CN113372479A - Cross-linked acetoacetoxy ethyl methacrylate copolymer prepared by utilizing functionalized amide dynamic covalent bond and preparation method thereof - Google Patents
Cross-linked acetoacetoxy ethyl methacrylate copolymer prepared by utilizing functionalized amide dynamic covalent bond and preparation method thereof Download PDFInfo
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Abstract
The invention provides a cross-linked acetoacetoxy ethyl methacrylate copolymer prepared by utilizing a functionalized amide dynamic covalent bond and a preparation method thereof, wherein a free radical copolymer of an AAEM copolymer and other comonomers is prepared firstly; then carrying out condensation reaction with a monoamine compound containing a target group to obtain a copolymer with the functionalized target group; and finally, the copolymer functionalized by the target group and polyisocyanate undergo addition reaction to form a cross-linked network structure, and the cross-linking point of the cross-linked network structure is a dynamic covalent bond of the functionalized amide. Compared with the prior art, the invention has wide selectable range of the comonomer and the monoamine compound of the AAEM, and is beneficial to regulating and controlling the performance of the cross-linked copolymer; the amide dynamic covalent bond can be functionalized by a monoamine compound containing a target group, so that the performance of the same copolymer matrix can be regulated and controlled in a very simple manner; the cross-linked copolymer can be reprocessed without a catalyst, and the material after repeated reprocessing has good performance.
Description
Technical Field
The invention belongs to the technical field of functional materials, and particularly relates to a cross-linked acetoacetoxy ethyl methacrylate copolymer prepared by utilizing a functionalized amide dynamic covalent bond and a preparation method thereof.
Background
Polymeric materials can be broadly classified into two categories according to thermal behavior: thermoplastic materials and thermoset materials. The thermoplastic material is formed by random entanglement of linear or branched polymer chains, and no chemical covalent bond interaction exists between the polymer chains, so that the thermoplastic polymer material can flow at a certain temperature through diffusion of the polymer chains, and the polymer chains are frozen again after cooling to fix the shape, and the process is reversible and can be carried out repeatedly. If side reactions such as degradation, oxidation and the like are not considered, the thermoplastic material can be recycled and reused for unlimited times in processing modes such as hot pressing, injection molding and the like theoretically. However, thermoplastic materials have poor creep resistance and solvent resistance, and thermosetting materials have been developed and used for these drawbacks. Thermoset materials differ from thermoplastic materials primarily in the presence of chemical covalent interactions between their macromolecular chains, which are usually present in the form of cross-links in the covalently cross-linked network structure of the thermoset material. The covalently cross-linked network structure will limit or prevent the diffusion of molecular chains to some extent, so that the thermoset material cannot be dissolved in common chemical solvents, nor melt to flow at high temperatures as does the thermoplastic material.
Although the insoluble and infusible characteristics of the thermosetting material make the thermosetting material popular in the application with the requirements of solvent resistance, creep resistance and the like, a plurality of challenges exist in recycling, which not only causes economic resource waste, but also brings great burden to the environment.
Disclosure of Invention
The invention aims to provide a cross-linked acetoacetoxy ethyl methacrylate copolymer prepared by utilizing a functionalized amide dynamic covalent bond and a preparation method thereof. The method for preparing the cross-linked acetoacetoxy ethyl methacrylate copolymer which can be reprocessed by using the functionalized amide dynamic covalent bond to replace the traditional covalent bond as a cross-linking point realizes the recycling of the thermosetting material. The preparation method is simple, and the prepared cross-linked copolymer has solvent resistance and creep resistance which are not different from those of the traditional thermosetting material under the use condition, but can reconstruct a cross-linked network by activating the functionalized amide dynamic covalent bond under a certain temperature condition, thereby realizing the recycling of the cross-linked copolymer.
The specific technical scheme of the invention is as follows:
a method of preparing a crosslinked acetoacetoxy ethyl methacrylate copolymer using functionalized amide dynamic covalent bonds comprising the steps of:
1) preparing acetoacetoxy ethyl methacrylate free radical copolymer;
2) reacting the acetoacetyl ethyl methacrylate free radical copolymer with a monoamine compound containing a target group to obtain a target group functionalized copolymer;
3) and reacting the target group functionalized copolymer with polyisocyanate to obtain the modified polyurethane.
In step 1), a radical copolymer of acetoacetoxyethyl methacrylate (hereinafter, referred to as AAEM) and other comonomers, which are alpha-olefin monomers capable of radical copolymerization, is prepared.
In the step 1), the molar percentage of the acetoacetoxy ethyl methacrylate in the total amount of the acetoacetoxy ethyl methacrylate and other comonomers is 10-90%, an initiator used for reaction is one of azo or organic peroxide, a solvent used for reaction is one of aromatic hydrocarbon, halogenated hydrocarbon, ester or diketone derivative, the reaction temperature is 50-70 ℃, the reaction time is 2-4 hours, and the next step can be carried out without treatment after the reaction is finished;
in the step 1), the initiator accounts for 1 to 10 percent of the total amount of the acetoacetoxy ethyl methacrylate and other comonomers; in the reaction of the step 1), the concentration of the total amount of acetoacetoxy ethyl methacrylate and other comonomers is 1-5 mol/L;
the other comonomer is selected from one or more of styrene, vinyl chloride, acrylonitrile, acrylic acid and alpha-olefin monomers capable of undergoing free radical copolymerization.
The acetoacetoxy ethyl methacrylate free radical copolymer in the step 2) is a solution which is not treated after the reaction in the step 1) is finished;
the step 2) is specifically as follows: adding a monoamine compound containing a target group into the system after the reaction in the step 1), and then carrying out condensation reaction on an acetoacetic acid group in the copolymer and an amino group of the monoamine compound containing the target group, wherein the feeding molar ratio of the monoamine compound to AAEM used for the reaction in the step 1) is 1: 1, the reaction temperature is 50-70 ℃, the reaction time is 4-8 h, after the reaction is finished, precipitation and washing are carried out in a poor solvent, and the precipitate is dried in vacuum at 60 ℃ to constant weight, so that the target group functionalized copolymer is obtained.
In step 2), the monoamine compound must contain only one reactive primary amine and no other active hydrogen capable of reacting with isocyanate groups.
The target groups in the step 2) refer to one or more of n-butyl, n-octyl, octadecyl, benzyl, acetyl, imidazolyl, furyl, adamantyl and anthracenyl, and after the target groups are introduced into the copolymer, the interchain interaction can be changed through a supermolecule action or a reversible covalent bond form, so that the final performance of the copolymer can be regulated and controlled, such as hydrogen bond interaction between acetyl groups, metal coordination between imidazolyl and zinc ions, Diels-Alder reaction between furyl and maleimide and dimerization reaction of anthracenyl, and the interactions can be complemented by the target groups themselves or other complexes.
The monoamine compound containing the target group in the step 2) can be one or more of N-butylamine, N-octylamine, octadecylamine, benzylamine, N-acetylethylenediamine, 1- (3-aminopropyl) imidazole, 2-furanmethylamine, 1-amantadine and 9-anthracenylethylamine.
When the target group in the step 2) is imidazolyl, the complex in the step 3) is selected to be zinc ions; the metal coordination of the imidazolyl and zinc ions further improves the crosslinking effect and achieves the double crosslinking effect;
when the target group in the step 2) is furyl, the complex in the step 3) is maleimide; the Diels-Alder reaction of furyl and maleimide can achieve the double cross-linking effect;
in the step 3), the copolymer functionalized by the target group and polyisocyanate or the copolymer functionalized by the target group, the polyisocyanate and the complex are uniformly mixed in a solvent, the mixture is poured into a mold and then is kept stand in a blast oven at the temperature of 60-100 ℃ until the solvent is completely volatilized, and finally a cross-linked network structure is formed, wherein the cross-linking point of the cross-linked network structure is a functionalized amide dynamic covalent bond.
In the step 3), the concentration of the target group functionalized copolymer is 0.05-0.2 g/mL;
the solvent used in the step 3) is one of aromatic hydrocarbon, halogenated hydrocarbon, ester and diketone derivative;
in the step 3), the polyisocyanate is a compound containing more than two isocyanate groups;
in the step 3), the polyisocyanate is any one of diphenylmethane diisocyanate (MDI), Toluene Diisocyanate (TDI) or isophorone diisocyanate (IPDI) containing more than two isocyanate groups.
The invention provides a cross-linked acetoacetoxy ethyl methacrylate copolymer prepared by utilizing a functionalized amide dynamic covalent bond, which is prepared by adopting the method. The chemical crosslinking points of the crosslinked copolymer are functionalized amide dynamic covalent bonds.
The cross-linked acetoacetoxy ethyl methacrylate copolymer prepared by the method has the characteristic of reprocessing, particularly, the cross-linked copolymer can be remolded by a flat vulcanizing machine after being crushed, and has certain service performance. In addition, the cross-linked copolymer can be endowed with different target groups only by changing the monoamine compound in the preparation process, the mechanical property of the cross-linked copolymer can be favorably regulated and controlled, and the reprocessing performance of the cross-linked copolymer is not influenced by changing the target groups. The setting parameters of the plate vulcanizing machine are that the temperature is 150 ℃, the pressure is 10MPa, and the pressure maintaining time is 0.5 h. The chemical crosslinking points of the crosslinked copolymer are functionalized amide dynamic covalent bonds, and the dynamic covalent bonds can undergo reversible fracture-generation reaction at 150 ℃, as shown in formula (1), so that exchange occurs between different crosslinking points, a network structure is reconstructed, and finally the crosslinked copolymer is remodeled.
Compared with the prior art, the invention has the beneficial effects that:
1) the selectable range of other monomers and monoamine compounds copolymerized with AAEM is wide, which is beneficial to the preparation and performance regulation of the cross-linked copolymer;
2) the amide dynamic covalent bond can be functionalized by a monoamine compound containing a target group, so that the mechanical property of the same copolymer matrix can be regulated and controlled in a very simple manner;
3) the cross-linked copolymer can be reprocessed without a catalyst, and the material after repeated reprocessing has good performance.
Drawings
FIG. 1 is a NMR spectrum of an imidazolyl-functionalized copolymer of example 1;
FIG. 2 is an infrared spectrum of a crosslinked imidazolyl-functionalized copolymer;
FIG. 3 is a comparison of the appearance of crosslinked imidazolyl-functionalized copolymers before and after rework;
FIG. 4 is a comparison of swelling experiments before and after three reworking of a crosslinked imidazolyl-functionalized copolymer;
FIG. 5 is a graph comparing stress-strain curves before processing and after a third processing of a crosslinked imidazolyl-functionalized copolymer;
FIG. 6 is a graph of stress-strain curves for cross-linked and double cross-linked imidazolyl-functionalized copolymers;
FIG. 7 is a graph of stress-strain curves comparing crosslinked acetyl-functionalized copolymers and crosslinked imidazolyl-functionalized copolymers.
Detailed Description
The present invention will be described in further detail with reference to specific examples. The following examples are intended to illustrate the invention but should not be construed as limiting it.
Styrene and acetoacetoxyethylmethacrylate (AAEM) in the examples were purchased from national institutes of chemical industries, Inc. 1- (3-aminopropyl) imidazole, N-acetylethylenediamine, diphenylmethane diisocyanate (MDI) were purchased from Chiese chemical industries, Inc. Initiators azobisisobutyronitrile and anhydrous zinc acetate were purchased from Adamas. Other chemical reagents were purchased from common reagent platforms and used directly without special instructions.
Example 1
A method of preparing a crosslinked acetoacetoxy ethyl methacrylate copolymer using functionalized amide dynamic covalent bonds comprising the steps of:
1)0.09mol of styrene and 0.01mol of acetoacetoxyethyl methacrylate are firstly uniformly mixed in 50mL of toluene, 1mmol of initiator azobisisobutyronitrile is then added, the mixture is placed in a 60 ℃ water bath kettle under the protection of nitrogen atmosphere and stirred for reaction for 4 hours, 0.01mol of 1- (3-aminopropyl) imidazole is then added into the reaction solution to continue to react for 8 hours under the same reaction conditions, finally the reaction solution is poured into 1L of absolute ethyl alcohol for precipitation and washing, the precipitate is dried in vacuum at 60 ℃ to constant weight to obtain the imidazolyl functionalized copolymer, the copolymer is characterized by nuclear magnetic resonance hydrogen spectrum, and the result of important peak assignment is shown in figure 1.
2) 3g of the imidazolyl functionalized copolymer is weighed and dissolved in 50ml of toluene, then 0.29g of diphenylmethane diisocyanate is added, and then the uniformly mixed solution is poured into a polytetrafluoroethylene mold and is kept stand in a forced air oven at the temperature of 80 ℃ until the solvent is completely volatilized, and finally the cross-linked imidazolyl functionalized copolymer film is obtained. Fourier transform infrared spectroscopy test results are shown in FIG. 2, 1687cm-1、1544cm-1And 1299cm-1The infrared absorption peaks at (A) are the I, II and III absorption bands of the secondary amide, respectively, indicating that the chemical crosslinking reaction as shown in formula (3) occurs.
3) After the crosslinked imidazolyl functionalized copolymer film is crushed, hot pressing operation is carried out on a flat vulcanizing machine, and the instrument parameters are set to be 150 ℃, 10MPa and 0.5 h. And cooling and taking out the film after the hot pressing operation is finished.
4) The appearance of the film after hot pressing is good, and no obvious visible defect is in the film after reprocessing, as shown in figure 3; as shown in fig. 4, the swelling experimental result (gel fraction GF 75%, swelling ratio SR 602%) of the crosslinked imidazolyl-functionalized copolymer after three times of reprocessing is substantially consistent with that before reprocessing (gel fraction GF 77%, swelling ratio SR 583%), which indicates that the reprocessed film still has a crosslinked network structure and good solvent resistance; for further analysis of the difference in mechanical properties between the films before and after the reworking, the stress-strain curve is shown in FIG. 5. after three times of the reworking, the toughness can still reach 16MJ/m3(initial toughness 20MJ/m3). The following conclusions can be drawn in conclusion: the reprocessed film still has a cross-linked network structure, has good solvent resistance and good reprocessing performance, and even after three times of reprocessing, the toughness of the reprocessed film can reach 80% of the original performance.
In example 1, acetoacetoxy groups in the copolymer reacted with 1- (3-aminopropyl) imidazole containing an imidazole target group as shown in formula (2).
The reaction of the imidazolyl-functionalized copolymer with the isocyanate group is shown in formula (3).
Example 2
A method of preparing a crosslinked acetoacetoxy ethyl methacrylate copolymer using functionalized amide dynamic covalent bonds comprising the steps of:
1) imidazolyl-functionalized copolymers were prepared as in example 1, step 1).
2) Weighing 3g of the imidazolyl functionalized copolymer, dissolving the imidazolyl functionalized copolymer in 50ml of toluene, adding 0.42g of anhydrous zinc acetate and 0.17g of diphenylmethane diisocyanate, pouring the uniformly mixed solution into a polytetrafluoroethylene mold, and standing in a forced air oven at 80 ℃ until the solvent is completely volatilized, thereby obtaining the double-crosslinked imidazolyl functionalized copolymer film.
3) The stress-strain curve is shown in FIG. 6, the elongation at break of the crosslinked imidazolyl-functionalized copolymer is 7%, the breaking strength is 5MPa, and the toughness is 19.8MJ/m3And the elongation at break of the double-crosslinking imidazolyl-functionalized copolymer is 5 percent, the breaking strength is 8MPa, and the toughness is 22.5MJ/m3. The crosslinked imidazolyl-functionalized copolymer has only one chemical crosslinking point, namely, the crosslinked imidazolyl-functionalized copolymer consists of functionalized amide dynamic covalent bonds, but the double crosslinked imidazolyl-functionalized copolymer has improved breaking strength and reduced breaking elongation because the coordination of imidazolyl and metal zinc ions forms physical crosslinking.
Example 3
A method of preparing a crosslinked acetoacetoxy ethyl methacrylate copolymer using functionalized amide dynamic covalent bonds comprising the steps of:
1)0.09mol of styrene and 0.01mol of acetoacetoxy ethyl methacrylate are firstly uniformly mixed in 50ml of toluene, 1mmol of initiator azobisisobutyronitrile is then added, the mixture is placed in a water bath kettle at 60 ℃ under the protection of nitrogen atmosphere and stirred for reaction for 4 hours, then 0.01mol of N-acetyl ethylenediamine is added into the reaction solution and continuously reacted for 8 hours under the same reaction conditions, finally the reaction solution is poured into 1L of absolute ethyl alcohol for precipitation and washing, and the precipitate is dried in vacuum at 60 ℃ until the constant weight is obtained, namely the acetyl functionalized copolymer.
2) 3g of the above-mentioned acetyl-functionalized copolymer are weighed out and dissolved in 50ml of toluene, 0.30g of diphenylmethane diisocyanate are then added, the uniformly mixed solution is poured into a polytetrafluoroethylene mould and is left to stand in a forced air oven at 80 ℃ until the solvent is dissolvedAnd finally obtaining the cross-linked acetyl functionalized copolymer film after complete volatilization. The stress-strain curve is shown in FIG. 7, wherein the elongation at break is 16%, the breaking strength is 47MPa, and the toughness is 434MJ/m3. It can be known from the figure that, compared with the cross-linked imidazolyl-functionalized copolymer, the cross-linked acetyl-functionalized copolymer has stronger mechanical properties because of the strong hydrogen bonding effect between acetyl groups and no imidazolyl group, which shows that the mechanical properties of the same copolymer matrix can be greatly regulated and controlled only by using different monoamines (1- (3-aminopropyl) imidazole and N-acetyl ethylenediamine).
3) Reprocessing was carried out as in example 1. The experimental result shows that the cross-linked acetyl functional copolymer can be reprocessed like the cross-linked imidazolyl functional copolymer, only the functional group of the copolymer is changed, and the reprocessing performance is not influenced.
In example 2, acetoacetoxy groups in the copolymer were reacted with N-acetylethylenediamine containing acetyl target groups as shown in formula (4).
The reaction of the acetyl functionalized copolymer with the isocyanate group is shown in formula (5).
The cross-linked acetoacetoxy ethyl methacrylate copolymer prepared by the invention has the characteristic of reprocessing, after the cross-linked copolymer is crushed, the cross-linked copolymer can be remolded by a flat vulcanizing machine, about 80 percent of initial toughness performance can be recovered after remolding, and the remolding time is only 0.5h, so that possible side reaction is avoided. In addition, the crosslinked copolymer can be functionalized with the target group in a very simple manner, and changing the target group does not affect the reworkability of the crosslinked copolymer.
Claims (10)
1. A method of making a crosslinked acetoacetoxy ethyl methacrylate copolymer using a dynamic covalent bond of a functionalizable amide, comprising the steps of:
1) preparing acetoacetoxy ethyl methacrylate free radical copolymer;
2) reacting the acetoacetyl ethyl methacrylate free radical copolymer with a monoamine compound containing a target group to obtain a target group functionalized copolymer;
3) and reacting the target group functionalized copolymer with polyisocyanate to obtain the modified polyurethane.
2. The process according to claim 1, wherein in step 1) a free-radical copolymer of acetoacetoxyethylmethacrylate with an α -olefinic monomer capable of free-radical copolymerization is prepared.
3. The method as claimed in claim 2, wherein in step 1), the alpha-olefin monomers capable of undergoing free radical copolymerization are selected from one or more of styrenes, vinyl chloride, acrylonitrile, acrylic acid and acrylates.
4. The method according to claim 2 or 3, wherein in the step 1), the reaction temperature is 50-70 ℃ and the reaction time is 2-4 h.
5. The method according to claim 1, wherein in step 2), the monoamine compound must contain only one reactive primary amine and no other active hydrogen reactive with isocyanate groups.
6. The method according to claim 1 or 5, wherein the target group in step 2) is one or more of n-butyl, n-octyl, octadecyl, benzyl, acetyl, imidazolyl, furyl, adamantyl and anthracenyl.
7. The method as claimed in claim 1, wherein in the step 3), the copolymer functionalized by the target group and the polyisocyanate or the copolymer functionalized by the target group, the polyisocyanate and the complex are uniformly mixed in the solvent, poured into a mold, and kept stand in a blast oven at 60-100 ℃ until the solvent is completely volatilized, so that a cross-linked network structure is finally formed, wherein the cross-linking point of the cross-linked network structure is a functionalized amide dynamic covalent bond.
8. The method according to claim 1 or 7, wherein in step 3), the polyisocyanate is a compound having two or more isocyanate groups.
9. The method according to claim 1 or 8, wherein in step 3), the polyisocyanate is any one of diphenylmethane diisocyanate, toluene diisocyanate, or isophorone diisocyanate, which contains two or more isocyanate groups.
10. A crosslinked acetoacetoxyethylmethacrylate copolymer prepared by the method of any of claims 1-9.
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