CN1519277A - Modified compsn. of asphaltum and preparation method - Google Patents

Abstract

A polymer modified asphalt composition for road is prepared from asphalt, oil-extended butadiene-styrene rubber and additive through proportional mixing and stirring. Its advantages are excellent low-temp flexibility and improved high-temp performance.

Description

Modified asphalt composite and preparation method thereof

Invention field

The present invention relates to a kind of modified asphalt composite and preparation method thereof, that this modified asphalt composition is particularly useful for is high-grade, high quality highway pavement, airfield runway etc.

Background technology

Pitch is the indispensable material of highway or motorway, has good cohesiveness, watertightness, insulativity and chemical stability.But because the bituminous temperature sensitivity, at high temperature its rigidity and intensity reduce, and the road surface is easily softening, thereby produce phenomenons such as rut, general song; Low temperature then very easily produces pavement cracking phenomenons such as shrinkage crack.The bituminous temperature sensitivity, badly damaged pavement quality, and influence the weather resistance and the usability of bituminous pavement.

So-called road bitumen is a kind of petroleum pitch that is mainly used in laying road, be by crude oil through dun or black semisolid material that processes such as underpressure distillation, solvent deasphalting or oxidation obtain, mainly form by hydro carbons and derivative thereof.

The performance of road bitumen is used following index evaluation usually:

Extensibility is mainly used in reflection bituminous low-temperature performance.The bituminous extensibility is under the draw speed and temperature of regulation, the length of the two ends of stretching standard specimen when rupturing.Extensibility is the length of fracture when shear pressure is greater than pitch force of cohesion on the shear surface, changes with temperature is different.Its reflection bituminous viscoelastic property.Extensibility can be measured according to ASTM D113 or GB/T 4508 methods.

Softening temperature has reflected the bituminous high-temperature behavior.The bituminous softening temperature is a pitch evt under certain condition.The high expression of softening temperature bituminous evt height, the high-temperature stability of compound is all right.The measuring method of softening temperature can be referring to ASTM D36 or GB/T 4507.

Penetration degree is the bituminous consistency factor, reflection pitch soft or hard degree under certain condition.Penetration of bitumens under certain load, time and temperature condition, vertically penetrates the depth representing of pitch sample with standard pin, and unit is 1/10mm.The logarithm of penetration degree and temperature are linear under the differing temps, i.e. lgP=AT+K, and the penetration degree when wherein P is temperature T, A reflection penetration degree logarithm is called for short the penetration degree temperature factor to the susceptibility of temperature, and K is a constant.

Usually can pass through two temperature T ₁, T ₂Under penetration degree P ₁, P ₂Be calculated as follows out penetrative index (PI):

$\mathrm{PI}=\frac{20(1-25A)}{1+50A}$

Wherein

$A=\frac{{\mathrm{lgP}}_1-\lg p_2}{T_1-T_2}$

Usually, the penetration degree of pitch when softening temperature is 800, therefore,

$A=\frac{\mathrm{lgP}-\lg 800}{T_1-T_{R\&B}}$ (T _{R﹠amp; B}Softening temperature for sample)

Penetrative index is the temperature sensitivity index of bituminous composition.The temperature sensitivity of bituminous composition descends with the increase of penetrative index value, and perhaps the decline with the A value descends.The penetrative index value of plain asphalt is near 0.

Generally speaking, plain asphalt can not have required all properties simultaneously, is that those skilled in the art are well-known and adopt polymkeric substance that road bitumen is carried out modification with the mechanical property of improving under its high low temperature.Can be used as properties-correcting agent and join polymkeric substance normally thermoplastic elastomer, for example random or segmented copolymer of vinylbenzene and conjugated diolefine, polyisoprene, isoprene-isobutylene rubber, polyisobutene, ethylene, ethylene/propene copolymer, ethylene/propylene/diene terpolymers etc. in the pitch.

In the polymkeric substance as asphalt modifier, the random or segmented copolymer (as: styrene-butadiene-styrene block copolymer etc.) of vinylbenzene and conjugated diolefine, especially vinylbenzene and divinyl is effective especially.They are dissolved in the pitch with comparalive ease and give the mechanical property and the dynamic performance of pitch excellence, especially extraordinary visco-elasticity.But its price is higher, simultaneously for to make modifying asphalt reach the required bigger consumption of performance need, the cost of modified asphalt composite is obviously improved.

Therefore, still need developing low-cost and have the modified asphalt material of excellent high temperature performance.

Summary of the invention

An object of the present invention is to provide a kind of have improved high temperature performance and the modified asphalt composite of long life more.

Another object of the present invention provides a kind of method for preparing described modified asphalt composite.

According to one aspect of the present invention, modified asphalt composite of the present invention comprises:

I) pitch; With

I) oil-filled many chelas styrene-butadiene copolymer rubber pitch modifier, wherein this asphalt modifier is a kind ofly to cause, adopt many chelas butadiene-styrene copolymer rubber (hereinafter referred is many chelas SSBR) that the random copolymerization of anionic solution polymerization method obtains, this rubber to obtain oil-filled many chelas butadiene-styrene copolymer rubber through oil-filled by multi-lithium initiator.

Many chelas SSBR that the present invention uses is a kind of butadiene-styrene copolymer rubber by the wide molecular weight distribution that multi-lithium initiator causes, the random copolymerization of employing anionic solution polymerization method obtains.The weight ratio of the Butadiene of wherein said many chelas SSBR is 85/15～60/40, is preferably 80/20～70/30.Contents of ethylene is a 10-90% weight in the monomeric unit of derived from butadiene, and preferred 20-70% weight is based on the weight of butadiene unit in many chelas styrene-butadiene copolymer rubber before oil-filled.The molecular weight distribution of described butadienecopolymer is at least three peaks and distributes, and the peak content of its high molecular part is 5-60% weight, preferred 10-40% weight; And the molecular weight of high molecular part is at least 5 times of low molecular weight part; The number-average molecular weight of lower molecular weight peak part is 5 * 10 ⁴-20 * 10 ⁴, preferred 8 * 10 ⁴-16 * 10 ⁴In the molecular weight distribution of butadiene copolymer rubber of the present invention, low molecular weight part is the single armed polydispersity polymer part of this polymkeric substance, also is that single lithium spike causes the prepared polymer moieties in back in the multi-lithium initiator; High molecular partly is the multi-arm polydispersity polymer part of this polymkeric substance, also is that many lithiums spike causes the prepared polymer moieties in back in the multi-lithium initiator; And first peak wherein is the single armed molecular weight peaks, also is the lower molecular weight peak, and second peak is two arm molecular weight peaks, the 3rd and be the multi-arm molecular weight peaks with superiors, and also be high molecular weight peak.

Prepare the method for above-mentioned many chelas SSBR copolymer rubber, comprise the steps:

1) inert solvent, optional conjugated diene and monovinylarene and many vinyl-arenes are joined in the reactor, the organic single-lithium initiator that adds significant quantity then, carrying out the synthetic of organic multi-lithium initiator in the presence of the organic single-lithium and under certain temperature of reaction, monomeric polymerization total conversion rate is reached more than 97%;

2) inert solvent, divinyl, vinylbenzene and structure regulator are joined in the reactor, wherein the adding weight ratio of divinyl and styrene monomer is 100: 0-50: 50, the organic multi-lithium initiator that adds significant quantity then carries out the synthetic of multipolymer in the presence of organic many lithiums;

3) not necessarily, treat that two kinds of monomeric transformation efficiencys reach more than 97% after, add coupling agent and carry out linked reaction; With

4) use the terminator termination reaction.

The used organolithium polymerization starter of styrene-butadiene copolymer rubber preparation process of the present invention is organic multi-lithium initiator (hereinafter representing with PLi), it is to react prepared by many vinyl-arenes (hereinafter representing with MVA) and organic single-lithium in inert solvent, the organic pair of lithium and the organic many lithiums mixture that wherein exist organic single-lithium and many vinyl aromatic (co)s hydrocarbon reaction to generate.In reaction process, can add conjugated diene or mono vinyl arenes monomer as additive, so that on organic single-lithium spike, two lithium spike and many lithiums spike initiator, form the polymkeric substance galianconism, improve the solubility property of organic multi-lithium initiator in inert solvent, obtain the homogeneous multi-lithium initiator, thereby multi-lithium initiator is the mixture of single lithium spike, two lithium spike and many lithiums spike.Conjugated diene or mono vinyl arenes monomer consumption are that every mole of organic single-lithium need add conjugated diene or mono vinyl arenes monomer 2-15mol, preferred 5-10mol.

What the used MVA of the present invention suited is 1,2-Vinylstyrene, 1,4-Vinylstyrene, 1,3-Vinylstyrene, 1,2,4-trivinylbenzene, 1,3,5-trivinylbenzene, 1,3-divinyl naphthalene, 1,8-divinyl naphthalene, 1,3,5-trivinyl naphthalene, 2,4-divinyl biphenyl, 1,2-divinyl-3,4-dimethyl benzene, 3,5,4 '-trivinyl biphenyl, preferred 1,2-Vinylstyrene, 1,3-Vinylstyrene, 1,4-Vinylstyrene, divinyl benzol mixture, or technical grade Vinylstyrene.The consumption of MVA is that every mole of organic single-lithium need add MVA0.05-1.00mol, preferred 0.1-0.8mol.

Organic single-lithium used in the styrene-butadiene copolymer rubber preparation process of the present invention can represent that wherein R is the C of straight or branched with formula RLi ₁-C ₂₀Alkyl, C ₃-C ₂₀Cycloalkyl, C ₆-C ₂₀Aryl.Its object lesson is lithium methide, lithium ethide, sec.-propyl lithium, tert-butyl lithium, allyl group lithium, n-Butyl Lithium, s-butyl lithium, isobutyl-lithium, n-pentyl lithium, cyclohexyl lithium, 4-heptyl cyclohexyl lithium, 4-cyclohexyl butyllithium, 4-butyl cyclohexyl lithium, phenyl lithium, 4-aminomethyl phenyl lithium, trityl group lithium, 2-naphthyl lithium etc., preferred n-Butyl Lithium or s-butyl lithium.

In the preparation feedback of organic multi-lithium initiator, suitable temperature of reaction is 0-70 ℃, and preferred temperature is 0-50 ℃.

In the preparation process of styrene-butadiene copolymer rubber of the present invention, adopt structure regulator to regulate vinyl structure content usually.In the preparation process of styrene-butadiene copolymer rubber of the present invention, structure regulator can be conventional use any in the anionoid polymerization solution polymerized rubber system.For example described structure regulator is selected from and contains oxygen, nitrogenous, sulfur-bearing and contain one or more mixture in the Phosphorus polar compound, preferred ether compound, tertiary amine compounds or alkoxyl group potassium compounds.Ether compound for example comprises the cyclic ether compounds, as tetrahydrofuran (THF), 1, and the 4-dioxane; Fats monoether compound is as ether, dibutyl ether; Fats polyetherization compound is suc as formula R ₁OCH ₂CH ₂OR ₂Shown compound (R wherein ₁And R ₂Be C _{1 ~ 4}Alkyl, and R ₁And R ₂Can be identical also can be inequality), as glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, formula R ₁OCH ₂CH ₂OCH ₂CH ₂OR ₂Shown compound (R wherein ₁And R ₂Be C _{1 ~ 4}Alkyl, and R ₁And R ₂Can be identical also can be inequality), as diglyme, diethyl carbitol, diethylene glycol dibutyl ether; The aryl oxide compounds is as phenyl ether, methyl-phenoxide, crown ether.Tertiary amine compounds for example comprises triethylamine, tripropyl amine, Tributylamine and other aminated compounds such as N, N, N ', N '-Tetramethyl Ethylene Diamine, N, N-Diethyl Aniline, pyridine, quinoline, two piperidines ethane (DPE).Alkoxyl group potassium compounds for example comprises tert.-butoxy potassium and uncle's pentyloxy potassium etc.Phosphorous compounds for example comprises HMPA (HMPA).The preferred construction conditioning agent is tetrahydrofuran (THF) (THF), glycol dimethyl ether (1G), diglyme (2G), N, N, N ', N '-Tetramethyl Ethylene Diamine (TMEDA), tert.-butoxy potassium (KTB) or uncle's pentyloxy potassium (KTA).The structure regulator consumption is the conventional equivalent that those skilled in the art can determine in the polymerization process, and preferable amount is that every mole of lithium atom adds 0.1-100mol.Preferred construction conditioning agent amount ranges is as follows: when selecting THF as structure regulator for use, every mole of lithium atom need add THF5-80mol; When selecting 1G as structure regulator for use, every mole of lithium atom need add 1G 0.5-40mol; When selecting 2G as structure regulator for use, every mole of lithium atom need add 2G 0.1-20mol; When selecting TMEDA as structure regulator for use, every mole of lithium atom need add TMEDA 0.1-20mol; When selecting KTB as structure regulator for use, every mole of lithium atom need add KTB 0.05-1.5mol; When selecting KTA as structure regulator for use, every mole of lithium atom need add KTA 0.15-0.30mol.

Used inert solvent can be non-polar aromatics such as benzene,toluene,xylene and ethylbenzene in the styrene-butadiene copolymer rubber preparation of the present invention, aliphatic hydrocrbon such as pentane, hexane, heptane and octane, alicyclic hydrocarbon such as pentamethylene, hexanaphthene and methylcyclohexane, or aliphatic hydrocrbon and alicyclic mixture, as hexane/hexanaphthene mixture and raffinating oil.Generally speaking, the inert solvent consumption is that every 100g monomer need add the 300-5000g inert solvent.

The consumption of organic multi-lithium initiator depends on the size of design single armed number-average molecular weight in the preparation process of styrene-butadiene copolymer rubber of the present invention, also be the size of the number-average molecular weight of low molecular weight part, its significant quantity (in lithium atom) is that those skilled in the art can determine.Generally speaking, the multi-lithium initiator consumption is that every 100g monomer need add 0.5-2.0mmol (in lithium atom).Organic multi-lithium initiator can once add, and also can add several times.

Copolymer rubber solution polymerization temperature involved in the present invention is the anionic polymerisation temperature that common organolithium causes, and for example Shi Yi temperature is 0-150 ℃.From economy and inhibition side reaction angle, preferred 30-100 ℃.

For molecular weight distribution of further widening multipolymer of the present invention and the anti-cold flow properties that further improves rubber, can add coupling agent and carry out linked reaction.The adding of coupling agent makes the different reactive polymer molecular moiety generation linked reaction of arm number, generates the more coupling polymer molecule of arm number.Along with the increase of coupling agent consumption, the molecular weight distribution of polymkeric substance is further widened.But its consumption can not be too high, otherwise will be easy to generate gel, so the mol ratio of coupling agent and organic multi-lithium initiator (in lithium atom) is 0.03-0.30, preferred 0.05-0.20.The available coupling agent is for example trifunctional or four sense coupling agents, as polyfunctional epoxy compounds, imine compound, aldehyde compound, ester compound and halogenide etc.Suitable multifunctional halogenide is that methyl trichlorosilicane, methyl tribromide are good, methyl triiodide silicon, methyl tin trichloride, methyl tribromide tin, methyl triiodide tin, butyl trichlorosilicane, butyl tribromide silicon, butyl triiodide silicon, silicon tetrachloride, Silicon bromide, silicon tetraiodide, tin tetrachloride, tin tetrabromide, tin tetraiodide; Also can use metal halide in addition, as tin, lead, germanium class halogenide.Suitable multifunctional ester compound is diethylene adipate, dimethyl adipate, Polycizer W 260, rutgers, diethyl phthalate, phthalic acid dibutyl ester and polyisocyanates compounds.Preferred coupling agent is tin tetrachloride, silicon tetrachloride.

After carrying out coupling as mentioned above, the termination mode commonly used by the anionoid polymerization field stops polyreaction.Used terminator for example can be conventional use any of anionoid polymerization system, and for example the mixture of one or more in water, alcohols, the acid compounds is preferably water or acid compounds.Acid compounds comprises mineral acid and organic acid, and the object lesson of mineral acid has hydrochloric acid, sulfuric acid, phosphoric acid, boric acid, carbonic acid; The organic acid object lesson has C _{1 ~ 10}Monoprotic acid is as formic acid, acetate, propionic acid, butyric acid, butenoic acid etc., C _{2 ~ 10}Diprotic acid is as oxalic acid, pentanedioic acid, hexanodioic acid, suberic acid, sebacic acid etc.

Many chelas SSBR of this method preparation makes oil-filled type rubber according to ordinary method.The oil-filled amount that can be used for the many chelas SSBR in the modified asphalt composite of the present invention is generally 30～60%, based on the weight of oil-filled many chelas SSBR.Described rubber filling oil is preferably aromatic hydrocarbon oil or naphthenic oil.Related rubber filling oil most preferably is an aromatic hydrocarbon oil among the oil-filled many chelas SSBR of the used asphalt modifier of the present invention.

In modified asphalt composite of the present invention, the amount ranges of oil-filled many chelas SSBR asphalt modifier is 1～10% weight, in the gross weight of modified asphalt composite.Though higher consumption also can adopt, consider that from economic angle right and wrong are preferred.

Randomly, can also comprise other additives such as sulphur, anti-aging agent, resin in the modified asphalt composite of the present invention, with the ageing resistance of further raising modified asphalt composite, high-temperature behavior etc.These other additives are well known by persons skilled in the art, and can use according to conventional amount used.

For example, can also comprise other additional polymer in the modified asphalt composite of the present invention, as random or segmented copolymer, polyethylene, polypropylene, polybutene, polyisobutene, ethylene/propene copolymer, ethylene/propylene/diene terpolymers, ethylene, ethylene/acrylic acid or the Sipacril 2739OF of vinylbenzene and conjugated diolefine, polyhutadiene, polyisoprene, polynorbornene etc.In modified asphalt composite, the consumption of described additional polymer is no more than 20% weight, based on the weight of said composition medium pitch.

For example, can also comprise in the modified asphalt composite of the present invention promote crosslinked polymer give sulphur body coupling agent, as elemental sulfur, hydroxyl polysulfide, or can under proper temperature, produce the superoxide etc. of free radical.These all are well known by persons skilled in the art.

The all available the inventive method modification of various in principle pitches.For example, pitch can be the pitch of air distillation or vacuum distilling pitch, oxidation or half oxide treatment, from propane or the deasphalting residue of pentane, viscosity breaking residue and composition thereof.

Though do not wish to be subjected to the restriction of particular theory, but it is believed that, because many chelas SSBR has quite wide molecular weight distribution, that is to say in many chelas SSBR, the polymer molecule of different molecular weight is coexistence continuously in very wide molecular weight ranges, add for example aromatic hydrocarbon oil of the oil that filled in this rubber, polymkeric substance can be dispersed or dissolved in the pitch preferably, thereby make polymer modified asphalt of the present invention have excellent performance.

According to another aspect of the present invention, the invention provides a kind of method for preparing described modified asphalt composite, this method comprises that the pitch that will treat modification, oil-filled many chelas SSBR reach the step of other optional additive even blend in mixing equipment.

According to one embodiment of the invention, the preparation method of described modified asphalt composite comprises the following steps: to add a certain amount of oil-filled many chelas SSBR of properties-correcting agent and other optional additive for the treatment of modifying asphalt, respective amount in mixing equipment (as asphalt tank); Content is heated to about 70～100 ℃, can be mobile fully up to pitch, start slurry formula whipping appts; Continue to be heated to 100～200 ℃ temperature, mixed 60～150 minutes, to obtain homodisperse fluid; Under 160～230 ℃ temperature, be 1500～10 with stirring velocity, the mulser of 000rpm is with polymer modified asphalt melt emulsification 5～20 minutes, to obtain modified asphalt composite.

Compare with the SBS asphalt modifier that prior art is commonly used, many chelas SSBR is the lower butylbenzene copolymer of a kind of price, and oil-filled many chelas SSBR makes the cost of many chelas SSBR descend greatly again.In addition, because the special structure of many chelas SSBR during with its modifying asphalt, uses very little consumption can obtain tangible modified effect.Therefore, compare with the SBS modifying asphalt, the modification cost of modified asphalt composite of the present invention significantly descends.In addition, the low-temperature performance of modified asphalt composite of the present invention is obviously improved than SBS modifying asphalt.With the bituminous material of modifier modifications such as SBS/SBR/S, SBS/PS/S, SBS/PE/S (referring to CN1324896, CN1324897, CN1287133, CN1121939) compare, the low-temperature performance of modified asphalt composite of the present invention is excellent more, high-temperature behavior is suitable substantially, and the modification cost descends, and operation steps is simple.

Brief Description Of Drawings

Fig. 1 has shown polymkeric substance and bituminous dispersion state in the modified asphalt composition of the embodiment of the invention 3;

Fig. 2. shown polymkeric substance and bituminous dispersion state in the modified asphalt composition of the embodiment of the invention 7.

Black part is divided into the pitch main body among the figure, and light-colored part is the polymeric asphalt modifiers that is wrapped in the pitch.

Embodiment

The invention will be further described below in conjunction with embodiment and Comparative Examples, if no special instructions, all content percentage ratios and umber all by weight, these embodiment and Comparative Examples only are illustration purposes, and do not limit the present invention.

The initiator concentration that relates in the embodiment of the invention records with two titration methods; Vinyl structure content is tested with U.S. Perkin-Elmer type infrared spectrometer in bonded styrene content and the butadiene monomer unit; The molecular weight distribution of polymkeric substance is tested (solvent: THF with day GPC-1OA type gel permeation chromatograph of island proper Tianjin company; Flow velocity: 1.0ml/min; Room temperature; GPC post: Water-HR4 * 2+HT5)

In the following example, the penetration degree of modified asphalt composite, extensibility and softening temperature are measured according to physical property measurement standard GB/T4509, GB/T4508, GB/T4507 respectively.

The oil that many chelas of filling SSBR is adopted among the embodiment is the aromatic hydrocarbon oil that oil seven factories in Dalian produce, and its performance index are as follows:

Table 1 rubber filling oil performance index

Project 1

The kind aromatic hydrocarbon oil

Outward appearance black

Kinematic viscosity, mm ²/ s (100 ℃) 33.89

Density, kg/m ³992.1

Flash-point, ℃ 240

Refractive index, (20 ℃) 1.5556

Acid number, mgKOH/g 0.3800

Viscosity index, VGC 0.9115

Refractivity intercept, RI 1.0470

Molecular weight, Mn 402

Fugitive constituent, % (163 ℃ * 3h) 0.0630

Carbon type analysis CP 32

CN?????????????????????????????????????????30

CA?????????????????????????????????????????38

Aromaticity content, % 90.74

Embodiment 1

Under the high pure nitrogen protection; press proportioning shown in the table 2 with hexanaphthene, 1; the 3-divinyl, join in the saline bottle of 500ml exsiccant band magnetic agitation rotor as the Vinylstyrene of MVA; mix the back and inject quantitative 100mmol n-Butyl Lithium with syringe; after reacting certain hour at a certain temperature; obtain the multi-lithium initiator of different MVA/Li, initiator concentration (in lithium atom) adopts two titration measurings, reaction conditions and the results are shown in Table 2.

The multi-lithium initiator of different MVA/Li batching condition and concentration among table 2. embodiment 1

Number 12

MVA/Li, mol ratio 0.10 0.20

The MVA consumption, mmol 10 20

The hexanaphthene amount, g 230 250

1,3-butadiene, g 30 30

Temperature of reaction, ℃ 50 50

In the reaction times, min 60 60

Concentration, mol/L 0.28 0.28

The polymkeric substance synthesis step is as follows: polymkeric substance synthesizes in 10L stainless steel still and carries out.Before the reaction 5.0kg raffinated oil and a certain amount of monomer, structure regulator join in the reactor, is warming up to required temperature of reaction after mixing, treat that the stainless steel temperature in the kettle is stable after, add n-Butyl Lithium (n-BuLi) or multi-lithium initiator and begin polymerization.After treating that monomer all transforms, add a certain amount of coupling agent in proportion and carry out linked reaction, treat after linked reaction is finished the water of 0.2ml to be joined and carry out termination reaction in the active glue, the antioxidant 264 (Jiangsu Province Yixing City foundation chemical industry company limited) of 4.8g is joined in the glue.Adding a certain amount of rubber filling oil then: aromatic hydrocarbon oil and mix after, the product after the poach cohesion obtains the oil filling copolymer rubber product after 110 ℃ of drum rolls are done.Polymeric reaction condition is listed in table 3, and wherein the multi-lithium initiator that adopts in the polymerization of numbering 1 and 2 in the table 3 is respectively the multi-lithium initiator of numbering 1 and 2 in the table 2.Polymer architecture and performance are listed in table 4.

Table 3. polymeric reaction condition

Number 12

Raffinate oil, g 5,000 5000

1,3-butadiene, g 450 492

Vinylbenzene, g 150 108

Structure regulator, g THF THF

2.2?????????????????2.5

Many lithiums cause 5.5 4.9

Agent, mmol

(in lithium atom)

SnCl ₄，mmol????????????????0.72????????????????0.64

SnCl ₄/Li???????????????????0.13????????????????0.13

(mol ratio)

Polymeric reaction temperature, ℃ 50 50

Aromatic hydrocarbon oil, g 225 225

Table 4. more than chela SSBR polymer architecture and performance

Numbering #1 #2

Combined styrene content, % 25 18

Contents of ethylene, % 25.05 29.07

Molecular weight distribution

Peak type number 33

The number-average molecular weight at lower molecular weight peak

11.3?????????????????12.1

(×10 ⁴)

High molecular weight peak/lower molecular weight peak * 5.05 5.13

High molecular weight peak content, % 14 20

* high molecular weight peak/lower molecular weight peak is expressed as the ratio of the number-average molecular weight at the number-average molecular weight of high molecular weight peak and lower molecular weight peak.

Modified asphalt composite is prepared as follows:

Earlier 300 gram Jinzhou 90# road bitumen samples are put into 1000 milliliters asphalt tank, adding 16 grams then, to fill described aromatic hydrocarbon oil content be many chelas of #1 SSBR of 37.5%, i.e. the oil-filled many chelas SSBR of #1.Asphalt tank is heated to 90 ℃, and pitch presents complete flow state, starts slurry formula mixing stirring device this moment.Stir down temperature is risen to 140 ℃ gradually, stir about is 120 minutes under the stirring velocity of 350rpm, makes polymkeric substance and bituminous blend melt present thorough mixing and homodisperse state.Withdraw from slurry formula whipping appts, change mulser into, and temperature is increased to 200 ℃, under this temperature, with the described polymer-asphalt blend melt of the stirring velocity emulsification of 3500rpm 8 minutes, promptly obtaining in modified asphalt composite gross weight properties-correcting agent consumption was 5% modified asphalt composite.Analysis and characterization the results are shown in following table 5.

Embodiment 2-4

Repeat the program of embodiment 1, just the oil-filled many chelas SSBR of #1 properties-correcting agent consumption is respectively 1%, 3%, 6%, in the modified asphalt composite gross weight.The analysis and characterization result is shown in embodiment in the table 52,3,4.

Fig. 1 is that the oil-filled amount of embodiment 3 is that 37.5% weight, consumption are oil-filled many chelas SSBR modifying asphalt sample optical microscope photograph (eyepiece * object lens: 10 * 10) of 3% weight.

Comparative example 1

Repeat the program of embodiment 1, just do not use properties-correcting agent, the result is as shown in table 5 for gained bituminous analysis and characterization.

The performance of oil-filled many chelas SSBR modified asphalt composite of table 5. oil-filled 37.5%

		Comparative example 1	Embodiment 2	Embodiment 3	Embodiment 1	Embodiment 4
							Oil-filled many chelas SSBR consumption (%)		????0	????1	????3	????5	????6
Performance
							Penetration degree (5 ℃)		????24	????23	????22.5	????22.5	????23
Penetration degree (25 ℃)		????78	????65.56	????61.67	????56.67	????62.09
							Penetration degree temperature factor A *		????0.037	????0.035	????0.034	????0.032	????0.030
Penetrative index PI *		????0.569	????0.909	????1.111	????1.539	????2
							Softening temperature (℃)		????52.5	????56	????58	????61.5	????62.0
Extensibility (cm)	??5℃	????5.5	????60	????75	????90	????120
							??25℃	????＞150	????＞150	????＞150	????＞150	????＞150

* is described: A=(lg800-lgP _{25 ℃})/(T _{R﹠amp; B}-25)

PI＝(20-500A)/(1+50A)

P _{25 ℃}: the penetration degree of sample in the time of 25 ℃;

T _{R﹠amp; B}: be the softening temperature of sample.

Embodiment 5-8

Repeat the program of embodiment 1, in embodiment 5,6,7,8, used properties-correcting agent is for to fill the oil-filled many chelas SSBR of #2 that described aromatic hydrocarbon oil 50% obtains by many chelas of #2 SSBR, and its consumption is respectively 1%, 3%, 5%, 8%, in the modified asphalt composite gross weight; The emulsification times of polymer-asphalt blend melt is 5 minutes, and emulsifying temperature is 190 ℃.Analysis and characterization the results are shown in table 6.

The performance of oil-filled many chelas SSBR modified asphalt composite of table 6. oil-filled 50%

		Embodiment 5	Embodiment 6	Embodiment 7	Embodiment 8
						Oil-filled many chelas SSBR consumption (%)		????1	????3	????5	????8
Performance
						Penetration degree (5 ℃)		????20.3	????23.3	????27.3	????30.3
Penetration degree (25 ℃)		????41.7	????57.7	????77.7	????83.7
						Penetration degree temperature factor A		????0.034	????0.032	????0.027	????0.027
Penetrative index PI		????1.11	????1.538	????2.766	????2.766
						Softening temperature (℃)		????61.5	????53	????62.5	????62.5
Extensibility cm	????5(℃)	????33	????55	????128.3	????＞150
						????25(℃)	????30	????55	????75	????90

Fig. 2 is that the oil-filled amount of embodiment 7 is that 50% weight, consumption are oil-filled many chelas SSBR modifying asphalt sample optical microscope photograph (eyepiece * object lens: 10 * 10) of 5% weight.

Comparative example 2-6

Repeat the program of embodiment 1, just select for use the SBS of different structure, different trade mark performances to come modification Jinzhou 90# road bitumen as properties-correcting agent, described properties-correcting agent consumption is 4%, in the modified asphalt composite gross weight.The analysis and characterization of SBS modifying asphalt the results are shown in table 7.

The various SBS performance of modified bitumen of table 7. index

		Comparative example 2	Comparative example 3	Comparative example 4	Comparative example 5	Comparative example 6
							??SBS		High mountainization 801	Swallowization 801	High mountainization 792	Swallowization 792	Kraton D1101C (Shell Co. Ltd)
Performance
							Penetration degree (25 ℃)		????66.53	????39.07	????57.08	????40.09	??42.05
Penetration degree temperature factor A		????0.027	????0.0298	????0.0364	????0.0317	??0.0301
							Penetrative index PI		????2.766	????2.044	????0.635	????1.596	??1.973
Softening temperature (℃)		????65	????69	????56.5	????66	??67.5
							Extensibility (cm)	????5(℃)	????19.5	????11.0	????15.5	????9.7	??12.2
????25(℃)	????94.2	????99.3	????98	????82	??140

Can see that from above result's comparison modifying asphalt of the present invention has obviously more excellent low high-temperature behavior, especially low-temperature performance than existing modifying asphalt.

In addition, from Fig. 1 and Fig. 2, light mesh portion is that properties-correcting agent is the dispersed texture state of many chelas SSBR in the picture, and the black part then is the bituminous contribution.These pictures show, properties-correcting agent be comparison evenly and be to be scattered in the middle of the pitch with continual reticulated structure form, and be intertwined with main body.Can see that the present invention has solved pitch simultaneously and polymkeric substance is difficult to mixed uniformly problem, show that modifying asphalt of the present invention has excellent mechanical property.

Claims (11)

1. modified asphalt composite comprises:

I) pitch; With

Ii) oil-filled many chelas styrene-butadiene copolymer rubber pitch modifier,

Wherein said asphalt modifier is caused, adopts the anionic solution polymerization method, obtained the oil-filled many chela butadiene-styrene copolymer rubber of styrene-butadiene copolymer through oil-filled gained by random copolymerization by multi-lithium initiator.

2. the described modified asphalt composite of claim 1, the molecular weight distribution that it is characterized in that described many chelas styrene-butadiene copolymer rubber is that three peaks distribute at least, wherein the content of multi-arm polydispersity polymer part is 5-60% weight, preferred 10-40% weight, and the molecular weight of multi-arm molecular weight partial polymer is at least 5 times of single armed molecular weight part.

3. the described modified asphalt composite of claim 2 is characterized in that the number-average molecular weight of single armed molecular weight part in described many chelas styrene-butadiene copolymer rubber is 5 * 10 ⁴To 20 * 10 ⁴

4. the described modified asphalt composite of claim 3 is characterized in that the number-average molecular weight of single armed molecular weight part in described many chelas styrene-butadiene copolymer rubber is 8 * 10 ⁴To 16 * 10 ⁴

5. the described modified asphalt composite of claim 1, the weight ratio that it is characterized in that the Butadiene of described many chelas styrene-butadiene copolymer rubber is 85/15～60/40.

6. the described modified asphalt composite of claim 5, the weight ratio that it is characterized in that the Butadiene of described many chelas styrene-butadiene copolymer rubber is 80/20～70/30.

7. the described modified asphalt composite of claim 1, the contents of ethylene that it is characterized in that described many chelas styrene-butadiene copolymer rubber is 10～90%, preferred 20%～70%, based on the weight of butadiene unit in many chelas styrene-butadiene copolymer rubber before oil-filled.

8. the described modified asphalt composite of claim 1, the oil-filled amount that it is characterized in that described many chelas styrene-butadiene copolymer rubber is 30～60%, based on the weight of oil-filled many chelas styrene-butadiene copolymer rubber.

9. the described modified asphalt composite of claim 1 is characterized in that the consumption of described oil-filled many chelas styrene-butadiene copolymer rubber in modified asphalt composite is 1～10% weight, in the gross weight of modified asphalt composite.

10. the preparation method of a modified asphalt composite, the step of other additive even blend in mixing equipment that comprises the pitch that will treat modification, oil-filled many chelas styrene-butadiene copolymer rubber pitch modifier and choose wantonly, wherein said asphalt modifier is caused, adopts the anionic solution polymerization method, obtained the oil-filled many chela Afpol of butadiene-styrene copolymer through oil-filled gained by random copolymerization by multi-lithium initiator.

11. the method for claim 10 comprises the following steps: to add in mixing equipment and treats that modifying asphalt, oil-filled many chelas styrene-butadiene copolymer rubber pitch modifier reach other optional additive; Content is heated to 70～100 ℃, can be mobile fully up to pitch, start whipping appts; Continue to be heated to 100～200 ℃ temperature, mixed 60～150 minutes, to obtain homodisperse fluid; Under 160～230 ℃ temperature, be 1500～10 with stirring velocity, the mulser of 000rpm is with polymer modified asphalt melt emulsification 5～20 minutes, to obtain modified asphalt composite.

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