Perfluoropolyether-modified polybutadiene liquid rubber, its preparation method and application

Abstract

The present application relates to perfluoropolyether modified polybutadiene liquid rubber and its preparation method and application. The perfluoropolyether modified polybutadiene liquid rubber comprises a first structural unit and a second structural unit, the first structural unit is composed of a structure derived from a conjugated diene monomer of polyconjugated diene including but not limited to isoprene or 1,3-butadiene and a structure derived from perfluoropolyether, and the second structural unit is composed of a structure derived from a conjugated diene monomer of polyconjugated diene including but not limited to isoprene or 1,3-butadiene and a structure derived from perfluoropolyether. The perfluoropolyether modified polybutadiene liquid rubber of the present application has excellent high temperature resistance, dimensional stability, low dielectric property, low moisture absorption and chemical corrosion resistance, and is suitable for electronic information fields such as high frequency high speed copper clad plate.

Description

Technical Field

[0001] This invention belongs to the field of synthetic rubber and relates to a method for preparing liquid rubber, particularly to a perfluoropolyether modified polybutadiene liquid rubber and its preparation method and application. Background Technology

[0002] Polybutadiene rubber is a general-purpose synthetic rubber obtained by polymerization of 1,3-butadiene as a monomer. Cis-butadiene rubber is the abbreviation for cis-1,4-polybutadiene rubber. Its cis structure content is more than 95%, and it has the advantages of high elasticity, good low temperature performance, and good wear resistance.

[0003] Liquid polybutadiene rubber is a viscous, flowable polymer with a number average molecular weight of 500-10000. It is an oligomer that is a viscous, flowing liquid at room temperature and is mainly used in the production of cast elastomers, aerospace seals, adhesives, high-performance tires, potting materials, waterproof and anti-corrosion materials, integrated circuit packaging and other fields.

[0004] Chinese patent CN113166534B discloses a perfluoropolyether-based rubber composition that provides a cured product with excellent heat resistance, low-temperature resistance, organic solvent resistance, and acid resistance. It contains: (a) a linear perfluoropolyether compound with a number average molecular weight of 1,000 to 100,000 having at least two azide groups in one molecule and a divalent perfluoroalkyl ether structure in the main chain; and (b) a linear perfluoropolyether compound having at least three acetylene groups in one molecule. However, this patent provides a novel perfluoropolyether-based rubber composition and is not a solution for modifying polybutadiene liquid rubber.

[0005] Chinese patent CN115368573A discloses the preparation and application of a silane polymer containing polyether segments, used to improve the compatibility of inorganic fillers such as silica and carbon black with the rubber matrix, as well as the dispersion state of the fillers in the rubber matrix. Simultaneously, the silane polymer containing polyether segments prepared by this invention can effectively reduce the VOC gas generated by traditional silane coupling agents during industrial production. Although this solution also states that the addition of the silane polymer coupling agent containing polyether segments significantly reduces the loss factor and compression fatigue temperature rise of the rubber composite material, and reduces the rolling resistance and hysteresis effect of the rubber, this solution does not address how to solve the problem of insufficient performance of liquid rubber.

[0006] Chinese patent CN117801143A discloses a modified polydiolefin liquid rubber. Specifically, the modified polydiolefin liquid rubber is grafted with acryloyloxy photosensitive groups. The purpose of grafting acryloyloxy photosensitive groups is to increase the polarity of the liquid rubber, thereby improving its adhesiveness. However, this solution does not address how to improve the high-temperature resistance, dimensional stability, or low dielectric properties of the polydiolefin liquid rubber.

[0007] Chinese patent CN116693958B discloses a highly wear-resistant organofluorine-modified solution-polymerized styrene-butadiene rubber (SBR) and its preparation method. This method involves mixing a functionalized fluoropolymer with SBR, followed by open milling and vulcanization to obtain the highly wear-resistant organofluorine-modified SBR. On one hand, this method uses fluoropolymer modification targeting SBR. On the other hand, the method of functionalizing the fluoropolymer involves blending two pre-reacted, end-capped raw rubbers or rubber compounds through extrusion and shearing. Essentially, it's a macroscopic mixing process using a mixing mill, without addressing the regulation of polymer molecular chain structure. Furthermore, this modification aims to alter its frictional properties; it doesn't address how to improve the high-temperature resistance, dimensional stability, or low dielectric properties of the polydiolefin liquid rubber. Summary of the Invention

[0008] To address the performance limitations of polybutadiene liquid rubber, this invention provides a perfluoropolyether-modified polybutadiene liquid rubber, its preparation method, and its applications.

[0009] This invention modifies polybutadiene liquid rubber by grafting perfluoropolyether, improving its performance and addressing its shortcomings. Perfluoropolyether-modified polybutadiene liquid rubber exhibits excellent high-temperature resistance, dimensional stability, low dielectric properties, low moisture absorption, and chemical resistance.

[0010] The objective of this invention can be achieved through the following technical solutions:

[0011] In a first aspect, the present invention provides a perfluoropolyether-modified polybutadiene liquid rubber, wherein the perfluoropolyether-modified polybutadiene liquid rubber is as shown in the first structural unit or the second structural unit.

[0012] The first structural unit is shown below:

[0013]

[0014] The second structural unit is shown below:

[0015]

[0016] In the first structural unit, the selection range of n is 20 to 100, the selection range of p is 10 to 50, and the selection range of q is 20 to 100.

[0017] In the second structural unit, the selection range of n is 20 to 100, the selection range of p is 10 to 50, and the selection range of q is 20 to 100.

[0018] The molar ratio of the first structure to the second structure in the perfluoropolyether modified polybutadiene rubber is 0.25 to 4:1.

[0019] The perfluoropolyether-modified polybutadiene liquid rubber has a molecular weight of 4000-10000 and a molecular weight distribution index of 1.2-1.5.

[0020] The perfluoropolyether-modified polybutadiene liquid rubber is a liquid rubber.

[0021] The first structural unit consists of structure I and structure III, and the second structural unit consists of structure II and structure III.

[0022] Structure I, Structure II, and Structure III are shown below:

[0023]

[0024] Structures I and II are derived from polyconjugated dienes, while structure III is derived from perfluoropolyethers.

[0025] In a second aspect, the present invention provides a method for preparing perfluoropolyether-modified polybutadiene liquid rubber, comprising the following steps:

[0026] 1) Mix the polyconjugated diene liquid rubber and the rubber solvent to completely dissolve the polyconjugated diene liquid rubber, thereby obtaining a polyconjugated diene liquid rubber solution;

[0027] 2) Mix the polyconjugated diene liquid rubber solution with perfluoropolyether and perfluoropolyether solvent evenly and wait for the reaction to proceed. The reaction is carried out in an inert atmosphere. After replacing the air in the container with an inert gas, a catalyst is added to carry out the olefin metathesis reaction to obtain perfluoropolyether modified polyconjugated diene liquid rubber, namely perfluoropolyether modified polybutadiene liquid rubber.

[0028] In one embodiment of the present invention, in step 1), the polyconjugated diene liquid rubber includes the following structures I and II:

[0029]

[0030] When the structure of the polyconjugated diene liquid rubber is selected as structure I, the reaction equation is as follows:

[0031]

[0032] When the structure of the polyconjugated diene liquid rubber is selected as structure II, the reaction equation is as follows:

[0033]

[0034] In one embodiment of the present invention, in step 1), the polyconjugated diene liquid rubber and solvent are mixed by stirring or shaking.

[0035] In one embodiment of the present invention, the rubber solvent used to dissolve the polyconjugated diene liquid rubber is selected from one or more of cyclopentane, hexane, cyclohexane, heptane, dichloromethane, chloroform, carbon tetrachloride, methyl propyl ketone, diacetone, acetone, benzene, toluene, xylene, chlorobenzene, tetrahydrofuran, or ethylene glycol butyl ether. Preferably, the rubber solvent is toluene and / or chlorobenzene, and more preferably, the rubber solvent is chlorobenzene.

[0036] In one embodiment of the present invention, in step 1), the amount of rubber solvent added is not particularly limited, and can be reasonably set according to the conventional addition amount in the current polybutadiene rubber preparation process. The selection basis is to ensure that the polyconjugated diene liquid rubber is completely dissolved.

[0037] In one embodiment of the present invention, the perfluoropolyether is selected from one of K-type perfluoropolyether, D-type perfluoropolyether, Y-type perfluoropolyether or Z-type perfluoropolyether, preferably, the perfluoropolyether is K-type perfluoropolyether.

[0038] In this invention, perfluoropolyether is an important substance used in the preparation process of perfluoropolyether-modified polybutadiene liquid rubber. Perfluoropolyether is a liquid polymer compound composed only of three elements: C, F, and O. It possesses properties such as heat resistance, oxidation resistance, corrosion resistance, radiation resistance, and non-flammability. In this invention, under the action of a catalyst, the polybutadiene rubber undergoes chain scission and then recombines with the perfluoropolyether to obtain perfluoropolyether-modified polybutadiene liquid rubber. This invention utilizes the olefin metathesis reaction to first break the carbon-carbon double bonds of the polybutadiene rubber, and then recombine the molecular chains with the perfluoropolyether.

[0039] In one embodiment of the present invention, the perfluoropolyether solvent is selected from at least one of fluorinated solvents and non-fluorinated solvents. The fluorinated solvents include, for example, p-trifluorotoluene and nonafluorobutyl methyl ether, and the non-fluorinated solvents include, for example, ethanol, ethyl acetate (such as methoxyethanol), butyl acetate, tetrahydrofuran, ethylene glycol dimethyl ether, and diethylene glycol dimethyl ether. The perfluoropolyether solvent is preferably a fluorinated solvent, and more preferably, trifluorotoluene.

[0040] In one embodiment of the present invention, the catalyst is an olefin metathesis catalyst selected from multiple or one of GrubbsⅠ (G1st), GrubbsⅡ (G2nd), GrubbsⅢ (G3rd), Hoveyda-GrubbsⅠ (H-G1st), and Hoveyda-GrubbsⅡ (H-G2nd), preferably using GrubbsⅡ (G2nd) or Hoveyda-GrubbsⅡ (H-G2nd) as the catalyst, and more preferably using GrubbsⅡ (G2nd) as the catalyst.

[0041] In one embodiment of the present invention, in step 2), the mass ratio of polyconjugated diene liquid rubber, catalyst, and perfluoropolyether is (100-8000):0.05:(100-800), preferably (2000-4000):0.05:(100-150).

[0042] In one embodiment of the present invention, in step 2), the inert gas is selected as nitrogen.

[0043] Since the reaction process of perfluoropolyether-modified polybutadiene liquid rubber should be completed in an inert environment to avoid the generated active polymer reacting with oxygen in the air, which would affect the reaction process and the performance of the reaction products, this invention introduces an inert gas into the reactor, such as high-purity nitrogen into the reaction vessel, to isolate it from air.

[0044] This invention does not impose any particular restrictions on the order of adding the components before the reaction. Typically, the polybutadiene rubber is first dissolved in a solvent to prepare a solution, which usually takes more than 10 hours. Then, the polybutadiene rubber solution and the perfluoropolyether solution are mixed evenly, and the system is heated to the temperature required for the reaction. Then, the catalyst is added to start the reaction.

[0045] In one embodiment of the present invention, in step 2), the temperature of the reaction system is controlled at 60-100°C during the reaction, and the reaction time from the addition of the catalyst to the termination of the reaction is more than 4 hours.

[0046] In one embodiment of the present invention, after the reaction is completed, the process further includes post-processing the reaction system to obtain a high-purity perfluoropolyether modified polybutadiene liquid rubber product.

[0047] In one specific embodiment, the post-processing includes: coagulating the crude product with anhydrous ethanol, placing the coagulated product in an oven, and removing the solvent by vacuum evaporation to obtain perfluoropolyether modified polybutadiene liquid rubber.

[0048] The perfluoropolyether-modified polybutadiene liquid rubber prepared by the above method of the present invention has a molecular weight of 4000-10000 and a molecular weight distribution index of 1.2-1.5.

[0049] The perfluoropolyether modified polybutadiene liquid rubber provided by this invention has excellent chemical stability, heat resistance, low temperature performance, lubricity, and low dielectric constant.

[0050] A third aspect of the invention provides applications of the perfluoropolyether-modified polybutadiene liquid rubber, which is used in the production of cast elastomers, aerospace seals, adhesives, high-performance tires, potting materials, waterproof and anti-corrosion materials, and integrated circuit packaging. It is particularly suitable for electronic information fields such as high-frequency, high-speed copper-clad laminates. The perfluoropolyether-modified polybutadiene liquid rubber is primarily used as a liquid binder.

[0051] Compared with the prior art, the present invention has the following advantages and beneficial effects:

[0052] This invention employs an olefin metathesis reaction to graft perfluoropolyether onto liquid polybutadiene rubber, yielding perfluoropolyether-modified liquid polybutadiene rubber. The glass transition temperature of liquid polybutadiene rubber is typically around -40°C. Through grafting with perfluoropolyether, the glass transition temperature of the perfluoropolyether-modified liquid polybutadiene rubber is even lower, exhibiting better low-temperature performance. Testing showed that the glass transition temperature of the perfluoropolyether-modified cis-butadiene rubber is -110°C. The perfluoropolyether-modified liquid polybutadiene rubber possesses excellent high-temperature resistance, dimensional stability, low dielectric properties, low moisture absorption, and chemical corrosion resistance, enabling it to withstand more demanding operating environments.

[0053] Compared with the existing patent CN116693958B, which discloses a physical mixing method to modify polystyrene-butadiene rubber, the modification principle of this application is to perform graft modification by controlling the opening and closing of the bonds of the two polymers. Essentially, it is a combination of open and broken chemical bonds of the polymers, which involves the regulation of the microstructure and mainly involves chemical changes, resulting in a better modification effect on polybutadiene rubber.

[0054] Compared with the existing patent CN117801143A, which discloses a solution that grafts acryloyloxy photosensitive groups to increase the polarity of liquid rubber, the solution in this application uses perfluoropolyether modification to improve its high temperature resistance, dimensional stability, and low dielectric properties. The solution in this application also improves its molecular weight distribution, glass transition temperature, and pyrolysis temperature, which is not covered in the prior art. Attached Figure Description

[0055] Figure 1 The infrared spectrum of the perfluoropolyether-modified polybutadiene liquid rubber prepared in Example 1;

[0056] Figure 2 The 1H NMR spectrum of the perfluoropolyether-modified polybutadiene liquid rubber prepared in Example 1;

[0057] Figure 3 The NMR fluorine spectrum of the perfluoropolyether modified polybutadiene liquid rubber prepared in Example 1 is shown. Detailed Implementation

[0058] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of the present invention, not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0059] Unless otherwise specified, the raw materials used in the following examples can be obtained by commercial purchase or conventional methods. Experimental methods without specific conditions are conventional methods and conditions well known in the art.

[0060] Example 1

[0061] This embodiment provides a perfluoropolyether-modified polybutadiene liquid rubber, the preparation method of which includes the following steps:

[0062] (1) Add 5g of polybutadiene liquid rubber and 50mL of toluene to a conical flask, fix the conical flask on an automatic shaker, and shake at room temperature for 2 hours until the polybutadiene liquid rubber is completely dissolved in the toluene to form a solution.

[0063] (2) Add 1 mL of K-type perfluoropolyether and 10 mL of perfluoropolyether solvent p-trifluorotoluene to the toluene solution of polybutadiene liquid rubber, mix well, heat to 60°C under nitrogen atmosphere, then add 0.01 g of olefin metathesis catalyst and react for 6 h; after the reaction is completed, cool to room temperature, add 100 mL of ethanol for extraction, collect the condensed perfluoropolyether modified polybutadiene liquid rubber, rotary evaporate, dry to remove solvent, and obtain the product perfluoropolyether modified polybutadiene liquid rubber.

[0064] Example 2

[0065] This embodiment provides a perfluoropolyether-modified polybutadiene liquid rubber, the preparation method of which includes the following steps:

[0066] (1) Add 5g of polybutadiene liquid rubber and 50mL of cyclopentane to a conical flask, fix the conical flask on an automatic shaker, and shake at room temperature for 2 hours until the polybutadiene liquid rubber is completely dissolved in the cyclopentane to form a solution.

[0067] (2) Add 2 mL of K-type perfluoropolyether and 10 mL of perfluoropolyether solvent nonafluorobutyl methyl ether to the cyclopentane solution of polybutadiene liquid rubber, mix well, heat to 50 °C under nitrogen atmosphere, then add 0.01 g of olefin metathesis catalyst and react for 4 h; after the reaction is completed, cool to room temperature, add 100 mL of ethanol for extraction, collect the condensed perfluoropolyether modified polybutadiene liquid rubber, rotary evaporate, dry to remove solvent, and obtain the product perfluoropolyether modified polybutadiene liquid rubber.

[0068] Example 3

[0069] This embodiment provides a perfluoropolyether-modified polybutadiene liquid rubber, the preparation method of which includes the following steps:

[0070] (1) Add 5g of polybutadiene liquid rubber and 100mL of cyclopentane to a conical flask, fix the conical flask on an automatic shaker, and shake at room temperature for 2 hours until the polybutadiene liquid rubber is completely dissolved in cyclopentane to form a solution.

[0071] (2) Add 1.8 mL of type D perfluoropolyether and 10 mL of perfluoropolyether solvent p-trifluorotoluene to the cyclopentane solution of cis-polybutadiene. After mixing evenly, heat to 40 °C under a nitrogen atmosphere, then add 0.01 g of olefin metathesis catalyst and react for 6 h. After the reaction is completed, cool to room temperature, add 100 mL of ethanol for extraction, collect the condensed perfluoropolyether modified polybutadiene liquid rubber, rotary evaporate, dry to remove solvent, and obtain the product perfluoropolyether modified polybutadiene liquid rubber.

[0072] Example 4

[0073] This embodiment provides a perfluoropolyether-modified polybutadiene liquid rubber, the preparation method of which includes the following steps:

[0074] (1) Add 8g of polybutadiene liquid rubber and 120mL of chlorobenzene to a conical flask, fix the conical flask on an automatic shaker, and shake at room temperature for 2 hours until the polybutadiene rubber is completely dissolved in the chlorobenzene to form a solution.

[0075] (2) Add 1.5 mL of K-type perfluoropolyether and the perfluoropolyether solvent nonafluorobutyl methyl ether to the chlorobenzene solution of polybutadiene, mix evenly, heat to 60 °C under nitrogen atmosphere, then add 0.02 g of olefin metathesis catalyst and react for 7 h; after the reaction is completed, cool to room temperature, add 120 mL of ethanol for extraction, collect the condensed perfluoropolyether modified polybutadiene liquid rubber, dry to remove solvent, and obtain the product perfluoropolyether modified polybutadiene liquid rubber.

[0076] Example 5

[0077] This embodiment provides a perfluoropolyether-modified polybutadiene liquid rubber, the preparation method of which includes the following steps:

[0078] (1) Add 10g of polybutadiene rubber and 150mL of cyclopentane to a conical flask, fix the conical flask on an automatic shaker, and shake at room temperature for 2 hours until the butadiene rubber is completely dissolved in the cyclopentane to form a solution.

[0079] (2) Add 3 mL of Y-type perfluoropolyether and 10 mL of perfluoropolyether solvent p-trifluorotoluene to the cyclopentane solution of polybutadiene. After mixing evenly, heat to 80 °C under a nitrogen atmosphere, then add 0.02 g of olefin metathesis catalyst and react for 10 h. After the reaction is completed, cool to room temperature, add 150 mL of ethanol for extraction, collect the condensed perfluoropolyether modified polybutadiene liquid rubber, dry to remove solvent, and obtain the product perfluoropolyether modified polybutadiene liquid rubber.

[0080] Example 6

[0081] This embodiment provides a perfluoropolyether-modified polybutadiene liquid rubber, the preparation method of which includes the following steps:

[0082] (1) Add 5g of polybutadiene rubber and 100mL of chlorobenzene to a conical flask, fix the conical flask on an automatic shaker, and shake at room temperature for 2 hours until the polybutadiene rubber is completely dissolved in the chlorobenzene to form a solution.

[0083] (2) Add 1.5 mL of Z-type perfluoropolyether and 10 mL of perfluoropolyether solvent p-trifluorotoluene to the chlorobenzene solution of polybutadiene rubber, mix well, heat to 80 °C under nitrogen atmosphere, then add 0.01 g of olefin metathesis catalyst and react for 8 h; after the reaction is completed, cool to room temperature, add 100 mL of ethanol for extraction, collect the condensed perfluoropolyether modified polybutadiene liquid rubber, dry to remove solvent, and obtain the product perfluoropolyether modified polybutadiene liquid rubber.

[0084] The raw material ratios and reaction conditions used in the different embodiments described above are shown in Table 1.

[0085] Table 1. Raw material ratios and reaction conditions used in different embodiments.

[0086]

[0087]

[0088] The microstructures of the samples obtained from the different embodiments described above are shown in Table 2.

[0089] Table 2. Microstructure of samples obtained from different embodiments

[0090]

[0091] Figure 1 The infrared spectrum of the perfluoropolyether-modified polybutadiene liquid rubber prepared in Example 1; Figure 2 The 1H NMR spectrum of the perfluoropolyether-modified polybutadiene liquid rubber prepared in Example 1; Figure 3 The image shows the NMR fluorine spectrum of the perfluorinated polyether-modified polybutadiene liquid rubber prepared in Example 1. The infrared spectroscopy was performed using a Bruker ALPHA II instrument; the CS2 film was dissolved and coated on a potassium bromide plate, and the fluorine spectrum was measured by transmission electron microscopy. In addition to the typical absorption peaks of cis-butadiene rubber, the infrared spectrum shows a strong and broad absorption peak at 1200 cm⁻¹, which is the typical absorption peak of the CF₂ bond in the CH₂=CF₂ sequence of fluorinated rubber. Further observation revealed… Figure 2 The hydrogen spectrum shows two symmetrical peaks at shifts of 3.5–4.2, which are characteristic peaks of CH2=CF2, proving that perfluorinated modified polybutadiene liquid rubber can be prepared by the described method.

[0092] The above description of the embodiments is provided to enable those skilled in the art to understand and use the invention. It will be apparent to those skilled in the art that various modifications can be made to these embodiments, and the general principles described herein can be applied to other embodiments without inventive effort. Therefore, the present invention is not limited to the above embodiments, and any improvements and modifications made by those skilled in the art based on the disclosure of the present invention without departing from the scope of the invention should be within the protection scope of the present invention.

Claims

1. A perfluoropolyether-modified polybutadiene liquid rubber, characterized in that, The perfluoropolyether-modified polybutadiene liquid rubber comprises a first structural unit and a second structural unit. The first structural unit is shown below: The second structural unit is shown below: In the first structural unit, the selection range of n is 100 to 1800, the selection range of p is 300 to 2000, and the selection range of q is 100 to 4000; In the second structural unit, the selection range of n is 100 to 2000, the selection range of p is 300 to 2000, and the selection range of q is 100 to 4000; The molar ratio of the first structure to the second structure in the perfluoropolyether modified polybutadiene rubber is 0.25 to 4:1; The perfluoropolyether-modified polybutadiene liquid rubber has a molecular weight of 4000-10000 and a molecular weight distribution index of 1.2-1.

5. The perfluoropolyether-modified polybutadiene liquid rubber is a liquid rubber.

2. The method for preparing a perfluoropolyether-modified polybutadiene liquid rubber according to claim 1, characterized in that, Includes the following steps: 1) Mix the polyconjugated diene liquid rubber and the rubber solvent to completely dissolve the polyconjugated diene liquid rubber, thereby obtaining a polyconjugated diene liquid rubber solution; 2) Mix the polyconjugated diene liquid rubber solution with perfluoropolyether and perfluoropolyether solvent evenly and wait for the reaction to proceed. The reaction is carried out in an inert atmosphere. After replacing the air in the container with an inert gas, a catalyst is added to carry out the olefin metathesis reaction to obtain perfluoropolyether modified polyconjugated diene liquid rubber, namely perfluoropolyether modified polybutadiene liquid rubber.

3. The method for preparing a perfluoropolyether-modified polybutadiene liquid rubber according to claim 2, characterized in that, In step 1), the polyconjugated diene liquid rubber includes the following structures I and II:

4. The method for preparing a perfluoropolyether-modified polybutadiene liquid rubber according to claim 2, characterized in that, The rubber solvent used to dissolve the polyconjugated diene liquid rubber is selected from one or more of cyclopentane, hexane, cyclohexane, heptane, dichloromethane, chloroform, carbon tetrachloride, methyl propyl ketone, diacetone, acetone, benzene, toluene, xylene, chlorobenzene, tetrahydrofuran, or ethylene glycol butyl ether.

5. The method for preparing a perfluoropolyether-modified polybutadiene liquid rubber according to claim 2, characterized in that, The perfluoropolyether is selected from one of the following: K-type perfluoropolyether, D-type perfluoropolyether, Y-type perfluoropolyether, or Z-type perfluoropolyether.

6. The method for preparing a perfluoropolyether-modified polybutadiene liquid rubber according to claim 2, characterized in that, The perfluoropolyether solvent is selected from at least one of fluorinated solvents and non-fluorinated solvents. The fluorinated solvents include trifluorotoluene and nonafluorobutyl methyl ether, and the non-fluorinated solvents include ethanol, methoxyethanol, ethyl acetate, butyl acetate, tetrahydrofuran, ethylene glycol dimethyl ether, and diethylene glycol dimethyl ether.

7. The method for preparing a perfluoropolyether-modified polybutadiene liquid rubber according to claim 2, characterized in that, The catalyst is an olefin metathesis catalyst, selected from one or more of GrubbsⅠ (G1st), GrubbsⅡ (G2nd), GrubbsⅢ (G3rd), Hoveyda-GrubbsⅠ (H-G1st), and Hoveyda-GrubbsⅡ (H-G2nd).

8. The method for preparing a perfluoropolyether-modified polybutadiene liquid rubber according to claim 2, characterized in that, In step 2), the mass ratio of polyconjugated diene liquid rubber, catalyst, and perfluoropolyether is (100-8000): 0.05: (100-800).

9. The method for preparing a perfluoropolyether-modified polybutadiene liquid rubber according to claim 2, characterized in that, In step 2), the temperature of the reaction system is controlled at 60-100℃ during the reaction, and the reaction time from the addition of the catalyst to the termination of the reaction is more than 4 hours.

10. The application of the perfluoropolyether-modified polybutadiene liquid rubber according to claim 1, characterized in that, The perfluoropolyether modified polybutadiene liquid rubber is used in the production of cast elastomers, aerospace seals, adhesives, high-performance tires, potting materials, waterproof and anti-corrosion materials, and integrated circuit packaging.

Images