CN114716610B - Thermosetting material capable of being chemically degraded and recycled and preparation method thereof - Google Patents

Thermosetting material capable of being chemically degraded and recycled and preparation method thereof Download PDF

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CN114716610B
CN114716610B CN202210556129.5A CN202210556129A CN114716610B CN 114716610 B CN114716610 B CN 114716610B CN 202210556129 A CN202210556129 A CN 202210556129A CN 114716610 B CN114716610 B CN 114716610B
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陈昶乐
司桂福
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University of Science and Technology of China USTC
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Abstract

The invention provides a thermosetting material capable of being chemically degraded and recycled and a preparation method thereof, wherein the thermosetting material capable of being chemically degraded and recycled has a structural general formula shown in a formula (I):
Figure DDA0003655012200000011
wherein X is selected from one or more of diene monomers or multiolefin monomers of ester groups, acid anhydrides, phosphine oxides, silicon ethers, amides and ethers.

Description

Thermosetting material capable of being chemically degraded and recycled and preparation method thereof
Technical Field
The invention relates to the technical field of high polymer material synthesis, in particular to a thermosetting material capable of being chemically degraded and recycled and a preparation method thereof.
Background
The thermosetting material is widely applied to various fields such as military use, civil use and the like due to the characteristics of high strength, durability and the like. With the increase of the use amount of the materials, the characteristics of insolubility and non-melting cause a large amount of solid wastes which are difficult to treat and recycle, and with the rapid increase of the use amount, the amount of the wastes is also rapidly increased, and the thermosetting materials cannot be reprocessed or reused because the permanently crosslinked structure after the crosslinked structure is formed generally does not change or break, and most of the thermosetting materials are treated by incineration or landfill and cause serious environmental problems, which also bring great burden to the natural environment.
Disclosure of Invention
Accordingly, the present invention is directed to a chemically degradable and recyclable thermosetting material and a method for preparing the same, which aims to at least partially solve one of the above-mentioned problems.
As one aspect of the present invention, there is provided a chemically degradable recycled thermosetting material having a general structural formula shown in formula (i):
Figure BDA0003655012180000011
wherein X is selected from one or more of diene monomers or multiolefin monomers of ester groups, acid anhydrides, phosphine oxides, silicon ethers, amides and ethers.
According to an embodiment of the invention, the diene monomer or multiolefin monomer comprises at least one of the following: carbonates, acrylates, pentenoates, butenanhydrides, phosphines, vinyl silyl ethers, pentenyl silyl ethers, acrylamides, spiro ethers, and propenes.
According to an embodiment of the present invention, the diolefin monomers of the silicone ethers comprise at least one of the following structural formulas:
Figure BDA0003655012180000021
according to the embodiment of the invention, a first compound with a structural formula (VI) is contacted with a second compound with a structural formula (VII) to react to obtain a structural formula (II) of a diolefin monomer of the silicone ether;
wherein, the liquid crystal display device comprises a liquid crystal display device,
Figure BDA0003655012180000022
according to the embodiment of the invention, the first compound with the structural formula (VI) is contacted with the third compound with the structural formula (VIII) to react to obtain the structural formula (III) of the diolefin monomer of the silicone ether;
wherein, the liquid crystal display device comprises a liquid crystal display device,
Figure BDA0003655012180000023
according to the embodiment of the invention, the first compound with the structural formula (VI) is contacted with the fourth compound with the structural formula (IX) to react to obtain the structural formula (IV) of the diolefin monomer of the silicone ether;
wherein, the liquid crystal display device comprises a liquid crystal display device,
Figure BDA0003655012180000024
according to the embodiment of the invention, the first compound with the structural formula (VI) is contacted with the fifth compound with the structural formula (X) to react to obtain the structural formula (V) of the diolefin monomer of the silicone ether;
wherein, the liquid crystal display device comprises a liquid crystal display device,
Figure BDA0003655012180000025
as another aspect of the present invention, there is also provided a method for preparing a chemically degradable recycled thermosetting material, comprising:
the dicyclopentadiene monomer is contacted with diene monomer or multiolefin monomer under the action of a second generation of grantab catalyst, and the thermosetting material which can be chemically degraded and recovered is obtained through reaction;
the thermosetting material capable of being chemically degraded and recovered has a structural general formula shown in a formula (I):
Figure BDA0003655012180000031
wherein X is selected from one or more of diene monomers or multiolefin monomers of ester groups, acid anhydrides, phosphine oxides, silicon ethers, amides and ethers.
According to an embodiment of the present invention, the molar ratio of dicyclopentadiene monomer to diene monomer or dicyclopentadiene monomer to multiolefin monomer comprises 10:1.
according to an embodiment of the invention, the temperature of the contact is 25-120 ℃.
Based on the technical scheme, the thermosetting material capable of being chemically degraded and recycled and the preparation method thereof have at least one or a part of the following beneficial effects compared with the prior art:
(1) The thermosetting material which is provided by the embodiment of the invention and has the structural general formula shown in the formula (I) and can be chemically degraded and recovered has stable mechanical properties;
(2) The fragment macromolecular compound obtained after degradation of the chemically degradable recycled thermosetting material with the structural general formula shown in the formula (I) provided by the embodiment of the invention can be subjected to double decomposition copolymerization thermosetting with dicyclopentadiene monomer again, and still can be used for preparing a thermosetting material with certain mechanical properties;
(3) The composite material prepared from the chemically degradable recycled thermosetting material with the structural general formula shown in the formula (I) and the carbon fiber material does not damage the surface structure after degradation.
Drawings
FIGS. 1 (a) and 1 (b) show a mold physical diagram of an embodiment of the present invention;
FIG. 2 (a) is a diagram showing the degradation process and recovery of a chemically degradable recovery thermosetting material according to an embodiment of the present invention;
FIG. 2 (b) shows a quantitative statistical plot of degradation process versus post recovery for chemically degradable recycled thermoset materials according to an embodiment of the present invention;
FIG. 3 (a) shows a nuclear magnetic resonance hydrogen spectrum of degradation recovery products of chemically degradable recovery thermoset materials of an embodiment of the present invention after degradation by tetrabutylammonium fluoride solution;
FIG. 3 (b) shows a nuclear magnetic resonance hydrogen spectrum of degradation recovery products of chemically degradable recovery thermoset materials of an embodiment of the present invention after degradation by potassium hydroxide solution;
FIG. 3 (c) shows a nuclear magnetic resonance hydrogen spectrum of degradation recovery products of a chemically degradable recovery thermosetting material according to an embodiment of the present invention after degradation by hydrochloric acid solution;
FIG. 4 (a) is a graph showing the "stress-strain" tensile curve of the material obtained by subjecting the degradation recovery product and dicyclopentadiene to metathesis copolymerization and thermosetting in example 4 of the present invention;
FIGS. 4 (b) to 4 (e) are graphs showing the "stress-strain" stretching curves of the chemically degradable and recyclable thermosetting materials prepared from the diene monomers and dicyclopentadiene monomers having the structural formulas of M1, M2, M3 and M4 in example 4 of the present invention;
fig. 4 (f) to fig. 4 (i) show "stress-strain" stretching graphs of chemically degradable and recyclable thermosetting materials prepared from diene monomers and dicyclopentadiene monomers of the silicone ethers with structural formulas of M7, M8, M9 and M10 in example 4 of the present invention, respectively;
FIG. 4 (j) is a graph showing the "stress-strain" tension of a chemically degradable recycled thermosetting material prepared from an ether-type diene monomer having the structural formula M11 and a dicyclopentadiene monomer in example 4 of the present invention;
FIG. 5 (a) is a graph showing the nuclear magnetic resonance hydrogen spectrum of a diolefin monomer of the silyl ether type having the structural formula M7 in example 4 of the present invention;
FIG. 5 (b) shows a nuclear magnetic resonance carbon spectrum of a diolefin monomer of a silyl ether having the structural formula M7 in example 4 of the present invention;
FIG. 6 (a) is a diagram showing the nuclear magnetic resonance hydrogen spectrum of a diolefin monomer having a structural formula M8 in example 4 of the present invention;
FIG. 6 (b) shows a nuclear magnetic resonance carbon spectrum of a diolefin monomer of a silyl ether having the structural formula M8 in example 4 of the present invention;
FIG. 7 shows the nuclear magnetic resonance hydrogen spectrum of a diolefin monomer having a structural formula M9 in example 4 of the present invention;
FIG. 8 (a) is a graph showing the nuclear magnetic resonance hydrogen spectrum of a diolefin monomer having a structural formula M10 in example 4 of the present invention;
FIG. 8 (b) is a chart showing the nuclear magnetic resonance carbon spectrum of a diolefin monomer having a structural formula M10 in example 4 of the present invention;
FIGS. 9 (a) to 9 (c) are graphs showing dynamic thermo-mechanical performance test of thermosetting materials prepared from diene monomers and dicyclopentadiene monomers, wherein the diene monomers and dicyclopentadiene monomers are respectively prepared from ester groups with structural formulas of M1, M5 and M6 in example 5;
FIG. 10 (a) is a diagram showing the degradation and recycling of a composite material prepared from a chemically degradable recycled thermosetting material according to example 6 of the present invention;
fig. 10 (b) shows raman spectrum test charts of the carbon fiber material recovered after degradation by three modes of organic degradation, acid degradation, and alkali degradation, respectively, in example 6 of the present invention.
Detailed Description
The present invention will be further described in detail below with reference to specific embodiments and with reference to the accompanying drawings, in order to make the objects, technical solutions and advantages of the present invention more apparent.
Research shows that for degradation and recovery of thermosetting materials, an octa-ring siloxane monomer and dicyclopentadiene (DCPD) monomer are subjected to double decomposition copolymerization and thermosetting to form a degradable and recoverable thermosetting material, but the synthesis difficulty of the monomer is high, and the method is not suitable for large-scale production.
Based on the method, the thermosetting material which can be chemically degraded and recovered is obtained by double decomposition copolymerization thermosetting of the simply prepared diene monomer and dicyclopentadiene monomer, the thermosetting material has stable mechanical property, and the segmented high molecular compound obtained after the thermosetting material is degraded is continuously subjected to double decomposition copolymerization thermosetting with the DCPD monomer again, so that the thermosetting material with certain mechanical property can be still prepared.
The following illustrates schematically a chemically degradable recycled thermoset material and a method of making the same. It should be noted that the examples are only specific embodiments of the present invention and are not intended to limit the scope of the present invention.
As one aspect of the present invention, there is provided a chemically degradable recycled thermosetting material having a general structural formula shown in formula (i):
Figure BDA0003655012180000051
wherein X is selected from one or more of diene monomers or multiolefin monomers of ester groups, acid anhydrides, phosphine oxides, silicon ethers, amides and ethers; a represents the number of polymer blocks in the crosslinked state; b represents the number of polymer blocks in the uncrosslinked state; c represents the amount of one or several diene monomers or multiolefin monomers; a. b and c are positive integers, and preferably, there may be a relationship of 0.5.ltoreq.c/(a+b). Ltoreq.2.
According to the embodiment of the invention, the chemically degradable and recyclable thermosetting material with the structural general formula shown in the formula (I) has stable mechanical properties, and the segmented high molecular compound obtained after degradation of the material can be subjected to double decomposition copolymerization thermosetting with dicyclopentadiene monomer again, so that the thermosetting material with certain mechanical properties can be prepared.
According to an embodiment of the invention, the diene monomer or multiolefin monomer comprises at least one of the following: carbonates, acrylates, pentenoates, butenanhydrides, phosphines, vinyl silyl ethers, pentenyl silyl ethers, acrylamides, spiro ethers, and propenes.
According to an embodiment of the present invention, the diolefin monomers of the silicone ethers may comprise at least one of the following structural formulas:
Figure BDA0003655012180000061
the structural formula of the diolefin monomer of the silicone ether can also comprise
Figure BDA0003655012180000062
According to embodiments of the present invention, the structural formula of the ester-based diene monomer may include at least one of:
Figure BDA0003655012180000063
Figure BDA0003655012180000064
according to an embodiment of the present invention, the structural formula of the diene monomer of the acid anhydride group may include:
Figure BDA0003655012180000065
according to embodiments of the present invention, the structural formula of the phosphane-type diene monomer may include:
Figure BDA0003655012180000066
according to an embodiment of the present invention, the structural formula of the diene monomer of the amide may include:
Figure BDA0003655012180000071
according to embodiments of the present invention, the structural formula of the ether-based diene monomer may include at least one of:
Figure BDA0003655012180000072
according to the embodiment of the invention, a first compound with a structural formula (VI) is contacted with a second compound with a structural formula (VII) to react to obtain a structural formula (II) of a diolefin monomer of the silicone ether;
wherein, the liquid crystal display device comprises a liquid crystal display device,
Figure BDA0003655012180000073
the contact temperature may be room temperature; the contact time may be 3 hours; the molar ratio of the first compound of the general structural formula (VI) to the second compound of the general structural formula (VII) may preferably be 2:1.
For example, the second compound with the structural formula (VII) and triethylamine are dissolved in tetrahydrofuran solvent at 0 ℃, then the first compound with the structural formula (VI) is added dropwise, and the mixture is reacted for 3 hours at room temperature, and then the mixture is distilled under reduced pressure to obtain the structural formula (II) of the diolefin monomer of the silicone ether.
According to the embodiment of the invention, the first compound with the structural formula (VI) is contacted with the third compound with the structural formula (VIII) to react to obtain the structural formula (III) of the diolefin monomer of the silicone ether;
wherein, the liquid crystal display device comprises a liquid crystal display device,
Figure BDA0003655012180000074
the contact temperature may be room temperature; the contact time may be 3 hours; the molar ratio of the first compound of formula (VI) to the third compound of formula (VIII) may preferably be 2:1.
According to the embodiment of the invention, the first compound with the structural formula (VI) is contacted with the fourth compound with the structural formula (IX) to react to obtain the structural formula (IV) of the diolefin monomer of the silicone ether;
wherein, the liquid crystal display device comprises a liquid crystal display device,
Figure BDA0003655012180000075
the contact temperature may be room temperature; the contact time may be 3 hours; the molar ratio of the first compound of formula (VI) to the fourth compound of formula (IX) may preferably be 2:1.
According to the embodiment of the invention, the first compound with the structural formula (VI) is contacted with the fifth compound with the structural formula (X) to react to obtain the structural formula (V) of the diolefin monomer of the silicone ether;
wherein, the liquid crystal display device comprises a liquid crystal display device,
Figure BDA0003655012180000081
the contact temperature may be room temperature; the contact time may be 3 hours; the molar ratio of the first compound of formula (VI) to the fifth compound of formula (X) may preferably be 2:1.
The specific methods of obtaining the structural formulae (iii), (iv) and (v) of the diene monomer of the silyl ether may be similar to the method of obtaining the structural formula (ii) of the diene monomer of the silyl ether, and will not be described here again.
Based on the thermosetting material capable of being chemically degraded and recycled, the invention also provides a preparation method of the thermosetting material capable of being chemically degraded and recycled, which comprises the following steps:
the dicyclopentadiene monomer is contacted with diene monomer or multiolefin monomer under the action of a second generation of grantab catalyst, and the thermosetting material which can be chemically degraded and recovered is obtained through reaction;
the thermosetting material capable of being chemically degraded and recovered has a structural general formula shown in a formula (I):
Figure BDA0003655012180000082
wherein X is selected from one or more of diene monomers or multiolefin monomers of ester groups, acid anhydrides, phosphine oxides, silicon ethers, amides and ethers.
According to embodiments of the present invention, the molar ratio of dicyclopentadiene monomer to diene monomer or dicyclopentadiene monomer to multiolefin monomer may include 10:1. the temperature of contact may be 25 to 120 ℃.
According to the embodiment of the invention, the second generation glatiramer catalyst (GII) can be dissolved in dichloromethane in a glass sample bottle, then the solvent is removed in vacuum, dicyclopentadiene and diene monomers are added, the mixture is uniformly mixed, poured into a mold, and cured for 30 minutes at room temperature, then the temperature is raised to 120 ℃, and the curing is continued for 2 hours. Cooling to room temperature to obtain the required thermosetting material.
The chemically degradable recycled thermoset and the method of making it are illustrated in detail by the following specific examples. It should be noted that the examples are only specific embodiments of the present invention and are not intended to limit the scope of the present invention.
Example 1 (method for preparing di (poly) olefin pentenyl silyl ether monomer):
Figure BDA0003655012180000091
compound B (20.0 mmol) and triethylamine (30.0 mmol) in the above chemical reaction formula are dissolved in 100mL of tetrahydrofuran solvent, the temperature is kept at 0 ℃, and then tetrahydrofuran solution (1 mol/L) of compound A (10.0 mmol) is slowly added dropwise; after the dripping is finished, the reaction is restored to room temperature and is continued for 3 hours; and filtering to remove triethylamine hydrochloride, concentrating the filtrate, and distilling under reduced pressure to obtain the target compound, namely the di (poly) olefin pentene silyl ether monomer corresponding to the chemical reaction formula.
Example 2 (preparation of chemically degradable recycled thermoset material):
Figure BDA0003655012180000092
in a glass sample bottle, the metathesis catalyst Grubbs second generation catalyst (GII) (0.008 mmol,6.8 mg) was dissolved in a small amount of dichloromethane and the solvent was removed in vacuo; dicyclopentadiene (40 mmol,5.3 g) and diene monomer (0.4 mmol) were added; after being mixed uniformly, the mixture is poured into a die shown in fig. 1a and 1b, and is cured for 30min at room temperature, then the temperature is raised to 120 ℃, and the curing is continued for 2h. Cooling to room temperature to obtain the required thermosetting material capable of being chemically degraded and recovered.
Example 3 (degradation and recovery of chemically degradable recovered thermoset material):
the material obtained by the preparation method of the chemically degradable recycled thermosetting material of the above example was put into a beaker, and a strong acid solution or a strong base solution or a tetrabutylammonium fluoride solution was added. After 12h, the material is degraded and dissolved in the solution, the solution is concentrated, methanol is added to precipitate the polymer, and the polymer is dried, so as to obtain degradation recovery products.
In fig. 2 (b), the abscissa indicates the content of the diene monomer of the silicone ether, and the ordinate indicates the ratio of the remaining solids to the initial solid mass. The chemically degradable recycled thermosets of fig. 2 (a) and 2 (b) were prepared using varying amounts of diene monomer of the silicone ethers and dicyclopentadiene monomer (DCPD).
As shown in fig. 2 (a) and 2 (b), when the content of the diolefin monomer of the silyl ether is 0.5%, 1% and 2%, degradation occurs after 12 hours of addition of the strong acid solution, the strong base solution or the tetrabutylammonium fluoride solution, and the degradation is more complete when the content of the diolefin monomer of the silyl ether is 2%.
As shown in fig. 3 (a) to 3 (c), the thermosetting materials prepared by different diene monomers with the content of 2% are respectively degraded by tetrabutylammonium fluoride solution, potassium hydroxide solution and hydrochloric acid solution for 12 hours to obtain degradation recovery products, the degradation recovery products are respectively dissolved by deuterated chloroform and then subjected to nuclear magnetic resonance hydrogen spectrum characterization, and the characterization results prove that the degradation is completed. Wherein the structural formula of the diene monomer comprises the following components:
Figure BDA0003655012180000101
specifically, as shown in fig. 3 (a), tetrabutylammonium fluoride solution can break the silicon oxide chemical bond in the thermosetting material to realize degradation. As shown in fig. 3 (b), the potassium hydroxide solution can break the oxygen-carbon chemical bond of the ester group in the thermosetting material, and degradation is achieved. As shown in fig. 3 (c), the hydrochloric acid solution can break the oxygen-carbon chemical bond of the ether in the thermosetting material, so as to realize degradation.
Example 4 (mechanical properties test of chemically degradable recycled thermoset):
the test pieces were dumbbell-shaped bars 28mm long by 3mm wide (narrowest) and 2.0mm thick according to standard test method ASTM 638. Strain experiments were performed at room temperature at a rate of 10 m/min. At least three specimens were tested for each sample.
(1) The mechanical property test is carried out on the material obtained by carrying out double decomposition copolymerization on the degradation recovery product and dicyclopentadiene monomer again, and as shown in fig. 4 (a), the material obtained by carrying out double decomposition copolymerization on the degradation recovery product and dicyclopentadiene monomer with the molar ratio of 2.5%, 5%, 10% and 20% is still a thermosetting material with certain mechanical property.
(2) The thermosetting materials which are prepared by the diene monomer and dicyclopentadiene monomer and can be recovered through chemical degradation and have the structural formulas of M1, M2, M3 and M4 are respectively subjected to mechanical property test, and as shown in fig. 4 (b) to 4 (e), the thermosetting materials have certain mechanical properties. Specifically, in FIG. 4 (b), DCPD was used as a control group, which had a tensile toughness (Tensile toughness) of 6.01MJ/M 3 Elongation at break (Strain at break) of 31.8%; thermosetting materials prepared from DCPD and M1 (0.5%) monomers have a tensile toughness of 6.98MJ/M 3 Elongation at break 33.1%; thermosetting materials prepared from DCPD and M1 (1.0%) monomers have a tensile toughness of 6.12MJ/M 3 Elongation at break of 30.3%; DCPD and method for producing the sameThe tensile toughness of the thermosetting material prepared by M1 (2.0%) monomer is 5.62MJ/M 3 The elongation at break was 31.8%. Compared with a control group, an experimental group of the thermosetting material prepared by DCPD and M1 monomers with different contents has similar tensile toughness and elongation at break, which shows that the thermosetting material has certain mechanical properties. In fig. 4 (c) to 4 (e), although the ester group-based diene monomer structure is different in the preparation of the thermosetting material, the ester group-based diene monomers having the structural formulae M2, M3, and M4 are used, respectively, they also have similar tensile toughness and elongation at break as compared with the control group, and also show that they have a certain mechanical property.
Wherein, M1, M2, M3 and M4 are respectively:
Figure BDA0003655012180000111
(3) The mechanical properties of the thermosetting materials which are prepared by the diolefin monomers and dicyclopentadiene monomers and can be chemically degraded and recycled and have the structural formulas of M7, M8, M9 and M10 are respectively tested, and the thermosetting materials have certain mechanical properties as shown in the figures 4 (f) to 4 (i). Specifically, in FIG. 4 (f), DCPD was used as a control group and had a tensile toughness of 6.01MJ/M 3 Elongation at break 31.8%; thermosetting materials prepared from DCPD and M1 (0.5%) monomers have a tensile toughness of 6.98MJ/M 3 Elongation at break 33.1%; thermosetting materials prepared from DCPD and M1 (1.0%) monomers have a tensile toughness of 6.12MJ/M 3 Elongation at break of 30.3%; thermosetting materials prepared from DCPD and M1 (2.0%) monomers have a tensile toughness of 5.62MJ/M 3 The elongation at break was 31.8%. Compared with a control group, an experimental group of the thermosetting material prepared by DCPD and M1 monomers with different contents has similar tensile toughness and elongation at break, which shows that the thermosetting material has certain mechanical properties.
Wherein, M7, M8, M9 and M10 are respectively:
Figure BDA0003655012180000112
(4) Mechanical property test is carried out on chemically degradable and recyclable thermosetting material prepared from ether diene monomer with structural formula of M11 and dicyclopentadiene monomer, as shown in fig. 4 (j), DCPD is also used as a control group, and the tensile toughness of the DCPD is 6.01MJ/M 3 Elongation at break 31.8%; thermosetting materials prepared from DCPD and M11 (0.5%) monomers have a tensile toughness of 5.81MJ/M 3 Elongation at break 31.2%; thermosetting materials prepared from DCPD and M11 (1.0%) monomers have a tensile toughness of 5.22MJ/M 3 Elongation at break 32.6%; thermosetting materials prepared from DCPD and M11 (2.0%) monomers have a tensile toughness of 4.44MJ/M 3 The elongation at break was 31.1%. Compared with a control group, an experimental group of the thermosetting material prepared by DCPD and M11 monomers with different contents has similar tensile toughness and elongation at break, which shows that the thermosetting material has certain mechanical properties.
Wherein M11 is:
Figure BDA0003655012180000121
the abscissa of fig. 4 (a) to 4 (j) represents strain; the ordinate indicates the pressure.
It should be noted that, the above-mentioned M7, M8, M9, and M10 may be obtained according to the preparation method in the embodiment of the present invention, which is not described herein. The nuclear magnetic resonance hydrogen spectrum of the diene monomer of the silyl ether having the structural formula M7 shown in fig. 5 (a) and the nuclear magnetic resonance carbon spectrum of the diene monomer of the silyl ether having the structural formula M7 shown in fig. 5 (b) both demonstrate successful production of the diene monomer of the silyl ether having the structural formula M7. The nuclear magnetic resonance hydrogen spectrum of the diene monomer of the silyl ether having the structural formula M8 shown in fig. 6 (a) and the nuclear magnetic resonance carbon spectrum of the diene monomer of the silyl ether having the structural formula M8 shown in fig. 6 (b) both demonstrate successful production of the diene monomer of the silyl ether having the structural formula M8. The nuclear magnetic resonance hydrogen spectrum of the diene monomer of the silyl ether of the formula M9 as shown in fig. 7 demonstrates the successful preparation of the diene monomer of the silyl ether of the formula M9. The nuclear magnetic resonance hydrogen spectrum of the diene monomer of the silyl ether type of the structural formula M10 shown in fig. 8 (a) and the nuclear magnetic resonance carbon spectrum of the diene monomer of the silyl ether type of the structural formula M10 shown in fig. 8 (b) both demonstrate successful production of the diene monomer of the silyl ether type of the structural formula M10.
Example 5 (dynamic thermo-mechanical property test of chemically degradable recycled thermoset):
DMA (dynamic thermo-mechanical analysis) is performed on Discovery DMA 850 system (TA). The measurements were recorded at a frequency of 1Hz and an amplitude of 10 μm, ranging from 50-225℃at a rate of 3℃for min -1 The data sampling interval was 3s/pt, using 125% force tracking and 0.01N pre-load.
The dynamic thermo-mechanical performance test is carried out on the thermosetting materials which are prepared by the diene monomers and dicyclopentadiene monomers and can be recovered through chemical degradation and have the structural formulas of M1, M5 and M6 respectively, as shown in the figure 9 (a), DCPD is used as a control group, and the storage modulus is 1286MPa; the storage modulus of the thermosetting material prepared by DCPD and M1 (0.5%) monomer is 1324MPa; the storage modulus of the thermosetting material prepared by DCPD and M1 (1.0%) monomer is 1252MPa; the storage modulus of the thermosetting material prepared by DCPD and M1 (2.0%) monomer is 1186MPa. As shown in fig. 9 (b), the same DCPD was used as a control group, and the storage modulus was 1286MPa; the storage modulus of the thermosetting material prepared by DCPD and M5 (0.5%) monomer is 1385MPa; the storage modulus of the thermosetting material prepared by DCPD and M5 (1.0%) monomer is 1181MPa; the storage modulus of the thermosetting material prepared by DCPD and M5 (2.0%) monomer is 1068MPa. As shown in fig. 9 (c), the same DCPD was used as a control group, and the storage modulus was 1286MPa; the storage modulus of the thermosetting material prepared by DCPD and M6 (0.5%) monomer is 1322MPa; the storage modulus of the thermosetting material prepared by DCPD and M6 (1.0%) monomer is 1167MPa; the storage modulus of the thermosetting material prepared by DCPD and M6 (2.0%) monomer is 985MPa. It can be demonstrated that after the preparation of the thermoset, dynamic thermo-mechanical properties are still present compared to DCPD.
The abscissa of fig. 9 (a) to 9 (c) represents the temperature; the ordinate indicates the storage modulus.
Example 6 (preparation of composite materials with chemically degradable recycled thermoset materials):
in a glass sample bottle, the metathesis catalyst Grubbs second generation catalyst (GII) (0.008 mmol,6.8 mg) was dissolved in a small amount of dichloromethane and the solvent was removed in vacuo; dicyclopentadiene (40 mmol,5.3 g) and diene monomer (0.4 mmol) were added, mixed well, poured into a mold where the carbon fiber material was placed in advance, cured at room temperature for 30min, then heated to 120 ℃ and cured for 2h. And cooling to room temperature to obtain the composite material.
As shown in fig. 10 (a), the composite material prepared by the above method was added with an organic degradation liquid, an acid degradation liquid, and an alkali degradation liquid, respectively, for 12 hours, and then the carbon fiber material was recovered.
The recovered carbon fiber material was subjected to raman spectroscopy, and as shown in fig. 10 (b), the surface structure of the recovered carbon fiber material was not destroyed after three degradation modes, i.e., organic degradation, acid degradation, and alkali degradation.
The foregoing description of the embodiments has been provided for the purpose of illustrating the general principles of the invention, and is not meant to limit the invention thereto, but to limit the invention thereto, and any modifications, equivalents, improvements and equivalents thereof may be made without departing from the spirit and principles of the invention.

Claims (5)

1. The thermosetting material capable of being chemically degraded and recovered is characterized by being obtained by double decomposition and copolymerization of a diene monomer or a multiolefin monomer and a dicyclopentadiene monomer, and the thermosetting material capable of being chemically degraded and recovered has a structural general formula shown in a formula (I):
Figure QLYQS_1
wherein X is derived from one or more of an ester group and an ether group of a diene monomer or a multiolefin monomer;
the structural formula of the ester-based diene monomer or the multiolefin monomer comprises at least one of the following components:
Figure QLYQS_2
the structural formula of the ether diene monomer comprises at least one of the following components:
Figure QLYQS_3
2. the chemically degradable recycled thermoset of claim 1, wherein the diene monomer or the multiolefin monomer comprises at least one of: carbonates, acrylates, pentenes, spiro ethers and propylene ethers.
3. A method of preparing a chemically degradable recycled thermoset according to claim 1 or 2, comprising:
the dicyclopentadiene monomer is contacted with the diene monomer or the multiolefin monomer under the action of a second generation of the grantab catalyst, and the thermosetting material which can be chemically degraded and recovered is obtained through reaction;
the thermosetting material capable of being chemically degraded and recycled has a structural general formula shown in a formula (I):
Figure QLYQS_4
wherein X is derived from the diene monomer or the multiolefin monomer of one or more of an ester group and an ether group.
4. A method of preparing a chemically degradable recycled thermoset according to claim 3 wherein the molar ratio of dicyclopentadiene monomer to diene monomer or dicyclopentadiene monomer to multiolefin monomer comprises 10:1.
5. a method of preparing a chemically degradable recycled thermoset according to claim 3 wherein the temperature of contact is from 25 to 120 ℃.
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