JPH0711144A - Asphalt composition - Google Patents

Abstract

PURPOSE:To obtain an asphalt compsn. excellent in binding power and applicability by compounding asphalt with a modified copolymer obtd. by reacting a specific copolymer with a specific modifier. CONSTITUTION:This asphalt compsn. is obtd. by compounding asphalt with a modified polymer obtd. by reacting a living vinylarom. hydrocarbon-conjugated diene random copolymer (e.g. a styrene-butadiene random copolymer) with a modifier which is selected from the group consisting of a carboxylic acid (ester), a nitrogen compd. selected from the group consisting of a compd. having a linkage of formula I (wherein X is O or S), an amino(thio)ketone, an amino(thio)aldehyde, and a (thio)isocyanate compd., a (thio)epoxy compd., a phosphorus compd. represented by (RO)3P or (RO)3P=O (wherein R is alkyl, alicyclic, or arom.), a halosilane or an organosilane compd. of formula II (wherein R<1> to R<4> are each alkyl or alkoxy), and an Sn compd. obtd. by replacing Si of formula II with Sn [e.g. 4,4'-bis(diethylamino)benzophenone].

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an asphalt-containing composition having excellent caking strength and good workability.

[0002]

BACKGROUND ART Asphalt is currently an inexpensive and easy-to-use material for road paving, roofing materials, sealing materials,
Widely used in fields such as adhesives, paints, and waterway linings. In addition, by mixing and dispersing natural rubber or synthetic rubber such as styrene / butadiene / rubber and chloroprene / rubber in asphalt, for example, when used for road paving, the size of vehicles and the increase in traffic volume cause "rutting". Attempts have been made to improve properties such as wear, cracks, flow. " In particular, recently, a block copolymer-containing bituminous composition having a solubility lower than that of a conventionally used natural rubber or synthetic rubber-containing bituminous composition at the time of mixing and having a relatively low viscosity at high temperature is preferably used. It is in. For example, Japanese Patent Publication No. 47-17319 and Japanese Patent Publication No.
JP-A 7-33058 discloses a block copolymer of a vinyl aromatic compound and a conjugated diene compound as a rubber-like substance,
Or a composition of a bituminous material using the hydrogenated product.

In JP-A-56-115354 and JP-A-58-40349, a vinyl aromatic compound-conjugated diene compound block copolymer modified with a dicarboxylic acid in the composition is used. Japanese Patent Publication No. 4-38777 discloses that in the composition, at least the functional group represented by the following general formula is added to the active terminal of the block copolymer of the vinyl aromatic compound and the conjugated diene compound. Compound containing one

[Chemical 4] (In the above formula, R is hydrogen, an alkyl group having 1 to 22 carbon atoms, a cycloalkyl group having 4 to 22 carbon atoms, and 6 to 2 carbon atoms.
2 aryl group, arylalkyl group, R'is the same as R or an alkoxy group, M is silicon or tin, X is halogen, Y is oxygen or sulfur, Z is oxygen, sulfur or nitrogen, and n is 1 to 3 It has been reported that the use of end-modified block copolymers having an (integer number) attached improves the strength and adhesion of the composition.

[0004]

However, in these techniques, workability in the case of using this composition has not been examined at all. Generally, this type of composition has a drawback that the viscosity of asphalt is increased and the workability is deteriorated, while the rubber can be mixed and dispersed in asphalt to increase its cohesive strength and improve its properties. Therefore, the object of the present invention is to overcome the drawbacks of the prior art,
The point is to provide an asphalt-based composition having excellent caking strength without impairing workability.

[0005]

The present invention includes (a) and (a).
Living vinyl aromatic hydrocarbon-conjugated diene random copolymer and (b) a modifier comprising a compound selected from the following group (i) carboxylic acid or its ester (ii) formula

[Chemical 5] A compound having a bond represented by: (wherein X is O or S
A nitrogen-containing compound selected from aminoketone, aminothioketone, aminoaldehyde, aminothioaldehyde, isocyanate compound and thioisocyanate compound (iii) epoxy compound or thioepoxy compound (iv) formula

Embedded image A phosphorus-containing compound represented by (RO) ₃ P or (RO) ₃ P═O (wherein R is an alkyl group, an alicyclic group, or an aromatic group). (V) Halogenated silane Or expression

[Chemical 7] An organic silane compound represented by the formula (wherein R ¹ , R ² , R ³ ,
R ⁴ is a group independently selected from the group consisting of an alkyl group and an alkoxy group.) (Vi) A modified polymer obtained by a reaction with a tin compound in which tin is used instead of silicon in (v) above, (B) An asphalt-based composition containing asphalt.

The living polymer of the present invention includes:
(I) A living polymer in which an alkali metal or an alkaline earth metal is bonded to at least one terminal of a copolymer obtained by randomly anionic copolymerizing a vinyl aromatic hydrocarbon and a conjugated diene, and (II) emulsion polymerization or solution polymerization There is a living polymer obtained by subjecting a random copolymer of a vinyl aromatic hydrocarbon and a conjugated diene produced by the above method to an addition reaction of an alkali metal or an alkaline earth metal. The proportion of the vinyl aromatic hydrocarbon and the conjugated diene in the random copolymer is 5 to 50% by weight, preferably 10 to 40% by weight, and the balance is the conjugated diene. The degree of polymerization of the polymer is 10 in terms of Muni viscosity.
The number average molecular weight is 150, preferably 30 to 100, and the number average molecular weight is 500 to 1,000,000, preferably 10,000 to 800,000.

As the vinyl aromatic hydrocarbon, styrene, o-methylstyrene, p-methylstyrene, pt
ert-butyl styrene, 1,3-dimethyl styrene,
Examples thereof include α-methylstyrene, vinyltoluene, vinylnaphthalene, vinylanthracene, divinylbenzene, trivinylbenzene, divinylnaphthalene and the like, but styrene is particularly common. These may be used alone or in combination of two or more.

Examples of the conjugated diene include 1,3-butadiene, isoprene, 1,3-pentadiene, 2,3-dimethyl-1,3-butadiene and 1,3-hexadiene. These may be used alone or in combination of two or more. To the extent that the gist of the present invention is not impaired, monomers copolymerizable with vinyl aromatic hydrocarbons and conjugated dienes, for example, acrylic acid, methacrylic acid, unsaturated carboxylic acids such as maleic acid and esters thereof, It is also possible to copolymerize allyl glycidyl methacrylate, allyl glycidyl ether and the like.

Specific examples of living polymers include living polymers of the following polymers. For example, styrene-butadiene random copolymer, styrene-isoprene random copolymer,
Examples thereof include styrene-piperylene random copolymer, vinylnaphthalene-butadiene random copolymer, and acenaphthylene-butadiene random copolymer.

The metal-based catalyst used in the polymerization and addition reaction is not particularly limited, and a catalyst conventionally used in anionic polymerization can be used. Examples of the alkali metal-based catalyst include organic lithium compounds having 2 to 20 carbon atoms such as n-butyl lithium and sec-butyl lithium.
Examples of alkaline earth metal-based catalysts include, but are not limited to, catalyst systems containing a compound such as barium, strontium, or calcium as a main component.

The polymerization reaction and the alkali metal and / or alkaline earth metal addition reaction are carried out in a hydrocarbon solvent conventionally used in anionic polymerization or in a solvent which does not decompose a metal-based catalyst such as tetrahydrofuran, tetrahydropyran or dioxane. Done in.

The amount of the metal-based catalyst used in the polymerization reaction is usually in the range of 0.1 to 200 mmol per 100 g of the monomer. The amount of the metal-based catalyst used in the addition reaction varies depending on the amount of the metal to be added, but is usually about 0.1 to 10 mmol per 100 g of the polymer.

The polymerization is generally carried out in the presence of a polar compound such as an ether compound, an amine compound or a phosphine compound as a randomizing agent and a vinylating agent. These polar compounds are also commonly used in addition reactions. The conditions of the polymerization and the addition reaction may be according to ordinary methods and are not particularly limited.

Examples of the carboxylic acid or its ester (i) which is the modifier of the present invention include carbon dioxide, acetic acid, butyric acid, caproic acid, stearic acid, benzoic acid, oxalic acid, maleic acid, fumaric acid and succinic acid. Carboxylic acids such as phthalic acid, isophthalic acid and terephthalic acid, and carboxylic acids, and methanol, ethanol, n-propyl alcohol, isopropyl chol, n-butyl alcohol,
Examples thereof include carboxylic acid ester compounds with alcohols such as sec-butyl alcohol and t-butyl alcohol.

Examples of the compound (ii) having the formula -CX-N <bond include carboxylic acid amide, carboxylic acid imide, urea or its derivative, carbamic acid ester, isocyanuric acid or its derivative, or lactam and its derivative. These corresponding sulfur-containing compounds can be cited.

Examples of the carboxylic acid amide include N, N
-Dimethylpropioamide, acrylamide, N, N-
Dimethylacrylamide, N, N-dimethylmethacrylamide, nicotinamide, isonicotinamide, picolinic acid amide, N, N-dimethylisonicotinamide, succinic acid amide, phthalic acid amide, N, N, N ', N'-
Tetramethylphthalamide, N, N, N ', N'-tetramethyloxamide, 1,2-cyclohexanedicarboxide, 2-furancarboxylic acid amide, N, N-dimethyl-2-furancarboxylic acid amide, Quinoline-2-carboxylic acid amide, N-ethyl-N-methyl-quinolinecarboxylic acid amide, oxamide, N, N, N ', N'-tetramethyloxamide, 2-furamide, N, N-dimethyl-2- Flamid, N, N-dimethyl-8-quinolinecarboxamide, N-ethyl-N-methyl-8-quinolinecarboxamide, 4-pyridylamide, N, N-dimethyl-4-pyridylamide, benzamide, N, N-
Dimethylbenzamide, p-aminobenzamide,
N ', N'-(p-dimethylamino) benzamide,
N ', N'-(p-diethylamino) benzamide,
N '-(p-methylamino) benzamide, N'-(p
-Ethylamino) benzamide, N, N-dimethyl-
N '-(p-ethylamino) benzamide, N, N-dimethyl-N', N '-(p-diethylamino) benzamide, N, N-dimethyl-p-aminobenzamide, N
-Methyldibenzamide, N-acetyl-N-2-naphthylbenzamide and the like can be mentioned.

Examples of the carboxylic acid imide include succinimide, N-methylsuccinimide, maleimide, N
Examples thereof include imide compounds such as -methylmaleimide, phthalimide, and N-methylphthalimide.

Examples of urea or its derivative include urea, N, N'-dimethylurea, N, N-diethylurea, N, N'-dimethylethyleneurea, N, N,
N ', N'-tetramethylurea, N, N-dimethyl-
N ', N'-diethylurea, N, N-dimethyl-N',
N'-diphenylurea etc. can be mentioned.

Examples of the carbamic acid ester include:
Examples thereof include methyl carbamate and ethyl N, N-diethylcarbamate.

Examples of isocyanuric acid and its derivatives include isocyanuric acid and N, N ', N "-trimethylisocyanuric acid.

Examples of lactams and their derivatives include:
ε-caprolactam, N-methyl-ε-caprolactam, N-acetyl-ε-caprolactam, 2-pyrrolidone, N-methyl-2-pyrrolidone, 2-piperidone, N
-Methyl-2-piperidone, 2-quinolone, N-methyl-2-quinolone and the like can be mentioned.

Examples of amino (thio) aldehydes include formamide, N, N-dimethylformamide, N, N-diethylformamide, acetamide, N, N-dimethylacetamide, N, N-diethylacetamide, aminoacetamide and N, N-dimethyl. -N ', N'-dimethylaminoacetamide, N', N'-dimethylaminoacetamide, N'-ethylaminoacetamide, N, N-
Dimethyl-N'-ethylaminoacetamide, N, N-
Dimethylaminoacetamide, N-phenyldiacetamide, N, N-dimethyl-p-amino-benzalacetamide, N, N-dimethyl-N ', N'-(p'-diethylamino) benzalacetamide, N, N- Examples thereof include dimethyl-N ′, N ′-(p′-dimethylamino) cinnamylidene acetamide, and thioaldehydes corresponding to these.

Examples of amino (thio) ketones include acetone, methyl ethyl ketone, dimethyl ketone, methyl propyl ketone, acetophenone, benzophenone,
4,4'-bis (dimethylamino) benzophenone,
4,4'-bis (diethylamino) benzophenone,
4,4'-bis (dibutylamino) benzophenone,
Examples thereof include 4,4′-diaminobenzophenone, 4-aminobenzophenone, and thioketones corresponding to these.

As the (thio) isocyanate compound,
Ethyl isocyanate, propyl isocyanate, n-
Butyl isocyanate, phenyl isocyanate, p-
Tolyl isocyanate, diphenylmethane diisocyanate, toluene diisocyanate, benzene-1,2,
4-triisocyanate, triphenylmethane triisocyanate and the like can be mentioned.

Examples of the epoxy compound or thioepoxy compound (iii) include ethylene oxide,
Examples thereof include propylene oxide, butadiene oxide, butene oxide, styrene oxide, epoxidized vegetable oil, and thioepoxy compounds corresponding to these.

Trialkyl or triallyl phosphite represented by the formula (RO) ₃ P in (iv), (RO) ₃
Trialkyl or triallyl phosphate represented by P = O, and examples of R include methyl, ethyl,
Examples thereof include alkyl groups such as n-butyl, hexyl, 2-ethylhexyl, cyclohexyl, nonyl and stearyl, and phenyl groups.

As an example of the halogenated silane or organosilane of (v), the silicon-containing compound used in the present invention is a halogen such as tetrachlorosilane, tetrabromosilane, trichloromethylsilane, dichlorodimethylsilane, dichlorodiphenylsilane. Silanes, compounds containing an organic group having a hydrolyzability other than halogen, for example, tetramethoxysilane, tetraethoxysilane, dimethyldimethoxysilane, trimethoxymonomethylsilane and the like.

Examples of the tin compound (vi) include halogen compounds such as tin compounds corresponding to the above silicon compounds, that is, tetrachlorotin, tetrabromotin, trichloromethyltin, dichlorodimethyltin, dichlorodiphenyltin and tributylchlorotin. Tin, tetramethoxy tin, tetraethoxy tin, dimethyl dimethoxy tin, etc. can be mentioned.

The amount of the modifier used is 0.05 mol to 10 mol, preferably 0.2 to 2 mol, per 1 mol of the living copolymer. Specific examples of the reaction between the modifier and the living copolymer are shown below, but the reaction is not limited thereto. As one specific example thereof, an alkali metal and / or an alkali is provided on at least one end of a polymer chain obtained by polymerizing the vinyl aromatic hydrocarbon and a conjugated diene with an alkali metal and / or alkaline earth metal-based catalyst. It is a method of reacting the modifier in the living state before termination of polymerization with the earth metal with the modifier. Another specific example is a method in which an alkali metal or alkaline earth metal is added to a vinyl aromatic hydrocarbon-conjugated diene random copolymer polymerized in advance by emulsion polymerization or the like, and then the modifier is subjected to a catalytic reaction. Since these reactions occur rapidly, the reaction temperature and reaction time can be selected within a wide range, but generally room temperature to 100 ° C. and several seconds to several hours. After the reaction,
The vinyl aromatic hydrocarbon-conjugated diene random copolymer having the modifier bonded thereto is separated from the reaction solution by a method such as steam stripping. It is dried according to a conventional method and provided as an asphalt modifier.

Asphalt used in the present invention includes straight asphalt, semi-blown asphalt,
Blown asphalt, tar, pitch, cutback asphalt with added oil, and asphalt emulsion can be used. These may be mixed and used.

The blending amount of the modified copolymer and asphalt in the present invention varies depending on the type of asphalt to be modified and the use, but generally, asphalt 10 is used.
0.5 to 100 parts by weight, preferably 1 to 0 parts by weight
30 parts by weight.

The composition of the present invention may contain any additive in any amount, if desired. The types of additives include crushed stone, crushed stone, gravel, sand, aggregate such as recycled aggregate, stone powder, talc, filler such as calcium carbonate, slaked lime, amines, amides and other peeling inhibitors, polyvinyl alcohol, polyester Examples include fibrous reinforcing materials such as and softening agents such as oils such as aroma type and naphthene type. It can also be used in combination with a modifier other than the modified copolymer, for example, styrene / butadiene / rubber, chloroprene / rubber, styrene / butadiene / styrene / block copolymer, or ethylene / ethyl acrylate copolymer. . The method for producing the composition of the present invention is not particularly limited, but it is generally a method in which the powder or latex of the modified copolymer is added to and mixed with heat-melted asphalt.

[0033]

The present invention will be described in detail with reference to the following examples. The copolymers used in the following examples and comparative examples were produced by the following production examples. Production Example 1 A polymerization reactor made of stainless steel having an internal volume of 2 liters was washed, dried, and purged with dry nitrogen, and then 1,3-butadiene 18 was used.
5-160 g, styrene 30-55 g, cyclohexane 600 g, N, N, N ', N'-tetramethylethylenediamine (TMEDA) 0.43 and 0.52 mmo
1 level, n-butyllithium 0.84 ml (1.5
(5 mol / l, cyclohexane solution) was added, and the contents were stirred, and a polymerization reaction was carried out at 45 ° C. for 30 to 60 minutes. After the completion of the polymerization, the modifier shown in Table 1 was added in an amount 1.5 times the amount of the polymerization catalyst, and the mixture was stirred for 5 minutes. Then, the polymer solution in the polymerization reactor was taken out into a methanol solution containing 1.5% by weight of 2,6-di-t-butyl-p-cresol (BHT) to coagulate the produced polymer. 24 at 60 ℃
It was dried under reduced pressure for an hour to obtain modified polymers (polymers A to I).

Production Example 2 In the same manner as in Production Example 1, 0.43 mmol of TMEDA was used to copolymerize 1,3-butadiene and styrene.
After completion of the polymerization, the polymer solution in the polymerization reactor was poured into a BHT-containing methanol solution to coagulate the produced polymer. The separated crumb was dissolved in cyclohexane, and the polymer was solidified by the same procedure as above. This operation was repeated 3 times to remove the catalyst residue in the polymer. Drying was performed under the same conditions as in Production Example 1 to obtain a produced and dried rubber polymer. To a solution prepared by dissolving 100 g of this dry rubber polymer in 1000 g of dry cyclohexane, 3.5 mmol of n-butyllithium and 3.5 mmol of TMEDA were added and reacted at 70 ° C. for 1 hour. Then, 2.7 mmol of 4,4'-bis (diethylamino) benzophenone used in Production Example 1 was added and reacted for 5 minutes, and then coagulated and dried in the same manner as above (polymer J).

Production Example 3 An unmodified polymer was obtained in the same manner as in Production Example 1 except that the modifier was not used and the polymerization was terminated with methanol instead (polymers K and L). The styrene content of the styrene-butadiene copolymer rubber prepared by the above method, 1,2 of the butadiene portion
-The bond content was determined by conventional infrared spectroscopy. The results are shown in Table 1.

[0036]

[Table 1]

Examples 1 to 10 and Comparative Examples 1 to 3 Copolymers A to D were dissolved in 100 parts by weight of straight asphalt (60/80, manufactured by Cosmo Oil Co., Ltd.) at the addition amounts shown in Table 2 to prepare an asphalt composition. Was produced. The dissolution was performed by heating straight asphalt to 170 to 180 ° C., adding the copolymer thereto, stirring the mixture for 60 minutes, and confirming that it was sufficiently dissolved. The properties of the obtained asphalt composition are shown in Table 2. Among the properties, the penetration and softening point were measured according to JIS-K-2207, and the toughness and tenacity were measured according to JEAAS.
60 ° C Viscosity is measured by Asphalt Institute
e Using a vacuum capillary viscometer, the measurement was carried out under the conditions of 60 ° C. and 300 mmHg. The kinematic viscosity at 180 ° C. was measured using a Canon-Fenske opaque liquid viscometer.

[Table 2]

[Table 3]

[Table 4]

[0038]

[Discussion] In this example, the toughness and tenacity were almost twice as high as those of Comparative Examples 1 and 2 having almost the same softening point and penetration, and the viscosity at 60 ° C. Although it is higher than Comparative Examples 1 and 2, the 180 ° C. kinematic viscosity is considerably lower than Comparative Examples 1 and 2, indicating that the workability is good. In Comparative Example 3 in which the toughness and tenacity were almost the same levels as those in the Examples, the kinematic viscosity at 180 ° C. was extremely high, and the workability was extremely deteriorated.

[0039]

The composition of the present invention has excellent cohesive strength,
Moreover, since it has a good workability due to its low viscosity at high temperatures, it makes good use of its characteristics to make road pavements, roofing materials,
It can be widely used in fields such as sealing materials, adhesives, paints, and waterway linings.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Office reference number FI Technical display location C08K 5/521 5/524 5/54 5/57 C08L 53/02 LLX

Claims (8)

[Claims] 1. A modifier comprising (a) (a) living vinyl aromatic hydrocarbon-conjugated diene random copolymer and (b) a compound selected from the following group: (i) carboxylic acid or ester thereof (ii) formula [Chemical 1] A compound having a bond represented by: (wherein X is O or S
A nitrogen-containing compound selected from aminoketones, aminothioketones, aminoaldehydes, aminothioaldehydes, isocyanate compounds and thioisocyanate compounds (iii) epoxy compounds or thioepoxy compounds (iv) compounds of formula (RO) ₃ A phosphorus-containing compound represented by P or (RO) ₃ P = O 2 (wherein R is an alkyl group, an alicyclic group, or an aromatic group). (V) A halogenated silane or a compound represented by the formula: An organic silane compound represented by the formula (wherein R ¹ , R ² , R ³ ,
R ⁴ is a group independently selected from the group consisting of an alkyl group and an alkoxy group.) (Vi) A modified polymer obtained by a reaction with a tin compound in which tin is used instead of silicon in (v) above, (B) An asphalt-based composition containing asphalt. 2. The asphalt-based composition according to claim 1, wherein the living random copolymer is the random copolymer having an alkali metal or an alkaline earth metal bonded to the terminal. 3. The asphalt-based composition according to claim 1, wherein the living random copolymer is the random copolymer in which an alkali metal or an alkaline earth metal is bonded to a molecular chain by an addition reaction. 4. The asphalt-based composition according to claim 2, wherein the modifier is the nitrogen-containing compound. 5. The asphalt-based composition according to claim 2, wherein the modifier is the tin compound. 6. The content ratio of vinyl aromatic hydrocarbon in the random copolymer is 5 to 50% by weight.
The asphalt-based composition according to 2, 3, 4 or 5. 7. The random copolymer as claimed in claim 1, which is a styrene-butadiene random copolymer.
The asphalt-based composition according to 4, 5, or 6. 8. The asphalt-based composition according to claim 1, wherein the modified polymer is used in an amount of 0.5 to 100 parts by weight per 100 parts by weight of asphalt.