WO2019098724A1 - Procédé de préparation d'une composition de copolymère séquencé, et composition d'asphalte comprenant une composition de copolymère séquencé préparée par ce procédé - Google Patents

Procédé de préparation d'une composition de copolymère séquencé, et composition d'asphalte comprenant une composition de copolymère séquencé préparée par ce procédé Download PDF

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WO2019098724A1
WO2019098724A1 PCT/KR2018/014040 KR2018014040W WO2019098724A1 WO 2019098724 A1 WO2019098724 A1 WO 2019098724A1 KR 2018014040 W KR2018014040 W KR 2018014040W WO 2019098724 A1 WO2019098724 A1 WO 2019098724A1
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Prior art keywords
block copolymer
asphalt
coupling agent
composition
mixed solution
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PCT/KR2018/014040
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English (en)
Korean (ko)
Inventor
이성두
김태중
이세경
이춘화
Original Assignee
주식회사 엘지화학
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Priority claimed from KR1020180136621A external-priority patent/KR102464763B1/ko
Application filed by 주식회사 엘지화학 filed Critical 주식회사 엘지화학
Priority to EP18879379.8A priority Critical patent/EP3712186B1/fr
Priority to US16/637,008 priority patent/US11603462B2/en
Priority to JP2020506344A priority patent/JP6902672B2/ja
Priority to RU2020105626A priority patent/RU2779797C2/ru
Priority to CN201880051309.XA priority patent/CN111032717B/zh
Publication of WO2019098724A1 publication Critical patent/WO2019098724A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
    • C08F297/02—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type
    • C08F297/04—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type polymerising vinyl aromatic monomers and conjugated dienes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L95/00—Compositions of bituminous materials, e.g. asphalt, tar, pitch

Definitions

  • the present invention relates to a process for producing a block copolymer composition for use as an asphalt modifier and an asphalt composition comprising the block copolymer composition prepared from the block copolymer composition.
  • Asphalt is a residue after most volatile oil components evaporate from petroleum crude oil. It retains a viscous liquid or semi-solid state at high temperature, but has a hard setting property at a temperature below room temperature. Since asphalt is rich in plasticity, has high water resistance, electrical insulation, adhesiveness, and is chemically stable, it is widely applied to building materials such as road pavement materials and waterproofing materials. However, such asphalt has plastic deformation when it is exposed to high temperature for a long time during use and cracks due to external impact at low temperature.
  • modified asphalt is intended to improve the functional properties including permanent deformation, fatigue cracking, low-temperature cracking, aging and the like.
  • softening point of the physical properties of modified asphalt is the most basic property of asphalt. The softening point is highly dependent on the characteristics of the aromatic vinyl hydrocarbon-conjugated diene block copolymer such as a styrene-butadiene-styrene (SBS) block copolymer added to the modified asphalt, Research is continuously underway.
  • SBS styrene-butadiene-styrene
  • the present invention has been conceived to solve the problems of the prior art, and it is an object of the present invention to provide a method for producing a block copolymer composition contained in an asphalt modifier for use in modified asphalt, To thereby provide an asphalt composition having an increased softening point while maintaining the overall physical properties at the same level or higher.
  • a process for preparing a first mixed solution by adding an aromatic vinyl monomer and a compound represented by the following formula (1) to a hydrocarbon solvent and stirring the same ); Adding a polymerization initiator to the first mixed solution and polymerizing the mixed solution to prepare a second mixed solution (S20); Adding a conjugated diene monomer to the second mixed solution and polymerizing to prepare a third mixed solution (S30); And (S40) adding a coupling agent to the third mixed solution and performing a coupling reaction, wherein the compound represented by the following formula (1) is added to the aromatic vinyl monomer and the conjugated diene monomer in a total amount of 100 parts by weight 0.26 parts by weight to 0.8 parts by weight, based on the total weight of the block copolymer composition.
  • M may be Li, Na, K, Rb or Cs
  • X may be N, O or S
  • R 1 and R 2 are each independently a monovalent hydrocarbon group having 1 to 12 carbon atoms, or the one having 1 to 12 carbon atoms containing an N or O atom itdoe be a hydrocarbon group, R 2 is not present when X is O or S.
  • the present invention also relates to an asphalt composition
  • an asphalt composition comprising a block copolymer composition and an asphalt
  • the block copolymer composition is a block copolymer composition comprising an aromatic vinyl monomer-derived repeating unit block, a conjugated diene monomer-derived repeating unit block and a coupling agent-
  • the coupling efficiency by the coupling agent derived from the coupling agent is 50% to 80%
  • the asphalt composition has an asphalt composition having a softening point of 71.2 ° C or higher as measured according to ASTM D36.
  • the present invention also relates to an asphalt composition
  • an asphalt composition comprising a block copolymer composition, asphalt and a crosslinking agent, wherein the block copolymer composition comprises a repeating unit block derived from an aromatic vinyl monomer, a repeating unit block derived from a conjugated diene monomer and a coupling agent derived from a coupling agent
  • the coupling efficiency by the coupling agent derived from the coupling agent is 50% to 80%
  • the asphalt composition has an asphalt composition having a softening point of 83.6 ° C or higher as measured according to ASTM D36.
  • the block copolymer composition is prepared according to the present invention and the block copolymer composition thus prepared is used as an asphalt modifier, the overall physical properties of the asphalt composition, that is, the modified asphalt, are maintained at the same or higher level, It is effective.
  • " derived repeating unit " and " derived connecting group " in the present invention may represent a constituent, a structure or the substance itself due to a substance, Refers to a repeating unit formed in a polymer participating in a polymerization reaction, and a 'derived linking group' means that, during a polymer-to-polymer coupling reaction, the coupling agent to be added participates in a coupling reaction, And the like.
  • the term 'block' may refer to a repeating unit group composed of only the same monomer and only the same monomer-derived repeating unit in the copolymer, and specific examples thereof include aromatic vinyl monomer- Refers to a block formed only of the repeating units derived from a vinyl monomer, and the conjugated diene monomer-derived repeating unit block may mean a block formed of only repeating units derived from a conjugated diene monomer.
  • the term "monovalent hydrocarbon group” means a monovalent atomic group in which a monovalent alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, a cycloalkyl group containing at least one unsaturated bond, And the minimum number of carbon atoms of the substituent represented by the monovalent hydrocarbon may be determined depending on the type of each substituent.
  • the monovalent hydrocarbon group may be substituted or unsubstituted with other monovalent hydrocarbon groups, and the monovalent hydrocarbon group may be substituted with another monovalent hydrocarbon group. When the monovalent hydrocarbon group is substituted, it may satisfy the total number of carbon atoms within the defined number of carbon atoms.
  • a method for preparing a block copolymer composition according to the present invention comprises: (S10) preparing a first mixed solution by adding an aromatic vinyl monomer and a compound represented by the following formula (1) to a hydrocarbon solvent and stirring the same; Adding a polymerization initiator to the first mixed solution and polymerizing the mixed solution to prepare a second mixed solution (S20); Adding a conjugated diene monomer to the second mixed solution and polymerizing to prepare a third mixed solution (S30); And (S40) adding a coupling agent to the third mixed solution and performing a coupling reaction, wherein the compound represented by the following formula (1) is added to the aromatic vinyl monomer and the conjugated diene monomer in a total amount of 100 parts by weight 0.26 parts by weight to 0.8 parts by weight.
  • M may be Li, Na, K, Rb or Cs
  • X may be N, O or S
  • R 1 and R 2 are each independently a monovalent hydrocarbon group having 1 to 12 carbon atoms, or the one having 1 to 12 carbon atoms containing an N or O atom itdoe be a hydrocarbon group, R 2 is not present when X is O or S.
  • the aromatic vinyl monomer and the compound represented by the formula (1) are subjected to a crosslinking reaction before introducing the polymerization initiator to initiate polymerization, May be evenly dispersed in the hydrocarbon solvent to further improve the reactivity upon introduction of the polymerization initiator.
  • the first mixed solution prepared in the step (S10) may include an aromatic vinyl monomer and a compound represented by the formula (1) on a hydrocarbon-based solvent.
  • the compound represented by the formula (1) serves to improve the reactivity of the polymerization reaction when the polymerization is initiated by the polymerization initiator and after the polymerization is initiated.
  • the catalyst may be a cocatalyst for a polymerization initiator that acts as a catalyst.
  • the polymerization initiator when the polymerization initiator is introduced in accordance with the step (S20) after the compound represented by the formula (1) is dispersed in the first mixed solution and the polymerization reaction is initiated, the polymerization initiator and the polymerization initiator The exchange of the metal ion between the compounds takes place and an alkalide in the form of [M: - ] is produced from the alkali metal represented by M in the above formula (1), and the polymerization reaction The overall reactivity of the block copolymer is improved, and the macrostructure of the block copolymer can be changed.
  • M may be Na or K, X may be N or O, and R 1 and R 2 are each independently a monovalent hydrocarbon group having 4 to 10 carbon atoms Lt; 2 > may not be present when X is O.
  • M may be Na or K, X may be N or O, and R 1 and R 2 are each independently n-butyl, iso-butyl, sec- Propyl, n-pentyl, n-hexyl, cyclopentyl, cyclohexyl, menthyl, where X is O Lt; 2 > may be absent.
  • the compound represented by Formula 1 may be at least one selected from the group consisting of sodium tert-pentoxide, sodium dicyclohexylamide, sodium mentholate, sodium tert-butoxide, potassium tert-pentoxide, potassium dicyclohexylamide, potassium mentholate, Potassium tert-butoxide, and the like. In this case, the reactivity of the polymerization reaction is maximized.
  • the compound represented by Formula 1 may be a compound represented by Formula 2 or 3.
  • the compound represented by Formula 1 may be used in an amount of 0.26 parts by weight to 0.8 parts by weight based on 100 parts by weight of the total amount of aromatic vinyl monomers and conjugated diene monomers to be added when preparing the block copolymer composition, 0.3 to 0.8 part by weight, or 0.4 to 0.6 part by weight, and within this range, the reactivity of the polymerization reaction is improved while preventing the side reaction, so that the prepared block copolymer composition is mixed with asphalt The solubility in the asphalt is increased, thereby improving the softening point of the asphalt composition.
  • the hydrocarbon solvent is not reacted with the polymerization initiator and can be used as long as it is usually used in the anionic polymerization reaction.
  • Specific examples thereof include butane, n-pentane, n-hexane, Linear or branched aliphatic hydrocarbon compounds such as octane; Cyclic aliphatic hydrocarbon compounds substituted or unsubstituted with alkyl groups such as cyclopentane, cyclohexane, cycloheptane, methylcyclohexane or methylcycloheptane; And an aromatic hydrocarbon compound which is substituted or unsubstituted with an alkyl group such as benzene, toluene, xylene or naphthalene. Any one or a mixture of two or more of them may be used.
  • the aromatic vinyl monomer to be added in the step (S10) may be at least one selected from the group consisting of styrene,? -Methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-cyclohexylstyrene, 4- (p-methylphenyl) styrene and 1-vinyl-5-hexyl naphthalene.
  • the aromatic vinyl monomer may be used in an amount of 10 to 50% by weight, 15 to 45% by weight, or 20 to 40% by weight, based on the total amount of the aromatic vinyl monomer and the conjugated diene monomer, %, And the content of the aromatic vinyl monomer-derived repeating unit block in the block copolymer is maintained at an appropriate level within this range, thereby improving the mechanical properties of the asphalt composition including the block copolymer composition.
  • the step (S10) may be carried out at a temperature of from 30 DEG C to 100 DEG C, or from 40 DEG C to 80 DEG C, and from 0.1 bar to 5.0 bar, or from 0.5 bar to 2.0 bar, Within this range, there is an effect of minimizing the prevention of by-products due to side reactions.
  • the step (S10) may be carried out by further adding a Lewis base.
  • the Lewis base may serve to improve the reactivity of the polymerization reaction by improving the polarity of the monomer throughout the polymerization reaction.
  • Specific examples thereof include tetrahydrofuran, ditetrahydrofuryl propane, diethyl ether, cycloalcohol ether, (Dimethylaminoethyl) ether, trimethylamine, triethylamine, diethylether, diethylether, diethylether, tertiary butoxyethoxyethane, bis (3-dimethylaminoethyl) Amine, tripropylamine, and tetramethylethylenediamine.
  • the step (S20) is a step of initiating polymerization at the time of polymerization of the block copolymer composition to form an aromatic vinyl monomer-derived repeating unit block for forming a block containing an aromatic vinyl monomer-
  • the second mixed solution prepared in the step (S20) may include a polymer for forming an aromatic vinyl monomer-derived repeating unit block.
  • the polymerization initiator may be an organometallic compound having a different kind from the compound represented by Formula 1.
  • Specific examples thereof include n-butyllithium, sec-butyllithium, tert-butyllithium, methyl
  • And may be at least one member selected from the group consisting of lithium, ethyl lithium, isopropyl lithium, cyclohexyl lithium, allyl lithium, vinyl lithium, phenyl lithium and benzyl lithium.
  • the polymerization initiator may be used in an amount of 0.01 mmol to 10 mmol, 0.05 mmol to 7 mmol, or 0.1 mmol to 5 mmol based on the total amount of the aromatic vinyl monomers and the conjugated diene monomers to be added in the preparation of the block copolymer composition, Within this range, the polymerization stability is excellent, the compound represented by the formula (1) is maximized in reactivity, and the obtained block copolymer composition has excellent physical properties.
  • the molar ratio (polymerization initiator: the compound represented by the formula (1)) of the polymerization initiator introduced in the step (S20) and the compound represented by the formula (1) can be 1: 0.05 to 1:15, 1: 0.2 to 1:10, or 1: 0.5 to 1: 5, and within this range, the reactivity of the polymerization reaction can be improved while preventing side reactions, There is an effect of improving the softening point of the asphalt composition containing the composite composition.
  • the polymerization reaction in the step (S20) is carried out at a temperature of from 30 DEG C to 100 DEG C, or from 40 DEG C to 80 DEG C and from 0.1 bar to 5.0 bar, or from 0.5 bar to 2.0 bar And the polymerization heat can be controlled within this range, and stable polymerization can be effected.
  • the polymerization initiator of the step (S20) is added simultaneously with the aromatic vinyl monomer of the step (S10) and the compound represented by the formula
  • the step (S10) and the step (S20) may be performed at the same time, and from the viewpoint of improving the polymerization reactivity, the step (S10) may be preferably carried out first.
  • step (S30) in the presence of the polymer for forming an aromatic vinyl monomer-derived repeating unit block contained in the second mixed solution prepared in the step (S20) A step for preparing a third mixed solution including a diblock copolymer containing an aromatic vinyl monomer-derived repeating unit block and a conjugated diene-based monomer-derived repeating unit block by adding and polymerizing a monomer.
  • the second mixed solution prepared in the step (S20) comprises a polymer for forming an aromatic vinyl monomer-derived repeating unit block, and the polymer is prepared by polymerizing the living anion in which the terminal of the polymer is in an anion active state Since the polymer is a polymer, the step (S30) may be carried out without the addition of a separate polymerization initiator. That is, in the step (S30), the polymerization reaction of the living anionic polymer and the conjugated diene monomer added thereto is carried out to obtain the aromatic vinyl monomer-derived repeating unit block followed by the conjugated diene monomer injected in the (S30) And a third mixed solution containing a diblock copolymer having a block formed thereon.
  • the conjugated diene-based monomer may be 1,3-butadiene, 2,3-dimethyl-1,3-butadiene, -1,3-butadiene, and 2-halo-1,3-butadiene (wherein halo means a halogen atom).
  • the conjugated diene monomer is used in an amount of 50 to 90% by weight, 55 to 85% by weight, or 60 to 80% by weight based on the total amount of the aromatic vinyl monomer and the conjugated diene monomer,
  • the content of the aromatic vinyl monomer-derived repeating unit block in the block copolymer can be maintained at an appropriate level within the above range to improve the mechanical properties of the asphalt composition comprising the block copolymer composition .
  • the polymerization reaction in step (S30) is carried out at a temperature of 30 to 150 DEG C, or 70 to 130 DEG C and a pressure of 0.1 to 10 bar, or 0.5 to 5 bar And the polymerization heat can be controlled within this range, and stable polymerization can be effected.
  • the living anion polymer distributed on the second mixed solution and the conjugated diene-based monomer do not contact with each other, It may happen that it is not carried out. Therefore, in addition to the diblock copolymer including the aromatic vinyl monomer-derived repeating unit block-conjugated dienic monomer-derived repeating unit block, the third mixed solution produced by the step (S30) A polymer comprising an aromatic vinyl monomer-derived repeating unit that has not been carried out.
  • a coupling agent &Lt
  • RTI ID 0.0 &gt
  • diblock &lt diblock &lt
  • / RTI &gt copolymer.
  • the third mixed solution prepared in the step (S30) comprises a diblock copolymer, and the terminal of the copolymer, specifically the terminal of the conjugated diene monomer-derived repeating unit block, is polymerized by polymerization in the preceding step (S30)
  • the living anionic copolymer is in an active state and therefore the functional group of the coupling agent is replaced with the living anionic copolymer depending on the number of functional groups that can be substituted or added in the coupling agent, A coupling reaction in which a living anionic copolymer is added can be performed.
  • the diblock copolymer may be linked by the coupling agent depending on the number of functional groups capable of substitution or addition contained in the coupling agent, and specifically, two or more diblock copolymers
  • the coalescent may be one that is coupled by the coupling agent-derived coupler, and more specifically, two to four diblock copolymers may be coupled by the coupling agent-derived coupler.
  • the block copolymer composition prepared according to the coupling reaction in the above step (S40) may further contain an aromatic group which does not undergo polymerization reaction with the conjugated diene monomer and does not participate in the coupling reaction
  • a diblock active copolymer including a polymer containing a vinyl monomer-derived repeating unit and an aromatic vinyl monomer-derived repeating unit block-conjugated diene monomer-derived repeating unit block that does not participate in the coupling reaction.
  • the coupling reaction of step (S40) is carried out at a temperature of from 30 DEG C to 150 DEG C, or from 60 DEG C to 130 DEG C, and from 0.1 bar to 10 bar, or from 0.5 bar to 5 bar And a stable reaction can be effected within this range.
  • the coupling agent introduced in the step (S40) is selected from the group consisting of a vinyl group-containing hydrocarbon compound, an ester compound, a silane compound, a polysiloxane compound and a polyketone
  • the coupling agent may be a polyfunctional coupling agent, a vinyl-containing hydrocarbon-based compound such as divinylbenzene, or the like; Ester compounds such as diethyl adipate, glycidyl methacrylate and the like; Silane compounds such as dimethyldichlorosilane, methyldichlorosilane, methoxysilane, glycidoxytrimethoxysilane, oxydipropyl bis (trimethoxysilane) and the like; polysiloxane-based compounds such as?,?
  • the coupling agent may be used in an amount of 0.01 mmol to 10 mmol, 0.05 mmol to 7 mmol, or 0.1 mmol to 5 mmol based on the total amount of the aromatic vinyl monomer and the conjugated diene monomer to be added in the preparation of the block copolymer composition Within this range, the coupling efficiency is increased, and the physical properties of the asphalt composition including the block copolymer composition produced are excellent, and the softening point is increased.
  • the block copolymer composition according to the present invention comprises a block copolymer comprising a repeating unit block derived from an aromatic vinyl monomer, a repeating unit block derived from a conjugated diene monomer, and a coupling agent derived from a coupling agent, Ring efficiency may be 50% to 80%.
  • the block copolymer composition may be a block copolymer composition prepared by the above-described method for producing a block copolymer composition.
  • the block copolymer composition has a weight average molecular weight of from 10,000 g / mol to 500,000 g / mol, or from 30,000 g / mol to 300,000 g / mol, or from 50,000 g / mol to 200,000 g / mol
  • the coupling efficiency by the coupler derived from the coupling agent may be 50% to 80%, 60% to 80%, or 70% to 80%.
  • the block copolymer composition preferably contains 10 to 50% by weight, 15 to 45% by weight, or 20 to 20% by weight, based on the entire block copolymer, of the total content of repeating units derived from aromatic vinyl monomers in the block copolymer
  • the vinyl content in the repeating unit block derived from the conjugated dienic monomer is 10 to 50 mol%, 15 to 40 mol%, or 20 mol% based on the total amount of the repeating units derived from the conjugated diene monomer, To 30 mol%.
  • the weight average molecular weight, the coupling efficiency, the content of the repeating unit derived from an aromatic vinyl monomer, and the vinyl content in the repeating unit block derived from the conjugated diene monomer are related to the structural characteristics of the block copolymer.
  • the mechanical properties of the asphalt composition containing the copolymer composition as a modifier are excellent.
  • the coupling efficiency may be calculated by the following equation (1).
  • Coupling efficiency (%) ⁇ (area of coupled polymer) / (area of whole polymer) ⁇ X 100
  • an asphalt composition comprising the block copolymer composition as an asphalt modifier.
  • the asphalt composition may comprise the block copolymer composition and asphalt.
  • the block copolymer composition may be contained in an amount of 1 wt% to 10 wt%, 3 wt% to 8 wt%, or 4 wt% to 6 wt% based on the entire content of the asphalt composition, The solubility of the copolymer composition in the asphalt is excellent, and the physical properties of the asphalt composition are excellent.
  • the asphalt composition may further include a cross-linking agent for cross-linking the asphalt composition.
  • the cross-linking agent may be a sulfur compound containing sulfur or iron sulfate.
  • Specific examples of the cross-linking agent may be a sulfur element (powder), and the cross-linking agent may be added in an amount of 0.01 to 3 parts by weight based on 100 parts by weight of the total amount of the asphalt and the block- Or 0.05 part by weight to 1 part by weight, or 0.05 part by weight to 0.5 part by weight, and the proper crosslinking reaction is maintained within this range to improve physical properties and elastic properties at high temperature, and to prevent gelation.
  • the asphalt composition has a softening point measured according to ASTM D36 of 71.2 ° C or more, or 72.5 ° C to 75.5 ° C, an elongation measured according to ASTM D113 of 39.6 cm or more, or 40.3 cm To 41.3 cm and a viscosity at 160 ⁇ ⁇ measured according to ASTM D4402 of 428 cps or less, or 405 cps to 422 cps.
  • the asphalt composition may have a phase separation temperature of 4.5 ⁇ or less, 0 ⁇ to 4.5 ⁇ , or 2.3 ⁇ to 2.7 ⁇ , and the block copolymer composition and the asphalt are excellent in compatibility with each other, The effect is excellent.
  • the asphalt composition when the asphalt composition further comprises a cross-linking agent, the asphalt composition has a softening point of 83.6 ° C or higher, measured according to ASTM D36, or 84.3 ° C to 86.5 ° C, The elongation measured is 30 cm or more, or 31.0 cm to 33.3 cm, and the viscosity at 160 ° C measured according to ASTM D4402 is 598 cps or less, or 570 cps to 588 cps.
  • the asphalt composition when the asphalt composition further comprises a crosslinking agent, the asphalt composition has a phase separation temperature of 3 ° C or lower, 0 ° C to 3 ° C, or 1.2 ° C to 1.7 ° C. Within this range, excellent compatibility of the block copolymer composition and asphalt is obtained, and the mechanical properties of the asphalt composition are excellent.
  • the asphalt composition may be a building material such as a road pavement material or a waterproof material.
  • a reactor of 10 L substituted with argon was set to a temperature of 50 ° C and a pressure of 1.0 bar, and 5,000 g of cyclohexane, 300 g of styrene and 50 g of tetrahydrofuran were added and stirred. During the stirring, 5 g of sodium tert-pentoxide was added and stirring was further continued for 10 minutes. Subsequently, 35 g of n-butyllithium was added to initiate polymerization. After the initiation of polymerization, 700 g of 1,3-butadiene was added to polymerize 10 minutes after the polymerization temperature reached the maximum temperature of 80 ⁇ .
  • Example 1 The procedure of Example 1 was repeated, except that 5 g of sodium dicyclohexylamide was added instead of sodium tert-pentoxide.
  • Example 1 The procedure of Example 1 was repeated, except that 5 g of sodium mentholate was added instead of sodium tert-pentoxide.
  • Example 1 The procedure of Example 1 was repeated, except that 5 g of sodium tert-butoxide was added instead of sodium tert-pentoxide in Example 1.
  • Example 1 The procedure of Example 1 was repeated, except that 5 g of potassium tert-pentoxide was added instead of sodium tert-pentoxide.
  • Example 1 The procedure of Example 1 was repeated, except that 5 g of potassium dicyclohexylamide was used instead of sodium tert-pentoxide.
  • Example 1 The procedure of Example 1 was repeated, except that 5 g of potassium mentholate was added instead of sodium tert-pentoxide.
  • Example 1 The procedure of Example 1 was repeated, except that 5 g of potassium tert-butoxide was added in place of sodium tert-pentoxide in Example 1.
  • Example 1 the same procedure as in Example 1 was carried out except that sodium tert-pentoxide was not added.
  • Example 1 The procedure of Example 1 was repeated, except that 5.8 g of sodium dimethoxymethylsilane was used instead of 5 g of sodium tert-pentoxide in Example 1.
  • Example 1 The procedure of Example 1 was repeated except that 9.1 g of sodium 4-methylcyclohexane-1-sulfonate was added instead of 5 g of sodium tert-pentoxide in Example 1. The same procedure was followed.
  • Example 1 the procedure of Example 1 was repeated, except that 9.5 g of sodium 2-naphthalenesulfonate was added instead of 5 g of sodium tert-pentoxide.
  • Example 1 The procedure of Example 1 was repeated, except that 12 g of sodium tert-pentoxide was added in place of 5 g in Example 1.
  • Example 1 In the same manner as in Example 1, except that 0.05 g of sodium tert-pentoxide was added instead of 5 g in Example 1.
  • a reactor of 10 L substituted with argon was set to a temperature of 50 ° C and a pressure of 1.0 bar, and 5,000 g of cyclohexane, 300 g of styrene and 50 g of tetrahydrofuran were added and stirred. During stirring, 35 g of n-butyllithium and 5 g of sodium tert-pentoxide were added to initiate polymerization. After the initiation of polymerization, 700 g of 1,3-butadiene was added to polymerize 10 minutes after the polymerization temperature reached the maximum temperature of 80 ⁇ .
  • the styrene-derived repeating unit (SM) content (wt%) and the vinyl content (mol%) in the repeating unit derived from 1,3-butadiene are shown in Tables 1 and 2.
  • the weight average molecular weight and each content were measured by GPC (Gel Permeation Chromatograph) analysis, and the coupling efficiency was calculated according to the following equation (1).
  • the GPC was used in combination with two PLgel Olexis (Polymer Laboratories) columns and one PLgel mixed-C (Polymer Laboratories) column.
  • the GPC standard material was polystyrene (PS) in molecular weight calculation.
  • Coupling efficiency (%) ⁇ (area of coupled polymer) / (area of whole polymer) ⁇ X 100
  • the block copolymer compositions of Examples 1 to 8 and the block copolymer compositions of Comparative Examples 1 to 7 prepared according to the present invention had equivalent weight average molecular weights, coupling efficiencies, Styrene content and vinyl content.
  • Viscosity (cps): After the asphalt composition was prepared, the viscosity at 160 ⁇ ⁇ was measured according to ASTM D4402 on the condition of spindle 27 using a Brookfiled DV-II + Pro Model.
  • phase separation temperature 50 g of the asphalt composition was weighed in an aluminum tube, stored in an oven at 163 DEG C for 48 hours, stored in a cooler at -5 DEG C for 4 hours or more, was measured according to ASTM D36 and the phase separation temperature was calculated from the difference in measured softening point.
  • phase separation temperature is within 3 ⁇ , it means that phase separation does not occur, and when the difference in softening point is small, dissolution with asphalt is good.
  • the inventors of the present invention have found that when the block copolymer composition is produced according to the present invention and the block copolymer composition thus prepared is used as an asphalt modifier, the overall physical properties of the asphalt composition, that is, the modified asphalt, , But it was confirmed that the softening point was increased.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Civil Engineering (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Graft Or Block Polymers (AREA)

Abstract

La présente invention concerne un procédé de préparation d'une composition de copolymère séquencé et, plus spécifiquement, un procédé de préparation d'une composition de copolymère séquencé, et une composition d'asphalte comprenant une composition de copolymère séquencé préparée par ce procédé, le procédé comprenant les étapes consistant à : (S10) préparer une première solution de mélange par injection d'un monomère de vinyle aromatique et d'un composé représenté par la formule chimique 1 dans un solvant à base d'hydrocarbure et agiter celui-ci ; (S20) préparer une deuxième solution de mélange par ajout d'un initiateur de polymérisation à la première solution de mélange et polymériser celle-ci ; (S30) préparer une troisième solution de mélange par ajout d'un monomère à base de diène conjugué à la deuxième solution de mélange et polymériser celle-ci ; et (S40) effectuer une réaction de couplage par ajout d'un agent de couplage à la troisième solution de mélange, le composé représenté par la formule chimique 1 étant injecté dans une quantité de 0,26 à 0,8 part massique sur la base de 100 parts massiques de la quantité totale du monomère de vinyle aromatique et du monomère à base de diène conjugué.
PCT/KR2018/014040 2017-11-17 2018-11-15 Procédé de préparation d'une composition de copolymère séquencé, et composition d'asphalte comprenant une composition de copolymère séquencé préparée par ce procédé WO2019098724A1 (fr)

Priority Applications (5)

Application Number Priority Date Filing Date Title
EP18879379.8A EP3712186B1 (fr) 2017-11-17 2018-11-15 Procédé de préparation d'une composition de copolymère séquencé
US16/637,008 US11603462B2 (en) 2017-11-17 2018-11-15 Method for preparing block copolymer composition, and asphalt composition comprising block copolymer composition prepared thereby
JP2020506344A JP6902672B2 (ja) 2017-11-17 2018-11-15 ブロック共重合体組成物の製造方法、これによって製造されたブロック共重合体組成物を含むアスファルト組成物
RU2020105626A RU2779797C2 (ru) 2017-11-17 2018-11-15 Способ получения блок-сополимерной композиции и асфальтовой композиции, содержащей полученную таким образом блок-сополимерную композицию
CN201880051309.XA CN111032717B (zh) 2017-11-17 2018-11-15 制备嵌段共聚物组合物的方法和包含由其制备的嵌段共聚物组合物的沥青组合物

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
KR10-2017-0153820 2017-11-17
KR20170153820 2017-11-17
KR1020180136621A KR102464763B1 (ko) 2017-11-17 2018-11-08 블록 공중합체 조성물 제조방법, 이로부터 제조된 블록 공중합체 조성물을 포함하는 아스팔트 조성물
KR10-2018-0136621 2018-11-08

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WO2019098724A1 true WO2019098724A1 (fr) 2019-05-23

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20060093669A (ko) * 2005-02-22 2006-08-25 롬 앤드 하아스 컴패니 보호된 촉매 조성물, 그의 제조 방법 및 에틸렌계 불포화모노머로부터 폴리머를 제조하기 위한 그의 용도
KR20120000539A (ko) * 2010-06-25 2012-01-02 차이나 페트로리움 앤드 케미컬 코포레이션 성상 블록 구조를 가진 3성분계 코폴리머 고무, 그 제조 방법 및 용도
KR20150037452A (ko) * 2013-09-30 2015-04-08 주식회사 엘지화학 아스팔트 개질제 및 이를 포함하는 개질 아스팔트 조성물
WO2017130065A1 (fr) * 2016-01-26 2017-08-03 Dynasol Elastómeros, S.A. De C.V. Élastomères thermoplastiques contre coniques

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20060093669A (ko) * 2005-02-22 2006-08-25 롬 앤드 하아스 컴패니 보호된 촉매 조성물, 그의 제조 방법 및 에틸렌계 불포화모노머로부터 폴리머를 제조하기 위한 그의 용도
KR20120000539A (ko) * 2010-06-25 2012-01-02 차이나 페트로리움 앤드 케미컬 코포레이션 성상 블록 구조를 가진 3성분계 코폴리머 고무, 그 제조 방법 및 용도
KR20150037452A (ko) * 2013-09-30 2015-04-08 주식회사 엘지화학 아스팔트 개질제 및 이를 포함하는 개질 아스팔트 조성물
WO2017130065A1 (fr) * 2016-01-26 2017-08-03 Dynasol Elastómeros, S.A. De C.V. Élastomères thermoplastiques contre coniques

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
BOISSON, C.: "Lanthanidocene catalysts for the homo- and copolymerization of ethylene with butadiene", 295052 MACROMOLECULAR CHEMISTRY AND PHYSICS, vol. 204, no. 14, 1 September 2003 (2003-09-01), pages 1747 - 1754, XP055295052 *
See also references of EP3712186A4 *

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