Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/67—Unsaturated compounds having active hydrogen
  • C08G18/69—Polymers of conjugated dienes
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/40—High-molecular-weight compounds
  • C08G18/48—Polyethers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
  • C08G18/72—Polyisocyanates or polyisothiocyanates
  • C08G18/73—Polyisocyanates or polyisothiocyanates acyclic
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
  • C08G18/72—Polyisocyanates or polyisothiocyanates
  • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
  • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
  • C08G18/758—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing two or more cycloaliphatic rings
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
  • C08G18/72—Polyisocyanates or polyisothiocyanates
  • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
  • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
  • C08G18/72—Polyisocyanates or polyisothiocyanates
  • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
  • C08G18/78—Nitrogen
  • C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L95/00—Compositions of bituminous materials, e.g. asphalt, tar, pitch

Definitions

• Polyurethane modifier for asphalt modified asphalt using the same, and use thereof
• the present invention relates to a modifier for asphalt, and more particularly to a polyurethane modifier which forms a polyurethane structure with a matrix asphalt by a chemical reaction method using an isocyanate material to improve the use properties of the matrix asphalt.
• Road asphalt modification methods are divided into physical modification and chemical modification.
• Physical modification methods include adding polyethylene (PE), polypropylene (PP), polyvinyl chloride (PVC), and polystyrene (PS).
• a plastic modifier such as ethylene-vinyl acetate copolymer (EVA), and a rubber modifier such as styrene-butadiene-styrene (SBS), styrene-butadiene rubber (SBR), or neoprene (CR).
• SBS physical modifiers have become the most commonly used asphalt modifiers due to their good modification effect, good applicability to asphalt, and moderate price.
• Cida patent application CN 101165102A discloses a asphalt physical modifier for traffic anti-rutting, which comprises a thermoplastic vinyl aromatic hydrocarbon-conjugated diene block copolymer (SBS type), polyolefin and lignocellulose. .
• the modifier can improve the high temperature performance, rutting resistance, low temperature cracking resistance of the modified asphalt, and the modified asphalt has good storage stability.
• U.S. Patent No. 5,339,811 discloses a sulfonation neutralization technique using SBS and matrix asphalt to improve the compatibility of SBS with matrix asphalt, but due to the presence of sulfonation and neutralization processes, the production process is complicated and the equipment is easily corroded. problem.
• the chemical modification method includes the addition of a two-component epoxy modifier, a styrene chemical modifier, a polyurethane prepolymer modifier, a rosin-modified phenolic resin modifier, and an acrylate polymer modifier.
• Chemical modifiers for road asphalt have limited their large-scale applications due to their modification effects or cost issues.
• the price of epoxy modifier is several times higher than that of current SBS resin, and it is only used in limited occasions such as bridge decks, and its performance cannot meet the requirements of road asphalt in high temperature or low temperature environment.
• Chinese patent application CN 101074322 A discloses an asphalt modifier and a bitumen composition containing a metal compound and a benzene ring-containing peroxide and a resinous substance.
• the modifier can effectively improve the penetration of the asphalt without reducing the properties such as ductility.
• Japanese Patent Application Laid-Open No. Hei 2-302425 discloses an asphalt modified with a polyepoxy compound and a specific modified polyamine compound.
• the modified asphalt is subjected to three-dimensional cross-linking of the modifier, so that the temperature sensitivity of the modified matrix asphalt is remarkably improved, the fluidity and the abrasion resistance are satisfied, and the service life of the pavement is prolonged.
• U.S. Patent No. 6,743,838 B2 discloses an asphalt modifier modified by reactive polymeric epoxy and enhanced by a glycidylated ethylene copolymer which is reactive with the active constituents of the asphalt to form a stable Highly flexible modified asphalt.
• Japanese Patent Application Laid-Open No. 62-50363 is a patent application for a polyurethane chemical modifier for road asphalt.
• the application adds a polyurethane prepolymer prepared by reacting a hydroxyl group-containing polybutadiene polyol and a polyisocyanate into a road matrix asphalt as a chemical modifier, and then adds a rubber latex which is physically modified, so the patent application It is reported that a hybrid modifier should be used together with a polyurethane chemical modifier and a rubber latex physical modifier. This patent application reports the addition of matrix leaching to the 60/80 straight-run bitumen.
• the softening point of the main index increases only 7.1 °C, and the physical modification with SBS is adopted.
• the agent increases the softening point of the asphalt by about 20 °C, and the modifier has no obvious improvement on the penetration of the matrix asphalt and the low temperature performance index, that is, the road asphalt modified by the modifier cannot It meets the requirements for road performance and the service life of roads under high temperature, hot or low temperature, severe cold weather, and its use range is limited.
• the modifier since the modifier must contain rubber latex, the viscosity is high, making it difficult to mix with the asphalt.
• the technical problem to be solved by the present invention is to provide a polyurethane modifier for asphalt modification, especially road asphalt modification, so that the asphalt composition added with the modifier of the invention can significantly improve the softening point relative to the matrix asphalt. , reduce penetration and improve low temperature performance.
• the modifier can meet the requirements of paved asphalt paved under different external temperature environments, prolong the service life of the road, simplify the processing process and reduce energy consumption.
• the present invention provides a polyurethane modifier for road asphalt, the components thereof comprising a prepolymer or a polymer of a polyisocyanate or an NCO terminal thereof, a compound having a terminal hydroxyl group or/and a terminal amino group, and an organic polyurethane.
• the catalyst or the like can form a component of the polyurethane structure, and other property adjusting components added according to actual needs.
• the modifier can improve the colloidal structure of the asphalt and greatly improve the heat resistance, temperature sensitivity and low temperature performance of the matrix asphalt. At the same time, the modifier is mixed with the matrix asphalt. The process is simple and the processing temperature is low, thus reducing energy consumption.
• the present invention provides a polyurethane modifier for asphalt comprising 20 to 70 parts by weight of a polyisocyanate or a NCO terminal prepolymer or polymer thereof, and 5 to 50 parts by weight a terminal hydroxyl group or/and a terminal amino group compound, 0.01 to 3 parts by weight of an organic polyurethane catalyst, 0 to 15 parts by weight of an organic interface agent, 0 to 40 parts by weight of a C 4 to C 45 polybasic acid or/and an acid anhydride.
• the polyurethane modifier for asphalt of the present invention comprises 25 to 60 parts by weight of a polyisocyanate or a NCO terminal prepolymer or polymer thereof, and 10 to 40 parts by weight of a compound having a terminal hydroxyl group or/and a terminal amino group, 0.01 to 2 parts by weight (more preferably 0.03 to 1.5 parts by weight) of the organic polyurethane catalyst, 0.1 to 10 parts by weight (more preferably 0.5 to 5) of the organic interface agent, and 1 to 35 parts by weight (more preferably 1.2 to 33 parts by weight) C 4 ⁇ C 45 polyacid or / and anhydride.
• the modifier of the present invention the polyisocyanate or its NCO terminal prepolymer or multimer NCO group relative to the terminal hydroxyl group or / and terminal amino group containing compound + organic interface agent +
• the terminal hydroxyl group-containing and/or terminal amino group-containing compound of the present invention may have two to three active hydrogens (ie, two to three hydroxyl groups) when it contains a terminal hydroxyl group, and if the compound contains a primary amino group, One primary amino group has two active hydrogens; the organic interface agent can have one active hydrogen; one of the polycarboxylic acids has one active hydrogen, and one of the polybasic anhydrides can be visualized Either polymerized from polyisocyanate and active hydrogen-containing oligomer, or polymerized from polyisocyanate.
• polyisocyanate examples may be selected from the group consisting of toluene diisocyanate (TDI), diphenylformamidine diisocyanate (MDI), dicyclohexylformamidine diisocyanate, hexamethylene diisocyanate (HDI), naphthalene diisocyanate, and poly Asia.
• TDI toluene diisocyanate
• MDI diphenylformamidine diisocyanate
• HDI hexamethylene diisocyanate
• naphthalene diisocyanate and poly Asia.
• methyl polyphenyl isocyanate In general, when two or more types are used, they are combined in any ratio.
• Toluene diisocyanate (TDI), diphenylformamidine diisocyanate (MDI) polymethylene polyphenyl isocyanate.
• the active hydrogen-containing oligomer may be a polyol oligomer.
• the active hydrogen-containing oligomer may be selected from the group consisting of polyoxypropylene polyols and polyoxypropylene-ethylene oxide copolyether polyols, polycaprolactone polyols, polymer polyols, polyolefin polyols (eg, polybutadiene binary) Any combination of one or more of an alcohol), a vegetable oil polyol, a polytetrahydrofuran polyol, and a polytetrahydrofuran-propylene oxide copolyether polyol.
• a polyoxypropylene-ethylene oxide copolyether polyol Preferably, a polyoxypropylene-ethylene oxide copolyether polyol, a polymer polyol, a polyolefin polyol, a vegetable oil polyol or a polytetrahydrofuran-propylene oxide copolyether polyol.
• the vegetable oil polyol referred to herein means soybean oil polyol, palm oil polyol or castor oil polyol. Soybean oil polyols are preferred.
• the polymer polyol referred to herein is preferably Aral 24-32 or Aral 1366 from Bayer.
• the weight average molecular weight of the active hydrogen-containing oligomer is generally in the range of from 300 to 10,000, preferably in the range of from 400 to 8,000, more preferably in the range of from 500 to 6,000.
• polyisocyanate multimer may be various TDI trimers, HDI trimers, and the like.
• the multimeric isocyanate is a TDI trimer.
• the terminal hydroxyl group means, in most cases, a primary hydroxyl group and/or a secondary hydroxyl group; the terminal amino group means a primary amino group and/or a secondary amino group.
• Examples of the compound having a terminal hydroxyl group or/and a terminal amino group of the present invention may be selected from the group consisting of 1,4-butanediol, glycerin, 3,5-diethyltoluenediamine, diethylene glycol, 1,2-propanediol, and the like.
• the polyoxypropylene polyol, the polymer polyol, the polyolefin polyol, the vegetable oil polyol, and the polytetrahydrofuran polyol have a weight average molecular weight of 400 to 6000, respectively.
• the vegetable oil polyol referred to herein may also be a soybean oil polyol, a palm oil polyol or a castor oil polyol. Soybean oil polyols are preferred. Polymer polyols are also preferably used in Bayer's Arol 24-32 or Aral 1366.
• the hydroxyl-containing or/and terminal amino-containing compound may be the same as the active hydrogen-containing oligomer used to prepare the polyisocyanate or its NCO terminal prepolymer or multimer.
• the same polymer polyol can be used as the compound having a terminal hydroxyl group or/and a terminal amino group and the active hydrogen-containing oligomer.
• the organic polyurethane catalyst of the present invention is a conventional catalyst for catalyzing a polyurethane reaction, and may be selected from one or two or more of a tertiary amine catalyst and an organometallic catalyst.
• the tertiary amine catalyst is, for example, diethylenediamine.
• the organometallic catalyst may be a monovalent C 2 -C 2Q mercaptocarboxylic acid metal salt, wherein the metal is selected from one or two or more of lead, tin, zinc, cerium, and zirconium.
• the organometallic catalyst is selected from one or two or more of the above-mentioned metal octoate, isooctanoate, acetate and laurate.
• the asphalt modifier may also include an organic interface agent to further improve the compatibility of the modifier with asphalt or to improve workability, if desired.
• the organic interface agent can be those conventionally used in polyurethane materials.
• it may be a silicon germanium coupling agent such as selected from the group consisting of aminopropyltrimethoxysilane, aminopropyltriethoxysilane, glycidoxypropyltrimethoxysilane and phenylaminomethyltriethyl One or two or more of oxysilanes.
• the asphalt modifier may further include a low molecular weight polybasic acid or/and an acid anhydride for adjusting acidity and alkalinity, specifically c 4 ⁇ c 45 polybasic acid. Or / and anhydride.
• the polybasic acid or/and anhydride of the present invention may be an aliphatic or aromatic polybasic acid or/and an acid anhydride. Preferably, it may be selected from the group consisting of c 4 ⁇ c 1Q dimercaptocarboxylic acid, o-/p-phenylene di-C 8 -decyl acid, C 4 ⁇ d.
• Specific examples may be: adipic acid, Azelaic acid, phthalic acid, etc.
• the polyurethane modifier of the present invention can also be used with at least one other asphalt modifier to utilize the characteristics of each modifier to achieve the desired asphalt properties, depending on the needs of use.
• Other asphalt modifiers can be any of the existing asphalt modifiers, including various physical or chemical asphalt modifiers such as SBS, epoxy modifiers, and the like.
• the ratio of the polyurethane modifier of the invention to other asphalt modifiers can be based on the performance of the modified asphalt The actual needs need to be determined.
• the present invention further provides a polyurethane modified asphalt to which the above asphalt modifier is added, particularly a modified road asphalt, and a place where the performance of the asphalt is higher than that of the ordinary matrix asphalt.
• the modified asphalt of the present invention contains 3 to 50% by weight, preferably 3.5 to 30% by weight, more preferably 4 to 15% by weight, most preferably 5 to 8% by weight based on the weight of the base asphalt.
• the modification mechanism of the modifier of the present invention to the matrix asphalt is as follows: the polyisocyanate reacts with the active hydrogen-containing oligomer, or the polyisocyanate itself polymerizes into a polyisocyanate and a prepolymer or multimer thereof, the polyisocyanate and The prepolymer or polymer contains a capping of an isocyanate reactive group.
• the component is added to the asphalt, it reacts with the chemically active structure contained in the asphalt composition, and the added terminal hydroxyl group-containing and/or terminal amino compound, organic polyurethane catalyst participates in the polyisocyanate and its prepolymer. Or the reaction of a multimeric component.
• the performance requirements of the modified asphalt may be further added to the modifier of the present invention.
• an organic interface agent ie, stone
• a low molecular polybasic acid/anhydride may be further added to the modifier of the present invention.
• one or more of the other auxiliaries commonly used in the above polyurethane materials may be further added to the modifier of the present invention.
• the asphalt modified with the asphalt modifier of the present invention has greatly improved heat resistance (ie, the softening point can be increased to 70 ° C or higher), and the temperature sensitivity is greatly reduced (ie, the penetration is reduced to 40 mm or less), and Improved low temperature performance (ie, ductility above 20 cm), which is suitable for road performance requirements in various high temperature or low temperature severe weather conditions and extends the service life of the road.
• the present invention further provides the use of the above modified asphalt.
• the modified asphalt obtained by using the polyurethane modifier of the invention can be used for laying, repairing, waterproofing and grouting of asphalt roads in harsh weather environments such as high temperature and low temperature, as well as runways and outdoor sites similar to asphalt roads. Ground laying, repair, waterproofing and grouting.
• the prepolymer or multipolymer component of the polyisocyanate or its NCO terminal may be directly or indirectly chemically reacted with the active hydrogen contained in the matrix pitch, the terminal hydroxyl group or/and the terminal amino compound, thereby
• the colloidal structure of the asphalt is improved, and the matrix asphalt obtained in the modified asphalt has good compatibility with the modifier, good storage stability, and stable and long-lasting modification effect.
• the polyurethane modifier of the present invention has a significant modification effect and a significant improvement in the performance of the matrix asphalt.
• the present invention does not need to add a rubber latex which is physically modified after adding a polyurethane modifier to the matrix asphalt, and is added to the overall modifier.
• the amount is significantly lower than the amount of addition reported in Japanese Patent Application Laid-Open No. 62-50363, a good modification effect can still be obtained.
• the heat resistance index ie, the softening point
• the temperature sensitivity index ie, the penetration degree
• the low temperature performance index ie, ductility
• the modified asphalt obtained by adding 3 to 40% by weight, preferably 4 to 30% by weight (based on the base asphalt) of the modifier of the present invention to the matrix pitch has a softening point of more than 70 ° C, which is equal to or lower than 40 mm penetration and ductility greater than 20 cm.
• the temperature of the modifier mixed with the matrix asphalt (about 130 °C) is much lower than the temperature when the SBS modifier is mixed with the matrix asphalt (about 180 °C), thereby reducing energy consumption and achieving low carbon environmental protection.
• the raw material cost of the polyurethane modifier is relatively low, between 20,000 and 50,000 yuan/ton, and the raw material cost of the modified asphalt produced is 0.6 to 0.8 million yuan/ Between tons, it is far lower than the price of tens of thousands of tons of modified asphalt produced by other chemical modifiers.
• Example 1 is intended to better illustrate the effects of the asphalt urethane modifier of the present invention, but the modifiers of the present invention are not limited to the examples.
• Example 1 is intended to better illustrate the effects of the asphalt urethane modifier of the present invention, but the modifiers of the present invention are not limited to the examples.
• the formulation of the polyurethane modifier is as follows: 60 parts by weight of diphenylformamidine diisocyanate is reacted with soybean oil polyol (purchased from USSC, soyoyl F672) (the reaction is stirred at 70-80 ° C for 1-3 hours, and the following is carried out
• the NCO terminal prepolymer (viscosity below 5000 m-Pa-s) obtained in Examples 2 to 4), 35 parts by weight of polymer polyol having a weight average molecular weight of 3,500 (purchased from Bayer Aral 24) -32), 0.8 parts by weight of bismuth octylate, 3 parts by weight of aminopropyltrimethoxysilane, 1.2 parts by weight of sebacic acid, wherein the NCO group of the NCO terminal prepolymer is relative to the polymer polyol + Hydroxy + amino + carboxylic acid group in aminopropyltrimethoxysilane + sebacic acid has an active hydrogen excess of 220 mol
• the softening point of the modified asphalt was determined to be 63.7 ° C, the penetration degree was 39 mm, the ductility was 18 cm, and the modified asphalt and aggregate were well wrapped, which can be used for laying and repairing the road surface layer and the middle layer. Filling the paddle.
• the formulation of the polyurethane modifier is as follows: 55 parts by weight of NCO formed by the reaction of diphenylformamidine diisocyanate with a polyoxyethylene-polyoxypropylene copolyether polyol having a weight average molecular weight of 5,500 (purchased from Tianjin Sankyo, DL5000) Terminal prepolymer, 1 part by weight of 1,4-butanediol, 15 parts by weight of polymer polyol (available from Bayer Corporation, Arol 24-32), 0.05 parts by weight of bismuth octoate, 3.95 parts by weight of benzene Aminomethyltriethoxysilane, 25 parts by weight of adipic acid, wherein the NCO group of the NCO terminal prepolymer is relative to 1,4-butanediol + aminomethyltrimethoxysilane + hexane The hydroxyl + amino + carboxylic acid group in the acid The excess of hydrogen is 335 mol%.
• the modifier and 70 straight-run road asphalt purchased from Qilu Petrochemical, Qilu brand AH 70
• dispersed and mixed at 135 ° C for 2 hours matured and cooled to After softening at room temperature, the softening point of the modified asphalt is 74.5 ° C, the penetration is 40 mm, and the ductility is 12 cm.
• the modified asphalt and aggregate are well wrapped and can be used for laying and repairing the asphalt runway or asphalt ground floor.
• the formulation of the polyurethane modifier is as follows: 35 parts by weight of a prepolymer of NCO terminal formed by reacting toluene diisocyanate with a polytetrahydrofuran-oxyalkylene copolyether having a weight average molecular weight of 1000 (purchased from Nippon Oil, Unisafe DCB-1000), 1 part by weight of trimethylolpropene, 12 parts by weight of polymer polyol (available from Bayer, Aral 24-32), 15 parts by weight of polyoxyethylene-polyoxypropylene copolyetheramine having a weight average molecular weight of 4000, 0.1 Parts by weight of bismuth octoate, 3.9 parts by weight of phenylaminomethyltriethoxysilane, 32 parts by weight of adipic acid, 1 part by weight of phthalic acid anhydride, wherein the NCO terminal of the NCO terminal prepolymer Compared to trimethylol propyl hydrazine + Arol 24-32 polymer
• the matrix asphalt, modifier and 70 straight run road asphalt (purchased from Ssangyong shares, Shuanglong brand re-delivery 70), Disperse and mix at 135 ° ⁇ for 2 hours.
• the softening point of the modified asphalt is 72.8 ° C
• the penetration is 29 mm
• the ductility is 17 cm
• the modified asphalt and aggregate are well wrapped. It can be used in asphalt runway. Or laying and repairing the ground floor of the asphalt field.
• the polyurethane modifier formulation is as follows: 45 parts by weight of an NCO terminal formed by the reaction of diphenylformamidine diisocyanate with a hydroxyl group-containing polybutadiene having a weight average molecular weight of 4000 (purchased from Qilong Chemical, L-4000) Polymer, 20 parts by weight of trimethylolpropene, 22 parts by weight of hydroxyl terminated polybutadiene, 1 weight An amount of bismuth octoate, 10 parts by weight of aminopropyltrimethoxysilane, 2 parts by weight of sebacic acid, wherein the NCO group of the NCO terminated prepolymer is relative to the trimethylol propyl hydrazine + terminal hydroxyl group
• the hydroxyl + amino + carboxylic acid group in the polybutadiene + aminopropyltrimethoxysilane has an active hydrogen excess of 35 mol%.
• the modifier is mixed with the No. 70 straight-run road asphalt (purchased from Qilu Petrochemical, Qilu brand AH 70) at a concentration of 5 wt% of the matrix asphalt, and dispersed and mixed at 130 ° C for 2 hours, aged and cooled to After room temperature, the softening point is 78.9 ° C, the penetration is 38 mm, the ductility is 20 cm, and the modified asphalt and aggregate are well wrapped, which can be used for laying and waterproofing the road surface layer.
• No. 70 straight-run road asphalt purchased from Qilu Petrochemical, Qilu brand AH 70
• Example 5 The formulation of the polyurethane modifier was as follows: 21 parts by weight of polymerized MDI (purchased from Yantai Wanhua, PM400), 1 part by weight of triethanolamine, 11 parts by weight of Bayer's Aral 24-32 polymer polyol, 32 Polyethylene oxide-polyoxypropylene copolyetheramine (purchased from Nippon Oil, Unisafe DCB-4000) having a weight average molecular weight of 4000 and polytetrahydrofuran-oxyalkylene copolyether having a molecular weight of 1000 (purchased from Nippon Oil, Unisafe DCB-1000) 0.1 parts by weight of a tertiary amine catalyst diethylenediamine, 4.9 parts by weight of benzylaminotriethoxysilane, 30 parts by weight of adipic acid, wherein the NCO group of the polymerized MDI is relative to triethanolamine + Arol 24-32 polymer polyol + polyoxyethylene-polyoxypropylene copolyetheramine
• the modifier was mixed with the No. 70 straight-run road asphalt (purchased from Qilu Petrochemical, Qilu brand AH 70) at 135 °C for 2 hours, matured and cooled to 9% by weight of the matrix asphalt.
• the modified asphalt After softening, the modified asphalt has a softening point of 69.1 °C, a penetration of 29 mm and a ductility of 10 cm.
• the modified asphalt and aggregate are well wrapped and can be used for laying and repairing asphalt pavement or asphalt pavement. Comparative example 1
• Preparation of SBS modified asphalt Preheat the No. 70 straight-run road asphalt (purchased from Qilu Petrochemical, Qilu AH 70) to 180 °C, then add about 5% of SBS white granular rubber compound (Yanshan Petrochemical, Daochang 4303), accompanied by high-speed shear Shearing and agitation of the cutting machine (MJ20 high-speed shearing machine of Wuxi Huatong Technology Group) makes SBS more soluble in matrix asphalt after being sheared. After high-speed stirring for 1-2 hours, the material is discharged to obtain SBS modified asphalt.
• SBS white granular rubber compound Yanshan Petrochemical, Daochang 4303
• SBS modified asphalt Preparation of SBS modified asphalt.
• a matrix asphalt 70 straight-run road asphalt purchased from Qilu Petrochemical, Qilu AH 70
• SBS Yanshan Petrochemical, Daochang 4303
• the shear dispersion of BWS modified asphalt colloid mill of De Machinery Co., Ltd. makes the dispersed SBS better dissolve in the matrix asphalt, and is discharged after 0.5-1 hour to obtain SBS modified asphalt.
• the softening point of the SBS modified asphalt prepared by the polyurethane modified asphalt prepared in Example 4, the straight-run road asphalt No. 70 (purchased from Qilu Petrochemical, Qilu brand AH 70) and Comparative Example 1 at 25 ° C was measured.
• the penetration and the ductility at 5 °C, the results are compared as shown in the table below.
• the test methods for softening point, penetration and ductility of asphalt are GB/T4507-1999, GB/T4509-1998, GB/T4508-1999, respectively.
• the polyurethane modified asphalt sample has a higher softening point at a lower processing temperature, and is significantly higher than the matrix asphalt, and has higher temperature resistance; the polyurethane modified asphalt sample has a lower needle.
• the degree of penetration is significantly lower than that of the matrix asphalt, and the temperature sensitivity is better.
• the polyurethane modified asphalt sample has higher ductility, is significantly higher than the matrix asphalt, and has excellent low temperature resistance.

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