CN116375989A - Modified crystalline polycarbonates - Google Patents
Modified crystalline polycarbonates Download PDFInfo
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- CN116375989A CN116375989A CN202310604204.5A CN202310604204A CN116375989A CN 116375989 A CN116375989 A CN 116375989A CN 202310604204 A CN202310604204 A CN 202310604204A CN 116375989 A CN116375989 A CN 116375989A
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- 229920000515 polycarbonate Polymers 0.000 title claims abstract description 47
- 239000004417 polycarbonate Substances 0.000 title claims abstract description 47
- 229920001577 copolymer Polymers 0.000 claims abstract description 62
- JJTUDXZGHPGLLC-UHFFFAOYSA-N lactide Chemical compound CC1OC(=O)C(C)OC1=O JJTUDXZGHPGLLC-UHFFFAOYSA-N 0.000 claims abstract description 51
- 238000006243 chemical reaction Methods 0.000 claims description 56
- 239000003054 catalyst Substances 0.000 claims description 54
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 40
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 32
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 claims description 26
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 claims description 26
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 19
- 239000001569 carbon dioxide Substances 0.000 claims description 16
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 16
- 238000007151 ring opening polymerisation reaction Methods 0.000 claims description 16
- 238000005406 washing Methods 0.000 claims description 16
- 238000002360 preparation method Methods 0.000 claims description 13
- CMHHITPYCHHOGT-UHFFFAOYSA-N tributylborane Chemical compound CCCCB(CCCC)CCCC CMHHITPYCHHOGT-UHFFFAOYSA-N 0.000 claims description 13
- 150000001875 compounds Chemical class 0.000 claims description 12
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical group CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 claims description 11
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- 239000000178 monomer Substances 0.000 abstract description 10
- 239000000203 mixture Substances 0.000 abstract description 3
- 229920002635 polyurethane Polymers 0.000 abstract description 3
- 239000004814 polyurethane Substances 0.000 abstract description 3
- 229920000728 polyester Polymers 0.000 abstract description 2
- 239000013078 crystal Substances 0.000 abstract 2
- 238000004566 IR spectroscopy Methods 0.000 description 10
- 238000005481 NMR spectroscopy Methods 0.000 description 10
- 239000000463 material Substances 0.000 description 7
- 238000006116 polymerization reaction Methods 0.000 description 5
- 238000007334 copolymerization reaction Methods 0.000 description 4
- 230000037048 polymerization activity Effects 0.000 description 3
- 239000002841 Lewis acid Substances 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 150000007517 lewis acids Chemical class 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- -1 polytrimethylene phthalate-propylene carbonate copolymer Polymers 0.000 description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- FPGGTKZVZWFYPV-UHFFFAOYSA-M tetrabutylammonium fluoride Chemical compound [F-].CCCC[N+](CCCC)(CCCC)CCCC FPGGTKZVZWFYPV-UHFFFAOYSA-M 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 239000002879 Lewis base Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- FESAXEDIWWXCNG-UHFFFAOYSA-N diethyl(methoxy)borane Chemical compound CCB(CC)OC FESAXEDIWWXCNG-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- DWGRAWXTWKMPOT-UHFFFAOYSA-N fluoro-bis(2,3,4-trimethylphenyl)borane Chemical compound CC1=C(C(=C(C=C1)B(C1=C(C(=C(C=C1)C)C)C)F)C)C DWGRAWXTWKMPOT-UHFFFAOYSA-N 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 150000007527 lewis bases Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 1
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 description 1
- DPKBAXPHAYBPRL-UHFFFAOYSA-M tetrabutylazanium;iodide Chemical compound [I-].CCCC[N+](CCCC)(CCCC)CCCC DPKBAXPHAYBPRL-UHFFFAOYSA-M 0.000 description 1
- BJQWBACJIAKDTJ-UHFFFAOYSA-N tetrabutylphosphanium Chemical compound CCCC[P+](CCCC)(CCCC)CCCC BJQWBACJIAKDTJ-UHFFFAOYSA-N 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- YUPAWYWJNZDARM-UHFFFAOYSA-N tri(butan-2-yl)borane Chemical compound CCC(C)B(C(C)CC)C(C)CC YUPAWYWJNZDARM-UHFFFAOYSA-N 0.000 description 1
- LALRXNPLTWZJIJ-UHFFFAOYSA-N triethylborane Chemical compound CCB(CC)CC LALRXNPLTWZJIJ-UHFFFAOYSA-N 0.000 description 1
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 1
- JQPMDTQDAXRDGS-UHFFFAOYSA-N triphenylalumane Chemical compound C1=CC=CC=C1[Al](C=1C=CC=CC=1)C1=CC=CC=C1 JQPMDTQDAXRDGS-UHFFFAOYSA-N 0.000 description 1
- MXSVLWZRHLXFKH-UHFFFAOYSA-N triphenylborane Chemical compound C1=CC=CC=C1B(C=1C=CC=CC=1)C1=CC=CC=C1 MXSVLWZRHLXFKH-UHFFFAOYSA-N 0.000 description 1
- ZMPKTELQGVLZTD-UHFFFAOYSA-N tripropylborane Chemical compound CCCB(CCC)CCC ZMPKTELQGVLZTD-UHFFFAOYSA-N 0.000 description 1
- POHPFVPVRKJHCR-UHFFFAOYSA-N tris(2,3,4,5,6-pentafluorophenyl)alumane Chemical compound FC1=C(F)C(F)=C(F)C(F)=C1[Al](C=1C(=C(F)C(F)=C(F)C=1F)F)C1=C(F)C(F)=C(F)C(F)=C1F POHPFVPVRKJHCR-UHFFFAOYSA-N 0.000 description 1
- OBAJXDYVZBHCGT-UHFFFAOYSA-N tris(pentafluorophenyl)borane Chemical compound FC1=C(F)C(F)=C(F)C(F)=C1B(C=1C(=C(F)C(F)=C(F)C=1F)F)C1=C(F)C(F)=C(F)C(F)=C1F OBAJXDYVZBHCGT-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/64—Polyesters containing both carboxylic ester groups and carbonate groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
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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)
- Compositions Of Macromolecular Compounds (AREA)
- Biological Depolymerization Polymers (AREA)
Abstract
Modified crystalline polycarbonate belongs to the technical field of degradable polyester. The composition is characterized by comprising ethylene carbonate-lactic acid copolymer (PECLA), ethylene phthalate-ethylene carbonate-lactic acid copolymer (PECPLA) or propylene phthalate-propylene carbonate-lactic acid copolymer (PPCPLA). The invention introduces lactide monomer into the comonomer of polycarbonate, so that the polyurethane can form crystals, and the crystal polycarbonate has good dimensional stability.
Description
Technical Field
The invention belongs to the technical field of degradable polyesters, and particularly relates to a crystalline polycarbonate with good dimensional stability and a preparation method thereof.
Background
Degradable polycarbonate-based copolymers such as propylene carbonate (PPC), polycyclohexene carbonate (PCHC), polytrimethylene phthalate-propylene carbonate copolymer (PPCP), are all amorphous materials. Polycarbonate copolymers of amorphous materials generally suffer from poor dimensional stability. For this problem, researchers in the field have presented different solutions.
For example, patent "CN1679097" filed by general electric company in the united states in 2003 as early as China discloses a dimensionally stable polycarbonate product prepared by a melt transesterification polymerization method of dihydroxyaryl cyclohexane, resulting in a polycarbonate product having outstanding dimensional stability. However, the polycarbonate product is not biodegradable and causes environmental pollution.
Patent "CN104918981a", filed in China by the company of sauter basic global technology, 2014, discloses a polycarbonate composition with improved thermal dimensional stability and high refractive index, the modified composition is modified by adding polysulfone to the polycarbonate to achieve the purpose of thermal dimensional stability, and is not realized by changing the structure of the polycarbonate itself. The prior art has not been able to produce a degradable polycarbonate copolymer having excellent dimensional stability.
Disclosure of Invention
The invention aims to solve the technical problems that: overcomes the defects of the prior art and provides a degradable modified crystalline polycarbonate with excellent dimensional stability.
The technical scheme adopted for solving the technical problems is as follows: the crystalline polycarbonate is characterized by comprising a component of ethylene carbonate-lactic acid copolymer (PECLA), ethylene phthalate-ethylene carbonate-lactic acid copolymer (PECLA) or propylene phthalate-propylene carbonate-lactic acid copolymer (PPCPLA).
The three copolymers are all crystalline polycarbonate, have good dimensional stability, and solve the problem of poor dimensional stability of the existing polycarbonate.
Preferably, the data molecular weight of the PECLA, the PECPLA and the PPCPLA is 1000g/mol to 3.0X10 5 g/mol。
Specifically, in the above crystalline polycarbonate, the structural formula of the ethylene carbonate-lactic acid copolymer is formula 1, formula 1:
wherein a is more than or equal to 1 and less than or equal to 10000, b is more than or equal to 1 and less than or equal to 5000, c is more than or equal to 0 and less than or equal to 600, and a, b and c are integers.
Specifically, in the above crystalline polycarbonate, the structural formula of the ethylene phthalate-ethylene carbonate-lactic acid copolymer is one or more of the formulas 2 to 4,
formula 2:
wherein a+c is more than or equal to 1 and less than or equal to 9000, b is more than or equal to 1 and less than or equal to 6000, d is more than or equal to 1 and less than or equal to 5000, e is more than or equal to 0 and less than or equal to 600, and a and b, c, d, e are integers;
formula 3:
wherein a is more than or equal to 1 and less than or equal to 6000, b is more than or equal to 1 and less than or equal to 9000, c is more than or equal to 1 and less than or equal to 5000, d is more than or equal to 0 and less than or equal to 600, and a, b, c and d are integers;
formula 4:
wherein a+d is more than or equal to 1 and less than or equal to 6000, b is more than or equal to 1 and less than or equal to 9000, c is more than or equal to 1 and less than or equal to 5000, e is more than or equal to 0 and less than or equal to 600, and a and b, c, d, e are integers.
Specifically, in the above crystalline polycarbonate, the structural formula of the propylene phthalate-propylene carbonate-lactic acid copolymer is one or more of the formulas 5 to 7,
formula 5:
wherein a+c is more than or equal to 1 and less than or equal to 9000, b is more than or equal to 1 and less than or equal to 6000, d is more than or equal to 1 and less than or equal to 5000, e is more than or equal to 0 and less than or equal to 600, and a and b, c, d, e are integers;
formula 6:
wherein a is more than or equal to 1 and less than or equal to 6000, b is more than or equal to 1 and less than or equal to 9000, c is more than or equal to 1 and less than or equal to 5000, d is more than or equal to 0 and less than or equal to 600, and a, b, c and d are integers;
formula 7:
wherein a+d is more than or equal to 1 and less than or equal to 6000, b is more than or equal to 1 and less than or equal to 9000, c is more than or equal to 1 and less than or equal to 5000, e is more than or equal to 0 and less than or equal to 600, and a and b, c, d, e are integers.
Specifically, the preparation method of the ethylene carbonate-lactic acid copolymer comprises the following steps: adding ethylene oxide, lactide and a catalyst A into a high-pressure reaction kettle, charging carbon dioxide, controlling pressure, heating to perform ternary ring-opening copolymerization reaction, and washing, devolatilizing and drying after the reaction is finished to obtain a finished product;
specifically, the preparation method of the ethylene phthalate-ethylene carbonate-lactic acid copolymer comprises the following steps: adding ethylene oxide, phthalic anhydride, lactide and a catalyst B into a high-pressure reaction kettle, charging carbon dioxide, controlling pressure, heating to carry out ring-opening copolymerization reaction, and washing, devolatilizing and drying after the reaction is finished to obtain a finished product.
Specifically, the preparation method of the propylene phthalate-propylene carbonate-lactic acid copolymer comprises the following steps: adding propylene oxide, phthalic anhydride, lactide and a catalyst C into a high-pressure reaction kettle, charging carbon dioxide, controlling pressure, heating to carry out ring-opening copolymerization reaction, and washing, devolatilizing and drying after the reaction is finished to obtain a finished product.
The present invention introduces lactide monomer into the comonomer of the polycarbonate to enable crystallization in the polyurethane. The lactide is a rigid monomer, so that the strength and softening temperature of the polycarbonate can be improved. The lactide itself has low polymerization activity, and ethylene oxide, propylene oxide or/and phthalic anhydride is selected as a monomer to be copolymerized with the lactide, so that the lactide is successfully polymerized uniformly in the copolymer, and the polycarbonate with stable size is obtained. Ethylene oxide is a flexible monomer, and the polycarbonate formed after the addition has good toughness. Phthalic anhydride is a rigid monomer, so that the strength and softening temperature of polycarbonate can be improved, and the barrier property of the material can be improved.
The catalyst A, the catalyst B and the catalyst C used in the preparation method of the ethylene carbonate-lactic acid copolymer, the preparation method of the ethylene phthalate-ethylene carbonate-lactic acid copolymer and the preparation method of the propylene phthalate-propylene carbonate-lactic acid copolymer can all adopt conventional Lewis acid/alkali pairs, and can all initiate copolymerization reaction to realize copolymerization. The Lewis acid comprises one or more of triethylboron, tripropylboron, tributylboron, tri-sec-butylborane, triphenylboron, tris (pentafluorophenyl) boron, diethylmethoxyborane, bis (trimethylphenyl) boron fluoride, trimethylaluminum, triethylaluminum, triisobutylaluminum, triphenylaluminum and tris (pentafluorophenyl) aluminum. The Lewis base comprises one or more of tetra-n-butyl ammonium fluoride, tetra-n-butyl ammonium chloride, tetra-n-butyl ammonium bromide, tetra-n-butyl ammonium iodide, tetra-butyl phosphine bromide and tetra-n-butyl amine.
Preferably, in the crystalline polycarbonate, the catalyst A, the catalyst B and the catalyst C are all compounds of tributyl boron, trialkyl aluminum and tetra-n-butylamine according to a molar ratio of 5:2-4:3-8, and the trialkyl aluminum is triethyl aluminum or/and triisobutyl aluminum. Lactide itself has lower polymerization activity, and polymerization with ethylene oxide, propylene oxide and phthalic anhydride is difficult and the polymerization rate is slow. The catalyst of the invention can accelerate the initiation of the copolymerization reaction, improve the reaction efficiency and ensure that lactide is polymerized in the copolymer uniformly.
Specifically, in the above crystalline polycarbonate, the method for producing a vinyl carbonate-lactic acid copolymer comprises: the molar ratio of the ethylene oxide to the lactide is 2-50:1, and the molar ratio of the ethylene oxide to the catalyst A is 3000:1-100. Preferably, the molar ratio of the ethylene oxide to the lactide is 11-23:1, and the molar ratio of the ethylene oxide to the catalyst A is 3000:1-2.
Specifically, in the above crystalline polycarbonate, the preparation method of the ethylene phthalate-ethylene carbonate-lactic acid copolymer comprises the following steps: the molar ratio of the ethylene oxide to the phthalic anhydride to the lactide is 2-50:1-10:1, and the molar ratio of the ethylene oxide to the catalyst B is 3000:1-100. Preferably, the molar ratio of the ethylene oxide to the phthalic anhydride to the lactide is 9-20:1.5-3:1.
Specifically, in the above crystalline polycarbonate, the preparation method of the propylene phthalate-propylene carbonate-lactic acid copolymer comprises the following steps: the molar ratio of the propylene oxide to the phthalic anhydride to the lactide is 2-50:0.5-10:1, and the molar ratio of the propylene oxide to the catalyst C is 3000:1-100. Preferably, the molar ratio of the propylene oxide, the phthalic anhydride and the lactide is 9.5-21:1.2-2.8:1.
The addition amount of the preferred lactide is matched with the copolymerization reaction conditions, so that the crystallinity of the copolymer can be controlled to be 10% -20%, the dimensional stability of the material can be ensured, and the better toughness, strength, ductility or/and barrier property of the copolymer can be maintained.
The reaction temperature is 30-80 ℃ and the reaction pressure is 1.0-2.0 MPa in the preparation method of the ethylene carbonate-lactic acid copolymer, the preparation method of the ethylene phthalate-ethylene carbonate-lactic acid copolymer and the preparation method of the propylene phthalate-propylene carbonate-lactic acid copolymer. The invention provides a reaction temperature capable of ensuring uniform polymerization of lactide in a polycarbonate material. Preferably, the reaction temperature is 40-70 ℃ and the reaction pressure is 1.2-1.5 MPa. Under the preferable reaction condition, the preferable catalyst is matched, so that the reaction rate can be better controlled, the lactide is more uniformly dispersed in a molecular chain, and each performance of the material is more excellent. The self-polymerization of each monomer is less, and the yield of the target copolymer is higher.
Compared with the prior art, the modified crystalline polycarbonate has the following beneficial effects: the invention is a crystalline polycarbonate with good dimensional stability. The present invention introduces lactide monomer into the comonomer of the polycarbonate to enable crystallization in the polyurethane. The lactide is a rigid monomer, so that the strength and softening temperature of the polycarbonate can be improved. The lactide itself has low polymerization activity, and ethylene oxide, propylene oxide or/and phthalic anhydride is selected as a monomer to be copolymerized with the lactide, so that the lactide is successfully polymerized uniformly in the copolymer, and the polycarbonate with stable size is obtained.
Detailed Description
The present invention will be specifically described below by way of examples. All materials are commercially available, unless otherwise indicated.
Example 1
Adding ethylene oxide, lactide and a catalyst into a high-pressure reaction kettle, wherein the molar ratio of the ethylene oxide to the lactide is 12:1, the molar ratio of the ethylene oxide to the catalyst is 3000:1.5, and the catalyst is a compound of tributyl boron, triethylaluminum, triisobutyl aluminum and tetra-n-butylamine according to the molar ratio of 5:1.5:1.5:5.5:5.5; heating to 55 ℃, charging carbon dioxide to 1.3MPa, performing ternary ring-opening copolymerization reaction, finishing the reaction for 10 hours, washing, devolatilizing and drying to obtain a copolymer, and measuring and calculating the mass content of the components which are in accordance with the structural formula 1 in the copolymer by nuclear magnetic resonance and Fourier infrared spectroscopy to be 97.8%.
Example 2
Adding ethylene oxide, lactide and a catalyst into a high-pressure reaction kettle, wherein the molar ratio of the ethylene oxide to the lactide is 11:1, the molar ratio of the ethylene oxide to the catalyst is 3000:2, and the catalyst is a compound of tributyl boron, triethylaluminum, triisobutyl aluminum and tetra-n-butylamine according to the molar ratio of 5:1:1:3; heating to 70 ℃, charging carbon dioxide to 1.5MPa, carrying out ternary ring-opening copolymerization reaction, finishing the reaction after 10.5 hours, washing, devolatilizing and drying to obtain a copolymer, and measuring and calculating the mass content of the components which are in accordance with the structural formula 1 in the copolymer by nuclear magnetic resonance and Fourier infrared spectroscopy to be 97.7%.
Example 3
Adding ethylene oxide, lactide and a catalyst into a high-pressure reaction kettle, wherein the molar ratio of the ethylene oxide to the lactide is 23:1, the molar ratio of the ethylene oxide to the catalyst is 3000:1, and the catalyst is a compound of tributyl boron, triethylaluminum, triisobutyl aluminum and tetra-n-butylamine according to the molar ratio of 5:2.8:1.2:8; heating to 40 ℃, charging carbon dioxide to 1.2MPa, performing ternary ring-opening copolymerization reaction, finishing the reaction after 11 hours, washing, devolatilizing and drying to obtain a copolymer, and measuring and calculating the mass content of the components which are in accordance with the structural formula 1 in the copolymer by nuclear magnetic resonance and Fourier infrared spectroscopy to be 98.0%.
Example 4
Adding ethylene oxide, phthalic anhydride, lactide and a catalyst into a high-pressure reaction kettle, wherein the molar ratio of the ethylene oxide to the phthalic anhydride to the lactide is 15:2:1, the molar ratio of the ethylene oxide to the catalyst is 3000:50, and the catalyst is a compound of tributylboron, triethylaluminum, triisobutylaluminum and tetra-n-butylamine according to the molar ratio of 5:1.5:1.5:5:5.5; heating to 55 ℃, charging carbon dioxide to 1.4MPa, carrying out ring-opening copolymerization reaction, finishing the reaction after 12 hours, obtaining a copolymer after washing, devolatilizing and drying, and measuring and calculating the mass content of the components which accord with the formulas 2-4 in the copolymer by nuclear magnetic resonance and Fourier infrared spectroscopy to be 96.4 percent.
Example 5
Adding ethylene oxide, phthalic anhydride, lactide and a catalyst into a high-pressure reaction kettle, wherein the molar ratio of the ethylene oxide to the phthalic anhydride to the lactide is 9:3:1, the molar ratio of the ethylene oxide to the catalyst is 3000:1, and the catalyst is a compound of tributyl boron, triethylaluminum and tetra-n-butylamine according to the molar ratio of 5:2:8; heating to 80 ℃, charging carbon dioxide to 1.5MPa, carrying out ring-opening copolymerization reaction, finishing the reaction after 14 hours, obtaining a copolymer after washing, devolatilizing and drying, and measuring and calculating the mass content of the components which accord with the formulas 2-4 in the copolymer by nuclear magnetic resonance and Fourier infrared spectroscopy to be 88.6%.
Example 6
Adding ethylene oxide, phthalic anhydride, lactide and a catalyst into a high-pressure reaction kettle, wherein the molar ratio of the ethylene oxide to the phthalic anhydride to the lactide is 20:1.5:1, the molar ratio of the ethylene oxide to the catalyst is 3000:100, and the catalyst is a compound of tributyl boron, triethylaluminum, triisobutyl aluminum and tetra-n-butylamine according to the molar ratio of 5:3.2:0.8:3; heating to 30 ℃, charging carbon dioxide to 1.0MPa, carrying out ring-opening copolymerization reaction, finishing the reaction after 11.5 hours, obtaining a copolymer after washing, devolatilizing and drying, and measuring and calculating the mass content of the components which accord with the formulas 2-4 in the copolymer by nuclear magnetic resonance and Fourier infrared spectroscopy to be 92.4 percent.
Example 7
Adding propylene oxide, phthalic anhydride, lactide and a catalyst into a high-pressure reaction kettle, wherein the molar ratio of the propylene oxide to the phthalic anhydride to the lactide is 29:7:1, the molar ratio of the propylene oxide to the catalyst is 3000:50, and the catalyst is a compound of tributylboron, triethylaluminum, triisobutylaluminum and tetra-n-butylamine according to the molar ratio of 5:1:2:6; heating to 55 ℃, charging carbon dioxide to 1.2MPa, carrying out ring-opening copolymerization reaction, finishing the reaction after 13.5 hours, obtaining a copolymer after washing, devolatilizing and drying, and measuring and calculating the mass content of the components which accord with the formulas 5-7 in the copolymer by nuclear magnetic resonance and Fourier infrared spectroscopy to be 93.5%.
Example 8
Adding propylene oxide, phthalic anhydride, lactide and a catalyst into a high-pressure reaction kettle, wherein the molar ratio of the propylene oxide to the phthalic anhydride to the lactide is 2:10:1, the molar ratio of the propylene oxide to the catalyst is 3000:100, and the catalyst is a compound of tributyl boron, triisobutyl aluminum and tetra-n-butylamine according to the molar ratio of 5:4:3; heating to 30 ℃, charging carbon dioxide to 1.0MPa, carrying out ring-opening copolymerization reaction, finishing the reaction after 14 hours, obtaining a copolymer after washing, devolatilizing and drying, and measuring and calculating the mass content of the components which accord with the formulas 5-7 in the copolymer by nuclear magnetic resonance and Fourier infrared spectroscopy to be 84.3%.
Example 9
Adding propylene oxide, phthalic anhydride, lactide and a catalyst into a high-pressure reaction kettle, wherein the molar ratio of the propylene oxide to the phthalic anhydride to the lactide is 50:0.5:1, the molar ratio of the propylene oxide to the catalyst is 3000:1, and the catalyst is a compound of tributyl boron, triethylaluminum, triisobutyl aluminum and tetra-n-butylamine according to the molar ratio of 5:1.5:0.5:8; heating to 80 ℃, charging carbon dioxide to 2.0MPa, carrying out ring-opening copolymerization reaction, finishing the reaction after 16 hours, obtaining a copolymer after washing, devolatilizing and drying, and measuring and calculating the mass content of the components which accord with the formulas 5-7 in the copolymer by nuclear magnetic resonance and Fourier infrared spectroscopy to be 88.7 percent.
Example 10
Adding ethylene oxide, lactide and a catalyst into a high-pressure reaction kettle, wherein the molar ratio of the ethylene oxide to the lactide is 12:1, the molar ratio of the ethylene oxide to the catalyst is 3000:1.5, and the catalyst is a compound of tributyl boron and tetra-n-butylamine according to the molar ratio of 8:5.5; heating to 55 ℃, charging carbon dioxide to 1.3MPa, carrying out ternary ring-opening copolymerization reaction, finishing the reaction for 15.5 hours, washing, devolatilizing and drying to obtain a copolymer, and measuring and calculating the mass content of the components which are in accordance with the structural formula 1 in the copolymer by nuclear magnetic resonance and Fourier infrared spectroscopy to be 97.8%.
Performance test:
1) The number average molecular weight was measured by GPC.
2) Crystallinity was tested by DSC.
Dimensional stability is characterized by the shrinkage of the product, specifically: the copolymer obtained in each example was extruded into a cylindrical sample of diameter 2cm and length 50cm and the volume V 0 The sample is placed in a closed environment with 30 ℃ and 70% air saturation humidity, and the volume V is measured after 30 days 30d Calculate volume shrinkage ratio = V 30d /V 0 。
The properties of the copolymers prepared in the examples of the present invention are shown in Table 1.
Table 1 sample performance index table
| Examples | Molecular weight (Mn/PDI) | Crystallinity (%) | Dimensional stability | Tensile Strength (MPa) |
| Example 1 | 2.23×10 5 /2.53 | 15.3 | 0.97 | 38 |
| Example 2 | 1.17×10 5 /2.49 | 39.6 | 0.99 | 42 |
| Example 3 | 2.48×10 5 /2.36 | 4.6 | 0.92 | 34 |
| Example 4 | 1.52×10 5 /2.56 | 17.6 | 0.98 | 79 |
| Example 5 | 1.46×10 5 /2.52 | 15.2 | 0.97 | 76 |
| Example 6 | 1.61×10 5 /2.55 | 11.8 | 0.96 | 72 |
| Example 7 | 8.62×10 4 /2.13 | 2.9 | 0.90 | 93 |
| Example 8 | 5.62×10 4 /2.06 | 16.7 | 0.98 | 97 |
| Example 9 | 8.84×10 4 /2.18 | 1.7 | 0.88 | 84 |
| Example 10 | 2.19×10 5 /2.51 | 14.7 | 0.96 | 37 |
The above description is only a preferred embodiment of the present invention, and is not intended to limit the invention in any way, and any person skilled in the art may make modifications or alterations to the disclosed technical content to the equivalent embodiments. However, any simple modification, equivalent variation and variation of the above embodiments according to the technical substance of the present invention still fall within the protection scope of the technical solution of the present invention.
Claims (10)
1. The modified crystalline polycarbonate is characterized by comprising a component of ethylene carbonate-lactic acid copolymer, ethylene phthalate-ethylene carbonate-lactic acid copolymer or propylene phthalate-propylene carbonate-lactic acid copolymer.
2. The modified crystalline polycarbonate of claim 1, wherein: the structural formula of the ethylene carbonate-lactic acid copolymer is shown in formula 1, and formula 1:
wherein a is more than or equal to 1 and less than or equal to 10000, b is more than or equal to 1 and less than or equal to 5000, c is more than or equal to 0 and less than or equal to 600, and a, b and c are integers.
3. The modified crystalline polycarbonate of claim 1, wherein: the structural formula of the ethylene phthalate-ethylene carbonate-lactic acid copolymer is one or more of the formulas 2-4,
formula 2:
wherein a+c is more than or equal to 1 and less than or equal to 9000, b is more than or equal to 1 and less than or equal to 6000, d is more than or equal to 1 and less than or equal to 5000, e is more than or equal to 0 and less than or equal to 600, and a and b, c, d, e are integers;
formula 3:
wherein a is more than or equal to 1 and less than or equal to 6000, b is more than or equal to 1 and less than or equal to 9000, c is more than or equal to 1 and less than or equal to 5000, d is more than or equal to 0 and less than or equal to 600, and a, b, c and d are integers;
formula 4:
wherein a+d is more than or equal to 1 and less than or equal to 6000, b is more than or equal to 1 and less than or equal to 9000, c is more than or equal to 1 and less than or equal to 5000, e is more than or equal to 0 and less than or equal to 600, and a and b, c, d, e are integers.
4. The modified crystalline polycarbonate of claim 1, wherein: the structural formula of the propylene phthalate-propylene carbonate-lactic acid copolymer is one or more of the formulas 5-7,
formula 5:
wherein a+c is more than or equal to 1 and less than or equal to 9000, b is more than or equal to 1 and less than or equal to 6000, d is more than or equal to 1 and less than or equal to 5000, e is more than or equal to 0 and less than or equal to 600, and a and b, c, d, e are integers;
formula 6:
wherein a is more than or equal to 1 and less than or equal to 6000, b is more than or equal to 1 and less than or equal to 9000, c is more than or equal to 1 and less than or equal to 5000, d is more than or equal to 0 and less than or equal to 600, and a, b, c and d are integers;
formula 7:
wherein a+d is more than or equal to 1 and less than or equal to 6000, b is more than or equal to 1 and less than or equal to 9000, c is more than or equal to 1 and less than or equal to 5000, e is more than or equal to 0 and less than or equal to 600, and a and b, c, d, e are integers.
5. The modified crystalline polycarbonate of claim 1, wherein the ethylene carbonate-lactic acid copolymer is prepared by a process comprising: adding ethylene oxide, lactide and a catalyst A into a high-pressure reaction kettle, charging carbon dioxide, controlling pressure, heating to perform ternary ring-opening copolymerization reaction, and washing, devolatilizing and drying after the reaction is finished to obtain a finished product;
the preparation method of the ethylene phthalate-ethylene carbonate-lactic acid copolymer comprises the following steps: adding ethylene oxide, phthalic anhydride, lactide and a catalyst B into a high-pressure reaction kettle, charging carbon dioxide, controlling pressure, heating to carry out ring-opening copolymerization reaction, and washing, devolatilizing and drying after the reaction is finished to obtain a finished product.
6. The modified crystalline polycarbonate of claim 1, wherein the propylene phthalate-propylene carbonate-lactic acid copolymer is prepared by the process of: adding propylene oxide, phthalic anhydride, lactide and a catalyst C into a high-pressure reaction kettle, charging carbon dioxide, controlling pressure, heating to carry out ring-opening copolymerization reaction, and washing, devolatilizing and drying after the reaction is finished to obtain a finished product.
7. The modified crystalline polycarbonate of claim 5 or 6, characterized in that: the catalyst A, the catalyst B and the catalyst C are all compounds of tributyl boron, trialkyl aluminum and tetra-n-butylamine according to a molar ratio of 5:2-4:3-8, and the trialkyl aluminum is triethyl aluminum or/and triisobutyl aluminum.
8. The modified crystalline polycarbonate of claim 5, wherein the ethylene carbonate-lactic acid copolymer is prepared by a process comprising: the molar ratio of the ethylene oxide to the lactide is 11-23:1, and the molar ratio of the ethylene oxide to the catalyst A is 3000:1-2.
9. The modified crystalline polycarbonate of claim 5, wherein the ethylene phthalate-ethylene carbonate-lactic acid copolymer is prepared by a process comprising: the molar ratio of the ethylene oxide to the phthalic anhydride to the lactide is 9-20:1.5-3:1, and the molar ratio of the ethylene oxide to the catalyst B is 3000:1-100.
10. The modified crystalline polycarbonate of claim 6, wherein the molar ratio of propylene oxide, phthalic anhydride to lactide is 2-50:0.5-10:1, and the molar ratio of propylene oxide to catalyst C is 3000:1-100.
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| CN117603570A (en) * | 2024-01-24 | 2024-02-27 | 山东联欣环保科技有限公司 | Dimensionally stable polycarbonate compositions |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110092900A (en) * | 2019-04-30 | 2019-08-06 | 华中科技大学 | A kind of preparation method of carbon dioxide group block copolymer |
| CN110746586A (en) * | 2019-11-08 | 2020-02-04 | 华中科技大学 | Preparation method of polyacrylate-polyester I-polyester II triblock copolymer |
| CN116053575A (en) * | 2022-12-19 | 2023-05-02 | 中国科学院长春应用化学研究所 | Carbon dioxide-based terpolymer electrolyte and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110092900A (en) * | 2019-04-30 | 2019-08-06 | 华中科技大学 | A kind of preparation method of carbon dioxide group block copolymer |
| CN110746586A (en) * | 2019-11-08 | 2020-02-04 | 华中科技大学 | Preparation method of polyacrylate-polyester I-polyester II triblock copolymer |
| CN116053575A (en) * | 2022-12-19 | 2023-05-02 | 中国科学院长春应用化学研究所 | Carbon dioxide-based terpolymer electrolyte and preparation method and application thereof |
Cited By (3)
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|---|---|---|---|---|
| CN117603569A (en) * | 2024-01-23 | 2024-02-27 | 山东联欣环保科技有限公司 | 3D printing material based on carbon dioxide copolymer and preparation method thereof |
| CN117603569B (en) * | 2024-01-23 | 2024-04-19 | 山东联欣环保科技有限公司 | 3D printing material based on carbon dioxide copolymer and preparation method thereof |
| CN117603570A (en) * | 2024-01-24 | 2024-02-27 | 山东联欣环保科技有限公司 | Dimensionally stable polycarbonate compositions |
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