CN116217904B - High-toughness carbon dioxide-based polyester-polycarbonate and preparation method thereof - Google Patents
High-toughness carbon dioxide-based polyester-polycarbonate and preparation method thereof Download PDFInfo
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- CN116217904B CN116217904B CN202211649383.6A CN202211649383A CN116217904B CN 116217904 B CN116217904 B CN 116217904B CN 202211649383 A CN202211649383 A CN 202211649383A CN 116217904 B CN116217904 B CN 116217904B
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- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 146
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 73
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 73
- 239000004417 polycarbonate Substances 0.000 title claims abstract description 51
- 229920000515 polycarbonate Polymers 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 claims abstract description 22
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 claims abstract description 22
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 claims abstract description 21
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 claims abstract description 21
- 229920000642 polymer Polymers 0.000 claims abstract description 20
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229920006037 cross link polymer Polymers 0.000 claims abstract description 13
- 238000004132 cross linking Methods 0.000 claims abstract description 13
- 239000003054 catalyst Substances 0.000 claims abstract description 11
- 239000000463 material Substances 0.000 claims abstract description 11
- 239000000654 additive Substances 0.000 claims abstract description 9
- 230000000996 additive effect Effects 0.000 claims abstract description 9
- 238000001125 extrusion Methods 0.000 claims abstract description 9
- 239000003999 initiator Substances 0.000 claims abstract description 9
- -1 trimethylolpropane tri (3-mercaptopropionic acid) ester Chemical class 0.000 claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims description 32
- 239000002879 Lewis base Substances 0.000 claims description 9
- 150000007527 lewis bases Chemical class 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 7
- 238000000746 purification Methods 0.000 claims description 7
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 6
- BGULNPVMQAPGLT-UHFFFAOYSA-N [Cl-].[NH4+].C1(=CC=CC=C1)P(C1=CC=CC=C1)C1=CC=CC=C1.C1(=CC=CC=C1)P(C1=CC=CC=C1)C1=CC=CC=C1 Chemical group [Cl-].[NH4+].C1(=CC=CC=C1)P(C1=CC=CC=C1)C1=CC=CC=C1.C1(=CC=CC=C1)P(C1=CC=CC=C1)C1=CC=CC=C1 BGULNPVMQAPGLT-UHFFFAOYSA-N 0.000 claims description 6
- 238000001556 precipitation Methods 0.000 claims description 6
- 238000007151 ring opening polymerisation reaction Methods 0.000 claims description 5
- LALRXNPLTWZJIJ-UHFFFAOYSA-N triethylborane Chemical group CCB(CC)CC LALRXNPLTWZJIJ-UHFFFAOYSA-N 0.000 claims description 5
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 4
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 4
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 4
- 229920000570 polyether Polymers 0.000 claims description 4
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 claims description 4
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 238000011049 filling Methods 0.000 claims description 3
- 238000005469 granulation Methods 0.000 claims description 3
- 230000003179 granulation Effects 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 239000000178 monomer Substances 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- CMHHITPYCHHOGT-UHFFFAOYSA-N tributylborane Chemical compound CCCCB(CCCC)CCCC CMHHITPYCHHOGT-UHFFFAOYSA-N 0.000 claims description 3
- MXSVLWZRHLXFKH-UHFFFAOYSA-N triphenylborane Chemical compound C1=CC=CC=C1B(C=1C=CC=CC=1)C1=CC=CC=C1 MXSVLWZRHLXFKH-UHFFFAOYSA-N 0.000 claims description 3
- 239000002585 base Substances 0.000 claims description 2
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000000758 substrate Substances 0.000 claims description 2
- 125000003396 thiol group Chemical group [H]S* 0.000 claims description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 abstract description 4
- 238000007334 copolymerization reaction Methods 0.000 abstract description 4
- 229920001897 terpolymer Polymers 0.000 abstract description 3
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000002834 transmittance Methods 0.000 description 5
- 238000001291 vacuum drying Methods 0.000 description 4
- 238000004090 dissolution Methods 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 238000010791 quenching Methods 0.000 description 2
- 230000000171 quenching effect Effects 0.000 description 2
- IMQFZQVZKBIPCQ-UHFFFAOYSA-N 2,2-bis(3-sulfanylpropanoyloxymethyl)butyl 3-sulfanylpropanoate Chemical group SCCC(=O)OCC(CC)(COC(=O)CCS)COC(=O)CCS IMQFZQVZKBIPCQ-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229920000704 biodegradable plastic Polymers 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 231100000989 no adverse effect Toxicity 0.000 description 1
- 230000005311 nuclear magnetism Effects 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
Classifications
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- 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
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- 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)
- Biological Depolymerization Polymers (AREA)
Abstract
The invention discloses a high-toughness carbon dioxide-based polyester-polycarbonate and a preparation method thereof. The invention uses commercial, simple and high-efficiency nonmetallic Lewis acid-base pair as a catalyst to catalyze and initiate propylene oxide, carbon dioxide, phthalic anhydride and norbornene dianhydride to carry out quaternary copolymerization reaction, so that the carbon dioxide-based polyester-polycarbonate containing double bonds is successfully prepared. The content of norbornene dianhydride in the polymer is 0.01-20%. The carbon dioxide-based polyester-polycarbonate containing double bonds is subjected to high-temperature melt extrusion in the presence of a thermal initiator and a crosslinking additive of trimethylolpropane tri (3-mercaptopropionic acid) ester, so that a crosslinked polymer containing pendent long side chains is obtained. The prepared crosslinked polymer has improved elongation at break and toughness compared with propylene oxide/phthalic anhydride/carbon dioxide terpolymer (PPC-P). The invention can be used for synthesizing modified polymethyl ethylene carbonate (PPC) biodegradable materials, and expands the application range of the PPC materials.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a preparation method of high-toughness carbon dioxide-based polyester-polycarbonate.
Background
Is prepared from propylene oxide, phthalic anhydride and carbon dioxide (CO 2 ) The terpolymer (PPC-P) prepared by copolymerization is novel biodegradable plastic, has high light transmittance and high barrier property, and has huge application scenes in the field of food packaging (CN 111378101A, J.CO) 2 Util.2021,49,101558). Compared with the traditional polymethyl ethylene carbonate (PPC) prepared by copolymerization of propylene oxide and carbon dioxide, the PPC-P material has the advantages of raised glass transition temperature (T g >45 ℃ C.) andmechanical properties [ (]>40 MPa), but the elongation at break is low<7%) exhibits low toughness (-3 MJ/m) 3 ). Therefore, new methods are sought to improve the toughness of PPC-P materials.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a preparation method of high-toughness carbon dioxide-based polyester-polycarbonate. The high-toughness carbon dioxide-based polyester-polycarbonate is a cross-linked carbon dioxide-based polyester-polycarbonate containing a pendent long side chain. The invention uses commercial, simple and high-efficiency nonmetallic Lewis acid-base pair as a catalyst to catalyze and initiate propylene oxide, carbon dioxide, phthalic anhydride and norbornene dianhydride to carry out quaternary copolymerization reaction, so that the carbon dioxide-based polyester-polycarbonate containing double bonds is successfully prepared. The content of norbornene dianhydride in the polymer is 0.01-20%. The carbon dioxide-based polyester-polycarbonate containing double bonds is subjected to high-temperature melt extrusion in the presence of a thermal initiator and a crosslinking additive of trimethylolpropane tri (3-mercaptopropionic acid) ester, so that a crosslinked polymer containing pendent long side chains is obtained. The prepared crosslinked polymer has improved elongation at break and toughness compared with propylene oxide/phthalic anhydride/carbon dioxide terpolymer (PPC-P).
In order to achieve the above purpose, the present invention adopts the following technical scheme:
the high-toughness carbon dioxide-based polyester-polycarbonate is characterized in that the substrate material is carbon dioxide-based polyester-polycarbonate containing double bonds, and the structure is shown as a formula (I); the functionalized crosslinked polymer has a structure shown in a formula (II), wherein a is more than or equal to 1, b is more than or equal to 1, c is more than or equal to 1, d is more than or equal to 0, a, b, c and d are integers, and (a+b)/(a+b+c+d) =0.2-0.5, and d/(a+b+c+d) <0.1.
The preparation method of the high-toughness carbon dioxide-based polyester-polycarbonate is characterized by comprising the following steps:
(1) Adding monomer norbornene dianhydride, phthalic anhydride, epoxypropane, a Lewis base catalyst and organoborane into a high-pressure reaction kettle, filling carbon dioxide, heating to carry out ring-opening copolymerization reaction, and obtaining purified carbon dioxide-based polyester-polycarbonate containing double bonds through precipitation, drying and granulation after the reaction is finished;
(2) And (3) carrying out high-temperature melt extrusion on the carbon dioxide-based polyester-polycarbonate containing double bonds obtained by purification by a screw in the presence of a thermal initiator and a crosslinking additive to obtain the crosslinked polymer containing the pendent long side chains.
Preferably, the structure of formula (I) or formula (II) contains polyether, and the mass fraction of polyether in the polymer is less than 5%.
Preferably, in the above-mentioned production method, the number average molecular weight of the carbon dioxide-based polyester-polycarbonate containing double bonds is 50 to 200kg/mol, the mass fraction of norbornene dianhydride in the carbon dioxide-based polyester-polycarbonate containing double bonds is 0.01 to 20%, and the mass fraction of phthalic anhydride in the carbon dioxide-based polyester-polycarbonate containing double bonds is 15 to 45%.
Preferably, the molar ratio of lewis base catalyst to organoborane is 1:0.5-10, the feed ratio of the Lewis base catalyst to phthalic anhydride is 1:50-5000, the feeding ratio of propylene oxide to phthalic anhydride is 1:2-16, the feed ratio of norbornene dianhydride to phthalic anhydride is 1:1-50. The carbon dioxide pressure of the ring-opening copolymerization reaction is 0.5-3MPa, the reaction temperature is 40-100 ℃, and the reaction time is 4-20h.
Preferably, the crosslinking additive is trimethylolpropane tris (3-mercaptopropionate).
Preferably, the carbon dioxide based polyester-polycarbonate containing double bonds has a molar ratio of double bonds to mercapto groups of the crosslinking additive of 1:1-2.
Preferably, the thermal initiator is one of dibenzoyl peroxide, azobisisobutyronitrile, dicumyl peroxide and di-tert-butyl peroxide; the thermal initiator accounts for 0.1-1% of the carbon dioxide-based polyester-polycarbonate containing double bonds, the crosslinking temperature is 130-190 ℃, and the crosslinking time is 0.1-2h.
Preferably, the lewis base catalyst is bis (triphenylphosphine) ammonium chloride or tetra-n-butyl ammonium chloride, and the organoborane is triethylboron, tributylboron, or triphenylboron.
Compared with the prior art, the invention has the following beneficial effects:
(1) The norbornene dianhydride adopted by the invention has low price, 100 percent conversion and high economy; the method has no adverse effect on the ternary polymerization reaction of propylene oxide/carbon dioxide/phthalic anhydride, and double bonds are not crosslinked in the polymerization and post-treatment processes, so that the polymerization and post-treatment can be carried out by adopting the prior art;
(2) The cross-linked carbon dioxide-based polyester-polycarbonate containing the pendent long side chain can be generated in situ in the processing process, and the preparation process is simple.
(3) The cross-linked carbon dioxide-based polyester-polycarbonate containing the pendent long side chain still keeps good light transmittance and degradation performance, and compared with a PPC-P material, the mechanical strength of the cross-linked carbon dioxide-based polyester-polycarbonate is slightly reduced, and the cross-linked carbon dioxide-based polyester-polycarbonate has improved elongation at break and toughness.
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.
Drawings
The drawings are to further illustrate and explain the present invention and are not to be construed as limiting the invention, and are intended to illustrate and explain the present invention by way of example only, and in the appended drawings:
FIG. 1 is a nuclear magnetic resonance hydrogen spectrum of a carbon dioxide-based polyester-polycarbonate having double bonds obtained in example 1 of the present invention.
FIG. 2 is an ultraviolet-visible light absorption spectrum of a cross-linked carbon dioxide-based polyester-polycarbonate having pendent long side chains obtained in example 3 of the present invention and a PPC-P material obtained in comparative example 1.
Detailed Description
Example 1:
16.0g of phthalic anhydride, 50.2g of propylene oxide, 164.4mg of norbornene dianhydride, 60.0mg of tetrabutylammonium chloride and 216. Mu.L of tributylboron are reacted in an anhydrous and oxygen-free environmentSequentially adding the solution into a high-pressure reaction kettle, charging 1.0MPa carbon dioxide, reacting for 10 hours at 80 ℃, releasing the pressure of the carbon dioxide after the reaction is finished, dissolving the product by using methylene dichloride, quenching the reaction by using a dilute hydrochloric acid/methanol solution, precipitating in ethanol to obtain a polymer, and carrying out molecular weight test and nuclear magnetic analysis on the polymer after vacuum drying. M is M n =82.1 kg/mol, pdi=1.28, and the content of norbornene dianhydride in the polymer was 1.0wt%. The carbon dioxide-based polyester-polycarbonate containing double bonds obtained by purification is reacted with trimethylolpropane tris (3-mercaptopropionic acid) ester ([ -SH) in azobisisobutyronitrile (0.7 wt.%)]/[-C＝C-]Melt extrusion at 160 ℃ with screw in the presence of =1.5/1) gave a crosslinked polymer containing pendent long side chains. Testing T thereof g At 48 ℃, the tensile strength is 44.8MPa, the elongation at break is 18.2 percent, and the toughness is 5.8MJ/m 3 . The properties of the resulting carbon dioxide-based polyester-polycarbonate are shown in Table 1.
Example 2:
in an anhydrous and anaerobic environment, 14.0g of phthalic anhydride, 50.2g of propylene oxide, 4.0g of norbornene dianhydride, 54.3mg of bis (triphenylphosphine) ammonium chloride and 324 mu L of triphenylboron solution are sequentially added into a high-pressure reaction kettle, 1.0MPa of carbon dioxide is filled, the reaction is carried out at 80 ℃ for 15 hours, the carbon dioxide pressure is released after the reaction is finished, a dichloromethane dissolution product is used, the reaction is quenched by a dilute hydrochloric acid/methanol solution, a polymer is obtained by precipitation in ethanol, and the polymer is subjected to molecular weight test and nuclear magnetism analysis after vacuum drying. M is M n =132 kg/mol, pdi=1.30, the mass fraction of norbornene dianhydride in the polymer is 9.8wt%. The carbon dioxide-based polyester-polycarbonate containing double bonds obtained by purification is treated with ([ -SH) trimethylolpropane tri (3-mercaptopropionic acid) ester in dicumyl peroxide (0.5 wt.%)]/[-C＝C-]Melt extrusion at 180 ℃ with screw in the presence of =1.8/1) gave a crosslinked polymer containing pendent long side chains. Testing T thereof g At 44 ℃, the tensile strength is 43.6MPa, the elongation at break is 42.8 percent, and the toughness is 12.3MJ/m 3 . The properties of the resulting carbon dioxide-based polyester-polycarbonate are shown in Table 1.
Example 3:
in anhydrous and anaerobic ringIn the environment, 60.0g of phthalic anhydride, 118.0g of propylene oxide, 8.6g of norbornene dianhydride, 232.5mg of bis (triphenylphosphine) ammonium chloride and 1.62mL of triethylboron solution are sequentially added into a high-pressure reaction kettle, 1.0MPa of carbon dioxide is filled, the reaction is carried out at 80 ℃ for 12 hours, the carbon dioxide pressure is released after the reaction is finished, a dichloromethane dissolution product is used, the reaction is quenched by a dilute hydrochloric acid/methanol solution, a polymer is obtained by precipitation in ethanol, and the polymer is subjected to molecular weight test and nuclear magnetic analysis after vacuum drying. M is M n =80.2 kg/mol, pdi=1.22, the mass fraction of norbornene dianhydride in the polymer is 4.7wt%. The carbon dioxide-based polyester-polycarbonate containing double bonds obtained by purification is treated with trimethylolpropane tris (3-mercaptopropionic acid) ester ([ -SH) in dibenzoyl peroxide (0.3 wt.%)]/[-C＝C-]Melt extrusion at 150 ℃ through a screw in the presence of =1.2/1) gives a crosslinked polymer containing pendent long side chains. Testing T thereof g At 46 ℃, the tensile strength is 44.2MPa, the elongation at break is 31.2 percent, and the toughness is 9.2MJ/m 3 . The properties of the resulting carbon dioxide-based polyester-polycarbonate are shown in Table 1.
Comparative example 1:
in an anhydrous and anaerobic environment, 16.0g of phthalic anhydride, 50.2g of propylene oxide, 120.0mg of bis (triphenylphosphine) ammonium chloride and 216 mu L of triethylboron solution are sequentially added into a high-pressure reaction kettle, 1.0MPa of carbon dioxide is filled, the reaction is carried out at 80 ℃ for 8 hours, the carbon dioxide pressure is released after the reaction is finished, a dichloromethane dissolution product is used, the reaction is quenched by a dilute hydrochloric acid/methanol solution, and the polymer is obtained by precipitation in ethanol. The polymer was vacuum dried and then subjected to molecular weight testing and nuclear magnetic analysis. M is M n 83.9kg/mol, pdi=1.26, norbornene dianhydride mass fraction in the polymer 0wt%, PPC-P material. Testing T thereof g At 50 ℃, the tensile strength is 45.3MPa, the elongation at break is 6.9 percent, and the toughness is 2.9MJ/m 3 . The properties of the obtained product are shown in Table 1.
Comparative example 2:
60.0g of phthalic anhydride, 118.0g of propylene oxide, 7.97g of norbornene dianhydride, 232.5mg of bis (triphenylphosphine) ammonium chloride and 1.62mL of triethylboron in an anhydrous and anaerobic environmentSequentially adding the solution into a high-pressure reaction kettle, charging 1.0MPa carbon dioxide, reacting for 12 hours at 80 ℃, releasing the pressure of the carbon dioxide after the reaction is finished, dissolving the product by using methylene dichloride, quenching the reaction by using a dilute hydrochloric acid/methanol solution, precipitating in ethanol to obtain a polymer, and carrying out molecular weight test and nuclear magnetic analysis on the polymer after vacuum drying. M is M n =78.9 kg/mol, pdi=1.24, the mass fraction of tetrahydroanhydride in the polymer is 4.6wt%. The carbon dioxide-based polyester-polycarbonate containing double bonds obtained by purification is treated with trimethylolpropane tris (3-mercaptopropionic acid) ester ([ -SH) in dibenzoyl peroxide (0.3 wt.%)]/[-C＝C-]Melt extrusion at 150 ℃ through a screw in the presence of =1.2/1) gives a crosslinked polymer containing pendent long side chains. Testing T thereof g At 43 ℃, the tensile strength is 33.6MPa, the elongation at break is 16.2 percent, and the toughness is 4.4MJ/m 3 . The properties of the obtained product are shown in Table 1.
As can be seen from Table 1, the toughness of examples 1-3 is significantly improved compared to comparative example 1. In addition, the toughness of example 3 is also much greater than that of comparative example 2. In addition, the crosslinked carbon dioxide-based polyester-polycarbonate containing long pendent side chains obtained in example 3 still maintained good light transmittance, and 1mm thick sheets still had light transmittance of 85% or more in the range of 600 to 800 nm. Therefore, compared with the PPC-P material, the cross-linked carbon dioxide-based polyester-polycarbonate containing the pendent long side chain, which is prepared by the invention, has the advantages of increased elongation at break and improved toughness, and keeps the basically unchanged mechanical strength and good light transmittance. The invention can be applied to the modification of PPC materials.
TABLE 1 Properties of crosslinked carbon dioxide based polyester-polycarbonates containing pendent long side chains
a Molecular weight of carbon dioxide-based polyester-polycarbonate containing double bonds. b Tetrahydrophthalic anhydride was used instead of norbornene dianhydride. c Tetrahydrophthalic anhydride content in the polymer.
Claims (6)
1. The high-toughness carbon dioxide-based polyester-polycarbonate is characterized in that the substrate material is carbon dioxide-based polyester-polycarbonate containing double bonds, and the structure is shown as a formula (I); the functionalized crosslinked polymer has a structure shown as a formula (II), wherein a is more than or equal to 1, b is more than or equal to 1, c is more than or equal to 1, d is more than or equal to 0, a, b, c and d are integers, (a+b)/(a+b+c+d) =0.2-0.5, and d/(a+b+c+d) <0.1;
the structure of the formula (I) or the formula (II) contains polyether, and the mass fraction of the polyether in the polymer is less than 5%;
the preparation method of the high-toughness carbon dioxide-based polyester-polycarbonate comprises the following steps:
(1) Adding monomer norbornene dianhydride, phthalic anhydride, epoxypropane, a Lewis base catalyst and organoborane into a high-pressure reaction kettle, filling carbon dioxide, heating to carry out ring-opening copolymerization reaction, and obtaining purified carbon dioxide-based polyester-polycarbonate containing double bonds through precipitation, drying and granulation after the reaction is finished;
(2) The carbon dioxide-based polyester-polycarbonate containing double bonds obtained by purification is subjected to high-temperature melt extrusion by a screw in the presence of a thermal initiator and a crosslinking additive, so as to obtain a crosslinked polymer containing pendent long side chains;
the molar ratio of the double bonds of the double bond-containing carbon dioxide-based polyester-polycarbonate to the mercapto groups of the crosslinking additive is 1:1-2;
the crosslinking additive is trimethylolpropane tri (3-mercaptopropionic acid) ester.
2. The method for preparing high toughness carbon dioxide based polyester-polycarbonate according to claim 1, comprising the steps of:
(1) Adding monomer norbornene dianhydride, phthalic anhydride, epoxypropane, a Lewis base catalyst and organoborane into a high-pressure reaction kettle, filling carbon dioxide, heating to carry out ring-opening copolymerization reaction, and obtaining purified carbon dioxide-based polyester-polycarbonate containing double bonds through precipitation, drying and granulation after the reaction is finished;
(2) And (3) carrying out high-temperature melt extrusion on the carbon dioxide-based polyester-polycarbonate containing double bonds obtained by purification by a screw in the presence of a thermal initiator and a crosslinking additive to obtain the crosslinked polymer containing the pendent long side chains.
3. The method according to claim 2, wherein the number average molecular weight of the carbon dioxide-based polyester-polycarbonate having a double bond is 50 to 200kg/mol, the mass fraction of norbornene dianhydride in the carbon dioxide-based polyester-polycarbonate having a double bond is 0.01 to 20%, and the mass fraction of phthalic anhydride in the carbon dioxide-based polyester-polycarbonate having a double bond is 15 to 45%.
4. The process according to claim 2, characterized in that the molar ratio of lewis base catalyst to organoborane is 1:0.5-10, the feed ratio of the Lewis base catalyst to the phthalic anhydride is 1:50-5000, the feeding ratio of propylene oxide to phthalic anhydride is 1:2-16, the feed ratio of norbornene dianhydride to phthalic anhydride is 1:1-50; the carbon dioxide pressure of the ring-opening copolymerization reaction is 0.5-3MPa, the reaction temperature is 40-100 ℃, and the reaction time is 4-20h.
5. The preparation method according to claim 2, characterized in that the thermal initiator is one of dibenzoyl peroxide, azobisisobutyronitrile, dicumyl peroxide and di-tert-butyl peroxide; the thermal initiator accounts for 0.1-1% of the carbon dioxide-based polyester-polycarbonate containing double bonds, the crosslinking temperature is 130-190 ℃, and the crosslinking time is 0.1-2h.
6. The preparation method according to claim 2, wherein the Lewis base catalyst is bis (triphenylphosphine) ammonium chloride or tetra-n-butyl ammonium chloride, and the organoborane is triethylboron, tributylboron or triphenylBoron base 。
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| CN110746586A (en) * | 2019-11-08 | 2020-02-04 | 华中科技大学 | Preparation method of polyacrylate-polyester I-polyester II triblock copolymer |
| CN111378101A (en) * | 2020-04-26 | 2020-07-07 | 中山大学 | Preparation method of biodegradable carbon dioxide-based polyester-polycarbonate terpolymer |
| CN114736360A (en) * | 2022-05-13 | 2022-07-12 | 中山大学 | In-situ crosslinkable ultralow-melt-index carbon dioxide-based polyester-polycarbonate and preparation method thereof |
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| CN111378101A (en) * | 2020-04-26 | 2020-07-07 | 中山大学 | Preparation method of biodegradable carbon dioxide-based polyester-polycarbonate terpolymer |
| CN114736360A (en) * | 2022-05-13 | 2022-07-12 | 中山大学 | In-situ crosslinkable ultralow-melt-index carbon dioxide-based polyester-polycarbonate and preparation method thereof |
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