CN114854000B - Bio-based polycarbonate copolymer and preparation method thereof - Google Patents
Bio-based polycarbonate copolymer and preparation method thereof Download PDFInfo
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- CN114854000B CN114854000B CN202210588252.5A CN202210588252A CN114854000B CN 114854000 B CN114854000 B CN 114854000B CN 202210588252 A CN202210588252 A CN 202210588252A CN 114854000 B CN114854000 B CN 114854000B
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- 239000004417 polycarbonate Substances 0.000 title claims abstract description 74
- 229920000515 polycarbonate Polymers 0.000 title claims abstract description 73
- 238000002360 preparation method Methods 0.000 title claims description 10
- 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 52
- 239000002994 raw material Substances 0.000 claims abstract description 33
- 239000003054 catalyst Substances 0.000 claims abstract description 29
- 229920000642 polymer Polymers 0.000 claims abstract description 24
- 150000005690 diesters Chemical class 0.000 claims abstract description 12
- 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 33
- 229960002479 isosorbide Drugs 0.000 claims description 32
- 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
- 238000006068 polycondensation reaction Methods 0.000 claims description 18
- 238000010438 heat treatment Methods 0.000 claims description 17
- 238000006243 chemical reaction Methods 0.000 claims description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 238000005809 transesterification reaction Methods 0.000 claims description 13
- 229910052783 alkali metal Inorganic materials 0.000 claims description 10
- 150000001340 alkali metals Chemical group 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
- 238000000034 method Methods 0.000 claims description 8
- 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
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 4
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 4
- -1 carbonic acid compound Chemical class 0.000 claims description 4
- 150000004650 carbonic acid diesters Chemical class 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
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 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
- 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
- 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
- 150000001875 compounds Chemical class 0.000 abstract description 17
- 229920001577 copolymer Polymers 0.000 abstract description 10
- 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 4
- 238000006555 catalytic reaction Methods 0.000 abstract description 3
- 229920001289 polyvinyl ether Polymers 0.000 abstract description 3
- 238000012545 processing Methods 0.000 abstract description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 21
- 230000009477 glass transition Effects 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 12
- 239000007858 starting material Substances 0.000 description 11
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 6
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 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 description 5
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 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
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 4
- 125000001931 aliphatic group Chemical group 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000007334 copolymerization reaction Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000000155 melt Substances 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 229940043375 1,5-pentanediol Drugs 0.000 description 3
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 description 3
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 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
- 229930185605 Bisphenol Natural products 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 229920006351 engineering plastic Polymers 0.000 description 2
- 150000002148 esters Chemical class 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
- 239000002608 ionic liquid Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 125000001453 quaternary ammonium group Chemical group 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
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical group C=1C=COC=1 YLQBMQCUIZJEEH-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
- 101150031934 Paics gene Proteins 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
- 229920000402 bisphenol A polycarbonate polymer Polymers 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
- 238000001514 detection method Methods 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 150000002009 diols Chemical class 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
- 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
- QAWMIDIJFWHLAQ-UHFFFAOYSA-N methyl 2-(2-methoxycarbonylphenoxy)carbonyloxybenzoate Chemical compound COC(=O)C1=CC=CC=C1OC(=O)OC1=CC=CC=C1C(=O)OC QAWMIDIJFWHLAQ-UHFFFAOYSA-N 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
- 229920000728 polyester Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 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
- 229920002994 synthetic fiber Polymers 0.000 description 1
- CBXCPBUEXACCNR-UHFFFAOYSA-N tetraethylammonium Chemical compound CC[N+](CC)(CC)CC CBXCPBUEXACCNR-UHFFFAOYSA-N 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 diester, dihydroxyl compound and bisphenol A polyvinyl ether as raw materials through catalysis of a catalyst. By adopting the technical scheme of the invention, the polycarbonate copolymer contains benzene rings and flexible long-chain-CH by introducing a third monomer hydroxyethylated bisphenol A 2 CH 2 The polycarbonate copolymer has the advantages that the polycarbonate copolymer can be endowed with certain rigidity and toughness at the same time, the rigidity and the toughness are compatible in a system of the polycarbonate copolymer, and the toughness of the polymer is improved on the premise of keeping high molecular weight characteristics, so that the thermophysical property and the processing property of the polycarbonate copolymer are further improved.
Description
Technical Field
The invention relates to the technical field of copolymerization of polycarbonate, in particular to a copolymer of bio-based polycarbonate and a preparation method thereof.
Background
Polycarbonates, also known as PC plastics; the polymer is a polymer having a carbonate group in a molecular chain, and can be classified into various types such as aliphatic, aromatic, aliphatic-aromatic, and the like, depending on the structure of the ester group. Wherein the application of aliphatic and aliphatic-aromatic polycarbonates in engineering plastics is limited 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 engineering plastic with wide application.
In industrial production, polycarbonates typically use bisphenol a as a polymeric monomer, which is derived from non-renewable petroleum resources and is biologically toxic. With the need for environmental protection and health, the development of a safe and environmentally friendly synthetic route for polycarbonate has become a focus of attention in the polycarbonate industry worldwide.
Isosorbide, which is derived from glucose, is a biobased monomer with a dihydroxyl structure, has the characteristics of high molecular rigidity, chiral structure and the like, has been industrially produced, and can be used for synthesizing polycarbonate instead of bisphenol A. However, the lower reactivity of isosorbide with hydroxyl groups compared to bisphenol A is detrimental to the rapid increase in molecular weight of the polymer, and therefore, the molecular weight of the synthesized polycarbonates is generally lower. In addition, two linked furan rings in the isosorbide molecular structure increase the rigidity of the polymer molecular chain, and the polymer prepared by using the isosorbide molecular structure has poor processability.
In the prior art, two methods of solution polymerization and melt polymerization exist for preparing polycarbonate by using isosorbide, wherein phosgene and chlorine-containing solvent are used as raw materials, and the environment pollution is high. And the melt polymerization produces agglomerates during the preparation of polycarbonate, which results in the inability to obtain high molecular weight polymers, while the need to adopt severe reaction conditions to remove agglomerates in order to obtain high molecular weight polycarbonate, which in turn results in the occurrence of side reactions, further resulting in degradation and coloration of the polymer.
Synthesis of Bis (hydroxyethyl ether) s of Aromatic Dihydroxy Compounds and Poly (ether-carbonyl) s with Bisphenol A, polymer International, 1998, 47, 439-444 discloses the Synthesis of modified bisphenol A polycarbonate 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℃and an initial decomposition temperature of 382 ℃; the molecular weight Mw ranges from 29000 to 112000g/mol. The melt phase polycondensation reaction of bisphenol diphenyl (hydroxyethyl ether) with bisphenol A and diphenyl carbonate is adopted to synthesize polyester (ether-carbonic ester) with Tg of 62-140 deg.C, and the wide poly (ether carbonic ester) can be synthesized by using the di (hydroxyethyl ether) of various bisphenols. However, the poly (ether carbonate) obtained by melt phase polycondensation reaction using the above method has a low glass transition temperature and poor hardness, resulting in poor processability. Catalyst screening for the melt polymerization of isosorbide-based polycarbonate, journal of Industrial and Engineering Chemistry,2016, 37, 42-46 disclose an isosorbide type polycarbonate prepared by melt transesterification using a catalyst common in a series of polycondensation reactions, having a weight average molecular weight of up to 32,600 and a glass transition temperature of 164 ℃. Synthesis of isosorbide-based polycarbonates via melt polycondensation catalyzed by quaternary ammonium ionic liquids, chinese Journal of catalysis, 2017, 38, 908-917 disclose the synthesis of a series of quaternary ammonium ionic liquid catalysts, using isosorbide and diphenyl carbonate as monomers, by melt polycondensation to synthesize isosorbide type polycarbonate, wherein, the imidazole Tetraethylammonium (TEAI) has the best catalytic effect, the weight average molecular weight of the polymer can reach 25,600g/mol, the isosorbide conversion rate reaches 92%, but PAICs are all amorphous, and the glass transition temperature is 50-110 ℃. And the polymer prepared by the above method has a large molecular weight range and is generally incapable of maintaining stable dimensional stability.
Chinese patent No. 101889041a discloses an isosorbide-based polycarbonate, a process for its preparation and articles formed therefrom, prepared using a melt polymerization process using an activated carbonate source including bis (o-methoxycarbonylphenyl) 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 polycarbonate comprising isosorbide units and C 14-44 Aliphatic diacids, C 14-44 A polycarbonate polymer of aliphatic units of aliphatic diols or combinations thereof having a molecular weight Mw of greater than 39,000g/mol and a glass transition temperature of less than or equal to 135 ℃, has preferred mechanical properties but has a low glass transition temperature. The invention of China patent CN111138650A discloses a high molecular weight high flexibility bio-based polycarbonate copolymer and a preparation method thereof, wherein carbonic diester, 1,4:3, 6-dianhydrohexanehexol and dihydroxyl compound are adopted as raw materials to obtain copolycarbonate containing C-O-C-bond aliphatic diol structure, so as to improve the flexibility of the copolymer. However, the isosorbide, isomannide and isoidide have low reactivity during the reaction, resulting in poor selectivity of copolymerization, and it is difficult to obtain a copolymer having a molecular weight of 5000 or more in practice due to the aliphatic diol structureThe impact is that in practice the glass transition temperature of the copolymers obtained by polycondensation is generally lower than 130 ℃.
Clearly, the problem to be solved in the prior art for synthesizing polycarbonate polymers from isosorbide-substituted bisphenol A is to increase the reactivity of the hydroxyl groups in the isosorbide to increase the molecular weight of the polymer while at the same time providing a high glass transition temperature for the polymer.
Disclosure of Invention
The invention aims to provide a copolymer of bio-based polycarbonate and a preparation method thereof, which comprises a rigid benzene ring structure and a flexible-CH structure by introducing 2 CH 2 The unit diols are used for the copolymerization of polycarbonates in order to further improve their thermophysical and processing properties while maintaining the relatively high molecular weight properties of the polycarbonates.
In order to achieve the above purpose, the present invention provides the following technical solutions:
a copolymer of a bio-based polycarbonate having the structural 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=1:20-2:1, preferably 1:9-1:1; the bio-based polycarbonate copolymer is prepared by taking carbonic diester, dihydroxyl compound and bisphenol A polyvinyl ether as raw materials through catalysis of a catalyst.
In the technical scheme, the adding ratio of the carbonic diester, the dihydroxyl compound and the hydroxyethylated bisphenol A is 1: (1-10): (0.25-5).
In the technical scheme, the catalyst is used in an amount of 1 multiplied by 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, chloride or carbonic acid compound of alkali metal.
Preferably, the alkali metal hydroxide is at least one of lithium hydroxide, sodium hydroxide, potassium hydroxide and cesium hydroxide; the chloride of the alkali metal 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 dihydroxyl compound is any one or a mixture of several of isosorbide, ethylene glycol, 1, 2-ethylene glycol, 1, 3-propylene glycol, 1, 4-butanediol, 1, 5-pentanediol, 1, 6-hexanediol, 1, 4-cyclohexanediol, 1, 4-cyclohexanedimethanol and bisphenol A.
In the above technical scheme, the carbonic acid diester is at least one selected from dimethyl carbonate, diethyl carbonate, dipropyl carbonate, dibutyl carbonate and diphenyl carbonate.
In the technical scheme, the weight average molecular weight of the prepared polycarbonate copolymer is 3.3X10 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) Transesterification stage: taking carbonic diester, dihydroxyl compound and bisphenol A polyvinyl ether as raw materials, adding a catalyst, heating to 130-160 ℃ under nitrogen atmosphere and normal pressure, continuously heating to 180-200 ℃ for reacting for 0.5-5 h after the raw materials are melted and uniformly mixed, and obtaining a prepolymer;
(2) Polycondensation stage: continuously heating to 220-260 ℃ and 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 employs dihydroxy compounds instead to synthesize bio-based polycarbonates. The invention is different from isosorbide, isomannide or isoidide, and besides isosorbide and bisphenol A, 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 are selected for better effect.
The inventionThe copolymerization modification is carried out 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 mol percent of the hydroxyethylated bisphenol A in the copolymer is 30%, the storage modulus at 25 ℃ is 2570Mpa, which is lower than that of 1,4:3,6 dianhydrohexitol homopolymerized polycarbonate, and the flexibility is obviously improved. This is due to the presence of benzene rings and-CH within the hydroxyethylated bisphenol A molecule 2 CH 2 The polymer can be endowed with certain rigidity and toughness at the same time, and the rigidity and the toughness are compatible in a system of the copolymer, so that the characteristics of high glass transition temperature and high breaking elongation are exhibited.
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 polycarbonate copolymer contains benzene rings and flexible long-chain-CH by introducing a third monomer hydroxyethylated bisphenol A 2 CH 2 Can simultaneously give the polycarbonate polymer a certain rigidity and toughness, make the rigidity and toughness compatible in the system of the polycarbonate copolymer, the polycarbonate copolymer has the advantages of improving the toughness of the polymer and further improving the thermophysical property and the processing property on the premise of keeping the high molecular weight characteristic.
2. The polycarbonate copolymer provided by the invention introduces the hydroxyethylated bisphenol A into the copolymer, and has high molecular weight and higher glass transition temperature on the premise of keeping the excellent performance of the aromatic polycarbonate copolymer, thereby improving the processability of the bio-based polycarbonate copolymer and having good thermal stability.
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 bio-based polycarbonate copolymer can be kept high, so that the industrial wide application of the bio-based polycarbonate copolymer is satisfied.
4. Compared with the traditional polymer, the bio-based polycarbonate copolymer obtained by taking the dicarbonate diester, the dihydroxy compound and the hydroxyethylated bisphenol A as raw materials has higher glass transition temperature and better optical performance, has no health risk in the material using process, and accords with the high-quality development concept of the green and environment-friendly synthetic material in terms of both the preparation route and the material performance.
Detailed Description
The following description of the embodiments of the present invention will clearly and fully describe the technical solutions of the embodiments of the present invention in conjunction with the specific contents of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to fall within the scope of the 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) Transesterification stage: taking carbonic diester, dihydroxyl compound and hydroxyethylated bisphenol A as raw materials, adding a catalyst, heating to 130-160 ℃ under nitrogen atmosphere and normal pressure, continuously heating to 180-200 ℃ for reacting for 0.5-5 h after the raw materials are melted and uniformly mixed, and obtaining a prepolymer; wherein, the adding proportion of carbonic diester, dihydroxyl compound and hydroxyethylated bisphenol A is 1: (1-10): (0.25-5).
The dihydroxyl compound can be any one or a mixture of several of isosorbide, ethylene glycol, 1, 2-ethylene glycol, 1, 3-propylene glycol, 1, 4-butanediol, 1, 5-pentanediol, 1, 6-hexanediol, 1, 4-cyclohexanediol, 1, 4-cyclohexanedimethanol and bisphenol A.
The carbonic diester is selected from any one or mixture of diphenyl carbonate, dimethyl carbonate, diethyl carbonate, dipropyl carbonate, dibutyl carbonate, dipentyl carbonate and dioctyl carbonate.
(2) Polycondensation stage: continuously heating to 220-260 ℃ and 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
42.9g of diphenyl carbonate, 29.2g of isosorbide and 61.6g of hydroxyethylated bisphenol A are taken as raw materials, added into a 250mL three-neck flask, added with 0.08g of sodium hydroxide, heated to 130-160 ℃ under nitrogen atmosphere and normal pressure, stirred after the raw materials are melted, and continuously heated to 180 ℃ after being uniformly mixed for transesterification for 0.5h, thus obtaining prepolymer; continuously heating to 220 ℃ and gradually reducing the pressure of the reaction system to 50Pa, and carrying out 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 the 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 are used as starting materials.
Example 11
This example differs from example 1 in that the catalyst employed in this example had an added amount of sodium hydroxide of 0.0008g.
Example 12
The difference between this example and example 1 is that the catalyst used in this example was sodium carbonate and the amount added was 0.212g.
Example 13
This example differs from example 1 in that the catalyst used in this example is sodium chloride, added in an amount of 0.107g.
Example 14
The difference between the present example and example 1 is that the raw materials and the catalyst in the present example are heated to 130-160 ℃ under nitrogen atmosphere and normal pressure after the raw materials are melted, stirred, and then heated to 180 ℃ continuously after being uniformly mixed for transesterification for 0.5h, thus obtaining prepolymer; continuously heating to 220 ℃ and gradually reducing the pressure of the reaction system to 300Pa, and carrying out polycondensation reaction to obtain the polycarbonate copolymer.
Example 15
The difference between the present example and example 1 is that the raw materials and the catalyst in the present example are heated to 130-160 ℃ under nitrogen atmosphere and normal pressure after the raw materials are melted, stirred, and then heated to 180 ℃ continuously after being uniformly mixed for transesterification for 0.5h, thus obtaining prepolymer; continuously heating to 220 ℃ and 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 present example and example 1 is that the raw materials and the catalyst in the present example are heated to 130-160 ℃ under nitrogen atmosphere and normal pressure after the raw materials are melted, stirred, and then heated to 180 ℃ continuously after being uniformly mixed for transesterification for 0.5h, thus obtaining prepolymer; continuously heating to 260 ℃ and gradually reducing the pressure of the reaction system to 50Pa, and carrying out polycondensation reaction to obtain the polycarbonate copolymer.
Example 17
The difference between the present example and example 1 is that the raw materials and the catalyst in the present example are heated to 130-160 ℃ under nitrogen atmosphere and normal pressure after the raw materials are melted, stirred, and then heated to 200 ℃ continuously after being uniformly mixed for transesterification for 0.5h, thus obtaining prepolymer; continuously heating to 220 ℃ and gradually reducing the pressure of the reaction system to 50Pa, and carrying out 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 the nitrogen atmosphere and normal pressure, and after the raw materials are melted, the raw materials are stirred for transesterification for 0.5h to obtain prepolymer; continuously heating to 220 ℃ and gradually reducing the pressure of the reaction system to 400Pa, and carrying out 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 of the comparative example are heated to 130-160 ℃ under nitrogen atmosphere and normal pressure after being mixed, and after the raw materials are melted, the raw materials are stirred, and the raw materials are continuously heated to 200 ℃ after being uniformly mixed for carrying out transesterification reaction for 0.5h, so as to obtain prepolymer; continuously heating to 300 ℃ and gradually reducing the pressure of the reaction system to 50Pa, and carrying out 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 a dihydroxy compound and 246.4g of hydroxyethylated bisphenol A were used as starting materials.
The polymers prepared in the above examples were tested for molecular weight, thermal and mechanical properties. The detection method comprises the following steps:
molecular weight: gel Permeation Chromatography (GPC) with N, N-Dimethylformamide (DMF) and monodisperse polystyrene as standard.
Thermal performance: detecting the glass transition temperature of the polymer by a Differential Scanning Calorimeter (DSC); thermogravimetric analyzer (TGA) characterizes the thermal weight loss temperature.
Tensile properties: elongation at break, UTM universal tester.
Storage modulus: DMA242C detects.
Table 1 molecular weight and performance parameters of the polymers prepared in examples and comparative examples
In examples 1-5, the ratio of diphenyl carbonate to dihydroxy compound was 1:1, the molar percentage of hydroxyethylated bisphenol A to be added is 30%, 60%, 50%, 20%, 10%, respectively, and the molar percentage of hydroxyethylated bisphenol A to be added is preferably 30%.
Examples 1 and examples 6 to 7 are examples with different isosorbide contents, the addition ratio of diphenyl carbonate, isosorbide and hydroxyethylated bisphenol A is 1:1: 1. 1:10:1 and 1:5:1, example 7 is most preferred.
Examples 1 and examples 8-10 are examples of different dihydroxy compounds, each of which achieves the object of the present invention using isosorbide, ethylene glycol, 1, 6-hexanediol and 1, 4-cyclohexanediol, respectively.
Comparative experiments with different catalysts in example 1 and examples 11-13 show that the catalytic effect with sodium hydroxide and sodium carbonate is better than that of sodium chloride.
In the comparative experiment with the reaction conditions of the embodiment 1 and the embodiments 14-17, in the transesterification stage, carbonic diester, dihydroxyl compound and hydroxyethylated bisphenol A are taken as raw materials, after a catalyst is added, the raw materials are heated to 130-160 ℃ under the atmosphere of nitrogen and normal pressure, and after the raw materials are melted and uniformly mixed, the temperature is continuously increased to 180-200 ℃ for reaction for 0.5-5 hours, so as to obtain a prepolymer; in the polycondensation stage, continuously heating to 220-260 ℃ and gradually reducing the pressure of a 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 3.3-4.3X10 4 g/mol. At the same time, the glass transition is kept highThe temperature ensures that the polycarbonate material has higher rigidity and higher breaking elongation, namely the polycarbonate copolymer system provided by the invention has the dual characteristics of compatible rigidity and toughness, the molecular weight can be kept in a certain range, and the dimensional stability of the material is highly maintained.
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 (4)
1. A bio-based polycarbonate copolymer, characterized in that the bio-based polycarbonate copolymer has the following 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=1:20 to 2:1;
the bio-based polycarbonate copolymer is prepared by taking carbonic diester, isosorbide and hydroxyethylated bisphenol A as raw materials and catalyzing the raw materials by a catalyst;
the addition ratio of carbonic acid diester, isosorbide and hydroxyethylated bisphenol A is 1: (1-10): (0.25-3);
the preparation method comprises the following steps:
(1) Transesterification stage: taking carbonic diester, isosorbide and hydroxyethylated bisphenol A as raw materials, adding a catalyst, heating to 130-160 ℃ under nitrogen atmosphere and normal pressure, continuously heating to 180-200 ℃ for reacting for 0.5-5 h after the raw materials are melted and uniformly mixed, and obtaining a prepolymer;
(2) Polycondensation stage: continuously heating to 220-260 ℃ and gradually reducing the pressure of a reaction system to 50-300 Pa, and reacting for 1-5 hours to obtain a polycarbonate copolymer;
the catalyst is used in an amount of 1×10 of the molar weight of the carbonic acid diester -5 ~1×10 -3 The method comprises the steps of carrying out a first treatment on the surface of the The catalyst is an alkali metal catalyst, and the alkali metal catalyst is at least one of hydroxide, chloride or carbonic acid compound of alkali metal.
2. The biobased polycarbonate copolymer of claim 1, wherein the alkali metal hydroxide is at least one of lithium hydroxide, sodium hydroxide, potassium hydroxide, cesium hydroxide; the chloride of the alkali metal 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.
3. The bio-based polycarbonate copolymer according to claim 1, wherein the carbonic acid diester is selected from any one or a mixture of several of diphenyl carbonate, dimethyl carbonate, diethyl carbonate, dipropyl carbonate, dibutyl carbonate, dipentyl carbonate, dioctyl carbonate.
4. The biobased polycarbonate copolymer of any of claims 1-3, wherein the biobased polycarbonate copolymer has a weight average molecular weight of 3.3 x 10 4 ~4.3×10 4 g/mol。
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