Use of allyl compounds containing leaving groups as capping agents

Abstract

This invention proposes the application of allyl compounds containing leaving groups as end-capping agents, relating to the field of polymer materials applications. Specifically, it involves using allyl compounds containing leaving groups as end-capping agents for the metathesis polymerization of ring-opening olefins; initiating the polymerization of ring-opening olefin monomers using a Grubbs-type catalyst, resulting in the polymerization product being end-capped with an active ruthenium carbene terminus; and then using the allyl compound containing leaving groups as the end-capping agent, reacting with the active ruthenium carbene terminus in an organic base, N... 2 The end-capping reaction is carried out in an atmosphere and organic solvent to obtain a polymer containing conjugated diene ends. This end-capping agent has high end-capping efficiency, rapid reaction, mild reaction conditions, is commercially available and requires no additional processing, and is low in cost.

Description

Application of allyl compounds containing leaving groups as end-capping agents Technical Field

[0001] This invention relates to the field of polymer material applications, specifically to the application of allyl compounds containing leaving groups as end-capping agents. Background Technology

[0002] Ring-opening olefin metathesis polymerization has important applications in academic research and industrial production. Through precise terminal functionalization, its applications in molecular labeling, self-assembly, and bioconjugation can be further broadened. Grubbs-type ruthenium catalysts, with their advantages of mild reaction conditions, good functional group tolerance, and controllable molecular weight and molecular weight distribution, have become the most commonly used initiators for ring-opening olefin metathesis polymerization. Therefore, how to achieve terminal functionalization in ring-opening olefin metathesis polymerization initiated by Grubbs-type catalysts is a noteworthy issue. Currently, terminal functionalization of ring-opening olefin metathesis polymerization can be achieved by using functionalized end-capping agents, functionalized chain transfer agents, and prefunctionalized initiators. In addition, terminal functionalized polymers can also be obtained through unimolecular addition or block copolymer hydrolysis. The simplest and most convenient method is to add an end-capping agent to the polymerization reaction system to directly quench the active chain, thus obtaining a terminal functionalized polymer. However, currently developed ring-opening olefin metathesis polymerization end-capping agents are based on olefin metathesis reactions for end-capping, which has the following drawbacks: 1) incomplete end-capping; 2) long reaction time; 3) complex synthesis of end-capping agents. Therefore, it is essential to develop a ring-opening olefin metathesis polymerization end-capping agent that is completely end-capped, reacts rapidly, is simple to synthesize, or is commercially available. Summary of the Invention

[0003] The purpose of this invention is to propose the application of allyl compounds containing leaving groups as end-capping agents, specifically as end-capping agents for the metathesis polymerization of ring-opening olefins. Under organic base conditions, these compounds can react with the active ruthenium carbene ends of the metathesis polymerization of ring-opening olefins to efficiently synthesize a series of metathesis polymers of ring-opening olefins containing conjugated diene ends.

[0004] To achieve the above objectives, the technical solution adopted by the present invention is as follows:

[0005] The application of allyl compounds containing leaving groups as end-capping agents, specifically, the use of allyl compounds containing leaving groups as end-capping agents for the metathesis polymerization of ring-opening olefins.

[0006] Furthermore, the structural formula of the allyl compound containing the leaving group is as follows:

[0007]

[0008] Where LG represents a chlorine atom, bromine atom, iodine atom, sulfone group, or acetoxy group, and R... 1 Represents a hydrogen atom, a fluorine atom, or a deuterium atom; R 2 It represents a hydrogen atom, a fluorine atom, a deuterium atom, or a cyano group.

[0009] Furthermore, the step of using an allyl compound containing a leaving group as a capping agent for the ring-opening olefin metathesis polymerization includes:

[0010] The polymerization of ring-opening olefin metathesis monomers was initiated using Grubbs-type catalysts, resulting in polymer products with active ruthenium carbene terminals.

[0011] An allyl compound containing a leaving group was used as a capping agent to react with the active ruthenium carbene terminal in an organic base, N2 atmosphere, and organic solvent to obtain a polymer containing a conjugated diene terminal. The reaction formula for the entire reaction process is as follows:

[0012]

[0013] in, This indicates a polymerization product with an active ruthenium carbene terminus, and Ru represents a Grubbs-type catalyst; This refers to polymers containing conjugated diene ends.

[0014] Furthermore, the ring-opening olefin metathesis polymerization monomer is one of norbornene, substituted norbornene, and norbornene imide, with the following structural formulas respectively:

[0015]

[0016] In Formula II, M1 represents norbornene, M2 and M3 represent two substituted norbornene products, and M4 represents norbornene imide; R 3 When referring to an alkyl group, it preferably refers to an alkyl group having 1 to 20 carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, sec-butyl, pentyl, neopentyl, etc.; more preferably, it refers to an alkyl group having 1 to 4 carbon atoms; R 4 When referring to an alkyl group, it is preferred to refer to an alkyl group having 1 to 20 carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, sec-butyl, pentyl, neopentyl, etc.; more preferably, it refers to an alkyl group having 1 to 4 carbon atoms, and particularly preferably methyl and isopropyl.

[0017] Furthermore, the Grubbs-type catalyst is a third-generation Grubbs catalyst with the general chemical formula RuCl. n (Py) m=CHR', where Cl represents chloride ions, Py represents pyridine ligands, n and m represent the number of chloride ions and pyridine ligands, respectively, and R' represents a hydrocarbon group, which is a commercially available reagent that does not require special treatment; the catalytic dosage of the Grubbs-type catalyst is based on a 5%-10% molar ratio of the ring-opening olefin metathesis polymerization monomer.

[0018] Further, the organic base has a pKa > 5, preferably one of the following organic bases: trimethylamine, triethylamine, diisopropylamine, n-butylamine, tert-butylamine, 1,8-diazobispyrocyclo[5.4.0]undecyl-7-ene, triethylenediamine, morpholine; the amount of the organic base is 2-20 times the molar ratio based on the Grubbs type catalyst.

[0019] Further, the organic solvent is selected from one of the following: dichloromethane, tetrahydrofuran, toluene, 1,2-dichloroethane; the amount used is: 0.1-1 ml of organic solvent for every 0.15 mmol of ring-opening olefin metathesis polymerization monomer.

[0020] Furthermore, the molar ratio of the Grubbs-type catalyst: allyl compound: organic base is 1:(2-20):(2-20), preferably 1:(3-5):(5-10).

[0021] Furthermore, the end-capping reaction takes place over a period of 1 to 30 minutes and the reaction temperature is within the range of -10 to 5°C.

[0022] Furthermore, after the end-capping reaction is completed, post-processing is carried out, which includes concentration or purification; concentration is carried out by methods such as atmospheric distillation, vacuum distillation, etc., for example, vacuum concentration using a rotary evaporator; purification is carried out by column chromatography or precipitation to obtain a pure product.

[0023] The technical effects achieved by this invention are as follows:

[0024] 1. This invention directly utilizes allyl compounds containing leaving groups as end-capping agents to obtain ring-opening metathesis polymers with conjugated diene ends under organic base conditions. This end-capping reaction can efficiently achieve terminal functionalization of ring-opening olefin metathesis polymerization with high end-capping efficiency (>95%); the reaction is rapid, completing within 1–30 minutes; it directly utilizes commercially available allyl compounds containing leaving groups and organic bases, requiring no additional processing, resulting in low cost; and it can be widely used for end-capping ring-opening olefin metathesis polymers. In contrast, traditional functionalized end-capping agents used for ring-opening olefin metathesis polymerization, such as functionalized symmetrical cis-olefins or functionalized alkenyl ethers, require end-capping reaction times of 1–2 hours and end-capping efficiencies between 80% and 95%, while also requiring 2–3 steps in preparation. Terminal-functionalized ring-opening metathesis polymers have promising applications in biomedicine, surface modification, and nanomaterials.

[0025] 2. The end-capping reaction of the end-capping agent proposed in this invention can efficiently achieve the terminal functionalization of ring-opening olefin metathesis polymerization.

[0026] 3. The end-capping agent proposed in this invention has mild end-capping reaction conditions, high end-capping efficiency, convenient and simple operation, and rapid reaction.

[0027] 4. The end-capping agent proposed in this invention has good tolerance to functional groups in its end-capping reaction, and the substituents can be cyano, fluorine atom, deuterium atom, etc.

[0028] 5. The capping reaction of the capping agent proposed in this invention uses allyl compounds and organic bases, both of which are commonly used commercial reagents, resulting in low reaction costs. Detailed Implementation

[0029] To make the various technical features, advantages, or effects of the present invention more apparent and understandable, detailed descriptions are provided below in conjunction with embodiments.

[0030] Example 1

[0031] In this embodiment, allyl bromide (an allyl compound containing a leaving group) is used as a capping agent for the ring-opening olefin metathesis polymerization. The specific reaction process is as follows.

[0032] Under a nitrogen atmosphere, 0.5 mL of a dichloromethane solution of norbornene (0.15 mmol, 14.1 mg, 10 equiv) was added to a 10 mL reaction tube. Then, 40 μL of a dichloromethane solution of Grubbs third-generation catalyst (0.015 mmol, 13.4 mg, 1 equiv) was added to the reaction system using a microsyringe. The reaction was carried out at 0 °C for 10 minutes. Then, 20 μL of triethylamine (0.15 mmol, 15.2 mg, 10 equiv) and 5 μL of allyl bromide (0.075 mmol, 9.1 mg, 5 equiv) were added sequentially to the system. After the reaction was complete, column chromatography was performed using dichloromethane as the eluent to obtain P1, whose structure is shown below.

[0033]

[0034] Its NMR data are as follows:

[0035] 1 H NMR (400MHz, Chloroform-d) δ7.40–7.10(m,5H), 6.40–6.24(m,2.3H), 6.20(m,0.4H), 6.09–5.98(m,1H), 5.69(m,1H), 5.58(m,1H), 5.35(m,1 5H), 5.28–5.13(m,21H), 5.09(m,1H), 4.96(m,1H), 2.79(m,23H), 2.44 (m,16H), 2.10–1.66(m,60H), 1.37(m,36H), 1.17–0.95(m,18H), n=18.

[0036] Example 2

[0037] In this embodiment, allyl chloride (an allyl compound containing a leaving group) is used as a capping agent for the ring-opening olefin metathesis polymerization. The specific reaction process is as follows.

[0038] Under a nitrogen atmosphere, 0.5 mL of a dichloromethane solution of norbornene (0.15 mmol, 14.1 mg, 10 equiv) was added to a 10 mL reaction tube. Then, 40 μL of a dichloromethane solution of Grubbs third-generation catalyst (0.015 mmol, 13.4 mg, 1 equiv) was added to the reaction system using a microsyringe. The reaction was carried out at 0 °C for 10 minutes. Next, 20 μL of triethylamine (0.15 mmol, 15.2 mg, 10 equiv) and 6 μL of allyl chloride (0.075 mmol, 5.7 mg, 5 equiv) were added sequentially to the system. After the reaction was complete, column chromatography was performed using dichloromethane as the eluent to obtain P1, whose structure is shown below.

[0039]

[0040] Its NMR data are as follows:

[0041] 1 H NMR (400MHz, Chloroform-d) δ7.40–7.10(m,5H), 6.40–6.24(m,2.3H), 6.20(m,0.4H), 6.09–5.98(m,1H), 5.69(m,1H), 5.58(m,1H), 5.35(m,1 5H), 5.28–5.13(m,21H), 5.09(m,1H), 4.96(m,1H), 2.79(m,23H), 2.44 (m,16H), 2.10–1.66(m,60H), 1.37(m,36H), 1.17–0.95(m,18H), n=18.

[0042] Example 3

[0043] In this embodiment, allyl iodine (an allyl compound containing a leaving group) is used as a capping agent for the metathesis polymerization of ring-opening olefins. The specific reaction process is as follows.

[0044] Under a nitrogen atmosphere, 0.5 mL of a dichloromethane solution of norbornene (0.15 mmol, 14.1 mg, 10 equiv) was added to a 10 mL reaction tube. Then, 40 μL of a dichloromethane solution of Grubbs third-generation catalyst (0.015 mmol, 13.4 mg, 1 equiv) was added to the reaction system using a microsyringe. The reaction was carried out at 0 °C for 10 minutes. Next, 20 μL of triethylamine (0.15 mmol, 15.2 mg, 10 equiv) and 7 μL of allyl iodine (0.075 mmol, 12.6 mg, 5 equiv) were added sequentially to the system. After the reaction was complete, column chromatography was performed using dichloromethane as the eluent to obtain P1, whose structure is shown below.

[0045]

[0046] Its NMR data are as follows:

[0047] 1H NMR (400MHz, Chloroform-d) δ7.40–7.10(m,5H), 6.40–6.24(m,2.3H), 6.20(m,0.4H), 6.09–5.98(m,1H), 5.69(m,1H), 5.58(m,1H), 5.35(m,1 5H), 5.28–5.13(m,21H), 5.09(m,1H), 4.96(m,1H), 2.79(m,23H), 2.44 (m,16H), 2.10–1.66(m,60H), 1.37(m,36H), 1.17–0.95(m,18H), n=18.

[0048] Example 4

[0049] In this embodiment, allyl acetate (an allyl compound containing a leaving group) is used as a capping agent for the ring-opening olefin metathesis polymerization. The specific reaction process is as follows.

[0050] Under a nitrogen atmosphere, 0.5 mL of norbornene in dichloromethane solution (0.15 mmol, 14.1 mg, 10 equiv) was added to a 10 mL reaction tube. Then, 40 μL of Grubbs third-generation catalyst in dichloromethane solution (0.015 mmol, 13.4 mg, 1 equiv) was added to the reaction system using a microsyringe. The reaction was carried out at 0 °C for 10 minutes. Then, 20 μL of triethylamine (0.15 mmol, 15.2 mg, 10 equiv) and 8 μL of allyl acetate (0.075 mmol, 7.5 mg, 5 equiv) were added sequentially to the system. After the reaction was complete, P1 was obtained by column chromatography using dichloromethane as the eluent. Its structure is shown below.

[0051]

[0052] Its NMR data are as follows:

[0053] 1 H NMR (400MHz, Chloroform-d) δ7.40–7.10(m,5H), 6.40–6.24(m,2.3H), 6.20(m,0.4H), 6.09–5.98(m,1H), 5.69(m,1H), 5.58(m,1H), 5.35(m,1 5H), 5.28–5.13(m,21H), 5.09(m,1H), 4.96(m,1H), 2.79(m,23H), 2.44 (m,16H), 2.10–1.66(m,60H), 1.37(m,36H), 1.17–0.95(m,18H), n=18.

[0054] Example 5

[0055] In this embodiment, 3-bromo-3,3-difluoropropylene (an allyl compound containing a leaving group) is used as a capping agent for the ring-opening olefin metathesis polymerization. The specific reaction process is as follows.

[0056] Under a nitrogen atmosphere, 0.5 mL of a dichloromethane solution of norbornene (0.15 mmol, 14.1 mg, 10 equiv) was added to a 10 mL reaction tube. Then, 40 μL of a dichloromethane solution of Grubbs third-generation catalyst (0.015 mmol, 13.4 mg, 1 equiv) was added to the reaction system using a microsyringe. The reaction was carried out at 0 °C for 10 minutes. Then, 20 μL of triethylamine (0.15 mmol, 15.2 mg, 10 equiv) and 8 μL of 3-bromo-3,3-difluoropropene (0.075 mmol, 11.8 mg, 5 equiv) were added sequentially to the system. After the reaction was complete, column chromatography was performed using dichloromethane as the eluent to obtain P2, whose structure is shown below.

[0057]

[0058] Its NMR data are as follows:

[0059] 1 H NMR (400MHz, Chloroform-d) δ7.33(m,2H), 7.29–7.15(m,3H), 6.40–6.31(m,1H), 6.19(m,0H), 5.88(m,1H), 5.63–5.53(m,2H), 5.35(m,16 H), 5.27–5.13(m,25H), 4.89(m,1H), 2.79(m,27H), 2.61–2.34(m,16H), 2.02–1.67(m,68H), 1.49–1.23(m,44H), 1.12–0.93(m,20H), n=20.

[0060] Example 6

[0061] In this embodiment, 1-cyano-2-propenyl acetate (an allyl compound containing a leaving group) is used as a capping agent for the ring-opening olefin metathesis polymerization. The specific reaction process is as follows.

[0062] Under a nitrogen atmosphere, 0.5 mL of a dichloromethane solution of norbornene (0.15 mmol, 14.1 mg, 10 equiv) was added to a 10 mL reaction tube. Then, 40 μL of a dichloromethane solution of Grubbs third-generation catalyst (0.015 mmol, 13.4 mg, 1 equiv) was added to the reaction system using a microsyringe. The reaction was carried out at 0 °C for 10 minutes. Next, 20 μL of triethylamine (0.15 mmol, 15.2 mg, 10 equiv) and 9 μL of 1-cyano-2-propenyl acetate (0.075 mmol, 9.4 mg, 5 equiv) were added sequentially to the system. After the reaction was complete, column chromatography was performed using dichloromethane as the eluent to obtain P3, whose structure is shown below.

[0063]

[0064] Its NMR data are as follows:

[0065] 1 H NMR (600MHz, Chloroform-d) δ7.29–7.23(m,2H), 7.19(s,2H), 7.13–7.08(m,1H), 6.95–6. 84(m,0.4H), 6.70(m,0.5H), 6.50–6.41(m,0.4H), 6.32–6.25(m,1H), 6.16–5.99(m,1.8H) , 5.56–5.46(m,0.6H), 5.28(m,13H), 5.21–5.07(m,21H), 5.02(m,0.5H), 3.04–2.51(m,22 H), 2.50–2.30(m,12H), 1.96–1.64(m,56H), 1.38–1.22(m,33H), 1.03–0.88(m,16H), n=17.

[0066] Example 7

[0067] In this embodiment, 1,1-D allyl acetate (an allyl compound containing a leaving group) is used as a capping agent for the ring-opening olefin metathesis polymerization. The specific reaction process is as follows.

[0068] Under a nitrogen atmosphere, 0.5 mL of a dichloromethane solution of norbornene (0.15 mmol, 14.1 mg, 10 equiv) was added to a 10 mL reaction tube. Then, 40 μL of a dichloromethane solution of Grubbs third-generation catalyst (0.015 mmol, 13.4 mg, 1 equiv) was added to the reaction system using a microsyringe. The reaction was carried out at 0 °C for 10 minutes. Then, 20 μL of triethylamine (0.15 mmol, 15.2 mg, 10 equiv) and 8 μL of 1,1-D allyl acetate (0.075 mmol, 7.5 mg, 5 equiv) were added sequentially to the system. After the reaction was complete, column chromatography was performed using dichloromethane as the eluent to obtain P4, whose structure is shown below.

[0069]

[0070] Its NMR data are as follows:

[0071] 1 H NMR (400MHz, Chloroform-d) δ7.33(m,4H), 7.24–7.15(m,1H), 6.39–6.24(m,2H), 6.19(m,0.5H), 6.09–5.98(m,1H), 5.69(m,1H), 5.58(m, 0.8H), 5.35(m,15H), 5.27–5.14(m,23H), 2.80(m,25H), 2.62–2.35(m,16H), 2.01–1.68(m,61H), 1.37(m,40H), 1.14–0.93(m,20H), n=20.

[0072] Example 8

[0073] In this embodiment, allyl bromide (an allyl compound containing a leaving group) is used as a capping agent for the ring-opening olefin metathesis polymerization. The specific reaction process is as follows.

[0074] Under a nitrogen atmosphere, 0.5 mL of a dichloromethane solution of norbornene imide (0.15 mmol, 30 mg, 10 equiv) was added to a 10 mL reaction tube. Then, 40 μL of a dichloromethane solution of Grubbs third-generation catalyst (0.015 mmol, 13.4 mg, 1 equiv) was added to the reaction system using a microsyringe. The reaction was carried out at 0 °C for 10 minutes. Next, 20 μL of triethylamine (0.15 mmol, 15.2 mg, 10 equiv) and 5 μL of allyl bromide (0.075 mmol, 9.4 mg, 5 equiv) were added sequentially to the system. After the reaction was complete, column chromatography was performed using dichloromethane as the eluent to obtain P5, whose structure is shown below.

[0075]

[0076] Its NMR data are as follows:

[0077] 1 H NMR (400MHz, Chloroform-d) δ7.37(m,1H), 7.30(m,3H), 7.24–7.17(m,1H), 6.55(m,1H), 6.31(m,1.5H), 6.19(m,1H), 5.84–5.66(m,16H), 5.62(m ,0.5H), 5.49(m,16H), 5.17(m,1H), 5.05(m,1H), 4.27(m,17H), 3.37–2.5 5(m,64H), 2.35–1.93(m,22H), 1.91–1.44(m,22H), 1.33(m,102H), n=17.

[0078] Example 9

[0079] In this embodiment, allyl bromide (an allyl compound containing a leaving group) is used as a capping agent for the ring-opening olefin metathesis polymerization. The specific reaction process is as follows.

[0080] Under a nitrogen atmosphere, 0.5 mL of a tetrahydrofuran solution of exo-norbornene-2-carboxylic acid methyl ester (0.15 mmol, 22.8 mg, 10 equiv) was added to a 10 mL reaction tube. Then, 40 μL of a dichloromethane solution of Grubbs third-generation catalyst (0.015 mmol, 13.4 mg, 1 equiv) was added to the reaction system using a microsyringe. The reaction was carried out at 0 °C for 10 minutes. Then, 20 μL of triethylamine (0.15 mmol, 15.2 mg, 10 equiv) and 5 μL of allyl bromide (0.075 mmol, 9.4 mg, 5 equiv) were added sequentially to the system. After the reaction was complete, column chromatography was performed using dichloromethane as the eluent to obtain P6, whose structure is shown below.

[0081]

[0082] Its NMR data are as follows:

[0083] 1H NMR (400MHz, Chloroform-d) δ6.51–6.22(m,2H), 6.22–5.98(m,1.5H), 5.60(m,1H), 5.52(m,0.5H), 5.38(m,67H), 5.10(m,1H), 4 .98(m,1H), 3.76–3.54(m,107H), 3.04(m,40H), 2.62(m,61H), 2.20–1.82(m,69H), 1.80–1.59(m,36H), 1.47–1.02(m,38H), n=37.

[0084] Example 10

[0085] In this embodiment, allyl bromide (an allyl compound containing a leaving group) is used as a capping agent for the ring-opening olefin metathesis polymerization. The specific reaction process is as follows.

[0086] Under a nitrogen atmosphere, 0.5 mL of a tetrahydrofuran solution of endo-norbornene-2-carboxylic acid methyl ester (0.15 mmol, 22.8 mg, 10 equiv) was added to a 10 mL reaction tube. Then, 40 μL of a dichloromethane solution of Grubbs third-generation catalyst (0.015 mmol, 13.4 mg, 1 equiv) was added to the reaction system using a microsyringe. The reaction was carried out at 0 °C for 10 minutes. Then, 20 μL of triethylamine (0.15 mmol, 15.2 mg, 10 equiv) and 5 μL of allyl bromide (0.075 mmol, 9.4 mg, 5 equiv) were added sequentially to the system. After the reaction was complete, column chromatography was performed using dichloromethane as the eluent to obtain P7, whose structure is shown below.

[0087]

[0088] Its NMR data are as follows:

[0089] 1 H NMR (400MHz, Chloroform-d) δ6.51–6.34(m,1H), 6.27(m,1H), 6.06(m,1H), 5.71(m,1H), 5.58(m,1H), 5.33(m,28H) , 5.11(m,1H), 4.98(m,1H), 3.61(m,48H), 2.95(m,36H), 2.47(m,7H), 2.18–1.64(m,45H), 1.49–1.28(m,15H), n=15.

[0090] Example 11

[0091] In this embodiment, allyl bromide (an allyl compound containing a leaving group) is used as a capping agent for the ring-opening olefin metathesis polymerization. The specific reaction process is as follows.

[0092] Under a nitrogen atmosphere, 0.5 mL of a dichloromethane solution of norbornene (0.15 mmol, 14.1 mg, 10 equiv) was added to a 10 mL reaction tube. Then, 40 μL of a dichloromethane solution of Grubbs third-generation catalyst (0.015 mmol, 13.4 mg, 1 equiv) was added to the reaction system using a microsyringe. The reaction was carried out at -10 °C for 10 minutes. Then, 20 μL of triethylamine (0.15 mmol, 15.2 mg, 10 equiv) and 5 μL of allyl bromide (0.075 mmol, 9.1 mg, 5 equiv) were added sequentially to the system. After the reaction was completed for 1 minute, column chromatography was performed using dichloromethane as the eluent to obtain P1, whose structure is shown below:

[0093]

[0094] Its NMR data are as follows:

[0095] 1 H NMR (400MHz, Chloroform-d) δ7.40-7.10(m,5H), 6.40–6.24(m,2.3H), 6.20(m,0.4H), 6.09–5.98(m,1H), 5.69(m,1H), 5.58(m,1H), 5.35(m,1 5H), 5.28–5.13(m,21H), 5.09(m,1H), 4.96(m,1H), 2.79(m,23H), 2.44 (m,16H), 2.10–1.66(m,60H), 1.37(m,36H), 1.17–0.95(m,18H), n=18.

[0096] Example 12

[0097] In this embodiment, allyl bromide (an allyl compound containing a leaving group) is used as a capping agent for the ring-opening olefin metathesis polymerization. The specific reaction process is as follows.

[0098] Under a nitrogen atmosphere, 0.5 mL of norbornene in dichloromethane solution (0.15 mmol, 14.1 mg, 10 equiv) was added to a 10 mL reaction tube. Then, 40 μL of Grubbs third-generation catalyst in dichloromethane solution (0.015 mmol, 13.4 mg, 1 equiv) was added to the reaction system using a microsyringe. The reaction was carried out at 5 °C for 10 minutes. Then, 20 μL of triethylamine (0.15 mmol, 15.2 mg, 10 equiv) and 5 μL of allyl bromide (0.075 mmol, 9.1 mg, 5 equiv) were added sequentially to the system. After the reaction was completed for 1 minute, column chromatography was performed using dichloromethane as the eluent to obtain P1, whose structure is shown below:

[0099]

[0100] Its NMR data are as follows:

[0101] 1 H NMR (400MHz, Chloroform-d) δ7.40–7.10(m,5H), 6.40–6.24(m,2.3H), 6.20(m,0.4H), 6.09–5.98(m,1H), 5.69(m,1H), 5.58(m,1H), 5.35(m,1 5H), 5.28–5.13(m,21H), 5.09(m,1H), 4.96(m,1H), 2.79(m,23H), 2.44 (m,16H), 2.10–1.66(m,60H), 1.37(m,36H), 1.17–0.95(m,18H), n=18.

[0102] Example 13

[0103] In this embodiment, allyl bromide (an allyl compound containing a leaving group) is used as a capping agent for the ring-opening olefin metathesis polymerization. The specific reaction process is as follows.

[0104] Under a nitrogen atmosphere, 0.5 mL of norbornene in dichloromethane solution (0.15 mmol, 14.1 mg, 10 equiv) was added to a 10 mL reaction tube. Then, 40 μL of Grubbs third-generation catalyst in dichloromethane solution (0.015 mmol, 13.4 mg, 1 equiv) was added to the reaction system using a microsyringe. The reaction was carried out at 5 °C for 10 minutes. Then, 20 μL of triethylamine (0.15 mmol, 15.2 mg, 10 equiv) and 5 μL of allyl bromide (0.075 mmol, 9.1 mg, 5 equiv) were added sequentially to the system. After the reaction was completed for 30 minutes, column chromatography was performed using dichloromethane as the eluent to obtain P1, whose structure is shown below:

[0105]

[0106] Its NMR data are as follows:

[0107] 1 H NMR (400MHz, Chloroform-d) δ7.40–7.10(m,5H), 6.40–6.24(m,2.3H), 6.20(m,0.4H), 6.09–5.98(m,1H), 5.69(m,1H), 5.58(m,1H), 5.35(m,1 5H), 5.28–5.13(m,21H), 5.09(m,1H), 4.96(m,1H), 2.79(m,23H), 2.44 (m,16H), 2.10–1.66(m,60H), 1.37(m,36H), 1.17–0.95(m,18H), n=18.

[0108] Example 14

[0109] In this embodiment, allyl bromide (an allyl compound containing a leaving group) is used as a capping agent for the ring-opening olefin metathesis polymerization. The specific reaction process is as follows.

[0110] Under a nitrogen atmosphere, 0.5 mL of norbornene in dichloromethane solution (0.15 mmol, 14.1 mg, 10 equiv) was added to a 10 mL reaction tube. Then, 40 μL of Grubbs third-generation catalyst in dichloromethane solution (0.015 mmol, 13.4 mg, 1 equiv) was added to the reaction system using a microsyringe. The reaction was carried out at 5 °C for 10 minutes. Then, 20 μL of triethylamine (0.3 mmol, 30.4 mg, 20 equiv) and 5 μL of allyl bromide (0.075 mmol, 9.1 mg, 5 equiv) were added sequentially to the system. After the reaction was completed for 15 minutes, column chromatography was performed using dichloromethane as the eluent to obtain P1, whose structure is shown below:

[0111]

[0112] Its NMR data are as follows:

[0113] 1 H NMR (400MHz, Chloroform-d) δ7.40–7.10(m,5H), 6.40–6.24(m,2.3H), 6.20(m,0.4H), 6.09–5.98(m,1H), 5.69(m,1H), 5.58(m,1H), 5.35(m,1 5H), 5.28–5.13(m,21H), 5.09(m,1H), 4.96(m,1H), 2.79(m,23H), 2.44 (m,16H), 2.10–1.66(m,60H), 1.37(m,36H), 1.17–0.95(m,18H), n=18.

[0114] Example 15

[0115] In this embodiment, allyl bromide (an allyl compound containing a leaving group) is used as a capping agent for the ring-opening olefin metathesis polymerization. The specific reaction process is as follows.

[0116] Under a nitrogen atmosphere, 0.5 mL of norbornene in dichloromethane solution (0.15 mmol, 14.1 mg, 10 equiv) was added to a 10 mL reaction tube. Then, 40 μL of Grubbs third-generation catalyst in dichloromethane solution (0.015 mmol, 13.4 mg, 1 equiv) was added to the reaction system using a microsyringe. The reaction was carried out at 5 °C for 10 minutes. Then, 20 μL of triethylamine (0.15 mmol, 15.2 mg, 10 equiv) and 5 μL of allyl bromide (0.075 mmol, 9.1 mg, 5 equiv) were added sequentially to the system. After the reaction was completed for 15 minutes, column chromatography was performed using dichloromethane as the eluent to obtain P1, whose structure is shown below:

[0117]

[0118] Its NMR data are as follows:

[0119] 1 H NMR (400MHz, Chloroform-d) δ7.40–7.10(m,5H), 6.40–6.24(m,2.3H), 6.20(m,0.4H), 6.09–5.98(m,1H), 5.69(m,1H), 5.58(m,1H), 5.35(m,1 5H), 5.28–5.13(m,21H), 5.09(m,1H), 4.96(m,1H), 2.79(m,23H), 2.44 (m,16H), 2.10–1.66(m,60H), 1.37(m,36H), 1.17–0.95(m,18H), n=18.

[0120] Although the present invention has been disclosed above with reference to embodiments, it is not intended to limit the present invention. Appropriate modifications or equivalent substitutions made by those skilled in the art to the technical solutions of the present invention should be covered within the protection scope of the present invention, which is defined by the claims.

Claims

1. The application of allyl compounds containing leaving groups as end-capping agents, characterized in that, Allyl compounds containing leaving groups are used as end-capping agents in the metathesis polymerization of ring-opening olefins. The structural formula of the allyl compounds containing leaving groups is as follows: Where LG represents a chlorine atom, bromine atom, iodine atom, sulfone group, or acetoxy group, and R... 1 Represents a hydrogen atom, a fluorine atom, or a deuterium atom; R 2 The term "ring-opening olefin metathesis polymerization" refers to the polymerization of hydrogen, fluorine, deuterium, or cyano groups. The steps involve using an allyl compound containing a leaving group as a capping agent for the ring-opening olefin metathesis polymerization. These steps include: initiating monomer polymerization of the ring-opening olefin metathesis polymerization using a Grubbs-type catalyst to attach an active ruthenium carbene terminus to the polymerization product; and then reacting the allyl compound containing the leaving group with the active ruthenium carbene terminus in an organic base, N2 atmosphere, and organic solvent to obtain a polymer containing a conjugated diene terminus. The reaction formula for the entire process is as follows: in, This indicates a polymerization product with an active ruthenium carbene terminus, and Ru represents a Grubbs-type catalyst; This refers to polymers containing conjugated diene ends.

2. The application as described in claim 1, characterized in that, The ring-opening olefin metathesis polymerization monomer is one of norbornene, substituted norbornene, and norbornene imide, with the following structural formulas respectively: Wherein, M1 represents norbornene, M2 and M3 represent two substituted norbornene, and M4 represents norbornene imide; R 3 When referring to an alkyl group, it means an alkyl group having 1 to 20 carbon atoms; R 4 When referring to an alkyl group, it means an alkyl group having 1 to 20 carbon atoms.

3. The application as described in claim 1, characterized in that, The Grubbs-type catalyst is a third-generation Grubbs catalyst, and the catalytic dosage of the Grubbs-type catalyst is 5%-10% molar ratio based on the ring-opening olefin metathesis polymerization monomer.

4. The application as described in claim 1, characterized in that, The organic base has a pKa >5 and is selected from one of trimethylamine, triethylamine, diisopropylamine, n-butylamine, tert-butylamine, 1,8-diazobisspirocyclo[5.4.0]undec-7-ene, triethylenediamine, and morpholine; the amount of the organic base is 2-20 times the molar ratio based on the Grubbs type catalyst.

5. The application as described in claim 1, characterized in that, The organic solvent is selected from one of dichloromethane, tetrahydrofuran, toluene, and 1,2-dichloroethane, and its dosage is: 0.1-1 ml of organic solvent is added for every 0.15 mmol of ring-opening olefin metathesis polymerization monomer.

6. The application as described in claim 1, characterized in that, The molar ratio of the Grubbs-type catalyst: allyl compound: organic base is 1: (2 ~ 20): (2 ~ 20).

7. The application as described in claim 3, characterized in that, The end-capping reaction takes 1 to 30 minutes and the reaction temperature is in the range of -10 to 5 °C.

8. The application as described in claim 1, characterized in that, After the end-capping reaction is completed, post-processing is carried out, which includes concentration or purification. Concentration is carried out by atmospheric distillation or vacuum distillation, and purification is carried out by column chromatography or precipitation to obtain a pure product.

Images