Pillar aromatic hydrocarbon-derived poly (pseudo-[1] rotaxane elastomer as well as preparation method and application thereof
By introducing carbon-carbon double bonds during column aromatic synthesis and using click reaction, column aromatic quasi-rotane is introduced into the polymer chain, which solves the problem of the difficulty of introducing polymer chains in the prior art. The problem is to improve the mechanical properties and toughness of the material.
Patent Information
- Application Number
- CN202411705255.8
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-11-26
- Publication Date
- 2025-02-18
AI Technical Summary
The prior art is difficult to effectively introduce quasi-roxane into polymer chains, resulting in limited improvement in the mechanical properties of materials.
The column aromatic quasi-rotorane is introduced into the polymer chain by introducing carbon-carbon double bonds during the synthesis of column aromatic hydrocarbons and converting them into hydroxyl or amino groups that are readily reacted with isocyanate.
The stable introduction of columnar aromatic hydrocarbon-derived polyquaternary rotanes has been achieved, and the mechanical properties and toughness of the material have been improved. It is suitable for shock absorption, buffering, sealing, sound insulation and other applications.
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Abstract
Description
Technical Field
[0001] The present invention belongs to the field of polymer materials, and in particular relates to a polyquasi[1]rotaxane elastomer derived from pillar aromatics, and a preparation method and application thereof. Background Art
[0002] The design and synthesis of new topological structures play a critical role in the research of new smart elastomers. Rotaxanes have a unique mechanical interlocking structure, and the cyclic components can move relative to each other along the axle components. This mechanical interlocking movement does not have much effect on the overall structure of the material, but can dissipate energy through dynamic movement. Covalently introducing the topological structure of rotaxane into the polymer chain can significantly affect the mechanical properties of the polymer, which is of great significance for guiding the synthesis of new elastomer materials.
[0003] The application of pseudorotaxanes and rotaxanes to improve the mechanical properties of polymers has received widespread attention. Pseudo[1]rotaxane is a special type of pseudorotaxane in which the cyclic component is connected to the axial component by covalent bonds. Therefore, when the cyclic component moves along the axial component and dissociates, the original molecular structure is still maintained. Although there are a large number of literature reports on the introduction of rotaxanes and pseudorotaxanes into polymer chains to improve the mechanical properties of materials, the introduction of pseudo[1]rotaxanes into polymer chains has always been a difficult problem. On the one hand, the pseudo[1]rotaxane structure constructed by supramolecular macrocycles such as crown ethers is unstable and easily dissociates into non-rotaxane structures during the introduction into polymer chains. On the other hand, the introduction of pseudo[1]rotaxanes into polymer chains requires complex synthesis.
[0004] Pillarene is a new type of supramolecular macrocycle. Due to its simple synthesis and easy modification, it is widely used in new intelligent materials and biomedicine. A large number of studies have shown that amide-modified pillararene derivatives tend to self-complex to form pseudo-[1]rotaxanes, and some amide derivatives can even maintain the pseudo-[1]rotaxane structure in the highly polar solvent dimethyl sulfoxide.
[0005] However, simple pillar aromatic amide derivatives can only react with isocyanate through one amino group, and it is still very difficult to introduce them into the polymer chain to form polyquasi[1]rotaxane. Summary of the invention
[0006] The first object of the present invention is to provide a polyquasi[1]rotaxane elastomer derived from pillar aromatic hydrocarbons in view of the shortcomings of the prior art, having a structural formula as shown in formula (I):
[0007]
[0008] Wherein, x is an integer from 1 to 11, y is an integer from 1 to 9, R is a C1 to C6 alkyl group, X and Y are polyurethane chains containing a carbamate structure, and the carbamate structure is
[0009] Pillarene is a class of electron-rich rigid macrocyclic entities whose cavities can complex alkyl diamines. The present invention introduces a carbon-carbon double bond during the synthesis of pillararene, introduces an amino group during the amide derivatization of pillararene, and finally utilizes a thiol-olefin click reaction to convert the carbon-carbon double bond into a hydroxyl or amino group that can react with isocyanate, thereby introducing the pillararene pseudo[1]rotaxane into a polymer chain to obtain a polypseudo[1]rotaxane.
[0010] The second object of the present invention is to provide a method for preparing the above-mentioned pillararene-derived polyquasi[1]rotaxane elastomer, comprising the following steps:
[0011] Step (1), under the action of potassium carbonate, hydroquinone reacts with bromoolefin and methyl bromoacetate in sequence to obtain an intermediate product represented by formula (V), wherein the molar ratio of hydroquinone to bromoolefin, methyl bromoacetate and potassium carbonate is 1:1:1:2;
[0012]
[0013] Step (2), reacting the intermediate product represented by formula (V) with terephthalic acid and paraformaldehyde in dichloroethane under the catalysis of boron trifluoride ether to obtain the intermediate product represented by formula (VI), wherein the molar ratio of the intermediate product represented by formula (V) to terephthalic acid and paraformaldehyde is 1:16:48;
[0014]
[0015] Step (3), reacting the intermediate product represented by formula (VI) with an excess of alkyl diamine to obtain the intermediate product represented by formula (VII), wherein the molar ratio of the intermediate product represented by formula (VI) to the alkyl diamine is 1:10 to 40;
[0016]
[0017] In step (4), the intermediate product represented by formula (VII) undergoes a thiol-olefin click reaction with a thiol compound and benzoin dimethyl ether under ultraviolet light to obtain an intermediate product represented by formula (VIII); the molar ratio of the intermediate product represented by formula (VII) to the thiol compound and benzoin dimethyl ether is 1:2:0.005.
[0018]
[0019] Wherein, x is an integer of 1 to 11, y is an integer of 1 to 9, z is an integer of 1 to 9, R is a C1 to C6 alkyl group, and A is O or NH;
[0020] The structural formula of the thiol compound is:
[0021] Where z is an integer from 1 to 9;
[0022] In step (5), the intermediate product represented by formula (VIII) reacts with diisocyanate and diol under the catalysis of dibutyltin dilaurate to obtain a polyquasi[1]rotaxane derived from pillar aromatic hydrocarbons; the molar ratio of the intermediate product represented by formula (VIII) to diisocyanate, diol and dibutyltin dilaurate is 50-500:1000:500-950:1.
[0023] The structural formula of the diol is: The structural formula of the diisocyanate is: Wherein m is an integer of 1 to 40; n is an integer of 1 to 19.
[0024] The alkyldiamine units of the pillararene pseudo[1]rotaxane can move in the cavity of the pillararene, and the amide groups and urea groups can form hydrogen bonds with the oxygen atoms of the alkoxy groups on the pillararene, making the pseudo[1]rotaxane more stable. When the polymer chain is subjected to force, the polymer chain forces the alkyldiamine units to destroy the host-guest self-complexation and hydrogen bonds, causing the pseudo[1]rotaxane to deform and release alkyl chains of a certain length, which can dissipate a large amount of energy and give the elastomer good toughness.
[0025] Therefore, the present invention also provides the use of the above-mentioned polyquasi[1]rotaxane elastomer derived from pillar aromatic hydrocarbons as a shock absorbing, buffering, sealing, sound insulating and other materials in the automotive and mechanical fields.
[0026] Compared with the prior art, the present invention has the following beneficial effects:
[0027] (1) The polyquasi[1]rotaxane derived from pillar aromatic hydrocarbons and the synthesis method thereof disclosed in the present invention are prepared by pre-introducing carbon-carbon double bonds into pillar aromatic hydrocarbons to obtain amide-modified pillar aromatic hydrocarbons, which are then converted into hydroxyl and amino groups that are easily reactive with isocyanate through an olefin-thiol click reaction. The polyquasi[1]rotaxane is easily reactive with isocyanate, has simple synthesis and convenient operation.
[0028] (2) The present invention introduces a pseudo[1]rotaxane self-complexing structure into the polymer molecular chain. The host-guest interaction between the pillar aromatic hydrocarbon and the alkyl chain and the hydrogen bonds formed between the amide bond and the urea group and the oxygen atom can stabilize the self-complexing structure, thereby making the introduced pseudo[1]rotaxane have higher stability.
[0029] (3) The method for synthesizing a polyquasi[1]rotaxane derived from pillar aromatic hydrocarbons disclosed in the present invention can be applied to synthesize elastomers with self-interlocking structures, providing a new type of elastomer material with a special topological structure. The pillar aromatic hydrocarbon quasi[1]rotaxane in the polymer chain can deform under stress, release the pre-shrinkage distance, dissipate energy, and give the material good toughness, and is widely used in materials such as shock absorption, cushioning, sealing, and sound insulation. BRIEF DESCRIPTION OF THE DRAWINGS
[0030] Figure 1 This is the hydrogen nuclear magnetic resonance spectrum of the intermediate product A-1 in Example 1.
[0031] Figure 2 This is the carbon NMR spectrum of the intermediate product A-1 of Example 1.
[0032] Figure 3 This is the hydrogen nuclear magnetic resonance spectrum of the intermediate product B-1 in Example 1.
[0033] Figure 4 This is the carbon NMR spectrum of the intermediate product B-1 of Example 1.
[0034] Figure 5 This is the hydrogen nuclear magnetic resonance spectrum of the intermediate product C-1 in Example 1.
[0035] Figure 6 This is the carbon NMR spectrum of the intermediate product C-1 of Example 1.
[0036] Figure 7 This is the hydrogen nuclear magnetic resonance spectrum of the intermediate product D-1 in Example 1.
[0037] Figure 8 This is the carbon NMR spectrum of the intermediate product D-1 in Example 1.
[0038] Fig. 9 This is the hydrogen nuclear magnetic resonance spectrum of the poly-quasi[1]rotaxane derived from pillar aromatics in Example 1. DETAILED DESCRIPTION
[0039] The present invention will be further described below in conjunction with the accompanying drawings and embodiments. It should be understood that these embodiments are only used to illustrate the present invention and are not intended to limit the scope of the present invention.
[0040] The present invention provides a polyquasi[1]rotaxane elastomer derived from pillar aromatic hydrocarbons, the structural formula of which is shown in the following formula (I):
[0041]
[0042] Wherein, x is an integer from 1 to 11, y is an integer from 1 to 9, R is a C1 to C6 alkyl group, X and Y are polyurethane chains containing a carbamate structure, and the structure of the carbamate is
[0043] In the following examples, the synthesis is carried out by taking x=9 and y=3 as an example. Specifically, the structural formula of the polyquasi[1]rotaxane derived from pillararene in the following examples is shown in formula (I-1):
[0044]
[0045] Example 1
[0046] (1) Preparation of intermediate product A-1:
[0047]
[0048] Hydroquinone (10.00 g, 90.82 mmol), potassium carbonate (12.55 g, 90.82 mmol) and 4-bromo-1-butene (12.26 g, 90.82 mmol) and 300 mL of acetonitrile were added to a round-bottom flask wrapped in aluminum foil, and the solution was bubbled with nitrogen for 20 minutes, then kept in a nitrogen atmosphere and heated to 80 ° C for 24 hours. Then methyl bromoacetate (16.67 g, 109.0 mmol) and additional potassium carbonate (15.06 g, 109.0 mmol) were added and the reaction continued for 24 hours. After the reaction was completed, the filtrate was filtered, concentrated, and purified by silica gel column chromatography (petroleum ether: ethyl acetate = 40: 1, v / v) to obtain intermediate product A-1 (white solid, 7.51 g, yield 35%).
[0049] The H NMR spectrum of intermediate product A-1 is as follows Figure 1 As shown, the carbon NMR spectrum is as follows Figure 2 shown.
[0050] (2) Preparation of intermediate product B-1:
[0051]
[0052] The intermediate product A-1 (1.50 g, 6.35 mmol), p-phenylene dimethyl ether (14.00 g, 101.5 mmol), polyformaldehyde (9.15 g, 304.5 mmol) and 300 mL of 1,2-dichloroethane were added to a round-bottom flask and stirred for 3 hours, and then boron trifluoride ether (13 mL, 101.5 mmol) was added. When the solution turned dark green, 200 mL of pure water was added to quench the reaction. The organic phase was then extracted with dichloromethane, concentrated, and purified by silica gel column chromatography (petroleum ether: ethyl acetate = 5: 1, v / v) to obtain the intermediate product B-1 (white solid, 2.11 g, yield 39%).
[0053] The H NMR spectrum of intermediate B-1 is as follows: Figure 3 As shown, the carbon NMR spectrum is as follows Figure 4 shown.
[0054] (3) Preparation of intermediate product C-1:
[0055]
[0056] The intermediate product B-1 (5.08 g, 5.98 mmol), excess 1,10-decanediamine (41.24 g, 239.3 mmol) and 50 mL of ethanol were heated to reflux in a round-bottom flask for 12 hours. After the reaction was completed, the temperature was lowered to room temperature, and the precipitated solid was collected and purified by silica gel column chromatography (dichloromethane: methanol = 20: 1, v / v) to obtain the intermediate product C-1 (white solid, 4.51 g, yield 76%).
[0057] The H NMR spectrum of the intermediate product C-1 is as follows Figure 5 As shown, the carbon NMR spectrum is as follows Figure 6 shown.
[0058] (4) Preparation of intermediate product D-1:
[0059]
[0060] Under nitrogen protection, the intermediate product C-1 (2.00 g, 6.34 mmol), 2-mercaptoethanol (0.99 g, 12.68 mmol), benzoin dimethyl ether (8 mg, 0.03 mmol) and 10 mL of dichloromethane were added to a round-bottom flask, and then stirred for 30 minutes under ultraviolet light. After the reaction, 50 mL of water was added to the system, and the organic phase was extracted with dichloromethane, dried with anhydrous sodium sulfate and concentrated, and then introduced into isopropyl ether, the insoluble matter was collected by centrifugation, and the intermediate product D-1 (white solid, 1.18 g, yield 83%) was obtained after vacuum drying.
[0061] The H NMR spectrum of the intermediate product D-1 is as follows Figure 7 As shown, the carbon NMR spectrum is as follows Figure 8 shown.
[0062] (5) Synthesis of polyquasi[1]rotaxane derived from pillararene: 1,4-Butanediol (61 mg, 0.68 mmol), hexamethylene diisocyanate (258 mg, 1.53 mmol), polytetrahydrofuran 2000 (1.50 g, 0.75 mmol) and 10 mL of N,N-dimethylacetamide were added to a round-bottom flask, and 0.5 mL of dibutyltin dilaurate (1 mg, 0.001 mmol) in DMF solution was added dropwise. The mixture was heated to 60 °C and stirred for 1 hour, and then the intermediate product D-1 (80 mg, 0.075 mmol) was added. After the reaction was continued for 1 hour, the solution was transferred to a glass petri dish and heated on a metal plate at 70 °C for 12 hours. After cooling to room temperature, a pillararene-derived polyquasi[1]rotaxane elastomeric film was obtained.
[0063] The H NMR spectrum of the polyquasi[1]rotaxane S-1 derived from pillararene in this example is shown in FIG. Fig. 9As shown, the successful synthesis of pillararene-derived polyquasi[1]rotaxanes was demonstrated.
[0064] The polyquasi[1]rotaxane S-1 derived from pillar aromatic hydrocarbon in Example 1 was subjected to a tensile test. The test results are shown in Table 1 below.
[0065] Table 1: Tensile properties of pillararene-derived polyquasi[1]rotaxane S-1
[0066]
[0067] The tensile test results show that the polyquasi[1]rotaxane S-1 derived from pillarnarene has excellent tensile strength, elongation at break and toughness. Therefore, as an elastomeric material, it can be widely used in shock absorption, cushioning, sealing, sound insulation and other materials in the fields of transportation and precision machinery.
[0068] The embodiments described above provide a detailed description of the technical solutions of the present invention. It should be understood that the above are only specific embodiments of the present invention and are not intended to limit the present invention. Any modifications, supplements or similar substitutions made within the scope of the principles of the present invention should be included in the protection scope of the present invention.
Claims
1. A polyquasi[1]rotaxane elastomer derived from pillarnarene, characterized in that: The structural formula is shown in formula (I): Wherein, x is an integer of 1 to 11, y is an integer of 1 to 9, R is a C1 to C6 alkyl group, and X and Y are both The structure of the polyurethane chain.
2. A method for preparing a pillararene-derived polyquasi[1]rotaxane elastomer as claimed in claim 1, characterized in that: The preparation method comprises the following steps: Step (1), under the action of potassium carbonate, hydroquinone reacts with bromoolefin and methyl bromoacetate in sequence to obtain an intermediate product represented by formula (V); Step (2), reacting the intermediate product represented by formula (V) with terephthalic acid and paraformaldehyde in dichloroethane under the catalysis of boron trifluoride ether to obtain the intermediate product represented by formula (VI); Step (3), reacting the intermediate product represented by formula (VI) with an alkyl diamine to obtain an intermediate product represented by formula (VII); Step (4), the intermediate product represented by formula (VII) undergoes a thiol-olefin click reaction with a thiol compound and benzoin dimethyl ether under ultraviolet light to obtain an intermediate product represented by formula (VIII); wherein x is an integer of 1 to 11, y is an integer of 1 to 9, z is an integer of 1 to 9, R is a C1 to C6 alkyl group, and A is O or NH; The structural formula of the thiol compound is: Wherein z is an integer from 1 to 9; Step (5), reacting the intermediate product represented by formula (VIII) with diisocyanate and diol under the catalysis of dibutyltin dilaurate to obtain a poly-quasi[1]rotaxane derived from pillararene; The structural formula of the diol is: The structural formula of the diisocyanate is: Wherein m is an integer of 1 to 40; n is an integer of 1 to 19.
3. The preparation method according to claim 2, characterized in that: In step (1), the molar ratio of hydroquinone to brominated olefin, methyl bromoacetate and potassium carbonate is 1:1:1:
2.
4. The preparation method according to claim 2, characterized in that: In step (2), the molar ratio of the intermediate product represented by formula (V) to p-phenylenedimethyl ether and polyformaldehyde is 1:16:
48.
5. The preparation method according to claim 2, characterized in that: In step (3), the molar ratio of the intermediate product represented by formula (VI) to the alkyl diamine is 1:10-40.
6. The preparation method according to claim 2, characterized in that: In step (4), the molar ratio of the intermediate product represented by formula (VII), the thiol compound and benzoin dimethyl ether is 1:2:0.
005.
7. The preparation method according to claim 2, characterized in that: In step (5), the molar ratio of the intermediate product represented by formula (VIII) to diisocyanate, diol and dibutyltin dilaurate is 50-500:1000:500-950:
1.
8. Use of the polyquasi[1]rotaxane elastomer derived from pillar aromatic hydrocarbons as claimed in claim 1 as a shock absorbing and buffering material.
9. Use of the poly-quasi[1]rotaxane elastomer derived from pillararene as claimed in claim 1 as a sealing material.
10. Use of the poly-quasi[1]rotaxane elastomer derived from pillararene as claimed in claim 1 as a sound insulation material.