KR20130010962A - Functionalized vinyl aromatic hydrocarbon-conjugated diene block copolymer composition, method of preparing the same and asphalt composition comprising the same - Google Patents
Functionalized vinyl aromatic hydrocarbon-conjugated diene block copolymer composition, method of preparing the same and asphalt composition comprising the same Download PDFInfo
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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
- C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
- C08F236/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
- C08F236/10—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated with vinyl-aromatic monomers
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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
- 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
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- 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
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- 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
Abstract
The functionalized vinyl aromatic hydrocarbon-conjugated diene block copolymer composition, which is composed of a multiblock copolymer and a diblock copolymer including an aldehyde structure according to the present invention, is functionalized without decreasing molecular weight and is compatible with asphalt. It is excellent in reducing the processing time of the asphalt composition, and also greatly improve the low temperature elongation and storage stability of the asphalt composition, the vinyl aromatic hydrocarbon-conjugated diene block copolymer, a method for preparing the same and an asphalt composition comprising the same have.
Description
The present invention relates to a functionalized vinyl aromatic hydrocarbon-conjugated diene block copolymer composition, a method for preparing the same, and an asphalt composition comprising the same. More specifically, the functionalized vinyl aromatic hydrocarbon-conjugated diene block copolymer composition is functionalized without lowering the molecular weight and has excellent compatibility with asphalt. A functionalized vinyl aromatic hydrocarbon-conjugated diene block copolymer composition having an effect of improving the dissolution rate of the composition and improving physical properties of the low temperature elongation and softening point of the asphalt composition, a preparation method thereof, and an asphalt composition comprising the same.
Block copolymers are widely used as modifiers to improve the physical properties of asphalt compositions, or impact modifiers of other resins. In particular, vinyl aromatic hydrocarbon-conjugated diene block copolymers are frequently used as asphalt modifiers. The dissolution of vinyl aromatic hydrocarbon-conjugated diene block copolymers in asphalt at high temperatures is time consuming and expensive. Therefore, the most important physical property of the block copolymer used as the asphalt modifier is compatibility with asphalt. Excellent compatibility with asphalt can shorten processing time and improve physical properties.
Asphalt is composed of four components, among which the least compatible with the block copolymer is asphaltenes. Asphaltene is an aggregate of aromatic hydrocarbons, and thus contains a large number of hydrophilic functional groups at its terminals, and thus is poor in compatibility with block copolymers having no hydrophilic functional groups. Thus, asphaltene is a component that greatly prolongs the processing time or production time of the asphalt composition.
Therefore, many studies have been conducted to introduce hydrophilic functional groups into the block copolymer in order to improve compatibility with asphalt. Typical among them is a method of mixing a vinyl aromatic hydrocarbon-conjugated diene block copolymer and a hydrophilic monomer at a high temperature in an extruder to introduce a hydrophilic functional group into the branches of the block copolymer.
However, this method requires additional installation of expensive manufacturing equipment, and also has a limitation in that uniform functionalization in the block copolymer is difficult. In particular, the block copolymer made of vinyl aromatic hydrocarbon-conjugated diene may be partially oxidized at high temperature and high pressure in the extruder, and also the breakage of the polymer chain occurs mainly, resulting in a decrease in molecular weight and severe degradation of physical properties.
Therefore, there is an urgent need to develop a block copolymer for asphalt modifiers having excellent compatibility and functionalization without lowering the molecular weight.
In order to solve the problems of the prior art as described above, the present invention is functionalized without lowering the molecular weight, and excellent compatibility with asphalt, having the effect of improving the dissolution rate of the asphalt composition, and at the same time low temperature elongation and softening point of the asphalt composition An object of the present invention is to provide a functionalized vinyl aromatic hydrocarbon-conjugated diene block copolymer composition having improved physical properties, a method for preparing the same, and an asphalt composition comprising the same.
These and other objects of the present invention can be achieved by the present invention described below.
In order to achieve the above object, the present invention provides a vinyl aromatic hydrocarbon-conjugated diene diblock copolymer having an aldehyde group bonded to a main chain of a conjugated diene block and a vinyl aromatic hydrocarbon-conjugated diene having an aldehyde group bonded to a main chain of a conjugated diene block. Provided is a functionalized vinyl aromatic hydrocarbon-conjugated diene block copolymer composition, a method for preparing the same, and an asphalt composition comprising the multiblock copolymer.
As described above, according to the present invention, functionalized without lowering the molecular weight, excellent compatibility with asphalt, significantly shortened the processing time of the asphalt composition, and also greatly improved low temperature elongation and softening point of the asphalt composition. There is an effect of providing a vinylated hydrocarbon aromatic-conjugated diene block copolymer composition, a preparation method thereof and an asphalt composition comprising the same.
1 is a micrograph of the state in which the functionalized block copolymer is not completely dissolved and the state in which the functionalized block copolymer is completely dissolved in the asphalt composition of the present invention at 400 times magnification.
Hereinafter, the present invention will be described in detail.
The present inventors can significantly improve the solubility in the production of modified asphalt including hydroformylated styrene-butadiene block copolymers, and can significantly shorten the dissolution time by 20% compared to the conventional styrene-butadiene block copolymers. In addition, the low temperature elongation properties and storage stability of the polymer modified asphalt (polymer modified asphalt) is confirmed that the other properties are maintained, and based on this, the present invention has been completed. In particular, when the styrene-butadiene block copolymer has an aldehyde group of less than 50ppm to less than 1,600ppm based on its mass, dissolution time is reduced by 20% compared with the conventional one when producing modified asphalt. This property can be demonstrated by observing the phase separation of the modified asphalt. Phase separation is a phenomenon in which the styrene-butadiene block copolymer is divided into an upper layer containing a large amount of styrene-butadiene block copolymer and a lower layer containing a small amount due to the incompatibility between the asphalt and the styrene-butadiene block copolymer. The presence or absence of such a phenomenon can be seen by the difference between the softening point of the upper layer and the lower layer of the modified asphalt, which was left at 163 ° C for 48 hours. The modified asphalt, in which the first two components are completely dissolved, has a difference in softening point between the upper and lower layers of 2 ° C or less. For modified asphalts using hydroformylated styrene-butadiene block copolymers, a total dissolution time of 9 hours is required before passing the phase separation test, but 11 hours of conventional styrene-butadiene block copolymers are required. Dissolution time is required.
The present invention provides A) a vinyl aromatic hydrocarbon-conjugated diene diblock copolymer having an aldehyde group bonded to the main chain of the conjugated diene block; And B) a vinyl aromatic hydrocarbon-conjugated diene multiblock copolymer in which an aldehyde group is bonded to the main chain of the conjugated diene block, thereby providing a functionalized vinyl aromatic hydrocarbon-conjugated diene block copolymer composition.
In a preferred embodiment, the functionalized styrene-butadiene block copolymer composition according to the present invention comprises: A) an aldehyde group (
The multiblock copolymer is 40 to 100% by weight, the diblock copolymer is preferably 0 to 60% by weight, more preferably the triblock copolymer is 50 to 99% by weight, the diblock air The coalescence is 1 to 50% by weight, solubility in asphalt and excellent physical properties within this range. Here, the multiblock copolymer is a copolymer composed of blocks of triblocks or more, for example, styrene-butadiene-styrene copolymer.
The content of the aldehyde structure in the polymer is preferably 50 to 1600ppm, more preferably 100 to 1600ppm, and most preferably 300 to 1600ppm based on the weight ratio (based on the total polymer weight 1), the asphalt within this range It has the effect of excellent compatibility with storage stability.
Carboxylic acid structure in the butadiene block (
The carboxylic acid structure is preferably 1600 ppm or less, more preferably 300 to 1600 ppm with respect to the total weight of the functionalized vinyl aromatic hydrocarbon-conjugated diene block copolymer, and compatibility with asphalt and storage stability within this range. This has an excellent effect.
The vinyl aromatic hydrocarbon and the conjugated diene preferably have a weight ratio of 5:95 to 50:50, and more preferably 15:85 to 40:60, and improve high and low temperature physical properties of the asphalt composition within this range. It is effective to let.
The functionalized vinyl aromatic hydrocarbon-conjugated diene block copolymer may have a weight average molecular weight of 10,000 to 1,000,000, preferably 30,000 to 500,000, more preferably 30,000 to 350,000, more preferably 40,000 to 120,000, Within this range, there is an effect of improving the high temperature and low temperature properties as the asphalt modifier.
The functionalized vinyl aromatic hydrocarbon-conjugated diene block copolymer may include a vinyl aromatic hydrocarbon-conjugated diene copolymer block in which the vinyl aromatic hydrocarbon and the conjugated diene are randomly or cross-aligned.
The vinyl aromatic hydrocarbons include styrene, α-methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-propylstyrene, 1-vinylnaphthalene, 4-cyclohexylstyrene, 4- (p-methylphenyl) styrene and 1-vinyl 1 or more types chosen from the group which consists of -5-hexyl naphthalene, etc. are preferable, More preferably, it is styrene.
The conjugated diene is composed of 1,3-butadiene, 2,3-dimethyl-1,3-butadiene, piperylene, 3-butyl-1,3-octadiene, isoprene and 2-phenyl-1,3-butadiene At least one selected from the group is preferred, and more preferably 1,3-butadiene.
The functionalized vinyl aromatic hydrocarbon-conjugated diene block copolymer may be preferably coupled with a coupling agent, and may be applied to a block copolymer prepared by continuously adding a monomer without using a coupling agent.
As the coupling agent, one or more groups of methyl tetrachloride, methyl trichloride, methyl dichloride, and the like can be selected and used. Preferably, methyl tetrachloride and methyl dichloride are used.
The coupling may be preferably an efficiency of 40 to 100%, within this range has excellent compatibility with asphalt and excellent effect of the high and low temperature properties of the asphalt composition.
The functionalized vinyl aromatic hydrocarbon-conjugated diene block copolymer is preferably represented by the following formula (1).
Wherein A to D are independently CH 2 -CH = CH-CH or CH 2 -CH when butadiene is used as the conjugated die, provided that all of A to D are CH 2 -CH = CH-CH or CH 2 May not be -CH), wherein W to Z is H when A, B, C or D is CH 2 -CH = CH-CH, and is one of a vinyl group, a carboxyl group or an aldehyde group when CH 2 -CH, d, e, f and g satisfy the number ratio of 1,4 structure, vinyl structure, carboxyl group and aldehyde structure, wherein G is one of vinyl aromatic hydrocarbon, CH 2 CHO or CH 2 COOH, and p is vinyl aromatic Represents the number ratio of A, B, C and D of hydrocarbon, CH 2 CHO or CH 2 COOH, wherein F is a vinyl aromatic hydrocarbon block, H, CH 2 CHO, CH 2 COOH or a coupling group, q is the number of arms around F.
And the A ~ D can include one or more of the hydrogen present in the 2 -CH = CH-CH or CH 2 CH -CH is substituted with a substituent such as an alkyl group.
[G] p − may be preferably a vinyl aromatic hydrocarbon block.
The q is preferably 1 to 10, more preferably 1 to 4, provided that q is 1 when F is H, CH 2 CHO or CH 2 COOH, and 1 to F when F is a vinyl aromatic hydrocarbon block. 2).
The coupling group is derived from a coupling agent and is produced by a coupling reaction of a polymer and a coupling agent.
The functionalized vinyl aromatic hydrocarbon-conjugated diene block copolymer is preferably a mixture of at least one of the block copolymers represented by the formula (1).
The functionalized vinyl aromatic hydrocarbon-conjugated diene block copolymer may be preferably composed of a triblock copolymer and a diblock copolymer. In this case, the solubility in asphalt and the physical properties are excellent.
The triblock copolymer is a copolymer in which two or more diblock copolymers are bonded by a coupling agent, and the diblock copolymer is a copolymer consisting of a conjugated diene block and a vinyl aromatic hydrocarbon block which is not coupled by a coupling agent. .
The oxidation is preferably carried out by hydroformylation or hydrocarbon decomposition using an active gas discharged without corona discharge. In the case of the hydroformylation reaction, the vinyl structure in the conjugated diene block is preferentially oxidized to generate an aldehyde group, and the degree of functionalization can be easily controlled through the catalyst and reaction time, temperature, and pressure. On the other hand, in the case of hydrocarbon decomposition reaction using an unactivated (corona) discharged active gas, there is an excellent effect on the thermal stability and discoloration of the product by not using a metal catalyst other than controlling the functionalization through the preferential oxidation and reaction time of the vinyl structure in the conjugated diene block. have.
The modifier of the present invention is characterized in that it comprises the functionalized vinyl aromatic hydrocarbon-conjugated diene block copolymer.
Asphalt composition of the present invention is characterized in that it comprises the modifier and asphalt.
The asphalt preferably contains asphaltenes. In this case, the viscosity of the asphalt modifier and the physical properties of the softening point are improved, but there is a phenomenon in which manufacturing time or dissolution time increases.
The weight ratio of the modifier and the asphalt is preferably 0.1: 99.1 to 20:80, and more preferably 1:99 to 10:90. In this case, the effect of the processing time and storage stability and the physical properties of the asphalt composition is excellent. have.
The storage stability can be evaluated by sampling the softening point by the method of American Association of State Highway and Transportation Officials (AASHTO) PP5, and then measuring each softening point by the American Society Testing and Materials (ASTM) D36 method. The phase separation does not occur when the temperature is within 2.5 ℃, and the smaller the difference is, the better the storage stability is.
The asphalt composition is preferably 6 to 15 hours, more preferably 8 to 13 hours, based on the non-vulcanizing conditions (without vulcanizing agent) containing 5% by weight of the modifier. Within this range, there is an excellent effect of balancing the physical properties of the asphalt composition.
In addition, the functionalized vinyl aromatic hydrocarbon-conjugated diene block copolymer composition according to the present invention comprises the steps of: a) preparing a vinyl aromatic hydrocarbon-conjugated diene diblock copolymer having an aldehyde group bonded to the main chain of the conjugated diene block; b) preparing a vinyl aromatic hydrocarbon-conjugated diene multiblock copolymer having an aldehyde group bonded to the main chain of the conjugated diene block; c) mixing the vinyl aromatic hydrocarbon-conjugated diene diblock copolymer and the vinyl aromatic hydrocarbon-conjugated diene multiblock copolymer in a weight ratio of 10 to 30:70 to 90; And d) the block copolymer mixture is prepared by performing a hydroformylation reaction.
The method for producing the functionalized vinyl aromatic hydrocarbon-conjugated diene block copolymer of the present invention includes the step of selectively oxidizing the vinyl structure in the conjugated diene block of the vinyl aromatic hydrocarbon-conjugated diene block copolymer to generate an aldehyde group. It features.
The method for producing the functionalized vinyl aromatic hydrocarbon-conjugated diene block copolymer has a molecular weight ratio of the vinyl aromatic hydrocarbon-conjugated diene block copolymer before oxidation and the vinyl aromatic hydrocarbon-conjugated diene block copolymer after oxidation (pre-oxidation block copolymer / Post-oxidation block copolymer) may be 0.9 to 1.1, preferably 1.005 to 1.105, more preferably 1.010 to 1.103, most preferably 1.010 to 1.100, within the range is commercially available when applied to asphalt compositions Stability, shortening of processing time, low temperature elongation and storage stability are greatly improved.
The oxidation is preferably carried out by a hydrocarbon decomposition reaction using a hydroformylation-free (corona) discharged active gas. In the case of the hydroformylation reaction, the vinyl structure in the conjugated diene block is preferentially oxidized to generate an aldehyde group, and the degree of functionalization can be easily controlled through the catalyst and reaction time, temperature, and pressure. On the other hand, in the case of hydrocarbon decomposition reaction using an unactivated (corona) discharged active gas, there is an excellent effect on the thermal stability and discoloration of the product by not using a metal catalyst other than controlling the functionalization through the preferential oxidation and reaction time of the vinyl structure in the conjugated diene block. have.
An example of ozone decomposition reaction of the vinyl aromatic hydrocarbon-conjugated diene block copolymer may be described in the following scheme 1 and scheme 2, and the functionalized vinyl aromatic hydrocarbon-conjugated diene block copolymer may be represented by the following Formula 2 It may include one or more selected from the group consisting of compounds represented by the formula (3) and formula (4).
[Reaction Scheme 1]
In the above formula, PS represents a polymer block composed of vinyl aromatic hydrocarbons, and m, n, a, b, and c are integers greater than 0, which are blocks of other conjugated diene systems. At this time, m + n ≧ 1 and n = a + b + c.
The reaction scheme 1 is a vinyl aromatic hydrocarbon-conjugated diene block copolymer is reacted with an active gas produced by a silent (corona) discharge, and partial oxidation proceeds as the double bond is decomposed in the vinyl structure, thereby the compound represented by Formula 2 Is generated.
Scheme 2
In the above formula, PS represents a polymer block made of vinyl aromatic hydrocarbon, and m, n, d, e, f, g, h, i, j, k are integers greater than 0, and the number of blocks of other conjugated diene systems. At this time, m + n ≧ 1, m = d + h + l, n = e + f + g + i + j + k.
In Scheme 2, the vinyl aromatic hydrocarbon-conjugated diene block copolymer is reacted with an active gas generated by an a silent (corona) discharge to partially oxidize in a vinyl structure to generate a compound represented by Chemical Formulas 3 and 4.
The vinyl aromatic hydrocarbon-conjugated diene block copolymer is not particularly limited as long as it can be commonly used as an asphalt modifier, but specific examples include sequentially adding vinyl aromatic hydrocarbon and conjugated diene to a reactor containing a hydrocarbon solvent and an organolithium compound. , -5 to 150 ℃ and under the pressure range (0.1 ~ 10 bar) in which the reactant can be maintained in the liquid phase to proceed with the polymerization until the consumption rate of the monomer is more than 99%, or after the addition of the coupling agent, the prepared block After connecting the conjugated diene blocks between the copolymers, water or alcohol may be added to remove the activity of the active polymer and terminate the polymerization.
The hydrocarbon solvent may be at least one selected from the group consisting of n-pentane, n-hexane, n-heptane, isooctane, cyclohexane, toluene, benzene, xylene and naphthalene hydrocarbon solvents, preferably n-hexane, Cyclohexane or a mixture thereof.
A polar solvent may be added to the hydrocarbon solvent, which serves to control the content of the vinyl structure and improve the polymerization rate during the conjugated diene polymerization.
The polar solvent may be at least one selected from the group consisting of tetrahydrofuran, ethyl ether, tetramethylethylene diamine, benzofuran, and the like, more preferably tetrahydrofuran.
It is preferable that the said free lithium compound is an alkyl lithium compound, More preferably, it is an alkyl lithium compound which has a C3-C10 alkyl group.
The organolithium compound may be methyl lithium, ethyl lithium, isopropyl lithium, n-butyl lithium, sec-butyl lithium or tert-butyl lithium, and the like, and more preferably n-butyl lithium or sec-butyl lithium.
The hydrocarbon decomposition reaction by the active gas may be carried out by adding an active gas generated by a silent (corona) discharge to a solution consisting of the vinyl aromatic hydrocarbon-conjugated diene block copolymer and the hydrocarbon solvent.
The solvent of the hydrocarbon decomposition reaction by the active gas may be the same as the contents of the hydrocarbon solvent and the polar solvent.
The polymer solution is a viscous solution, preferably containing 1 to 30% by weight of a vinyl aromatic hydrocarbon-conjugated diene block copolymer.
The active gas is preferably added while the solution is maintained at a predetermined temperature.
The temperature range is preferably 0 to 100 ° C, more preferably 25 to 90 ° C. Within this range, the viscosity of the solution is reduced and the reactivity with the active gas is greatly improved.
The active gas may be manufactured by an a silent (corona) discharge, and a mixed gas containing one of gases such as nitrogen, oxygen, carbon monoxide, carbon dioxide, and argon may be used as a raw material gas.
The active gas is preferably flowed into the solution.
It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the spirit or scope of the present invention. Such variations and modifications are intended to be within the scope of the appended claims.
[Example]
<Production of SB Diblock Copolymer>
5,600 g of purified cyclohexane and 322 g of styrene were added to a 20 L reactor substituted with nitrogen, and the temperature was raised to 50 ° C. while stirring. At 50 ° C., 1.1 g of n-butyllithium was added to the cyclohexane and styrene mixed solution to polymerize a styrene block, and then 717 g of butadiene was added thereto, followed by polymerization until the butadiene was completely consumed.
After completion of the reaction, 0.2g of water was added to the reactor to terminate the activity of the active polymer to proceed with a terminating reaction. The weight average molecular weight was 55.151 g / mol, and the styrene block content was diblock styrene-butadiene block. Copolymers were prepared.
After the termination reaction, 7.5 g of Irganox1076 (Ciba Specialty Chemicals Co.) and 15.0 g of TNPP (Weston Chemical Co.), an antioxidant, were added to the polymerization solution to prepare a styrene-butadiene block copolymer solution.
<Production of SBS Triblock Copolymer>
5,600 g of purified cyclohexane and 322 g of styrene were added to a 20 L reactor substituted with nitrogen, and the temperature was raised to 50 ° C. while stirring. 1.1 g of n-butyllithium was added to the cyclohexane and styrene mixed solution at 50 ° C. to polymerize a styrene block, and then 1434 g of butadiene was added thereto, followed by polymerization until the butadiene was completely consumed.
After the butadiene was completely consumed, 322 g of styrene was added thereto, followed by polymerization to prepare a linear block copolymer.
After completion of the polymerization reaction, 0.2g of water was added to the reactor to terminate the activity of the active polymer, followed by a termination reaction to remove the active polymer. Copolymers were prepared.
After the termination reaction, 7.5 g of Irganox1076 (Ciba Specialty Chemicals Co.) and 15.0 g of TNPP (Weston Chemical Co.), an antioxidant, were added to the polymerization solution to prepare a styrene-butadiene block copolymer solution.
Example One
Preparation of Functionalized Copolymers
100 g of the styrene-butadiene diblock copolymer solution and 900 g of the styrene-butadiene-styrene triblock copolymer were mixed so that the ratio of styrene-butadiene diblock copolymer and styrene-butadiene-styrene triblock copolymer was 10:90 (weight ratio ) Into a 3L reaction vessel with an external temperature jacket to which a gas activator was connected and set at 65 ° C., followed by stirring at 500 rpm. When the temperature of the reaction vessel was kept constant at 65 ° C, turn on the gas activator connected to the air cylinder, set the voltage of the gas activator to 12% and the flow rate to 1LPM (Liter per minute), and then press the operation button. (Run) was pressed and the active gas was flowed into the styrene-butadiene block copolymer solution stirred for 10 minutes.
After turning off the run (Run), by flowing only 10 minutes to the block copolymer solution to remove the active gas to prepare a functionalized styrene-butadiene block copolymer having a weight average molecular weight of 103,000g / mol.
<Production of Asphalt Composition>
500 g of AP-5 asphalt purchased from SK Innovation Co., Ltd. was placed in a mixing vessel, and the temperature was maintained at 170 ° C. and the stirring speed was 2000 rpm. Then, 26 g of the functionalized block copolymer mixture prepared in Example 1 was added thereto.
At this time, the AP-5 has a penetration of 60 to 70 measured at 25 ° C. according to ASTM D946, and has the physical properties shown in Table 1 below.
After the addition of the functionalized block copolymer mixture, the stirring speed was slowly raised to 2,500 rpm, the temperature was raised to 190 ° C. and maintained for 1 hour, and then the speed was lowered to 300 rpm and the functionalized styrene was observed under a microscope. Asphalt composition was prepared by stirring until the butadiene block copolymer was completely dissolved. For reference, the functionalized styrene-butadiene block copolymer that was not initially dissolved may appear large in white as shown in the photo (A) of FIG. 1, but the fully dissolved block copolymer may be as shown in the photo (B) of FIG. 1. Most of the white part disappears, making it difficult to distinguish it from the asphalt part.
It took 10 hours until the functionalized block copolymer completely dissolved, and the dissolved asphalt composition was sampled for physical property measurement.
Example 2
In Example 1, 200 g of the styrene-butadiene diblock copolymer and 800 g of the styrene-butadiene-styrene triblock copolymer were mixed so that the ratio of the styrene-butadiene diblock copolymer and the styrene-butadiene-styrene triblock copolymer was 20:80. A mixture of (weight ratio) was prepared in the same manner as in Example 1 except that a block copolymer having an aldehyde-functionalized weight average molecular weight of 97,692 g / mol was prepared. It took 8 hours until the functionalized block copolymer completely dissolved, and the dissolved asphalt composition was sampled for physical property measurement.
Example 3
In Example 1, 300 g of the styrene-butadiene diblock copolymer and 700 g of the styrene-butadiene-styrene triblock copolymer were mixed so that the ratio of the styrene-butadiene diblock copolymer and the styrene-butadiene-styrene triblock copolymer was 30:70. A mixture of (weight ratio) was prepared in the same manner as in Example 1 except that a block copolymer having an aldehyde-functionalized weight average molecular weight of 86,888 g / mol was prepared. It took 7 hours until the functionalized block copolymer completely dissolved, and this dissolved asphalt composition was sampled for physical property measurement.
Comparative example One
Except that in Example 1 using only 1,000g of styrene-butadiene diblock copolymer, a block copolymer having an aldehyde-functionalized weight average molecular weight of 55,250g / mol was prepared in the same manner as in Example 1. . It took 5 hours until the functionalized styrene-butadiene diblock copolymer was completely dissolved, and this dissolved asphalt composition was sampled for physical property measurement.
Comparative example 2
In Example 1, except that the block copolymer having an aldehyde-functionalized weight average molecular weight of 119,300 g / mol using only 1,000 g of styrene-butadiene-styrene triblock copolymer was prepared as in Example 1. Was carried out. It took 12 hours for the functionalized styrene-butadiene-styrene triblock copolymer to dissolve completely, and this dissolved asphalt composition was sampled for physical property measurement.
Comparative example 3
In Example 2, 200 g of the styrene-butadiene diblock copolymer and 800 g of the styrene-butadiene-styrene triblock copolymer were mixed so that the ratio of the styrene-butadiene diblock copolymer and the styrene-butadiene-styrene triblock copolymer was 20:80. A mixture of (weight ratio) was prepared in the same manner as in Example 2 except that the mixture was not functionalized. It took 10 hours until the block copolymer mixture completely dissolved, and the dissolved asphalt composition was sampled for physical property measurement.
[Test Example]
The properties of the block copolymer or asphalt composition prepared in Examples 1 to 3 and Comparative Examples 1 to 3 were measured by the following method, and the results are shown in Table 2 below.
* Softening point-measured according to ASTM D36.
* Elongation at low temperature-After leaving the specimen for 1 hour at 5 ℃, measure according to ASTM D113.
Storage stability-Sampled by the method of American Association of State Highway and Transportation Officials (AASHTO PP5) to measure the softening point by the ASTM D36 method. In more detail, 50 g of asphalt composition in an aluminum tube was improved, and After leaving for 48 hours in the oven, take out and divide into three parts to measure the softening point of the upper and lower parts and measure the temperature difference. The smaller the temperature difference, the better the storage stability, and usually does not occur when the phase separation within 2.5 ℃.
* Content of aldehyde group (ppm)-Each sample was dissolved in 1,1,2,2-ethane tetrachloride-d 2 and loaded onto 500 MHz 1 H NMR (Varian, Model: VNMRS500), followed by 9.75 The content of each aldehyde group was calculated using the following equation 1 from values obtained from peaks near ppm.
[Equation 1]
Hydrogen number of aldehyde group = (aldehyde group content (ppm) * block copolymer molecular weight (-> 110,000 g / mol) / 1,000,000 / 56 g / mol (-> CH-CH (CHO)-))
* Weight average molecular weight (g / mol)-Dissolve each sample in THF for 30 minutes, load it into GPC (Gel Permeation Chromatography, manufacturer: Waters), and flow it, then standard of PS (Polystyrene) standard The molecular weight was measured in comparison with the molecular weight.
As shown in Table 2, in the case of preparing a mixture of styrene-butadiene diblock copolymer and styrene-butadiene-styrene triblock copolymer in a weight ratio of 10 to 30:70 to 90 and functionalizing it with an aldehyde according to the present invention The dissolution rate was shortened from 1 hour to 3 hours based on the existing 10 hours, and the low temperature elongation properties were improved from 200 mm to 250 mm. In Comparative Example 1, which is 100% by weight of styrene-butadiene diblock copolymer, the preparation time is 5 hours faster, but the low temperature property or softening point is reduced by more than 50%, which is very bad, and 100% by weight of styrene-butadiene-styrene triblock copolymer In the case of Phosphorus Comparative Example 2, the low temperature property and the softening point are increased slightly (10%), and the physical properties are maintained, but it can be seen that there is no effect of improving the dissolution rate by showing a similar dissolution rate. By functionalizing the aldehyde group, which is a polar molecule in the styrene-butadiene copolymer, in the butadiene block, the solubility was increased to reduce the manufacturing time by 20% or more, and the low temperature elongation in the physical properties of the asphalt was improved by 20% or more.
Claims (18)
B) a vinyl aromatic hydrocarbon-conjugated diene multiblock copolymer having an aldehyde group bonded to the main chain of the conjugated diene block; and a functionalized vinyl aromatic hydrocarbon-conjugated diene block copolymer composition.
The diblock copolymer is 0 to 60% by weight, and the multiblock copolymer is 40 to 100% by weight. The functionalized vinyl aromatic hydrocarbon-conjugated diene block copolymer composition.
The functionalized vinyl aromatic hydrocarbon-conjugated diene block copolymer is a functionalized vinyl aromatic hydrocarbon-conjugated diene block copolymer composition, characterized in that represented by the following formula (1).
[Formula 1]
Wherein A to D are independently CH 2 -CH = CH-CH or CH 2 -CH when butadiene is used as the conjugated die, provided that all of A to D are CH 2 -CH = CH-CH or CH 2 May not be -CH), wherein W to Z is H when A, B, C or D is CH 2 -CH = CH-CH, and is one of a vinyl group, a carboxyl group or an aldehyde group when CH 2 -CH, d, e, f and g satisfy the number ratio of 1,4 structure, vinyl structure, carboxyl group and aldehyde structure, wherein G is one of vinyl aromatic hydrocarbon, CH 2 CHO or CH 2 COOH, and p is vinyl aromatic Represents the number ratio of A, B, C and D of hydrocarbon, CH 2 CHO or CH 2 COOH, wherein F is a vinyl aromatic hydrocarbon block, H, CH 2 CHO, CH 2 COOH or a coupling group, q is the number of arms around F.
The aldehyde group is 50 to 1600ppm functionalized vinyl aromatic hydrocarbon-conjugated diene block copolymer composition.
And the functionalized vinyl aromatic hydrocarbon-conjugated diene block copolymer is coupled with a coupling agent.
Functionalized vinyl aromatic hydrocarbon-conjugated diene block copolymer composition comprising a carboxylic acid group in the butadiene block.
The vinyl aromatic hydrocarbon and the conjugated diene have a weight ratio of 5:95 to 50:50, wherein the functionalized vinyl aromatic hydrocarbon-conjugated diene block copolymer composition.
The functionalized vinyl aromatic hydrocarbon-conjugated diene block copolymer has a number average molecular weight of 10,000 to 1,000,000.
The vinyl aromatic hydrocarbons include styrene, alpha-methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-propylstyrene, 1-vinylnaphthalene, 4-cyclohexylstyrene, 4- (para-methylphenyl) styrene, and 1- A functionalized vinyl aromatic hydrocarbon-conjugated diene block copolymer composition, characterized in that at least one member selected from the group consisting of vinyl-5-hexyl naphthalene.
The conjugated diene is composed of 1,3-butadiene, 2,3-dimethyl-1,3-butadiene, piperylene, 3-butyl-1,3-octadiene, isoprene and 2-phenyl-1,3-butadiene Functionalized vinyl aromatic hydrocarbon-conjugated diene block copolymer composition, characterized in that at least one member selected from the group.
b) preparing a vinyl aromatic hydrocarbon-conjugated diene multiblock copolymer having an aldehyde group bonded to the main chain of the conjugated diene block;
c) mixing the vinyl aromatic hydrocarbon-conjugated diene diblock copolymer and the vinyl aromatic hydrocarbon-conjugated diene multiblock copolymer in a weight ratio of 10 to 30:70 to 90 to prepare a vinyl aromatic hydrocarbon-conjugated diene block copolymer mixture. step; And
d) subjecting the block copolymer mixture to a hydroformylation reaction to prepare a functionalized vinyl aromatic hydrocarbon-conjugated diene block copolymer composition; and the functionalized vinyl aromatic hydrocarbon-conjugated diene Process for the preparation of block copolymer composition.
Of the conjugated diene block copolymer composition wherein the vinyl aromatic hydrocarbon-conjugated diene block copolymer mixture of the conjugated functionalized vinyl aromatic hydrocarbons by selective oxidation of the vinyl structure in the diene block, characterized in that it comprises the step of generating an aldehyde group Manufacturing method.
Functionalization characterized in that the molecular weight ratio (pre-oxidation block copolymer / post-oxidation block copolymer) of the vinyl aromatic hydrocarbon-conjugated diene block copolymer before oxidation and the vinyl aromatic hydrocarbon-conjugated diene block copolymer after oxidation is 0.9 to 1.1. Of the prepared vinyl aromatic hydrocarbon-conjugated diene block copolymer composition.
Asphalt, asphalt composition comprising asphaltenes.
The asphalt composition, the asphalt composition, characterized in that the weight mixing ratio of the modifier and asphalt is 0.1: 99.1 to 20:80.
The asphalt composition, the asphalt composition, containing 5% of the block copolymer, characterized in that the dissolution time is 5 to 36 hours at 190 ℃ and 300rpm conditions.
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