CN114437320A - Preparation method of poly (2-benzyl caprolactone) - Google Patents
Preparation method of poly (2-benzyl caprolactone) Download PDFInfo
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- CN114437320A CN114437320A CN202210154091.9A CN202210154091A CN114437320A CN 114437320 A CN114437320 A CN 114437320A CN 202210154091 A CN202210154091 A CN 202210154091A CN 114437320 A CN114437320 A CN 114437320A
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- caprolactone
- benzyl
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- alcohol
- catalyst
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- JEHNLMDRQXUAOQ-UHFFFAOYSA-N 3-benzyloxepan-2-one Chemical compound O=C1OCCCCC1CC1=CC=CC=C1 JEHNLMDRQXUAOQ-UHFFFAOYSA-N 0.000 title claims abstract description 99
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 36
- 239000003054 catalyst Substances 0.000 claims abstract description 33
- 238000010438 heat treatment Methods 0.000 claims abstract description 23
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 81
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 claims description 77
- 238000000034 method Methods 0.000 claims description 37
- 239000003999 initiator Substances 0.000 claims description 30
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 28
- 229910052749 magnesium Inorganic materials 0.000 claims description 25
- 239000011777 magnesium Substances 0.000 claims description 25
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 17
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- -1 alkoxy magnesium Chemical compound 0.000 claims description 10
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 8
- PVFSDGKDKFSOTB-UHFFFAOYSA-K iron(3+);triacetate Chemical compound [Fe+3].CC([O-])=O.CC([O-])=O.CC([O-])=O PVFSDGKDKFSOTB-UHFFFAOYSA-K 0.000 claims description 8
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 claims description 8
- 239000011654 magnesium acetate Substances 0.000 claims description 8
- 229940069446 magnesium acetate Drugs 0.000 claims description 8
- 235000011285 magnesium acetate Nutrition 0.000 claims description 8
- YJGJRYWNNHUESM-UHFFFAOYSA-J triacetyloxystannyl acetate Chemical compound [Sn+4].CC([O-])=O.CC([O-])=O.CC([O-])=O.CC([O-])=O YJGJRYWNNHUESM-UHFFFAOYSA-J 0.000 claims description 8
- 239000004246 zinc acetate Substances 0.000 claims description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- 239000007809 chemical reaction catalyst Substances 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 4
- AQIXEPGDORPWBJ-UHFFFAOYSA-N pentan-3-ol Chemical compound CCC(O)CC AQIXEPGDORPWBJ-UHFFFAOYSA-N 0.000 claims description 4
- 229920000642 polymer Polymers 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 3
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 claims description 3
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000003153 chemical reaction reagent Substances 0.000 claims description 2
- 238000009826 distribution Methods 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- QWDJLDTYWNBUKE-UHFFFAOYSA-L magnesium bicarbonate Chemical compound [Mg+2].OC([O-])=O.OC([O-])=O QWDJLDTYWNBUKE-UHFFFAOYSA-L 0.000 claims description 2
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 claims description 2
- 150000003138 primary alcohols Chemical class 0.000 claims description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 2
- 150000003333 secondary alcohols Chemical class 0.000 claims description 2
- 150000003509 tertiary alcohols Chemical class 0.000 claims description 2
- 229910052718 tin Inorganic materials 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- 239000011135 tin Substances 0.000 claims 1
- 229920001610 polycaprolactone Polymers 0.000 abstract description 20
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 abstract description 12
- 238000006467 substitution reaction Methods 0.000 abstract description 8
- 239000004632 polycaprolactone Substances 0.000 abstract 1
- 235000019445 benzyl alcohol Nutrition 0.000 description 25
- 230000002194 synthesizing effect Effects 0.000 description 16
- 150000001412 amines Chemical class 0.000 description 15
- 230000015572 biosynthetic process Effects 0.000 description 13
- 238000003786 synthesis reaction Methods 0.000 description 13
- 239000000463 material Substances 0.000 description 7
- 239000003208 petroleum Substances 0.000 description 7
- 229920003023 plastic Polymers 0.000 description 4
- 239000004033 plastic Substances 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 150000003384 small molecules Chemical class 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 238000010146 3D printing Methods 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920003232 aliphatic polyester Polymers 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 229920006238 degradable plastic Polymers 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- PHTQWCKDNZKARW-UHFFFAOYSA-N isoamylol Chemical compound CC(C)CCO PHTQWCKDNZKARW-UHFFFAOYSA-N 0.000 description 1
- 229960004592 isopropanol Drugs 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 230000029553 photosynthesis Effects 0.000 description 1
- 238000010672 photosynthesis Methods 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000010898 silica gel chromatography Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/06—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids
- C08G63/08—Lactones or lactides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D313/00—Heterocyclic compounds containing rings of more than six members having one oxygen atom as the only ring hetero atom
- C07D313/02—Seven-membered rings
- C07D313/04—Seven-membered rings not condensed with other rings
-
- 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
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/823—Preparation processes characterised by the catalyst used for the preparation of polylactones or polylactides
-
- 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
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/83—Alkali metals, alkaline earth metals, beryllium, magnesium, copper, silver, gold, zinc, cadmium, mercury, manganese, or compounds thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/87—Non-metals or inter-compounds thereof
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- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Polyesters Or Polycarbonates (AREA)
- Biological Depolymerization Polymers (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a preparation method of poly-2-benzyl caprolactone. The epsilon-caprolactone is substituted under the action of a catalyst at low temperature, and polymerization is carried out under the heating condition to obtain poly-2-benzyl caprolactone so as to realize chiral substitution of the poly-epsilon-caprolactone. Compared with polycaprolactone, the poly-2-benzyl caprolactone obtained by polymerization has better thermal stability and mechanical property, and the application range of the poly-2-benzyl caprolactone product is greatly expanded.
Description
Technical Field
The invention relates to a preparation method of poly-2-benzyl caprolactone, belonging to the technical field of substituted cyclic lactone.
Background
One of the most important achievements in the 20 th century is the development of petroleum compounds, which brings abundant and cheap chemical products to us. A series of petroleum-based compounds, which are inexpensive, simple in preparation process, excellent in physical and mechanical properties, and mature in technology, have been developed in the past 80 years, and have been widely used in clothing, tableware, medical instruments, electronic products, and infrastructure. However, the widespread use of these materials also brings with it a series of inconveniences and environmental problems, such as the "white pollution" problem now being of great concern, which is caused by the petroleum-based compound plastics. The amount of these plastics is now increasing, from 165 million tons in 1950 to 4 million tons in 2019, which is seen to increase rapidly and now much. Petroleum resources are limited and non-renewable, so that sustainable development is one of the main targets of scientific research in the 21 st century. With the exhaustion and fluctuation of petroleum resources, the price of petroleum raw materials is constantly changing, and an increasingly strict environmental protection method is foreseeable and faces the fact immediately, which is an insurmountable red line for the commercialization of products, so that the industrial preparation of recyclable plastics becomes an important problem in the current industry. Aliphatic polyester-based biomass materials, which are perfect substitutes for petroleum-derived materials, can be produced by biological photosynthesis from carbon dioxide, water and sunlight available in the atmosphere, have been used for the production of fuels and fine chemicals with the goal of achieving zero carbon emissions. Polyester materials, particularly poly-epsilon-caprolactone materials, are widely used in packaging materials, 3D printing industry, biomedical field and tissue engineering due to their biocompatibility and degradability, and therefore have gained more and more attention all over the world. However, the poly epsilon-caprolactone material limits the application range due to lower melting temperature and thermal stability, and in order to fundamentally solve the problem, the research of the invention finds that the poly epsilon-caprolactone material needs to start from the molecular structure; the mechanical property and biocompatibility of the poly-epsilon-caprolactone can be further improved by changing the substituent group of the poly-epsilon-caprolactone.
In order to further improve the performance, various polychlorinated carbons with different substituents on the main chain have been studied and obtained and exhibit unique properties. However, the absolute configuration of the chiral center in the polymer chain is not regarded as important as that of the chiral small molecule, and the chiral small molecule has great potential influence on the mechanical property and biocompatibility of the polymer. Therefore, the chiral polymerization of the epsilon-caprolactone is completed by asymmetric resolution polymerization starting from the chiral substitution of the epsilon-caprolactone, and finally the poly epsilon-caprolactone with a chiral center is synthesized.
With regard to the synthesis of different substituted poly-epsilon-caprolactones, few people currently regulate the mechanical properties and biocompatibility of poly-epsilon-caprolactone by chirality. The rigidity of the poly epsilon-caprolactone chain is enhanced by using the benzyl substituent, so that the thermal stability and the mechanical property of the poly epsilon-caprolactone chain are improved. The practicality of poly-epsilon-caprolactone is more desirable as long as the problem of melting temperature, which limits the application range and potential of poly-epsilon-caprolactone, is solved.
Therefore, the invention increases the importance of the melting temperature and the mechanical property of the poly-epsilon-caprolactone on the further application of the poly-epsilon-caprolactone by substituting the side group of the poly-epsilon-caprolactone, has important significance for completing the application of degradable plastics in human society to further replace polyolefin plastics, and can promote the green sustainable development.
Disclosure of Invention
The invention provides a preparation method of poly-2-benzyl caprolactone for solving the technical problems. The epsilon-caprolactone is substituted under the action of a catalyst at low temperature, and polymerization is carried out under the heating condition to obtain poly-2-benzyl caprolactone, so as to realize chiral substitution of the poly-epsilon-caprolactone.
The technical scheme of the invention is as follows:
a method for preparing poly-2-benzylcaprolactone, which comprises the following steps: under the low temperature condition, under the catalysis of metal or chiral phosphoric acid catalyst, the epsilon-caprolactone is subjected to substitution reaction to generate 2-BnCL; under the heating condition, under the catalysis of a metal or chiral phosphoric acid catalyst, the polymerization of the poly 2-benzyl caprolactone is completed, and the chiral substitution of the poly epsilon-caprolactone is realized.
Preferably, the epsilon-caprolactone and the substituted 2-benzylcaprolactone are neat monomers.
Preferably, the polymerization reaction needs to be carried out in a solvent.
Preferably, the solvent is preferably one or more of n-hexane, tetrahydrofuran and toluene.
Preferably, the number average molecular weight of the poly-2-benzylcaprolactone is 102–105g/mol。
Preferably, the reaction temperature is from 0 ℃ to 150 ℃.
Preferably, the reaction catalyst is one or more of magnesium-based, iron-based, tin-based, zinc-based metal reagents, and organic phosphoric acid.
Preferably, the reaction catalyst is one of magnesium bis (bistrimethylsilyl) amine, chiral phosphoric acid, magnesium acetate, iron acetate, zinc acetate, tin acetate and alkoxy magnesium.
Preferably, the molecular weight distribution is between 1.05 and 1.6.
Preferably, the reaction catalyst is added in an amount of 0.05 mol% to 50 mol% based on the polymer.
Preferably, the reaction initiator is one or more of aromatic alcohol, monohydric alcohol, dihydric alcohol, trihydric alcohol, primary alcohol, secondary alcohol and tertiary alcohol.
Preferably, the reaction initiator is one or more of benzyl alcohol, methanol, ethanol, ethylene glycol, glycerol, n-butanol, iso-butanol, secondary butanol, tertiary butanol, propanol, iso-propanol, 3-pentanol, iso-pentanol.
The invention has the following beneficial effects:
1. the invention substitutes the epsilon-caprolactone side group to form 2-BnCL by the substitution reaction participated by metal or organic phosphoric acid catalyst, thereby realizing the substitution of the epsilon-caprolactone, and the product 2-BnCL obtained by substitution is the raw material for synthesizing the poly-2-benzyl caprolactone.
2. The invention adopts various metal or organic phosphoric acid catalysts with simple structures to catalyze the polymerization of the poly-2-benzyl caprolactone, and the used catalysts have simple structures, few synthesis steps, low price and easy obtaining, so that the production cost is more economic.
3. The invention can realize the polymerization of the poly-2-benzyl caprolactone under the condition of the solvent, and has mild condition and environmental protection.
4. The catalytic system adopted by the invention has good universality and good polymerization effect on various substituted epsilon-caprolactone with different structures.
5. The poly-2-benzyl caprolactone prepared by the invention has good thermal stability and mechanical property, and is greatly improved compared with poly-epsilon-caprolactone.
Drawings
FIG. 1 is a nuclear magnetic spectrum of the product of example 1.
Detailed Description
The present invention is further illustrated by the following specific examples.
Example 1: the synthesis of 2-benzyl caprolactone participated by bis (bistrimethylsilyl) amine magnesium.
The experimental process comprises the following steps:
tetrahydrofuran was added as a solvent to a three-necked flask, then epsilon-caprolactone monomer (11.4g,1000equiv.), bis (bis-trimethylsilyl) magnesium amine catalyst (0.138g,4equiv.) was added to a glove box, the temperature was cooled to-78 ℃ and stirred for reaction for 3h, and finally the obtained product was quenched with a saturated aqueous ammonium chloride solution. Extraction with ethyl acetate followed by purification by silica gel chromatography gave 2-benzylcaprolactone as a colorless solid in 43% yield.
Example 2: the synthesis of poly-2-benzyl caprolactone participated by bis (bistrimethylsilyl) amine magnesium.
The experimental process comprises the following steps:
toluene and 2-benzylcaprolactone (20.4g,1000equiv.) were added to a three-necked flask, followed by bis (bistrimethylsilyl) amine magnesium catalyst (138mg,4equiv.) and benzyl alcohol initiator (100mL,1mol/L,10 equiv.) in a glove box. Heating the temperature to 90 ℃, and reacting for 21h to obtain a polymerization product poly-2-benzyl caprolactone. The yield was 92%.
Example 3: the synthesis of poly-2-benzyl caprolactone participated by bis (bistrimethylsilyl) amine magnesium.
The experimental process comprises the following steps:
toluene and 2-benzylcaprolactone (20.4g,1000equiv.) were added to a three-necked flask, followed by bis (bistrimethylsilyl) amine magnesium catalyst (34.5mg,1equiv.) and benzyl alcohol initiator (100mL,1mol/L,10 equiv.) in a glove box. Heating the temperature to 90 ℃, and reacting for 49 hours to obtain a polymerization product poly-2-benzyl caprolactone. The yield was 91%.
Example 4: the synthesis of poly-2-benzyl caprolactone participated by bis (bistrimethylsilyl) amine magnesium.
The experimental process comprises the following steps:
toluene and 2-benzylcaprolactone (20.4g,1000equiv.) were added to a three-necked flask, followed by bis (bistrimethylsilyl) amine magnesium catalyst (34.5mg,1equiv.) and benzyl alcohol initiator (20mL,1mol/L,2 equiv.) in a glove box. The temperature is heated to 90 ℃ and the reaction is carried out for 56h to obtain the polymerization product poly 2-benzyl caprolactone. The yield was 94%.
Example 5: the synthesis of poly-2-benzyl caprolactone participated in by bis (trimethylsilyl) amine magnesium.
The experimental process comprises the following steps:
toluene and 2-benzylcaprolactone (20.4g,100equiv.) were added to a three-necked flask, followed by bis (bistrimethylsilyl) amine magnesium catalyst (345mg,1equiv.) and benzyl alcohol initiator (200mL,1mol/L,2 equiv.) in a glove box. Heating the temperature to 90 ℃, and reacting for 17h to obtain a polymerization product poly-2-benzyl caprolactone. The yield was 96%.
Example 6: the synthesis of poly-2-benzyl caprolactone participated by bis (bistrimethylsilyl) amine magnesium.
The experimental process comprises the following steps:
toluene and 2-benzylcaprolactone (20.4g,50equiv.) were added to a three-necked flask, followed by bis (bistrimethylsilyl) amine magnesium catalyst (690mg,1equiv.) and benzyl alcohol initiator (400mL,1mol/L,2 equiv.) in a glove box. The temperature is heated to 90 ℃ and the reaction lasts for 15 hours to obtain the polymerization product poly 2-benzyl caprolactone. The yield was 94%.
Example 7: the synthesis of poly-2-benzyl caprolactone participated by bis (bistrimethylsilyl) amine magnesium.
The experimental process comprises the following steps:
toluene and 2-benzylcaprolactone (20.4g,100equiv.) were added to a three-necked flask, followed by bis (bistrimethylsilyl) amine magnesium catalyst (345mg,1equiv.) and benzyl alcohol initiator (200mL,1mol/L,2 equiv.) in a glove box. Heating the temperature to 150 ℃, and reacting for 13h to obtain a polymerization product poly 2-benzyl caprolactone. The yield was 90%.
Example 8: the synthesis of poly-2-benzyl caprolactone participated by bis (bistrimethylsilyl) amine magnesium.
The experimental process comprises the following steps:
toluene and 2-benzylcaprolactone (20.4g,100equiv.) were added to a three-necked flask, followed by bis (bistrimethylsilyl) amine magnesium catalyst (345mg,1equiv.) and benzyl alcohol initiator (200mL,1mol/L,2 equiv.) in a glove box. Heating the temperature to 25 ℃, and reacting for 76h to obtain a polymerization product poly-2-benzyl caprolactone. The yield was 83%.
Example 9: synthesizing poly 2-benzyl caprolactone participated by chiral phosphoric acid.
The experimental process comprises the following steps:
toluene and 2-benzylcaprolactone (20.4g,100equiv.) were added to a three-necked flask, followed by chiral phosphoric acid (786mg,1equiv.) and benzyl alcohol initiator (200mL,1mol/L,2 equiv.) in a glove box. The temperature is heated to 90 ℃ and the reaction lasts for 26h to obtain the polymerization product poly 2-benzyl caprolactone. The yield was 93%.
Example 10: synthesizing poly 2-benzyl caprolactone participated by chiral phosphoric acid.
The experimental process comprises the following steps:
toluene and 2-benzylcaprolactone (20.4g,1000equiv.) were added to a three-necked flask, followed by chiral phosphoric acid catalyst (78.6mg,1equiv.) and benzyl alcohol initiator (20mL,1mol/L,2 equiv.) in a glove box. The temperature is heated to 90 ℃ and the reaction lasts for 37 hours to obtain the polymerization product poly 2-benzyl caprolactone. The yield was 91%.
Example 11: synthesizing poly 2-benzyl caprolactone participated by chiral phosphoric acid.
The experimental process comprises the following steps:
toluene and 2-benzylcaprolactone (20.4g,1000equiv.) were added to a three-necked flask, followed by chiral phosphoric acid catalyst (78.6mg,1equiv.) and benzyl alcohol initiator (20mL,1mol/L,2 equiv.) in a glove box. Heating the temperature to 150 ℃, and reacting for 13h to obtain a polymerization product poly 2-benzyl caprolactone. The yield was 95%.
Example 12: and (3) synthesizing the poly-2-benzyl caprolactone by the participation of magnesium acetate.
The experimental process comprises the following steps:
toluene and 2-benzylcaprolactone (20.4g,1000equiv.) were added to a three-necked flask, followed by magnesium acetate catalyst (57mg,1equiv.) and benzyl alcohol initiator (20mL,1mol/L,2 equiv.) in a glove box. Heating the temperature to 90 ℃, and reacting for 31h to obtain a polymerization product poly-2-benzyl caprolactone. The yield was 81%.
Example 13: and (3) synthesizing the poly-2-benzyl caprolactone by the participation of magnesium acetate.
The experimental process comprises the following steps:
toluene and 2-benzylcaprolactone (20.4g,100equiv.) were added to a three-necked flask, followed by magnesium acetate catalyst (570mg,1equiv.) and benzyl alcohol initiator (200mL,1mol/L,2 equiv.) in a glove box. Heating the temperature to 90 ℃, and reacting for 21h to obtain a polymerization product poly-2-benzyl caprolactone. The yield was 85%.
Example 14: and (3) synthesizing the poly-2-benzyl caprolactone by the participation of magnesium acetate.
The experimental process comprises the following steps:
toluene and 2-benzylcaprolactone (20.4g,100equiv.) were added to a three-necked flask, followed by magnesium acetate catalyst (570mg,1equiv.) and benzyl alcohol initiator (200mL,1mol/L,2 equiv.) in a glove box. Heating the temperature to 150 ℃, and reacting for 11h to obtain a polymerization product poly-2-benzyl caprolactone. The yield was 82%.
Example 15: and (3) synthesizing the poly-2-benzyl caprolactone by the participation of zinc acetate.
The experimental process comprises the following steps:
toluene and 2-benzylcaprolactone (20.4g,1000equiv.) were added to a three-necked flask, followed by zinc acetate catalyst (73mg,1equiv.) and benzyl alcohol initiator (20mL,1mol/L,2 equiv.) in a glove box. The temperature is heated to 90 ℃ and the reaction lasts for 43 hours to obtain the poly 2-benzyl caprolactone. The yield was 84%.
Example 16: and (3) synthesizing the poly-2-benzyl caprolactone by the participation of zinc acetate.
The experimental process comprises the following steps:
toluene and 2-benzylcaprolactone (20.4g,100equiv.) were added to a three-neck flask, followed by zinc acetate catalyst (730mg,1equiv.) and benzyl alcohol initiator (200mL,1mol/L,2 equiv.) in a glove box. Heating the temperature to 90 ℃, and reacting for 32h to obtain a polymerization product poly-2-benzyl caprolactone. The yield was 87%.
Example 17: and (3) synthesizing the poly-2-benzyl caprolactone by the participation of zinc acetate.
The experimental process comprises the following steps:
toluene and 2-benzylcaprolactone (20.4g,100equiv.) were added to a three-necked flask, followed by zinc acetate catalyst (730mg,1equiv.) and benzyl alcohol initiator (200mL,1mol/L,2 equiv.) in a glove box. Heating the temperature to 150 ℃, and reacting for 17h to obtain a polymerization product poly 2-benzyl caprolactone. The yield was 84%.
Example 18: synthesizing poly-2-benzyl caprolactone by iron acetate.
The experimental process comprises the following steps:
toluene and 2-benzylcaprolactone (20.4g,1000equiv.) were added to a three-necked flask, followed by an iron acetate catalyst (70mg,1equiv.) and benzyl alcohol initiator (20mL,1mol/L,2 equiv.) in a glove box. Heating the temperature to 90 ℃, and reacting for 37h to obtain a polymerization product poly-2-benzyl caprolactone. The yield was 88%.
Example 19: synthesizing poly-2-benzyl caprolactone by iron acetate.
The experimental process comprises the following steps:
toluene and 2-benzylcaprolactone (20.4g,100equiv.) were added to a three-necked flask, followed by an iron acetate catalyst (700mg,1equiv.) and benzyl alcohol initiator (200mL,1mol/L,2 equiv.) in a glove box. Heating the temperature to 90 ℃, and reacting for 25h to obtain a polymerization product poly-2-benzyl caprolactone. The yield was 86%.
Example 20: synthesizing poly-2-benzyl caprolactone by iron acetate.
The experimental process comprises the following steps:
toluene and 2-benzylcaprolactone (20.4g,100equiv.) were added to a three-necked flask, followed by an iron acetate catalyst (700mg,1equiv.) and benzyl alcohol initiator (200mL,1mol/L,2 equiv.) in a glove box. Heating the temperature to 150 ℃, and reacting for 15h to obtain a polymerization product poly 2-benzyl caprolactone. The yield was 81%.
Example 21: and (3) synthesizing the poly-2-benzyl caprolactone by using tin acetate.
The experimental process comprises the following steps:
toluene and 2-benzylcaprolactone (20.4g,1000equiv.) were added to a three-necked flask, followed by tin acetate catalyst (95mg,1equiv.) and benzyl alcohol initiator (20mL,1mol/L,2 equiv.) in a glove box. Heating the temperature to 90 ℃, and reacting for 36h to obtain a polymerization product poly-2-benzyl caprolactone. The yield was 90%.
Example 22: and (3) synthesizing the poly-2-benzyl caprolactone by using tin acetate.
The experimental process comprises the following steps:
toluene and 2-benzylcaprolactone (20.4g,100equiv.) were added to a three-necked flask, followed by tin acetate catalyst (950mg,1equiv.) and benzyl alcohol initiator (200mL,1mol/L,2 equiv.) in a glove box. Heating the temperature to 90 ℃, and reacting for 25h to obtain a polymerization product poly-2-benzyl caprolactone. The yield was 93%.
Example 23: and (3) synthesizing the poly-2-benzyl caprolactone by using tin acetate.
The experimental process comprises the following steps:
toluene and 2-benzylcaprolactone (20.4g,100equiv.) were added to a three-neck flask, followed by tin acetate catalyst (950mg,1equiv.) and benzyl alcohol initiator (200mL,1mol/L,2 equiv.) in a glove box. Heating the temperature to 150 ℃, and reacting for 12h to obtain a polymerization product poly 2-benzyl caprolactone. The yield was 89%.
Example 24: the synthesis of poly-2-benzyl caprolactone in which alkoxy magnesium participates.
The experimental process comprises the following steps:
toluene and 2-benzylcaprolactone (20.4g,1000equiv.) were added to a three-neck flask, followed by an alkoxy magnesium catalyst (1equiv.) and benzyl alcohol initiator (20mL,1mol/L,2 equiv.) in a glove box. The temperature is heated to 90 ℃ and the reaction lasts for 32 hours to obtain the polymerization product poly 2-benzyl caprolactone. The yield was 97%.
Example 25: the synthesis of poly-2-benzyl caprolactone in which alkoxy magnesium participates.
The experimental process comprises the following steps:
toluene and 2-benzylcaprolactone (20.4g,100equiv.) were added to a three-neck flask, followed by an alkoxy magnesium catalyst (1equiv.) and benzyl alcohol initiator (200mL,1mol/L,2 equiv.) in a glove box. Heating the temperature to 90 ℃, and reacting for 21h to obtain a polymerization product poly-2-benzyl caprolactone. The yield was 91%.
Example 26: the synthesis of poly-2-benzyl caprolactone in which alkoxy magnesium participates.
The experimental process comprises the following steps:
toluene and 2-benzylcaprolactone (20.4g,100equiv.) were added to a three-neck flask, followed by an alkoxy magnesium catalyst (1equiv.) and benzyl alcohol initiator (200mL,1mol/L,2 equiv.) in a glove box. Heating the temperature to 150 ℃, and reacting for 11h to obtain a polymerization product poly 2-benzyl caprolactone. The yield was 89%.
Although the present invention has been described with reference to the preferred embodiments, it should be understood that various changes and modifications can be made therein by those skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (10)
1. A preparation method of poly-2-benzyl caprolactone is characterized in that 2-benzyl caprolactone is subjected to polymerization reaction under the action of a catalyst and under the heating condition to obtain poly-2-benzyl caprolactone, so that the preparation of the poly-2-benzyl caprolactone is realized.
2. The method of claim 1, wherein a reaction initiator is added, and the reaction initiator is one or more of aromatic alcohol, monohydric alcohol, dihydric alcohol, trihydric alcohol, primary alcohol, secondary alcohol, and tertiary alcohol.
3. The method of claim 1, wherein the polymerization is carried out in a solvent.
4. The method of claim 1, wherein the solvent is one or more of n-hexane, tetrahydrofuran and toluene.
5. The method of claim 1, wherein the poly-2-benzyl caprolactone has a number average molecular weight of 102–105g/mol。
6. The method of claim 1, wherein the reaction temperature is 0 ℃ to 150 ℃.
7. The method of claim 1, wherein the reaction catalyst is one or more of magnesium, iron, tin, zinc, metal reagents and organic phosphoric acid; or the reaction catalyst is one of magnesium bis (bistrimethylsilyl) amide, chiral phosphoric acid, magnesium acetate, iron acetate, zinc acetate, tin acetate and alkoxy magnesium.
8. The method of claim 1, wherein the molecular weight distribution is between 1.05 and 1.6.
9. The method of claim 1, wherein the amount of the reaction catalyst is 0.05 mol% to 50 mol% of the polymer.
10. The method of claim 2, wherein the reaction initiator is one or more selected from benzyl alcohol, methanol, ethanol, ethylene glycol, glycerol, n-butanol, i-butanol, secondary butanol, tertiary butanol, propanol, i-propanol, 3-pentanol, and i-pentanol.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10168171A (en) * | 1996-12-16 | 1998-06-23 | Daicel Chem Ind Ltd | Production of polylactone |
| CN102491874A (en) * | 2011-12-08 | 2012-06-13 | 中国科学院长春应用化学研究所 | Metallic alkoxy complex, catalyst composition and preparation method of poly-caprolactone or poly-lactide |
| CN109679081A (en) * | 2018-12-14 | 2019-04-26 | 泰山医学院 | Utilize the method for double-core Chiral Amine imines magnesium complex catalysis caprolactone polymerization |
| CN112778505A (en) * | 2021-01-26 | 2021-05-11 | 中国科学院青岛生物能源与过程研究所 | Synthesis method of gradual change type polyester |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10168171A (en) * | 1996-12-16 | 1998-06-23 | Daicel Chem Ind Ltd | Production of polylactone |
| CN102491874A (en) * | 2011-12-08 | 2012-06-13 | 中国科学院长春应用化学研究所 | Metallic alkoxy complex, catalyst composition and preparation method of poly-caprolactone or poly-lactide |
| CN109679081A (en) * | 2018-12-14 | 2019-04-26 | 泰山医学院 | Utilize the method for double-core Chiral Amine imines magnesium complex catalysis caprolactone polymerization |
| CN112778505A (en) * | 2021-01-26 | 2021-05-11 | 中国科学院青岛生物能源与过程研究所 | Synthesis method of gradual change type polyester |
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