Block polymers and methods of making, brominated block polymers and uses

Abstract

The application relates to the technical field of high polymer material synthesis and preparation, and discloses a block polymer, a preparation method, a brominated block polymer and application. 1 -HVBR / HPIR-PS 2 The block polymer has a block structure as shown in the figure; at least 80 mol% of vinyl structural units are contained based on the total number of butadiene structural units in the block polymer; at least 80 mol% of propylene structural units are contained based on the total number of isoprene structural units in the block polymer; and the molecular weight distribution of the block polymer is 1-1.2. The block polymer has a phase separation structure, high side group content and narrow molecular weight distribution, can effectively improve the selectivity of bromination, and obtains a brominated block polymer with high thermal decomposition temperature and glass transition temperature.

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 application. 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 HBCD will be withdrawn from the global exterior wall insulation flame retardant market.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 high molecular weights, increasing resistance to migration, extraction, and evaporation, thereby reducing the risk of flame retardants being released from the polymer into the environment. The high molecular weight of polymers limits their passage 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 are the most efficient and sustainable solution among polymeric flame retardants due to their high molecular weight and excellent flame retardant properties.

[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] In view of the above-mentioned situation of the prior art, the inventors of the present invention have conducted in-depth and extensive research on styrene and conjugated diene block polymers in order to invent a styrene and conjugated diene block polymer that can be effectively brominated, has stable bromination efficiency, and produces bromination products with high thermal decomposition temperature and glass transition temperature, thereby meeting the requirements of environmentally friendly flame retardants for exterior walls regarding the molecular structure of styrene and conjugated diene block polymers. The results showed that when the styrene and conjugated diene block polymer has a phase-separated structure and the side group content of the conjugated diene is increased to more than 80 mol%, the selectivity of bromination can be effectively improved. Furthermore, when the block copolymer has a narrow molecular weight distribution, the thermal stability of the brominated block polymer can be significantly improved, resulting in a brominated block polymer with high thermal decomposition temperature and glass transition temperature, thus completing the present invention.

[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 / HPIR-PS 2 The block structure shown;

[0007] Among them, PS 1 and PS 2 Each is an independent styrene block, and HVBR / HPIR is a random copolymer segment containing butadiene and isoprene structural units;

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

[0009] The block polymer has a molecular weight distribution of 1-1.2.

[0010] 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:

[0011] (1) In a nonpolar hydrocarbon solvent, in the presence of a composite structure modifier and an initiator, styrene monomer I undergoes a first anionic polymerization reaction to obtain a product containing PS. 1 Polymer solutions with a specific structure;

[0012] (2) To the substance containing PS 1 Butadiene and isoprene monomers are added to a polymer solution containing PS, and a second anionic solution polymerization is carried out to obtain a product containing PS. 1 -HVBR / HPIR structured polymer solution;

[0013] (3) To the substance containing PS 1Styrene monomer II was added to a polymer solution with a -HVBR / HPIR structure to carry out a third anionic polymerization reaction, yielding a product containing PS. 1 -HVBR / HPIR-PS 2 The polymer solution with the structure, for the PS-containing 1 -HVBR / HPIR-PS 2 The polymer solution of the structure is dried to obtain the block polymer;

[0014] 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.

[0015] The polymerization temperatures of the first anionic polymerization reaction, the second anionic polymerization reaction, and the third anionic polymerization reaction are each independently 0-50°C.

[0016] A third aspect of the present invention provides a block polymer prepared by the above-described preparation method.

[0017] 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.

[0018] The fifth aspect of the present invention provides an application of the above-mentioned brominated block polymer in an exterior wall insulation flame retardant.

[0019] 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:

[0020] The block polymer provided by this invention contains random copolymer segments comprising butadiene and isoprene structural units and has a narrow molecular weight distribution. The random copolymer segments contain a high content of side groups; specifically, the isoprene structural unit (HPIR) has a propenyl group content of over 80 mol%, and the butadiene structural unit (HVBR) has a vinyl group content of over 80 mol%. This results in over 95% of the double bonds in the block polymer undergoing bromination addition, effectively improving the selectivity and efficiency of bromination. Consequently, the obtained brominated block copolymer exhibits a high thermal decomposition temperature and a high glass transition temperature, making it particularly suitable as a polystyrene foam exterior wall insulation flame retardant.

[0021] 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 / HPIR-PS 2 The block copolymers with the specific structure shown, in particular, 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 polystyrene foam exterior wall insulation flame retardants. Detailed Implementation

[0022] 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.

[0023] A first aspect of the present invention provides a block polymer, characterized in that the block polymer has PS 1 -HVBR / HPIR-PS 2 The block structure shown;

[0024] Among them, PS 1 and PS 2 Each is an independent styrene block, and HVBR / HPIR is a random copolymer segment containing butadiene and isoprene structural units;

[0025] 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.

[0026] The block polymer has a molecular weight distribution of 1-1.2.

[0027] 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.

[0028] In this invention, the block polymer provided by this invention contains random copolymer segments comprising butadiene and isoprene structural units and has a narrow molecular weight distribution. The random copolymer segments contain a high content of side groups, which effectively improves 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 a polystyrene foam exterior wall insulation flame retardant.

[0029] 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, 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.

[0030] In this invention, to prepare brominated block polymers with better thermal stability, PS before bromination is required. 1 -HVBR / HPIR-PS 2 Block polymers have a narrow molecular weight distribution, PS 1 -HVBR / HPIR-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.

[0031] In this invention, the content (Ia%) of propylene structural units in isoprene structural units (HPIR) and the content (Bv%) of vinyl structural units in butadiene structural units (HVBR) were determined by proton nuclear magnetic resonance spectroscopy.

[0032] 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.

[0033] 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.

[0034] Furthermore, the molecular weight distribution of the block polymer is 1.01-1.15, preferably 1.02-1.1.

[0035] According to the present invention, based on the total weight of the block polymer, the styrene block (PS)1 +PS 2 The content (St%) of ) is 20-40 wt%.

[0036] According to the present invention, PS 1 and PS 2 The weight ratio is 3 / 7-7 / 3.

[0037] In this invention, PS 1 and PS 2 Each is an independent styrene block, PS 1 and PS 2 Same or different.

[0038] In this invention, the content of styrene blocks and PS in the block polymer are controlled. 1 and PS 2 The weight ratio must meet the above range to ensure that PS 1 and PS 2 Segment length, further, PS 1 and PS 2 The number average molecular weight is at least 8,000, 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.

[0039] In this invention, the content (St%) of styrene blocks in the block polymer was determined by proton nuclear magnetic resonance spectroscopy. 1 and PS 2 The weight ratio is calculated directly using the amount of styrene monomer added.

[0040] Furthermore, based on the total weight of the block polymer, the styrene block (PS) 1 +PS 2 The content (St%) of ) is 22-35wt%.

[0041] Furthermore, PS 1 and PS 2 The weight ratio is 4 / 6-6 / 4.

[0042] According to the present invention, the content of the butadiene structural unit is 30-70 wt%, based on the total weight of the block polymer.

[0043] According to the present invention, the content of the isoprene structural unit is 5-40 wt%, based on the total weight of the block polymer.

[0044] In this invention, controlling the content of butadiene and isoprene structural units in the block polymer is to ensure that the block polymer has enough double bonds that can undergo addition reactions, thereby increasing the bromine content in the final brominated block polymer and ensuring that the brominated product has high thermal stability and glass transition temperature.

[0045] Furthermore, based on the total weight of the block polymer, the content of the butadiene structural unit is 35-65 wt%.

[0046] Furthermore, based on the total weight of the block polymer, the content of the isoprene structural unit is 10-30 wt%.

[0047] According to the present invention, the number average molecular weight of the block polymer is 50,000-200,000, preferably 80,000-150,000.

[0048] 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.

[0049] 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:

[0050] (1) In a nonpolar hydrocarbon solvent, in the presence of a composite structure modifier and an initiator, styrene monomer I undergoes a first anionic polymerization reaction to obtain a product containing PS. 1 Polymer solutions with a specific structure;

[0051] (2) To the substance containing PS 1 Butadiene and isoprene monomers are added to a polymer solution containing PS, and a second anionic solution polymerization is carried out to obtain a product containing PS. 1 -HVBR / HPIR structured polymer solution;

[0052] (3) To the substance containing PS 1 Styrene monomer II was added to a polymer solution with a -HVBR / HPIR structure to carry out a third anionic polymerization reaction, yielding a product containing PS. 1 -HVBR / HPIR-PS 2 The polymer solution with the structure, for the PS-containing 1-HVBR / HPIR-PS 2 The polymer solution of the structure is dried to obtain the block polymer;

[0053] 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.

[0054] The polymerization temperatures of the first anionic polymerization reaction, the second anionic polymerization reaction, and the third anionic polymerization reaction are each independently 0-50°C.

[0055] 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 the block copolymer with a specific structure as described in the first aspect of this invention. In particular, the block copolymer contains a high content of side groups, which can effectively improve the selectivity and efficiency of bromination, and makes the obtained brominated block copolymer have a high thermal decomposition temperature and a high glass transition temperature, making it particularly suitable as a polystyrene foam exterior wall insulation flame retardant.

[0056] 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, 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.

[0057] In this invention, by independently controlling the polymerization temperatures of the first, second, and third anionic polymerization reactions to 0-50°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 regulator to control the microstructure of the block copolymer decreases, which is not conducive to the preparation of block polymers with high side group content.

[0058] According to the present invention, component A has the structure shown in Formula I;

[0059]

[0060] 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.

[0061] 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.

[0062] 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.

[0063] According to the present invention, component B has the structure shown in Formula II;

[0064]

[0065] Wherein, R1 and R2 are each independently H or CH3, and R3 is a C2-C6 alkoxy group.

[0066] 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.

[0067] 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.

[0068] 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.

[0069] 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.

[0070] According to the present invention, the amount of component A is 0.2-0.8 mol relative to 1 mol of initiator.

[0071] In this invention, the main function of component A is to control the side group content of conjugated diene segments (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.

[0072] Furthermore, the amount of component A is 0.3-0.6 mol relative to 1 mol of initiator.

[0073] According to the present invention, the amount of component B is 0.5-3 mol relative to 1 mol of initiator.

[0074] 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 copolymer.

[0075] Furthermore, the amount of component B is 0.8-2 mol relative to 1 mol of initiator.

[0076] According to the present invention, the amount of component C is 0.03-0.1 mol relative to 1 mol of initiator.

[0077] 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.

[0078] Furthermore, the amount of component C used is 0.04-0.08 mol relative to 1 mol of initiator.

[0079] 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.

[0080] In this invention, there is no particular limitation on the type of initiator; commonly used anionic polymerization initiators in the art, such as butyllithium, can be used. The amount of initiator can also follow conventional methods in the art; for example, based on 100g of polymeric monomers (styrene, butadiene, and isoprene), the amount of initiator is 0.5-2 mmol.

[0081] According to the present invention, the polymerization temperature of the first anionic polymerization reaction, the second anionic polymerization reaction and the third anionic polymerization reaction are each independently 0-40°C.

[0082] In this invention, the time for the first anionic polymerization reaction is 5-15 min, preferably 8-12 min.

[0083] In one specific embodiment of the present invention, step (1) includes: mixing a nonpolar hydrocarbon solvent, a composite structure modifier, and styrene monomer I under a relatively low temperature condition to obtain a mixture; then adding an initiator to the mixture to carry out the first anionic polymerization reaction to obtain a product containing PS. 1 Polymer solution.

[0084] In this invention, the second anionic polymerization reaction takes 30-60 minutes, preferably 40-60 minutes.

[0085] In this invention, the time for the third anionic polymerization reaction is 5-15 min, preferably 8-12 min.

[0086] According to the present invention, based on the total weight of styrene monomer, isoprene monomer and butadiene monomer, the amount of styrene monomer is 20-40 wt%, preferably 22-35 wt%.

[0087] According to the present invention, the weight ratio of styrene monomer I to styrene monomer II is 3 / 7-7 / 3, preferably 4 / 6-6 / 4.

[0088] According to the present invention, based on the total weight of styrene monomer, isoprene monomer and butadiene monomer, the amount of butadiene monomer is 30-70 wt%, preferably 35-65 wt%.

[0089] According to the present invention, based on the total weight of styrene monomer, isoprene monomer and butadiene monomer, the amount of isoprene monomer is 5-40 wt%, preferably 10-30 wt%.

[0090] 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.

[0091] According to the present invention, the preparation method further includes: processing the PS-containing... 1 -HVBR / HPIR-PS 2 The polymer solution terminates 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.

[0092] In this invention, the preparation method is carried out in the presence of nitrogen.

[0093] A third aspect of the present invention provides a block polymer prepared by the above-described preparation method.

[0094] 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.

[0095] In this invention, when the block polymer provided in the first or third aspect of this invention is brominated, the bromination reaction occurs only on the random copolymer segments of HVBR / HPIR. 1 and PS 2 The blocks do not participate in the bromination reaction. More than 95% of the double bonds in the random copolymer blocks of HVBR / HPIR 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%.

[0096] 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.

[0097] In this invention, during the bromination process, some molecular chains of the block polymer 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.

[0098] 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.

[0099] 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 260-270°C, and more preferably 262-268°C.

[0100] 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 122-128°C.

[0101] The fifth aspect of this invention provides the application of the above-mentioned brominated block copolymer in an external wall insulation flame retardant.

[0102] The present invention will be described in detail below through embodiments.

[0103] PS 1 -HVBR / HPIR-PS 2 The content of vinyl structural units, propylene structural units, styrene structural units, butadiene structural units, and isoprene structural units in the block polymers, as well as the bromine content in the 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.

[0104] S 1 -B / IS 2 The molecular weights and distributions of the 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 SuperMultipore 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.

[0105] 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.

[0106] 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.

[0107] The experimental setup and process are as follows.

[0108] PS 1 -HVBR / HPIR-PS 2 Polymer Segmentation: The experiment was conducted 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 mixture was treated with steam and dried in a plasticizer to obtain PS. 1 -HVBR / HPIR-PS 2 Block polymers.

[0109] Brominated block copolymer: 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 copolymer.

[0110] All pressures mentioned in this experiment refer to gauge pressure.

[0111] Antioxidant 1076 and Antioxidant 1010 were purchased from Inokai Reagents.

[0112] 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.

[0113] Chloroform, industrial grade, sourced from Yanshan Petrochemical;

[0114] Styrene, polymer grade, sourced from Yanshan Petrochemical;

[0115] Butadiene, polymer grade, sourced from Yanshan Petrochemical;

[0116] 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;

[0117] Diethylene glycol dimethyl ether (2G) was purchased from Inocare Reagents, with a purity >99wt%.

[0118] Bis(dimethylaminoethyl) ether (BDMAEE) was purchased from Inokai Reagents, with a purity >98 wt%.

[0119] The bis(tetrahydrofurfuryl) propane (DTHFP) was purchased from Bailingwei Reagent Company with a purity >98wt%.

[0120] Tetrahydrofurfuryl ethyl ether (ETE) was purchased from Bailingwei Reagent Company, with a purity >98wt%.

[0121] Sodium terpineol (STP) was purchased from Qingkai Huafeng Reagent Company in 1.0 mol / L hexane solution;

[0122] Sodium dodecylbenzenesulfonate (SDBS) was purchased from Bailingwei Reagent Company, with a purity >98wt%.

[0123] Liquid bromine (Br) is sourced from Qingkai Huafeng Reagent Company, with a purity greater than 99%.

[0124] Calcium stearate (Ca) is available from Qingkai Huafeng Reagent Company, industrial grade;

[0125] Epoxidized soybean oil (OA) is available from Qingkai Huafeng Reagent Company, industrial grade;

[0126] Sodium hydroxide (Na) is available from Qingkai Huafeng Reagent Company, industrial grade.

[0127] Example 1

[0128] This embodiment is used to illustrate the present invention PS. 1 -HVBR / HPIR-PS 2 Block polymers and their preparation methods.

[0129] S1. Under nitrogen protection, cyclohexane solvent, composite structure modifier, and styrene monomer I (types and amounts are shown in Table 1; all amounts listed in the table are measured as pure compounds, the same below) are added to a 5L reactor. The polymerization reaction temperature is controlled within the range of 0-50℃ (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 0-50℃. After 10 minutes, a product containing PS is obtained. 1 Polymer solutions with a specific structure;

[0130] S2, Towards PS 1 A designed amount of butadiene and isoprene monomers were added to a polymer solution containing PS. The polymerization reaction temperature was controlled at 0-50℃. After 50 minutes, a product containing PS was obtained. 1 -HVBR / HPIR structured polymer solution;

[0131] S3, To contain PS 1 Styrene monomer II was added to a polymer solution with a -HVBR / HPIR structure, and the polymerization reaction temperature was controlled at 0-50℃. After 10 minutes, a polymer containing PS was obtained. 1 -HVBR / HPIR-PS2 Polymer solutions with a specific structure;

[0132] S4, To contain PS 1 -HVBR / HPIR-PS 2 The reaction was terminated by adding sufficient deionized water to the polymer solution of the structure. After complete termination, antioxidant 1076 was added, followed by coagulation and drying to obtain PS. 1 -HVBR / HPIR-PS 2 Block copolymer P1 was analyzed, and the results are shown in Table 3.

[0133] Examples 2-9

[0134] This embodiment is used to illustrate the PS of the present invention. 1 -HVBR / HPIR-PS 2 Block polymers and their preparation methods.

[0135] The method described in Example 1 is different in that PS is prepared using the parameters shown in Tables 1 and 2. 1 -HVBR / HPIR-PS 2 Block polymers, thus obtaining PS respectively 1 -HVBR / HPIR-PS 2 The analytical results of block polymers P2-P9 are shown in Table 3.

[0136] Comparative Example 1

[0137] The method described in Example 1 is different except that 2G is not added. Specific parameters are shown in Tables 1 and 2, and the PS is obtained. 1 -HVBR / HPIR-PS 2 The analytical results of the block polymer DP1 are shown in Table 3.

[0138] Comparative Example 2

[0139] The method described in Example 1 is different except that DTHFP is not added. Specific parameters are shown in Tables 1 and 2. The reaction is exceptionally slow, yielding PS. 1 -HVBR / HPIR-PS 2 The block polymer DP2 was analyzed, and the results are shown in Table 3. The residual monomer content of styrene was 6.4 wt%, the residual monomer content of butadiene was 16.7 wt%, and the residual monomer content of isoprene was 3.4 wt%.

[0140] Comparative Example 3

[0141] The method described in Example 1 is different except that STP is not added. Specific parameters are shown in Tables 1 and 2, and PS is obtained. 1 -HVBR / HPIR-PS2 The analytical results of the block polymer DP3 are shown in Table 3.

[0142] Comparative Example 4

[0143] 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 / HPIR-PS 2 The results of the analysis and testing of the block polymer DP4 are shown in Table 3.

[0144] Table 1

[0145]

[0146]

[0147] Table 1 (continued)

[0148]

[0149]

[0150] Table 2

[0151] serial number <![CDATA[St 1 Polymerization temperature / ℃ B / I polymerization temperature / °C <![CDATA[St 2 Polymerization temperature / ℃ Pressure / MPa Example 1 20 20 20 0.3 Example 2 20 20 20 0.3 Example 3 30 30 30 0.3 Example 4 40 40 40 0.3 Example 5 20 20 20 0.3 Example 6 30 30 30 0.3 Example 7 40 40 40 0.3 Example 8 20 20 20 0.3 Example 9 20 20 20 0.3 Comparative Example 1 20 20 20 0.3 Comparative Example 2 20 20 20 0.3 Comparative Example 3 20 20 20 0.3 Comparative Example 4 60 60 60 0.3

[0152] Table 3

[0153] example <![CDATA[Mn / 10 4 ]]> MDW Bv / % Ia / % St / % Bd / % Ip / % <![CDATA[PS 1 / PS 2 ]]> P1 10.2 1.05 88.4 87.9 30.2 59.9 9.9 5 / 5 P2 11.9 1.06 88.2 87.8 30.1 54.2 15.7 5 / 5 P3 10.1 1.05 86.3 86.1 25.3 64.6 10.1 5 / 5 P4 10.4 1.06 84.6 84.4 34.9 59.8 5.3 5 / 5 P5 10.2 1.06 82.2 82.1 30.1 60.1 9.8 5 / 5 P6 10.2 1.05 80.7 80.5 30.1 59.9 10 5 / 5 P7 10.3 1.06 84.3 84.1 30.1 60.1 9.8 7 / 3 P8 10.1 1.14 87.9 87.6 30.2 59.9 9.9 5 / 5 P9 6.1 1.05 88.2 87.8 30.2 59.9 9.9 5 / 5 DP1 10.1 1.04 77.6 77.4 30.1 60.1 9.8 5 / 5 DP2 7.6 1.36 84.5 84.2 32.1 58.9 9 5 / 5 DP3 9.7 1.21 80.2 80.1 30.1 60.2 9.7 5 / 5 DP4 10.1 1.06 76.3 76 30.2 59.9 9.9 5 / 5 SBS1301 11.4 1.04 12.4 0 30.4 69.6 0 5 / 5 SBS1401 8.4 1.04 12.1 0 40.6 59.4 0 5 / 5

[0154] Note: Bv% represents the content of vinyl structural units in the butadiene segment; Ia% represents the content of propylene structural units in the isoprene segment; St% represents the content of styrene blocks (PS) in the block copolymer. 1 +PS 2 The content of ) is; Ip% is the content of isoprene structural units in the block copolymer; Bd% is the content of butadiene structural units in the block copolymer.

[0155] As can be seen from Table 3, the PS prepared by this invention 1 -HVBR / HPIR-PS 2 Block polymers, especially those with high vinyl content in polybutadiene blocks and narrow molecular weight distribution in polyisoprene blocks, are particularly suitable as precursors for brominated block polymers used in exterior wall insulation.

[0156] Application Example 1

[0157] This application example illustrates the PS prepared according to the present invention. 1 -HVBR / HPIR-PS 2 Application of block polymers in brominated block polymers.

[0158] 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, a constant temperature water bath was used to maintain the reaction system temperature at 10℃. 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 polymer XP1. The analytical results are shown in Table 4.

[0159] Application Example 2-9

[0160] Brominated block polymers were prepared using the same method as in Application Example 1, except that block polymers P2-P9 were used instead of P1. The resulting brominated block polymers XP2-XP9 are shown in Table 4.

[0161] Compare and contrast examples 1-4

[0162] Brominated block polymers were prepared using the same method as in Application Example 1, except that block polymers DP1-DP4 were used instead of P1. The resulting brominated block polymers XDP1-XDP4 are shown in Table 4.

[0163] Compare and contrast examples 5-6

[0164] 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 P1. The resulting brominated block polymers XSBS1301-XSBS1401 are shown in Table 3, and the analytical results of XSBS1301-XSBS1401 are shown in Table 4.

[0165] Table 4

[0166] example Molecular weight / 10,000 Molecular weight distribution Bromine content / wt% 5wt% thermogravimetric temperature / ℃ Glass transition temperature / °C XP1 11.1 1.07 66.2 268 127 XP2 12.4 1.08 66.3 267 128 XP3 10.9 1.07 66.7 267 122 XP4 11.2 1.08 63.6 262 126 XP5 11.0 1.10 64.4 264 124 XP6 10.8 1.09 63.5 261 122 XP7 10.7 1.08 65.2 260 123 XP8 10.9 1.15 65.9 262 125 XP9 6.8 1.07 66.0 261 124 XDP1 10.9 1.08 61.9 258 120 XDP2 7.7 1.44 62.2 242 122 XDP3 10.2 1.27 62.8 247 121 XDP4 10.9 1.08 61.5 254 119 XSBS1301 11.2 1.07 33.9 228 110 XSBS1401 8.8 1.08 29.8 216 106

[0167] As can be seen from Table 4, by using the PS provided by this invention... 1 -HVBR / HPIR-PS 2 Block polymers can be used as precursors to prepare brominated block polymers with narrow molecular weight distribution, high bromine content, and high 5wt% thermal decomposition temperature and glass transition temperature. These brominated block polymers are particularly suitable as environmentally friendly flame retardants for exterior wall insulation.

[0168] 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 in that, The block polymer has PS 1 -HVBR / HPIR-PS 2 The block structure shown; Among them, PS 1 and PS 2 Each is an independent styrene block, and HVBR / HPIR is a random copolymer segment containing butadiene and isoprene structural units; 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. 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 styrene block is 20-40 wt%; Based on the total weight of the block polymer, the content of the butadiene structural unit is 30-70 wt%; Based on the total weight of the block polymer, the content of the isoprene structural unit is 5-40 wt%.

2. The block polymer according to 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; And / or, based on the total number of moles of HPIR in the block polymer, it contains at least 82 mol% of propylene-based structural units; And / or, the molecular weight distribution of the block polymer is 1.01-1.

15.

3. The block polymer according to claim 2, wherein, Based on the total molar number of HVBR in the block polymer, it contains at least 84 mol% of vinyl structural units; And / or, based on the total number of moles of HPIR in the block polymer, it contains at least 84 mol% of propylene-based structural units; And / or, the molecular weight distribution of the block polymer is 1.02-1.

1.

4. The block polymer according to claim 3, wherein, Based on the total molar number of HVBR in the block polymer, it contains at least 86 mol% of vinyl structural units; And / or, based on the total number of moles of HPIR in the block polymer, it contains at least 86 mol% of propylene-based structural units.

5. The block polymer according to claim 1 or 2, wherein, Based on the total weight of the block polymer, the content of the styrene block is 22-35 wt%; And / or, PS 1 and PS 2 The weight ratio is 3 / 7-7 / 3.

6. The block polymer according to claim 5, wherein, PS 1 and PS 2 The weight ratio is 4 / 6-6 / 4.

7. The block polymer according to claim 1 or 2, wherein, Based on the total weight of the block polymer, the content of the butadiene structural unit is 35-65 wt%.

8. The block polymer according to claim 1 or 2, wherein, Based on the total weight of the block polymer, the content of the isoprene structural unit is 10-30 wt%.

9. The block polymer according to claim 1 or 2, wherein, The number average molecular weight of the block polymer is 50,000-200,000.

10. The block polymer according to claim 9, wherein, The number-average molecular weight of the block polymer is 80,000-150,000.

11. A method for preparing the block polymer according to any one of claims 1-10, characterized in that, 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 I undergoes a first anionic polymerization reaction to obtain a product containing PS. 1 Polymer solutions with a specific structure; (2) To the substance containing PS 1 Butadiene and isoprene monomers are added to a polymer solution containing PS, and a second anionic solution polymerization is carried out to obtain a product containing PS. 1 -HVBR / HPIR structured polymer solution; (3) To the substance containing PS 1 Styrene monomer II was added to a polymer solution with a -HVBR / HPIR structure to carry out a third anionic polymerization reaction, yielding a product containing PS. 1 -HVBR / HPIR-PS 2 The polymer solution with the structure, for the PS-containing 1 -HVBR / HPIR-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, and the third anionic polymerization reaction are each independently 0-50°C.

12. The preparation method according to claim 11, wherein, Component A has the structure shown in Formula I; Equation 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.

13. The preparation method according to claim 12, wherein, Component A is selected from at least one of diethylene glycol dimethyl ether, tetramethylethylenediamine, pentamethyldivinyltriamine, and dimethylaminoethyl ether.

14. The preparation method according to claim 13, wherein, Component A is diethylene glycol dimethyl ether and / or bis(dimethylaminoethyl) ether.

15. The preparation method according to claim 11 or 12, wherein, Component B has the structure shown in Formula II; Formula II; Wherein, R1 and R2 are each independently H or CH3, and R3 is a C2-C6 alkoxy group. or .

16. The preparation method according to claim 15, wherein, Component B is selected from at least one of bis(tetrahydrofurfuryl)propane, tetrahydrofurfuryl ethyl ether, and N,N-dimethyltetrahydrofurfurylamine.

17. The preparation method according to claim 11 or 12, wherein, Component C is selected from sodium alkoxides and / or sodium alkylbenzene sulfonates.

18. The preparation method according to claim 17, wherein, Component C is selected from at least one of sodium terpineol, sodium menthol, and sodium dodecylbenzenesulfonate.

19. The preparation method according to claim 11 or 12, 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.

20. The preparation method according to claim 19, 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.

21. The preparation method according to claim 11 or 12, wherein, The polymerization temperatures of the first anionic polymerization reaction, the second anionic polymerization reaction, and the third anionic polymerization reaction are each independently 0-40°C.

22. The preparation method according to claim 11 or 12, wherein, Based on the total weight of styrene monomer, isoprene monomer, and butadiene monomer, the amount of styrene monomer used is 20-40 wt%; And / or, the weight ratio of styrene monomer I to styrene monomer II is 3 / 7 to 7 / 3.

23. The preparation method according to claim 22, wherein, Based on the total weight of styrene monomer, isoprene monomer, and butadiene monomer, the amount of styrene monomer used is 22-35 wt%. And / or, the weight ratio of styrene monomer I to styrene monomer II is 4 / 6 to 6 / 4.

24. The preparation method according to claim 11 or 12, wherein, Based on the total weight of styrene monomer, isoprene monomer, and butadiene monomer, the amount of butadiene monomer used is 30-70 wt%; And / or, based on the total weight of styrene monomer, isoprene monomer and butadiene monomer, the amount of isoprene monomer is 5-40 wt%.

25. The preparation method according to claim 24, wherein, Based on the total weight of styrene monomer, isoprene monomer, and butadiene monomer, the amount of butadiene monomer used is 35-65 wt%; And / or, based on the total weight of styrene monomer, isoprene monomer and butadiene monomer, the amount of isoprene monomer is 10-30 wt%.

26. The preparation method according to claim 11 or 12, wherein, The preparation method further includes: processing the PS-containing... 1 -HVBR / HPIR-PS 2 The polymer solution with the structure undergoes a termination reaction.

27. The preparation method according to claim 26, wherein, The terminator in the termination reaction is deionized water.

28. A brominated block polymer, characterized in that, The brominated block polymer is obtained by bromination of the block polymer according to any one of claims 1-10.

29. The brominated block polymer according to claim 28, wherein, Based on the total weight of the brominated block polymer, the bromine content is 60-68 wt%.

30. The brominated block polymer according to claim 29, wherein, Based on the total weight of the brominated block polymer, the bromine content is 61-67 wt%.

31. The brominated block polymer according to claim 30, wherein, Based on the total weight of the brominated block polymer, the bromine content is 62-66 wt%.

32. The brominated block polymer according to claim 28 or 29, wherein, The number-average molecular weight of the brominated block polymer is 50,000-300,000. And / or, the molecular weight distribution of the brominated block polymer is 1-1.2; And / or, the 5wt% thermal weight loss temperature of the brominated block polymer is greater than or equal to 260°C; And / or, the glass transition temperature of the brominated block polymer is greater than or equal to 120°C.

33. The brominated block polymer according to claim 32, wherein, The number-average molecular weight of the brominated block polymer is 80,000-200,000; And / or, the molecular weight distribution of the brominated block polymer is 1.01-1.15; And / or, the 5wt% thermal weight loss temperature of the brominated block polymer is 260-270°C; And / or, the glass transition temperature of the brominated block polymer is 120-130°C.

34. The brominated block polymer according to claim 33, wherein, The brominated block polymer has a molecular weight distribution of 1.02-1.1; And / or, the 5wt% thermal weight loss temperature of the brominated block polymer is 262-268°C; And / or, the glass transition temperature of the brominated block polymer is 122-128°C.

35. The application of the brominated block polymer according to any one of claims 28-34 in exterior wall insulation flame retardants.

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