CN1281677C - Grafting type asphalt modified masterbatch and method for preparation - Google Patents
Grafting type asphalt modified masterbatch and method for preparation Download PDFInfo
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- 239000004594 Masterbatch (MB) Substances 0.000 title claims description 62
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- 238000002360 preparation method Methods 0.000 title description 28
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- 238000012986 modification Methods 0.000 claims abstract description 51
- 239000000463 material Substances 0.000 claims abstract description 40
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- 239000011295 pitch Substances 0.000 claims description 109
- 239000003607 modifier Substances 0.000 claims description 25
- 239000002904 solvent Substances 0.000 claims description 25
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 17
- 238000011282 treatment Methods 0.000 claims description 17
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- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 14
- -1 olefin carboxylicesters Chemical class 0.000 claims description 14
- 150000001993 dienes Chemical class 0.000 claims description 13
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- 239000011301 petroleum pitch Substances 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 11
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 10
- 239000004698 Polyethylene Substances 0.000 claims description 7
- 150000002148 esters Chemical class 0.000 claims description 7
- 229920000573 polyethylene Polymers 0.000 claims description 7
- 239000011294 coal tar pitch Substances 0.000 claims description 6
- 239000011435 rock Substances 0.000 claims description 6
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 5
- 239000005977 Ethylene Substances 0.000 claims description 5
- 125000002947 alkylene group Chemical group 0.000 claims description 5
- 239000011280 coal tar Substances 0.000 claims description 5
- 239000003208 petroleum Substances 0.000 claims description 5
- 239000004033 plastic Substances 0.000 claims description 5
- 229920003023 plastic Polymers 0.000 claims description 5
- 238000004230 steam cracking Methods 0.000 claims description 5
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- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 4
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- MSAVICZWFPQFPO-UHFFFAOYSA-N acetic acid;ethene Chemical group C=C.C=C.CC(O)=O MSAVICZWFPQFPO-UHFFFAOYSA-N 0.000 claims description 3
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- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 6
- 229920001971 elastomer Polymers 0.000 description 5
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- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 4
- 230000008961 swelling Effects 0.000 description 4
- UDATXMIGEVPXTR-UHFFFAOYSA-N 1,2,4-triazolidine-3,5-dione Chemical compound O=C1NNC(=O)N1 UDATXMIGEVPXTR-UHFFFAOYSA-N 0.000 description 2
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- NPSJHQMIVNJLNN-UHFFFAOYSA-N 2-ethylhexyl 4-nitrobenzoate Chemical compound CCCCC(CC)COC(=O)C1=CC=C([N+]([O-])=O)C=C1 NPSJHQMIVNJLNN-UHFFFAOYSA-N 0.000 description 1
- 239000004808 2-ethylhexylester Substances 0.000 description 1
- VSKJLJHPAFKHBX-UHFFFAOYSA-N 2-methylbuta-1,3-diene;styrene Chemical compound CC(=C)C=C.C=CC1=CC=CC=C1.C=CC1=CC=CC=C1 VSKJLJHPAFKHBX-UHFFFAOYSA-N 0.000 description 1
- 101000809257 Homo sapiens Ubiquitin carboxyl-terminal hydrolase 4 Proteins 0.000 description 1
- 206010067482 No adverse event Diseases 0.000 description 1
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- 239000006229 carbon black Substances 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical group O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
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- 235000012204 lemonade/lime carbonate Nutrition 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
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- 239000005077 polysulfide Substances 0.000 description 1
- 229920001021 polysulfide Polymers 0.000 description 1
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Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Working-Up Tar And Pitch (AREA)
Abstract
The present invention relates to a graft type asphalt modified parent material comprising 65 to 95 wt% of polymer modifying agent, 0.5 to 30 wt% of asphalt, 0.5 to 30 wt% of compatiblizing agent and 4 to 12 wt% of auxiliary agent for grafting reaction. Firstly, 65 to 95 wt% of polymer modifying agent, 0.5 to 30 wt% of asphalt, 0.5 to 30 wt% of compatiblizing agent and 4 to 12 wt% of auxiliary agent for grafting reaction are uniformly mixed; secondly, the fused mass temperature of the mixture is controlled between 80 and 200DEG C, and the mixture is extruded on a double-screw extruding machine and granulated to obtain the graft type asphalt modified parent material; and thirdly, 85 to 98 wt% of asphalt is heated to 100 to 220DEG C, and 2 to 15 wt% of graft type asphalt modified parent material is added and stirred for 30 to 80 minutes to obtain modified asphalt. The asphalt modified parent material effectively improving the dispersivity of the polymer modifying agent in the asphalt can furthest exert the modification effect of the polymer modifying agent, obviously improve the performance of the modified asphalt and improve the storage stability of the modified asphalt.
Description
Technical field
The present invention relates to a kind of bituminous material composition and method of making the same, more particularly, is a kind of graft type asphalt modification masterbatch and preparation method thereof.
Background technology
Pitch is as the pavement material of road, building and water conservancy industry, develops very fastly, but pitch is bigger to the susceptibility of temperature, has the summer high temperature trickling, and therefore winter low temperature rimose problem, has brought certain restriction to its application.
Therefore, adding polymer modifiers in pitch improves the bituminous temperature sensitivity and more and more is subject to people's attention.The adding of different sorts polymer modifiers can improve the bituminous high temperature resistant property, improve the bituminous cold resistance can or improve the bituminous high temperature performance simultaneously, thereby reaches the effect that reduces asphalt temperature susceptibility.
Polymer modifiers self molecular weight is big (being generally several ten thousand～hundreds of thousands of), and the bituminous molecular weight has only about 1,000, qualitative gap causes polymer modifiers and bituminous consistency relatively poor, the modifying asphalt system of preparation is very unstable, separation phenomenon easily takes place in storage process, thereby influences the use and the performance of modified bitumen of modifying asphalt.At present, people adopt the mode of high temperature, long-time, high-shear or strong mixing that polymer modifiers is distributed in the pitch more, can cause the decline of pitch, polymer modifiers self performance so undoubtedly, and finally cause the modified bitumen product performance decrease, also can bring equipment attrition, energy consumption to increase and waste of time simultaneously, very uneconomical economically.Nonetheless, also can not change the stability in storage of modifying asphalt.
CN1300801A discloses a kind of mother particles for modifying road asphalt and production method thereof, and this master batch is made up of the tetraphenyl urazole of SBS, the 35 heavy %～pitch of 50 heavy % of 45 heavy %～60 heavy %, 4%～15% weighting agent, the heavy % in 0.005 heavy %～0.01; The preparation method of this master batch at first mixes a certain proportion of SBS, pitch, weighting agent, tetraphenyl urazole, granulation on twin screw extruder then, and melt temperature is at 140～180 ℃.Described weighting agent is talcum powder, white carbon black, lime carbonate, these components can be brought disadvantageous effect to bituminous following process and bituminous performance, existence as weighting agent will cause can not using colloidal mill and high-speed shearing machine (bigger to equipment attrition) in follow-up modifying asphalt production, this will restrict the further dispersion of properties-correcting agent in pitch, and will be unfavorable to the finished product asphaltum of producing steady heat storage.
A kind of rubber modified asphalt material for road and preparation method thereof is disclosed among the CN1364823A, rubber modified asphalt material is made up of 100 parts of pitches, 0.5-25 part rubber, the organic grafts of 0-10 part and 0-5 part cross-linked composite, this rubber modified asphalt material has two kinds of preparation methods, one of method is to add organic grafts reaction in rubber solutions earlier, add the pitch mixing then, add the cross-linked composite reaction again and form modified bitumen product; Two of method is earlier pitch to be scattered in the pitch, adds the reaction of organic grafts and cross-linked composite again and forms modified bitumen product.But there are problems such as solvent recuperation, expense height, pollution in one of method, two of method exist polymkeric substance in pitch fully swelling, to problem such as performance of modified bitumen is influential.
CN1365986A discloses the method for a kind of SBS of raising and pitch compatible stability, this method adopts chemical graft process to form the segment polarity group on SBS, polar group in these polar groups and the pitch or physical adsorption or chemical covalency form reticulated structure, reach the compatible stable effect of SBS and pitch.But this method exist polymkeric substance in pitch fully swelling, to problem such as performance of modified bitumen is influential.
USP4, related masterbatch is to mix with pitch after with the dissolving of polymkeric substance and polysulfide with the normal vacuum distillate of crude oil again in 567, the 222 disclosed SBS process for preparing modified asphalt, need be with the lights removal in the mother liquor in the operating process later stage.But there are problems such as solvent recuperation, expense height, pollution in this method.
Summary of the invention
The purpose of this invention is to provide a kind of graft type asphalt modification masterbatch and preparation method thereof, improve the dispersiveness of polymer modifiers in pitch with improvement, improve the performance of modified bitumen product, reduce the production cost of modifying asphalt, improve the stability in storage of modifying asphalt.
Another object of the present invention provides a kind of method that is prepared modifying asphalt by graft type asphalt modification masterbatch.
Graft type asphalt modification masterbatch provided by the invention comprises 65～95 heavy % polymer modifiers, 0.5～30 heavy % pitches, 0.5～30 heavy % compatilizers, 4～12 heavy % graft reaction auxiliary agents, wherein said polymer modifiers is vinylbenzene/conjugated diolefin polymer and/or polyolefin polymer, described compatilizer is to be selected from by petroleum fractions, coal tar fraction, catalytically cracked oil, deasphalted oil, oil is extracted in solvent treatment out, the tar of preparing ethylene by steam cracking, Yatall MA, contain sour Yatall MA, naphthenic oil, the mixture of one or more in this group material that white oil and ester constitute, described graft reaction auxiliary agent is to be selected from by organic ethylenic unsaturation alkylene dicarboxylate, organic unsaturated olefin carboxylicesters, the mixture of one or more in this group material that organic unsaturated olefin carboxylic acid anhydride constitutes.
Graft type asphalt modification masterbatch preparation process provided by the invention comprises: earlier with 65～95 heavy % polymer modifiers, 0.5～30 heavy % pitch, 0.5～30 heavy % compatilizer, 4～12 heavy % graft reaction auxiliary agent uniform mixing, the melt temperature of controlling mixture is then extruded on twin screw extruder, granulation between 80～200 ℃.
Process for preparing modified asphalt provided by the invention comprises: the pitch of 85～98 heavy % is heated to 100～220 ℃, and the above-mentioned graft type asphalt modification masterbatch of adding 2～15 heavy % also stirred 30～80 minutes.
This masterbatch of graft type asphalt modification masterbatch provided by the invention can improve the polymer modifiers processing characteristics effectively, improve the intermiscibility of polymer modifiers and matrix pitch, give full play to the modified effect of polymer modifiers, significantly improve the stability in storage of modifying asphalt.Modified bitumen product with this masterbatch production can be widely used in fields such as road, building, waterproof.
Embodiment
Graft type asphalt modification masterbatch provided by the invention is formed the polymer modifiers that comprises 65～95 heavy %, the pitch of 0.5～30 heavy %, the compatilizer of 0.5～30 heavy %, the graft reaction auxiliary agent of 4～12 heavy %.
Polymer modifiers described in the graft type asphalt modification masterbatch is vinylbenzene/conjugated diolefin polymer and/or polyolefin polymer, in other words, but polymer modifiers vinylbenzene/conjugated diolefin polymer, also polyolefin polymer, the also mixture of vinylbenzene/conjugated diolefin polymer and polyolefin polymer.Wherein vinylbenzene/conjugated diolefin polymer is meant conjugated diolefine diblock polymer and three inlay section thermal plastic elastic bodies that contain different vinylbenzene ratios, as styrene-butadiene-styrene triblock copolymer (SBS), styrene-isoprene-styrene copolymer-(SIS) etc.; Polyolefin polymer is to be selected from by polyethylene (PE) and/or ethene-acetic acid-ethylene copolymer (EVA).
Described pitch is to be selected from this group of being made of petroleum pitch, coal-tar pitch and rock asphalt one or more mixture in material, and wherein petroleum pitch is one or more the mixture that is selected from this group material that is made of straight-run pitch, solvent deoiling pitch, oxidized bitumen, mediation pitch.
Described compatilizer be selected from by petroleum fractions, coal tar fraction, catalytically cracked oil, deasphalted oil, solvent treatment extract out oil, preparing ethylene by steam cracking tar, Yatall MA, contain one or more the mixture in this group material that sour Yatall MA, naphthenic oil, white oil and ester constitute.Its boiling range requires greater than 200 ℃; Ester be dibutyl phthalate (DBP), phthalic acid two (2-ethylhexyl ester) (DOP), dimixo-octyl phthalate (DIOP), heptyl phthalate ester (DnHP) etc.The effect of compatilizer is to make polymer modifiers and pitch be fused into homogeneous system better, and this compatilizer finally becomes the part of graft type asphalt modification concentrate composition.
Described graft reaction auxiliary agent is to be selected from this group of being made of organic ethylenic unsaturation alkylene dicarboxylate, organic unsaturated olefin carboxylicesters, organic unsaturated olefin carboxylic acid anhydride one or more mixture in material, as methacrylic acid, Jia Jibingxisuanyizhi, MALEIC ANHYDRIDE etc.The effect of graft reaction auxiliary agent is at polymer surfaces grafting some and the good polar group of pitch affinity, reaches the purpose of improving polymkeric substance and pitch affinity, thereby suppresses the segregation of the two.
Graft type asphalt modification masterbatch preparation process provided by the invention comprises: earlier with the polymer modifiers of 65～95 heavy %, the pitch of 0.5～30 heavy %, the compatilizer of 0.5～30 heavy %, the graft reaction auxiliary agent uniform mixing of 4～12 heavy %, the melt temperature of controlling mixture is then extruded on twin screw extruder, granulation between 80～200 ℃ preferred 100～180 ℃.
Polymer modifiers described in the graft type asphalt modification masterbatch preparation process is vinylbenzene/conjugated diolefin polymer and/or polyolefin polymer, in other words, but polymer modifiers vinylbenzene/conjugated diolefin polymer, also polyolefin polymer, the also mixture of vinylbenzene/conjugated diolefin polymer and polyolefin polymer.Wherein vinylbenzene/conjugated diolefin polymer is meant conjugated diolefine diblock polymer and three inlay section thermal plastic elastic bodies that contain different vinylbenzene ratios, as SBS, SIS etc.; Polyolefin polymers is PE and/or EVA.
Described pitch is to be selected from this group of being made of petroleum pitch, coal-tar pitch and rock asphalt one or more mixture in material, and wherein petroleum pitch is one or more the mixture that is selected from this group material that is made of straight-run pitch, solvent deoiling pitch, oxidized bitumen, mediation pitch.
Described compatilizer be selected from by petroleum fractions, coal tar fraction, catalytically cracked oil, deasphalted oil, solvent treatment extract out oil, preparing ethylene by steam cracking tar, Yatall MA, contain one or more the mixture in this group material that sour Yatall MA, naphthenic oil, white oil and ester constitute.Wherein the boiling range of white oil requires greater than 200 ℃; Ester is DBP, DOP, DIOP, DnHP etc.The effect of compatilizer is to make polymer modifiers and pitch be fused into homogeneous system better, and this compatilizer finally becomes the part of graft type asphalt modification concentrate composition.
Described graft reaction auxiliary agent is to be selected from this group of being made of organic ethylenic unsaturation alkylene dicarboxylate, organic unsaturated olefin carboxylicesters, organic unsaturated olefin carboxylic acid anhydride one or more mixture in material, as methacrylic acid, Jia Jibingxisuanyizhi, MALEIC ANHYDRIDE etc.The effect of graft reaction auxiliary agent is at polymer surfaces grafting some and the good polar group of pitch affinity, reaches the purpose of improving polymkeric substance and pitch affinity, thereby suppresses the segregation of the two.
Process for preparing modified asphalt provided by the invention comprises: the pitch of 85～98 heavy % is heated to 100～220 ℃, and the above-mentioned graft type asphalt modification masterbatch of adding 2～15 heavy % also stirred 30～80 minutes.
Pitch described in the process for preparing modified asphalt is to be selected from this group of being made of petroleum pitch, coal-tar pitch and rock asphalt one or more mixture in material, and wherein petroleum pitch is one or more the mixture that is selected from this group material that is made of straight-run pitch, solvent deoiling pitch, oxidized bitumen, mediation pitch.
The present invention is in the process of preparation graft type asphalt modification masterbatch, at twin screw extruder interpolymer properties-correcting agent by abundant swelling, disrumpent feelings and carry out graft reaction, because whole process is to carry out in forcing machine, ingress of air and time weak point does not almost have no adverse effects to polymkeric substance and bituminous performance.Compatilizer makes the abundant swelling of polymkeric substance, can bring into play the modified effect of polymkeric substance to greatest extent, graft reaction will be grafted on the polymkeric substance with the good group of pitch affinity, thereby polymkeric substance and bituminous consistency have been improved, masterbatch and bituminous consistency with this method preparation are better, during with its preparation modifying asphalt, can significantly reduce preparation temperature and time, and modified bitumen product with this modified master preparation, its stability in storage obviously is better than the modifying asphalt that direct method is produced, and in addition, this masterbatch is better to different oil sources bituminous adaptability, can be widely used in the modification of different oil sources bituminous, the comprehensive cost of producing modifying asphalt obviously reduces.
The following examples will give further instruction to present method, but therefore not limit present method.Penetration degree in embodiment and the Comparative Examples, softening temperature, ductility and segregation are tested according to GB/T4509, GB/T4508, GB/T4507 and ASTM D5976 standard method respectively.
Embodiment 1
Take by weighing 1600 gram SBS respectively; 200 gram straight-run pitches (its character is as shown in table 1); oil is extracted in 200 gram compatilizer solvent treatments out; 100 gram graft reaction auxiliary agent MALEIC ANHYDRIDE; thorough mixing in the above-mentioned material adding mix pot is even; join barrel temperature then being 165 ℃ (is melt temperature; (model is SHJ-38 to twin screw extruder down together); the safe plastics machinery of orchid company limited produces by Lanzhou; down together) in the hopper; start forcing machine; and will extrude masterbatch and be cut into the pellet that thickness is not more than 2mm through dicing machine, this pellet is the prepared graft type asphalt modification masterbatch A of the present invention
m
Take by weighing 564 gram mediation pitches and 36 gram graft type asphalt modification masterbatch A respectively
m, earlier pitch is poured in the stirring tank, after pitch is heated to 175 ℃ again with graft type asphalt modification masterbatch A
mAdd, turn on agitator stirs discharging after 60 minutes, and the gained sample is modified bitumen product A.Graft type asphalt modification masterbatch A
mComposition and the character of composition, modifying asphalt A as shown in table 2.As can be seen from Table 2, the segregation softening temperature difference of the modifying asphalt A of preparation only is 8 ℃.
Comparative Examples 1
Compare with embodiment 1, this Comparative Examples does not have the graft type asphalt modification masterbatch of preparation, but directly mixes with pitch with properties-correcting agent.
Take by weighing 570 gram mediation pitches and 30 gram properties-correcting agent SBS respectively, earlier pitch is poured in the stirring tank, after pitch is heated to 175 ℃, again SBS is added, turn on agitator, stir discharging after 90 minutes, the gained sample is modified bitumen product, and the composition and the character of this modifying asphalt are as shown in table 2.As can be seen from Table 2, this Comparative Examples needs 90 minutes, the modifying asphalt segregation softening temperature of preparation is poor＞30 ℃ be poor storage stability, and 1 need of embodiment 60 minutes, the modifying asphalt segregation softening temperature difference of preparation only is 8 ℃.
Comparative Examples 2
Compare with embodiment 1, this Comparative Examples does not add the graft reaction auxiliary agent, and other situation is identical.
Take by weighing 1600 gram SBS, 200 gram straight-run pitches (its character is as shown in table 1), 200 gram compatilizer solvent treatments extraction oil respectively; thorough mixing in the above-mentioned material adding mix pot is even; join barrel temperature then and be in 175 ℃ the twin screw extruder hopper; start forcing machine, and will extrude masterbatch and be cut into the pellet that thickness is not more than 2mm through dicing machine.
Take by weighing 564 gram mediation pitch and 36 gram particle material respectively, earlier pitch is poured in the stirring tank, pellet is added after pitch is heated to 175 ℃ again, turn on agitator stirs discharging after 90 minutes, and the gained sample is modifying asphalt.The composition of pellet, the composition of modifying asphalt and character are as shown in table 2.As can be seen from Table 2, the segregation softening temperature difference of the modifying asphalt A of preparation is up to more than 30 ℃, poor storage stability.
Embodiment 2
Take by weighing 1600 gram SBS, 200 gram straight-run pitches (its character is as shown in table 1), 200 gram compatilizer solvent treatments extraction oil, 200 gram graft reaction auxiliary agent MALEIC ANHYDRIDE respectively; thorough mixing in the above-mentioned material adding mix pot is even; join barrel temperature then and be 165 ℃, extruder head temperature and be in 150 ℃ the twin screw extruder hopper; start forcing machine; and will extrude masterbatch and be cut into the pellet that thickness is not more than 2mm through dicing machine, this pellet is the prepared graft type asphalt modification masterbatch B of the present invention
m
Take by weighing 564 gram mediation pitches and 36 gram graft type asphalt modification masterbatch B respectively
m, earlier pitch is poured in the stirring tank, after pitch is heated to 175 ℃ again with graft type asphalt modification masterbatch B
mAdd, turn on agitator stirs discharging after 60 minutes, and the gained sample is modified bitumen product B.Graft type asphalt modification masterbatch B
mComposition and the character of composition, modifying asphalt B as shown in table 3.As can be seen from Table 3, only below 5 ℃, stability in storage is better for the segregation softening temperature difference of the modifying asphalt A of preparation.
Embodiment 3
Take by weighing 1600 gram SBS, 200 gram straight-run pitches (its character is as shown in table 1), 200 gram compatilizer solvent treatments extraction oil and DOP (both weight ratios 1: 1), 200 gram graft reaction auxiliary agent MALEIC ANHYDRIDE respectively; thorough mixing in the above-mentioned material adding mix pot is even; join barrel temperature then and be 165 ℃, extruder head temperature and be in 150 ℃ the twin screw extruder hopper; start forcing machine; and will extrude masterbatch and be cut into the pellet that thickness is not more than 2mm through dicing machine, this pellet is the prepared graft type asphalt modification masterbatch C of the present invention
m
Take by weighing 564 gram mediation pitches and 36 gram graft type asphalt modification masterbatch C respectively
m, earlier pitch is poured in the stirring tank, after pitch is heated to 175 ℃ again with graft type asphalt modification masterbatch C
mAdd, turn on agitator stirs discharging after 60 minutes, and the gained sample is modified bitumen product C.Graft type asphalt modification masterbatch C
mComposition and the character of composition, modifying asphalt C as shown in table 3.As can be seen from Table 3, only below 5 ℃, stability in storage is better for the segregation softening temperature difference of the modifying asphalt A of preparation.
Embodiment 4
Take by weighing 1200 gram SBS, 400 gram PE, 200 gram straight-run pitches (its character is as shown in table 1), 200 gram compatilizer solvent treatments extraction oil, 200 gram graft reaction auxiliary agent MALEIC ANHYDRIDE respectively; thorough mixing in the above-mentioned material adding mix pot is even; join barrel temperature then and be 165 ℃, extruder head temperature and be in 150 ℃ the twin screw extruder hopper; start forcing machine; and will extrude masterbatch and be cut into the pellet that thickness is not more than 2mm through dicing machine, this pellet is the prepared graft type asphalt modification masterbatch D of the present invention
m
Take by weighing 564 gram mediation pitches and 36 gram graft type asphalt modification masterbatch D respectively
m, earlier pitch is poured in the stirring tank, after pitch is heated to 175 ℃ again with graft type asphalt modification masterbatch D
mAdd, turn on agitator stirs discharging after 60 minutes, and the gained sample is modified bitumen product D.Graft type asphalt modification masterbatch D
mComposition and the character of composition, modifying asphalt D as shown in table 4.As can be seen from Table 4, only below 5 ℃, stability in storage is better for the segregation softening temperature difference of the modifying asphalt A of preparation.
Embodiment 5
Take by weighing 1200 gram SBS, 400 gram EVA, 200 gram straight-run pitches (its character is as shown in table 1), 200 gram compatilizer solvent treatments extraction oil, 200 gram graft reaction auxiliary agent MALEIC ANHYDRIDE respectively; thorough mixing in the above-mentioned material adding mix pot is even; join barrel temperature then and be 165 ℃, extruder head temperature and be in 150 ℃ the twin screw extruder hopper; start forcing machine; and will extrude masterbatch and be cut into the pellet that thickness is not more than 2mm through dicing machine, this pellet is the prepared graft type asphalt modification masterbatch E of the present invention
m
Take by weighing 564 gram mediation pitches and 36 gram graft type asphalt modification masterbatch E respectively
m, earlier pitch is poured in the stirring tank, after pitch is heated to 175 ℃ again with graft type asphalt modification masterbatch E
mAdd, turn on agitator stirs discharging after 60 minutes, and the gained sample is modified bitumen product E.Graft type asphalt modification masterbatch E
mComposition and the character of composition, modifying asphalt E as shown in table 4.As can be seen from Table 4, only below 5 ℃, stability in storage is better for the segregation softening temperature difference of the modifying asphalt A of preparation.
Table 1
| Pitch | Straight-run pitch | Mediation pitch |
| Penetration degree (25 ℃), 1/10 millimeter | 110 | 73 |
| Softening temperature (ring and ball method), ℃ | 42 | 47 |
| Ductility (5 ℃), centimetre | 13 | 7 |
Table 2
| Embodiment 1 | Comparative Examples 1 | Comparative Examples 2 | |
| Graft type asphalt modification masterbatch composition/weight % | |||
| Properties-correcting agent | SBS/76.2 | - | SBS/80.0 |
| Pitch | Straight-run pitch/9.5 | - | Straight-run pitch/10.0 |
| Compatilizer | Oil/9.5 are extracted in solvent treatment out | - | Oil/10.0 are extracted in solvent treatment out |
| The graft reaction auxiliary agent | MALEIC ANHYDRIDE/4.8 | - | |
| Melt temperature, ℃ | 165 | - | 175 |
| Modifying asphalt composition/weight % | |||
| Pitch | Straight-run pitch/94.0 | Straight-run pitch/95.0 | Straight-run pitch/94.0 |
| Modified master or properties-correcting agent | A m/6.0 | SBS/5.0 | 6.0 |
| The modifying asphalt preparation time, minute | 60 | 90 | 90 |
| Modifying asphalt character | |||
| Penetration degree (25 ℃), 1/10 millimeter | 55 | 51 | 56 |
| Softening temperature (ring and ball method), ℃ | 74 | 73 | 78 |
| Ductility (5 ℃), centimetre | 43 | 30 | 40 |
| The segregation softening temperature is poor, ℃ | 8 | ＞30 | ＞30 |
Table 3
| Embodiment 2 | Embodiment 3 | |
| Graft type asphalt modification masterbatch composition/weight % | ||
| Properties-correcting agent | SBS/72.7 | SBS/72.7 |
| Pitch | Straight-run pitch/9.1 | Straight-run pitch/9.1 |
| Compatilizer | Oil/9.1 are extracted in solvent treatment out | Oil/4.55 DOP/4.55 are extracted in solvent treatment out |
| The graft reaction auxiliary agent | MALEIC ANHYDRIDE/9.1 | MALEIC ANHYDRIDE/9.1 |
| Melt temperature, ℃ | 165 | 165 |
| Modifying asphalt composition/weight % | ||
| Pitch | Straight-run pitch/94.0 | Straight-run pitch/93.0 |
| Modified master or properties-correcting agent | B m/6.0 | C m/7.0 |
| The modifying asphalt preparation time, minute | 60 | 60 |
| Modifying asphalt character | ||
| Penetration degree (25 ℃), 1/10 millimeter | 59 | 54 |
| Softening temperature (ring and ball method), ℃ | 72 | 71 |
| Ductility (5 ℃), centimetre | 44 | 46 |
| The segregation softening temperature is poor, ℃ | 4.0 | 3.6 |
Table 4
| Embodiment 4 | Embodiment 5 | |
| Graft type asphalt modification masterbatch composition/weight % | ||
| Properties-correcting agent | SBS/54.5 PE/18.2 | SBS/54.5 EVA/18.2 |
| Pitch | Straight-run pitch/9.1 | Straight-run pitch/9.1 |
| Compatilizer | Oil/9.1 are extracted in solvent treatment out | Oil/9.1 are extracted in solvent treatment out |
| The graft reaction auxiliary agent | MALEIC ANHYDRIDE/9.1 | MALEIC ANHYDRIDE/9.1 |
| Melt temperature, ℃ | 165 | 165 |
| Modifying asphalt composition/weight % | ||
| Pitch | Straight-run pitch/94.0 | Straight-run pitch/94.0 |
| Modified master or properties-correcting agent | D m/6.0 | E m/6.0 |
| The modifying asphalt preparation time, minute | 60 | 60 |
| Modifying asphalt character | ||
| Penetration degree (25 ℃), 1/10 millimeter | 57 | 56 |
| Softening temperature (ring and ball method), ℃ | 68 | 68 |
| Ductility (5 ℃), centimetre | 28 | 32 |
| The segregation softening temperature is poor, ℃ | 4.2 | 4.5 |
Claims (19)
1, a kind of graft type asphalt modification masterbatch, it is characterized in that this masterbatch consists of the polymer modifiers of 65～95 heavy %, 0.5～30 heavy % pitches, 0.5～30 heavy % compatilizers, 4～12 heavy % graft reaction auxiliary agents, wherein said polymer modifiers is vinylbenzene/conjugated diolefin polymer and/or polyolefin polymer, described compatilizer is to be selected from by petroleum fractions, coal tar fraction, catalytically cracked oil, deasphalted oil, oil is extracted in solvent treatment out, the tar of preparing ethylene by steam cracking, Yatall MA, contain sour Yatall MA, naphthenic oil, the mixture of one or more in this group material that white oil and ester constitute, described graft reaction auxiliary agent is to be selected from by organic ethylenic unsaturation alkylene dicarboxylate, organic unsaturated olefin carboxylicesters, the mixture of one or more in this group material that organic unsaturated olefin carboxylic acid anhydride constitutes.
2,, it is characterized in that described vinylbenzene/conjugated diolefin polymer is meant conjugated diolefine diblock polymer and three inlay section thermal plastic elastic bodies that contain different vinylbenzene ratios according to the graft type asphalt modification masterbatch of claim 1.
3,, it is characterized in that described polyolefin polymer is polyethylene and/or ethene-acetic acid-ethylene copolymer according to the graft type asphalt modification masterbatch of claim 1.
4,, it is characterized in that described pitch is to be selected from this group of being made of petroleum pitch, coal-tar pitch and rock asphalt one or more mixture in material according to the graft type asphalt modification masterbatch of claim 1.
5,, it is characterized in that described petroleum pitch is to be selected from this group of being made of straight-run pitch, solvent deoiling pitch, oxidized bitumen, mediation pitch one or more mixture in material according to the graft type asphalt modification masterbatch of claim 4.
6,, it is characterized in that described graft reaction auxiliary agent is to be selected from this group of being made of methacrylic acid, Jia Jibingxisuanyizhi, MALEIC ANHYDRIDE one or more mixture in material according to the graft type asphalt modification masterbatch of claim 1.
7, a kind of graft type asphalt modification master batch method for preparing claim 1, it is characterized in that this method comprises: earlier with 65～95 heavy % polymer modifiers, 0.5～30 heavy % compatilizer, 4～12 heavy % graft reaction auxiliary agent uniform mixing, the melt temperature of controlling mixture is then extruded on twin screw extruder, granulation between 80～200 ℃.
8,, it is characterized in that described melt temperature is 100～180 ℃ according to the method for claim 7.
9,, it is characterized in that described polymer modifiers is vinylbenzene/conjugated diolefin polymer and/or polyolefin polymer according to the method for claim 7.
10,, it is characterized in that described vinylbenzene/conjugated diolefin polymer is meant conjugated diolefine diblock polymer and three inlay section thermal plastic elastic bodies that contain different vinylbenzene ratios according to the method for claim 9.
11,, it is characterized in that described polyolefin polymer is polyethylene and/or ethene-acetic acid-ethylene copolymer according to the method for claim 10.
12,, it is characterized in that described pitch is to be selected from this group of being made of petroleum pitch, coal-tar pitch and rock asphalt one or more mixture in material according to the method for claim 7.
13,, it is characterized in that described petroleum pitch is to be selected from this group of being made of straight-run pitch, solvent deoiling pitch, oxidized bitumen, mediation pitch one or more mixture in material according to the method for claim 12.
14, according to the method for claim 7, it is characterized in that described compatilizer be selected from by petroleum fractions, coal tar fraction, catalytically cracked oil, deasphalted oil, solvent treatment extract out oil, preparing ethylene by steam cracking tar, Yatall MA, contain one or more the mixture in this group material that sour Yatall MA, naphthenic oil, white oil and ester constitute.
15,, it is characterized in that described graft reaction auxiliary agent is to be selected from this group of being made of organic ethylenic unsaturation alkylene dicarboxylate, organic unsaturated olefin carboxylicesters, organic unsaturated olefin carboxylic acid anhydride one or more mixture in material according to the method for claim 7.
16,, it is characterized in that described graft reaction auxiliary agent is to be selected from this group of being made of methacrylic acid, Jia Jibingxisuanyizhi, MALEIC ANHYDRIDE one or more mixture in material according to the method for claim 15.
17, a kind of method for preparing modifying asphalt by the described graft type asphalt modification of claim 1 masterbatch, it is characterized in that the pitch of 85～98 heavy % is heated to 100～220 ℃, add the above-mentioned graft type asphalt modification masterbatch of 2～15 heavy % and stir and obtained modifying asphalt in 30～80 minutes.
18,, it is characterized in that described pitch is to be selected from this group of being made of petroleum pitch, coal-tar pitch and rock asphalt one or more mixture in material according to the method for claim 17.
19,, it is characterized in that described petroleum pitch is to be selected from this group of being made of straight-run pitch, solvent deoiling pitch, oxidized bitumen, mediation pitch one or more mixture in material according to the method for claim 18.
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| CN 200310122457 CN1281677C (en) | 2003-12-25 | 2003-12-25 | Grafting type asphalt modified masterbatch and method for preparation |
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| CN 200310122457 CN1281677C (en) | 2003-12-25 | 2003-12-25 | Grafting type asphalt modified masterbatch and method for preparation |
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| CN1281677C true CN1281677C (en) | 2006-10-25 |
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| FR2919294B1 (en) * | 2007-07-24 | 2012-11-16 | Total France | GRAFT POLYMER AND THERMOREVERSIBLE CROSSLINKING BITUMEN COMPOSITION COMPRISING SAID GRAFTED POLYMER. |
| CN101759894A (en) * | 2008-12-23 | 2010-06-30 | 刘鹰 | Modified polyethylene additive master batch for road asphalt and preparation method thereof |
| CN102952407B (en) * | 2011-08-30 | 2015-05-20 | 中国石油化工股份有限公司 | High-heat-storage-stability MBS (methyl methacrylate-butadiene-styrene)-asphalt composition and preparation method thereof |
| CN118165456A (en) * | 2024-04-03 | 2024-06-11 | 吉林市铭元科技有限公司 | EVA copolymer charring agent and preparation method and application thereof |
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