CN100398578C - Block (co)polymer, block copolymer composition for asphalt modification, process for producing the same, and asphalt composition - Google Patents
Block (co)polymer, block copolymer composition for asphalt modification, process for producing the same, and asphalt composition Download PDFInfo
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- CN100398578C CN100398578C CNB200480006157XA CN200480006157A CN100398578C CN 100398578 C CN100398578 C CN 100398578C CN B200480006157X A CNB200480006157X A CN B200480006157XA CN 200480006157 A CN200480006157 A CN 200480006157A CN 100398578 C CN100398578 C CN 100398578C
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Abstract
A composition for asphalt modification which comprises (a) a block (co)polymer represented by general formula (I); (S-B)m-S'n (in formula (I), S and S' are each a polymer block mainly composed of an aromatic vinyl compound, B is a polymer block mainly composed of a conjugated diene, and m and n are each an integer of 0 or 1, provided that m+n is 1 or more), wherein the total combined aromatic vinyl compound content in the block (co) polymer is from more than 10% by weight to 100% by weight, and (b) a block copolymer represented by general formula (II) ; S-B-S, general formula (III); S-B-S' and/or general formula (IV) ; (S-B)2-X (in formulas (II) to (IV), S, S' and B have the same meanings as given in general formula (I), and X is a residue of a coupling agent), at a block copolymer (a) /block copolymer (b) ratio (weight ratio) of 10-40/90-60; and further, an asphalt composition in which this composition for modification is added to asphalt. There are provided the composition for asphalt modification excellent in solubility in asphalt, excellent in storage stability at high temperatures, further low in melt viscosity and excellent in asphalt characteristics, and the asphalt composition available for road pavement or waterproof sheets.
Description
Technical field
The present invention relates to the aromatic ethenyl compound of (1) ad hoc structure, or the block of this vinyl compound and conjugated diolefine (being total to) polymkeric substance, more particularly, relate to asphalt modification with block (being total to) polymkeric substance or its composition, as can improve suitable block (being total to) polymkeric substance that deliquescent compatilizer uses to straight-run pitch, (2) contain this block (being total to) polymkeric substance and asphalt modification with segmented copolymer, the block copolymer composition for asphalt modification good to the solvability of straight-run pitch, (3) manufacture method of said composition, (4) above-mentioned block copolymer composition for asphalt modification is engaged in the straight-run pitch, or be engaged in straight-run pitch, the stability that the is separated during storage that obtains in aromatic hydrocarbon resin and/or the mink cell focus (below, claim storage stability) good, low and the processibility of viscosity, good operability, softening temperature again, the good bituminous composition of bituminous cement rerum natura of elongation and tough viscosity (toughnesstenacity) etc., for example, be suitable for the high-viscosity modified asphalt composition that draining/low noise is paved the way and used.
Background technology
In the past, cheap, the easy acquisition of pitch is widely used in the purposes of the usefulness of paving the way, waterproof purposes, baffle-board, vibration isolating material etc.
Yet, the tough viscosity of straight-run pitch, softening temperature, penetration degree equal difference.
In addition, the quality that straight-run pitch also occurs reduces further along with the raising of refining degree in the refining of petroleum that the performance that causes bituminous composition reduces and then some new problems such as stability the during storage of bituminous composition prolonged preservation.Stability during so-called storage is the performance of bituminous composition, for example softening temperature integrally reduce or cause when preserve be separated, the different phenomenon of performance appearance of upper strata and lower floor.
Such phenomenon still is not resolved so far, becomes a big problem.
In addition, in recent years increasing or the situation of high speed and so on along with road running vehicle, because heavy traffic road or expressway require to keep better intensity, wearability, in addition, to improve drainage or to reduce noise is purpose, for paving the way of high voidage constructed, then the demand to high performance bituminous composition (draining road tar tackiness agent) increases, and requires the physical strength of higher softening temperature or tough viscosity etc.
In order to improve these problem, attempt having carried out adding the research of the modifying asphalt of various co-polymer compositions.
As the concrete example of these various co-polymer compositions, use styrene butadiene random copolymerization latex (SBR latex), ethylene-vinyl acetate copolymer (EVA), ethylene-ethyl acrylate copolymer etc. in the past.Though but the tough viscosity of the multipolymer that adds these, softening temperature, elongation obtain to a certain degree improvement but and insufficient, require further to improve.
In addition, explored the segmented copolymer (SB segmented copolymer) that adds aromatic ethenyl compound and conjugated diolefine in recent years pitch has been carried out modification.
For example, in order to improve all rerum naturas of bituminous, proposed to use various ether compounds or tertiary amine compound as the microtexture control agent, adding organolithium compound is the various schemes of bituminous composition (special public clear 47-17319 communique, special public clear 59-36949 communique) of the segmented copolymer that ad hoc structure is arranged of initiator.That is, A-B-A molded lines shape block copolymer, (A-B)
nX type free radical block copolymer uses separately, or two kinds of asphalt modifications that use together.
Yet in these the open example, though the tackiness agent rerum natura of bituminous softening temperature, tough viscosity and so on is greatly improved, the storage stability during high temperature is not necessarily abundant.
At this situation, in recent years delivered to use that the content of aromatic ethenyl compound is limited to the interior block copolymer of certain certain scope, made the report (spy opens flat 1-254768 communique, special fair 5-420 communique) of good bituminous composition such as the balance of properties of elongation, tough viscosity etc.
In addition, also delivered and use specific coupling agent to carry out the being separated property of link coupled block copolymer, the report (spy opens flat 8-225711 communique) of bituminous composition that solvability is good.
Yet in these the open example, the balance of properties of pitch solvability, storage stability, elongation, tough viscosity, softening temperature etc. can not be referred to as fully.
In addition, also delivered and used the report (spy open flat 6-41439 communique, spy are opened flat 9-12898 communique, the spy opens flat 10-212416 communique) that the structure qualification segmented copolymer within the specific limits of aromatic ethenyl compound and conjugated diolefine is had the bituminous composition of excellent storage stability.
Yet, these open examples since molecular weight increase, so melt viscosity height, operation variation has problem aspect processibility.Expectation improves these physical properties balance, the better bituminous composition of exploitation processibility.
At present, general adopt polymer by block copolymer to quantize or be increased in addition in the pitch improve softening temperature, tough viscosity, guarantee the method with the balance of elongation.
Yet, this method, block copolymer obviously reduces the bituminous solvability, and dissolution time is elongated, and gained bituminous melt viscosity obviously raises in addition, produces the problem of destroying processibility.Therefore, even also explore to use at present pitch carried out modification as above-mentioned SB block copolymer, but do not obtain satisfied result, not find also so far that solvability in pitch is good, the good modification co-polymer of balance of properties of the tough viscosity of bituminous, softening temperature and elongation, hope is improvement further.
The object of the invention is by controlling molecular structure to heavens, providing good and when making bituminous composition to the bituminous solvability, the asphalt modifier that storage stability under the high temperature is good, melt viscosity is low again, asphalt characteristic is good, and then the spendable bituminous compositions such as usefulness or waterproof sheet of paving the way are provided.
Summary of the invention
Present inventors are in order to develop the bituminous composition with above-mentioned performance, with great concentration repeatedly research the result, discovery contains the aromatic ethenyl compound with certain specified range structure in specific scope, or the block of this aromatic ethenyl compound and conjugated diolefine (being total to) polymkeric substance and the aromatic ethenyl compound of certain specified range structure is arranged and the asphalt modification of conjugated diolefine demonstrates extraordinary performance with the bituminous composition of block copolymer, can reach this purpose, thereby finish the present invention.
Promptly, the present invention relates to block (being total to) polymkeric substance (to call " (a) block (being total to) polymkeric substance " in the following text), it is characterized in that be have more than 1 polymerization of aromatic vinyl thing block for must composition, contain this polymerization of aromatic vinyl thing block and the conjugated diolefine more than 1 is block (being total to) polymkeric substance of the polymer blocks of main body, wherein, with general formula (I); (S-B)
mIn-S ' n[the formula (I), S, S ' is that aromatic ethenyl compound is the polymer blocks of main body, B is that conjugated diolefine is the polymer blocks of main body, m and n are 0 or 1 integers, more than the m+n=1] expression, total bonding aromatic ethenyl compound content in this block (being total to) polymkeric substance is greater than 10 weight %～100 weight %, conjugated diolefine is that the vinyl bonding content among the polymer blocks B of main body is 10～50 weight %, and the weight-average molecular weight of this polymer blocks S is 500～20000, and the total amount of the weight-average molecular weight of this polymer blocks S+S ' is 1000～30000.
Here, the total weight-average molecular weight of block (being total to) polymkeric substance preferably 5000～50000.
In addition, the total bonding aromatic ethenyl compound content in above-mentioned block (being total to) polymkeric substance is preferably greater than 10 weight %, less than 100 weight %.
Secondly, the present invention relates to block copolymer composition for asphalt modification, wherein, contain above-mentioned (a) block (being total to) polymkeric substance, (b) promptly by at least 2 aromatic ethenyl compound be main body polymer blocks, with at least 1 conjugated diolefine be the block copolymer that the polymer blocks of main body constitutes, use general formula (II); S-B-S, general formula (III) S-B-S ' and/or general formula (IV) are (S-B)
2In-X[the general formula (II)～(IV), S, S ', B are identical with general formula (I), X is the coupling agent residue] expression, total bonding aromatic ethenyl compound content in this segmented copolymer is that 20～70 weight %, conjugated diolefine are that vinyl bonding content among the polymer blocks B of main body is that the weight-average molecular weight of 10～50 weight % and polymer blocks S is 10000～20000, the weight-average molecular weight of polymer blocks S ' is 10000～20000 (to call " (b) segmented copolymer " in the following text), (a)/(b) (weight ratio)=10～40/90～60.
Here, adopt the peak molecular weight of (a) block (being total to) polymkeric substance that gel permeation chromatograph (GPC) measures, preferably be equivalent to (b) segmented copolymer the peak molecular weight 1/80～less than 1/3.
In addition, the present invention relates in unreactive hydrocarbons solvent, organolithium compound is an initiator, adopt solution polymerization process respectively polymerization make each polymers soln of above-mentioned (a) block (be total to) polymkeric substance and (b) block copolymer, after mixing, the asphalt modification that desolventizing the makes manufacture method of block copolymer composition.
In addition, the invention still further relates to polymerization manufacturing side by side (a) block (being total to) polymkeric substance, method with (b) block copolymer, and be that organolithium compound is the solution polymerization process of initiator in unreactive hydrocarbons solvent, in the polymerization process that inserts in order with aromatic ethenyl compound, when conjugated diolefine is carried out polymerization, at least insert initiator 2 times, insert the manufacture method of the asphalt modification of 1 aromatic ethenyl compound, conjugated diolefine at least with block copolymer composition.
In addition, the invention still further relates to the bituminous composition (to call " bituminous composition (1) " in the following text) that contains above-mentioned block copolymer composition and straight-run pitch, makes the ratio of said composition/straight-run pitch (weight ratio)=2～15/85～98).
In addition, the invention still further relates to and contain above-mentioned block copolymer composition and straight-run pitch, aromatic hydrocarbon resin and mink cell focus, with respect to straight-run pitch 100 weight parts, making said composition is that 1～20 weight part, aromatic hydrocarbon resin are that 0～40 weight part, mink cell focus are the bituminous composition that adds up to 1～60 weight part ratio (to call " bituminous composition (2) " in the following text) of 0～40 weight part and aromatic hydrocarbon resin and mink cell focus.
The simple declaration of accompanying drawing
Fig. 1 is the figure that the block copolymer of expression embodiment 1 use adopts the molecular weight distribution of gel permeation chromatography survey.Moreover, X-coordinate is molecular weight (log molecular weight), ordinate zou is molecular weight distribution (weight %).
Fig. 2 represents that the pitch of bituminous composition of embodiment 1 is compatible with polymer phase, and island structure is the microphotograph of single phase, and the still isolating microphotograph of bituminous composition of comparative example 2.
Fig. 3 is the graph of molecular weight distribution that the segmented copolymer of embodiment 3 uses adopts gel permeation chromatography to survey.Moreover X-coordinate is that molecular weight (log molecular weight), ordinate zou are molecular weight distribution (weight %).
The preferred plan that carries out an invention
Below, the present invention is at length described.
(a) block (being total to) polymkeric substance that the present invention uses be have aromatic ethenyl compound as the polymer blocks S of main body and/or S ' for must composition, containing this block and conjugated diolefine is block (being total to) polymkeric substance of the polymer blocks B of main body, (b) segmented copolymer is to be the polymer blocks S and/or the S ' of main body by aromatic ethenyl compound, and conjugated diolefine is block (being total to) polymers that the polymer blocks B of main body constitutes.
Here, as in order to obtain (a) block (being total to) polymkeric substance or (b) aromatic ethenyl compound that uses of block copolymer, can enumerate vinylbenzene, t-butyl styrene, alpha-methyl styrene, p-methylstyrene, Vinylstyrene, 1,1-diphenyl benzene ethene, N, N-dimethyl-right-aminoethyl vinylbenzene, N, N-diethyl-right-aminoethyl vinylbenzene, vinyl pyridine etc.Special optimization styrene, alpha-methyl styrene.
In addition, as in order to obtain (a) block (being total to) polymkeric substance or (b) conjugated diolefine used of block copolymer, can enumerate 1,3-divinyl, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 2-methyl isophthalic acid, 3-pentadiene, 1,3-hexadiene, 4,5-diethyl-1,3-octadiene, 3-butyl-1,3-octadiene, chloroprene etc., preferred 1,3-butadiene, isoprene, 1,3-pentadiene, be more preferably 1,3-butadiene.
(a) block (being total to) polymkeric substance, be that to have as above-mentioned aromatic ethenyl compound be that the polymer blocks of main body is for must composition, contain the block that this polymer blocks and conjugated diolefine are the polymer blocks of main body (being total to) polymkeric substance, the polymer blocks that has aromatic ethenyl compound more than 1 and be a main body is for must composition, containing this polymer blocks and the conjugated diolefine more than 1 is the polymer blocks of main body, uses general formula (I): (S-B)
mIn-S ' n[the formula (I), S, S ' be aromatic ethenyl compound be polymer blocks, the B of main body be conjugated diolefine be polymer blocks, m and the n of main body be 0 or 1 integer, more than the m+n=1] expression.
(a) of the present invention block (being total to) polymers, though give full play to performance as the asphalt modification effect owing to have in the technology that makes in the past, but problem is being arranged aspect the operability such as processibility or storage stability, be unsuitable for practical asphalt modifier the bituminous solvability is greatly improved, remedies the effect of above-mentioned shortcoming, use so be suitable as these bituminous compatibility agents.
(a) the total bonding aromatic ethenyl compound content in block (being total to) polymkeric substance is greater than 10 weight %～100 weight %, is preferably greater than 10 weight %, less than 100 weight %.This content is during greater than 10 weight %, is the compatible effect that can further improve bituminous composition medium pitch and in the past compatilizer beyond expectationly.In addition, when (a) the total bonding aromatic ethenyl content in block (being total to) polymkeric substance is 100 weight %, be the occasion that does not have polymer blocks B, even but such occasion also can be brought into play the compatible effect of pitch and in the past compatilizer.
In addition, (a) conjugated diolefine in block (being total to) polymkeric substance is that the vinyl bonding content of the polymer blocks B of main body is 10～50 weight %.This content is during less than 10 weight %, and compatible effect reduces, be difficult to make this (being total to) polymkeric substance simultaneously in the manufacture method of this (being total to) polymers on reaction property and bad.And during greater than 50 weight %, become the tendency of the cold property difference of bituminous composition, or dissolution time is long because compatible effect is insufficient, or storage stability difference and bad.12～40 weight % preferably.
In addition, (a) weight-average molecular weight of the polymer blocks S (aromatic ethenyl compound is the polymer blocks of main body) in block (being total to) polymkeric substance be 500～20000 and the total amount of the weight-average molecular weight of this polymer blocks S+S ' be 1000～30000.The weight-average molecular weight of polymer blocks S is greater than 20000, and/or the total amount of S+S ' is greater than 30000 o'clock, (b) segmented copolymer to improve effect insufficient, particularly the bituminous dissolution time is obviously prolonged, storage stability does not improve effect.And, the weight-average molecular weight of polymer blocks S less than 500 and/or the total amount of S+S ' less than 1000 o'clock, dissolution time shortens, and the easy processing because viscosity is low, but the softening temperature of bituminous composition, tough viscosity are insufficient and bad.
In addition, (a) the total weight-average molecular weight preferred 5000～50000 of block (being total to) polymkeric substance.Less than 5000 o'clock, dissolution time shortened, because the low effect that can obtain processibility of viscosity, but the softening temperature of bituminous composition is insufficient, and greater than 50000 o'clock, (b) segmented copolymer to improve effect insufficient, particularly the bituminous dissolution time is prolonged and bad.
In addition, the polymer blocks that the B of general formula (I) represents is that conjugated diolefine is the polymer blocks of main body, but also can contain aromatic ethenyl compound etc.For example, can make the bonding aromatic ethenyl compound contain 0～40 weight % of the total bonding aromatic ethenyl compound in (a), 0～30 weight % preferably again.In addition, the structure of polymer blocks both can be random shape, also can be cumulative tapered block.By making conjugated diolefine is that the B block of main body contains the bonding aromatic ethenyl compound, owing to regulate the chain length of S (and/or S ') and B, so can regulate compatible effect.The amount of the bonding aromatic ethenyl compound of B block is during greater than 40 weight %, because the molecular weight of S (and/or S ') block is too little, so compatible effect is insufficient and bad.
In addition, (b) block copolymer that asphalt modification of the present invention uses with composition uses S-B-S, S-B-S ' or (S-B)
2-X (S, S ', B are identical with general formula (I), and X is the coupling agent residue) expression.
Here, (b) total bonding content of the aromatic ethenyl compound in the block copolymer is 20～70 weight %.This total bonding content is during less than 20 weight %, and softening temperature, tough viscosity are insufficient, and the anti-flow deformation under the high temperature is also insufficient.During greater than 70 weight %, the penetration degree of bituminous composition is little, hardening, and the low temperature elongation reduces.20～50 weight % preferably.
In addition, (b) conjugated diolefine in the segmented copolymer is that vinyl bonding content among the polymer blocks B of main body is 10～50 weight %.This vinyl bonding content is difficult to obtain in this manufacture method less than the polymer blocks of 10 weight %.And during greater than 50 weight %, the penetration degree of bituminous composition is little, hardening, and the low temperature elongation reduces.12～45 weight % preferably.
In addition, S-B-S, the S-B-S ' of conduct (b) segmented copolymer that uses with composition of asphalt modification of the present invention or (S-B)
2The weight-average molecular weight of S among the X and S ' (aromatic ethenyl compound is the polymer blocks of main body) is preferred 10000～20000, more preferably 12000～18000.Weight-average molecular weight is less than 10000 o'clock, and the softening temperature of gained bituminous composition, tough viscosity are insufficient, and the reduction of anti-flowability is also big, thereby bad.And greater than 20000 o'clock, even under the condition that contains (a) block (being total to) polymkeric substance, solvability was also obviously bad, and storage stability is poor, is separated easily sometimes.
In addition, conjugated diolefine is that the B block of main body also can contain and (a) same aromatic ethenyl compound.For example, can make the bonding aromatic ethenyl compound contain 0～40 weight % of the total bonding aromatic ethenyl compound in (b), again 0～30 weight % preferably.In addition, the structure of B block both can be random shape, also can be cumulative tapered block.By making conjugated diolefine is that the B block of main body contains the bonding aromatic ethenyl compound, owing to regulate the chain length of S (and/or S ') and B, so can regulate compatible effect.The amount of the bonding aromatic ethenyl compound of B block is during greater than 40 weight %, because the molecular weight of S (and/or S ') block is too little, so compatible effect is insufficient and bad.
The B block also can be cumulative tapered block.
In addition, (b) weight-average molecular weight of segmented copolymer is preferred 60000～400000, and is preferred again 100000～300000, and especially preferably 120000～300000.This molecular weight is less than 60000 o'clock, and the softening temperature of gained bituminous composition, tough viscosity are insufficient, and the reduction of anti-flowability is big and bad.And greater than 400000 o'clock, though tough viscosity increase fully, solvability, storage stability variation, generation is separated, and the melt viscosity of bituminous composition is very high, processing sometimes, operability is difficult and bad.
Preferred 0～30 as the melt flow rate (MFR) (the G method of JIS K7210) of the liquidity scale, preferred again 0.01～15, especially preferably 0.01～10.
(a) block (being total to) polymkeric substance that the present invention uses for example can be in unreactive hydrocarbons solvent, uses organolithium compound etc. to be polymerization starter, by make aromatic ethenyl compound and conjugated diolefine in order polymerization make.
For example, can make polymerization of aromatic vinyl earlier, make polymerization of conjugated dienes again, reaction is stopped or inserting aromatic ethenyl compound, conjugated diene compound more in order, stopped reaction is made when obtaining desired structure, can also be in the polymerization of conjugated diolefine, the aromatic ethenyl compound that adds desired quantity as required carries out copolymerization.
In addition, (b) segmented copolymer for example can be in unreactive hydrocarbons solvent, use organolithium compound etc. to be polymerization starter, make polymerization of aromatic vinyl earlier, make polymerization of conjugated dienes again after, make the coupling agent reaction, or by the aromatic ethenyl compound reaction is made.
In addition, in the polymerization of conjugated diolefine, the aromatic ethenyl compound that also can add desired quantity as required carries out copolymerization.
As above-mentioned unreactive hydrocarbons solvent, can use the hydrocarbon of pentane, normal hexane, heptane, octane, methylcyclopentane, hexanaphthene, benzene, dimethylbenzene etc., wherein preferred hexanaphthene.
As the organic alkali metal compound of polymerization starter, preferred organolithium compound.As this organolithium compound, can use an organic lithium, organic two lithiums, organic many lithium compounds.
As these concrete example, can enumerate lithium ethide, n-propyl lithium, sec.-propyl lithium, n-Butyl Lithium, s-butyl lithium, prenyl two lithiums etc., per 100 weight parts monomers can be used by 0.02～2 weight part.
In addition, at this moment, microtexture, promptly can enumerate Lewis base as the conditioning agent of conjugated diolefine vinyl bonding content partly, for example ether, amine etc., can enumerate the ether derivant of many ethylene glycol of diethyl ether, tetrahydrofuran (THF), propyl ether, butyl ether, senior ether or butyl glycol ether, diethylene glycol dimethyl ether, dibutyl ethylene glycol ether, triethylene glycol butyl ether, ethylene glycol dibutyl ether etc. particularly, can enumerate the tertiary amine of Tetramethyl Ethylene Diamine, pyridine, Tributylamine etc. etc. as amine, can use with unreactive hydrocarbons solvent.
These compounds are in the polymerization of polymer blocks of main body in conjugated diolefine, and when making the aromatic ethenyl compound copolymerization, the structure regulator that also can be used as aromatic ethenyl compound/conjugated diolefine uses.
Polyreaction is preferably implemented down at 30～100 ℃ usually at 20～120 ℃.In addition, polymerization both can control to steady temperature and implement, and also can not remove and reduce phlegm and internal heat, implements under ascending temperature.
Coupling agent as (b) block copolymer uses preferably uses 2 functionality coupling agents.As such coupling agent, for example, can enumerate methylene bromide, ethylene dibromide, dibromopropane, methylene dichloride, ethylene dichloride, propylene dichloride, the dihalide alkane of dichlorobutane etc., dichlorosilane, dimethyl dichlorosilane (DMCS), dimethyldichlorosilane(DMCS), one ethyl dichlorosilane, diethyl dichlorosilane, the monobutyl dichlorosilane, the dibutyl dichlorosilane, one hexyl dichlorosilane, the dihexyl dichlorosilane, two bromo-silicanes, monomethyl two bromo-silicanes, the halogenated silicon compound of dimethyl two bromo-silicanes etc., Vinylstyrene, two aromatic ethenyl compounds of divinyl naphthalene etc., ethyl formate, ethyl acetate, butylacetate, methyl propionate, phenylacetate, ethyl benzoate, the ester cpds of phenol benzoate and so on, dibutyl dichloro tin, the tin compound of tetrachloro tin etc., dihydroxyphenyl propane, dihydroxyphenyl propane D, Bisphenol F, other epoxy compounds, propionyl chloride, the acyl chlorides of hexanodioic acid diacid chloride etc., 1, the 4-chloromethylbenzene, tolylene diisocyanate etc.
(a) block (being total to) polymkeric substance or (b) binding capacity of the aromatic ethenyl compound in the block copolymer, monomer feed rate when utilizing polymerization in each stage is regulated, and the vinyl bonding content of the conjugated diolefine of being regulated is regulated by the one-tenth component that changes above-mentioned micro adjusting agent as required.In addition, conjugated diolefine is the structure of aromatic ethenyl compound/conjugated diolefine of the polymer blocks of main body: also use above-mentioned micro adjusting agent to regulate.Here the structure of so-called aromatic ethenyl compound/conjugated diolefine is regulated the bonding state of random, the alternation (taper) be meant the aromatic ethenyl compound that is controlled at bonding in the conjugated diolefine, block structure etc.
In addition, the weight-average molecular weight of block (a)～(b) (being total to) polymkeric substance is utilized polymerization starter, and for example the addition of s-butyl lithium is regulated.
Asphalt modification composition of the present invention is a main component with above-mentioned (b) block copolymer, wherein, contains (a) block (being total to) polymkeric substance as compatilizer.(a) composition in the said composition is 10～40/90～60 with (b) weight ratio of composition.(a) weight ratio of composition is insufficient to deliquescent effect less than 10 o'clock, and insufficient greater than 40 o'clock tackiness agent rerum naturas.Preferably 10～30/90～70.
In addition, asphalt modification of the present invention is with in the composition, adopt the peak molecular weight of (a) block (being total to) polymkeric substance that gel permeation chromatography (GPC) measures preferably be equivalent to (b) segmented copolymer the peak molecular weight 1/80～less than 1/3.This value because molecular weight is too low, so pitch softening point is insufficient, can not obtain compatible effect and bad less than 1/80 o'clock fully.
And, when above, can not obtain effect greater than 1/3 fully as compatilizer, elongated and bad to the bituminous dissolution time.
Here, the ratio at peak is the ratio at the climax (main peak) in each a plurality of peaks of segmented copolymer.
In order to make asphalt modification composition of the present invention, preferably in hydrocarbon solvent be that initiator adopts solution polymerization process polymerization individually (a) block (being total to) polymkeric substance respectively with the organolithium compound, with (b) block copolymer, after resulting each mixing of polymers soln, the method that desolventizing makes.For example, after making (b) segmented copolymer, by above-mentioned (a) block (being total to) polymers soln being carried out carrying out the desolventizing manufacturing after solution mixing, the homogenizing more above-mentionedly.
Here, (a) composition can use independent the finishing of special manufacture method, but (b) in fact the general producing apparatus that uses such as segmented copolymer can not be made because of gluing wall or dry incomplete problem.In addition, even special equipment also is not suitable for producing in enormous quantities, because unfavorable and improper on the cost, historical facts or anecdotes is used after preferred and (b) the mixing of composition, carries out desolventizing, drying.
In addition, block copolymer composition of the present invention is made in the polymerization that can carry out (a) block (being total to) polymkeric substance and above-mentioned (b) segmented copolymer simultaneously.For example, be that the general formula that is fit to be defined in (a) block (being total to) polymkeric substance is that the general formula of S-B structure, (b) segmented copolymer is the method for the occasion of S-B-S structure etc., as the 1st stage in order to make (b) segmented copolymer, after making aromatic ethenyl compound and polymerization starter (initiator-1) contact reacts, add conjugated diolefine, after reaction finishes basically, add polymerization starter (initiator-2), add conjugated diolefine again, the limit continues to make (b) segmented copolymer, and the limit begins the manufacturing of (a) block (being total to) polymkeric substance.At last, make the aromatic ethenyl compound reaction, carry out the manufacturing of (a) and (b) segmented copolymer simultaneously, also can make composition.Here, molecular structure for the polymkeric substance of controlling manufacturing, second section initiator adds, preferably after the polymerization of first section conjugated diolefine finishes, but initiator is added in conjugated diolefine addition, the limit of also can the limit regulating the 1st section in the polymeric way, save the interpolation of second section conjugated diolefine.In addition, the molecular structure of the polymkeric substance of making for pinpoint accuracy ground control can utilize the addition of first section, second section initiator, first section aromatic ethenyl compound and the addition of conjugated diolefine and second section conjugated diolefine and the adjusting of aromatic ethenyl compound addition to control.
In addition, bituminous composition of the present invention (1) is to contain the composition of above-mentioned asphalt modification with composition and straight-run pitch.
Here, the straight-run pitch that bituminous composition (1) uses is after crude asphaltic petroleum is carried out air distillation and water vapor or vacuum distilling, the material that obtains as residue.Because straight-run pitch makes block copolymer composition of the present invention dissolving easily, so process, processing ease.
The pitch of straight-run pitch preferred pin in-degree 50～200.Penetration degree is lower than at 50 o'clock, has the flexible destructive tendency under the low temperature, and greater than 200 o'clock, has wearability, the anti-mobile tendency that reduces.
As the pitch that composition for modifying of the present invention is suitable for, preferred straight-run pitch, but also can use oxidized bitumen (with the above-mentioned pitch that similarly obtains semiasphalt base crude oil) to wait the replacement straight-run pitch.
Modification in the bituminous composition (1) is 2～15/98～85 with the weight ratio of block copolymer composition and straight-run pitch, preferably 3～13/97～87.Modification less than 2 o'clock, does not present the bituminous modified effect with the weight of block copolymer composition, and softening temperature is insufficient, and penetration degree, tough viscosity are low.And greater than 15 o'clock, though it is softening temperature, tough viscosity are abundant, obviously elongated to the bituminous dissolution time, consistency is also bad.And the melt viscosity of bituminous composition obviously increases, and makes processing, operational difficulty.
In addition, modification block copolymer composition of the present invention, usually, can be in pelletized form, the shape of shred or powder etc. uses.
In addition, bituminous composition (2), be except above-mentioned asphalt modification use composition and with above-mentioned same straight-run pitch outside, also contain aromatic hydrocarbon resin, and/or the composition of mink cell focus.
Here, so-called aromatic hydrocarbon resin is meant the resin that contains rosin and derivative, terpine resin or petroleum resin and derivative thereof, coumarone-indene resin, alkyl phenol resin, Synolac etc.
In addition, so-called mink cell focus is meant the vegetables oil of Rice pollard oil, soybean wet goods; The animal oil of fish oil, whale oil etc., the oil of locomotive oil, lubricated wet goods is a heavy hydrocarbon oil, is heavy hydrocarbon oil but use oil from considerations such as economy, the fragrant family of wherein preferred use is processed with oil.
Cooperation ratio in the bituminous composition (2), with respect to above-mentioned straight-run pitch 100 weight parts, above-mentioned asphalt modification composition is 1～20 weight part, preferred 3～18 weight parts, aromatic hydrocarbon resin is 1～60 weight part that adds up to of 0～40 weight part, mink cell focus 0～40 weight part and aromatic hydrocarbon resin and mink cell focus, should the total amount be 5～40 weight parts preferably.
Here, asphalt modification is with the use level of composition during less than 1 weight part, do not present the bituminous modified effect, softening temperature is insufficient, and penetration degree, tough viscosity are low, and during greater than 20 weight parts, though softening temperature, tough viscosity are abundant, obviously elongated to the bituminous dissolution time, consistency is variation also.And the melt viscosity of bituminous composition obviously raises, and makes processing, operational difficulty.
In addition, mobile, poorly soluble when the total use level of aromatic hydrocarbon resin and mink cell focus is lower than 1 weight part, and during greater than 60 weight parts, softening temperature, tough viscosity reduce, and become fragile.
Above-mentioned modification block copolymer composition in the straight-run pitch under the stirring of 140～190 ℃ of heating and meltings, is dropped into usually in bituminous composition of the present invention (1)～(2), or said composition and aromatic hydrocarbon resin and/or mink cell focus mixing manufacturing.
In addition, in bituminous composition of the present invention (1)～(2), can be on a small quantity and with other styrene-butadiene-styrene block copolymer, styrene isoprene styrene block copolymer (SIS).In addition, can also and with other thermoplastic elastomer or thermoplastic resin, for example styrene butadiene rubbers latex, ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, Atactic Polypropelene, 1, the polymkeric substance of other of 2-polyhutadiene or ethylene-propylene rubber etc.
This occasion, can be in advance modification of the present invention with block copolymer composition and above-mentioned other polymkeric substance in ratio arbitrarily mixing after, use after granulation and/or the powderization.
In addition, in bituminous composition of the present invention (1)～(2), can also cooperate the additive of the weighting agent, pigment, antiaging agent, linking agent, fire retardant etc. of silicon oxide, talcum, lime carbonate etc.In addition, also can add sand grains etc. as the occasion of using of paving the way.
Embodiment
Below, enumerate embodiment and be described more specifically the present invention, but the invention is not restricted to these embodiment.
Moreover, " part " among the embodiment and " % ", short of specified otherwise then is a weight basis.
In addition, the various evaluations among the embodiment are the results that obtain as follows.
The characteristic of segmented copolymer
(1) weight-average molecular weight (Mw)
Weight-average molecular weight is measured, and is to use eastern Cao's corporate system gel permeation chromatograph (HLC-8220), spectrum post to use the Ultrabondagel E750A of Waters corporate system.Solvent uses tetrahydrofuran (THF), measures under 45 ℃ of temperature, flow velocity 1.0ml/ branch, sample solution concentration 0.1%, injection rate 20 μ l condition determinations, presses the value that polystyrene standard converts.
(2) peak molecular weight and the analysis on Content of SBS, SB
The peak molecular weight uses polystyrene standard (Shell Chemical Co.Ltd (U.S.) system) drawing standard curve, calculated by the above-mentioned chromatogram that obtains, and content is similarly calculated by the area ratio of each composition of stratographic.
(3) bonding styrene content
Use infrared spectroscopic analysis device (Perkin-Elmer corporate system fourier transformation type infrared spectroscopic analysis device), adopt calibration curve method by wavelength 699cm
-1Absorption intensity calculate cinnamic content.
(4) quantitative analysis of vinyl bonding content in the divinyl
With 450～1200cm
-1Be measurement range, the analytical results of the above-mentioned mensuration that obtains is the basis, adopt Mo Lailuofa to calculate vinyl bonding content in the divinyl.
(5) analysis of melt flow rate (MFR) (MFR (G))
テ ス -automatic melt index apparatus of industry corporate system (TP-404 type) is used in this analysis.Analytical sample is measured above-mentioned composition group according to the G method (200 ℃, the 5kg loading) of JIS-K 7210.
The characteristic of bituminous composition
(1) dissolution time A/B
Dissolution time A, when being the preparation bituminous composition, the content that takes a morsel in asphalt mixture is coated on visual observation on polyester (Tetron) sheet, up to the time that the segmented copolymer solids do not occur.
Past, bituminous composition uses and utilizes dissolution time A judgement dissolved sample to estimate, judge performance, but the result of research, the pitch in the discovery microscopic fields and the phase structure of polymkeric substance have great effect to the pitch rerum natura, when using dissolution time A to judge, even it is the occasion that occurs being separated at microscopic fields is also arranged in the dissolved composition, especially poor as the storage stability of bituminous composition.Even on the market, in order to give full play to product performance, and prevent that quality is inhomogeneous as bituminous composition, generally acknowledge that at microscopic fields must be the state that forms single phase.In view of above situation, use following dissolution time B to estimate.
Dissolution time B adopts following method to determine.Preparation and above-mentioned same bituminous composition, the content in mixing of taking a morsel is placed at asphalt mixture on the hot plate on the heated glass slide glass, puts cover glass on this glass slide again, launches thinly.Using the infiltration type microscope to amplify 200 times to unfolded mixture on the glass slide observes contrast, determines that the pitch and the island structure of polymer phase form the single time mutually.
(2) tough viscosity
When making the mixing of bituminous composition, as above-mentioned in order to give full play to performance, best pitch disperses equably with polymer phase, island structure is mutually single, but in a part of comparative example, also has and mix above 15 hours the combination that does not still form single phase, is actually the non-conforming system.Can not be even the composition that does not also form single phase is stirred in mixing more than 8 hours for using in reality, even half-compulsory ground mechanically mixes the occasion of making bituminous composition, the performance of storage stability representative is also insufficient.Consider in this comparative example that the practical tolerable limit that goes up adopts mixing to finish in 8 hours, is used for performance evaluation.In addition, consider the simplicity of evaluation, comprising the embodiment mixing time is 8 hours without exception, and following physical property measurement also uses the bituminous composition that mixes 8 hours to implement.
For the test method of the asphalt mixture of this test usefulness, measure according to " the test method(s) brief guide of paving the way " (clear and 63 years 11 days, Japanese road association of Corporation issues).
The test method of the asphalt mixture that (3) is for experiment is measured according to JIS K2207.
(4) melt viscosity
The test method of the asphalt mixture that this test is used uses Brookfield viscometer to measure under 160 ℃.
(5) storage stability
The asphalt mixture that this test is used is added in the container of aluminium pot system, in baking oven, leave standstill 72 hours under 180 ℃, nitrogen ambient environment after, at room temperature cooling makes to be divided into upper, middle and lower three positions in the aluminium pot.Remove middle body, use the sample of top, bottom to carry out following evaluation.
The judgement of surface skining situation
The condition of surface on observation sample top will be designated as " * " because of the aging state that produces skinning of polymkeric substance, not have the state of skinning to be decided to be " zero ".Judged result is shown in table 1, table 2.
Softening temperature after the storage is poor
Measure the softening temperature of top and lower specimen, estimate the poor of the softening temperature of representing the polymkeric substance separation degree, the results are shown in table 1, table 2.
Embodiment 1
The manufacturing of block copolymer composition
(1) (a) polymerization of block (being total to) polymkeric substance
After using nitrogen fully to replace to the stainless steel aggregation container of 100 liters of strap clamps of internal volume cover and stirrer, add 20kg hexanaphthene, 0.6kg vinylbenzene, leading to warm water in chuck, to make content be 40 ℃.
Then, add the 6g s-butyl lithium and begin polymerization.After styrene polymerization finished, it was 80 ℃ that the limit attemperation makes the content temperature, and the 1.4kg 1,3-butadiene is slowly added on the limit.
After the polymerization of B block finishes, add 3ml methyl alcohol, stir after 10 minutes, liquid is moved on in the mixing vessel.
(2) (b) polymerization of segmented copolymer
With (1) similarly, use nitrogen fully to replace to the stainless steel aggregation container of 100 liters of strap clamps of internal volume cover and stirrer after, add the 50kg hexanaphthene, 2.4kg vinylbenzene, leading to warm water in chuck, to make content be 40 ℃.
Then, add the 11g s-butyl lithium and begin polymerization.After styrene polymerization finished, it was 80 ℃ that the limit attemperation makes the content temperature, and the 5.6kg 1,3-butadiene is slowly added on the limit.After the polymerization of B block finishes, add the ethylene dibromide of 4g, reacted 30 minutes as coupling agent.After the reaction, add 1ml methyl alcohol, stir after 10 minutes, be pipetted in the mixing vessel.
(3) manufacturing of composition
After the mixing of above-mentioned segmented copolymer (a)～(b) composition, from mixing vessel, take out content, add 50g as 2 of oxidation inhibitor, 6-di-t-butyl-4-cresols (BHT).The polymkeric substance that this mixed polymerization solution water steam stripped is obtained 80 ℃ of warm air dryings, obtains block copolymer composition after using pulverizer to be ground into fragmental.
The Fig. 1 that is illustrated in of the molecular weight distribution of this block copolymer composition use gel permeation chromatography survey of expression.
The manufacturing of bituminous composition
570g uses stirrer [special machine chemical industry corporate system, TK uniform mixer, 10000rpm] to mix with above-mentioned block copolymer composition 30g, limit 180 ℃ of heating edge the straight-run pitch of penetration degree=70 [common oil company system, 60/80], makes bituminous composition.The evaluation result of each characteristic is shown in table 1.
Said composition is shown in Fig. 2 through 8 hours mixed microphotographs.Find out by figure, the state of the dissolution time of bituminous composition, what be separated into the phase that is rich in block copolymer composition (position, island) at white yellow position and dark brown position is rich in pitch (extra large position) mutually, becomes single phase (with reference to Fig. 2) through pitch after 8 hours with block copolymer composition island structure mutually.
Except the add-on that changes vinylbenzene, 1,3-butadiene, s-butyl lithium, other make segmented copolymer, the asphalt modification block copolymer composition of table 1 and 2 expressions similarly to Example 1, make bituminous composition, estimate the performance of composition.The evaluation result of each characteristic is shown in table 1 and 2.
(b) segmented copolymer, in stainless steel aggregation container similarly to Example 1, add 50kg hexanaphthene, 1.2g ethylene glycol diethyl ether, 1.2kg vinylbenzene, to make content be 40 ℃ to logical warm water in chuck, then, add the 6g s-butyl lithium and begin polymerization, after styrene polymerization finished, it was 80 ℃ that limit logical cold water in chuck makes content, the 1,3-butadiene of 5.6kg is slowly added on the limit.The polymerization of butadiene block is added 1.2kg vinylbenzene after finishing again, after roughly polyreaction finishes fully, adds 1ml methyl alcohol, stirs after 10 minutes, is pipetted in the mixing vessel.Then, after similarly to Example 1 block copolymer (a), above-mentioned (b) composition mixed, carry out operation similarly to Example 1, estimate the performance of this block copolymer composition.The evaluation result of each characteristic is shown in table 1.In addition, the Fig. 3 that is illustrated in of the molecular weight distribution of this block copolymer composition employing gel permeation chromatography survey of expression.
Make (a) segmented copolymer as described below.That is, in stainless steel aggregation container similarly to Example 1, add 20kg hexanaphthene, 0.45kg vinylbenzene, to make content be 40 ℃ to logical warm water in chuck.
Then, add the 7g s-butyl lithium and begin polymerization.
After styrene polymerization finished, it was the 1,3-butadiene that 80 ℃, limit slowly add 2.1kg that limit logical cold water in chuck makes the content temperature.The polymerization of B block is added 0.45kg vinylbenzene after finishing again, and roughly polyreaction finishes the back fully and adds 3ml methyl alcohol, stirs after 10 minutes, is pipetted in the mixing vessel.
(b) segmented copolymer, except changing vinylbenzene, 1, beyond the add-on of 3-divinyl, s-butyl lithium, ethylene glycol diethyl ether, other carry out polymerization similarly to Example 1, make the represented block copolymer of table 1, carry out operation similarly to Example 1, make block copolymer composition, bituminous composition, estimate the performance of composition.The evaluation result of each characteristic is shown in table 1.
Embodiment 8
Use the aggregation container of embodiment 1 usefulness, add 50kg hexanaphthene, 0.8kg vinylbenzene, to make the content temperature be 40 ℃ to logical warm water in chuck.
Then, add the 3.2g s-butyl lithium and begin polymerization.After styrene polymerization finished, it was 80 ℃ that limit logical cold water in chuck makes the content temperature, and the 1,3-butadiene of 1.8kg is slowly added on the limit.The polymerization of B block is added the 2.2g s-butyl lithium after finishing again, slowly adds the 1,3-butadiene of 2.4kg, after the reaction of B block finishes, add the vinylbenzene of 1.1kg again, after reaction finishes, add 1ml methyl alcohol, stir after 10 minutes, add 2 of 50g, 6-di-t-butyl-4-cresols (BHT).
This polymers soln is carried out the water vapor stripping similarly to Example 1, the polymkeric substance that obtains is carried out drying, make block copolymer composition, estimate the performance of said composition.The evaluation result of each characteristic is shown in table 1.
Embodiment 9
Use the aggregation container of embodiment 1 usefulness, the vinylbenzene that adds 20kg hexanaphthene, 0.32kg, to make the content temperature be 40 ℃ to logical warm water in chuck, add the 6g s-butyl lithium then and begin polymerization, after cinnamic polymerization finished, it was 80 ℃ that limit logical cold water in chuck makes the content temperature, and the limit is divided three times, add 1,3-butadiene and the 0.3kg vinylbenzene of 1.38kg equably at leisure.After polymerization finishes, add 3ml methyl alcohol, stirred 10 minutes, make (a) block copolymer.Then, make (b) block copolymer similarly to Example 1, make bituminous composition, estimate the performance of composition, the evaluation result of each characteristic is shown in table 1.
Use the aggregation container of embodiment 1 usefulness, add the 20kg hexanaphthene, 8g ethylene glycol diethyl ether, 0.44kg vinylbenzene, to make the content temperature be 40 ℃ to logical warm water in chuck, add the 5g s-butyl lithium then and begin polymerization, after cinnamic polymerization finished, it was 1,3-butadiene and the 0.18g vinylbenzene that 80 ℃, limit side by side slowly add 1.38kg that limit logical cold water in chuck makes the content temperature, after roughly polyreaction finishes fully, add 3ml methyl alcohol, stirred 10 minutes, make (a) block copolymer.Then, make (b) block copolymer similarly to Example 1, mix, make block copolymer composition, make bituminous composition, estimate the performance of said composition with above-mentioned (a) block copolymer.The evaluation result of each characteristic is shown in table 1.
Embodiment 11,19
During except polymerization (a) block copolymer, change beyond the add-on of vinylbenzene, 1,3-butadiene, s-butyl lithium, ethylene glycol diethyl ether, other all carry out similarly to Example 10, make block copolymer composition, bituminous composition, estimate the performance of composition.The evaluation result of each characteristic is shown in table 1 and 2.
Embodiment 12
During except polymerization (b) segmented copolymer, change beyond the add-on of vinylbenzene, 1,3-butadiene, s-butyl lithium, ethylene glycol diethyl ether, other all carry out similarly to Example 1, make block copolymer composition, bituminous composition, estimate the performance of composition.The evaluation result of each characteristic is shown in table 1.
Embodiment 14,21
Except the add-on that changes vinylbenzene, 1,3-butadiene, s-butyl lithium, other make block copolymer, the block copolymer composition for asphalt modification of table 2 expression similarly to Example 4, make bituminous composition, estimate the performance of composition.The evaluation result of each characteristic is shown in table 2.
Embodiment 17
(a) block copolymer, except the add-on that changes vinylbenzene, 1,3-butadiene, s-butyl lithium, ethylene glycol diethyl ether, other all carry out similarly to Example 11, make (a) block copolymer.
(b) block copolymer is except the add-on that changes vinylbenzene, 1,3-butadiene, s-butyl lithium, ethylene glycol diethyl ether, other similarly to Example 4, make block copolymer, the block copolymer composition of table 2 expression, make bituminous composition, estimate the performance of composition.The evaluation result of each characteristic is shown in table 2.
Embodiment 22
Except event became the add-on of vinylbenzene, 1,3-butadiene, s-butyl lithium, other made block copolymer, the block copolymer composition for asphalt modification of table 2 expression similarly to Example 3, make bituminous composition, estimate the performance of composition.The evaluation result of each characteristic is shown in table 2.
Comparative example 1
Except not using (a) segmented copolymer, other all carry out similarly to Example 1.The results are shown in table 3.
Comparative example 2,3,6～10
Except the add-on that changes vinylbenzene, 1,3-butadiene, s-butyl lithium, ethylene glycol diethyl ether, other make block copolymer similarly to Example 1, make bituminous composition, estimate the performance of composition.The evaluation result of each characteristic is shown in table 3.In addition, the microphotograph of the composition of comparative example 2 is shown in Fig. 2.Fig. 2 illustrates that this bituminous composition is still the state that block copolymer composition and pitch are separated.
Comparative example 4
Except not using (a) segmented copolymer, other all carry out similarly to Example 3.The results are shown in table 3.
Comparative example 5
Except the add-on that changes vinylbenzene, 1,3-butadiene, s-butyl lithium, other make block copolymer similarly to Example 3, make bituminous composition, estimate the performance of composition.The evaluation result of each characteristic is shown in table 3.
Found out that by table 1 and table 2 bituminous composition of the present invention is short to the bituminous dissolution time, melt viscosity is a low viscosity, storage stability is good, demonstrates good tough viscosity, softening temperature and elongation.
On the contrary, find out by table 3, poor as comparative example 1, comparative example 4 dissolution times length or melt viscosity height, the storage stability of the bituminous composition that does not contain (a) of the present invention block copolymer.Comparative example 2, comparative example 5, the molecular weight of the polymer blocks S of the block copolymer (a) that cooperates with (b) block copolymer are outside scope of the present invention, and dissolution time is long, storage stability is also poor.Comparative example 3, the use level of (a) of the present invention block copolymer is many, softening temperature, toughness, viscosity and elongation rate variance.And comparative example 6～10 is to break away from (a) block copolymer or (b) composition formed of the co-polymer of block copolymer scope, all can not obtain satisfied rerum natura.
Embodiment 25～27 (also using the embodiment of aromatic hydrocarbon resin and mink cell focus)
Except changing vinylbenzene, 1, beyond the add-on of 3-divinyl, s-butyl lithium, the block copolymer composition 60g of other table 4 that makes similarly to Example 12 expressions, and aromatic hydrocarbon resin (Yasuhara chemical company system: Mighty Ace 150) 30g, fragrant family processing oil (the emerging product corporate system of bright dipping: the AE20H) straight-run pitch of 60g, penetration degree=70 [common oil company system, 60/80] 600g, stirrer is used 180 ℃ of heating edge in the limit, and [special machine chemical industry corporate system TK all mixes machine, 10000rpm] mix, make bituminous composition.The evaluation result of each characteristic is shown in table 4.
Comparative example 11
Except the add-on that changes vinylbenzene, 1,3-butadiene, s-butyl lithium, the block copolymer composition of other tables 4 that make similarly to Example 12 expressions, adopt embodiment 25 same methods to make bituminous composition.The evaluation result of each characteristic is shown in table 4.
Comparative example 12～15
(b) block copolymer that uses embodiment 25 to use is pressed the cooperation of table 4 expression and is formed, and adopts embodiment 25 same methods to make bituminous composition.The evaluation result of each characteristic is shown in table 4.
Find out by table 4, embodiment 25～27th, and with the aromatic hydrocarbon resin in the scope of the invention and the bituminous composition of mink cell focus,, melt viscosity short to the bituminous dissolution time is low viscosity, and storage stability is good, demonstrate good toughness, viscosity, softening temperature and elongation.
On the contrary, the comparative example 11 of table 4, the molecular weight of polymer blocks (a) are outside scope of the present invention, and dissolution time is long, storage stability is also poor.Comparative example 12～15th does not contain the bituminous composition of (a) of the present invention block copolymer, and the balanced differences of dissolution time, softening temperature, penetration degree, toughness, viscosity, storage stability all can not obtain satisfied rerum natura.
The possibility of utilizing on the industry
(a) of the present invention block (being total to) polymer can easily make pitch and aromatic vinyl The co-polymer of based compound and conjugated diene is that the asphalt modifier of main component is compatible, and root According to used pitch or asphalt modifier also can designing optimal structure, be suitable as compatilizer and make With.
In addition, asphalt modification composition of the present invention is (a) of the present invention block (being total to) polymerization The composition of thing and asphalt modifier, dissolubility are very good. By being used, such asphalt modification organizes Compound is engaged in straight asphalt etc., can make tough viscosity, softening point and the percentage elongation of pitch The bituminous composition that balance of properties is good, so can make can pave the way with or waterproof sheet, sound insulation Sheet, water shutoff material, roof Material, encapsulant, lining material, bloop are used, steel pipe coating With the bituminous composition that uses in the grade.
Claims (6)
1. asphalt modification block copolymer composition is characterized in that containing:
(a) block (being total to) polymkeric substance, be have more than 1 polymerization of aromatic vinyl thing block for must composition, can contain this polymerization of aromatic vinyl thing block and block (being total to) polymkeric substance more than 1 based on the polymer blocks of conjugated diolefine, wherein, (S-B) with general formula (I)
m-S '
nExpression, in the formula (I), S, S ' is that aromatic ethenyl compound is the polymer blocks of main body, B is that conjugated diolefine is the polymer blocks of main body, m and n are 0 or 1 integers, more than the m+n=1, total bonding aromatic ethenyl compound content in this block (being total to) polymkeric substance is greater than 10 weight %～100 weight %, conjugated diolefine is that the vinyl bonding content among the polymer blocks B of main body is 10～50 weight %, and the weight-average molecular weight of this polymer blocks S is 500～20000, the total amount of the weight-average molecular weight of this polymer blocks S and S ' is 1000～30000, the total weight-average molecular weight of this block (being total to) polymkeric substance be 5000～50000 and
(b) by at least 2 aromatic ethenyl compound be main body polymer blocks, with at least 1 conjugated diolefine be the segmented copolymer that the polymer blocks of main body constitutes, use general formula (II) S-B-S, general formula (III) S-B-S ' and/or general formula (IV) (S-B)
2-X represents, in the general formula (II)～(IV), S, S ', B are identical with general formula (I), X is the coupling agent residue, total bonding aromatic ethenyl compound content in this segmented copolymer is 20～70 weight %, conjugated diolefine is that the vinyl bonding content among the polymer blocks B of main body is 10～50 weight %, and the weight-average molecular weight of polymer blocks S and S ' is 10000～20000, (a)/(b) weight ratio=10～40/90～60;
Adopt the peak molecular weight of (a) block (being total to) polymkeric substance that gel permeation chromatography GPC measures be equivalent to (b) block copolymer the peak molecular weight 1/80～less than 1/3.
2. the described asphalt modification block copolymer composition of claim 1, wherein, (a) the total bonding aromatic ethenyl compound content in block (being total to) polymkeric substance is greater than 10 weight %, less than 100 weight %.
3. the manufacture method of claim 1 or 2 described block copolymer composition for asphalt modification, it is characterized in that, in unreactive hydrocarbons solvent, organolithium compound is an initiator, adopt solution polymerization process respectively polymerization make (a) block (be total to) polymkeric substance and (b) block copolymer, after each polymers soln that obtains like this mixed, carry out desolventizing and make described composition.
4. the manufacture method of claim 1 or 2 described block copolymer composition for asphalt modification, it is characterized in that, polymerization manufacturing side by side (a) block (being total to) polymkeric substance and (b) block copolymer, and be in unreactive hydrocarbons solvent, to be the solution polymerization process of initiator with the organolithium compound, in insertion polymerization operation in order with aromatic ethenyl compound, when conjugated diolefine is carried out polymerization, at least insert initiator 2 times, insert 1 aromatic ethenyl compound, conjugated diolefine at least.
5. bituminous composition, its characteristic is to contain claim 1 or 2 described composition and straight-run pitches, makes claim 1 or 2 described composition/straight-run pitch weight ratio=2～15/85～98.
6. bituminous composition, it is characterized in that containing claim 1 or 2 described compositions, straight-run pitch, aromatic hydrocarbon resin and mink cell focus, with respect to straight-run pitch 100 weight parts, claim 1 or 2 described compositions are that 1～20 weight part, aromatic hydrocarbon resin are that 0～40 weight part, mink cell focus are 0～40 weight part, and the total weight part of aromatic hydrocarbon resin and mink cell focus is 1～60 weight part.
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| KR101984725B1 (en) * | 2016-10-21 | 2019-05-31 | 주식회사 엘지화학 | Asphalt Modifier Containing Blowing Agent and Asphalt Composition Comprising the same |
| JP2021042282A (en) * | 2019-09-09 | 2021-03-18 | ジェイエスアール クレイトン エラストマー株式会社 | Block copolymer for photosensitive printing plate material having both flexibility and abrasion resistance, and its production method |
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| CN1228454A (en) * | 1998-03-05 | 1999-09-15 | 日本合成橡胶株式会社 | Block copolymer composition for modifying asphalt and asphalt composition comprising the same |
| CN1338487A (en) * | 2000-08-11 | 2002-03-06 | Jsr克莱顿·伊利斯特摩股份有限公司 | Copolymer for modifying asphalt and asphalt composition |
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| CN1228454A (en) * | 1998-03-05 | 1999-09-15 | 日本合成橡胶株式会社 | Block copolymer composition for modifying asphalt and asphalt composition comprising the same |
| CN1338487A (en) * | 2000-08-11 | 2002-03-06 | Jsr克莱顿·伊利斯特摩股份有限公司 | Copolymer for modifying asphalt and asphalt composition |
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