CN108395715A - A kind of anti-aging high-viscosity asphalt additive and preparation method thereof - Google Patents
A kind of anti-aging high-viscosity asphalt additive and preparation method thereof Download PDFInfo
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- CN108395715A CN108395715A CN201710066722.0A CN201710066722A CN108395715A CN 108395715 A CN108395715 A CN 108395715A CN 201710066722 A CN201710066722 A CN 201710066722A CN 108395715 A CN108395715 A CN 108395715A
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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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/92—Measuring, controlling or regulating
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/9258—Velocity
- B29C2948/9259—Angular velocity
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92704—Temperature
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- 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
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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
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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
- 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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Abstract
The invention discloses a kind of anti-aging high-viscosity asphalt additives and preparation method thereof.The additive includes following raw material components by weight：100 parts of SBS, 20~40 parts of Petropols, 10~40 parts of aromatic naphtha, 10~20 parts of butadiene-styrene rubber, 5~8 parts of modified mesoporous molecular sieve；Wherein, the modified mesoporous molecular sieve is the mesopore molecular sieve that amino silane, hydrosulphonyl silane and hindered phenol type antioxidant are modified, and the hindered phenol type antioxidant is the hindered phenol type antioxidant containing carboxylic group.The high-viscosity asphalt additive of the present invention not only significantly improves the viscosity and caking property of pitch, but also the anti-aging property of pitch has been significantly increased, to extend the service life of road.
Description
Technical field
The present invention relates to a kind of high adhered modification asphalt additives and preparation method thereof, more particularly to a kind of to have ageing resistance
The high adhered modification asphalt additive and preparation method thereof of energy.
Background technology
High-viscosity asphalt refers generally to the pitch that 60 DEG C of dynamic viscosities are more than 20000 Pas, is suitable for open gradation antiskid and wears away
Layer（OGFC）The application on equal road surfaces.Since with larger voidage, the road surfaces OGFC have good draining, noise reduction, skid resistance
Energy.But the architectural characteristic of large porosity also results in pitch and increases with the contact area of air and ultraviolet light, accelerates pitch
Aging, shorten the service life on road surface.
Currently, asphaltum with high viscosity mainly by adding polymer in pitch, can significantly improve the high and low temperature of pitch
The problems such as performance improves the viscosity of pitch, but there are polymer dispersion is uneven, and compatibility is bad.It concurrently there are anti-aging
The problem of performance deficiency.
CN101457009A discloses a kind of asphalt modifier with high viscosity and preparation method thereof, which includes SIS, Gu
The grand resin of horse, oleamide etc..The modifying agent has preferable compatibility with pitch, hence it is evident that improves the adhesiveness of pitch.But
It is the anti-aging problem for not accounting for asphaltum with high viscosity, anti-aging property is insufficient, influences the service life of asphaltum with high viscosity.
CN102838874A discloses a kind of asphalt modifier, modified pitch and asphalt.The high-viscosity asphalt changes
Property agent is by waste-tyre rubber-powder, polyethylene waste, Styrene-Butadiene-Styrene Block Copolymer, styrene-isoamyl two
The compositions such as alkene-styrene block copolymer, terpene resin, solvent naphtha, alcohol ether carboxylate.Modified pitch made from the modifying agent has
There are preferable high and low temperature performance and water stability.But its waste-tyre rubber-powder used there are still with bitumen compatibility is bad asks
Topic, while there is also the problems of anti-aging property deficiency.
To sum up, although the prior art can improve the viscosity and adhesiveness of pitch to a certain extent, there are polymer phases
Capacitive is bad and the problem of anti-aging property deficiency.
Invention content
In view of the deficiencies of the prior art, the present invention provides a kind of anti-aging high-viscosity asphalt additives and preparation method thereof.
The high-viscosity asphalt additive of the present invention not only significantly improves the viscosity and caking property of pitch, but also pitch has been significantly increased
Anti-aging property, to extend the service life of road.
The present invention provides a kind of anti-aging high-viscosity asphalt additives, include following raw material components by weight：
100 parts of SBS；
20~40 parts of Petropols；
10~40 parts of aromatic naphtha；
10~20 parts of butadiene-styrene rubber；
5~8 parts of modified mesoporous molecular sieve；
Wherein, the modified mesoporous molecular sieve is the mesoporous molecular that amino silane, hydrosulphonyl silane and hindered phenol type antioxidant are modified
Sieve, the hindered phenol type antioxidant are the hindered phenol type antioxidant containing carboxylic group.
In the modified mesoporous molecular sieve, the amino silane, hydrosulphonyl silane graft on the table of mesopore molecular sieve respectively
Face, hindered phenol type antioxidant are reacted with amino silane, to which hindered phenol type antioxidant to be connected on the mesopore molecular sieve.
The hindered phenol type antioxidant is 3,5- di-tert-butyl-4-hydroxybenzoic acids, 3- (3,5- di-t-butyl -4- hydroxyls
Phenyl) propionic acid, 3- (3,5- di-tert-butyl-hydroxy phenyls) acrylic acid, 3- (3,5- dimethyl -4- hydroxy phenyls) acrylic acid,
One kind or several in 3- (3,5- dimethoxy-4 's-hydroxy phenyl) acrylic acid and 3- (3- methoxyl group -4- hydroxy phenyls) acrylic acid
Kind.Wherein, 3- (3,5- di-tert-butyl-hydroxy phenyl) propionic acid, can be indicated by following chemical formula：
Formula（Ⅰ）.
The mesopore molecular sieve, amino silane, hydrosulphonyl silane, hindered phenol type antioxidant mass ratio be 100：（3~20）：
（2~10）：（5~25）.
The amino silane is 3- aminopropyl trimethoxysilanes, 3- aminopropyl triethoxysilanes, γ-aminopropyltriethoxy
One or more of diethoxy silane.
The hydrosulphonyl silane is γ-mercaptopropyl trimethoxysilane, gamma-mercaptopropyltriethoxysilane, γ-mercapto propyl first
One or more of base diethoxy silane.
The mesopore molecular sieve is one kind in MCM-41, MCM-22, MCM-48, SBA-15, SBA-16, HMS molecular sieve
Or several, preferably one or more of MCM-41, SBA-15 and SBA-16 molecular sieve.
The specific surface area of the mesopore molecular sieve is preferably 600m2/ g~1250m2/g。
The SBS is linear structure, and molecular weight is 5~250,000.
The Petropols are C 5 petroleum resin, and softening point is 90 DEG C~120 DEG C.
In the aromatic naphtha, the weight content of aromatic hydrocarbon is 40%~80%.The aromatic naphtha is a kind of rich in aromatic hydrocarbons
Component may originate from tapped oil of the lube base oil in solvent refining processes, such as the extraction of furfural extract oil, phenol treating
Oil etc..
The butadiene-styrene rubber is industrial products, and molecular weight is 20 ~ 800,000.
The present invention also provides a kind of preparation methods of above-mentioned anti-aging high-viscosity asphalt additive comprising following step
Suddenly：
（1）Mesopore molecular sieve, amino silane and hydrosulphonyl silane are added in the first organic solvent, under reflux condition into
Row surface modification is reacted, and is dried using filter, washing, first after cooling, is obtained Jie for being grafted with amino silane and hydrosulphonyl silane
Porous molecular sieve；
（2）Under an inert atmosphere, hindered phenol type antioxidant and thionyl chloride are added in the second organic solvent, heating reaction,
Then it distills, obtains the hindered phenol type antioxidant of chloride；
（3）The mesopore molecular sieve of amino silane and hydrosulphonyl silane will be grafted with, the hindered phenol type antioxidant of chloride is added to
In three organic solvents, triethylamine is added, is stirred to react under inert atmosphere conditions, using filter, washing, the second drying, obtained
To modified mesoporous molecular sieve；
（4）After mixing by SBS, Petropols, aromatic naphtha, butadiene-styrene rubber, modified mesoporous molecular sieve, extruded machine, which is blended, squeezes
Go out, be granulated to get to the anti-aging high-viscosity asphalt additive.
In step（1）In, the temperature of the surface modification reaction is 100 DEG C~120 DEG C, and the time is 1~3h.
In step（1）In, the weight ratio of the mesopore molecular sieve and the first organic solvent is 1：（10~30）.
First organic solvent is one or more of dimethylbenzene, toluene, cyclohexanone, chlorobenzene and pyridine.
In step（1）In, it is described be filtered, washed, dry all can be routine techniques.Washing can use ethyl alcohol, chloroform,
Acetone equal solvent is washed, and drying makes solvent vapor away.The temperature of first drying can be 80 DEG C~120 DEG C,
Time is 0.5~5h.
In step（2）In, the temperature of the heating reaction is 40 DEG C~60 DEG C, and the time is 6~8h.
In step（2）In, the weight ratio of the hindered phenol type antioxidant, thionyl chloride and the second organic solvent is 1：
（1.0~1.8）：（10~50）, preferably 1：（1.2~1.5）：（15~30）.
In step（2）In, second organic solvent be chloroform, carbon tetrachloride, acetone, ethyl alcohol, hexamethylene, benzene,
One or more of toluene, dimethylbenzene and cyclohexanone.
In step（3）In, the temperature being stirred to react is 15~50 DEG C, and the time is 15~20h.
In step（3）In, the mesopore molecular sieve for being grafted with amino silane and hydrosulphonyl silane, chloride hindered phenol type
Antioxidant, triethylamine, third organic solvent weight ratio be 1：（0.07~0.3）：（1.0~2.5）：（10~50）, preferably
It is 1：（0.07~0.21）：（1.2~1.8）：（10~30）.
In step（3）In, the third organic solvent be chloroform, carbon tetrachloride, acetone, ethyl alcohol, hexamethylene, benzene,
One or more of toluene, dimethylbenzene and cyclohexanone.
In step（3）In, it is described be filtered, washed, dry all can be routine techniques.Washing can use ethyl alcohol, toluene
Equal solvent is washed, and drying makes solvent vapor away, and the temperature of second drying can be 80 DEG C~120 DEG C, the time
For 3~8h.
In step（4）In, conventional use of extruder, preferably screw extruder may be used in the extruder, squeezes out
Temperature is 130~160 DEG C, and screw speed is 30~150 r/min.Further preferably double screw extruder, two screw rods exist
It being mutually parallel in machine barrel, multistage control may be used in the temperature in machine barrel, if the machine barrel of extruder can be divided into eight temperature sections, tool
Body operating condition is as follows：One section 130~150 DEG C；Two sections 135~155 DEG C；Three sections 140~160 DEG C；Four sections 140~160 DEG C；Five
150~160 DEG C of section；Six sections 150~160 DEG C；Seven sections 145~160 DEG C；Eight sections 150~160 DEG C.
Step（1）、（2）With（3）Reaction process such as flows down by taking 3- (3,5- di-tert-butyl-hydroxy phenyl) propionic acid as an example
Shown in journey：。
Compared with prior art, anti-aging high-viscosity asphalt additive and preparation method thereof of the invention has the following advantages that：
（1）Amino silane is grafted to mesopore molecular sieve by the present invention first, then passes through the carboxyl and ammonia in hindered phenol type antioxidant
The reaction of amino group in base silane grafts antioxidant to molecular sieve, and antioxidant is made to be fixed on molecular sieve surface, reduces
Loss caused by volatilization, physical migration etc., has better stability, and the specific surface area that mesopore molecular sieve is larger so that anti-
Oxygen agent has dispersibility well, is conducive to improve anti-oxidant efficiency, so that high-viscosity asphalt additive not only significantly improves
The viscosity and caking property of pitch, while there is preferable ageing resistance.
（2）Sulfydryl in modified mesoporous molecular sieve of the present invention can be used as auxiliary antioxidant and carry out hydroperoxide decomposition, and turn
Turn to no free radical, stabilization product, to avoid the free radical chain that further causes of free radical that hydroperoxides generate
Reaction, and the hindered phenol type antioxidant in modified mesoporous molecular sieve can eliminate the free radical in pitch there are organic matter, avoid
Free chain reaction, such sulfydryl and primary antioxidant（Hindered phenol type antioxidant）Synergistic effect is generated, major-minor antioxidant
Effect complements each other, and anti-aging property has been significantly increased.
（3）The present invention carries out surface modification using amino silane, hydrosulphonyl silane and antioxidant to mesopore molecular sieve, is improving
While anti-aging property, mercapto groups can promote the cross-linking reaction of additive and pitch, form reticular structure, improve its with
The compatibility of pitch.
（4）Modified mesoporous molecular sieve of the present invention is in particle（Or powder）Shape, it is easy to use, convenient for storage and transport.
Specific implementation mode
The technical characterstic that the invention is further illustrated by the following examples, but these embodiments cannot limit the present invention,
The wt% being related to is mass fraction.
Embodiment 1
（1）By 1 parts by weight MCM-41 mesopore molecular sieves（Specific surface area is 1000 m2/g）, account for MCM-41 mesopore molecular sieves 15wt%
3- aminopropyl trimethoxysilanes and account for the γ-mercaptopropyl trimethoxysilane of MCM-41 mesopore molecular sieves 4wt% and be added to 20
In parts by weight of toluene.The constant temperature at 110 DEG C, it is lasting to stir, it is heated to reflux 3h, cooled and filtered is washed, 100 with a large amount of ethyl alcohol
DEG C dry 5h, obtains the mesopore molecular sieve for being grafted with amino silane and hydrosulphonyl silane.
（2）Under nitrogen protection, by 1 parts by weight 3- (3,5- di-tert-butyl-hydroxy phenyl) acrylic acid and 1.4 parts by weight chlorine
Change sulfoxide to be added in 30 parts by weight chloroforms, 50 DEG C of heating reaction 8h, vacuum distillation obtains 3- (3,5- di-t-butyl -4-
Hydroxy phenyl) acryloyl chloride.
（3）1 parts by weight are grafted with to mesopore molecular sieve, 0.2 parts by weight 3- (bis- uncles of 3,5- of amino silane and hydrosulphonyl silane
Butyl -4- hydroxy phenyls) acryloyl chloride is added in 30 parts by weight of toluene, then 1.8 parts by weight triethylamines are added dropwise, and 25 DEG C,
It is stirred continuously 20h under the conditions of nitrogen protection, is washed using filter, a large amount of ethyl alcohol, 100 DEG C of dry 8h, obtains modified mesoporous molecular
Sieve.
（4）By 100 parts by weight SBS（Molecular weight is 100,000）, 40 parts by weight C 5 petroleum resins（Softening point is 95 DEG C）、20
Parts by weight aromatic naphtha（Aromatic hydrocarbon content is 40wt%）, 10 parts by weight butadiene-styrene rubber（Molecular weight 800,000）, it is 5 part by weight modified mesoporous
Molecular sieve after mixing, through double screw extruder blending extrusion, is granulated, obtains anti-aging high-viscosity asphalt additive.Extruder
Operating condition is：One section is 150 DEG C；Two sections are 155 DEG C；Three sections are 160 DEG C；Four sections are 160 DEG C；Five sections are 160 DEG C；Six sections are
160℃；Seven sections are 160 DEG C；Eight sections are 160 DEG C, and screw speed is 50 r/min.
Embodiment 2
（1）By 1 parts by weight SBA-15 mesopore molecular sieves（Specific surface area is 1100 m2/g）, account for SBA-15 mesopore molecular sieves 10wt%
3- aminopropyl triethoxysilanes and account for the gamma-mercaptopropyltriethoxysilane of SBA-15 mesopore molecular sieves 6wt% and be added to 20
In parts by weight of toluene.The constant temperature at 110 DEG C, it is lasting to stir, it is heated to reflux 3h, cooled and filtered is washed, 100 with a large amount of ethyl alcohol
DEG C dry 5h, obtains the mesopore molecular sieve for being grafted with amino silane and hydrosulphonyl silane.
（2）Under nitrogen protection, by 1 parts by weight 3,5- di-tert-butyl-4-hydroxybenzoic acids and 1.3 parts by weight thionyl chlorides add
Enter into 25 parts by weight chloroforms, 50 DEG C of heating reaction 8h, vacuum distillation obtains 3,5- di-t-butyl -4- (2-hydroxybenzoyl)s
Chlorine.
（3）1 parts by weight are grafted with to mesopore molecular sieve, 0.15 parts by weight 3,5-, the bis- tertiary fourths of amino silane and hydrosulphonyl silane
Base -4- hydroxybenzoyl chlorides are added in 30 parts by weight of toluene, then 1.5 parts by weight triethylamines are added dropwise, 30 DEG C, nitrogen protection
Under the conditions of be stirred continuously 18h, washed using filter, a large amount of ethyl alcohol, 100 DEG C of dry 8h obtain modified mesoporous molecular sieve.
（4）By 100 parts by weight SBS（Molecular weight is 150,000）, 30 parts by weight C 5 petroleum resins（Softening point is 100 DEG C）、
30 parts by weight aromatic naphtha（Aromatic hydrocarbon content is 60wt%）, 15 parts by weight butadiene-styrene rubber（Molecular weight 600,000）, 7 part by weight modified Jie
Porous molecular sieve after mixing, through double screw extruder blending extrusion, is granulated, obtains anti-aging high-viscosity asphalt additive.It squeezes out
Machine operating condition is：One section is 140 DEG C；Two sections are 145 DEG C；Three sections are 150 DEG C；Four sections are 150 DEG C；Five sections are 155 DEG C；Six sections
It is 155 DEG C；Seven sections are 155 DEG C；Eight sections are 155 DEG C, and screw speed is 80 r/min.
Embodiment 3
（1）By 1.5 parts by weight SBA-16 mesopore molecular sieves（Specific surface area is 900 m2/g）, account for SBA-16 mesopore molecular sieves 5wt%
γ-aminopropyltriethoxy diethoxy silane and account for γ-mercapto hydroxypropyl methyl diethoxy silicon of SBA-16 mesopore molecular sieves 10wt%
Alkane is added in 20 parts by weight of toluene.The constant temperature at 110 DEG C, it is lasting to stir, it is heated to reflux 3h, cooled and filtered, with a large amount of second
Alcohol washs, and 100 DEG C of dry 5h obtain the mesopore molecular sieve for being grafted with amino silane and hydrosulphonyl silane.
（2）Under nitrogen protection, by 1 parts by weight 3- (3,5- di-tert-butyl-hydroxy phenyl) propionic acid and 1.2 parts by weight chlorinations
Sulfoxide is added in 25 parts by weight chloroforms, and 50 DEG C of heating reaction 7h, vacuum distillation obtains 3- (3,5- di-t-butyl -4- hydroxyls
Base phenyl) propionyl chloride.
（3）1.5 parts by weight are grafted with to mesopore molecular sieve, the 0.1 parts by weight 3- (3,5- bis- of amino silane and hydrosulphonyl silane
Tert-butyl-hydroxy phenyl) propionyl chloride is added in 30 parts by weight of toluene, then 1.2 parts by weight triethylamines are added dropwise, and 35 DEG C,
It is stirred continuously 20h under the conditions of nitrogen protection, is washed using filter, a large amount of ethyl alcohol, 100 DEG C of dry 8h, obtains modified mesoporous molecular
Sieve.
（4）By 100 parts by weight SBS（Molecular weight is 200,000）, 20 parts by weight C 5 petroleum resins（Softening point is 110 DEG C）、
40 parts by weight aromatic naphtha（Aromatic hydrocarbon content is 80 wt%）, 20 parts by weight butadiene-styrene rubber（Molecular weight 200,000）, 8 part by weight modified Jie
Porous molecular sieve after mixing, through double screw extruder blending extrusion, is granulated, obtains anti-aging high-viscosity asphalt additive.It squeezes out
Machine operating condition is：One section is 130 DEG C；Two sections are 135 DEG C；Three sections are 140 DEG C；Four sections are 140 DEG C；Five sections are 150 DEG C；Six sections
It is 150 DEG C；Seven sections are 145 DEG C；Eight sections are 150 DEG C, and screw speed is 120 r/min.
Comparative example 1
By 100 parts by weight SBS（Molecular weight is 100,000）, 40 parts by weight C 5 petroleum resins（Softening point is 95 DEG C）, 20 parts by weight
Aromatic naphtha（Aromatic hydrocarbon content is 40 wt%）, 10 parts by weight butadiene-styrene rubber（Molecular weight 800,000）, 3.5 parts by weight are without modified
MCM-41 mesopore molecular sieves（Specific surface area is 1000 m2/g）, 0.5 parts by weight 3- aminopropyl trimethoxysilanes, 0.2 parts by weight
γ-mercaptopropyl trimethoxysilane, 0.8 parts by weight 3- (3,5- di-tert-butyl-hydroxy phenyl) acryloyl chloride after mixing,
It through double screw extruder blending extrusion, is granulated, obtains anti-aging high-viscosity asphalt additive.Extruder operating condition is：One section is
150℃；Two sections are 155 DEG C；Three sections are 160 DEG C；Four sections are 160 DEG C；Five sections are 160 DEG C；Six sections are 160 DEG C；Seven sections are 160
℃；Eight sections are 160 DEG C, and screw speed is 50 r/min.
Comparative example 2
By 100 parts by weight SBS（Molecular weight is 100,000）, 40 parts by weight C 5 petroleum resins（Softening point is 95 DEG C）, 20 parts by weight
Aromatic naphtha（Aromatic hydrocarbon content is 40 wt%）, 10 parts by weight butadiene-styrene rubber（Molecular weight 800,000）, 0.8 parts by weight 3- (bis- uncles of 3,5-
Butyl -4- hydroxy phenyls) acryloyl chloride after mixing, through double screw extruder blending extrusion, be granulated, obtain anti-aging high viscous
Asphalt additive.Extruder operating condition is：One section is 150 DEG C；Two sections are 155 DEG C；Three sections are 160 DEG C；Four sections are 160 DEG C；
Five sections are 160 DEG C；Six sections are 160 DEG C；Seven sections are 160 DEG C；Eight sections are 160 DEG C, and screw speed is 50 r/min.
Test case
The anti-aging high adhered modification asphalt additive of 12 parts by weight is added to the matrix pitch of 100 parts by weight melting（Decompression residuum,
25 DEG C of needle penetrations are 71 1/10mm）In, at 175 DEG C, high speed shear 1h stirs 0.5h at identical temperature, it is made uniformly to divide
It dissipates in matrix pitch, gained high adhered modification pitch is tested, the result is shown in tables 1.Wherein, Thin Film Oven Test TFOT is according to mark
Quasi- GB/T5304-2001 is tested.
The property of modified pitch obtained by 1 matrix pitch of table and embodiment and comparative example
| Matrix pitch | Embodiment 1 | Embodiment 2 | Embodiment 3 | Comparative example 1 | Comparative example 2 | |
| Needle penetration/25 DEG C, 0.1mm | 71 | 59 | 58 | 56 | 59 | 60 |
| 5 DEG C of ductility/cm | 11 | 44 | 46 | 47 | 44 | 45 |
| 60 DEG C of dynamic viscosity/Pas | 210 | 110824 | 113954 | 116005 | 108653 | 107320 |
| Softening point/DEG C | 47.9 | 90.5 | 90.8 | 91.3 | 90.3 | 90.1 |
| After Thin Film Oven Test TFOT | ||||||
| Penetration ratio/% | 67 | 78 | 80 | 84 | 71 | 69 |
| Remain Ductility ratio/% | - | 27 | 20 | 32 | 22 | 18 |
By in table 1 as it can be seen that the anti-aging high adhered modification asphalt additive of the present invention can significantly improve the viscosity of pitch.With comparative example 1
It is compared with 2, the pitch being modified using the method for the present invention, after Thin Film Oven Test TFOT, needle penetration loss is small, and residual Ductility ratio is high,
This shows that the synergistic effect for the hydrosulphonyl silane and amino silane and primary antioxidant that mesopore molecular sieve surface introduces significantly improves drip
Green anti-aging property.
1 antiageing effect of comparative example is not so good as embodiment 1-3, main reason is that：Amino silane, hydrosulphonyl silane and main antioxygen
Agent unreacted is grafted to mesopore molecular sieve, and there are volatilization, physical migration and thermal decompositions, cause damages, therefore its anti-aging effect
Surface modification mesopore molecular sieve of the fruit not as good as the present invention.2 antiageing effect of comparative example is not so good as Examples 1 to 3, main reason is that
It is not added with surface modification mesopore molecular sieve, therefore its antiageing effect is not as good as the modified pitch of the present invention.
Claims (19)
1. a kind of anti-aging high-viscosity asphalt additive, which is characterized in that include following raw material components by weight：
100 parts of SBS；
20~40 parts of Petropols；
10~40 parts of aromatic naphtha；
10~20 parts of butadiene-styrene rubber；
5~8 parts of modified mesoporous molecular sieve；
Wherein, the modified mesoporous molecular sieve is the mesoporous molecular that amino silane, hydrosulphonyl silane and hindered phenol type antioxidant are modified
Sieve, the hindered phenol type antioxidant are the hindered phenol type antioxidant containing carboxylic group.
2. additive according to claim 1, which is characterized in that in the modified mesoporous molecular sieve, the amino silicone
Alkane, hydrosulphonyl silane graft on the surface of mesopore molecular sieve respectively, and hindered phenol type antioxidant is reacted with amino silane, to be obstructed
Phenol type antioxidant is connected on the mesopore molecular sieve.
3. additive according to claim 1 or 2, which is characterized in that the hindered phenol type antioxidant is 3,5-, bis- tertiary fourths
Base -4-HBA, 3- (3,5- di-tert-butyl-hydroxy phenyls) propionic acid, 3- (3,5- di-tert-butyl-hydroxy phenyls) third
Olefin(e) acid, 3- (3,5- dimethyl -4- hydroxy phenyls) acrylic acid, 3- (3,5- dimethoxy-4 's-hydroxy phenyl) acrylic acid and 3- (3-
One or more of methoxyl group -4- hydroxy phenyls) acrylic acid.
4. additive according to claim 1 or 2, which is characterized in that the mesopore molecular sieve, amino silane, sulfydryl silicon
Alkane, hindered phenol type antioxidant mass ratio be 100：（3~20）：（2~10）：（5~25）.
5. additive according to claim 1 or 2, which is characterized in that the amino silane is 3- aminopropyl trimethoxies
One or more of silane, 3- aminopropyl triethoxysilanes, γ-aminopropyltriethoxy diethoxy silane.
6. additive according to claim 1 or 2, which is characterized in that the hydrosulphonyl silane is γ-mercapto propyl trimethoxy
One or more of silane, gamma-mercaptopropyltriethoxysilane, γ-mercapto hydroxypropyl methyl diethoxy silane.
7. additive according to claim 1 or 2, which is characterized in that the mesopore molecular sieve be MCM-41, MCM-22,
One or more of MCM-48, SBA-15, SBA-16, HMS molecular sieve, preferably MCM-41, SBA-15 and SBA-16 molecule
One or more of sieve, the specific surface area of the mesopore molecular sieve is preferably 600m2/ g~1250m2/g。
8. additive according to claim 1 or 2, which is characterized in that the SBS is linear structure, and molecular weight is 5~25
Ten thousand, the molecular weight of the butadiene-styrene rubber is 20~800,000.
9. additive according to claim 1 or 2, which is characterized in that the Petropols are C 5 petroleum resin, soft
It is 90 DEG C~120 DEG C to change point.
10. additive according to claim 1 or 2, which is characterized in that in the aromatic naphtha, the weight content of aromatic hydrocarbon
It is 40%~80%.
11. a kind of preparation method of additive as described in any one of claim 1-10 comprising following steps：
（1）Mesopore molecular sieve, amino silane and hydrosulphonyl silane are added in the first organic solvent, under reflux condition into
Row surface modification is reacted, and is dried using filter, washing, first after cooling, is obtained Jie for being grafted with amino silane and hydrosulphonyl silane
Porous molecular sieve；
（2）Under an inert atmosphere, hindered phenol type antioxidant and thionyl chloride are added in the second organic solvent, heating reaction,
Then it distills, obtains the hindered phenol type antioxidant of chloride；
（3）The mesopore molecular sieve of amino silane and hydrosulphonyl silane will be grafted with, the hindered phenol type antioxidant of chloride is added to
In three organic solvents, triethylamine is added, is stirred to react under inert atmosphere conditions, using filter, washing, the second drying, obtained
To modified mesoporous molecular sieve；
（4）After mixing by SBS, Petropols, aromatic naphtha, butadiene-styrene rubber, modified mesoporous molecular sieve, extruded machine, which is blended, squeezes
Go out, be granulated to get to the anti-aging high-viscosity asphalt additive.
12. according to the method for claim 11, which is characterized in that in step（1）In, the temperature of the surface modification reaction
It it is 100 DEG C~120 DEG C, the time is 1~3h.
13. according to the method for claim 11, which is characterized in that in step（1）In, the mesopore molecular sieve has with first
The weight ratio of solvent is 1：（10~30）, first organic solvent be preferably dimethylbenzene, toluene, cyclohexanone, chlorobenzene and
One or more of pyridine.
14. according to the method for claim 11, which is characterized in that in step（2）In, the temperature of the heating reaction is 40
DEG C~60 DEG C, the time is 6~8h.
15. according to the method for claim 11, which is characterized in that in step（2）In, the hindered phenol type antioxidant, chlorine
The weight ratio for changing sulfoxide and the second organic solvent is 1：（1.0~1.8）：（10~50）, preferably 1：（1.2~1.5）：（15
~30）, second organic solvent is preferably chloroform, carbon tetrachloride, acetone, ethyl alcohol, hexamethylene, benzene,toluene,xylene
One or more of with cyclohexanone.
16. according to the method for claim 11, which is characterized in that in step（3）In, the temperature being stirred to react is 15
~50 DEG C, the time is 15~20h.
17. according to the method for claim 11, which is characterized in that in step（3）In, it is described to be grafted with amino silane and mercapto
The mesopore molecular sieve of base silane, the hindered phenol type antioxidant of chloride, triethylamine, third organic solvent weight ratio be 1：
（0.07~0.3）：（1.0~2.5）：（10~50）, preferably 1：（0.07~0.21）：（1.2~1.8）：（10~30）, described
Third organic solvent is preferably in chloroform, carbon tetrachloride, acetone, ethyl alcohol, hexamethylene, benzene,toluene,xylene and cyclohexanone
One or more.
18. according to the method for claim 11, which is characterized in that the temperature of first drying is 80 DEG C~120 DEG C, when
Between be 0.5~5h；The temperature of second drying can be 80 DEG C~120 DEG C, and the time is 3~8h.
19. according to the method for claim 11, which is characterized in that in step（4）In, the extruder is Screw Extrusion
Machine, extrusion temperature are 130~160 DEG C, and screw speed is 30~150 r/min；It is preferred that extruder is double screw extruder, use
Eight temperature section operations, wherein operating condition is as follows：One section is 130~150 DEG C；Two sections are 135~155 DEG C；Three sections for 140~
160℃；Four sections are 140~160 DEG C；Five sections are 150~160 DEG C；Six sections are 150~160 DEG C；Seven sections are 145~160 DEG C；Eight
Section is 150~160 DEG C.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110922768A (en) * | 2018-09-20 | 2020-03-27 | 中国石油化工股份有限公司 | Direct-throwing type high-viscosity asphalt modifier and preparation method thereof |
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