Block polymers, methods for making the same, brominated block polymers and uses thereof

Abstract

This invention relates to the field of polymer synthesis and preparation, and discloses a block polymer and its preparation method, a brominated block polymer and its applications. The block polymer possesses PS... 1 -HVBR 1 -HPIR-HVBR 2 -PS 2 The block structure shown contains at least 80 mol% vinyl structural units based on the total molar number of HVBR; at least 80 mol% propylene structural units based on the total molar number of HPIR; styrene block content is 20-40 wt%; and the molecular weight distribution of the block polymer is 1-1.2. This block polymer, comprising polyisoprene blocks with high propylene content and polybutadiene blocks with high vinyl content, effectively improves the selectivity and efficiency of bromination, and results in a brominated block copolymer with a high thermal decomposition temperature and a high glass transition temperature, making it suitable as a flame retardant for polystyrene foam exterior wall insulation materials.

Description

Technical Field

[0001] This invention relates to the field of polymer material synthesis and preparation technology, specifically to a block polymer and its preparation method, a brominated block polymer and its applications. Background Technology

[0002] Hexabromocyclododecane (HBCD) is the most important flame retardant for expanded polystyrene (EPS) and extruded polystyrene (XPS) exterior wall insulation materials. However, HBCD has poor thermal stability, decomposing to produce hydrogen bromide at 150°C and undergoing a violent debromination reaction at 190°C, causing damage to the eyes, skin, and respiratory system. Although HBCD has excellent flame retardant effects, it poses a potential long-term hazard to the human environment. With the increasing use of HBCD, its persistence and long-distance migration in environmental media such as air, water, soil sediments, and sludge are becoming increasingly prominent, and its bioaccumulation and biomagnification in fish, birds, and mammals are also becoming more serious. To strengthen the management of chemicals and reduce the hazards caused by chemicals, especially toxic and hazardous chemicals, the Stockholm Convention stipulates a time-limited withdrawal of HBCD from the flame retardant market. HBCD will be withdrawn from the global exterior wall insulation flame retardant market.

[0003] Following the development trends of flame retardants and combining them with the production process of polystyrene insulation foam, polymeric additives will become a sustainable flame retardant solution in the production and application of polystyrene foam. Polymeric additives have higher molecular weights, increasing resistance to migration, extraction, and evaporation, thereby reducing the risk of flame retardants being released from the polymer into the environment. High molecular weight polymers are difficult to pass through biofilms, making them less susceptible to absorption by the intact digestive tract, reducing bioavailability, potential exposure risks, and adverse health effects. Among all polymeric additives, the brominated products of thermoplastic elastomers obtained from the polymerization of styrene and conjugated dienes, due to their high molecular weight and excellent flame retardant properties, represent the most efficient and sustainable solution among polymeric flame retardants.

[0004] The conventional styrene and conjugated diene block polymers on the market mainly include SBS and SIS. However, due to the low content of side groups of conjugated dienes, there are fewer double bonds that can participate in the bromination reaction. As a result, the thermal decomposition temperature of the bromination products of the prepared styrene and conjugated diene block polymers is low, which cannot meet the requirements for the use of exterior wall insulation flame retardants. Summary of the Invention

[0005] The purpose of this invention is to overcome the problems of low double bond content in the bromination reaction of existing block polymers, resulting in low bromination efficiency and low thermal decomposition temperature and glass transition temperature of the obtained brominated block polymers. This invention provides a block polymer, its preparation method, and the brominated block polymer and its applications. The block polymer comprises polyisoprene blocks with high propylene content and polybutadiene blocks with high vinyl content. Specifically, the propylene content in the polyisoprene blocks is above 80 mol%, and the vinyl content in the polybutadiene blocks is above 80 mol%. This effectively improves the selectivity and efficiency of bromination, and results in brominated block copolymers with high thermal decomposition temperature and high glass transition temperature.

[0006] To achieve the above objectives, a first aspect of the present invention provides a block polymer, characterized in that the block polymer has PS 1 -HVBR 1 -HPIR-HVBR 2 -PS 2 The block structure shown;

[0007] Among them, PS 1 and PS 2 Each is an independent styrene block, HVBR 1 and HVBR 2 Each is independently a high-vinyl polybutadiene block, while HPIR is a high-propylene polyisoprene block;

[0008] Based on the total molar number of HVBR in the block polymer, it contains at least 80 mol% of vinyl structural units; based on the total molar number of HPIR in the block polymer, it contains at least 80 mol% of propylene structural units.

[0009] Based on the total weight of the block polymer, the content of the styrene block is 20-40 wt%.

[0010] The block polymer has a molecular weight distribution of 1-1.2.

[0011] A second aspect of the present invention provides a method for preparing a block polymer, characterized in that the preparation method includes the following steps:

[0012] (1) In a nonpolar hydrocarbon solvent, in the presence of a composite structure modifier and an initiator, styrene monomer 1 undergoes a first anionic polymerization reaction to obtain a product containing PS. 1 Polymer solutions with a specific structure;

[0013] (2) To the substance containing PS 1 Butadiene monomer 1 was added to the polymer solution, and a second anionic solution polymerization was carried out to obtain a product containing PS.1 -HVBR 1 Polymer solutions with a specific structure;

[0014] (3) To the substance containing PS 1 -HVBR 1 Isoprene monomer is added to a polymer solution containing PS to carry out a third anionic polymerization reaction, yielding a product containing PS. 1 -HVBR 1 -HPIR structured polymer solution;

[0015] (4) To the substance containing PS 1 -HVBR 1 Butadiene monomer 2 was added to a polymer solution with an HPIR structure to carry out a fourth anionic polymerization reaction, yielding a product containing PS. 1 -HVBR 1 -HPIR-HVBR 2 Polymer solutions with a specific structure;

[0016] (5) To the substance containing PS 1 -HVBR 1 -HPIR-HVBR 2 Styrene monomer 2 was added to a polymer solution containing PS to perform a fifth anionic polymerization, yielding a product containing PS. 1 -HVBR 1 -HPIR-HVBR 2 -PS 2 The polymer solution with the structure, for the PS-containing 1 -HVBR 1 -HPIR-HVBR 2 -PS 2 The polymer solution of the structure is dried to obtain the block polymer;

[0017] The composite structure modifier comprises component A, component B, and component C. Component A is a polar ether compound and / or a polar amine compound, component B is a polar ether compound and / or a polar amine compound, and component C is at least one selected from sodium alkoxide, potassium alkoxide, sodium alkylbenzene sulfonate, and potassium alkylbenzene sulfonate.

[0018] The polymerization temperatures of the first anionic polymerization reaction, the second anionic polymerization reaction, the third anionic polymerization reaction, the fourth anionic polymerization reaction, and the fifth anionic polymerization reaction are each independently 0-50℃;

[0019] Based on the total weight of styrene monomer, isoprene monomer, and butadiene monomer, the amount of styrene monomer used is 20-40 wt%.

[0020] A third aspect of the present invention provides a block polymer prepared by the above-described preparation method.

[0021] A fourth aspect of the present invention provides a brominated block polymer, characterized in that the brominated block polymer is obtained by bromination of the above-mentioned block polymer.

[0022] The fifth aspect of the present invention provides an application of the above-mentioned brominated block polymer in an exterior wall insulation flame retardant.

[0023] Through the above technical solutions, the block polymers and their preparation methods, brominated block polymers and their applications provided by the present invention achieve the following beneficial effects:

[0024] The block polymer provided by this invention comprises polyisoprene blocks with high propylene content and polybutadiene blocks with high vinyl content. Specifically, the propylene content in the polyisoprene blocks is above 80 mol%, and the vinyl content in the polybutadiene blocks is above 80 mol%, which results in more than 95% of the double bonds in the block polymer being brominated, effectively improving the selectivity and efficiency of bromination. Consequently, the obtained brominated block copolymer has a high thermal decomposition temperature and a high glass transition temperature, making it particularly suitable as a flame retardant for exterior wall insulation materials such as polystyrene foam.

[0025] In the method for preparing block polymers provided by this invention, styrene, butadiene, and isoprene undergo anionic polymerization in the presence of a composite modifier containing specific components, and the polymerization temperature of the anionic polymerization reaction is controlled, thereby producing a product with PS... 1 -HVBR 1 -HPIR-HVBR 2 -PS 2 The block copolymers with a specific structure shown, in particular, contain polyisoprene blocks with high propylene content and polybutadiene blocks with high vinyl content. As a result, the block copolymers contain a high content of side groups, which can effectively improve the selectivity and efficiency of bromination, and make the resulting brominated block copolymers have high thermal decomposition temperature and high glass transition temperature, making them particularly suitable as flame retardants for exterior wall insulation materials such as polystyrene foam. Detailed Implementation

[0026] 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.

[0027] A first aspect of the present invention provides a block polymer, characterized in that the block polymer has PS 1 -HVBR 1 -HPIR-HVBR 2 -PS 2 The block structure shown;

[0028] Among them, PS 1 and PS 2 Each is an independent styrene block, HVBR 1 and HVBR 2 Each is independently a high-vinyl polybutadiene block, while HPIR is a high-propylene polyisoprene block;

[0029] Based on the total molar number of HVBR in the block polymer, it contains at least 80 mol% of vinyl structural units; based on the total molar number of HPIR in the block polymer, it contains at least 80 mol% of propylene structural units.

[0030] Based on the total weight of the block polymer, the content of the styrene block is 20-40 wt%.

[0031] The block polymer has a molecular weight distribution of 1-1.2.

[0032] Generally, for butadiene structural units, the vinyl structure has the highest bromination efficiency, followed by the trans structure, and the cis structure has the lowest bromination efficiency; for isoprene structural units, the bromination efficiency of the propenyl structure is higher than that of the 1,4- structure. To obtain brominated block polymers with higher bromine content while maintaining the same number of double bonds, it is necessary to increase the side group content of both butadiene and isoprene.

[0033] In this invention, the block polymer provided by this invention comprises polyisoprene blocks with high propylene content and polybutadiene blocks with high vinyl content. That is, the block polymer contains a high content of side groups capable of bromination addition, which can effectively improve the selectivity and efficiency of bromination. As a result, the brominated block copolymer has a high thermal decomposition temperature and a high glass transition temperature, making it particularly suitable as an exterior wall insulation flame retardant.

[0034] Specifically, based on the total molar number of HVBR in the block polymer, it contains at least 80 mol% of vinyl structural units; based on the total molar number of HPIR in the block polymer, it contains at least 80 mol% of propylene structural units, and the content of styrene blocks in the block polymer is 20-40 wt%, so that more than 95% of the double bonds in the block polymer are brominated, effectively improving the selectivity and efficiency of bromination, thereby making the obtained brominated block copolymer have a high thermal decomposition temperature and a high glass transition temperature, making it particularly suitable as an exterior wall insulation flame retardant.

[0035] Furthermore, the block polymer provided by the present invention has a narrow molecular weight distribution, which enables the brominated block polymer prepared from the block polymer to have better thermal stability.

[0036] In this invention, the content (Ia%) of propylene structural units in high-propylene polyisoprene block (HPIR) and high-vinyl polybutadiene block (HVBR) are specified. 1 and HVBR 2 The content (Bv%) of vinyl structural units in the sample was determined by proton nuclear magnetic resonance spectroscopy.

[0037] Furthermore, based on the total molar number of HVBR in the block polymer, it contains at least 82 mol% of vinyl structural units, preferably at least 84 mol% of vinyl structural units, and more preferably at least 86 mol% of vinyl structural units.

[0038] Furthermore, based on the total number of moles of HPIR in the block polymer, it contains at least 82 mol% of propylene-based structural units, preferably at least 84 mol% of propylene-based structural units, and more preferably at least 86 mol% of propylene-based structural units.

[0039] Furthermore, based on the total weight of the block polymer, the styrene block (PS) 1 +PS 2 The content (St%) of ) is 22-35wt%.

[0040] According to the present invention, PS 1 and PS 2 The weight ratio is 3 / 7-7 / 3.

[0041] In this invention, PS 1 and PS 2 Independent representation of styrene blocks, PS 1 and PS 2 Same or different. In this invention, the content of styrene blocks in the block polymer and PS are controlled. 1 and PS 2The weight ratio is to ensure PS 1 and PS 2 Segment length, further, preferably, PS 1 and PS 2 The number average molecular weight is at least 8000, PS 1 and PS 2 The number-average molecular weight is too low to effectively form a phase-separated structure; PS 1 and PS 2 The number-average molecular weight should not exceed 20,000; otherwise, the processing performance of block polymers will be too poor, which is not conducive to stable industrial production.

[0042] In this invention, the content (St%) of styrene blocks in the block polymer was determined by 1H NMR spectroscopy. 1 and PS 2 The weight ratio is calculated based on the amount of styrene monomer added.

[0043] Furthermore, PS 1 and PS 2 The weight ratio is 4 / 6 to 6 / 4.

[0044] According to the present invention, the content of the high vinyl polybutadiene block (Bd%) is 40-70 wt% based on the total weight of the block polymer.

[0045] In this invention, when the content of high-vinyl polybutadiene blocks (HPIR) in the block polymer is controlled to meet the above-mentioned range, it can be ensured that there are enough double bonds in the block polymer that can undergo addition reactions, so as to increase the bromine content in the final brominated block polymer, thereby ensuring that the brominated product has high thermal stability and glass transition temperature.

[0046] Furthermore, based on the total weight of the block polymer, the content of the high-vinyl polybutadiene block is 45-65 wt%.

[0047] According to the present invention, HVBR 1 and HVBR 2 The weight ratio is 4 / 6 to 6 / 4.

[0048] In this invention, the block copolymer contains high-vinyl polybutadiene (HVBR) 1 +HVBR 2 The content of HVBR was determined by proton nuclear magnetic resonance spectroscopy. 1 and HVBR 2 The weight ratio is calculated based on the amount of butadiene monomer added.

[0049] According to the present invention, the content of the high-propylene polyisoprene block (1p%) is 5-20 wt% based on the total weight of the block copolymer.

[0050] In this invention, when the content of high-propylene polyisoprene blocks (HPIR) in the block polymer is controlled to meet the above-mentioned range, it can be ensured that there are enough double bonds in the block polymer that can undergo addition reactions, so as to increase the bromine content in the final brominated block polymer, thereby ensuring that the brominated product has high thermal stability and glass transition temperature.

[0051] In this invention, the content of high-propylene polyisoprene (HPIR) in the block copolymer was determined by proton nuclear magnetic resonance spectroscopy.

[0052] Furthermore, based on the total weight of the block copolymer, the content of the high-propylene polyisoprene block (1p%) is 5-15 wt%.

[0053] According to the present invention, the number average molecular weight of the block polymer is 50,000-200,000, preferably 80,000-150,000.

[0054] In this invention, controlling the number-average molecular weight of the block polymer serves three purposes: first, to provide more double bonds capable of bromination; second, to ensure good phase separation; and third, to guarantee the processability of the block polymer. When the number-average molecular weight of the block polymer is below 50,000, the number of double bonds capable of bromination on a single molecular chain is relatively small, which is detrimental to the preparation of brominated block polymers with good thermal stability. When the number-average molecular weight of the block polymer is greater than 200,000, the processability of the block polymer becomes poor, which is unfavorable for stable industrial production.

[0055] According to the present invention, the molecular weight distribution of the block polymer is 1.01-1.15, preferably 1.02-1.1.

[0056] In this invention, to further improve the thermal stability of the brominated block polymer prepared from this block polymer, PS before bromination is required. 1 -HVBR 1 -HPIR-HVBR 2 -PS 2 Block polymers have a narrow molecular weight distribution, PS 1 -HVBR 1 -HPIR-HVBR 2 -PS 2 Low molecular weight components in block polymers can have an adverse effect on the properties of brominated products, so it is necessary to control the content of low molecular weight components as much as possible.

[0057] A second aspect of the present invention provides a method for preparing a block polymer, characterized in that the preparation method includes the following steps:

[0058] (1) In a nonpolar hydrocarbon solvent, in the presence of a composite structure modifier and an initiator, styrene monomer 1 undergoes a first anionic polymerization reaction to obtain a product containing PS. 1 Polymer solutions with a specific structure;

[0059] (2) To the substance containing PS 1 Butadiene monomer 1 was added to the polymer solution, and a second anionic solution polymerization was carried out to obtain a product containing PS. 1 -HVBR 1 Polymer solutions with a specific structure;

[0060] (3) To the substance containing PS 1 -HVBR 1 Isoprene monomer is added to a polymer solution containing PS to carry out a third anionic polymerization reaction, yielding a product containing PS. 1 -HVBR 1 -HPIR structured polymer solution;

[0061] (4) To the substance containing PS 1 -HVBR 1 Butadiene monomer 2 was added to a polymer solution with an HPIR structure to carry out a fourth anionic polymerization reaction, yielding a product containing PS. 1 -HVBR 1 -HPIR-HVBR 2 Polymer solutions with a specific structure;

[0062] (5) To the substance containing PS 1 -HVBR 1 -HPIR-HVBR 2 Styrene monomer 2 was added to a polymer solution containing PS to perform a fifth anionic polymerization, yielding a product containing PS. 1 -HVBR 1 -HPIR-HVBR 2 -PS 2 The polymer solution with the structure, for the PS-containing 1 -HVBR 1 -HPIR-HVBR 2 -PS 2 The polymer solution of the structure is dried to obtain the block polymer;

[0063] The composite structure modifier comprises component A, component B, and component C. Component A is a polar ether compound and / or a polar amine compound, component B is a polar ether compound and / or a polar amine compound, and component C is selected from at least one of sodium alkoxide, potassium alkoxide, sodium alkylbenzene sulfonate, and potassium alkylbenzene sulfonate.

[0064] The polymerization temperatures of the first anionic polymerization reaction, the second anionic polymerization reaction, the third anionic polymerization reaction, the fourth anionic polymerization reaction, and the fifth anionic polymerization reaction are each independently 0-50℃;

[0065] Based on the total weight of styrene monomer, isoprene monomer, and butadiene monomer, the amount of styrene monomer used is 20-40 wt%.

[0066] In this invention, styrene, butadiene, and isoprene are anionicly polymerized in the presence of a composite modifier containing specific components, and the polymerization temperature of the anionic polymerization reaction is controlled. This allows the preparation of a block polymer with a specific structure as described in the first aspect of this invention. In particular, the block polymer contains polyisoprene blocks with high propylene content and polybutadiene blocks with high vinyl content. As a result, the block polymer contains a high side group content, which can effectively improve the selectivity and efficiency of bromination, and makes the obtained brominated block polymer have a high thermal decomposition temperature and a high glass transition temperature, making it particularly suitable as a flame retardant for exterior wall insulation materials such as polystyrene foam.

[0067] Specifically, in the block polymer provided by the present invention, the polyisoprene block contains at least 80 mol% of propylene structural units and the polybutadiene block contains at least 80 mol% of vinyl structural units, and the styrene block content in the block polymer is 20-40 wt%. This enables more than 95% of the double bonds in the block polymer to be brominated, thereby giving the brominated block polymer a high thermal decomposition temperature and a high glass transition temperature, making it particularly suitable as a flame retardant for exterior wall insulation materials such as polystyrene foam.

[0068] In this invention, by independently controlling the polymerization temperatures of the first, second, third, fourth, and fifth anionic polymerization reactions to be between 0 and 50°C, the microstructure of the block polymer can be controlled, resulting in a block polymer with the special block structure described in the first aspect of this invention. Specifically, when the polymerization temperature is too low, the polymerization rate is slow, which is not conducive to large-scale production and results in high energy consumption per unit product; when the polymerization temperature is too high, the ability of the composite structure modifier to control the microstructure of the block polymer decreases, which is not conducive to the preparation of block polymers with high side group content.

[0069] Furthermore, the polymerization temperatures of the first anionic polymerization reaction, the second anionic polymerization reaction, the third anionic polymerization reaction, the fourth anionic polymerization reaction, and the fifth anionic polymerization reaction are each independently 0-40°C.

[0070] In this invention, the time for the first anionic polymerization reaction is 5-15 min, preferably 8-12 min.

[0071] In one specific embodiment of the present invention, step (1) includes: mixing a nonpolar hydrocarbon solvent, a composite structure modifier, and styrene monomer 1 at a lower temperature, then adding an initiator to the mixture to carry out the first anionic polymerization reaction, thereby obtaining a product containing PS. 1 Polymer solutions with a specific structure.

[0072] In this invention, the second anionic polymerization reaction takes 15-30 min, preferably 18-25 min.

[0073] In this invention, the time for the third anionic polymerization reaction is 15-25 min, preferably 18-22 min.

[0074] In this invention, the time for the fourth anionic polymerization reaction is 15-30 min, preferably 18-25 min.

[0075] In this invention, the time for the fifth anionic polymerization reaction is 5-15 min, preferably 8-12 min.

[0076] According to the present invention, component A has the structure shown in Formula I;

[0077]

[0078] In this context, Q1, Q2, and Q3 are each independently N or O, n1 is an integer from 2 to 6, m is 0 or 1, r is 0 or 1, n2 is an integer from 0 to 4, and q1 and q2 are each independently 1 or 2.

[0079] In this invention, component A, which has the above-mentioned specific structure, is selected. It has strong structural control over the anionic polymerization of butadiene and isoprene, and can prepare block polymers with high side group content.

[0080] Further, component A is selected from at least one of diethylene glycol dimethyl ether (2G) (Q1, Q2 and Q3 are 0, q1 and q2 are 1, m is 1, r is 0, n1 and n2 are 2), tetramethylethylenediamine (Q1 and Q3 are N, q1 and q2 are 2, m is 0, r is 0, n1 is 2, n2 is 0), pentamethyldivinyltriamine (Q1, Q2 and Q3 are N, q1 and q2 are 2, m is 1, r is 1, n1 and n2 are 2) and bis(dimethylaminoethyl) ether (BDMAEE) (Q1 and Q3 are N, Q2 is 0, q1 and q2 are 2, m is 1, r is 0, n1 and n2 are 2); preferably diethylene glycol dimethyl ether and / or bis(dimethylaminoethyl) ether.

[0081] According to the present invention, component B has the structure shown in Formula II;

[0082]

[0083] Wherein, R1 and R2 are each independently H or CH3, and R3 is a C2-C6 alkoxy group.

[0084] In this invention, component B, which has the above-mentioned specific structure, is selected. It has low temperature sensitivity and strong ability to adjust the polymerization rate, which can significantly improve the anionic polymerization rate and reduce the degree of side reaction of component A.

[0085] Furthermore, component B is selected from bis(tetrahydrofurfuryl)propane (DTHFP) (R1 and R2 are CH3, R3 is CH3). Tetrahydrofurfuryl ethyl ether (ETE) (R1 and R2 are H, R3 is ethoxy) and N,N-dimethyltetrahydrofurfurylamine (R1 and R2 are H, R3 is ethoxy) At least one of the following.

[0086] According to the present invention, component C is selected from sodium alkoxide and / or sodium alkylbenzene sulfonate, preferably selected from at least one of sodium terpineol (STP), sodium menthol and sodium dodecylbenzene sulfonate (SDBS), and more preferably sodium terpineol.

[0087] In this invention, component C, which has the above-mentioned specific type, is selected. It has a synergistic effect with component A, which can significantly reduce the temperature sensitivity of component A and improve the control of component A over the microstructure of butadiene and styrene anionic polymerization.

[0088] According to the present invention, the amount of component A is 0.2-0.8 mol relative to 1 mol of initiator.

[0089] In this invention, the main function of component A is to control the side group content of the conjugated diene block (polybutadiene and / or polyisoprene). When the amount of component A is too small, the side group content of the block polymer cannot meet the requirements. When the amount of component A is too large, the degree of side reaction increases and the molecular weight distribution of the product becomes wider.

[0090] Furthermore, the amount of component A is 0.3-0.6 mol relative to 1 mol of initiator.

[0091] According to the present invention, the amount of component B is 0.5-3 mol relative to 1 mol of initiator.

[0092] In this invention, component B is mainly used to adjust the polymerization rate of the anionic polymerization reaction. In order to reduce the side reactions caused by component A, it is necessary to increase the anionic polymerization rate. When the amount of component B is too small, the polymerization rate is not significantly increased. When the amount of component B is too large, the polymerization rate is not easy to control and it will affect the ability of component A to control the content of conjugated diene side groups in the block polymer.

[0093] Furthermore, the amount of component B is 0.8-2 mol relative to 1 mol of initiator.

[0094] According to the present invention, the amount of component C is 0.03-0.1 mol relative to 1 mol of initiator.

[0095] In this invention, component C is mainly used to enhance the control of component A over the microstructure of the conjugated diene in the block copolymer, while reducing the temperature sensitivity and side reaction degree of component A. If the amount of component C is too small, it cannot fully exert the above-mentioned effects; if the amount of component C is too large, it will lead to an increased degree of side reaction and a wider molecular weight distribution.

[0096] Furthermore, the amount of component C used is 0.04-0.08 mol relative to 1 mol of initiator.

[0097] In this invention, there is no particular limitation on the type of nonpolar hydrocarbon solvent; conventional nonpolar hydrocarbon solvents in the art, such as cyclohexane, can be used. There is no particular limitation on the amount of nonpolar hydrocarbon solvent used, as long as it is sufficient to fully dissolve the composite structure modifier, etc.

[0098] In this invention, there is no particular limitation on the type of initiator; commonly used anionic polymerization initiators in the art, such as n-butyllithium, can be used. The amount of initiator can also follow conventional methods in the art, using 0.5-2 mmol of initiator as a basis for 100 g of polymeric monomers (styrene, butadiene, and isoprene).

[0099] According to the present invention, the total amount of styrene monomer is 22-35 wt%, based on the total weight of styrene monomer, isoprene monomer and butadiene monomer.

[0100] According to the present invention, the weight ratio of styrene monomer 1 to styrene monomer 2 is 3 / 7-7 / 3, preferably 4 / 6-6 / 4.

[0101] According to the present invention, based on the total weight of styrene monomer, isoprene monomer and butadiene monomer, the total amount of butadiene monomer is 40-70 wt%, preferably 45-65 wt%.

[0102] According to the present invention, the weight ratio of butadiene monomer 1 to butadiene monomer 2 is 4 / 6 to 6 / 4.

[0103] According to the present invention, based on the total weight of styrene monomer, isoprene monomer and butadiene monomer, the amount of isoprene monomer is 5-20 wt%, preferably 5-15 wt%.

[0104] In this invention, controlling the order of adding the monomers styrene, butadiene, and isoprene, as well as the amount added in each step, can yield a block polymer with a phase-separated structure, thereby enabling the brominated block polymer obtained by bromination to have higher thermal stability.

[0105] According to the present invention, the preparation method further includes: processing the PS-containing... 1 -HVBR 1 -HPIR-HVBR 2 -PS 2 The polymer solution with the structure shown is used to terminate the reaction. Generally, the terminator for anionic polymerization can be acid, alcohol, or water, but acid and alcohol have an adverse effect on bromination reactions. Therefore, deionized water is preferred as the terminator in the termination reaction of this invention.

[0106] In this invention, the preparation method is carried out in the presence of nitrogen.

[0107] A third aspect of the present invention provides a block polymer prepared by the above-described preparation method.

[0108] A fourth aspect of the present invention provides a brominated block polymer, characterized in that the brominated block polymer is obtained by bromination of the above-mentioned block polymer.

[0109] In this invention, when the block polymer provided in the first or third aspect of this invention is brominated, the bromination reaction occurs only in the HVBR. 1 HVBR 2 Performed on HPIR blocks, PS 1 and PS 2 Blocks do not participate in the bromination reaction, HVBR1 HVBR 2 In HPIR blocks, more than 95% of the double bonds are brominated. The number of unreacted double bonds in the block polymer determines the bromine content of the brominated block polymer. Preferably, the bromine content of the brominated block polymer is 60-68 wt%, more preferably 61-67 wt%, and more preferably 62-66 wt%.

[0110] According to the present invention, the number average molecular weight of the brominated block polymer is 50,000-200,000, preferably 80,000-150,000.

[0111] In this invention, during the bromination of the conjugated diene block polymer, some molecular chains break down, and the number-average molecular weight of the final brominated block polymer is basically the same as that of the block polymer before bromination.

[0112] According to the present invention, the molecular weight distribution of the brominated block polymer is 1-1.2, preferably 1.01-1.15, and more preferably 1.02-1.1. In this invention, the molecular weight distribution of the brominated block polymer is substantially the same as that of the unbrominated block polymer.

[0113] According to the present invention, the 5wt% thermal weight loss temperature of the brominated block polymer is greater than or equal to 260°C, preferably 261-271°C, and more preferably 263-269°C.

[0114] According to the present invention, the glass transition temperature of the brominated block polymer is greater than or equal to 120°C, preferably 120-130°C, and more preferably 121-127°C.

[0115] The fifth aspect of this invention provides the application of the above-mentioned brominated block copolymer in an external wall insulation flame retardant.

[0116] The present invention will be described in detail below through embodiments.

[0117] The content of vinyl structural units, propylene structural units, styrene structural units, butadiene structural units, and isoprene structural units in styrene and conjugated diene block polymers, as well as the bromine content in brominated block polymers, was determined using a Bruker AVANCE 400 superconducting nuclear magnetic resonance spectrometer. 1 H-NMR analysis was performed using a 5 mm diameter sample tube, deuterated chloroform (CDCl3) as the solvent, a 15% (w / v) sample concentration, room temperature, and 16 scans. Calibration was performed with a tetramethylsilane chemical shift of 0 ppm.

[0118] The molecular weights and distributions of styrene, conjugated diene block polymers, and brominated block polymers were determined using an HLC-8320 gel permeation chromatograph from Tosoh Corporation, Japan. The test conditions included: a TSKgel SuperMultipore HZ-N column, a TSKgel Super Multipore HZ standard column, chromatographically pure THF solvent, polystyrene as the calibration standard, a sample concentration of 1 mg / mL, an injection volume of 10 μL, a flow rate of 0.35 mL / min, and a test temperature of 40 °C.

[0119] The glass transition temperature of the brominated block polymer was determined using a TA-2980DSC differential scanning calorimeter according to the method specified in GB / T29611-2013 Raw Rubber, Glass Transition Temperature, with a heating rate of 20℃ / min.

[0120] The 5wt% thermogravimetric loss of the brominated block polymer was determined using a TA-2980DSC differential scanning calorimeter. The specific procedure was as follows: first, the temperature was raised to 100℃ and held for 5 min, and then the temperature was raised to 600℃ at a rate of 10℃ / min under a nitrogen atmosphere.

[0121] The experimental setup and process are as follows.

[0122] PS 1 -HVBR 1 -HPIR-HVBR 2 -PS 2 Block polymer: The experiment was carried out in a 5L polymerization reactor. Solvent, butadiene, isoprene, and styrene monomers were added through the polymerization line. Initiator and structure modifier were added from the top of the polymerization reactor using a syringe. After polymerization, the polymer was condensed with steam and dried in a plasticizer to obtain PS. 1 -HVBR 1 -HPIR-HVBR 2 -PS 2 Block polymers.

[0123] Brominated block polymer: The reaction was carried out in a 10L stainless steel reactor lined with polytetrafluoroethylene. The obtained basic block copolymer was redissolved in chloroform. A chloroform solution containing liquid bromine was added dropwise under high-speed stirring. During the addition, a constant temperature water bath was used to maintain the temperature of the reaction system. After the addition was completed, stirring was continued to ensure the reaction proceeded fully. Then, an aqueous solution prepared from deionized water, sodium hydroxide, and sodium sulfite was added and stirred thoroughly. The reaction mixture was allowed to settle, and the aqueous phase and solid residue were separated and removed. The resulting brominated block copolymer solution was repeatedly washed with deionized water until the pH was neutral. Calcium stearate, epoxidized soybean oil, and antioxidants were added. Finally, the solvent was removed and the mixture was dried to obtain the desired product, the brominated block polymer.

[0124] All pressures mentioned in this experiment refer to gauge pressure.

[0125] Antioxidant 1076 and Antioxidant 1010 were purchased from Inokai Reagents.

[0126] Cyclohexane was purchased from Sinopharm Reagent Company, with a purity >99.9%. It was soaked in a molecular weight sieve for 15 days, and the water content was less than 5 ppm.

[0127] Chloroform, industrial grade, sourced from Yanshan Petrochemical;

[0128] Styrene, polymer grade, sourced from Yanshan Petrochemical;

[0129] Butadiene, polymer grade, sourced from Yanshan Petrochemical;

[0130] Butyllithium (Li) was purchased from Bailingwei Reagent Company, 100ml specification, 1.6mol·L⁻¹. -1 Cyclohexane solution, diluted to 0.4 mol·L⁻¹ -1 Cyclohexane solution;

[0131] Diethylene glycol dimethyl ether (2G) was purchased from Inocare Reagents, with a purity >99wt%.

[0132] Bis(dimethylaminoethyl) ether (BDMAEE) was purchased from Inokai Reagents, with a purity >98 wt%.

[0133] The bis(tetrahydrofurfuryl) propane (DTHFP) was purchased from Bailingwei Reagent Company with a purity >98wt%.

[0134] Tetrahydrofurfuryl ethyl ether (ETE) was purchased from Bailingwei Reagent Company, with a purity >98wt%.

[0135] Sodium terpineol (STP) was purchased from Qingkai Huafeng Reagent Company in 1.0 mol / L hexane solution;

[0136] Sodium dodecylbenzenesulfonate (SDBS) was purchased from Bailingwei Reagent Company, with a purity >98wt%.

[0137] Liquid bromine (Br) is sourced from Qingkai Huafeng Reagent Company, with a purity greater than 99%.

[0138] Calcium stearate (Ca) is available from Qingkai Huafeng Reagent Company, industrial grade;

[0139] Epoxidized soybean oil (OA) is available from Qingkai Huafeng Reagent Company, industrial grade;

[0140] Sodium hydroxide (Na) is available from Qingkai Huafeng Reagent Company, industrial grade.

[0141] Example 1

[0142] This embodiment is used to illustrate PS.1 -HVBR 1 -HPIR-HVBR 2 -PS 2 Block polymers and their preparation methods.

[0143] S1. Under nitrogen protection, cyclohexane solvent (2300g), composite structure modifier, and styrene monomer 1 (types and amounts are shown in Table 1; all amounts listed in the table are based on pure compounds, the same below) are added to a 5L reactor. The initiation reaction temperature is controlled within the range of 0-15℃ (polymerization temperature and pressure are shown in Table 2, the same below). The designed amount of n-butyllithium is added to the 5L reactor, and the polymerization reaction temperature is controlled within the range of 0-20℃. After 10 minutes, a product containing PS is obtained. 1 Polymer solutions with a specific structure;

[0144] S2, Towards PS 1 Butadiene monomer 1 was added to a polymer solution containing PS, and the polymerization reaction temperature was controlled at 0-50℃. After 20 minutes, a product containing PS was obtained. 1 -HVBR 1 Polymer solutions with a specific structure;

[0145] S3, To contain PS 1 -HVBR 1 Isoprene monomer was added to a polymer solution containing PS, and the polymerization reaction temperature was controlled at 0-50℃. After 20 minutes, a product containing PS was obtained. 1 -HVBR 1 -HPIR structured polymer solution;

[0146] S4, To PS 1 -HVBR 1 Butadiene monomer 2 was added to a polymer solution with an HPIR structure, and the polymerization reaction temperature was controlled at 0-50℃. After 20 minutes, a product containing PS was obtained. 1 -HVBR 1 -HPIR-HVBR 2 Polymer solutions with a specific structure;

[0147] S5, To contain PS 1 -HVBR 1 -HPIR-HVBR 2 Styrene monomer 2 was added to a polymer solution containing PS, and the polymerization reaction temperature was controlled at 0-50℃. After 10 minutes, a product containing PS was obtained. 1 -HVBR 1 -HPIR-HVBR 2 -PS 2 Polymer solutions with a specific structure;

[0148] S6, To contain PS1 -HVBR 1 -HPIR-HVBR 2 -PS 2 The reaction was terminated by adding sufficient deionized water to the polymer solution of the structure. After complete termination, 1g of antioxidant 1076 was added, followed by coagulation and drying to obtain PS. 1 -HVBR 1 -HPIR-HVBR 2 -PS 2 The block polymer P1 was analyzed and tested, and the results are shown in Table 3.

[0149] Example 2-12

[0150] This embodiment is used to illustrate PS. 1 -HVBR 1 -HPIR-HVBR 2 -PS 2 Block polymers and their preparation methods.

[0151] According to the method described in Example 1, except that the block polymers were prepared using the parameters shown in Tables 1 and 2, thereby obtaining PS respectively. 1 -HVBR 1 -HPIR-HVBR 2 -PS 2 The analytical results of the block polymers P2-P12 are shown in Table 3.

[0152] Comparative Example 1

[0153] The method described in Example 1 is different except that 2G (component A) is not added. Specific parameters are shown in Tables 1 and 2, and PS is obtained. 1 -HVBR 1 -HPIR-HVBR 2 -PS 2 The analysis results of the block polymer DP1 are shown in Table 3.

[0154] Comparative Example 2

[0155] The method described in Example 1 is different except that DTHFP (component B) is not added. Specific parameters are shown in Tables 1 and 2. The reaction is exceptionally slow, yielding PS. 1 -HVBR 1 -HPIR-HVBR 2 -PS 2 The block polymer DP2 was analyzed, and the results are shown in Table 3. The residual monomer content of styrene was 6.9 wt%, the residual monomer content of butadiene was 14.8 wt%, and the residual monomer content of isoprene was 2.9 wt%.

[0156] Comparative Example 3

[0157] The method described in Example 1 is different except that STP (component C) is not added. Specific parameters are shown in Tables 1 and 2, and PS is obtained. 1 -HVBR 1 -HPIR-HVBR 2 -PS 2 The analysis results of the block polymer DP3 are shown in Table 3.

[0158] Comparative Example 4

[0159] The method described in Example 1 is different except that the initiation temperature is adjusted. Specific parameters are shown in Tables 1 and 2, and the PS is obtained. 1 -HVBR 1 -HPIR-HVBR 2 -PS 2 The analysis results of the block polymer DP4 are shown in Table 3.

[0160] Comparative Example 5

[0161] The method described in Example 1 is different only in the amount of styrene and butadiene used. Specific parameters are shown in Tables 1 and 2, and PS is obtained. 1 -HVBR 1 -HPIR-HVBR 2 -PS 2 The analysis results of the block polymer DP5 are shown in Table 3.

[0162] Table 1

[0163]

[0164]

[0165] Table 1 (continued)

[0166] serial number Styrene 1 / g Butadiene 1 / g Isoprene / g Butadiene 2 / g Styrene 2 / g Example 1 56 113 37 113 56 Example 2 56 113 37 113 56 Example 3 56 103 57 103 56 Example 4 47 122 37 122 47 Example 5 65 113 19 113 65 Example 6 56 113 37 113 56 Example 7 56 135 37 90 56 Example 8 67 113 37 113 45 Example 9 56 113 37 113 56 Example 10 56 113 37 113 56 Example 11 56 113 37 113 56 Example 12 56 113 37 113 56 Comparative Example 1 56 113 37 113 56 Comparative Example 2 56 113 37 113 56 Comparative Example 3 56 113 37 113 56 Comparative Example 4 56 113 37 113 56 Comparative Example 5 34 134 38 134 34

[0167] Table 1 (continued)

[0168]

[0169]

[0170] Table 2

[0171]

[0172] Table 3

[0173]

[0174]

[0175] Note: Bv% represents high vinyl polybutadiene block (HVBR). 1 and HVBR 2 The content of vinyl structural units in the medium; Ia% is the content of propylene structural units in HPIR; St% is the content of styrene blocks (PS) in the block copolymer. 1 +PS 2 The content of ); Ip% is the content of polyisoprene blocks in the block copolymer; Bd% is the content of polybutadiene blocks in the block copolymer.

[0176] As can be seen from Table 3, the PS prepared by this invention 1 -HVBR 1 -HPIR-HVBR 2 -PS 2 Block polymers, with high vinyl content in polybutadiene blocks and propylene group content in polyisoprene blocks, and narrow molecular weight distribution, are particularly suitable as precursors for brominated block polymers used in exterior wall insulation and flame retardants.

[0177] Application Example 1

[0178] This application example illustrates the PS prepared according to the present invention. 1 -HVBR 1 -HPIR-HVBR 2 -PS 2 Application of block polymers in brominated block polymers.

[0179] In a 10L stainless steel reactor lined with polytetrafluoroethylene, the obtained basic block polymer P1 was redissolved in chloroform to obtain a 10% by weight solution. 4000g of a chloroform solution containing 750g of liquid bromine was added dropwise under high-speed stirring. During the addition, the temperature of the reaction system was maintained at 10℃ using a constant-temperature water bath. After the addition was complete, stirring continued for 300 minutes to ensure the reaction proceeded fully. Then, an aqueous solution prepared with 1500g of deionized water, 160g of sodium hydroxide, and 275g of sodium sulfite was added, and the mixture was stirred thoroughly for 20 minutes. The reaction mixture was allowed to settle, and the aqueous phase and solid residue were separated and removed. The resulting brominated block copolymer solution was repeatedly washed with deionized water until the pH was neutral. 11g of calcium stearate, 11g of epoxidized soybean oil, and 1g of antioxidant 1010 were added. Finally, the solvent was removed and the mixture was dried to obtain the desired product, the brominated block copolymer XP1. The analytical results are shown in Table 4.

[0180] Application Example 2-12

[0181] PS was prepared using the same method as in Example 1. 1 -HVBR 1 -HPIR-HVBR 2 -PS2 The brominated block polymers were prepared by replacing block polymer P1 with P2-P12. The results of the analysis are shown in Table 4.

[0182] Compare and contrast examples 1-5

[0183] PS was prepared using the same method as in Example 1. 1 -HVBR 1 -HPIR-HVBR 2 -PS 2 The brominated block polymers were prepared by replacing block polymer P1 with DP1-DP5. The analytical results are shown in Table 4.

[0184] Compare and contrast examples 6-7

[0185] Brominated block polymers were prepared using the same method as in Application Example 1, except that commercially available SBS grades SBS1301 and SBS1401 were used instead of PS. 1 -HVBR 1 -HPIR-HVBR 2 -PS 2 The block polymers P1-P12 were used to prepare brominated block polymers XSBS1301-XSBS1401. The analytical results of SBS1301 and SBS1401 are shown in Table 3, and the analytical test results of XSBS1301-XSBS1401 are shown in Table 4.

[0186] Table 4

[0187]

[0188]

[0189] As can be seen from Table 4, by using the PS provided by this invention... 1 -HVBR 1 -HPIR-HVBR 2 -PS 2 Block copolymers can be used as precursors to prepare brominated block copolymers with narrow molecular weight distribution, high bromine content, and high thermal decomposition temperature and glass transition temperature at 5wt%. These brominated block copolymers are particularly suitable as environmentally friendly flame retardants for exterior wall insulation.

[0190] The preferred embodiments of the present invention have been described in detail above; however, the present invention is not limited thereto. Within the scope of the inventive concept, various simple modifications can be made to the technical solutions of the present invention, including combinations of various technical features in any other suitable manner. These simple modifications and combinations should also be considered as the content disclosed in the present invention and are all within the protection scope of the present invention.

Claims

1. A block polymer characterized by, The block polymer has PS 1 -HVBR 1 -HPIR-HVBR 2 -PS 2 the block structure shown; Among them, PS 1 and PS 2 Each is an independent styrene block, HVBR 1 and HVBR 2 Each is independently a high vinyl content polybutadiene block, while HPIR is a high propylene content polyisoprene block; Based on the total molar number of HVBR in the block polymer, it contains at least 80 mol% of vinyl structural units; based on the total molar number of HPIR in the block polymer, it contains at least 80 mol% of propylene structural units. Based on the total weight of the block polymer, the content of the styrene block is 20-40 wt%; The block polymer has a molecular weight distribution of 1-1.2; Based on the total weight of the block polymer, the content of the high vinyl content polybutadiene block is 40-70 wt%; Based on the total weight of the block polymer, the content of the high-propylene-content polyisoprene block is 5-20 wt%.

2. The block polymer of claim 1, wherein, Based on the total molar number of HVBR in the block polymer, it contains at least 82 mol% of vinyl structural units.

3. The block polymer of claim 1, wherein, Based on the total molar number of HVBR in the block polymer, it contains at least 84 mol% of vinyl structural units.

4. The block polymer according to claim 1, wherein, Based on the total molar number of HVBR in the block polymer, it contains at least 86 mol% of vinyl structural units.

5. The block polymer of claim 1, wherein, Based on the total number of moles of HPIR in the block polymer, it contains at least 82 mol% of propylene-based structural units.

6. The block polymer of claim 1, wherein, Based on the total number of moles of HPIR in the block polymer, it contains at least 84 mol% of propylene-based structural units.

7. The block polymer of claim 1, wherein, Based on the total number of moles of HPIR in the block polymer, it contains at least 86 mol% of propylene-based structural units.

8. The block polymer according to any one of claims 1-7, wherein, Based on the total weight of the block polymer, the content of the styrene block is 22-35 wt%.

9. The block polymer of any one of claims 1-7, wherein, The PS 1 and the PS 2 in a weight ratio of 3 / 7-7 / 3.

10. The block polymer of any one of claims 1-7, wherein, The PS 1 and the PS 2 in a weight ratio of 4 / 6-6 / 4.

11. The block polymer of any one of claims 1-7, wherein, Based on the total weight of the block polymer, the content of the high vinyl content polybutadiene block is 45-65 wt%.

12. The block polymer of any one of claims 1-7, wherein, The HVBR 1 and the HVBR 2 in a weight ratio of 4 / 6-6 / 4.

13. The block polymer of any one of claims 1-7, wherein, Based on the total weight of the block polymer, the content of the high-propylene-content polyisoprene block is 5-15 wt%.

14. The block polymer of any one of claims 1-7, wherein, The number average molecular weight of the block polymer is 50,000-200,000.

15. The block polymer of any one of claims 1-7, wherein, The number-average molecular weight of the block polymer is 80,000-150,000.

16. The block polymer of any one of claims 1-7, wherein, The block polymer has a molecular weight distribution of 1.01-1.

15.

17. The block polymer of any one of claims 1-7, wherein, The block polymer has a molecular weight distribution of 1.02-1.

1.

18. A process for the preparation of the block polymer of any one of claims 1 to 17, characterized by, The preparation method includes the following steps: (1) In a nonpolar hydrocarbon solvent, in the presence of a composite structure modifier and an initiator, styrene monomer 1 undergoes a first anionic polymerization reaction to obtain a product containing PS. 1 Polymer solutions with a specific structure; (2) adding butadiene monomer 1 to the PS 1 containing polymer solution and performing a second anionic solution polymerization to obtain a polymer solution containing PS 1 -HVBR 1 structured polymer solution; (3) adding isoprene monomer to the polymer solution containing PS 1 -HVBR 1 of the third anionic polymerization reaction to obtain a polymer solution containing PS 1 -HVBR 1 -HPIR structure; (4) adding butadiene monomer 2 to the polymer solution containing PS 1 -HVBR 1 -HPIR structure, and adding butadiene monomer 2 to the polymer solution containing PS 1 -HVBR 1 -HPIR-HVBR 2 structure; (5) To the substance containing PS 1 -HVBR 1 -HPIR-HVBR 2 Styrene monomer 2 is added to a polymer solution containing PS to carry out a fifth anionic polymerization reaction, yielding a product containing PS. 1 -HVBR 1 -HPIR-HVBR 2 -PS 2 The polymer solution with the structure, for the PS-containing 1 -HVBR 1 -HPIR-HVBR 2 -PS 2 The polymer solution of the structure is dried to obtain the block polymer; The composite structure modifier comprises component A, component B, and component C. Component A is a polar ether compound and / or a polar amine compound, component B is a polar ether compound and / or a polar amine compound, and component C is selected from at least one of sodium alkoxide, potassium alkoxide, sodium alkylbenzene sulfonate, and potassium alkylbenzene sulfonate. The polymerization temperatures of the first anionic polymerization reaction, the second anionic polymerization reaction, the third anionic polymerization reaction, the fourth anionic polymerization reaction, and the fifth anionic polymerization reaction are each independently 0-50℃; Based on the total weight of styrene monomer, isoprene monomer, and butadiene monomer, the amount of styrene monomer used is 20-40 wt%; Component A has the structure shown in Formula I; Formula I; In this context, Q1, Q2, and Q3 are each independently N or O, n1 is an integer from 2 to 6, m is 0 or 1, r is 0 or 1, n2 is an integer from 0 to 4, and q1 and q2 are each independently 1 or 2. Component B has the structure shown in Formula II; Formula II; wherein R1and R2are each independently H or CH3, R3is C2-C6alkoxy, or .

19. The method of making according to claim 18, wherein, Component A is selected from at least one of diethylene glycol dimethyl ether, tetramethylethylenediamine, pentamethyldivinyltriamine, and dimethylaminoethyl ether.

20. The method of making according to claim 18, wherein, Component A is diethylene glycol dimethyl ether and / or bis(dimethylaminoethyl) ether.

21. The method of making according to any one of claims 18-20, wherein, Component B is selected from at least one of bis(tetrahydrofurfuryl)propane, tetrahydrofurfuryl ethyl ether, and N,N-dimethyltetrahydrofurfurylamine.

22. The preparation method according to any one of claims 18-20, wherein, Component C is selected from sodium alkoxides and / or sodium alkylbenzene sulfonates.

23. The method of making according to any one of claims 18-20, wherein, Component C is selected from at least one of sodium terpineol, sodium menthol, and sodium dodecylbenzenesulfonate.

24. The method of making according to any one of claims 18-20, wherein, The amount of component A is 0.2-0.8 mol relative to 1 mol of initiator, the amount of component B is 0.5-3 mol, and the amount of component C is 0.03-0.1 mol.

25. The method of making according to any one of claims 18-20, wherein, The amount of component A is 0.3-0.6 mol relative to 1 mol of initiator, the amount of component B is 0.8-2 mol, and the amount of component C is 0.04-0.08 mol.

26. The method of making according to any one of claims 18-20, wherein, The polymerization temperatures of the first anionic polymerization reaction, the second anionic polymerization reaction, the third anionic polymerization reaction, the fourth anionic polymerization reaction, and the fifth anionic polymerization reaction are each independently 0-40℃.

27. The preparation method according to any one of claims 18-20, wherein, Based on the total weight of styrene monomer, isoprene monomer and butadiene monomer, the amount of styrene monomer used is 22-35 wt%.

28. The method of making according to any one of claims 18-20, wherein, The weight ratio of styrene monomer 1 to styrene monomer 2 is 3 / 7 to 7 / 3.

29. The method of making according to any one of claims 18-20, wherein, The weight ratio of styrene monomer 1 to styrene monomer 2 is 4 / 6 to 6 / 4.

30. The method of making according to any one of claims 18-20, wherein, Based on the total weight of styrene monomer, isoprene monomer and butadiene monomer, the amount of butadiene monomer used is 40-70 wt%.

31. The method of making according to any one of claims 18-20, wherein, Based on the total weight of styrene monomer, isoprene monomer and butadiene monomer, the amount of butadiene monomer is 45-65 wt%.

32. The method of making according to any one of claims 18-20, wherein, The weight ratio of butadiene monomer 1 to butadiene monomer 2 is 4 / 6 to 6 / 4.

33. The method of making according to any one of claims 18-20, wherein, Based on the total weight of styrene monomer, isoprene monomer and butadiene monomer, the amount of isoprene monomer used is 5-20 wt%.

34. The method of making according to any one of claims 18-20, wherein, Based on the total weight of styrene monomer, isoprene monomer and butadiene monomer, the amount of isoprene monomer used is 5-15 wt%.

35. The method of making according to any one of claims 18-20, wherein, The preparation method further comprises: performing a termination reaction on the polymer solution containing PS 1 -HVBR 1 -HPIR-HVBR 2 -PS 2 of the structure.

36. The method of manufacturing according to claim 35, wherein, The terminator in the termination reaction is deionized water.

37. A block polymer prepared by the method according to any one of claims 18-36.

38. A brominated block polymer characterized by, The brominated block polymer is prepared by bromination of the block polymer according to any one of claims 1-17 and 37.

39. The brominated block polymer of claim 38, wherein, Based on the total weight of the brominated block polymer, the bromine content is 60-68 wt%.

40. The brominated block polymer of claim 38, wherein, Based on the total weight of the brominated block polymer, the bromine content is 61-67 wt%.

41. The brominated block polymer according to claim 38, wherein, Based on the total weight of the brominated block polymer, the bromine content is 62-66 wt%.

42. The brominated block polymer according to any one of claims 38-41, wherein, The number-average molecular weight of the brominated block polymer is 50,000-300,000.

43. The brominated block polymer of any one of claims 38-41, wherein, The number-average molecular weight of the brominated block polymer is 80,000-200,000.

44. The brominated block polymer of any of claims 38-41, wherein, The brominated block polymer has a molecular weight distribution of 1-1.

2.

45. The brominated block polymer of any of claims 38-41, wherein, The brominated block polymer has a molecular weight distribution of 1.01-1.

15.

46. The brominated block polymer of any of claims 38-41, wherein, The brominated block polymer has a molecular weight distribution of 1.02-1.

1.

47. The brominated block polymer of any one of claims 38-41, wherein, The 5wt% thermogravimetric temperature of the brominated block polymer is greater than or equal to 260°C.

48. The brominated block polymer of any one of claims 38-41, wherein, The 5wt% thermogravimetric temperature of the brominated block polymer is 261-271℃.

49. The brominated block polymer of any one of claims 38-41, wherein, The 5wt% thermogravimetric temperature of the brominated block polymer is 263-269℃.

50. The brominated block polymer of any one of claims 38-41, wherein, The glass transition temperature of the brominated block polymer is greater than or equal to 120°C.

51. The brominated block polymer of any of claims 38-41, wherein, The glass transition temperature of the brominated block polymer is 120-130℃.

52. The brominated block polymer of any of claims 38-41, wherein, The glass transition temperature of the brominated block polymer is 121-127℃.

53. The application of the brominated block polymer according to any one of claims 38-52 in exterior wall insulation flame retardants.

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