CN111548483B - Use of Salen manganese complexes in tandem catalytic reactions involving unsaturated anhydride-epoxy copolymers - Google Patents

Use of Salen manganese complexes in tandem catalytic reactions involving unsaturated anhydride-epoxy copolymers Download PDF

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CN111548483B
CN111548483B CN202010492724.8A CN202010492724A CN111548483B CN 111548483 B CN111548483 B CN 111548483B CN 202010492724 A CN202010492724 A CN 202010492724A CN 111548483 B CN111548483 B CN 111548483B
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陈昶乐
谭忱
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University of Science and Technology of China USTC
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    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
    • C08G65/2603—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen
    • C08G65/2615—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen the other compounds containing carboxylic acid, ester or anhydride groups
    • C—CHEMISTRY; METALLURGY
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    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
    • C08G65/2642—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds characterised by the catalyst used
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Abstract

The invention relates to the use of a Salen manganese complex as a tandem catalyst in a tandem catalytic reaction involving an unsaturated anhydride-epoxy copolymer, the tandem catalytic reaction comprising the synthesis, epoxidation modification and subsequent crosslinking curing or arylamination modification of the unsaturated anhydride-epoxy copolymer, wherein the Salen manganese complex is added in an amount of 5 to 20 wt.% relative to the unsaturated anhydride used only in the first step of synthesizing the copolymer by ring-opening copolymerization of the unsaturated anhydride and epoxide, and is used for the subsequent tandem reaction without separation during the entire tandem catalytic reaction. According to the invention, the Salen manganese complex is added at one time in a specific adding amount to serve as the series catalyst, so that the operation of series reaction is simplified, the utilization value of the catalyst is improved, and the performance and application of the unsaturated anhydride-epoxy copolymer are expanded.

Description

Use of Salen manganese complexes in tandem catalytic reactions involving unsaturated anhydride-epoxy copolymers
Technical Field
The invention relates to the field of tandem catalytic chemistry of polymer synthesis, polymer modification and polymer processing, in particular to application of a Salen manganese complex serving as a tandem catalyst in tandem catalytic reaction of unsaturated anhydride-epoxy copolymer.
Background
Aliphatic polyester is one of the most potential degradable high molecular materials and biomedical materials. Among them, the aliphatic anhydride/epoxy copolymer has the remarkable advantages that the monomer sources are rich and various, the polymer performance can be adjusted through different monomer combinations, and the like, and is widely concerned and researched in recent years. The anhydride/epoxy copolymer is mainly obtained by anhydride/epoxy copolymerization reaction catalyzed by metal complexes such as porphyrin metal complex, Salen metal complex and the like. The metal includes chromium, manganese, cobalt, aluminum, etc. Among them, r.duchateau, luxing et al reported Salen manganese catalyzed anhydride/epoxy copolymerization [ review article: longo, J.M., Sanford, M.J. & coats, G.W.Ring-polymerization of epoxides and cyclic amides with discrete components: structure-property relationships, chem.Rev.116, 15167-15197 (2016). The Salen manganese catalyst has the capability of catalyzing a variety of reactions, and is capable of catalyzing a variety of different reactions.
However, in the prior art, the Salen manganese catalyst is used only as a catalyst for the copolymerization reaction, and is separated from the polymer product after the polymerization is completed and discarded or recovered. Meanwhile, the structure of the acid anhydride/epoxy copolymer obtained by the Salen manganese catalyst has no obvious difference with the structure and the performance of the acid anhydride/epoxy copolymer obtained by catalysts with higher activity, such as Salen complexes of chromium, aluminum and cobalt. This leaves the Salen manganese catalyst lacking competitive advantages and also fails to exploit the value of Salen manganese as a catalyst capable of catalyzing a variety of reactions.
Disclosure of Invention
Based on the foregoing, it is an object of the present invention to provide the use of Salen manganese complexes as tandem catalysts in the synthesis, modification, crosslinking and/or reprocessing of unsaturated anhydride-epoxy copolymers in tandem reactions in which only Salen manganese complexes are used as tandem catalysts and which can be used directly in subsequent tandem reactions without separation.
To this end, the present invention provides the use of a Salen manganese complex as a tandem catalyst in a tandem catalytic reaction involving an unsaturated anhydride-epoxy copolymer, the tandem catalytic reaction comprising:
(a) the unsaturated anhydride of formula (I) is subjected to a ring-opening copolymerization with an epoxide of formula (II) to synthesize an anhydride-epoxy copolymer of formula (III)
Figure BDA0002520046910000021
(b) Epoxidizing the acid anhydride-epoxy copolymer of the formula (III) obtained in (a) to obtain an epoxidized modified product of the formula (IV) or the formula (V),
Figure BDA0002520046910000022
(c) subjecting the epoxidized modified product of formula (IV) or formula (V) obtained in (b) to crosslinking curing modification to obtain a thermosetting vitrimer material, or subjecting the epoxidized modified product of formula (IV) or formula (V) obtained in (b) to crosslinking curing modification using a compound of formula Ar-NH-R5By arylamination ofThe compound is subjected to arylamine modification to obtain an arylamine modified polymer of formula (VI) or formula (VII),
Figure BDA0002520046910000023
Figure BDA0002520046910000024
or
Figure BDA0002520046910000031
Wherein R is1、R3And R5Independently of one another are hydrogen, C1-C10Alkyl, halogen or halogeno C1-C10An alkyl group; r2Is C1-C10Alkylene or halogeno C1-C10An alkylene group; r4Is hydrogen, C1-C10Alkyl, halogen, halogeno C1-C10Alkyl radical, C1-C10Alkoxy, allyloxy C1-C10Alkyl, phenyl or halophenyl; ar is phenyl or halogenated phenyl, n is an integer of 10 to 1000, x is an integer of 0 to 1000, and n + x is not less than 10 and not more than 1000,
and wherein the tandem catalytic reaction is achieved only by adding the Salen manganese complex in an amount of 5 to 20 wt% with respect to the unsaturated acid anhydride of formula (I) in the ring-opening copolymerization reaction in (a), and the tandem catalyst is continuously used for the epoxidation modification in (b) and the crosslinking curing modification or arylamine modification in (c) without separation during the entire tandem catalytic reaction.
In a preferred embodiment, the tandem catalytic reaction further comprises reprocessing the thermoset Vitrimer material obtained in (c) for recycling.
In a preferred embodiment, the epoxidation modification in (b) is carried out using an aqueous hypochlorite solution and, if desired, solvent replacement.
In a preferred embodiment, the crosslinking curing modification in (c) is carried out using a cyclic acid anhydride-based compound as a curing agent, an epoxy-based compound as a diluent, and a polyol as an additive; preferably, the curing agent is maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, nadic anhydride, methyl nadic anhydride, pyromellitic anhydride, hexahydrobenzoic anhydride, tetrahydrophthalic anhydride, eleostearic anhydride, chlorendic anhydride, glutaric anhydride, or mixtures thereof, and the diluent is ethylene oxide, propylene oxide, C1-C10Alkyl-substituted oxiranes or C1-C10An alkyl-substituted propylene oxide, and the polyol is a diol.
In a preferred embodiment, the arylamine modification in (c) comprises: reacting the epoxidised modified product of formula (IV) obtained in (b) with an aromatic amine in an organic solvent at a temperature of from 0 to 50 ℃ in the presence of an optional silver salt as a promoter for a period of from 1 to 5 days.
In a preferred embodiment, the organic solvent is selected from the group consisting of methanol, ethanol, n-propanol, isopropanol, t-butanol, tetrahydrofuran, petroleum ether, toluene, benzene, dichloromethane, trichloroethylene, tetrachloromethane, diethyl ether, 1, 4-dioxane, 1, 2-dichloroethane or mixtures thereof.
In a preferred embodiment, the silver salt is selected from silver tetrafluoroborate, silver hexafluorophosphate, silver triflate, silver trifluoroacetate, silver hexafluoroantimonate, bis (trifluoromethylsulfonyl) imide, silver tetraphenylborate, silver tetrakis (3, 5-bis (trifluoromethyl) phenyl) borate, silver tetrakis (pentafluorophenyl) borate or mixtures thereof.
In a preferred embodiment, the Salen manganese complex has the following structure of formula (VIII) or (X):
Figure BDA0002520046910000041
wherein R is6Is C1-C10Alkylene or C6-C10An arylene group; preferably R6Is ethylene or 1,2-a phenylene group.
The method comprises the steps of applying a Salen manganese complex as a series catalyst to a series catalytic reaction involving an unsaturated anhydride-epoxy copolymer, wherein the series catalytic reaction comprises the synthesis, the epoxidation modification and the subsequent crosslinking curing or arylamine modification of the unsaturated anhydride-epoxy copolymer, the Salen manganese complex is added in an amount of 5-20 wt% relative to the used unsaturated anhydride only in a first step of synthesizing the copolymer by the ring-opening copolymerization reaction of the unsaturated anhydride and the epoxide, and the Salen manganese complex is continuously used for the subsequent series reaction without being separated in the whole series catalytic reaction process. According to the invention, the Salen manganese complex is added at one time in a specific adding amount to serve as the series catalyst, so that the whole operation process of the series reaction is simplified, the utilization value of the catalyst is improved, the performance and the application of the unsaturated anhydride-epoxy copolymer are expanded, the waste utilization and regeneration are completed, and the method has good environmental and economic advantages.
In addition, the invention also relates to a thermosetting Vitrimer material which is difficult to recycle and causes environmental pollution, for example, the thermosetting Vitrimer material can be recycled after being reprocessed after being damaged or broken by mechanical force, is processed and formed again after being processed and formed by hot pressing for 1h at the temperature of 190-230 ℃ and under the pressure of 10-250 MPa, becomes a new complete sample, and can recover the mechanical property by more than 70 percent, and has the properties of recycling and reprofiling.
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FIG. 1 shows a schematic diagram of a process for recycling and reprocessing a dumbbell polymer sample into a wafer-shaped sample after being pulverized according to an embodiment of the invention;
FIG. 2 shows a stress-strain plot (solid line) of a Virimer material sample synthesized according to one embodiment of the present invention and a stress-strain plot (dashed line) of a recycled material reprocessed;
fig. 3 shows a stress-strain plot (solid line) of a Vitrimer material sample synthesized according to one embodiment of the present invention and a stress-strain plot (dashed line) of a recycled material reprocessed.
Detailed Description
As a result of intensive and extensive studies, the inventors of the present invention have unexpectedly found that, in the synthesis of an anhydride-epoxy copolymer of formula (III) from an unsaturated acid anhydride of formula (I) and an epoxide of formula (II), when a Salen manganese complex (Mn-Salen complex) is used as a catalyst in an amount of 5 to 20% by weight relative to the unsaturated acid anhydride of formula (I), the Salen manganese complex can not only complete the ring-opening copolymerization reaction of the synthesis, but also such a catalyst can continue to catalyze, without separation, the subsequent epoxidation modification reaction, crosslinking curing reaction and/or arylamination modification reaction of the resulting anhydride-epoxy copolymer, and the reprocessing treatment of the resulting thermosetting vitemer material after crosslinking curing to recover the reaction for reuse.
The Mn-Salen complex has the function of a series catalyst in the whole series reaction process, which is specifically shown in the following steps: (1) catalyzing the ring-opening alternating copolymerization reaction of unsaturated anhydride and epoxide; (2) catalyzing the epoxidation modification reaction of the obtained anhydride-epoxy copolymer, wherein cheap hypochlorite such as sodium hypochlorite aqueous solution is used as an oxidant to obtain the completely or partially epoxidized modified anhydride-epoxy copolymer; (3) catalyzing the ring-opening amination reaction between aromatic amine and the epoxidized modified anhydride-epoxy copolymer to obtain an arylamine modified anhydride-epoxy copolymer; (4) catalyzing the crosslinking curing reaction of the epoxidized modified anhydride-epoxy copolymer, wherein the cyclic anhydride is used as a curing agent, and an epoxy compound is used as a diluent to obtain a thermosetting Vitrimer material; (5) the thermoset Vitrimer material obtained as described above (especially in the presence of hydroxyl groups) is subjected to a transesterification reaction to produce dynamic covalent bonds, thereby rendering the thermoset Vitrimer material recyclable, e.g., reprocessable.
According to the invention, the Salen manganese complex is added at one time in a specific adding amount to serve as the series catalyst, so that the operation of series reaction is simplified, the utilization value of the catalyst is improved, and the performance and application of the unsaturated anhydride-epoxy copolymer are expanded.
The invention provides the use of a Salen manganese complex as a tandem catalyst in a tandem catalytic reaction involving an unsaturated anhydride-epoxy copolymer, the tandem catalytic reaction comprising:
(a) the unsaturated anhydride of formula (I) is subjected to a ring-opening copolymerization with an epoxide of formula (II) to synthesize an anhydride-epoxy copolymer of formula (III)
Figure BDA0002520046910000061
(b) Epoxidizing the acid anhydride-epoxy copolymer of the formula (III) obtained in (a) to obtain an epoxidized modified product of the formula (IV) or the formula (V),
Figure BDA0002520046910000062
(c) subjecting the epoxidized modified product of formula (IV) or formula (V) obtained in (b) to crosslinking curing modification to obtain a thermosetting vitrimer material, or subjecting the epoxidized modified product of formula (IV) or formula (V) obtained in (b) to crosslinking curing modification using a compound of formula Ar-NH-R5Is subjected to arylamine modification to obtain an arylamine-modified polymer of formula (VI) or formula (VII),
Figure BDA0002520046910000071
Figure BDA0002520046910000072
or
Figure BDA0002520046910000073
Wherein R is1、R3And R5Independently of one another are hydrogen, C1-C10Alkyl, halogen or halogeno C1-C10An alkyl group; r2Is C1-C10Alkylene or halogeno C1-C10An alkylene group; r4 is hydrogen, C1-C10Alkyl, halogen, halogeno C1-C10Alkyl radical, C1-C10Alkoxy, allyloxy C1-C10Alkyl, phenyl or halophenyl; ar is phenyl or halogenated phenyl, n is an integer of 10-1000, x is an integer of 0-1000, and n + x is not less than 10 and not more than 1000.
In the application of the invention, the series catalytic reaction is realized only by adding the Salen manganese complex in an amount of 5-20 wt% relative to the unsaturated anhydride of the formula (I) in the ring-opening copolymerization reaction in the step (a), and the series catalyst is continuously used for epoxidation modification in the step (b) and crosslinking curing modification or arylamine modification in the step (c) without separation in the whole series catalytic reaction process.
In the present invention, C1-C10Examples of alkyl groups include, but are not limited to, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, or isomeric forms thereof.
In the present invention, examples of halogen are fluorine, chlorine, bromine or iodine.
In the present invention, a halogen atom is C1-C10Alkyl refers to the above alkyl substituted with one or more halogens.
In the present invention, C1-C10Examples of alkylene groups include, but are not limited to, ethylene, isopropyl, butylene, pentylene, hexylene, and the like, or isomeric forms thereof.
In the present invention, a halogen atom is C1-C10Alkylene refers to alkylene groups as described above substituted with one or more halogens.
In the present invention, C1-C10Examples of alkoxy groups include, but are not limited to, methoxy, ethoxy, propoxy, butoxy, and the like, or isomeric forms thereof.
In the present invention, allyloxy group C1-C10Examples of alkyl groups include, but are not limited to, allyloxymethyl, allyloxyethyl, and the like.
In the present invention, n and x each represent a degree of polymerization. It is noted that, in the above-mentioned formula (V) or (VII), for example, since the partially epoxidized modified product is a random copolymer, in the art, the random copolymer is generally characterized in terms of the number-average molecular weight (Mn) or weight-average molecular weight (Mw) of the obtained random copolymer and the molecular weight distribution (Mw/Mn) thereof without providing specific values of n and x.
Examples of unsaturated anhydrides of formula (I) that may be used in the present invention include, but are not limited to, the following formula (Ia)
Figure BDA0002520046910000081
Or formula (Ib)
Figure BDA0002520046910000082
(wherein1Pr represents isopropyl group and Me represents methyl group).
Examples of epoxides of formula (II) that may be used in the present invention include, but are not limited to, the following formula (IIa)
Figure BDA0002520046910000083
Formula (IIb)
Figure BDA0002520046910000084
Formula (IIc)
Figure BDA0002520046910000085
Formula (IId)
Figure BDA0002520046910000086
Or formula (IIe)
Figure BDA0002520046910000087
(wherein Ph represents a phenyl group).
In the present invention, preferably, the tandem catalytic reaction further comprises reprocessing the thermosetting Vitrimer material obtained in (c) for recycling.
In the present invention, it is preferable that the epoxidation modification in (b) is carried out using an aqueous hypochlorite such as sodium hypochlorite solution, and if necessary, solvent replacement is carried out.
In the present invention, it is preferable to use a cyclic acid anhydride compound as the curing agent and an epoxy compoundThe compound is used as a diluent and a polyol is used as an additive to perform crosslinking curing modification in (c). More preferably, the curing agent is maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, nadic anhydride, methyl nadic anhydride, pyromellitic anhydride, hexahydrobenzoic anhydride, tetrahydrophthalic anhydride, elaeostearic anhydride, chlorendic anhydride, glutaric anhydride or mixtures thereof, and the diluent is ethylene oxide, propylene oxide, C1-C10Alkyl-substituted oxiranes or C1-C10An alkyl-substituted propylene oxide, and the polyol is a diol.
In the present invention, preferably, the arylamine modification in (c) includes: reacting the epoxidation-modified product of formula (IV) obtained in (b) with an aromatic amine in an organic solvent at a temperature of from 0 to 50 ℃, e.g. 30 ℃, optionally in the presence of a silver salt as a promoter for 1 to 5 days, e.g. 3 days.
In the present invention, preferably, the organic solvent used in the arylamine modification process may be selected from methanol, ethanol, n-propanol, isopropanol, t-butanol, tetrahydrofuran, petroleum ether, toluene, benzene, dichloromethane, trichloroethylene, tetrachloromethane, diethyl ether, 1, 4-dioxane, 1, 2-dichloroethane, or a mixture thereof.
In the present invention, preferably, the silver salt used in the arylamine modification process may be selected from silver tetrafluoroborate, silver hexafluorophosphate, silver trifluoromethanesulfonate (AgOTf), silver trifluoroacetate, silver hexafluoroantimonate, bis (trifluoromethylsulfonyl) imide, silver tetraphenylborate, silver tetrakis (3, 5-bis (trifluoromethyl) phenyl) borate, silver tetrakis (pentafluorophenyl) borate or a mixture thereof.
In the present invention, preferably, the Salen manganese complex used has a structure of the following formula (VIII) or (X):
Figure BDA0002520046910000091
wherein R is6Is C1-C10Alkylene or C6-C10An arylene group; preferably R6Is ethylene or 12-phenylene. Further, tBu in the formula (VII) or (X) represents a tert-butyl group.
The following examples illustrate the details of the invention and give data including reaction process parameters, mechanical properties of the resulting polymers, etc. All the raw materials were purchased and used as they were unless otherwise specified.
The nuclear magnetism detection is carried out by a Bruker 400MHz nuclear magnetism instrument. Molecular weight and molecular weight distribution were determined by GPC. The crosslinking curing reaction is carried out in a constant temperature oven. Silicone grease was used as the release agent. The mechanical properties of the polymers were determined by means of a universal test tensile machine. And (4) reprocessing after recycling based on the vitrier material principle, and implementing hot press molding through a vacuum film pressing machine.
Synthesis examples S1-S9: ring-opening copolymerization of unsaturated acid anhydride and epoxide to synthesize target anhydride-epoxy copolymer
In a 100mL round bottom flask, as indicated in Table 1 below, the monomer of formula (I) (i.e., 14 grams of formula (Ia) or 20 grams of (Ib) was mixed with the monomer of formula (II) (i.e., one of formulae (IIa) to (IIe)) in 50mL Tetrahydrofuran (THF), and based on the monomer of formula (I), Salen manganese complex was added as the tandem catalyst and 0.01 equivalent of p-Dimethylaminopyridine (DMAP) initiator in an amount of 0.1 equivalents the mixture was stirred at the indicated reaction temperature for 24 hours all volatiles (THF and excess epoxide) were removed under vacuum at 60 ℃ the crude product was used directly in the subsequent epoxidation reaction.
The structure of the monomer/catalyst, the specific conditions of the reaction, and the reaction results are as follows:
Figure BDA0002520046910000101
TABLE 1A Mn-Salen catalyzed Ring opening metathesis polymerization of unsaturated cyclic anhydrides and epoxidesa
Figure BDA0002520046910000111
aThe overall reaction conditions were: quality of foodQuantitative ratio of [ acid anhydride ]]/[ epoxide)]/[ catalyst)]/[ Paradimethylaminopyridine ]]100/300/10/1; the epoxide is 5mol/L tetrahydrofuran solution, the reaction temperature is 70 ℃, and the reaction time is 24 hours.
bBy passing1Conversion of cyclic anhydride (conv.) determined by H NMR.
cNumber average molecular weight M determined by GPC analysis in THF at room temperature using polystyrene standardsnAnd molecular weight distribution Mw/Mn。
dPolymerization Using anhydride monomer of formula Ia CaH2And (5) drying.
eDifferent reaction conditions are as follows: mass ratio of [ acid anhydride ]]/[ epoxide)]/[ catalyst)]/[ Paradimethylaminopyridine ]]100/300/10/1; the epoxide is 5mol/L tetrahydrofuran solution, 70 ℃ and 24 hours.
fDifferent reaction conditions are as follows: mass ratio of [ acid anhydride ]]/[ epoxide)]/[ catalyst)]/[ Paradimethylaminopyridine ]]100/300/10/1; the epoxide is a 3mol/L tetrahydrofuran solution at 70 ℃ for 24 h.
gDifferent reaction conditions are as follows: mass ratio of [ acid anhydride ]]/[ epoxide)]/[ catalyst)]/[ Paradimethylaminopyridine ]]100/150/10/1; the epoxide is 5mol/L tetrahydrofuran solution, 100 ℃, 24 h.
Epoxidation modified examples H1-H12: epoxidation modification of anhydride-epoxy copolymers
For the acid anhydride-epoxy copolymer obtained in the above synthetic example, the solvent in the flask was replaced with methylene Chloride (CH) without performing catalyst separation2Cl2) To dissolve in dichloromethane, and then add a mixed aqueous solution of sodium hypochlorite (0.55mol/L, 5.0 equivalents) and disodium hydrogen phosphate (0.05mol/L) at 4 ℃. As shown in table 2 below, after vigorously stirring at room temperature for a given time, the mixture was allowed to stand for at least 2 hours, and then separated to remove the aqueous phase. The organic phase was dried over anhydrous sodium sulfate. The solvent is then removed under vacuum to yield the epoxy-modified unsaturated anhydride/epoxy copolymer.
The specific conditions and the reaction results are shown in the following table 2:
table 2: epoxidation modification of anhydride-epoxy copolymersa
Figure BDA0002520046910000121
aThe overall reaction conditions were: the copolymer obtained in example S1 of Table 1, which was 50g/L CH, was used2Cl2Solution, NaClO5.0 equiv, NaClO 0.55mol/L aqueous solution, Na2HPO4Is 0.05mol/L aqueous solution at 25 ℃.
bBy passing1Conversion of C ═ C bond (conv.) determined by H NMR.
cNumber average molecular weight M determined by GPC analysis in THF at room temperature using polystyrene standardsnAnd molecular weight distribution Mw/Mn。
dThe copolymer obtained in example S2 of Table 1 was used.
eThe copolymer obtained in example S3 of Table 1 was used.
fThe copolymer obtained in example S4 of Table 1 was used.
gUsing THF instead of CH2Cl2。
hThe copolymer obtained in example S5 of Table 1 was used.
iThe copolymer obtained in example S6 of Table 1 was used.
jThe copolymer obtained in example S7 of Table 1 was used.
kThe copolymer obtained in example S8 of Table 1 was used.
1The copolymer obtained in example S9 of Table 1 was used.
The partial structures of the completely or partially modified products EP1 to EP6 obtained are shown below:
Figure BDA0002520046910000131
wherein conv represents the conversion.
Arylamine modification examples F1 to F3: arylamine modification of epoxidized modification products
Without catalyst separation, the epoxidized modified copolymer EP2 obtained in the above epoxidized modified example was dissolved in methylene chloride in a flask so that the copolymer concentration was 500mg/mL, silver trifluoromethanesulfonate (0.1 equivalent) was added thereto as a co-catalyst, and aniline, N-methylaniline or 2-methyl-4-methoxyaniline (each 2.0 equivalents) were added, respectively, and then the reaction mixture was stirred at room temperature for 3 days. After the reaction is finished, petroleum ether is added to precipitate the obtained arylamine modified polymer, so that an arylamine modified product can be separated. Conversion rate was1H NMR determined about 95%.
The structures of the obtained arylamine modified polymers A1-A3 are shown in the following figures:
Figure BDA0002520046910000132
crosslinking curing example J1: the epoxy modified product is crosslinked and cured to obtain the thermosetting Vivitrimer material
In the absence of catalyst isolation, the epoxidized modified copolymer EP2 obtained in the above epoxidation modified example was taken in an amount of 1.5 g in a flask, and bisphenol A diglycidyl ether 8.5 g and glutaric anhydride 5.7 g were added and completely dissolved in acetone. The acetone was then removed by rotary evaporation at room temperature. The resulting viscous mixture was dried under vacuum at room temperature for 24 hours, then transferred to a teflon mold and cured in a constant temperature oven at 100 ℃/2h +150 ℃/2h +170 ℃/2h +190 ℃/1 h. Silicone grease was used as the release agent. After curing, the mixture was cooled to room temperature and the sample was removed to obtain the desired thermoset Vitrimer material.
Reprocessing recovery example Z1: the thermoset Vitrimer material is reprocessed into recyclable material
Samples of the thermoset Vitrimer material obtained by crosslinking only and curing as described above to be recovered were heated to 150 ℃ and ground into a powder. After cooling to room temperature, the obtained powder material is poured into a stainless steel mold to be heated and pressurized (temperature: 200 ℃, pressure: 200MPa, time: 1h) for hot-pressing reprocessing, and silicone grease is used as a mold release agent. After cooling to room temperature, the recovered material sample was taken out for mechanical property measurement.
According to this embodiment, a schematic diagram of the process of pulverizing the recycled material sample and then processing it into a wafer-shaped sample is shown in fig. 1.
The stress-strain curves (solid line) of the Vitrimer material samples synthesized according to the invention (formulation: molar ratio EP2/DGEBA/GA/TEG 1/2/2.5/0.5, liquid mixture obtained by mechanical stirring) and of the recycled material obtained after reprocessing (dashed line) are shown in fig. 2; and the stress-strain curves (solid line) of the Vitrimer material samples synthesized according to the present invention (formulation: molar ratio EP2/DGEBA/GA/TEG 1/2/2.5/0.25, liquid mixture obtained by mechanical stirring) and the recovered material obtained after reprocessing (dotted line) are shown in fig. 3, wherein EP2 is the epoxidized modified product obtained in the epoxy modified example, DGEBA means bisphenol a diglycidyl ether, GA means glutaric anhydride, and TEG means tetraethylene glycol.
From the results shown in fig. 2 and 3, it can be seen that the synthetic thermosetting vitrimer material of the present invention is a resin material which can be recycled after being reprocessed, and has a good mechanical strength after being reprocessed and recycled.
The above embodiments are only intended to aid understanding of the method of the present invention and its core concept. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention.

Claims (10)

  1. Use of a Salen manganese complex as a tandem catalyst in a tandem catalytic reaction involving an unsaturated anhydride-epoxy copolymer, said tandem catalytic reaction comprising:
    (a) the unsaturated anhydride of formula (I) is subjected to a ring-opening copolymerization with an epoxide of formula (II) to synthesize an anhydride-epoxy copolymer of formula (III)
    Figure FDA0003080258360000011
    (b) Epoxidizing the acid anhydride-epoxy copolymer of the formula (III) obtained in (a) to obtain an epoxidized modified product of the formula (IV) or the formula (V),
    Figure FDA0003080258360000012
    (c) subjecting the epoxidized modified product of formula (IV) or formula (V) obtained in (b) to crosslinking curing modification to obtain a thermosetting vitrimer material, or subjecting the epoxidized modified product of formula (IV) or formula (V) obtained in (b) to crosslinking curing modification using a compound of formula Ar-NH-R5Is subjected to arylamine modification to obtain an arylamine-modified polymer of formula (VI) or formula (VII),
    Figure FDA0003080258360000013
    → thermosetting vitomer material, or
    Figure FDA0003080258360000021
    Wherein R is1、R3And R5Independently of one another are hydrogen, C1-C10Alkyl, halogen or halogeno C1-C10An alkyl group; r2Is C1-C10Alkylene or halogeno C1-C10An alkylene group; r4Is hydrogen, C1-C10Alkyl, halogen, halogeno C1-C10Alkyl radical, C1-C10Alkoxy, allyloxy C1-C10Alkyl, phenyl or halophenyl; ar is phenyl or halogenated phenyl, n is an integer of 10 to 1000, x is an integer of 0 to 1000, and n + x is not less than 10 and not more than 1000,
    wherein the tandem catalytic reaction is realized by adding 5-20 wt% of Salen manganese complex relative to the unsaturated acid anhydride of the formula (I) in the ring-opening copolymerization reaction of the (a), and the tandem catalyst is continuously used for the epoxidation modification of the (b) and the crosslinking curing modification or arylamine modification of the (c) without separation in the whole tandem catalytic reaction process,
    and wherein the Salen manganese complex has the structure of formula (VIII):
    Figure FDA0003080258360000022
    wherein R is6Is C1-C10Alkylene or C6-C10An arylene group.
  2. 2. The use of claim 1, wherein the tandem catalytic reaction further comprises reprocessing the thermoset Vitrimer material obtained in (c) for recycling.
  3. 3. Use according to claim 1, characterized in that the epoxidation modification in (b) is carried out using an aqueous hypochlorite solution and, if desired, solvent replacement.
  4. 4. The use according to claim 1, characterized in that the crosslinking curing modification in (c) is carried out using a cyclic acid anhydride-based compound as a curing agent, an epoxy-based compound as a diluent and a polyol as an additive.
  5. 5. Use according to claim 4, wherein the curing agent is maleic anhydride, succinic anhydride, itaconic anhydrideAnhydride, phthalic anhydride, nadic anhydride, methylnadic anhydride, pyromellitic anhydride, hexahydrobenzoic anhydride, tetrahydrophthalic anhydride, elaeostearic anhydride, chlorendic anhydride, glutaric anhydride or mixtures thereof, the diluent being ethylene oxide, propylene oxide, C1-C10Alkyl-substituted oxiranes or C1-C10An alkyl-substituted propylene oxide, and the polyol is a diol.
  6. 6. Use according to claim 1, wherein the arylamine modification in (c) comprises: reacting the epoxidised modified product of formula (IV) obtained in (b) with a compound of formula Ar-NH-R in an organic solvent at a temperature of from 0 to 50 ℃ in the presence of an optional silver salt as a promoter5For 1 to 5 days.
  7. 7. Use according to claim 6, wherein the organic solvent is selected from methanol, ethanol, n-propanol, isopropanol, tert-butanol, tetrahydrofuran, petroleum ether, toluene, benzene, dichloromethane, trichloroethylene, tetrachloromethane, diethyl ether, 1, 4-dioxane, 1, 2-dichloroethane or mixtures thereof.
  8. 8. Use according to claim 6, wherein the silver salt is selected from silver tetrafluoroborate, silver hexafluorophosphate, silver trifluoromethanesulfonate, silver trifluoroacetate, silver hexafluoroantimonate, bis (trifluoromethylsulfonyl) imide, silver tetraphenylborate, silver tetrakis (3, 5-bis (trifluoromethyl) phenyl) borate, silver tetrakis (pentafluorophenyl) borate or a mixture thereof.
  9. 9. Use according to claim 1, wherein R is6Is ethylene or 1, 2-phenylene.
  10. 10. Use according to claim 1, wherein the Salen manganese complex has the following structure of formula (X):
    Figure FDA0003080258360000031
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