CN108148187B - Method for activity-controlled polymerization of (gamma-methyl) -alpha-methylene-gamma-butyrolactone - Google Patents
Method for activity-controlled polymerization of (gamma-methyl) -alpha-methylene-gamma-butyrolactone Download PDFInfo
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Abstract
The invention relates to a method for the activity-controlled polymerization of (gamma-methyl) -alpha-methylene-gamma-butyrolactone, belonging to the technical field of polymer synthesis. The polymerization monomer is a renewable resource, has wide application prospect, and the polymerization system has the advantages of convenient operation, mild reaction condition, rapidness, high conversion rate and the like, and the obtained polymer has controllable molecular weight and narrow molecular weight distribution, and is active controllable polymerization.
Description
Technical Field
The invention belongs to the technical field of polymer synthesis, and particularly relates to an activity-controllable polymerization catalytic system, which uses Lewis acid as a catalyst, and silyl enol ether as an initiator can be applied to the activity-controllable polymerization of a renewable monomer (gamma-methyl) -alpha-methylene-gamma-butyrolactone ((M) MBL) and the copolymerization between the two monomers.
Background
Energy problems are a major problem in today's human society. Since the beginning of the use of fossil energy by humans. Coal, oil and gas are rapidly developing into the most important sources of energy and chemicals. Currently, approximately 86% of the energy and 96% of the chemicals are derived from these non-renewable petroleum products. It is anticipated that petroleum products will certainly not meet the ever-increasing demands of human society in the near future. More serious are: according to the expert predictions, the oil reserves ascertained on earth are only sufficient for more than 40 years of human recovery at the current production rate.
The polymeric materials (e.g., polyethylene, polypropylene, polystyrene, polymethacrylate, etc.) used in large amounts in human society today are derived from petroleum products. With the continuous consumption of petroleum resources, a great challenge facing human society is how to replace traditional petroleum-based polymers with renewable resources in nature. Therefore, the research of producing renewable polymers by using biomass as a raw material and developing novel monomers and a polymerization reaction process thereof conforms to the strategy of sustainable development and is more and more concerned by people.
As cyclic analogues of methacrylate (MMA), vinylcyclobutyrolactone: the application prospect of two renewable monomers, namely alpha-methylene-gamma-butyrolactone (MBL) and gamma-methyl-alpha-methylene-gamma-butyrolactone (MMBL) is very wide. MBL, also known as tulip lactone, is a compound that can be directly extracted from tulip, and the ring structure of MBL is the basic building block of many natural products. Whereas its gamma-methyl homologue MMBL can be synthesized from the biomass derivative levulinic acid in a two-step process. Although structurally they are cyclic analogs of the petroleum-based monomer MMA. However, due to the presence of nearly planar five-membered ring structures (five-membered ring structures allow the carbonyl group to be on the same side of the ring as the double bond, and the tension can increase the energy of the carbon-carbon double bond while providing a highly resonance-stable structure), the polymerization activity of such monomers is far greater than that of their analogs MMA.
More importantly, the polymers PMBL and PMMBL show superior material characteristics compared with PMMA which is an analogue of the polymers due to a rigid conformation structure formed by the interaction of a polymer chain and a cyclic lactone unit. For example, the glass transition temperature T of random PMBL obtained by radical polymerizationg195 ℃ C, which is compared with the T of random PMMAgAbout 90 ℃ higher; and by the silicon cation R3Si+T of catalytically polymerized random PMMBLgUp to 225 ℃. In addition, compared to PMMA, PMBL and PMMBL exhibit better anti-solvent (insoluble in general organic solvents such as THF, dichloromethane, toluene, and the like), heat resistance, and friction resistance, and the like.
In summary, the comparative advantages of renewable poly (γ -methyl) - α -methylene- γ -butyrolactone over petroleum-based polymer are shown in fig. 17.
MBL is known to polymerize by a variety of polymerization processes. Including free radical polymerization, group transfer polymerization, anionic polymerization, and metallocene-catalyzed coordination polymerization. MBL can also be copolymerized with various monomers such as MMA, styrene, methoxystyrene, vinyl thiophene and the like. Polymerization of MMBL was relatively less studied than for MBL. Free radical emulsion polymerization or free radical, anionic and group transfer polymerization have been reported. The polymerization requires a long reaction time and it is difficult to achieve complete conversion of the monomers.
Disclosure of Invention
The technical problem to be solved by the present invention is to provide a catalytic polymerization system capable of efficiently and rapidly realizing activity control of renewable (γ -methyl) - α -methylene- γ -butyrolactone ((M) MBL).
The technical scheme of the invention is as follows:
a method for the activity-controlled polymerization of (gamma-methyl) -alpha-methylene-gamma-butyrolactone is characterized in that silyl enol ether (short for short) is usedRSKA，Me2C＝C(OMe)OSiR3) The method is characterized in that a Lewis acid is used as a catalyst to catalyze the controllable activity polymerization of gamma-methyl-alpha-methylene-gamma-butyrolactone (MMBL for short) and alpha-methylene-gamma-butyrolactone (MBL for short) and the copolymerization of the gamma-methyl-alpha-methylene-gamma-butyrolactone (MMBL for short) and the alpha-methylene-gamma-butyrolactone (MBL for short) under the condition of a polar solvent; the molar ratio of the monomer to the silyl enol ether in the polymerization system is 10-3200: 1, the reaction temperature is normal temperature, and the reaction time is 0.2 to 24 hours;
the structural formula of the enol silyl ether is shown in the specification
The Lewis acid is tri (pentafluorophenyl) aluminum, tri (pentafluorophenyl) boron, aluminum trichloride, trimethylaluminum, triethylaluminum, triphenylaluminum, tri (p-fluorophenyl) aluminum and di (2, 6-di-tert-butyl-4-methylphenoxy) methylaluminum;
the gamma-methyl-alpha-methylene-gamma-butyrolactone (MMBL) and the alpha-methylene-gamma-butyrolactone (MBL) are renewable monomers, and the specific structural formula is
In the method for the activity-controlled polymerization of (gamma-methyl) -alpha-methylene-gamma-butyrolactone, the structural formula of the silyl enol ether is preferably
The Lewis acids mentioned are preferably tris (pentafluorophenyl) aluminium and tris (pentafluorophenyl) boron.
In the method for the activity-controlled polymerization of (γ -methyl) - α -methylene- γ -butyrolactone, the polar solvent is preferably used in an amount such that the monomer concentration is 0.5 to 4mol/L, and the polar solvent is preferably dichloromethane, tetrahydrofuran, or N, N-dimethylformamide.
The method utilizes silyl enol ether (SKA) as an initiator, utilizes Lewis acid as a catalyst to activate a monomer, and generates an electrically neutral active species with a silyl enol ether structure through the reaction of the silyl enol ether and the Lewis acid activated monomer, wherein the active species can realize the activity controllable polymerization of MMBL and MBL. The living polymerization characteristics are specified by the following aspects: 1, the molecular weight of the resulting polymer can be very close to the theoretical molecular weight, while maintaining a very low molecular weight distribution; 2, the molecular weight of the polymer increases linearly with the conversion of the monomers, while maintaining a very low molecular weight distribution; 3, the molecular weight of the resulting polymer increases linearly with the monomer/initiator ratio, while maintaining a very low molecular weight distribution; 4, ideal chain extension can be realized; 5, MMBL and MBL can realize ideal copolymerization (including random polymerization, diblock polymerization and triblock polymerization).
In conclusion, the invention has the following beneficial effects:
1. the catalyst system has the advantages of easily available raw materials, convenient operation, mild and rapid reaction conditions, high conversion rate (up to 100 percent) and no need of precious metals.
2. The catalyst system of the invention uses a small amount of catalyst (the molar ratio of the monomer to the catalyst can reach 3600: 1).
3. The molecular weight of the polymer synthesized by the catalytic system of the invention increases with the ratio of the monomer to the catalyst, so that the system can realize the molecular weight of the polymer of 106Higher g/mol grade, narrow molecular weight distribution (PDI)<1.5)。
4. The catalytic system of the invention can well maintain the active structure of the enol silyl ether at the tail end of a polymer chain, thereby realizing good chain extension.
5. The catalytic system of the invention can realize the copolymerization (random copolymerization and block copolymerization) between MMBL and MBL.
Drawings
FIG. 1 is a schematic view ofDimethylketene-methyl-dimethylethoxyacetal Me prepared in example 12C＝C-(OMe)OSiMe2(EtO)(Me2(EtO)SKA) of1H NMR chart.
FIG. 2 is the dimethylketene-methyl-dimethylethoxyacetal Me prepared in example 12C＝C-(OMe)OSiMe2(EtO)(Me2(EtO)SKA) of13C NMR chart.
FIG. 3 is a gel permeation chromatogram of polymers obtained for different monomer/initiator ratios of example 2.
FIG. 4 is a MALDI-TOF plot of the poly-MMBL prepared in example 2 and a partially enlarged view thereof.
FIG. 5 is a structural analysis of the main peaks of the MALDI-TOF plot of the poly-MMBL of example 2.
FIG. 6 is a structural analysis of the secondary peaks of the MALDI-TOF plot of the poly-MMBL of example 2.
FIG. 7 is a gel permeation chromatogram of the chain extension experiment of example 3.
FIG. 8 is a gel permeation chromatogram of the random copolymerization experiment of example 4.
FIG. 9 is a gel permeation chromatogram of the triblock copolymerization experiment of example 4.
FIG. 10 is the in situ formation of intermediate 1 of example 51H NMR chart.
FIG. 11 is a preparation of intermediate 1 from example 5 generated in situ19F NMR chart.
FIG. 12 is a MALDI-TOF plot of the poly-MMBL prepared in example 5 and a partially enlarged view thereof.
FIG. 13 is a structural analysis of the main peaks of the MALDI-TOF plot of the poly-MMBL of example 5.
FIG. 14 is a structural analysis of the secondary peaks of the MALDI-TOF plot of the poly-MMBL of example 5.
FIG. 15 is of intermediate 2 generated in situ in example 61H NMR chart.
FIG. 16 is of the tetrahedral intermediate 2 of example 6 generated in situ19F NMR chart.
Fig. 17 is a graph comparing the characteristics of renewable poly (γ -methyl) - α -methylene- γ -butyrolactone to petroleum-based polymers.
Detailed Description
The present invention is further illustrated by the following examples, which are intended to be illustrative of the invention and not to be limiting, and the scope of the invention is not limited thereto.
EXAMPLE 1A specific Synthesis method of silyl enol ether described in the present invention
Synthesis of Dimethylketene-methyl-Dimethylethoxyacetal Me2C＝C(OMe)OSiMe2(EtO)(Me2(EtO)SKA)。
1) Synthesis of Dimethylethoxychlorosilane (Me)2(EtO)SiCl)
In a glove box filled with nitrogen, ethanol (5.08mL, 90.0mmol) and B (C) were taken6F5)3(461mg, 0.90mmol) in a 200mL Schlenk flask, dichloromethane (100mL) was added and capped with a flip-top stopper, the glovebox was taken out and attached to the Schlenk line, cooled to-78 deg.C and held for 20 min. Dimethylchlorosilane (10.0mL,90.0mmol) was slowly added dropwise to the system via syringe. Slowly warm to room temperature (over 30min), remove dichloromethane in vacuo (care was taken not to pump off the product), and distill under reduced pressure to give the product as a colorless oil. The product was obtained in 12.48g, 91% yield.1H NMR(500MHz,Benzene‐d6)δ3.61(q,J＝7.0Hz,2H,OCH2),1.06(t,J＝7.0Hz,3H,OCH2CH3),0.26(s,6H,SiMe2).
2) Synthesis of Dimethylketene-methyl-Dimethylethoxyacetal Me2C＝C(OMe)OSi-Me2(EtO)(Me2 (EtO)SKA)。
In a glove box filled with nitrogen, diisopropylamine (7.05mL, 50.0mmol) was taken in a 200mL Schlenk flask, tetrahydrofuran (100mL) was added and the flask was closed with a flip-top stopper, taken out of the glove box and attached to a Schlenk line, and cooled to 0 ℃. Slowly dropping through a syringeButyllithium (32.0mL,1.6M in n-hexane, 51.2mmol) was added to the system and after reaction at 0 ℃ for 30min, methyl isobutyrate (5.74mL, 50.0mmol) was added slowly. After the system was reacted at 0 ℃ for 30min, dimethylethoxychlorosilane (7.61g, 50.0mmol) was slowly added dropwise. And slowly warmed to room temperature and stirred overnight. The solvent was removed in vacuo, n-hexane was added and solid LiCl was filtered off, the n-hexane solvent was again drained and distilled under reduced pressure to give the final colorless transparent oil. Product 8.79g, yield 86%.1H NMR(500MHz,Benzene-d6)δ3.72(q,J＝7.0Hz,2H,OCH2CH3),3.39(s,3H,OMe),1.72(s,3H,＝CMe),1.68(s,3H,＝CMe),1.13(t,J＝7.0Hz,3H,OCH2CH3),0.21(s,6H,SiMe2) (attached FIG. 1)13C NMR(126MHz,Benzene-d6) δ 149.8,90.7,58.6,56.6,18.5,17.1,16.5, -2.5. (fig. 2)
Example 2 polymerization of gamma-methyl-alpha-methylene-gamma-butyrolactone (MMBL) with alpha-methylene-gamma-butyrolactone (MBL)
The polymerization reaction is carried out in a glove box, Lewis acid is weighed in a 20 mL reaction bottle, MMBL (0.5mL, 4.68mmol) or MBL (0.41mL, 4.68mmol) is added, after the monomer and the Lewis acid fully react, dichloromethane solvent is added (the total volume of the solution after the addition is 5mL), weighed enol silyl ether (the total volume of the solution after the addition is 5mL) is addedRSKA), and starting timing, stirring for a period of time until the monomer is completely converted, taking the reaction bottle out of the glove box, and adding 5% HCl/methanol solution to terminate the polymerization reaction. The polymer was filtered off, washed thoroughly with methanol and dried under vacuum at 60 ℃ to constant weight. The molecular weight and molecular weight distribution of the resulting polymer were determined by gel permeation chromatography.
The results of the characterization of the polymer molecular weight and molecular weight distribution show that the polymerization system enables the molecular weight of the polymer to increase linearly with the monomer/initiator ratio while maintaining a very low molecular weight distribution. The relative GPC chart is shown in FIG. 3.
Low molecular weight MMBL polymer (3.1X 10)3g/mol) was detected by matrix assisted laser desorption ionization time of flight mass spectrometry (MALDI-TOF) (FIG. 4), indicating that the structure of the silyl enol ether was still maintained at the end of the polymer (FIG. 5),this is also why the catalytic polymerization system can maintain living polymerization. The enolsilyl ether structure at the end of the chain can also be hydrolyzed to a hydrogen atom (FIG. 6).
The results obtained by catalysis with different Lewis acids and bases and different reaction conditions are summarized in tables 1-2.
TABLE 1 Al (C)6F5)3[Al]Catalyzed polymerization of MMBL
Note: the conversion in parentheses is calculated by weighing the mass of the final polymerization.
TABLE 2.B (C)6F5)3[B]Catalyzed polymerization of MMBL and MBL
Example 3 chain extension of MMBL
The polymerization was carried out in a glove box, and Al (C) was weighed6F5)3Adding MMBL (0.5mL, 4.68mmol) into a 20 mL reaction bottle, adding tetrahydrofuran solvent (the total volume of the solution after adding is 5mL) after the monomer and Lewis acid are fully reacted, and adding weighed solutioniBuSKA, and starting timing, stirring for a period of time until the monomer is completely converted, then adding MMBL (0.5ml, 4.68mmol), after all the monomers are completely converted, taking out the reaction bottle from the glove box, and adding 5% HCl/methanol solution to terminate the polymerization reaction. The polymer was filtered off, washed thoroughly with methanol and dried under vacuum at 60 ℃ to constant weight. Molecular weight and molecular weight of the resulting PolymerThe distribution was determined by gel permeation chromatography.
Use ofiBuSKA and Al (C)6F5)3The results of the chain extension experiments performed on the system are summarized in Table 3. The relative GPC chart is shown in FIG. 7. This ideal chain extension experiment shows that the catalytic polymerization system can achieve good activity retention of the polymer chain ends.
TABLE 3 chain extension test results for MMBL polymerization
EXAMPLE 4 copolymerization of MMBL and MBL
Taking the preparation of poly (MMBL-block-MBL-block-MMBL) as an example: the polymerization reaction is carried out in a glove box, Lewis acid is weighed in a 20 mL reaction bottle, MMBL (0.5mL, 4.68mmol) is added, after the monomer and the Lewis acid fully react, N-dimethylformamide solvent is added (the total volume of the solution after the addition is 5mL), and the weighed solution is addediBuSKA, and starting timing, stirring for a period of time until the monomer is completely converted, then adding MBL (0.41ml, 4.68mmol), adding MMBL (0.5ml, 4.68mmol) after the monomer is completely converted, taking out the reaction bottle from the glove box after all the monomers are completely converted, and adding 5% HCl/methanol solution to terminate the polymerization reaction. The polymer was filtered off, washed thoroughly with methanol and dried under vacuum at 60 ℃ to constant weight. The molecular weight and molecular weight distribution of the resulting polymer were determined by gel permeation chromatography. GPC charts of related homopolymers and copolymers are shown in FIG. 8 and FIG. 9.
TABLE 5 copolymerization of MMBL and MBL
aRandom copolymerization: both monomers are added simultaneously.
Example 5 characterization of reactive intermediate 1
In a glove box, takingiBuSKA (3.01mg,0.01mmol) and 0.3mLC6D6Adding into a J.Young-type nuclear magnetic tube. Pipette 0.3mL of Al (C)6F5)3C of MMA6D6Adding the solution (0.01mmol) into a nuclear magnetic tube, mixing uniformly, reacting for 15min, and performing nuclear magnetic test. To obtain the intermediate Me3SiO(OMe)C＝C(Me)CH2CMe2C(OMe)＝O···Al(C6F5)3The compound has cis-trans isomers, mainly a structure 1A and a secondary structure 1B, and specific nuclear magnetic data are as follows: 1A:1HNMR(500MHz,Benzene‐d6)δ3.22(s,3H,OMe),3.08(s,3H,COOMe),2.16(s,2H,CH2),1.35(s,3H,Me),0.97(s,6H,Me2),0.058(s,9H,SiMe3)；1B:δ3.27(s,3H,OMe),3.24(s,3H,COOMe),2.18(s,2H,CH2),1.43(s,3H,Me),1.01(s,6H,Me2),0.063(s,9H,SiMe3) (ii) a (FIG. 10)19F NMR(471MHz,Benzene‐d6) δ -122.88 (d, J ═ 18.8Hz,6F, o-F), -151.75 (t, J ═ 19.7Hz,3F, p-F), -160.94 (m,6F, m-F) (fig. 11)
Using this dimer structure polymerization, a low molecular weight MMBL polymer (3.3X 10)3g/mol) was examined by matrix assisted laser desorption ionization time of flight mass spectrometry (MALDI-TOF) (FIG. 12), which showed that the structure of the enolsilyl ether was still maintained at the end of the polymer, and that the other end was in the form of MMA-dimerized structure (FIG. 13), which showed that the end was capable of maintaining the structure of the enolsilyl ether, and more importantly, that the intermediate of this dimerization was the active species of the polymerization system. As in example 2, the enolsilyl ether structure at the end of the chain can also be hydrolyzed to a hydrogen atom (FIG. 14).
Example 6 isolation of tetrahedral intermediate 2
In a glove box, takingiBuSKA (3.01mg,0.01mmol) and 0.3mLC6D6Adding into a J.Young-type nuclear magnetic tube. By moving0.3mL of Al (C) was taken in the liquid container6F5)3C of MMBL6D6Adding the solution (0.01mmol) into a nuclear magnetic tube, mixing uniformly, reacting for 15min, and performing nuclear magnetic test. To obtain an intermediateiBu3Si-MMBL-CMe2C(OMe)＝O···Al(C6F5)3(2) Due to the special cyclic structure of MMBL, no cis-trans isomer occurs, and the specific nuclear magnetic data are as follows:1H NMR(500MHz,Benzene‐d6)δ4.30(ddq,J＝9.4,6.6,6.2Hz,1H,OCH),3.24(s,3H,OMe),2.29(dd,J＝12.9,9.4Hz,1H,CH2),2.27(d,J＝14.2Hz,1H,CH2),2.20(d,J＝14.3Hz,1H,CH2),1.88(hept,J＝6.7Hz,3H,CH),1.79(dd,J＝12.8,6.6Hz,1H,CH2),1.10(d,J＝6.2Hz,3H,Me),1.04(s,3H,Me2),1.03(s,3H,Me2),1.00(d,J＝6.6Hz,18H,CHMe2),0.78(d,J＝7.0Hz,6H,SiCH2) (FIG. 15)19F NMR(471MHz,Benzene‐d6) δ -122.91 (d, J ═ 21.3Hz,6F, o-F), -151.63 (t, J ═ 19.8Hz, p-F), -160.85 (m,6F, m-F) (fig. 16).
Claims (3)
1.A method for the activity-controlled polymerization of (gamma-methyl) -alpha-methylene-gamma-butyrolactone is characterized in that silyl enol ether is used as an initiator, Lewis acid is used as a catalyst, and the controllable activity polymerization of the gamma-methyl-alpha-methylene-gamma-butyrolactone and the copolymerization of the gamma-methyl-alpha-methylene-gamma-butyrolactone and the alpha-methylene-gamma-butyrolactone are catalyzed under the condition of a polar solvent; the molar ratio of the monomer to the silyl enol ether in the polymerization system is 10-3200: 1, the reaction temperature is normal temperature, and the reaction time is 0.2 to 24 hours;
the structural formula of the enol silyl ether is shown in the specification
The Lewis acid is tri (pentafluorophenyl) aluminum or tri (pentafluorophenyl) boron;
the gamma-methyl-alpha-methylene-gamma-butyrolactone is abbreviated as MMBL, the alpha-methylene-gamma-butyrolactone is abbreviated as MBL, and the gamma-methyl-alpha-methylene-gamma-butyrolactone is a renewable monomer, and the specific structural formula is
2. The process of claim 1, wherein the silyl enol ether has the formula (i) of
3. The method of claim 1, wherein the polar solvent is dichloromethane, tetrahydrofuran, or N, N-dimethylformamide, and is used in an amount such that the monomer concentration is 0.5 to 4 mol/L.
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