A method for high-throughput preparation of functionalized polyolefins based on macro-microreactors

Abstract

The application discloses a method for high-throughput preparation of functionalized polyolefin based on a macro-micro reactor, and the functionalized polyolefin is obtained by reacting a norbornene monomer, a catalyst and a solvent in the macro-micro reactor. The application is suitable for the norbornene monomer, and compared with a traditional synthesis method, the macro-micro reactor containing an inner member can significantly shorten the ring-opening metathesis polymerization reaction time and improve the conversion rate. The characteristic scale of the macro-micro reactor reaches a centimeter level, and high-throughput synthesis can be realized. The application provides a technical scheme for the functionalized polyolefin, and has an industrial conversion prospect.

Description

Technical Field

[0001] This invention relates to the field of polymer synthesis technology, and more specifically to a method for preparing functionalized polyolefins based on macro-microreactors. Background Technology

[0002] This section provides only background information relevant to this disclosure and is not necessarily prior art.

[0003] Since the pioneering progress made by Karl Ziegler and Giulio Natta in polyolefin synthesis in the early 1950s, significant research breakthroughs and industrial innovations have been achieved in areas such as catalyst design, polymerization processes, and processing methods, greatly simplifying polyolefin production processes and reducing production costs. Polyolefins possess many advantages, including being lightweight, corrosion-resistant, low-cost, having tunable properties, and being easy to process. These advantages are closely related to their mature production technologies, large-scale raw material production, and excellent structural tunability. Meanwhile, due to their good chemical stability, biocompatibility, and bioinertness, polyolefins have been widely used in biomedical materials since their inception.

[0004] Currently, the main synthesis strategies for functionalized polyolefins are as follows: (1) olefin metathesis polymerization, (2) ylide homopolymerization, (3) post-functionalization, (4) copolymerization with polar monomers, and (5) chain transfer.

[0005] Ring-opening metathesis polymerization (ROMP) is a type of olefin metathesis reaction. Since the invention of molybdenum-based and ruthenium-based catalysts in the 1990s, ROMP has experienced rapid development. Under the action of these highly efficient single-component homogeneous catalysts, cyclic olefins with high ring strain (such as norbornene) are driven by the release of ring strain to synthesize polymers with unsaturated double bonds in the main chain through the continuous formation and ring cleavage of metal cyclobutane structures. ROMP has advantages such as mild reaction conditions, high catalytic efficiency, and good reaction control. Currently, ROMP has become an important tool for synthesizing functionalized polyolefins due to the unique structure of its products and the good tolerance of catalysts to various functional groups.

[0006] Compared to batch reactors, continuous flow reactors, with their advantages of high mass and heat transfer efficiency, good mixing performance, and good spatiotemporal control, are receiving increasing attention in polymer synthesis, with typical microreactors at the hundred-micrometer scale being the most widely used. However, in typical microreactors, the pressure drop inside the channels increases with the increase of the reaction liquid flow rate or viscosity, accompanied by the risk of pipe blockage and rupture, placing higher demands on the reliability of pipe materials and connections. Therefore, research on macro-microreactors is needed to achieve higher efficiency than typical reactors and continuous flow reactors of the same scale by incorporating internal components. Macro-microreactors have higher synthesis efficiency, providing a foundation for high-throughput preparation of functionalized polyolefins and are of great significance for the industrial production of functionalized polyolefins. Summary of the Invention

[0007] Purpose of the invention: The technical problem to be solved by the present invention is to provide a method for high-throughput preparation of functionalized polyolefins based on macro-micro reactors, addressing the shortcomings of existing technologies.

[0008] Invention Concept: Ring-opening metathesis polymerization (ROMP) is a type of olefin metathesis reaction. Since the invention of molybdenum-based and ruthenium-based catalysts in the 1990s, ROMP has experienced rapid development. Under the action of these highly efficient single-component homogeneous catalysts, cyclic olefins with high ring strain (such as norbornene) are driven by the release of ring strain to synthesize polymers with unsaturated double bonds in the main chain through the continuous formation and ring cleavage of metal cyclobutane structures. ROMP offers advantages such as mild reaction conditions, high catalytic efficiency, and good reaction control. Currently, ROMP has become an important tool for synthesizing functionalized polyolefins due to the unique structure of its products and the good tolerance of the catalysts to various functional groups.

[0009] Continuous flow reactors, with their advantages of high mass and heat transfer efficiency, good mixing performance, and good spatiotemporal control, are receiving increasing attention in the field of polymer synthesis, among which typical microreactors at the hundred-micrometer scale are the most widely used. However, in typical microreactors, as the flow rate or viscosity of the reaction liquid increases, the pressure drop inside the channel increases, accompanied by the risk of pipe blockage and rupture, placing higher demands on the reliability of pipe materials and connections. Therefore, research on macro-microreactors is needed to achieve higher efficiency than typical reactors and continuous flow reactors of the same scale by incorporating internal components. Macro-microreactors have higher synthesis efficiency, providing a foundation for high-throughput preparation of functionalized polyolefins and are of great significance for the industrial production of functionalized polyolefins.

[0010] To solve the above-mentioned technical problems, the present invention discloses the following technical solution:

[0011] In a first aspect, the present invention discloses the application of a macro-microreactor in the preparation of functionalized polyolefins. Specifically, the application involves preparing functionalized polyolefins using norbornene monomers as raw materials. Specifically, in a macro-microreactor, the norbornene monomers, a ruthenium catalyst or a molybdenum catalyst, and a solvent are reacted to obtain functionalized polyolefins.

[0012] Secondly, this invention discloses a method for preparing functionalized polyolefins based on a macro-microreactor, specifically a method for preparing functionalized polyolefins based on ring-opening metathesis polymerization in a macro-microreactor, which includes reacting norbornene monomers, ruthenium catalysts or molybdenum catalysts, and solvents in a macro-microreactor to obtain functionalized polyolefins.

[0013] In the first and second aspects mentioned above,

[0014] The general formula for the reaction is any one of the following:

[0015] When preparing functionalized polyolefins from a single norbornene monomer, the general reaction formula is as follows:

[0016]

[0017] Wherein, R is selected from carboxylic acid methyl ester group, carboxylic acid tert-butyl ester group, cyano group, and methanol group, and n is selected from 50-500.

[0018] When preparing functionalized polyolefins from multiple norbornene monomers, the general reaction formula is as follows:

[0019]

[0020] R1 and R2 are independently selected from carboxylic acid methyl ester group, carboxylic acid tert-butyl ester group, cyano group, and methanol group, respectively, and R1 and R2 are different. n is selected from 50-500, and m is selected from 50-500.

[0021] Further, the monomer is norbornene, methyl 5-norbornene-2-carboxylate, tert-butyl 5-norbornene-2-carboxylate, 2-cyano-5-norbornene, 5-norbornene-2-methanol, or any combination thereof, preferably methyl 5-norbornene-2-carboxylate.

[0022]

[0023] The ruthenium catalyst is one of the following: phenylmethylene bis(tricyclohexylphosphine) ruthenium dichloride (G1), 1,3-bis(2,4,6-trimethylphenyl)-2-(imidazolidinedimethyl))(dichlorophenylmethylene)(tricyclohexylphosphine) ruthenium (G2), dichloro[1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinedimethyl](benzylidene)bis(3-bromopyridine) ruthenium (II) (G3), and 2,6-diisopropylphenylmolybdenum (Schrock), preferably dichloro[1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinedimethyl](benzylidene)bis(3-bromopyridine) ruthenium (II) (G3).

[0024] The molybdenum catalyst is 2,6-diisopropylphenylmolybdenum.

[0025] The solvent for the reaction is any one or a combination of several of THF, toluene, and dichloromethane, preferably THF.

[0026] The molar ratio of the monomer to the catalyst is 50-500:1, such as 150:1, 200:1, 300:1, 400:1, preferably 100:1.

[0027] In the reaction system, the concentration of the monomer is 0.1-1 mol / L, preferably 0.2 mol / L.

[0028] The flow rate of the reaction is 3-30 mL / min, preferably 20 mL / min.

[0029] The reaction temperature is 15-35℃, preferably 25℃.

[0030] The reaction apparatus described in this invention includes a feed pump, a sampler, a mixer, a macro-microreactor, and a receiver. Norbornene monomers are mixed with ruthenium or molybdenum catalysts in the mixer, and then reacted fully in the macro-microreactor to obtain functionalized polyolefins.

[0031] In some embodiments, two injectors are included; the first and second injectors are connected in parallel to a mixer, and the mixer, macro / microreactor, and receiver are connected in series.

[0032] In some embodiments, the system includes three injectors, two mixers, and two macro-microreactors; the first injector and the second injector are connected in parallel to the first mixer, and the first mixer is connected in series with the first macro-microreactor; the first macro-microreactor and the third injector are connected in parallel to the second mixer, and the second mixer, the second macro-microreactor, and the receiver are connected in series.

[0033] In some embodiments, the reaction apparatus further includes a magnetically heated stirrer.

[0034] In some embodiments, the mixer is a T-type mixer (T-type inlet channel), a Y-type mixer (Y-type inlet channel), a cross-type mixer, etc.

[0035] In some embodiments, the structural parameters of the T-shaped inlet channel are as follows: the included angle between the two inlet channels is fixed at 180° and they are symmetrical about the center line of the mixing channel; the inner diameter of the channel is 0.3-1cm, the outer diameter is 0.5-1.2cm, the length is 0.5-2cm, and the outer wall thickness is 1mm. The structural parameters of the annular inlet channel are as follows: the included angle between the two inlet channels is fixed at 90° and one of the inlet channels is collinear with the mixing channel; the inner diameter of the channel is 0.3-1cm, the outer diameter is 0.5-1.2cm, the length is 0.5-2cm, and the outer wall thickness is 1mm. The structural parameters of the Y-shaped inlet channel are as follows: the included angle between the two inlet channels is fixed at 60° and they are symmetrical about the center line of the mixing channel; the inner diameter of the channel is 0.3-1cm, the outer diameter is 0.5-1.2cm, the length is 0.5-2cm, and the outer wall thickness is 1mm.

[0036] In some embodiments, the injector has a capacity of 50 mL.

[0037] In some embodiments, the feed pump is connected to the injector; in some embodiments, the feed pump is a Refer injection pump.

[0038] In this invention, the macro-micro reactor is a centimeter-scale helical internal component continuous flow reactor.

[0039] like Figure 3 As shown, a centimeter-scale spiral internal component continuous flow reactor includes a channel shell and internal components within the channel, wherein the internal components are made of copper. In some embodiments, the macro-micro reactor is a macro-micro reactor with a straight internal component (SLSI), a macro-micro reactor with a serpentine internal component (SSI), a macro-micro reactor with a circular internal component (OSI), and a macro-micro reactor with a spiral internal component (HSI). In some embodiments, the spiral internal component is formed by three-dimensionally rotating a straight cylindrical internal component around a central axis. The fluid flows along the spiral and generates vortices around the spiral. The flow velocity increases near the spiral, enhancing fluid turbulence and improving mixing efficiency. In some embodiments, the spiral internal component is formed by scanning a circular cross-section along a spiral within the channel. The spiral internal component is rigidly connected to the inner wall of the channel shell. The diameter of the circular cross-section is 0.2-3 mm, and the spiral pitch is 0.3-1 cm. Changing the pitch allows for flexible design of the internal component to enhance fluid mixing performance. Reducing the pitch can increase the turbulence effect of the fluid in the spiral internal component and the formation of secondary flows, thereby enhancing the mixing efficiency of the fluid in the continuous flow reactor.

[0040] Furthermore, the pipe thickness of the outer shell of the channel is 1-2 mm, the inner diameter of the channel is 0.3-1 cm, the outer diameter is 0.5-1.2 cm, and the length is 2-30 cm. The diameter of the reactor is limited to the centimeter level.

[0041] Furthermore, the inner diameter of the macro-micro reactor is 1-10 mm, preferably 8 mm, the diameter of the spiral inner component is 0.5-3 mm, preferably 1.8 mm, and the pitch is 3-10 mm, preferably 4 mm.

[0042] Furthermore, the retention volume of the macro-micro reactor is 1-30 mL; the internal component is a straight internal component, a spiral internal component, a serpentine internal component, or an O-shaped internal component; when the internal component is a spiral internal component, a serpentine internal component, or an O-shaped internal component, it has a pitch, and the pitch of the internal component is 3-10 mm.

[0043] The functionalized polyolefins described in this invention include polyolefin copolymers.

[0044] The continuous flow reactor proposed in this invention incorporates a spiral internal component, which exhibits excellent mixing performance and a short effective time even at high Reynolds numbers. The mixing achieves complete effectiveness in a short time, with the shortest effective time being 2 seconds, and also has a low pressure drop (8Pa-40Pa).

[0045] The centimeter-scale spiral internal component continuous flow reactor designed in this invention has good mass transfer performance. The scaled-up centimeter-scale spiral internal component continuous flow reactor (pipe diameter greater than 3 mm) can improve the mass transfer coefficient by 7 times compared with the traditional 1 mm microreactor, while reducing the pressure drop by 54%, which proves the advantages of the centimeter-scale spiral internal component continuous flow reactor in mass transfer in liquid-liquid homogeneous and liquid-liquid heterogeneous chemical systems.

[0046] The internal components provided by this invention have a significant strengthening effect, improving the mixing efficiency and polymerization activity of the continuous flow reactor. Compared with typical microreactors and continuous flow reactors, the macro-microreactor has better advantages, with higher conversion rate, lower molecular weight distribution index, and higher throughput than typical microreactors. This invention provides a novel approach to the synthesis and fluid chemistry of functionalized polyolefins by constructing a macro-microreactor platform, and has significant industrial value.

[0047] This invention utilizes macro- and micro-reactors to achieve better mixing during the reaction process and improve mass and heat transfer within the reactor, enabling convenient and efficient production of a series of functionalized polyolefins. A continuous flow ring-opening metasomatic polymerization platform has been developed. Through the study of polymerization reaction kinetics, copper wire internal components can significantly expand the characteristic scale of the continuous flow reactor, reduce the molecular weight distribution index of the products, and achieve efficient spatiotemporal control of polyolefin products.

[0048] This invention utilizes macro- and micro-reactors to achieve better mixing during the reaction process and improve mass and heat transfer within the reactor, enabling convenient and efficient production of a series of functionalized polyolefins. A continuous flow ring-opening metasomatic polymerization platform has been developed. Through the study of polymerization reaction kinetics, copper wire internal components can significantly expand the characteristic scale of the continuous flow reactor, reduce the molecular weight distribution index of the products, and achieve efficient spatiotemporal control of polyolefin products.

[0049] Beneficial effects: This technical solution has the following advantages:

[0050] (1) The operation method described in this invention is simple and solves the problems of long reaction time, low flow rate, and easy blockage of pipelines in the prior art. It can also realize large-scale production of functionalized polyolefins.

[0051] (2) This invention uses continuous flow micro-reaction as a reaction platform and copper wire internal components to effectively increase the specific surface area in the reaction process, enhance the spatiotemporal control of the reaction process, and effectively shorten the reaction time.

[0052] (3) In the method provided by this invention, the introduction of the helical internal component results in a continuous flow reactor with a flow rate of 8-1.8-4 at high speeds exhibiting a reaction effect stronger than or comparable to a typical microreactor, and stronger than a continuous flow reactor of the same scale without internal components. This achieves the preparation of functionalized polyolefins while maintaining the microscale effect. Furthermore, the laboratory results from small-scale synthesis comprehensively reflect the actual situation of the industrial process, enabling large-scale production of functionalized polyolefins. This invention provides new ideas for the synthesis of functionalized polyolefins in fluid chemistry and has significant industrial value.

[0053] (4) This invention utilizes macro- and micro-reactors to enhance the ring-opening metathesis polymerization process, enabling rapid and high-throughput preparation of a series of functionalized polyolefin monomers. The operation method described in this invention is simple, and the post-processing separation and purification are easy and convenient, and it can achieve scale-up production of high-value functionalized polyolefins.

[0054] (5) Compared with traditional batch reactors, this invention, based on a macro-micro reactor, significantly shortens the reaction time and improves the conversion rate. For example, when using G3 to catalyze methyl 5-norbornene-2-carboxylate, the conversion rate increased from 89% to 92.5%. The reaction time was shortened from 15 min to 30 s. This invention, by introducing a macro-micro reactor as a reaction platform and copper wire as an internal component, effectively increases the specific surface area during the reaction process, enhances the spatiotemporal control of the reaction process, and effectively shortens the reaction time.

[0055] (6) Compared with a typical microreactor (characteristic scale = 1.0 mm), the present invention significantly increases the reaction flux based on the macro-microreactor, for example, the flow rate is increased from 3 mL / min to 20 mL / min, and the yield per unit time is increased from 80.66 mg / min to 534.94 mg / min.

[0056] (7) Compared with a continuous flow reactor (>2.0 mm without internal components), the present invention significantly shortens the reaction time and improves the conversion rate based on a macro-micro reactor. For example, when G3 is used to catalyze methyl 5-norbornene-2-carboxylate, the conversion rate is increased from 75% to 92.5%. Attached Figure Description

[0057] The present invention will be further described in detail below with reference to the accompanying drawings and specific embodiments, and the advantages of the present invention in the above and / or other aspects will become clearer.

[0058] Figure 1 It is one of the microreactors.

[0059] Figure 2 It is one of the microreactors.

[0060] Figure 3 This is a diagram of a macro-microreactor device.

[0061] Figure 4 The poly(5-norbornene-2-carboxylic acid methyl ester) in Example 4 1 H-NMR spectrum.

[0062] Figure 5 For example, polynorbornene in Example 7 1 H-NMR spectrum.

[0063] Figure 6 The poly(5-norbornene-2-carboxylic acid tert-butyl ester) in Example 8 1 H-NMR spectrum.

[0064] Figure 7 The methyl 5-norbornene-2-carboxylate and tert-butyl 5-norbornene-2-carboxylate block copolymer in Example 15 1 H-NMR spectrum. Detailed Implementation

[0065] The present invention can be better understood from the following embodiments. However, those skilled in the art will readily understand that the descriptions in the embodiments are for illustrative purposes only and should not, and will not, limit the invention as detailed in the claims.

[0066] Unless otherwise specified, the experimental methods described in the following examples are conventional methods; unless otherwise specified, the reagents and materials are commercially available.

[0067] The 1H NMR spectra of the products obtained in the following examples are as follows: Figure 4-7 As shown.

[0068] The following embodiments use a 400MHz Bruker nuclear magnetic resonance instrument.1 HNMR and 13 The structure of the polymerization product was characterized by CNMR. 6 mg of the product was placed in an NMR tube, deuterated chloroform was added, and the mixture was shaken until completely dissolved before analysis.

[0069] The following example uses a Wyatt WISH-01 gel permeation chromatography instrument equipped with a flow pump (SSISeries 1500), a high-resolution gel chromatography column (Waters Styragel HR, 2.5 μm, 300 × 7.8 mm), and a static laser scattering instrument (Wyatt DAWNHELEOS II). Tetrahydrofuran (THF) was used as the mobile phase at a flow rate of 0.7 mL / min. Molecular weight and molecular weight distribution were determined using an absolute method, with dn / dc = 0.1755. 4 mg of dried polymer sample was dissolved in 1.5 mL of tetrahydrofuran.

[0070] The following examples were all carried out in a microreactor.

[0071] In some embodiments, the reaction is Microreactors, such as Figure 1 As shown, injection device 1 and injection device 2 are connected to a tubular microreactor or a macro-microreactor containing internal components via a T-type mixer. The microreactor is equipped with a heating device and is then connected to a material receiving device.

[0072] In some embodiments, the reaction is Microreactors, such as Figure 2 As shown, syringe 1 and syringe 2 are connected to a tubular microreactor or a macro-microreactor containing internal components via a T-type mixer. The microreactor is equipped with a heating device. Syringe 3 is then connected to the tubular microreactor or the macro-microreactor containing internal components via a T-type mixer. The microreactor is also equipped with a heating device. Finally, it is connected to a material receiving device.

[0073] The macro / micro reactor, such as Figure 3As shown, the macro-microreactor comprises internal components, which are classified into the following types according to different internal components: Macro-microreactor HSI(xxx): The first x represents the reactor inner diameter x mm (D), the second x represents the helix diameter x mm (d4), and the third x represents the pitch x mm (l3); Macro-microreactor SLSI(xx-0): The first x represents the reactor inner diameter x mm (D), and the second x represents the helix diameter x mm (d1); Macro-microreactor SSI(xxx): The first x represents the reactor inner diameter x mm (D), the second x represents the helix diameter x mm (d2), and the third x represents the pitch x mm (l1); Macro-microreactor OSI(xxx): The first x represents the reactor inner diameter x mm (D), the second x represents the helix diameter x mm (d3), and the third x represents the pitch x mm (l2). Specific data are shown in the table below.

[0074] Table 1 Detailed data on the internal components of macro-microreactors

[0075]

[0076] As an effective process intensification device, microreactors, compared to traditional batch reactors, offer superior mixing and mass transfer due to their higher specific surface area. Microreactor technology offers significant advantages in increasing yield, enhancing reaction controllability, and improving process heat transfer, leading to significant progress in continuous pharmaceutical synthesis and microfluidic analytical chemistry. Based on the excellent mixing and mass transfer capabilities of continuous flow microreactors, liquid-liquid chemical processes can be intensified. In the development of continuous flow microreactor structures, methods for enhancing mixing can generally be categorized as passive or active. Passive mixing relies on the geometric characteristics of the channels or fluid flow to increase diffusion, while active mixing relies on the disturbance of external energy fields. In a continuous microfluidic reactor without internal components, the fluid flows linearly along the channels, relying on molecular diffusion for mixing. When this invention introduces helical internal components, the fluid flows along the helix and generates vortices around it. The flow velocity increases near the helix, enhancing fluid disturbance and improving mixing efficiency.

[0077] Example 1

[0078] Two 50 mL Schlenk flasks were prepared and filled three times using a double-row tube, with repeated baking and dehydration using an electronic Bunsen burner during the process. Under an argon atmosphere, Grubbs 3rd generation catalyst (35.36 mg, 0.04 mmol) was added to reaction flask A, and monomer methyl 5-norbornene-2-carboxylate (608.8 mg, 4 mmol, approximately 0.5 mL) was added to reaction flask B. 10 mL and 9.5 mL of ultra-dry tetrahydrofuran were added respectively to prepare solution A (10 mL) and solution B (10 mL), and the mixtures were stirred thoroughly. Solutions A and B were transferred to two 50 mL SGE glass syringes pre-rinsed with ultra-dry tetrahydrofuran and attached to a syringe pump. The flow rate of syringe pump A was set to 10 mL / min, the flow rate of syringe pump B to 10 mL / min, and the total flow rate to 20 mL / min. A macro-microreactor containing 10 mL of HSI 8-1.8-4 (corresponding to a retention time of 30 s) was connected to two syringes via a T-mixer. The reaction tubing was placed in a 25°C water bath. The syringe pump was turned on, and after 30 s of reaction, the reaction solution was collected and quenched with excess vinyl ether. 1 The conversion rate was calculated by ¹H-NMR. The remaining reaction solution was poured into cold methanol to precipitate the product, which was then collected by centrifugation after being incubated overnight at -20°C. The process of dissolution, precipitation, and centrifugation was repeated three times to thoroughly wash the product. Finally, the product was dried in a vacuum drying oven at 35°C for 3 days to obtain pure poly(5-norbornene-2-carboxylic acid methyl ester). The conversion rate was 92.5%, the number-average molecular weight was 15170 g / mol, and the molecular weight distribution index was 1.09. The yield per unit time was 534.94 mg / min.

[0079] Example 2

[0080] Two 50 mL Schlenk flasks were prepared and filled three times using a double-row tube, with repeated baking and dehydration using an electronic Bunsen burner during the process. Under an argon atmosphere, Grubbs 3rd generation catalyst (35.36 mg, 0.04 mmol) was added to reaction flask A, and monomer methyl 5-norbornene-2-carboxylate (608.8 mg, 4 mmol, approximately 0.5 mL) was added to reaction flask B. 10 mL and 9.5 mL of ultra-dry tetrahydrofuran were added respectively to prepare solution A (10 mL) and solution B (10 mL), and the mixtures were stirred thoroughly. Solutions A and B were transferred to two 50 mL SGE glass syringes pre-rinsed with ultra-dry tetrahydrofuran and attached to syringe pumps. The flow rate of syringe pump A was set to 1.5 mL / min, the flow rate of syringe pump B to 1.5 mL / min, and the total flow rate to 3 mL / min. A macro-microreactor containing 1.5 mL of HSI 3-1-3 (corresponding to a retention time of 30 s) was connected to two syringes via a T-mixer. The reaction tubing was placed in a 25°C water bath. The syringe pump was turned on, and after 30 s of reaction, the reaction solution was collected and quenched with excess vinyl ether.1 The conversion rate was calculated by ¹H-NMR. The remaining reaction solution was poured into cold methanol to precipitate the product, which was then collected by centrifugation after being incubated overnight at -20°C. The process of dissolution, precipitation, and centrifugation was repeated three times to thoroughly wash the product. Finally, the product was dried in a vacuum drying oven at 35°C for 3 days to obtain pure poly(5-norbornene-2-carboxylic acid methyl ester). The conversion rate was 89.5%, the number-average molecular weight was 13920 g / mol, and the molecular weight dispersion index was 1.12. The yield per unit time was 75.19 mg / min.

[0081] Example 3

[0082] Two 50 mL Schlenk flasks were prepared and filled three times using a double-row tube, with repeated baking and dehydration using an electronic Bunsen burner during the process. Under an argon atmosphere, Grubbs 3rd generation catalyst (35.36 mg, 0.04 mmol) was added to reaction flask A, and monomer methyl 5-norbornene-2-carboxylate (608.8 mg, 4 mmol, approximately 0.5 mL) was added to reaction flask B. 10 mL and 9.5 mL of ultra-dry tetrahydrofuran were added respectively to prepare solution A (10 mL) and solution B (10 mL), and the mixtures were stirred thoroughly. Solutions A and B were transferred to two 50 mL SGE glass syringes pre-rinsed with ultra-dry tetrahydrofuran and attached to a syringe pump. The flow rate of syringe pump A was set to 10 mL / min, the flow rate of syringe pump B to 10 mL / min, and the total flow rate to 20 mL / min. A macro-microreactor containing 10 mL of HSI 10-1.8-4 (corresponding to a retention time of 30 s) was connected to two syringes via a T-mixer and placed in a 25°C water bath. The syringe pump was turned on, and after 30 s of reaction, the reaction solution was collected and quenched with excess vinyl ether. 1 The conversion rate was calculated by ¹H-NMR. The remaining reaction solution was poured into cold methanol to precipitate the product, which was then collected by centrifugation after being incubated overnight at -20°C. The process of dissolution, precipitation, and centrifugation was repeated three times to thoroughly wash the product. Finally, the product was dried in a vacuum drying oven at 35°C for 3 days to obtain pure poly(5-norbornene-2-carboxylic acid methyl ester). The conversion rate was 85.3%, the number-average molecular weight was 14920 g / mol, and the molecular weight distribution index was 1.12. The yield per unit time was 498.5 mg / min.

[0083] Example 4

[0084] Two 50 mL Schlenk flasks were prepared and filled three times using a double-row tube, with repeated baking and dehydration using an electronic Bunsen burner during the process. Under an argon atmosphere, Grubbs 3rd generation catalyst (35.36 mg, 0.04 mmol) was added to reaction flask A, and monomer methyl 5-norbornene-2-carboxylate (608.8 mg, 4 mmol, approximately 0.5 mL) was added to reaction flask B. 10 mL and 9.5 mL of ultra-dry tetrahydrofuran were added respectively to prepare solution A (10 mL) and solution B (10 mL), and the mixtures were stirred thoroughly. Solutions A and B were transferred to two 50 mL SGE glass syringes pre-rinsed with ultra-dry tetrahydrofuran and attached to syringe pumps. The flow rate of syringe pump A was set to 1.5 mL / min, the flow rate of syringe pump B to 1.5 mL / min, and the total flow rate to 3 mL / min. A macro-microreactor containing 1.5 mL of HSI 4-1-3 (corresponding to a retention time of 30 s) was connected to two syringes via a T-mixer. The reaction tubing was placed in a 25°C water bath. The syringe pump was turned on, and after 30 s of reaction, the reaction solution was collected and quenched with excess vinyl ether. 1 The conversion rate was calculated by ¹H-NMR. The remaining reaction solution was poured into cold methanol to precipitate the product, which was then collected by centrifugation after being incubated overnight at -20°C. The process of dissolution, precipitation, and centrifugation was repeated three times to thoroughly wash the product. Finally, the product was dried in a vacuum drying oven at 35°C for 3 days to obtain pure poly(5-norbornene-2-carboxylic acid methyl ester). The conversion rate was 87.1%, the number-average molecular weight was 13650 g / mol, and the molecular weight distribution index was 1.25. The yield per unit time was 73.8 mg / min.

[0085] Example 5

[0086] Two 50 mL Schlenk flasks were prepared and filled three times using a double-row tube, with repeated baking and dehydration using an electronic Bunsen burner during the process. Under an argon atmosphere, Schrock catalyst (30.24 mg, 0.04 mmol) was added to reaction flask A, and monomer methyl 5-norbornene-2-carboxylate (608.8 mg, 4 mmol, approximately 0.5 mL) was added to reaction flask B. 10 mL and 9.5 mL of ultra-dry tetrahydrofuran were added respectively to prepare solution A (10 mL) and solution B (10 mL), and the mixtures were stirred thoroughly. Solutions A and B were transferred to two 50 mL SGE glass syringes pre-rinsed with ultra-dry tetrahydrofuran and attached to syringe pumps. The flow rate of syringe pump A was set to 1.5 mL / min, the flow rate of syringe pump B to 1.5 mL / min, and the total flow rate to 3 mL / min. A macro-microreactor containing 1.5 mL of HSI3-1-3 (corresponding to a retention time of 30 s) was connected to two syringes via a T-type mixer. The reaction tubing was placed in a 25°C water bath. The syringe pump was turned on, and after 30 s of reaction, the reaction solution was collected and quenched with excess vinyl ether. 1The conversion rate was calculated by ¹H-NMR. The remaining reaction solution was poured into cold methanol to precipitate the product, which was then collected by centrifugation after being incubated overnight at -20°C. The process of dissolution, precipitation, and centrifugation was repeated three times to thoroughly wash the product. Finally, the product was dried in a vacuum drying oven at 35°C for 3 days to obtain pure poly(5-norbornene-2-carboxylic acid methyl ester). The conversion rate was 78.1%, the number-average molecular weight was 11080 g / mol, and the molecular weight distribution index was 1.54. The yield per unit time was 67.5 mg / min.

[0087] Example 6

[0088] Two 50 mL Schlenk flasks were prepared and filled three times using a double-row tube, with repeated baking and dehydration using an electronic Bunsen burner during the process. Under an argon atmosphere, Grubbs 3rd generation catalyst (35.36 mg, 0.04 mmol) was added to reaction flask A, and monomer methyl 5-norbornene-2-carboxylate (608.8 mg, 4 mmol, approximately 0.5 mL) was added to reaction flask B. 10 mL and 9.5 mL of ultra-dry tetrahydrofuran were added respectively to prepare solution A (10 mL) and solution B (10 mL), and the mixtures were stirred thoroughly. Solutions A and B were transferred to two 50 mL SGE glass syringes pre-rinsed with ultra-dry tetrahydrofuran and attached to syringe pumps. The flow rate of syringe pump A was set to 1.5 mL / min, the flow rate of syringe pump B to 1.5 mL / min, and the total flow rate to 3 mL / min. A macro-microreactor containing 1.5 mL of HSI 5-1-3 (corresponding to a retention time of 30 s) was connected to two syringes via a T-mixer. The reaction tubing was placed in a 25°C water bath. The syringe pump was turned on, and after 30 s of reaction, the reaction solution was collected and quenched with excess vinyl ether. 1 The conversion rate was calculated by ¹H-NMR. The remaining reaction solution was poured into cold methanol to precipitate the product, which was then collected by centrifugation after being incubated overnight at -20°C. The process of dissolution, precipitation, and centrifugation was repeated three times to thoroughly wash the product. Finally, the product was dried in a vacuum drying oven at 35°C for 3 days to obtain pure poly(5-norbornene-2-carboxylic acid methyl ester). The conversion rate was 75%, the number-average molecular weight was 11490 g / mol, and the molecular weight dispersion index was 1.77. The yield per unit time was 65.4 mg / min.

[0089] Example 7

[0090] Two 50 mL Schlenk flasks were prepared and filled three times using a double-row tube, with repeated baking and dehydration using an electronic Bunsen burner during the process. Under an argon atmosphere, Grubbs 1st generation catalyst (32.96 mg, 0.04 mmol) was added to reaction flask A, and norbornene monomer (188.3 mg, 2 mmol) was added to reaction flask B. 10 mL and 10 mL of ultra-dry toluene were added respectively to prepare solution A (10 mL) and solution B (10 mL), and the mixtures were stirred thoroughly. Solutions A and B were transferred to two 50 mL SGE glass syringes pre-rinsed with ultra-dry toluene and attached to syringe pumps. The flow rate of syringe pump A was set to 15 mL / min, the flow rate of syringe pump B to 15 mL / min, and the total flow rate to 30 mL / min. A macro-microreactor containing 15 mL of HSI 8-1.8-10 (corresponding to a retention time of 30 s) was connected to two syringes via a T-mixer. The reaction tubing was placed in a 25°C water bath. The syringe pump was turned on, and after 30 s of reaction, the reaction solution was collected and quenched with excess vinyl ether. 1 The conversion rate was calculated by ¹H-NMR. The remaining reaction solution was poured into cold methanol to precipitate the product, which was then collected by centrifugation after being incubated overnight at -20°C. The process of dissolution, precipitation, and centrifugation was repeated three times to thoroughly wash the product. Finally, the product was dried in a vacuum drying oven at 35°C for 3 days to obtain pure polynorbornene. At this point, the conversion rate was 79.3%, the number-average molecular weight was 5780 g / mol, and the molecular weight distribution index was 1.48. The yield per unit time was 210.5 mg / min.

[0091] Example 8

[0092] Two 50 mL Schlenk flasks were prepared and filled three times using a double-row tube, with repeated baking and dehydration using an electronic Bunsen burner during the process. Under an argon atmosphere, Grubbs 2 catalyst (33.96 mg, 0.04 mmol) was added to reaction flask A, and monomer 5-norbornene-2-carboxylic acid tert-butyl ester (3885.4 mg, 20 mmol, approximately 3.6 mL) was added to reaction flask B. 10 mL and 6.4 mL of ultra-dry dichloromethane were added respectively to prepare solution A (10 mL) and solution B (10 mL), and the mixtures were stirred thoroughly. Solutions A and B were transferred to two 50 mL SGE glass syringes pre-washed with ultra-dry dichloromethane and attached to syringe pumps. The flow rate of syringe pump A was set to 10 mL / min, the flow rate of syringe pump B to 10 mL / min, and the total flow rate to 20 mL / min. A macro-microreactor containing 10 mL of HSI 10-3-10 (corresponding to a retention time of 30 s) was connected to two syringes via a T-mixer. The reaction tubing was placed in a 25°C water bath. The syringe pump was turned on, and after 30 s of reaction, the reaction solution was collected and quenched with excess vinyl ether. 1The conversion rate was calculated by 1H-NMR. The remaining reaction solution was poured into cold methanol to precipitate the product. After incubation at -20°C overnight, the product was collected by centrifugation. The process of dissolution, precipitation, and centrifugation was repeated three times to thoroughly wash the product. Finally, the product was dried in a vacuum drying oven at 35°C for 3 days to obtain pure poly(5-norbornene-2-carboxylic acid tert-butyl ester). The chemical shift of dichloromethane in the 1H NMR spectrum coincides with the chemical shift of the hydrogen atoms in the polymer double bond, making it difficult to calculate the monomer conversion rate when dichloromethane is used as a solvent. However, the characteristic peak of the monomer at 5.8-6.0 ppm almost disappears, indicating a high monomer conversion rate. The number average molecular weight is...

[0093] The concentration was 107135 g / mol, and the molecular weight distribution index was 1.29. The yield per unit time was 3112.2 mg / min.

[0094] Example 9

[0095] Two 50 mL Schlenk flasks were prepared and filled three times using a double-row tube, with repeated baking and dehydration using an electronic Bunsen burner during the process. Under an argon atmosphere, Grubbs 3rd generation catalyst (35.36 mg, 0.04 mmol) was added to reaction flask A, and monomer 2-cyano-5-norbornene (476.64 mg, 4 mmol, approximately 0.5 mL) was added to reaction flask B. 10 mL and 9.5 mL of ultra-dry tetrahydrofuran were added respectively to prepare solution A (10 mL) and solution B (10 mL), and the mixtures were stirred thoroughly. Solutions A and B were transferred to two 50 mL SGE glass syringes pre-rinsed with ultra-dry tetrahydrofuran and attached to syringe pumps. The flow rate of syringe pump A was set to 1.5 mL / min, the flow rate of syringe pump B to 1.5 mL / min, and the total flow rate to 3 mL / min. A macro-microreactor containing 1.5 mL of HSI 3-0.5-3 (corresponding to a retention time of 30 s) was connected to two syringes via a T-mixer. The reaction tubing was placed in a 35°C water bath. The syringe pump was turned on, and after 30 s of reaction, the reaction solution was collected and quenched with excess vinyl ether. 1 The conversion rate was calculated by ¹H-NMR. The remaining reaction solution was poured into cold methanol to precipitate the product, which was then collected by centrifugation after being incubated overnight at -20°C. The process of dissolution, precipitation, and centrifugation was repeated three times to thoroughly wash the product. Finally, the product was dried in a vacuum drying oven at 35°C for 3 days to obtain pure poly(2-cyano-5-norbornene). The conversion rate was 76.4%, the number-average molecular weight was 10120 g / mol, and the molecular weight distribution index was 1.42. The yield per unit time was 53.45 mg / min.

[0096] Example 10

[0097] Two 50 mL Schlenk flasks were prepared and filled three times using a double-row tube, with repeated baking and dehydration using an electronic Bunsen burner during the process. Under an argon atmosphere, Grubbs 3rd generation catalyst (35.36 mg, 0.04 mmol) was added to reaction flask A, and monomer 5-norbornene-2-methanol (484.72 mg, 4 mmol, approximately 0.5 mL) was added to reaction flask B. 10 mL and 9.5 mL of ultra-dry tetrahydrofuran were added respectively to prepare solution A (10 mL) and solution B (10 mL), and the mixtures were stirred thoroughly. Solutions A and B were transferred to two 50 mL SGE glass syringes pre-rinsed with ultra-dry tetrahydrofuran and attached to syringe pumps. The flow rate of syringe pump A was set to 1.5 mL / min, the flow rate of syringe pump B to 1.5 mL / min, and the total flow rate to 3 mL / min. A macro-microreactor containing 1.5 mL of HSI 4-1-3 (corresponding to a retention time of 30 s) was connected to two syringes via a T-mixer. The reaction tubing was placed in a 15°C water bath. The syringe pump was turned on, and after 30 s of reaction, the reaction solution was collected and quenched with excess vinyl ether. 1 The conversion rate was calculated by ¹H-NMR. The remaining reaction solution was poured into cold methanol to precipitate the product. After incubation at -20°C overnight, the product was collected by centrifugation. The process of dissolution, precipitation, and centrifugation was repeated three times to thoroughly wash the product. Finally, the product was dried in a vacuum drying oven at 35°C for 3 days to obtain pure poly(5-norbornene-2-methanol). The conversion rate was 77.4%, the number-average molecular weight was 10610 g / mol, and the molecular weight distribution index was 1.58. The yield per unit time was 55.9 mg / min.

[0098] Example 11

[0099] Two 50 mL Schlenk flasks were prepared and filled three times using a double-row tube, with repeated baking and dehydration using an electronic Bunsen burner during the process. Under an argon atmosphere, Grubbs 3rd generation catalyst (35.36 mg, 0.04 mmol) was added to reaction flask A, and monomer methyl 5-norbornene-2-carboxylate (608.8 mg, 4 mmol, approximately 0.5 mL) was added to reaction flask B. 10 mL and 9.5 mL of ultra-dry tetrahydrofuran were added respectively to prepare solution A (10 mL) and solution B (10 mL), and the mixtures were stirred thoroughly. Solutions A and B were transferred to two 50 mL SGE glass syringes pre-rinsed with ultra-dry tetrahydrofuran and attached to a syringe pump. The flow rate of syringe pump A was set to 10 mL / min, the flow rate of syringe pump B to 10 mL / min, and the total flow rate to 20 mL / min. A macro-microreactor (SLSI 5-1) with a 10 mL retention volume (corresponding to a retention time of 30 s), an inner diameter of 5 mm, and a spiral diameter of 1 mm, was connected to two syringes via a T-type mixer. The reaction tubing was placed in a 25°C water bath. The syringe pump was turned on, and after 30 s of reaction, the reaction solution was collected and quenched with excess vinyl ether. 1 The conversion rate was calculated by ¹H-NMR. The remaining reaction solution was poured into cold methanol to precipitate the product, which was then collected by centrifugation after being incubated overnight at -20°C. The process of dissolution, precipitation, and centrifugation was repeated three times to thoroughly wash the product. Finally, the product was dried in a vacuum drying oven at 35°C for 3 days to obtain pure poly(5-norbornene-2-carboxylic acid methyl ester). The conversion rate was 83.5%, the number-average molecular weight was 13110 g / mol, and the molecular weight distribution index was 1.24. The yield per unit time was 496.7 mg / min.

[0100] Example 12

[0101] Two 50 mL Schlenk flasks were prepared and filled three times using a double-row tube, with repeated baking and dehydration using an electronic Bunsen burner during the process. Under an argon atmosphere, Grubbs 3rd generation catalyst (35.36 mg, 0.04 mmol) was added to reaction flask A, and monomer methyl 5-norbornene-2-carboxylate (608.8 mg, 4 mmol, approximately 0.5 mL) was added to reaction flask B. 10 mL and 9.5 mL of ultra-dry tetrahydrofuran were added respectively to prepare solution A (10 mL) and solution B (10 mL), and the mixtures were stirred thoroughly. Solutions A and B were transferred to two 50 mL SGE glass syringes pre-rinsed with ultra-dry tetrahydrofuran and attached to a syringe pump. The flow rate of syringe pump A was set to 10 mL / min, the flow rate of syringe pump B to 10 mL / min, and the total flow rate to 20 mL / min. A macro-microreactor containing an OSI circular internal component with an inner diameter of 8 mm and a retention volume of 10 mL (corresponding to a retention time of 30 s) was connected to two syringes via a T-type mixer. The reaction tubing was placed in a 25°C water bath. The syringe pump was turned on, and after 30 s of reaction, the reaction solution was collected and quenched with excess vinyl ether. 1 The conversion rate was calculated by ¹H-NMR. The remaining reaction solution was poured into cold methanol to precipitate the product, which was then collected by centrifugation after being incubated overnight at -20°C. The process of dissolution, precipitation, and centrifugation was repeated three times to thoroughly wash the product. Finally, the product was dried in a vacuum drying oven at 35°C for 3 days to obtain pure poly(5-norbornene-2-carboxylic acid methyl ester). The conversion rate was 84.2%, the number-average molecular weight was 13810 g / mol, and the molecular weight distribution index was 1.22. The yield per unit time was 481.8 mg / min.

[0102] Example 13

[0103] Two 50 mL Schlenk flasks were prepared and filled three times using a double-row tube, with repeated baking and dehydration using an electronic Bunsen burner during the process. Under an argon atmosphere, Grubbs 3rd generation catalyst (35.36 mg, 0.04 mmol) was added to reaction flask A, and monomer methyl 5-norbornene-2-carboxylate (608.8 mg, 4 mmol, approximately 0.5 mL) was added to reaction flask B. 10 mL and 9.5 mL of ultra-dry tetrahydrofuran were added respectively to prepare solution A (10 mL) and solution B (10 mL), and the mixtures were stirred thoroughly. Solutions A and B were transferred to two 50 mL SGE glass syringes pre-rinsed with ultra-dry tetrahydrofuran and attached to a syringe pump. The flow rate of syringe pump A was set to 10 mL / min, the flow rate of syringe pump B to 10 mL / min, and the total flow rate to 20 mL / min. A 10 mL (corresponding retention time of 30 s) SSI(D-1) macro-microreactor reaction pipeline containing a horizontally placed serpentine internal component and an inner diameter of 8 mm was connected to two syringes via a T-type mixer. The reaction pipeline was placed in a 25°C water bath, the syringe pump was turned on, and after 30 s of reaction, the reaction solution was collected and quenched with excess vinyl ether. 1 The conversion rate was calculated by ¹H-NMR. The remaining reaction solution was poured into cold methanol to precipitate the product, which was then collected by centrifugation after being incubated overnight at -20°C. The process of dissolution, precipitation, and centrifugation was repeated three times to thoroughly wash the product. Finally, the product was dried in a vacuum drying oven at 35°C for 3 days to obtain pure poly(5-norbornene-2-carboxylic acid methyl ester). The conversion rate was 87.8%, the number-average molecular weight was 14360 g / mol, and the molecular weight distribution index was 1.18. The yield per unit time was 494.4 mg / min.

[0104] Example 14

[0105] Two 50 mL Schlenk flasks were prepared and filled three times using a double-row tube, with repeated baking and dehydration using an electronic Bunsen burner during the process. Under an argon atmosphere, Grubbs 3rd generation catalyst (35.36 mg, 0.04 mmol) was added to reaction flask A, and monomer methyl 5-norbornene-2-carboxylate (608.8 mg, 4 mmol, approximately 0.5 mL) was added to reaction flask B. 10 mL and 9.5 mL of ultra-dry tetrahydrofuran were added respectively to prepare solution A (10 mL) and solution B (10 mL), and the mixtures were stirred thoroughly. Solutions A and B were transferred to two 50 mL SGE glass syringes pre-rinsed with ultra-dry tetrahydrofuran and attached to a syringe pump. The flow rate of syringe pump A was set to 10 mL / min, the flow rate of syringe pump B to 10 mL / min, and the total flow rate to 20 mL / min. A vertically placed serpentine internal component containing SSI(D-2) with a retention volume of 10 mL (corresponding to a retention time of 30 s) and an inner diameter of 8 mm was used in a macro-microreactor channel connected to two syringes via a T-type mixer. The reaction channel was placed in a 25°C water bath, the syringe pump was turned on, and after 30 s of reaction, the reaction solution was collected and quenched with excess vinyl ether. 1 The conversion rate was calculated by ¹H-NMR. The remaining reaction solution was poured into cold methanol to precipitate the product, which was then collected by centrifugation after being incubated overnight at -20°C. The process of dissolution, precipitation, and centrifugation was repeated three times to thoroughly wash the product. Finally, the product was dried in a vacuum drying oven at 35°C for 3 days to obtain pure poly(5-norbornene-2-carboxylic acid methyl ester). The conversion rate was 86.4%, the number-average molecular weight was 14260 g / mol, and the molecular weight distribution index was 1.17. The yield per unit time was 493.3 mg / min.

[0106] Example 15

[0107] Take three 50mL Schlenk flasks and fill them three times using double-row tubes, repeatedly baking them with an electronic Bunsen burner to remove moisture during the process. In a glove box, add Grubbs 3rd generation catalyst (106.08mg, 0.12mmol) to reaction flask A, add methyl 5-norbornene-2-carboxylate (1.826g, 12mmol, approximately 1.7mL) to reaction flask B, and add tert-butyl 5-norbornene-2-carboxylate (2.328g, 12mmol, approximately 2.2mL) to reaction flask C. Add 30mL, 28.3mL, and 27.8mL of ultra-dry THF (30mL) respectively to prepare solutions A (30mL), B (30mL), and C (30mL), and stir thoroughly. Transfer solutions A, B, and C to three 50mL SEG glass syringes pre-rinsed with ultra-dry THF and attach them to the syringe pump. The flow rates of syringe pumps A, B, and C are all set to 10 mL / min. In the first stage of the reaction, the total flow rate is 20 mL / min. The reactor HSI... The retention volume of 8-1.8-4 was 15 mL (retention time 45 s). In the second stage of the reaction, the total flow rate was 30 mL / min, and the retention volume of HSI8-1.8-4 in the reactor was 22.5 mL (retention time 45 s). The reaction tubing was placed in a 25℃ water bath. Injection pumps A and B were turned on. After the reaction liquid from the first stage entered the T-type mixer, injection pump C was turned on. After two retention volumes of liquid flowed out, the reaction liquid was collected and quenched with excess vinyl ether. The conversion rate was calculated using 1H-NMR. The remaining reaction liquid was poured into cold methanol to precipitate. After incubating overnight in a -20℃ refrigerator, the product was collected by centrifugation. The process of dissolving, precipitating, and centrifuging was repeated three times to thoroughly wash the product. Finally, the product was dried in a 35℃ vacuum drying oven for 48 h to obtain a pure block copolymer of methyl 5-norbornene-2-carboxylate and tert-butyl 5-norbornene-2-carboxylate. At this point, the conversion rate of 5-norbornene-2-carboxylic acid tert-butyl ester was 89%, the number-average molecular weight of the block copolymer was 28980 g / mol, and the molecular weight distribution index was 1.14. The yield per unit time was 1.38 g / min.

[0108] Example 16

[0109] Two 50 mL Schlenk flasks were prepared and filled three times using a double-row tube, with repeated heating and dehydration using an electronic Bunsen burner during the process. Grubbs 3rd generation catalyst (70.72 mg, 0.08 mmol) was added to reaction flask A. Monomers methyl 5-norbornene-2-carboxylate (1.217 g, 8 mmol, approximately 1.1 mL) and tert-butyl 5-norbornene-2-carboxylate (1.552 g, 8 mmol, approximately 1.5 mL) were added to reaction flask B. 20 mL and 17.4 mL of ultra-dry tetrahydrofuran were added respectively to prepare solution A (20 mL) and solution B (20 mL), and the mixtures were stirred thoroughly. Solutions A and B were transferred to two SGE glass syringes pre-washed with ultra-dry tetrahydrofuran and attached to syringe pumps. The flow rate of syringe pump A was set to 10 mL / min, the flow rate of syringe pump B to 10 mL / min, and the total flow rate to 20 mL / min. A reactor HSI10-1.8-4 with a retention volume of 15 mL (retention time of 45 s) was connected to two syringes via a T-type mixer. The reaction tubing was placed in a 25°C water bath. The syringe pump was turned on, and after two retention volumes of liquid flowed out, the reaction solution was collected and quenched with excess vinyl ether. The conversion rate was calculated using 1H-NMR. The remaining reaction solution was poured into cold methanol to precipitate the product. After incubating overnight at -20°C, the product was collected by centrifugation. The process of dissolving, precipitating, and centrifuging was repeated three times to thoroughly wash the product. Finally, the product was dried in a 35°C vacuum drying oven for 48 h to obtain a pure random copolymer of methyl 5-norbornene-2-carboxylate and tert-butyl 5-norbornene-2-carboxylate. At this point, the monomer conversion rate of methyl 5-norbornene-2-carboxylate was 95.6%, the monomer conversion rate of tert-butyl 5-norbornene-2-carboxylate was 92.3%, the number-average molecular weight of the random copolymer was 25810 g / mol, and the molecular weight distribution index was 1.25. The yield per unit time is 1.23 g / min.

[0110] Comparative Example 1

[0111] Two 50 mL Schlenk flasks were prepared and filled three times using a double-row tube, with repeated baking and dehydration using an electronic Bunsen burner during the process. Under an argon atmosphere, Grubbs 3rd generation catalyst (35.36 mg, 0.04 mmol) was added to reaction flask A, and monomer methyl 5-norbornene-2-carboxylate (608.8 mg, 4 mmol, approximately 0.5 mL) was added to reaction flask B. 10 mL and 9.5 mL of ultra-dry tetrahydrofuran were added respectively to prepare solution A (10 mL) and solution B (10 mL), and the mixtures were stirred thoroughly. Solutions A and B were transferred to two 50 mL SGE glass syringes pre-rinsed with ultra-dry tetrahydrofuran and attached to syringe pumps. The flow rate of syringe pump A was set to 1.5 mL / min, the flow rate of syringe pump B to 1.5 mL / min, and the total flow rate to 3 mL / min. A typical 1-0-0 microreactor with a retention volume of 1.5 mL (corresponding to a retention time of 30 s) was connected to two syringes via a T-mixer. The reaction tubing was placed in a 25°C water bath. The syringe pump was turned on, and after 30 s of reaction, the reaction solution was collected and quenched with excess vinyl ether. 1 The conversion rate was calculated by ¹H-NMR. The remaining reaction solution was poured into cold methanol to precipitate the product, which was then collected by centrifugation after being incubated overnight at -20°C. The process of dissolution, precipitation, and centrifugation was repeated three times to thoroughly wash the product. Finally, the product was dried in a vacuum drying oven at 35°C for 3 days to obtain pure poly(5-norbornene-2-carboxylic acid methyl ester). The conversion rate was 92.3%, the number-average molecular weight was 12450 g / mol, and the molecular weight distribution index was 1.13. The yield per unit time was 80.66 mg / min.

[0112] Comparative Example 2

[0113] Two 50 mL Schlenk flasks were prepared and filled three times using a double-row tube, with repeated baking and dehydration using an electronic Bunsen burner during the process. Under an argon atmosphere, Grubbs 3rd generation catalyst (35.36 mg, 0.04 mmol) was added to reaction flask A, and monomer methyl 5-norbornene-2-carboxylate (608.8 mg, 4 mmol, approximately 0.5 mL) was added to reaction flask B. 10 mL and 9.5 mL of ultra-dry tetrahydrofuran were added respectively to prepare solution A (10 mL) and solution B (10 mL), and the mixtures were stirred thoroughly. Solutions A and B were transferred to two 50 mL SGE glass syringes pre-rinsed with ultra-dry tetrahydrofuran and attached to a syringe pump. The flow rate of syringe pump A was set to 10 mL / min, the flow rate of syringe pump B to 10 mL / min, and the total flow rate to 20 mL / min. A typical 1-0-0 microreactor with a retention volume of 10 mL (corresponding to a retention time of 30 s) was connected to two syringes via a T-type mixer. The reaction pipeline was placed in a 25°C water bath. When the syringe pump was turned on, it reported an error due to excessive pressure and could not continue the reaction.

[0114] Comparative Example 3

[0115] Two 50 mL Schlenk flasks were prepared and filled three times using a double-row tube, with repeated baking and dehydration using an electronic Bunsen burner during the process. Under an argon atmosphere, Grubbs 3rd generation catalyst (35.36 mg, 0.04 mmol) was added to reaction flask A, and monomer methyl 5-norbornene-2-carboxylate (608.8 mg, 4 mmol, approximately 0.5 mL) was added to reaction flask B. 10 mL and 9.5 mL of ultra-dry tetrahydrofuran were added respectively to prepare solution A (10 mL) and solution B (10 mL), and the mixtures were stirred thoroughly. Solutions A and B were transferred to two 50 mL SGE glass syringes pre-rinsed with ultra-dry tetrahydrofuran and attached to a syringe pump. The flow rate of syringe pump A was set to 10 mL / min, the flow rate of syringe pump B to 10 mL / min, and the total flow rate to 20 mL / min. A 10 mL (30 s) continuous flow reactor (8-0-0 type) was connected to two syringes via a T-mixer. The reaction tubing was placed in a 25°C water bath. The syringe pump was turned on, and after 30 s of reaction, the reaction solution was collected and quenched with excess vinyl ether. 1 The conversion rate was calculated by ¹H-NMR. The remaining reaction solution was poured into cold methanol to precipitate the product, which was then collected by centrifugation after being incubated overnight at -20°C. The process of dissolution, precipitation, and centrifugation was repeated three times to thoroughly wash the product. Finally, the product was dried in a vacuum drying oven at 35°C for 3 days to obtain pure poly(5-norbornene-2-carboxylic acid methyl ester). The conversion rate was 76.4%, the number-average molecular weight was 11370 g / mol, and the molecular weight distribution index was 1.45. The yield per unit time was 450.8 mg / min.

[0116] Comparative Example 4

[0117] Two 50 mL Schlenk flasks were prepared and filled three times using a double-row tube, with repeated baking and dehydration using an electronic Bunsen burner during the process. Under an argon atmosphere, Grubbs 3rd generation catalyst (35.36 mg, 0.04 mmol) was added to reaction flask A, and monomer methyl 5-norbornene-2-carboxylate (608.8 mg, 4 mmol, approximately 0.5 mL) was added to reaction flask B. 10 mL and 9.5 mL of ultra-dry tetrahydrofuran were added respectively to prepare solution A (10 mL) and solution B (10 mL), and the mixtures were stirred thoroughly. Solutions A and B were transferred to two 50 mL SGE glass syringes pre-rinsed with ultra-dry tetrahydrofuran and attached to syringe pumps. The flow rate of syringe pump A was set to 1.5 mL / min, the flow rate of syringe pump B to 1.5 mL / min, and the total flow rate to 3 mL / min. A 4-0-0 continuous flow reactor with a retention volume of 1.5 mL (corresponding to a retention time of 30 s) was connected to two syringes via a T-mixer. The reaction tubing was placed in a 25°C water bath. The syringe pump was turned on, and after 30 s of reaction, the reaction solution was collected and quenched with excess vinyl ether. 1 The conversion rate was calculated by ¹H-NMR. The remaining reaction solution was poured into cold methanol to precipitate the product, which was then collected by centrifugation after being incubated overnight at -20°C. The process of dissolution, precipitation, and centrifugation was repeated three times to thoroughly wash the product. Finally, the product was dried in a vacuum drying oven at 35°C for 3 days to obtain pure poly(5-norbornene-2-carboxylic acid methyl ester). The conversion rate was 75.0%, the number-average molecular weight was 11290 g / mol, and the molecular weight distribution index was 1.69. The yield per unit time was 63.7 mg / min.

[0118] Comparative Example 5

[0119] A 50 mL Schlenk flask was used in a batch reactor. The flask was purged three times using a double-row tube, and repeatedly heated with an electronic Bunsen burner to remove moisture during the process. Under an argon atmosphere, Grubbs 3rd generation catalyst (35.36 mg, 0.04 mmol), monomer methyl 5-norbornene-2-carboxylate (608.8 mg, 4 mmol, approximately 0.5 mL), and 19.5 mL of ultra-dry tetrahydrofuran were added to prepare the reaction solution, which was then stirred and mixed thoroughly. The reaction was carried out for 15 min under an argon atmosphere. After the reaction was completed in a 25°C water bath, the reaction solution was collected and quenched with excess vinyl ether. 1 The conversion rate was calculated by ¹H-NMR. The remaining reaction solution was poured into cold methanol to precipitate the product, which was then collected by centrifugation after being incubated overnight at -20°C. The process of dissolution, precipitation, and centrifugation was repeated three times to thoroughly wash the product. Finally, the product was dried in a vacuum drying oven at 35°C for 3 days to obtain pure poly(5-norbornene-2-carboxylic acid methyl ester). The conversion rate was 89.3%, the number-average molecular weight was 11850 g / mol, and the molecular weight distribution index was 1.57. The yield per unit time was 509.4 mg / min.

[0120] The embodiments described above are merely illustrative of several implementations of the present invention, and while the descriptions are specific and detailed, they should not be construed as limiting the scope of the present invention. It should be noted that those skilled in the art can make various modifications and improvements without departing from the concept of the present invention, and these modifications and improvements all fall within the scope of protection of the present invention. Therefore, the scope of protection of this patent should be determined by the appended claims.

Claims

1. The application of a macro-microreactor in the preparation of functionalized polyolefins, characterized in that, In a macro-microreactor, norbornene monomers, a ruthenium catalyst, and a solvent are reacted to obtain functionalized polyolefins. The macro-microreactor includes a channel shell and internal components within the channel, wherein the internal components are made of copper. The retention volume of the macro-microreactor is 1-30 mL. The internal components are helical, serpentine, or O-shaped. The inner diameter of the macro-microreactor is 1-10 mm, and the diameter of the internal components is 0.5-3 mm. When the internal components are helical, serpentine, or O-shaped, they have a pitch of 3-10 mm. The flow rate of the reaction is 20-30 mL / min.

2. A method for preparing functionalized polyolefins based on macro / micro reactors, characterized in that, In a macro-microreactor, norbornene monomers, a ruthenium catalyst, and a solvent are reacted to obtain functionalized polyolefins. The macro-microreactor includes a channel shell and internal components within the channel, wherein the internal components are made of copper. The retention volume of the macro-microreactor is 1-30 mL. The internal components are linear, spiral, serpentine, or O-shaped. The inner diameter of the macro-microreactor is 1-10 mm, and the diameter of the internal components is 0.5-3 mm. When the internal components are spiral, serpentine, or O-shaped, they have a pitch of 3-10 mm. The reaction flow rate is 20-30 mL / min.

3. The application according to claim 1 or the method according to claim 2, characterized in that, The norbornene monomer is ; The functionalized polyolefin is ; R is selected from methyl carboxylate, tert-butyl carboxylate, cyano, and methanol; n is selected from 50-500.

4. The application according to claim 1 or the method according to claim 2, characterized in that, The norborneol-based monomer includes , ; The functionalized polyolefin is ; R1 and R2 are independently selected from carboxylic acid methyl ester group, carboxylic acid tert-butyl ester group, cyano group, and methanol group, respectively, and R1 and R2 are different. n is selected from 50-500, and m is selected from 50-500.

5. The application according to claim 1 or the method according to claim 2, characterized in that, The monomers are norbornene, methyl 5-norbornene-2-carboxylate, tert-butyl 5-norbornene-2-carboxylate, 2-cyano-5-norbornene, and 5-norbornene-2-methanol.

6. The application according to claim 1 or the method according to claim 2, characterized in that, The ruthenium catalyst is any one or a combination of several of the following: phenylmethylene bis(tricyclohexylphosphine) ruthenium dichloride, 1,3-bis(2,4,6-trimethylphenyl)-2-(imidazolidinedimethyl))(dichlorophenylmethylene)(tricyclohexylphosphine) ruthenium, and dichloro[1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinedimethyl](benzylidene)bis(3-bromopyridine) ruthenium (II).

7. The application according to claim 1 or the method according to claim 2, characterized in that, The solvent for the reaction is any one or a combination of tetrahydrofuran, toluene, and dichloromethane; The molar ratio of the monomer to the catalyst is 50-500:1; In the reaction system, the monomer concentration is 0.1-1 mol / L; the reaction temperature is 15-35 ℃.

8. The application according to claim 1 or the method according to claim 2, characterized in that, The molar ratio of the monomer to the catalyst is 100:1; the concentration of the monomer in the reaction system is 0.2 mol / L; and the reaction temperature is 25 °C.

9. The application according to claim 1 or the method according to claim 2, characterized in that, The macro-micro reactor has an inner diameter of 8 mm, a spiral inner component diameter of 1.8 mm, and a pitch of 4 mm.

10. A method for preparing functionalized polyolefins based on macro / micro reactors, characterized in that, In a macro-microreactor, norbornene monomer, molybdenum catalyst, and solvent are reacted to obtain functionalized polyolefins; the macro-microreactor includes a channel shell and internal components within the channel; the retention volume of the macro-microreactor is 1-30 mL; the inner diameter of the macro-microreactor is 1-10 mm, and the diameter of the internal components is 0.5-3 mm; the internal components are linear internal components; or the internal components are helical internal components, serpentine internal components, or O-shaped internal components, which have a pitch of 3-10 mm.

11. The method according to claim 10, characterized in that, The norbornene monomer is The functionalized polyolefin is Wherein, R is selected from methyl carboxylate, tert-butyl carboxylate, cyano, and methanol; n is selected from 50-500; or, The norborneol-based monomer includes , The functionalized polyolefin is R1 and R2 are independently selected from carboxylic acid methyl ester group, carboxylic acid tert-butyl ester group, cyano group, and methanol group, respectively, and R1 and R2 are different. n is selected from 50-500, and m is selected from 50-500.

12. The method according to claim 10, characterized in that, The monomer is any combination of norbornene, methyl 5-norbornene-2-carboxylate, tert-butyl 5-norbornene-2-carboxylate, 2-cyano-5-norbornene, and 5-norbornene-2-methanol. The molybdenum catalyst is 2,6-diisopropylphenylmolybdenum; The solvent for the reaction is any one or a combination of tetrahydrofuran, toluene, and dichloromethane.

13. The method according to claim 10, characterized in that, The molar ratio of the monomer to the catalyst is 50-500:1; the concentration of the monomer in the reaction system is 0.1-1 mol / L; the flow rate of the reaction is 3-30 mL / min; and the temperature of the reaction is 15-35 ℃.

14. The method according to claim 10, characterized in that, The molar ratio of the monomer to the catalyst is 100:1; In the reaction system, the monomer concentration is 0.2 mol / L; the reaction flow rate is 20 mL / min; and the reaction temperature is 25 °C.

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