A mono-terminated diblock copolymer, its preparation and use

Abstract

The present application relates to a kind of single end of diblock copolymer and its preparation method and application, the structural formula of single end of diblock copolymer is: R1-A-B-R2-R3, R1 is C1-C 10 Alkyl, A is the polymer segment of monoalkenyl arene, B is the polymer segment of butadiene and / or isoprene, R2 is C1-C8 Alkyl or C1-C 12 Alkyl ether, R3 is hydroxyl or epoxy group.The aggregate structure of the single end of diblock copolymer of the present application cannot form effective physical crosslinking point, compared with SBS or SIS has lower solution temperature and melt viscosity, can effectively reduce the preparation temperature of modified asphalt material, shorten preparation time, reduce energy loss, effectively slow down the degradation, coking, gel and other adverse consequences generated in high temperature process of polymer.The application thereof in the preparation of hot melt adhesive or modified asphalt material, only needs to introduce crosslinking component in formula, can form in situ similar SBS or SIS triblock copolymer, does not affect the use performance of terminal product.

Description

Technical Field

[0001] This invention specifically relates to a single-end capped diblock copolymer, its preparation method, and its application. Background Technology

[0002] Styrene-based thermoplastic elastomers (SBCs) are triblock copolymers composed of sequentially bonded hard polystyrene chains, soft rubber chains, and more hard polystyrene chains. They exhibit rubber-like elasticity at room temperature but can be molded at high temperatures. In the structure of SBCs, physical cross-linking and reinforcing effects are achieved through the aggregation of styrene segments, replacing vulcanization cross-linking. However, the physical cross-linking of the hard polystyrene chains also results in higher processing temperatures and melt viscosity.

[0003] Styrene-based thermoplastic elastomers (SBCs) mainly include four types: styrene-butadiene-styrene block copolymers (SBS), styrene-isoprene-styrene block copolymers (SIS), styrene-ethylene-butene-styrene block copolymers (SEBS), and styrene-ethylene-propylene-styrene (SEPS) block copolymers. SEBS and SEPS are hydrogenation products of SBS and SIS, respectively. The structural formulas of SBS and SIS are shown below:

[0004]

[0005] The aforementioned thermoplastic elastomers, represented by styrene-butadiene-styrene block copolymers (SBS) and styrene-isoprene-styrene block copolymers (SIS), possess both rubber and plastic properties due to their unique structure. They exhibit rubber-like elasticity at room temperature and become plastic materials at high temperatures. They can be widely used as modifiers for asphalt, improving the high and low temperature performance, anti-aging properties, and fatigue resistance of asphalt materials, making them the main modifiers for modified asphalt in my country.

[0006] However, the current use of styrene-based thermoplastic elastomers (SBCs) in asphalt modification still has certain problems, such as:

[0007] In the field of asphalt modification, styrene-based thermoplastic elastomers need to swell at high temperatures for a considerable period before they can be dispersed in the base asphalt to prepare polymer-modified asphalt, which is then used for asphalt concrete road paving or for molding modified asphalt waterproof membranes on a production line. This polymer swelling and dissolution process consumes a large amount of energy and also causes polymer degradation and performance loss during the high-temperature process.

[0008] In addition, thermoplastic elastomer modified bitumen generally has a high viscosity and generally needs to be molded at a high temperature. For example, modified bitumen waterproof membranes generally need to be molded at 150-180℃ during the production process, while hot melt modified bitumen waterproof coatings also need to be heated to 150-180℃ during the construction process to change the coating from solid to liquid, so that it can be applied by scraping, brushing or spraying. After cooling, a waterproof coating of a certain thickness is formed.

[0009] In general, in existing technologies, styrene-based thermoplastic elastomers (SBCs) are used in modified asphalt materials. Due to the physical cross-linking and reinforcing effects of styrene segments, the polymer materials have high dissolution temperatures and melt viscosities. The preparation process mainly involves heating SBCs to high temperatures (usually above 160°C) and allowing them to swell and dissolve over a long period before they can be dispersed in the modified asphalt. Heating is also required for molding and construction, which results in significant energy consumption. At this temperature, the polymer is also prone to adverse consequences such as degradation, coking, gelation, and loss of adhesion. Summary of the Invention

[0010] The technical problem to be solved by the present invention is that the application of existing styrene-based thermoplastic elastomers requires high-temperature treatment, which results in energy loss and adverse consequences such as polymer degradation, coking, gelation, and loss of adhesion. The present invention provides a novel single-end capped diblock copolymer.

[0011] A second objective of this invention is to provide a method for preparing the above-mentioned single-end capped diblock copolymer.

[0012] A third object of the present invention is to provide an application of the above-mentioned single-ended diblock copolymer in modified bitumen materials.

[0013] To achieve the above objectives, the technical solution adopted by the present invention is as follows:

[0014] A single-terminated diblock copolymer, wherein the structural formula of the single-terminated diblock copolymer is: R1-AB-R2-R3, wherein R1 is C1-C 10 The alkyl group, A is a polymer segment of a monoalkenyl aromatic hydrocarbon, B is a polymer segment of butadiene and / or isoprene, and R2 is a C1-C8 alkyl group or a C1-C8 alkyl group. 12 Alkyl ethers, where R3 is OH or an epoxy group.

[0015] According to some embodiments of the present invention, the monoalkenyl aromatic hydrocarbon constituting A is selected from one or more combinations of styrene, p-methylstyrene, methylstyrene, p-tert-butylstyrene, 2,4-dimethylstyrene, α-methylstyrene, vinylnaphthalene, vinyltoluene, vinylxylene, and 1,1-diphenylethylene.

[0016] Preferably, the monoalkenyl aromatic hydrocarbon is selected from one or more combinations of styrene, p-methylstyrene, and α-methylstyrene. More preferably, the monoalkenyl aromatic hydrocarbon is styrene.

[0017] According to some embodiments of the present invention, R1 is selected from C1-C6 alkyl groups. Preferably, R1 is selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, and hexyl. More preferably, R1 is selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, and tert-butyl.

[0018] According to some embodiments of the present invention, R2 is selected from C2-C6 alkyl or C2-C8 alkyl ethers. Preferably, R2 is selected from ethylene, propylene, isopropylene, butylene, isobutylene, pentylene, hexylene, methyl ethyl ether, methyl isopropyl ether, methyl butyl ether, methyl isobutyl ether, methyl pentylene, methyl hexyl ether, diethyl ether, ethyl isopropyl ether, ethyl butyl ether, ethyl isobutyl ether, ethyl pentylene, and ethyl hexyl ether. More preferably, R2 is selected from ethylene, propylene, isopropylene, butylene, isobutylene, hexylene, methyl ethyl ether, methyl isopropyl ether, diethyl ether, and ethyl isopropyl ether.

[0019] According to some specific embodiments of the present invention, the single-terminated diblock copolymer is a hydroxyl-terminated styrene-butadiene / isoprene diblock copolymer or a monoepoxy-terminated styrene-butadiene / isoprene diblock copolymer. When used in modified asphalt materials, such as by adding a certain amount of a substance capable of reacting with hydroxyl or epoxy groups to the formulation, SBS or SIS triblock copolymers can be formed in situ without affecting the performance of the modified asphalt material. Meanwhile, the hydroxyl-terminated styrene-butadiene / isoprene diblock copolymer or the epoxy-terminated styrene-butadiene / isoprene diblock copolymer has a lower dissolution temperature and melt viscosity than SBS or SIS, which can effectively reduce the preparation temperature of thermoplastic elastomer-based hot melt adhesives or modified asphalt materials, shorten the preparation time, reduce energy consumption, and effectively mitigate the adverse consequences of polymer degradation, coking, gelation and other adverse effects caused by high temperature processes.

[0020] According to some embodiments of the present invention, the mass content of A in the single-terminated diblock copolymer is 10-50%, preferably 20-40%.

[0021] According to some embodiments of the present invention, the number average molecular weight of the single-terminated diblock copolymer is 5,000-150,000, preferably 30,000-80,000.

[0022] The second technical solution adopted by the present invention is: the preparation method of the single-terminated diblock copolymer as described above, wherein R3 is a hydroxyl group, and the preparation method includes the following steps:

[0023] The monoalkenyl aromatic monomers constituting A are anionicly polymerized to generate a polymer with an activated end.

[0024] The polymer of the monoalkenyl aromatic hydrocarbon with the activated end is polymerized with butadiene and / or isoprene to generate a diblock copolymer with the activated end.

[0025] R3 is OH. The diblock copolymer with the activated end is reacted with an epoxide, followed by acidification to obtain a monohydroxy-terminated diblock copolymer with an R1-AB-R2-OH structure. Alternatively, R3 is an epoxy group. The diblock copolymer with the activated end is reacted sequentially with an epoxide and an epoxide haloalkane to obtain a monohydroxy-terminated diblock copolymer with an R1-AB-R2-OH structure. A diblock copolymer with a monocyclic epoxy end-capped structure.

[0026] Furthermore, the specific implementation of the method for preparing the single-end capped diblock copolymer includes:

[0027] Step S1: In the presence of a saturated hydrocarbon solvent and an anionic polymerization initiator, the monoalkenyl aromatic monomer is reacted to generate the polymer with the monoalkenyl aromatic hydrocarbon having an activated end, thereby obtaining a solution system containing the polymer with the monoalkenyl aromatic hydrocarbon having an activated end.

[0028] Step S2: Add butadiene and / or isoprene to the solution system containing the polymer with the activated end monoalkenyl aromatic hydrocarbon, so that the polymer with the activated end monoalkenyl aromatic hydrocarbon reacts with butadiene and / or isoprene to generate the diblock copolymer with the activated end, and obtain the solution system containing the diblock copolymer with the activated end.

[0029] Step S3: Add alkylene oxide to the solution system containing the diblock copolymer with activated ends, allowing the diblock copolymer with activated ends to react with the alkylene oxide, and then add acid for acidification to obtain the monohydroxy-terminated diblock copolymer; or,

[0030] Step S3: Add epoxide and epoxide haloalkane sequentially to the solution system containing the diblock copolymer with activated ends, so that the diblock copolymer with activated ends reacts sequentially with epoxide and epoxide haloalkane to obtain the monoepoxide-terminated diblock copolymer.

[0031] In some specific embodiments, the saturated hydrocarbon solvent is at least one selected from pentane, octane, heptane, cyclohexane, n-hexane, benzene, toluene, ethylbenzene, and xylene.

[0032] In some specific embodiments, in step S1, the anionic polymerization initiator is an alkyl lithium initiator, which is selected from one or more combinations of R and Li, where R is an alkyl group with 1-10 carbon atoms and Li is a lithium atom. Preferably, the alkyl lithium initiator is selected from methyl lithium, ethyl lithium, propyl lithium, isopropyl lithium, n-butyl lithium, sec-butyl lithium, tert-butyl lithium, pentyl lithium, hexyl lithium, and tert-octyl lithium. More preferably, the alkyl lithium initiator is selected from methyl lithium, ethyl lithium, propyl lithium, isopropyl lithium, n-butyl lithium, sec-butyl lithium, and tert-butyl lithium.

[0033] In some specific embodiments, in step S1, the reaction is carried out at 40–60°C; in step S2, the reaction is carried out at 40–60°C; in step S3, the reaction with the epoxide is carried out at 40–60°C, and the acidification reaction is carried out at 40–60°C; or, in step S3, the reactions with the epoxide and the epoxide haloalkane are carried out sequentially at 40–60°C respectively.

[0034] In some specific embodiments, in step S3, the epoxide is one or more of ethylene oxide, propylene oxide, 1,2-epoxide butane, 1,2-epoxide pentane, epoxide hexane, and phenyl ethylene oxide, and the acid is hydrochloric acid with a mass concentration of 25-40 wt%; or, in step S3, the epoxide is selected from one or more of ethylene oxide, propylene oxide, 1,2-epoxide butane, 1,2-epoxide pentane, epoxide hexane, or phenyl ethylene oxide, and the epoxide haloalkane is selected from one or more of epichlorohydrin, epibromopropane, and 1,2-epoxide chlorobutane.

[0035] In some specific embodiments, the mass ratio of butadiene and / or isoprene to the monoalkenyl aromatic monomer is 50:50 to 90:10, preferably 60:40 to 80:20.

[0036] The third technical solution adopted by the present invention is: the use of the above-mentioned single-end diblock copolymer in modified asphalt materials.

[0037] Due to the application of the above technical solution, the present invention has the following advantages compared with the prior art:

[0038] The aggregated structure of the single-end-capped diblock copolymer of this invention cannot form effective physical crosslinking points. Compared with SBS or SIS, it has a lower dissolution temperature and melt viscosity, which can effectively reduce the preparation temperature of thermoplastic elastomer-based modified asphalt materials, shorten the preparation time, reduce energy consumption, and effectively mitigate the adverse consequences of polymer degradation, coking, and gelation during high-temperature processes. When the single-end-capped diblock copolymer is used to prepare modified asphalt coatings, through formulation design and adjustment, coatings that are liquid at room temperature can be prepared, thus enabling room-temperature application of modified asphalt coatings. Asphalt materials modified with single-end-capped diblock copolymers can form triblock copolymers similar to SBS or SIS in situ simply by introducing components that can react and crosslink with hydroxyl or epoxy groups into the formulation, without affecting the performance of the end product. Detailed Implementation

[0039] The technical solutions of the present invention will be described in detail below with reference to specific embodiments, so that those skilled in the art can better understand and implement the technical solutions of the present invention, but the present invention is not limited to the scope of the examples described.

[0040] Example 1

[0041] The styrene-butadiene diblock copolymer with single hydroxyl end capping provided in this embodiment

[0042]

[0043] The specific preparation method is as follows:

[0044] In a polymerization flask (under nitrogen protection), 125g of a cyclohexane solution containing 25g of styrene was injected, and 0.27g of tetrahydrofuran was added as an activator. A cyclohexane solution of n-butyllithium was slowly added using a syringe to break down impurities. When the system changed from colorless to pale yellow without change, 1.5ml of an effective n-butyllithium solution (molar concentration 1.2mol / L) was rapidly added at 50°C to initiate polymerization for 30min, yielding a solution system of a polymer with activated alkenyl aromatic hydrocarbons. Then, 300g of a cyclohexane solution containing 75g of butadiene was added in one step, and polymerization was carried out at 50°C for 30min, yielding a solution system of a styrene-butadiene diblock copolymer with activated ends. Finally, 2.1ml of ethylene oxide was added, and the reaction was carried out for 15min. The mixture was then acidified with 7.5mL of dilute hydrochloric acid (31.5wt%), and 1.5% (by mass) of antioxidant 264 was added according to the mass of the final polymerization product. After polymerization, the reaction product was rotary evaporated to remove the solvent, and then dried in a vacuum chamber to obtain a hydroxyl-terminated styrene-butadiene block copolymer. GPC analysis showed that the number average molecular weight of the hydroxyl-terminated styrene-butadiene block copolymer was 55,640, and the molecular weight distribution was 1.05.

[0045] Example 2

[0046] The styrene-butadiene diblock copolymer with single hydroxyl end capping provided in this embodiment

[0047]

[0048] The specific preparation method is as follows:

[0049] In a polymerization flask (under nitrogen protection), 175g of a cyclohexane solution containing 35g of styrene was injected, and 0.11g of tetrahydrofuran was added as an activator. A cyclohexane solution of n-butyllithium was slowly added using a syringe to break down impurities. When the system changed from colorless to pale yellow without change, 0.6ml of an effective n-butyllithium solution (molar concentration 1.2mol / L) was rapidly added at 50°C to initiate polymerization for 30min, yielding a solution system of a polymer with activated alkenyl aromatic hydrocarbons. Then, 260g of a cyclohexane solution containing 65g of butadiene was added in one step, and polymerization was carried out at 50°C for 30min, yielding a solution system of a styrene-butadiene diblock copolymer with activated ends. Finally, 0.9ml of propylene oxide was added, and the reaction was carried out for 15min. The mixture was then acidified with 3mL of dilute hydrochloric acid (31.5wt%), and 1.5% (by mass) of antioxidant 264 was added according to the mass of the final polymerization product. After polymerization, the solvent was removed from the reaction product by rotary evaporation, and then dried in a vacuum chamber to obtain the monohydroxyl-terminated styrene-butadiene block copolymer. GPC analysis showed that the number average molecular weight of the monohydroxyl-terminated styrene-butadiene block copolymer was 138,500, and the molecular weight distribution was 1.03.

[0050] Example 3

[0051] The styrene-isoprene diblock copolymer with single hydroxyl end capping provided in this embodiment

[0052]

[0053] The specific preparation method is as follows:

[0054] In a polymerization flask (under nitrogen protection), 125g of a cyclohexane solution containing 25g of styrene was injected, and 0.36g of tetrahydrofuran was added as an activator. A cyclohexane solution of n-butyllithium was slowly added using a syringe to break down impurities. When the system changed from colorless to pale yellow without change, 2.0ml of an effective n-butyllithium solution (molar concentration 1.2mol / L) was rapidly added at 50°C to initiate polymerization for 30min, yielding a solution system of a polymer with activated monoalkenyl aromatic hydrocarbons. Then, 300g of a cyclohexane solution containing 75g of isoprene was added in one step, and polymerization was carried out at 50°C for 30min, yielding a solution system of a styrene-isoprene diblock copolymer with activated ends. Finally, 2.8ml of ethylene oxide was added, and the reaction was carried out for 15min. The mixture was then acidified with 10.0mL of dilute hydrochloric acid (31.5wt%), and 1.5% (by mass) of antioxidant 264 was added according to the mass of the final polymerization product. After polymerization, the solvent was removed from the reaction product by rotary evaporation, and then dried in a vacuum chamber to obtain a hydroxyl-terminated styrene-isoprene block copolymer. GPC analysis showed that the number average molecular weight of the hydroxyl-terminated styrene-isoprene block copolymer was 42,600, and the molecular weight distribution was 1.04.

[0055] Example 4

[0056] The styrene-isoprene diblock copolymer with single hydroxyl end capping provided in this embodiment

[0057]

[0058] The specific preparation method is as follows:

[0059] In a polymerization flask (under nitrogen protection), 175g of a cyclohexane solution containing 35g of styrene was injected, and 0.90g of tetrahydrofuran was added as an activator. A cyclohexane solution of n-butyllithium was slowly added using a syringe to break down impurities. When the system changed from colorless to pale yellow without change, 5.0ml of an effective n-butyllithium solution (molar concentration 1.2mol / L) was rapidly added at 50°C to initiate polymerization for 30min, yielding a solution system of a polymer with activated alkenyl aromatic hydrocarbons. Then, 240g of a cyclohexane solution containing 65g of isoprene was added in one step, and polymerization was carried out at 50°C for 30min, yielding a solution system of a styrene-isoprene diblock copolymer with activated ends. Finally, 7.0ml of propylene oxide was added, and the reaction was carried out for 15min. The mixture was then acidified with 25mL of dilute hydrochloric acid (31.5wt%), and 1.5% (by mass) of antioxidant 264 was added according to the mass of the final polymerization product. After polymerization, the solvent was removed from the reaction product by rotary evaporation, and then dried in a vacuum chamber to obtain the monohydroxyl-terminated styrene-isoprene block copolymer. GPC analysis showed that the number average molecular weight of the monohydroxyl-terminated styrene-butadiene block copolymer was 16,720, and the molecular weight distribution was 1.05.

[0060] Example 5

[0061] The styrene-butadiene diblock copolymer with monoepoxide end capping provided in this embodiment

[0062]

[0063] The specific preparation method is as follows:

[0064] In a polymerization flask (under nitrogen protection), 125g of a cyclohexane solution containing 25g of styrene was injected, and 0.27g of tetrahydrofuran was added as an activator. A cyclohexane solution of n-butyllithium was slowly added using a syringe to break down impurities. When the system changed from colorless to pale yellow without change, 1.5ml of an effective n-butyllithium solution (molar concentration 1.2mol / L) was rapidly added at 50°C to initiate polymerization for 30 minutes, yielding a solution system of a polymer with activated alkenyl aromatic hydrocarbons. Then, 300g of a cyclohexane solution containing 75g of butadiene was added in one step, and polymerization was carried out at 50°C for 30 minutes, yielding a solution system of a styrene-butadiene diblock copolymer with activated ends. Finally, 1.0ml of ethylene oxide was added, and the reaction was carried out for 15 minutes, followed by the addition of 1.2ml of epichlorohydrin, and the reaction was carried out for another 15 minutes. The polymerization was terminated with 1.8ml of ethanol. Based on the mass percentage of the final product, 1.5% of antioxidant 264 was added. After polymerization, the reaction product was rotary evaporated to remove the solvent, and then dried in a vacuum chamber to obtain a monoepoxy-terminated styrene-butadiene block copolymer. GPC analysis showed that the number average molecular weight of the monoepoxy-terminated styrene-butadiene block copolymer was 56,400, and the molecular weight distribution was 1.08.

[0065] Example 6

[0066] The styrene-butadiene diblock copolymer with monoepoxide end capping provided in this embodiment

[0067]

[0068] The specific preparation method is as follows:

[0069] In a polymerization flask (under nitrogen protection), 175g of a cyclohexane solution containing 35g of styrene was injected, and 0.11g of tetrahydrofuran was added as an activator. A cyclohexane solution of n-butyllithium was slowly added using a syringe to break down impurities. When the system changed from colorless to pale yellow without change, 0.6ml of an effective n-butyllithium solution (molar concentration 1.2mol / L) was rapidly added at 50°C to initiate polymerization for 30 minutes, yielding a solution system of a polymer with activated monoalkenyl aromatic hydrocarbons. Then, 260g of a cyclohexane solution containing 65g of butadiene was added in one step, and polymerization was carried out at 50°C for 30 minutes, yielding a solution system of a styrene-butadiene diblock copolymer with activated ends. Finally, 0.5ml of propylene oxide was added, and the reaction was allowed to proceed for 15 minutes. Then, 0.6ml of epichlorohydrin was added, and the reaction was allowed to proceed for another 15 minutes. The polymerization was terminated with 0.9ml of ethanol. Based on the mass percentage of the final product, 1.5% (by mass) of antioxidant 264 was added. After polymerization, the solvent was removed from the reaction product by rotary evaporation, and then dried in a vacuum chamber to obtain a monoepoxy-terminated styrene-butadiene block copolymer. GPC analysis showed that the number average molecular weight of the monoepoxy-terminated styrene-butadiene block copolymer was 142,500, and the molecular weight distribution was 1.10.

[0070] Example 7

[0071] The styrene-isoprene diblock copolymer with monoepoxide end capping provided in this embodiment is

[0072]

[0073] The specific preparation method is as follows:

[0074] In a polymerization flask (under nitrogen protection), 125g of a cyclohexane solution containing 25g of styrene was injected, and 0.36g of tetrahydrofuran was added as an activator. A cyclohexane solution of n-butyllithium was slowly added using a syringe to break down impurities. When the system changed from colorless to pale yellow without change, 2.0ml of an effective n-butyllithium solution (molar concentration 1.2mol / L) was rapidly added at 50°C to initiate polymerization for 30 minutes, yielding a solution system of a polymer with activated monoalkenyl aromatic hydrocarbons. Then, 300g of a cyclohexane solution containing 75g of isoprene was added in one step, and polymerization was carried out at 50°C for 30 minutes, yielding a solution system of a styrene-isoprene diblock copolymer with activated ends. Finally, 1.4ml of ethylene oxide was added, and the reaction was carried out for 15 minutes, followed by the addition of 1.6ml of epichlorohydrin, and the reaction was carried out for another 15 minutes. The polymerization was terminated with 2.4ml of ethanol. Based on the mass percentage of the final product, 1.5% of antioxidant 264 was added. After polymerization, the reaction product was rotary evaporated to remove the solvent, and then dried in a vacuum chamber to obtain a monoepoxy-terminated styrene-isoprene block copolymer. GPC analysis showed that the number average molecular weight of the monoepoxy-terminated styrene-isoprene block copolymer was 43,500, and the molecular weight distribution was 1.06.

[0075] Example 8

[0076] The styrene-isoprene diblock copolymer with monoepoxide end capping provided in this embodiment is

[0077]

[0078] The specific preparation method is as follows:

[0079] In a polymerization flask (under nitrogen protection), 175g of a cyclohexane solution containing 35g of styrene was injected, and 0.90g of tetrahydrofuran was added as an activator. A cyclohexane solution of n-butyllithium was slowly added using a syringe to break down impurities. When the system changed from colorless to pale yellow without change, 5.0ml of an effective n-butyllithium solution (molar concentration 1.2mol / L) was rapidly added at 50°C to initiate polymerization for 30 minutes, yielding a solution system of a polymer with activated monoalkenyl aromatic hydrocarbons. Then, 240g of a cyclohexane solution containing 65g of isoprene was added in one step, and polymerization was carried out at 50°C for 30 minutes, yielding a solution system of a styrene-isoprene diblock copolymer with activated ends. Finally, 3.5ml of propylene oxide was added, and the reaction was carried out for 15 minutes, followed by the addition of 4.2ml of epichlorohydrin, and the reaction was carried out for another 15 minutes. The polymerization was terminated with 6.0ml of ethanol. Based on the mass percentage of the final product, 1.5% (by mass) of antioxidant 264 was added. After polymerization, the reaction product was rotary evaporated to remove the solvent, and then dried in a vacuum chamber to obtain a monoepoxy-terminated styrene-isoprene block copolymer. GPC analysis showed that the number average molecular weight of the monoepoxy-terminated styrene-butadiene block copolymer was 18250, and the molecular weight distribution was 1.08.

[0080] Application Example 1

[0081] Comparative Example 1 is Baling Petrochemical's 1301SBS, and Comparative Example 2 is Baling Petrochemical's 1105SIS.

[0082] 1. Modified asphalt materials were prepared using the diblock copolymers of Examples 1-4 as modifiers according to the following method:

[0083] The formula for the modified asphalt material is as follows: 100 parts of 70# asphalt (Maoming Branch of China Petroleum & Chemical Corporation), 14 parts of modifier, 80 parts of aromatic oil, 1.4 parts of isophorone diisocyanate, 0.28 parts of stannous octoate, 40 parts of heavy calcium carbonate, and 1.0 part of coupling agent KH550.

[0084] It is prepared by the following method:

[0085] (1) Heat 70# asphalt, aromatic oil and heavy calcium carbonate to 95°C, mix them, and then stir and heat to 115°C under a relative vacuum of -0.08MPa to dehydrate and obtain the first mixture;

[0086] (2) Heat the first mixture to 120°C (or 140°C or 160°C), add the modifier, and wait for the modifier to completely dissolve to obtain the second mixture;

[0087] (3) Cool the second mixture to 80°C, then add isophorone diisocyanate to allow the isophorone diisocyanate to react with the modifier, then cool to 65°C, then add stannous octoate and coupling agent, mix, and obtain modified asphalt coating.

[0088] In step (2), the diblock copolymers of Examples 1 to 4 were used as modifiers to record the dissolution phenomenon and dissolution time at 120°C, 140°C and 160°C, respectively. The results are shown in Table 1.

[0089] 2. Modified asphalt materials were prepared using the diblock copolymers of Examples 5-8 as modifiers according to the following method:

[0090] The formula for the modified asphalt material is as follows: 100 parts of 70# asphalt (Maoming Branch of China Petroleum & Chemical Corporation), 14 parts of modifier, 80 parts of plasticizer aromatic oil, 2 parts of ketimine latent curing agent DA315, 1 part of curing accelerator DMP30, 1 part of reactive diluent 1,6-hexanediol diglycidyl ether, 40 parts of filler heavy calcium carbonate, and 1.0 part of coupling agent KH550.

[0091] The preparation method is as follows:

[0092] (1) Heat the asphalt, plasticizer and filler to 95°C, mix them, and stir and heat to 115°C under a relative vacuum of -0.09MPa for 3 hours to obtain the first mixture;

[0093] (2) Heat the first mixture to 120°C (or 140°C or 160°C), add the modifier, and wait for the modifier to completely dissolve to obtain the second mixture;

[0094] (3) The second mixture is cooled to 60°C, and ketimine latent curing agent, curing accelerator, reactive diluent, coupling agent, etc. are added and mixed evenly to obtain modified asphalt material.

[0095] In step (2), the diblock copolymers of Examples 5 to 8 were used as modifiers to record the dissolution phenomenon and dissolution time at 120°C, 140°C and 160°C, respectively. The results are shown in Table 1.

[0096] 3. Using SBS from Comparative Example 1 and SIS from Comparative Example 2 as modifiers, modified asphalt materials were prepared according to the following method:

[0097] The formula for the modified asphalt material is as follows: 100 parts of 70# asphalt, 14 parts of modifier, 80 parts of plasticizer aromatic oil, 40 parts of filler heavy calcium carbonate, and 1 part of coupling agent KH550.

[0098] The preparation method is as follows:

[0099] Heat 70# asphalt, plasticizer, and filler to 120℃ (or 140℃ or 160℃), stir and melt them. Then add the modifier and stir at a shear rate of 400r / min until the modifier is completely dissolved. Add the coupling agent and stir evenly. Cool and discharge to obtain the modified asphalt material.

[0100] The dissolution phenomena and dissolution times of SBS (Comparative Example 1) and SIS (Comparative Example 2) as modifiers at 120℃, 140℃, and 160℃ were recorded. The results are shown in Table 1.

[0101] Table 1 shows the dissolution times of modified asphalt materials prepared using Examples 1-8 and Comparative Examples 1-2 as modifiers.

[0102]

[0103] The results show that the single-end diblock copolymer of the representative embodiment of the present invention, due to its structure, cannot form effective physical crosslinking points, which can effectively reduce the preparation temperature of the modified asphalt material based on thermoplastic elastomer, shorten the preparation time, and reduce energy consumption.

[0104] The performance of modified asphalt materials prepared using the diblock copolymers of Examples 1-8 as modifiers and heated at 140°C were tested respectively. The results are shown in Table 2.

[0105] The performance of modified asphalt materials prepared using SBS (Comparative Example 1) and SIS (Comparative Example 2) as modifiers and heated at 160℃ were tested respectively. The results are shown in Table 2.

[0106] Viscosity at 25℃ was tested according to GB / T 10247-2008 "Viscosity Test Method". Heat resistance, low-temperature flexibility, impermeability and bonding strength were tested according to GB / T 16777-2008 "Test Methods for Waterproof Coatings for Buildings" and JC / T852-1999 "Soluble-based Rubber Asphalt Waterproof Coatings".

[0107] Table 2 shows the performance test results of the modified asphalt materials prepared using Examples 1-8 and Comparative Examples 1-2 as modifiers.

[0108]

[0109] The modified asphalt materials prepared using Comparative Examples 1 and 2 as modifiers were solid at room temperature, their viscosity could not be tested, and they could not be applied at room temperature; heating was required for application and construction. In contrast, the modified asphalt materials prepared using Examples 1-8 as modifiers were all viscous liquids and could be applied at room temperature. The results indicate that using a single-terminated diblock copolymer as a modifier for the preparation of modified asphalt materials results in lower cohesive strength and lower viscosity due to the inability of its aggregated structure to form effective physical crosslinking points. This allows for application and construction at lower temperatures, even at room temperature, overcoming the complex construction and flue gas pollution problems associated with high-temperature application of modified asphalt materials.

[0110] Furthermore, after curing according to GB / T 16777-2008 "Test Methods for Waterproof Coatings for Buildings", modified asphalt materials can form a coating with certain cohesive strength. This is because polyisocyanate compounds are introduced into the formulation. During the preparation process, hydroxyl-terminated diblock copolymers can react with polyisocyanate compounds to generate isocyanate-terminated diblock copolymers, or ketimine latent curing agents can be introduced into the formulation. After construction, under the action of moisture in the substrate or air, isocyanate-terminated diblock copolymers can undergo cross-linking reactions, or ketimine latent curing agents can undergo cross-linking reactions with epoxy groups in the modifier, thereby giving the coating a certain mechanical strength, meeting the standard requirements of JC / T852-1999 "Soluble-based Rubber Asphalt Waterproof Coatings". The final performance of modified asphalt materials can reach or even exceed the performance of commercially available SBS or SIS modified asphalt materials.

[0111] The above embodiments are only for illustrating the technical concept and features of the present invention, and are intended to enable those skilled in the art to understand the content of the present invention and implement it accordingly. They should not be construed as limiting the scope of protection of the present invention. All equivalent changes or modifications made in accordance with the spirit and essence of the present invention should be covered within the scope of protection of the present invention.

[0112] The endpoints and any values ​​of the ranges disclosed herein are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein.

Claims

1. A modified asphalt material, characterized in that: The modified asphalt material includes asphalt, a single-ended diblock copolymer, and a crosslinking component that can react with hydroxyl or epoxy groups; The structural formula of the single-terminated diblock copolymer is: R1-AB-R2-R3, where R1 is C1-C 10 The alkyl group, A is a polymer segment of a monoalkenyl aromatic hydrocarbon, B is a polymer segment of butadiene and / or isoprene, and R2 is a C1-C8 alkyl group or a C1-C8 alkyl group. 12 Alkyl ethers, where R3 is OH or an epoxy group; The monoalkenyl aromatic hydrocarbon constituting A is selected from one or more combinations of styrene, methylstyrene, p-tert-butylstyrene, α-methylstyrene, vinylnaphthalene, vinylxylene, and 1,1-diphenylethylene; The mass content of A in the single-ended diblock copolymer is 10-50%; The number-average molecular weight of the single-end capped diblock copolymer is 5,000-150,000.

2. The modified bitumen material according to claim 1, characterized in that: The monoalkenyl aromatic hydrocarbon constituting A is selected from one or more combinations of styrene, p-methylstyrene, p-tert-butylstyrene, α-methylstyrene, vinylnaphthalene, 2,4-dimethylstyrene, and 1,1-diphenylethylene.

3. The modified bitumen material according to claim 1, characterized in that: The monoalkenyl aromatic hydrocarbon is selected from one or more combinations of styrene, p-methylstyrene, and α-methylstyrene.

4. The modified bitumen material according to claim 1, characterized in that: R1 is selected from alkyl groups that are C1-C6.

5. The modified bitumen material according to claim 1, characterized in that: R2 is selected from alkyl groups of C2-C6 or alkyl ethers of C2-C8.

6. The modified bitumen material according to any one of claims 1 to 5, characterized in that: The single-ended diblock copolymer is a hydroxyl-terminated styrene-butadiene / isoprene diblock copolymer or a epoxide-terminated styrene-butadiene / isoprene diblock copolymer.

7. The modified bitumen material according to claim 1, characterized in that: The mass content of A in the single-ended diblock copolymer is 20-40%.

8. The modified bitumen material according to claim 1, characterized in that: The number-average molecular weight of the single-end capped diblock copolymer is 30,000-80,000.

9. The modified bitumen material according to any one of claims 1 to 5, characterized in that: The structural formula of the single-terminated diblock copolymer is: R1-AB-R2-OH.

10. The modified bitumen material according to any one of claims 1 to 5, characterized in that: The structural formula of the single-end capped diblock copolymer is: .

11. The modified bitumen material according to claim 1, characterized in that, The single-end capped diblock copolymer is prepared by a method including the following steps: The monoalkenyl aromatic monomers constituting A are anionicly polymerized to generate a polymer with an activated end. The polymer of the monoalkenyl aromatic hydrocarbon with the activated end is polymerized with butadiene and / or isoprene to generate a diblock copolymer with the activated end. R3 is OH. The diblock copolymer with the activated end is reacted with an epoxide, followed by acidification to obtain a monohydroxy-terminated diblock copolymer with an R1-AB-R2-OH structure. Alternatively, R3 is an epoxy group. The diblock copolymer with the activated end is reacted sequentially with an epoxide and an epoxide haloalkane to obtain a monohydroxy-terminated diblock copolymer with an R1-AB-R2-OH structure. A diblock copolymer with a monocyclic epoxy end-capped structure.

12. The modified bitumen material according to claim 11, characterized in that: The single-end capped diblock copolymer is prepared by a method including the following steps: Step S1: In the presence of a saturated hydrocarbon solvent and an anionic polymerization initiator, the monoalkenyl aromatic monomer is reacted to generate the polymer with the monoalkenyl aromatic hydrocarbon having an activated end, thereby obtaining a solution system containing the polymer with the monoalkenyl aromatic hydrocarbon having an activated end. Step S2: Add butadiene and / or isoprene to the solution system containing the polymer with the activated end monoalkenyl aromatic hydrocarbon, so that the polymer with the activated end monoalkenyl aromatic hydrocarbon reacts with butadiene and / or isoprene to generate the diblock copolymer with the activated end, and obtain the solution system containing the diblock copolymer with the activated end. Step S3: Add alkylene oxide to the solution system containing the diblock copolymer with activated ends, allowing the diblock copolymer with activated ends to react with the alkylene oxide, and then add acid for acidification to obtain the monohydroxy-terminated diblock copolymer; or, Step S3: Add epoxide and epoxide haloalkane sequentially to the solution system containing the diblock copolymer with activated ends, so that the diblock copolymer with activated ends reacts sequentially with epoxide and epoxide haloalkane to obtain the monoepoxide-terminated diblock copolymer.

13. The modified bitumen material according to claim 1, characterized in that: According to parts by weight, the modified asphalt material is composed of the following components: 100 parts of 70# asphalt, 14 parts of single-ended diblock copolymer, 80 parts of aromatic oil, 1.4 parts of isophorone diisocyanate, 0.28 parts of stannous octoate, 40 parts of heavy calcium carbonate, and 1.0 part of coupling agent KH550.

14. The modified bitumen material according to claim 1, characterized in that: According to parts by weight, the modified asphalt material is composed of the following components: 100 parts of 70# asphalt, 14 parts of single-end-capped diblock copolymer, 80 parts of aromatic oil, 2 parts of ketimine latent curing agent DA315, 1 part of curing accelerator DMP30, 1 part of reactive diluent 1,6-hexanediol diglycidyl ether, 40 parts of filler heavy calcium carbonate, and 1.0 part of coupling agent KH550.

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