Self-healing tung oil-based shape memory polymer and its preparation method

Abstract

The self-healing tung oil-based shape memory polymer and its preparation method are as follows: First, maleic anhydride is reacted with tung oil in a certain proportion to obtain intermediate product A; second, intermediate product A is reacted with furfuryl alcohol to obtain intermediate product B; third, a certain proportion of bismaleimide is added, along with different proportions of epoxy resin and ion exchange catalyst, and the mixture is cured in an oven at 120℃ to obtain the self-healing tung oil-based shape memory polymer. The Diels-Alder dynamic bonds and transesterification dynamic bonds in the self-healing tung oil-based shape memory polymer prepared by this patent endow the polymer with excellent self-healing ability and shape memory properties. This polymer is prepared using bio-based materials, the process is simple, the mechanical properties are controllable, and it can achieve self-healing and shape memory functions under heating conditions. The shape memory and mechanical properties are minimally lost after repeated use.

Description

Technical Field

[0001] This invention belongs to the field of bio-based smart polymer materials, specifically relating to a self-healing tung oil-based shape memory polymer and its preparation method. Background Technology

[0002] Shape memory materials are materials that, after being deformed and fixed into another shape, can recover their original shape upon treatment with physical or chemical stimuli such as heat, light, or electricity. Shape memory materials have wide applications in various fields of industry and daily life, such as smart fabrics, flexible electronics, 3D or 4D printing, and smart medical devices. However, most of the raw materials commonly used to synthesize shape memory polymers are derived from petrochemical resources. With increasing carbon emissions and the continuous depletion of petroleum resources, using biomass resources to replace unsustainable resources is becoming the mainstream of modern development.

[0003] Traditional synthetic polymer materials can be divided into thermoplastics and thermosettings. When thermoplastic materials are heated to a certain temperature, the intermolecular forces are broken, resulting in fluidity and thus reprocessing properties. However, most common shape memory polymers are thermosetting. Due to the limitations of their cross-linked networks, traditional thermosetting materials lack reprocessing properties; once cured, they cannot be melted or dissolved. While thermosetting materials generally have better stability than thermoplastics, their recycling remains a major challenge in the polymer field. Traditional landfilling and incineration not only fail to effectively utilize the remaining value of materials but also burden the environment. With increasing environmental awareness, research on the recycling of thermosetting materials has gained attention. The best approach to this problem is to develop new thermosetting materials that are easy to process, repair, and degrade.

[0004] On the other hand, bio-based materials possess characteristics that traditional polymer materials lack, such as being green, environmentally friendly, using renewable and biodegradable raw materials. In particular, tung oil, furfuryl alcohol, and dimer epoxy resins, with their readily available, renewable, low-toxicity, and highly versatile raw materials, have become a hot topic in bio-based polymer research. This invention utilizes bio-based resources to prepare intelligent functional polymer materials. It has certain theoretical guidance and application significance for promoting the advancement of plant oil-based intelligent polymer application technologies. Summary of the Invention

[0005] Technical problem solved: This invention provides a self-healing tung oil-based shape memory polymer and its preparation method. A shape memory polymer integrating dynamic Diels-Alder bonds and dynamic ester exchange is prepared using tung oil as raw material. In this invention, dynamic bonds are used as the reversible phase, and the strong interaction of rigid groups is used as the stationary phase, which ensures that the material has excellent self-healing and shape memory properties. Its own flexible chain also ensures the excellent flexibility of the material.

[0006] Technical Solution: A method for preparing a self-healing tung oil-based shape memory polymer. Step 1: Tung oil and maleic anhydride are added to a reaction vessel at a molar ratio of 1:(2.5-2.9), and 0.5% hydroquinone (by total mass) of the system is added. The mixture is reacted at 180℃ for 3 hours to obtain intermediate product A, which is then cooled to room temperature. Step 2: Intermediate product A and furfuryl alcohol are added to a reaction vessel at a molar ratio of 1:3, and 0.5% hexadecyltrimethylammonium chloride (by total mass) of the system is added. The mixture is reacted at 85℃ for 4 hours to obtain intermediate product B, which is then cooled to room temperature. Step 3: Intermediate product B is mixed with 4,4'-bismaleimide diphenylmethane, epoxy resin, and 1.5% zinc acetylacetone (by total mass). The molar ratio of intermediate product B to 4,4'-bismaleimide diphenylmethane is 2:3, and the molar ratio of intermediate product B to epoxy resin is (1-2):3. The mixture is cured at 120℃ for 2 hours to obtain the self-healing tung oil-based shape memory polymer.

[0007] The epoxy resin mentioned in the third step is E51 or dimer acid epoxy.

[0008] The molar ratio of tung oil to maleic anhydride mentioned in the first step is 1:2.9.

[0009] The molar ratio of intermediate product B to epoxy resin in the third step is 1:3.

[0010] The self-healing tung oil-based shape memory polymer was prepared by the above method.

[0011] The above polymers are used in the preparation of self-healing shape memory products.

[0012] Beneficial effects: (1) The introduction of reversible dynamic covalent bonds and dynamic ester bonds in this invention can not only improve the shape memory ability of polymer materials, but also make the materials have certain self-healing properties. (2) The preparation process of this invention is simple, the reaction is controllable, and the product obtained is stable and has certain utilization value. (3) The rigidity and flexibility properties can be adjusted by adjusting the ratio of 4,4'-bismaleimide diphenylmethane and epoxy resin added in the third curing process. Attached Figure Description

[0013] Figure 1 Initial fragmented materials;

[0014] Figure 2 This is a preview of the repaired result.

[0015] Figure 3 The initial material is solidified in the mold into a curved, serpentine initial state;

[0016] Figure 4 It is an intermediate shape when cooled to room temperature;

[0017] Figure 5 To restore the initial shape within 10 seconds after reheating at 65°C;

[0018] Figure 6 The infrared spectra of tung oil, intermediate product A, and intermediate product B in Examples 1-7 are shown.

[0019] In the infrared spectrum of tung oil, 1740 cm⁻¹ -1 The obvious peak is the absorption peak of the C=O stretching vibration of the ester group. In the infrared spectrum of intermediate product A, the peak is at 1849 cm⁻¹. -1 and 1775cm -1 The two prominent peaks at 1849 cm⁻¹ are characteristic peaks of the anhydride group, and the intensity of the low-frequency peak is higher than that of the high-frequency peak, indicating that intermediate product A contains a cyclic structure of anhydride group. A comparison of the infrared spectra of intermediate product A and intermediate product B shows that the anhydride group in intermediate product B is present at 1849 cm⁻¹. -1 and 1775cm -1 The two characteristic peaks disappeared at 1708 cm⁻¹ -1 The newly added peak at this point is the absorption peak of the C=O bond in the carboxyl and ester groups, indicating the formation of a carboxyl group and an ester group from the ring opening of the acid anhydride. Meanwhile, the 2500-3000 cm⁻¹ peak in intermediate product B... -1 The formation of the broad peak also confirms the formation of carboxyl groups. Detailed Implementation

[0020] All parts not mentioned herein are the same as or can be implemented using existing technology. The following are preferred embodiments of the present invention, but the present invention is not limited to the following limited embodiments, and minor modifications to the embodiments shall also be considered within the scope of protection of the present invention.

[0021] Example 1

[0022] Step 1: Add tung oil and maleic anhydride to a reaction vessel at a molar ratio of 1:2.9, add 0.5% hydroquinone by mass of the total system, and react at 180℃ for 3 hours to obtain intermediate product A, then cool to room temperature. Step 2: Add intermediate product A and furfuryl alcohol to a reaction vessel at a molar ratio of 1:3, add 0.5% hexadecyltrimethylammonium chloride by mass of the total system, and react at 85℃ for 4 hours to obtain intermediate product B, then cool to room temperature. Step 3: Mix intermediate product B with 4,4'-bismaleimide diphenylmethane (molar amount is 150% of the molar amount of intermediate product B), E51 epoxy resin (molar amount is 300% of the molar amount of intermediate product B), and zinc acetylacetonate (mass is 1.5% of the total system mass), and cure at 120℃ for 2 hours to obtain a self-healing tung oil-based shape memory polymer.

[0023] Example 2

[0024] Step 1: Tung oil and maleic anhydride were added to a reaction vessel at a molar ratio of 1:2.9, along with 0.5% hydroquinone by mass of the total system mass. The mixture was reacted at 180°C for 3 hours to obtain intermediate product A, which was then cooled to room temperature. Step 2: Intermediate product A and furfuryl alcohol were added to a reaction vessel at a molar ratio of 1:3, along with 0.5% hexadecyltrimethylammonium chloride by mass of the total system mass. The mixture was reacted at 85°C for 4 hours to obtain intermediate product B, which was then cooled to room temperature. Step 3: Intermediate product B was mixed with 4,4'-bismaleimide diphenylmethane (150% of the molar amount of intermediate product B), E51 epoxy resin (225% of the molar amount of intermediate product B, i.e., reduced to 75% of the original amount from the amount added in Example 1), and zinc acetylacetonate (1.5% of the total system mass). The mixture was cured at 120°C for 2 hours to obtain a self-healing tung oil-based shape memory polymer.

[0025] Example 3

[0026] Step 1: Add tung oil and maleic anhydride to a reaction vessel at a molar ratio of 1:2.9, add 0.5% hydroquinone by mass of the total system, and react at 180℃ for 3 hours to obtain intermediate product A, then cool to room temperature. Step 2: Add intermediate product A and furfuryl alcohol to a reaction vessel at a molar ratio of 1:3, add 0.5% hexadecyltrimethylammonium chloride by mass of the total system, and react at 85℃ for 4 hours to obtain intermediate product B, then cool to room temperature. Step 3: Mix intermediate product B with 4,4'-bismaleimide diphenylmethane (molar amount is 150% of the molar amount of intermediate product B) and dimer epoxy (molar amount is 150% of the molar amount of intermediate product B), and cure at 120℃ for 2 hours to obtain a self-healing tung oil-based shape memory polymer.

[0027] Example 4

[0028] Step 1: Add tung oil and maleic anhydride to a reaction vessel at a molar ratio of 1:2.9, add 0.5% hydroquinone by mass of the total system, and react at 180℃ for 3 hours to obtain intermediate product A, then cool to room temperature. Step 2: Add intermediate product A and furfuryl alcohol to a reaction vessel at a molar ratio of 1:3, add 0.5% hexadecyltrimethylammonium chloride by mass of the total system, and react at 85℃ for 4 hours to obtain intermediate product B, then cool to room temperature. Step 3: Mix intermediate product B with 4,4'-bismaleimide diphenylmethane (molar amount is 150% of the molar amount of intermediate product B), dimer epoxy (molar amount is 150% of the molar amount of intermediate product B), and zinc acetylacetonate (mass is 1.5% of the total system mass), and cure at 120℃ for 2 hours to obtain a self-healing tung oil-based shape memory polymer.

[0029] Example 5

[0030] Step 1: Tung oil and maleic anhydride were added to a reaction vessel at a molar ratio of 1:2.9, along with 0.5% hydroquinone by mass of the total system mass. The mixture was reacted at 180°C for 3 hours to obtain intermediate product A, which was then cooled to room temperature. Step 2: Intermediate product A and furfuryl alcohol were added to a reaction vessel at a molar ratio of 1:3, along with 0.5% hexadecyltrimethylammonium chloride by mass of the total system mass. The mixture was reacted at 85°C for 4 hours to obtain intermediate product B, which was then cooled to room temperature. Step 3: Intermediate product B was mixed with 4,4'-bismaleimide diphenylmethane (molar amount 150% of the molar amount of intermediate product B), dimer epoxy (molar amount 112.5% ​​of the molar amount of intermediate product B, i.e., the amount added was reduced to 75% based on Example 4), and zinc acetylacetonate (mass 1.5% of the total system mass). The mixture was cured at 120°C for 2 hours to obtain a self-healing tung oil-based shape memory polymer.

[0031] Example 6

[0032] Step 1: Add tung oil and maleic anhydride to a reaction vessel at a molar ratio of 1:2.9, add 0.5% hydroquinone by mass of the total system, and react at 180℃ for 3 hours to obtain intermediate product A, then cool to room temperature. Step 2: Add intermediate product A and furfuryl alcohol to a reaction vessel at a molar ratio of 1:3, add 0.5% hexadecyltrimethylammonium chloride by mass of the total system, and react at 85℃ for 4 hours to obtain intermediate product B, then cool to room temperature. Step 3: Mix intermediate product B with E51 epoxy resin (molar amount is 300% of the molar amount of intermediate product B) and zinc acetylacetonate (mass is 1.5% of the total system mass), and cure at 120℃ for 2 hours to obtain a self-healing tung oil-based shape memory polymer.

[0033] Example 7

[0034] Step 1: Add tung oil and maleic anhydride to a reaction vessel at a molar ratio of 1:2.9, add 0.5% hydroquinone by mass of the total system, and react at 180℃ for 3 hours to obtain intermediate product A, then cool to room temperature. Step 2: Add intermediate product A and furfuryl alcohol to a reaction vessel at a molar ratio of 1:3, add 0.5% hexadecyltrimethylammonium chloride by mass of the total system, and react at 85℃ for 4 hours to obtain intermediate product B, then cool to room temperature. Step 3: Mix intermediate product B with dimer epoxy (molar amount is 150% of the molar amount of intermediate product B) and zinc acetylacetonate (mass is 1.5% of the total system mass), and cure at 120℃ for 2 hours to obtain a self-healing tung oil-based shape memory polymer.

[0035] The polymer materials prepared in each embodiment were made into test strips and subjected to tensile mechanical property tests. The results are shown in Table 1.

[0036] Table 1 Performance comparison of each embodiment group

[0037]

[0038] The polymer material of Example 5 was subjected to a self-healing performance test: the initial fragment material (such as...) was... Figure 1 After being hot-pressed at 120℃ for 10 minutes, the dynamic bonds in the fragmented material are reconnected, achieving a complete restoration effect (e.g., Figure 2 ).

[0039] The polymer material of Example 5 was subjected to shape memory performance testing: the initial material was cured in a mold into a curved serpentine shape as the initial state, such as... Figure 3 It is reshaped at 65°C to unfold the curved serpentine shape, and then cooled to room temperature to fix it into an intermediate shape, such as... Figure 4 Reheating at 65°C will restore the object to its original shape within 10 seconds. Figure 5 。

Claims

1. A method for preparing a self-healing tung oil-based shape memory polymer, characterized in that, Step 1: Add tung oil and maleic anhydride to a reaction vessel at a molar ratio of 1:(2.5~2.9), add 0.5% hydroquinone by mass of the total system, and react at 180℃ for 3 hours to obtain intermediate product A, then cool to room temperature; Step 2: Add intermediate product A and furfuryl alcohol to a reaction vessel at a molar ratio of 1:3, add 0.5% hexadecyltrimethylammonium chloride by mass of the total system, and react at 85℃ for 4 hours to obtain intermediate product B, then cool to room temperature; Step 3: Mix intermediate product B with 4,4'-bismaleimide diphenylmethane, epoxy resin, and 1.5% zinc acetylacetone by mass of the total system, wherein the molar ratio of intermediate product B to 4,4'-bismaleimide diphenylmethane is 2:3, and the molar ratio of intermediate product B to epoxy resin is (1~2):3, and cure at 120℃ for 2 hours to obtain a self-healing tung oil-based shape memory polymer.

2. The preparation method of the self-healing tung oil-based shape memory polymer according to claim 1, characterized in that, The epoxy resin mentioned in the third step is E51 or dimer acid epoxy.

3. The preparation method of the self-healing tung oil-based shape memory polymer according to claim 1, characterized in that, The molar ratio of tung oil to maleic anhydride mentioned in the first step is 1:2.

9.

4. The preparation method of the self-healing tung oil-based shape memory polymer according to claim 1, characterized in that, The molar ratio of intermediate product B to epoxy resin in the third step is 1:

3.

5. The self-healing tung oil-based shape memory polymer prepared by any of the preparation methods described in claims 1-4.

6. The use of the polymer of claim 5 in the preparation of self-healing shape memory products.

Images