CN108148187A - The method of living control polymerization (γ-methyl)-ɑ-methylene-y-butyrolactone - Google Patents
The method of living control polymerization (γ-methyl)-ɑ-methylene-y-butyrolactone Download PDFInfo
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- CN108148187A CN108148187A CN201810013511.5A CN201810013511A CN108148187A CN 108148187 A CN108148187 A CN 108148187A CN 201810013511 A CN201810013511 A CN 201810013511A CN 108148187 A CN108148187 A CN 108148187A
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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
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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
- C08G63/823—Preparation processes characterised by the catalyst used for the preparation of polylactones or polylactides
Abstract
The method of living control polymerization (γ methyl) ɑ methylene gamma butyrolactones of the present invention belongs to macromolecule synthesising technology field, using silyl enol ether as initiator, using Lewis acid as catalyst, under conditions of polar solvent, it is catalyzed controllable living polymerization and their copolymerization of MMBL and MBL.The polymerized monomer of the present invention is renewable resource, it is with a wide range of applications, polymerization system has many advantages, such as that easy to operate, reaction condition is mild, quick, high conversion rate, and the molecular weight of resulting polymers is controllable, narrow molecular weight distribution is a kind of living control polymerization.
Description
Technical field
The invention belongs to macromolecule synthesising technology fields, and in particular to a kind of living control polymerization catalyst system and catalyzing, the system
Using Lewis acid as catalyst, silyl enol ether can be applied to renewable monomer (γ-methyl)-ɑ-methylene as initiator
Copolymerization between the living control polymerization and two kinds of monomers of base-gamma-butyrolacton ((M) MBL).
Background technology
Energy problem is the main problem of mankind nowadays society.Since the mankind start with fossil energy.Coal, stone
Oil and gas, which rapidly develops, becomes the energy and the most important source of chemicals.At present, about 86% energy and 96% change
Product are derived from these non-renewable oil products.It is contemplated that oil product certainly will cannot meet the mankind in the near future
The growing demand of society.More severe is：It is predicted according to relevant expert, with current exploitation rate, has been visited on the earth
Bright oil reserve is only sufficient to the mankind and exploited for more than 40 years again.
Polymer material (such as polyethylene, polypropylene, polystyrene and the polymethyl that human society largely uses at present
Acid esters etc.) all it is derived from oil product.With the continuous consumption of petroleum resources, human society huge chooses face one
War is how to substitute traditional oil based polyalcohol using the renewable resource in nature.Therefore, using biomass as raw material,
Novel monomeric and its polymerization technology are developed, the research of renewable polymer is produced, meets the strategy of sustainable development, increasingly
It gets more and more people's extensive concerning.
As the cyclic analogs of methacrylate (MMA), ethylene basic ring butyrolactone：ɑ-methylene-y-butyrolactone
(MBL) and the application prospect of γ-methyl-ɑ-methylene-y-butyrolactone (MMBL) the two renewable monomers will be boundless.
MBL also known as tulipalin are a kind of compounds that can be directly extracted from tulip, and the ring structure of MBL is many natural
The basic structural unit of product.And its γ-Methyl Homologue MMBL can be by two step process from biomass derivatives acetyl
Propionic acid synthesizes to obtain.Although they are the cyclic analogs of petroleum base monomer MMA from structure.However, due near plane
The presence of five-membered cyclic structure (five-membered ring structure causes carbonyl and double bond homonymy outside ring, and tension can improve carbon carbon
The energy of double bond, while the resonance stabilized structure of height is provided) so that the polymerization activity of such monomer is far longer than their class
Like object MMA.
What is more important is caused due to the rigid conformation structure that the interaction of polymer chain and cyclic lactone unit is formed
Such polymer P MBL and PMMBL illustrates material property more more superior than its analog PMMA.For example, pass through free radical
It polymerize the glass transition temperature T of the random PMBL of gainedgIt it is 195 DEG C, this is than the T of random PMMAgIt has been higher by about 90 DEG C；
And pass through silicon cation R3Si+The T of the random PMMBL of catalytic polymerizationgUp to 225 DEG C.In addition, compared to PMMA, PMBL and
PMMBL shown better anti-solvent (insoluble in general organic solvent such as THF, dichloromethane and toluene etc.), heat resistanceheat resistant and
The performances such as anti-friction.
To sum up, the comparative benefits of reproducible poly- (γ-methyl)-ɑ-methylene-y-butyrolactone and oil based polyalcohol
As shown in figure 17.
Know that MBL can be polymerize by a variety of polymerization processes.Gather including free radical polymerization, group transfer
The coordination polymerization of conjunction, anionic polymerisation and metallocene catalysis.MBL can also be with MMA, styrene, methoxy styrene and ethylene
The various of monomer such as base thiophene realize copolymerization.It is relatively fewer to the polymerisation research of MMBL for MBL.It has been reported that
Have free-radical emulsion polymerization or free radical, anion and group transfer polymerization.The polymerization needs the longer reaction time, and very
Difficulty reaches complete monomer conversion.
Invention content
The technical problem to be solved in the present invention is, provide it is a kind of efficiently and rapidly realize reproducible (γ-methyl)-ɑ-
The active controllable catalytic polymerization system of methylene-y-butyrolactone ((M) MBL).
Technical scheme is as follows：
A kind of method of living control polymerization (γ-methyl)-ɑ-methylene-y-butyrolactone, which is characterized in that with enol
Silicon ether is (referred to asRSKA, Me2C=C (OMe) OSiR3) it is initiator, using Lewis acid as catalyst, in the condition of polar solvent
Under, be catalyzed γ-methyl-ɑ-methylene-y-butyrolactone (abbreviation MMBL) and ɑ-methylene-y-butyrolactone (abbreviation MBL) can
Control living polymerization and their copolymerization；The monomer of polymerization system and the molar ratio of silyl enol ether are 10~3200：1, reaction temperature
It spends for room temperature, the reaction time is 0.2 hour~24 hours；
The silyl enol ether structural formula is
The Lewis acid is three (pentafluorophenyl group) aluminium, three (pentafluorophenyl group) boron, alchlor, trimethyl aluminium, triethyl group
Aluminium, triphenyl aluminum, three (p-fluorophenyl) aluminium, two (2,6- di-t-butyl -4- methylphenoxies) aluminium methyls；
The γ-methyl-ɑ-methylene-y-butyrolactone (MMBL) and ɑ-methylene-y-butyrolactone (MBL) are can
Regenerated monomer, specific structural formula are
It is described in a kind of method of living control polymerization (γ-methyl)-ɑ-methylene-y-butyrolactone of the present invention
The structural formula of silyl enol ether is preferably
The Lewis acid is preferably three (pentafluorophenyl group) aluminium and three (pentafluorophenyl group) boron.
It is described in a kind of method of living control polymerization (γ-methyl)-ɑ-methylene-y-butyrolactone of the present invention
The dosage of polar solvent is preferably to make a concentration of 0.5~4mol/L of monomer, and the polar solvent is preferably dichloromethane, four
Hydrogen furans or N,N-dimethylformamide.
The present invention is initiator using silyl enol ether (SKA), using Lewis acid as the catalyst to activated monomer, passes through
Silyl enol ether and electroneutral active specy of the monomer reaction generation with silyl enol ether structure of Lewis acid activations, this activity
Species can realize the living control polymerization of MMBL and MBL.Its living polymerization feature is illustrated by the following aspects：1,
Keep the molecular weight of obtained polymer in the case of low-down molecular weight distribution can be very close with theoretical molecular weight；
2, in the case where keeping low-down molecular weight distribution, the molecular weight of polymer linearly increases with the conversion ratio of monomer；3,
In the case where keeping low-down molecular weight distribution, the molecular weight of obtained polymer is in the ratio of monomers/initiator
Linear increase；4, it can realize ideal chain extension；5, MMBL can realize that ideal copolymerization is (double including polymerizeing at random with MBL
Block polymerization and three block polymerization).
To sum up, the present invention has following advantageous effect：
1st, catalyst system and catalyzing raw material of the invention is easy to get, is easy to operate, reaction condition is mild, quick, high conversion rate is (reachable
100%), without precious metal.
2nd, few (molar ratio of monomer and catalyst can reach 3600 to catalyst system and catalyzing catalyst usage amount of the invention:
1)。
3rd, the molecular weight of the polymer synthesized by catalyst system and catalyzing of the invention increases with the increase of monomer and catalyst ratio
Greatly, thus the system can realize the molecular weight of polymer up to 106More than g/mol ranks, narrow molecular weight distribution (PDI<1.5).
4th, catalyst system and catalyzing of the invention can be good at keeping silyl enol ether active structure, therefore energy in polymer chain terminal
Enough realize good chain extension.
4th, catalyst system and catalyzing of the invention can realize the copolymerization (random copolymerization and block copolymerization) between MMBL and MBL.
Description of the drawings
Fig. 1 is dimethyl ketene-methyl-dimethyl ethyoxyl acetal Me prepared by embodiment 12C=C- (OMe)
OSiMe2(EtO)(Me2(EtO)SKA)1H NMR scheme.
Fig. 2 is dimethyl ketene-methyl-dimethyl ethyoxyl acetal Me prepared by embodiment 12C=C- (OMe)
OSiMe2(EtO)(Me2(EtO)SKA)13C NMR scheme.
Fig. 3 is the gel permeation chromatography figure for the polymer that different monomers/ratio of initiator of embodiment 2 obtains.
Fig. 4 is the MALDI-TOF figure and its partial enlarged view of poly- MMBL prepared by embodiment 2.
Fig. 5 is the structural analysis of the MALDI-TOF figure main peaks of 2 poly- MMBL of embodiment.
Fig. 6 is the structural analysis of the MALDI-TOF figure secondary peaks of 2 poly- MMBL of embodiment.
Fig. 7 is the gel permeation chromatography figure of the chain extension experiment of embodiment 3.
Fig. 8 is the gel permeation chromatography figure of the random copolymerization experiments of embodiment 4.
Fig. 9 is the gel permeation chromatography figure of the triblock copolymer experiment of embodiment 4.
Figure 10 is 5 generated in-situ intermediate 1 of embodiment1H NMR scheme.
Figure 11 is 5 generated in-situ intermediate 1 of embodiment19F NMR scheme.
Figure 12 is the MALDI-TOF figure and its partial enlarged view of poly- MMBL prepared by embodiment 5.
Figure 13 is the structural analysis of the MALDI-TOF figure main peaks of 5 poly- MMBL of embodiment.
Figure 14 is the structural analysis of the MALDI-TOF figure secondary peaks of 5 poly- MMBL of embodiment.
Figure 15 is 6 generated in-situ intermediate 2 of embodiment1H NMR scheme.
Figure 16 is 6 generated in-situ tetrahedral intermediate 2 of embodiment19F NMR scheme.
Figure 17 is reproducible poly- (γ-methyl)-ɑ-methylene-y-butyrolactone and comparison diagram the characteristics of oil based polyalcohol.
Specific embodiment
It can be further illustrated the present invention by following embodiment, embodiment is to illustrate the invention without limitation originally
Invention, protection scope of the present invention are not limited to this.
A kind of specific synthetic method of 1 silyl enol ether of the present invention of embodiment
Synthesize dimethyl ketene-methyl-dimethyl ethyoxyl acetal Me2C=C (OMe) OSiMe2(EtO) (Me2 (EtO)SKA)。
1) synthesis dimethylethyloxy chlorosilane (Me2(EtO)SiCl)
In the glove box full of nitrogen, ethyl alcohol (5.08mL, 90.0mmol) and B (C are taken6F5)3(461mg,
0.90mmol) in 200mLSchlenk bottles, add in dichloromethane (100mL) and sealed with turned welt plug, take out glove box and be connected in
On Schlenk lines, it is cooled to -78 DEG C and keeps 20min.By syringe be slowly added dropwise dimethylchlorosilane (10.0mL,
90.0mmol) in system.Room temperature (more than 30min) is slowly increased to, dichloromethane (being careful not to take out product) is removed in vacuum,
Vacuum distillation obtains colorless oil as product.Obtain product 12.48g, yield 91%.1H NMR(500MHz,Benzene-d6)δ
3.61 (q, J=7.0Hz, 2H, OCH2), 1.06 (t, J=7.0Hz, 3H, OCH2CH3),0.26(s,6H,SiMe2).
2) dimethyl ketene-methyl-dimethyl ethyoxyl acetal Me is synthesized2C=C (OMe) OSi- Me2(EtO)(Me2 (EtO)SKA)。
In the glove box full of nitrogen, diisopropylamine (7.05mL, 50.0mmol) is taken in 200mLSchlenk bottles,
It adds in tetrahydrofuran (100mL) and is sealed with turned welt plug, take out glove box and be connected on Schlenk lines, be cooled to 0 DEG C.Pass through note
N-BuLi (32.0mL, 1.6M in n-hexane, 51.2 mmol) is slowly added dropwise in system in emitter, and is reacted at 0 DEG C
After 30min, it is slowly added to methyl isobutyrate (5.74mL, 50.0mmol).After system reacts 30min at 0 DEG C, slowly drip
Add dimethylethyloxy chlorosilane (7.61g, 50.0mmol).And room temperature is slowly increased to, it is stirred overnight.Solvent is removed in vacuum, adds
Enter n-hexane and filter out solid LiCl, drain vacuum distillation after n-hexane solvent again and obtain final water white transparency oily
Object.Product 8.79g, yield 86%.1H NMR(500MHz,Benzene-d6) δ 3.72 (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 drawing 1)13C NMR(126MHz, Benzene-d6)δ149.8,90.7,58.6,56.6,18.5,
17.1,16.5-2.5. (attached drawing 2)
2 γ of embodiment-methyl-ɑ-methylene-y-butyrolactone (MMBL) is poly- with ɑ-methylene-y-butyrolactone (MBL)
It closes
Polymerisation carries out in glove box, weighs Lewis acid in 20 milliliters of reaction bulbs, addition MMBL (0.5ml,
4.68mmol) or MBL (0.41mL, 4.68mmol), after monomer is fully reacted with Lewis acid, addition dichloromethane solvent (adds
Enter rear overall solution volume for 5mL), add in weighed silyl enol ether (RSKA), and start timing, stirring a period of time treats
After complete monomer conversion, reaction bulb from glove box is taken out, adds in 5%HCl/ methanol solutions and terminates polymerisation.It filters out poly-
Object is closed, is fully washed with methanol, 60 DEG C are dried under vacuum to constant weight.The molecular weight and molecualr weight distribution of resulting polymers passes through solidifying
Glue penetration chromatography measures.
The characterization result of polymer molecular weight and molecular weight distribution is shown, which can keep low-down
The molecular weight of polymer is made linearly to increase with the ratio of monomers/initiator in the case of molecular weight distribution.Related GPC figures ginseng
See attached drawing 3.
The MMBL polymer (3.1 × 10 of low molecular weight3G/mol) pass through substance assistant laser desorpted ionized flight time matter
(MALDI-TOF) detection (attached drawing 4) is composed, showing to remain unchanged in the end of polymer remains the structure (attached drawing 5) of silyl enol ether, this
And catalytic polymerization system can keep the reason of living polymerization.The silyl enol ether structure of chain end can also be hydrolyzed into hydrogen atom
(attached drawing 6).
The result obtained with different Lewis soda acids and different reaction conditions to catalysis is summarized in table 1~2.
Table 1.Al (C6F5)3The polymerization of the MMBL of [Al] catalysis
Note：Conversion ratio in bracket is as obtained by weighing the Mass Calculation finally polymerizeing.
Table 2.B (C6F5)3The polymerization of the MMBL and MBL of [B] catalysis
The chain extension of 3 MMBL of embodiment
Polymerisation carries out in glove box, weighs Al (C6F5)3In 20 milliliters of reaction bulbs, addition MMBL (0.5ml,
4.68mmol), after monomer is fully reacted with Lewis acid, tetrahydrofuran solvent (overall solution volume is 5mL after addition) is added in,
Add in what is weighediBuSKA, and start timing, stirring a period of time adds MMBL after complete monomer conversion
(0.5ml, 4.68mmol) so that adding MMBL (0.5ml, 4.68mmol) after complete monomer conversion after a period of time, treats institute
After having complete monomer conversion, reaction bulb from glove box is taken out, adds in 5%HCl/ methanol solutions and terminates polymerisation.It filters out
Polymer is fully washed with methanol, and 60 DEG C are dried under vacuum to constant weight.The molecular weight and molecualr weight distribution of resulting polymers passes through solidifying
Glue penetration chromatography measures.
It usesiBuSKA and Al (C6F5)3System carries out the result that chain extension is tested and is summarized in table 3.Related GPC figures
Referring to attached drawing 7.This ideal chain extension experiment shows that the catalytic polymerization system can realize the good work of polymer chain terminal
Property keep.
The chain extension experimental result of table 3.MMBL polymerizations
The copolymerization of embodiment 4 MMBL and MBL
For preparing poly- (MMBL- block-MBL- blocks-MMBL)：Polymerisation carries out in glove box, weighs
Lewis acid adds in MMBL (0.5ml, 4.68mmol) in 20 milliliters of reaction bulbs, after monomer is fully reacted with Lewis acid, adds
Enter n,N-Dimethylformamide solvent (overall solution volume is 5 mL after addition), add in what is weighediBuSKA, and start to count
When, stirring a period of time adds MBL (0.41ml, 4.68mmol), monomer is complete after a period of time after complete monomer conversion
MMBL (0.5ml, 4.68mmol) is added after conversion, after all complete monomer conversions, reaction bulb is taken from glove box
Go out, add in 5%HCl/ methanol solutions and terminate polymerisation.Polymer is filtered out, is fully washed with methanol, 60 DEG C are dried under vacuum to
Constant weight.The molecular weight and molecualr weight distribution of resulting polymers is measured by gel permeation chromatography.Related homopolymer and copolymer
GPC figures are referring to attached drawing 8, attached drawing 9.
The copolymerization of table 5 MMBL and MBL
aRandom copolymerization：Two kinds of monomers add in simultaneously.
The characterization of 5 reactive intermediate 1 of embodiment
In glove box, takeiBuSKA (3.01mg, 0.01mmol) and 0.3mLC6D6It is added to J. Young-type nuclear-magnetisms
Guan Zhong.0.3mL Al (C are taken with pipettor6F5)3The C of MMA6D6Solution (0.01mmol) is added in nuclear magnetic tube, and mixing is equal
It is even, carry out nuclear-magnetism test after reacting 15min.Obtain intermediate Me3SiO (OMe) C=C (Me) CH2CMe2C (OMe)=O
Al(C6F5)3, which has a cis-trans-isomer, mainly structure 1A and secondary structure 1B, and specific nuclear magnetic data is as follows：1A:1H
NMR(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)；(attached drawing 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) (attached drawing 11)
It polymerize to obtain the MMBL polymer (3.3 × 10 of low molecular weight using this dimeric structure3G/mol) pass through matrix
Assisted laser desorption ionisation flight time mass spectrum (MALDI-TOF) detects (attached drawing 12), shows still to protect in the end of polymer
The structure of silyl enol ether is hold, and the structure type (attached drawing 13) that another end is MMA dimerization, this shows on the one hand to show end
The characteristics of end can keep silyl enol ether structure, it is often more important that the intermediate for showing this dimerization is exactly the work of polymerization system
Property species.In the same manner as in Example 2, the silyl enol ether structure of chain end can also be hydrolyzed into hydrogen atom (attached drawing 14).
The separation of 6 tetrahedral intermediate 2 of embodiment
In glove box, takeiBuSKA (3.01mg, 0.01mmol) and 0.3mLC6D6It is added to J. Young-type nuclear-magnetisms
Guan Zhong.0.3mL Al (C are taken with pipettor6F5)3The C of MMBL6D6Solution (0.01mmol) is added in nuclear magnetic tube, and mixing is equal
It is even, carry out nuclear-magnetism test after reacting 15min.Obtain intermediateiBu3Si-MMBL-CMe2C (OMe)=OAl (C6F5)3
(2) does not occur cis-trans-isomer, specific nuclear magnetic data is as follows due to the particularly ring-shaped structures of MMBL：1H NMR
(500MHz,Benzene-d6) δ 4.30 (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) (attached drawing 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) (attached drawing 16).
Claims (3)
- A kind of 1. method of living control polymerization (γ-methyl)-ɑ-methylene-y-butyrolactone, which is characterized in that with enol silicon Ether is initiator, using Lewis acid as catalyst, under conditions of polar solvent, is catalyzed γ-methyl-ɑ-methylene-γ-fourth The controllable living polymerization and their copolymerization of lactone and ɑ-methylene-y-butyrolactone；The monomer and silyl enol ether of polymerization system Molar ratio be 10~3200：1, reaction temperature is room temperature, and the reaction time is 0.2 hour~24 hours；The silyl enol ether structural formula isThe Lewis acid for three (pentafluorophenyl group) aluminium, three (pentafluorophenyl group) boron, alchlor, trimethyl aluminium, triethyl aluminum, Triphenyl aluminum, three (p-fluorophenyl) aluminium, two (2,6- di-t-butyl -4- methylphenoxies) aluminium methyls；The γ-methyl-ɑ-methylene-y-butyrolactone is referred to as MMBL, and the ɑ-methylene-y-butyrolactone is referred to as MBL, is renewable monomer, and specific structural formula is
- 2. a kind of method of living control polymerization (γ-methyl)-ɑ-methylene-y-butyrolactone according to claim 1, It is characterized in that, the structural formula of the silyl enol ether isThe Lewis acid is three (pentafluorophenyl group) aluminium and three (pentafluorophenyl group) boron.
- 3. a kind of method of living control polymerization (γ-methyl)-ɑ-methylene-y-butyrolactone according to claim 1, It is characterized in that, the dosage of the polar solvent is to make a concentration of 0.5~4mol/L of monomer, the polar solvent is two Chloromethanes, tetrahydrofuran or n,N-Dimethylformamide.
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| CN109503816A (en) * | 2018-10-29 | 2019-03-22 | 三明学院 | A kind of amphipathic ester type block polymer, preparation method and its usage |
| CN111499783A (en) * | 2020-05-29 | 2020-08-07 | 深圳市鑫元素新材料科技有限公司 | Preparation method of polyacrylate with extremely narrow molecular weight distribution |
| CN113896875A (en) * | 2021-10-11 | 2022-01-07 | 吉林大学 | Intramolecular trifunctional Lewis acid-base pair catalyst, annular topological structure PMMBL polymer, preparation method and application |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1544221A2 (en) * | 2000-02-28 | 2005-06-22 | E.I. du Pont de Nemours and Company | Coating compositions containing substituted and unsubstituted exomethylene lactone or lactam monomers |
| CN103304715A (en) * | 2012-03-13 | 2013-09-18 | 怀化学院 | Stereoregular poly (beta-alkyl-alpha-methylene gamma-butyrolactone) and copolymer thereof |
| WO2013148933A1 (en) * | 2012-03-30 | 2013-10-03 | Segetis, Inc. | Reactive diluents, methods of reacting, and thermoset polymers derived therefrom |
| JP2013227457A (en) * | 2012-04-26 | 2013-11-07 | Hiroshima Univ | Ring-opening polymerization catalyst of cyclic ester and method for ring-opening polymerization of cyclic ester |
| WO2014075051A1 (en) * | 2012-11-12 | 2014-05-15 | Segetis, Inc. | Crosslinkable polyketal esters, methods of manufacture and uses thereof |
| CN105073826A (en) * | 2013-03-25 | 2015-11-18 | 赢创德固赛有限公司 | Lactone polymerization with latent initiators |
| CN106977708A (en) * | 2017-03-30 | 2017-07-25 | 南京工业大学 | A kind of cyclic compound ring-opening polymerization method |
-
2018
- 2018-01-08 CN CN201810013511.5A patent/CN108148187B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1544221A2 (en) * | 2000-02-28 | 2005-06-22 | E.I. du Pont de Nemours and Company | Coating compositions containing substituted and unsubstituted exomethylene lactone or lactam monomers |
| CN103304715A (en) * | 2012-03-13 | 2013-09-18 | 怀化学院 | Stereoregular poly (beta-alkyl-alpha-methylene gamma-butyrolactone) and copolymer thereof |
| WO2013148933A1 (en) * | 2012-03-30 | 2013-10-03 | Segetis, Inc. | Reactive diluents, methods of reacting, and thermoset polymers derived therefrom |
| JP2013227457A (en) * | 2012-04-26 | 2013-11-07 | Hiroshima Univ | Ring-opening polymerization catalyst of cyclic ester and method for ring-opening polymerization of cyclic ester |
| WO2014075051A1 (en) * | 2012-11-12 | 2014-05-15 | Segetis, Inc. | Crosslinkable polyketal esters, methods of manufacture and uses thereof |
| CN105073826A (en) * | 2013-03-25 | 2015-11-18 | 赢创德固赛有限公司 | Lactone polymerization with latent initiators |
| CN106977708A (en) * | 2017-03-30 | 2017-07-25 | 南京工业大学 | A kind of cyclic compound ring-opening polymerization method |
Non-Patent Citations (2)
| Title |
|---|
| GARRET M.MIYAKE ET AL: ""Living Polymerization of Naturally Renewable Butyrolactone-Based Vinylidene Monomers by Amibiphilic Silicon Propagators"", 《MACROMOLECULES》 * |
| YUETAO ZHANG ET AL: ""Dinuclear Silylium-enolate Bifunctional Active Species：Remarkable Activity and Stereoselectivity toward Polymerization of Methacrylate and Renewable Methylene Butyrolactone Monomers"", 《JACS》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109503816A (en) * | 2018-10-29 | 2019-03-22 | 三明学院 | A kind of amphipathic ester type block polymer, preparation method and its usage |
| CN109503816B (en) * | 2018-10-29 | 2021-01-05 | 三明学院 | Amphiphilic polyester type block polymer, preparation method and application thereof |
| CN111499783A (en) * | 2020-05-29 | 2020-08-07 | 深圳市鑫元素新材料科技有限公司 | Preparation method of polyacrylate with extremely narrow molecular weight distribution |
| CN113896875A (en) * | 2021-10-11 | 2022-01-07 | 吉林大学 | Intramolecular trifunctional Lewis acid-base pair catalyst, annular topological structure PMMBL polymer, preparation method and application |
| CN113896875B (en) * | 2021-10-11 | 2022-05-31 | 吉林大学 | Intramolecular trifunctional Lewis acid-base pair catalyst, annular topological structure PMMBL polymer, preparation method and application |
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