A reactive liquid ethylene-propylene rubber and a method for producing the same

Abstract

The application discloses a reactive liquid ethylene-propylene rubber and a preparation method thereof, and belongs to the technical field of polymer materials. The method comprises the following steps: S1, a solution containing monomers and an organic solvent is added into a closed container, and then an initiator is added to obtain an isoprene-butadiene polymer solution through polymerization; the monomers are isoprene and / or butadiene; S2, a functionalization reagent is added into the closed container, mixed with the isoprene-butadiene polymer solution, and subjected to end-capping reaction to obtain a hydroxylated isoprene-butadiene polymer solution; S3, a terminating agent is added into the hydroxylated isoprene-butadiene polymer solution to terminate the reaction, and then a hydrogenation catalyst is added, and hydrogenation reaction is carried out in a hydrogen atmosphere to obtain a reactive ethylene-propylene rubber polymer solution; and S4, a catalyst removal agent and water are added into the reactive ethylene-propylene rubber polymer solution, and then water washing, centrifugation and rotary evaporation are carried out to obtain the reactive liquid ethylene-propylene rubber which is high in reactivity, narrow in distribution, and controllable in molecular weight and structure.

Description

TECHNICAL FIELD

[0001] The application relates to a reactive liquid ethylene-propylene rubber and a preparation method thereof, and belongs to the technical field of high polymer materials. BACKGROUND

[0002] Liquid rubber has many characteristics such as low relative molecular mass and low glass transition temperature, and has low viscosity, good flowability at room temperature, high temperature shear stability, and the like. Compared with high molecular weight solid rubber, the liquid rubber can be realized by casting and injection molding, has the advantages of simple processing, low energy consumption, easy realization of mechanization and continuous production, and the like, and can be used for manufacturing adhesives and sealing materials, and can also be used as rubber processing aids, plastic toughening agents, electronic potting agents, asphalt modifiers, lubricating oil modifiers and the like, and has a wide application prospect.

[0003] Liquid ethylene-propylene rubber is composed of ethylene-propylene copolymer or ethylene-propylene-diene terpolymer, has low molecular weight and low viscosity, is suitable for lubricating oil and plasticizer, and is also suitable for being used as a sealing agent for on-site spraying or smearing, and can vulcanize a thin film and a sealing pad at room temperature. In the rubber processing process, liquid terpolymer ethylene-propylene rubber with carbon-carbon double bonds can be used as a reactive plasticizer to form a co-crosslinking system with vulcanized rubber, avoid the phenomena of molecular migration, volatilization and solvent extraction, and effectively prevent the problems of shrinkage, deformation, pollution and the like of the product, and has excellent performance in improving the physical mechanical properties and chemical stability of the rubber. In addition, the liquid ethylene-propylene rubber can be crosslinked through vulcanization reaction of peroxide, sulfur and resin, and has a longer aging life than other types of liquid rubber. The use of appropriate amount of liquid ethylene-propylene rubber instead of high molecular weight ethylene-propylene rubber can significantly reduce the viscosity of the rubber mixture, improve the processing performance, and has no obvious influence on the physical properties after vulcanization. With the development of application in various fields, the market prospect of the liquid ethylene-propylene rubber is very good.

[0004] Liquid EP rubber is usually prepared by coordination copolymerization method or EP rubber thermal cracking method. The coordination copolymerization method uses ethylene and propylene monomers to carry out coordination polymerization under the action of a catalyst. For example, Jilin Petrochemical Company developed a series of products J-0050 and J-0030 with low Mooney viscosity for lubricating oil modification by using a metallocene catalyst. The American Lion Company synthesized liquid EP rubber with the product name Trilene by a solution method, and the molecular weight of each product is between 8000 and 50000. The product synthesized by this method is reacted by introducing double bonds through the addition of dicyclopentadiene, ethylidene norbornene and other third monomers for copolymerization, so as to obtain reactivity. The product obtained by this method has a wide distribution, and the catalyst and the product are difficult to separate after polymerization, the residual metal content is high, and the product does not contain a polar group, the surface or interfacial force is weak, and the blending modification of the product on a polar material is affected. The traditional thermal cracking method is to crack solid EP rubber by using external force, heat, light or chemical action under the action of a catalyst to generate short-chain liquid rubber. The patent with the publication number CN110078848A uses peroxide to catalytically crack solid EP rubber into liquid EP rubber, and the molecular weight of the obtained liquid EP rubber is 2300-18000. However, the molecular weight of the product obtained by this method is not easy to control, the molecular weight distribution is very wide PDI (2.9-3.1), and the microstructure cannot be controlled. The patent with the publication number CN100549148A uses a hot solution stirring method to catalytically crack high molecular weight EP rubber mixed in base oil, and the obtained liquid EP rubber is dissolved in base oil to become an oil mixture. The product is difficult to separate, and the application range is limited to viscosity modifiers. As can be seen from the above, the two preparation methods have unavoidable defects, such as poor structure control ability, wide molecular weight distribution, high residual metal content, poor compatibility of non-polar polymers with polar materials, and the liquid EP rubber prepared by individual method does not contain easy crystallization ethylene segments. SUMMARY

[0005] In order to solve the problems of poor controllability of molecular weight, wide distribution, low reactivity and high residual metal content in the existing technology for preparing liquid EP rubber, the application provides a reactive liquid EP rubber and a preparation method thereof. The reactive liquid EP rubber is prepared by the method of butadiene / isoprene anion polymerization-epoxy end-capping-catalytic hydrogenation, that is, a functionalized low molecular weight polymer is obtained by designing and controlling the molecular weight through active anion polymerization, then the low molecular weight polymer is catalytically hydrogenated and treated after catalyst removal to obtain the reactive liquid EP rubber. The preparation process uses the characteristics of anion active polymerization to accurately control the rubber molecular weight and distribution, copolymer composition, sequence structure and microstructure, realizes the functionalization of the rubber, and flexibly adjusts the double bond content by controlling the hydrogenation degree. The end hydroxyl group can be introduced at the chain end by the end capping method, so that the polymer has good polar compatibility.

[0006] The application adopts the following technical solutions:

[0007] According to an aspect of the present application, a reactive liquid ethylene-propylene rubber is provided, the reactive liquid ethylene-propylene rubber having a polymer of a general structure shown in Formula I:

[0008]

[0009] wherein x, n1-n4, m1-m4 are the number of each structural unit in the structure shown in Formula I, respectively;

[0010] 2n3+m3 is the number of ethylene structural units in the polymer main chain;

[0011] m3 is the number of propylene structural units in the polymer main chain;

[0012] m4 is the number of isopropyl short-chain structural units in the polymer;

[0013] n4 is the number of ethyl short-chain structural units in the polymer;

[0014] m1 is the number of isoprene unhydrogenated double-bond-containing 1,4- structural units in the polymer;

[0015] m2 is the number of isoprene unhydrogenated double-bond-containing 3,4- structural units in the polymer;

[0016] n1 is the number of butadiene unhydrogenated double-bond-containing 1,4- structural units in the polymer;

[0017] n2 is the number of butadiene unhydrogenated double-bond-containing 1,4- structural units in the polymer;

[0018] The ethylene and propylene structural units in the polymer main chain are obtained by hydrogenation after butadiene 1,4-addition and isoprene 1,4-addition polymerization, and the numbers thereof are represented by 2n3+m3 and m3, respectively; the isopropyl short-chain and ethyl short-chain are obtained by hydrogenation after isoprene 3,4-addition and butadiene 1,2-addition polymerization, and the numbers thereof are represented by m4 and n4, respectively. The isoprene unhydrogenated double-bond-containing 1,4- and 3,4- structural units in the polymer are represented by m1 and m2, respectively; the butadiene unhydrogenated double-bond-containing 1,4- and 1,2- structural units are represented by n1 and n2, respectively.

[0019] Optionally, the ratio of (n1+n2+n3+n4) to (m1+m2+m3+m4) is 0-2.

[0020] Optionally, the ratio of (n1+n2+n3+n4) to (m1+m2+m3+m4) is 0.3-1.5.

[0021] Optionally, the ratio of (n2+n4) to (n1+n2+n3+n4) is 0.05-0.1.

[0022] Optionally, the ratio of (n2+n4) to (n1+n2+n3+n4) is 0.06-0.08.

[0023] Optionally, the ratio of (m2+m4) to (m1+m2+m3+m4) is 0.05-0.1.

[0024] Optionally, the ratio of (m2+m4) to (m1+m2+m3+m4) is 0.06-0.08.

[0025] Optionally, the ratio of (n3+n4+m3+m4) to (n1+n2+n3+n4+m1+m2+m3+m4) is 0-1;

[0026] Optionally, the ratio of (n3+n4+m3+m4) to (n1+n2+n3+n4+m1+m2+m3+m4) is 0.9-1.

[0027] Optionally, the value of x is 0-1.

[0028] Optionally, the value of x is 0.7-1.

[0029] Optionally, the molecular weight of the reactive liquid ethylene-propylene rubber is 3000-50000.

[0030] Optionally, the molecular weight of the reactive liquid ethylene-propylene rubber is selected from any value or a range between any two values selected from 3000, 10000, 20000, 30000, 40000, 50000.

[0031] Optionally, the polydispersity index (PDI) of the reactive liquid ethylene-propylene rubber is 1.00-1.50.

[0032] Optionally, the polydispersity index (PDI) of the reactive liquid ethylene-propylene rubber is selected from any value or a range between any two values selected from 1.00, 1.05, 1.10, 1.15, 1.20, 1.25, 1.30, 1.35, 1.40, 1.45, 1.50.

[0033] Optionally, the iodine value of the reactive liquid ethylene-propylene rubber is 0-432.

[0034] Optionally, the iodine value of the reactive liquid ethylene-propylene rubber is 0-42.

[0035] Optionally, the metal ion content of the reactive liquid ethylene-propylene rubber is 0-10 ppm.

[0036] Optionally, the metal ion content of the reactive liquid ethylene-propylene rubber is 5-10 ppm.

[0037] Optionally, the reactive liquid ethylene-propylene rubber has a viscosity of 0-5000 Pa.s at 60℃.

[0038] Optionally, the reactive liquid ethylene-propylene rubber has a viscosity of 900-2000 Pa.s at 60℃.

[0039] Optionally, the reactive liquid ethylene-propylene rubber has a crystallization peak temperature of 0-50℃.

[0040] Optionally, the reactive liquid ethylene-propylene rubber has a crystallization peak temperature selected from any value of 0℃, 10℃, 20℃, 30℃, 40℃, 50℃ or a range value between any two of them.

[0041] Compared with the product obtained by coordination copolymerization, the polymer can regulate the sequence structure and branching degree of ethylene and propylene in the chain by adjusting the proportion of butadiene and the feeding mode, and the increase of polyethylene segment content can also make the polymer crystallize; the double bond content in the chain can be regulated by controlling the hydrogenation degree; the terminal hydroxyl group can be introduced at the chain end by the end capping method, so that the polymer has good polar compatibility. Based on the above structural characteristics, the polymer has good reactivity, more excellent performance, and wider application field.

[0042] According to another aspect of the present application, a preparation method of the above-mentioned reactive liquid ethylene-propylene rubber is provided, comprising the following steps:

[0043] S1, a solution containing monomers and an organic solvent is added to a closed container, reacted, then an initiator is added, and a polyisoprene-butadiene polymer solution is obtained by polymerization;

[0044] The monomers are isoprene and / or butadiene;

[0045] S2, a functionalization reagent is added to the closed container and mixed with the polyisoprene-butadiene polymer solution to carry out end capping reaction, and a hydroxylated polyisoprene-butadiene polymer solution is obtained;

[0046] S3, a terminating agent is added to the hydroxylated polyisoprene-butadiene polymer solution to terminate the reaction, then a hydrogenation catalyst is added, and hydrogenation reaction is carried out in a hydrogen atmosphere to obtain a reactive ethylene-propylene rubber polymer solution;

[0047] S4, a catalyst removal agent and water are added to the reactive ethylene-propylene rubber polymer solution, stirred, washed with water, centrifuged, and rotary evaporated to obtain the reactive liquid ethylene-propylene rubber.

[0048] Optionally, in step S1, the reaction conditions include controlling the reaction temperature to be 50-90℃ and stirring until the system temperature is stable.

[0049] In step S1, the reaction releases heat, and the temperature rise is controlled by a cooling cycle to control the reaction temperature between 50℃ and 90℃.

[0050] Optionally, in step S1, the reaction conditions include: the reaction temperature is controlled between 50℃ and 90℃, and the reaction time is between 1h and 12h.

[0051] Optionally, in step S1, the initiator is added in an amount of 130ppm to 1300ppm.

[0052] Optionally, in step S1, the polymerization conditions include: the polymerization temperature is between 50℃ and 90℃, the polymerization pressure is between 0.1MPa and 0.5MPa, and the polymerization time is between 1h and 12h.

[0053] Optionally, in step S1, the polymerization temperature in the polymerization conditions is between 60℃ and 80℃.

[0054] Optionally, in step S1, the polymerization time in the polymerization conditions is between 1h and 3h.

[0055] Optionally, in step S1, the reaction and polymerization conditions further independently include: the stirring rate is between 50rpm and 500rpm.

[0056] Optionally, in step S1, the reaction and polymerization conditions further independently include: the stirring rate is between 100rpm and 200rpm.

[0057] Optionally, in step S1, the initiator is selected from at least one of n-butyllithium, sec-butyllithium, and tert-butyllithium.

[0058] Optionally, in step S1, the molar ratio of butadiene to isoprene in the monomer is between 0 and 2:1.

[0059] Optionally, in step S1, the concentration of the monomer in the solution is between 10wt% and 30wt%.

[0060] Optionally, in step S1, the concentration of the monomer in the solution is between 10wt% and 20wt%, and the monomer in this mass fraction range is more conducive to controlling temperature changes during the polymerization reaction, and is conducive to obtaining liquid ethylene-propylene rubber with a narrower molecular weight distribution.

[0061] Optionally, in step S1, the organic solvent is selected from at least one of cyclohexane, cyclopentane, n-hexane, and n-pentane. Preferably, the organic solvent is ethylene oxide.

[0062] Optionally, in step S2, the functionalization reagent is selected from at least one of ethylene oxide and propylene oxide. The functionalization reagent is a capping agent.

[0063] Optionally, in step S2, the molar ratio of the functional reagent to the initiator in step S1 is 1-8:1.

[0064] Optionally, in step S2, the molar ratio of the functional reagent to the initiator in step S1 is 5-6:1.

[0065] Optionally, in step S2, the conditions of the end-capping reaction include that the temperature of the end-capping reaction is 50-80°C, and the time of the end-capping reaction is 1-12h.

[0066] Optionally, in step S2, the temperature of the end-capping reaction in the conditions of the end-capping reaction is 60-70°C.

[0067] Optionally, in step S2, the time of the end-capping reaction in the conditions of the end-capping reaction is 1-3h.

[0068] Optionally, in step S3, the molar ratio of the terminating agent to the initiator in step S1 is 1-2:1.

[0069] Optionally, in step S3, the molar ratio of the terminating agent to the initiator in step S1 is 1.2-1.5:1.

[0070] Optionally, in step S3, the conditions of the termination reaction include that the pressure is 0.5-2MPa, and the termination time is 5-30min.

[0071] Optionally, in step S3, the conditions of the termination reaction further include that the stirring rate is 50-800rpm.

[0072] Optionally, in step S3, the conditions of the termination reaction further include that the stirring rate is 50-300rpm.

[0073] Optionally, in step S3, the terminating agent is at least one selected from hydrogen, methanol, water, isooctanol, isooctanoic acid, 2,6-di-tert-butyl-p-cresol, and 2,4,6-tri-tert-butylphenol.

[0074] Optionally, in step S3, the amount of the hydrogenation catalyst added is 100-1000ppm.

[0075] Optionally, in step S3, the amount of the hydrogenation catalyst added is 100-800ppm.

[0076] Optionally, in step S3, the hydrogenation catalyst includes a main catalyst and a co-catalyst, the main catalyst is selected from cobalt neodecanoate and / or nickel neodecanoate, and the co-catalyst is selected from triisobutylaluminum.

[0077] Optionally, in step S3, the molar ratio of the main catalyst to the co-catalyst is 1-3:1.

[0078] Optionally, in step S3, the molar ratio of the main catalyst to the co-catalyst is 2-3:1.

[0079] Optionally, in step S3, the hydrogenation reaction conditions include: the hydrogenation reaction temperature is 50-140℃, the hydrogenation gas pressure is 1-10 MPa, and the hydrogenation reaction time is 1-12 h.

[0080] Optionally, in step S3, the hydrogenation reaction temperature in the hydrogenation reaction conditions is 70-120℃.

[0081] Optionally, in step S3, the hydrogenation gas pressure in the hydrogenation reaction conditions is 1.5-2.5 MPa.

[0082] Optionally, in step S3, the hydrogenation reaction time in the hydrogenation reaction conditions is 2-4 h.

[0083] Optionally, in step S3, the hydrogenation reaction conditions further include: the stirring rate is 50-800 rpm.

[0084] Optionally, in step S3, the hydrogenation reaction conditions further include: the stirring rate is 200-400 rpm.

[0085] Optionally, in step S4, the added amount of the catalyst removal agent is 3000-6000 ppm.

[0086] Optionally, in step S4, the added amount of the catalyst removal agent is 4000-5000 ppm, and the catalyst removal agent and water in this mass concentration range are more likely to remove the catalyst and lithium salt in the glue solution.

[0087] Optionally, in step S4, the catalyst removal agent is citric acid and adipic acid.

[0088] Optionally, in step S4, the molar ratio of citric acid to adipic acid in the catalyst removal agent is 10-20:1.

[0089] Optionally, in step S4, the molar ratio of citric acid to adipic acid in the catalyst removal agent is 15-18:1.

[0090] Optionally, in step S4, the ratio of the added amount of water to the amount of the reactive ethylene-propylene rubber polymer solution is 5-30 ml:1 kg.

[0091] Optionally, in step S4, the ratio of the added amount of water to the amount of the reactive ethylene-propylene rubber polymer solution is 10-20 ml:1 kg.

[0092] Optionally, in step S4, the stirring condition is that the stirring rate is 300-500 rpm and the stirring time is 30-60 min.

[0093] In step S4, the purpose of water washing and centrifugation is to remove the catalyst and lithium, and the purpose of rotary evaporation is to remove the organic solvent, and the water washing and centrifugation and rotary evaporation conditions can be selected and adjusted by those skilled in the art as needed.

[0094] Optionally, in step S4, the water washing and centrifugation process comprises centrifuging the stirred solution, adding water to the supernatant, stirring uniformly, and then centrifuging again.

[0095] Optionally, in step S4, the water washing and centrifugation condition comprises a water washing time of 10-60 min and a centrifugation rate of 2000-8000 rpm.

[0096] Optionally, in step S4, the water washing and centrifugation condition comprises a water washing time of 30-50 min.

[0097] Optionally, in step S4, the water washing and centrifugation condition comprises a centrifugation rate of 3000-5000 rpm.

[0098] The liquid ethylene-propylene rubber obtained by the preparation method of the present application has double bonds and hydroxyl groups, and has good reactivity; the liquid rubber prepared by controlling the synthesis conditions contains a long polyethylene segment and can crystallize. These characteristics make the liquid ethylene-propylene rubber of the present application have more excellent performance. The prepared polymer has controllable molecular weight and distribution, copolymer composition, sequence structure and microstructure, and double bond content, and can realize crystallization and terminal functionalization.

[0099] The preparation method of the present application is simple and effective, and the liquid ethylene-propylene rubber obtained by the characteristics of active anion polymerization has a narrow molecular weight distribution, controllable molecular weight and structure, controllable double bond content on the molecular chain, and hydroxyl functional groups at the chain end. The hydrogenation and catalyst removal process of the present application is simple, and the residual metal ion content is low, among which the hydrogenation degree is stable and controllable and can reach more than 99% within 2 h, the metal ion content of the obtained ethylene-propylene rubber is less than 5 ppm, which can be ignored, and is very suitable for electronic fields such as wires and circuits, and can also be used for rubber processing aids, plastic modification, and lubricating oil modifiers.

[0100] The beneficial effects that can be produced by the present application include:

[0101] (1) The new structure of the reactive liquid ethylene-propylene rubber provided by the present application is prepared by taking isoprene and butadiene as monomers and adopting anionic polymerization to obtain reactive ethylene-propylene rubber with narrow distribution, controllable molecular weight and structure, and terminal functionalization. Compared with the existing method, the polymer can regulate the sequence structure of ethylene and propylene groups in the chain by adjusting the proportion of butadiene and the feeding method, and the increase of polyethylene segment content can also make the polymer crystallize, and the double bond content in the chain can be effectively regulated by controlling the degree of catalytic hydrogenation; the use of active anionic polymerization makes the polymer have the characteristics of narrow distribution and stable and controllable molecular weight; and the active chain terminal capping method can introduce hydroxyl groups to the chain terminal, so that the polymer has polarity compatibility. The reactive ethylene-propylene rubber obtained by the method has two reactive structures of double bond and hydroxyl group, has good reactivity, and widens the application field of the reactive ethylene-propylene rubber.

[0102] (2) The preparation method of the reactive ethylene-propylene rubber provided by the present application is compared with the current preparation technology. The method provided by the present application adopts butadiene / isoprene anionic polymerization-ethylene oxide capping-catalytic hydrogenation-water washing and catalyst removal method, the preparation process is very simple, the catalyst removal is convenient, the metal ion content of the product is less than 5 ppm, the molecular weight is stable and controllable, the molecular weight distribution is narrow, the molecular weight of the obtained liquid ethylene-propylene rubber is 3000-30000, the molecular weight distribution is less than 1.2, the iodine value is 0-42, the end group is introduced with a hydroxyl functional group, the chain contains double bonds, the application range of the material is expanded, and the material can be widely applied in the fields of lubricating oil, plasticizer, processing aid, oil additive and the like. At the same time, the low metal content makes the polymer more suitable for electronic fields such as wires and circuits. BRIEF DESCRIPTION OF DRAWINGS

[0103] Figure 1 is the infrared spectrum of the low molecular weight polyisoprene in steps (1) and (2) of Example 1, the hydroxylated low molecular weight isoprene and the liquid ethylene-propylene rubber prepared in step (4), and the liquid ethylene-propylene rubber prepared by copolymerization of butadiene and isoprene in Example 28 provided by the present application.

[0104] Figure 2 is the nuclear magnetic resonance hydrogen spectrum of (a) the structure general formula of the reactive ethylene-propylene rubber, (b) the low molecular weight polyisoprene in steps (1) and (2) of Example 1 and the liquid ethylene-propylene rubber prepared in step (4), and the liquid ethylene-propylene rubber prepared by copolymerization of butadiene and isoprene in Example 28 provided by the present application.

[0105] Figure 3 is the GPC chart of the liquid ethylene-propylene rubber prepared in step (4) of Example 1 provided by the present application before and after hydrogenation.

[0106] Figure 4 is the molecular weight distribution chart of the liquid ethylene-propylene rubber prepared in step (4) of Examples 16-20 provided by the present application.

[0107] Figure 5 DSC cooling curve of liquid ethylene-propylene rubber prepared by the embodiments 1, 2, 3, 6, 9, 10, 13, 14 and 15 provided in the present application. DETAILED DESCRIPTION

[0108] The present application will be described in detail below with reference to the examples, but the present application is not limited to the examples.

[0109] The raw materials in the examples of the present application are all purchased through commercial channels unless otherwise specified.

[0110] The hydrogenation catalyst solution is prepared by the following method:

[0111] Take 500 ml of a clean glass three-necked flask to prepare the solution, replace the air in the flask with high-purity nitrogen, then use a disposable syringe to extract 163 ml of a cyclohexane solution of triisobutylaluminum with a concentration of 0.57 mol / L, inject it into the three-necked flask, then use a disposable syringe to extract 27 ml of a cobalt neodecanoate reagent with a concentration of 0.076 g / ml, also inject it into the three-necked flask, then place the three-necked flask in a water bath with a magnetic stirrer at room temperature and stir for 10 min, and the two reagents are dissolved in each other and a deep brown homogeneous solution is simultaneously generated.

[0112] The test methods are all conventional methods unless otherwise specified, and the instrument settings are all recommended by the manufacturers.

[0113] The following methods are used in the present application to characterize and test the products:

[0114] The relative molecular mass and distribution of the polymers are determined by using an LC1260 GPC instrument produced by Agilent, USA;

[0115] The microstructure of the polymerization is analyzed by using a Nicolet-iz10 Fourier transform microscopic infrared imaging spectrometer produced by Nicolet, USA;

[0116] The sequence structure of the polymer and the calculation of the hydroxyl end-capping rate are determined by using an AV-600 NMR instrument produced by Bruker, Germany;

[0117] The Brookfield viscosity of the polymer at 60°C is determined by using a DV3T spine plate viscometer produced by BROOKFIELD, USA;

[0118] The crystallization temperature and glass transition temperature of the polymer are determined by using a Netzsch differential calorimeter, model DSC21400A-0800-L;

[0119] The content of lithium, aluminum and cobalt in the polymer was quantitatively analyzed by using a SPECTRO ARCO inductively coupled plasma emission spectrometer according to the JY / T 015-1996 inductively coupled plasma atomic emission spectrometry general method.

[0120] The iodine value was determined by iodimetry according to the national standard GB / T 34247.1-2017, and the hydrogenation degree was calculated.

[0121] Example 1

[0122] (1) In a 5L polymerization kettle, 260g of isoprene and 3L of cyclohexane were added to prepare a monomer solution with a concentration of 10%. After the polymerization kettle was uniformly stirred and heated to 65℃, the temperature was controlled to rise by less than 10℃, 13.42mmol of n-butyllithium was added to initiate the polymerization reaction, the stirring rate was set to 170rpm, and the polymerization reaction time was 2h to obtain an isoprene polymer solution.

[0123] (2) After the polymerization reaction, 67.1mmol of ethylene oxide was added to the polymerization kettle for end-capping reaction, and the temperature was controlled to 60℃. After 1h of end-capping reaction, the polymer solution in the polymerization kettle was transferred to a hydrogenation kettle, and hydrogen gas was introduced as a terminator. The hydrogen pressure was 1MPa, the termination time was 10min, and the stirring rate was 170rpm. The termination obtained a hydroxylated isoprene polymer solution.

[0124] (3) Cobalt neodecanoate and triisobutylaluminum were used as hydrogenation catalysts, and a catalyst solution with a concentration of 800ppm was added to the hydrogenation kettle. After the hydrogenation kettle was uniformly stirred and heated to 70℃, the hydrogen pressure was 2MPa, the stirring rate was 350rpm, and the hydrogenation time was 2h to obtain a hydrogenated polymer solution, i.e., a reactive ethylene-propylene rubber polymer solution.

[0125] (4) The hydrogenated polymer solution was transferred to a 5L three-necked flask, and citric acid and adipic acid were used as catalyst removal agents. 11.9g of citric acid, 0.53g of adipic acid and 30ml of deionized water were added to the polymer solution, and high-speed stirring was performed for 40min at a stirring rate of 300rpm. After centrifugation for 15min at a centrifugation rate of 4600rpm, the supernatant was collected and washed by centrifugation once with 60ml of water. After rotary evaporation to remove the organic solvent, a reactive liquid ethylene-propylene rubber was obtained by vacuum drying at 80℃.

[0126] Examples 2-15

[0127] The process conditions in the polymerization and hydrogenation processes were the same as in Example 1, except that the monomer composition in step (1) was as shown in Table 1.

[0128] Liquid ethylene-propylene rubber prepared in Examples 1-15 has the general structure shown in Formula I Figure 2 a),

[0129]

[0130] wherein x, n1-n4, m1-m4 are the number of each structural unit, (n1+n2+n3+n4) / (m1+m2+m3+m4) is the molar ratio of butadiene to isoprene; (m2+m4) / (m1+m2+m3+m4) is the molar ratio of 3,4-PI structural unit to all isoprene structural units; (n2+n4) / (n1+n2+n3+n4) is the molar ratio of 1,2-PB structural unit to all butadiene structural units.

[0131] The molecular weight and distribution of the liquid ethylene-propylene rubber prepared in Examples 1-15 were determined by GPC, the hydrogenation degree was determined by iodine value method, the hydroxyl end-capping rate was calculated by HNMR, the crystallization temperature of the polymer was determined by Netzsch differential calorimeter, and the Brookfield viscosity of the polymer at 60°C was determined by cone-plate viscometer, and the data are shown in Table 1.

[0132] Table 1 Monomer components, structure and property parameters of the prepared product in Examples 1-15

[0133]

[0134] Note: 3,4-PI% refers to the molar fraction of 3,4-PI structural unit to all isoprene structural units, i.e. the percentage of the aforementioned (m2+m4) / (m1+m2+m3+m4); 1,2-PB% refers to the molar fraction of 1,2-PB structural unit to all butadiene structural units, i.e. the percentage of the aforementioned (n2+n4) / (n1+n2+n3+n4); (n1+n2+n3+n4) / (m1+m2+m3+m4) refers to the molar ratio of butadiene to isoprene.

[0135] Example 16

[0136] The process conditions in the polymerization and hydrogenation process were basically the same as in Example 14, except that the amount of initiator added in step (1) was 120.1 mmol, and the amount of ethylene oxide added in step (2) was 600.5 mmol. The 1,2-PB content of the polymer was 7.3% and the 3,4-PI content was 6.5% as determined by HNMR characterization, and the crystallization temperature of the polymer was 30.2°C as determined by DSC characterization.

[0137] Example 17

[0138] The procedure for polymerization and hydrogenation was the same as in Example 14, except that in step (1) 86.6 mmol of initiator was added and in step (2) 433 mmol of ethylene oxide was added. The polymer was characterized by HNMR to have 1,2-PB content of 7.7% and 3,4-PI content of 6.8%, and by DSC to have a crystallization temperature of 31.8°C.

[0139] Example 18

[0140] The procedure for polymerization and hydrogenation was the same as in Example 14, except that in step (1) 52.8 mmol of initiator was added and in step (2) 264 mmol of ethylene oxide was added. The polymer was characterized by HNMR to have 1,2-PB content of 7.5% and 3,4-PI content of 6.6%, and by DSC to have a crystallization temperature of 32.1°C.

[0141] Example 19

[0142] The procedure for polymerization and hydrogenation was the same as in Example 14, except that in step (1) 33 mmol of initiator was added and in step (2) 165 mmol of ethylene oxide was added. The polymer was characterized by HNMR to have 1,2-PB content of 7.6% and 3,4-PI content of 6.2%, and by DSC to have a crystallization temperature of 33.8°C.

[0143] Example 20

[0144] The procedure for polymerization and hydrogenation was the same as in Example 14, except that in step (1) 25.74 mmol of initiator was added and in step (2) 128.7 mmol of ethylene oxide was added. The polymer was characterized by HNMR to have 1,2-PB content of 7.7% and 3,4-PI content of 8.0%, and by DSC to have a crystallization temperature of 34.1°C.

[0145] Example 21

[0146] The procedure for polymerization and hydrogenation was the same as in Example 14, except that in step (1) 15.8 mmol of initiator was added and in step (2) 79.25 mmol of ethylene oxide was added. The polymer was characterized by HNMR to have 1,2-PB content of 8.1% and 3,4-PI content of 6.7%, and by DSC to have a crystallization temperature of 34.6°C.

[0147] Example 22

[0148] The polymerization and hydrogenation processes were the same as in Example 14, except that in step (1) the initiator was added in an amount of 10.43 mmol and in step (2) the ethylene oxide was added in an amount of 52.15 mmol. The polymer was characterized by HNMR to have a 1,2-PB content of 7.8% and a 3,4-PI content of 6.5%, and by DSC to have a crystallization temperature of 34.8°C.

[0149] Example 23

[0150] The polymerization and hydrogenation processes were the same as in Example 14, except that in step (1) the initiator was added in an amount of 8.8 mmol and in step (2) the ethylene oxide was added in an amount of 44 mmol. The polymer was characterized by HNMR to have a 1,2-PB content of 7.7% and a 3,4-PI content of 7.5%, and by DSC to have a crystallization temperature of 35.4°C.

[0151] Example 24

[0152] The polymerization and hydrogenation processes were the same as in Example 14, except that in step (2) the ethylene oxide was added in an amount of 80.52 mmol. The polymer was characterized by HNMR to have a 1,2-PB content of 7.6% and a 3,4-PI content of 6.8%, and by DSC to have a crystallization temperature of 35.2°C.

[0153] Example 25

[0154] The polymerization and hydrogenation processes were the same as in Example 14, except that in step (2) the ethylene oxide was added in an amount of 53.68 mmol. The polymer was characterized by HNMR to have a 1,2-PB content of 7.4% and a 3,4-PI content of 6.2%, and by DSC to have a crystallization temperature of 34.6°C.

[0155] Example 26

[0156] The polymerization and hydrogenation processes were the same as in Example 14, except that in step (2) the ethylene oxide was added in an amount of 40.26 mmol. The polymer was characterized by HNMR to have a 1,2-PB content of 7.6% and a 3,4-PI content of 6.2%, and by DSC to have a crystallization temperature of 34.5°C.

[0157] Example 27

[0158] The conditions of the polymerization and hydrogenation process were the same as in Example 14, except that in step (2) 26.84 mmol of ethylene oxide was added. The polymer was characterized by HNMR to have a 1,2-PB content of 7.7% and a 3,4-PI content of 6.3%, and by DSC to have a crystallization temperature of 34.5°C.

[0159] Example 28

[0160] The conditions of the polymerization and hydrogenation process were the same as in Example 14, except that in step (2) 13.42 mmol of ethylene oxide was added. The polymer was characterized by HNMR to have a 1,2-PB content of 7.2% and a 3,4-PI content of 6.4%, and by DSC to have a crystallization temperature of 34.1°C.

[0161] Example 29

[0162] The conditions of the polymerization and hydrogenation process were the same as in Example 14, except that in step (3) the catalyst concentration was 700 ppm and the hydrogenation time was 30 min. The polymer was characterized by HNMR to have a 1,2-PB content of 7.7% and a 3,4-PI content of 6.6%, and by DSC to have a crystallization temperature of 33.1°C.

[0163] Example 30

[0164] The conditions of the polymerization and hydrogenation process were the same as in Example 14, except that in step (3) the catalyst concentration was 600 ppm. The polymer was characterized by HNMR to have a 1,2-PB content of 7.7% and a 3,4-PI content of 6.7%, and by DSC to have a crystallization temperature of 31.5°C.

[0165] Example 31

[0166] The conditions of the polymerization and hydrogenation process were the same as in Example 14, except that in step (3) the catalyst concentration was 550 ppm and the hydrogenation time was 1 h. The polymer was characterized by HNMR to have a 1,2-PB content of 7.2% and a 3,4-PI content of 6.5%, and by DSC to have a crystallization temperature of 27.7°C.

[0167] Example 32

[0168] The process conditions in polymerization and hydrogenation were the same as in Example 14, except that the catalyst concentration in step (3) was 500 ppm. The 1,2-PB content of the polymer was 7.6% and the 3,4-PI content was 6.9% as determined by HNMR. The crystallization temperature of the polymer was 25.8°C as determined by DSC.

[0169] Example 33

[0170] The process conditions in polymerization and hydrogenation were the same as in Example 14, except that the catalyst concentration in step (3) was 400 ppm. The 1,2-PB content of the polymer was 7.0% and the 3,4-PI content was 7.0% as determined by HNMR. The crystallization temperature of the polymer was 10.3°C as determined by DSC.

[0171] Example 34

[0172] The process conditions in polymerization and hydrogenation were the same as in Example 14, except that the catalyst concentration in step (3) was 300 ppm. The 1,2-PB content of the polymer was 7.7% and the 3,4-PI content was 6.2% as determined by HNMR.

[0173] Example 35

[0174] The process conditions in polymerization and hydrogenation were the same as in Example 14, except that the catalyst concentration in step (3) was 200 ppm. The 1,2-PB content of the polymer was 7.1% and the 3,4-PI content was 6.8% as determined by HNMR.

[0175] Example 36

[0176] The process conditions in polymerization and hydrogenation were the same as in Example 14, except that the initiator in step (1) was changed to sec-butyllithium and the amount was unchanged. The 1,2-PB content of the polymer was 7.0% and the 3,4-PI content was 6.9% as determined by HNMR. The crystallization temperature of the polymer was 34.5°C as determined by DSC.

[0177] Example 37

[0178] The process conditions in polymerization and hydrogenation were the same as in Example 14, except that the end-capping agent in step (2) was changed to propylene oxide and the amount was unchanged. The 1,2-PB content of the polymer was 7.2% and the 3,4-PI content was 6.7% as determined by HNMR. The crystallization temperature of the polymer was 34.4°C as determined by DSC.

[0179] The liquid ethylene-propylene rubber prepared in Examples 16-37 was subjected to GPC to determine the molecular weight and distribution, to iodine value method to determine the hydrogenation degree, to HNMR to calculate the hydroxyl end-capping rate, and to cone-plate viscometer to determine the Brookfield viscosity of the polymer at 60°C. The data results and the amount of initiator, end-capping agent and catalyst are shown in Table 2.

[0180] Table 2 Reaction parameters and product property parameters of Examples 16-37

[0181]

[0182]

[0183] The polymer prepared in Examples 1-37 was subjected to DV3T cone-plate viscometer produced by American BROOKFIELD Company to determine the Brookfield viscosity of the polymer at 60°C, and to inductively coupled plasma optical emission spectrometer (ICP-OES) to analyze the residual cobalt, aluminum and lithium metal element content in the polymer. The data results are shown in Table 3.

[0184] Table 3 Viscosity and metal content of the polymer prepared in Examples 1-37

[0185]

[0186]

[0187] Taking Examples 1 and 28 as examples, the product prepared in step (1) (labeled as before end-capping), the product of step (2) (labeled as after end-capping), the product of step (3) and (4) (labeled as after hydrogenation) were subjected to infrared spectrometer, HNMR and GPC to obtain the spectra as shown in Figure 1 、 Figure 2 、 Figure 3 .

[0188] As can be seen from Figure 1 , after the end-capping by ethylene oxide, the spectrum of the liquid ethylene-propylene rubber has a stretching vibration absorption peak of -OH at 3419 cm -1 , and the peak type is obvious, indicating that the hydroxyl group is introduced at the end of the polymer. After hydrogenation, the characteristic absorption peak of 3,4-addition double bond structure at 888 cm -1 and the characteristic absorption peak of 1,4-addition double bond structure at 830 cm -1 are obviously reduced. As can be seen from Figure 2It can be seen that after the epoxy ethane end-capping of Example 1, the characteristic peak of -OH appears at 3.65 ppm in the nuclear magnetic hydrogen spectrum, and the end-capping rate reaches 85% by calculating the peak area ratio; after catalytic hydrogenation, most of the olefin hydrogen characteristic peaks at 4.60-4.80 ppm and 5.00-5.20 ppm in the spectrum disappear, but a certain amount of double bond is still retained. It can be seen from the above that the molecular weight of the liquid ethylene-propylene rubber prepared by the anionic polymerization process of the present application is controlled by the amount of initiator, and the molecular weight of the liquid ethylene-propylene rubber can be controlled by the amount of initiator. Figure 3 It can be seen that after the hydrogenation of the liquid ethylene-propylene rubber, the peak position shifts to the left. This indicates that the present application retains a certain amount of reactive double bonds in the liquid rubber by polymerization, end-capping and partial hydrogenation, and the molecular chain end contains a hydroxyl functional group, which is a reactive rubber with both double bonds and hydroxyl groups. Figure 2 The characteristic peaks of butadiene 1,2-double bond structure and 1,4-double bond structure appear at 4.90-5.60 ppm in the nuclear magnetic hydrogen spectrum of Example 28, and the molar ratio of butadiene to isoprene in the rubber can be calculated by the peak area ratio to be 1.5. The reactive liquid ethylene-propylene rubber with the structure as shown in Formula I can be prepared by end-capping and hydrogenation of the polymer, and different structures of ethylene-propylene rubber can be prepared by changing the ratio of co-monomers isoprene and butadiene.

[0189] The molecular weight and its distribution of the liquid ethylene-propylene rubber prepared in Examples 16-20 are shown in Figure 4 As the amount of initiator decreases from 120 mmol to 25 mmol, the peak position of the rubber continuously moves to the left. It indicates that in the anionic polymerization process of the present application, as the amount of initiator decreases, the molecular weight can be gradually increased, that is, the amount of initiator can control the molecular weight of the liquid ethylene-propylene rubber.

[0190] The DSC cooling curves of the liquid ethylene-propylene rubber prepared in Examples 1-3, Example 6, Example 9, Example 10, Examples 13-15 are shown in Figure 5 As the molar ratio of butadiene to isoprene in the liquid ethylene-propylene rubber increases from 0 to about 0.5, the crystallization peak appears in the curve, indicating that as the ethylene segment is introduced and the content increases, the segment order increases and begins to crystallize. And as the ratio further increases to 2, the crystallization peak continuously moves to the right, and the crystallization temperature increases from -38.7°C to 29.3°C. This indicates that by adjusting the ratio of butadiene to isoprene, the length of the ethylene chain in the ethylene-propylene rubber can be accurately controlled, thereby preparing reactive liquid ethylene-propylene rubber with different crystallization temperatures and crystallization degrees.

[0191] As can be seen from Table 1, by anionic copolymerization, a reactive liquid ethylene-propylene rubber with PDI <1.2, i.e. narrow distribution, can be obtained, and different structures of ethylene-propylene rubber can be obtained by controlling the different proportions of monomers. As the proportion of butadiene monomer increases, the ethylene segment in the product increases after hydrogenation, which can make the product crystallize and its crystallization temperature increase to 50°C.

[0192] From Table 2, by controlling the amount of initiator, capping agent, hydrogenation catalyst, reactive liquid ethylene-propylene rubber with different molecular weight, capping rate, hydrogenation degree can be prepared.

[0193] From the data in Tables 1, 2 and 3, the liquid ethylene-propylene rubber prepared by the catalyst removal process of the present application has a metal ion content of less than 5 ppm, for example, in Examples 1-32, which indicates that the lithium salt and catalyst residue of the liquid ethylene-propylene rubber prepared by the present application are very low. The viscosity of the liquid ethylene-propylene rubber is influenced by the molecular weight, hydrogenation degree, proportion of butadiene structural units, and capping rate, and the viscosity is between 3-4477 Pa·s (60°C). Thus, by designing different molecular structures and molecular weights, and controlling different hydrogenation degrees, reactive liquid ethylene-propylene rubber with different viscosities and crystallinity can be obtained.

[0194] In summary, the reactive ethylene-propylene rubber prepared by the present application has a metal ion content of less than 5 ppm, stable and controllable molecular weight, narrow molecular weight distribution, a molecular weight of 3000-30000, and a molecular weight distribution of less than 1.2. The main chain microstructure and sequence structure and hydrogenation degree are controllable, the end groups can be introduced with hydroxyl functional groups, and the capping rate can be as high as 96%.

[0195] The preparation process of the present application is simple and the catalyst removal process is convenient. Compared with the polymers obtained by the current technology, which have problems such as wide distribution, uncontrollable molecular weight, and catalyst residue, the reactive ethylene-propylene rubber prepared by the present application has controllable molecular weight and microstructure, controllable hydrogenation degree, and thus has reactivity, can participate in vulcanization and crosslinking reaction, and can control the length of ethylene chains in the chain to enable the polymer to crystallize. In addition, the hydroxylation of the molecular chain end improves the polarity and further reactivity of the product, the metal ion content is very low, and different molecular structures and functionalization modifications can be designed according to actual needs through anionic polymerization to synthesize products with different physical and chemical properties, so that they can be applied to more fields such as reactive plasticizers, adhesives, viscosity improvers, processing aids, cables and wires, and meet more extensive market application requirements.

[0196] The above is only a few embodiments of the present application, and does not limit the present application in any form. Although the preferred embodiments are disclosed above, they are not intended to limit the present application. Any skilled person in the art can make some changes or modifications to the disclosed technical content without departing from the scope of the technical solution of the present application, which are equivalent to equivalent embodiments and belong to the scope of the technical solution.

Claims

1. A reactive liquid ethylene propylene rubber, characterized in that, The reactive liquid ethylene propylene rubber is prepared by a method comprising the following steps: S1. Add a solution containing monomers and organic solvents to a sealed container, react, then add an initiator to polymerize and obtain an isoprene-butadiene polymer solution. The monomers are isoprene and butadiene; S2. Add the functionalizing reagent to a closed container, mix it with the isoprene-butadiene polymer solution, and perform a capping reaction to obtain a hydroxylated isoprene-butadiene polymer solution. S3. Add a terminator to the hydroxylated isoprene-butadiene polymer solution to terminate the reaction, then add a hydrogenation catalyst and perform a hydrogenation reaction in a hydrogen atmosphere to obtain a reactive ethylene propylene rubber polymer solution. S4. Add the decatalyst and water to the reactive ethylene propylene rubber polymer solution, stir, wash with water, centrifuge, and rotary evaporate to obtain the reactive liquid ethylene propylene rubber. The reactive liquid ethylene propylene rubber is a polymer of the general structural formula shown in Formula I: Formula I; Where x, n1~n4, and m1~m4 are the number of various structural units in the structure shown in Equation I, respectively; The ratio of (n1+n2+n3+n4) to (m1+m2+m3+m4) is 0~2; The ratio of (n2+n4) to (n1+n2+n3+n4) is 0.05~0.1; The ratio of (m2+m4) to (m1+m2+m3+m4) is 0.05~0.1; The value of x is 0 to 1.

2. The reactive liquid ethylene propylene rubber according to claim 1, characterized in that, The molecular weight of the reactive liquid ethylene propylene rubber is 3000~50000.

3. The reactive liquid ethylene propylene rubber according to claim 1, characterized in that, The polydispersity index of the reactive liquid ethylene propylene rubber is 1.00~1.

50.

4. The reactive liquid ethylene propylene rubber according to claim 1, characterized in that, The iodine value of the reactive liquid ethylene propylene rubber is 0~432.

5. The reactive liquid ethylene propylene rubber according to claim 1, characterized in that, The reactive liquid ethylene propylene rubber has a metal ion content of 0~10ppm.

6. The reactive liquid ethylene propylene rubber according to claim 1, characterized in that, The viscosity of the reactive liquid ethylene propylene rubber at 60°C is 0~5000 Pa·s.

7. The reactive liquid ethylene propylene rubber according to claim 1, characterized in that, The crystallization peak temperature of the reactive liquid ethylene propylene rubber is 0~50℃.

8. The method for preparing the reactive liquid ethylene propylene rubber according to any one of claims 1 to 7, characterized in that, Includes the following steps: S1. Add a solution containing monomers and organic solvents to a sealed container, react, then add an initiator to polymerize and obtain an isoprene-butadiene polymer solution. The monomers are isoprene and butadiene; S2. Add the functionalizing reagent to a closed container, mix it with the isoprene-butadiene polymer solution, and perform a capping reaction to obtain a hydroxylated isoprene-butadiene polymer solution. S3. Add a terminator to the hydroxylated isoprene-butadiene polymer solution to terminate the reaction, then add a hydrogenation catalyst and perform a hydrogenation reaction in a hydrogen atmosphere to obtain a reactive ethylene propylene rubber polymer solution. S4. Add the decatalyst and water to the reactive ethylene propylene rubber polymer solution, stir, wash with water, centrifuge, and rotary evaporate to obtain the reactive liquid ethylene propylene rubber.

9. The preparation method according to claim 8, characterized in that, In step S1, the reaction conditions include: controlling the reaction temperature to 50℃~90℃ and stirring until the system temperature stabilizes.

10. The preparation method according to claim 8, characterized in that, In step S1, the reaction conditions include: controlling the reaction temperature to be 50℃~90℃ and the reaction time to be 1h~12h.

11. The preparation method according to claim 8, characterized in that, In step S1, the amount of initiator added is 130ppm to 1300ppm.

12. The preparation method according to claim 8, characterized in that, In step S1, the polymerization conditions include: polymerization reaction temperature of 50℃~90℃, polymerization reaction pressure of 0.1MPa~0.5MPa, and polymerization reaction time of 1h~12h.

13. The preparation method according to claim 8, characterized in that, In step S1, the initiator is selected from at least one of n-butyllithium, sec-butyllithium, and tert-butyllithium.

14. The preparation method according to claim 8, characterized in that, In step S1, the molar ratio of butadiene to isoprene in the monomer is 0~2:

1.

15. The preparation method according to claim 8, characterized in that, In step S1, the concentration of the monomer in the solution is 10wt%~30wt%.

16. The preparation method according to claim 8, characterized in that, In step S1, the organic solvent is selected from at least one of cyclohexane, cyclopentane, n-hexane, and n-pentane.

17. The preparation method according to claim 8, characterized in that, In step S2, the functionalizing agent is selected from at least one of ethylene oxide and propylene oxide.

18. The preparation method according to claim 8, characterized in that, In step S2, the molar ratio of the functionalizing agent to the initiator in step S1 is 1~8:

1.

19. The preparation method according to claim 8, characterized in that, In step S2, the conditions for the end-capping reaction include: the end-capping reaction temperature is 50℃~80℃, and the end-capping reaction time is 1h~12h.

20. The preparation method according to claim 8, characterized in that, In step S3, the molar ratio of the terminator to the initiator in step S1 is 1~2:

1.

21. The preparation method according to claim 8, characterized in that, In step S3, the terminating agent is selected from at least one of hydrogen, methanol, water, isooctyl alcohol, isooctanoic acid, 2,6-di-tert-butyl-p-cresol, and 2,4,6-tri-tert-butylphenol.

22. The preparation method according to claim 8, characterized in that, In step S3, the amount of hydrogenation catalyst added is 100ppm to 1000ppm.

23. The preparation method according to claim 8, characterized in that, In step S3, the hydrogenation catalyst includes a main catalyst and a co-catalyst. The main catalyst is selected from cobalt neodecanoate and / or nickel neodecanoate, and the co-catalyst is selected from triisobutylaluminum.

24. The preparation method according to claim 23, characterized in that, In step S3, the molar ratio of the main catalyst to the co-catalyst is 1~3:

1.

25. The preparation method according to claim 8, characterized in that, In step S3, the conditions for the hydrogenation reaction include: a hydrogenation reaction temperature of 50℃~140℃, a hydrogen gas pressure of 1 MPa~10 MPa, and a hydrogenation reaction time of 1h~12h.

26. The preparation method according to claim 8, characterized in that, In step S4, the amount of the decatalyst added is 3000ppm to 6000ppm.

27. The preparation method according to claim 8, characterized in that, In step S4, the decatalyst is citric acid and adipic acid.

28. The preparation method according to claim 8, characterized in that, In step S4, the molar ratio of citric acid to adipic acid in the decatalyst is 10~20:

1.

29. The preparation method according to claim 8, characterized in that, In step S4, the ratio of the amount of water added to the amount of reactive ethylene propylene rubber polymer solution is 5 ml to 30 ml: 1 kg.

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