Preparation method of amido-functionalized SBS (styrene butadiene styrene) and amido-functionalized SEBS (styrene-ethylene-butylene-styrene)

Abstract

The invention discloses a preparation method of amido-functionalized SBS and amido-functionalized SEBS, and the preparation method of the amido-functionalized SBS comprises the following steps: carrying out polymerization reaction on a solvent, a styrene monomer, an amido-functionalized reagent and an initiator 1, and then carrying out end capping with butadiene to obtain a macromolecular amido-functionalized monomer; carrying out polymerization reaction on a solvent, a styrene monomer, a structure regulator and an initiator 2; butadiene is added for continuous reaction; and continuously adding the styrene monomer, and reacting again to obtain the amido-functionalized SBS glue solution. According to the invention, a macromolecular amido functionalized monomer is introduced to a polymerization terminal, and a functionalized group is connected to a main chain of SBS, so that the polarity of SBS and a hydrogenated product SEBS thereof is enhanced, and the problem of poor compatibility between a traditional hydrogenated polymer and polar resins such as polyethylene glycol benzoate (PET), acrylonitrile-butadiene-styrene copolymer (ABS) and nylon is solved.

Description

Technical Field

[0001] The present invention belongs to the technical field of hydrogenated styrenic thermoplastic elastomers, and relates to a method for preparing amino-functionalized SBS and its hydrogenated product amino-functionalized SEBS through macromolecular amino-functionalized monomers. Background Art

[0002] SBS is a styrene-based thermoplastic elastomer with properties similar to rubber. SBS can be used as a polymer modifier. When added in small amounts and blended with resins such as polypropylene (PP), polyethylene (PE), polystyrene (PS), and polyvinyl chloride (PVC) respectively, it can improve the impact resistance and low-temperature performance of the materials, and is widely used in automotive steering wheels, bumpers, and seals, etc. However, since SBS is a weakly polar polymer, its compatibility with materials such as polypropylene and polyvinyl chloride is not ideal enough. By introducing other comonomers to synthesize polar-functionalized SBS, more excellent properties can be endued to it. Polar SBS is a new type of thermoplastic elastomer, which is synthesized by an anionic polymerization method, that is, after the polymerization of the initiator segment or the third segment of SBS is completed, a polar monomer is added to continue the polymerization, thereby introducing the polar monomer to the end of the SBS molecular chain, and finally synthesizing a new type of multi-block copolymer of styrene-butadiene-styrene polar monomer.

[0003] Styrene-ethylene / butylene-styrene (SEBS) is a styrenic thermoplastic elastomer. There are soft and hard segments in the molecular chain of this elastic material, and it has the characteristic of interpenetrating soft and hard phases in the material matrix. At room temperature, the hard segments act as crosslinking points to inhibit the flow of the soft segments, and the material shows high elasticity; at high temperature, the hard segments flow, and the material as a whole shows thermoplasticity. Such materials are prepared by hydrogenation modification of styrene-butadiene-styrene (SBS). Since the hydrogenation reaction eliminates the unstable double bonds in SBS, SEBS not only has the plasticity, high elasticity and high strength of SBS, but also has excellent aging resistance. In addition to the properties of thermoplastic elastomers, due to the molecular polarity of polar SEBS, its adhesion and compatibility stability with other materials can be improved, and it can be better applied to industries such as adhesives, plastic toughening modifiers, asphalt modification, and shoemaking.

[0004] Currently, the preparation method of SEBS is mainly obtained by selective hydrogenation of the polymer SBS. Selective hydrogenation means that the diene segment in SDS is mainly hydrogenated (the hydrogenation degree is generally greater than 90%), while the benzene ring of the polystyrene segment is basically not hydrogenated (the hydrogenation degree is less than 10%). Traditional hydrogenation catalysts include heterogeneous catalytic systems and homogeneous catalyst systems. Heterogeneous catalytic systems such as nickel, molybdenum, palladium, platinum, etc. supported on diatomaceous earth have large catalyst consumption, high hydrogen pressure and reaction temperature, difficult reaction control, poor reproducibility, low hydrogenation selectivity, and are prone to benzene ring hydrogenation, polymer decomposition or coking. Therefore, homogeneous hydrogenation systems are currently used for SEBS hydrogenation catalysts.

[0005] Homogeneous catalyst systems are widely used in the hydrogenation of SBS and SIS because of their low catalyst consumption, high activity, low hydrogen pressure and reaction temperature, and good selectivity. Homogeneous hydrogenation catalysts are mainly based on nickel / cobalt systems and metallocene titanium systems. The metallocene hydrogenation catalytic process, represented by dicyclopentadienyl titanium dichloride, is the most active catalytic system in the current research on SBS hydrogenation. Because metallocenes have high activity, low concentration, and small dosage, the residual ash content in the final polymer product is extremely low. When used in low-end applications, the purification and removal process can be omitted, simplifying the process flow and saving investment. However, in recent years, with the rapid development of new energy vehicles, especially the short supply of lithium batteries, the price of raw material lithium has skyrocketed, making the cost advantage of metallocene titanium no longer exist. At the same time, when SEBS is used in high-end applications, the metal ions remaining in the glue solution must also be removed, which is equivalent to the nickel-based catalytic system process. The nickel-based catalytic system is a hydrogenation catalytic system with relatively high popularity in recent years because it can be used not only for the hydrogenation of SBS but also for the hydrogenation of SIS, and has a wide adaptability.

[0006] Chinese Patent CN201510974228.5 discloses a functionalized SEBS material and its preparation method. The material is made of the following components in parts by weight: SEBS, azide compound, dicumyl peroxide, antioxidant, ethylene bisstearamide. After functionalizing SEBS, the tensile strength and elongation at break are improved, and it also becomes polar, increasing the application fields. However, this technology is a product obtained by physically blending ordinary SEBS with functionalizing reagents through a post-processing method, and it only involves physical blending.

[0007] Chinese Patent CN202010668717.9 discloses a silicone-oxygen / amino-functionalized SEBS and its preparation method. The functionalized SEBS is a hydride of a silicone-oxygen / amino-functionalized thermoplastic elastomer SBS, and its number average molecular weight is 1×10 4 -1×10 6, with a molecular weight distribution of 1.0 - 1.5. By mass percentage, the content of styrene units is 0 - 50%, and the content of butadiene units is 50 - 100%. Each molecular chain contains 1 - 20 siloxane / amino groups. The siloxane / amino-functionalized SEBS obtained by this technology significantly improves the compatibility with polar materials and remarkably enhances the toughness and impact resistance of the composite material on the premise of excellent thermal-oxidative stability; however, this technology prepares end-chain or mid-chain amino / siloxane-functionalized SEBS through DPE derivatives. Since there are no industrial products of DPE derivatives, they are expensive and difficult to obtain, so this technology mainly focuses on laboratory research and cannot be used in actual industrial production processes. Summary of the Invention

[0008] The technical problem to be solved by the present invention is to introduce macromolecular amino-functionalized monomers onto the polymerization chain, graft functionalized groups onto the main chain of SBS, enhance the polarity of SBS and its hydrogenated product SEBS, and solve the problem of poor compatibility between traditional hydrogenated polymers and polar resins such as polyethylene glycol benzoate (PET), acrylonitrile-butadiene-styrene copolymer (ABS), and nylon.

[0009] To solve the problems existing in the prior art, the present invention provides a preparation method of amino-functionalized SBS, which includes the following steps:

[0010] (1) Polymerize a solvent, styrene monomer, amino-functionalized reagent, and initiator 1, and then cap with butadiene to obtain a macromolecular amino-functionalized monomer;

[0011] (2) Polymerize a solvent, styrene monomer, structure regulator, and initiator 2;

[0012] (3) Add butadiene to the product of step (2) and continue the reaction;

[0013] (4) Subsequently, add styrene monomer to the product of step (3) and react again to obtain an amino-functionalized SBS solution;

[0014] Among them, the macromolecular amino-functionalized monomer obtained in step (1) is added in step (2), or added together with the styrene monomer in step (4), or added separately after the reaction in step (4).

[0015] For the preparation method of amino-functionalized SBS of the present invention, the general structural formula of the macromolecular amino-functionalized monomer is as follows:

[0016]

[0017] Among them, x, y, a, and b are the same or different and are each independently selected from integers of 1 - 3; R1, R2, R3, R4 identical or different, each independently selected from C 1 -C 10 alkyl, C 1 -C 10 cycloalkane; n is the number of repeating units, a positive integer where n ≥ 1; B is a capped 1,3-butadiene; the number average molecular weight (Mn) of the macromolecular amino-functionalized monomer is 5000 - 7000.

[0018] For the preparation method of the amino-functionalized SBS of the present invention, the amino-functionalizing reagent is selected from at least one of 4-vinylbenzylpyrrolidine, 4-vinyl-N-(1-methylpropyl)-N-phenylbenzylamine, N-4-vinylphenyl-N,N-dimethylamine, 4-vinyl-N,N-diethylbenzylamine, N,N-dimethylvinylbenzylamine, 4-vinyl-N,N-dipropylbenzylamine, N,N-dibutyl-4-vinylbenzylamine, 4-vinyl-N-propylbenzylamine, 1-[(4-vinylphenyl)methyl]piperidine, 4-(N-hexamethyleneiminomethyl)benzene.

[0019] For the preparation method of the amino-functionalized SBS of the present invention, in step (1), the mass ratio of the solvent, styrene monomer, amino-functionalizing reagent, initiator 1 and butadiene is (300 - 500):(30 - 40):(60 - 70):(0.08 - 0.15):(1 - 3).

[0020] For the preparation method of the amino-functionalized SBS of the present invention, the addition amount of the macromolecular amino-functionalized monomer is 3 - 7 wt% of the mass of the styrene monomer.

[0021] For the preparation method of the amino-functionalized SBS of the present invention, the amino-functionalized SBS is at least one of a linear triblock, a linear diblock and a star polymer.

[0022] For the preparation method of the amino-functionalized SBS of the present invention, a coupling agent needs to be added in step (2) during the preparation of the star polymer, and the coupling agent is at least one of a polyvinyl compound, a halide, an ether, an aldehyde, a ketone, an ester.

[0023] The coupling agent is at least one of divinylbenzene, tetravinylsilane, carbon tetrachloride, silicon tetrachloride, tin tetrachloride, dimethyl terephthalate. Preferably divinylbenzene, silicon tetrachloride or tin tetrachloride.

[0024] The molar ratio of the amount of the coupling agent used to initiator 2 is 0.1 - 2.

[0025] The addition sequence of the macromolecular amino-functionalized monomer of the present invention is not particularly limited. The macromolecular amino-functionalized monomer can be added during the polymerization of styrene in step (2), or during the polymerization of styrene in step (4), or after the polymerization of styrene in step (4) is completed. When adding the macromolecular amino-functionalized monomer, it can be added after the styrene monomer has reacted, or it can be added together after being blended with the styrene monomer.

[0026] For the preparation method of amino-functionalized SBS of the present invention, the solvent includes at least one of aromatic hydrocarbons, aliphatic alkanes, and cycloalkanes.

[0027] Preferably, the aromatic hydrocarbon includes at least one of benzene, toluene, and ethylbenzene.

[0028] Preferably, the aliphatic alkane includes at least one of pentane, hexane, heptane, and octane.

[0029] Preferably, the cycloalkane includes at least one of cyclopentane and cyclohexane.

[0030] Preferably, the solvent is cyclopentane and cyclohexane.

[0031] For the preparation method of amino-functionalized SBS of the present invention, in step (2), the addition amount of the solvent is 300wt% - 1000wt% of the total mass of the styrene monomer and the butadiene monomer.

[0032] For the preparation method of amino-functionalized SBS of the present invention, the initiator 1 is a redox initiator, selected from cumene hydroperoxide, diisopropylbenzene hydroperoxide, tert-butyl peroxyisopropyl carbonate, and n-butyl peroxyisopropyl carbonate, and preferably diisopropylbenzene hydroperoxide. The dosage of the initiator 1 is the conventional dosage in the art, and its addition amount is preferably 0.05 - 0.20 parts, more preferably 0.08 - 0.15 parts, based on 100 parts by mass of the total mass of the styrene monomer and the butadiene monomer in step (1).

[0033] For the preparation method of amino-functionalized SBS of the present invention, the initiator 2 is selected from at least one of n-butyllithium, sec-butyllithium, tert-butyllithium, and hexyllithium, and preferably n-butyllithium.

[0034] For the preparation method of amino-functionalized SBS of the present invention, the dosage of the initiator 2 is 0.2 - 3 mmol per 100 grams of the total monomer, and the total monomer refers to the sum of the styrene monomer and the butadiene.

[0035] For the preparation method of amino-functionalized SBS of the present invention, the structure regulator is a heterocyclic organic compound containing nitrogen, oxygen, etc. with a certain polarity, selected from at least one of tetrahydrofuran, ethyl tetrahydrofurfuryl ether, tetramethyldivinyldiamine, tetrahydrofurfuryl alcohol, and diethylene glycol dimethyl ether (2G).

[0036] The preparation method of the amino-functionalized SBS of the present invention, the addition amount of the structure regulator is 20 wt% to 2000 wt% of initiator 2.

[0037] The structure regulator can adjust the vinyl content of butadiene to be between 25% and 65%, and at the same time can cause polarization or solvation effect to initiator 2, reduce its degree of association, and increase the initiation reaction rate of initiator 2 such as n-butyllithium. The present invention does not particularly limit the source of the structure regulator, and it can be a commercially available product or prepared by a conventional method in the art.

[0038] The preparation method of the amino-functionalized SBS of the present invention, in step (1), the temperature of the polymerization reaction is 50 - 80 °C, preferably 55 - 75 °C, the time is 20 - 80 min, preferably 30 - 50 min; the capping reaction time is 10 - 20 min.

[0039] The preparation method of the amino-functionalized SBS of the present invention, in step (2), the temperature of the polymerization reaction is 40 - 80 °C, preferably 45 - 55 °C, the time is 10 - 60 min, preferably 30 - 40 min.

[0040] The preparation method of the amino-functionalized SBS of the present invention, in step (3), the temperature of the reaction is 40 - 80 °C, preferably 50 - 60 °C, the time is 10 - 80 min, preferably 50 - 60 min.

[0041] The preparation method of the amino-functionalized SBS of the present invention, in step (4), the temperature of the reaction is 50 - 80 °C, preferably 55 - 65 °C, the time is 10 - 60 min, preferably 30 - 40 min.

[0042] The present invention also provides a preparation method of amino-functionalized SEBS, and this preparation method includes the following steps:

[0043] Adding the amino-functionalized SBS glue solution into a hydrogenation kettle, adding a homogeneous hydrogenation catalyst and hydrogen, reacting to obtain an amino-functionalized SEBS glue solution; subjecting the amino-functionalized SEBS glue solution to demetallization and post-treatment to obtain amino-functionalized SEBS.

[0044] The present invention does not particularly limit the type of the hydrogenation catalyst, and the homogeneous hydrogenation catalyst includes but is not limited to a hydrogenation catalyst containing a Group VIII metal, a metallocene titanium-based hydrogenation catalyst or a hydrogenation catalyst containing a noble metal.

[0045] The Group VIII metal is selected from at least one of iron, cobalt, and nickel.

[0046] The preparation method of the amino-functionalized SEBS of the present invention, wherein the homogeneous hydrogenation catalyst is a nickel-based homogeneous hydrogenation catalyst, and the preparation method of the nickel-based homogeneous hydrogenation catalyst is not particularly limited. Preferably, the preparation method of the nickel-based homogeneous hydrogenation catalyst comprises the following steps:

[0047] Dissolve the main catalyst in a solvent, stir, and then add the cocatalyst, and carry out reaction aging to obtain the nickel-based homogeneous hydrogenation catalyst.

[0048] The nickel-based homogeneous hydrogenation catalyst is prepared by reacting and aging the main catalyst and the cocatalyst;

[0049] The main catalyst is at least one of nickel naphthenate, nickel isooctanoate, nickel 2-ethylhexanoate, nickel acetylacetonate, nickel carbonyl, preferably at least one of nickel naphthenate and nickel isooctanoate; the cocatalyst is at least one of n-butyllithium, sec-butyllithium, ethylmagnesium bromide, benzylmagnesium chloride, phenylmagnesium bromide, triethylaluminum, triisobutylaluminum, diethylzinc, preferably at least one of triethylaluminum and triisobutylaluminum.

[0050] In the preparation method of the amino-functionalized SEBS of the present invention, the molar ratio of the addition amounts of the main catalyst and the cocatalyst is 1:2 - 6.

[0051] In the preparation method of the amino-functionalized SEBS of the present invention, the molar ratio of the addition amounts of the main catalyst and the cocatalyst is 1:3 - 4.

[0052] In the preparation method of the amino-functionalized SEBS of the present invention, the temperature of the reaction aging is 40°C to 60°C, preferably 45°C to 55°C, the pressure is 0.1 MPa to 0.60 MPa, preferably 0.2 - 0.4 MPa, and the time is 10 min to 30 min, preferably 20 min to 25 min.

[0053] In the preparation method of the amino-functionalized SEBS of the present invention, the mass ratio of the main catalyst to the volume of the solvent is 10 - 40 g:1 L, preferably 20 - 30 g:1 L.

[0054] In the preparation method of the amino-functionalized SEBS of the present invention, a third component is further added and aging is continued. The third component is at least one of phenylsilane, p-tolyltrimethylsilane, methylphenylsilanol, methyldiphenylsilanol, triphenylsilane, diphenylsilane, trimethylphenylsilane, 1,4-bis(dimethylhydroxysilyl)benzene, and unsubstituted C4 - C10 monohydric and polyhydric alcohols, preferably at least one of phenylsilane and methyldiphenylsilanol.

[0055] In the preparation method of the amino-functionalized SEBS of the present invention, the molar ratio of the addition amounts of the main catalyst and the third component is 1:1 - 3.

[0056] The preparation method of the amino-functionalized SEBS of the present invention, wherein the time for continued aging is 5 min to 15 min.

[0057] The preparation method of the amino-functionalized SEBS of the present invention, wherein the remaining rate of olefin double bonds in the product obtained after the reaction is not more than 5 wt%, preferably not more than 3 wt%, and the content of unsaturated benzene rings is not less than 95 wt%, preferably not less than 98 wt%.

[0058] The preparation method of the amino-functionalized SEBS of the present invention, wherein the post-treatment process is to add an antioxidant.

[0059] The preparation method of the amino-functionalized SEBS of the present invention, wherein the antioxidant is at least one of 1520L, 1076, 1010, 264, TNPP, and triisopropanolamine, preferably 1520L, and the addition amount is 0.5 to 5 wt%, preferably 0.5 to 2 wt%.

[0060] The preparation method of the amino-functionalized SEBS of the present invention, wherein the separation of the amino-functionalized SEBS from the solution can adopt the traditional stripping and coagulation method or a devolatilization type screw extruder.

[0061] The preparation method of the amino-functionalized SBS or the amino-functionalized SEBS of the present invention, wherein the preparation method is carried out in an oxygen-free and water-free environment and belongs to solution polymerization.

[0062] By the macromolecular amino-functionalized monomer of the present invention, phenyl and amino are integrated on a macromolecular chain. This structure fully exerts the "group effect" and "accumulation effect" in the process of preparing amino-functionalized SBS and amino-functionalized SEBS, so that the modification effect is very remarkable in improving the polarity and strength of SBS and SEBS with a low addition amount. It can not only be compatible with non-polar resins, but also be blended with polar resins, thereby significantly improving the toughness and impact resistance of the composite material. Description of the Drawings

[0063] Figure 1 1H NMR spectrum of the amino-functionalized SEBS of Example 1. Detailed Description of the Invention

[0064] The following examples are selected to further illustrate the method of the present invention, but should not be limited thereto in practical applications.

[0065] In the examples, the polymer was characterized using the following instruments; US Varian INOVA400 NMR nuclear magnetic resonance was used. 11H-NMR was used for qualitative and quantitative analysis of the copolymer composition sequence distribution, microstructure, and hydrogenation degree; a TDA302 gel permeation chromatograph (GPC) from Viscotek Corporation, USA was used to analyze the molecular weight of the copolymer; a 4465 universal material testing machine produced by Instron Corporation, USA was used for mechanical property testing; the tensile strength and elongation at break were tested according to GB / T 528-2009; the volume resistivity at 20 °C was tested according to GBT 1410-2006.

[0066] Example 1

[0067] (1) In a polymerization kettle evacuated and replaced with argon, 300 g of cyclopentane, 30 g of styrene, and 70 g of 4-vinylbenzylpyrrolidine were added. When the temperature rose to 55 °C, 0.06 g of dicumyl peroxide was added to initiate polymerization. After reacting for 30 min, 1 g of butadiene was added for a capping reaction for 10 min to obtain a macromolecular amino-functionalized monomer (Mn = 5500).

[0068] (2) In a 3 L polymerization kettle evacuated and replaced with argon, 1300 g of cyclopentane, 25 g of styrene, 1.4 mL of ethyltetrahydrofurfuryl ether, 1.2 mL of the macromolecular amino-functionalized monomer, and 50 g of solvent were rinsed. When the temperature rose to 50 °C, 2.1 mL of n-butyllithium was added to initiate polymerization, and the reaction was carried out for 40 min; then 120 g of butadiene was added and the reaction continued for 60 min; then 25 g of styrene was added and the reaction was carried out for 40 min to obtain an amino-functionalized SBS latex.

[0069] (3) The obtained amino-functionalized SBS latex was transferred to a hydrogenation kettle, and a well-aged homogeneous nickel-based hydrogenation catalyst (Ni dosage 0.03 g / 100 g SBS, Ni / Al molar ratio = 1:3) was added. Stirring was started, and when the temperature rose to 60 °C, hydrogen was introduced, and the pressure was maintained at 2.0 MPa. The reaction was carried out for 3 h. The amino-functionalized SEBS latex was subjected to demetallization, antioxidant 1520L was added, and then devolatilization and drying were carried out to obtain an amino-functionalized SEBS product L1.

[0070] The indicators and application results of the amino-functionalized SEBS product are shown in Table 1.

[0071] Comparative Example 1

[0072] (1) In a 3 L polymerization kettle evacuated and replaced with argon, 1300 g of cyclopentane, 25 g of styrene, 1.4 mL of ethyltetrahydrofurfuryl ether, and 50 g of solvent were rinsed. When the temperature rose to 50 °C, 2.1 mL of n-butyllithium was added to initiate polymerization, and the reaction was carried out for 40 min; then 120 g of butadiene was added and the reaction continued for 60 min; then 25 g of styrene was added and the reaction was carried out for 40 min to obtain an SBS latex.

[0073] (2) Transfer the obtained SBS solution to a hydrogenation reactor, add the aged homogeneous nickel-based hydrogenation catalyst (Ni dosage: 0.03 g / 100 g SBS, Ni / Al molar ratio = 1:3), start stirring, when the temperature rises to 60 °C, introduce hydrogen, maintain the pressure at 2.0 MPa, react for 3 h, subject the SEBS solution to demetallization, add antioxidant 1520L, and then remove volatiles and dry to obtain SEBS product C1.

[0074] The indicators and application results of the SEBS products are shown in Table 1.

[0075] Example 2

[0076] According to the method of Example 1, the difference is that in step (2), "1.8 mL of macromolecular amino-functionalized monomer" is used to replace "1.2 mL of macromolecular amino-functionalized monomer" to obtain amino-functionalized SEBS product L2.

[0077] The indicators and application results of the amino-functionalized SEBS products are shown in Table 1.

[0078] Example 3

[0079] According to the method of Example 1, the difference is that in step (2), "2.16 mL of macromolecular amino-functionalized monomer" is used to replace "1.2 mL of macromolecular amino-functionalized monomer" to obtain amino-functionalized SEBS product L3.

[0080] The indicators and application results of the amino-functionalized SEBS products are shown in Table 1.

[0081] Example 4

[0082] According to the method of Example 2, the difference is that in step (2), "25 g of styrene" is used to replace "25 g of styrene, 1.2 mL of macromolecular amino-functionalized monomer", and in step (2), "subsequently add 25 g of styrene and 1.2 mL of macromolecular amino-functionalized monomer and react for 40 min" is used to replace "subsequently add 25 g of styrene and react for 40 min" to obtain amino-functionalized SEBS product L4.

[0083] The indicators and application results of the amino-functionalized SEBS products are shown in Table 1.

[0084] Example 5

[0085] According to the method of Example 1, the difference is that in step (1), "70 g of N,N-dimethylvinylbenzylamine" is used to replace "70 g of 4-vinylbenzylpyrrolidine" to obtain amino-functionalized SEBS product L5.

[0086] The indicators and application results of the amino-functionalized SEBS products are shown in Table 1.

[0087] Example 6

[0088] According to the method of Example 2, the difference is that in step (1), "70 g of N-4-vinylphenyl-N,N-dimethylamine" is used to replace "70 g of 4-vinylbenzylpyrrolidine", and the amino-functionalized SEBS product L6 is obtained.

[0089] The indexes and application results of the amino-functionalized SEBS product are shown in Table 1.

[0090] Example 7

[0091] According to the method of Example 2, the difference is that in step (1), "70 g of 4-vinyl-N-(1-methylpropyl)-N-phenylbenzylamine" is used to replace "70 g of 4-vinylbenzylpyrrolidine", and the amino-functionalized SEBS product L7 is obtained.

[0092] The indexes and application results of the amino-functionalized SEBS product are shown in Table 1.

[0093] Example 8

[0094] According to the method of Example 2, the difference is that in step (1), "70 g of 1-[(4-vinylphenyl)methyl]piperidine" is used to replace "70 g of 4-vinylbenzylpyrrolidine", and the amino-functionalized SEBS product L8 is obtained.

[0095] The indexes and application results of the amino-functionalized SEBS product are shown in Table 1.

[0096] Example 9

[0097] According to the method of Example 2, the difference is that in step (2), "when the temperature rises to 60 °C" is used to replace "when the temperature rises to 50 °C", and the amino-functionalized SEBS product L9 is obtained.

[0098] The indexes and application results of the amino-functionalized SEBS product are shown in Table 1.

[0099] Example 10

[0100] According to the method of Example 2, the difference is that in step (2), "when the temperature rises to 40 °C" is used to replace "when the temperature rises to 50 °C", and the amino-functionalized SEBS product L10 is obtained.

[0101] The indexes and application results of the amino-functionalized SEBS product are shown in Table 1.

[0102] Example 11

[0103] According to the method of Example 2, except that in step (2), "adding 3.5 mL of n-butyllithium to initiate polymerization" is used to replace "adding 2.1 mL of n-butyllithium to initiate polymerization", the amino-functionalized SEBS product L11 is obtained.

[0104] The indexes and application results of the amino-functionalized SEBS products are shown in Table 1.

[0105] Example 12

[0106] According to the method of Example 1, except that in step (1), "40 g of styrene and 60 g of 4-vinylbenzylpyrrolidine" are used to replace "30 g of styrene and 70 g of 4-vinylbenzylpyrrolidine", the amino-functionalized SEBS product L12 is obtained.

[0107] The indexes and application results of the amino-functionalized SEBS products are shown in Table 1.

[0108] Example 13

[0109] According to the method of Example 1, except that in step (1), "adding 3 g of butadiene for capping reaction for 10 min" is used to replace "adding 1 g of butadiene for capping reaction for 10 min", the amino-functionalized SEBS product L13 is obtained.

[0110] The indexes and application results of the amino-functionalized SEBS products are shown in Table 1.

[0111] Table 1 Indexes and application results of amino-functionalized SEBS products

[0112]

[0113] It can be seen from the results of CI to L13 that when SEBS is amino-functionalized, with the increase of polarity, the tensile strength and elongation at break increase to a certain extent, and the volume resistivity decreases significantly. Of course, the stronger the polarity, a small part of the mechanical properties may be lost. The larger the molecular weight, the lower the capping efficiency of the functional groups.

[0114] 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 technical concept of the present invention, various simple modifications can be made to the technical solutions of the present invention, including any other suitable combination of each technical feature. These simple modifications and combinations should also be regarded as the content disclosed by the present invention and fall within the protection scope of the present invention.

Claims

1. A preparation method of amino-functionalized SBS, characterized in that, it comprises the following steps: (1) Polymerize a solvent, styrene monomer, amino-functionalizing reagent, and initiator 1, and then cap with butadiene to obtain a macromolecular amino-functionalized monomer; (2) Polymerize a solvent, styrene monomer, structure regulator, and initiator 2; (3) Add butadiene to the product of step (2) and continue the reaction; (4) Subsequently, add styrene monomer to the product of step (3) and react again to obtain an amino-functionalized SBS solution; wherein, the macromolecular amino-functionalized monomer obtained in step (1) is added in step (2), or added together with the styrene monomer in step (4), or added separately after the reaction in step (4).

2. The preparation method of amino-functionalized SBS according to claim 1, characterized in that, the general structural formula of the macromolecular amino-functionalized monomer is as follows: wherein x, y, a, and b are the same or different and are each independently selected from integers of 1 to 3; R 1 , R 2 , R 3 , R 4 are the same or different and are each independently selected from C 1 -C 10 alkyl groups, C 1 -C 10 cycloalkanes; n is the number of repeating units, a positive integer of n≥1; B is a capped 1,3-butadiene; the number average molecular weight (Mn) of the macromolecular amino-functionalized monomer is 5000 to 7000.

3. The preparation method of amino-functionalized SBS according to claim 1, characterized in that, the amino-functionalizing reagent is selected from at least one of 4-vinylbenzylpyrrolidine, 4-vinyl-N-(1-methylpropyl)-N-phenylbenzylamine, N-4-vinylphenyl-N,N-dimethylamine, 4-vinyl-N,N-diethylbenzylamine, N,N-dimethylvinylbenzylamine, 4-vinyl-N,N-dipropylbenzylamine, N,N-dibutyl-4-vinylbenzylamine, 4-vinyl-N-propylbenzylamine, 1-[(4-vinylphenyl)methyl]piperidine, 4-(N-hexamethyleneiminomethyl)benzene.

4. The preparation method of amino-functionalized SBS according to claim 1, characterized in that, in step (1), the mass ratio of the solvent, styrene monomer, amino-functionalizing reagent, initiator 1, and butadiene is (300-500):(30-40):(60-70):(0.08-0.15):(1-3).

5. The preparation method of amino-functionalized SBS according to claim 1, characterized in that, the addition amount of the macromolecular amino-functionalized monomer is 3-7 wt% of the mass of the styrene monomer.

6. The preparation method of amino-functionalized SBS according to claim 1, characterized in that, the amino-functionalized SBS is at least one of a linear triblock, a linear diblock, and a star polymer.

7. The preparation method of amino-functionalized SBS according to claim 1, characterized in that, a coupling agent needs to be added in step (2) during the preparation of the star polymer, and the coupling agent is at least one of a polyvinyl compound, a halide, an ether, an aldehyde, a ketone, and an ester; preferably, the coupling agent is at least one of divinylbenzene, tetravinylsilane, carbon tetrachloride, silicon tetrachloride, tin tetrachloride, dimethyl terephthalate; the molar ratio of the amount of the coupling agent to initiator 2 is 0.1-2.

8. The preparation method of amino-functionalized SBS according to claim 1, characterized in that, the solvent comprises at least one of an aromatic hydrocarbon, an aliphatic alkane, and a cycloalkane; Preferably, the aromatic hydrocarbon includes at least one of benzene, toluene, and ethylbenzene; Preferably, the aliphatic alkane includes at least one of pentane, hexane, heptane, and octane; Preferably, the cycloalkane includes at least one of cyclopentane and cyclohexane; Preferably, the solvent is cyclopentane and cyclohexane; In step (2), the addition amount of the solvent is 300wt% - 1000wt% of the total mass of styrene monomer and butadiene monomer.

9. The preparation method of the amino-functionalized SBS according to claim 1, characterized in that the initiator 1 is selected from one of cumene hydroperoxide, diisopropylbenzene hydroperoxide, tert-butyl isopropyl peroxide, and n-butyl isopropyl peroxide; the addition amount of the initiator 1 is 0.05 - 0.20 parts based on 100 parts of the total mass of styrene monomer and butadiene monomer in step (1).

10. The preparation method of the amino-functionalized SBS according to claim 1, characterized in that the initiator 2 is selected from at least one of n-butyllithium, sec-butyllithium, tert-butyllithium, and hexyllithium; the dosage of the initiator 2 is 0.2 - 3 mmol per 100 grams of the total monomer.

11. The preparation method of the amino-functionalized SBS according to claim 1, characterized in that the structure regulator is selected from at least one of tetrahydrofuran, ethyltetrahydrofurfuryl ether, tetramethyldivinyldiamine, tetrahydrofurfuryl alcohol, and diethylene glycol dimethyl ether (2G); the addition amount of the structure regulator is 20wt% - 2000wt% of the initiator 2.

12. The preparation method of the amino-functionalized SBS according to claim 1, characterized in that in step (1), the temperature of the polymerization reaction is 50 - 80°C, and the time is 20 - 80 min; the reaction time for capping is 10 - 20 min; in step (2), the temperature of the polymerization reaction is 40 - 80°C, and the time is 10 - 60 min; in step (3), the temperature of the reaction is 40 - 80°C, and the time is 10 - 80 min; in step (4), the temperature of the reaction is 50 - 80°C, and the time is 10 - 60 min.

13. A preparation method of amino-functionalized SEBS, characterized in that comprises the following steps: Adding the amino-functionalized SBS rubber solution according to any one of claims 1 - 12 into a hydrogenation kettle, adding a homogeneous hydrogenation catalyst and hydrogen, reacting to obtain an amino-functionalized SEBS rubber solution; subjecting the amino-functionalized SEBS rubber solution to demetallization and post-treatment to obtain amino-functionalized SEBS.

14. The preparation method of the amino-functionalized SEBS according to claim 13, characterized in that the homogeneous hydrogenation catalyst is a hydrogenation catalyst containing a Group VIII metal, a metallocene titanium-based hydrogenation catalyst, or a hydrogenation catalyst containing a noble metal; the Group VIII metal is selected from at least one of iron, cobalt, and nickel.

15. The preparation method of the amino-functionalized SEBS according to claim 13, characterized in that the process of the post-treatment is adding an antioxidant; the antioxidant is selected from at least one of 1520L, 1076, 1010, 264, TNPP, and triisopropanolamine.

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