CN117004007A - Crystalline aliphatic polycarbonate with high molecular weight and high mechanical property and preparation method thereof - Google Patents
Crystalline aliphatic polycarbonate with high molecular weight and high mechanical property and preparation method thereof Download PDFInfo
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- CN117004007A CN117004007A CN202311058065.7A CN202311058065A CN117004007A CN 117004007 A CN117004007 A CN 117004007A CN 202311058065 A CN202311058065 A CN 202311058065A CN 117004007 A CN117004007 A CN 117004007A
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- 229920000515 polycarbonate Polymers 0.000 title claims abstract description 80
- 239000004417 polycarbonate Substances 0.000 title claims abstract description 80
- 125000001931 aliphatic group Chemical group 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 229920000642 polymer Polymers 0.000 claims abstract description 80
- 238000006243 chemical reaction Methods 0.000 claims abstract description 57
- 238000007151 ring opening polymerisation reaction Methods 0.000 claims abstract description 32
- 239000003054 catalyst Substances 0.000 claims abstract description 26
- 239000000178 monomer Substances 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 24
- 239000000463 material Substances 0.000 claims abstract description 14
- 239000002841 Lewis acid Substances 0.000 claims abstract description 13
- 150000007517 lewis acids Chemical class 0.000 claims abstract description 13
- 239000002879 Lewis base Substances 0.000 claims abstract description 12
- 150000007527 lewis bases Chemical class 0.000 claims abstract description 12
- 239000002904 solvent Substances 0.000 claims abstract description 8
- 238000002844 melting Methods 0.000 claims abstract description 7
- 230000008018 melting Effects 0.000 claims abstract description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000003999 initiator Substances 0.000 claims abstract description 6
- 238000001556 precipitation Methods 0.000 claims abstract description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical group ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 48
- 239000011701 zinc Substances 0.000 claims description 41
- GQHTUMJGOHRCHB-UHFFFAOYSA-N 2,3,4,6,7,8,9,10-octahydropyrimido[1,2-a]azepine Chemical compound C1CCCCN2CCCN=C21 GQHTUMJGOHRCHB-UHFFFAOYSA-N 0.000 claims description 30
- 238000009826 distribution Methods 0.000 claims description 19
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 16
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 claims description 16
- OEBXWWBYZJNKRK-UHFFFAOYSA-N 1-methyl-2,3,4,6,7,8-hexahydropyrimido[1,2-a]pyrimidine Chemical compound C1CCN=C2N(C)CCCN21 OEBXWWBYZJNKRK-UHFFFAOYSA-N 0.000 claims description 14
- 229910052725 zinc Inorganic materials 0.000 claims description 13
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 11
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 10
- OISVCGZHLKNMSJ-UHFFFAOYSA-N 2,6-dimethylpyridine Chemical compound CC1=CC=CC(C)=N1 OISVCGZHLKNMSJ-UHFFFAOYSA-N 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 8
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- MKRVHLWAVKJBFN-UHFFFAOYSA-N diphenylzinc Chemical compound C=1C=CC=CC=1[Zn]C1=CC=CC=C1 MKRVHLWAVKJBFN-UHFFFAOYSA-N 0.000 claims description 5
- FVKFHMNJTHKMRX-UHFFFAOYSA-N 3,4,6,7,8,9-hexahydro-2H-pyrimido[1,2-a]pyrimidine Chemical compound C1CCN2CCCNC2=N1 FVKFHMNJTHKMRX-UHFFFAOYSA-N 0.000 claims description 4
- HQWPLXHWEZZGKY-UHFFFAOYSA-N diethylzinc Chemical compound CC[Zn]CC HQWPLXHWEZZGKY-UHFFFAOYSA-N 0.000 claims description 4
- HPYNZHMRTTWQTB-UHFFFAOYSA-N dimethylpyridine Natural products CC1=CC=CN=C1C HPYNZHMRTTWQTB-UHFFFAOYSA-N 0.000 claims description 4
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 claims description 4
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 claims description 4
- 239000000853 adhesive Substances 0.000 claims description 3
- 230000001070 adhesive effect Effects 0.000 claims description 3
- 239000002585 base Substances 0.000 claims description 3
- 239000000806 elastomer Substances 0.000 claims description 3
- 229920001971 elastomer Polymers 0.000 claims description 3
- 150000003384 small molecules Chemical class 0.000 claims description 3
- BWVAOONFBYYRHY-UHFFFAOYSA-N [4-(hydroxymethyl)phenyl]methanol Chemical compound OCC1=CC=C(CO)C=C1 BWVAOONFBYYRHY-UHFFFAOYSA-N 0.000 claims description 2
- 150000001298 alcohols Chemical class 0.000 claims description 2
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 claims description 2
- 238000006116 polymerization reaction Methods 0.000 abstract description 38
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 239000006227 byproduct Substances 0.000 abstract description 2
- 238000012643 polycondensation polymerization Methods 0.000 abstract description 2
- 238000004458 analytical method Methods 0.000 description 60
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 45
- VKSWWACDZPRJAP-UHFFFAOYSA-N 1,3-dioxepan-2-one Chemical compound O=C1OCCCCO1 VKSWWACDZPRJAP-UHFFFAOYSA-N 0.000 description 38
- XVWXTEGZTKSUQZ-UHFFFAOYSA-N 4-hydroxybutyl hydrogen carbonate Chemical compound OCCCCOC(O)=O XVWXTEGZTKSUQZ-UHFFFAOYSA-N 0.000 description 33
- 238000005227 gel permeation chromatography Methods 0.000 description 33
- 238000012360 testing method Methods 0.000 description 32
- 238000000113 differential scanning calorimetry Methods 0.000 description 26
- 238000001914 filtration Methods 0.000 description 16
- 230000009471 action Effects 0.000 description 15
- 239000012298 atmosphere Substances 0.000 description 15
- 238000004062 sedimentation Methods 0.000 description 15
- 238000003756 stirring Methods 0.000 description 15
- 238000001291 vacuum drying Methods 0.000 description 15
- 238000005406 washing Methods 0.000 description 15
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 description 8
- 238000001938 differential scanning calorimetry curve Methods 0.000 description 6
- 229960000549 4-dimethylaminophenol Drugs 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 238000007086 side reaction Methods 0.000 description 4
- 230000002194 synthesizing effect Effects 0.000 description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 3
- 238000005481 NMR spectroscopy Methods 0.000 description 3
- 125000005587 carbonate group Chemical group 0.000 description 3
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 3
- 238000006068 polycondensation reaction Methods 0.000 description 3
- 229920000379 polypropylene carbonate Polymers 0.000 description 3
- 238000005809 transesterification reaction Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- -1 Polypropylene Carbonate Polymers 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 229920006125 amorphous polymer Polymers 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 150000005676 cyclic carbonates Chemical class 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 150000002009 diols Chemical class 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 2
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- LELOWRISYMNNSU-UHFFFAOYSA-N Hydrocyanic acid Natural products N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 description 1
- 238000004639 Schlenk technique Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 238000010539 anionic addition polymerization reaction Methods 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- UURSXESKOOOTOV-UHFFFAOYSA-N dec-5-ene Chemical compound CCCCC=CCCCC UURSXESKOOOTOV-UHFFFAOYSA-N 0.000 description 1
- 239000012024 dehydrating agents Substances 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002118 epoxides Chemical class 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- DOIRQSBPFJWKBE-UHFFFAOYSA-N phthalic acid di-n-butyl ester Natural products CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- YFHICDDUDORKJB-UHFFFAOYSA-N trimethylene carbonate Chemical compound O=C1OCCCO1 YFHICDDUDORKJB-UHFFFAOYSA-N 0.000 description 1
- 239000003643 water by type Substances 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
- C08G64/20—General preparatory processes
- C08G64/30—General preparatory processes using carbonates
-
- 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
- C08G64/02—Aliphatic polycarbonates
- C08G64/0208—Aliphatic polycarbonates saturated
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J169/00—Adhesives based on polycarbonates; Adhesives based on derivatives of polycarbonates
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
The invention discloses a crystalline aliphatic polycarbonate with high molecular weight and high mechanical property and a preparation method thereof, belonging to the field of polymer synthesis, wherein the preparation method comprises the following steps: under the condition of solvent or bulk melting, a Lewis pair consisting of Lewis acid and Lewis base is used as a catalyst, an alcohol micromolecule is used as an initiator, and a monomer 1, 3-dioxacyclohepta-2-one is subjected to ring opening polymerization reaction, and after the polymerization reaction is completed, precipitation is carried out to obtain the polycarbonate. Compared with the condensation polymerization method commonly used at present, the polymerization method provided by the invention does not need high temperature and high pressure to remove small molecular byproducts, has relatively mild reaction conditions, better controllability and higher polymer molecular weight, can obtain crystalline polycarbonate with high molecular weight, high elongation at break and high mechanical strength, and has important significance in realizing high performance of polycarbonate and widening the application range of degradable polycarbonate materials.
Description
Technical Field
The invention belongs to the technical field of high molecular material synthesis, and particularly relates to crystalline aliphatic polycarbonate with high molecular weight and high mechanical property and a preparation method thereof.
Background
The aliphatic polycarbonate has good biodegradability and biocompatibility, and has important application in the fields of film materials, elastomers, biomedical applications, adhesives and the like. CO 2 And high pressure ring opening copolymerization of alkylene oxides are important methods for synthesizing aliphatic polycarbonates, which have been successfully used for industrial Production of Polypropylene Carbonate (PPC) and polycyclohexenyl carbonate (PCHC). However, it is suitable for CO 2 The copolymerized epoxy compound is limited to ternary and quaternary epoxy compounds with larger ring tension, and the monomer types are fewer, so that the product structure and performance are relatively single. Meanwhile, side reactions such as olefin oxide homopolymerization, small molecule cyclic carbonate formation and the like are easy to occur in the copolymerization process. In addition, the resulting products PPC and PCHC are generally amorphous polymers with poor mechanical properties.
The thermal and mechanical properties of polycarbonates depend on their chain structure. Increasing the number of consecutive methylene groups between adjacent carbonate groups can cause the polycarbonate to change from an amorphous state to a crystalline state. For example: the two carbonate groups are respectively 2 and 3 carbon atoms of the poly (ethylene carbonate) and the poly (trimethylene carbonate) which are amorphous polymers and have poor mechanical properties; and when the number of methylene groups in adjacent two carbonate groups increases to 4, i.e., poly (1, 4-butylene carbonate) polymer exhibits crystallinity. Due to the existence of the crystal structure, the poly (1, 4-butanediol carbonate) has higher extension strength while keeping flexibility, and further widens the application range of the polycarbonate.
Poly (1, 4-butanediol carbonate) and crystalline polycarbonates containing more methylene units cannot be produced from CO 2 And tetrahydrofuran and macrocyclic ether, and is mainly due to the low ring tension of tetrahydrofuran and macrocyclic epoxide, and difficult to carry out coordination anion polymerization. Thus, the current principal method for synthesizing crystalline polycarbonates is transesterification-polycondensation of dialkyl carbonates with α, ω -diols. The method has better control on the structure and molecular weight of the polymerAnd (3) difference. Meanwhile, since the transesterification method is required to be carried out under severe conditions such as high temperature, high vacuum, etc., many side reactions are usually accompanied in the polymerization process. For example: back biting at the chain ends to form cyclic low molecular weight polycarbonates; dehydration of 1, 4-butanediol to tetrahydrofuran, etc. (ref.: lee B.Y.et al, macromolecules 2013,46,3301-330). Patent CN200810117766.2 discloses a process for preparing crystalline polycarbonate by transesterification-polycondensation of diol/dialkyl carbonate at high temperature. The polycarbonate obtained by the transesterification-polycondensation method has the number average molecular weight range of only 6000-20000 kDa and relatively low molecular weight; and there is no information related to the thermal and mechanical properties of polycarbonate.
Crystalline polycarbonates can also be prepared by reacting carbon dioxide with diols in the presence of catalysts, dehydrating agents, and the like. For example: tomishige, K.et al reported that carbon dioxide and a long chain glycol can be used to prepare polycarbonates in the presence of ceria (catalyst) and furofurancarbonitrile (dehydrating agent) (ref: ACS Sustainable chem. Eng.2019,7, 6304-6315). This process requires the use of not only large amounts of furan, carbonitrile, which are expensive, but also the number average molecular weight (M) n ) And at most only 5000kDa. At such low molecular weights, polycarbonates have little mechanical strength and are difficult to use as materials.
Polycarbonate can also be prepared by ring-opening polymerization of cyclic carbonate monomers in the presence of a catalyst. Compared with the three previous methods, the method has the advantages of mild polymerization reaction conditions, controllable polymer structure, wide usable substrate range, easy regulation of polymer structure and performance, and is the optimal method for preparing the polycarbonate with definite structure. The most representative example is the preparation of amorphous poly (trimethylene carbonate) from ring-opening polymerization of 6-membered ring monomeric trimethylene carbonate (j. Chem. Duc.2015,92, 708-713). Zhu J. Et al report a process for preparing high molecular weight polycarbonates from the ring-opening polymerization of substituted 1, 3-dioxepan-2-ones. Despite the relatively high molecular weight of these polycarbonates, the polymers remain non-crystalline (ACS Macro lett.2022,11,2,173-178). Subsequently, zhu j. Et al report a class of crystalline polycarbonates containing rigid cyclic units in the main chain. Although such polycarbonates are crystalline, the elongation at break of these polycarbonates is no more than 300% due to rigid cyclic substituents which increase the brittleness of the polymer and decrease the flexibility of the polymer (Macromolecules 2022,55,9232-9241). Buchard A et al report a process for preparing crystalline polycarbonates containing unsaturated double bonds in the main chain by ring opening polymerization of 1, 3-dioxepan-2-one derivatives. Because the method takes organic alkali as a catalyst, transesterification side reaction easily occurs in the polymerization process, so that the molecular weight of the polymer is not high, and the number average molecular weight is only 20kDa at most. Meanwhile, the literature does not disclose information about mechanical properties and the like of polycarbonate (J.Am.chem. Soc.2019,141, 13301-13305).
From the above analysis, it is known that there is still a great challenge in the field of polycarbonate synthesis to produce crystalline aliphatic polycarbonates having both high molecular weight, high elongation at break and high mechanical strength by ring-opening polymerization. And the polycarbonate has a wider application range due to high molecular weight, high elongation at break and high mechanical strength. Therefore, it is necessary to provide a method for synthesizing a polycarbonate having a high molecular weight, a high elongation at break and a high mechanical strength, in order to promote the development of a high-performance polycarbonate.
Disclosure of Invention
The invention aims to provide crystalline aliphatic polycarbonate with high molecular weight, high elongation at break and high mechanical strength and a preparation method thereof, so as to solve the problems in the prior art, realize high performance of the polycarbonate and promote the development of degradable polycarbonate materials.
In order to achieve the above object, the present invention provides a method for preparing crystalline aliphatic polycarbonate having a high molecular weight and high mechanical properties, comprising the steps of: under the condition of solvent or bulk melting, a Lewis acid-base pair (Lewis pair) consisting of Lewis acid and Lewis base is used as a catalyst, micromolecular alcohols are used as an initiator, the ring-opening polymerization reaction is carried out on the monomer 1, 3-dioxacyclohepta-2-ketone, and after the ring-opening polymerization reaction is finished, the crystalline aliphatic polycarbonate with high molecular weight and high mechanical property is obtained by precipitation.
The invention provides a method for preparing crystalline aliphatic polycarbonate with high molecular weight, high elongation at break and high mechanical strength by ring-opening polymerization of seven-membered cyclic carbonate monomer, wherein the reaction formula is shown in formula I:
further, the molar ratio of the Lewis acid to the Lewis base in the Lewis pair is 1:1.
Further, the Lewis acid is diethyl zinc (ZnEt) 2 ) Diphenylzinc (Zn (C) 6 H 5 ) 2 ) Zinc difluorophenyl (Zn (C) 6 F 5 ) 2 ) Trimethylaluminum (AlMe) 3 ) And triisobutylaluminum (Al) i Bu 3 ) One of the following;
the Lewis base is one of lutidine (DMAP), 1, 8-diazabicyclo [5.4.0] undec-7-ene (DBU), 1,5, 7-triazabicyclo [4.4.0] dec-5-ene (TBD) and 7-methyl-1, 5, 7-triazabicyclo [4.4.0] dec-5-ene (MTBD).
Further, the small molecule alcohol is benzyl alcohol, terephthalyl alcohol or butanediol.
Further, the solvent is dichloromethane, tetrahydrofuran or toluene, and the concentration is 0.5-5 mol/L.
Further, the mol ratio of the catalyst to the initiator to the monomer is 1:1:500-50000.
Further, the temperature of the ring-opening polymerization reaction is 25-120 ℃ and the time is 1-720 min.
Further, the precipitant used for precipitation is ethanol or n-hexane.
Further, the steps of filtering and drying are included after the precipitation.
Crystalline aliphatic polycarbonate with high molecular weight and high mechanical property is prepared by the preparation method, and is crystalline polymer with number average molecular weight of 60000-600000 Da, molecular weight distribution of 1.2-1.6 and melting temperature of 51-58 ℃.
Further, the crystalline aliphatic polycarbonate with high molecular weight and high mechanical property has a yield strength of 6-7 MPa, an elongation at break of 480-800% and a breaking strength of 14-25 MPa.
The crystalline aliphatic polycarbonate with high molecular weight and high mechanical property is applied to the fields of film materials, elastomers, biomedical materials and adhesives.
Compared with the prior art, the invention has the following advantages and technical effects:
compared with the condensation polymerization method which is frequently used for synthesizing poly (1, 4-butanediol carbonate) at present, the polymerization method provided by the invention does not need to remove small molecule byproducts at high temperature and high pressure, the reaction condition is relatively mild, the controllability is better, and the molecular weight of the polymer is higher. The invention takes the Lewis pair composed of the Lewis acid and the Lewis base as the catalyst, the synergistic effect of the Lewis acid and the Lewis base can effectively inhibit the transesterification side reaction of the polymerization reaction, and the high molecular weight polycarbonate material is easy to prepare. The preparation method can ensure that the conversion rate of the 1, 3-dioxepan-2-one monomer reaches 100 percent at most, the obtained poly (1, 4-butylene carbonate) has a definite structure, the content of the carbonate is more than 99 percent, the number average molecular weight of the polycarbonate is 60000-600000 Da, and the molecular weight distribution is 1.2-1.6. The polycarbonate obtained by the invention is a crystalline polymer, and the melting temperature is 51-58 ℃. The obtained polycarbonate has excellent mechanical properties, the yield strength is 6-7 MPa, the elongation at break is 480-800%, and the breaking strength is 14-25 MPa.
The preparation of the crystalline polycarbonate with high molecular weight, high elongation at break and high mechanical strength by ring-opening polymerization of the 1, 3-dioxepin-2-ketone has important significance for realizing high performance of the polycarbonate and widening the application range of the degradable polycarbonate material.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the invention. In the drawings:
FIG. 1 is a poly (1, 4-butylene carbonate) prepared in example 2 of the present invention 1 H NMR spectrum;
FIG. 2 is a DSC curve of poly (1, 4-butylene carbonate) prepared in example 11 of the present invention;
FIG. 3 is a stress-strain curve of poly (1, 4-butylene carbonate) prepared in example 11 of the present invention;
FIG. 4 is a DSC curve of poly (1, 4-butylene carbonate) prepared in example 12 of the present invention;
FIG. 5 is a stress-strain curve of poly (1, 4-butylene carbonate) prepared in example 12 of the present invention;
FIG. 6 is a stress-strain curve of poly (1, 4-butylene carbonate) prepared in example 13 of the present invention;
FIG. 7 is a DSC curve of poly (1, 4-butylene carbonate) prepared in example 14 of the present invention.
Detailed Description
Various exemplary embodiments of the invention will now be described in detail, which should not be considered as limiting the invention, but rather as more detailed descriptions of certain aspects, features and embodiments of the invention.
It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. In addition, for numerical ranges in this disclosure, it is understood that each intermediate value between the upper and lower limits of the ranges is also specifically disclosed. Every smaller range between any stated value or stated range, and any other stated value or intermediate value within the stated range, is also encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.
Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention. All documents mentioned in this specification are incorporated by reference for the purpose of disclosing and describing the methods and/or materials associated with the documents. In case of conflict with any incorporated document, the present specification will control.
It will be apparent to those skilled in the art that various modifications and variations can be made in the specific embodiments of the invention described herein without departing from the scope or spirit of the invention. Other embodiments will be apparent to those skilled in the art from consideration of the specification of the present invention. The specification and examples of the present invention are exemplary only.
As used herein, the terms "comprising," "including," "having," "containing," and the like are intended to be inclusive and mean an inclusion, but not limited to.
Room temperature in the examples of the present invention refers to 25±2 ℃ unless otherwise specified.
In the invention, lewis acid and Lewis base are used as catalysts, alcohol micromolecules are used as initiators, and under the condition of solvent or bulk melting, monomer 1, 3-dioxepan-2-one is subjected to ring-opening polymerization, and after the polymerization reaction is completed, precipitation is carried out to obtain the polycarbonate, wherein the reaction formula is shown as formula (I):
the Lewis acid is diethyl zinc (ZnEt) 2 ) Diphenylzinc (Zn (C) 6 H 5 ) 2 ) Zinc difluorophenyl (Zn (C) 6 F 5 ) 2 ) Trimethylaluminum (AlMe) 3 ) Triisobutylaluminum (Al) i Bu 3 ) One of the following; the Lewis base is lutidine (DMAP), 1, 8-diazabicyclo [5.4.0]Undec-7-ene (DBU), 1,5, 7-triazabicyclo [4.4.0]Dec-5-ene (TBD), 7-methyl-1, 5, 7-triazabicyclo [4.4.0]One of dec-5-ene (MTBD); the Lewis pair is formed by combining any one of the Lewis acids and any one of the Lewis bases in an equimolar ratio.
In the preparation of aliphatic polycarbonate esters by ring-opening polymerization of 1, 3-dioxepan-2-one, all procedures sensitive to moisture and oxygen are carried out by the person skilled in the art in an MBraun glove box or under nitrogen protection using standard Schlenk techniques.
When the prepared polymer is subjected to relevant tests, the structure of the polymer is determined by nuclear magnetic resonance spectroscopy, the molecular weight and the molecular weight distribution index of the polymer are determined by gel chromatography (GPC), the thermal performance of the polymer is determined by a differential scanning calorimeter, and the mechanical performance of the polymer is determined by a universal stretcher. Wherein the polymer is 1 H and 13 c NMR was determined by Bruker-400 NMR at 25℃with TMS as internal standard and deuterated chloroform as solvent; gel chromatography was determined using a Waters gel permeation chromatograph: tetrahydrofuran (THF) was used as a solvent (0.05 wt% of 2, 6-di-t-butyl-4-methylphenol was added as an antioxidant) at a test temperature of 40℃and a flow rate of 1.0mL/min, using PL EasiCal PS-1 as a standard; the differential scanning calorimeter is measured by TA, firstly, the temperature is raised to 150.00 ℃ at the speed of 5.000 ℃/min, the temperature is kept for 5.00min, then the temperature is reduced at the speed of 5.000 ℃/min until the temperature reaches-50.00 ℃ and the temperature is kept for 5.00min for the second time; when the mechanical properties are measured by a universal stretcher, the polymer is firstly hot-pressed into a sample at 120 ℃, and is cut into a stretching spline with the length of 5 multiplied by 10mm, and the stretching rate is 10mm/min.
Example 1
The catalyst used in this example was commercially available zinc dipentafluorophenylate (Zn (C) 6 F 5 ) 2 ) And lutidine (DMAP).
The preparation method comprises the following steps:
(1) 10. Mu. Mol of Zn (C) was charged into a dry 50mL reaction vessel under an inert atmosphere 6 F 5 ) 2 And DMAP,10 mu mol of benzyl alcohol, 5000 mu mol of 1, 3-dioxacyclohepta-2-one, and then 20mL of dichloromethane are added for ring-opening polymerization at room temperature, and polymerization reaction is carried out for 720min under the stirring action of 500 rmp;
(2) After the polymerization is finished, the reaction system in the kettle is poured into 100mL of methanol for sedimentation, and then the poly (1, 4-butanediol carbonate) is obtained through filtration, washing and vacuum drying.
The 1, 3-dioxepan-2-one monomer conversion of this example was 100%.
Performing nuclear magnetic analysis, GPC analysis, DSC analysis and mechanical property test on the prepared poly (1, 4-butanediol carbonate): nuclear magnetic analysis shows the content of the polymer polycarbonate>99 percent; GPC analysis revealed that polymer molecular weight was 60.4kDa and molecular weight distribution was 1.05; DSC analysis showed Polymer T m 57.5 ℃; the result of the universal stretcher test shows that the yield strength of the polymer prepared in the example 1 is 6.06MPa, the elongation at break is 483% and the breaking strength is 14.1MPa.
Example 2
The catalyst used in this example was commercially available zinc dipentafluorophenylate (Zn (C) 6 F 5 ) 2 ) And 1, 8-diazabicyclo [5.4.0]Undec-7-ene (DBU).
The preparation method comprises the following steps:
(1) 10. Mu. Mol of Zn (C) was charged into a dry 50mL reaction vessel under an inert atmosphere 6 F 5 ) 2 And DBU,10 mu mol of benzyl alcohol, 5000 mu mol of 1, 3-dioxacyclohepta-2-one, and then 20mL of dichloromethane are added for ring-opening polymerization at room temperature, and polymerization is carried out for 480min under the stirring action of 500 rmp;
(2) After the polymerization is finished, the reaction system in the kettle is poured into 100mL of methanol for sedimentation, and then the poly (1, 4-butanediol carbonate) is obtained through filtration, washing and vacuum drying.
The 1, 3-dioxepan-2-one monomer conversion of this example was 100%.
Performing nuclear magnetic analysis and GPC analysis on the prepared poly (1, 4-butanediol carbonate): FIG. 1 is a poly (1, 4-butylene carbonate) prepared in example 2 1 H NMR spectrum, result shows the content of polymer polycarbonate>99 percent; GPC analysis revealed that polymer molecular weight was 64.5kDa and molecular weight distribution was 1.11; DSC analysis showed Polymer T m 57.1 ℃; the result of the universal stretcher test shows that the yield strength of the polymer prepared in example 2 is 6.28MPa, the elongation at break is 511% and the breaking strength is 14.8MPa.
Example 3
The catalyst used in this example was two commercially available catalystsPentafluorophenyl zinc (Zn (C) 6 F 5 ) 2 ) And 1, 8-diazabicyclo [5.4.0]Undec-7-ene (DBU).
The preparation method comprises the following steps:
(1) 10. Mu. Mol of Zn (C) was charged into a dry 50mL reaction vessel under an inert atmosphere 6 F 5 ) 2 And DBU,5000 mu mol of 1, 3-dioxepan-2-one, adding 20mL of dichloromethane, and carrying out ring-opening polymerization at room temperature, wherein polymerization is carried out for 720min under the stirring action of 500 rmp;
(2) After the polymerization is finished, the reaction system in the kettle is poured into 100mL of methanol for sedimentation, and then the poly (1, 4-butanediol carbonate) is obtained through filtration, washing and vacuum drying.
The 1, 3-dioxepan-2-one monomer conversion of this example was 100%.
Performing nuclear magnetic analysis, GPC analysis, DSC analysis and mechanical property test on the prepared poly (1, 4-butanediol carbonate): nuclear magnetic analysis shows the content of the polymer polycarbonate>99 percent; GPC analysis revealed that polymer molecular weight was 66.5kDa and molecular weight distribution was 1.12; DSC analysis showed Polymer T m 57.4 ℃; the result of the universal stretcher test shows that the yield strength of the polymer prepared in the example 3 is 6.02MPa, the elongation at break is 487% and the breaking strength is 14.2MPa.
Example 4
The catalyst used in this example was commercially available zinc dipentafluorophenylate (Zn (C) 6 F 5 ) 2 ) And 1,5, 7-triazabicyclo [4.4.0]Dec-5-ene (TBD).
The preparation method comprises the following steps:
(1) 10. Mu. Mol of Zn (C) was charged into a dry 50mL reaction vessel under an inert atmosphere 6 F 5 ) 2 And TBD,10 mu mol of benzyl alcohol, 5000 mu mol of 1, 3-dioxacyclohepta-2-one, and then 20mL of dichloromethane are added for ring-opening polymerization at room temperature, and polymerization reaction is carried out for 270min under the stirring action of 500 rmp;
(2) After the polymerization is finished, the reaction system in the kettle is poured into 100mL of methanol for sedimentation, and then the poly (1, 4-butanediol carbonate) is obtained through filtration, washing and vacuum drying.
The 1, 3-dioxepan-2-one monomer conversion of this example was 100%.
Performing nuclear magnetic analysis, GPC analysis, DSC analysis and mechanical property test on the prepared poly (1, 4-butanediol carbonate): nuclear magnetic analysis shows the content of the polymer polycarbonate>99 percent; GPC analysis revealed that polymer molecular weight was 61.9kDa and molecular weight distribution was 1.29; DSC analysis showed Polymer T m 57.4 ℃; the result of the universal stretcher test shows that the yield strength of the polymer prepared in the example 4 is 5.98MPa, the elongation at break is 485%, and the breaking strength is 14.3MPa.
Example 5
The catalyst used in this example was commercially available zinc dipentafluorophenylate (Zn (C) 6 F 5 ) 2 ) And 7-methyl-1, 5, 7-triazabicyclo [4.4.0]Dec-5-ene (MTBD).
The preparation method comprises the following steps:
(1) 10. Mu. Mol of Zn (C) was charged into a dry 50mL reaction vessel under an inert atmosphere 6 F 5 ) 2 And MTBD,10 mu mol of benzyl alcohol, 5000 mu mol of 1, 3-dioxacyclohepta-2-one, and then 20mL of dichloromethane are added for ring-opening polymerization at room temperature, and polymerization reaction is carried out for 240min under the stirring action of 500 rmp;
(2) After the polymerization is finished, the reaction system in the kettle is poured into 100mL of methanol for sedimentation, and then the poly (1, 4-butanediol carbonate) is obtained through filtration, washing and vacuum drying.
The 1, 3-dioxepan-2-one monomer conversion of this example was 100%.
Performing nuclear magnetic analysis, GPC analysis, DSC analysis and mechanical property test on the prepared poly (1, 4-butanediol carbonate): nuclear magnetic analysis shows the content of the polymer polycarbonate>99 percent; GPC analysis revealed that polymer molecular weight was 72.2kDa and molecular weight distribution was 1.39; DSC analysis showed Polymer T m 56.9 ℃; the result of the universal stretcher test shows that the yield strength of the polymer prepared in the example 5 is 6.21MPa, the elongation at break is 508% and the breaking strength is 15.6MPa.
Example 6
The embodiment adoptsThe catalyst was commercially available diethyl zinc (ZnEt 2 ) And 1, 8-diazabicyclo [5.4.0]Undec-7-ene (DBU).
The preparation method comprises the following steps:
(1) 10. Mu. Mol of ZnEt are charged in a dry 50mL reaction vessel under an inert atmosphere 2 And DBU,10 mu mol of benzyl alcohol, 5000 mu mol of 1, 3-dioxacyclohepta-2-one, and then 20mL of dichloromethane are added for ring-opening polymerization at room temperature, and polymerization reaction is carried out for 180min under the stirring action of 500 rmp;
(2) After the polymerization is finished, the reaction system in the kettle is poured into 100mL of methanol for sedimentation, and then the poly (1, 4-butanediol carbonate) is obtained through filtration, washing and vacuum drying.
The 1, 3-dioxepan-2-one monomer conversion of this example was 100%.
Performing nuclear magnetic analysis, GPC analysis, DSC analysis and mechanical property test on the prepared poly (1, 4-butanediol carbonate): nuclear magnetic analysis shows the content of the polymer polycarbonate>99 percent; GPC analysis revealed that polymer molecular weight was 71.4kDa and molecular weight distribution was 1.59; DSC analysis showed Polymer T m 57.1 ℃; the result of the universal stretcher test shows that the yield strength of the polymer prepared in the example 6 is 6.32MPa, the elongation at break is 519% and the breaking strength is 15.4MPa.
Example 7
The catalyst used in this example was commercially available diphenylzinc (Zn (C) 6 H 5 ) 2 ) And 1, 8-diazabicyclo [5.4.0]Undec-7-ene (DBU).
The preparation method comprises the following steps:
(1) 10. Mu. Mol of Zn (C) was charged into a dry 50mL reaction vessel under an inert atmosphere 6 H 5 ) 2 And DBU,10 mu mol of benzyl alcohol, 5000 mu mol of 1, 3-dioxacyclohepta-2-one, and then 20mL of dichloromethane are added for ring-opening polymerization at room temperature, and polymerization reaction is carried out for 180min under the stirring action of 500 rmp;
(2) After the polymerization is finished, the reaction system in the kettle is poured into 100mL of methanol for sedimentation, and then the poly (1, 4-butanediol carbonate) is obtained through filtration, washing and vacuum drying.
The 1, 3-dioxepan-2-one monomer conversion of this example was 100%.
Performing nuclear magnetic analysis, GPC analysis, DSC analysis and mechanical property test on the prepared poly (1, 4-butanediol carbonate): nuclear magnetic analysis shows the content of the polymer polycarbonate>99 percent; GPC analysis revealed that the molecular weight of the polymer was 87.4kDa and the molecular weight distribution was 1.10; DSC analysis showed Polymer T m 56.5 ℃; the result of the universal stretcher test shows that the yield strength of the polymer prepared in the example 7 is 6.39MPa, the elongation at break is 525% and the breaking strength is 16.5MPa.
Example 8
The catalyst used in this example was commercially available trimethylaluminum (AlMe) 3 ) And 1, 8-diazabicyclo [5.4.0]Undec-7-ene (DBU).
The preparation method comprises the following steps:
(1) Under inert atmosphere, 10 mu mol of AlMe is added into a dried 50mL reaction kettle 3 And DBU,10 mu mol of benzyl alcohol, 5000 mu mol of 1, 3-dioxacyclohepta-2-one, and then 20mL of dichloromethane are added for ring-opening polymerization at room temperature, and polymerization reaction is carried out for 660min under the stirring action of 500 rmp;
(2) After the polymerization is finished, the reaction system in the kettle is poured into 100mL of methanol for sedimentation, and then the poly (1, 4-butanediol carbonate) is obtained through filtration, washing and vacuum drying.
The 1, 3-dioxepan-2-one monomer conversion of this example was 100%.
Performing nuclear magnetic analysis, GPC analysis, DSC analysis and mechanical property test on the prepared poly (1, 4-butanediol carbonate): nuclear magnetic analysis shows the content of the polymer polycarbonate>99 percent; GPC analysis revealed that the polymer molecular weight was 63.2kDa and molecular weight distribution was 1.55; DSC analysis showed Polymer T m 57.6 ℃; the result of the universal stretcher test shows that the yield strength of the polymer prepared in the example 8 is 6.17MPa, the elongation at break is 500% and the breaking strength is 14.7MPa.
Example 9
The catalyst used in this example was commercially available triisobutylaluminum (Al i Bu 3 ) And 1, 8-diazabicyclo [5.4.0]Undec-7-ene (DBU).
The preparation method comprises the following steps:
(1) 10 mu mol of Al is added into a dried 50mL reaction kettle under inert atmosphere i Bu 3 And DBU,10 mu mol of benzyl alcohol, 5000 mu mol of 1, 3-dioxacyclohepta-2-one, and then 20mL of dichloromethane are added for ring-opening polymerization at room temperature, and polymerization reaction is carried out for 720min under the stirring action of 500 rmp;
(2) After the polymerization is finished, the reaction system in the kettle is poured into 100mL of methanol for sedimentation, and then the poly (1, 4-butanediol carbonate) is obtained through filtration, washing and vacuum drying.
The 1, 3-dioxepan-2-one monomer conversion of this example was 100%.
Performing nuclear magnetic analysis, GPC analysis, DSC analysis and mechanical property test on the prepared poly (1, 4-butanediol carbonate): nuclear magnetic analysis shows the content of the polymer polycarbonate>99 percent; GPC analysis revealed that polymer molecular weight was 60.7kDa and molecular weight distribution was 1.35; DSC analysis showed Polymer T m 57.5 ℃; the result of the universal stretcher test shows that the yield strength of the polymer prepared in the example 9 is 6.05MPa, the elongation at break is 495% and the breaking strength is 14.5MPa.
Example 10
The catalyst used in this example was commercially available zinc dipentafluorophenylate (Zn (C) 6 F 5 ) 2 ) And 1, 8-diazabicyclo [5.4.0]Undec-7-ene (DBU).
The preparation method comprises the following steps:
(1) 10. Mu. Mol of Zn (C) was charged into a dry 50mL reaction vessel under an inert atmosphere 6 F 5 ) 2 And DBU,10 mu mol of benzyl alcohol, 5000 mu mol of 1, 3-dioxacyclohepta-2-one, and then 20mL of tetrahydrofuran are added for ring-opening polymerization at room temperature, and polymerization is carried out for 720min under the stirring action of 500 rmp;
(2) After the polymerization is finished, the reaction system in the kettle is poured into 100mL of methanol for sedimentation, and then the poly (1, 4-butanediol carbonate) is obtained through filtration, washing and vacuum drying.
The 1, 3-dioxepan-2-one monomer conversion of this example was 100%.
Performing nuclear magnetic analysis, GPC analysis, DSC analysis and mechanical property test on the prepared poly (1, 4-butanediol carbonate): nuclear magnetic analysis shows the content of the polymer polycarbonate>99 percent; GPC analysis revealed that polymer molecular weight was 74.2kDa and molecular weight distribution was 1.11; DSC analysis showed Polymer T m 57.2 ℃; the result of the universal stretcher test shows that the yield strength of the polymer prepared in example 10 is 6.27MPa, the elongation at break is 512% and the breaking strength is 15.3MPa.
Example 11
The catalyst used in this example was commercially available zinc dipentafluorophenylate (Zn (C) 6 F 5 ) 2 ) And 1, 8-diazabicyclo [5.4.0]Undec-7-ene (DBU).
The preparation method comprises the following steps:
(1) 10. Mu. Mol of Zn (C) was charged into a dry 50mL reaction vessel under an inert atmosphere 6 F 5 ) 2 And DBU,10 mu mol of benzyl alcohol, 5000 mu mol of 1, 3-dioxacyclohepta-2-one, 10mL of dichloromethane is added, ring-opening polymerization is carried out at room temperature, and polymerization reaction is carried out for 540min under the stirring action of 500 rmp;
(2) After the polymerization is finished, the reaction system in the kettle is poured into 100mL of methanol for sedimentation, and then the poly (1, 4-butanediol carbonate) is obtained through filtration, washing and vacuum drying.
The 1, 3-dioxepan-2-one monomer conversion of this example was 100%.
Performing nuclear magnetic analysis, GPC analysis, DSC analysis and mechanical property test on the prepared poly (1, 4-butanediol carbonate): nuclear magnetic analysis shows the content of the polymer polycarbonate>99 percent; GPC analysis revealed that the polymer molecular weight was 64.3kDa and molecular weight distribution was 1.12; FIG. 2 is a DSC curve of poly (1, 4-butylene carbonate) prepared in example 11, showing the T of the polymer m 57.1 ℃; FIG. 3 is a stress strain curve of poly (1, 4-butylene carbonate) prepared in example 11, and the result of a universal stretcher test shows that the yield strength of the polymer prepared in example 11 is 6.10MPa, the elongation at break is 490% and the breaking strength is 14.4MPa。
Example 12
The catalyst used in this example was commercially available zinc dipentafluorophenylate (Zn (C) 6 F 5 ) 2 ) And 1, 8-diazabicyclo [5.4.0]Undec-7-ene (DBU).
The preparation method comprises the following steps:
(1) 10. Mu. Mol of Zn (C) was charged into a dry 50mL reaction vessel under an inert atmosphere 6 F 5 ) 2 And DBU,10 mu mol of benzyl alcohol, 10000 mu mol of 1, 3-dioxacyclohepta-2-ketone, and then 20mL of dichloromethane are added for ring-opening polymerization at room temperature, and polymerization reaction is carried out for 480min under the stirring action of 500 rmp;
(2) After the polymerization is finished, the reaction system in the kettle is poured into 100mL of methanol for sedimentation, and then the poly (1, 4-butanediol carbonate) is obtained through filtration, washing and vacuum drying.
The 1, 3-dioxepan-2-one monomer conversion of this example was 100%.
Performing nuclear magnetic analysis, GPC analysis, DSC analysis and mechanical property test on the prepared poly (1, 4-butanediol carbonate): nuclear magnetic analysis shows the content of the polymer polycarbonate>99 percent; GPC analysis revealed that polymer molecular weight was 122.4kDa and molecular weight distribution was 1.11; FIG. 4 is a DSC curve of poly (1, 4-butylene carbonate) prepared in example 12, showing the T of the polymer m 56.3 ℃; FIG. 5 is a stress strain curve of the poly (1, 4-butylene carbonate) prepared in example 12. The result of the universal stretcher test shows that the yield strength of the polymer prepared in example 12 is 6.45MPa, the elongation at break is 549% and the breaking strength is 17.4MPa.
Example 13
The catalyst used in this example was commercially available diphenylzinc (Zn (C) 6 H 5 ) 2 ) And 1, 8-diazabicyclo [5.4.0]Undec-7-ene (DBU).
The preparation method comprises the following steps:
(1) 10. Mu. Mol of Zn (C) was charged into a dry 50mL reaction vessel under an inert atmosphere 6 H 5 ) 2 And DBU, 10. Mu. Mol of benzyl alcohol, 10000. Mu. Mol of 1,3-dioxepan-2-one, adding 20mL of dichloromethane, and carrying out ring-opening polymerization at room temperature, wherein polymerization is carried out for 120min under the stirring action of 500 rmp;
(2) After the polymerization is finished, the reaction system in the kettle is poured into 100mL of methanol for sedimentation, and then the poly (1, 4-butanediol carbonate) is obtained through filtration, washing and vacuum drying.
The 1, 3-dioxepan-2-one monomer conversion of this example was 100%.
Performing nuclear magnetic analysis, GPC analysis, DSC analysis and mechanical property test on the prepared poly (1, 4-butanediol carbonate): nuclear magnetic analysis shows the content of the polymer polycarbonate>99 percent; GPC analysis revealed that polymer molecular weight was 121.2kDa and molecular weight distribution was 1.54; DSC analysis showed Polymer T m 55.2 ℃; FIG. 6 is a stress strain curve of the poly (1, 4-butylene carbonate) prepared in example 13, and the result of the universal stretcher test shows that the yield strength of the polymer prepared in this example is 6.75MPa, the elongation at break is 574% and the breaking strength is 17.2MPa.
Example 14
The catalyst used in this example was commercially available zinc dipentafluorophenylate (Zn (C) 6 F 5 ) 2 ) And 1, 8-diazabicyclo [5.4.0]Undec-7-ene (DBU).
The preparation method comprises the following steps:
(1) 4. Mu. Mol of Zn (C) was charged into a dry 50mL reaction vessel under an inert atmosphere 6 F 5 ) 2 And DBU,4 mu mol of benzyl alcohol, 10000 mu mol of 1, 3-dioxacyclohepta-2-ketone, and then 20mL of dichloromethane are added for ring-opening polymerization at room temperature, and polymerization reaction is carried out for 720min under the stirring action of 500 rmp;
(2) After the polymerization is finished, the reaction system in the kettle is poured into 100mL of methanol for sedimentation, and then the poly (1, 4-butanediol carbonate) is obtained through filtration, washing and vacuum drying.
The 1, 3-dioxepan-2-one monomer conversion of this example was 100%.
Performing nuclear magnetic analysis, GPC analysis, DSC analysis and mechanical property test on the prepared poly (1, 4-butanediol carbonate): nuclear magnetic analysis shows polymer aggregationCarbonate content>99 percent; GPC analysis revealed that polymer molecular weight was 206.5kDa and molecular weight distribution was 1.22; FIG. 7 is a DSC curve of poly (1, 4-butylene carbonate) prepared in example 14, showing the T of the polymer m 51.5 ℃; the test result of the universal stretcher shows that the yield strength of the polymer prepared in the embodiment is 6.55MPa, the elongation at break is 664% and the breaking strength is 19.6MPa.
Example 15
The catalyst used in this example was commercially available zinc dipentafluorophenylate (Zn (C) 6 F 5 ) 2 ) And 1, 8-diazabicyclo [5.4.0]Undec-7-ene (DBU).
The preparation method comprises the following steps:
(1) 4. Mu. Mol of Zn (C) was charged into a dry 50mL reaction vessel under an inert atmosphere 6 F 5 ) 2 And DBU,4 mu mol of benzyl alcohol, 50000 mu mol of 1, 3-dioxacyclohepta-2-one, and then adding 20mL of dichloromethane, and carrying out ring-opening polymerization at room temperature, wherein polymerization is carried out for 720min under the stirring action of 500 rmp;
(2) After the polymerization is finished, the reaction system in the kettle is poured into 100mL of methanol for sedimentation, and then the poly (1, 4-butanediol carbonate) is obtained through filtration, washing and vacuum drying.
The 1, 3-dioxepan-2-one monomer conversion of this example was 100%.
Performing nuclear magnetic analysis, GPC analysis, DSC analysis and mechanical property test on the prepared poly (1, 4-butanediol carbonate): nuclear magnetic analysis shows the content of the polymer polycarbonate>99 percent; GPC analysis revealed that polymer molecular weight was 596.5kDa and molecular weight distribution was 1.22; DSC analysis shows T of the polymer m 51.5 ℃; the test result of the universal stretcher shows that the yield strength of the polymer is 6.55MPa, the elongation at break is 800% and the breaking strength is 25MPa.
The present invention is not limited to the above-mentioned embodiments, and any changes or substitutions that can be easily understood by those skilled in the art within the technical scope of the present invention are intended to be included in the scope of the present invention. Therefore, the protection scope of the present invention should be subject to the protection scope of the claims.
Claims (10)
1. A method for preparing crystalline aliphatic polycarbonate with high molecular weight and high mechanical property, which is characterized by comprising the following steps: under the condition of solvent or bulk melting, a Lewis acid-base pair formed by Lewis acid and Lewis base is used as a catalyst, micromolecular alcohols are used as an initiator, the ring-opening polymerization reaction is carried out on monomer 1, 3-dioxacyclohepta-2-ketone, and after the ring-opening polymerization reaction is finished, the high molecular weight and high mechanical property crystalline aliphatic polycarbonate is obtained by precipitation.
2. The method for producing a crystalline aliphatic polycarbonate having a high molecular weight and high mechanical properties according to claim 1, wherein the molar ratio of the lewis acid base to the lewis acid to the lewis base is 1:1.
3. The method for preparing a crystalline aliphatic polycarbonate having a high molecular weight and high mechanical properties according to claim 2, wherein the lewis acid is one of diethyl zinc, diphenyl zinc, dipentafluorophenyl zinc, trimethylaluminum and triisobutylaluminum;
the Lewis base is one of lutidine, 1, 8-diazabicyclo [5.4.0] undec-7-ene and 1,5, 7-triazabicyclo [4.4.0] dec-5-ene, and 7-methyl-1, 5, 7-triazabicyclo [4.4.0] dec-5-ene.
4. The method for producing a crystalline aliphatic polycarbonate having a high molecular weight and high mechanical properties according to claim 1, wherein the small molecule alcohol is benzyl alcohol, terephthalyl alcohol or butanediol.
5. The method for producing a crystalline aliphatic polycarbonate having a high molecular weight and high mechanical properties according to claim 1, wherein the solvent is methylene chloride, tetrahydrofuran or toluene.
6. The method for producing a crystalline aliphatic polycarbonate having a high molecular weight and high mechanical properties according to claim 1, wherein the molar ratio of the catalyst, the initiator and the monomer is 1:1:500 to 50000.
7. The method for producing a crystalline aliphatic polycarbonate having a high molecular weight and high mechanical properties according to claim 1, wherein the ring-opening polymerization reaction is carried out at a temperature of 25 to 120℃for a period of 1 to 720 minutes.
8. Crystalline aliphatic polycarbonate with high molecular weight and high mechanical property, which is characterized in that the crystalline aliphatic polycarbonate is prepared by the preparation method of claims 1-7, and is a crystalline polymer with number average molecular weight of 60000-600000 Da, molecular weight distribution of 1.2-1.6 and melting temperature of 51-58 ℃.
9. The crystalline aliphatic polycarbonate having a high molecular weight and high mechanical properties according to claim 8, wherein the yield strength is 6 to 7MPa, the elongation at break is 480 to 800% and the breaking strength is 14 to 25MPa.
10. Use of the crystalline aliphatic polycarbonate of high molecular weight and high mechanical properties according to claim 8 or 9 in the fields of film materials, elastomers, biomedical materials and adhesives.
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| CN109705331A (en) * | 2018-12-25 | 2019-05-03 | 浙江大学 | A kind of Lewis Acids and Bases are to catalysis initiator and its application |
| CN111592644A (en) * | 2020-06-01 | 2020-08-28 | 南京工业大学 | Ring-opening polymerization method for cyclic monomer |
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| CN1091142A (en) * | 1988-08-12 | 1994-08-24 | 拜尔公司 | polycarbonate film |
| KR100878453B1 (en) * | 2007-08-29 | 2009-01-19 | 한국화학연구원 | Process for the preparation of high molecular weight copolycarbonates by solid state polymerization |
| CN105164180A (en) * | 2013-04-30 | 2015-12-16 | 株式会社理光 | Polymer product, film, molded article, sheet, particle, fiber, and method for producing polymer |
| CN107207712A (en) * | 2014-12-17 | 2017-09-26 | Sabic环球技术有限责任公司 | For the product for preparing the method for the graft copolymer comprising polyolefin backbone and one or more polymer lateral chains and being obtained from methods described |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN117024399A (en) * | 2023-08-22 | 2023-11-10 | 天津大学 | Seven-membered cyclic carbonate and synthesis method thereof |
| CN117024399B (en) * | 2023-08-22 | 2024-03-12 | 天津大学 | Seven-membered cyclic carbonate and synthesis method thereof |
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