CN106700578B - A kind of high additive high resiliency pitch Special modifier and preparation method thereof - Google Patents

A kind of high additive high resiliency pitch Special modifier and preparation method thereof Download PDF

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CN106700578B
CN106700578B CN201710025768.8A CN201710025768A CN106700578B CN 106700578 B CN106700578 B CN 106700578B CN 201710025768 A CN201710025768 A CN 201710025768A CN 106700578 B CN106700578 B CN 106700578B
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styrene
block copolymer
butadiene block
butadiene
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CN106700578A (en
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卞嘉祺
杨维成
罗勇
柴冲冲
段敏伟
乔拟春
曹亚东
林家祥
王静
李雪坤
陈国顺
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SHANGHAI URBAN CONSTRUCTION RILI SPECIAL ASPHALT CO., LTD.
Shanghai Research Institute of Chemical Industry SRICI
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SHANGHAI URBAN CONSTRUCTION RILI SPECIAL ASPHALT Co Ltd
Shanghai Research Institute of Chemical Industry SRICI
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    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend

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  • Engineering & Computer Science (AREA)
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  • Polymers & Plastics (AREA)
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  • Processes Of Treating Macromolecular Substances (AREA)
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Abstract

The invention belongs to asphalt modifier technical fields, it is related to high additive high resiliency pitch Special modifier and preparation method thereof, modifying agent is made of 65~90 parts by weight of main body modifying agent, 0.1~36 parts by weight of viscosity modifier, 0.5~30 parts by weight of age resister and 0.2~37 parts by weight of stabilizer.It when preparation, by main body modifying agent, viscosity modifier, age resister and stabilizer at -10~5 DEG C, is crushed with pulverizer, screens out 60~150 mesh powders with sieve, obtain high additive high resiliency pitch Special modifier.Compared with prior art, the method can significantly improve the high-temperature stability of pitch, low temperature anti-cracking performance, anti-aging property and elastic recovery properties, and are able to solve existing Styrene-Butadiene-Styrene Block Copolymer modifying agent in high additive amount the problems such as processing difficulties, long processing time.

Description

A kind of high additive high resiliency pitch Special modifier and preparation method thereof
Technical field
The present invention relates to asphalt modifier technical fields, and in particular to high additive, high resiliency pitch Special modifier and its The material proportion and preparation method of modified asphalt composite.
Background technique
In recent years, with Chinese society, economy and Highway Cause build fast development, Longspan Bridge, especially greatly Development of the type across river Oversea bridge is rapid.And in Large Span Bridges, the application range of steel bridge is especially extensive.But by Steel bridge has the influence of large curved and local deformation characteristics, and Steel Bridge Deck is mated formation vulnerable to destruction, therefore paving steel bridge deck is used Modified pitch require can be significantly bent under low temperature, deformation compliance and the characteristics of cracking resistance.
Pitch has certain waterproofness and anticorrosive property as road pavement material, and country's plain asphalt is as road at present Pipeline material is generally mixed with aggregate to be used as asphalt.There are wearabilities, impact resistance for such plain asphalt mixture The shortcomings that property, bending resistance and poor performance at low temperatures.In order to solve this problem, SBS (styrene-fourth two is added in pitch Alkene block copolymer) its temperature sensitivity can be reduced and improve wearability, impact resistance, bending resistance.In addition to this, moreover it is possible to Increase the adhesiveness between pitch and aggregate structure, improves the service life of road.However for rigid bridge face, common A series of problems, such as SBS performance of modified bitumen is far from satisfying its special warp architecture, and slight crack easily occurs for road surface.
High additive SBS modified pitch, which compares common low-dosage modified pitch, has excellent viscoplasticity, has again under low temperature Significantly bendability is very suitable for mating formation for steel bridge road surface.However, domestic conventional SBS modified material is applied to production at present It is poor with the intermiscibility of pitch when higher there are SBS modifier volume during high adulteration modified pitch, long processing time, very Excessively high and lead to not to continue the serious problems of processing to there is high-temperature viscosity, the modified pitch that only a few can complete processing has again Storage stability it is very poor, the disadvantages of performance is unable to satisfy high-elastic asphalt standard.
Summary of the invention
It is an object of the present invention to overcome the above-mentioned drawbacks of the prior art and provide a kind of preparation processes simply, Modifying agent additive amount is big, the high additive high resiliency pitch Special modifier haveing excellent performance and preparation method thereof.
The purpose of the present invention can be achieved through the following technical solutions: a kind of high additive high resiliency pitch is dedicated modified Agent, which is characterized in that the component including consisting of and parts by weight content:
The main body modifying agent is formed by following each component by mass parts mixed preparing, is matched as follows:
The styrene-butadiene block copolymer is line style styrene-butadiene block copolymer, star-like benzene second Alkene-butadiene block copolymer, the styrene-butadiene block copolymer of graft modification and blocking modification-styrene-fourth two The composition of one or more of alkene block copolymer；The weight average molecular weight range of styrene-butadiene block copolymer exists Between 20000~350000g/mol.
The graft modification group that the styrene-butadiene block copolymer of the graft modification uses is selected from hydroxyl, carboxylic One of base, amino, sulfydryl, ester group, amide groups, sulfonic group, acrylic acid, methacrylic acid, cysteine and maleic anhydride Or it is several, the grafting rate of the styrene-butadiene block copolymer of graft modification is 0.1~70%；The blocking modification The blocking modification group of styrene-butadiene block copolymer is selected from hydroxyl, carboxyl, amino, sulfydryl, ester group, amide groups, sulfonic acid One or more of base, acrylic acid, methacrylic acid, cysteine and maleic anhydride, the styrene-butadiene of blocking modification The degree of functionality of block copolymer is 0.1~76%.
The grafted moiety is preferred: one or more of hydroxyl, carboxyl, maleic anhydride, amino, the benzene of graft modification The grafting rate of ethylene-butadiene block copolymer preferably 25~45%；The blocking modification Styrene-Butadiene block copolymerization Object, blocking modification group are preferred: one or more of carboxyl, sulfydryl, acrylic acid, ester group, styrene-fourth of blocking modification The degree of functionality of diene block copolymer preferably 16~31%.
The Polystyrene-Butadiene Copolymer is the Polystyrene-Butadiene Copolymer of graft modification；Grafted moiety Selected from one or more of styrene, hydroxyl, carboxyl, amino, sulfydryl, amide groups, acrylic acid；
The ethylene-vinyl acetate copolymer is the ethylene-vinyl acetate copolymer of graft modification, grafted moiety Selected from hydroxyl, carboxyl, amino, sulfydryl, ester group, amide groups, sulfonic group, acrylic acid, methacrylic acid, cysteine and maleic acid One or more of acid anhydride；
The styrene-isoprene block copolymer is the styrene-isoprene block copolymer of graft modification, Grafted moiety is selected from hydroxyl, carboxyl, amino, sulfydryl, ester group, amide groups, sulfonic group, acrylic acid, methacrylic acid, cysteine One or more of with maleic anhydride.
The viscosity modifier be selected from polyethylene wax, oxidized polyethylene wax, hydrogenated rosin, terpene resin, sodium pyrophosphate, One or more of sodium cellulose glycolate, ammonium polyacrylate, Sodium Polyacrylate, hydroxyethyl cellulose and aluminum magnesium silicate are mixed It closes.
The age resister is selected from 2,6 di tert butyl 4 methyl phenol, styrenated phenol, 4,4 '-dihydroxy connection Benzene, 2,5 di tert butyl hydroquinone, 2-mercaptobenzimidazole, zinc salt of 2 mercaptobenzimidazole, N- cyclohexyl are to ethoxybenzene The mixing of one or more of amine.
The stabilizer is selected from aliphatic hydrocarbon resin, aromatic hydrocarbon resin, cycloalkanes hydrocarbon resin, sodium sulfonate, odium stearate, tristearin Sour calcium, zinc stearate, zinc oxide, calcium oxide, methylene dinaphthalene sulfonate, sodium methylene diisopropyl naphthalene sulphonate sulfonate, alkylbenzene oxygen Ethyl polyethylene-oxide sodium sulphate, polyvinyl alcohol, polyacrylic acid, sodium laurate, N- cyclohexyl para toluene sulfonamide, N- ethyl are to first The mixing of one or more of benzsulfamide, p-methyl benzenesulfonic acid o-cresol ester.
A kind of preparation method of high additive high resiliency pitch Special modifier, by main body modifying agent, viscosity modifier, anti-ageing Agent and stabilizer are crushed at -10~5 DEG C with pulverizer, are screened out 60~150 mesh powders with sieve, are obtained high additive High resiliency pitch Special modifier.
It is above-mentioned high additive, high resiliency pitch Special modifier production modified pitch method is as follows: by matrix pitch, modification Agent, aromatic naphtha are added in the matched blend tank of high-speed shearing machine, start high-speed shearing machine, and shearing to modifying agent is evenly distributed on base In matter pitch, turn off shearing equipment, be cooled to room temperature, obtains modified pitch.
Compared with prior art, the invention has the following advantages that
(1) the pitch Special modifier made of the present invention can relatively rapid dispersion under conditions of being greater than 10% volume In pitch, solve the problems, such as that domestic conventional SBS modified dose is difficult to high additive, high-elastic asphalt, process time is reduced 50% or more.
(2) using the Special modifier preparation 10% adulteration modified pitch with common 10% adulteration modified pitch phase Than high-temperature stability improves 10%, low temperature anti-cracking performance and improves 30%, anti-aging property raising 25%, elastic recovery capability Improve 36%.
(3) simple production process of the present invention, economy and use value are good, have preferable promotion prospect.
Specific embodiment
It elaborates below to the embodiment of the present invention, the present embodiment carries out under the premise of the technical scheme of the present invention Implement, the detailed implementation method and specific operation process are given, but protection scope of the present invention is not limited to following implementation Example.
In following each embodiments, each test is according to " highway engineering pitch and Asphalt Mixture Experiment regulation " (JTG E20-2011 it) carries out.The dosage unit of raw material is parts by weight unless otherwise specified in following embodiment:
Embodiment 1
1) successively by 65 parts of main body modifying agent, 15 portions of viscosity modifiers, 10 parts of age resisters and 10 parts of stabilizations at -10 DEG C Agent is added pulverizer and crushes, then is sieved to obtain high additive, high resiliency pitch Special modifier with 60 mesh sieve.
2) main body modifying agent includes: 68 parts of styrene-butadiene block copolymers, 9 parts of styrene-butadiene copolymerization Object, 11 parts of ethylene-vinyl acetate copolymers and 12 parts of styrene-iso pentane two floride block copolymer.
Wherein styrene-butadiene block copolymer includes: the Styrene-Butadiene block of 20 parts of sulfonic group graft modifications Copolymer, the styrene-butadiene block copolymer of 23 parts of methacrylic acid graft modifications, 31 parts of cysteine blocking modifications Styrene-butadiene block copolymer, the 15 parts of amides of styrene-butadiene block copolymer, 11 parts of sulfonic group blocking modifications The styrene-butadiene block copolymer of base blocking modification, used graft modification styrene-butadiene block copolymer connect Branch rate is 10%, and terminal groups modification styrene-butadiene block copolymer degree of functionality is 16%.
3) viscosity modifier includes: 36 parts of polyethylene waxes, 13 parts of hydrogenated rosins, 6 parts of terpene resins, 40 parts of hydroxylmethyl celluloses Plain sodium and 5 parts of Sodium Polyacrylates.
4) age resister includes: 47 parts of 2,6 di tert butyl 4 methyl phenol, 21 parts of 2-mercaptobenzimidazole and 32 The 4,4 '-dihydroxybiphenyls of part.
5) stabilizer includes: 16 parts of aliphatic hydrocarbon resins, 16 parts of aromatic hydrocarbon resins, 16 parts of cycloalkanes hydrocarbon resins, 29 parts of stearic acid Sodium, 3 parts of zinc oxide, 9 parts of polyvinyl alcohol, 11 parts of sodium laurates.
Embodiment 2
1) successively by 75 parts of main body modifying agent, 8 portions of viscosity modifiers, 6 parts of age resisters and 11 parts of stabilizers at -10 DEG C Pulverizer is added to crush, then is sieved to obtain high additive, high resiliency pitch Special modifier with 60 mesh sieve.
2) main body modifying agent includes: 68 parts of styrene-butadiene block copolymers, 11 parts of styrene-butadiene copolymerization Object, 6 parts of ethylene-vinyl acetate copolymers and 11 parts of styrene-iso pentane two floride block copolymer.
Wherein styrene-butadiene block copolymer includes: the Styrene-Butadiene block of 16 parts of hydroxyl base graft modifications The benzene second of copolymer, the styrene-butadiene block copolymer of 28 parts of carboxyl graft modifications, 19 parts of modified by maleic acid anhydride graft The modified styrene-butadiene block copolymer of alkene-butadiene block copolymer, 11 parts of carboxy blockings, 15 parts of propylene acid blockeds Modified styrene-butadiene block copolymer, 11 parts of ester terminated modifications styrene-butadiene block copolymer, made Graft modification styrene-butadiene block copolymer grafting rate is 10%, the copolymerization of terminal groups modification Styrene-Butadiene block Object degree of functionality is 16%.
3) viscosity modifier includes: 31 parts of oxidized polyethylene wax, 13 parts of hydrogenated rosins, 32 parts of sodium cellulose glycolates, 19 Part hydroxyethyl cellulose and 5 parts of aluminum magnesium silicates.
4) age resister includes: 18 parts of 2,6 di tert butyl 4 methyl phenol, 13 parts of 2,5- di-t-butyl are to benzene two Phenol, 22 parts of 2-mercaptobenzimidazole, 17 parts of zinc salt of 2 mercaptobenzimidazole and 32 parts of 4,4 '-dihydroxybiphenyls.
5) stabilizer includes: 7 parts of aliphatic hydrocarbon resins, 9 parts of aromatic hydrocarbon resins, 2 parts of cycloalkanes hydrocarbon resins, 43 parts of odium stearate, 1 Part zinc oxide, 19 parts of alkyl phenoxy polyethylene glycol oxide sodium sulphate, 9 parts of polyvinyl alcohol, 10 parts of sodium laurates.
Embodiment 3
1) successively by 90 parts of main body modifying agent, 6 portions of viscosity modifiers, 2 parts of age resisters and 2 parts of stabilizers at -10 DEG C Pulverizer is added to crush, then is sieved to obtain high additive, high resiliency pitch Special modifier with 60 mesh sieve.
2) main body modifying agent includes: 68 parts of styrene-butadiene block copolymers, 9 parts of styrene-butadiene copolymerization Object, 11 parts of ethylene-vinyl acetate copolymers and 12 parts of styrene-iso pentane two floride block copolymer.
Wherein styrene-butadiene block copolymer includes: 7 parts of acrylic graft-modified Styrene-Butadiene blocks Copolymer, the styrene-butadiene block copolymer of 9 parts of hydroxyl graft modifications, 28 parts of carboxyl graft modifications styrene-fourth two Alkene block copolymer, the styrene-butadiene block copolymer of 19 parts of modified by maleic acid anhydride graft, 11 parts of carboxy blockings are modified Styrene-butadiene block copolymer, the 11 parts of ester groups of styrene-butadiene block copolymer, 15 parts of acrylic acid blocking modifications The styrene-butadiene block copolymer of blocking modification, used graft modification styrene-butadiene block copolymer grafting Rate is 10%, and terminal groups modification styrene-butadiene block copolymer degree of functionality is 16%.
3) viscosity modifier includes: 31 parts of oxidized polyethylene wax, 13 parts of hydrogenated rosins, 32 parts of sodium cellulose glycolates, 19 Part hydroxyethyl cellulose and 5 parts of aluminum magnesium silicates.
4) age resister includes: 18 parts of 2,6 di tert butyl 4 methyl phenol, 13 parts of 2,5- di-t-butyl are to benzene two Phenol, 22 parts of 2-mercaptobenzimidazole, 17 parts of zinc salt of 2 mercaptobenzimidazole and 32 parts of 4,4 '-dihydroxybiphenyls.
5) stabilizer includes: 7 parts of aliphatic hydrocarbon resins, 9 parts of aromatic hydrocarbon resins, 2 parts of cycloalkanes hydrocarbon resins, 43 parts of odium stearate, 1 Part zinc oxide, 19 parts of alkyl phenoxy polyethylene glycol oxide sodium sulphate, 9 parts of polyvinyl alcohol, 10 parts of sodium laurates.
Embodiment 4
1) successively by 75 parts of main body modifying agent, 20 portions of viscosity modifiers, 2 parts of age resisters and 2 parts of stabilizers at -5 DEG C Pulverizer is added to crush, then is sieved to obtain high additive, high resiliency pitch Special modifier with 100 mesh sieve.
2) main body modifying agent includes: 81 parts of styrene-butadiene block copolymers, 6 parts of styrene-butadiene copolymerization Object, 7 parts of ethylene-vinyl acetate copolymers and 6 parts of styrene-iso pentane two floride block copolymer.
Wherein styrene-butadiene block copolymer includes: the Styrene-Butadiene block of 14 parts of hydroxyl graft modifications is total Polymers, the styrene-butadiene block copolymer of 21 parts of carboxyl graft modifications, 8 parts of methacrylic acid graft modifications styrene- The modified styrene-butadiene block copolymer of butadiene block copolymer, 40 parts of carboxy blockings, 17 parts of acrylic acid blocking modifications Styrene-butadiene block copolymer, used graft modification styrene-butadiene block copolymer grafting rate is 10%, terminal groups modification styrene-butadiene block copolymer degree of functionality is 16%.
3) viscosity modifier includes: 31 parts of oxidized polyethylene wax, 29 parts of polyethylene waxes, 2 parts of sodium pyrophosphates, 26 parts of methylols Sodium cellulosate, 7 parts of hydroxyethyl celluloses and 5 parts of aluminum magnesium silicates.
4) age resister includes: 14 parts of 2,6 di tert butyl 4 methyl phenol, 21 parts of 2,5- di-t-butyl are to benzene two Phenol, 22 parts of N- cyclohexyl p-ethoxyaniline, 17 parts of zinc salt of 2 mercaptobenzimidazole and 26 parts of 4,4 '-dihydroxy connection Benzene.
5) stabilizer includes: 7 parts of aliphatic hydrocarbon resins, 9 parts of aromatic hydrocarbon resins, 2 parts of cycloalkanes hydrocarbon resins, 43 parts of odium stearate, 1 Part zinc oxide, 19 parts of alkyl phenoxy polyethylene glycol oxide sodium sulphate, 9 parts of p-methyl benzenesulfonic acid o-cresol esters, 10 parts of sodium laurates.
Embodiment 5
1) successively by 75 parts of main body modifying agent, 17 portions of viscosity modifiers, 6 parts of age resisters and 2 parts of stabilizers at -5 DEG C Pulverizer is added to crush, then is sieved to obtain high additive, high resiliency pitch Special modifier with 100 mesh sieve.
2) main body modifying agent includes: 90 parts of styrene-butadiene block copolymers, 6 parts of styrene-butadiene copolymerization Object, 3 parts of ethylene-vinyl acetate copolymers and 1 part of styrene-iso pentane two floride block copolymer.
Wherein styrene-butadiene block copolymer includes: the Styrene-Butadiene block of 56 parts of hydroxyl graft modifications is total The modified styrene-butadiene block copolymer of polymers, 18 parts of carboxy blockings, 26 parts of hydroxy-end capped modifications styrene-fourth two Alkene block copolymer, used graft modification styrene-butadiene block copolymer grafting rate are 10%, terminal groups modification benzene second Alkene-butadiene block copolymer degree of functionality is 16%.
3) viscosity modifier includes: 3 parts of oxidized polyethylene wax, 7 parts of polyethylene waxes, 26 parts of sodium pyrophosphates, 34 parts of methylols Sodium cellulosate, 19 parts of hydroxyethyl celluloses and 11 parts of aluminum magnesium silicates.
4) age resister includes: 14 parts of 2,6 di tert butyl 4 methyl phenol, 21 parts of 2,5- di-t-butyl are to benzene two Phenol, 22 parts of N- cyclohexyl p-ethoxyaniline, 17 parts of zinc salt of 2 mercaptobenzimidazole and 26 parts of 4,4 '-dihydroxy connection Benzene.
5) stabilizer includes: 7 parts of aliphatic hydrocarbon resins, 9 parts of aromatic hydrocarbon resins, 2 parts of cycloalkanes hydrocarbon resins, 43 parts of odium stearate, 1 Part zinc oxide, 19 parts of alkyl phenoxy polyethylene glycol oxide sodium sulphate, 9 parts of p-methyl benzenesulfonic acid o-cresol esters, 10 parts of sodium laurates.
Embodiment 6
1) successively by 75 parts of main body modifying agent, 17 portions of viscosity modifiers, 6 parts of age resisters and 2 parts of stabilizers at -5 DEG C Pulverizer is added to crush, then is sieved to obtain high additive, high resiliency pitch Special modifier with 100 mesh sieve.
2) main body modifying agent includes: 90 parts of styrene-butadiene block copolymers, 8 parts of styrene-butadiene copolymerization Object, 1 part of ethylene-vinyl acetate copolymer and 1 part of styrene-iso pentane two floride block copolymer.
Wherein styrene-butadiene block copolymer includes: the Styrene-Butadiene block of 11 parts of ester group graft modifications is total Modified styrene-the fourth two of polymers, the styrene-butadiene block copolymer of 21 parts of hydroxyl graft modifications, 18 parts of carboxy blockings Alkene block copolymer, the styrene-butadiene block copolymer of 24 parts of amide groups graft modifications, 26 parts of hydroxy-end capped modifications benzene Ethylene-butadiene block copolymer, used graft modification styrene-butadiene block copolymer grafting rate are 34%, end Base modified styrene-butadiene's block copolymer degree of functionality is 21%.
3) viscosity modifier includes: 1 part of oxidized polyethylene wax, 1 part of polyethylene wax, 12 parts of ammonium polyacrylates, 26 parts of burnt phosphorus Sour sodium, 31 parts of sodium cellulose glycolates, 18 parts of hydroxyethyl celluloses and 11 parts of aluminum magnesium silicates.
4) age resister includes: 10 parts of 2,6 di tert butyl 4 methyl phenol, 21 parts of 2,5- di-t-butyl are to benzene two Phenol, 26 parts of N- cyclohexyl p-ethoxyaniline, 17 parts of zinc salt of 2 mercaptobenzimidazole and 26 parts of 4,4 '-dihydroxy connection Benzene.
5) stabilizer includes: 7 parts of aliphatic hydrocarbon resins, 9 parts of aromatic hydrocarbon resins, 2 parts of cycloalkanes hydrocarbon resins, 43 parts of odium stearate, 1 Part zinc oxide, 12 parts of alkyl phenoxy polyethylene glycol oxide sodium sulphate, 9 parts of p-methyl benzenesulfonic acid o-cresol esters, 10 parts of sodium laurates, 2 Part calcium stearate, 5 parts of zinc stearates.
Embodiment 7
1) successively by 75 parts of main body modifying agent, 17 portions of viscosity modifiers, 6 parts of age resisters and 2 parts of stabilizers at -5 DEG C Pulverizer is added to crush, then is sieved to obtain high additive, high resiliency pitch Special modifier with 100 mesh sieve.
2) main body modifying agent includes: 90 parts of styrene-butadiene block copolymers, 9 parts of Polystyrene-Butadiene Copolymer With 1 part of styrene-iso pentane two floride block copolymer.
Wherein styrene-butadiene block copolymer includes: the Styrene-Butadiene block of 53 parts of carboxyl graft modifications is total Styrene-fourth of polymers, the styrene-butadiene block copolymer of 17 parts of hydroxyl graft modifications, 2 parts of modified by maleic acid anhydride graft The modified styrene-butadiene block copolymer of diene block copolymer, 8 parts of carboxy blockings, 5 parts of amide groups graft modifications benzene Ethylene-butadiene block copolymer, 15 parts of hydroxy-end capped modifications styrene-butadiene block copolymer, used grafting Modified styrene-butadiene's block copolymer grafting rate is 45%, terminal groups modification styrene-butadiene block copolymer degree of functionality It is 31%.
3) viscosity modifier includes: 37 parts of oxidized polyethylene wax, 1 part of polyethylene wax, 12 parts of ammonium polyacrylates, 14 parts of burnt phosphorus Sour sodium, 17 parts of sodium cellulose glycolates, 8 parts of hydroxyethyl celluloses and 11 parts of aluminum magnesium silicates.
4) age resister includes: 60 parts of 2,6 di tert butyl 4 methyl phenol, 27 parts of 2,5- di-t-butyl are to benzene two Phenol, 5 parts of N- cyclohexyl p-ethoxyaniline and 8 parts of 4,4 '-dihydroxybiphenyls.
5) stabilizer includes: 9 parts of aromatic hydrocarbon resins, 2 parts of cycloalkanes hydrocarbon resins, 43 parts of odium stearate, 1 part of zinc oxide, 12 parts Alkyl phenoxy polyethylene glycol oxide sodium sulphate, 9 parts of p-methyl benzenesulfonic acid o-cresol esters, 10 parts of sodium laurates, 2 parts of calcium stearates, 12 Part zinc stearate.
Embodiment 8
1) successively 65 parts of main body modifying agent, 30 portions of viscosity modifiers, 3 parts of age resisters and 2 parts of stabilizers are added at 0 DEG C Enter pulverizer crushing, then is sieved to obtain high additive, high resiliency pitch Special modifier with 100 mesh sieve.
2) main body modifying agent includes: 90 parts of styrene-butadiene block copolymers, 9 parts of Polystyrene-Butadiene Copolymer With 1 part of styrene-iso pentane two floride block copolymer.
Wherein styrene-butadiene block copolymer includes: the Styrene-Butadiene block of 11 parts of ester group graft modifications is total Modified styrene-the fourth two of polymers, the styrene-butadiene block copolymer of 21 parts of hydroxyl graft modifications, 18 parts of carboxy blockings Alkene block copolymer, the styrene-butadiene block copolymer of 24 parts of amide groups graft modifications, 26 parts of hydroxy-end capped modifications benzene Ethylene-butadiene block copolymer, used graft modification styrene-butadiene block copolymer grafting rate are 19%, end Base modified styrene-butadiene's block copolymer degree of functionality is 24%.
3) viscosity modifier includes: 6 parts of polyethylene waxes, 13 parts of hydrogenated rosins, 6 parts of terpene resins, 39 parts of hydroxylmethyl celluloses Plain sodium and 36 parts of Sodium Polyacrylates.
4) age resister includes: 14 parts of 2,6 di tert butyl 4 methyl phenol, 21 parts of 2,5- di-t-butyl are to benzene two Phenol, 22 parts of N- cyclohexyl p-ethoxyaniline, 17 parts of zinc salt of 2 mercaptobenzimidazole and 26 parts of 4,4 '-dihydroxy connection Benzene.
5) stabilizer includes: 40 parts of aliphatic hydrocarbon resins, 6 parts of aromatic hydrocarbon resins, 11 parts of cycloalkanes hydrocarbon resins, 29 parts of stearic acid Sodium, 3 parts of zinc oxide, 11 parts of sodium laurates.
Embodiment 9
1) successively 90 parts of main body modifying agent, 6 portions of viscosity modifiers, 2 parts of age resisters and 2 parts of stabilizers are added at 5 DEG C Enter pulverizer crushing, then is sieved to obtain high additive, high resiliency pitch Special modifier with 100 mesh sieve.
2) main body modifying agent includes: 90 parts of styrene-butadiene block copolymers, 9 parts of Polystyrene-Butadiene Copolymer With 1 part of styrene-iso pentane two floride block copolymer.
Wherein styrene-butadiene block copolymer includes: 2 parts of acrylic graft-modified Styrene-Butadiene blocks Copolymer, the styrene-butadiene block copolymer of 14 parts of hydroxyl graft modifications, 22 parts of carboxyl graft modifications styrene-fourth Diene block copolymer, styrene-butadiene block copolymer, the 11 parts of carboxy blockings of 19 parts of modified by maleic acid anhydride graft are modified Styrene-butadiene block copolymer, 15 parts of acrylic acid blocking modifications styrene-butadiene block copolymer, 17 parts of esters The styrene-butadiene block copolymer of base blocking modification, used graft modification styrene-butadiene block copolymer connect Branch rate is 12%, and terminal groups modification styrene-butadiene block copolymer degree of functionality is 5%.
3) viscosity modifier includes: 31 parts of oxidized polyethylene wax, 13 parts of Sodium Polyacrylates, 32 parts of sodium cellulose glycolates, 19 parts of hydroxyethyl celluloses and 5 parts of aluminum magnesium silicates.
4) age resister includes: 70 parts of 2,6 di tert butyl 4 methyl phenol, 6 parts of 2,5- di-t-butyl are to benzene two Phenol, 7 parts of 2-mercaptobenzimidazole, 3 parts of zinc salt of 2 mercaptobenzimidazole and 14 parts of 4,4 '-dihydroxybiphenyls.
5) stabilizer includes: 37 parts of aliphatic hydrocarbon resins, 9 parts of aromatic hydrocarbon resins, 2 parts of cycloalkanes hydrocarbon resins, 39 parts of odium stearate, 3 parts of zinc oxide, 1 part of alkyl phenoxy polyethylene glycol oxide sodium sulphate, 2 parts of polyvinyl alcohol, 7 parts of sodium laurates.
The method for preparing modified pitch using the modifying agent that Examples 1 to 9 produces are as follows: by matrix pitch, modifying agent, aromatic hydrocarbons Oil is added in the matched blend tank of high-speed shearing machine, starts high-speed shearing machine, and shearing to modifying agent is evenly distributed on matrix pitch In, turn off shearing equipment, be cooled to room temperature, obtains modified pitch.
Subordinate list 1 is the high additive produced using embodiment 5, high elasticity modified asphalt Special modifier to the shadow of matrix pitch Ring (in table 10%, 15%, 18% for modifying agent in modified pitch additive amount).
Subordinate list 2 be the high additive produced using embodiment 5, high elasticity modified asphalt Special modifier with it is conventional SBS modified Influence comparison of the agent to matrix pitch.
Subordinate list 3 is high additive, the high elasticity modified asphalt Special modifier produced using the Examples 1 to 9 of 10% volume Influence to matrix pitch (example 1~9 represents Examples 1 to 9 in table).
Subordinate list 1:
The influence table of 5 high additive of embodiment, high resiliency pitch Special modifier to matrix pitch
Test item Unit 10% 15% 18%
Process time h 5 6 7
Needle penetration (25 DEG C, 100g, 5s) 0.1mm 64.5 66 69
Softening point ℃ 99.7 101 113
Ductility (5cm/min, 5 DEG C) cm 76 80 86.9
Aging ductility (5cm/min, 5 DEG C) cm 59.9 63.4 66
135 DEG C of viscosity Pa.s 3.21 3.96 4.32
Subordinate list 2:
Special modifier and the conventional SBS modified dose of influence contrast table to matrix pitch in embodiment 5
Test item Unit Embodiment 5 Common SBS
Process time h 5 8
Needle penetration (25 DEG C, 100g, 5s) 0.1mm 64.5 59
Softening point ℃ 99.7 97
Ductility (5cm/min, 5 DEG C) cm 76 57
Aging ductility (5cm/min, 5 DEG C) cm 59.9 38
135 DEG C of viscosity Pa.s 3.21 7.9
Subordinate list 3:
Influence contrast table of the Special modifier to matrix pitch in Examples 1 to 9
From above-mentioned 1~subordinate list of subordinate list 3 as can be seen that the pitch Special modifier made of the present invention can be greater than 10% It is relatively rapid under conditions of volume to be dispersed in pitch, when doping is up to 18%, jitter time 7, still less than common The jitter time that the yield of SBS10% needs.
Using Special modifier preparation 10% adulteration modified pitch compared with common 10% adulteration modified pitch, it is high Temperature stability improves 10%, low temperature anti-cracking performance and improves 30%, anti-aging property raising 25%, elastic recovery capability raising 36%.
Modified pitch is used for using modifying agent made from inventive formulation technique, each performance is stablized.
Embodiment 10
1) successively that 90 parts of main body modifying agent, 0.1 portion of viscosity modifier, 0.5 part of age resister and 0.2 part is steady at 5 DEG C Determine agent and pulverizer crushing is added, then is sieved to obtain high additive, high resiliency pitch Special modifier with 150 mesh sieve.
2) main body modifying agent includes: 97 parts of styrene-butadiene block copolymers, 2 parts of styrene-butadiene copolymerization Object.The weight average molecular weight range of styrene-butadiene block copolymer is between 20000~350000g/mol.
Styrene-butadiene block copolymer is the styrene-butadiene block copolymer of hydroxyl graft modification, grafting rate It is 0.1%；Polystyrene-Butadiene Copolymer is the Polystyrene-Butadiene Copolymer of hydroxyl graft modification.
Embodiment 11
1) successively by 65 parts of main body modifying agent, 36 portions of viscosity modifiers, 30 parts of age resisters and 37 parts of stabilizations at -10 DEG C Agent is added pulverizer and crushes, then is sieved to obtain high additive, high resiliency pitch Special modifier with 60 mesh sieve.
2) main body modifying agent includes: 68 parts of styrene-butadiene block copolymers, 30 parts of styrene-butadiene copolymerization Object, 16 parts of ethylene-vinyl acetate copolymers and 47 parts of styrene-isoprene block copolymers.
The weight average molecular weight range of styrene-butadiene block copolymer is between 20000~350000g/mol.Benzene second Alkene-butadiene block copolymer is the styrene-butadiene block copolymer of amino graft modification, grafting rate 70%；Polyphenyl Ethylene-butadiene copolymer is the Polystyrene-Butadiene Copolymer of hydroxyl graft modification.Ethylene-vinyl acetate copolymer For the ethylene-vinyl acetate copolymer of amino graft modification；Styrene-isoprene block copolymer is amino graft modification Styrene-isoprene block copolymer；Age resister group is divided into 2,6 di tert butyl 4 methyl phenol；Stabilizer is rouge Fat hydrocarbon resin.
Embodiment 12
1) successively by 70 parts of main body modifying agent, 1 portion of viscosity modifier, 15 parts of age resisters and 10 parts of stabilizers at 0 DEG C Pulverizer is added to crush, then is sieved to obtain high additive, high resiliency pitch Special modifier with 80 mesh sieve.
2) main body modifying agent includes: 70 parts of styrene-butadiene block copolymers, 10 parts of styrene-butadiene copolymerization Object, 5 parts of ethylene-vinyl acetate copolymers and 5 parts of styrene-isoprene block copolymers.
The weight average molecular weight range of styrene-butadiene block copolymer is between 20000~350000g/mol.Benzene second Alkene-butadiene block copolymer be hydroxy-end capped modification-styrene-butadiene block copolymer, degree of functionality 0.1%；It is poly- Styrene-butadiene copolymer is the Polystyrene-Butadiene Copolymer of hydroxyl graft modification.Ethylene-vinyl acetate copolymerization Object is the ethylene-vinyl acetate copolymer of sulfydryl graft modification；Styrene-isoprene block copolymer is that sulfydryl grafting changes The styrene-isoprene block copolymer of property；Age resister group is divided into 2-mercaptobenzimidazole；Stabilizer is cycloalkane tree Rouge.
Embodiment 13
1) successively by 78 parts of main body modifying agent, 10 portions of viscosity modifiers, 3 parts of age resisters and 30 parts of stabilizers at 0 DEG C Pulverizer is added to crush, then is sieved to obtain high additive, high resiliency pitch Special modifier with 120 mesh sieve.
2) main body modifying agent includes: 80 parts of styrene-butadiene block copolymers, 20 parts of styrene-butadiene copolymerization Object, 10 parts of ethylene-vinyl acetate copolymers and 10 parts of styrene-isoprene block copolymers.
The weight average molecular weight range of styrene-butadiene block copolymer is between 20000~350000g/mol.Benzene second Alkene-butadiene block copolymer be amide groups blocking modification-styrene-butadiene block copolymer, degree of functionality 76%；It is poly- Styrene-butadiene copolymer is the Polystyrene-Butadiene Copolymer of amide groups graft modification.Ethylene-vinyl acetate is total Polymers is the ethylene-vinyl acetate copolymer of amide groups graft modification；Styrene-isoprene block copolymer is amide groups The styrene-isoprene block copolymer of graft modification；Age resister group is divided into styrenated phenol；Stabilizer be N- ring Base para toluene sulfonamide.

Claims (2)

1. a kind of high additive high resiliency pitch Special modifier, which is characterized in that the group including consisting of and parts by weight content Point:
The main body modifying agent includes the formula of following parts by weight of component: 90 parts of styrene-butadiene block copolymers, 6 parts Polystyrene-Butadiene Copolymer, 3 parts of ethylene-vinyl acetate copolymers and 1 part of styrene-isoprene block copolymerization Object；
Wherein styrene-butadiene block copolymer includes: the Styrene-Butadiene block copolymerization of 56 parts of hydroxyl graft modifications The modified styrene-butadiene block copolymer of object, 18 parts of carboxy blockings, 26 parts of hydroxy-end capped modifications styrene-butadiene Block copolymer, used graft modification styrene-butadiene block copolymer grafting rate are 10%, terminal groups modification benzene second Alkene-butadiene block copolymer degree of functionality is 16%；
The viscosity modifier includes the formula of following parts by weight of component: 3 parts of oxidized polyethylene wax, 7 parts of polyethylene waxes, 26 parts Sodium pyrophosphate, 34 parts of sodium cellulose glycolates, 19 parts of hydroxyethyl celluloses and 11 parts of aluminum magnesium silicates；
The age resister includes the formula of following parts by weight of component: 14 parts of 2,6 di tert butyl 4 methyl phenol, 21 parts 2,5 di tert butyl hydroquinone, 22 parts of N- cyclohexyl p-ethoxyaniline, 17 parts of zinc salt of 2 mercaptobenzimidazole and 26 parts of 4,4 '-dihydroxybiphenyls；
The stabilizer includes the formula of following parts by weight of component: 7 parts of aliphatic hydrocarbon resins, 9 parts of aromatic hydrocarbon resins, 2 parts of cycloalkanes Hydrocarbon resin, 43 parts of odium stearate, 1 part of zinc oxide, 19 parts of alkyl phenoxy polyethylene glycol oxide sodium sulphate, 9 parts of p-methyl benzenesulfonic acid neighbours Cresols ester, 10 parts of sodium laurates.
2. a kind of preparation method of high additive high resiliency pitch Special modifier as described in claim 1, which is characterized in that will Main body modifying agent, viscosity modifier, age resister and stabilizer are crushed at -10~5 DEG C with pulverizer, are screened out with sieve 60~150 mesh powders obtain high additive high resiliency pitch Special modifier.
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