Method for high-throughput preparation of functionalized polyolefin based on macro-micro reactor

Abstract

The invention discloses a method for high-throughput preparation of functionalized polyolefin based on a macro-micro reactor, which is characterized in that in the macro-micro reactor, a norbornene monomer, a catalyst and a solvent react to obtain the functionalized polyolefin. The method is suitable for norbornene monomers, and compared with a traditional synthesis method, the macro-micro reactor containing the internal component can remarkably shorten the ring-opening metathesis polymerization reaction time and improve the conversion rate. The characteristic scale of the macro-micro reactor reaches centimeter level, and high-flux synthesis can be realized. The invention provides a technical scheme for functionalized polyolefin, and has industrial conversion prospects.

Description

Technical Field

[0001] The invention relates to the technical field of polymer synthesis, and in particular to a method for preparing functionalized polyolefin based on macro- and micro-reactors. Background Art

[0002] This section merely provides background information related to the present disclosure and is not necessarily prior art.

[0003] Since Karl Ziegler and Giulio Natta made groundbreaking progress in polyolefin synthesis in the early 1950s, a series of major research breakthroughs and industrial innovations have been made in the fields of catalyst design, polymerization technology and processing methods of polyolefins, which have greatly simplified the polyolefin production process and reduced production costs. Polyolefins have many advantages such as light weight, corrosion resistance, low cost, adjustable performance and easy processing, which are closely related to their mature production technology, large scale of raw materials and excellent structural adjustability. At the same time, polyolefins have been widely used in biomedical materials since their birth due to their good chemical stability, biocompatibility and biological inertness.

[0004] At present, the synthesis strategies of functionalized polyolefins mainly include the following: (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 and ruthenium catalysts in the 1990s, ROMP has entered a rapid development stage. Under the action of these highly efficient single-component homogeneous catalysts, cyclic olefins with high ring tension (such as norbornene) are driven by the release of ring tension. Through the continuous formation and ring cleavage of metal cyclobutane structures, polymers with unsaturated double bonds in the main chain are synthesized. It has the advantages of mild reaction conditions, high catalytic efficiency, and good reaction controllability. At present, ROMP has become an important tool for the synthesis of functionalized polyolefins due to the particularity of its product structure and the good tolerance of the catalyst to various functional groups.

[0006] Compared with kettle reactors, continuous flow reactors have gained more and more attention in the field of polymer synthesis due to their advantages such as high mass and heat transfer efficiency, good mixing performance, and good time and space controllability. Among them, typical microreactors of hundreds of micrometers are the most widely used. However, when the flow rate of the reaction liquid increases or the viscosity increases, the pressure drop inside the channel of a typical microreactor increases, and there is a risk of pipeline blockage and rupture, which places higher requirements on the reliability of pipeline materials and joints. Therefore, macro-microreactors are studied to achieve effects higher than those of typical reactors and continuous flow reactors of the same scale by adding internal components. Macro-microreactors have higher synthesis efficiency, provide a basis for the high-throughput preparation of functionalized polyolefins, and are of great significance to 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 preparing functionalized polyolefins with high throughput based on macro-micro reactors in view of the deficiencies in the prior art.

[0008] Inventive 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 entered a rapid development stage. Under the action of these highly efficient single-component homogeneous catalysts, cyclic olefins with high ring tension (such as norbornene) are driven by the release of ring tension. Through the continuous formation and ring cleavage of metal cyclobutane structures, polymers containing unsaturated double bonds in the main chain are synthesized, which has the advantages of mild reaction conditions, high catalytic efficiency, and good reaction controllability. At present, ROMP has become an important tool for synthesizing functionalized polyolefins due to the particularity of its product structure and the good tolerance of the catalyst to various functional groups.

[0009] Continuous flow reactors have gained more and more attention in the field of polymer synthesis due to their advantages such as high mass and heat transfer efficiency, good mixing performance, and good spatiotemporal controllability. Among them, typical microreactors of hundreds of micrometers are the most widely used. However, when the flow rate of the reaction liquid increases or the viscosity increases, the pressure drop inside the channel of a typical microreactor increases, and there is a risk of pipe blockage and rupture, which places higher requirements on the reliability of pipe materials and joints. Therefore, macro-microreactors are studied to achieve effects higher than those of typical reactors and continuous flow reactors of the same scale by adding internal components. Macro-microreactors have higher synthesis efficiency, provide a basis for the high-throughput preparation of functionalized polyolefins, and are of great significance to the industrial production of functionalized polyolefins.

[0010] In order to solve the above technical problems, the present invention discloses the following technical solutions:

[0011] In the first aspect, the present invention discloses an application of a macro-microreactor in the preparation of functionalized polyolefins, wherein the application is specifically to prepare functionalized polyolefins using norbornene-based monomers as raw materials, specifically to react norbornene-based monomers, ruthenium catalysts or molybdenum catalysts, and solvents in macro-microreactors to obtain functionalized polyolefins.

[0012] In the second aspect, the present invention discloses a method for preparing functionalized polyolefins based on a macro-microreactor, that is, a method for preparing functionalized polyolefins based on ring-opening metathesis polymerization in a macro-microreactor, which specifically includes reacting a norbornene-based monomer, a ruthenium catalyst or a molybdenum catalyst, and a solvent in a macro-microreactor to obtain a functionalized polyolefin.

[0013] In the above first and second aspects,

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

[0015] When a single norbornene-based monomer is used to prepare a functionalized polyolefin, the general reaction formula is as follows:

[0016]

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

[0018] When multiple norbornene-based monomers are used to prepare functionalized polyolefins, the general reaction formula is as follows:

[0019]

[0020] Wherein, R1 and R2 are independently selected from methyl carboxylate, tert-butyl carboxylate, cyano, and methanol, 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, 5-norbornene-2-carboxylic acid methyl ester, 5-norbornene-2-carboxylic acid tert-butyl ester, 2-cyano-5-norbornene, 5-norbornene-2-methanol, or any combination of the foregoing, preferably 5-norbornene-2-carboxylic acid methyl ester.

[0022]

[0023] Among them, the ruthenium catalyst is phenylmethylenebis(tricyclohexylphosphine)dichlororuthenium (G1), 1,3-bis(2,4,6-trimethylphenyl)-2-(imidazolidinyl) (dichlorobenzylidene) (tricyclohexylphosphine) ruthenium (G2), dichloro[1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinyl](benzylidene)bis(3-bromopyridine)ruthenium (II) (G3), 2,6-diisopropylphenylmolybdenum (Schrock), preferably dichloro[1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinyl](benzylidene)bis(3-bromopyridine)ruthenium (II) (G3).

[0024] Wherein, the molybdenum catalyst is 2,6-diisopropylphenyl molybdenum.

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

[0026] Wherein, 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] Wherein, in the reaction system, the monomer concentration is 0.1-1 mol / L, preferably 0.2 mol / L.

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

[0029] Wherein, the reaction temperature is 15-35°C, preferably 25°C.

[0030] The reaction device of the present invention comprises a feed pump, a sample injector, a mixer, a macro-micro reactor and a receiver. The norbornene-based monomer is mixed with a ruthenium catalyst or a molybdenum catalyst in the mixer and fully reacts in the macro-micro reactor to obtain a functionalized polyolefin.

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

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

[0033] In some embodiments, the reaction apparatus further comprises a magnetic heating 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 mixer, etc.

[0035] In some embodiments, the structural parameters of the T-shaped inlet channel are: the 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 shell wall thickness is 1mm; the structural parameters of the annular tube type inlet channel are: the 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 shell wall thickness is 1mm; the structural parameters of the Y-shaped inlet channel are: the 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 shell wall thickness is 1mm.

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

[0037] In some embodiments, the feed pump is connected to an injector; in some embodiments, the feed pump is a Revet syringe pump.

[0038] In the present invention, the macro-microreactor is a centimeter-level spiral internal component continuous flow reactor.

[0039] like Figure 3 As shown, a centimeter-level spiral internal continuous flow reactor includes a channel shell and an internal component in the channel, and the internal component is a copper internal component. In some embodiments, the macro-microreactor is a macro-microreactor SLSI of a linear internal component, a macro-microreactor SSI of a serpentine internal component, a macro-microreactor OSI of a ring-shaped internal component, and a macro-microreactor HSI of a spiral internal component. In some embodiments, the spiral internal component is formed by three-dimensional rotation around the central axis on the basis of a linear cylindrical internal component, and the fluid flows along the spiral and generates a vortex around the spiral. The flow rate near the spiral becomes high, the fluid disturbance is enhanced, and the mixing efficiency is improved. In some embodiments, the spiral internal component is formed by a circular cross-section along the spiral scanning in the channel, and the spiral internal component is rigidly connected to the inner wall of the channel shell, the diameter of the circular cross-section is 0.2-3mm, and the pitch of the spiral is 0.3-1cm. The change of the pitch can realize the flexible design of the internal component to enhance the mixing performance of the fluid. The reduction of the pitch can increase the disturbance effect of the fluid in the spiral internal component and the formation of secondary flow, thereby enhancing the mixing efficiency of the fluid in the continuous flow reactor.

[0040] Furthermore, the thickness of the channel shell 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 centimeter level defines the diameter size of the reactor.

[0041] Furthermore, the inner diameter of the macro-microreactor 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-microreactor is 1-30 mL; the internal component is a linear internal component, a spiral internal component, a serpentine internal structure, or an O-shaped internal component; when the internal component is a spiral internal component, a serpentine internal structure, or an O-shaped internal component, it has a pitch, and the pitch of the internal component is 3-10 mm.

[0043] The functionalized polyolefin in the present invention includes polyolefin copolymers.

[0044] The continuous flow reactor proposed in the present invention has a spiral internal component, which has good mixing performance and a shorter effective time under a larger Reynolds number. The mixing is completely effective in a short time, the shortest effective time is 2s, and it has a lower pressure drop (8Pa-40Pa).

[0045] The centimeter-scale spiral internal component continuous flow reactor designed by the present invention has good mass transfer performance. The enlarged-scale (tube diameter greater than 3mm) centimeter-scale spiral internal component continuous flow reactor can increase the mass transfer coefficient by 7 times compared with the traditional 1mm microreactor, and reduce the pressure drop by 54%, which proves the mass transfer advantage of the centimeter-scale spiral internal component continuous flow reactor in liquid-liquid homogeneous and liquid-liquid heterogeneous chemical systems.

[0046] The internal components provided by the present invention play a significant reinforcing role, improving the mixing efficiency and polymerization activity of the continuous flow reactor. The macro-micro reactor has good advantages over the typical micro reactor and the continuous flow reactor, with improved conversion rate, reduced molecular weight distribution index, and higher flux than the typical micro reactor. The present invention provides a new idea for the synthesis and fluid chemistry of functionalized polyolefins by constructing a macro-micro reactor platform, which has important industrial value.

[0047] The present invention uses macro-micro reactors to achieve better mixing during the reaction process, improve the mass transfer and heat transfer effect in the reactor, and obtain a series of functionalized polyolefins conveniently and efficiently. A continuous flow ring-opening metathesis polymerization platform has been developed. Through the study of polymerization reaction kinetics, the copper wire internal components can significantly expand the characteristic scale of the continuous flow reactor, reduce the product molecular weight distribution index, and achieve efficient spatiotemporal control of polyolefin products.

[0048] The present invention uses macro-micro reactors to achieve better mixing during the reaction process, improve the mass transfer and heat transfer effect in the reactor, and obtain a series of functionalized polyolefins conveniently and efficiently. A continuous flow ring-opening metathesis polymerization platform has been developed. Through the study of polymerization reaction kinetics, the copper wire internal components can significantly expand the characteristic scale of the continuous flow reactor, reduce the product molecular weight distribution index, and achieve efficient spatiotemporal control of polyolefin products.

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

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

[0051] (2) The present invention uses a continuous flow micro-reaction as a reaction platform and adopts copper wire internal components to effectively increase the specific surface area during the reaction process, enhance the spatiotemporal controllability of the reaction process, and effectively shorten the time required for the reaction.

[0052] (3) In the method provided by the present invention, the introduction of the spiral internal component makes the reaction effect of the 8-1.8-4 continuous flow reactor at high flow rate stronger than or similar to the typical microreactor, and stronger than the continuous flow reactor of the same scale without internal components, so that the preparation of functionalized polyolefins can be achieved while still maintaining the microscale effect. And through the laboratory results of small-scale synthesis, the actual situation of the industrial process is reflected as comprehensively as possible, and the large-scale production of functionalized polyolefins is carried out. The present invention provides new ideas for the synthesis of functionalized polyolefins and fluid chemistry, and has important industrial value.

[0053] (4) The present invention is based on the macro-microreactor enhanced ring-opening metathesis polymerization process, and quickly and high-throughput prepares a series of functionalized polyolefin material monomers. The operation method of the present invention is simple, the post-treatment separation and purification is simple and convenient, and it can achieve scaled-up production of high-value functionalized polyolefins.

[0054] (5) Compared with the traditional kettle reactor, the present invention significantly shortens the reaction time and improves the conversion rate based on the macro-micro reactor. For example, the conversion rate of 5-norbornene-2-carboxylic acid methyl ester catalyzed by G3 is increased from 89% to 92.5%. The reaction time is shortened from 15min to 30s. The present invention effectively increases the specific surface area during the reaction process by introducing the macro-micro reactor as the reaction platform and the copper wire as the internal component, strengthens the time and space controllability of the reaction process, and effectively shortens the time required for the reaction.

[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 output per unit time is increased from 80.66 mg / min to 534.94 mg / min.

[0056] (7) Compared with the continuous flow reactor (>2.0 mm without internal components), the present invention significantly shortens the reaction time and improves the conversion rate based on the macro-micro reactor. For example, the conversion rate of 5-norbornene-2-carboxylic acid methyl ester catalyzed by G3 is increased from 75% to 92.5%. BRIEF DESCRIPTION OF THE DRAWINGS

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

[0058] Figure 1 It is one of the micro-reaction devices.

[0059] Figure 2 It is one of the micro-reaction devices.

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

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

[0062] Figure 5 is the polynorbornene in Example 7 1 H-NMR spectrum.

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

[0064] Figure 7 is the block copolymer of 5-norbornene-2-carboxylic acid methyl ester and 5-norbornene-2-carboxylic acid tert-butyl ester in Example 15 1 H-NMR spectrum. DETAILED DESCRIPTION

[0065] The present invention can be better understood according to the following examples. However, it is easy for those skilled in the art to understand that the contents described in the examples are only used to illustrate the present invention, and should not and will not limit the present invention described in detail in the claims.

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

[0067] The nuclear magnetic hydrogen spectrum of the products obtained in the following examples is as follows Figure 4-7 shown.

[0068] In the following examples, a 400 MHz Bruker nuclear magnetic resonance instrument was used to1 HNMR and 13 CNMR was used to characterize the structure of the polymerized product. 6 mg of the product was placed in a nuclear magnetic resonance tube, deuterated chloroform was added, and the sample was measured after shaking until it was completely dissolved.

[0069] In the following examples, Wyatt, WISH-01 gel permeation chromatography test instrument was used, equipped with a flow pump (SSI Series 1500), a high-resolution gel chromatography column (Waters Styragel HR, 2.5 μm, 300×7.8 mm), and a static laser scattering instrument (Wyatt DAWN HELEOS II). Tetrahydrofuran (THF) was used as the mobile phase at a flow rate of 0.7 mL / min. The molecular weight and molecular weight distribution were tested by the absolute method, and dn / dc=0.1755. 4 mg of the 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, the injection device 1 syringe and the injection device 2 syringe are connected to a tubular microreactor or a macro-microreactor containing internal components through a T-type mixer. The microreactor is provided with a heating device and 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 through a T-type mixer, and the microreactor is provided with a heating device, and then further connected to syringe 3 through a T-type mixer to connect it to a tubular microreactor or a macro-microreactor containing internal components, and the microreactor is provided with a heating device, and then connected to a material receiving device.

[0073] The macro-micro reactor is Figure 3As shown, the macro-microreactor comprises internal components, which are divided 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 helical 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), the second x represents the helical diameter x mm (d1); macro-microreactor SSI (xxx) the first x represents the reactor inner diameter x mm (D), the second x represents the helical 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 helical 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 of macro and micro reactor internal components

[0075]

[0076] As an effective process intensification device, the higher specific surface area of ​​the continuous flow microreactor produces better mixing and mass transfer effects compared to the traditional kettle reactor. The use of microreactor technology has significant advantages in improving yield, enhancing reaction controllability and enhancing process heat transfer, making it have made good progress in continuous synthesis of drugs, microfluidic analytical chemistry and other aspects. Based on the good mixing and mass transfer capabilities of the continuous flow microreactor, the liquid-liquid chemical process can be intensified. In the process of continuous flow microreactor structure development, the means of enhancing mixing can generally be divided into passive or active. Passive mixing depends on the geometric structure characteristics of the channel or fluid flow to increase the degree of diffusion, while active mixing depends on the disturbance of external field energy to achieve mixing. In a continuous microfluidic reactor without internal components, the fluid flows in a straight line along the channel and relies on molecular diffusion mixing; when the present invention introduces a spiral internal component, the fluid flows along the spiral and generates a vortex around the spiral. The flow rate becomes higher near the spiral, which enhances the fluid disturbance and improves the mixing efficiency.

[0077] Example 1

[0078] Take two 50mL Schlenk bottles, use double-row pipes to pump and fill three times, during which time they are repeatedly baked with an electronic Bunsen burner to remove water. In an argon atmosphere, add Grubbs 3rd generation catalyst (35.36mg, 0.04mmol) to reaction bottle A, add monomer 5-norbornene-2-carboxylic acid methyl ester (608.8mg, 4mmol, about 0.5mL) to reaction bottle B, add 10mL and 9.5mL ultra-dry tetrahydrofuran to prepare solution A (10mL) and solution B (10mL), respectively, and stir to mix. Transfer solution A and solution B to two 50mL SGE glass syringes pre-rinsed with ultra-dry tetrahydrofuran and fix them on the syringe pump. Set the flow rate of syringe pump A to 10mL / min, the flow rate of syringe pump B to 10mL / min, and the total flow rate to 20mL / min. The macro-microreactor of HSI 8-1.8-4 with a retention volume of 10 mL (corresponding to a retention time of 30 s) was connected to two syringes through a T-type mixer. The reaction pipeline was placed in a 25°C water bath, and the syringe pump was turned on. After reacting for 30 s, the reaction solution was collected and quenched with excess vinyl ether. 1 The conversion rate was calculated by H-NMR, and the remaining reaction solution was poured into cold methanol for precipitation. After being placed in a -20°C refrigerator overnight, the product was collected by centrifugation. The dissolution, precipitation, and centrifugation process were repeated three times to fully wash the product, and finally placed in a 35°C vacuum drying oven for 3 days to obtain pure poly-5-norbornene-2-carboxylic acid methyl ester. At this time, 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 output per unit time was 534.94 mg / min.

[0079] Example 2

[0080] Take two 50mL Schlenk bottles, use double-row pipes to pump and fill three times, during which time they are repeatedly baked with an electronic Bunsen burner to remove water. Under an argon atmosphere, add Grubbs 3rd generation catalyst (35.36mg, 0.04mmol) to reaction bottle A, add monomer 5-norbornene-2-carboxylic acid methyl ester (608.8mg, 4mmol, about 0.5mL) to reaction bottle B, add 10mL and 9.5mL ultra-dry tetrahydrofuran to prepare solution A (10mL) and solution B (10mL), respectively, and stir to mix. Transfer solution A and solution B to two 50mL SGE glass syringes pre-rinsed with ultra-dry tetrahydrofuran and fix them on the syringe pump. Set the flow rate of syringe pump A to 1.5mL / min, the flow rate of syringe pump B to 1.5mL / min, and the total flow rate to 3mL / min. The macro-microreactor of HSI 3-1-3 with a retention volume of 1.5 mL (corresponding to a retention time of 30 s) was connected to two syringes through a T-type mixer. The reaction pipeline was placed in a 25°C water bath and the syringe pump was turned on. After reacting for 30 s, the reaction solution was collected and quenched with excess vinyl ether.1 The conversion rate was calculated by H-NMR, and the remaining reaction solution was poured into cold methanol for precipitation. After being placed in a -20°C refrigerator overnight, the product was collected by centrifugation. The dissolution, precipitation, and centrifugation process were repeated three times to fully wash the product, and finally placed in a 35°C vacuum drying oven for 3 days to obtain pure poly-5-norbornene-2-carboxylic acid methyl ester. At this time, 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 output per unit time was 75.19 mg / min.

[0081] Example 3

[0082] Take two 50mL Schlenk bottles, use double-row pipes to pump and fill three times, during which time they are repeatedly baked with an electronic Bunsen burner to remove water. In an argon atmosphere, add Grubbs 3rd generation catalyst (35.36mg, 0.04mmol) to reaction bottle A, add monomer 5-norbornene-2-carboxylic acid methyl ester (608.8mg, 4mmol, about 0.5mL) to reaction bottle B, add 10mL and 9.5mL ultra-dry tetrahydrofuran to prepare solution A (10mL) and solution B (10mL), respectively, and stir to mix. Transfer solution A and solution B to two 50mL SGE glass syringes pre-rinsed with ultra-dry tetrahydrofuran and fix them on the syringe pump. Set the flow rate of syringe pump A to 10mL / min, the flow rate of syringe pump B to 10mL / min, and the total flow rate to 20mL / min. The macro-microreactor of HSI 10-1.8-4 with a retention volume of 10 mL (corresponding to a retention time of 30 s) was connected to the reaction pipeline with two syringes through a T-type mixer and placed in a 25°C water bath. The syringe pump was turned on. After reacting for 30 s, the reaction solution was collected and quenched with excess vinyl ether. 1 The conversion rate was calculated by H-NMR, and the remaining reaction solution was poured into cold methanol for precipitation. After being placed in a -20°C refrigerator overnight, the product was collected by centrifugation. The dissolution, precipitation, and centrifugation process were repeated three times to fully wash the product, and finally placed in a 35°C vacuum drying oven for 3 days to obtain pure poly-5-norbornene-2-carboxylic acid methyl ester. At this time, 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 output per unit time was 498.5 mg / min.

[0083] Example 4

[0084] Take two 50mL Schlenk bottles, use double-row pipes to pump and fill three times, during which time they are repeatedly baked with an electronic Bunsen burner to remove water. Under an argon atmosphere, add Grubbs 3rd generation catalyst (35.36mg, 0.04mmol) to reaction bottle A, add monomer 5-norbornene-2-carboxylic acid methyl ester (608.8mg, 4mmol, about 0.5mL) to reaction bottle B, add 10mL and 9.5mL ultra-dry tetrahydrofuran to prepare solution A (10mL) and solution B (10mL), respectively, and stir to mix. Transfer solution A and solution B to two 50mL SGE glass syringes pre-rinsed with ultra-dry tetrahydrofuran and fix them on the syringe pump. Set the flow rate of syringe pump A to 1.5mL / min, the flow rate of syringe pump B to 1.5mL / min, and the total flow rate to 3mL / min. The macro-microreactor of HSI 4-1-3 with a retention volume of 1.5 mL (corresponding to a retention time of 30 s) was connected to two syringes through a T-type mixer. The reaction pipeline was placed in a 25°C water bath and the syringe pump was turned on. After reacting for 30 s, the reaction solution was collected and quenched with excess vinyl ether. 1 The conversion rate was calculated by H-NMR, and the remaining reaction solution was poured into cold methanol for precipitation. After being placed in a -20°C refrigerator overnight, the product was collected by centrifugation. The dissolution, precipitation, and centrifugation process were repeated three times to fully wash the product, and finally placed in a 35°C vacuum drying oven for 3 days to obtain pure poly-5-norbornene-2-carboxylic acid methyl ester. At this time, 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 output per unit time was 73.8 mg / min.

[0085] Example 5

[0086] Take two 50mL Schlenk bottles, use double-row pipes to pump and fill three times, during which time they are repeatedly baked with an electronic Bunsen burner to remove water. Under an argon atmosphere, add Schrock catalyst (30.24mg, 0.04mmol) to reaction bottle A, add monomer 5-norbornene-2-carboxylic acid methyl ester (608.8mg, 4mmol, about 0.5mL) to reaction bottle B, add 10mL and 9.5mL ultra-dry tetrahydrofuran to prepare solution A (10mL) and solution B (10mL), respectively, and stir to mix. Transfer solution A and solution B to two 50mL SGE glass syringes pre-rinsed with ultra-dry tetrahydrofuran and fix them on the syringe pump. Set the flow rate of syringe pump A to 1.5mL / min, the flow rate of syringe pump B to 1.5mL / min, and the total flow rate to 3mL / min. The macro-microreactor of HSI3-1-3 with a retention volume of 1.5 mL (corresponding to a retention time of 30 s) was connected to two syringes through a T-type mixer. The reaction pipeline was placed in a 25°C water bath, and the syringe pump was turned on. After reacting for 30 s, the reaction solution was collected and quenched with excess vinyl ether. 1The conversion rate was calculated by H-NMR, and the remaining reaction solution was poured into cold methanol for precipitation. After being placed in a -20°C refrigerator overnight, the product was collected by centrifugation. The dissolution, precipitation, and centrifugation process were repeated three times to fully wash the product, and finally placed in a 35°C vacuum drying oven for 3 days to obtain pure poly-5-norbornene-2-carboxylic acid methyl ester. At this time, 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 output per unit time was 67.5 mg / min.

[0087] Example 6

[0088] Take two 50mL Schlenk bottles, use double-row pipes to pump and fill three times, during which time they are repeatedly baked with an electronic Bunsen burner to remove water. Under an argon atmosphere, add Grubbs 3rd generation catalyst (35.36mg, 0.04mmol) to reaction bottle A, add monomer 5-norbornene-2-carboxylic acid methyl ester (608.8mg, 4mmol, about 0.5mL) to reaction bottle B, add 10mL and 9.5mL ultra-dry tetrahydrofuran to prepare solution A (10mL) and solution B (10mL), respectively, and stir to mix. Transfer solution A and solution B to two 50mL SGE glass syringes pre-rinsed with ultra-dry tetrahydrofuran and fix them on the syringe pump. Set the flow rate of syringe pump A to 1.5mL / min, the flow rate of syringe pump B to 1.5mL / min, and the total flow rate to 3mL / min. The macro-microreactor of HSI 5-1-3 with a retention volume of 1.5 mL (corresponding to a retention time of 30 s) was connected to two syringes through a T-type mixer. The reaction pipeline was placed in a 25°C water bath, and the syringe pump was turned on. After reacting for 30 s, the reaction solution was collected and quenched with excess vinyl ether. 1 The conversion rate was calculated by H-NMR, and the remaining reaction solution was poured into cold methanol for precipitation. After being placed in a -20°C refrigerator overnight, the product was collected by centrifugation. The dissolution, precipitation, and centrifugation process were repeated three times to fully wash the product, and finally placed in a 35°C vacuum drying oven for 3 days to obtain pure poly-5-norbornene-2-carboxylic acid methyl ester. At this time, the conversion rate was 75%, the number average molecular weight was 11490 g / mol, and the molecular weight dispersion index was 1.77. The output per unit time was 65.4 mg / min.

[0089] Example 7

[0090] Take two 50mL Schlenk bottles, use double-row pipes to pump and fill three times, and use an electronic Bunsen burner to repeatedly bake and remove water during the process. In an argon atmosphere, add Grubbs 1 generation catalyst (32.96mg, 0.04mmol) to reaction bottle A, add monomer norbornene (188.3mg, 2mmol) to reaction bottle B, add 10mL and 10mL ultra-dry toluene to prepare solution A (10mL) and solution B (10mL), respectively, and stir to mix. Transfer solution A and solution B to two 50mL SGE glass syringes pre-rinsed with ultra-dry toluene and fix them on the injection pump. Set the flow rate of injection pump A to 15mL / min, the flow rate of injection pump B to 15mL / min, and the total flow rate to 30mL / min. The HSI 8-1.8-10 macro-microreactor with a retention volume of 15 mL (corresponding to a retention time of 30 s) was connected to two syringes through a T-type mixer. The reaction pipeline was placed in a 25°C water bath and the syringe pump was turned on. After reacting for 30 s, the reaction solution was collected and quenched with excess vinyl ether. 1 The conversion rate was calculated by H-NMR, and the remaining reaction solution was poured into cold methanol for precipitation. After being placed in a -20°C refrigerator overnight, the product was collected by centrifugation. The dissolution, precipitation, and centrifugation process were repeated three times to fully wash the product, and finally placed in a 35°C vacuum drying oven for 3 days to obtain pure polynorbornene. At this time, 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 output per unit time was 210.5 mg / min.

[0091] Example 8

[0092] Take two 50mL Schlenk bottles, use double-row pipes to pump and fill three times, and use an electronic Bunsen burner to repeatedly bake and remove water during the process. In an argon atmosphere, add Grubbs2 generation catalyst (33.96mg, 0.04mmol) to reaction bottle A, add monomer 5-norbornene-2-carboxylic acid tert-butyl ester (3885.4mg, 20mmol, about 3.6mL) to reaction bottle B, add 10mL and 6.4mL ultra-dry dichloromethane to prepare solution A (10mL) and solution B (10mL), respectively, and stir to mix. Transfer solution A and solution B to two 50mL SGE glass syringes pre-rinsed with ultra-dry dichloromethane and fix them on the injection pump. Set the flow rate of injection pump A to 10mL / min, the flow rate of injection pump B to 10mL / min, and the total flow rate to 20mL / min. The macro-microreactor of HSI 10-3-10 with a retention volume of 10 mL (corresponding to a retention time of 30 s) was connected to two syringes through a T-type mixer. The reaction pipeline was placed in a 25°C water bath and the syringe pump was turned on. After reacting for 30 s, the reaction solution was collected and quenched with excess vinyl ether. 1The conversion rate was calculated by H-NMR, and the remaining reaction solution was poured into cold methanol for precipitation. After being placed in a -20°C refrigerator overnight, the product was collected by centrifugation. The dissolution, precipitation, and centrifugation process were repeated three times to fully wash the product. Finally, it was placed in a 35°C vacuum drying oven and dried for 3 days to obtain pure poly-5-norbornene-2-carboxylic acid tert-butyl ester. The chemical shift of dichloromethane in the nuclear magnetic hydrogen spectrum coincides with the chemical shift of the double bond hydrogen of the polymer, so it is difficult to calculate the monomer conversion rate when dichloromethane is used as a solvent, but the characteristic peak of the monomer at 5.8-6.0ppm almost disappears, which can explain the high conversion rate of the monomer. The number average molecular weight is

[0093] 107135g / mol, molecular weight distribution index is 1.29, and output per unit time is 3112.2mg / min.

[0094] Example 9

[0095] Take two 50mL Schlenk bottles, use double-row pipes to pump and fill three times, during which time they are repeatedly baked with an electronic Bunsen burner to remove water. In an argon atmosphere, add Grubbs 3rd generation catalyst (35.36mg, 0.04mmol) to reaction bottle A, add monomer 2-cyano-5-norbornene (476.64mg, 4mmol, about 0.5mL) to reaction bottle B, add 10mL and 9.5mL ultra-dry tetrahydrofuran to prepare solution A (10mL) and solution B (10mL), respectively, and stir to mix. Transfer solution A and solution B to two 50mL SGE glass syringes pre-rinsed with ultra-dry tetrahydrofuran and fix them on the syringe pump. Set the flow rate of syringe pump A to 1.5mL / min, the flow rate of syringe pump B to 1.5mL / min, and the total flow rate to 3mL / min. The macro-microreactor of HSI 3-0.5-3 with a retention volume of 1.5 mL (corresponding to a retention time of 30 s) was connected to two syringes through a T-type mixer. The reaction pipeline was placed in a 35°C water bath and the syringe pump was turned on. After reacting for 30 s, the reaction solution was collected and quenched with excess vinyl ether. 1 The conversion rate was calculated by H-NMR, and the remaining reaction solution was poured into cold methanol for precipitation. After being placed in a -20°C refrigerator overnight, the product was collected by centrifugation. The dissolution, precipitation, and centrifugation process were repeated three times to fully wash the product, and finally placed in a 35°C vacuum drying oven for 3 days to obtain pure poly 2-cyano-5-norbornene. At this time, 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 output per unit time was 53.45 mg / min.

[0096] Example 10

[0097] Take two 50mL Schlenk bottles, use double-row pipes to pump and fill three times, and use an electronic Bunsen burner to repeatedly bake and remove water during the process. In an argon atmosphere, add Grubbs 3rd generation catalyst (35.36mg, 0.04mmol) to reaction bottle A, add monomer 5-norbornene-2-methanol (484.72mg, 4mmol, about 0.5mL) to reaction bottle B, and add 10mL and 9.5mL ultra-dry tetrahydrofuran to prepare solution A (10mL) and solution B (10mL), respectively, and stir to mix. Transfer solution A and solution B to two 50mL SGE glass syringes pre-rinsed with ultra-dry tetrahydrofuran and fix them on the injection pump. Set the flow rate of injection pump A to 1.5mL / min, the flow rate of injection pump B to 1.5mL / min, and the total flow rate to 3mL / min. The macro-microreactor of HSI 4-1-3 with a retention volume of 1.5 mL (corresponding to a retention time of 30 s) was connected to two syringes through a T-type mixer. The reaction pipeline was placed in a 15°C water bath and the syringe pump was turned on. After reacting for 30 s, the reaction solution was collected and quenched with excess vinyl ether. 1 The conversion rate was calculated by H-NMR, and the remaining reaction solution was poured into cold methanol for precipitation. After being placed in a -20°C refrigerator overnight, the product was collected by centrifugation. The dissolution, precipitation, and centrifugation process were repeated three times to fully wash the product, and finally placed in a 35°C vacuum drying oven for 3 days to obtain pure poly-5-norbornene-2-methanol. At this time, 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 output per unit time was 55.9 mg / min.

[0098] Embodiment 11

[0099] Take two 50mL Schlenk bottles, use double-row pipes to pump and fill three times, during which time they are repeatedly baked with an electronic Bunsen burner to remove water. In an argon atmosphere, add Grubbs 3rd generation catalyst (35.36mg, 0.04mmol) to reaction bottle A, add monomer 5-norbornene-2-carboxylic acid methyl ester (608.8mg, 4mmol, about 0.5mL) to reaction bottle B, add 10mL and 9.5mL ultra-dry tetrahydrofuran to prepare solution A (10mL) and solution B (10mL), respectively, and stir to mix. Transfer solution A and solution B to two 50mL SGE glass syringes pre-rinsed with ultra-dry tetrahydrofuran and fix them on the syringe pump. Set the flow rate of syringe pump A to 10mL / min, the flow rate of syringe pump B to 10mL / min, and the total flow rate to 20mL / min. A reaction tube with a retention volume of 10 mL (corresponding to a retention time of 30 s) and a macro-microreactor (SLSI 5-1) with an inner diameter of 5 mm and a spiral diameter of 1 mm was connected to two syringes through a T-type mixer. The reaction tube was placed in a 25°C water bath and the syringe pump was turned on. After reacting for 30 s, the reaction solution was collected and quenched with excess vinyl ether. 1 The conversion rate was calculated by H-NMR, and the remaining reaction solution was poured into cold methanol for precipitation. After being placed in a -20°C refrigerator overnight, the product was collected by centrifugation. The dissolution, precipitation, and centrifugation process were repeated three times to fully wash the product, and finally placed in a 35°C vacuum drying oven for 3 days to obtain pure poly-5-norbornene-2-carboxylic acid methyl ester. At this time, 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 output per unit time was 496.7 mg / min.

[0100] Example 12

[0101] Take two 50mL Schlenk bottles, use double-row pipes to pump and fill three times, during which time they are repeatedly baked with an electronic Bunsen burner to remove water. In an argon atmosphere, add Grubbs 3rd generation catalyst (35.36mg, 0.04mmol) to reaction bottle A, add monomer 5-norbornene-2-carboxylic acid methyl ester (608.8mg, 4mmol, about 0.5mL) to reaction bottle B, add 10mL and 9.5mL ultra-dry tetrahydrofuran to prepare solution A (10mL) and solution B (10mL), respectively, and stir to mix. Transfer solution A and solution B to two 50mL SGE glass syringes pre-rinsed with ultra-dry tetrahydrofuran and fix them on the syringe pump. Set the flow rate of syringe pump A to 10mL / min, the flow rate of syringe pump B to 10mL / min, and the total flow rate to 20mL / min. A macro-microreactor with a retention volume of 10 mL (corresponding to a retention time of 30 s) containing an OSI circular internal component with an inner diameter of 8 mm was connected to two syringes through a T-type mixer. The reaction pipeline was placed in a 25°C water bath, and the syringe pump was turned on. After reacting for 30 s, the reaction solution was collected and quenched with excess vinyl ether. 1 The conversion rate was calculated by H-NMR, and the remaining reaction solution was poured into cold methanol for precipitation. After being placed in a -20°C refrigerator overnight, the product was collected by centrifugation. The dissolution, precipitation, and centrifugation process were repeated three times to fully wash the product, and finally placed in a 35°C vacuum drying oven for 3 days to obtain pure poly-5-norbornene-2-carboxylic acid methyl ester. At this time, 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 output per unit time was 481.8 mg / min.

[0102] Embodiment 13

[0103] Take two 50mL Schlenk bottles, use double-row pipes to pump and fill three times, during which time they are repeatedly baked with an electronic Bunsen burner to remove water. In an argon atmosphere, add Grubbs 3rd generation catalyst (35.36mg, 0.04mmol) to reaction bottle A, add monomer 5-norbornene-2-carboxylic acid methyl ester (608.8mg, 4mmol, about 0.5mL) to reaction bottle B, add 10mL and 9.5mL ultra-dry tetrahydrofuran to prepare solution A (10mL) and solution B (10mL), respectively, and stir to mix. Transfer solution A and solution B to two 50mL SGE glass syringes pre-rinsed with ultra-dry tetrahydrofuran and fix them on the syringe pump. Set the flow rate of syringe pump A to 10mL / min, the flow rate of syringe pump B to 10mL / min, and the total flow rate to 20mL / min. The SSI (D-1) with a retention volume of 10 mL (corresponding to a retention time of 30 s) containing a horizontally placed serpentine internal component and a macro-microreactor reaction channel with an inner diameter of 8 mm was connected to two syringes through a T-type mixer. The reaction channel was placed in a 25°C water bath, and the injection pump was turned on. After reacting for 30 s, the reaction solution was collected and quenched with excess vinyl ether. 1 The conversion rate was calculated by H-NMR, and the remaining reaction solution was poured into cold methanol for precipitation. After being placed in a -20°C refrigerator overnight, the product was collected by centrifugation. The dissolution, precipitation, and centrifugation process were repeated three times to fully wash the product, and finally placed in a 35°C vacuum drying oven for 3 days to obtain pure poly-5-norbornene-2-carboxylic acid methyl ester. At this time, 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 output per unit time was 494.4 mg / min.

[0104] Embodiment 14

[0105] Take two 50mL Schlenk bottles, use double-row pipes to pump and fill three times, during which time they are repeatedly baked with an electronic Bunsen burner to remove water. In an argon atmosphere, add Grubbs 3rd generation catalyst (35.36mg, 0.04mmol) to reaction bottle A, add monomer 5-norbornene-2-carboxylic acid methyl ester (608.8mg, 4mmol, about 0.5mL) to reaction bottle B, add 10mL and 9.5mL ultra-dry tetrahydrofuran to prepare solution A (10mL) and solution B (10mL), respectively, and stir to mix. Transfer solution A and solution B to two 50mL SGE glass syringes pre-rinsed with ultra-dry tetrahydrofuran and fix them on the syringe pump. Set the flow rate of syringe pump A to 10mL / min, the flow rate of syringe pump B to 10mL / min, and the total flow rate to 20mL / min. A serpentine internal component containing SSI (D-2) with a retention volume of 10 mL (corresponding to a retention time of 30 s) was placed vertically. The macro-microreactor with an inner diameter of 8 mm was connected to two syringes through a T-type mixer. The reaction pipeline was placed in a 25°C water bath, and the syringe pump was turned on. After reacting for 30 s, the reaction solution was collected and quenched with excess vinyl ether. 1 The conversion rate was calculated by H-NMR, and the remaining reaction solution was poured into cold methanol for precipitation. After being placed in a -20°C refrigerator overnight, the product was collected by centrifugation. The dissolution, precipitation, and centrifugation process were repeated three times to fully wash the product, and finally placed in a 35°C vacuum drying oven for 3 days to obtain pure poly-5-norbornene-2-carboxylic acid methyl ester. At this time, 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 output per unit time was 493.3 mg / min.

[0106] Embodiment 15

[0107] Take three 50mL Schlenk bottles, use double-row pipes to pump and fill three times, and use electronic Bunsen burners to repeatedly bake and remove water during the process. In the glove box, add Grubbs 3rd generation catalyst (106.08mg, 0.12mmol) to reaction bottle A, add monomer 5-norbornene-2-carboxylic acid methyl ester (1.826g, 12mmol, about 1.7mL) to reaction bottle B, add monomer 5-norbornene-2-carboxylic acid tert-butyl ester (2.328g, 12mmol, about 2.2mL) to reaction bottle C, add 30mL, 28.3mL, and 27.8mL ultra-dry THF (30mL) respectively to prepare solution A (30mL), solution B (30mL) and solution C (30mL), and stir to mix. Transfer solution A, solution B, and solution C to three 50mL SEG glass syringes pre-rinsed with ultra-dry THF and fix them on the syringe pump. Set the flow rates of injection pumps A, B, and C to 10 mL / min. In the first stage of the reaction, the total flow rate is 20 mL / min. The retention volume of 8-1.8-4 is 15 mL (retention time is 45 s). In the second stage of the reaction, the total flow rate is 30 mL / min, the retention volume of the reactor HSI8-1.8-4 is 22.5 mL (retention time is 45 s), the reaction pipeline is placed in a 25°C water bath, and the injection pumps A and B are turned on. After the first stage reaction liquid enters the T-type mixer, the injection pump C is turned on. After two retention volumes of liquid flow out, the reaction liquid is collected and quenched with excess vinyl ethyl ether. The conversion rate is calculated using 1H-NMR, and the remaining reaction liquid is poured into cold methanol for precipitation. After being placed in a -20°C refrigerator overnight, the product is collected by centrifugation, and the dissolution, precipitation, and centrifugation processes are repeated three times to fully wash the product. Finally, it is placed in a 35°C vacuum drying oven and dried for 48 hours to obtain a pure 5-norbornene-2-carboxylic acid methyl ester and 5-norbornene-2-carboxylic acid tert-butyl ester block copolymer. At this time, the conversion rate of tert-butyl 5-norbornene-2-carboxylate was 89%, the number average molecular weight of the block copolymer was 28980 g / mol, the molecular weight distribution index was 1.14, and the output per unit time was 1.38 g / min.

[0108] Example 16

[0109] Take two 50mL Schlenk bottles, use double-row pipes to pump and fill three times, and use an electronic Bunsen burner to repeatedly bake and remove water during the process. Add Grubbs 3rd generation catalyst (70.72mg, 0.08mmol) to reaction bottle A, add monomer 5-norbornene-2-carboxylic acid methyl ester (1.217g, 8mmol, about 1.1mL) and 5-norbornene-2-carboxylic acid tert-butyl ester (1.552g, 8mmol, about 1.5mL) to reaction bottle B, add 20mL and 17.4mL ultra-dry tetrahydrofuran to prepare solution A (20mL) and solution B (20mL), respectively, and stir to mix. Transfer solution A and solution B to two SGE glass syringes pre-rinsed with ultra-dry tetrahydrofuran and fix them on the injection pump. Set the flow rate of injection pump A to 10mL / min, the flow rate of injection pump B to 10mL / min, and the total flow rate to 20mL / min. A reactor HSI10-1.8-4 with a retention volume of 15 mL (retention time of 45 s) was connected to two syringes through a T-type mixer, the reaction pipeline 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 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 for precipitation, and the product was collected by centrifugation after being placed in a -20°C refrigerator overnight, the dissolution, precipitation, and centrifugation processes were repeated three times to fully wash the product, and finally placed in a 35°C vacuum drying oven for drying for 48 h to obtain a pure random copolymer of 5-norbornene-2-carboxylic acid methyl ester and 5-norbornene-2-carboxylic acid tert-butyl ester. At this time, the monomer conversion rate of 5-norbornene-2-carboxylic acid methyl ester was 95.6%, the monomer conversion rate of 5-norbornene-2-carboxylic acid tert-butyl ester 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 output per unit time is 1.23g / min.

[0110] Comparative Example 1

[0111] Take two 50mL Schlenk bottles, use double-row pipes to pump and fill three times, during which time they are repeatedly baked with an electronic Bunsen burner to remove water. Under an argon atmosphere, add Grubbs 3rd generation catalyst (35.36mg, 0.04mmol) to reaction bottle A, add monomer 5-norbornene-2-carboxylic acid methyl ester (608.8mg, 4mmol, about 0.5mL) to reaction bottle B, add 10mL and 9.5mL ultra-dry tetrahydrofuran to prepare solution A (10mL) and solution B (10mL), respectively, and stir to mix. Transfer solution A and solution B to two 50mL SGE glass syringes pre-rinsed with ultra-dry tetrahydrofuran and fix them on the syringe pump. Set the flow rate of syringe pump A to 1.5mL / min, the flow rate of syringe pump B to 1.5mL / min, and the total flow rate to 3mL / 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 through a T-type mixer. The reaction pipeline was placed in a 25°C water bath, and the syringe pump was turned on. After reacting for 30 s, the reaction solution was collected and quenched with excess vinyl ether. 1 The conversion rate was calculated by H-NMR, and the remaining reaction solution was poured into cold methanol for precipitation. After being placed in a -20°C refrigerator overnight, the product was collected by centrifugation. The dissolution, precipitation, and centrifugation process were repeated three times to fully wash the product, and finally placed in a 35°C vacuum drying oven for 3 days to obtain pure poly-5-norbornene-2-carboxylic acid methyl ester. At this time, 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 output per unit time was 80.66 mg / min.

[0112] Comparative Example 2

[0113] Take two 50mL Schlenk bottles, use double-row pipes to pump and fill three times, during which time they are repeatedly baked with an electronic Bunsen burner to remove water. In an argon atmosphere, add Grubbs 3rd generation catalyst (35.36mg, 0.04mmol) to reaction bottle A, add monomer 5-norbornene-2-carboxylic acid methyl ester (608.8mg, 4mmol, about 0.5mL) to reaction bottle B, add 10mL and 9.5mL ultra-dry tetrahydrofuran to prepare solution A (10mL) and solution B (10mL), respectively, and stir to mix. Transfer solution A and solution B to two 50mL SGE glass syringes pre-rinsed with ultra-dry tetrahydrofuran and fix them on the syringe pump. Set the flow rate of syringe pump A to 10mL / min, the flow rate of syringe pump B to 10mL / min, and the total flow rate to 20mL / 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 through a T-type mixer. The reaction pipeline was placed in a 25°C water bath. The injection pump was turned on. The injection pump gave an error due to excessive pressure and could not continue the reaction.

[0114] Comparative Example 3

[0115] Take two 50mL Schlenk bottles, use double-row pipes to pump and fill three times, during which time they are repeatedly baked with an electronic Bunsen burner to remove water. In an argon atmosphere, add Grubbs 3rd generation catalyst (35.36mg, 0.04mmol) to reaction bottle A, add monomer 5-norbornene-2-carboxylic acid methyl ester (608.8mg, 4mmol, about 0.5mL) to reaction bottle B, add 10mL and 9.5mL ultra-dry tetrahydrofuran to prepare solution A (10mL) and solution B (10mL), respectively, and stir to mix. Transfer solution A and solution B to two 50mL SGE glass syringes pre-rinsed with ultra-dry tetrahydrofuran and fix them on the syringe pump. Set the flow rate of syringe pump A to 10mL / min, the flow rate of syringe pump B to 10mL / min, and the total flow rate to 20mL / min. A 8-0-0 continuous flow reactor with a retention volume of 10 mL (corresponding to a retention time of 30 s) was connected to two syringes through a T-type mixer. The reaction pipeline was placed in a 25°C water bath and the syringe pump was turned on. After reacting for 30 s, the reaction solution was collected and quenched with excess vinyl ether. 1 The conversion rate was calculated by H-NMR, and the remaining reaction solution was poured into cold methanol for precipitation. After being placed in a -20°C refrigerator overnight, the product was collected by centrifugation. The dissolution, precipitation, and centrifugation process were repeated three times to fully wash the product, and finally placed in a 35°C vacuum drying oven for 3 days to obtain pure poly-5-norbornene-2-carboxylic acid methyl ester. At this time, 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 output per unit time was 450.8 mg / min.

[0116] Comparative Example 4

[0117] Take two 50mL Schlenk bottles, use double-row pipes to pump and fill three times, during which time they are repeatedly baked with an electronic Bunsen burner to remove water. Under an argon atmosphere, add Grubbs 3rd generation catalyst (35.36mg, 0.04mmol) to reaction bottle A, add monomer 5-norbornene-2-carboxylic acid methyl ester (608.8mg, 4mmol, about 0.5mL) to reaction bottle B, add 10mL and 9.5mL ultra-dry tetrahydrofuran to prepare solution A (10mL) and solution B (10mL), respectively, and stir to mix. Transfer solution A and solution B to two 50mL SGE glass syringes pre-rinsed with ultra-dry tetrahydrofuran and fix them on the syringe pump. Set the flow rate of syringe pump A to 1.5mL / min, the flow rate of syringe pump B to 1.5mL / min, and the total flow rate to 3mL / 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 through a T-type mixer. The reaction pipeline was placed in a 25°C water bath and the syringe pump was turned on. After reacting for 30 s, the reaction solution was collected and quenched with excess vinyl ether. 1 The conversion rate was calculated by H-NMR, and the remaining reaction solution was poured into cold methanol for precipitation. After being placed in a -20°C refrigerator overnight, the product was collected by centrifugation. The dissolution, precipitation, and centrifugation process were repeated three times to fully wash the product, and finally placed in a 35°C vacuum drying oven for 3 days to obtain pure poly-5-norbornene-2-carboxylic acid methyl ester. At this time, 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 output per unit time was 63.7 mg / min.

[0118] Comparative Example 5

[0119] In a kettle reactor, take a 50mL Schlenk bottle, use a double-row tube to pump and fill three times, during which time use an electronic Bunsen burner to repeatedly bake and remove water, add Grubbs third-generation catalyst (35.36mg, 0.04mmol) and monomer 5-norbornene-2-carboxylic acid methyl ester (608.8mg, 4mmol, about 0.5mL) to the reaction bottle under an argon atmosphere, add 19.5mL ultra-dry tetrahydrofuran to prepare a reaction solution, and stir to mix. React for 15min under an argon atmosphere, collect the reaction solution after the reaction is completed in a 25℃ water bath, and quench it with excess vinyl ether. 1 The conversion rate was calculated by H-NMR, and the remaining reaction solution was poured into cold methanol for precipitation. After being placed in a -20°C refrigerator overnight, the product was collected by centrifugation. The dissolution, precipitation, and centrifugation process were repeated three times to fully wash the product, and finally placed in a 35°C vacuum drying oven for 3 days to obtain pure poly-5-norbornene-2-carboxylic acid methyl ester. At this time, 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 output per unit time was 509.4 mg / min.

[0120] The above-mentioned embodiments only express several implementation methods of the present invention, and the description thereof is relatively specific and detailed, but it cannot be understood as limiting the scope of the patent of the present invention. It should be pointed out that, for ordinary technicians in this field, several variations and improvements can be made without departing from the concept of the present invention, which all belong to the protection scope of the present invention. Therefore, the protection scope of the patent of the present invention shall be subject to the attached claims.

Claims

1. An application of a macro-microreactor in preparing functionalized polyolefin; preferably, the functionalized polyolefin is prepared using norbornene-based monomer as raw material; preferably, in the macro-microreactor, norbornene-based monomer, ruthenium catalyst and solvent are reacted to obtain the functionalized polyolefin.

2. A method for preparing functionalized polyolefin based on macro-micro reactor, characterized in that: In a macro-microreactor, a norbornene-based monomer, a ruthenium catalyst and a solvent are reacted to obtain a functionalized polyolefin.

3. The use according to claim 1 or the method according to claim 2, characterized in that: The norbornene-based monomer is The functionalized polyolefin is R is selected from the group consisting of methyl carboxylate, tert-butyl carboxylate, cyano and methanol.

4. The use or method according to claim 3, characterized in that: n is selected from 50-500.

5. The use according to claim 1 or the method according to claim 2, characterized in that: The norbornene-based monomer includes The functionalized polyolefin is wherein R1 and R2 are independently selected from methyl carboxylate, tert-butyl carboxylate, cyano, and methanol, and R1 and R2 are different, n is selected from 50-500, and m is selected from 50-500; Preferably, the macro-microreactor comprises a channel shell and an internal component in the channel; preferably, the retention volume of the macro-microreactor is 1-30 mL; preferably, the inner diameter of the macro-microreactor is 1-10 mm, and the diameter of the internal component is 0.5-3 mm; preferably, the internal component is a linear internal component; preferably, the internal component is a spiral internal component, a serpentine internal structure, or an O-shaped internal component, which has a pitch, and the pitch of the internal component is 3-10 mm.

6. The use according to claim 1 or the method according to claim 2, characterized in that: The monomer is norbornene, 5-norbornene-2-carboxylic acid methyl ester, 5-norbornene-2-carboxylic acid tert-butyl ester, 2-cyano-5-norbornene, 5-norbornene-2-methanol, preferably 5-norbornene-2-carboxylic acid methyl ester.

7. The use according to claim 1 or the method according to claim 2, characterized in that: The ruthenium catalyst is any one or a combination of phenylmethylenebis(tricyclohexylphosphine)ruthenium dichloride, 1,3-bis(2,4,6-trimethylphenyl)-2-(imidazolidinyl)(dichlorobenzylidene)(tricyclohexylphosphine)ruthenium and dichloro[1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinyl](benzylidene)bis(3-bromopyridine)ruthenium(II), preferably dichloro[1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinyl](benzylidene)bis(3-bromopyridine)ruthenium(II).

8. The use according to claim 1 or the method according to claim 2, characterized in that: The solvent of the reaction is any one or a combination of tetrahydrofuran, toluene and dichloromethane, preferably tetrahydrofuran; Preferably, the molar ratio of the monomer to the catalyst is 50-500:1, preferably 100:1; Preferably, in the reaction system, the monomer concentration is 0.1-1 mol / L, preferably 0.2 mol / L; the reaction flow rate is 3-30 mL / min, preferably 20 mL / min; preferably, the reaction temperature is 15-35°C, preferably 25°C.

9. The use according to claim 1 or the method according to claim 2, characterized in that: The macro-microreactor comprises a channel shell and a spiral internal component in the channel; preferably, the spiral internal component is formed by scanning a circular cross-section along a spiral line in the channel, the diameter of the circular cross-section is 0.2-3mm, the pitch of the spiral line is 0.3-1cm, and the central axis of the spiral line is colinear with the central axis of the mixing channel; preferably, the inner diameter of the macro-microreactor is 1-10mm, preferably 8mm, the diameter of the spiral internal component is 0.5-3mm, preferably 1.8mm, and the pitch is 3-10mm, preferably 4mm.

10. A method for preparing functionalized polyolefin based on macro-micro reactor, characterized in that: In a macro-microreactor, a norbornene-based monomer, a molybdenum catalyst, and a solvent are reacted to obtain a functionalized polyolefin; Preferably, the norbornene-based 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 norbornene-based monomer includes The functionalized polyolefin is Wherein, R1 and R2 are independently selected from methyl carboxylate, tert-butyl carboxylate, cyano, and methanol, and R1 Different from R2, n is selected from 50-500, and m is selected from 50-500; Preferably, the monomer is a combination of any of norbornene, 5-norbornene-2-carboxylic acid methyl ester, 5-norbornene-2-carboxylic acid tert-butyl ester, 2-cyano-5-norbornene and 5-norbornene-2-methanol; Preferably, the molybdenum catalyst is 2,6-diisopropylphenyl molybdenum; Preferably, the solvent of the reaction is any one or a combination of tetrahydrofuran, toluene and dichloromethane, preferably tetrahydrofuran; Preferably, the molar ratio of the monomer to the catalyst is 50-500:1, preferably 100:1; Preferably, in the reaction system, the monomer concentration is 0.1-1 mol / L, preferably 0.2 mol / L; the reaction flow rate is 3-30 mL / min, preferably 20 mL / min; preferably, the reaction temperature is 15-35° C., preferably 25° C.; Preferably, the macro-microreactor comprises a channel shell and an internal component in the channel; preferably, the retention volume of the macro-microreactor is 1-30 mL; preferably, the inner diameter of the macro-microreactor is 1-10 mm, and the diameter of the internal component is 0.5-3 mm; preferably, the internal component is a linear internal component; preferably, the internal component is a spiral internal component, a serpentine internal structure, or an O-shaped internal component, which has a pitch, and the pitch of the internal component is 3-10 mm.

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