CN109054056B - Interlocking network crosslinked polymer based on reversible covalent bond and preparation method and application thereof - Google Patents
Interlocking network crosslinked polymer based on reversible covalent bond and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to an interlocking network cross-linked polymer based on reversible covalent bonds, and a preparation method and application thereof. The interlocking network cross-linked polymer comprises the following components in parts by weight: 25-75 parts of a crosslinked polymer C containing a dynamic reversible C-ON bond; 25-75 parts of a crosslinked polymer D containing reversible DA bonds. The invention selects the cross-linked polymer containing two temperature response type reversible covalent bonds which are not interfered with each other, and obtains the cross-linked polymer with the self-adaptive interlocking structure after dissociation, mixing and recombination, can fully utilize the effect of limited phase separation of a network, realizes the interlocking at the molecular level, fully exerts the forced compatibility action of the interlocking structure, greatly improves the mechanical property and obviously improves the tensile strength.
Description
Technical Field
The invention belongs to the field of high molecular materials, and particularly relates to an interlocking network crosslinked polymer based on a reversible covalent bond, and a preparation method and application thereof.
Background
Interpenetrating Polymer Network (IPN) refers to a Polymer Network formed by two or more polymers Interpenetrating with each other, and the interaction between different Polymer networks is not a chemical bond but a mechanical entanglement. The entanglement can play a role in forced compatibilization, increase the interfacial affinity, realize the performance complementation of different components, and is an effective method for modifying polymer materials. double-Network polymer (DN) is a special IPN polymer, which introduces a sacrificial bond concept (Sacrifice bond) into an IPN system, is commonly used for preparing hydrogel materials with high toughness and high compressive strength, and has application in the field of elastomers in recent years.
Interpenetrating polymer networks are typically prepared by either a synchronous or a stepwise process, i.e., two monomers are polymerized simultaneously, or one monomer is polymerized in a polymer network to form an interpenetrating network. Because of compatibility issues, the components of conventional IPN systems tend to phase separate, and the crosslinked network has the effect of limiting phase separation, microphase structures with diameters of a few nanometers to tens of nanometers tend to exist in IPN systems. Generally, interpenetrating networks refer to the interpenetration on the supramolecular level, i.e. the interpenetration of the phase structure. The structural design of the double-network hydrogel or elastomer follows the principle that the content of the first network component is much smaller than that of the second network and the crosslinking density of the first network is much larger than that of the second network. Because the proportions of the two components are very different and the selected raw materials are mostly the research objects with good compatibility, although the obtained sample has no obvious phase separation in the original state, the component fluctuation in the stretching process can be gradually shown. The phase separation phenomenon cannot exert the 'forced compatibility' effect brought by network interpenetration to the maximum extent on one hand, and on the other hand, excessive phase separation can also cause the reduction of the mechanical property, the transparency and the like of the material.
From the material preparation point of view, the preparation method of the IPN polymer mainly comprises the steps of IPN, synchronous IPN, latex IPN, thermoplastic IPN and the like. In most cases, the preparation involves swelling, diffusion, polymerization and crosslinking of the monomers or prepolymers. The double-network polymer is a special IPN polymer, and the preparation process of the double-network polymer has stricter requirements compared with the traditional IPN. At present, in order to introduce a sacrificial bond into a double-network system, a method of pre-stretching (fully swelling) a primary network or introducing a non-covalent bond is mainly adopted, and the preparation method is similar to the traditional IPN and involves swelling, diffusion, polymerization and crosslinking processes of monomers or prepolymers. In general, the design and preparation of IPN or double-network polymer requires strict control of the types of raw monomers or prepolymers, the component ratios and the network structure, which brings many limitations to the development and application of IPN or double-network polymer.
In recent years, adaptive networks constructed using reversible covalent bonds have become a focus of research. By adaptive network is meant that it can undergo reorganization of the network structure under conditions of reversible covalent bond excitation, even to achieve reversible conversion of crosslinked polymers to linear polymers (e.g., retro-DA reactions). This concept provides a new idea for the preparation of crosslinked polymers with an interlocking network: the method is characterized in that reversible bonds in a cross-linked network are excited, so that an insoluble cross-linked polymer can be dissociated and recombined in a proper solvent, even completely dissolved, and further provides possibility for mixing different components at a molecular level, nanogel or linear polymers formed by dissociation of different networks in the process are mutually permeated and intertwined in a solution environment, after the mixing process is completed, the reconstruction and interlocking of the cross-linked network are realized while the solvent is gradually removed, and the cross-linked polymer with an interlocking network structure is constructed at the molecular level.
Therefore, the development of the cross-linked polymer with the interlocking network structure has important research significance and application value.
Disclosure of Invention
The invention aims to overcome the defects and defects that IPN or double-network polymer is easy to phase separate in the stretching process so that the forced compatibility effect and the reduction of mechanical property caused by network interpenetration cannot be exerted to the maximum extent in the prior art, and provides an interlocking network crosslinked polymer based on reversible covalent bonds. The interlocking network cross-linked polymer provided by the invention adopts the combination of non-interfering reversible covalent bonds-C-ON and DA bonds to avoid chemical bond linkage among different networks in the forming process of the interlocking network, obviously improve the tensile strength and avoid the problem of mechanical property reduction caused by phase separation.
Another object of the present invention is to provide a process for producing the above-mentioned interlocking network crosslinked polymer.
Another object of the present invention is to provide the use of the above-mentioned interlocking network crosslinked polymer for the preparation of rubber articles.
In order to achieve the purpose, the invention adopts the following technical scheme:
an interlocking network cross-linked polymer based on reversible covalent bonds comprises the following components in parts by weight:
25-75 parts of crosslinked polymer C containing dynamic reversible C-ON bond
25-75 parts of a crosslinked polymer D containing reversible DA bonds.
The forming process of the interlocking network cross-linked polymer relates to a dynamic exchange or dissociation-bonding process of two or more reversible covalent bonds, and the key of the interlocking network cross-linked polymer is how to select the combination of the reversible covalent bonds without mutual interference to avoid chemical bond linkage between different networks in the preparation process of the interlocking network.
The inventor of the invention discovers through research that the crosslinked polymer C containing the dynamic reversible C-ON bond and the crosslinked polymer D containing the reversible DA bond have two temperature response type reversible covalent bonds which are not interfered with each other and have self-adaptive characteristics, when the two are mixed after being dissociated, the two can be mutually permeated, intertwined and recombined to form the crosslinked polymer with the self-adaptive interlocking structure ON the molecular level, the effect of limiting phase separation of the network is fully utilized, the interlocking ON the molecular level can be realized, the forced compatibility effect of the interlocking structure is fully exerted, and the mechanical property of the interlocking network is obviously improved compared with that of a single network.
It should be understood that the crosslinked polymer C referred to in the present invention contains only one dynamic reversible bond of C-ON bond and does not contain other dynamic reversible bonds; the crosslinked polymer D only contains one reversible bond of DA bond (thermally reversible Diels-Alder covalent bond) and does not contain other dynamic reversible bonds; the kind and number of irreversible chemical bonds in the crosslinked polymers C and D are not limited.
The proportion and the degree of polymerization of the two are also important factors influencing the cross-linked polymer with the interlocking structure, and the proportion and the degree of polymerization of the two are reasonably optimized, so that the tensile strength or the elongation at break of the finally obtained cross-linked polymer with the interlocking structure is greatly improved, and the phase separation phenomenon cannot occur.
Preferably, the interlocking network cross-linked polymer consists of the following components in parts by weight:
25-75 parts of crosslinked polymer C containing dynamic reversible C-ON bond
25-75 parts of a crosslinked polymer D containing reversible DA bonds.
More preferably, the interlocking network cross-linked polymer is composed of the following components in parts by weight:
crosslinked polymer C50 parts containing dynamic reversible C-ON bond
And D50 parts of crosslinked polymer containing reversible DA bonds.
There have been many reports ON crosslinked polymers containing a dynamically reversible C-ON bond in the prior art, such as crosslinked polymers obtained by reacting diolefin with mercapto groups, crosslinked polymers obtained by reacting diols with isocyanates, crosslinked polymers obtained by reacting diepoxy monomers with mercapto groups, crosslinked polymers obtained by copolymerizing acrylate monomers with diolefin, and the like.
The invention herein provides two specific crosslinked polymers C containing dynamically reversible C-ON bonds.
Preferably, the crosslinked polymer C is composed of the following raw materials in parts by weight:
60-80 parts of double-bond monomer
20-40 parts of a sulfydryl curing agent;
or
The number average molecular weight of the dihydroxy polyether is 850-10000.
More preferably, the crosslinked polymer C is composed of the following raw materials in parts by weight:
71.4 parts of double-bond monomer
28.6 parts of a sulfydryl curing agent;
or
The double bond monomer in the invention refers to an olefin monomer with two carbon-carbon double bonds and reversible C-ON bonds, such as 2- (4- (2-carbamate) ethyl acrylate) -2,2,6, 6-tetramethyl piperidine-1-oxygen) -N- (2-hydroxyethyl) -2-methylpropionamide.
The mercapto curing agent in the present invention means a crosslinking agent having a plurality of thiols, such as pentaerythritol tetrakis (3-mercaptobutanoate), trimethylolpropane tris (3-mercaptopropionate), 2, 3-dithio (2-mercapto) -1-propanethiol, propane-1, 2, 3-trithiol, polythiol and the like.
Preferably, the double-bond monomer is prepared from the following raw materials in parts by weight:
49 parts of diol monomer
51 parts of isocyano ethyl methacrylate;
the sulfydryl curing agent is pentaerythritol tetrakis (3-mercaptobutanoate), trimethylolpropane tris (3-mercaptopropionate), 2, 3-dithio (2-mercapto) -1-propanethiol, propane-1, 2, 3-trithiol, poly-thiol and the like.
The diol monomer of the present invention refers to a monomer having two hydroxyl groups and a reversible C-ON bond, such as: 2- (4-hydroxy-2, 2,6, 6-tetramethylpiperidin-1-oxy) -N- (2-hydroxyethyl) -2-methylpropanamide.
Preferably, the diol monomer is composed of the following raw materials in parts by weight:
50.4-75.6 parts of hydroxyl-containing heterocyclic nitroxide free radical monomer
29.6-44.4 parts of 2,2' -azo [ 2-methyl-N- (2-hydroxyethyl) propionamide;
the dihydroxy polyether is one or more of the following structural formulas:
the diisocyanate is one or more of the following structural formulas:
more preferably, the hydroxyl-containing heterocyclic nitroxide free radical monomer is one or more of the following structural formulas:
there have been many reports on the cross-linked polymer D having DA bond in the prior art, such as a cross-linked polymer obtained by reacting a polymer having a furan/maleimide side group with a polymaleimide/furan monomer, a cross-linked polymer obtained by reacting a polyether or polyester polyol with an isocyanate and a polyol monomer having DA bond, a cross-linked polymer obtained by reacting an epoxy monomer with a polyamine monomer having DA bond, and the like.
The present invention herein provides a specific crosslinked polymer D containing reversible DA bonds.
Preferably, the crosslinked polymer D is composed of the following raw materials in parts by weight:
15 to 150 parts of diepoxy monomer
60-90 parts of an amino curing agent.
More preferably, the crosslinked polymer D is composed of the following raw materials in parts by weight:
60 parts of diepoxy monomer
40 parts of amino curing agent.
The diepoxy monomer of the present invention refers to a monomer having a reversible DA bond and two epoxy groups, such as an addition product of furfuryl glycidyl ether and one of bismaleimides in the following structural formula.
The amino curing agent refers to a polymer curing agent with a plurality of amine groups and soft chain segments, such as difunctional polyether amine, trifunctional polyether amine, multifunctional amino silicone oil and the like.
Preferably, the diepoxy monomer is composed of the following raw materials in parts by weight:
41-62.5 parts of glycidyl furfuryl ether
30-48 parts of bismaleimide monomer;
the amino curing agent is one or more of polyether amine D230, polyether amine D400, polyether amine ED900 or polyether amine D2000.
More preferably, the bismaleimide monomer is N, N "- (4, 4" -methylenediphenyl) bismaleimide:
the invention provides a preparation method of the interlocking network crosslinked polymer, which comprises the following steps: respectively dissociating the crosslinked polymer C containing the dynamic reversible C-ON bond and the crosslinked polymer D containing the reversible DA bond, and mixing to obtain the interlocking network crosslinked polymer.
The preparation method provided by the invention does not need monomer and polymerization process in the process of constructing the interlocking network due to the characteristic of self-adaptive network recombination, thereby avoiding the possible catalyst and monomer residues in the preparation process of the material and simultaneously avoiding the limitation of the swelling capacity of the monomer or prepolymer on the selection of the polymer matrix. The preparation method is simple and easy to implement, and the components and the performance are easy to regulate and control.
Preferably, the dissociation conditions of the crosslinked polymer C are: reacting in a solvent for 30-90 min at the temperature of 60-100 ℃ under the condition of nitrogen; the dissociation conditions of the crosslinked polymer D were: reacting in a solvent for 30-90 min at 130-150 ℃ under the condition of nitrogen; the mixing conditions were: mixing for 10-60 min at 80-100 ℃ under nitrogen, and then removing the solvent.
Preferably, the solvent is dimethyl sulfoxide or dimethylformamide.
Preferably, the process of removing the solvent is: evaporating for 20-40 min under vacuum at 70-90 ℃, and then continuing to evaporate for more than 24h under the condition of 60-80 ℃.
The use of the above-described interlocking network crosslinked polymers in the preparation of rubber articles is also within the scope of the present invention.
Compared with the prior art, the invention has the following beneficial effects: the invention selects the cross-linked polymer containing two temperature response type reversible covalent bonds which are not interfered with each other, and obtains the cross-linked polymer with the self-adaptive interlocking structure after dissociation, mixing and recombination, can fully utilize the effect of limited phase separation of a network, realizes the interlocking at the molecular level, fully exerts the 'forced compatibility' effect of the interlocking structure, greatly improves the mechanical property and obviously improves the tensile strength.
Drawings
FIG. 1 comparison of tensile curves for examples 1 to 5;
FIG. 2 DMA dynamic mechanical Properties of example 4;
FIG. 3 measurement of the nanoscale modulus distribution of example 4 using AFM-QNM;
FIG. 4 nuclear magnetic hydrogen spectrum of diepoxy monomer containing reversible DA bond in example 1;
FIG. 5 nuclear magnetic hydrogen spectrum of a diol monomer containing a dynamically reversible C-ON bond in example 2.
Detailed Description
The invention is further illustrated by the following examples. These examples are intended to illustrate the invention and are not intended to limit the scope of the invention. Experimental procedures without specific conditions noted in the examples below, generally according to conditions conventional in the art or as suggested by the manufacturer; the raw materials, reagents and the like used are, unless otherwise specified, those commercially available from the conventional markets and the like. Any insubstantial changes and substitutions made by those skilled in the art based on the present invention are intended to be covered by the claims.
Example 1 intermediate reversible DA bond containing cross-linked network D: ED900-DA
This example provides a crosslinked network D containing reversible DA bonds: ED900-DA, the synthetic steps are as follows: 16g of glycidyl furfuryl ether and 18.81g N, N '- (4, 4' -methylenediphenyl) bismaleimide are dissolved in 150mL of tetrahydrofuran, added into a round-bottom three-neck flask with a condensing device, a nitrogen protection device and a mechanical stirring device, reacted at 70 ℃ for 24 hours, cooled to room temperature, and distilled under reduced pressure to remove the solvent to obtain yellow viscous liquid. Purifying with silica gel chromatographic column, eluting with dichloromethane/methanol 50:1, collecting corresponding eluate, distilling under reduced pressure to remove solvent to obtain white powdery solid product with structural formula shown in the following formula, and obtaining nuclear magnetic hydrogen spectrum shown in figure 4. 10g of polyether amine ED900 and 14.8g of the product are fully stirred and mixed at 80 ℃ for 20min, then poured into a silica gel mold, and cured at 70 ℃ for 48h to obtain a yellow elastomer product, which is recorded as ED 900-DA.
Example 2 intermediate crosslinked network C containing dynamic reversible C-ON bonds: 4-CON
This example provides a crosslinked network C containing a dynamically reversible C-ON bond: 4-CON, the synthesis process is as follows: 5g of 4-OH-TEMPO and 8.37g of 2,2' -azo [ 2-methyl-N- (2-hydroxyethyl) propionamide ] are dissolved in 150mL of dimethylformamide, added to a round-bottom three-neck flask with a condensing device, a nitrogen protection device and a mechanical stirring device, reacted at 120 ℃ for 3 hours, cooled to room temperature, and the solvent is distilled off under reduced pressure to obtain a yellow viscous liquid. Purifying with silica gel chromatographic column, eluting with petroleum ether/ethyl acetate 5:3 and pure ethyl acetate, collecting corresponding eluate, distilling under reduced pressure to remove solvent to obtain colorless oily liquid product with structure shown in the following formula, and obtaining nuclear magnetic hydrogen spectrum shown in figure 5. 5g of the product and 5.13g of isocyano ethyl methacrylate are dissolved in 100mL of chloroform, added into a round-bottom three-neck flask with a condensing device, a nitrogen protection device and a mechanical stirring device, reacted for 24 hours at 30 ℃, and then the solvent is removed by reduced pressure distillation to obtain a light yellow viscous liquid product. And (2) fully mixing 5g of the product and 2g of pentaerythritol tetra-3-mercaptopropionate at room temperature, adding 0.5 wt% of 1, 8-diazabicycloundecen-7-ene serving as a catalyst, uniformly stirring, pouring into a silica gel mold, placing in a nitrogen atmosphere for curing under the conditions of 24 hours at room temperature, 6 hours at 60 ℃ and 1 hour at 120 ℃ in sequence, and obtaining a light yellow elastomer product after curing, wherein the product is marked as 4-CON.
Example 3 interlock network CD-13
This example provides an interlocking network CD-13 consisting of 25 parts of a crosslinked network C containing dynamically reversible C-ON bonds: 4-CON (provided in example 2) and 75 parts of a crosslinked network D containing reversible DA bonds: ED900-DA (provided in example 1), prepared by dissociation and mixing.
Preparation of the interlocking network CD-13: 7.5g of the product ED900-DA obtained in example 1 was taken, crushed and placed in 150ml of dimethylformamide, after being fully swollen for 24h, the mixture was added into a round-bottom three-neck flask with a condensing device, a nitrogen protection device and a mechanical stirring device, and stirred at 130 ℃ for 30min to obtain a transparent solution. 2.5g of the product 4-CON obtained in example 2 was crushed and placed in 50ml of dimethylformamide to be fully swollen for 24h, and then added into a round-bottom three-neck flask with a condensing device, a nitrogen protection device and a mechanical stirring device, and stirred at 90 ℃ for 30min to obtain a transparent solution. Mixing the two solutions in a flask, continuously stirring at 90 ℃ for 60min under the nitrogen atmosphere, filtering to remove a small amount of insoluble gel, distilling under reduced pressure to remove most of the solvent, pouring into a silica gel mold, placing in a vacuum oven at 70 ℃ and continuously drying for 12h to remove the residual solvent to obtain a brown elastomer product, which is recorded as CD-13.
Example 4 interlock network CD-11
This example provides an interlocking network CD-11 consisting of 50 parts of a crosslinked network C containing dynamically reversible C-ON bonds: 4-CON (provided in example 2) and 50 parts of a crosslinked network D containing reversible DA bonds: ED900-DA (provided in example 1), prepared by dissociation and mixing.
Preparation of the interlocking network CD-11: 5g of the product ED900-DA obtained in example 1 was taken, crushed and placed in 150ml of dimethylformamide, after having been fully swollen for 24h, added to a round-bottom three-neck flask with a condenser, a nitrogen guard and a mechanical stirrer and stirred at 130 ℃ for 30min to obtain a transparent solution. 5g of the product 4-CON obtained in example 2 was crushed and placed in 50ml of dimethylformamide, after swelling for 24h, the mixture was added to a round-bottom three-neck flask equipped with a condenser, a nitrogen blanket and a mechanical stirrer and stirred at 90 ℃ for 30min to obtain a clear solution. Mixing the two solutions in a flask, continuously stirring at 90 ℃ for 60min under the nitrogen atmosphere, filtering to remove a small amount of insoluble gel, distilling under reduced pressure to remove most of the solvent, pouring into a silica gel mold, placing in a vacuum oven at 70 ℃ and continuously drying for 12h to remove the residual solvent to obtain a brown elastomer product, which is recorded as CD-11.
Example 5 interlock network CD-31
This example provides an interlocking network CD-31 consisting of 75 parts of a crosslinked network C containing dynamically reversible C-ON bonds: 4-CON (provided in example 2) and 25 parts of a crosslinked network D containing reversible DA bonds: ED900-DA (provided in example 1), prepared by dissociation and mixing.
Preparation of the interlocking network CD-31: 2.5g of the product ED900-DA obtained in example 1 was taken, crushed and placed in 150ml of dimethylformamide, after having been fully swollen for 24h, added to a round-bottom three-neck flask with a condensing unit, a nitrogen protection unit and a mechanical stirring unit, and stirred at 130 ℃ for 30min to obtain a transparent solution. 7.5g of the product 4-CON obtained in example 2 was crushed and placed in 50ml of dimethylformamide, after swelling for 24h, the mixture was added to a round-bottom three-neck flask with a condenser, a nitrogen blanket and a mechanical stirrer and stirred at 90 ℃ for 30min to obtain a clear solution. Mixing the two solutions in a flask, continuously stirring at 90 ℃ for 60min under the nitrogen atmosphere, filtering to remove a small amount of insoluble gel, distilling under reduced pressure to remove most of the solvent, pouring into a silica gel mold, placing in a vacuum oven at 70 ℃ and continuously drying for 12h to remove the residual solvent to obtain a brown elastomer product, and recording the brown elastomer product as CD-31.
Example 6 intermediate reversible DA bond containing cross-linked network D: D2000-DA
This example provides a crosslinked network D containing reversible DA bonds: D2000-DA, the synthetic steps are as follows: 16g of glycidyl furfuryl ether and 18.81g N, N '- (4, 4' -methylenediphenyl) bismaleimide are dissolved in 150mL of tetrahydrofuran, added into a round-bottom three-neck flask with a condensing device, a nitrogen protection device and a mechanical stirring device, reacted at 70 ℃ for 24 hours, cooled to room temperature, and distilled under reduced pressure to remove the solvent to obtain yellow viscous liquid. Purifying by silica gel chromatographic column, eluting with dichloromethane/methanol at 50:1, collecting the corresponding eluate, and distilling under reduced pressure to remove solvent to obtain white powdery solid product. 10g of polyether amine ED900 and 6.66 of the product are fully stirred and mixed for 20min at 80 ℃, then poured into a silica gel mold, and cured for 48h at 70 ℃ to obtain a yellow elastomer product, which is recorded as D2000-DA.
Example 7 intermediate crosslinked network C containing dynamic reversible C-ON bonds: 4-CON2
The present embodiment provides aCrosslinked network C containing dynamically reversible C-ON bonds: 4-CON, the synthesis process is as follows: 5g of 4-OH-TEMPO with 8.37g of 2,2' -azo [ 2-methyl-N- (2-hydroxyethyl) propionamide]Dissolving in 150mL of dimethylformamide, adding into a round-bottom three-neck flask with a condensing device, a nitrogen protection device and a mechanical stirring device, reacting at 120 ℃ for 3h, cooling to room temperature, and distilling under reduced pressure to remove the solvent to obtain yellow viscous liquid. Purifying by silica gel chromatographic column, eluting with petroleum ether/ethyl acetate (5: 3) and pure ethyl acetate, collecting the corresponding eluent, and distilling under reduced pressure to remove the solvent to obtain colorless oily liquid product. Dissolving 10g of PTMEG-850, 3.69g of the product and 5.88g of isophorone diisocyanate in 100mL of chloroform, adding the solution into a round-bottom three-neck flask with a condensing device, a nitrogen protection device and a mechanical stirring device, dripping 2 drops of dibutyltin dilaurate as a catalyst, reacting at 60 ℃ for 8 hours, adding 1.1g of pentaerythritol tetra-3-mercaptopropionate, continuing to react for 2 hours, pouring the mixture into a silica gel mold, curing at 60 ℃ for 24 hours to obtain a light yellow transparent elastomer product, and recording the product as 4-CON2。
Example 8 interlock network C2D-11
The present embodiment provides an interlock network C2D-11, consisting of 50 parts of a crosslinked network C containing dynamically reversible C-ON bonds: 4-CON2(provided in example 7) and 50 parts of a crosslinked network D containing reversible DA bonds: D2000-DA (provided in example 6), prepared by dissociation and mixing.
Interlock network C2Preparation of D-11: 5g of the product D2000-DA obtained in example 8 was taken, crushed and placed in 150ml of dimethylformamide, after having been fully swollen for 24h, was added to a round-bottom three-neck flask with a condenser, nitrogen guard and mechanical stirrer and stirred at 130 ℃ for 30min to give a clear solution. 5g of the product 4-CON from example 9 were taken2The solution is crushed, placed in 50ml of dimethylformamide, fully swelled for 24h, added into a round bottom three-neck flask with a condensing device, a nitrogen protection device and a mechanical stirring device, and stirred for 30min at 90 ℃ to obtain a transparent solution. Mixing the above two solutions in a flask, stirring at 90 deg.C under nitrogen atmosphere for 60min, filtering to remove small amount of insoluble gelDistilling under reduced pressure to remove most of solvent, pouring into a silica gel mold, placing in a vacuum oven at 70 deg.C, and continuously drying for 12 hr to remove residual solvent to obtain brown elastomer product denoted as C2D-11。
Example 9 interlock network C2D-13
The present embodiment provides an interlock network C2D-13, consisting of 25 parts of a crosslinked network C containing dynamically reversible C-ON bonds: 4-CON2(provided in example 7) and 75 parts of a crosslinked network D containing reversible DA bonds: D2000-DA (provided in example 6), prepared by dissociation and mixing.
Interlock network C2Preparation of D-13: 7.5g of the product D2000-DA obtained in example 8 were taken, crushed and placed in 150ml of dimethylformamide, and after swelling for 24h, the mixture was added to a round-bottom three-neck flask with a condenser, a nitrogen blanket and a mechanical stirrer and stirred at 130 ℃ for 30min to obtain a clear solution. 2.5g of the product 4-CON from example 9 were taken2The solution is crushed, placed in 50ml of dimethylformamide, fully swelled for 24h, added into a round bottom three-neck flask with a condensing device, a nitrogen protection device and a mechanical stirring device, and stirred for 30min at 90 ℃ to obtain a transparent solution. Mixing the two solutions in a flask, stirring at 90 deg.C for 60min under nitrogen atmosphere, filtering to remove a small amount of insoluble gel, distilling under reduced pressure to remove most of solvent, pouring into a silica gel mold, and drying in a vacuum oven at 70 deg.C for 12 hr to remove the residual solvent to obtain brown elastomer product denoted as C2D-13。
Example 10 intermediate crosslinked network C containing dynamic reversible C-ON bonds: 4-CON3
This example provides a crosslinked network C containing a dynamically reversible C-ON bond: 4-CON3The synthesis process comprises the following steps: reference Macromolecules,2001.34(3) Synthesis of diol monomers with dynamically reversible C-ON bonds from p.447-455 by dissolving 10g of PTMEG-850, 4.67g of the above product and 5.88g of isophorone diisocyanate in 100mL of chloroform, charging into a round-bottomed three-necked flask with a condenser, nitrogen blanket and mechanical stirrer, adding 2 drops of dibutyltin dilaurate as catalyst dropwise, reacting at 60 ℃ for 8h, addingAdding 1.1g pentaerythritol tetra-3-mercaptopropionate, continuously reacting for 2h, pouring into a silica gel mold, curing at 60 deg.C for 24h to obtain a light yellow transparent elastomer product, and recording as 4-CON3。
Example 11 intermediate reversible DA bond containing cross-linked network D: D2000-DA2
This example provides a crosslinked network D containing reversible DA bonds: D2000-DA2The synthesis steps are as follows: adding 10g of polyetheramine D2000 and 3.08g of glycidyl furfuryl ether into a round bottom three-neck flask with a condensing device, a nitrogen protection device and a mechanical stirring device, mixing for 10min at 80 ℃, adding 2.48g of 1, 4-bis (maleimide) butane, continuously mixing for 10min, pouring into a silica gel mold, curing for 48h at 70 ℃ to obtain a yellow transparent elastomer product, which is recorded as D2000-DA2。
Performance testing
Examples 1 to 11 are given as examples. And (3) detecting the performance:
(1) and (3) testing tensile property:
the material obtained in the examples 1 to 11 was cut into dumbbell-shaped sample strips with a width of 2mm, and the dumbbell-shaped sample strips were put into a vacuum oven at 50 ℃ and dried overnight to perform a tensile test, and the stress-strain curve of the dumbbell-shaped sample strips at a tensile rate of 50mm/min was recorded, wherein the test temperature was room temperature, and the results of the comparison between the tensile strength and the elongation at break of the interlocking network and the single network are shown in table 1 and fig. 1 to 2. FIG. 3 shows the nanoscale modulus distribution of example 4 measured using AFM-QNM.
As shown in table 1 and fig. 1, the tensile properties of the interlocking network are significantly improved compared to the single network, and the tensile strength or elongation at break of the interlocking network increases with the change of the ratio of the two single networks, wherein the maximum value of the tensile strength of the interlocking network is reached when the raw material mass ratio is 1: 1. As shown in fig. 2, the loss factor of the interlocking network has a single peak, indicating that there is no significant phase separation in the interlocking network, and fig. 3 shows that the interlocking network has a uniform modulus distribution on the nanometer scale, further demonstrating the uniform phase structure of the material.
TABLE 1 comparison of tensile Properties of crosslinked polymers having an interlocking network Structure with Single-network crosslinked polymers
Claims (8)
1. The interlocking network crosslinked polymer based on the reversible covalent bond is characterized by comprising the following components in parts by weight:
25-75 parts of crosslinked polymer C containing dynamic reversible C-ON bond
25-75 parts of a crosslinked polymer D containing reversible DA bonds;
the crosslinked polymer C containing the dynamic reversible C-ON bond is prepared from the following raw materials in parts by weight:
60-80 parts of double-bond monomer
20-40 parts of a sulfydryl curing agent;
or
The number average molecular weight of the dihydroxy polyether is 850-10000;
the cross-linked polymer D is prepared from the following raw materials in parts by weight:
15 to 150 parts of diepoxy monomer
60-90 parts of an amino curing agent.
2. The interlocking network crosslinked polymer of claim 1, wherein the interlocking network crosslinked polymer is composed of the following components in parts by weight:
crosslinked polymer C50 parts containing dynamic reversible C-ON bond
And D50 parts of crosslinked polymer containing reversible DA bonds.
3. The interlocking network crosslinked polymer of claim 1, wherein the di-double bond monomer is composed of the following raw materials in parts by weight:
40-60 parts of glycol monomer
40-60 parts of isocyano ethyl methacrylate;
the mercapto curing agent is pentaerythritol tetra-3-mercaptopropionate or trimethylolpropane tri (3-mercaptopropionate).
4. The interlocking network crosslinked polymer of claim 1, wherein the diol monomer is composed of the following raw materials in parts by weight:
50.4-75.6 parts of hydroxyl-containing heterocyclic nitroxide free radical monomer
29.6-44.4 parts of 2,2' -azo [ 2-methyl-N- (2-hydroxyethyl) propionamide;
the dihydroxy polyether is one or more of the following structural formulas:
the diisocyanate is one or more of the following structural formulas:
5. the interlocking network crosslinked polymer of claim 1, wherein the diepoxy monomer is composed of the following raw materials in parts by weight:
41-62.5 parts of glycidyl furfuryl ether
30-48 parts of bismaleimide monomer;
the amino curing agent is one or more of polyether amine D230, polyether amine D400, polyether amine ED900 or polyether amine D2000.
6. A process for preparing an interlocking network crosslinked polymer according to any of claims 1 to 5, characterized in that the process comprises: respectively dissociating the crosslinked polymer C containing the dynamic reversible C-ON bond and the crosslinked polymer D containing the reversible DA bond, and mixing to obtain the interlocking network crosslinked polymer.
7. The method for preparing an interlocking network crosslinked polymer according to claim 6, wherein the dissociation condition of the crosslinked polymer C is: reacting in a solvent for 30-90 min at the temperature of 60-100 ℃ under the condition of nitrogen; the dissociation conditions of the crosslinked polymer D were: reacting in a solvent for 30-90 min at 130-150 ℃ under the condition of nitrogen; the mixing conditions were: mixing for 10-60 min under the condition of nitrogen at 80-100 ℃.
8. Use of the interlocking network crosslinked polymer of any one of claims 1 to 5 in the preparation of rubber and plastic articles.
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| CN109721732B (en) * | 2019-01-04 | 2020-05-29 | 北京理工大学 | Modified pentaerythritol ester cross-linked network polymer containing sulfhydryl groups, preparation method and application thereof |
| CN110669225B (en) * | 2019-09-11 | 2022-03-18 | 复旦大学 | Synthetic method of thermosetting polymer capable of being repeatedly processed |
| CN112159556B (en) * | 2020-05-08 | 2022-02-15 | 华南理工大学 | Preparation method of rubber composite material with thermal reversible repeated processing performance |
| CN112707984B (en) * | 2021-01-11 | 2022-04-05 | 西安交通大学 | 4D printing photosensitive resin based on dynamic covalent bond and preparation method thereof |
| CN112898734B (en) * | 2021-01-22 | 2022-03-15 | 中山大学 | Liquid crystal polymer interlocking network and preparation method and application thereof |
| CN113861457A (en) * | 2021-09-07 | 2021-12-31 | 清华大学 | Method for welding cross-linked polymer parts |
| CN114752019B (en) * | 2022-04-08 | 2022-10-25 | 哈尔滨工业大学 | Two-stage preparation method of double-network shape memory polymer and method for in-situ regulation and control of glass transition temperature of double-network shape memory polymer |
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