CN113265044B - Preparation method of high molecular weight poly-gamma-butyrolactone with adjustable structure - Google Patents
Preparation method of high molecular weight poly-gamma-butyrolactone with adjustable structure Download PDFInfo
- Publication number
- CN113265044B CN113265044B CN202110653165.9A CN202110653165A CN113265044B CN 113265044 B CN113265044 B CN 113265044B CN 202110653165 A CN202110653165 A CN 202110653165A CN 113265044 B CN113265044 B CN 113265044B
- Authority
- CN
- China
- Prior art keywords
- butyrolactone
- gamma
- molecular weight
- polymer
- poly
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 title claims abstract description 133
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 32
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 12
- 239000003054 catalyst Substances 0.000 claims description 10
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 5
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 239000011777 magnesium Substances 0.000 claims description 3
- 229920000642 polymer Polymers 0.000 abstract description 71
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 57
- 238000006243 chemical reaction Methods 0.000 description 54
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 30
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 30
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 26
- 238000001840 matrix-assisted laser desorption--ionisation time-of-flight mass spectrometry Methods 0.000 description 26
- 239000000203 mixture Substances 0.000 description 26
- 239000006185 dispersion Substances 0.000 description 25
- 239000007787 solid Substances 0.000 description 25
- 239000005711 Benzoic acid Substances 0.000 description 15
- 235000010233 benzoic acid Nutrition 0.000 description 15
- 238000001914 filtration Methods 0.000 description 13
- 239000000047 product Substances 0.000 description 13
- 238000001291 vacuum drying Methods 0.000 description 13
- 239000003708 ampul Substances 0.000 description 12
- 238000001035 drying Methods 0.000 description 12
- 238000002156 mixing Methods 0.000 description 12
- 238000003756 stirring Methods 0.000 description 10
- QILSFLSDHQAZET-UHFFFAOYSA-N diphenylmethanol Chemical group C=1C=CC=CC=1C(O)C1=CC=CC=C1 QILSFLSDHQAZET-UHFFFAOYSA-N 0.000 description 8
- KJJBSBKRXUVBMX-UHFFFAOYSA-N magnesium;butane Chemical compound [Mg+2].CCC[CH2-].CCC[CH2-] KJJBSBKRXUVBMX-UHFFFAOYSA-N 0.000 description 8
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical group OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 7
- 239000003999 initiator Substances 0.000 description 7
- VCTCXZDCRFISFF-UHFFFAOYSA-N magnesium;butane;butane Chemical compound [Mg+2].CCC[CH2-].CC[CH-]C VCTCXZDCRFISFF-UHFFFAOYSA-N 0.000 description 5
- 229920003023 plastic Polymers 0.000 description 5
- 239000004033 plastic Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 229920003232 aliphatic polyester Polymers 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 238000001196 time-of-flight mass spectrum Methods 0.000 description 3
- GIMDPFBLSKQRNP-UHFFFAOYSA-N 1,1-diphenylethanol Chemical compound C=1C=CC=CC=1C(O)(C)C1=CC=CC=C1 GIMDPFBLSKQRNP-UHFFFAOYSA-N 0.000 description 2
- WRMNZCZEMHIOCP-UHFFFAOYSA-N 2-phenylethanol Chemical compound OCCC1=CC=CC=C1 WRMNZCZEMHIOCP-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 235000019445 benzyl alcohol Nutrition 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- YHNWUQFTJNJVNU-UHFFFAOYSA-N magnesium;butane;ethane Chemical compound [Mg+2].[CH2-]C.CCC[CH2-] YHNWUQFTJNJVNU-UHFFFAOYSA-N 0.000 description 2
- 238000010907 mechanical stirring Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- -1 cyclic lactones Chemical class 0.000 description 1
- 229920005565 cyclic polymer Polymers 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000007857 degradation product Substances 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- JJTUDXZGHPGLLC-UHFFFAOYSA-N lactide Chemical compound CC1OC(=O)C(C)OC1=O JJTUDXZGHPGLLC-UHFFFAOYSA-N 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 229920000052 poly(p-xylylene) Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—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
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
The invention belongs to the field of polymer synthetic chemistry, and discloses a preparation method of high molecular weight poly-gamma-butyrolactone with an adjustable structure, wherein the number average molecular weight of the poly-gamma-butyrolactone is 1000-300000 g/mol. The method is simple to operate, the topological structure of the poly-gamma-butyrolactone can be effectively controlled by simply changing the feeding mode, a single linear polymer is synthesized, and the number average molecular weight of the prepared poly-gamma-butyrolactone is higher than that of the existing polymer.
Description
Technical Field
The invention belongs to the technical field of polymer synthesis, and relates to a preparation method of high molecular weight poly-gamma-butyrolactone with an adjustable structure.
Background
Along with the increasing of the global plastic pollution problem, the attention of people is more and more attracted by the treatment of waste plastics, the traditional plastics are difficult to naturally degrade, and the aliphatic polyester has unique degradability and good biocompatibility, so that the emerging chemical recyclable recovery method gradually comes into the visual field of people, the ring-opening polymerization of cyclic lactones (such as epsilon-caprolactone, lactide and the like) is an important method for preparing the degradable aliphatic polyester, but the components of the degradation products of the aliphatic polyester are relatively complex, so that the later-stage recovery process is complex, the difficulty is high, and the recovery cost is high. Therefore, it is required to develop an environmentally friendly green polymer material that can realize economic recycling of plastics.
Poly gamma-butyrolactone has infinite polymer-monomer-polymer cycling capability and can be completely depolymerized back to the initial raw material, but is always considered as a non-polymerizable monomer due to the thermodynamic stability of a five-membered ring of poly gamma-butyrolactone, and the pioneering work of Chen group realizes the breakthrough of high-efficiency polymerization of non-polymerizable gamma-butyrolactone, thereby providing a new idea for the subsequent preparation of green recyclable high molecular materials. Although the polymerization of gamma butyrolactone has progressed significantly, challenges remain. The synthesis process of poly-gamma-butyrolactone generates linear and cyclic polymers, the topology of the polymer determines the unique viscoelasticity, thereby affecting the thermal performance and mechanical strength, the difference of the topology can cause the polymer to show different properties, and the preparation of poly-gamma-butyrolactone with a single structure still has great challenges. As the molecular weight of the polymer increases, the poly gamma-butyrolactone shows better mechanical properties, tensile strength and elongation at break. Higher molecular weights are required to meet the requirements of different applications, whereas the number average molecular weight of the currently prepared poly-gamma-butyrolactone only reaches 83200 g/mol. Therefore, the method has important research significance for effectively regulating and controlling the topological structure of the polymer and preparing the poly gamma-butyrolactone with high molecular weight.
Disclosure of Invention
The purpose of the invention is as follows: the technical problem to be solved by the invention is to provide the high molecular weight poly-gamma-butyrolactone aiming at the defects of the prior art.
The technical problem to be solved by the invention is to provide a preparation method of the high molecular weight poly-gamma-butyrolactone.
The technical problem to be solved by the invention is to provide the application of the high molecular weight poly-gamma-butyrolactone.
In order to solve the first technical problem, the invention discloses a high molecular weight poly-gamma-butyrolactone represented by formula I1 or formula I2:
wherein R is selected from-CH 3 、-CHPh 2 -Ph or-CH 2 CHPh 2 ；
Wherein n is 10-3000.
Wherein, when R is-CH 3 When the gamma-butyrolactone is represented by formula I1 a; when R is-CHPh 2 When the gamma-butyrolactone is represented by formula I1 b; when R is-Ph, the poly gamma-butyrolactone is shown as a formula I1 c; when R is-CH 2 CHPh 2 When the gamma-butyrolactone is represented by formula I1 d;
wherein the number average molecular weight of the poly gamma-butyrolactone is 1000-300000 g/mol; preferably, the number average molecular weight of the poly gamma-butyrolactone is 10000-300000 g/mol; more preferably, the number average molecular weight of the poly gamma-butyrolactone is 20000-300000 g/mol.
Wherein the elongation at break of the high molecular weight poly-gamma-butyrolactone is 10.5% -735%.
Wherein the tensile strength of the high molecular weight poly gamma-butyrolactone is 20.6-50.1 MPa.
In order to solve the second technical problem, the present invention discloses a method for preparing the high molecular weight poly-gamma-butyrolactone, which is any one of the following modes:
the method a comprises the following steps: precooling an initiator, a solvent and a catalyst, adding gamma-butyrolactone, and reacting;
the method b: precooling gamma-butyrolactone and a solvent, adding a catalyst, and reacting;
the method c comprises the following steps: precooling the initiator, the solvent and the gamma-butyrolactone, adding the catalyst, and reacting.
Wherein the initiator is aromatic alcohol; preferably, the initiator is any one or combination of several of the structural formulas shown in the formula II; further preferably, the initiator is diphenyl methanol and/or benzyl alcohol
Wherein, the solvent is an organic solvent, including but not limited to any one or a combination of several of toluene, tetrahydrofuran and dichloromethane; preferably, the solvent is toluene.
Wherein the catalyst is an organic magnesium catalyst shown in a formula III; wherein R is 1 And R 2 Each independently selected from ethyl, n-butyl or isobutyl;
wherein the concentration of the gamma-butyrolactone is 6-8 mol/L; preferably, the concentration of the gamma-butyrolactone is 8 mol/L.
In the method a and the method c, the molar ratio of the gamma-butyrolactone to the initiator to the catalyst is (10-500): 1: (0.1-5); preferably, the molar ratio of the gamma-butyrolactone, the initiator and the catalyst is (10-200): 1: (0.1 to 1).
In the method b, the molar ratio of the gamma-butyrolactone to the catalyst is (10-200): 1.
wherein the pre-cooling temperature is-60 to-40 ℃.
Wherein the precooling time is more than 1 min; preferably, the precooling time is more than 5 min; further preferably, the precooling time is 5-15 min; more preferably, the pre-cooling time is 8-12 min.
Wherein the reaction temperature is-60 to-40 ℃; preferably, the temperature of the reaction is-50 ℃.
Wherein the reaction time is 5-1440 min; preferably, the reaction time is 1440 min.
After the reaction is finished, adding a benzoic acid/dichloromethane solution to dissolve the mixture, taking out the mixture, adding the mixture into a cold methanol solution, separating out a polymer, filtering and separating to obtain a white solid, and transferring the white solid to a vacuum drying oven for drying to obtain the poly gamma-butyrolactone.
Wherein, when the preparation method is the method a, the topological structure of the poly gamma-butyrolactone is linear and annular, and specifically is any one of the compound shown in formula I1b, formula I1c and formula I1d and the combination shown in formula I2.
Wherein, when the preparation method is the method b, the topological structure of the poly gamma-butyrolactone is linear, and is specifically shown in I1 a.
Wherein, when the preparation method is the method c, the topological structure of the poly gamma-butyrolactone is linear, and the poly gamma-butyrolactone is any one of the structures shown in the formulas I1b, I1c and I1 d.
Wherein, the molecular weight of the poly gamma-butyrolactone prepared by the method a and the method b is far higher than that of the poly gamma-butyrolactone prepared by the method c.
Wherein, when the method a is adopted to prepare the poly-gamma-butyrolactone, the number average molecular weight of the poly-gamma-butyrolactone is 10000-300000 g/mol, preferably 20000-300000 g/mol, and more preferably 25000-300000 g/mol.
Wherein, when the method b is adopted to prepare the poly-gamma-butyrolactone, the number average molecular weight of the poly-gamma-butyrolactone is 10000-300000 g/mol, preferably 50000-300000 g/mol, and more preferably 100000-300000 g/mol.
In order to solve the third technical problem, the invention discloses the application of the high molecular weight poly-gamma-butyrolactone in the preparation of the bio-based material.
Wherein, the bio-based material includes but is not limited to recyclable plastics, and relates to the fields of biomedicine, tissue engineering packaging and the like.
Has the advantages that: compared with the prior art, the invention has the following advantages:
the method disclosed by the invention is simple to operate, the topological structure of the poly-gamma-butyrolactone can be effectively controlled by simply changing the feeding mode, a single linear polymer is synthesized, and the number average molecular weight of the prepared poly-gamma-butyrolactone is higher than that of the existing polymer.
Drawings
The foregoing and/or other advantages of the invention will become further apparent from the following detailed description of the invention when taken in conjunction with the accompanying drawings.
FIG. 1 is a matrix-assisted laser ionization time-of-flight mass spectrum of poly-gamma-butyrolactone prepared using method a (example 1) with a gamma-butyrolactone/benzhydrol/di-n-butylmagnesium ratio of 50/1/1.
FIG. 2 is a matrix-assisted laser ionization time-of-flight mass spectrum of poly-gamma-butyrolactone prepared using method c (example 2) with a gamma-butyrolactone/benzhydrol/n-butyl-sec-butylmagnesium ratio of 50/1/1.
FIG. 3 is a matrix-assisted laser ionization time-of-flight mass spectrum of poly-gamma-butyrolactone prepared using method b (example 3) with a gamma-butyrolactone/di-n-butylmagnesium ratio of 10/1.
FIG. 4 is a GPC chart of two different poly gamma-butyrolactone types of number average molecular weights (example 7 and example 8).
Figure 5 is a tensile stress-strain curve for two different number average molecular weights (example 7 and example 8) of poly gamma-butyrolactone.
Detailed Description
The experimental methods described in the following examples are all conventional methods unless otherwise specified; the reagents and materials are commercially available, unless otherwise specified.
In the following examples, the topology of the polymer product was structurally characterized by matrix-assisted laser desorption ionization time-of-flight mass spectrometry (MALDI-TOF MS), and the number average molecular weight and the degree of dispersion of the polymer were determined by GPC.
The ultra-dry toluene described in the examples below was obtained by redistilling toluene.
The ratio of benzoic acid to methylene chloride in the benzoic acid/methylene chloride solution described in the examples below was 10 mg/mL.
Example 1
Adding diphenylmethanol (0.0368g, 0.2mmol) into an anhydrous and oxygen-free treated ampoule bottle, adding 0.281mL of ultra-dry toluene, mechanically stirring and uniformly mixing, adding di-n-butylmagnesium (0.2mL, 0.2mmol), precooling at-50 ℃ for 10min, adding gamma-butyrolactone (0.8609g, 10mmol), and reacting at-50 ℃ for 24 h. After the reaction was completed, a benzoic acid/methylene chloride solution was added to dissolve the mixture, and the mixture was taken out and added to a cold methanol solution, whereby a polymer was precipitated. Filtering to obtain white solid, transferringDrying in a vacuum drying oven to obtain the polymer. Conversion rate is controlled by the reaction solution 1 H NMR was calculated and the topology of the polymer product was characterized by matrix assisted laser desorption ionization time of flight mass spectrometry (MALDI-TOF MS), as shown in figure 1. The molecular weight and the degree of dispersion of the polymer were determined by GPC. The conversion was 65%, the polymer molecular weight was 32400g/mol, and the dispersion coefficient was 1.59.
Example 2
Adding diphenylethanol (0.0397g, 0.2mmol) into an anhydrous and oxygen-free treated ampoule bottle, adding 0.281mL of ultra-dry tetrahydrofuran, mechanically stirring and uniformly mixing, adding gamma-butyrolactone (0.8609g, 10mmol), precooling at-40 ℃ for 10min, adding n-butyl-sec-butyl magnesium (0.28mL, 0.2mmol), and reacting at-40 ℃ for 12 h. After the reaction was completed, a benzoic acid/methylene chloride solution was added to dissolve the mixture, and the reaction was terminated. Filtering and separating to obtain a white solid, and transferring the white solid to a vacuum drying oven for drying to obtain the polymer. The conversion rate of which is controlled by the reaction solution 1 H NMR was calculated and the topology of the polymer product was characterized by matrix assisted laser desorption ionization time of flight mass spectrometry (MALDI-TOF MS), as shown in figure 2. The molecular weight and the degree of dispersion of the polymer were determined by GPC. The conversion was 41%, the number-average molecular weight of the polymer was 9870g/mol, and the dispersion coefficient was 1.28.
Example 3
Adding gamma-butyrolactone (0.4305g, 5mmol) into an ampoule bottle which is treated with no water and oxygen, adding 0.141mL of ultra-dry dichloromethane, mechanically stirring and mixing uniformly, precooling for 10min at-50 ℃, adding di-n-butyl magnesium (0.5mL, 0.5mmol), and reacting for 10h at-50 ℃. After the reaction was completed, a benzoic acid/methylene chloride solution was added to dissolve the mixture, and the reaction was terminated. Filtering and separating to obtain a white solid, and transferring the white solid to a vacuum drying oven for drying to obtain the polymer. The conversion rate of which is controlled by the reaction solution 1 H NMR is calculated, the topological structure of the polymer product is characterized by matrix-assisted laser desorption ionization time-of-flight mass spectrometry (MALDI-TOF MS),as shown in fig. 3. The molecular weight and the degree of dispersion of the polymer were determined by GPC. The conversion was 27%, the number-average molecular weight of the polymer was 106500g/mol, and the dispersion coefficient was 1.65.
Example 4
Adding benzyl alcohol (0.0216g, 0.2mmol) into an ampoule bottle which is subjected to anhydrous and anaerobic treatment, adding 0.281mL of ultra-dry tetrahydrofuran, mechanically stirring and uniformly mixing, adding di-n-butylmagnesium (0.2mL, 0.2mmol), precooling at-40 ℃ for 10min, adding gamma-butyrolactone (0.8609g, 10mmol), and reacting at-40 ℃ for 6 h. After the reaction was completed, a benzoic acid/methylene chloride solution was added to dissolve the mixture, and the mixture was taken out and added to a cold methanol solution, whereby a polymer was precipitated. Filtering and separating to obtain a white solid, and transferring the white solid to a vacuum drying oven for drying to obtain the polymer. The conversion rate of which is controlled by the reaction solution 1 H NMR is calculated, and the topological structure of the polymer product is characterized by matrix-assisted laser desorption ionization time-of-flight mass spectrometry (MALDI-TOF MS). The molecular weight and the degree of dispersion of the polymer were determined by GPC. The conversion was 46%, the number-average molecular weight of the polymer was 27800g/mol, and the dispersion coefficient was 1.66.
Example 5
Diphenylmethanol (0.0368g, 0.2mmol) was added to an anhydrous and oxygen-free treated ampoule, 0.281mL of ultra-dry methylene chloride was added, and after mechanical stirring and mixing, n-butyl-sec-butylmagnesium (0.28mL, 0.2mmol) was added, and after precooling at-60 ℃ for 10min, γ -butyrolactone (0.8609g, 10mmol) was added, and the mixture was allowed to react at-60 ℃ for 30 min. After the reaction was completed, a benzoic acid/methylene chloride solution was added to dissolve the mixture, and the mixture was taken out and added to a cold methanol solution, whereby a polymer was precipitated. Filtering and separating to obtain a white solid, and transferring the white solid to a vacuum drying oven for drying to obtain the polymer. The conversion rate of which is controlled by the reaction solution 1 H NMR calculation is carried out, and the topological structure of the polymer product is characterized by matrix-assisted laser desorption ionization time-of-flight mass spectrometry (MALDI-TOF MS). The molecular weight and the degree of dispersion of the polymer were determined by GPC. The conversion was 47%, the number-average molecular weight of the polymer was 29780g/mol, and the dispersion coefficient was 1.61.
Example 6
Will twoAdding phenyl ethanol (0.0397g, 0.2mmol) into an anhydrous oxygen-free treated ampoule bottle, adding 0.281mL of ultra-dry toluene, mechanically stirring and uniformly mixing, adding n-butyl ethyl magnesium (0.2mL, 0.2mmol), precooling at-50 ℃ for 10min, adding gamma-butyrolactone (0.8609g, 10mmol), and reacting at-50 ℃ for 12 h. After the reaction was completed, a benzoic acid/methylene chloride solution was added to dissolve the mixture, and the mixture was taken out and added to a cold methanol solution, whereby a polymer was precipitated. Filtering and separating to obtain a white solid, and transferring the white solid to a vacuum drying oven for drying to obtain the polymer. The conversion rate of which is controlled by the reaction solution 1 H NMR calculation is carried out, and the topological structure of the polymer product is characterized by matrix-assisted laser desorption ionization time-of-flight mass spectrometry (MALDI-TOF MS). The molecular weight and the degree of dispersion of the polymer were determined by GPC. The conversion was 65%, the number-average molecular weight of the polymer was 34340g/mol, and the dispersion coefficient was 1.54.
Example 7
Adding diphenylmethanol (0.0184g, 0.1mmol) into an anhydrous and oxygen-free treated ampoule bottle, adding 0.381mL of ultra-dry toluene, mechanically stirring and uniformly mixing, adding di-n-butylmagnesium (0.1mL, 0.1mmol), precooling at-60 ℃ for 10min, adding gamma-butyrolactone (0.8710g, 10mmol), and reacting at-60 ℃ for 8 h. After the reaction was completed, a benzoic acid/methylene chloride solution was added to dissolve the mixture, and the mixture was taken out and added to a cold methanol solution, whereby a polymer was precipitated. Filtering and separating to obtain a white solid, and transferring the white solid to a vacuum drying oven for drying to obtain the polymer. The conversion rate of which is controlled by the reaction solution 1 H NMR calculation is carried out, and the topological structure of the polymer product is characterized by matrix-assisted laser desorption ionization time-of-flight mass spectrometry (MALDI-TOF MS). The molecular weight and the degree of dispersion of the polymer were determined by GPC. The conversion was 61%, the number-average molecular weight of the polymer was 43200g/mol (FIG. 4), and the dispersion coefficient was 1.46.
Example 8
Adding gamma-butyrolactone (1.7218g, 20mmol) into an ampoule bottle which is treated without water and oxygen, adding 0.863mL of super-dry tetrahydrofuran, mechanically stirring and mixing uniformly, precooling for 10min at-50 ℃, adding di-n-butyl magnesium (0.1mL, 0.1mmol), and reacting for 90min at-50 ℃. Inverse directionAfter the reaction was completed, a benzoic acid/methylene chloride solution was added to dissolve the mixture, the reaction was terminated, and the mixture was taken out and added to a cold methanol solution, whereby a polymer was precipitated. Filtering and separating to obtain a white solid, and transferring the white solid to a vacuum drying oven for drying to obtain the polymer. The conversion rate of which is controlled by the reaction solution 1 H NMR calculation is carried out, and the topological structure of the polymer product is characterized by matrix-assisted laser desorption ionization time-of-flight mass spectrometry (MALDI-TOF MS). The molecular weight and the degree of dispersion of the polymer were determined by GPC. The conversion was 36%, the polymer number average molecular weight was 295600g/mol (FIG. 4), and the dispersion coefficient was 1.81.
Example 9
Diphenylmethanol (0.0368g, 0.2mmol) was added to an anhydrous and oxygen-free treated ampoule, 0.860mL of ultra-dry toluene was added, after mechanical stirring and mixing, n-butyl-sec-butylmagnesium (0.14mL, 0.2mmol) was added, after precooling at-60 ℃ for 10min, gamma-butyrolactone (3.4840g, 40mmol) was added, and the mixture was allowed to react at-40 ℃ for 12 h. After the reaction was completed, a benzoic acid/methylene chloride solution was added to dissolve the mixture, and the mixture was taken out and added to a cold methanol solution, whereby a polymer was precipitated. Filtering and separating to obtain a white solid, and transferring the white solid to a vacuum drying oven for drying to obtain the polymer. The conversion rate of which is controlled by the reaction solution 1 H NMR calculation is carried out, and the topological structure of the polymer product is characterized by matrix-assisted laser desorption ionization time-of-flight mass spectrometry (MALDI-TOF MS). The molecular weight and the degree of dispersion of the polymer were determined by GPC. The conversion was 53%, the number-average molecular weight of the polymer was 55640g/mol, and the dispersion coefficient was 1.71.
Example 10
Adding diphenylethanol (0.0397g, 0.2mmol) into an anhydrous and oxygen-free treated ampoule bottle, adding 0.760mL of ultra-dry dichloromethane, mechanically stirring and uniformly mixing, adding n-butyl ethyl magnesium (0.2mL, 0.2mmol), precooling at-60 ℃ for 10min, adding gamma-butyrolactone (1.742g, 20mmol), and reacting at-60 ℃ for 7 h. After the reaction was completed, a benzoic acid/methylene chloride solution was added to dissolve the mixture, and the mixture was taken out and added to a cold methanol solution, whereby a polymer was precipitated. Filtering and separating to obtain a white solid, and transferring the white solid to a vacuum drying oven for drying to obtain the polymer.The pattern is seen in the reaction solution 1 H NMR calculation is carried out, and the topological structure of the polymer product is characterized by matrix-assisted laser desorption ionization time-of-flight mass spectrometry (MALDI-TOF MS). The molecular weight and the degree of dispersion of the polymer were determined by GPC. The conversion was 54%, the number-average molecular weight of the polymer was 49480g/mol, and the dispersion coefficient was 1.91.
Example 11
Adding gamma-butyrolactone (0.8609g, 10mmol) into an anhydrous and oxygen-free treated ampoule bottle, adding 0.281mL of ultra-dry tetrahydrofuran, mechanically stirring and mixing uniformly, precooling for 10min at-50 ℃, adding n-butyl sec-butyl magnesium (0.28mL, 0.2mmol), and reacting for 12h at-50 ℃. After the reaction was completed, a benzoic acid/methylene chloride solution was added to dissolve the mixture, and the reaction was terminated. Filtering and separating to obtain a white solid, and transferring the white solid to a vacuum drying oven for drying to obtain the polymer. The conversion rate of which is controlled by the reaction solution 1 H NMR calculation is carried out, and the topological structure of the polymer product is characterized by matrix-assisted laser desorption ionization time-of-flight mass spectrometry (MALDI-TOF MS). The molecular weight and the degree of dispersion of the polymer were determined by GPC. The conversion was 24%, the number-average molecular weight of the polymer was 113400g/mol, and the dispersion coefficient was 1.64.
Example 12
Adding diphenylmethanol (0.0184g, 0.1mmol) into an anhydrous and anaerobic treated ampoule bottle, adding ultra-dry toluene 3.387mL, mechanically stirring and uniformly mixing, adding di-n-butylmagnesium (0.2mL, 0.2mmol), precooling at-50 ℃ for 10min, adding gamma-butyrolactone (3.4436g, 40mmol), and reacting at-50 ℃ for 24 h. After the reaction was completed, a benzoic acid/methylene chloride solution was added to dissolve the mixture, and the mixture was taken out and added to a cold methanol solution, whereby a polymer was precipitated. Filtering and separating to obtain a white solid, and transferring the white solid to a vacuum drying oven for drying to obtain the polymer. Conversion rate is controlled by the reaction solution 1 H NMR calculation is carried out, and the topological structure of the polymer product is characterized by matrix-assisted laser desorption ionization time-of-flight mass spectrometry (MALDI-TOF MS). The molecular weight and the degree of dispersion of the polymer were determined by GPC. Conversion was 38%, polymer molecular weightIt was 136500g/mol, and the dispersion coefficient was 1.68.
Example 13
The poly-gamma-butyrolactone prepared in example 7 (method a) and example 8 (method b) was subjected to tensile property test, and the results are shown in fig. 5, from which it can be seen that good mechanical properties are laterally reflected in high number average molecular weight.
The invention provides a method and a method for preparing high molecular weight poly-gamma-butyrolactone with controllable structure, and a plurality of methods and ways for realizing the technical scheme, and the above description is only a preferred embodiment of the invention, and it should be noted that, for those skilled in the art, without departing from the principle of the invention, a plurality of improvements and embellishments can be made, and these improvements and embellishments should be regarded as the protection scope of the invention. All the components not specified in the present embodiment can be realized by the prior art.
Claims (4)
1. A preparation method of high molecular weight poly-gamma-butyrolactone shown in formula I1a is characterized in that the number average molecular weight of the poly-gamma-butyrolactone is 295600-300000 g/mol;
wherein the high molecular weight poly gamma-butyrolactone is prepared in the following way: precooling gamma-butyrolactone and tetrahydrofuran for 10min at-50 ℃, adding an organic magnesium catalyst, and reacting for 90min at-50 ℃;
wherein the molar ratio of the gamma-butyrolactone and the organic magnesium catalyst is 200: 1.
2. the method of preparing high molecular weight poly-gamma-butyrolactone according to claim 1, characterized in that the elongation at break of high molecular weight poly-gamma-butyrolactone is 10.5% to 735%.
3. The method for preparing high molecular weight poly-gamma-butyrolactone according to claim 1, wherein the high molecular weight poly-gamma-butyrolactone has a tensile strength of 20.6 to 50.1 Mpa.
4. Use of high molecular weight poly-gamma-butyrolactone prepared by the process of any one of claims 1 to 3 in the preparation of bio-based materials.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110653165.9A CN113265044B (en) | 2021-06-11 | 2021-06-11 | Preparation method of high molecular weight poly-gamma-butyrolactone with adjustable structure |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110653165.9A CN113265044B (en) | 2021-06-11 | 2021-06-11 | Preparation method of high molecular weight poly-gamma-butyrolactone with adjustable structure |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113265044A CN113265044A (en) | 2021-08-17 |
| CN113265044B true CN113265044B (en) | 2022-09-27 |
Family
ID=77234981
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110653165.9A Active CN113265044B (en) | 2021-06-11 | 2021-06-11 | Preparation method of high molecular weight poly-gamma-butyrolactone with adjustable structure |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113265044B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9480780B2 (en) | 2013-11-05 | 2016-11-01 | Tepha, Inc. | Compositions and devices of poly-4-hydroxybutyrate |
| CN115322345A (en) * | 2022-09-08 | 2022-11-11 | 南京先进生物材料与过程装备研究院有限公司 | High-molecular-weight poly-delta-caprolactone and preparation method and application thereof |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9388275B2 (en) * | 2009-06-01 | 2016-07-12 | International Business Machines Corporation | Method of ring-opening polymerization, and related compositions and articles |
| CN107022070B (en) * | 2017-04-28 | 2019-10-01 | 南京工业大学 | Method for preparing polyester by ring-opening polymerization |
| CN109627429B (en) * | 2018-10-23 | 2024-04-16 | 青岛博远高分子材料研究院有限公司 | Preparation method of high molecular weight poly (gamma-butyrolactone) |
-
2021
- 2021-06-11 CN CN202110653165.9A patent/CN113265044B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN113265044A (en) | 2021-08-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN113265044B (en) | Preparation method of high molecular weight poly-gamma-butyrolactone with adjustable structure | |
| KR101160980B1 (en) | Polysiloxane-polylactide block copolymer and preparation method thereof | |
| CN110804163B (en) | Preparation method of bio-based copolyester containing modifiable functional group | |
| Li et al. | Synthesis and AIE properties of PEG–PLA–PMPC based triblock amphiphilic biodegradable polymers | |
| CN113150375B (en) | Method for recycling polylactic acid material under catalysis of zinc catalyst | |
| CN102105502A (en) | Process to make a diblock copolymer having a monovinylaromatic polymer block | |
| CN109851764B (en) | Preparation method of polylactone | |
| Tian et al. | Integration of upcycling and closed-loop recycling through alternative cyclization–depolymerization | |
| Wang et al. | Copolymerization of carbon dioxide and propylene oxide using zinc adipate as catalyst | |
| Wang et al. | Synthesis of poly (D, L‐lactic acid) modified by cholic acid via direct melt copolycondensation and its characterization | |
| CN102627760A (en) | Catalyst composition and preparation method of polylactic acid | |
| US10759899B2 (en) | Recyclable polymers based on ring-fused gamma-butyrolactones | |
| WO2020087221A1 (en) | Controlled production of polyglycolic acid and glycolide | |
| CN106496613B (en) | Preparation method of stereo composite polylactic acid porous membrane material | |
| CN111253558B (en) | Hybrid polymerization amphiphilic block copolymer and synthesis method and application thereof | |
| CN111320747A (en) | Functionalized high-molecular polymer and preparation method thereof | |
| CN112851918B (en) | High-performance aliphatic polyester elastomer and preparation method thereof | |
| Malinová et al. | Ethyl magnesium bromide as an efficient anionic initiator for controlled polymerization of ε-caprolactone | |
| CN109749065A (en) | A kind of macrolide copolymer high-efficiency preparation method of binary catalyst catalysis | |
| CN110330637B (en) | Rare earth macrolide/valerolactone/caprolactone terpolymer and preparation method thereof | |
| CN115403748A (en) | Polycaprolactone derivative and preparation method thereof | |
| CN101302283B (en) | Rare earth compound-containing polylactic acid and preparation thereof | |
| CN102174136A (en) | Circular polymer and preparation method thereof | |
| JP2525043B2 (en) | Method for producing block copolymer | |
| CN101704831B (en) | Chiral aluminum complex, preparation method thereof and application thereof in catalyzing stereoselectivity polymerization of lactide |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |