CN1923870A - Synthesis for copolymer of terminal amino and carboxyl styrene/butadiene and method of preparing storage stabilized modified asphalt - Google Patents
Synthesis for copolymer of terminal amino and carboxyl styrene/butadiene and method of preparing storage stabilized modified asphalt Download PDFInfo
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- CN1923870A CN1923870A CN 200610047441 CN200610047441A CN1923870A CN 1923870 A CN1923870 A CN 1923870A CN 200610047441 CN200610047441 CN 200610047441 CN 200610047441 A CN200610047441 A CN 200610047441A CN 1923870 A CN1923870 A CN 1923870A
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Abstract
The invention discloses a preparing method of three-element block copolymer (SBS) of phenylethene/butadiene/phenylethene, which is characterized by the following: adopting Li nitrogen as initiator of polymeric anion; making carbon dioxide as terminator of anion; preparing end base with double polar functional group SBS(N-SBS-COOH) of amido and carboxy group; fitting for preparing modified bitumen with stable reserving property.
Description
Technical field
The invention belongs to the polymer modified asphalt technical field.Relate to the preparation method of a class both-end base functionalized styrene/Butadiene block polymer and be used to prepare the modifying asphalt of stable storing.
Background technology
Thermoplastic elastic body styrene/Butadiene segmented copolymer (SBS) is by vinylbenzene and two kinds of monomer synthetic of divinyl segmented copolymer, has plastics fusion workability and caoutchouc elasticity concurrently.The important applied field of current SBS is exactly the laying that modifying asphalt is used for highway pavement.The fact is verified, the over-all properties of SBS modifying asphalt is best in the polymer modified asphalt, can obviously improve the stable of bituminous cold plasticity, high-temperature stability, ageing-resistant, adhesivity, elasticity, compound, improve performances such as bituminous wear resistance and work-ing life.
Because pitch and SBS chemical property, structure, composition and relative molecular mass exist than big-difference, SBS/ pitch mixed system belongs to the incompatible system of thermodynamics.For an incompatible system of thermodynamics, its both macro and micro all is unsettled, therefore, the main shortcoming of SBS modifying asphalt is that thermostability is relatively poor, SBS and pitch easily take place to be separated, can not long storage, this gives and produces and use brings big difficulty and inconvenience.Obviously, for the SBS/ asphalt system, have only and improve the basic problem that solves package stability of consistency ability between SBS and the pitch, this point is most important.
In order to improve the consistency of SBS modifying asphalt, improve package stability, main at present physics and the chemical process of adopting.Physical method comprises: adopt specific equipments such as colloidal mill or shears to grind and shear; Dose solvent, various oil product dissolving SBS, improve SBS dispersed and stable in pitch.Physical method is simple to operate, also often use in the practice, but physical method has just quickened SBS at bituminous swelling and dissolution process, it is a kind of process compatible, the consistency between material alterations SBS and the pitch not, therefore, in order to improve the consistency between SBS and the pitch, improve the stability of modifying asphalt, chemical modification becomes a kind of inevitable development trend.
Chemical modification method is varied, and wherein adopting functionalized polymer modified pitch is a kind of novel modifying asphalt means.Contain unsaturated double-bond at SBS, introduce polarity or reactable functional group, to improve and the bituminous consistency by chemical reaction.Mainly SBS is carried out grafting and epoxidation modification at present, introduce carboxyl, maleic anhydride, ester group and epoxy isopolarity group.Chemical reaction takes place in the polar compound in these polar groups and the pitch such as carboxyl, phenolic hydroxyl group etc., forms chemical bond and improves SBS and bituminous consistency.Yet present employed sense SBS all is by macromole secondary chemical reaction preparation, the cost height, and complex process is used on a large scale and is promoted than difficulty.The destroy integrity of molecular chain after the macromole modification, himself performance also are subjected to influence to a certain degree.
But and the SBS that adopts the functional group initiator or the synthetic end of the chain of closed-end technology in-situ polymerization to have polarity and reactive functionality.This method is compared with epoxidation modification with the SBS grafting, neither can obviously increase the SBS cost, can not change the integrity of the molecular chain of SBS itself again, does not also change the original synthesis technique of SBS, in technology and P/C analogy mask remarkable advantages is arranged.Owing on the SBS molecular chain-end, introduce polar group, can improve SBS and bituminous consistency, again in conjunction with advanced hybrid technique and technology, can fundamentally solve the problem of SBS modifying asphalt package stability difference, the improvement of system consistency also can produce wholesome effect to other performance simultaneously.
But active anionic polymerization adopts functional group initiator or closed-end technology in-situ polymerization to prepare functionalized polymkeric substance in building-up process.It is as follows to adopt the anion in-situ polymerization to prepare the pertinent literature that terminal group functional phenylethylene/butadiene block polymer delivers in recent years abroad.
(1) be the synthetic SBS of initiator with the butyllithium, when not stopping, available chlorine is carried out end-blocking for polyvalent alcohol (as chlorohydrin) and is ended, further use the TDI chain extension, the synthetic SBS that contains isocyanic ester, this SBS-polyurethane coating can be cast, and can be used as physical culture runway, water-proof and anti-corrosive material.
(2) employing [3-(dimethyl amido)-propyl group]-lithium such as Stergios be nitrogenous functionalized lithium initiator prepared a series of α-amido official can SBS, will hold the amido ionization after, in non-polar solution, have stronger association behavior; Because end group has stronger polarity, it has stronger adsorptivity and cohesiveness in the metallic surface simultaneously.
(3) employing carbonic acid gas such as Milkovich, sulfurous gas and ethylene oxide-capped dose have prepared the star-like butadiene-styrene block copolymer of terminal group functional.Experiment show star-shaped sbs behind the terminal group functional and the consistency between the polar polymer, polarity filler improve a lot.
(4) German BASF (BASF) company adopt the west not alkali and cyclic amine compound be the anionoid polymerization capping reagent, prepared two block compounds of a series of vinylbenzene, divinyl.
Functionalized styrene/butadiene block the polymkeric substance of nitrogen-lithium initiators preparation that these researchs are adopted adopts active and the equal hexamethylene imine base-N-lithium preferably of solvability, also type SBS is not carried out amido, carboxyl and hydroxy-end capped research.The sense SBS of preparation is used in modifying asphalt and is not seen that also report is arranged.
Summary of the invention
The method that the object of the invention is to provide the synthetic of a kind of end amido and carboxyl styrene/butadiene multipolymer and prepares the modifying asphalt of shelf-stable, promptly two ends of a class are distinguished the preparation methods of aminated and carboxyl SBS, be according to living anion polymerization mechanism, adopt nitrogen-lithium initiator initiation and closed-end technology in-situ polymerization to prepare the SBS that end group is respectively amido and carboxyl bipolarity functional group.Adopt this method not change the original production technique of SBS, do not need that SBS is carried out secondary processing and handle.
The technical solution adopted for the present invention to solve the technical problems is: the method for the modifying asphalt of the synthetic and preparation shelf-stable of a kind of end amido and carboxyl styrene/butadiene multipolymer, and this method steps is:
(1) end amido and carboxyl styrene/butadiene/styrene block copolymer is synthetic:
(1) earlier varsol is added reactor, add vinylbenzene and polar additive again, stir, be warming up to 45-80 ℃, add nitrogen-lithium initiator, begin to carry out polyreaction, reaction times 30-90min.
Various reactant quality, weight ratio: vinylbenzene/varsol=5-20, mol ratio: vinylbenzene/Li=1 * 10
4-3 * 10
4, polar additive/Li=0.5-20;
(2) the ratio S/B=40/60-30/70 according to vinylbenzene in the product and divinyl quality adds divinyl, reacts 30-90 minute;
(3) after divinyl has reacted, add with (1) in the vinylbenzene of first section quality such as reinforced, reaction 30-90min;
The structural formula of nitrogen-lithium initiator is expressed as follows:
Wherein, f is the integer more than or equal to 1; N=0-20, m=0-20,3＜m+n＜20, and m and n are integer;
(4) after the 3rd section vinylbenzene reaction finishes in above-mentioned (3), add polar additive, mol ratio: polar additive/Li=1-50;
(5) feed carbonic acid gas then, the pressure of carbonic acid gas between 0.01-0.5Mpa, temperature of reaction 0-25 ℃, reaction times 1-36 hour;
(6) add terminator ethanol to polymkeric substance after total overall reaction finishes and all be settled out, use N again
2Extrude glue, add 1% anti-aging agent, antioxidant 264 generally commonly used boils the glue desolventizing with water vapour then, rolls in the mill dehydration and is pressed into sheet two, obtains the Bifunctionalized styrene/butadiene/styrene block copolymers of amido and carboxyl.
(2) preparation modifying asphalt:
(1) fused pitch is joined in the container, be warming up to 140-230 ℃, press mass fraction in 100 parts of pitches, add 1-15 part amido and the Bifunctionalized styrene/butadiene/styrene block copolymers of carboxyl, start the emulsification pretreatment stirrer, under 2500-6500 rev/min of condition, stirred 10-60 minute;
(2) add 1-5 part sulphur, continue to stir 10-60 minute, form uniform dispersion liquid after, obtain the sense SBS modifying asphalt of shelf-stable, the difference of its softening temperature is less than 2.5 ℃.
Described hydrocarbon organic solvent is benzene, toluene, ethylbenzene, dimethylbenzene, pentane, hexane, heptane, octane, hexanaphthene, Mixed XYLENE, the mixture of one or more hydrocarbon organic solvents in raffinating oil.
Polar additive used in the present invention is selected from and contains oxygen, nitrogenous, sulfur-bearing, contains a kind of polar compound in the Phosphorus polar compound or the mixture of several polar compounds, as: (1) nitrogenous compound, generally be selected from: triethylamine, N, N '-Tetramethyl Ethylene Diamine, two piperidines ethane; (2) oxygenatedchemicals generally is selected from: ether, tetrahydrofuran (THF), R
1OCH
2CH
2OR
2, wherein: R
1, R
2Be that carbonatoms is the alkyl of 1-6, R
1, R
2Can be identical or different, with R
1, R
2Be not all good, as ethylene glycol ethyl ethers diether, R
1OCH
2CH
2OCH
2CH
2OR
2(wherein: R
1, R
2Be that carbonatoms is the alkyl of 1-6, R
1, R
2Can be identical or different, with R
1, R
2Be not all good, as symmetric ethers: dibutyl ethylene glycol ether; Asymmetric ethers, ethylene glycol ethyl tertbutyl ether, Ethylene Glycol Methyl tertbutyl ether); (3) P contained compound is generally selected HMPA for use.(4) alkoxy base metallic compound is as tert.-butoxy potassium, uncle's pentyloxy potassium.
The pitch that is adopted is distillation pitch, oxidized bitumen, solvent pitch or the pitch that is in harmonious proportion, grade meet defined among " the asphalt highway construction technique normalizing JTG F40-2004 " of Chinese transportation portion song cloth in, light and heavy-duty road asphalt.Stablizer is a sulphur, or rubber such as sulphur and thiazoles, inferior sulphonyl class, thiurams, guanidine class is used with all kinds of promotor, or modifying asphalt is stabilizing agent specially used.
The invention has the beneficial effects as follows that preparation technology is simple, with low cost, be easy to industrialization.The sense SBS of the present invention's preparation is used for modifying asphalt, can effectively improves the consistency of mixed system, obviously improve stability in storage.
Description of drawings
The invention will be further described below in conjunction with drawings and Examples.
Fig. 1 is that content of the present invention is the Photomicrograph of 5%SBS modifying asphalt.
Fig. 2 is that content of the present invention is the Photomicrograph of 5%SBS-OH modifying asphalt.
Fig. 3 is that content of the present invention is the Photomicrograph of 5%N-SBS modifying asphalt.
Fig. 4 is that content of the present invention is the Photomicrograph of 5%N-SBS-CO modifying asphalt.
Embodiment
The pitch that is adopted among the embodiment is the joyful mountain range pitch factory in the Liaohe River, and the trade mark is liked mountain range AH-90.
Embodiment 1
Hexanaphthene N with 2.2kg
2Be pressed into polymeric kettle, be preheated to 50 ℃ behind the vinylbenzene of adding metering, setting THF/Li is 1.0, behind the adding THF, adds n-butyl lithium initiator initiation reaction 30min rapidly; According to first section cinnamic quality, get a certain amount of neat liquid divinyl with the goat's horn bottle of 1000ml, use N
2Go in the reactor from the still base pressure, and reaction 45min; Under identical temperature, use N
2Be pressed into broken the 3rd section assorted vinylbenzene, continue reaction 30min, use through ethanol to stop, add 1% antioxidant 264.Desolventizing dewaters and tablet forming then, obtains SBS, and GPC test gained SBS molecular weight is 8.1 * 10
4G/mol, molecular weight distribution is 1.03.Its mechanical property sees Table 1.
Embodiment 2
Hexanaphthene N with 2.2kg
2Be pressed into polymeric kettle, be preheated to 50 ℃ behind the adding vinylbenzene, after setting THF/Li is 1.0 adding THF, breaks with n-Butyl Lithium then and mix, add quantitative nitrogen-lithium initiator initiation reaction 30min rapidly; Be warming up to 60 ℃, the one section cinnamic quality in base area is got a certain amount of neat liquid divinyl with the goat's horn bottle of 1000ml, uses N
2Go in the reactor from the still base pressure, and reaction 50min; Under identical temperature, use N
2Be pressed into broken the 3rd section assorted vinylbenzene, continue reaction 40min, stop, add 1% antioxidant 264 with ethanol.Desolventizing dewaters and tablet forming then, obtains N-SBS.The functionalized efficient of test shows polymer ends amido is 95%.GPC test gained N-SBS molecular weight is 8.1 * 10
4G/mol, molecular weight distribution is 1.35, mechanical property sees Table 1, shows that the N-SBS performance and the example 2 that adopt the nitrogen-lithium initiator preparation adopt the SBS structure and the performance of n-Butyl Lithium initiation preparation suitable.
Embodiment 3
With example 2, difference is after the 3rd section vinylbenzene reaction finishes, temperature of reaction to be reduced to 10 ℃, adds the TMEDA polar modifier, stirs 5min, feeds high-purity carbon dioxide, keep-ups pressure at 0.2MPa ventilatory response 24 hours.Stop with ethanol, add 1% antioxidant 264, desolventizing and water and tablet forming obtain N-SBS-COOH.The functionalized efficient of test SBS terminal amido is 93%, and carboxy-functionalized efficient is 95%.GPC test products therefrom molecular weight is 8.3 * 10
4, molecular weight distribution is 1.38
Table 1SBS and sense SBS performance are relatively
| Shao Er hardness | Tension set, % | 300% tensile modulus, MPa | Tensile strength, MPa | Elongation at break, % | |
| SBS | 76 | 13 | 2.7 | 18.1 | 856 |
| The nitrogen lithium causes (N-SBS)) | 68 | 28 | 2.2 | 18.8 | 980 |
Embodiment 4
The pitch that takes by weighing quality and be 250g is heated to 160 ℃ in mixing vessel, add 16g SBS glue sample, under the shearing rate of 3700r/min, stir 20min, the sulphur that adds 3 parts then, be heated to 180 ℃, under the shearing rate of constant temperature and 3700r/min, continue to stir 40min, SBS and pitch are mixed.Traditional performance by GB test SBS modifying asphalt the results are shown in Table 2.
The traditional performance of table 2 SBS and dissimilar terminal group functional SBS modifying asphalts
| The SBS type | Penetration degree (mm) | Softening temperature (℃) | Ductility (5 ℃, cm) | The upper strata softening temperature (℃) | Lower floor's softening temperature (℃) | Segregation (℃) |
| SBS N-SBS SBS-N SBS-COOH SBS-OH N-SBS-COOH | 51.0 52.0 50.3 50.0 50.7 51.7 | 64.0 63.0 67.0 58.0 68.5 63.5 | 27.0 48.0 37.5 37.0 34.0 34.0 | 91 64 65 59.5 84 58.5 | 59.5 62.8 63.5 59.3 64 57.5 | 31.5 1.2 1.4 0.2 20.0 1.0 |
Embodiment 5
With example 4, difference is to add functionalized SBS glue sample N-SBS, SBS-N, SBS-COOH, SBS-OH, the N-SBS-COOH of different end group, and the traditional performance by GB test SBS modifying asphalt the results are shown in Table 2.
The low-temperature ductility that adopts terminal group functional SBS modifying asphalt has all had than the ductility of SBS modifying asphalt and has significantly improved (seeing Table 2), shows that the snappiness of modifying asphalt and consistency are improved significantly.The difference of softening temperature has reflected the bituminous stability in storage, also is the important evaluation index of reflection pitch and SBS consistency.By table 2 as seen, adopt the difference of the softening temperature of non-sense SBS modifying asphalt to be far longer than 2.5 ℃, show that stability is very poor, and the difference of employing N-SBS, SBS-N, SBS-COOH, N-SBS-COOH modifying asphalt softening temperature is all less than 2.5 ℃, segregation significantly reduces, show that package stability is greatly improved, also further proof has effectively improved SBS and bituminous consistency.
Accompanying drawing has shown the phase difference of non-sense SBS and sense SBS modifying asphalt.For the relatively poor SBS modifying asphalt (Fig. 1) of hot storage stability, in pitch SBS size difference, also heterogeneity distributes, obviously there is the reunion of SBS, and in end amido and the end carboxyl SBS modifying asphalt system (Fig. 3, Fig. 4), the SBS size obviously diminishes, the homogeneous that also becomes that distributes shows that end amido and end carboxyl SBS and bituminous consistency are improved significantly.And in the terminal hydroxy group SBS modifying asphalt system (Fig. 2), the SBS size differs, and skewness one shows the good consistency of shortage between terminal hydroxy group SBS and the pitch, and this is consistent with the traditional performance test result.
Claims (9)
1. method of holding the modifying asphalt of the synthetic of amido and carboxyl styrene/butadiene multipolymer and preparation shelf-stable thereof is characterized in that this method steps is:
(1) end amido and carboxyl styrene/butadiene/styrene block copolymer is synthetic:
(1) earlier varsol is added reactor, add vinylbenzene and polar additive again, stir, be warming up to 45-80 ℃, add nitrogen-lithium initiator, begin to carry out polyreaction, the reaction times is 30-90min, various reactant quality: vinylbenzene/varsol=5-20, mol ratio: vinylbenzene/Li=1 * 10
4-3 * 10
4, polar additive/Li=0.5-20;
(2) the ratio S/B=40/60-30/70 according to vinylbenzene in the product and divinyl quality adds divinyl, reacts 30-90 minute;
(3) after divinyl has reacted, add with (1) in the vinylbenzene of first section quality such as reinforced, reaction 30-90min;
The structural formula of nitrogen-lithium initiator is expressed as follows:
Wherein, f is the integer more than or equal to 1; N=0-20, m=0-20,3＜m+n＜20, and m and n are integer;
(4) after the 3rd section vinylbenzene reaction finishes in above-mentioned (3), add polar additive, mol ratio: polar additive/Li=1-50;
(5) feed carbonic acid gas then, the pressure of carbonic acid gas between 0.01-0.5Mpa, temperature of reaction 0-25 ℃, reaction times 1-36 hour;
(6) add terminator ethanol to polymkeric substance after total overall reaction finishes and all be settled out, use N again
2Extrude glue, add 1% anti-aging agent, boil the glue desolventizing with water vapour then, roll in the mill dehydration and be pressed into sheet, obtain the Bifunctionalized styrene/butadiene/styrene block copolymers of amido and carboxyl two;
(2) preparation modifying asphalt:
(1) fused pitch is joined in the container, be warming up to 140-230 ℃, press mass fraction in 100 parts of pitches, add 1-15 part amido and the Bifunctionalized styrene/butadiene copolymers of carboxyl, start the emulsification pretreatment stirrer, under 2500-6500 rev/min of condition, stirred 10-60 minute;
(2) add 1-5 part sulphur, continue to stir 10-60 minute, form uniform dispersion liquid after, obtain the sense SBS modifying asphalt of shelf-stable, the difference of its softening temperature is less than 2.5 ℃.
2. the method for the modifying asphalt of the synthetic and preparation shelf-stable of a kind of end amido according to claim 1 and carboxyl styrene/butadiene multipolymer, it is characterized in that described hydrocarbon organic solvent is benzene, toluene, ethylbenzene, dimethylbenzene, pentane, hexane, heptane, octane, hexanaphthene, Mixed XYLENE, the mixture of one or more hydrocarbon organic solvents in raffinating oil.
3, the method for the modifying asphalt of the synthetic and preparation shelf-stable of a kind of end amido according to claim 1 and carboxyl styrene/butadiene multipolymer, it is characterized in that it is to contain oxygen, nitrogenous, sulfur-bearing, contain a kind of polar compound in the Phosphorus polar compound or the mixture of several polar compounds that described polarity is added polar additive.
4. according to the method for the modifying asphalt of the synthetic of claim 1 and 3 described a kind of end amidos and carboxyl styrene/butadiene multipolymer and preparation shelf-stable thereof, it is characterized in that, described polar additive is selected from nitrogenous compound, be triethylamine, N, N '-Tetramethyl Ethylene Diamine, diethylene glycol dimethyl ether, two piperidines ethane.
5. according to the method for synthesizing and prepare the modifying asphalt of shelf-stable of claim 1 and 3 described a kind of end amidos and carboxyl styrene/butadiene multipolymer, it is characterized in that described polar additive is selected from oxygenatedchemicals, be ether, tetrahydrofuran (THF), R
1OCH
2CH
2OR
2, R
1OCH
2CH
2OCH
2CH
2OR
2, wherein: R
1, R
2Be that carbonatoms is the alkyl of 1-6, R
1, R
2Can be identical or different.
6, according to the method for synthesizing and prepare the modifying asphalt of shelf-stable of claim 1 and 3 described a kind of end amidos and carboxyl styrene/butadiene multipolymer, it is characterized in that described polar additive is selected from P contained compound, be HMPA.
7. according to the method for the modifying asphalt of the synthetic of claim 1 and 3 described a kind of end amidos and carboxyl styrene/butadiene multipolymer and preparation shelf-stable thereof, it is characterized in that, described polar additive is selected from alkyl metal cpd, is tert.-butoxy clock or uncle's pentyloxy potassium.
8. the method for the modifying asphalt of the synthetic and preparation shelf-stable of a kind of end amido according to claim 1 and carboxyl styrene/butadiene multipolymer, it is characterized in that, described pitch is selected from petroleum pitch, is distillation pitch, oxidized bitumen, solvent pitch or the pitch that is in harmonious proportion.
9. the method for the modifying asphalt of the synthetic and preparation shelf-stable of a kind of end amido according to claim 1 and carboxyl styrene/butadiene multipolymer, it is characterized in that, described stablizer is a sulphur, or sulphur and thiazoles, inferior sulphonyl class, thiurams, guanidine class rubber is used with all kinds of promotor, or modifying asphalt is stabilizing agent specially used.
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