CN-121991309-A - Preparation method of styrene thermoplastic elastomer

Abstract

The invention relates to a preparation method of a styrene thermoplastic elastomer, which comprises the steps of firstly adding an aliphatic hydrocarbon solvent, monovinylarene and an initiator to perform a first-stage anionic polymerization reaction, then dissolving an alkoxy potassium compound by an ether amine regulator A to obtain a randomizing reagent solution, adding the randomizing reagent solution and the ether amine regulator B into a polymerization solution which completes the first-stage reaction, adding monovinylarene and conjugated diene to perform an intermediate-stage polymerization reaction, then adding monovinylarene into a glue solution which completes the intermediate-stage polymerization reaction to perform a third-stage polymerization reaction, adding a catalyst into the glue solution after the reaction is completed to hydrogenate unsaturated double bonds of the intermediate-stage conjugated diene to obtain a hydrogenated styrene thermoplastic elastomer glue solution, and performing condensation to obtain a target intermediate-stage styrene thermoplastic elastomer. The invention solves the dispersion problem of randomizing agent in anion polymerization system and solves the industrialization problem of special middle TPS product.

Inventors

• LIU DONG
• ZHAO SHUAI
• JIN YONGHUI
• JIANG XIANGBAO
• YANG JUN
• TANG JIE
• SHI JUNYAN

Assignees

• 浙江众立合成材料科技股份有限公司

Dates

Publication Date

20260508

Application Date

20251223

Claims (10)

1. 1. The preparation method of the styrene thermoplastic elastomer is characterized by comprising the following steps: (1) Under the protection of inert gas and in an anhydrous and anaerobic atmosphere, adding an aliphatic hydrocarbon solvent, monovinylarene and an initiator into a reaction device, heating and stirring to perform a first-stage anionic polymerization reaction; (2) Adding the randomizing reagent solution and the ether amine regulator B into a polymerization solution which completes the first-stage reaction, controlling the temperature, adding monovinylarene and conjugated diene, and carrying out intermediate-stage polymerization reaction; (3) Adding monovinylarene into the glue solution after finishing the intermediate polymerization reaction to perform the third polymerization reaction, adding catalyst into the glue solution after finishing the reaction to hydrogenate the intermediate conjugated diene unsaturated double bond to obtain hydrogenated styrene thermoplastic elastomer glue solution, and condensing to obtain the target intermediate styrene thermoplastic elastomer.
2. 2. The method for producing a styrenic thermoplastic elastomer according to claim 1, wherein in the step (1), the aliphatic hydrocarbon solvent is one or a mixture of cyclohexane and hexane.
3. 3. The method for producing a styrenic thermoplastic elastomer according to claim 1, wherein in the step (1), the initiator is one of n-butyllithium, sec-butyllithium and tert-butyllithium.
4. 4. The method for producing a styrene-based thermoplastic elastomer according to claim 1, wherein the monovinylarene is one or a combination of two or more of styrene, α -methylstyrene, 3-methylstyrene and 4-methylstyrene, and the conjugated diene is one or a combination of two or more of butadiene, isoprene, myrcene and farnesene.
5. 5. The preparation method of the styrene thermoplastic elastomer according to claim 1, wherein in the step (2), the ether amine regulator is ether amine containing a plurality of coordination sites, the number of the coordination sites is more than or equal to 3, and the alkoxy potassium compound is one or more of potassium tert-butoxide, potassium tert-amyl alcohol, potassium triethylmethoxide and potassium p-methylphenol.
6. 6. The method for producing a styrenic thermoplastic elastomer according to claim 5, wherein the number of coordination sites of the ether amine regulator A is not less than 5, and the number of coordination sites of the ether amine regulator B is not less than 3.
7. 7. The preparation method of the styrene thermoplastic elastomer according to claim 1, wherein in the step (2), the mass ratio of the ether amine regulator A to the alkoxy potassium compound is 10:1-3, and the mass ratio of the ether amine regulator B to the randomizing agent solution is 10:0.2-2.
8. 8. The method for producing a styrenic thermoplastic elastomer according to claim 1, wherein the reaction temperature in the step (2) is 60 to 70 ℃.
9. 9. The method for producing a styrene-based thermoplastic elastomer according to claim 1, wherein in the step (2), the mass ratio of monovinylarene to conjugated diene is 10:5 to 10.
10. 10. The method for producing a styrenic thermoplastic elastomer according to claim 1, wherein in the step (2), monovinylarene and conjugated diene are fed in 6 to 8 times simultaneously.

Description

Preparation method of styrene thermoplastic elastomer Technical Field The invention belongs to the technical field of polymerization and modification of high polymer materials, and particularly relates to a preparation method of a styrene thermoplastic elastomer. Background The unique phase separation structure imparts excellent mechanical properties and high elasticity to styrenic thermoplastic elastomers (TPS) due to the thermodynamic incompatibility of the polystyrene units and the poly conjugated diene units. However, this significant phase separation also affects TPS properties, e.g. the large size of the polystyrene phase region, the phase interface adversely affecting the optical properties of the material, ozone crack resistance. Meanwhile, the content of the traditional TPS polystyrene unit is not higher than 35%, otherwise, the material is too hard, the elasticity and the flexibility are reduced, and the high polystyrene unit content is a key way for solving the tear resistance, the wear resistance and the damping performance of the material. Therefore, introducing part of styrene into the TPS soft segment to realize random copolymerization of styrene and conjugated diene in the middle segment is the most effective method for balancing the service performance and flexibility of TPS, under the existing scheme, the randomness of styrene units is difficult to be improved to 60% under the condition that the mass ratio of styrene to butadiene in the middle segment is more than or equal to 1, and therefore, the regulation and control of the randomness of styrene and conjugated diene in the middle segment are the most critical factors for solving the problem. Chinese patent CN1209440A discloses a polymerization method of solution polymerized styrene-butadiene rubber, which uses 2-methyl-2-hexanol potassium as randomizing agent to carry out random copolymerization of styrene-butadiene, solves the problem of solubility of randomizing agent in solvent, but the randomizing agent has no industrial product, the scheme does not have industrial value, chinese patent CN102101902A discloses a preparation method of conjugated diene and monovinylarene random copolymer, and uses tetrahydrofurfuryl alcohol ether regulator and sodium dodecyl benzene sulfonate randomizing agent in a compound way, in the scheme, the solubility of sodium dodecyl benzene sulfonate in aliphatic hydrocarbon solvent is extremely poor, the interaction between tetrahydrofurfuryl alcohol ether regulator and active center is insufficient, and the intermediate vinyl growth is unstable at high temperature, which is unfavorable for preparing high vinyl styrene-butadiene copolymer. Disclosure of Invention In order to overcome the defects in the prior art, the invention provides a preparation method of a styrene thermoplastic elastomer. The method takes the etheramine as a structure regulator to dissolve the alkoxy metal compound, solves the dispersion problem of the randomizing agent in an anionic polymerization system, and simultaneously, the etheramine containing a plurality of coordination sites has stronger interaction with the active center of the anionic polymerization, reduces the temperature sensitivity of the regulation and control of the vinyl structure of the middle section, and solves the industrialization problem of the TPS product of the special middle section. In order to achieve the aim of the invention, the invention adopts the following technical scheme: A preparation method of a styrene thermoplastic elastomer comprises the following steps: (1) Under the protection of inert gas and in an anhydrous and anaerobic atmosphere, adding an aliphatic hydrocarbon solvent, monovinylarene and an initiator into a reaction device, heating and stirring to perform a first-stage anionic polymerization reaction; (2) Adding the randomizing reagent solution and the ether amine regulator B into a polymerization solution which completes the first-stage reaction, controlling the temperature, adding monovinylarene and conjugated diene, and carrying out intermediate-stage polymerization reaction; (3) Adding monovinylarene into the glue solution after finishing the intermediate polymerization reaction to perform the third polymerization reaction, adding catalyst into the glue solution after finishing the reaction to hydrogenate the intermediate conjugated diene unsaturated double bond to obtain hydrogenated styrene thermoplastic elastomer glue solution, and condensing to obtain the target intermediate styrene thermoplastic elastomer. Preferably, in the step (1), the aliphatic hydrocarbon solvent is one or a mixture of cyclohexane and hexane. Preferably, in the step (1), the initiator is one of n-butyllithium, sec-butyllithium and tert-butyllithium. Preferably, the monovinylarene is one or more than two of styrene, alpha-methylstyrene, 3-methylstyrene and 4-methylstyrene, and the conjugated diene is one or more than two of butadiene, isoprene, myrcene and f