Comonomers for direct olefin metathesis polymerization to make high molecular weight materials and methods of making

Abstract

The present disclosure provides a comonomer for directly preparing a high molecular material by olefin metathesis polymerization, the comonomer has norbornene as an end-capping group, and the structure of the comonomer is shown in the following formula M1-M3. The present disclosure also provides a preparation method of the comonomer, a structural monomer directly prepared by olefin metathesis polymerization using the comonomer, and a high molecular material.

Description

Technical Field

[0001] This disclosure relates to the field of polymer material synthesis, specifically to a comonomer for the direct preparation of polymer materials by olefin metathesis polymerization and a preparation method thereof. Background Technology

[0002] With the rapid development of modern science and technology, various industries are placing increasingly stringent demands on the performance of polymer materials. While polymer materials prepared using traditional methods may exhibit excellent performance in some aspects, they often struggle to simultaneously achieve superior levels in multiple key performance indicators such as strength, toughness, thermal stability, and recyclability. This limitation significantly restricts the widespread application of polymer materials in high-end manufacturing, environmental protection and energy conservation, and medical and health fields.

[0003] Finding suitable structural monomers and appropriate preparation methods is a complex and challenging process that requires interdisciplinary knowledge and technical support. The search for suitable structural monomers and appropriate preparation methods among numerous compounds is of profound significance. The synthesis of polymer materials typically involves many complex chemical reactions, such as polymerization, addition, and condensation. These reactions require precise control of conditions such as temperature, pressure, and reactant ratios; even slight errors can lead to poor product performance or even synthesis failure. This complexity increases the difficulty and uncertainty of polymer synthesis. Furthermore, the synthesis of polymer materials usually involves the use of large amounts of solvents and catalysts, which are often difficult to fully recover and dispose of after the reaction, thus causing environmental pollution. In addition, some polymer materials may release harmful substances during use, posing a threat to the environment and human health.

[0004] Therefore, finding suitable synthetic monomers and designing scientifically sound preparation methods to achieve green synthesis and sustainable development of polymer materials is one of the important challenges we face today. Summary of the Invention

[0005] In view of this, in order to solve at least one technical problem in related technologies and other aspects, this disclosure proposes a comonomer for the direct preparation of polymer materials by olefin metathesis polymerization, characterized in that the comonomer uses norbornene as the end group, and the structure of the comonomer is shown in the following formulas M1~M3:

[0006] .

[0007] In another aspect of this disclosure, a method for preparing the aforementioned comonomer is also provided, comprising:

[0008] The compound shown in formula A is dissolved in toluene solvent and reacted with the compound shown in formula B or C at a first temperature to obtain comonomer M1 or comonomer M2; or,

[0009] The compound shown in formula D and the compound shown in formula E were dissolved in N,N-dimethylimide solvent and reacted at a first temperature to obtain comonomer M3.

[0010] .

[0011] According to embodiments of this disclosure, the molar ratio of compound A to compound B or compound C is 1:2; the molar ratio of compound D to compound E is 1:2; and the first temperature is 70-80°C.

[0012] In another aspect of this disclosure, a structural monomer for the direct preparation of polymer materials by olefin metathesis polymerization is also proposed, the structural monomer being shown in formula (Ⅰ) below.

[0013] Equation (Ⅰ);

[0014] Wherein, X is selected from borate ester groups or maleamide groups; Y is selected from C1-C6 alkanes, C1-C6 cycloalkanes, and C1-C8 cycloalkenes; m and n are each independently selected from integers between 100 and 1000.

[0015] According to embodiments of this disclosure,

[0016] X is selected from or Group; Y is selected from , or Group.

[0017] According to embodiments of this disclosure, the structural unit is shown in formulas (Ⅰ-1) to (Ⅰ-3):

[0018] .

[0019] According to embodiments of this disclosure, polymeric materials include thermoplastic materials, thermosetting materials, and elastomer materials.

[0020] In another aspect of this disclosure, a method for directly preparing polymeric materials by olefin metathesis polymerization is also proposed, comprising:

[0021] The aforementioned comonomer and cyclic olefin monomer are mixed, and a metathesis catalyst is added under oil bath conditions to undergo a metathesis polymerization reaction to obtain the aforementioned structural monomer; wherein, the cyclic olefin monomer includes any one of dicyclopentadiene, norbornene, and cyclooctene.

[0022] According to embodiments of this disclosure, the oil bath temperature is 40-45°C.

[0023] According to embodiments of this disclosure, the metathesis catalyst is a Grignard catalyst.

[0024] According to embodiments of this disclosure, the comonomer uses norbornene as the end-capping group. Norbornene possesses a unique chemical structure and reactivity, enabling this comonomer to exhibit reactivity during olefin metathesis polymerization. Using this comonomer for olefin metathesis polymerization helps simplify the polymerization process, improve polymerization efficiency, and reduce the generation of byproducts. Furthermore, it is used in an olefin ring-opening metathesis polymerization reaction with dicyclopentadiene (DCPD), norbornene (NB), or cyclooctene (COE) monomers. In this reaction, the cyclic olefin monomers form chain-like polymers through the breaking and recombination of double bonds, while retaining the double bonds in the monomers as dynamic covalent bonds, thus obtaining a thermoplastic, thermosetting, and elastomer polymer material in one step. This polymer material exhibits excellent mechanical, self-healing, and recyclable properties, meeting the requirements of green environmental protection. Attached Figure Description

[0025] Figure 1 This is the 1H NMR spectrum of the comonomer M1 prepared in Example 1-1 of this disclosure;

[0026] Figure 2 This is the carbon NMR spectrum of the comonomer M1 prepared in Example 1-1 of this disclosure;

[0027] Figure 3 This is the mass spectrum of the comonomer M1 prepared in Example 1-1 of this disclosure;

[0028] Figure 4 This is the 1H NMR spectrum of the comonomer M2 prepared in Examples 1-2 of this disclosure;

[0029] Figure 5 This is the carbon NMR spectrum of the comonomer M2 prepared in Examples 1-2 of this disclosure;

[0030] Figure 6 This is the mass spectrum of the comonomer M2 prepared in Examples 1-2 of this disclosure;

[0031] Figure 7 This is the 1H NMR spectrum of the comonomer M3 prepared in Examples 1-3 of this disclosure;

[0032] Figure 8 This is the carbon NMR spectrum of the comonomer M3 prepared in Examples 1-3 of this disclosure;

[0033] Figure 9 This is the mass spectrum of the comonomer M3 prepared in Examples 1-3 of this disclosure;

[0034] Figure 10This is a stress-strain curve of the elastomeric polymer material L1 (polymerized from comonomer M3) recycled in the test examples of this disclosure under tension.

[0035] Figure 11 This is a stress-strain curve of the elastomeric polymer material L1 (polymerized from comonomer M3) in the test examples of this disclosure under tensile repetition.

[0036] Figure 12 This is a stress-strain curve of the thermosetting polymer material L3 (polymerized from comonomer M1) in the test examples of this disclosure under tension during fracture self-repair.

[0037] Figure 13 This is a stress-strain curve of the thermosetting polymer material L3 (polymerized from comonomer M2) in the test examples of this disclosure under tension during fracture self-repair.

[0038] Figure 14 This is a stress-strain curve of the thermosetting polymer material L3 (polymerized from comonomer M3) in the test examples of this disclosure under tension during fracture self-repair.

[0039] Figure 15 This is a stress-strain curve of the thermoplastic polymer material L2 (polymerized from comonomers M1, M2, and M3) under tension in the test examples of this disclosure. Detailed Implementation

[0040] To make the objectives, technical solutions, and advantages of this disclosure clearer, the following detailed description is provided in conjunction with specific embodiments and the accompanying drawings.

[0041] The endpoints and any values ​​of the ranges disclosed in this disclosure are not limited to the precise ranges or values, and such ranges or values ​​should be understood to include values ​​close to such ranges or values. For numerical ranges, the endpoint values ​​of the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be regarded as specifically disclosed in this disclosure.

[0042] The terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit this disclosure. The terms “comprising,” “including,” etc., as used herein indicate the presence of the stated features, steps, operations, and / or components, but do not exclude the presence or addition of one or more other features, steps, operations, or components.

[0043] All terms used herein (including technical and scientific terms) have the meanings commonly understood by those skilled in the art, unless otherwise defined. It should be noted that the terms used herein are to be interpreted in a manner consistent with the context of this specification, and not in an idealized or overly rigid way.

[0044] It should be noted that, unless otherwise defined, the technical or scientific terms used in this disclosure should have the ordinary meaning understood by a person with ordinary skill in the art to which this disclosure pertains. Where the terms "first," "second," etc., are used throughout, they are used only to distinguish similar objects and should not be construed as indicating or implying their relative importance, order of precedence, or implicitly specifying the number of technical features indicated. It should be understood that the data described by "first," "second," etc., can be interchanged where appropriate.

[0045] Similarly, to simplify this disclosure and aid in understanding one or more of the various aspects of the disclosure, in the above description of exemplary embodiments of the present disclosure, various features of the present disclosure are sometimes grouped together in a single embodiment, figure, or description thereof. The use of terms such as "one embodiment," "some embodiments," "example," "specific example," or "some examples," etc., refers to a specific feature, structure, material, or characteristic described in connection with that embodiment or example, which is included in at least one embodiment or example of the present disclosure. In this specification, illustrative expressions of the above terms do not necessarily refer to the same embodiment or example. Furthermore, the specific features, structures, materials, or characteristics described may be combined in any suitable manner in one or more embodiments or examples.

[0046] Furthermore, the technical solutions of the various embodiments can be combined with each other, but only if they are based on the ability of a person skilled in the art to implement them. When the combination of technical solutions is contradictory or cannot be implemented, it should be considered that such combination of technical solutions does not exist and is not within the scope of protection claimed in this disclosure.

[0047] To overcome the technical challenges of complex preparation methods and difficulty in finding suitable compounds in existing technologies, this disclosure focuses on developing a series of novel methods for synthesizing polymer materials. Specifically, the direct preparation of thermoplastic, thermosetting, and elastomer materials with dynamically exchangeable covalent bonds has become the research focus of this disclosure. This method can not only endow polymer materials with superior physical and chemical properties, such as higher strength, better toughness, and excellent thermal stability, but more importantly, it can also achieve the recyclability and reusability of materials, thereby greatly reducing the burden on the environment.

[0048] In the process of realizing this disclosure, it was discovered that ring-opening metathesis polymerization (ROMP) is a highly distinctive polymerization method in the preparation of polymer materials. As a highly efficient and flexible polymerization technology, ROMP has demonstrated unique advantages in the preparation of functionalized polyolefins. The development and application of this novel synthetic method will not only promote theoretical innovation and technological progress in the field of polymer materials science, but also provide strong scientific and technological support for solving current global challenges such as resource scarcity and environmental pollution. Simultaneously, it will inject new vitality and impetus into the transformation, upgrading, and sustainable development of related industries, leading the future polymer materials industry towards a greener, more environmentally friendly, and more efficient direction.

[0049] This disclosure proposes a comonomer for the direct preparation of polymer materials by olefin metathesis polymerization, characterized in that the comonomer uses norbornene as the end group, and the structure of the comonomer is shown in formulas M1~M3 below:

[0050] .

[0051] According to embodiments of this disclosure, the comonomer uses norbornene as the end-capping group. The norbornene group possesses a unique chemical structure and reactivity, enabling this comonomer to exhibit reactivity during olefin metathesis polymerization. Using this comonomer for olefin metathesis polymerization helps simplify the polymerization process, improve polymerization efficiency, and reduce the generation of byproducts.

[0052] In another aspect of this disclosure, a method for preparing the aforementioned comonomer is also provided, comprising:

[0053] The compound shown in formula A is dissolved in toluene solvent and reacted with the compound shown in formula B or C at a first temperature to obtain comonomer M1 or comonomer M2; or,

[0054] The compound shown in formula D and the compound shown in formula E were dissolved in N,N-dimethylimide solvent and reacted at a first temperature to obtain comonomer M3.

[0055] .

[0056] According to embodiments of this disclosure, the molar ratio of compound A to compound B or compound C is 1:2; the molar ratio of compound D to compound E is 1:2; and the first temperature is 70-80°C.

[0057] In another aspect of this disclosure, a structural monomer for the direct preparation of polymer materials by olefin metathesis polymerization is also proposed, the structural monomer being shown in formula (Ⅰ) below.

[0058] Equation (Ⅰ);

[0059] Wherein, X is selected from borate ester groups or maleamide groups; Y is selected from C1-C6 alkanes, C1-C6 cycloalkanes, and C1-C8 cycloalkenes; m and n are each independently selected from integers between 100 and 1000.

[0060] According to the embodiments of this disclosure, the polymer materials directly prepared by olefin metathesis polymerization proposed in this disclosure have excellent mechanical, self-healing and recyclable properties due to the abundance of dynamic covalent bonds in their structural monomers, which meets the requirements of green environmental protection.

[0061] According to embodiments of this disclosure,

[0062] X is selected from or Group; Y is selected from , or Group.

[0063] According to embodiments of this disclosure, the structural unit is shown in formulas (Ⅰ-1) to (Ⅰ-3):

[0064] .

[0065] According to embodiments of this disclosure, polymeric materials include thermoplastic materials, thermosetting materials, and elastomer materials.

[0066] In another aspect of this disclosure, a method for directly preparing polymeric materials by olefin metathesis polymerization is also proposed, comprising:

[0067] The aforementioned comonomer and cyclic olefin monomer are mixed, and a metathesis catalyst is added under oil bath conditions to undergo a metathesis polymerization reaction to obtain the aforementioned structural monomer; wherein, the cyclic olefin monomer includes any one of dicyclopentadiene, norbornene, and cyclooctene.

[0068] According to embodiments of this disclosure, an olefin ring-opening metathesis polymerization reaction is carried out by a easily prepared copolymerizable monomer containing dynamic covalent bonds and a monomer of dicyclopentadiene (DCPD), norbornene (NB), or cyclooctene (COE). In this process, the cyclic olefin monomers form chain-like polymers through the breaking and recombination of double bonds, while retaining the double bonds in the monomers as dynamic covalent bonds, thus obtaining a thermoplastic, thermosetting, and elastomer polymer material in one step. Specifically, the reaction of dicyclopentadiene (DCPD) with the comonomer yields a thermosetting polymer material, the reaction of norbornene (NB) with the comonomer yields a thermoplastic polymer material, and the reaction of cyclooctene (COE) with the comonomer yields an elastomer polymer material.

[0069] According to embodiments of this disclosure, the oil bath temperature is 40-45°C.

[0070] According to embodiments of this disclosure, the metathesis catalyst is a Grignard catalyst.

[0071] According to embodiments of this disclosure, Grignard catalysts have high catalytic activity and, when applied to ROMP reactions, can initiate and accelerate the ROMP reaction while improving reaction efficiency and stability.

[0072] It should be noted that the described embodiments are merely some, not all, of the embodiments disclosed herein. Other embodiments obtained by those skilled in the art based on the embodiments of this disclosure without inventive effort are all within the scope of protection of this disclosure.

[0073] Example 1-1

[0074] Compound A (2.0 eq.) was dissolved in toluene (concentration: 0.2 M), and compound B (1.0 eq.) was added at room temperature. After reacting for 10 h, the target comonomer M1 was obtained by vacuum distillation. The specific reaction formula is as follows:

[0075] .

[0076] Figure 1 , 2 3 and 4 are respectively the 1H NMR spectra of the comonomer M1 prepared in Examples 1-1 of this disclosure. 1 HNMR (CDCl3) spectrum, carbon NMR spectrum 13 CNMR (CDCl3) and mass spectrum.

[0077] like Figure 1-3 As shown, NMR and mass spectrometry tests were performed on the comonomer M1 to verify its structure and composition.

[0078] Examples 1-2

[0079] Compound A (2.0 eq.) was dissolved in toluene (concentration: 0.2 M), and compound C (1.0 eq.) was added at room temperature. After reacting for 10 h, the target comonomer M2 was obtained by vacuum distillation. The specific reaction formula is as follows:

[0080] .

[0081] Figure 4 , 5 6 and 6 are respectively the 1H NMR spectra of the comonomer M2 prepared in Examples 1-2 of this disclosure. 1 HNMR (CDCl3) spectrum, carbon NMR spectrum 13CNMR (CDCl3) and mass spectrum.

[0082] like Figure 4-6 As shown, NMR and mass spectrometry tests were performed on the comonomer M2 to verify its structure and composition.

[0083] Examples 1-3

[0084] Compound D (2.0 eq.) was dissolved in 100 mL of N,N-dimethylimide solvent (concentration: 0.2 M), and compound E (1.0 eq.) was added at 70-80 °C. After reacting for 3 h, the target comonomer M3 was obtained by vacuum distillation. The specific reaction formula is as follows:

[0085] .

[0086] Figure 7 , 8 9 and 9 are respectively the 1H NMR spectra of the comonomer M3 prepared in Examples 1-3 of this disclosure. 1 HNMR (CDCl3) spectrum, carbon NMR spectrum 13 CNMR (CDCl3) and mass spectrum.

[0087] like Figure 7-9 As shown, NMR and mass spectrometry tests were performed on the comonomer M3 to verify its structure and composition.

[0088] Example 2-1

[0089] Under a nitrogen atmosphere, dicyclopentadiene (DCPD) (50 eq.), any one of the comonomers M1, M2, and M3 (1 eq.) prepared in Examples 1-1 to 1-3, and anhydrous dichloromethane (concentration: 0.4 M) were added to a Schlenk reaction flask. The reaction flask was placed in an oil bath at 40-45 °C, and Grignard catalyst GII (0.005 eq.) was added to the reaction flask. The reaction was continued for 2 hours. After the reaction was completed, the solvent was concentrated, and an appropriate amount of methanol (concentration: 0.3 M) was added to precipitate the polymer. The polymer was then filtered, washed, and dried to obtain the elastomer polymer material L1, whose reaction formula is shown below:

[0090] .

[0091] Example 2-2

[0092] In Example 2-2, a thermoplastic polymer material was prepared using the same or similar preparation method as in Example 2-1. The difference from Example 2-1 is that dicyclopentadiene (DCPD) was replaced with norbornene (NB) in Example 2-1, resulting in thermoplastic polymer material L2. The reaction formula is shown below:

[0093] .

[0094] Example 2-3

[0095] In Examples 2-3, a thermosetting polymer material was prepared using the same or similar methods as in Example 2-1. The difference was that dicyclopentadiene (DCPD) in Example 2-1 was replaced with cyclooctene (COE), resulting in thermosetting polymer material L3. The reaction formula is shown below:

[0096]

[0097] Mechanical property testing

[0098] The mechanical properties of the elastomeric polymer L1, thermoplastic polymer L2, and thermosetting polymer L3 prepared in Examples 2-1 to 2-3 were tested. The test specimens were dumbbell-shaped strips, 25 mm long, 2 mm wide (at their narrowest point), and 0.5 mm thick, according to the standard test method ASTM 638. Stress / strain tests were conducted at room temperature at a speed of 10 m / min. At least two specimens were tested for each sample.

[0099] Figure 10 This is a stress-strain curve of the elastomeric polymer material L1 (polymerized from comonomer M3, denoted as L1-M3) recycled in the test examples of this disclosure under tension.

[0100] like Figure 10 As shown, five curves represent the strain changes of the elastomer after the first, second, third, and fourth cycles. With increasing stress, the strain of the elastomer gradually increases after each cycle. It can be seen that after multiple cycles of repeated processing, the elastomer polymer material L1-M3 still maintains good mechanical properties.

[0101] Figure 11 This is a stress-strain curve of the elastomeric polymer material L1 (polymerized from comonomer M3, denoted as L1-M3) recycled in the test examples of this disclosure during tensile repetition.

[0102] like Figure 11The figure shows the strain changes of the elastomer polymer material L1-M3 under different stress levels after multiple cycles. The elastomer exhibits the largest strain during the first cycle. This is likely because the molecular chain structure within the elastomer material undergoes significant adjustments during the initial cycle, resulting in a more pronounced strain response. With increasing cycle count, the strain gradually increases, but the rate of increase may gradually slow down. This indicates that the strain performance of the elastomer may gradually stabilize after multiple cycles. However, by the fourth cycle, the strain begins to decrease again. This may be due to some degree of fatigue or damage occurring in the elastomer material after multiple cycles, leading to a weakened strain response at the same stress level.

[0103] Figure 12 This is a stress-strain curve of the thermosetting polymer material L3 (polymerized from comonomer M1, denoted as L3-M1) in the test examples of this disclosure, under tensile stress during fracture self-repair.

[0104] like Figure 12 As shown, the presence of dynamic covalent bonds within the structural monomers enables the material to repair itself under heating conditions. Furthermore, the thorough self-healing process allows the thermosetting polymer L3-M1 to exhibit stronger resistance to deformation and higher strength and stiffness after self-repair following fracture. The self-healing time significantly impacts the material's mechanical properties; thermosetting polymer L3-M1 can recover to a high performance level within a short period.

[0105] Figure 13 , Figure 14 These are the stress-strain curves of the thermosetting polymer material L3 (polymerized from comonomer M2, denoted as L3-M2, and M3, denoted as L3-M3) in the test examples of this disclosure, under tensile stress during fracture self-repair.

[0106] like Figure 13 , Figure 14 As shown, it is verified that the thermosetting polymer materials L3-M2 and L3-M3 obtained by polymerization of comonomers M2 and M3 also have excellent self-healing properties.

[0107] Figure 15 This is a stress-strain curve of the thermoplastic polymer material L2 (polymerized from comonomers M1, M2, and M3, respectively, and denoted as L2-M1, L2-M2, and L2-M3) under tension in the test examples of this disclosure.

[0108] like Figure 15 As shown, the stress in all three materials increases with increasing strain. This indicates that the material needs to withstand greater force to continue deforming during the tensile process. Among them, the L2-M1 material with a larger slope exhibits higher stress at the same strain, implying that it has greater stiffness or higher strength.

[0109] The specific embodiments described above further illustrate the purpose, technical solutions, and beneficial effects of this disclosure. It should be understood that the above descriptions are merely specific embodiments of this disclosure and are not intended to limit this disclosure. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of this disclosure should be included within the protection scope of this disclosure.

Claims

1. A comonomer for the direct preparation of polymer materials by olefin metathesis polymerization, characterized in that, The comonomer uses norbornene as the end-capping group, and the structure of the comonomer is shown in formulas M1 to M3 below: 。 2. A method for preparing the comonomer as described in claim 1, comprising: The compound represented by formula A is dissolved in toluene solvent and reacted with the compound represented by formula B or C at a first temperature to obtain the comonomer M1 or the comonomer M2; or, The compound shown in formula D and the compound shown in formula E were dissolved in N,N-dimethylimide solvent and reacted at a first temperature to obtain comonomer M3. 。 3. The method according to claim 2, wherein, The molar ratio of compound A to either compound B or compound C is 1:2; The molar ratio of compound D to compound E is 1:2; The first temperature is 70-80℃.

4. A method for directly preparing polymer materials by olefin metathesis polymerization, comprising: The comonomer as described in claim 1 is mixed with a cyclic olefin monomer, and a metathesis catalyst is added under oil bath conditions to undergo a metathesis polymerization reaction to obtain the structural monomer. The cyclic olefin monomer is any one of dicyclopentadiene, norbornene, and cyclooctene.

5. The method according to claim 4, wherein, The oil bath temperature is 40-45℃.

6. The method according to claim 4, wherein, The metathesis catalyst is a Grignard catalyst.

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