyl carbonate, dimethyl carbonate, diethyl carbonate, dipropyl carbonate, dibutyl carbonate, dipentyl carbonate, and dioctyl carbonate.
8. The bio-based polycarbonate copolymer according to any one of claims 1 to 4 and 6 to 7, wherein the bio-based polycarbonate copolymer has a weight average molecular weight of 3.3 x 10 4 ～4.3×10 4 g/mol。
9. The method for preparing a bio-based polycarbonate copolymer according to any one of claims 1 to 8, comprising the steps of:
(1) and (3) ester exchange stage: using carbonic acid diester, dihydroxy compound and hydroxyethylated bisphenol A as raw materials, adding a catalyst, heating to 130-160 ℃ under nitrogen atmosphere and normal pressure, continuing to heat to 180-200 ℃ after the raw materials are melted and uniformly mixed, and reacting for 0.5-5 h to obtain a prepolymer;
(2) a polycondensation stage: and continuously heating to 220-260 ℃, gradually reducing the pressure of the reaction system to 50-300 Pa, and reacting for 1-5 h to obtain the polycarbonate copolymer.
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