阅读说明：本技术 改性引发剂的制备方法和制备装置 (Preparation method and preparation device of modified initiator ) 是由 李泰喆 李羲承 金鲁马 崔兴烈 罗六烈 于 2020-10-12 设计创作，主要内容包括：本发明涉及一种制备改性引发剂的方法,该方法能够将副反应减少至最小程度并且以高转化率得到改性引发剂；以及本发明涉及一种制备改性引发剂的装置,该装置用于进行所述制备改性引发剂的方法,其中,所述方法包括：(S1)使包含含有改性官能团的化合物和共轭二烯类单体的第一流体与包含含有聚合引发官能团的化合物的第二流体反应；和(S2)得到包含通过步骤S1的反应制备的改性引发剂的第三流体,其中,基于1摩尔的所述含有聚合引发官能团的化合物,所述含有改性官能团的化合物以大于1摩尔的比例使用；基于1摩尔的所述含有改性官能团的化合物,所述共轭二烯类单体以1摩尔至4摩尔的比例使用,并且步骤S1和步骤S2连续进行。(The present invention relates to a method for preparing a modified initiator, which is capable of minimizing side reactions and obtaining a modified initiator at a high conversion rate; and an apparatus for preparing a modification initiator for performing the method for preparing a modification initiator, wherein the method comprises: (S1) reacting a first fluid comprising the compound having the modifying functional group and the conjugated diene-based monomer with a second fluid comprising the compound having the polymerization initiating functional group; and (S2) obtaining a third fluid including the modification initiator prepared by the reaction of step S1, wherein the compound having a modifying functional group is used in a proportion of more than 1 mole based on 1 mole of the compound having a polymerization initiating functional group; the conjugated diene-based monomer is used in a ratio of 1 to 4 moles based on 1 mole of the modified functional group-containing compound, and step S1 and step S2 are continuously performed.)

1. A method of preparing a modified initiator, the method comprising:

s1, reacting a first fluid containing a compound having a modifying functional group and a conjugated diene monomer with a second fluid containing a compound having a polymerization initiating functional group; and

s2, obtaining a third fluid comprising the modified initiator prepared by the reaction of step S1, wherein:

the compound containing a modifying functional group is used in a proportion of more than 1 mole based on 1 mole of the compound containing a polymerization initiating functional group;

the conjugated diene-based monomer is used in a proportion of 1 to 4 moles based on 1 mole of the modified functional group-containing compound; and is

Step S1 and step S2 are continuously performed.

2. The method according to claim 1, wherein the compound containing a modifying functional group is used in a ratio of 1.5 to 10.0 moles based on 1 mole of the compound containing a polymerization initiating functional group.

3. The method according to claim 1, wherein the compound containing a modifying functional group is used in a ratio of 3.0 mol to 5.0 mol based on 1 mol of the compound containing a polymerization initiating functional group.

4. The method of claim 1, wherein at least one of the first fluid and the second fluid further comprises a polar additive.

5. The method according to claim 1, wherein the first fluid further comprises a polar additive, and the first fluid is prepared by sequentially and continuously mixing the modified functional group-containing compound, the conjugated diene-based monomer, and the polar additive.

6. The method of claim 1, wherein the reaction of step S1 is performed at-50 ℃ to 50 ℃.

7. The method according to claim 1, wherein step S1 is performed by adding a first fluid through the first fluid inlet and a second fluid through the second fluid inlet and mixing the first fluid and the second fluid into a reactor provided with the first fluid inlet and the second fluid inlet,

wherein, upon mixing, the flow rate of the first fluid and the flow rate of the second fluid remain constant and the flow rate of the first fluid increases.

8. The method of claim 7, wherein the flow of each fluid is laminar when the first and second fluids are added.

9. The method of claim 7, wherein the flow direction of the first fluid and the flow direction of the second fluid are perpendicular to each other when the first fluid and the second fluid are added.

10. An apparatus for preparing a modification initiator for carrying out the method for preparing a modification initiator according to claim 1, wherein the apparatus is a reactor provided with a first fluid inlet, a second fluid inlet, a mixing section in which the first fluid is mixed with the second fluid, and an outlet through which a third fluid is discharged.

11. The apparatus of claim 10, further comprising a deformation for increasing the flow rate of the first fluid.

Technical Field

[ Cross-reference to related applications ]

This application claims the benefit of korean patent application No.10-2019-0126517, filed in the korean intellectual property office at 10, 11, 2019, the disclosure of which is incorporated herein by reference in its entirety.

[ technical field ]

The present invention relates to a method for preparing a modified initiator capable of minimizing side reactions and obtaining a modified initiator at a high conversion rate, and a modified initiator preparation apparatus for performing the method.

Background

In accordance with recent demands for low fuel consumption of automobiles, there is a demand for a conjugated diene-based polymer as a rubber material for tires, wherein the polymer has low rolling resistance, excellent abrasion resistance and tensile properties, and control stability represented by wet resistance.

In order to reduce the rolling resistance of a tire, there is a method of reducing the hysteresis loss of a vulcanized rubber, and as an evaluation index of such a vulcanized rubber, rebound resilience at 50 ℃ to 80 ℃, tan δ, Goodrich heat generation (Goodrich heat generation), and the like are used. That is, a rubber material having a large rebound resilience at the above temperature, or having a low tan δ value or heat generation by Goodrich is preferable.

As rubber materials having a small hysteresis loss, natural rubber, polyisoprene rubber, polybutadiene rubber, and the like are known, but these have a problem of low wet resistance. Therefore, in recent years, conjugated diene-based polymers or copolymers such as styrene-butadiene rubber (hereinafter referred to as SBR) or butadiene rubber (hereinafter referred to as BR) have been produced by emulsion polymerization or solution polymerization and used as rubber for tires. In the above polymerization method, the solution polymerization has the greatest advantage over the emulsion polymerization that the vinyl structure content and the styrene content, which determine the physical properties of the rubber, can be arbitrarily adjusted, and the molecular weight, the physical properties, and the like of the rubber can be adjusted by coupling or modification. Therefore, the structure of the finally prepared SBR or BR can be easily changed, and the movement of the chain ends can be reduced by the coupling or modification of the chain ends and the coupling force with a filler such as silica or carbon black can be increased, and thus, the SBR prepared by solution polymerization is widely used as a rubber material for tires.

When such solution-polymerized SBR is used as a rubber material for tires, the content of vinyl groups in the SBR is increased to raise the glass transition temperature of the rubber to adjust physical properties required for tires such as running resistance and braking force, and further, the glass transition temperature can be appropriately adjusted to reduce fuel consumption. The solution-polymerized SBR is prepared using an anionic polymerization initiator, and is used by coupling or modifying chain ends of the formed polymer using various modifying agents. For example, U.S. patent No.4,397,994 discloses one of the following techniques: a coupling agent such as a tin compound is used to couple the living anions, and the anions at the chain ends of the polymer obtained by polymerizing styrene-butadiene in the presence of a non-polar solvent using an alkyllithium as a monofunctional initiator.

Meanwhile, carbon black and silica are used as reinforcing fillers for tire treads. When silica is used as the reinforcing filler, there is an advantage in that low hysteresis loss properties and wet road resistance are improved. However, silica of a hydrophilic surface has a disadvantage of low affinity with rubber and thus poor dispersibility, as compared with carbon black of a hydrophobic surface, and therefore, it is necessary to use a separate silane coupling agent to improve dispersibility or to impart coupling between silica and rubber. Therefore, there is a method of introducing a functional group having affinity or reactivity with silica into the end of a rubber molecule, but the effect of this method is insufficient.

In addition, as a method of introducing a functional group, a method of initiating polymerization by a modification initiator and introducing a functional group derived from the modification initiator at one end of a polymer has been proposed. Such a modification initiator is prepared by reacting a modifying group-containing substance with a polymerization initiating substance, and when the reaction is carried out, the ratio of the modifying group-containing substance to the polymerization initiating substance can be adjusted, thereby adjusting the ratio of units derived from the modifying group-containing substance in the prepared modification initiator. At this time, when the proportion of units derived from the modifying group-containing substance in the modification initiator is high, that is, when the modifying group-containing substance is used in excess compared with the polymerization initiating substance, the effect of introducing the functional group into the polymer becomes greater.

However, when the modifying group-containing substance is used in excess compared to the polymerization initiating substance, undesirable oligomers are excessively generated during the reaction due to anionic polymerization between reactants. Therefore, there are problems in that the reactor tube is clogged, which stops the reaction, thereby reducing the production efficiency of the modified initiator, and in that the reactants are not uniformly mixed, thereby reducing the conversion rate of the modified initiator. Therefore, it is required to develop a method capable of easily preparing a modification initiator having a high modification ratio without interrupting the reaction.

[ Prior art documents ]

(patent document 1) JP1994-271706A

Disclosure of Invention

Technical problem

An aspect of the present invention provides a method for preparing a modification initiator, which can obtain a modification initiator of a high modification ratio at a high conversion rate without a problem of excessively generating an oligomer to inhibit a reaction, and which is used in the preparation of a polymer and can simultaneously easily modify the polymer at a high modification ratio and easily initiate polymerization.

Another aspect of the present invention provides an apparatus for preparing a modification initiator, which is capable of performing the method for preparing a modification initiator of the present invention.

Technical scheme

According to an embodiment of the present invention, there is provided a method for preparing a modified initiator, the method including: reacting a first fluid comprising a compound containing a modifying functional group and a conjugated diene-based monomer with a second fluid comprising a compound containing a polymerization initiating functional group (S1); and obtaining a third fluid including the modification initiator prepared by the reaction of step S1, wherein the compound having the modification functional group is used in a ratio of more than 1 mole based on 1 mole of the compound having the polymerization initiating functional group, the conjugated diene-based monomer is used in a ratio of 1 to 4 moles based on 1 mole of the compound having the modification functional group, and steps S1 and S2 are continuously performed.

According to another aspect of the present invention, there is provided an apparatus for preparing a modification initiator for performing the above-mentioned method for preparing a modification initiator, wherein the apparatus is a reactor provided with a first fluid inlet, a second fluid inlet, a mixing part in which the first fluid is mixed with the second fluid, and an outlet through which a third fluid is discharged.

Advantageous effects

The preparation method of the modified initiator according to the present invention is performed by continuous reaction so that the ratio of the first fluid to the second fluid can be kept constant during the reaction, and thus, side reactions such as remaining non-reactants and remaining unmodified initiator can be minimized, thereby preparing the modified initiator with high conversion.

In addition, when the modification initiator is prepared, the method of preparing the modification initiator performs the reaction while maintaining an excess ratio of the compound having the modification functional group relative to the compound having the polymerization initiating functional group, to further improve the modification ratio. At this time, the compound having a modifying functional group and the conjugated diene-based monomer are mixed in advance and then are allowed to participate in the reaction, whereby solvent solubility can be excellent, and generation of excessive oligomers and reactor clogging due to the oligomers can be suppressed, and therefore, a modification initiator having a high modification rate can be easily prepared without lowering the conversion rate.

Detailed Description

Hereinafter, the present invention will be described in more detail to help understanding the present invention.

It should be understood that the words or terms used in the specification and claims of this invention should not be construed as having the meanings defined in commonly used dictionaries. It should also be understood that these words or terms should be interpreted as having meanings consistent with their meanings in the background of the related art and the technical idea of the present invention based on the principle that the inventor can appropriately define the meanings of the words or terms to best explain the present invention.

In the present invention, the term "modification initiator" may refer to a polymerization initiator used to initiate polymerization, and may refer to a polymerization initiator comprising a modification functional group of a polymer. The modification initiator may be, for example, a modification initiator for initiating polymerization of the conjugated diene-based polymer, and in this case, the modification initiator may have high activity and ensure sufficient randomness of the monomer.

In the present invention, the term "functional group-containing compound" may refer to a compound in which a functional group, which is an atomic group exhibiting a specific property, is substituted in a molecule.

In the present invention, the term "monovalent hydrocarbon group" may refer to a monovalent radical in which carbon is bonded to hydrogen, such as a monovalent alkyl group, alkenyl group, alkynyl group, cycloalkyl group, or aryl group containing one or more unsaturated bonds.

The present invention provides a method for preparing a modification initiator, which is capable of obtaining a modification initiator of a high modification ratio at a high conversion rate without the problem of excessively generating an oligomer to inhibit the reaction, and which is capable of simultaneously easily modifying a polymer at a high modification ratio and easily initiating polymerization.

The method for preparing the modified initiator according to the present invention comprises: reacting a first fluid comprising a compound containing a modifying functional group and a conjugated diene-based monomer with a second fluid comprising a compound containing a polymerization initiating functional group (S1); and obtaining a third fluid including the modification initiator prepared by the reaction of step S1, wherein the compound having the modification functional group is used in a ratio of more than 1 mole based on 1 mole of the compound having the polymerization initiating functional group, the conjugated diene-based monomer is used in a ratio of 1 to 4 moles based on 1 mole of the compound having the modification functional group, and steps S1 and S2 are continuously performed.

When the modified initiator is prepared according to the above-described method for preparing a modified initiator, the method is performed by a continuous reaction such that the first fluid and the second fluid can be kept constant at a desired ratio during the reaction, and thus, side reactions such as remaining non-reactants and remaining unmodified initiator can be minimized, thereby preparing the modified initiator at a high conversion rate.

In addition, in general, when the compound having the modifying functional group is reacted in an excess ratio relative to the compound having the polymerization initiating functional group, the compound having the modifying functional group and the compound having the polymerization initiating functional group are coupled in the form of an oligomer, so that a highly modified modification initiator having a high ratio of the modifying functional group can be formed. However, when a large amount of a compound containing a modifying functional group is present in the reactants, the polarity increases, so that the solubility of the solvent decreases, and oligomers are excessively generated, whereby there may be a problem of reactor clogging or the like, which prevents the reaction from continuing. However, the method for preparing a modified initiator according to the present invention mixes a compound having a modifying functional group with a conjugated diene-based monomer in advance and then reacts the mixture with a compound having a polymerization initiating functional group, so that the solubility of a solvent is improved, thereby enabling the reaction to be continuously performed. Further, the generation of excessive oligomers and the clogging of the reactor due to the oligomers can be suppressed, and therefore, a modification initiator having a high modification ratio with a high proportion of modified functional groups and excellent solvent solubility can be prepared.

The compound having a modifying functional group is a compound for introducing a modifying functional group to one end of a polymer obtained by polymerization initiated by a modifying initiator, and may be selected according to the purpose of modifying the polymer, and for example, may be a compound containing a hydrocarbon group for improving the affinity for a solvent, a compound containing a hetero atom for improving the affinity for a filler, or the like. Further, the compound having a modification functional group is a compound that is anionized by reacting with the compound having a polymerization initiating functional group to produce a modification initiator, and may be a compound containing an unsaturated bond to which the compound having a polymerization initiating functional group is easily added, or may be a compound containing a hydrogen atom that is easily removed from the compound having a polymerization initiating functional group.

As a specific example, the compound having a modifying functional group may be a compound represented by formula 1 below.

[ formula 1]

In the above formula 1, R¹To R⁴May each independently be a C1-C30 monovalent hydrocarbon group; a C1-C30 heteroalkyl containing one or more heteroatoms selected from N, O and S; or a C4-C30 heterocyclyl containing one or more heteroatoms selected from N, O and S.

As a more specific example, the compound represented by formula 1 above may be an aromatic vinyl compound such as styrene, α -methylstyrene and p-methylstyrene; an aromatic vinyl compound derivative in which a monovalent hydrocarbon group, a heteroalkyl group containing one or more heteroatoms selected from N, O and S, or a heterocyclic group is substituted on one or more carbons constituting the aromatic vinyl compound; conjugated dienes such as 1, 3-butadiene and isoprene; or a conjugated diene compound derivative in which a monovalent hydrocarbon group, a heteroalkyl group containing one or more heteroatoms selected from N, O and S, or a heterocyclic group is substituted on one or more carbons constituting the conjugated diene compound.

As another example, the compound having a modifying functional group may be a compound represented by formula 2 below.

[ formula 2]

In the above formula 2, R⁵To R⁷May each independently be a C1-C30 monovalent hydrocarbon group; a C1-C30 heteroalkyl containing one or more heteroatoms selected from N, O and S; or C4-C30 heterocyclyl containing one or more heteroatoms selected from N, O and S, or R⁵And R⁶、R⁶And R⁷Or R⁵And R⁷May be bonded to each other to form a C5-C30 hydrocarbon ring group. When R is⁵And R⁶、R⁶And R⁷Or R⁵And R⁷When bonded to each other to form a C5-C30 hydrocarbon ring group, the hydrocarbon ring group may contain-CR in the ring⁸R⁹-、-NR¹⁰-, -O-, or-S-, and R⁸、R⁹And R¹⁰May each independently be hydrogen; C1-C30 monovalent hydrocarbon radicals; a C1-C30 heteroalkyl containing one or more heteroatoms selected from N, O and S; or a C4-C30 heterocyclyl containing one or more heteroatoms selected from N, O and S.

In addition, the conjugated diene-based monomer may be mixed with the compound having a modifying functional group to suppress a decrease in solubility of a solvent with an increase in the proportion of the compound having a modifying functional group in a reactant, thereby facilitating a reaction, or may suppress generation of an excessive amount of oligomers and reactor clogging with an increase in the proportion of the compound having a modifying functional group, thereby facilitating preparation of a highly modified modification initiator. Therefore, when the modification initiator thus prepared is used in the preparation of a polymer, polymerization can be facilitated and the polymer can be highly modified at the same time.

In the present invention, the conjugated diene-based monomer in the first fluid may be contained in a proportion of 1 to 4 moles, specifically 1 to 2 moles, based on 1 mole of the compound containing a modifying functional group. When within the above range, it is possible to initiate a reaction with a high conversion rate without causing side reactions caused by the unreacted conjugated diene-based monomer in the absence of an unreacted compound having a modifying functional group.

Although not particularly limited, the conjugated diene-based monomer may be, for example, one or more selected from the group consisting of 1, 3-butadiene, 2, 3-dimethyl-1, 3-butadiene, piperylene, 3-butyl-1, 3-octadiene, isoprene and 2-phenyl-1, 3-butadiene.

In addition, the compound having a polymerization initiating functional group may be a compound that reacts with the compound having a modifying functional group to prepare a modification initiator, and may be, for example, an anionic compound. As a specific example, the compound having a polymerization initiating functional group may be a compound in which an organic group representing an anion is coupled with a metal representing a cation by ionic coupling.

As a more specific example, the compound having a polymerization initiating functional group may be a compound represented by formula 3 below.

[ formula 3]

In the above formula 3, R¹¹Can be used forIs a C1-C30 monovalent hydrocarbon radical and M can be a metal, specifically an alkali metal.

As a more specific example, the compound represented by the above formula 3 may be an anionic compound in which a proton of any one or more carbons constituting the C1-C30 alkyl group or the C4-C30 cycloalkyl group is substituted with M. That is, M may be coupled to an adjacent carbon by ionic coupling.

According to an embodiment of the present invention, the first fluid containing the compound having a modifying functional group and the conjugated diene-based monomer in the above step S1 may be a mixture in which the compound having a modifying functional group and the conjugated diene-based monomer are directly mixed, or may be a solution in which the compound having a modifying functional group and the conjugated diene-based monomer are dissolved in a solvent.

In addition, according to an embodiment of the present invention, the second fluid containing the compound having a polymerization initiating functional group of the above step S1 may be the compound itself having a polymerization initiating functional group, or may be a solution in which the compound having a polymerization initiating functional group is dissolved in a solvent.

When the first fluid and the second fluid are each a solution, the solvent may be a solvent capable of dissolving the compound having the modification functional group, the compound having the polymerization initiating functional group, and the conjugated diene-based monomer, and may be, for example, a hydrocarbon solvent such as hexane, cyclohexane, methylcyclohexane, toluene, and ethylbenzene.

According to an embodiment of the present invention, at least one of the first fluid and the second fluid may further include a polar additive, and the polar additive may be included in a molar ratio to the compound having the modifying functional group and the compound having the polymerization initiating functional group (the compound having the modifying functional group or the compound having the polymerization initiating functional group: the polar additive) of 10:1 to 1:10, 5:1 to 1:5, 3:1 to 1:3, or 2:1 to 1:2, respectively, depending on which fluid of the first fluid and the second fluid the polar additive is included in. When within the above range, the difference in reaction rate between the compound having a modifying functional group and the compound having a polymerization initiating functional group is compensated for, thereby having the effect of minimizing side reactions. The polar additive may be, for example, one or more selected from tetrahydrofuran, 2-bis (2-tetrahydrofuryl) propane, diethyl ether, cyclopentyl ether, dipropyl ether, ethylene glycol methyl ether (ethylene methyl ether), ethylene glycol dimethyl ether (ethylene dimethyl ether), diethylene glycol (dimethyl glycol), dimethyl ether, t-butoxyethoxyethane, bis (2-dimethylaminoethyl) ether, (dimethylaminoethyl) ethyl ether, trimethylamine, triethylamine, tripropylamine, and tetramethylethylenediamine.

As another example, in the production method according to an embodiment of the present invention, the first fluid may further include a polar additive. In this case, the first fluid may contain a compound containing a modifying functional group, a conjugated diene-based monomer, and a polar additive. At this time, the first fluid may be prepared by sequentially and continuously mixing the compound having the modifying functional group, the conjugated diene-based monomer, and the polar additive.

As another example, in step S1, the compound containing a modifying functional group may be used in a proportion exceeding 1 mole based on 1 mole of the compound containing a polymerization initiating functional group, that is, may be used in an excess amount compared to the compound containing a polymerization initiating functional group. Specifically, the compound containing a modifying functional group may be used in a ratio of 1.5 to 10.0 moles, 1.5 to 5 moles, or 3.0 to 5.0 moles, based on 1 mole of the compound containing a polymerization initiating functional group. In this case, two or more compounds having a modifying functional group may be combined, whereby dimer, trimer, tetramer or more multimeric oligomers may be produced, and when the thus-prepared modification initiator having a high modification ratio is used in the preparation of a polymer, the polymer may be modified at a high modification ratio, so that the physical properties of the polymer may be improved. Therefore, the method for preparing a modified initiator according to the present invention may be performed such that a compound containing a modifying functional group and a compound containing a polymerization initiating functional group are reacted in an appropriate molar ratio according to the conditions of a polymer to be prepared from the modified initiator to obtain a product.

Further, according to an embodiment of the present invention, the temperature inside the reactor may be-50 ℃ to 50 ℃, -40 ℃ to 40 ℃, or-30 ℃ to 40 ℃, preferably 10 ℃ to 40 ℃. When within the above range, the reaction rate is excellent, and has the effect of minimizing side reactions.

According to an embodiment of the present invention, step S1 and step S2 may be continuously performed. When the step S1 and the step S2 are continuously performed, the modification initiator can be continuously prepared, thereby having an effect of excellent productivity. Further, when the modification initiator is prepared, no modification initiator remains in the reactor after the reaction is completed, so that the continuously introduced compound containing the modification functional group and the compound containing the polymerization initiating functional group smoothly react, and thus there is an effect that the modification initiator has an excellent conversion rate.

Meanwhile, step S1 is performed by adding a first fluid through a first fluid inlet and a second fluid through a second fluid inlet to a reactor provided with the first fluid inlet and the second fluid inlet, and then mixing the first fluid and the second fluid, wherein, at the time of mixing, the flow rates of the first fluid and the second fluid may be kept constant, and the flow rate of the first fluid may be increased.

Specifically, step S1 may be a step of introducing the first fluid and the second fluid into their own inlets and mixing with each other in the reactor, and as a result of the mixing, the compound containing the modification functional group and the conjugated diene-based monomer contained in the first fluid react with the compound containing the polymerization initiating functional group contained in the second fluid to prepare the modification initiator.

According to an embodiment of the present invention, in step S1, the flow rate of the first fluid and the flow rate of the second fluid may be kept constant while mixing the first fluid and the second fluid. The flow rate may be a flow rate when being introduced into each fluid inlet, and may be controlled by adjusting the flow rate when each fluid is introduced into each fluid inlet in consideration of reactivity, a reaction rate, a reaction environment, and the like.

In addition, according to an embodiment of the present invention, in step S1, the flow rate of the first fluid may be increased while mixing the respective fluids. As the first fluid flows through the deformation provided in the reactor, the flow rate of the first fluid may increase. The deformation portion through which the first fluid flows serves to instantaneously increase the flow rate of the first fluid when the first fluid is mixed with the second fluid, and the inner diameter, outer diameter, or cross-sectional area of the reactor through which the first fluid flows before mixing may be reduced to a predetermined range, or may be gradually reduced. As described above, when the instantaneous flow rate of the first fluid increases as the first fluid flows through the deformation in the reactor, there is an effect of improving the mixing force of the respective fluids without a separate stirrer or mixer. Meanwhile, only when the first fluid passes through the deformation portion, the flow rate of the first fluid may temporarily increase, and then the respective fluids are mixed.

According to an embodiment of the present invention, when each fluid is added in step S1, the flow of each of the first fluid and the second fluid may be laminar flow. In the present invention, the term "laminar flow" refers to a reynolds number (N) representing a dimensionless exponent of a flow state of a fluid_Re) Is 2,100 or less.

The reynolds number is the ratio of the dynamic force of a fluid to its viscous force, and can be calculated by equation 1 below.

[ equation 1]

Reynolds number (N)_Re)＝ρvd/μ

In equation 1 above, ρ is the density of the fluid, V is the flow rate of the fluid at the inlet and in the reactor, d is the internal diameter of the inlet and the reactor, and μ is the viscosity of the fluid.

Generally, as the velocity of the fluid decreases, its dynamic force decreases, causing the reynolds number of the fluid to decrease. As the viscosity of the fluid increases, its viscosity increases, causing the reynolds number of the fluid to decrease. At this time, the fluid having a relatively small power flows relatively smoothly, and the flow of the fluid continuously faces the resistance at the inner wall of the inlet, the deformation, the outlet, etc., so that the velocity of the fluid is reduced, and at the center of the inlet, the deformation, the outlet, etc., the velocity of the fluid reaches the highest point, so that a parabolic velocity distribution in which the outflow is large is exhibited from the inner wall to the center. Laminar flow may refer to a flow pattern having the velocity profile described above.

As a specific example, when the first fluid is added in step S1, the Reynolds number (N) of the first fluid_Re) May be 2,100 or less, 1 to 2,100, 10 to 1,500, or 30 to 1,000, preferably 50 to 500. When within the above range, laminar flow is maintained, and at the same time, since the flow rate of the first fluid is appropriately maintained, there is an effect of reducing side reactions to a minimum.

As another example, when the second fluid is added in step S1, the Reynolds number (N) of the second fluid_Re) May be 2,100 or less, 1 to 2,100, 10 to 1,500, or 30 to 1,000, preferably 50 to 500. When within the above range, laminar flow is maintained, and at the same time, since the flow rate of the second fluid is appropriately maintained, there is an effect of reducing side reactions to a minimum.

Meanwhile, the first fluid according to the present invention is introduced into the reactor through the first fluid inlet, flows through the deformation portion, and then is mixed with the second fluid. The reynolds number of the first fluid may be kept constant from the time when the first fluid is introduced through the first fluid inlet and flows to the deformation portion, and may be gradually reduced while passing through the deformation portion and then mixed with the second fluid. This may be due to a decrease in the inner diameter, outer diameter, or cross-sectional area of the deformation portion having a shape in which the inner diameter, outer diameter, or cross-sectional area of the reactor decreases to within a predetermined range, although the flow velocity of the first fluid increases due to the deformation portion when mixing the respective fluids.

In addition, a second fluid according to the present invention is introduced into the reactor through the second fluid inlet and then mixed with the first fluid. The reynolds number of the second fluid may be held constant from the time when the second fluid is introduced through the second fluid inlet and flows until the respective fluids are mixed.

According to an embodiment of the present invention, when the first fluid and the second fluid are added in step S1, the respective flow directions of the first fluid and the second fluid may be perpendicular to each other. The flow direction of each of the first fluid and the second fluid may be adjusted from the installation position of each of the first fluid inlet and the second fluid inlet, and may be adjusted by disposing each of the first fluid inlet and the second fluid inlet in a direction perpendicular to each other in the reactor. When the respective flow directions of the first fluid and the second fluid are thereby perpendicular to each other, there is an effect of facilitating uniform mixing while maintaining laminar flow when mixing the first fluid and the second fluid. As another example, the respective flow directions of the first fluid and the second fluid may be perpendicular to each other when the first fluid and the second fluid are added, but may be parallel to each other when the first fluid is added to the reactor and flows through the deformation portion. In this case, the contact area of the first fluid and the second fluid when the first fluid and the second fluid are mixed is large, so that there is an excellent effect of uniform mixing.

Meanwhile, the flow of the third fluid obtained in step S2 through step S1 may be a laminar flow.

As a specific example, the Reynolds number (N) of the third fluid obtained in step S2_Re) May be 2,100 or less, 1 to 2,100, 10 to 1,500, or 30 to 1,000, preferably 50 to 500. When within the above range, laminar flow is maintained, and at the same time, since the flow rate of the third fluid is appropriately maintained, there is an effect of minimizing side reactions.

The apparatus for preparing a modification initiator according to the present invention is used for performing the above-described method for preparing a modification initiator, wherein the apparatus may be a reactor provided with: a first fluid inlet; a second fluid inlet; a deformation portion for increasing a flow velocity of the first fluid; a mixing section in which the first fluid and the second fluid are mixed; and an outlet through which the third fluid is discharged.

The reactor may be, for example, a tubular reactor. The inner diameter, outer diameter, or cross-sectional area of the first fluid inlet, second fluid inlet, and outlet disposed in the reactor can each independently be 0.01 to 0.99 times, 0.05 to 0.95 times, 0.1 to 0.9 times, or 0.3 to 0.7 times the inner diameter, outer diameter, or cross-sectional area of the reactor. When within the above range, there is an excellent effect of increasing the flow rate of the first fluid.

The first fluid inlet and the second fluid inlet may each be provided, for example, at an end or a side of the reactor, or may be provided in the form of an insert into the interior of the reactor.

The outlet may be connected to a polymerization reactor for initiating polymerization by the modified initiator, and the polymerization reactor may be a continuous reactor.

The deformation portion is to instantaneously increase the flow rate of the first fluid when mixing the respective fluids, and the inner diameter, outer diameter, or cross-sectional area of the reactor through which the first fluid flows before mixing the respective fluids may be reduced to a predetermined range, or may be gradually reduced in a direction from the inlet to the outlet of the first fluid. As another example, the shape of the deformation where the inner diameter, outer diameter, or cross-sectional area decreases or tapers may be a shape where the inner diameter, outer diameter, or cross-sectional area of the reactor tapers to the inner diameter, outer diameter, or cross-sectional area of the outlet. According to an embodiment of the present invention, the time point at which the respective fluids are mixed in the mixing portion may be a time point when the first fluid passes through the end of the deformation portion.

The mixing portion may be separately provided in the reactor, or may refer to a position where the first fluid having passed through the deformation portion and the second fluid having passed through the second fluid inlet are mixed in the reactor.

Hereinafter, the present invention will be described in detail with reference to examples. However, the following examples are merely illustrative of the present invention and are not intended to limit the scope of the present invention.

Examples

Example 1

A tubular reactor provided with a first fluid inlet, a second fluid inlet, a deformation portion, and an outlet was prepared. The tubular reactor body had an outer diameter of 1/4 inches, and the first fluid inlet was disposed on the side of the tubular reactor and had an outer diameter of 1/8 inches. The second fluid inlet was provided in the form of an insert inserted from one end of the tubular reactor to the connection of the deformation and the outlet while being spaced apart from the connection of the deformation and the outlet, and had an outer diameter of 1/8 inches. The outlet was placed at the other end of the tubular reactor and had an outside diameter of 1/8 inches. The deformation is spaced from the location where the first fluid inlet of the reactor is located and is connected to the outlet in such a way that its outer diameter gradually decreases from the outer diameter of the tubular reactor to the outer diameter of the outlet.

Through the second fluid inlet, a solution in which n-butyllithium, a compound having a polymerization initiating functional group, was dissolved at 1.5% by weight in n-hexane, was fed at 350g/hr, and the Reynolds number was about 53. Meanwhile, a solution in which Dimethylvinylbenzylamine (DMVBA) compound having a modifying functional group was dissolved in n-hexane at 5.7 wt%, Tetramethylethylenediamine (TMEDA) as a polar additive at 3.1 wt%, and 1, 3-butadiene at 3.8 wt% together was added through the first fluid inlet at 350g/hr, and the reynolds number was about 230. At this time, the molar ratio of n-butyllithium to dimethylvinylbenzylamine was 1:1.5, and the molar ratio of dimethylvinylbenzylamine to tetramethylethylenediamine was 1: 0.77. The molar ratio of dimethylvinylbenzylamine to 1, 3-butadiene was 1: 2.

The n-butyllithium solution added through the second fluid inlet was moved at a flow rate of 18 mm/sec and mixed with a solution of dimethylvinylbenzylamine, 1, 3-butadiene and tetramethylethylenediamine, which passed through the deformation part of the reactor and the flow rate increased to 90 mm/sec, passed through the first fluid inlet and moved to the start of the outlet. Subsequently, a mixed solution in which the n-butyllithium solution and a solution of dimethylvinylbenzylamine, 1, 3-butadiene, and tetramethylethylenediamine were mixed was introduced into an outlet at the time of mixing, and the mixed solution was reacted at 20 ℃ while passing through a tube having an outer diameter of 1/4 inches and a length of 1.1m provided at the outlet during a residence time of about 1 minute. The modified initiator thus prepared was continuously obtained from a tube disposed at the outlet, at which time the reynolds number of the outlet and the tube disposed at the outlet was about 180.

The thus-obtained modification initiator compound was hydrogenated using an excess of ethanol, and when confirmed by gas chromatography, dimethylvinylbenzylamine added as the compound containing a modifying functional group was not detected, and it could be confirmed that the modification initiator compound was produced at a conversion rate of 99 mol% or more.

Example 2

Example 2 was performed in the same manner as in example 1, except that in example 1, a solution in which dimethylvinylbenzylamine was dissolved in n-hexane at 11.3 wt%, tetramethylethylenediamine as a polar additive was dissolved at 3.2 wt%, and 1, 3-butadiene was dissolved together at 6.3 wt% was added through the first fluid inlet at 350 g/hr. At this time, the molar ratio of n-butyllithium to dimethylvinylbenzylamine was 1:3, and the molar ratio of dimethylvinylbenzylamine to 1, 3-butadiene was 1: 1.67. The reaction was carried out at 40 ℃.

The thus-obtained modification initiator compound was hydrogenated using an excess of ethanol, and when confirmed by gas chromatography, dimethylvinylbenzylamine added as the compound containing a modifying functional group was not detected, and it could be confirmed that the modification initiator compound was produced at a conversion rate of 99 mol% or more.

Example 3

Example 3 was performed in the same manner as in example 1, except that in example 1, a solution in which dimethylvinylbenzylamine was dissolved in n-hexane at 18.9 wt%, tetramethylethylenediamine as a polar additive was dissolved at 3.1 wt%, and 1, 3-butadiene was dissolved together at 10.1 wt% was added through the first fluid inlet at 350 g/hr. At this time, the molar ratio of n-butyllithium to dimethylvinylbenzylamine was 1:5, and the molar ratio of dimethylvinylbenzylamine to 1, 3-butadiene was 1: 1.6. The reaction was carried out at 40 ℃.

The thus-obtained modification initiator compound was hydrogenated using an excess of ethanol, and when confirmed by gas chromatography, dimethylvinylbenzylamine added as the compound containing a modifying functional group was not detected, and it could be confirmed that the modification initiator compound was produced at a conversion rate of 99 mol% or more.

Example 4

Example 4 was performed in the same manner as in example 1, except that in example 1, a solution in which dimethylvinylbenzylamine was dissolved in n-hexane at 11.3 wt%, tetramethylethylenediamine as a polar additive was dissolved at 3.2 wt%, and 1, 3-butadiene was dissolved together at 15.2 wt% was added through the first fluid inlet at 350 g/hr. At this time, the molar ratio of n-butyllithium to dimethylvinylbenzylamine was 1:3, and the molar ratio of dimethylvinylbenzylamine to 1, 3-butadiene was 1: 4. The reaction was carried out at 40 ℃.

The thus-obtained modification initiator compound was hydrogenated using an excess of ethanol, and when confirmed by gas chromatography, dimethylvinylbenzylamine added as the compound containing a modifying functional group was not detected, and it could be confirmed that the modification initiator compound was produced at a conversion rate of 99 mol% or more.

Comparative example 1

Comparative example 1 was performed in the same manner as in example 1, except that in example 1, a solution in which dimethylvinylbenzylamine was dissolved in n-hexane at 5.7 wt% together with tetramethylethylenediamine as a polar additive at 3.2 wt% was added through the first fluid inlet at 350 g/hr. At this time, the molar ratio of n-butyllithium to dimethylvinylbenzylamine was 1:1.5, and the reaction was carried out at 20 ℃.

The thus-obtained modification initiator compound was hydrogenated using an excess of ethanol, and when confirmed by gas chromatography, dimethylvinylbenzylamine added as the compound containing a modifying functional group was not detected, and it could be confirmed that the modification initiator compound was produced at a conversion rate of 99 mol% or more.

Meanwhile, 9 hours after the first start of the reaction, the outlet of the reactor was blocked, so that the preparation reaction of the modification initiator could not be performed any more.

Comparative example 2

Comparative example 2 was performed in the same manner as in example 1, except that in example 1, a solution in which dimethylvinylbenzylamine was dissolved in n-hexane at 11.3 wt% together with tetramethylethylenediamine as a polar additive at 3.1 wt% was added through the first fluid inlet at 350 g/hr. At this time, the molar ratio of n-butyllithium to dimethylvinylbenzylamine was 1:3, and the reaction was carried out at 20 ℃.

The thus-obtained modification initiator compound was hydrogenated using an excess of ethanol, and when confirmed by gas chromatography, dimethylvinylbenzylamine added as the compound containing a modifying functional group was not detected, and it could be confirmed that the modification initiator compound was produced at a conversion rate of 53 mol% or more.

Meanwhile, 5 hours after the first start of the reaction, the outlet of the reactor was blocked, so that the preparation reaction of the modification initiator could not be performed any more.

Comparative example 3

Comparative example 3 was performed in the same manner as in example 1, except that in example 1, a solution in which dimethylvinylbenzylamine was dissolved in n-hexane at 11.3 wt%, tetramethylethylenediamine as a polar additive was dissolved in n-hexane at 3.1 wt%, and 1, 3-butadiene was dissolved together at 6.3 wt% was added through the first fluid inlet at 350 g/hr. At this time, the molar ratio of n-butyllithium to dimethylvinylbenzylamine was 1:3, and the molar ratio of dimethylvinylbenzylamine to 1, 3-butadiene was 1: 0.67. The reaction was carried out at 20 ℃.

The thus-obtained modification initiator compound was hydrogenated using an excess of ethanol, and when confirmed by gas chromatography, dimethylvinylbenzylamine added as the compound containing a modifying functional group was not detected, and it could be confirmed that the modification initiator compound was produced at a conversion rate of 73 mol% or more.

Comparative example 4

Comparative example 4 was conducted in the same manner as in example 1, except that in example 1, a solution in which dimethylvinylbenzylamine was dissolved in n-hexane at 11.3 wt%, tetramethylethylenediamine as a polar additive was dissolved in n-hexane at 3.1 wt%, and 1, 3-butadiene was dissolved together at 22.8 wt% was added through the first fluid inlet at 350 g/hr. At this time, the molar ratio of n-butyllithium to dimethylvinylbenzylamine was 1:3, and the molar ratio of dimethylvinylbenzylamine to 1, 3-butadiene was 1: 6. The reaction was carried out at 40 ℃.

The thus-obtained modification initiator compound was hydrogenated using an excess of ethanol, and when confirmed by gas chromatography, dimethylvinylbenzylamine added as the compound containing a modifying functional group was not detected, and it could be confirmed that the modification initiator compound was produced at a conversion rate of 67 mol% or more.

Experimental example 1

In order to confirm the yield and the long-term operation possibility of the method for preparing a modified initiator according to the present invention, the conversion rate of the modified initiator and the time for reactor clogging in each of examples 1 to 4 and comparative examples 1 to 4 were measured and are shown in table 1 below. At this time, the time when the reactor is clogged is the time elapsed from the start of the reaction to the time when the reactor is completely clogged so that the reaction can no longer be carried out.

[ Table 1]

As shown in table 1, the method for preparing a modified initiator according to the present invention applied in example 1 to example 4 suppressed the clogging of the reactor, so that the reaction could be performed for a longer time as compared with comparative example 1 and comparative example 2. In addition, the method enables the preparation of a modification initiator with a high conversion rate, and thus, has also been confirmed to have a very high reaction yield. At this time, comparative examples 1 and 2 were each prepared by the same preparation method as in example, except that 1, 3-butadiene was not used as a reactant. Comparative example 1 has a ratio level of 1:1 of dimethylvinylbenzylamine compound having a modifying functional group and n-butyllithium compound having a polymerization initiating functional group, and thus, there are not many compounds having a modifying functional group, thereby maintaining the reaction for a long time to prepare a modifying initiator at a high conversion rate, as compared with comparative example 2 having a high ratio of compounds having a modifying functional group. However, after several hours, the reactor is plugged such that the reaction stops, and thus the process efficiency, i.e., the total available production of modified initiator, is significantly reduced compared to an example where the reaction can be run for a significantly increased time of three or more times. Meanwhile, comparative examples 3 and 4 use 1, 3-butadiene as a reactant, but comparative example 3 is used in a ratio range lower than that proposed in the present invention, so that the content of 1, 3-butadiene in the reactant is too small. Therefore, the effect of improving the solubility of the solvent is not significant, so that the generation of excessive oligomers cannot be suppressed, the conversion rate of the modification initiator is caused to be low, and the effect of suppressing the clogging of the reactor is also not significant. In addition, comparative example 4 using 1, 3-butadiene of a ratio higher than the range of the ratio proposed in the present invention has a high ratio of 1, 3-butadiene in the reactants, and therefore, a side reaction of forming a butadiene polymer through a polymerization reaction between 1, 3-butadiene using n-butyllithium as an initiator occurs, causing a significant decrease in the conversion rate of the modified initiator.

Experimental example 2

Using the modification initiators of examples 1 to 4 and comparative examples 3 and 4, modified conjugated diene-based polymers were prepared, and rubber samples were prepared therefrom. After that, the rolling resistance performance (fuel economy performance) was analyzed, and the results are shown in the following table 3.

In addition, an unmodified conjugated diene-based polymer was prepared for comparison, and a rubber sample was prepared therefrom. Thereafter, the rolling resistance performance (fuel economy performance) was analyzed, and the results are also shown in table 3 below.

(1) Preparation of modified conjugated diene Polymer

Into a 20L autoclave reactor were charged 3kg of n-hexane, 270g of styrene, 710g of 1, 3-butadiene, 4.7mmol of the modification initiator prepared in each example, and 1.29g of 2, 2-bis (2-oxetanyl) propane as a polar additive. Thereafter, the temperature inside the reactor was set to 60 ℃, and then an adiabatic heating reaction was performed. After about 30 minutes, 20g of 1, 3-butadiene was added to cap the end of the polymer with butadiene, and the reaction was carried out for 10 minutes. After that, the reaction was terminated with ethanol, and 33g of a solution in which the antioxidant windstay K was dissolved at 30% by weight in hexane was added. The thus-obtained polymer was placed in hot water heated with steam, followed by stirring to remove the solvent, followed by roll drying to remove the remaining solvent and water, thereby preparing each modified styrene-butadiene copolymer.

(2) Comparative example 5: preparation of unmodified conjugated diene-based polymers

Into a 20L autoclave reactor were charged 3kg of n-hexane, 270g of styrene, 710g of 1, 3-butadiene, 4.7mmol of n-butyllithium and 1.29g of 2, 2-bis (2-oxetanyl) propane as a polar additive. Thereafter, the temperature inside the reactor was set to 60 ℃, and then an adiabatic heating reaction was performed. After about 30 minutes, 20g of 1, 3-butadiene was added to cap the end of the polymer with butadiene, and the reaction was carried out for 10 minutes. After that, the reaction was terminated with ethanol, and 33g of a solution in which the antioxidant windstay K was dissolved at 30% by weight in hexane was added. The thus-obtained polymer was placed in hot water heated with steam, followed by stirring to remove the solvent, followed by roll drying to remove the remaining solvent and water, thereby preparing an unmodified styrene-butadiene copolymer.

(3) Preparation of rubber test specimens

Each of the modified or unmodified styrene-butadiene copolymers prepared above was used as a raw material rubber, and mixed under the mixing conditions shown in the following table 2. The contents of the raw materials in table 2 are parts by weight of the respective raw materials based on 100 parts by weight of the raw rubber.

[ Table 2]

Specifically, the rubber sample was kneaded by first-stage kneading and second-stage kneading. In the first-stage kneading, a raw material rubber, silica (filler), an organic silane coupling agent (X50S, Evonik), a processing oil (TADE oil), zinc oxide (ZnO), stearic acid, an antioxidant (tmq (rd)) (2,2, 4-trimethyl-1, 2-dihydroquinoline polymer), an antioxidant (6PPD ((dimethylbutyl) -N-phenyl-phenylenediamine)), and a wax (microcrystalline wax) were kneaded using a banbury mixer having a temperature control device. At this time, the initial temperature of the kneading apparatus was controlled to 70 ℃, and after the end of mixing, a first mixture was obtained at a discharge temperature of 145 ℃ to 155 ℃. In the second stage mixing, the first mixture was cooled to room temperature, and then the first mixture, sulfur, a rubber accelerator (DPG (diphenylguanidine)) and a vulcanization accelerator (CZ (N-cyclohexyl-2-benzothiazylsulfenamide)) were added to a mixer, followed by mixing at a temperature of 100 ℃ or lower to obtain a second mixture. Thereafter, a curing process was performed at 160 ℃ for 20 minutes to prepare a rubber sample.

(4) Rolling resistance performance

The rolling resistance performance (fuel economy performance) was determined from the tan δ value by measuring the viscoelastic behavior of the thermodynamic deformation at a frequency of 10Hz in the film stretching mode at various measurement temperatures (-60 ℃ to 60 ℃) using a dynamic mechanical analyzer (gaboco., Ltd.). In the measurement results, the lower the tan δ value at 60 ℃, the smaller the hysteresis loss and the better the rotation resistance performance (fuel efficiency performance). However, in the following table 3, the obtained values are shown by indication based on the measured values of comparative example 5. The larger the value, the better the rotation resistance performance.

[ Table 3]

In table 3 above, the numerical values of example 1 to example 4, comparative example 3, and comparative example 4 are shown by indication based on the measured value of comparative example 5. The larger the value, the better. As confirmed by table 3 above, the polymer prepared using the modified initiator prepared by the preparation method according to one embodiment of the present invention exhibited significantly improved rolling resistance properties, as compared to unmodified comparative example 5.

In addition, in comparison with comparative examples 3 and 4, examples 2,4, 3 and 4 using the modification initiator prepared using the compound having the modification functional group and the compound having the polymerization initiating functional group in the same ratio can confirm that the rolling resistance performance of the rubber composition material can be significantly improved by more than 10%. At this time, comparative examples 3 and 4 used 1, 3-butadiene in different ratios in preparing the modification initiator, but other conditions were the same level as in examples 2 and 4.

In view of the above, it was confirmed that the modification initiator prepared by the preparation method according to the present invention can be used in polymerization of a polymer to introduce a functional group into the polymer upon initiation of polymerization, thereby easily modifying the polymer.